Blends Dyeing

Blends Dyeing
John Shore
Formerly of BTTG-Shirley and ICI (now BASF), Manchester, UK
1998
Society of Dyers and Colourists
iii
Copyright 1998 Society of Dyers and Colourists. All rights reserved. No part
of this publication may be reproduced, stored in a retrieval system or transmitted
in any form or by any means without the prior permission of the copyright
owners.
Published by the Society of Dyers and Colourists, PO Box 244, Perkin House,
82 Grattan Road, Bradford, West Yorkshire BD1 2JB, England, on behalf of the
Dyers Company Publications Trust.
This book was produced under the auspices of the Dyers Company
Publications Trust. The Trust was instituted by the Worshipful Company of
Dyers of the City of London in 1971 to encourage the publication of textbooks
and other aids to learning in the science and technology of colour and coloration
and related fields. The Society of Dyers and Colourists acts as trustee to the
fund, its Textbooks Committee being the Trusts technical subcommittee.
Typeset by the Society of Dyers and Colourists and printed by H Charlesworth
& Co. Ltd, Huddersfield, UK.
ISBN 0 901956 74 0
iv
Contents
Preface
CHAPTER 1
1.1
1.2
1.3
1.4
1.5
1.6
1.7
3.7
Classification of fibre types and their blends
21
Dynamic competition between fibre types

in the dyeing of blends
26
Introduction 26
The distribution of acid dyes on nylon/wool blends 29
The distribution of acid dyes on nylon/polyurethane blends 35
The cross-staining of wool by disperse dyes 36
The cross-staining of wool by basic dyes 41
The transfer of disperse dyes during thermofixation of
polyester/cellulosic blends 44
References 45
CHAPTER 4
4.1
4.2
4.3
4.4
Classification of fibre types in terms of dyeability 21

Colour distribution attainable on binary blends 22
References 25
CHAPTER 3
3.1
3.2
3.3
3.4
3.5
3.6
Why blending is necessary
Blending from the dyers viewpoint 1

The composition of blend fabrics 2
The relative importance of individual blends 3
Reasons for the development of fibre blends 5
Colour effects achieved by blending 10
Sighting colours for identification purposes 19
References 20
CHAPTER 2
2.1
2.2
2.3
ix
Minimising incompatibility between dyes

from different classes
Interaction between disperse dyes and reactive dyes 46

Interaction between disperse or vat dyes and basic dyes 47
Interaction between anionic dyes and basic dyes 48
References 52
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46
CHAPTER 5
5.1
5.2
5.3
5.4
5.5
5.6
7.4
7.5
7.6
7.7
7.8
77
Wool/acrylic and other AB blends
86
Dyeing of wool/acrylic blends 86

Dyeing of nylon/acrylic blends 90
Blends of acid-dyeable and basic-dyeable acrylic
variants 91
Blends of modacrylic and acrylic fibres 93
Blends of amide fibres with modacrylic or acid-dyeable
acrylic variants 94
Blends of basic-dyeable polyester with wool or nylon 96
Dyeing methods and dye selection for AB blends 99
References 99
CHAPTER 8
8.1
8.2
8.3
8.4
8.5
Nylon/wool and other AA blends
Dyeing of nylon/wool blends 77

Blends of wool with other acid-dyeable fibres 79
Blends of nylon with other acid-dyeable fibres 82
Dyeing methods and dye selection for AA blends 84
References 85
CHAPTER 7
7.1
7.2
7.3
53
Design of differential-dyeing variant synthetic-polymer

yarns 53
Dyeing of acid-dyeable nylon variants 57
Dyeing of acid-dyeable/basic-dyeable nylon
variants 61
Design of differential-dyeing cellulosic fabrics 63
Design of differential-dyeing wool keratin
derivatives 71
References 76
CHAPTER 6
6.1
6.2
6.3
6.4
6.5
Principles of design and colouring of

differential-dyeing blends
Wool/cellulosic and other AC blends
Dyeing of wool/cellulosic blends 100

Exhaust dyeing of nylon/cellulosic blends 108
Continuous dyeing of nylon/cellulosic blends 113
Dyeing methods and dye selection for AC blends 115
References 118
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100
CHAPTER 9
9.1
9.2
9.3
9.4
9.5
9.6
Cellulosic/acrylic and other CB blends
119
Exhaust dyeing of cellulosic/acrylic blends 119

Continuous dyeing of cellulosic/acrylic blends 122
Blends of cellulosic fibres with modacrylic or
acid-dyeable acrylic variants 124
Blends of basic-dyeable polyester with cotton 126
Dyeing methods and dye selection for CB blends 126
References 128
CHAPTER 10
Cotton/viscose and other CC blends
129
10.1 Properties and performance of cellulosic fibres in

their blends 129
10.2 Dyeing behaviour of cellulosic fibres in their
blends 133
10.3 Dyeing methods and dye selection for CC blends 136
10.4 References 137
CHAPTER 11
Polyester/wool and other DA blends
138
11.1 Dyeing of polyester/wool blends 138

11.2 Blends of cellulose acetate or triacetate with
wool 149
11.3 Dyeing of polyester/nylon blends 152
11.4 Blends of cellulose acetate or triacetate with
nylon 154
11.5 Blends of poly(vinyl chloride) fibres with wool or
nylon 157
11.6 Dyeing methods and dye selection for DA blends 160
11.7 References 160
CHAPTER 12
Polyester/acrylic and other DB blends
12.1 Dyeing of polyester/acrylic blends 161

12.2 Blends of cellulose acetate or triacetate with acrylic
fibres 163
12.3 Dyeing of normal/basic-dyeable polyester blends 165
12.4 Dyeing methods and dye selection for DB blends 168
12.5 References 168
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161
CHAPTER 13
Polyester/cellulosic and other DC blends
169
13.1 Exhaust dyeing of polyester/cellulosic blends 169

13.2 Continuous dyeing of polyester/cellulosic blends 187
13.3 Blends of cellulose acetate or triacetate with cellulosic
fibres 197
13.4 Blends of poly(vinyl chloride) fibres with cellulosic
fibres 201
13.5 Dyeing methods and dye selection for DC blends 201
13.6 References 204
CHAPTER 14
Triacetate/polyester and other DD blends
206
14.1 Dyeing properties of disperse-dyeable fibre blends 206

14.2 Dyeing methods and dye selection for DD blends 210
14.3 References 211
CHAPTER 15
Dyeing properties of three-component

blends
15.1
15.2
15.3
15.4
15.5
15.6
15.7
15.8
15.9
15.10
15.11
15.12
Introduction 212
Dyeing of AAA blends 213
Dyeing of AAB blends 215
Dyeing of AAC blends 216
Dyeing of CBA blends 217
Dyeing of DAA blends 217
Dyeing of DAC blends 218
Dyeing of DBA blends 219
Dyeing of DBC blends 220
Dyeing of DDA blends 221
Dyeing of DDC blends 222
Dyeing methods and dye selection for three-component
blends 222
15.13 References 225
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212
Preface
This book is an addition to the series on coloration technology issued by the
Textbooks Committee of the Society of Dyers and Colourists under the aegis
of the Dyers Company Publications Trust Management Committee, which
administers the fund generously provided by the Worshipful Company of
Dyers.
Earlier books on dyeing technology in this series, namely The dyeing of
synthetic-polymer and acetate fibres (1979), The dyeing of cellulosics fibres
(1986) and Wool dyeing (1992), each contained a chapter on the dyeing of
those fibre blends most relevant to their respective titles. Inevitably, this
approach lacked balance, and material on specific blends was either partially
duplicated or, more often, entirely overlooked. When replacements for the
1979 and 1986 books were under consideration in the early 1990s, the
decision was taken to produce a separate volume dedicated to the dyeing of
fibre blends. This book is the result of that change of approach.
Very few books have been devoted solely to this subject. The best known
is undoubtedly the classic Dyeing of fibre blends (1966), written by Roy
Cheetham of Courtaulds. Invaluable in its time, Cheethams book was a
mine of practical information and detailed recommendations for every
conceivable blend. The treatment in this present book is intended to provide
only general guidelines in this respect, since a dyer encountering an
unfamiliar blend for the first time cannot avoid undertaking preliminary
development work. An attempt is made in the first five chapters of this book
to express some general principles applicable to the theme. A classification of
blends according to the dyeing properties of their component fibres is
introduced in Chapter 2. These categories form the respective topics of the
remaining ten chapters on dyeing methods.
The author is indebted to the referee of this book and to Jim Park for
valuable comments and suggestions for improvement of the text. Grateful
thanks are due to Paul Dinsdale (the editor of the Society), Gina Walker
(copy editing and proof reading) and Sue Petherbridge (typesetting and
layout).
JOHN SHORE
ix
CHAPTER 1
Why blending is necessary
1.1 BLENDING FROM THE DYERS VIEWPOINT

The term blending is used by the yarn manufacturer to describe specifically the
sequence of processes required to convert two or more kinds of staple fibres into
a single yarn composed of an intimate mixture of the component fibres. This
may be necessary to obtain a uniform yarn from different varieties of the same
fibrous polymer, as in the blending of wool qualities differing in origin, or in the
blending of two colours of mass-pigmented man-made fibre to give a target hue.
Any blend must have acceptable properties for the spinner. Important factors
include the relative diameters, staple lengths and extensibilities of the fibres
present. A mismatch can create a blend that has lower strength than that of either
of the component fibre types. Polyester has an advantage over nylon in blends
with cotton in that its initial modulus matches that of cotton more closely.
To the dyer, however, the significant type of staple-fibre blend is that in which
the components are two different fibrous polymers, each with its own
characteristic dyeing properties. The term blend has therefore been used more
loosely by the dyer to refer to any combination of fibre types, whether they occur
as different filaments or staple fibres in the same yarn, or as different yarns
assembled in the same fabric or garment. This is the sense in which blend is
used here, the essential difference between the components being that of dyeing
characteristics.
Blended-staple yarns occupy a highly important position alongside the major
types of homogeneous staple-fibre yarns in the textile industry. Blends of
synthetic fibres, notably polyester, with cellulosics are produced in such
quantities, for shirtings, dresswear, outerwear, rainwear, workwear and
household textiles, that continuous dyeing methods for these blends are as
important as for the parent cellulosic fabrics. Polyester/wool blends are
particularly useful in suitings, dresswear and outerwear, whilst wool yarns in
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WHY BLENDING IS NECESSARY
hand-knitting, hosiery, knitwear and carpets have yielded much ground to nylon/
wool blends.
Mixed-ply yarns have been incorporated in woven fabrics for many years,
often to introduce special effect threads, or in more substantial proportion to
confer stretch, bulk or resilience. The contrasting dyeability of the component
yarns may give attractive marl effects and prove useful in carpets, knitwear or
hand-knitting yarns. In support hosiery and foundation garments elastomeric
warp yarns are often covered with nylon filament yarn.
Fabrics woven from polyester staple-core/cotton wrap yarns in both warp and
weft directions can be successfully desized, bleached, dyed to solid shades and
given a durable press finish without difficulty using conventional procedures
with only slight modifications. The finished fabrics are soft but exceptionally
strong. They are especially useful where high strength, durability, moisture
absorbency and easy-care performance are important features [1]. Fabrics
constructed from these staple-core yarns and from intimate-blend yarns have
been compared before and after durable press finishing. The superior properties
of the treated staple-core fabrics are attributed to the consolidation of the
stronger but more extensible polyester staple in the core of the yarns [2].
Ingenious methods of combining man-made fibrous polymers in the same
extruded filament or bundle of filaments have been developed from time to time
but have failed to generate much more than novelty interest. Filaments made
from two different polymers fused together within the material are known as
bicomponent filaments [3,4]. Multifilament yarns, formed by the intermingling
of two types of filament by extrusion from a special spinneret, contain a random
distribution of the individual components [5].
1.2 THE COMPOSITION OF BLEND FABRICS
Staple-fibre yarn blends are long-established in woven fabrics and there is an
exceedingly wide variety of fabric constructions woven or knitted from two (or
more) types of homogeneous yarn. Materials of the latter kind have often been
referred to as union fabrics, but to avoid confusion this term will be avoided
here. The broader description blend fabrics will be used where necessary to
describe all types of construction made from two or more fibrous polymers or
variants that differ in dyeing characteristics, including filament unions, blendedstaple fabrics, pile fabrics and carpets.
Apparel and domestic textiles are important for such blend fabrics, which may
exhibit desirable two-way differences in physical properties and often provide
scope for attractive multicolour patterning. The availability of wholly synthetic
blend fabrics, such as polyester/acrylic dresswear, polyester/nylon outerwear or
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THE COMPOSITION OF BLEND FABRICS
nylon/acrylic half-hose, as well as the differential-dyeing variants of these

individual fibres, offers considerable scope for striking coloured effects.
Pile fabrics play an important part in the upholstery and furnishings market.
They often consist of a nylon or cellulosic backing fabric with a resilient pile
made from wool or acrylic staple. Cotton pile in nylon support fabric is widely
used in lightweight towelling, leisurewear and childrens clothing. The carpet
industry is a long-established outlet for fibre blends. Apart from the notable
share of nylon/wool blended staple in the traditional woven field, the availability
of differential-dyeing nylon has simplified the production of multicoloured
designs in tufted carpeting, made by needling the appropriately identified pile
yarns into a suitable backing.
1.3 THE RELATIVE IMPORTANCE OF INDIVIDUAL BLENDS

It is often difficult to obtain detailed information on the relative demand for
different types of fibre blends. Statistics of production or consumption of textile
fibres are almost always classified in terms of the total amount of each fibre type,
irrespective of whether that fibre is used alone in a garment or other textile, or as
a component of blended material. The figures in Tables 1.1 and 1.2 are taken
from part of a confidential market research survey for 1985, in which the
information was gathered for each market according to whether the amounts of
fibres were used alone or in one of several major categories of fibre blends. In
order to exclude from consideration those industrial uses of fibres (normally not
blended) where coloration is not a possibility, the statistics were limited to those
Table 1.1 Textile fibres available for coloration worldwide
Fibres
Amount
(kg 106)
Proportion
(%)
Cotton
Polyester/cellulosic blends
Nylon (including polyurethane)
Polyester
Acrylic (including modacrylic)
Viscose (including modal, polynosic)
Wool (including other animal fibres)
All other blends
Linen (including other bast fibres)
Cellulose acetate and triacetate
Silk
11640
4520
3090
2840
2210
2030
1560
1220
370
285
65
39.0
15.2
10.4
9.5
7.4
6.8
5.2
4.1
1.2
1.0
0.2
Total
29830
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Table 1.2 Blends of fibres available for coloration worldwide
Blends
Amount
(kg 106)
Proportion
(%)
Polyester/cotton
Polyester/viscose
Miscellaneous blendsa
Polyester/wool
Wool/acrylic
Other synthetic blendsb
Other cotton blendsc
Nylon/wool
3350
1170
545
410
80
75
65
45
58.4
20.4
9.5
7.1
1.4
1.3
1.1
0.8
Total
5740
a Includes wool/polyurethane, wool/viscose, cellulose acetate/nylon, ...

b Includes nylon/acrylic, polyester/nylon, polyester/acrylic, ...
c Includes nylon/cotton, cotton/acrylic, cotton/viscose, ...
quantities of each fibre or blend that were available for coloration, i.e. to be
dyed, printed or finished as white apparel or household textiles.
Several interesting facts emerge from these tables. About 20% of the total
fibres in Table 1.1 are constituents of blended materials and about 80% of this
total, broken down in Table 1.2, is represented by the polyester/cellulosic sector.
As a substrate type, polyester/cellulosic is more significant than any of the three
main all-synthetic types and is second only to cotton in importance (Table 1.1).
All other cotton or viscose blends are very much less significant than either
polyester/cotton or polyester/viscose. Polyester/wool is also a more important
blend than either nylon/wool or wool/acrylic, but here the differences in demand
are less dramatic. The numerous synthetic blends and miscellaneous blends
making up the remaining 10% of the total in Table 1.2 are individually of minor
significance but collectively they have presented a wide variety of problems to
those devising satisfactory dyeing procedures for them.
The blending and processing of an above-average proportion (i.e. more than
20%) of total fibres in the form of blended materials is characteristic of the
relatively complex and sophisticated textile industries found in economically
developed or developing countries. In the Asia Pacific region this figure exceeds
40% in some instances (Thailand, Malaysia and Indonesia) and is above average
in several others (Australia, Burma, PR China, Hong Kong, Japan, Korea,
Philippines, Singapore and Taiwan). South Africa, Canada, USA, Mexico and
Brazil are other markets with an above-average proportion of blended fibres.
Most European textile industries process 1020% of total fibres as blends, with
above-average values in Germany, Spain, Portugal, Greece, Bulgaria, Rumania
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THE RELATIVE IMPORTANCE OF INDIVIDUAL BLENDS
and Poland. The overall figure for blends in the UK textile industry is 17.5% of
total fibres, but the proportions represented by polyester/wool (42% of UK
blends) and nylon/wool (16%) are substantially above average, reflecting the
continuing importance of suitings and carpets respectively in the UK industry.
1.4 REASONS FOR THE DEVELOPMENT OF FIBRE BLENDS
Several interrelated factors may contribute to the justification for replacing a
homogeneous textile material by a blend:
(1) Economy: the dilution of an expensive fibre by blending with a cheaper
substitute.
(2) Durability: the incorporation of a more durable component to extend the
useful life of a relatively fragile fibre.
(3) Physical properties: a compromise to take advantage of desirable
performance characteristics contributed by both fibre components.
(4) Colour: the development of novel garment or fabric designs incorporating
multicolour effects.
(5) Appearance: the attainment of attractive appearance and tactile qualities
using combinations of yarns of different lustre, crimp or denier, which still
differ in appearance even when dyed uniformly to the same colour.
1.4.1 Balance of economy and physical properties
Cellulosic fibres, especially viscose staple, have been used for many years in
blending with more expensive wool or synthetic fibres. In such blends the
balance of physical properties is at least as important as economic
considerations. During the 1930s the cheaper fibres from regenerated cellulose,
i.e. viscose and cellulose acetate, as well as regenerated protein fibres helped to
compensate for fluctuations in the price of wool by providing blend yarns at
more stable prices in periods of high demand for wool. When synthetic staple
fibres became available for blending in the 1950s, prices were high and blending
with natural or regenerated fibres was a valuable means of establishing outlets
for them using existing methods of processing. As the price levels of synthetic
fibres fell with the tremendous growth in competition and volume of production
that followed, the cost differentials between these blends and the component
fibres lost most of their significance. In recent years there has been some
movement from 80:20 wool/nylon to 50:50 wool/polypropylene yarns in carpets
on price grounds [6,7].
Fibre blending can be regarded as a contribution to fabric engineering. By
using fibres that differ in absorbency, fabrics with specific moisture regain values
can be created. With fibres that differ in denier, desired stiffness and drape
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qualities can be designed into the fabric. Blends of synthetic fibres with natural
fibres offer the most valuable possibilities for combining desirable physical
properties, because the two components are so dissimilar. In blends of polyester
or acrylic fibres with cotton or viscose the synthetic component provides crease
recovery, dimensional stability, tensile strength, abrasion resistance and easy-care
properties, whilst the cellulosic fibre contributes moisture absorption, antistatic
characteristics and reduced pilling. The antistatic effect is particularly significant:
for example, only 1020% of viscose (or a smaller proportion of metallic
filaments) is required to confer antistatic properties on an acrylic fibre.
Apparel fabrics, hosiery and carpet yarns combining the durability and elastic
recovery of nylon with the warmth, bulk and softness of wool or high-bulk
acrylic staple are important examples of a desirable balance of properties. Mens
socks in 100% nylon were heavily promoted in the 1960s for their stretch, easycare properties and durability compared with traditional wool socks. However,
these garments had not been designed to meet comfort needs [8] and were soon
perceived to be hot and uncomfortable when worn in shoes. It was at this time
that coarse-filament nylon blends with wool or cotton began to appear. This
development resulted in nylon/wool and nylon/cotton socks that were more
comfortable and had the added benefits of dimensional stability with stretch
properties, easy-care laundering, attractive appearance and excellent durability.
Spun-dyed yarns and differential-dyeing variants were exploited to provide
increased colour and design potential.
Stretch fabrics for leisurewear are available in a wide range of qualities, often
based on a crimped nylon warp with a wool, acrylic or viscose staple weft. The
development of durable flame-retardant finishes for conventional synthetic
fabrics and their blends has proved difficult and there has been considerable
exploitation of the inherent flame resistance and thermal insulation properties of
poly(vinyl chloride) fibres, or certain modacrylic copolymers with chloro
substitution, in blends with wool for thermal underwear, nightwear garments,
childrens clothing and knitwear.
Many characteristics of all-wool cloths can be simulated by blending longstaple polyester or acrylic fibres with wool. These blends generally do not possess
equivalent suitability for milling because of the absence of any directional friction
effect with the smooth synthetic fibres, although small amounts (up to about
20%) of these fibres can accelerate wool shrinkage during milling. Such blends
exhibit the valuable features of excellent dimensional stability (often at least
equal to shrink-resist wool), abrasion resistance and durable pleat retention.
The beneficial effect on crease recovery of blending polyester with wool is
illustrated in Table 1.3. The value for the intact synthetic fibre alone is
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REASONS FOR THE DEVELOPMENT OF FIBRE BLENDS
approximately 1.5 times that for wool, and when blended at a typical 55:45 ratio
the crease recovery of the blend fabric is significantly higher (74) than the value
anticipated from this composition (68). When dyed with carrier, however,
changes in the fine structure of the polyester involving chain folding result in a
marked reduction in crease recovery, by about 6% in this instance [9].
Table 1.3 Crease recovery of blended polyester and wool [9]

Crease recovery (%)a after dyeing at 105C
Fabric
No carrier
With carrier
100% Wool
55:45 Polyester/wool
100% Polyester
55
74
80
55
68
74
a Data obtained by the CSIRO multiple pleat test
The improvement in dimensional stability that takes place when wool is

blended with an ester fibre is demonstrated in Figure 1.1. This records the
marked decrease in milling shrinkage observed in worsted blend fabrics as the
proportion of cellulose triacetate staple to 48s wool increases. In this instance the
shrinkage is halved (or the dimensional stability is doubled) when the proportion
of triacetate reaches about 40%. The stabilising effect of the man-made fibre
component is more pronounced in the case of coarser wool qualities.
Weft shrinkage/%
50
40
30
20
10
20
40
60
80
Triacetate in blend/%
Figure 1.1 Milling shrinkage of cellulose triacetate/wool
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1.4.2 Development of microfibre variants

Microfibres feel pleasant against the skin, combining the easy-care properties of
a synthetic fibre with the silky appearance and comfort of a natural fibre. The
rate of growth of the market for polyester microfibres (less than 1 dtex per
filament) and supermicrofibres (<0.3 dtex fil1) will depend on their success in
penetrating the polyester/cellulosic blend apparel sectors in Europe, the USA and
Asia Pacific regions. So far the uses of polyester microfibres have been mainly
confined to unblended (mainly filament) materials, such as:
(1) fashionable woven outerwear suede and velour fabrics with attractive
handle and drape [10];
(2) woven sportswear and skiwear with improved transfer of moisture;
(3) polar fleece garments, which provide excellent thermal insulation [11];
(4) tightly woven rainwear fabrics affording effective protection with
breathability;
(5) warp- and weft-knitted twin-layer microliner fabrics [12];
(6) imitation silks with attractive lustre and drape.
In 1992, microfibre variants represented less than 1% of total demand for all
forms of polyester but by 2000 AD they are expected to achieve a 1025%
share. In woven fabrics, filament blends of polyester microfibres and viscose are
gaining popularity in dresswear and blouses. Polyester microfilaments and
cotton are being introduced into knitted sportswear. So far, unfortunately,
spinning problems and pilling behaviour have inhibited the potential uses of
intimate staple blends of polyester microfibres with cotton [12].
Supermicrofibres have a filament diameter less than one-tenth of that of fibres
in conventional filament or staple yarns (23 dtex fil1). In contrast with
standard polyester, microfilament yarns of 0.6 denier or less cannot be packageor beam-dyed because the high density of the wet material prevents adequate
liquor circulation. Fabrics woven from these yarns are preferably dyed in
winches, jets or overflow machines to preserve their bulky characteristics.
Approximately twice as much disperse dye is required for microfilaments of 0.3
1.0 dtex fil1 compared with conventional polyester of 23 dtex fil1 for the same
visual depth. Cost increases of 1520% are anticipated because of the higher dye
concentrations that have to be used to dye standard-depth shades [13]. One
factor contributing to this difference is the smaller proportion of microcrystalline
material in the microfilament structure. The absorbed dye forms larger
aggregates in the amorphous regions and the tinctorial power is correspondingly
reduced [11].
The rate of dye absorption is inversely proportional to the square root of the
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REASONS FOR THE DEVELOPMENT OF FIBRE BLENDS
filament diameter. Thus another important difference between microfibres and

conventional polyester is a markedly increased rate of dyeing, which tends to give
rise more often to levelling problems. These can arise from:
(1) commencing dyeing at too high a temperature;
(2) raising the temperature too rapidly above 90C;
(3) incompatibility in mixture recipes because of differences in rates of
exhaustion;
(4) poor fabric agitation at slow running speeds [14].
Improvements can be made by selecting dye combinations with greater
compatibility, starting at a low temperature and heating the dyebath at a slow
rate of rise. A hold period at 90100C may well be advantageous [13], although
diffusion into the fibre only proceeds rapidly at 130C. Rapid jet or overflow
machines are recommended, loaded with relatively short lengths of fabric to
facilitate agitation.
The exploitation of polyester microfibres blended with viscose in wovens or
with cotton in knitgoods will depend to some extent on parallel advances in
developing new disperse dyes to meet these more stringent demands in dyeing
microfibres. Such dyes must combine outstanding build-up, excellent fastness
and minimum cross-staining of the cellulosic component. Application techniques
must optimise right-first-time productivity without sacrificing the aesthetic
appeal of the microfibre-based fabric constructions [12].
It is essential to select dyes of high fastness to light for microfibre polyester, as
the fastness ratings are inferior to those on standard polyester [15]. The
standards for fastness to washing and rubbing are also lower than on standard
polyester because of the higher concentration of dye required to give the target
shade. Clearing of loose dye from the microfibre surfaces is more difficult and
reduction clearing is always necessary on these variants. Post-dyeing heat
treatments and inappropriate finishing chemicals often enhance these problems.
Durable press characteristics of microfibre fabrics are inferior to those woven
from standard yarns and crease-resist treatments must be applied carefully to
achieve satisfactory results [13].
In 1983 the introduction of Tactel (ICI) nylon heralded a marked revival of
interest in nylon apparel. The most notable features of Tactel were enhanced
aesthetic and comfort properties. Cotton-look Tactel fabrics became highly
popular for skiwear, anoraks, beachwear and track suits, combining the
established assets of nylon, i.e. strength, easy-care performance and abrasion
resistance, with enhanced handle and attractive appearance. In 1989 Tactel
Micro (<1 dtex fil1) was introduced to yield fabrics that may be modified during
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10
finishing by sueding or coating to give novel effects. Blends of Tactel Micro with
cotton or wool have broadened the variety of constructions being offered to
garment designers and consumers. Lightweight, soft, comfortable apparel fabrics
with enhanced easy-care performance result from these blends [8]. Microfilament nylon fabrics tend to float in winches or atmospheric jets because they
do not readily absorb liquid, but this problem can be obviated by pressure dyeing
at 105110C. In blends with elastomerics such as Lycra (DUP), Tactel Micro
produces a revolutionary combination of handle, comfort, garment fit and shape
retention in stretch-knit constructions that are highly suitable for bodywear and
aerobic sportswear.
1.5 COLOUR EFFECTS ACHIEVED BY BLENDING
There are four major types of coloured effect (Figure 1.2) achieved by dyeing a
blend of two fibres:
(1) Solid: both fibres are dyed as closely as possible to the same hue, depth and
brightness.
(2) Reserve: only one fibre is dyed and the other is kept as white as possible.
(3) Shadow: the two fibres are dyed to the same hue and brightness but the
depth on one fibre is only a fraction of that on the other.
(4) Contrast: usually the intention is to achieve the maximum possible contrast
in hue at approximately the same depth on both fibres, but sometimes more
subtle contrasts are preferred. In either case, optimum brightness on both
component fibres enhances the pleasing appearance of the contrast effect.
Reserve, shadow and contrast effects are mainly of interest for mixed-ply
hand-knitting yarns, fabric woven or knitted from homogeneous yarns, as well
as garments or tufted carpets made from differential-dyeing variants. The fact
that synthetic fibres tend to absorb dyes less readily than the natural fibres is an
advantage in achieving reserve or contrast effects, which are thus less prone to
contamination by cross-staining problems.
1.5.1 Solid effects
A solid effect (sometimes called a union-dye effect) is most frequently the
objective of dyeing a binary blend, since most of those blends developed for
reasons of economy, durability or physical properties, especially the blendedstaple yarns, are not intended for use in multicoloured designs. The attainment of
a solid effect is most difficult with those blends in which an ester fibre that can
only be dyed with disperse dyes is blended with another disperse-dyeable type,
i.e. cellulose acetate or any synthetic fibre. If nylon or an acrylic fibre is present,
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COLOUR EFFECTS ACHIEVED BY BLENDING
11
Shadow
Applied depth
50
Solid
or
contrast
67
Colour
and
reserve
50
33
Differences between fibre components A and B

Solid
Contrast
Shadow
Reserve
Matching hue and depth

Matching depth but contrasting hues
Matching hue at a ratio of depths
Contrast between colour and white
Figure 1.2 Diagrammatic representation of colour effects in blends
there is some scope for adjustment towards solidity by shading with acid dyes or
basic dyes respectively, but distribution of the disperse dyes between the fibre
components can be controlled to only a limited extent by adjustment of dyeing
temperature or (more objectionably) by addition of a carrier. Solid dyeings on
blends of cellulose acetate with polyester or acrylic fibres are impracticable
because the acetate fibre is damaged under the relatively severe conditions
required to achieve reasonable depths on the synthetic component.
Much more control of distribution is possible in blends of nylon with wool,
polyurethane or cellulosic fibres, because anionic reserving or blocking agents
can be added to control the degree of uptake of the anionic dyes by nylon below
the saturation limit. Solid effects are not difficult to achieve on other types of
binary blend, the easiest situation being found with blends of acid-dyeable
variants of nylon or acrylic fibres with basic-dyeable nylon, polyester or acrylic
variants, where the relative freedom from cross-staining gives optimum
reproducibility of effect and control of shading.
1.5.2 Reserve effects
Cross-staining constitutes a serious problem if a reserve effect is required.
Staining is more likely to occur in blends of fibres with distinctly different dyeing
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properties. It is especially prevalent in blends of a natural fibre with a synthetic

one that can only be dyed with disperse dyes. In these circumstances it is
impracticable to dye the latter component without some cross-staining of the
natural fibre.
It is difficult to obtain a satisfactory reserve of any acid-dyeable fibre and none
of the blends with wool will give a reserve effect on the wool component.
Reserve effects are impracticable on either component of blends of wool, nylon
or polyurethane with one another. Nylon does not give a good reserve in its
blends with cellulose acetate, triacetate, polyester or cellulosic fibres. Acrylic
fibres cannot be reserved in the presence of the disperse-dyeable ester fibres. In
blends of ester fibres with one another, only the less dyeable component can be
reserved. This principle also applies to blends of normal and deep-dye variants,
where the latter cannot be reserved. Both fibres can be reserved satisfactorily in
blends of acrylic or the ester fibres with cellulosics, and in synthetic blends of
acid-dyeable and basic-dyeable variants.
Fastness standards may be impaired by the cross-staining of one fibre by a
class of dyes intended for the other component. Several measures can be
considered with a view to minimising the degree of cross-staining in blends
where this is a potential problem:
(1) selection of dyes with the lowest affinity for the fibre to be reserved, as well
as those with the highest affinity for the component that is to be dyed with
them;
(2) selection of dyeing conditions that favour maximum exhaustion by the
component fibre to be dyed and hence the minimum cross-staining of the
adjacent fibre;
(3) addition to the dyebath of a colourless agent that is preferentially absorbed
on the dyeing sites of the fibre to be reserved and is able to act as a resist
against subsequent staining by dyes with sorption behaviour similar to that
of the agent;
(4) a clearing treatment with a detergent to desorb, or a reducing agent to
destroy, the dye stain that has been taken up by the adjacent fibre during
dyeing. In two-bath sequences it is often advisable to interpose a clearing
step after the first dyeing stage in order to remove any stain from the
component to be dyed in the second stage.
1.5.3 Shadow effects
The shadow effect (cumbersome expressions like two-tone, tone-in-tone, or toneon-tone have also been used) may be regarded as an intermediate stage between
solid and reserve effects (see Figure 1.2). The most pleasing shadow effects are
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obtained when the paler depth is between about one-third and one-half the depth
of the deeper component. If the two depths are closer together, the effect
approaches that of incomplete solidity, whereas if the paler component is too
weak it resembles a stained reserve.
It is obviously much simpler to obtain shadow effects using one class of dyes
as in blends of cellulosic fibres with one another, with disperse dyes on blends of
triacetate with polyester or acetate, or with acid dyes on blends of nylon with
wool or polyurethane than to attempt to achieve a similar effect on those
blends requiring different classes of dyes on the component fibres. The most
attractive shadow dyeings are seen on the differential-dyeing variants, such as
pale-dye/deep-dye nylon or normal/deep-dye polyester, where the appeal of the
depth difference is not impaired by distracting differences of surface texture or
lustre of the two components.
1.5.4 Contrast effects
Contrast effects (also called cross-dye or two-colour effects) represent the
primary justification for the development of differential-dyeing yarns and have
contributed much to the design of patterned apparel fabrics and tufted carpeting
over the years. Colour contrasts cannot be obtained on blends in which the two
fibres resemble one another too closely in dyeing properties, as in blends of
cellulosic fibres with one another, blends of ester fibres with one another, or
blends of wool, nylon or polyurethane with one another. The best contrast effects
are shown by fabrics containing acid-dyeable with basic-dyeable synthetic yarns
(e.g. nylon/acrylic blends), since the freedom from significant cross-staining
under optimum dyeing conditions permits the contrast of complementary pairs
i.e. redgreen, blueorange or violetyellow.
In those blends where considerable cross-staining is unavoidable, the
sharpness of the contrast is obviously seriously muted. In many instances only
partial contrast effects are possible by using a disperse dye on both components
and an ionic dye on the more dyeable component, as on normal/deep-dye nylon
or the blends of ester fibres with ionic-dyeable fibres. In these circumstances, the
hue on the more dyeable fibre is partly determined by that on the other fibre and
the resulting contrasts are limited (Table 1.4).
It is obviously easier, when selecting dyes for contrast effects, to dye the deeper
and/or duller colour on the fibre component that is most prone to cross-staining.
This general approach, however, may have to be modified if the two fibres differ
greatly in abrasion resistance. For example, the polyester component of a
polyester/viscose shirting fabric dyed in contrasting hues should be dyed more
heavily, because differential abrasion at the collar and cuffs leaves a higher
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Table 1.4 Limitations of colour contrast on a disperse-dyeable/ionicdyeable blend

Colours of individual dyes
Colours on component fibres
Disperse dye
Ionic dye
Disperse-dyeable
Yellow
Yellow
Red
Red
Blue
Blue
Red
Blue
Yellow
Blue
Red
Yellow
Yellow
Yellow
Red
Red
Blue
Blue
Ionic-dyeable
Orange
Green
Orange
Violet
Violet
Green
proportion of polyester on those edges and the abraded areas become much
more evident if the polyester is dyed to a paler hue.
A particularly striking example of a pronounced contrast effect is provided by
the use of Lurex metallic threads in decorative apparel fabrics. Even here the
familiar problem of staining by disperse dyes often arises. The degree of staining
of silver and gold Lurex threads by typical disperse dyes in the dyeing of
polyester/Lurex blends by carrier and high-temperature methods has been
tabulated. The stability of Lurex threads to various chemical treatments, and
application of a sodium dithionite clearing treatment to minimise disperse dye
staining, have been examined [16].
1.5.5 Colour matching problems and colour measurement of dyed blends
The degree of solidity that will prove acceptable to the customer varies according
to the end-product. Whilst piece-dyed fabrics woven from blended yarns call for
high standards of solidity, carpet yarns may prove less critical, since for certain
designs and qualities of carpet a slightly broken appearance better simulates
that presented by a blend of different qualities of wool. Furthermore, on tufted
carpets and pile fabrics the upper surface of the material is uneven in height and
the interplay of incident lighting with the effects of differential crushing ensure
that the uniformity of appearance presented by a woven fabric can never be
approached.
Nevertheless, spinning of a staple blend must be carefully controlled. Even a
carpet yarn containing 20:80 nylon/wool may give an unlevel appearance in the
piece if there are clumps of nylon fibres that have not been thoroughly opened
and mixed. The minimum level of each component in a staple blend should be at
least 5% to ensure uniformity of mixing. Collaboration between ICS at
Newbury and IWS at Ilkley in the 1980s resulted in a programme to enable fibre
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blending to be carried out by computer. This could be used to predict the

proportions of various fibre-dyed components to match a target blended sample
[17].
A particularly critical substrate from the viewpoint of solidity of shade is
polyester/wool, which is complicated by serious staining of the wool by disperse
dyes. Another limitation is the need to employ a carrier to achieve satisfactory
yield and penetration on the polyester component at a temperature that does not
seriously damage the wool. The problems of achieving solidity of hue, brightness
and saturation between textured polyester filament yarns and 55:45 polyester/
wool staple yarns in the same fabric have been examined in detail [18], by
reference to colorimetric data obtained by dyeing in the presence of various
concentrations of carriers based on o-phenylphenol, trichlorobenzene, or
mixtures of them.
Perhaps the most complex and intractable challenges have been faced by dyers
of wool shoddy over the years since synthetic fibres became important. The three
sources of raw material for the dyers of reclaimed waste are:
(1) collected rags or worn-out garments;
(2) cuttings and fents left over from the making-up of garments or household
textiles;
(3) fibre producers waste, which is often uncoloured and does not require
sorting.
When military uniforms were all-wool materials, outworn uniforms were a
prime source of recovered wool. Trade in these used garments declined, however,
when polyester blends were adopted and difficulties arose at the stripping and redyeing stage. Special dye selections were devised, particularly from those
products not affected by the iron content of the stripped wool arising from the
crude equipment in use at the time. There was significant conversion to wool/
viscose unions, often dyed wool way only in fabric form.
Category 1 causes most problems as the rags and garments must be sorted by
colour and fibre type. They often contain blended materials that only become
clearly identifiable after dyeing. Disperse dye staining is much more troublesome
when dyeing a 99:1 blend of wool shoddy and polyester than in conventional
55:45 polyester/wool blends [19]. Carrier dyeing of these synthetic fibre
impurities is highly inefficient. It is not difficult to achieve acceptable solidity on
all-wool shoddy, but reclaimed acrylic material usually contains several different
acrylic variants that may differ widely in dyeability.
A novel method has been devised to cover synthetic fibre impurities in deepshade dyeings on fabrics made from reclaimed wool [20]. This is to pass the wool
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fabric, together with a textured polyester fabric already dyed to a matching

shade, through the nip of a transfer printing calendar. The synthetic fibre
impurities in the reclaimed fabric are dyed by vapour-phase transfer but the wool
fibres remain virtually unstained because the disperse dyes have such high
affinity for polyester at the heat transfer temperature. Conventional transfer
coloration from a disperse dye transfer paper is uneconomic and carries a greater
risk of wool staining. The textured polyester reservoir fabric can be used
repeatedly in this way with only very slow loss of disperse dye.
Shade matching problems are often more difficult to deal with in union fabrics
than in fabrics made from intimately blended yarns [21]. Recipes based on
difluoropyrimidine reactive dyes were applied to both components of a viscose
warp/nylon weft fabric dyed by the one-bath two-stage process. Reflectance data
for the dyed fabric and colour difference values between the viscose warp and
nylon weft yarns were measured [22]. It was shown that objective matching is
possible and that the reproducibility of the matching operation can be improved
by careful selection of the dyes used.
The development of computer colour matching programmes for the dyeing of
blends presents specific difficulties. Dyes that cause minimal cross-staining are
preferred for better reproducibility of matching. Preliminary calibration work on
the laboratory scale must be carried out at the effective liquor ratio that
corresponds to bulk conditions for the blend. All fibre components must be
present in the calibration dyeings in order to account for the competitive effects
between them.
Fibre fragments taken from dyed blends can be used to produce felt-like discs
that retain the colour properties of both constituent fibres. These discs are
prepared using a new type of press that has been described and illustrated [23].
The discs are easy to prepare and are thus preferred to yarn windings for
calibration purposes. Two methods utilising this technique were described for
prediction of the initial recipe for the acrylic pile and cotton backing of a cotton/
acrylic velour fabric.
Instrumental techniques have been applied to the colour effects obtained on
differential-dyeing nylon. Loop-pile carpet and pile yarns dyed with CI Acid Blue
277 on deep-dye and normal variants, and CI Basic Yellow 45 on a basic-dyeable
variant, were measured using a colour computer system, a spectrophotometer to
measure small areas of the design and a goniophotometric colorimeter [24].
Methods of determining the levelness of wool dyeings and of union dyeings on
wool/cotton textiles by digital image analysis have been developed [25].
Levelness values were derived from the standard deviations of the grey scale
ratings corresponding to individual histograms of the dyed fabrics. The levelness
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of union dyeings could be assessed by analysing the shapes of the histograms

obtained from the wool/cotton dyeings.
Correct formulation of the pad liquor is an essential element in the quality
assurance of continuous dyeing. Transmission measurement is a viable
alternative to control dyeings prepared in the laboratory to check pad liquors in
bulk. Practical experience has demonstrated [26] that this method can be used
not only for soluble systems such as reactive dyes but also dispersions of disperse
or vat dyes, as well as mixtures of soluble dyes with disperse dyes in polyester/
cellulosic dyeing. With extensive automation of the measuring process, high
operational reliability and continuous monitoring are feasible.
Potential causes of incorrectly set pad liquors include:
(1) varying dye deliveries from the supplier;
(2) moisture sorption of powder brands;
(3) sedimentation of liquid brands;
(4) incorrect choice of dye from storage;
(5) incorrect weighing;
(6) incorrect dissolution or dispersion;
(7) inadequate stirring during mixing;
(8) soiling during transfer to pad trough;
(9) lack of temperature control in storage or padding.
Commercial mixture recipes containing (a) disperse dyes with vat, vat leuco ester
or reactive dyes, for the dyeing of polyester/cellulosic blends, or (b) disperse dyes
with 1:2 metal-complex or acid dyes, for polyester/wool blends, were examined
in pad liquors made up in readiness for continuous dyeing. Photometric
measurements using analogue, digital and turbidity photometers [27] were used
as alternatives to conventional control dyeings to save time and running costs.
Calibration curves confirmed that the BeerLambert law was sufficiently
applicable to these mixtures, yielding adequate reproducibility for on-line control
purposes. These approaches virtually eliminate the production of faulty batches
attributable to incorrectly set pad liquors, as well as freeing laboratory dyeing
effort for other tasks.
1.5.6 Colour effects on three-component blends
With the exception of nylon/wool/viscose blends in carpet yarns, ternary blends
are seldom dyed in solid shades because of the matching difficulties involved.
Three-depth shadow effects are given by acid dyes on pale-dye/normal/deep-dye
or normal/deep-dye/ultra-deep nylon (see Chapter 15), but a three-way contrast
with primary colours on all three components is most difficult because of the
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problems of cross-staining. Multicoloured designs on ternary blends can be

based on two-way shadow or contrast effects with white reserve of the third
component, or more often, a two-way shadow effect with a contrasting hue on
the third fibre. Ternary blends on which disperse, basic and acid dyes can be used
will give a limited range of three-way contrasts, but the hues on the ionic-dyeable
variants are dependent on the hue of the disperse dye, which cannot be restricted
to only one of the component fibres (Table 1.5).
Table 1.5 Limitations of colour contrast on a typical three-component blend

Colours of individual dyes
Colours on component fibres
Disperse
dye
Basic
dye
Acid
dye
Dispersedyeable
Basicdyeable
Aciddyeable
Yellow
Red
Blue
Red
Yellow
Yellow
Blue
Blue
Red
Yellow
Red
Blue
Orange
Orange
Green
Green
Violet
Violet
1.5.7 Scintillant effects on staple blends

Colour contrast effects on intimate blends of two different fibre types can be
accentuated by deliberately modifying the distribution of the constituent fibres
within the yarns. In conventionally blended staple yarns sufficient doublings are
given to ensure that this distribution is regular and uniform in cross-section. This
uniformity is an inherent property of a conventional blend and it results in
reproducible spinning and weaving characteristics and reliable in-service
performance.
Not all natural fibres exist as single or ultimate fibres, however. Flax and
other bast fibres occur naturally in bundles of ultimate fibres held together by
interstitial material, varying in size from about 10 to 40 ultimates. When these
are dry spun the bundles do not break down but remain as groups within the
spun yarn. Thus the intimacy of blend found in a conventional polyester/cotton
is not found in a typical polyester/linen yarn. The flax bundles are distributed
through a matrix of the individual polyester staple fibres (Figure 1.3).
This grouping of fibres can be utilised to produce striking colour contrast
effects using the dye selectivity of the constituent fibres. The fibre groups can be
accentuated by incorporating short fibres into the blend to produce slubs, or by
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Cellulosic
fibres
Polyester
fibres
Conventional
fibre blend
Grouped
fibre blend
Figure 1.3 Diagrammatic cross-sections of conventional and grouped polyester/cellulosic

blend yarns [28]
injecting clumps of fibres into the yarn during spinning [28]. Fabrics made from
coarse dry spun yarns exhibit particularly attractive scintillant effects and can be
produced with pronounced slub content. It is necessary to have at least 30% of
each fibre present to make a significant contribution to the differential colour
contrast. Yarns with a short slub character are of great interest because these
slubs create focal points of colour that can be utilised by the designer. The most
effective results are achieved when the paler or brighter colour is applied to the
slub component so that it is highlighted against the darker background.
1.6 SIGHTING COLOURS FOR IDENTIFICATION PURPOSES
Sighting colours are especially useful in knitting or weaving plants that handle a
wide variety of man-made fibres and blended staple yarns. Selected low-fastness
dyes are used to stain the surface of the fibres, but they must be readily and
completely removable in scouring before dyeing and finishing. They may become
difficult to extract if the sighted yarn is steamed or dry heat set before scouring.
Specially designed varieties of sighting colours include [29]:
(1) an ionic dye complexed with a surfactant of opposite charge;
(2) a water-soluble vinyl polymer associated with a dye of opposite charge;
(3) a water-soluble starch derivative covalently linked to a reactive dye via the
hydroxy groups;
(4) a water-soluble dye in which the replaceable hydrogen atoms in the
structure (as in OH, NH or CONH groups) are substituted by long
polyoxyethylene chains;
(5) an analogous polyoxyethylene-substituted disperse dye structure with
sufficient hydrophobic character to inhibit penetration into the intermicellar
regions of highly swollen cellulosic fibres.
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1.7 REFERENCES
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
12.
13.
14.
15.
16.
17.
18.
19.
20.
21.
22.
23.
24.
25.
26.
27.
28.
29.
A P S Sawhney, R J Harper, K Q Robert and.G F Ruppenicker, Text. Res. J., 61 (1991) 393.
L B Kimmel, A P S Sawhney, G F Ruppenicker and R J Harper, Text. Chem. Colorist, 26 (Mar
1994) 22.
P A Koch, Textilveredlung, 7 (1972) 570; Chemiefasern und Textilind., 29/81 (1979) 431.
S Shiomura, Textile Asia, 22 (Sep 1991) 140.
P Lennox-Kerr, Text. Horizons, 11 (Jan 1991) 33.
P Lennox-Kerr, Text. Horizons, 2 (Nov 1982) 18.
S Roberts, Dyer, 178 (June 1993) 10.
L Jacques, J.S.D.C., 109 (1993) 315.
I B Angliss and J D Leeder, J.S.D.C., 93 (1977) 387.
G Jerg and J Baumann, Text. Chem. Colorist, 22 (Dec 1990) 12.
A Lallam, J Michalowska, L Schacher and P Viallier, J.S.D.C., 113 (1997) 107.
P W Leadbetter and S Dervan, J.S.D.C., 108 (1992) 369.
J C Dupeuble, Chemiefasern und Textilind., 40/92 (1990) 986.
D Wiegner, Chemiefasern und Textilind., 41/93 (1991) 148.
C L Chong, Textile Asia, 25 (Mar 1994) 59.
V Walther, Chemiefasern und Textilind., 35/87 (1985) 321.
J Park, Wool Record, (Aug 1987) 23.
G Rmer, Teinture et Apprets, No 145 (Dec 1974) 203.
K Barras, Dyer, 153 (13 June 1975) 612.
M E Fielding, Dyer, 157 (21 Jan 1977) 68.
W Pape, Melliand Textilber., 69 (1988) 737.
A Gantsheva and E Kantscher, Textilveredlung, 26 (1991) 116.
P Medilek, Melliand Textilber., 75 (1994) 822.
K Konno, I Hirai and T Gunji, J. Text. Mach. Soc. Japan, 37 (Apr 1992) 93.
J M Cardamone, W C Damert and W N Marmer, AATCC International Conference and
Exhibition, (Oct 1994) 246; Text. Chem. Colorist, 27 (Oct 1995) 13.
H P Locher and H Firmann, Textilveredlung, 26 (1991) 393.
V Reith, Melliand Textilber., 72 (1991) 774.
B Hill and G Gray, J.S.D.C., 108 (1992) 419.
K Marquardt, Chemiefasern, 24 (1974) 940.
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CHAPTER 2
Classification of fibre types and their blends
2.1 CLASSIFICATION OF FIBRE TYPES IN TERMS OF DYEABILITY

The examples mentioned in Chapter 1 have given an indication of the wide
variety of fibre blends available and the complex ways in which they may be
assembled and dyed as blended yarns or in certain types of fabric, garment or
carpet. Before considering the fundamental principles of blends dyeing and the
methods devised to colour them, it is useful to classify fibres and their blends in
terms of their dyeing characteristics. This is more appropriate in this context then
the usual division into natural, regenerated and synthetic fibres.
Although more than one class of dyes is important on cellulosic fibres, and
disperse dyes are often used in pale depths on all types of synthetic fibre, a simple
classification based on the classes of dyes used to obtain fast dyeings in full
depths can be made (Table 2.1). This can then be applied to classify binary
blends (Table 2.2) and ternary blends (Table 15.1) in a similar way [1,2]. The
dyeing characteristics of the component fibres in full depths are particularly
important because many of the problems associated with the dyeing of blends are
more serious under such conditions. These problems include:
(1) the interference with solidity caused by differences in the saturation limits
on the component fibres;
(2) the greater degree of staining of reserved fibres, often making it necessary to
employ a two-bath method;
(3) more critical fastness requirements that must be achieved adequately on
both fibres;
(4) more serious incompatibility of dyes and auxiliaries of opposite charge at
higher concentrations.
The variations from alphabetical order in the codes for blend categories listed in
Table 2.2 are deliberate. When referring to blends of polyester with natural fibres
it is customary to name the synthetic fibre first, i.e. polyester/cotton (DC) or even
poly/cotton is heard far more than cotton/polyester, which is usually
21
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CLASSIFICATION OF FIBRE TYPES AND THEIR BLENDS
Table 2.1 Classification of fibres by dyeing properties
A Fibres (dyed with acid dyes in full depths)

Wool and other animal fibres
Silk
Nylon homopolymer
Acid-dyeable nylon variants
Polyurethane fibres
Acid-dyeable polypropylene
Acid-dyeable acrylic and modacrylic fibres
B Fibres (dyed with basic dyes in full depths)

Basic-dyeable acrylic and modacrylic fibres
Basic-dyeable nylon
Basic-dyeable polyester
C Fibres (dyed with cellulosic dyes in full depths)

Cotton
Viscose
Lyocell, modal and polynosic fibres
Linen and other bast fibres
D Fibres (dyed with disperse dyes in full depths)

Cellulose acetate
Cellulose triacetate
Polyester homopolymer
Deep-dye polyester variants
Poly(vinyl chloride) fibres
encountered if cotton-rich blends are being considered. Furthermore, when a

fibre type is referred to by an adjectival term, such as acrylic or cellulosic, it is
preferable to name this component second, as in nylon/acrylic (AB) or wool/
cellulosic (AC) blends. Where both adjectival terms occur in the same category,
i.e. the cellulosic/acrylic (CB) category, this order is preferred for the individual
blends, such as cotton/acrylic and viscose/acrylic, rather than their reversals.
2.2 COLOUR DISTRIBUTION ATTAINABLE ON BINARY BLENDS
General comments can be made regarding the dyeing characteristics of the major
classes of binary blends (Table 2.3). The AA blends, based mainly on nylon and
the protein fibres, are particularly important in knitting and carpet yarns.
Physical properties usually provide the main justification for developing these
blends, which are often blended-staple yarns. Solid dyeings are therefore most
important and not too difficult to obtain because preferential uptake by nylon in
pale depths can be controlled using reserving agents. These blends are ideally
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COLOUR DISTRIBUTION ATTAINABLE ON BINARY BLENDS
23
Table 2.2 Classification of binary blends
AA blends
CC blends
Wool/silk
Wool/mohair
Wool/cashmere
Wool/angora
Nylon/wool
Nylon/silk
Wool/polyurethane
Nylon/polyurethane
Wool/acid-dyeable polypropylene
Nylon/acid-dyeable polypropylene
Normal/deep-dye nylon
Cotton/viscose
Cotton/modal fibre
Cotton/polynosic fibre
Cotton/linen
Linen/viscose
Linen/modal fibre
AB blends
Wool/acrylic fibre
Silk/acrylic fibre
Nylon/acrylic fibre
Polyurethane/acrylic fibre
Acid-dyeable polypropylene/acrylic fibre
Wool/modacrylic fibre
Mohair/modacrylic fibre
Nylon/modacrylic fibre
Acid-dyeable/basic-dyeable acrylic fibre
Modacrylic fibre/acrylic fibre
Deep-dye/basic-dyeable nylon
Wool/basic-dyeable polyester
Nylon/basic-dyeable polyester
AC blends
Wool/cotton
Silk/cotton
Nylon/cotton
Polyurethane/cotton
Acid-dyeable polypropylene/cotton
Wool/viscose
Silk/viscose
Nylon/viscose
Wool/modal fibre
Nylon/modal fibre
Nylon/linen
CB blends
Cotton/acrylic fibre
Viscose/acrylic fibre
Modal fibre/acrylic fibre
Polynosic fibre/acrylic fibre
Cotton/modacrylic fibre
Viscose/modacrylic fibre
Contents
DA blends
Cellulose acetate/wool
Cellulose acetate/silk
Cellulose acetate/nylon
Cellulose triacetate/wool
Cellulose triacetate/silk
Cellulose triacetate/nylon
Polyester/wool
Polyester/silk
Polyester/nylon
Polyester/acid-dyeable polypropylene
Poly(vinyl chloride)/wool
Poly(vinyl chloride)/nylon
DB blends
Cellulose acetate/acrylic fibre
Cellulose triacetate/acrylic fibre
Polyester/acrylic fibre
Cellulose acetate/modacrylic fibre
Cellulose triacetate/modacrylic fibre
Polyester/modacrylic fibre
Normal/basic-dyeable polyester
DC blends
Cellulose acetate/cotton
Cellulose triacetate/cotton
Polyester/cotton
Poly(vinyl chloride)/cotton
Cellulose acetate/viscose
Cellulose triacetate/viscose
Polyester/viscose
Poly(vinyl chloride)/viscose
Cellulose triacetate/modal fibre
Polyester/modal fibre
Polyester/polynosic fibre
Polyester/linen
DD blends
Cellulose acetate/triacetate
Cellulose acetate/polyester
Cellulose triacetate/polyester
Normal/deep-dye polyester
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24
CLASSIFICATION OF FIBRE TYPES AND THEIR BLENDS
Table 2.3 Colour effects attainable on binary blends

Colour effect
Blend type
(example)
Solid
Reserve
Shadow
Contrast
AA
(nylon/wool)
Use of
auxiliaries
Neither
component
Easily
controlled
Not
possible
AB
(nylon/acrylic)
Easily
controlled
Acrylic
reserve
Seldom
required
Wide range
available
AC
(nylon/cellulosic)
Easily
controlled
Cellulosic
reserve
Seldom
required
Wide range
available
CB
(cellulosic/acrylic)
Easily
controlled
Either
component
Seldom
required
Wide range
available
CC
(cotton/viscose)
Dyeing
conditions
Neither
component
Viscose
deeper
Not
possible
DA
(polyester/wool)
Dyeing
conditions
Polyester
reserve
Seldom
required
Limited
range
DB
(polyester/acrylic)
Easily
controlled
Polyester
reserve
Acrylic
deeper
Limited
range
DC
(polyester/cellulosic)
Easily
controlled
Either
component
Seldom
required
Wide range
available
DD
(triacetate/polyester)
Dyeing
conditions
Polyester
reserve
Easily
controlled
Not
possible
suited to shadow effects because one class of dyes can be used for both
components. Contrast and reserve effects are generally impracticable.
Optimum reproducibility of bright complementary colour contrasts is
achieved on AB blends, containing nylon or a protein fibre with an acrylic or
basic-dyeable copolymer. Good reserve of the basic-dyeable fibre, or solid effects,
can be obtained if required. Two-bath dyeing methods are generally preferred,
because of the need to inhibit precipitation between the classes of dyes of
opposite charge.
The anionic dyes applicable to both components of an AC blend are, in most
cases, fully compatible with one another. This facilitates the exploitation of onebath dyeing methods and gives ample opportunity for controlled shade matching
in either solid effects or colour contrasts. There is less interest in shadow or
reserve effects on these blends.
Colour contrasts and solid effects are readily obtainable on CB blends. Either
the cellulosic or the acrylic fibre may be reserved if desired, so this is a versatile
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COLOUR DISTRIBUTION ATTAINABLE ON BINARY BLENDS
25
type of blend from the viewpoint of design. Two-bath methods are preferable,
however, because basic dyes are incompatible with all classes of dyes for the
cellulosic component.
Dye selection and control of dyeing conditions provide reasonable scope for
solidity on staple blends of the CC category, but there may have to be some
sacrifice of optimum fastness and colour gamut. The CC blends are ideally suited
to shadow effects, as in brocade designs for furnishing or curtaining fabrics. As
with the AA blends, reserve effects and colour contrasts are not attainable.
Blends of an ester fibre with nylon or a protein fibre (DA blends) are mostly
blended-staple yarns and solidity is therefore often important. The acid-dyeable
component cannot be reserved because of disperse dye staining, but good reserve
of the ester fibre is attainable. Colour contrasts are limited because of the dulling
effect of the disperse dye on the acid-dyeable fibre.
The attainment of contrast or reserve effects by differential dyeing is the main
justification for DB blends, which contain an ester fibre with an acrylic or other
basic-dyeable copolymer. The basic-dyeable component cannot be reserved
satisfactorily, but good reserve of the ester fibre is possible. Contrast effects are
limited by cross-staining of disperse dye on the basic-dyeable yarn.
The DC blends represent the most important category and solid effects are a
primary objective. Disperse dye staining of the cellulosic fibre is much less serious
than for the DA and DB types, so either component of a DC blend can be
reserved. Colour contrasts are possible but not of much interest in practice.
Disperse dyes offer the only possibility for colouring DD blends and this
completely eliminates the contrast option. Shadow and reserve effects are
particularly appropriate because the ester fibres differ so much in dyeability.
Cellulosic acetate absorbs dye much more readily than the triacetate at low
temperatures, making it easy to reserve the latter component. The degree of
distribution on triacetate/polyester can be controlled using dyeing temperature
and carrier additions, but solid effects are difficult to achieve.
2.3 REFERENCES
1.
2.
J Shore in The dyeing of synthetic-polymer and acetate fibres, Ed. D M Nunn (Bradford: SDC,
1979) 419.
J R Aspland, Textile dyeing and coloration (North Carolina: AATCC, 1997) 331.
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26
DYNAMIC COMPETITION BETWEEN FIBRE TYPES IN THE DYEING OF BLENDS
CHAPTER 3
Dynamic competition between fibre types in

the dyeing of blends
3.1 INTRODUCTION
Dyeing systems in which more than one fibre type is present have been almost
completely neglected by those researching the mechanisms of dyeing processes.
This is not surprising, because the complications that arise when attempting to
predict quantitatively the uptake of a single dye by one fibre type are
considerable. Theories of dyeing established on the basis of careful
measurements of one such dye at various depths under a variety of dyeing
conditions can seldom be transferred intact to other members of the same range
of dyes, especially if these are distinctly different in structure from the first dye
chosen. Further difficulties arise with the binary or ternary combinations of dyes
that are used routinely in practice to achieve the wide gamut of colours with
which design colourists and dyers must work. Two dyes undergoing absorption
by the fibre simultaneously rarely reproduce the dyeing rate curves that they give
alone. There is almost invariably an interaction between them, often (but not
always) resulting in a slower rate of uptake and a lower equilibrium exhaustion
for each of the dyes in combination, compared with the corresponding values
when applied individually.
An entirely different dimension is introduced when two fibres are present in
the same dyebath. A single dye may be distributed between them according to a
complex relationship that is determined by the differences in dyeability
characteristics between the two substrates, the dyeing conditions and the applied
depth of the dye. An unequal distribution that may be found in an early stage of
the process, arising from differing rates of uptake by the competing substrates,
may later undergo a levelling effect as dye is desorbed from the initially more
heavily dyed fibre and is taken up by the other fibre type for which the dye has
inherently higher affinity.
When two different substrates are present in the same dyebath, initial kinetic
26
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INTRODUCTION
27
conditions and later the energetic characteristics of the system will dictate which
of the substrates a given dye will tend to favour. More dye will ultimately be
absorbed by the substrate to which it is more substantive. This favoured
substrate will require less energy for the sorption process because the dyefibre
forces of interaction are stronger. When a combination of two or three dyes is
applied to two different substrates, however, it does not always follow that the
dyes present will all be absorbed preferentially by the same fibre component to
the same extent.
It is certainly possible in practice to choose a set of dyeing conditions in which
a trichromatic combination of dyes with similar dyeing properties will yield a
matching hue on both substrates at equal depth (a solid effect) or at markedly
different depths (a shadow effect). To arrive at such ideal combinations of dyes
and dyeing conditions, however, implies considerable preliminary laboratory
work, especially when other important factors, such as fastness demands and
non-metameric matching, must be taken into account [1]. This task can be
facilitated by deriving characteristic thermodynamic parameters of the dyeing
system from the sorption behaviour of the individual dyes on the separate
homogeneous substrates. It is claimed that these parameters allow computation
of the sorption behaviour of the dyes in combination on more than one substrate
simultaneously [2].
The substantivity ratio (Df /Ds) for each dye on each substrate depends on
temperature, pH, liquor ratio, concentrations of dye and electrolyte, and
particularly in this case on the other dyes and substrates involved in the
competitive sorption process. According to the Gouy-Chapman theory, the
substantivity ratio is related to the electrolyte concentration or ionic strength and
the total amount of ionic charge imparted to the substrate by the absorption of
dye ions. This factor encapsulates the mutual restraining effects of the dyes on
one another. The three characteristic constants in the Gouy-Chapman equation
are as follows:
A0 is a function of the standard affinity and thus the substantivity ratio under
the relevant conditions.
A1 is proportional to the charge density and is a measure of the overall charge
on the substrate.
A2 is related to the specific surface of the substrate accessible for dye sorption.
The simplest dyeing system that may be considered as representative of the
dyeing of a blend is that in which one dye is distributed between two different
fibres that have broadly similar dyeing properties, so that the same dye will give
an economic colour yield on both. Even if solidity of colour between them is the
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28
objective, there is no guarantee that the dyeing conditions to achieve this at the
target depth will ensure satisfactory penetration and fastness on both substrates.
It is often easier to adopt this approach when a shadow effect is desired, because
any inherent difference in dyeability between the substrates can be exploited in
adjusting dye uptake levels towards the target difference in depth. The serious
limitations of this simple dyeing system become clear when reserve and colour
contrast effects are considered. By definition it is usually extraordinarily difficult
to suppress the dyeability of the less dyeable component to zero in order to
reserve it as white or to dye it in another colour, which means introducing a dye
from another dyeing class.
Another deceptively simple approach to the dyeing of a binary blend of fibres
is to dye each in turn with an appropriate class of dyes in two completely
separate dyeing processes, using the optimum conditions of application in each
case just as if they were entirely separate substrates. At first sight, this appears an
ideal way in which to dye for solidity, reserve, shadow or contrast effects at will.
In practice, however, technical limitations do arise here too. The wet fastness
characteristics of the dyeing achieved in the first process must be such that no
significant desorption from it occurs during the second one. In other words, the
fastness to cross-dyeing must be excellent. Thus the order in which the two
processes are carried out is important and the dyeing that requires the higher
dyeing temperature is normally applied first.
The two-bath process is also less than ideal unless both classes of dyes are free
from cross-staining problems, i.e. a class selected to dye one of the fibre types
should not cause significant staining of the other fibre present. In a majority of
instances, however, cross-staining of one or both fibre types must be taken into
account and a clearing process introduced after one or both of the dyeing
processes. Thus the so-called two-bath process may require several baths for
completion. It is easy to see why this technically straightforward possibility turns
out to be the least attractive from an economic viewpoint.
Between these fairly obvious extremes of the single-class and the two-bath
methods there are two other compromises that offer greater flexibility than the
former and economic savings over the latter. These are the simultaneous onebath and the one-bath two-stage methods. For clarification the four possibilities
are summarised in Table 3.1. These will be referred to frequently in later chapters
and it is convenient to use the four hyphenated abbreviations listed in the first
column to distinguish between them. In general, the progressive increase in cost
in moving down this list is compensated by a wider choice of suitable dyes and
greater freedom from the practical problems discussed in terms of typical
examples in the remainder of this chapter. Another general rule is that the greater
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INTRODUCTION
29
Table 3.1 Summary of general dyeing methods for binary blends

Method
Dyebaths
Dye classes
Stages
Single-class
One-bath
Two-stage
Two-bath
One
One
One
Two
One
Two simultaneously
Two in sequence
Two
One
One
Two
Two
the depth of shade required, the more likely is it necessary to move to a method
lower down this list.
3.2 THE DISTRIBUTION OF ACID DYES ON NYLON/WOOL BLENDS
Nylon/wool blends are often dyed with a single class of anionic dyes, which may
be levelling acid, milling acid or metal-complex types. Ensuring solidity of shade
is normally the main requirement and this calls for careful selection of
combinations of dyes with similar rates of dyeing and build-up characteristics.
Partitioning of the dyes between the two fibres can be influenced by many
factors, including dye structure, applied depth, dyebath pH, blend ratio and the
quality of the component fibres.
Wool and nylon contain both basic and acidic groups, amongst which by far
the most important are amino and carboxyl groups respectively. Just like the
parent amino acids from which all proteins are derived, both of these polymeric
amides show zwitterionic characteristics at pH values close to the isoelectric
point, i.e. the pH at which the fibre contains equal numbers of protonated basic
and ionised acidic groups. As the pH decreases below this point, the carboxylate
anions are progressively neutralised by the adsorption of protons and the fibre
acquires a net positive charge (Scheme 3.1).
+
H3N
[fibre]
COO + H+
H3N
[fibre]
COOH
Scheme 3.1
Conversely, as the pH rises above the isoelectric point, the fibre becomes
negatively charged as a result of deprotonation of the amino groups by
adsorption of hydroxide ions or other simple anions (Scheme 3.2).
+
H3N
[fibre]
COO + OH
H2N
[fibre]
COO
+ H2O
Scheme 3.2
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30
The rate of dyeing of anionic dyes on nylon is much more rapid than on wool,
particularly at 6080C and low applied depths, so that pale dyeings on nylon/
wool show a marked preferential dyeing of the nylon. Even at 1% applied depth,
for example, the uptake by nylon is much more rapid than by wool and the
difference in rate is greater for dyes with a lower degree of sulphonation. Figures
3.1 and 3.2 are rate-of-dyeing curves for disulphonated and tetrasulphonated
dyes (Figure 3.3) respectively on these two fibres, at 93C and an initial pH of
4.2 in aqueous acetic acid [3]. As dyeing proceeds, the pH rises towards 5 as a
result of sorption of acetic acid, particularly by wool.
100
Exhaustion/%
80
60
40
Nylon
20
Wool
20
40
60
80
100
Dyeing time/min
Figure 3.1 Rate of dyeing of CI Acid Red 1 [3]
100
Exhaustion/%
80
60
40
20
10
20
40
60
80
100
Dyeing time/min
Figure 3.2 Rate of dyeing of CI Acid Red 41 [3] (for key see Figure 3.1)
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THE DISTRIBUTION OF ACID DYES ON NYLON/WOOL BLENDS
COCH3
H O
HN
NaO3S
H O
N
31
SO3Na
N
N
SO3Na
N
NaO3S
SO3Na
NaO3S
CI Acid Red 1
CI Acid Red 41
Figure 3.3 Disulphonated and tetrasulphonated acid dyes
The origin of the markedly different rates of dyeing lies in the differences in
hydrophobic character between the two dyes and between the two fibres. The
nylon polymer is much more hydrophobic than wool and so it attracts the more
hydrophobic of the two dyes preferentially. Thus the disulphonated dye shows
the most rapid rate of absorption on nylon, with a time of half dyeing (time for
50% of the equilibrium exhaustion) of only about 2 minutes. The
tetrasulphonated dye is relatively hydrophilic and is therefore absorbed more
slowly by either fibre, showing the slowest rate of dyeing on wool, with a time of
half dyeing of approximately 3 hours.
Although nylon absorbs acid dyes more readily than does wool, partition
between the two fibres is not constant at all depths since the saturation
concentration on nylon is much lower than that on wool. The saturation limit on
wool is not approached at the applied depth necessary to saturate the amine end
group content of the nylon. In pale depths both the initial uptake and the
ultimate exhaustion are higher on nylon. In full depths, on the other hand, the
initial strike still occurs on nylon but eventually the wool becomes more heavily
dyed because it has a much higher saturation uptake. At some intermediate depth
depending on dyeing conditions, there is a point at which both fibres are dyed to
the same depth even though the nylon reaches this equilibrium position more
quickly.
This critical depth is specific for the dye and is much higher for a
monosulphonated dye than for a disulphonated analogue, since a disulphonated
dye requires about twice as many amine end groups for a given tinctorial yield
(Figure 3.4). Blocking effects may occur if monosulphonates and disulphonates
are applied together, resulting in a heavier depth on the wool that is closer in hue
to the disulphonated dye. Above the critical depth the nylon becomes
progressively more difficult to dye with levelling acid dyes and the distribution
on the nylon/wool blend increasingly favours the wool.
The blocking of disulphonates by analogous monosulphonated dyes may be
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32
NH
CO
+
NH3
H
O
3S
CH2
(CH2)6
CH2
CH2
CH2
NH
CO
CO
NH
CI Acid Red 88
CO
H
NH3 O3S
(CH2)6
N
N
NH
NH
(CH2)3
CH2
CH2
CO
CH2
CI Acid Red 13
SO3 NH3
+
Figure 3.4 Electrostatic and hydrophobic bonding of acid dyes on nylon
exploited by applying mixtures of selected mono- and disulphonated pairs of

similar hue, varying the proportions according to applied depth in order to
minimise the disparity in depth on the two fibre components. The preferred
monosulphonated dyes are mainly monoazo yellows and reds with anthraquinone blues. The disulphonates have lower saturation values on nylon and so
they can only be used for pale and medium depths. They are virtually all yellow
to red monoazo and disazo types, or violet to green anthraquinone derivatives.
Given the widely varying qualities of the two fibre types, as well as possible
variations in the blend proportions, it is not surprising that specific dyeing
conditions for solidity cannot be laid down, only guideline starting points for
initial experimentation [4]. Anionic agents capable of controlling the uptake of
anionic dyes by the nylon component below the critical depth are of two general
types:
(1) levelling or blocking agents that are preferentially absorbed by nylon and
act as a partial reserve for levelling acid dyes;
(2) retarding agents of higher relative molecular mass capable of controlling the
distribution of dyes of higher wet fastness on nylon/wool blends.
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Typical examples of the moderately substantive agents used to control the uptake
of levelling acid dyes are shown in Figure 3.5. They compete with these dyes for
the basic groups and facilitate the approach to an equilibrium distribution that
does not alter even on prolonged boiling, unless further additions of agent are
made to shift the equilibrium more in favour of the wool. Such products improve
the coverage of any dye-affinity variation in the nylon but have insufficient
affinity to exert a blocking effect with premetallised or milling acid dyes. A novel
agent developed recently, however, permits either equalisation or a total reserve
to be obtained even with metal-complex or milling dyes [5].
R
R
SO3Na
SO3Na
Sodium alkylbenzene sulphonate
R OSO3Na
Sodium alkylnaphthalene sulphonate
CH3(CH2)5 CH
CH2CH CH(CH2)7COONa
OSO3Na
Sodium alkanol sulphate
Disodium sulphoricinoleate
Figure 3.5 Levelling or blocking agents for nylon/wool dyeing (R = long-chain alkyl)
Retarding agents that control the initial uptake of these dyes by the nylon
component have higher affinity than the typical levelling agents defined in Figure
3.5 Many of these are also used as syntan aftertreating agents for dyed nylon.
These belong to a distinct group of condensates of formaldehyde with certain
sulphonated phenols, thiophenols or naphthylaminesulphonic acids [6]. The
rapid sorption of syntans by nylon is mainly attributed to electrostatic bonding
between negatively charged sulpho groups in the syntan and the protonated
amino groups in the fibre. Hydrogen bonding between uncharged polar groups
and hydrophobic interaction between nonpolar moieties in the syntan and the
nylon also contribute to the mechanism [4].
Maximum retarding effect is found when the syntan molecules are retained
close to the fibre surface, since any treatment leading to diffusion of the syntan
into the fibre interior tends to lower its effectiveness. When used with levelling
acid dyes, this type of agent does not prevent migration from wool to nylon on
prolonged boiling. With metal-complex and milling acid dyes, however, the
initial distribution is preserved on boiling because these dyes show only limited
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34
migration. It is not normally necessary to employ levelling or retarding agents on

the rare occasions when chrome dyes are preferred, since these give quite good
solidity on nylon/wool blends at the heavy depths where they may offer an
advantage. Some of the syntans darken on exposure to light and this significantly
lowers the light fastness of the dyeings.
Considerable attention has been given in recent years to devising suitable
procedures for dyeing wool at lower temperatures and near the isoelectric point
(pH 45) in order to avoid the damage that inevitably occurs when dyeing at the
boil. The low-temperature dyeing of wool offers:
(1) optimum handle and durability;
(2) improved carding, spinning and weaving performance;
(3) brighter shades because of the lower degree of yellowing of the wool;
(4) shorter dyeing cycles, higher productivity and lower process costs;
(5) a better-quality end-product.
Problems associated with low-temperature dyeing include:
(1) slower diffusion into the interior of the wool fibres, resulting in inadequate
wet fastness;
(2) inadequate exhaustion and poor reproducibility.
The epicuticle of wool is the main barrier to penetration and this is mainly
responsible for the dyeing problems. These problems can be overcome by
damaging the fibre scales in a chlorination process before dyeing, but this lowers
wool quality too. The best results are achieved using monosulphonated 1:2
metal-complex and milling acid dyes.
Shade partition between wool and nylon in blend dyeing is dependent on
dyeing temperature. As already discussed, the tendency at the boil is for the
nylon to absorb dye more quickly than wool and to dye more deeply below the
critical depth. This is easily corrected by adding an anionic agent to retard uptake
by the nylon and achieve solidity of shade over a range of depths. At lower
temperatures (e.g. 80C) the wool is generally dyed more heavily than the nylon
even without an anionic agent present. As dyeing proceeds there is some
migration from wool to nylon until the final partition is reached, but this is a
different equilibrium at the lower temperature than in conventional dyeing at the
boil. In general, partition favours the wool and solidity is difficult to attain. This
difficulty can be overcome, however, using a specific equalising agent in place of
the conventional anionic agent normally employed when dyeing at the boil [7].
When dyes of high substantivity are applied below the boil, surface dyeing of the
wool occurs to give dyeings of inadequate wet fastness.
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Premetallised and milling acid dyes (relative molecular mass 7001000)

demand more energy input for good fibre penetration. There is a close relationship between dye substantivity, exhaustion and diffusion into the fibre and this is
mainly determined by the relative molecular mass and degree of sulphonation of
the dye. Addition of an equalising agent shifts the partition in favour of the nylon
at the lower temperatures, allowing solidity to be achieved at any temperature in
the 80100C range, depending on the amount of auxiliary required at a given
depth of shade. The optimum dyeing temperature is recipe-specific and a
temperature selector system has been developed for use with the specific
equalising agent. In pale depths (below ca. 0.6% total dye) the conventional
syntan-type retarder may be used at a relatively low concentration [8].
3.3 THE DISTRIBUTION OF ACID DYES ON NYLON/POL

YURETHANE
BLENDS
The polyurethane elastomeric fibres vary in their ability to absorb anionic dyes,
depending on their content of basic groups, but in general the equilibrium
distribution on a nylon/polyurethane blend tends to favour the nylon
component. The higher rate of dyeing of the elastomeric fibre at lower
temperatures, however, results in preferential dyeing of that component in the
early stage. There are two main methods of controlling this distribution, both of
them depending on the use of dyeing auxiliaries.
Anionic agents, such as sodium alkanesulphonates, sulphated castor oil,
disodium dinaphthylmethanedisulphonate or selected syntans, can be added to
promote dye uptake by the polyurethane at equilibrium by becoming absorbed
by the nylon and restraining subsequent migration of dye from the polyurethane
to the nylon. This method is more effective when dyeing with 1:2 metal-complex
or milling acid dyes of the monosulphonate type with good levelling properties.
The amount of agent required decreases progressively as the applied depth of the
dyeing increases.
Cationic agents (Figure 3.6) will form labile ionic complexes with typical
anionic dyes. This type of complex is absorbed more slowly and tends to favour
the polyurethane component more than does the parent dye. Acid dyes of the
disulphonate type with only moderate levelling properties can be readily
controlled on nylon/polyurethane materials by this method. The concentration of
cationic agent required increases with applied depth and the degree of
sulphonation of the dyes. A nonionic dispersing agent of the alkanol polyoxyethylene class is necessary to solubilise the dyeagent complex (Figure 3.7).
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CH3
H33C16
H33C16
Cetylpyridinium
chloride
N+ CH3
CH3
Cl
CH3
H35C17
N + CH2
CH3
Br
Cetyltrimethylammonium
bromide
Cl
Stearyldimethylbenzylammonium
chloride
Figure 3.6 Cationic complexing agents for nylon/polyurethane dyeing
H
CH3
+
O3S
(OCH2CH 2)x OH
N
N
R N CH3
Alkanol polyoxyethylene
CH3
CH3
SO3 CH3
CI Acid Red 13
as bis-alkyltrimethylammonium complex
N R
(OCH2CH2)x
OH
CH3
Figure 3.7 Schematic representation of solubilised dyeagent complex (R = long-chain alkyl)
3.4 THE CROSS-STAINING OF WOOL BY DISPERSE DYES

Wool keratin is the most sensitive of textile fibres towards staining by dyes of all
types because it is a natural protein containing many different functional groups.
The staining of wool by disperse dyes is a serious problem in dyeing blends with
any of the ester fibres. Cellulose acetate suffers a loss in lustre if it is treated at the
boil, as is normally necessary to dye the wool component during the second stage
of a two-stage or two-bath sequence. Migration from the acetate to the wool
increases with dyeing time and temperature of the wool-dyeing stage. Migration
from cellulose triacetate to wool is slower under these conditions but treatment
at 105C or at the boil with carrier, in order to attain full depth and penetration
on the triacetate, usually results in serious staining of the wool.
Polyester/wool presents the most difficult problem and studies have revealed
numerous factors that may affect the degree of staining observed in practice [9].
The stain on the wool is dull in hue and exhibits poor fastness to light and wet
treatments. Staining implies a loss of colour yield on the polyester and makes
shade matching more difficult because individual dyes differ in their propensity
to staining. Bulky, low-twist wool becomes stained more easily then fine, hightwist yarns. Wool quality is another factor influencing the degree of staining.
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THE CROSS-STAINING OF WOOL BY DISPERSE DYES
37
Dye structure (molecular size, number, type and distribution of polar groups)
has less influence on the initial level of staining than dyebath conditions and the
quality of the dye dispersion. The mechanism of wool staining involves:
(1) hydrogen bonding between proton donor groups (e.g. amino, amido,
hydroxy) in the disperse dye molecules and in wool keratin;
(2) interaction by means of secondary (dipolar and van der Waals) forces
between the dye molecules and wool;
(3) physical sorption of aggregated particles of disperse dyes on the scaly
surface of the wool fibre.
The preferred disperse dyes for these blends have low intrinsic saturation values
on wool, low tendency to aggregate at the dyeing temperature, rapid rates of
diffusion into polyester and high equilibrium exhaustion. Mechanical retention
in yarn crevices may play a part in the initial deposition, since particle size and
stability of the dye dispersion are important. Staining tends to decrease with the
concentration and anionic charge of the stabilising agents present in the dye
dispersion, but the magnitude of the effect is specific to the types of dye and
agent.
In a recent investigation of the kinetics of polyester/wool dyeing and the wool
staining problem, polyester and wool fabrics in the weight ratio 55:45 were used
to allow the disperse dye uptake by both components to be determined
independently [10]. Dyeings with CI Disperse Blue 185 (Figure 3.8) and CI Acid
Red 211 were carried out at the isoelectric point (pH 4.5) and wool damage was
assessed by measuring tensile properties and alkali solubility. Both disperse and
acid dyes are absorbed by wool far more quickly and easily than the disperse
dyes are taken up by the polyester at relatively low temperatures, because the
rates of diffusion in wool are so much more rapid. After only 30 minutes at
110C, therefore, the amount of disperse dye that has stained the wool is more
than twice that absorbed by the polyester (Figure 3.9).
O2N
NH2
CH3
HO
NHCH
CH2CH3
Figure 3.8 CI Disperse Blue 185
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Dye uptake/%
1
Wool
Polyester
15
30
60
90
120
Dyeing time/min at 110 oC
Figure 3.9 Rate of uptake of disperse dye by polyester and wool [10]
As dyeing proceeds, desorption from the wool occurs at a rate determined by

the slow diffusion of the disperse dye into the polyester. The distribution
coefficient for a disperse dye between polyester and wool is controlled by the
difference in affinity values of the dye for the two substrates. After about an hour
at 110C, an equilibrium partition is approached but the degree of staining of the
wool is not much less than after the first 15 minutes. As the disperse dye diffuses
slowly into the polyester, the wool stain slowly desorbs at a rate that keeps the
low concentration of disperse dye in the dyebath roughly constant.
After a dyeing time of 30 minutes, wool staining is considerable at all dyeing
temperatures up to about 115C (Figure 3.10). However, above around 120C
the diffusion of the disperse dye into the interior of the polyester fibre is
sufficiently rapid to give much lower staining of the wool. The pH dependence of
wool staining is not critical under the mildly acidic conditions preferred for
dyeing both components of this blend (Figure 3.11). At pH values below the
isoelectric point, wool staining is at a minimum. As the pH increases towards the
alkaline side, so does the degree of wool staining.
When tested in the presence of the premetallised CI Acid Red 211, the staining
of wool by the disperse dye was markedly greater [11]. This was attributed to
possible hindering of disperse dye desorption from the wool by the presence of
the metal-complex dye. Since anionic dyes of this kind interact strongly with
wool keratin they desorb again very slowly and incompletely. Sequestering agents
such as ethylenediaminetetra-acetic acid (EDTA) and citric acid are useful to
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39
Dye uptake/%
30
60
90
120
Dyeing temperature/oC for 30 min
Figure 3.10 Temperature dependence of disperse dye uptake [10] (for key see Figure 3.9)
Dye uptake/%
2
2
Dyebath pH for 60 min at 110oC
Figure 3.11 pH dependence of disperse dye uptake [10] (for key see Figure 3.9)
minimise wool staining, particularly the former. It is claimed that such agents
interact with certain disperse dyes (e.g. the 1-amino-4-s-butylamino system in CI
Disperse Blue 185) to hinder diffusion into wool (Figure 3.12). These agents have
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40
low affinity for wool and formation of the dyeagent complex favours retention
of the disperse dye in the dyebath, allowing the polyester to absorb more dye as it
is released from the complex at higher temperatures and improving the ultimate
exhaustion.
O2N
OOC
NH3
CH2
CH OH
OOC
CH2
CH3
HO
NH2CH
+
CH2CH3
Figure 3.12 Interaction between CI Disperse Blue 185 and citric acid
When dyeing wool-rich blends, the problems of wool staining and the
attainment of solidity at equilibrium are greatly aggravated. Uptake of disperse
dyes by the polyester in full depths can be 25% less on a 20:80 polyester/wool
blend than on a 50:50 blend [12]. If a 50:50 blend is dyed at a liquor ratio of
10:1, then the individual components are each actually at 20:1 with respect to
the dyebath. When the blend ratio is 20:80, however, the polyester is being dyed
at 50:1, making exhaustion far more difficult. To compound this, the liquor ratio
for the wool is only 12.5:1 and absorption of the disperse dyes by wool is
favoured preferentially. Less dye remains in the bath for dyeing the polyester
directly and this component becomes even more dependent on disperse dye
transfer from the wool [12].
Wool progressively loses its strength at elevated dyeing temperatures,
especially about 110C, although at this temperature the damage is not severe for
dyeing times of 60 minutes or less. In the isoelectric region (pH 45) the keratin
structure is reinforced by electrostatic linkages between protonated amino
groups and carboxylate-containing amino acid residues. Hydrolysis of peptide
and disulphide bonds is also at a minimum under these conditions. The loss in
strength increases rapidly at pH values above 5 and temperatures above 110C.
The sensitivity of wool to degradation makes the use of a carrier essential to dye
full depths on the polyester at a relatively low temperature. Carrier addition
lowers the degree of staining at a given temperature and also tends to lower the
temperature of maximum staining.
Carriers are able to minimise wool staining by accelerating the rate of uptake
of disperse dyes by polyester. It is believed that the sorption of carrier molecules
weakens the attractive forces between polyester segments, making them more
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41
mobile at lower temperatures than when the carrier is absent, thus changing the
internal structure of the fibre and lowering the glass-transition temperature.
Hence carriers accelerate dye diffusion within polyester and so indirectly increase
the rate of transfer from wool to polyester. The chemical type of carrier exerts
only a marginal influence, the degree of staining tending to increase slightly in the
series: aryl esters < chlorobenzenes < aryl ethers < phenylphenols. Dyebath
conditions are more important. Unfortunately, carriers are harmful to the health
of operatives and to the environment.
The wool staining problem is an important criterion in the decision whether to
dye polyester/wool sequentially in the one-bath mode or by the two-bath method
with an intermediate clear to remove the disperse dye stain from the wool. In the
two-stage sequence, the wool is cleared after dyeing by scouring with a nonionic
detergent at pH 45 and 5070C. This causes no significant damage to the wool
but is only moderately effective and this process is only suitable for pale and
medium depths because of fastness limitations. Nevertheless, it offers shorter
processing times and higher productivity at lower cost. During the wool dyeing
stage, disperse dye can migrate from the surface of the dyed polyester and cause
back-staining of the wool [13]. There is no obvious relationship between the
degree of back-staining and the heat fastness class of the disperse dyes.
Full depths are usually dyed by a two-bath method. In the absence of the
anionic dyes the blend can be given an intermediate reduction clear after
applying the disperse dyes to the polyester. This is more effective than nonionic
scouring, especially for azo disperse dyes, but the wool suffers some loss in
strength and elasticity. When dyeing wool-rich blends, the two-bath sequence
gives better shade partition than the one-bath method, especially when the
polyester component is dyed first [12]. Two-bath dyeing allows a wider choice of
disperse dyes, since the wool staining is less important provided the intermediate
clearing is adequate and the wool is dyed at a lower temperature than the
polyester. Certain anthraquinone-based disperse dyes, however, are reduced but
not destroyed by the reducing conditions. The degradation products may still
discolour the wool, especially after reoxidising back to the quinone form during
the wool dyeing stage. In heavy depths the two-bath process gives improved
fastness to rubbing and perspiration [14]. These advantages are particularly
significant for the dyeing of deep navy and black shades on polyester/wool [15].
3.5 THE CROSS-STAINING OF WOOL BY BASIC DYES
Although ultimately less serious than staining by disperse dyes, the uptake of
basic dyes by wool in the initial stage of the one-bath dyeing process for wool/
acrylic blends with milling acid and basic dyes can be troublesome. Above the
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42
second-order transition temperature, however, dyeing of the acrylic component

can take place. The thermodynamic affinity of a basic dye for the acrylic fibre is
much higher than for wool. By the time that the dyebath reaches the boiling
temperature, most of the basic dye initially taken up by the wool has been
transferred to the acrylic component. This transfer proceeds during treatment of
the fibre blend at the boil even after exhaustion of the basic dye from the dyebath
is virtually complete. The degree of initial staining of the wool by the basic dye
varies with the type of acrylic fibre present in the blend. This variation becomes
particularly important when the applied depth approaches saturation of the
dyeing sites in the acrylic fibre.
Cationic dyeing auxiliaries have been widely used in wool dyeing, ranging in
ionic character from the weakly basic alkylamine polyoxyethylene types to the
much more strongly basic fatty alkyl quaternary ammonium salts. These
products are used as levelling agents and it is not surprising that the cationic
retarders necessary when dyeing acrylic fibres with basic dyes behave in a similar
manner when added to the wool/acrylic dyeing system. The pronounced
retarding effect of a typical cationic retarder on the rate of dyeing of wool with a
milling acid dye of the disulphonated anthraquinone type (Figure 3.13) is
illustrated in Figure 3.14. The time of half dyeing is increased from about 22 to
33 minutes by addition of the agent [16].
Dyeing rate curves for this milling acid dye and a typical monoazo basic dye
(Figure 3.13) on a 50:50 wool/Orlon (DUP) blend in the presence (Figure 3.15)
and absence (Figure 3.16) of the cationic retarder demonstrate that the anionic
NaO3S
O
HN
HN
NaO3S
CH2CH2CH2CH3
CH2CH2CH2CH3
Cl
CI Acid Green 27
CH2CH3
O2N
N N
CH3
CH2CH2 N CH3
+
CI Basic Red 18
CH3 X
Figure 3.13 Structures of typical milling acid and basic dyes
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THE CROSS-STAINING OF WOOL BY BASIC DYES
43
100
Exhaustion/%
80
60
40
1% Dye, no retarder
20
1% Dye, 1% retarder
10
20
30
40
50
60
90
100
100
Dyeing time/min
60
70
80
Temperature/oC
Figure 3.14 Rates of dyeing of CI Acid Green 27 on wool [16]
dye is highly sensitive to the agent of opposite charge. Under these conditions the
agent increases the time of half dyeing from about 17 to 32 minutes for the acid
dye but only about 26 to 32 minutes for the basic dye.
These results indicate that in the initial stage of a wool/acrylic dyeing the
cationic retarder is either absorbed by the wool or forms with the acid dye a
labile complex that has lower affinity for wool than the parent dye. Either effect
will significantly decrease the rate of dyeing of the acid dye. It is also evident that
100
CI Acid Green 27
CI Basic Red 18
Exhaustion/%
80
60
40
20
10
20
25
30
35
40
45
50
100
100
100
Dyeing time/min
66
84
92
100
100
Temperature/oC
Figure 3.15 Rates of dyeing of wool/Orlon with 1% retarder [16]
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44
100
Exhaustion/%
80
60
40
20
10
15
20
25
30
35
92
100
100
Dyeing time/min
58
66
75
84
Temperature/oC
Figure 3.16 Rates of dyeing of wool/Orlon with no retarder [16] (for key see Figure 3.15)
ca. 20% exhaustion of the basic dye occurs at temperatures below 80C (i.e.
below the glass-transition temperature of the acrylic fibre) and this dye must be
absorbed by the wool. This effect is irrespective of whether the cationic retarder
is present or not, implying that complex formation between the acid dye and the
retarder is the most probable explanation of the mechanism [16].
3.6 THE TRANSFER OF DISPERSE DYES DURING THERMOFIXATION

OF POLYESTER/CELLULOSIC BLENDS
The padthermofix dyeing of polyester/cellulosic fabrics is one of the few systems
of dyeing of blends that has been subjected to theoretical study. During the early
stages of padding and drying, much of the dye applied becomes deposited on the
relatively more absorbent cellulosic component. Several possible mechanisms of
transfer of the disperse dyes from cellulose to polyester during the
thermofixation stage have been proposed, but it is now widely accepted that the
transfer proceeds through the vapour phase [17]. The extent to which this
transfer takes place depends on the time and temperature of thermofixation.
As heating of the polyester/cellulosic fabric is continued, the total amount of
disperse dye available for colouring the polyester decreases as a result of
volatilisation into the atmosphere inside the heating chamber and deposition on
the inner surfaces of the latter. Some disperse dyes of low relative molecular mass
(Mr) and relatively high volatility may suffer oxidative decomposition,
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THE TRANSFER OF DISPERSE DYES DURING THERMOFIXATION
45
particularly if they contain sensitive substituents such as primary amino groups.

It follows that a critical combination of fixation time and temperature gives
optimum yield of a specific dye, when the supply of dye from the reservoir
provided by the cellulosic component is sufficiently depleted for these progressive
losses to begin to favour desorption rather than adsorption of vapour at the
polyester surface.
Low-energy disperse dyes (approx. Mr <300) suffer relatively serious losses
under the conditions required for optimum transfer and fixation on the polyester.
Maximum transfer for these dyes is found at 200210C. For most dyes of
intermediate energy (approx. Mr 300400) a temperature of 210220C is
needed. Good fixation of high-energy dyes (approx. Mr >400) often requires a
temperature of 220230C, but optimum transfer is limited by the onset of
thermal degradation and yellowing of the cellulosic fibres, or even some
softening of the polyester.
3.7 REFERENCES
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
12.
13.
14.
15.
16.
17.
J Park and J Shore, Rev. Prog. Coloration, 12 (1982) 1.

O Annen, H Gerber and B Seuthe, J.S.D.C., 108 (1992) 215.
B C Burdett, C C Cook and J C Guthrie, J.S.D.C., 93 (1977) 55.
T M Baldwinson in Colorants and auxiliaries, Vol. 2 Ed. J Shore (Bradford: SDC, 1990) 568.
Anon, Dyer. 177 (Apr 1992) 31.
C C Cook, Rev. Prog. Coloration, 12 (1982) 73.
A F Doran, Dyer, 176 (Aug 1991) 49.
A F Doran, J.S.D.C., 109 (1993) 15.
R E Lacey, V S Salvin and W A Schoeneberg, Am. Dyestuff Rep., 50 (1951) 978.
J Wang and H Asnes, J.S.D.C., 107 (1991) 274.
J Wang and H Asnes, J.S.D.C., 107 (1991) 314.
A F Doran, unpublished work.
K Trschmann and K H Rstermundt, Z. Ges. Textilind., 71 (1969) 326.
K H Rstermundt, Deutscher Frber Kalender, 80 (1976) 247.
W T Sherrill, Text. Chem. Colorist, 10 (1978) 210.
D R Lemin, J.S.D.C., 91 (1975) 168.
C J Bent, T D Flynn and H H Sumner, J.S.D.C., 85 (1969) 606.
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46
MINIMISING INCOMPATIBILITY BETWEEN DYES FROM DIFFERENT CLASSES
CHAPTER 4
Minimising incompatibility between dyes from

different classes
4.1 INTERACTION BETWEEN DISPERSE DYES AND REACTIVE DYES

The risk of interaction between these two dye classes is a significant factor
limiting the selection of suitable dyes for the one-bath padthermofix dyeing of
polyester/cellulosic blends. These problems may arise as a result of covalent
reaction between reactive dyes and certain disperse dyes, interaction between
reactive dyes and dispersing agents, or instability of the dye dispersion system
under the alkaline conditions of padding. Interaction leads to losses of yield on
both fibre components and may result in gelling or settling of the pad liquor.
High reactivity dyes are unsuitable because of chemical reaction in many
cases. For example, the monochlorotriazine dye formed by reaction (Scheme 4.1)
between CI Reactive Red 11 and the phenolic group in CI Disperse Yellow 1 was
isolated from a pad liquor containing 8 g l1 sodium bicarbonate and identified
by chromatographic analysis [1]. Further evidence for chemical reaction between
monochlorotriazine reactive dyes and primary amino or phenolic groups in
disperse dyes has been presented [2]. The reaction products formed tend to be
unstable and are readily decomposed by alkaline hydrolysis.
Since these problems of chemical reaction in the alkaline pad liquors necessary
for one-bath application are closely connected with structural features of the
individual dyes, most of them can be avoided. Where possible, disperse dyes that
do not contain nucleophilic primary amino or phenolic groups should be
selected. Low-reactivity ranges of reactive dyes should be chosen in preference to
high-reactivity types, so the selection of compatible disperse dyes that can be
used becomes much wider.
Control of the pH of the pad liquor is a most important technique to minimise
problems of chemical reaction between dyes from the two classes. Thus the
mixture of disperse and reactive dyes can be padded from a neutral bath
containing migration inhibitor and sodium m-nitrobenzenesulphonate to prevent
46
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47
INTERACTION BETWEEN DISPERSE DYES AND REACTIVE DYES
Cl
CI Reactive Red 11
N
Cl
CI Disperse Yellow 1
N
O2N
NH
SO3Na
H O
N
N
+
SO3Na
HO
NH
NO2
NaHCO3
NaO3S
Cl
O2N
N
NH
NO2
N
NH
SO3Na
H O
N
N
SO3Na
+ NaCl + CO2 + H2O
NaO3S
Scheme 4.1
reductive degradation of certain azo reactive dyes. After drying and

thermofixation to ensure diffusion of the disperse dyes into the polyester fibres,
the fabric is padded in an alkaline brine bath to minimise desorption of the
reactive dyes, steamed to achieve fixation of these dyes on the cellulosic
component, rinsed cold and soaped at the boil. This two-stage method has few
restrictions attributable to dye interaction and the choice of suitable dyes is much
greater than in the simple paddrythermofix application of both classes.
4.2 INTERACTION BETWEEN DISPERSE OR VAT DYES AND

BASIC DYES
In the one-bath dyeing of a typical DB blend (see Chapter 2), i.e. a blend of one
of the ester fibres with an acrylic fibre, it is most important to minimise the risks
of incompatibility between a cationic species, such as one of the basic dyes or a
cationic retarder used with them for dyeing the acrylic fibre, and an anionic
moiety that has an important function in dyeing the ester fibre, such as a disperse
dye stabiliser or a carrier emulsifying agent (Figure 4.1).
There are three aspects to minimising the risks of incompatibility in the onebath dyeing of DB blends of the ester/acrylic type. An anionic retarder can be
used to control uptake of the basic dyes by the acrylic fibre, but this tends to be
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48
Cl
CH2CH3
O2 N
N N
CH3
CH2CH2 N CH3
+
CH3
CI Basic Red 18
H33C16
3SO(CH2CH2O)x
Alkanol polyoxyethylene sulphate

(carrier emulsifier)
O S
3
SO3
Cetylpyridinium
(retarder)
N C16H33
Cetylpyridinium
(retarder)
CH2
Dinaphthylmethanedisulphonate
(dispersant)
Figure 4.1 Possible interactions in dyeing a DB blend (R = long-chain alkyl)
less effective than a cationic retarder and more prone to restrain the ultimate
exhaustion of the basic dyes. It is possible to select a carrier formulation
containing a nonionic emulsifier instead of a conventional anionic carrier type.
Anionic dispersing agents are best avoided but it is not normally possible to
exclude the anionic stabilising agents that are already present in disperse dye
formulations as marketed.
More severe limitations apply to the simultaneous application of vat and basic
dyes to cellulosic/acrylic CB blends. The dispersing agents present in vat dye
formulations are incompatible with the basic dyes and cationic retarders
normally used for dyeing acrylic fibres. A more serious problem, however, is that
almost all basic dyes show chemical instability in even moderately alkaline
conditions. The highly alkaline reducing conditions of a vat dyebath are even
more extreme. One-bath methods generally are thus excluded and only a twobath sequence can be considered.
4.3 INTERACTION BETWEEN ANIONIC DYES AND BASIC DYES

The range of bright colour contrasts is much wider on AB blends than on all
other types of binary blend because the fibres carry opposite charges and ionic
dyes are much more selective than disperse dyes. The opposite charges carried by
the dyes, however, lead to incompatibility in one-bath dyeing. There is a strong
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INTERACTION BETWEEN ANIONIC DYES AND BASIC DYES
49
tendency for water-soluble anionic dyes and basic dyes to interact (Figure 4.2). It
is highly likely that precipitation of the complex formed would occur even when
applied in pale depths. Even where this does not occur the interaction seriously
interferes with reproducibility and causes increased cross-staining.
CI Basic Yellow 21
H3C
CH3
HC CH N
N+
CH3
H3C
O S
3
CI Acid Blue 27
O
CH3
HN
NHCH3
Figure 4.2 Interaction between typical basic and acid dyes
Addition of ca. 1% of an alkanol polyoxyethylene surfactant is sufficient to

inhibit co-precipitation of basic dyes and milling acid dyes when used at
concentrations up to 1/1 standard depth in a one-bath exhaust dyeing process for
wool/acrylic blends, for example [3]. With many combinations of basic dyes and
the relatively hydrophilic levelling acid dyes, it is possible to go to much heavier
depths with no problems. In practice, however, it is advisable, for dyeings above
1/1 standard depth, to check that a specific combination of dyes will be suitable
for one-bath application.
Direct and reactive dyes present similar problems when applied with basic
dyes in one-bath methods for the dyeing of cellulosic/acrylic CB blends. A further
problem in the case of reactive dyes is that an alkaline fixation stage must be
given to fix them on the cellulosic fibre. Almost all basic dyes are chemically
unstable under alkaline conditions.
The best and most reliable method of dealing with these problems of
interaction is to dye each fibre component separately. However, it has been
possible to develop viable one-bath methods of applying acid/basic combinations
to AB blends and direct/basic combinations to CB blends. These involve the
addition of anti-precipitants to overcome the problems of dye interaction. Many
proprietary products are marketed specifically as anti-precipitants for use in
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blend dyeing (Table 4.1) but some levelling agents used with acid dyes on wool
or nylon, e.g. fatty amine polyoxyethylenes, will also function effectively in this
role, either alone or with the addition of a nonionic dispersing agent (Figure 4.3).
Nonionic agents are by far the most common anti-precipitants and their
solubilising power by disaggregation is well known.
Table 4.1 Chemical types of anti-precipitant [4,5]
Type
Composition
OCH2CH2 units
per molecule
Nonionic
Fatty alcohol or alkylphenol

polyoxyethylenes
20
Block copolymers of ethylene oxide

and propylene oxide
40
Weakly
cationic
Coco, oleyl, soya or tallow fatty

amine polyoxyethylenes
20
Weakly
anionic

polyoxyethylene sulphates
Weakly
anionic

polyoxyethylene phosphates
412
Weakly
anionic
Alkali metal, amine or alkanolamine

salts of fatty alcohol or alkylphenol
polyoxyethylene acetates
Alkyl chloride or dialkyl sulphate

salts of quaternary ammonium
polyoxyethylene sulphates or
phosphates
15
Nonionic
Amphoteric
Numerous nonionic and weakly cationic surfactants with at least 20

oxyethylene units per molecule are available, as well as block copolymers of
ethylene oxide and propylene oxide. Suitable hydrophobic groups include fatty
alcohols, alkylphenols, alkylamines and alkanolamines. Weakly anionic polyoxyethylene sulphates and phosphates with polyoxyethylene chains approximately 10 units in length are also widely available [4]. Mixed formulations often
function better than single products and many proprietary products are
empirically balanced mixtures [5].
In dye liquors containing substantial concentrations of both anionic and basic
dyes, purely nonionic agents may be inadequate to effect complete solubilisation
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INTERACTION BETWEEN ANIONIC DYES AND BASIC DYES
51
CI Acid Blue 27
O
NHCH3
R
(OCH2CH2)x OH
HN
CH3
3S
(CH2CH2O)x H
+
R = long-chain alkyl
R NH
(CH2CH2O)x H
Alkylamine polyoxyethylene
Figure 4.3 Schematic representation of solubilised acid dyeagent complex
of the complex. If an anionic surfactant is added, this will tend to disrupt the
dyedye complex to form a basic dyeagent complex that responds more readily
to addition of the nonionic stabiliser (Figure 4.4). If strongly basic dyes are
present, however, the complexes formed by this method may be too stable,
leading to restraining of the basic dyes. Azo and anthraquinone derivatives with
a localised charge tend to show this behaviour. Surface deposition may result in
poor fastness to rubbing and a tendency for the basic dyeagent complex to stain
the acid-dyeable fibre.
CI Basic Yellow 21
H3C
CH3
HC CH N
N+
CH3
H3C
O SO(CH CH O)
3
2
2 x
R = long-chain alkyl
Alkanol polyoxyethylene sulphate
R (OCH2CH2)x OH
Figure 4.4 Schematic representation of solubilised basic dyeagent complex
Mixtures of another type that may be useful for minimising the cross-staining
of fibres by complexes of basic and acid dyes contain a weakly cationic
alkylamine polyoxyethylene with a weakly anionic alkanol polyoxyethylene
sulphate or phosphate. In many systems of interacting anionic and cationic
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52
surfactants an excess of either one may have a solubilising effect by

disaggregating the complex formed between them. The hybrid surfactants
generally characterised as weakly cationic or weakly anionic are particularly
useful in this respect, since the oxyethylene chains inhibit ionisation and exert a
solubilising and stabilising action on the complex entities present. Care should be
taken to rinse off all traces of anti-precipitants after dyeing to avoid potential
problems later. For example, residual nonionic surfactants can interfere with the
syntan aftertreatment of dyed nylon and its blends.
4.4 REFERENCES
1.
2.
3.
4.
5.
B Taylor and J Shore, unpublished work.

M Duscheva, L Jankov and K Dimov, Melliand Textilber., 56 (1975) 147.
D R Lemin, J.S.D.C., 91 (1975) 168.
H D Pratt, Am. Dyestuff Rep., 68 (Sep 1979) 39.
T M Baldwinson in Colorants and auxiliaries, Vol. 2, Ed. J Shore (Bradford: SDC, 1990) 568.
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CHAPTER 5
Principles of design and colouring of

differential-dyeing blends
5.1 DESIGN OF DIFFERENTIAL-DYEING VARIANT SYNTHETICPOLYMER YARNS

The development of novel fabric constructions by combining variants of the
same man-made fibre differing in lustre, denier or cross-sectional shape presents
no serious problems for the dyer. The introduction in the 1970s of acid-dyeable
and basic-dyeable variants of the conventional synthetic fibres, with excellent
resistance to staining by dyes of opposite charge to those for which they show
affinity, greatly enhanced the variety of multicoloured effects that could be
achieved [1]. After initial popularity, the use of differential-dyeing yarns declined
somewhat. However, in recent years there has been a revival of interest following
the development of sophisticated tufting machine controllers with the ability to
produce a wide range of patterned effects, e.g. the shifting needle bar technique
controlled by computer, and this trend is continuing [2].
The advantages of differential dyeing of fabrics, compared with the longestablished alternative of knitting or weaving with coloured yarns, include the
avoidance of stockholding of dyed yarn, easier adaptation to minor changes in
fashion and quicker delivery of finished goods. These advantages proved
particularly relevant in tufted carpets, yielding an attractive range of bold or
subdued colour combinations in versatile designs. As indicated later, however,
there are restrictions of colour gamut in certain styles and careful attention to
stringent conditions of processing is necessary to ensure reproducible effects.
The use of differential-dyeing nylon yarns has made an impact on the styling
of automotive upholstery in multicolour patterns, ranging from tonals to bold
saturated colours. Colour with a white reserve is obtained with nylon and
polyester and shadow effects with the acid-dyeable nylon variants. Basic-dyeable
nylon or polyester cannot be included, however, because basic dyes do not meet
the unusually high light fastness standards specified by the car manufacturers [3].
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54
PRINCIPLES OF DESIGN AND COLOURING OF DIFFERENTIAL-DYEING BLENDS
Four types of nylon yarn with dyeing properties different from those of the
parent homopolymer were introduced in the 1970s for weaving, warp-knitting
and weft-knitting, as well as carpets. Tufted carpeting, however, was the sector
where this development was fully exploited. The variant yarns introduced then
were as follows:
(1) Ultra-deep: acid-dyeable variant with a higher concentration (>80 milliequivalents per kg polymer) of basic groups than the deep-dye variant
(2) Deep-dye: acid-dyeable variant with a higher concentration (6070 milliequivalents per kg) of basic groups than the normal fibre
(3) Normal fibre: poly(hexamethylene adipamide) containing 3545 milliequivalents per kg basic groups
(4) Pale-dye: acid-dyeable variant with a lower concentration (1520 milliequivalents per kg) of basic groups than the normal fibre
(5) Basic-dyeable: variant containing acidic groups to provide affinity for basic
dyes.
The amine end group content of nylon 6.6 can be increased by adding excess
diamine to the polymer salt or by lowering the Mr of the polymer by limiting the
amount of water liberated during the melt polycondensation reaction between
hexamethylenediamine and adipic acid [4]. The deep-dye and ultra-deep
variants, however, were obtained by the inclusion of a small proportion of a
primary aliphatic diamine containing a tertiary amino group, e.g. N-(2-aminoethyl)- or N,N-bis(2-aminoethyl)piperazine, in place of some of the
hexamethylenediamine used in manufacture of the normal nylon 6.6 polymer
(Figure 5.1).
CH2CH2
CONH(CH2)6NHCO(CH2)4CONHCH2CH2 N
N CH2CH2NHCO
CH2CH2
Major component
Minor component
Figure 5.1 Segment of deep-dye nylon 6.6 variant
This change in structure provided new basic sites to increase the equilibrium
uptake of anionic dyes at a given pH. The pale-dye variant (sometimes called
low-dyeing or light-dyeing) was made by reacting a proportion of the amine
end groups in the normal polymer with a suitable blocking reagent such as
-butyrolactone (Scheme 5.1).
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DESIGN OF DIFFERENTIAL-DYEING VARIANT SYNTHETIC-POLYMER YARNS
CONH(CH2)6NH2
N-terminal group
55
CONH(CH2)6NHCO(CH2)3OH
Blocked N-terminal group
-Butyrolactone
Scheme 5.1
Basic-dyeable (or acid-dye-resist) nylon 6.6 was produced by replacing some

of the adipic acid used in the polymerisation by a suitable tribasic acid, such as 5sulphoisophthalic acid (Figure 5.2). All these structural changes decrease the
degree of crystallinity of the nylon, so that the rates of diffusion of dyes into (and
out of) the variant fibres are more rapid than in the homopolymer.
SO3H
NHCO(CH2)4CONH(CH2)6NHCO
Major component
Minor component
CONH(CH2)6NHCO
Figure 5.2 Segment of basic-dyeable nylon 6.6 variant
Similar multicolour effects can be derived from a single variant yarn, preferably
a deep-dye type, using readily available reactive chemicals. Acid-dye-resist agents,
e.g. condensates of the dihydroxyarylsulphone-formaldehyde-aminoarylsulphonate
type, offer the simplest approach for temporarily neutralising the basic groups of
an acid-dyeable variant yarn. Permanent acid-dye-resist effects can be obtained
by reaction of amino end groups with an active halogen derivative, such as
4-(dichlorotriazinylamino)benzenesulphonic acid (Figure 5.3).
Cl
N
N
NH
SO3H
N
Cl
Figure 5.3 Typical acid-dye-resist agent
Deep-dye modifications of poly(ethylene terephthalate) were developed by

varying the proportions of ethylene glycol and dimethyl terephthalate and
including other diols, such as propylene glycol [5], n-butylene glycol [6] or
diethylene glycol [7], or an aliphatic dicarboxylic acid, e.g. adipic acid
(Figure 5.4), to lower the glass-transition temperature by increasing the extent of
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56
COO CH2CH2
COO CH2CH2
OOC
OOC
OOC
COO CH2CH2CH2CH2 OOC
COO CH2CH2OCH2CH2
OOC
COO CH2CH2 OOC CH2CH2CH2CH2 COO
Major component
Minor component
Figure 5.4 Segments of deep-dye polyester variants
amorphous regions in the polymer. Some of these copolymer fibres were designed
for dyeing in medium or full depths at the boil without addition of a carrier.
Unfortunately, there are problems associated with excessive soiling of carrier-free
polyester variants under domestic washing conditions [8].
Basic-dyeable polyester copolymers, in which some of the terephthalic acid
units are replaced by a tribasic acid, e.g. 5-sulphoisophthalic acid (Figure 5.5),
have proved useful in differential-dyeing blends, but anionic-dyeable polyester
fibres failed to progress beyond the development scale. The basic-dyeable
variants have a more accessible structure than normal polyester, lower strength
but a reduced tendency to pilling in blends with wool. They are readily dyeable
with disperse dyes below 120C in the absence of a carrier. The use of basic dyes,
however, results in less staining of wool compared with disperse dyes.
SO3H
OOC
COO
CH2CH2
OOC
COO CH2CH2
Major component
OOC
Minor component
Figure 5.5 Segment of basic-dyeable polyester variant
Conventional acrylic fibres are readily dyed with basic dyes at the boil because
they are copolymers of acrylonitrile with up to 15% of an inert comonomer, such
as an acrylate or methacrylate ester, to make the structure more amorphous and
lower the glass-transition temperature. The anionic sites include end groups
arising from residues of the polymerisation catalyst (e.g. a persulphate or benzoyl
peroxide) as well as carboxylate groups introduced in the form of an acidic
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DESIGN OF DIFFERENTIAL-DYEING VARIANT SYNTHETIC-POLYMER YARNS
57
comonomer. Acid-dyeable acrylic fibres are also copolymers containing basic

comonomer units, such as vinyl-pyridine, acrylamide or methacrylamide
(Figure 5.6).
Acid-dyeable
CONH2
CH2CH
CN
Major
component
Basic-dyeable
COOCH3
CH2CH CH2CH
CH2CH
N
Minor
components
CN
CH2CH CH2CH
n
Major
component
COOH
Minor
components
Figure 5.6 Segments of acrylic-fibre copolymers
Conventional acrylic fibres can also be rendered dyeable with acid dyes by
treatment with hydroxylamine sulphate (HONH3)2SO4 (a) alone at pH 4 and
120C, (b) in the presence of sodium tripolyphosphate, glycerol and sodium
alginate at pH 6, or (c) in the presence of benzyl alcohol as a plasticiser at 80C
and pH 5. Substantivity for acid dyes is conferred by the introduction of basic
sidechains into the polymer structure [9].
5.2 DYEING OF ACID-DYEABLE NYLON VARIANTS
It has been shown that many of the practical features of the differential dyeing of
acid-dyeable nylon variant yarns are consistent with a simple theoretical model.
This is based on the assumption that the electrical phenomena determining the
sorption at equilibrium by the individual substrates in competition with one
another conform to a Donnan-type membrane equilibrium [10]. Attempts have
been made to combine this model with colour match prediction calculations for
finite dyebath conditions with a view to improving performance in practical
situations. The dyer, however, does not normally have access to sufficient prior
details about substrate variability that would be necessary to adopt a
quantitative approach of this kind.
Blends of normal or pale-dye nylon with the deep-dye variant yarn are ideally
suitable for shadow effects. The distribution of an acid dye between the
components of these blends depends considerably on the dyeing conditions and
the molecular structure of the dye, especially the degree of sulphonation. At a
given pH in the neutral region, dyebath exhaustion of a series of dyes differing
only in degree of sulphonation decreases as the number of sulpho groups in the
molecule increases. These differences in substantivity become more marked as
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58
the content of basic groups in the fibre increases, so that the deep-dye variant is
more sensitive than the normal fibre to differences in degree of sulphonation
within the series of dyes. Consequently, more highly sulphonated dyes give better
differentiation between the variant yarns at a given pH than the less-sulphonated
dyes with higher neutral-dyeing affinity.
The reason for this sensitivity is the variation with pH of the partition of
individual dyes between the fibre variants. The relative sensitivity to pH of acid
dyes of increasing polarity (Figure 5.7), and therefore of increasing contrast
effect, is shown in Figure 5.8. A carpet made from 50:50 pale-dye/deep-dye
nylon was dyed at various pH values and the degree of contrast between the two
fibre variants expressed as a ratio:
Contrast ratio =
Dye uptake by deep - dye nylon

Dye uptake by pale - dye nylon
(5.1)
As the pH decreases so the contrast ratio approaches unity (i.e. solidity

between the variants). The more polar the dyes used to obtain high contrast at
pH 6.5 the usual pH for differential-dyeing the more marked the variations in
contrast ratio if the dyebath pH is not closely controlled [11]. If the pH varies
from batch to batch it will cause the partition to vary accordingly. This
fluctuation will become apparent either as a strength difference between the
dyeings of the two fibre variants or, less acceptably, a hue difference in a mixture
recipe. The dyebath pH preferred for a given blend of acid-dyeable nylon
variants is determined mainly by the most dyeable component. It is necessary to
control the pH carefully using a suitable buffer, preferably a mixture of sodium
dihydrogen phosphate and disodium hydrogen phosphate, to ensure optimum
reproducibility of shadow and contrast effects.
If the desired degree of contrast can be achieved with dyes of high neutral
affinity, then these should be selected in the interest of good reproducibility. Table
5.1 shows the percentage change in contrast that a pH variation of 6.5 0.3
would produce for the three dyes compared in Figure 5.7 [11]. As indicated in
Table 5.1 Variation of contrast with pH and dye affinity [11]
CI Acid
Neutral
affinity
Contrast
type
Contrast
change (%)
Blue 25
Blue 41
Blue 175
Very high
High
Moderate
Low
Medium
High
4
11
20
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DYEING OF ACID-DYEABLE NYLON VARIANTS
59
NH2
SO3Na
SO3Na
H2C
O
HN
O
HN
HN
CI Acid Blue 25
O
NH2
SO3Na
H2C
O
HN
SO3Na
N
CI Acid Blue 41
CH3
CI Acid Blue 175
CH3
Figure 5.7 Acid dyes of increasing polarity (25 < 41 < 175)
CI Acid Blue 175
CI Acid Blue 41
CI Acid Blue 25
Contrast ratio
1
5
pH
Figure 5.8 Effect of pH on contrast ratio [11]
Figure 5.8, the higher the dyebath pH the greater the differentiation between the
variant yarns and the better the reservation of the less dyeable component.
However, other factors must be taken into account in deciding the optimum
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60
dyebath pH. Total exhaustion begins to decrease at higher pH values and the
degree of differentiation attainable is limited by the need to achieve economic
exhaustion on the more dyeable variant. If subdued shadow effects are required,
dyes of lower sulphonation are preferred and are applied at a carefully controlled
pH in the 56 region. For sharper differentiation, more highly sulphonated dye
can be used at pH 67.
There are three approaches to selection of dyes for binary blends of aciddyeable nylon. They differ only in the dyes used and the colour effect obtained,
since the same dyeing conditions can be employed in all cases:
(1) Shadow effects using acid dyes giving differentiation between the variant
yarns. Selected direct dyes can also be used but these are more sensitive to
any physical irregularities in the variant yarns.
(2) A limited degree of colour contrast using appropriate combinations of
monosulphonated and disulphonated acid dyes. It is advisable to evaluate
whether the mixtures selected have satisfactory fastness to light on the deepdye yarn.
(3) A wider but still limited degree of contrast using highly sulphonated acid
dyes with selected disperse dyes that give the same depth on both
components of the blend. The hue on the deep-dye nylon is dependent on
that of the disperse dye (section 1.5.4) and the wet fastness of these dyeings
is generally lower than that of contrast dyeings produced by method (2).
The acid dyes showing only moderate differentiation are mainly monosulphonated monoazo or anthraquinone dyes, whereas those dyes showing
sharper differentiation are almost all disulphonated monoazo, disazo or
anthraquinone types. The direct dyes recommended for method (1) are almost all
disazo disulphonates, although a few disazo tetrasulphonates can be used where
sharper differentiation is required. The disperse dyes preferred for solidity on
these blends in method (3) are mainly low-energy monoazo or anthraquinone
types.
The distribution of acid dyes between acid-dyeable variant yarns is affected
significantly by anionic levelling agents, such as alkylarylsulphonates and
sulphated oils (Figure 3.5). These agents are preferentially absorbed by the deepdye variant, so that the degree of differentiation is markedly reduced. Weakly
cationic levelling agents for nylon, however, such as long-chain alkylamine
polyoxyethylenes, provide control of the rate of dyeing of acid-dyeable nylon
blends without suppressing the differentiation, as they operate by complexing
with the anionic dyes. For similar reasons, a nonionic dispersing agent should be
used in preference to anionic alternatives when using disperse and acid dyes for
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DYEING OF ACID-DYEABLE NYLON VARIANTS
61
contrast effects by method (3). Acid-dyeable nylon blends may be aftertreated

with a syntan to improve wet fastness, but if disperse dyes are present the
treatment temperature should not exceed 70C or desorption may occur and the
degree of improvement in fastness is only marginal.
In the case of differential-dyeing tufted carpets or mats made with a jute
backing, it is particularly important to avoid too low a dyebath pH because the
lignin impurities in the jute tend to become transferred to the nylon pile,
especially the deeper-dyeing variants. This yellow-brown staining tends to dull
the brighter hues and to lower the light fastness because it discolours further on
exposure to light. Staining at pH 68 is usually only slight and confined to the
deep-dye or ultra-deep yarns, which are often dyed to a full depth. Much of the
lignin and identification sighting colours on the variant yarns can be removed by
alkaline scouring at 80C before dyeing. When dyeing unusually bright or pale
colours it may be necessary to scour-bleach with alkaline dithionite at 70C,
followed by sodium perborate and a nonionic detergent at the same temperature.
5.3 DYEING OF ACID-DYEABLE/BASIC-DYEABLE NYLON VARIANTS

The diffusion kinetics of CI Basic Blues 3 and 9 (Figure 5.9) on a basic-dyeable
nylon 6 variant containing 5-sulphoisophthalic acid N-terminal residues (Figure
5.10) demonstrated that diffusion was much more rapid than on the parent
homopolymer [12]. Measurements of zeta potentials by the flow-potential
method showed that the modified fibres have an unusually high negative charge
at the surface, which decisively promotes sorption of the dye cations. The uptake
of dye can be regarded as an ion-exchange reaction. The agreement of dye
saturation data with the 5-sulphoisophthalic acid content confirmed that these
oxazine and thiazine dyes of the delocalised-charge type become bound
stoichiometrically to the terminal sulphonated residues in the modified fibre [13].
The scope for bright colours on normal/basic-dyeable blends is narrower than
on deep-dye/basic-dyeable blends, because basic dyes stain normal nylon more
than the deep-dye variant. It is also more difficult to achieve heavier depths on
normal nylon without cross-staining of acid dyes on the basic-dyeable
component. For these reasons it is usual to dye normal/basic-dyeable combinations in pale shades below one-third standard depth on both components.
Anionic scouring agents should be avoided because they may complex with the
basic dyes and increase the basic dye staining of the acid-dyeable nylon variants.
After scouring with a nonionic detergent at 70C, the basic and acid dyes are
added separately after an alkanol polyoxyethylene anti-precipitant, sodium
thiosulphate and a sequestering agent. A cationic retarder can be used to slow
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62

+
(CH3CH2)2N
N(CH2CH3)2 X
O
N
CI Basic Blue 3
(CH3)2N
N(CH3)2 X
N
CI Basic Blue 9
Figure 5.9 Basic blue dyes of the delocalised-charge type

SO3H
NHCOCH2CH2CH2CH2CH2NHCO
COOH
Figure 5.10 Sulpho-containing terminal group in basic-dyeable nylon 6
down the initial strike of basic dyes on the basic-dyeable component at ambient
temperature, permitting improved levelling without impairing the ultimate
exhaustion [14]. Dyeing proceeds readily at 85C and pH 6. A phosphate buffer
is essential to ensure stability of pH for reproducible results on the normal/basicdyeable blend. When dyeing the deep-dye/basic-dyeable combination, however,
pH control with ammonium acetate is satisfactory and more economical. Acid
dye staining of the basic-dyeable nylon is cleared by boiling in dilute acetic acid
at pH 45.
The acid dyes recommended for reserve of the basic-dyeable component of a
differential-dyeing nylon AB blend are mainly mono- or disulphonated monoazo
or anthraquinone types. Levelling acid dyes of this type give better reserve of
basic-dyeable nylon than do milling acid dyes or especially 1:2 metal-complex
types. Monoazo and anthraquinone basic dyes of the localised-charge type are
preferred for reserve of the acid-dyeable component of these blends. The light
fastness and wet fastness of basic dyes on basic-dyeable nylon are markedly
inferior to those of corresponding dyeings on acrylic fibres, and syntans are only
moderately effective in improving wet fastness on this type of nylon. Many
anionic dyes on the acid-dyeable nylon variants show much better wet fastness,
so it is preferable to dye the basic-dyeable fibre only to no more than a medium
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DYEING OF ACID-DYEABLE/BASIC-DYEABLE NYLON VARIANTS
63
depth and to select the acid-dyeable component for the heavier depth in the
design.
5.4 DESIGN OF DIFFERENTIAL-DYEING CELLULOSIC FABRICS

5.4.1 Aminisation of cellulosic fibres
The concept of pretreating cellulosic material with a cationic compound in order
to confer affinity for acid dyes has been explored since long before reactive dyes
were discovered. In those days the approach was of little practical value because
of poor fastness to washing of the cationic agents themselves and the dyeings that
could be obtained with them. In the last twenty years or so, however, there has
been much activity in this area by applying the principles of reactive dyeing and
reactant finishing to the application of these pretreating agents [1519]. Much of
this research has been mainly intended to improve the utilisation of reactive dyes
on cotton or viscose, however, rather than the development of colour effects on
binary cellulosic blends.
Deep-dye viscose can be produced by incorporating additives containing
amino groups into the spinning dope before extrusion. Thus aminoethylcellulose,
prepared by condensation of 2-chloroethylamine with cellulose (Scheme 5.2)
confers enhanced dyeability with direct or acid dyes under mildly acidic dyeing
conditions. These primary amino dyeing sites enable reactive dyes to form
covalent bonds without requiring an alkaline fixation step after exhaustion.
[cellulose]
[cellulose]
OH + ClCH2CH2NH2
[cellulose]
OCH2CH2NH2 + HO3S
[cellulose]
OCH2CH2NH2 + Cl
[dye]
[dye]
OCH2CH2NH2
[cellulose]
[cellulose]
OCH2CH2NH3 O3S
OCH2CH2NH
[dye]
[dye]
Scheme 5.2
Yarns of deep-dye viscose can be knitted or woven into designs with normal
viscose yarn. These are suitable for obtaining either of the following:
(a) shadow effects with direct or alkali-fixed reactive dyes;
(b) normal viscose reserve using acid dyes or neutral-fixed reactive dyes.
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By incorporating an acrylic yarn into the fabric, three-way shadow-contrast or

reserve-contrast designs can be produced using basic dyes with these two
approaches [20].
Diethylaminoethylated cotton or linen can be prepared in a similar way by
reacting the substrate with the tertiary amine 2-chloroethyldiethylamine in the
presence of alkali at 95C. The diethylaminoethyl substituents act as built-in
catalysts, capable of initiating fixation of reactive dyes even in the absence of
alkali. A more effective approach to the aminisation of cotton fabric involved
padding with caustic soda solution, followed by immersion in an acetone
solution of epichlorohydrin and triethanolamine. The etherifying agent is
believed to be the reactive tertiary amine formed by the initial condensation
between the starting materials (Scheme 5.3).
3 H2C CHCH2Cl + (HOCH2CH2)3N
O
(H2C CHCH2OCH2CH2)3N
O
Scheme 5.3
5.4.2 Monofunctional quaternary ammonium reactants

Many of the early attempts to incorporate quaternary nitrogen sites in cellulose
depended on the use of epoxy reactants. The first product of this type on the
market [21] was Glytac A (Protex). This is readily available from epichlorohydrin and trimethylamine (Scheme 5.4) [22].
CH3
H2C CHCH2Cl + N(CH3)3
O
H2C CHCH2
O
Cl
N+ CH3
CH3
Scheme 5.4
Reaction with cellulose proceeds via the glycidyl group at alkaline pH.
Reactive dyes can be fixed to the modified fibres at neutral pH without salt,
conditions that are environmentally attractive. This behaviour has been
attributed to predomination of the zwitterionic form of the sidechain after
alkaline fixation (Scheme 5.5). Thus the anionic dye is absorbed on the
quaternary site and, if reactive, it is attacked by the nucleophilic ionised alcoholic
group nearby [23]. A reagent exhibiting some features in common with Glytac is
1,1-dimethyl-3-hydroxyazetidinium chloride (DMAC). It reacts with cellulose by
a similar ring-opening etherification. The results from the two quaternised
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DESIGN OF DIFFERENTIAL-DYEING CELLULOSIC FABRICS
CH3
[cellulose]
OCH2CHCH2
OH
Cl
N+ CH3
CH3
65
OH
CH3
[cellulose]
OCH2CHCH2
O
N+ CH3 + Cl + H2O
CH3
Scheme 5.5
cellulose ethers are similar, but there is marginally better reactive dye fixation to
the DMAC grouping [17].
Certain problems are characteristic of epoxy quaternising agents [15].
Discoloration of the substrate can occur during the alkaline cure necessary for
epoxy fixation. Loss of trimethylamine by thermal instability destroys the
effectiveness and simultaneously gives rise to objectionable odour in the treated
fabric. This difficulty can be only partly overcome by incorporating more bulky
substituents at higher cost. Probably the most important limitation of the
epoxypropyl agents is their very low substantivity. Not only are they unsuitable
for exhaust application but poor dye penetration arises from agent migration at
the drying stage of the paddrybake application process.
The N-methylolation reaction that has been so important in traditional
chemical finishing can be exploited as a first step to the aminisation of cellulose
using N-methylolacrylamide. This acrylamidomethylated cellulose reacts readily
with ammonia or alkylamines to yield cellulose derivatives containing amino,
imino or quaternary groups (Scheme 5.6). Dyeing tests on these derivatives
showed generally good colour yields and high fixation, but reactive dyes on those
aminised with di- or trimethylamine gave poor fixation. The dyefibre linkage is
labile owing to the strongly electron-withdrawing quaternary group [23].
cell OH + HOCH2NHCOCH CH2
cell OCH2NHCOCH CH2
cell OCH2NHCOCH CH2 + H R
cell OCH2NHCOCH2CH2
R = NH2, NHCH3, NHCH2CH2OH, N(CH3)2 or N(CH3)3Cl
Scheme 5.6
Groups of the haloheterocyclic type found in traditional reactive dyes, such as

aminochlorotriazine or difluoropyrimidine, have been exploited in aminising
agents that also contain mono- or bis-quaternary ammonium groups to boost the
uptake of anionic dyes by the aminised substrate. Such agents react more readily
with cellulose and show higher thermal stability than the ring-opening types such
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66
as Glytac or DMAC. Both classes of monofunctional reactive system, however,

share the disadvantage of low substantivity for cellulose and must be applied by
padding. More complex multifunctional structures were designed for exhaust
application [15] and these gave impressive colour yields. There are practical
drawbacks to all these agents, however, including lower light fastness [17], hue
changes and poor penetration into the fibre [15].
In a differential-dyeing evaluation of aminochlorotriazine agents, colourless
cationic and anionic products of this type (Figure 5.11) were applied to cotton
yarns [24]. Yarn pretreated with the quaternary ammonium agents showed
enhanced uptake of CI Acid Red 13 or CI Direct Blue 10. The degree of
differential uptake was dependent on the amount of agent applied, so fabrics
exhibiting a range of shadow effects were obtained. Pretreatment with the
sulphonaphthylamine agent gave cotton dyeable with CI Basic Yellow 15.
Combinations of anionic- and cationic-modified yarns yielded contrast effects
with minimal cross-staining. The pretreated cotton samples were sufficiently
stable to be converted to viscose or cellulose triacetate without loss of the
modified dyeability, providing potential routes to differential-dyeing viscose or
triacetate variants.
Cl
N
N
N
HN
CH2CH3
NHCH2CH2 N + R
X
CH2CH3
Cl
N
HN
N
N
NH
SO3Na
Figure 5.11 Cationic and anionic aminochlorotriazine agents
This approach to differential-dyeing is flawed because the costly pretreatment

with a sophisticated reactive agent is not justifiable. The fastness of the colour
effects to washing with detergent will be inadequate because the dyes are linked
to the ionic dyeing sites mainly by electrostatic bonds. In the case of basic dyes on
the sulphonaphthylamine sites, low fastness to light is also anticipated.
An alternative approach to the aminisation of cellulose involves esterification
using chloropropionyl chloride. This chloropropionate ester condenses readily
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with ammonia or alkylamines at 50C to yield aminised cellulose derivatives

(Scheme 5.7). If the aminisation treatment is carried out at the boil, however,
chloropropionic acid is eliminated and the cellulose is regenerated. The ester
bond remains intact during reactive dyeing but it is hydrolysed during alkaline
soaping at the boil [25].
[cellulose]
[cellulose]
OH + ClCOCH2CH2Cl
OCOCH2CH2Cl + H R
50C
[cellulose]
OCOCH2CH2Cl
[cellulose]
OCOCH2CH2 R
R = NH2, NHCH3, N(CH3)2 or N(CH3)3Cl
Scheme 5.7
Sodium or ammonium phosphates can be used to produce chambray or other

special colour effects on cotton fabrics. Yarn treated with the phosphorylating
agent (Scheme 5.8) is dried, cured and then woven as the weft with an untreated
warp. The fabric is then piece dyed with reactive, vat or direct dyes. Only the
warps absorb dye because the phosphorylated cellulose resists these conventional
dyes for cotton. It can be cross-dyed, however, using 1:1 metal-complex dyes at
pH 4. Interesting colour contrast effects are obtained by treating selected areas of
a cotton pile fabric with the phosphorylating agent before selective dyeing [26].
These techniques offer the advantage of a cheap and effective modifying reactant
but the coordinate bonds linking the metal-complex dyes to the phosphate
dyeing sites will show only limited fastness to acidic perspiration tests.
[cellulose]
ONa
OH + NaO P O
ONa
[cellulose]
ONa
O P O + NaOH
ONa
Scheme 5.8
5.4.3 Polymeric cationic reactants

Many cationic polymers have been applied to cellulosic fibres with a view to
enhancing uptake of anionic dyes [18]. It is considerably more difficult in these
instances to interpret the precise mechanisms involved, apart from the obvious
participation of electrostatic attraction between dye anions and basic groups in
the polymer. Recent studies have included the application to cotton [17] of the
polyamide-epichlorohydrin resin Hercosett 125 (Hercules), originally marketed
as a shrink-resist treatment for wool. Improved dyeability with reactive dyes and
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good wet fastness were obtained, but dullness of hue and impaired light fastness
were disadvantages.
Incorporation of thiourea into the Hercosett polymer during application was
intended to overcome deficiencies when using low-reactivity dyes on Hercosett
alone. Thiourea reacts with azetidinium groups in the resin to form
isothiouronium groups. These are more strongly nucleophilic and improve the
fixation of low-reactivity dyes. Some of the isothiouronium groups decompose
during dyeing to yield thiol groups, which form further sites for dye fixation and
may also react with remaining azetidinium groups to form thioether crosslinks in
the resin (Scheme 5.9).
CH2
NH2
CHOH + S
NH2
CH2
Cl
+
NH2
N CH2CHCH2 S
OH
+
Cl
NH2
N CH2CHCH2 S
OH
NH2
Cl
OH
NH2
NH2
N CH2CHCH2SH + O
NH2
OH
CH2
CHOH + HSCH2CHCH2 N
N
CH2
Cl
OH
N CH2CHCH2 S CH2CHCH2N
OH
OH
Scheme 5.9
Differences in colour yield were still observed between dyes of high and low
reactivity and therefore ethylenediamine was evaluated as an additive to the
Hercosett resin [27]. This reacts readily with azetidinium groups to form
primary, secondary and tertiary amino sites for fixation of reactive dyes (Scheme
5.10). Enhanced substantivity, good brightness and excellent fastness to washing
were achieved but the light fastness was still impaired in most cases.
+
CH2
CHOH + H2NCH2CH2NH2
N
CH2
N CH2CHCH2NHCH2CH2NH2
OH
Cl
N CH2CHCH2NHCH2CH2NHCH2CHCH2 N
OH
OH
Scheme 5.10
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Cotton has little inherent substantivity for disperse dyes, but a water-soluble
benzoylating agent, sodium benzoylthioglycolate, can be applied by a paddry
thermofix process in the presence of alkali (Scheme 5.11) to yield a benzoylated
cellulose for which disperse dyes show enhanced substantivity. Dyeings of high
colour strength and good fastness to ISO 3 washing are obtained [28]. Disperse
dyeings on benzoylated cellulose exhibit much better fastness to washing than
corresponding dyeings on cotton esterified using long-chain acylating agents
[29]. The ease of application of sodium benzoylthioglycolate is a great advantage
over earlier processes based on the SchottenBaumann reaction of cellulose with
benzoyl chloride. This process is of interest for the single-class dyeing of blends
of ester fibres with cellulosic fibres using disperse dyes to colour both
components.
NaOH
C S
CH2COONa + HO
[cellulose]
O
Sodium benzoylthioglycolate
C O
[cellulose] + HSCH2COONa
O
Sodium thioglycolate
Scheme 5.11
Polymer treatments devised to increase the versatility of cotton as a dyeable

substrate [30] included:
(1) treatment with a disperse-dyeable polymer followed by disperse dyeing;
(2) addition of basic or acid dyes to a crosslinking formulation so that the dyes
are retained by interaction with the finish;
(3) application of reactive or vat dyes with an anionic-dyeable polymer.
Bicoloured contrast effects can be produced by selective coating of the two sides
of the fabric with different combinations of dye and finish. Disperse and basic
dyes exhibit poor light fastness on cotton although the brightness of basic dyes
may appear superficially attractive. Reactive dyes give the best balance of
properties, since vat dyes sometimes show unlevelness under these conditions.
A two-stage dyeing sequence has been proposed for the contrast dyeing of
cotton terry towelling using reactive dyes [31]. The first step involves continuous
dyeing of the fabric using a polyelectrolyte that promotes coloration of the tips of
the terry towelling loops. Adverse drying conditions on hot cans (fry drying)
favour dye migration to the tips of the loops. The dried fabric is then padded
with a highly alkaline concentrated salt solution to minimise dye desorption and
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70
steamed to complete alkaline fixation of the dyes. Unfixed dye is removed by

rinsing. The second stage consists of uniformly dyeing on a winch or atmospheric
jet in a contrasting colour also formulated with reactive dyes in conventional
exhaust dyeing.
5.4.4 Introduction of activated sites for nucleophilic dyes

In this approach the reactive function is incorporated into the substrate and a
reactive dyeing is carried out using a non-reactive dye containing nucleophilic
groups. A model dye of this kind was prepared by reacting the
aminochlorotriazine dye CI Reactive Red 58 with ethylene diamine to form a 2aminoethylaminotriazine derivative (Scheme 5.12). Acrylamidomethylated
cellulose prepared by condensation of N-methylolacrylamide with cotton
(Scheme 5.6) reacts readily with nucleophilic dyes of this kind, which show no
hydrolysis during dyeing.
O
3S
[dye] HN
N
N
Cl
N
+ H2NCH2CH2NH2
O
3S
OH
[dye] HN
NHCH2CH2NH2
NHAr
+ HCl
N
N
NHAr
Scheme 5.12
High fixation is achieved either by exhaustion at pH 10.5 in salt solution or

by padbatch at the same pH for 24 hours [23]. These aminoalkyl dyes show
zwitterionic character below pH 8 and this lowers the nucleophilicity of the
primary amino group. Nucleophilic dyes containing thiol groups would be more
reactive than aminoalkyl analogues but there would be problems of toxicity,
odour and a tendency to oxidise to disulphide. Aminoaryl or hydroxyalkyl
analogues would be less reactive than the aminoalkyl derivatives.
The novel reactant 2,4-dichloro-6-(2-pyridinoethylamino)-s-triazine
(DCPEAT, Figure 5.12) was evaluated [32] as a means of activating cellulose by
padbatch application at pH 8.5 for 24 hours. After a cold water wash, the
modified substrate was dyed with aminoalkyl dyes. High fixation was achieved
by exhaust dyeing at pH 9 without salt. Nucleophilic dyes can also be fixed on
cotton or nylon that has been pretreated [33] with the trifunctional reactant 2chloro-4,6-bis(4-sulphatoethylsulphonylanilino)-s-triazine (CSESAT, Figure
5.12).
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N CH2CH2NH
N
DCPEAT
NaO3SO
CH2CH2SO2
Cl
N
Cl
N
HN
N
CSESAT
71
NH
SO2CH2CH2
OSO3Na
N
Cl
Figure 5.12 Bifunctional and trifunctional reactants for cellulose
Developments in this area seem to be leading to daunting complexity rather

than elegant simplicity. Certain aspects of this concept inspire unease rather than
confidence:
(1) The risk of premature hydrolysis leading to impaired fixation has been
transferred from the dye to the substrate.
(2) The pretreatment with a colourless reactant necessary to activate the
substrate must be exceptionally uniform if dye fixation is to be consistent.
(3) If penetration of the reactant is poor, ring dyeing will follow and the fastness
properties will be adversely affected.
(4) Only the aminoalkyl dyes will react with the activated substrate and other
classes of dyes for unmodified cellulose may be inapplicable.
(5) Cost implications give concern because both dye and substrate must be
specially modified before the desired reaction can occur.
5.5 DESIGN OF DIFFERENTIAL-DYEING WOOL KERATIN

DERIVATIVES
Wool is routinely chlorinated with a dilute acid solution of hypochlorite or with
gaseous chlorine to give shrink-resist effects, whereby absorption of acid dyes is
appreciably increased. The production of shadow effects on blends of
chlorinated and untreated wool depends not only on a selection of
multisulphonated dyes but also on dyeing conditions. Dyeing at low
temperatures will favour absorption by chlorinated wool, particularly in the case
of aggregated milling acid dyes that are less readily absorbed by the unmodified
fibre except at higher temperatures. Certain chrome dyes will also produce
distinctive colours on blends of chlorinated and unchlorinated wool. Levelling
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acid dyes are unsuitable because of the rapid migration of these dyes even at
temperatures below the boil.
The differential dyeing of wool can be achieved using several other techniques
[34]:
(1) localised pretreatment with acid-dye-resist agents of the dichlorotriazinylaminoarylsulphonate type (Figure 5.3) before dyeing the untreated areas
with acid dyes;
(2) pretreatment with cationic agents such as Glytac A (section 5.4.2) to confer
deep-dye characteristics;
(3) overdyeing of fabrics containing wool yarns predyed with e.g. the
chromium complex of CI Mordant Black 9 (Figure 5.13) to give colour/
black effects;
(4) application of mordant dyes to prechromed and unchromed wool yarns, but
this is not of much value owing to poor shade reproducibility.
OH
SO3Na
N N
O
O
CrIII
O
O
N N
NaO3S
OH
Figure 5.13 CI Mordant Black 9 chrome complex
Provided that the nucleophilic sites of reaction within the accessible regions of
wool keratin can be blocked, there will be no remaining opportunity for reactive
dyes to become fixed. By choosing reactive dyes of high reactivity but relatively
low substantivity it should be possible to achieve a high degree of resist effect.
The principal nucleophilic groups are primary amino (lysine), secondary imino
(histidine) and free thiol groups (cysteine). A reactive dichlorotriazinylaminoarylsulphonate (Figure 5.3) effectively blocks these nucleophilic sites.
Acid-dye-resist agents of this kind that introduce extra anionic sidechain
groups into wool keratin will confer enhanced basic-dyeable character.
Conversely, a reactive agent with a cationic centre, such as Glytac A (section
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DESIGN OF DIFFERENTIAL-DYEING WOOL KERATIN DERIVATIVES
73
5.4.2), will act as a basic-dye-resist and confer increased acid-dyeable behaviour.

Sandospace R (S) at weight gains of 8% or more resisted all the reactive, mordant and acid dyes tested to 70% resist or higher, except for a monosulphonated
acid dye. Uptake of the reactive and acid dyes was increased by prior reaction of
the wool with Glytac A, a moderately effective resist treatment with respect to
basic dyes (4080% resist) but hydrophobic dyefibre forces appeared to
predominate over cationic repulsion effects [35].
There is no universally effective reactive resist that will reserve all classes of
dyes normally applied to wool. Dyes of high Mr become attached to wool by
nonpolar van der Waals forces between the hydrophobic dye anions and
hydrophobic sidechains in the wool fibre, their strength being proportional to the
area of contact. High wet fastness is often achieved by increasing the Mr with
substituents that do not form part of the chromogenic system, such as dodecyl or
arylsulphonyl groups. As wool dyes become more hydrophobic they show a
greater tendency to aggregate in the dyebath. Aggregation within voids in the
keratin structure is probably partly responsible for the poor migration, high wet
fastness and excellent light fastness of these dyes.
The benzoylation of wool using benzoic anhydride forms benzoylamino
residues on lysine sidechains and N-terminal end groups, as well as benzoate
ester groups on the hydroxy-containing sidechains of serine and threonine
(Scheme 5.13). This destroys most of the sites for reactive dye fixation and also
acts as an effective resist for acid dyes with two or more sulphonate groups.
[wool]
[wool]
NHCO
NH2
O
+
+ H2O
O
O
[wool]
OH
[wool]
OCO
Scheme 5.13
If a water-soluble bifunctional arylating agent (Scheme 5.14) is applied by

exhaustion at pH 6.5 together with conventional disperse dyes, absorption by
wool takes place with the agent held initially by electrostatic attraction and
hydrophobic interaction as if it were a colourless milling acid dye. Fixation
occurs during subsequent treatment for an hour at the boil, the active
vinylsulphone group being released by -elimination and reaction taking place
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74
Cl
N
HN
NH
Cl
SO2CH2CH2OSO3Na
Cl + H2N [wool]
HN
N
NH
+ NaHSO4
HN
SO2CH
NH
SO2CH
CH2 + H2N
CH2
[wool]
NH [wool]
N
HN
N
N
NH
SO2CH2CH2NH [wool]
Scheme 5.14
with nucleophilic groups in the fibre. Some reaction also occurs via the less
reactive chlorotriazine group. Hydrophobic groupings attached to the wool in
this way confer enhanced substantivity for disperse dyes. This approach is of
interest for the single-class dyeing of blends of ester fibres with wool using
disperse dyes to colour both components [36].
Sulphamic acid reacts with the amino groups of lysine sidechains and the Nterminal end groups in wool to form ammonium sulphamate groups, and with
the hydroxy groups of serine and threonine to form ammonium sulphate groups
(Scheme 5.15). Wool that has been treated with sulphamic acid and urea in a
paddrybake process shows increased uptake of basic dyes. Milling acid dyes
that depend mainly on hydrophobic dyefibre interaction are poorly resisted by
sulphamylated wool, but levelling acid dyes absorbed mainly by electrostatic
[wool] NH2 + HO3SNH2

[wool]
OH + HO3SNH2
[wool] NHSO3
[wool] OSO3
NH4+
NH4+
Scheme 5.15
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DESIGN OF DIFFERENTIAL-DYEING WOOL KERATIN DERIVATIVES
75
attraction are strongly resisted. Reactive dyes, almost all of which are highly
sulphonated with no hydrophobic alkyl substituents, are also effectively resisted.
Sulphamylated wool shows much higher exhaustion of typical basic dyes than
acrylic fibres. These contain only about 50150 milli-equivalents per kg of
anionic groups, whereas wool treated with sulphamic acid contains up to ca.
1000 milli-equivalents per kg of acidic dyeing sites [37]. Sulphamylation of wool
has a marked effect on the light fastness of basic dyes. The fastness ratings on the
modified wool are much higher than on untreated wool (Table 5.2). This brings
the ratings of the modified wool close to values obtained for the same dyes on
acrylic fibres. This effect is attributed to the beneficial influence of the strongly
anionic groups introduced by the sulphamylation reactions. Basic dyes on
untreated wool are absorbed because of the presence of the carboxyl groups in
aspartic and glutamic acid sidechains and the C-terminal end groups.
Unfortunately, the fastness to washing of basic dyes on untreated and
sulphamylated wool is extremely poor. The treatment with sulphamic acid makes
the wool more hydrophilic. Marginal improvement of the wet fastness is possible
by aftertreatment with tannic acid but this causes dulling of the dyeings.
Table 5.2 Exhaustion and light fastness of typical basic dyes [37]
Exhaustion (%)
Light fastness
2% o.w.f. of
CI Basic
Acrylic
fibre
Sulphamylated
wool
Acrylic
fibre
Untreated
wool
Sulphamylated
wool
Yellow 11
Red 51
Blue 3
71
30
33
99
97
98
6
6
45
4
34
1
6
6
4
The treatment of merino wool with ethanolamine in aqueous isopropanol to

confer enhanced dyeability and a shrink-resist effect was investigated using a
factorial design experiment with three variables [38]. These effects of
ethanolamine have been attributed to alkaline hydrolysis of the cystine
disulphide groups to form dehydroalanine residues that can react with the amine
to form -aminoalanine groups, which are able to interact with anionic dyes. A
vinylsulphone reactive dye was used to assess the improvement in dyeability. The
optimum conditions found were 1 mol l1 ethanolamine in 50% aqueous
isopropanol at 55C, which gave the best dyeability and shrink resistance with
only 3% weight loss and acceptable whiteness.
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76
5.6 REFERENCES
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
12.
13.
14.
15.
16.
17.
18.
19.
20.
21.
22.
23.
24.
25.
26.
27.
28.
29.
30.
31.
32.
33.
34.
35.
36.
37.
38.
C Baur, Teinture et Apprets, 144 (Oct 1974) 163.

J Park, J.S.D.C., 109 (1993) 133.
A Anton and J C Browne, Text. Chem. Colorist, 16 (Sep 1984) 135.
A Anton, Text. Chem. Colorist, 13 (Feb 1981) 46.
R Gutmann, T Barth and H Herlinger, Chemiefasern und Textilind., 40/92 (1990) 104.
T Sato, Chemiefasern und Textilind., 40/92 (1990) 35.
M D Teli and N M Prasad, Am. Dyestuff Rep., 80 (June 1991) 18.
S M Doughty, Rev. Prog. Coloration, 16 (1986) 25.
M M Marie, Am. Dyestuff Rep., 82 (Sep 1993) 86.
R McGregor, AATCC Int. Tech. Conf., (Oct 1976) 124.
T L Dawson and B P Roberts, J.S.D.C., 95 (1979) 47.
H Muller and V Rossbach, Text. Research J., 47 (1977) 44.
H Muller, Text. Research J., 47 (1977) 71.
M A Herlant, Am. Dyestuff Rep., 81 (June 1992) 15.
G E Evans, J Shore and C V Stead, J.S.D.C., 100 (1984) 304.
R L Stone and R J Harper, AATCC International Conference and Exhibition, (Oct 1986) 214.
D M Lewis and X P Lei, Text. Chem. Colorist, 21 (Oct 1989) 23.
J Shore, Rev. Prog. Coloration, 21 (1991) 23.
J Shore, Indian J. Fibre Text. Res., (Mar 1996) 1.
R Aitken, J.S.D.C., 99 (1983) 150.
M Rupin, G Veaute and J Balland, Textilveredlung, 5 (1970) 829.
T S Wu and K M Chen, J.S.D.C., 108 (1992) 388.
D M Lewis and X P Lei, J.S.D.C., 107 (1991) 102.
J A Clipson and G A F Roberts, J.S.D.C., 105 (1989) 158.
X P Lei and D M Lewis, Dyes and Pigments, 16 (1991) 273.
E J Blanchard, J T Lofton, J S Bruno and G A Gautreaux, Text. Chem. Colorist,
11 (Apr 1979) 76.
X P Lei and D M Lewis, J.S.D.C., 106 (1990) 352.
D M Lewis and P J Broadbent, J.S.D.C., 113 (1997) 159.
E Einsele, H Sadeli and H Herlinger, Melliand Textilber., 63 (1981) 967; 64 (1982) 61.
R J Harper, E J Blanchard, J T Lofton, J S Bruno and G A Gautreaux, Text. Chem. Colorist,
6 (Sep 1974) 201.
J N Etters, Am. Dyestuff Rep., 83 (Sep 1993) 70.
D M Lewis and X P Lei, AATCC International Conference and Exhibition, (Oct 1992) 259.
D M Lewis and Y C Ho, AATCC International Conference and Exhibition, (Oct 1994) 419.
A C Welham, Am. Dyestuff Rep., 81 (Oct 1992) 15.
V A Bell, D M Lewis and M T Pailthorpe, J.S.D.C., 100 (1984) 223.
D M Lewis, J.S.D.C., 113 (1997) 193.
B A Cameron and M T Pailthorpe, J.S.D.C., 103 (1987) 257.
L Coderch, A M Manich, J L Narra and P Erra, J.S.D.C., 107 (1991) 19.
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CHAPTER 6
Nylon/wool and other AA blends
6.1 DYEING OF NYLON/WOOL BLENDS

Blends in which both fibres are dyeable with anionic dyes in full depths (AA
blends) are usually developed because of a desirable balance of physical
characteristics. The attainment of solid colour effects is therefore usually
necessary. As soon as nylon was readily available for commercial outlets after the
Second World War, it was recognised that the exceptional strength, durability
and abrasion resistance made it the ideal fibre for blending with wool. Blended
twill fabrics gave the same performance as the all-wool counterpart but at half
the weight. Hand-knitting yarns and half-hose blended from 20:80 to 40:60
nylon/wool give a valuable combination of softness and strength. Stretch fabrics
woven from a crimped nylon warp and a wool weft are established in winter
sportswear, particularly skiwear, and leisure clothing.
Woven carpets and high-quality tufted carpets are most important outlets for
blended-staple nylon/wool yarns, usually containing about 20% of nylon to confer improved durability and abrasion resistance whilst retaining the absorbency,
softness and antistatic qualities of the natural fibre. An interesting anomaly of
the 1990s market, however, is a demand for carpets made from blended nylon/
wool but dyed and woven to simulate sisal, a natural cellulosic fibre viewed as a
fashionable floor covering by ecology-conscious consumers [1].
The quality of the wool and its base colour will influence the visual effect
obtained between the two fibre types when dyed. Even when the depth of colour
is the same, the yellowness of the wool can result in the shade appearing duller
on that component. Blends containing nylon 6 show higher saturation uptake
and critical depth than nylon 6.6 blends and require more retarding or levelling
agent. Supplies of the same nylon type from different sources, or even different
merges from the same source, may also vary in dyeing properties [2].
Good solidity is generally easier to achieve on staple-fibre blends, such as
hand-knitting yarns or carpets, because the blend often contains only 1020% of
nylon and the distribution can be controlled using an appropriate auxiliary.
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78
NYLON/WOOL AND OTHER AA BLENDS
Solidity is a more serious problem when dyeing nylon/wool furnishings or

sportswear woven with a crimped nylon warp and a wool weft. Apart from the
quality and proportions of wool and nylon present, the distribution of dye
between them depends on several factors already discussed (section 3.2),
including the constitution and degree of sulphonation of the dyes, applied depth,
agent concentration, pH and temperature of dyeing [3].
Like the disulphonated levelling acid dyes, the 1:1 metal-complex dyes have
low substantivity for nylon and the critical depth on nylon/wool is relatively low
compared with monosulphonated acid dyes and 1:2 metal-complexes. Dyes of
the 1:1 metal-complex type and the levelling acid disulphonates are dyed at pH
23 with formic or sulphuric acid and salt at the boil. Monosulphonated acid
dyes and premetallised 1:2 types dye nylon more readily, so they are applied to
nylon/wool at pH 56 with ammonium acetate and acetic acid. A near-neutral
pH is necessary to control levelness in pale depths, but more acetic acid can be
used for full depths.
Medium or heavy depths on nylon/wool carpet blends are usually dyed with
1:2 premetallised dyes in order to ensure good fastness to light and shampooing.
The monosulphonated type offers the best economic compromise of good
partition with moderate usage of retarding agent. Partition is, however,
dependent on control of pH, being improved in favour of the wool with
decreasing pH and increasing temperature. The control of both of these factors
can be ensured using an automatic dosing system [4]. Coverage of physical
variations in the nylon is limited but an alkanol polyoxyethylene levelling agent
gives some improvement. Heavy, dull colours can be dyed by a two-stage method
in which the nylon is first dyed preferentially with 1:2 metal-complexes at pH 6
and the wool is then filled in with selected 1:1 metal-complex types.
It is difficult to attain satisfactory solidity on nylon/wool with chrome dyes,
which tend to favour wool. Some solid hues can be based on mixtures of selected
chrome and 1:2 premetallised types. The chrome dyes giving acceptable solidity
on nylon/wool are mainly monosulphonated naphthylazo derivatives of Mr
350450. They are used only for economical dull orange, red, brown and black
dyeings of high wet fastness. At such depths no anionic retarder is required.
Chroming of the dye is more difficult on nylon/wool than on nylon alone
because the chromium tends to be absorbed preferentially by the wool. Chelation
with the dye can be improved by adding a mild reducing agent, such as sodium
thiosulphate.
Novel black 1:2 metal-complex azo dyes containing chelated iron(III) instead
of chromium(III) atoms have been synthesised. Results from in vitro hazard
testing reveal that these iron complexes are satisfactory with regard to
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DYEING OF NYLON/WOOL BLENDS
79
genotoxicity [5]. The fastness properties of these new dyes on both nylon and
wool are comparable with those of their chromium analogues. It is anticipated
that they will be strong candidates for nylon/wool dyeing in carpets or
furnishings requiring high light fastness [6].
Disperse dyes are rarely used on nylon/wool because their light fastness and
wet fastness ratings are low, and the heavy stain on wool has poor fastness to
light, rubbing and perspiration. If heavy depths are dyed with disulphonated
levelling acid dyes above the critical depth, disperse dyes can be applied with an
alkanol polyoxyethylene dispersant from the same bath to fill in the nylon
component. The disperse dyes chosen for this shading purpose are mainly lowenergy monoazo or anthraquinone types. Owing to the cross-staining of wool
that inevitably occurs, the fastness of the dyeing may be impaired.
If dye partition between nylon and wool is unequal, particularly if there is an
off-tone shade variation, this can lead to a stripy appearance in plain woven or
tufted carpet constructions. Further problems can arise after wear, for if there is a
marked tonal difference between the fibre components in a loop-pile
construction, the carpet begins to show pronounced local colour changes where
the wool fibres become abraded away in worn areas [4].
Unmetallised acid dyes fade more slowly in wool than in nylon and the fading
mechanism appears to be different, probably because oxidative degradation in
nylon is not inhibited, whereas the reducing environment of the wool fibre has a
retarding effect. The differences are also consistent with the formation of dye
aggregates in wool, which has a much higher amine end group content [7].
6.2 BLENDS OF WOOL WITH OTHER ACID-DYEABLE FIBRES
Owing to its characteristic lustre and excellent physical and chemical properties,
silk has remained the traditional dress fabric for kimonos and saris in Asia. It is
becoming increasingly important in other forms of dresswear, either alone or
blended with wool, cotton, nylon or polyester. Natural silk is blended in equal
proportions with wool to make high-class apparel, contributing lustre and
strength. Intimate blends are usually dyed in solid shades, but it is not difficult to
achieve shadow effects because of the higher initial rate of dyeing of the silk
component, especially at low pH. Silk yarns are also used as effect threads in fine
wool dress fabrics. Effect threads are preferably yarn dyed before weaving and
the wool is then cross-dyed, making allowance for staining of the silk at this
stage.
Attempts have been made to dye the wool and reserve the silk, although
careful dye selection is necessary and considerable skill is required to formulate a
wide range of shades in this way. Any cross-staining cannot be completely
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cleared without affecting the shade on the wool. Strongly acidic dyebaths
increase the depth on the silk component. Wool is favoured at higher pH values
and at pH 56 the silk is almost completely reserved. Monosulphonated milling
acid dyes of Mr 450550 give the best reserve under these conditions.
If solidity is required on wool/silk blends it is necessary to dye at a low pH
below the boil. Under these conditions, however, levelling acid and 1:1 metalcomplex dyes do not give adequate fastness on the wool. It is possible to apply
some selected milling acid dyes but level dyeing is difficult. Common salt and a
mildly cationic retarder are necessary to control the rate of dyeing. The
distribution of direct, acid and metal-complex dyes between wool and silk has
been examined by dyeing simulated blends [8].
Blends of natural silk and virgin wool can be dyed at ambient temperature
with high-reactivity dyes for the silk and then the wool is filled in with milling
acid or 1:2 metal-complex dyes at pH 56 and 90C, to minimise cross-staining
of the reactive-dyed silk. The fastness to light, water and alkaline perspiration of
reactive dyes from the aminofluorotriazine and -bromoacrylamide classes is
satisfactory and superior to that of copper-complex direct or 1:2 chromiumcomplex acid dyes on silk [9].
Besides wool, the animal fibres of interest include mohair and cashmere from
species of goat, alpaca and vicuna from camel species, and angora fur from
rabbits. These are relatively scarce and costly but may be blended with wool to
increase lustre and give a distinctive appearance. Blends of wool with silk,
mohair, cashmere or alpaca are largely subject to the dictates of fashion. Handknitting yarns are luxury items and processing costs tend to be low relative to
retail prices, so that more attention can be paid to high quality rather than productivity and materials cost. Typical blends for such yarns include wool/angora,
wool/cashmere, wool/mohair and nylon/mohair. Some cashmere is diluted with
fine wools for economic reasons but may still carry a cashmere label.
The outstanding properties of angora and cashmere in knitwear apparel are
well known. These fibres will not withstand prolonged boiling, so reproducible
colour matching and first-class levelness are essential [10]. Angora is only
processed in blends with wool, sometimes with the addition of a small
proportion of nylon to improve the durability. For economic and technical
reasons 1:2 metal-complex and milling acid dyes are preferred. Chrome dyes and
1:1 metal-complex types are seldom used because strongly acidic dyebaths may
damage the angora. A simple test using CI Acid Red 18 and CI Basic Blue 9
(Figure 6.1) can be used to assess the degree of oxidation damage to the angora.
The bluer the staining with this mixture, the greater the degree of damage [11].
In pale dyeings, any nylon present dyes more intensely, whereas in full depths it is
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BLENDS OF WOOL WITH OTHER ACID-DYEABLE FIBRES
81
H O
NaO3S
N
S
(CH3)2N
N
NaO3S
CI Acid Red 18
N(CH3)2 X
N
SO3Na
CI Basic Blue 9
Figure 6.1 Components of stain test for damage in angora fibres
the wool that gives the deeper shade. Solidity can be achieved using a retarding
agent, the addition needed being dependent on the applied depth and blend
proportion, particularly the amount and quality of any nylon present. The
amount of retarder required varies inversely with dye concentration.
Major outlets for wool/mohair blends are worsted outerwear and suitings.
Such fabrics may be made from intimate blends for both warp and weft, but they
often consist of a mohair warp with a botany wool weft. The enhanced lustre
and good wear properties make these blends suitable for lightweight suitings and
dresswear. Wool/mohair fabrics may be piece dyed with 1:2 premetallised dyes,
or more economically with levelling acid dyes. If the blend is to be used in
suitings, it is customary to dye the wool and mohair separately in sliver or top
form for subsequent blending.
The rate of dyeing and equilibrium exhaustion on mohair fibres are higher
than for wool fibres of similar diameter. Visual and instrumental assessment of
depth of shade, however, shows little difference between the two fibre types dyed
separately with the same dyebath concentration of an acid dye. These
measurements support the view that the pronounced surface lustre associated
with mohair is responsible for its apparently slightly lower content of absorbed
dye when compared with other less-lustrous wools dyed from the same bath
[12]. Mohair and wool show a similar tendency to yellow as a result of aqueous
oxidation or thermal treatments. Urea-bisulphite solubility data indicate that
mohair suffers less modification under mild conditions but this position is
gradually reversed with increasing severity of treatment [13]. Thus the loss in
weight during aqueous treatment is ultimately greater for mohair than for wool.
The dyeing of wool/polyurethane blends has much in common with the
dyeing of blends of nylon with either of these fibres. Anionic dyes are used in a
similar way with anionic agents (sections 3.2 and 3.3) to control the tendency of
milling and 1:2 premetallised dyes to favour the polyurethane component.
Chrome and metal-complex dyes generally give better wet fastness on wool/
polyurethane than milling acid dyes, but 1:1 metal-complex and levelling acid
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dyes are unsuitable because of degradation of the polyurethane under the

strongly acidic dyeing conditions required.
Blends of acid-dyeable polypropylene staple with wool are of interest for
tufted carpets, upholstery and certain apparel outlets, such as mens socks. Both
fibres are dyeable with anionic dyes and the blend gives a full handle at low
fabric weight per unit area, only moderate formation of electrostatic surface
charge and a high fibrefibre frictional coefficient. This leads to softness of
handle and a high resistance to pilling. Blends of 50:50 to 20:80 wool/aciddyeable polypropylene are also of growing importance in Axminster carpets [1].
It is difficult to control the distribution of anionic dyes between these fibres
owing to their high substantivity but slow rate of diffusion in the synthetic
component. At temperatures below about 75C the polypropylene is only ringdyed. Only at 80C and above does diffusion into the polymer matrix become
appreciable and dyeing of the acid-dyeable fibrillar regions begin.
The attainment of satisfactory solidity entails commencing dyeing at 7580C
and pH 3 to 5, according to applied depth. The initial distribution favours the
polypropylene surface but as the temperature approaches the boil the wool
becomes heavily dyed. Penetration of the acid-dyeable regions of the synthetic
fibre proceeds steadily at the boil and some improvement in solidity is possible at
this stage with those dyes showing good migration properties. A weakly cationic
levelling agent of the alkylamine polyoxyethylene type is recommended with
metal-complex dyes and the level dyeing of milling acid and chrome dyes can be
promoted by addition of a nonionic agent of the alkanol polyoxyethylene class.
6.3 BLENDS OF NYLON WITH OTHER ACID-DYEABLE FIBRES
Elastomeric polyurethane yarns are mostly of interest to provide stretch
properties for characteristic nylon outlets in the knitting industry. Warp-knit
swimwear and sportswear, and Raschel-knit foundation garments, underwear,
surgical hose and half-hose tops, are important outlets for nylon/polyurethane
blends. Although the elastomeric fibre is often covered by the nylon in the
relaxed fabric, penetration of the close construction during dyeing is essential
because the elastomeric fibre is revealed on stretching the fabric. Careful control
of processing tensions, as well as the pH, time and temperature of treatment, is
necessary to preserve the optimum strength and elastic properties of
polyurethane fibres. Nylon/polyurethane fabrics are normally scoured at
6070C with tetrasodium pyrophosphate and an anionic detergent.
Disperse dyes diffuse into polyurethane fibres even more readily than into
nylon or cellulose acetate, but the wet fastness properties of the dyeings are
correspondingly low. Selected dyes give solidity on nylon/polyurethane, but for
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BLENDS OF NYLON WITH OTHER ACID-DYEABLE FIBRES
83
acceptable wet fastness these dyes can only be used for pale depths on hosiery or
warp-knit stretch garments. The preferred dyes have good migration properties
and are mainly monoazo yellows with anthraquinone reds and blues.
Anionic dyes are widely used for solid effects on nylon/polyurethane. The
factors influencing partition between these components have been outlined in
section 3.3. Shadow effects are of no interest because the pale-dyed polyurethane
is revealed only on stretching the fabric. Reserve or contrast effects are
impracticable. Acid dyes are most useful for bright full depths and moderate
depths of all hues. Levelling acid dyes are absorbed preferentially by the
polyurethane at 4060C, but migrate in favour of the nylon at higher
temperatures. Some milling acid dyes favour the polyurethane considerably and
these dyes do not migrate readily to nylon.
Metal-complex dyes generally give better wet fastness on polyurethane than
most acid dyes but 1:1 metal-complexes are unsuitable because the strongly
acidic dyeing conditions required would impair the physical properties of the
elastomeric fibre. Duller and heavier depths are usually dyed with 1:2 metalcomplex dyes, but the economy offered by chrome dyes is still preferred in some
instances. Chrome blacks give the best solidity and fastness. Poor migration is a
problem with 1:2 metal-complex dyes and these dyes are generally more sensitive
to dye-affinity variations in the nylon filament yarns, which often form the outer
surface of a nylon/polyurethane fabric. Basic complexing agents such as
ethylenediaminetetra-acetic acid or hydroxylamine derivatives are used as
protecting agents to minimise the acidic degradation of polyurethane when
dyeing nylon/polyurethane blends at low pH [14].
Acid dyes readily giving solid effects on nylon/polyurethane are mainly yellow
to red monoazo monosulphonates and violet to blue anthraquinone
monosulphonates with generally good levelling properties but only moderate wet
fastness. The wet fastness of acid dyes on nylon/polyurethane can be improved
with syntan aftertreatment. Alternatively, better wet fastness but only moderate
migration and coverage properties can be achieved using selected yellow to red
monoazo disulphonates, red to blue disazo disulphonates and blue to green
disulphonated anthraquinone dyes. The preferred 1:2 metal-complex dyes are
monoazo types with no more than one solubilising group in general. Most of the
chrome dyes suitable for this blend are monoazo structures. There are more
monosulphonates than disulphonates, but some have one or two additional
carboxyl groups, one of which usually participates in complexing with the
chromium atom.
Many of the problems encountered in one-bath dyeing methods for wool/silk
blends (section 6.2) are even more critical on nylon/silk. Experimental disperse
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reactive dyes of the sulphatoethylsulphone type (Figure 6.2) have been evaluated
by applying them to nylon and silk fabrics simultaneously [15]. Maximum
uptake occurred at pH 8 on silk and at pH 68 on nylon. Optimum solidity
between the two fibres was found at pH 6. The ratio of fixation to exhaustion
was very high. Exhaustion and fixation increased slowly with dyeing time and
temperature, even after 4 hours at 90C, and the rates of dyeing were similar on
the two fibres. Regrettably, no fastness values were recorded for these dyeings.
R
N
SO2CH2CH2OSO3H
N N
R CH3 or CH2CH2OH
R
Figure 6.2 Experimental reactive disperse dyes for nylon/silk blends
6.4 DYEING METHODS AND DYE SELECTION FOR AA BLENDS

The preferred dyeing method for all binary blends of acid-dyeable fibres is the
application (Table 6.1) of a single class of anionic dyes, usually premetallised 1:2
Table 6.1 Dye selections for AA blends
Blend
Colour
effect
Dyeing
method
Dye
selection
Wool/silk
Solid
Two-stage
Reactive dyes on silk, then milling acid

and 1:2 metal-complex dyes
on wool at 90C
Silk
reserve
Single-class
Monosulphonated milling acid dyes

at pH 56
Wool/mohair
Solid
Single-class
Levelling acid or 1:2 metal-complex dyes
Wool/angora
Solid
Single-class
Milling acid and 1:2 metal-complex dyes

with anionic retarder
Nylon/wool
Solid
Single-class
Monosulphonated 1:2 metal-complex

and acid dyes with anionic retarder
Wool/polyurethane
Solid
Single-class
Milling acid and 1:2 metal-complex dyes

with retarder
Nylon/polyurethane
Solid
Single-class
Chrome, 1:2 metal-complex or milling

acid dyes with retarder
Wool/acid-dyeable
polypropylene
Solid
Single-class
Chrome, 1:2 metal-complex or

milling acid dyes at pH 3.5
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DYEING METHODS AND DYE SELECTION FOR AA BLENDS
85
or milling acid types, with an anionic retarder to control uptake by the

component that is dyed preferentially. This component is wool in its blends with
silk or angora, but the other component in wool blends with mohair, nylon,
polyurethane or acid-dyeable polypropylene. In nylon/polyurethane blends it is
the polyurethane that is preferentially dyed in the early stage. It is possible to
reserve silk in its blends with wool or nylon but in general there is virtually no
interest in shadow, reserve or contrast effects on AA blends.
6.5 REFERENCES
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
12.
13.
14.
15.
S Roberts, Dyer, 178 (Jun 1993) 10.

J Park, Carpet Manufacturer Int., (Autumn 1987) 21.
D Schwer, H Ritter and K Zesiger, Textilveredlung, 16 (1981) 479.
T L Dawson, Rev. Prog. Coloration, 15 (1985) 29.
H S Freeman, J Sokolowska-Gajda, A Reife, Z D Claxton and V S Houk, AATCC International
Conference and Exhibition, (Oct 1993) 254.
J Sokolowska-Gajda, H S Freeman and A Reife, AATCC International Conference and
Exhibition, (Oct 1994) 388.
H L Needles and I Weatherall, Text. Chem. Colorist, 24 (Dec 1992) 7.
J H Qian and Z T Song, Proc. 7th Int. Wool Text. Res. Conf., Tokyo (1985) 249.
R Rohrer, Textilveredlung, 20 (1985) 85.
J A Galek, Dyer, 163 (22 Feb 1980) 133.
F Sakli, M van Parys, R Dubois and J Knott, Melliand Textilber., 69 (1988) 191.
M B Roberts and E Gee, SAWTRI Bull., 11 (Sep l977) 32.
M B Roberts, SAWTRI Tech. Report, 351 (1977).
D Schwer, Textilveredlung, 23 (1988) 296.
M Dohmyou, Y Shimizu and M Kimura, J.S.D.C., 106 (1990) 395.
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WOOL/ACRYLIC AND OTHER AB BLENDS
CHAPTER 7
Wool/acrylic and other AB blends
7.1 DYEING OF WOOL/ACRYLIC BLENDS

The dimensional stability, strength and abrasion resistance of wool/acrylic blends
(usually 50:50 to 20:80) are superior to those of all-wool fabrics. They are of
particular interest for garments in which thermal insulation is important, as in
woven or knitted sweaters, skirts and outerwear. Blends containing the coarser
quality wools are used in blankets and floor coverings. Acrylic fibres dyed in gel
form or as loose stock before blending with wool are stable to conventional wool
processes, such as milling, decatising and blowing. Acrylic fibres may also be
blended with mohair, angora or silk to lower costs and improve physical
performance.
Wool/acrylic blends may be carbonised to remove vegetable debris from the
wool and it is sometimes possible to carbonise after dyeing. Basic dyes showing
little or no change of hue when subjected to carbonising with sulphuric acid,
followed by prompt neutralisation, are mainly yellow, orange and red methine
dyes with selected azo reds and anthraquinone blues. Certain other basic dyes
change colour substantially on carbonising, however. Although a subsequent
treatment with ammonia at 40C will fully restore the original hue there is
invariably a loss in depth.
Worsted-spun wool/acrylic yarns are scoured at pH 5 and 60C with a
nonionic detergent. Woollen-spun yarns are scoured at 30C with soda ash and
an anionic detergent. Blend yarns containing high-bulk acrylic fibres should be
fully relaxed before dyeing by autoclave treatment in saturated steam or by
immersion in boiling water in the dyeing vessel. Blend fabrics are prepared for
dyeing by conventional techniques for all-wool materials but precautions should
be taken to allow for the thermoplastic properties of the acrylic fibres.
Relaxation to remove inherent tensions is important, particularly if the fabric is
to be subsequently steamed or pleated.
Blends in the AB category are of particular interest for reserve or colour
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DYEING OF WOOL/ACRYLIC BLENDS
87
contrast effects because the fibre components are dyeable with ionic dyes of
appropriate charge. Good solidity is also important, however, and can be
obtained without difficulty when required. Although either component can be
reserved, it is often more convenient to reserve the acrylic fibre using anionic
dyes. The range of bright colour contrasts is much wider on AB blends than on
all other types of binary blend because the fibres carry opposite charges and ionic
dyes are much more selective than disperse dyes. The opposite charges carried by
the dyes, however, can lead to incompatibility in one-bath dyeing (section 4.3).
Disperse dyes are of little interest for the acrylic component of wool/acrylic
blends because of inadequate fastness and severe staining of the wool. It is
necessary that the dyed material has adequate fastness to pleating, pressing and
ironing, particularly in the case of knitwear and jersey fabrics. Combinations of
disperse and acid dyes can only be used in pale depths. Because of the relatively
slow rate of absorption of disperse dyes by acrylic fibres, these often give rise to
considerable staining of wool (section 3.4). There is markedly less cross-staining
by basic dyes because these have much higher affinity for acrylic fibres.
Dispersion stability is much more important in package or beam dyeing, as is the
limited efficiency of clearing treatments.
Wool/acrylic blends can be readily dyed to reserve the acrylic fibre. It is less
convenient to reserve the wool because of the cross-staining by basic dyes
(section 3.5). Solidity of shade is often required in dyeing these blends for
dresswear or knitwear and is invariably specified for carpet yarns. Solidity is
readily obtained by applying combinations of anionic and basic dyes with an
anti-precipitant, either at pH 23 for 1:1 metal-complex types or at pH 67 for
milling acid dyes or 1:2 metal-complexes, with or without sulpho groups.
Cationic retarders are not required, except for pastel shades, as the anionic
dyes exert a marked retarding effect. Mildly cationic agents of the alkylamine
polyoxyethylene type form water-soluble complexes with 1:1 metal-complex
dyes under strongly acidic conditions. The alternative method of improving
compatibility by complexing the basic dyes with an anionic retarder gives better
control of the rate of dyeing of the acrylic component (section 4.3).
For pale depths the dyebath is set at 50C and pH 45 with acetic acid, salt,
an anionic retarder and an alkanol polyoxyethylene anti-precipitant. The anionic
and basic dyes are added separately and then the temperature is raised and held
at 90C to slow down the rate of uptake of the basic dyes. Finally, the wool
component is dyed to shade with the anionic dyes at the boil. Better
compatibility is found in intermediate depths by commencing at 50C and pH 6
7 with salt, nonionic anti-precipitant and neutral-dyeing anionic dyes. After
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raising slowly to 80C to promote level dyeing of the wool, acetic acid (to give
pH 45), an anionic retarder and the basic dyes are added and dyeing of the
acrylic component completed at the boil.
In those instances where adding the basic dyes at 80C gives levelling
problems, particularly when 1:1 metal-complex dyes are being used on wool
with an alkylamine polyoxyethylene complexing agent, it may be preferable to
set the initial dyebath at 60C and pH 23 (sulphuric acid) with the basic dyes
and complexing agent, and to raise the temperature to 80C before adding the
premetallised dyes. Under these conditions the rates of dyeing of the two classes
of dyes are more closely synchronised in the final stage at the boil. The
zwitterionic character of the 1:1 metal-complexes at low pH confers greater
compatibility with basic dyes than the more anionic neutral-dyeing dyes.
At one time, wool/acrylic blends were mainly dyed by two-bath methods in
medium or heavy depths to avoid cross-staining of wool or dye precipitation
problems. Two-stage processes are now usually employed with the basic dyes
applied first at the boil, followed by cooling to 60C, adding the anionic dyes
and completing the wool dyeing at the boil. Heavy depths may still be obtained
by a two-bath sequence with the basic dyes and a cationic retarder at the boil and
pH 5 in the first stage. After an intermediate scour with nonionic detergent at
8090C, or with acidified formaldehyde-sulphoxylate at 7075C if necessary
to clear the basic dye stain, the wool component may be dyed to shade at the boil
and pH 67 with 1:2 metal-complex or milling acid dyes in the presence of an
alkylamine polyoxyethylene levelling agent.
The degree of staining of conventional acrylic fibres by reactive, premetallised
or milling acid dyes is very slight and does not present a problem in the dyeing of
wool/acrylic blends. Because of this, when dyeing union fabrics where light and
dark contrasting colours are present in the design, e.g. black/yellow, it is usual to
dye the wool to the darker colour where possible [1]. On the other hand, since
wool contains amino acid residues with carboxyl-containing sidechains, as well
as C-terminal end groups that are ionised under the mildly acidic dyeing
conditions usually used for these blends, sites are available for the sorption of
basic dyes (Figure 7.1). Thus there will always be some sorption by wool and the
extent to which this occurs is of considerable practical interest. At the boil,
decomposition products of the wool are produced, particularly at pH 7 or above,
that have a reducing action on certain basic dyes, thus necessitating careful dye
selection [2].
Basic dyes of the localised-charge monoazo and anthraquinone types are
widely used, but cyanine and oxazine types are also important. The staining of
wool by basic dyes is particularly troublesome in the early stage of dyeing at
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DYEING OF WOOL/ACRYLIC BLENDS
NH
CH CH2COO
CO
Aspartic acid residue
89
R
CONH
CH
COO
C-terminal residue
Figure 7.1 Sites in wool for sorption of basic dyes
temperatures below 80C. As the boil is approached, transfer of basic dyes from
wool to the acrylic component proceeds, so that the wool exerts an effective
retarding influence on the acrylic dyeing process (section 3.5). This migration
and hence the final distribution of the basic dyes depends on many factors,
including the presence of surfactants (anti-precipitants and levelling agents),
electrolyte, time, temperature and pH. Thus the degree of wool staining is
determined by dyebath conditions and is minimised by dyeing for at least one
hour at the boil and pH 5. Nonionic auxiliaries promote transfer to the acrylic
fibre but cationic products tend to increase staining of the wool.
Certain basic dyes of small molecular size exhibit exceptionally good
migration properties and are reasonably compatible with anionic dyes, allowing
minimal use of nonionic anti-precipitant [3]. These dyes have proved especially
suitable for dyeing wool/acrylic blends. IWS fastness requirements must be met
for machine-washable performance of shrink-resist garments made from these
blends [4]. Dye selection for both components is important. Basic dyes should be
used on the acrylic fibre and reactive, premetallised or chrome dyes for the wool.
Mordant dyes are usually chosen for black and navy blue on economic grounds,
a pH of 3.5 being used for chroming.
The use of basic dyes and -bromoacrylamide or vinylsulphone reactive dyes
is a popular one-bath method, as a wide range of bright hues can be obtained
with optimum fastness [4,5] and simultaneous yarn bulking and dyeing is
possible. Pale dyeings can be produced with mixtures of reactive or selected 1:1
metal-complex dyes and basic dyes at pH 45 together with special levelling
agents that also function as precipitation inhibitors. In medium and full depths,
ammonia treatment after dyeing is recommended to complete the fixation of
reactive dyes on the wool and give dyeings of good fastness to perspiration [6].
Problems of interaction with basic dyes are encountered in the one-bath
dyeing of these blends in the following order of increasing difficulty: chrome <
reactive < 1:1 metal-complex < levelling acid < milling acid < sulphonated 1:2
metal-complex < unsulphonated 1:2 metal-complex. Hence chrome and reactive
dyes give the best compatibility with basic dyes and can be used for wool in the
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90
isoelectric region at pH 45. The high degree of exhaustion of chrome dyes leads
to virtually complete avoidance of precipitation. With chrome dyes the oxidative
chromium compounds present in the aftertreatment bath help to counteract any
tendency for the basic dyes to be decomposed by any reductive products formed
in wool at the boil.
7.2 DYEING OF NYLON/ACRYLIC BLENDS
Nylon/acrylic blends are used mainly for half-hose, knitted sweaters, sportswear
and swimwear, blankets, furnishing fabrics and floor coverings. These have a
wool-like handle and appearance, but better tensile strength, abrasion resistance
and durability. Nylon contributes more to the strength, extensibility, wrinkle
recovery and resistance to wear, whilst the acrylic fibre confers softness, bulk and
warmth. Blends of acrylic fibres with nylon are more durable but less bulky than
wool/acrylic blends.
Nylon/acrylic blends (typically 20:80) have been popular in carpets for many
years, particularly for Axminster designs [7]. The physical characteristics of
Dralon U325(BAY) acrylic fibre in blended carpet yarns have been described.
This modified fibre has high substantivity for basic dyes and virtually complete
exhaustion of the dyebath can be achieved in a short time at 8085C [8]. It is
suitable not only for yarn dyeing but also for piece dyeing on a carpet winch or
jet machine. Blends containing 2030% nylon for carpets can be dyed on
winches or atmospheric jets with basic and acid dyes in the presence of a cationic
retarder, a migration assistant and a nonionic anti-precipitant.
Thus velour carpets tufted from 30:70 nylon/Dralon yarn can be dyed by first
applying acid dyes to the nylon as the temperature is raised to 70C, then adding
the basic dyes and heating to 8085C to dye the Dralon U325 component.
Although these carpets have good resistance to pile deformation during dyeing,
slow indirect cooling to 60C is recommended at the end of the dyeing cycle [8].
Nylon/acrylic apparel fabrics are normally scoured with dilute ammonia and
an alkylphenol polyoxyethylene detergent at 5060C and then dyed by a onebath method. Thus selected levelling acid dyes may be complexed with a weakly
cationic alkylamine polyoxyethylene and added to a bath containing Glaubers
salt and acetic acid at pH 45 and 40C before the basic dyes. After the acid dyes
have become absorbed by the nylon at 8085C, the dyebath is heated to the boil
and the acrylic component dyed to shade with the basic dyes. Any cross-staining
of nylon by the basic dyes may be cleared using acidified formaldehydesulphoxylate at pH 45 and 70C.
An alternative one-bath method is based on a similar temperature/time cycle
but the initial dyebath is set at pH 23 (sulphuric acid) with the basic dyes, an
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DYEING OF NYLON/ACRYLIC BLENDS
91
alkanol polyoxyethylene sulphate complexing agent and an alkanol polyoxyethylene anti-precipitant. When the temperature reaches 80C, selected mono- or
disulphonated monoazo 1:1 chromium-complexes are added and heating
continued slowly to the boil.
Full depths are usually dyed by a more prolonged two-stage process. The
acrylic fibre is first dyed with the basic dyes at the boil and pH 45. The dyebath
is then cooled slowly to 70C and adjusted to pH 23 with sulphuric acid. The
1:1 metal-complex dyes and an alkylamine polyoxyethylene complexing agent
are added and the nylon component dyed to shade at the boil.
The opposite sequence is preferred for full depths dyed with 1:2 metalcomplex dyes. The nylon is dyed first at the boil with the selected premetallised
dyes in dilute ammonia and the alkanol polyoxyethylene sulphate complexing
system. After cooling the dyebath slowly to 80C, the acrylic fibre is dyed
conventionally with basic dyes at the boil and pH 45. If a two-bath method is
preferred for optimum fastness and freedom from any risk of co-precipitation,
the basic dyes are applied first at the boil and pH 45. After an intermediate
rinse, a fresh dyebath is set at pH 67 and the nylon is dyed at 8085C with
neutral-dyeing 1:2 metal-complex or milling acid dyes.
Polyurethane/acrylic blends for sweaters and leisurewear are usually made
from core-spun yarns and complete solidity is not essential. Basic dye stains show
low fastness on the polyurethane component, however, so that it is often
necessary to use a two-bath method. Selected basic dyes are applied to the acrylic
fibre at the boil from a near-neutral bath and an intermediate clear is given using
sodium dithionite, soda ash and a nonionic detergent. The polyurethane is then
filled in with selected neutral-dyeing 1:2 metal-complex or milling acid dyes.
Some chrome dyes are also suitable on the polyurethane if heavy, dull dyeings are
required.
7.3 BLENDS OF ACID-DYEABLE AND BASIC-DYEABLE ACRYLIC
VARIANTS
Conventional acrylic fibres made from acrylonitrile and up to 15% of an inert
comonomer (section 5.1) are readily dyeable with basic dyes at the boil. Aciddyeable acrylic variants contain basic comonomer units that provide sites for
sorption of anionic dyes. Blends of acid-dyeable and basic-dyeable acrylic fibres
are used in typical wool outlets, such as jersey dresswear, sweaters, hand-knitting
yarns, blankets and pile fabrics.
Basic-dyeable and acid-dyeable acrylic fibres both absorb basic dyes under
neutral conditions, but the uptake of basic dyes by the acid-dyeable variant
decreases markedly as the pH falls from 7 to 2. The exhaustion of these dyes on
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basic-dyeable acrylic fibres is almost independent of pH over this range. Basic

and acid dyes, therefore, can be applied selectively to the two types of fibre at pH
2 because most basic dyes are stable and reserve the acid-dyeable variant
reasonably well under these conditions. Chlorite bleaching of blends containing
acid-dyeable acrylic fibres results in increased uptake of basic dyes. It is usual to
prescour with an alkanol polyoxyethylene at 6070C before dyeing.
Blends of acid-dyeable and basic-dyeable acrylic fibres offer interesting
possibilities for solid, reserve or colour contrast effects. The basic-dyeable
variants can only be dyed with disperse or basic dyes, whereas acid-dyeable types
can be dyed with either of these classes as well as direct, levelling acid,
premetallised and chrome dyes. The inherent wet fastness of anionic dyes on
acid-dyeable acrylic fibres is far superior to that of the same dyes on wool or
nylon, or of direct dyes on cellulosic fibres [9].
The 1:2 metal-complex dyes are not used extensively but selected monoazo
1:1 metal-complex types (Mr 450550) are widely used for deep shades of good
fastness to light and wet treatments. These and the levelling acid dyes for brighter
shades are applied with sulphuric acid at pH 23 to obtain full yield, penetration
and fastness. Chrome dyes of the monoazo monosulphonate type (Mr 350450)
can also be used for dark shades of good fastness to light, washing and pleating.
Chrome dyes sensitive to low pH should be avoided, as a strongly acidic dyebath
is essential for optimum yield.
Disperse dyes with good dyeing properties and adequate pleating fastness on
acid-dyeable acrylic fibres are the intermediate-energy nitro, monoazo and
anthraquinone types (Mr 300400). Basic dyes exhibit similar fastness properties
on both types of acrylic fibre but give higher yields and dye more rapidly on the
basic-dyeable fibre, requiring a cationic retarder to control the rate of
absorption. Shadow effects are achieved at neutral pH but at pH 2 all of the
basic dyes are absorbed by the basic-dyeable variant, leaving the acid-dyeable
fibre reserved. Basic dyes stable to strongly acidic conditions and giving effective
reservation of the acid-dyeable variant are almost all delocalised-charge types,
including yellow, orange and red methines or monoazothiazole derivatives and
oxazine blues.
Since basic-dyeable acrylic fibres have no affinity for acid dyes it is possible to
reserve them in blends with acid-dyeable variants. The wet fastness of acid dyes
on these fibres is superior to that on wool but light fastness is sometimes inferior.
Levelling acid dyes that offer optimum light fastness and good reservation of the
basic-dyeable component are mainly mono- or disulphonated monoazo or
anthraquinone derivatives.
The recommended method of application is at the boil and pH 23 with
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BLENDS OF ACID-DYEABLE AND BASIC-DYEABLE ACRYLIC VARIANTS
93
sulphuric acid and Glaubers salt to obtain adequate penetration and fastness of
these dyes. Careful control of temperature rise is necessary because the rate of
strike is rapid and the migration properties on these fibres are relatively poor. An
alkylamine polyoxyethylene levelling agent helps to decrease the initial rate of
dyeing. The dyebath is cooled back to 80C before shading additions are made.
Reserve of the acid-dyeable component is obtained with basic dyes and a
suitable anionic retarder at pH 2. Dyes of the methine, cyanine, monoazo,
oxazine and anthraquinone types are usually satisfactory. Colour contrasts can
be produced on these blends with suitable combinations of basic and levelling
acid dyes by a one-bath method, although the most economical effects are those
with a deep shade on the acid-dyeable type and a paler depth on the basicdyeable component.
Complexing between the basic dyes and a combination of anionic and
nonionic anti-precipitants, or between the acid dyes and a weakly cationic
alkylamine polyoxyethylene (section 4.3), must be adopted in order to minimise
the risk of co-precipitation and each of these measures exerts a retarding
influence on the corresponding class of dyes. Specific retarding agents for the
basic dyes should be avoided if possible when dyeing solid or contrast effects on
this type of blend. Cationic retarders are preferentially absorbed by the basicdyeable fibre and this may impair the development of crimp in high-bulk yarns.
Absorption of an anionic retarder by the acid-dyeable variant may cause
restraining of the acid dyes in heavier depths.
The levelling acid dyes are applied at 80C and pH 2 with Glaubers salt and
an alkanol polyoxyethylene anti-precipitant. The basic dyes are then added and
both components dyed to shade at the boil. Scouring at 70C with an alkanol
polyoxyethylene detergent clears any stain of basic dyes from the acid-dyeable
variant. Full depths are dyed by a two-stage method. The acid-dyeable
component is first dyed at the boil and pH 23 with the levelling acid dyes and
salt. After cooling to 6070C, the basic dyes, nonionic anti-precipitant and
more salt are added and the basic-dyeable fibre is dyed to shade at the boil.
7.4 BLENDS OF MODACRYLIC AND ACRYLIC FIBRES

Modacrylic fibres, e.g. Dynel (Union Carbide), that contain less than 85%
acrylonitrile with other inert or basic comonomers, form blends with acrylic
fibres that are mainly used in traditional wool outlets. Blends of Dynel with an
acrylic fibre in pile fabrics and floor coverings are less flammable than the acrylic
fibre alone. There is a legal requirement to have at least 15% modacrylic fibre in
an acrylic carpet. A blend of 50:50 modacrylic/acrylic fibres may be dyed by a
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one-bath method at the boil with disperse dyes for the modacrylic component
and basic dyes for the acrylic fibre. A dependent range of colour contrasts with
light fastness 5 can be obtained in this way, although the fastness ratings of the
basic dyes on acrylic are approximately 1 to 1.5 units higher than the disperse
dyes on the modacrylic fibre.
Dynel is delustred during dyeing at temperatures above 80C but the lustre
can be restored by subsequent treatment at a higher temperature, i.e. by drying at
120130C or by hydrosetting. For example, after dyeing at 80C the lustre is
restored at 105C. After dyeing at the boil a treatment at 120C is required, and
if dyed under pressure at 105C the lustre returns at 130C. Increased quantities
of salt in the dyebath may also be used to maintain lustre in circumstances where
the adoption of higher temperatures in drying or hydrosetting is not acceptable.
Blends of modacrylic fibres with conventional acrylic fibres may be dyed in
solid or shadow effects with basic dyes applied to both components by a twostage method. The acrylic component is dyed preferentially by temperature
control in the absence of a retarder, raising slowly to the boil to avoid
unlevelness. When the target depth has been reached on the acrylic fibre, the
dyebath is cooled to 80C, a butyl benzoate carrier is added and the modacrylic
fibre dyed to shade at the lower temperature. Blends of modacrylic fibres with
acid-dyeable acrylic variants provide more scope for reserve and contrast effects.
Selected disperse dyes will give satisfactory solidity in pale or medium depths but
fastness ratings are barely adequate. Reserve effects or bright colour contrasts in
moderate or full depths are obtained by methods similar to those already
outlined for acid-dyeable/basic-dyeable acrylic blends (section 7.3).
7.5 BLENDS OF AMIDE FIBRES WITH MODACRYLIC OR ACIDDYEABLE ACRYLIC VARIANTS
Further AB blends of minor importance are those containing an amide fibre
(wool, silk, mohair or nylon) with a modacrylic or acid-dyeable acrylic variant.
Dynel (Union Carbide) is a modacrylic fibre made from acrylonitrile and vinyl
chloride. The controlled shrinkage properties of the fibre can be turned to
practical use in the manufacture of bulked fabrics and of backing yarns in knitted
pile fabrics. Dynel has been blended with amide fibres and used in pile fabrics
intended for apparel or furnishings.
Blends containing 75:25 Dynel/mohair are scoured and dyed at 80C, care
being taken to avoid fabric distortion. Basic dyes are used on the modacrylic
fibre and then milling acid dyes on the mohair. Butyl benzoate is recommended
to give adequate colour yields on Dynel at 80C. Pale and many medium depths
can be achieved by a two-stage sequence but for deep shades it is advisable to
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BLENDS OF AMIDE FIBRES WITH ACRYLIC VARIANTS
95
operate a two-bath method with an intermediate clear of the basic dyes from the
mohair. The basic dyes must be selected for minimum staining of mohair.
Clearing is carried out at 60C with a mildly acidic solution of zinc
formaldehyde-sulphoxylate (Figure 7.2).
HO Zn2+
O S O CH2OH
Figure 7.2 Zinc formaldehyde-sulphoxylate
Possible dyed effects on Dynel/wool include solidity of shade, shadow or

contrast effects, normally obtained by one-bath methods. Selected basic dyes are
applied to the modacrylic fibre and 1:2 metal-complex or milling acid dyes to the
wool. A butyl benzoate carrier for Dynel, a levelling agent and an antiprecipitant are also required. The fabric is first treated with these agents at 40C
and the dissolved anionic dyes added. The temperature is raised to 70C, the pH
lowered to 45 (acetic acid) and the basic dyes added gradually before raising the
temperature slowly to the boil.
Verel (Eastman) is a modacrylic fibre of high flame resistance and a soft
handle. It has been blended with wool for use in pile fabrics and floor coverings,
in 30:70 blends with wool in knitwear and in 50:50 blends for half-hose. The
dyes used include disperse, basic and 1:2 metal-complex dyes. The premetallised
dyes give satisfactory fastness to light and washing for apparel or furnishing
fabrics. Verel is preferably dyed at 8090C, or at 7080C in the presence of an
organophosphate carrier. If it is dyed at or near the boil, however, loss of lustre
and deformation of the fibre take place, resulting in fabric creasing. Verel and
wool can be dyed simultaneously with selected 1:2 metal-complex dyes. Wool
can also be dyed and Verel reserved using 1:1 metal-complex types applied at a
low pH.
Fabrics containing 50:50 Dynel/nylon may be dyed in colour contrasts or with
reservation of the modacrylic component. Those acid dyes for nylon with least
affinity for Dynel, mainly disulphonated premetallised or milling acid dyes of Mr
700800, are preferred, a levelling agent being recommended with the 1:2 metalcomplex types. Suitable basic dyes for Dynel showing good reserve of nylon are
delocalised-charge structures of the azomethine, azothiazole and azotriazole
classes.
The nylon component of blends with acid-dyeable acrylic fibres may be dyed
with selected acid dyes that show good neutral-dyeing affinity to reserve the
acrylic variant. Nylon can be almost completely reserved by applying basic dyes
in the presence of 3% urea after dissolving with the aid of methanol or a
nonionic surfactant. The dyebath pH changes from slightly acidic to slightly
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alkaline during dyeing. Solid or contrast effects are achieved by a one-bath

method with selected milling acid and basic dyes in the presence of a nonionic
anti-precipitant.
In general, acid-dyeable acrylic fibres will readily absorb the dyes usually
applied to wool but the basic groups in the acrylic variant are less strongly basic
than those in wool and adequate dyebath exhaustion requires appreciably higher
concentrations of acid. Under normal wool-dyeing conditions a heavier depth is
attained on the wool, giving a shadow effect. Solidity of shade can be achieved,
however, by adding a nonionic agent that controls the rate of dyeing of the wool
as well as promoting levelness. The most critical factor is the acid concentration
needed to achieve solidity in the presence of the retarder. Suitable dyes include
selected milling acid or chrome dyes, as well as certain premetallised types.
Wool may be dyed and the acid-dyeable acrylic reserved by applying milling
acid or 1:2 metal-complex dyes with good neutral-dyeing affinity in the presence
of a weakly cationic levelling agent. The best reserve effect is obtained at
9095C. Basic dyes can be applied to the acrylic component at low pH if a
limited range of colour contrasts is desired.
7.6 BLENDS OF BASIC-DYEABLE POLYESTER WITH WOOL OR NYLON

Although more costly than normal polyester, the basic-dyeable variant (section
5.1) can be used in blends with nylon or wool to achieve a wider and more
attractive gamut of coloured effects, since the problems of cross-staining of wool
or nylon by disperse dyes are absent. One-bath methods using basic and acid
dyes are available for bright colour contrasts or reserve styles. Solid or shadow
effects can also be obtained without difficulty, but are less often required.
Disperse dyes show lower light fastness on the basic-dyeable variant than on
SO3H
COO CH2CH2
OOC
COO CH2CH2
OOC
SO3H
COO CH2CH2
OH +
HOOC
+ HO
CH2CH2
OOC
COOH
Scheme 7.1
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BLENDS OF BASIC-DYEABLE POLYESTER WITH WOOL OR NYLON
97
normal polyester and basic dyes on basic-dyeable polyester are significantly less
fast to light than on acrylic fibres.
A blend of basic-dyeable polyester and nylon can be dyed with excellent
contrast by the following one-bath method. After scouring at 6070C with
soda ash and a nonionic detergent, the dyebath is prepared at 50C and pH 5
with an alkanol sulphate as a retarder for the basic dyes, an alkanol
polyoxyethylene anti-precipitant, Glaubers salt to inhibit hydrolysis of the basicdyeable variant (Scheme 7.1), and finally the acid dyes and the basic dyes
separately. The temperature is raised slowly from 80C to the boil and the two
components dyed simultaneously. Similar methods have been devised for blends
of basic-dyeable polyester with wool [10]. A reserve effect on either fibre can be
obtained using the above procedure by simply omitting the appropriate class of
dyes from the recipe. When using basic dyes only, the reserve of the wool or
nylon can be improved by a final treatment with sodium dithionite, ammonia
and a nonionic detergent at 50C.
Table 7.1 Dye selections for AB blends
Blend
Colour effect
Dyeing method
Dye selection
Wool/acrylic
Acrylic
reserve
Single-class
Reactive, metal-complex or milling

acid dyes
Solid or
contrast
One-bath
(pale depths)
Premetallised or milling acid dyes

and basic dyes with anti-precipitant
Two-stage
(full depths)
Basic dyes with retarder, then 1:2

metal-complex or milling acid dyes
One-bath
(machinewashable)
Reactive dyes and migrating basic

dyes with levelling/stabilising
agents
One-bath
(pale depths)
Levelling acid or 1:1 metal-complex

dyes and basic dyes with
anti-precipitant
Two-stage
(full depths)
Basic dyes at pH 45, then premetallised dyes at appropriate pH
Nylon/acrylic
Solid or
contrast
Polyurethane/
acrylic
Solid
Two-bath
Basic dyes, reduction clear, then 1:2

Wool/modacrylic
Solid or
contrast
One-bath

and basic dyes with carrier and
anti-precipitant
Mohair/
modacrylic
Solid or
contrast
Two-stage
Basic dyes with carrier, then milling

acid dyes at pH 67
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98
Table 7.1 Continued

Blend
Colour effect
Dyeing method
Dye selection
Nylon/modacrylic
Modacrylic
reserve
Single-class
Disulphonated 1:2 metal-complex

or milling acid dyes
Contrast
One-bath

and basic dyes with anti-precipitant
Acid-dyeable
reserve
Single-class
Delocalised-charge basic dyes with

anionic retarder at pH 2
Basic-dyeable
reserve
Single-class
Monoazo 1:1 metal-complex or

levelling acid dyes at pH 23
Solid or
contrast
One-bath
(pale depths)
Levelling acid dyes and basic dyes

with anti-precipitant at pH 23
Two-stage
(full depths)
Levelling acid dyes, then

basic dyes
Solid
Single-class
Basic dyes at the boil, then at 80C

with carrier
Solid or
contrast
One-bath
Disperse dyes and basic dyes
Acrylic
reserve
Single-class

at 90C
Solid or
shadow
Single-class
Selected chrome, metal-complex or

milling dyes
Limited
contrast
Two-stage
Basic dyes at low pH, then

premetallised or milling acid dyes
at pH 7
Acrylic
reserve
Single-class

at pH 67
Nylon
reserve
Single-class
Basic dyes with urea
Solid or
contrast
One-bath
Milling acid dyes and basic dyes with

anti-precipitant
Nylon
reserve
Single-class
Basic dyes with cationic retarder
Polyester
reserve
Single-class

at pH 67
Contrast
One-bath
Acid dyes and basic dyes with

anti-precipitant
Acid-dyeable/
basic dyeable
acrylic
Modacrylic/acrylic
Wool/acid-dyeable
acrylic
Nylon/acid-dyeable
acrylic
Wool or nylon/
basic-dyeable
polyester
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DYEING METHODS AND DYE SELECTION FOR AB BLENDS
99
7.7 DYEING METHODS AND DYE SELECTION FOR AB BLENDS

This range of versatile blends offers valuable opportunities for bright colour
contrast, shadow or reserve effects with relative freedom from cross-staining
problems. One-bath methods, normally using basic dyes and acid dyes with a
nonionic anti-precipitant, are available in most cases to give solid or contrast
effects, although two-stage procedures may be preferred for full depths on the
various blends with acrylic variants, the latter component being dyed first (Table
7.1). Excellent white reserve effects are attainable on all the synthetic fibre
components in these blends. Reactive dyes are recommended to meet machinewashable standards on wool/acrylic blends.
7.8 REFERENCES
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
D R Lemin. J.S.D.C., 91 (1975) 168.

W Haertl, Textil Praxis, 44 (1989) 285; Melliand Textilber., 70 (1989) 354; Textilveredlung, 24
(1989) 214.
R Parham, Am. Dyestuff Rep., 71 (Sep 1982) 42.
H Flensberg and A Laepple, Textilveredlung, 26 (1991) 342.
R Hls, Textilveredlung, 10 (1975) 399.
W G Prinzel, Textilveredlung, 18 (1983) 230.
R Block and J Honsel, Chemiefasern und Textilind., 34/86 (1984) 345.
K Nagawa, Japan Textile News, No. 251 (Oct 1975) 74.
J Park and S Davis, J.S.D.C., 89 (1973) 37.
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100
WOOL/CELLULOSIC AND OTHER AC BLENDS
CHAPTER 8
Wool/cellulosic and other AC blends
8.1 DYEING OF WOOL/CELLULOSIC BLENDS

The wool/cotton blend is superior in durability to all-wool fabrics but there is a
loss in other desirable characteristics, such as handle, drape, pleat retention and
crease recovery. There is a resurgence of interest in blending these two natural
fibres throughout the developed world, where such blends in garments
traditionally made from cotton are seen as conferring desirability and exclusivity
in high-quality dresswear and shirting fabrics [1]. Developments in shrink-resist
treatment of the wool component have greatly improved the washability of such
materials, which offer value, comfort, versatility and styling.
Typical examples of traditional union fabrics with a cotton warp and a
woollen weft include blazer cloths, gabardine rainwear, shirtings and pyjamas.
The traditional linsey-woolsey fabric, closely woven for household or apparel
uses, was made from a linen warp to give strength and a wool weft to provide the
aesthetic qualities of the construction. Blended worsted yarns containing
approximately equal proportions of wool and cotton have been long-established
in knitwear, dresswear, underwear, childrens clothing, lightweight shirtings,
pyjama cloths and blankets. For washable wear such blends have been stabilised
by a gaseous chlorination treatment. The original Viyella shirt fabric was a wool/
cotton blend.
The 20:80 wool/cotton yarn is the best for achieving washable apparel
without the use of chlorinated wool. Draw blending and intimate blending yield
different fabric properties but both give satisfactory dyeing and finishing
performance in woven or knitted constructions. Finishing techniques and
formulations have been optimised to provide fully washable performance with
easy-care and low shrinkage properties [2].
Attractive pile fabrics are made with a cotton backing cloth and a worstedspun pile yarn of either mohair or wool. Mohair gives higher lustre and better
crush resistance than wool. Fabrics of this kind have been used to cover toys and
as outerwear. Grey cotton is often chosen as a backing cloth unless a white is
100
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DYEING OF WOOL/CELLULOSIC BLENDS
101
specified, when the fabric is peroxide bleached to minimise any risk of damage to
the pile. After scouring on the winch, mohair pile fabrics are dyed in open width.
Higher tensile strength and lower shrinkage on washing are positive attributes
contributed by viscose to blends with wool. Traditional outlets for wool/viscose
blends include lightweight suiting, outerwear, dresswear, knitwear, blankets and
floor coverings. These are usually made from intimate blends of the two fibres
but outerwear, dresswear and knitwear may include two-fold or fancy yarns for
novelty effects. There has never been more than limited interest in blends of silk
with viscose, usually encountered in dresswear if at all. Economy-priced blazer
cloths have been made with a viscose warp and a wool/viscose blended weft. Pile
fabrics for low-cost apparel are sometimes made with a wool pile and a viscose
backing cloth.
Ramie has distinctive features that do not appear to be fully recognised. The
tensile strength is high and an outstanding feature is the high wet strength [3].
Attractive lustre and good abrasion resistance make the fibre applicable in
numerous outlets. Blends of 70:30 wool/ramie have been used for dress fabrics.
The satisfactory dimensional stability of these blends makes them suitable as
shirtings, although the texture is somewhat heavy and firm. Such blends may
give rise to prickle-itch problems, however, when worn next to the skin. Ramie
has dyeing properties similar to those of cotton and these blends are normally
piece dyed by a one-bath method using direct and milling acid dyes.
Traditionally, solid shades on blended wool/cotton apparel fabrics and wool/
viscose woven carpeting were dyed with prepared mixtures of direct and acid
dyes called union dyes, selected to give matching colours on the two fibres with
good fastness to light. Some dyers preferred to formulate their own recipes,
however, containing direct dyes selected to dye both components together with
acid dyes to adjust the shade on the wool. Self-levelling or temperaturecontrollable direct dyes with a low degree of sulphonation are substantive to
both substrates, whereas multisulphonated salt-controllable types often tend to
reserve the wool [4]. Dyeing under slightly acidic conditions with ammonium
sulphate at 90C gives optimum partition of the direct dyes. The wet fastness
achieved in this way is largely determined by that of the direct dyes on the
cellulosic component but some improvement is possible by aftertreatment with a
cationic dye-fixing agent [5].
Mohair/cotton pile fabrics are dyed in open width with direct and milling acid
dyes from the same bath, or by a two-stage process involving application of
levelling acid dyes to the mohair pile from a sulphuric acid bath, followed by
dyeing of the cotton backing with suitable direct dyes. The latter method ensures
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102
a superior handle and appearance of the pile but some acidic hydrolysis of the
cotton may occur in the first stage.
Blends containing chlorinated or stripped wool, or wool damaged in wet
processing, are likely to offer difficulty in union dyeing. Blends of chlorinated or
damaged wool with cotton are more difficult to dye level than those containing
virgin wool because of more rapid absorption of direct dyes by the wool. It is
necessary to add an anionic retarding agent to slow down this absorption. Wet
fastness on chlorinated or damaged wool is also inferior to that on the intact
substrate. Pale or medium depths in bright shades on cotton and chlorinated
wool can be achieved with high-reactivity dyes applied at low temperatures,
however, together with an anionic retarder.
Solidity of shade is normally required on intimate blends of wool and viscose
for dresswear, knitting yarns and carpets, but in knitwear and dresswear the two
fibre types are sometimes dyed in contrasting colours. One-bath dyeing with
combinations of direct and acid dyes is generally used, although appropriate
reactive dyes can be applied to either fibre type and direct or acid dyes used to fill
in the other component. Optimum fastness is given by reactive dyes on the
viscose component, followed by milling acid or 1:2 metal-complex dyes on the
wool. Vat, sulphur and azoic dyes are not considered for these blends because of
the strongly alkaline dyeing conditions necessary, which would damage both
fibre types.
Direct dyes should be selected with good build-up on viscose to minimise
cross-staining of the wool. The preferred dyes are mostly disazo tetrasulphonates, particularly those of the symmetrical diarylurea type. Preferred dyes
for the wool are disulphonated milling acid dyes of Mr 500800 and
unsulphonated 1:2 metal-complex monoazo types of Mr 850950. Levelling acid
or 1:1 metal-complex dyes should be avoided because the sulphuric acid required
for adequate exhaustion would damage the cellulosic fibre.
The absorption of direct dyes by wool can be reduced using anionic retarding
agents of the syntan type. Dyeing for long periods at the boil or under acidic
conditions will result in increased absorption of direct dyes by the wool
component. Chemically damaged wool also absorbs direct dyes more quickly.
Alkaline conditions favour the absorption of acid dyes by viscose and also tend
to damage the wool fibre. The products of wool hydrolysis may cause reductive
attack of certain sensitive azo direct and acid dyes in the dyebath. All these
undesirable complications can be minimised using ammonium sulphate to
maintain an acidic pH.
Advantages of dyeing wool/cellulosic blends under mildly acidic conditions
include those listed on the following page.
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103
(1) The method is applicable to a wide range of blend proportions.

(2) Better penetration of yarn or fabric is achieved by the freedom to dye at the
boil without fibre damage.
(3) Higher exhaustion of the dyebath results in better shade reproducibility.
(4) Independent shading of the two fibres is facilitated.
(5) Contrast effects can be produced by selective dyeing of the two fibres
simultaneously with direct and acid dyes.
(6) Mildly acidic dyebaths permit selective dyeing of the wool fibre and reserve
of the cellulosic component without significant hydrolytic damage of the
cellulose.
(7) Dyeing wool under acidic conditions results in improved handle and less
risk of damage. Pile fabrics dyed in this way are more resilient and lustrous.
(8) Satisfactory results may be obtained on blends of carbonised wool with
cellulosic fibres that are difficult to dye under neutral conditions.
(9) Sensitive azo direct or acid dyes are less likely to be chemically attacked.
(10) Rubbing fastness is improved compared with dyeing under neutral
conditions.
A two-stage process for the exhaust dyeing of wool/viscose blends with direct
and acid dyes has been examined by a factorial design method. The influence of
seven independent parameters (dyeing time, concentrations of auxiliaries, pH
and temperature of the two stages) on colour yield and fastness was evaluated.
The optimum conditions were found to be acid dyeing for one hour at pH 4.5
and 100C with urea but no reserving agent (to inhibit direct dye staining of
wool), followed by direct dyeing at pH 7 and 95C. Significant improvements in
fastness to perspiration and wet rubbing were achieved [6].
Exhaust dyeing techniques are well established using two classes of fibrespecific reactive dyes on wool/cotton blends. Padbatch is also a viable option,
though not yet fully adopted in the production environment [7]. Bifunctional
aminochlorotriazine-sulphatoethylsulphone dyes (Figure 8.1) exhibit a high
degree of fixation on wool under acidic conditions and are particularly suitable
for wool/cellulosic blends. Two-stage and two-bath dyeing methods have been
devised [8] to give high colour yields with good levelling and excellent fastness on
garments, hosiery, knitgoods, yarn and loose stock. The relationships between
exhaustion, fixation and dyebath pH have been illustrated and fastness ratings
on wool recorded [9].
Using a special selection of difluoropyrimidine reactive dyes (Figure 8.2),
wool/cellulosic blends can be dyed with good solidity by a two-stage procedure.
The cellulosic component is dyed first at low temperature and high pH, followed
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104
Cl
N
SO3Na
H O
N
N
HN
N
N
NH
SO2CH2CH2OSO3Na
SO3Na
NaO3S
Figure 8.1 Typical bifunctional cellulose-reactive dye
H3CO
SO3Na
H O
N
N
NaO3S
NH
F
N
Cl
F
Figure 8.2 Typical difluoropyrimidine cellulose-reactive dye
by adjustment to an acidic pH and an increase in temperature to dye the wool.

The pH changes are controlled by a programmable multiproduct injection device
capable of providing continuous monitoring of pH [10]. The main advantages of
this method are a considerable reduction in dyeing time and improved wool
quality on blended goods where high wet fastness is demanded.
Vinylsulphone dyes of the cellulose-reactive type (Figure 8.3) can be applied to
wool/cotton blend fabrics by the one-bath padbatch method using sodium
silicate and caustic soda. The wool should be prechlorinated to give improved
substantivity for these vinylsulphone dyes. After padding at ambient temperature
and batching overnight, the alkali is washed out by cold rinsing and the dyeing is
soaped and rinsed under neutral or mildly acidic conditions. Advantages of this
technique include low energy consumption, effective penetration of thick fabrics,
maintenance of wool quality, high wet fastness, good reproducibility and
satisfactory yield compared with exhaust dyeing methods [11].
When dyeing wool/cellulosic blends with reactive dyes in one-bath methods,
blue dyes derived from bromamine acid (1-amino-2-bromoanthraquinone-4sulphonic acid) can not be selected in most instances because they tend to react
preferentially with wool. Nevertheless, azo reactive blues can be absorbed and
fixed about equally on both components if applied under appropriate conditions.
The lower uptake by cellulose of bromamine acid derivatives is probably
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105
OCH3
H O
N
N
O2S
SO3Na
CH2CH2OSO3Na
Figure 8.3 Typical vinylsulphone cellulose-reactive dye
NH2
SO3Na
HN
SO3Na
Cl
N
N
HN
N
NH
SO3Na
Figure 8.4 CI Reactive Blue 2
attributable to their non-planarity. It has been shown that the triazine ring of CI
Reactive Blue 2 (Figure 8.4), and of other dyes containing the triazinylaminoanilinoanthraquinone grouping, is twisted by almost 90 degrees from the plane
of the anthraquinone nucleus. All three NH links in such structures cause
twisting of the adjacent ring system on both sides [12].
A serious drawback of most reactive dyeing techniques for wool/cellulosic
blends is the adverse effect of alkaline fixation treatment on the quality of the
dyed wool fibres. The influence of various concentrations of sodium carbonate
on degradation of the wool fibres in a wool/cotton blend was estimated in terms
of urea-bisulphite solubility. It was demonstrated that an acceptable two-stage
exhaust method entails dyeing the wool first from a mildly acidic dyebath and
then dyeing the cotton with salt and alkali at a pH of no more than 10, and a
temperature of not more than 50C for a dyeing time of not more than 1 hour
[13].
In a later study of this problem, samples of merino slubbing were treated (a)
under exhaust dyeing conditions with 212 g l1 sodium carbonate and salt at
40C, or (b) as recommended for padbatch dyeing in carbonate/hydroxide
mixtures at pH 1013 and ambient temperature. The wool samples were
analysed in detail to assess the degree of damage [14]. Batching treatments for
various times (2050 hours) at ambient temperature in the pH range 10.512.5
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were carried out on a wool/cotton fabric. Amino acid analysis after enzymatic
hydrolysis of the wool component revealed the detailed effects of the alkaline
degradation. Only in the case of cystine was decomposition extensive. A
minority of the aspartic and glutamic acid residues showed deamination
reactions and certain other amino acid units had undergone racemisation [15].
Dyeing of the wool portion in a wool/cotton blend presents few difficulties
and high wet fastness on machine-washable goods can be attained using woolreactive dyes, chrome dyes or, in certain cases, 1:2 metal-complex or milling acid
dyes with a suitable aftertreatment. As already noted, however, it is the cotton
portion that causes problems. Until the 1980s, all the dye classes that could
provide satisfactory fastness on cotton required strongly alkaline conditions.
These caused significant damage to the wool and consequently impaired
acceptability and performance of the finished garment in use.
Those vat dyes that are capable of reduction with relatively low
concentrations of caustic soda can be used but even with these dyes decreased
abrasion resistance is observed. Certain azoic combinations can also be applied
but fastness to rubbing is limited and the processing sequence is complicated.
High-reactivity cellulose-reactive dyes are often adopted but these generally
require a two-bath or at least a two-stage process, as already discussed. With an
appropriate cationic pretreatment for the cotton, however, such as paddrycure
application of dimethyloldihydroxyethyleneurea and choline chloride, wool/
cotton blends can be dyed by a one-bath method using selected reactive dyes
designed for wool [16,17].
The introduction of Indosol SF(S) reactant-fixable dyes (Figure 8.5) in the
1980s provided the opportunity to use fast dyes for wool (wool-reactive,
premetallised or milling acid dyes) with them in a one-bath process. The dyebath
is set at pH 6 with a syntan to minimise cross-staining of the wool by the Indosol
dyes. The reactant-fixable dyes and 1:2 metal-complex or milling acid dyes are
applied simultaneously at the boil in the presence of Glaubers salt. The
recommended aftertreating agent is applied from a fresh bath of Glaubers salt
and soda ash solution at 40C. This enhances the wet fastness of the anionic dyes
on wool as well as the reactant-fixable dyes on cotton [1].
For certain deep shades chrome dyes are preferred for the wool but a two-bath
technique is necessary in these cases, the wool being dyed and chromed first at
the boil and pH 4. The cotton is then dyed at the boil from a fresh bath
containing the reactant-fixable dyes, electrolyte, an alkylamine polyoxy-ethylene
levelling agent and a weakly anionic blocking agent to minimise surface staining
of the dyed wool by the dyes. If the undyed wool is shrink-resist treated by an
oxidative process such as chlorination, the affinity of the wool for all anionic
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OH2
H2NO2S
H2O
CuII
CuII
SO2NH2
O
N N
N N
NaO3S
107
SO3Na
Figure 8.5 Typical reactant-fixable direct dye
dyes is increased substantially. In these circumstances, the reactant-fixable dyes

can be used for both fibres, with the degree of uptake by wool being controlled
by means of a blocking agent of the syntan type.
Reactive dyes represent an obvious choice for dyeing wool/linen blends in
view of their brightness and high wet fastness. Application of reactive dyes to the
linen component can give rise to bleeding of acid dyes from wool, especially
when exhaustion and fixation temperatures higher than 40C have to be used.
The alkaline conditions required to fix the reactive dyes on linen may cause
damage of the wool fibre as well as dye desorption. Bleeding of the dyed wool
can be minimised if a reserving agent of the syntan type is added during the
alkaline fixation step of the linen dyeing stage [18]. The dyeing of blends of
shrink-resist wool with linen by a one-bath process often leads to differential
uptake. Deeper dyeing of the wool component can be inhibited using reactive
dichlorotriazinyl-substituted anionic auxiliaries in carefully controlled amounts
[19].
Further problems include tendering of the linen by acid and hydrolytic
degradation of the wool keratin by alkali. Several reactive dyes were evaluated
on wool/linen yarns and fabrics at pH 4.5 (ammonium sulphate and acetic acid),
followed by fixation to wool in ammonia solution at pH 8, rinsing and
neutralisation with acetic acid. The dyeings were tested for levelness and fastness
to rubbing and perspiration. Damage of the wool was assessed by alkali
solubility, ureabisulphite solubility, cysteine content and wet strength [20]. The
substantivity of the linen can be enhanced using a suitable cationic pretreating
agent. This yields a solid effect with wool-reactive dyes but lowers the light
fastness.
Blends of silk and cellulosic fibres can be dyed with vinylsulphone reactive
dyes (Figure 8.3) using the normal padbatch conditions devised for all-cellulosic
fabrics. The fastness of these dyes on silk is generally good, the light fastness
being comparable with that established on cellulosic fibres [21]. Decomposition
of silk can occur during dyeing under extreme pH conditions and this mainly
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108
entails rupture of peptide bonds to form new chain-terminal groups, with

progressive lowering of Mr (Scheme 8.1).
R1
CONH CH
CONH
CH
R2
CONH
R1
CONH CH
COOH + H2N
Scheme 8.1
CH
CONH
R2
To investigate this behaviour, degummed silk was treated in blank dyebaths at

various pH values at the boil and tested for strength, extensibility, N-terminal
amino group content, viscosity and protein loss. The results confirmed that silk is
relatively stable under dyeing conditions between pH 4 and pH 9. This moderate
stability, even in the mildly alkaline region, indicates that the dyeing of silk/
cotton blends with high-reactivity dyes is much less damaging to the protein
structure than the dyeing of wool/cotton blends in the same way [22].
8.2 EXHAUST DYEING OF NYLON/CELLULOSIC BLENDS
Serious problems were encountered with the early nylon/cotton blends in the
1950s. Blends containing less than 50% nylon were actually weaker than allcotton yarns. Owing to the lower modulus of the nylon, the load on the yarn as it
was extended was increasingly borne by the cotton fibres in the blend. This
problem was solved by developing nylon with a stressstrain curve closer to that
of cotton [23].
Nylon/cellulosic staple blends containing 1030% nylon with cotton or
viscose are used in lightweight suiting and dresswear, leisure shirts and half-hose.
Many of these blends, as well as workwear fabrics with a 25:75 nylon/cotton
warp and a cotton weft, or 20:80 nylon/viscose carpet yarns, contain relatively
minor proportions of nylon and acceptable solid effects are not difficult to
achieve. Similar considerations apply to pile fabrics, such as upholstery with a
nylon pile in a woven cotton backing, or cotton-pile terry towelling with a weftknit nylon backing for beachwear, childrens clothing or leisure shirts, where
slight two-sided differentiation may present no problem in made-up garments or
covers.
Tactel (ICI) nylon/cotton blends have been strongly promoted in sportswear.
Good solidity of hue and depth is more critical in 50:50 blends and in union
fabrics, such as nylon warp stretch fabrics containing cotton or nylon/cotton
wefts for swimwear and narrow fabrics, crimped nylon warp/viscose weft
sportswear or swimwear, nylon/viscose filament dresswear, or cotton warp/nylon
weft constructions for uniforms, rainwear and workwear.
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EXHAUST DYEING OF NYLON/CELLULOSIC BLENDS
109
Warp-knitted velvet fabrics with a viscose pile and a nylon backing are useful
as furnishing fabrics, outerwear, trimmings and lining fabrics, often on cost
grounds. Dyeing and printing are usually completed before raising. Overprinting
of these dyed fabrics with metallic pigments is popular [24]. Plush velour and
velvet fabrics with a nylon or nylon/wool pile and a cotton backing are
encountered in the upholstery sector. Occasionally the pile is made from novelty
yarns in which the filaments vary in denier and crystallinity along their length, so
that an attractive shadow effect is obtained within each filament.
When jet bleaching nylon/cotton blends with hydrogen peroxide at the boil,
the amount of peroxide should be decreased according to the proportion of
nylon present and complex organic bases are added as protective agents to
minimise oxidative damage of the nylon, i.e. deamination of N-terminal end
groups. An organic stabiliser for the peroxide, e.g. an aminocarboxylate,
aminophosphonate or hydroxycarboxylate, should be present as this has a
sequestering action on any Fe(III) or Cu(II) ions present, which may cause
catalytic degradation of the cellulose. Peroxide scavengers containing
thiosulphite may be used to ensure that there is no residual peroxide in the goods
at the end of the bleaching operation [25].
There are various possibilities regarding the choice of dye classes for solid
effects on nylon/cellulosic blends. Apart from fastness considerations, the choice
of dye system is much influenced by blend construction. Single-class methods are
mainly used where the nylon is a minor component, i.e. where only the cellulosic
fibre plays a significant part in the surface appearance of the blend fabric, the
nylon occupying the interior or the reverse side of the construction.
Reserve, shadow and limited contrast effects are practicable on nylon/
cellulosic blends, but seldom encountered in practice. Shadow effects are
sometimes required in certain woven upholstery designs, for example. The nylon
may be reserved by applying selected direct dyes to the cellulosic fibre at 80
90C, with the usual salt addition and a syntan to protect the nylon from crossstaining. Many direct dyes are suitable, but the most important are the
salt-controllable disazo or trisazo types with two to four anionic groups per
molecule. A smaller range of yellow to red disazo dyes with two solubilising
groups and a disulphonated phthalocyanine blue have been recommended for
solid effects in pale or medium depths with good levelling characteristics. Solidity
is favoured by applying these dyes at pH 56 with sodium dihydrogen phosphate
as buffer and with limited salt addition at the boil.
A wider gamut in good solidity is attainable if disperse and direct dyes are
applied by a one-bath method at pH 8 and 70C. An alkanol polyoxyethylene is
recommended as dispersing and levelling agent, together with a syntan to
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110
minimise uptake of direct dyes by the nylon. Multisulphonated direct dyes of the
salt-controllable type are used and the preferred disperse dyes are low-energy
types with good levelling properties on nylon. The wet fastness properties of
nylon/cellulosic blends dyed in this way are severely limited and the method is
restricted to low-quality fabrics.
Many suitable neutral-dyeing 1:2 metal-complex and milling acid dyes are
available to give good reserve of the cellulosic fibre when applied to the nylon
component by conventional methods in the presence of ammonium acetate.
Disulphonated disazo and anthraquinone dyes with excellent wet fastness, but
only moderate levelling properties, can be used widely. Coverage of dye-affinity
variations in the nylon is much less of a problem than on filament nylon fabrics,
especially when nylon/cellulosic staple-blends are to be dyed. Most of the
premetallised dyes used are monosulphonated monoazo 1:2 chromium
complexes.
If premetallised or milling acid dyes of this kind are applied with the saltcontrollable direct dyes already described above, solid-effect dyeings of good
fastness to light and moderately good wet fastness can be obtained economically
on nylon/cellulosic blends. This method is especially important where both fibres
make a major contribution to the appearance of the material. It is often useful to
include a syntan to inhibit staining of the nylon by the direct dyes.
Dyeing commences with the acid dyes, a weakly cationic alkylamine
polyoxyethylene retarder if necessary and the minimum amount of syntan,
depending on the applied depth and the direct dyes selected. If a cationic levelling
agent is found necessary, sufficient of an alkanol polyoxyethylene antiprecipitant should be added to solubilise the dyeretarder complex. The dyebath
is buffered to an optimum pH between 56 for full depths of milling acid dyes
and 78 for pale depths of premetallised dyes. The direct dyes are added at about
60C and the temperature raised to the boil, adding salt to promote exhaustion
of the direct dyes by the cellulosic fibre.
Bright hues with excellent fastness can be achieved on nylon/cellulosic blends
using reactive dyes. Unfortunately, reactive dyes are highly sensitive to the type of
nylon present and to dye-affinity variations in filament nylon. Many reactive
dyes contain several sulphonic acid groups per molecule and pronounced
blocking on the nylon component is observed when attempting to apply a
multisulphonated dye in the presence of a less-sulphonated dye of higher affinity.
The problems of incompatibility arising from this phenomenon are particularly
difficult when dyeing the blend because differences in distribution of individual
dyes between the component fibres are accentuated.
In spite of these difficulties, methods employing one class of reactive dyes to
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111
colour both fibres have been established, especially for those fabrics composed
mainly of cotton in which the nylon is hidden when the fabric is made into a
garment. Weft-knitted terry towelling with a strong nylon filament base and an
absorbent cotton pile has proved popular for childrens wear, beachwear and
leisure shirts. Bright hues with very good fastness to washing and light are
required. This is usually achieved with reactive dyes and metal-complex or
milling acid dyes, but a wide variety of reactive dyes can be used satisfactorily on
both fibres if the proportion of nylon is not too high.
In a typical three-stage method from a single bath, the reactive dyes are first
exhausted on to the nylon from weakly acidic solution in the absence of salt.
Electrolyte is then added to promote further uptake by the cellulosic fibre and a
final alkaline fixation treatment is given. Some control over the distribution
between nylon and cellulose is possible by selection of dyebath pH, temperature
and electrolyte concentration. Nylon is favoured at low applied depths but the
distribution shifts in favour of the cellulosic fibre as the saturation level of nylon
is approached.
Reactive dyes with good neutral-dyeing properties in the presence of salt can
be applied by a simpler two-stage sequence of neutral exhaustion and alkaline
fixation, as for 100% cellulosic materials. Most metal-complex reactive dyes, as
well as multisulphonated unmetallised types, require pH values of 4 or lower for
reasonable uniformity of distribution. This gives some risk of degradation of the
cellulosic fibre, especially if it is viscose, and may lead to inefficient utilisation of
dye on the cellulosic component by acid hydrolysis of the reactive group.
Many 1:2 metal-complex and several milling acid dyes are fast to soda boiling.
This means that they can be applied with reactive dyes in the two-stage method,
provided no serious interaction occurs. Reactive dyes are applied in the presence
of alkali, together with non-reactive metal-complex dyes for the nylon. Free acid
is added to give pH 7 and the temperature raised to the boil to fill in the nylon
portion. There is only slight staining of the cellulosic fibre under these conditions.
It is important to keep the pH slightly alkaline during washing and rinsing to
avoid possible reaction of nylon with residual reactive dyes.
When selecting reactive and milling acid dyes for this blend, it is more usual to
adopt a two-bath method that gives a wider choice of suitable dyes. In this case,
an important criterion is that the bond between the reactive dye and cellulose
must be stable to acid hydrolysis during dyeing of the nylon component in full
depths. Anionic dyes with high neutral-dyeing affinity are therefore preferred and
vinylsulphone reactive dyes (Figure 8.3) are generally unsuitable.
The facility to attain high wet fastness standards on nylon/cellulosic blends by
a one-bath technique at mildly acidic pH is a substantial advantage over the two-
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112
bath or two-stage procedures based on reactive dyes [1]. Reactant-fixable direct

dyes (Figure 8.5) and 1:2 metal-complex or milling acid dyes are applied
simultaneously. The bath is set at pH 6 with Glaubers salt and a syntan to
minimise staining of the nylon by the reactant-fixable dyes. The 1:2 metalcomplex or milling acid dyes are added with a weakly cationic retarder and a
nonionic anti-precipitant if necessary. The reactant-fixable dyes are then added
and dyeing of both fibres is completed at the boil.
Kayacelon React (KYK) bis(aminonicotinotriazine) dyes (Figure 8.6) are hightemperature neutral-fixing reactive dyes especially suitable for the one-bath
dyeing of nylon/cellulosic blends. By choosing acid dyes that are relatively
insensitive to salt it is possible to dye solid shades on nylon/cotton in one bath.
The reproducibility of the method depends on buffering the dyebath carefully to
pH 67 with a phosphate buffer [26].
OOC
COO
N
N
SO3Na
H O
N
N
HN
N
N
HN
NH
NH
O
SO3Na
NaO3S
NaO3S
NaO3S
H
N
N
SO3Na
Figure 8.6 Typical bis(aminonicotinotriazine) reactive dye
Knitwear made from polyurethane/cotton blends, in which the elastomeric

fibre may range from 5% to 20%, has been widely popular in recent years for
stretch garments, such as skiwear, sportswear, underwear and leisure clothing. If
the content of polyurethane is higher than about 8%, the slitted tubular-knit
goods show a strong tendency to roll at the edges, leading to a cigarette form
that is most difficult to penetrate during dyeing. This problem has been solved by
presetting on a stenter at 190C after slitting and then either carefully bag
stitching to restore the tubular form, or preferably dyeing in an overflow
machine capable of achieving satisfactory penetration and levelness [27].
Blends of polyurethane and cellulosic fibres are dyed by methods similar to
those for nylon/cellulosic blends. Monosulphonated monoazo or disulphonated
anthraquinone acid dyes, or 1:2 metal-complex monoazo types, are preferred for
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the polyurethane component and practically all direct dyes for cellulose will give
low staining of polyurethane fibres at pH 88.5. Similar considerations apply to
the dyeing of blends of acid-dyeable polypropylene with cellulosic fibres. Selected
premetallised or milling acid dyes are applied to the synthetic component at the
boil and pH 34 in the presence of an anionic retarder. Selected direct dyes are
then applied from the same bath after adjusting to 70C and pH 78. A syntan is
included to minimise staining of the polypropylene by the direct dyes.
8.3 CONTINUOUS DYEING OF NYLON/CELLULOSIC BLENDS
The carpet industry is the most important field in which AC blends have been
used in quantities sufficient to justify the development of continuous dyeing
processes. Another area for the adoption of continuous methods has been the
dyeing of heavy-duty nylon/cotton woven fabrics, which are closely related to the
much more extensively used polyester/cotton blends for this outlet. Similar
principles of application are relevant for the continuous dyeing of plush and
velvet upholstery fabrics made in nylon pile/cotton backing constructions.
Continuous dyeing systems have also been developed for nylon warp/cotton weft
sportswear materials that have proved exceptionally popular in recent years [28].
Warps in these sportswear fabrics are usually treated with acrylate sizes so
that desizing with enzymes is unnecessary. Pretreatment comprises singeing, cold
bleaching, alkaline boiling out, washing-off and drying. After dyeing, these
goods are often given a hydrophobic finish usually based on a glyoxal-fluorocarbon resin or a silicone polymer. This can contribute to improvements in fastness of anionic dyes to perspiration and water, as well as giving the desired finish.
Modified viscose carpets containing only 1020% nylon can be dyed
continuously with direct dyes that give an acceptably solid effect on the two
fibres. The preferred dyes are mostly disazo types with two solubilising groups
and good levelling properties, but for mode shades the best results are obtained
with salt-controllable dyes. Migration of the disazo disulphonates during drying
and steaming may lead to colour variations in mixture dyeings. Temperaturecontrollable direct dyes tend to give poor penetration and inferior fastness to
rubbing. A wetting and levelling agent of the nonylphenol polyoxyethylene type
is added to the pad liquor, with urea if necessary to improve solubility of the
direct dyes. Solidity at full depths requires careful control of pH and anionic
surfactants should be avoided as these may interfere with uptake of the direct
dyes by nylon.
An alternative process, recommended for plush or velvet upholstery with a
nylon pile and cotton backing, is based on the same selection of acid or metalcomplex dyes used on all-nylon carpets, together with the salt-controllable
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114
multisulphonated direct dyes that give low staining of nylon. Suitable foaming
agents are added to improve levelness and penetration. These avoid undesirable
migration and frosting of the nylon pile. Steaming for 515 minutes is necessary
according to depth applied. Continuous methods that include direct dyes suffer
from problems of substantive tailing and differential affinity for the two fibres, as
well as limited brightness and inferior fastness to light and wet treatments in
many instances.
Reactive dyes for the cellulosic component offer advantages in most of these
aspects and they are suitable for one-bath application methods in general.
Satisfactory fastness in pale depths is given by padding with reactive and disperse
dyes, urea and an anionic migration inhibitor, followed by thermofixation at
180200C. Low-energy monoazo and anthraquinone disperse dyes are
recommended. Slight discoloration and stiffening of the fabric may occur if a
high proportion of nylon is present. Batching for two hours after padding may
improve fixation of the reactive dyes when viscose is the cellulosic component.
A modification of this process can be used to dye full depths with reactive dyes
and selected metal-complex or acid dyes. Less urea is required and after
thermofixation under alkaline conditions the dyes on nylon are developed fully
by an acid shock treatment in dilute formic acid solution at the boil. An
alternative one-bath sequence for reactive dyes and unsulphonated 1:2 metalcomplex dyes is:
(1) neutral paddrythermofix treatment for fixation of the metal-complex
dyes on nylon;
(2) padding with caustic soda in near-saturated brine;
(3) batching to fix the reactive dyes on the cellulosic fibre.
The relative merits of wet steaming without intermediate drying, a padsteam
process with intermediate drying and a padbatchsteam sequence for the
fixation of metal-complex and acid dyes on the nylon component have been
evaluated in terms of the resulting wet fastness [28]. Selected reactive or reactantfixable dyes can be used for the cellulosic fibre. Improvements in colour fastness
are possible using a syntan to fix the anionic dyes on the nylon and a cationic
aftertreatment for the reactant-fixable dyes.
Dull dyeings of high fastness to light and wet treatments may be required on
nylon/cotton fabrics for workwear or uniforms. Vat and metal-complex dyes are
often used in these circumstances, although selected sulphur and milling acid
dyes provide more economical recipes where fastness standards permit. Stability
of the premetallised and milling acid dyes to reduction and oxidation is an
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CONTINUOUS DYEING OF NYLON/CELLULOSIC BLENDS
115
essential criterion of selection for application with vat or sulphur dyes. Sulphur
dyes can be used for the cotton by a simplified method in which the metalcomplex dyes are applied alone by paddrythermofix and the reduced sulphur
dyes included in a subsequent chemical padsteam stage. A costly two-bath
application of 1:2 metal-complex dyes by padsteam on nylon, followed by a vat
pigment paddrychemical padsteam process for the cotton, may be necessary
to achieve maximum fastness.
8.4 DYEING METHODS AND DYE SELECTION FOR AC BLENDS
Solid effects are mainly of interest on these blends. They can be readily obtained
(Table 8.1) by single-class (reactive dyes) or one-bath methods on blends of wool,
Table 8.1 Dye selections for exhaust dyeing of AC blends

Blend
Colour effect
Dyeing method
Dye selection
Wool/cotton
Wool
reserve
One-bath
Multisulphonated
salt-controllable direct dyes
Solid
One-bath
Acid dyes and

low-sulphonated direct dyes
Solid
Single-class
Monofunctional or bifunctional
cellulose-reactive dyes
One-bath

and reactant-fixable dyes
Two-stage
Wool-reactive and then

Two-bath
Chrome dyes, then

reactant-fixable dyes
Single-class
High-reactivity dyes with

anionic retarder
One-bath
Acid dyes and direct dyes

with anionic retarder
One-bath
Milling acid dyes and direct dyes
Two-stage
Levelling acid dyes at pH 23,

then direct dyes
Single-class
Disulphonated milling acid dyes or

unsulphonated 1:2 metal-complex
dyes
Wool/cotton
(machinewashable)
Chlorinated
wool/cotton
Mohair/
cotton
Wool/viscose
Contents
Solid
Solid
Viscose
reserve
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116
Table 8.1 Continued

Blend
Colour effect
Dyeing method
Dye selection
Wool/viscose
Solid or
contrast
One-bath

Wool-reactive dyes and direct dyes
Milling acid dyes and
Wool/linen
Solid
Two-stage
Milling acid dyes, then

Wool/ramie
Solid
One-bath
Nylon/
cellulosic
Nylon
reserve
Single-class
Salt-controllable direct dyes

with syntan
Cellulosic
Single-class
Monosulphonated 1:2
metal-complex or disulphonated
Solid
Single-class
(pale depths)
Disulphonated disazo and

phthalocyanine direct dyes
Solid
Single-class
Reactive dyes at pH 45,

then salt and alkali
One-bath
Low-energy disperse dyes

and salt-controllable
direct dyes
reserve
milling acid dyes
Nylon/cellulosic
Premetallised or milling acid

dyes and salt-controllable
direct dyes
Premetallised or milling acid
dyes and reactant-fixable dyes
Selected acid dyes and
bis(aminonicotinotriazine)
neutral-fixing dyes
Polyurethane/
cotton
Acid-dyeable
polypropylene/
cotton
Contents
Two-stage
Reactive dyes with alkali, then

selected premetallised and milling
acid dyes
Polyurethane
reserve
Single-class
Direct dyes at pH 8 with syntan
Solid
One-bath

and direct dyes at pH 8
Solid
Two-stage

at pH 4, then direct dyes at pH 8
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DYEING METHODS AND DYE SELECTION FOR AC BLENDS
117
chlorinated wool, mohair, nylon or polyurethane with cotton, or blends of wool

or nylon with viscose. Two-stage procedures are necessary for wool/linen or aciddyeable polypropylene/cotton blends, the non-cellulosic fibre being dyed first.
The higher wet fastness standards provided by reactive dyes with premetallised
or milling acid dyes on nylon/cellulosic blends or machine-washable wool/cotton
goods also require two-stage or two-bath processes. On wool/cotton the wool is
dyed first but on nylon/cotton it is preferable to first dye the cotton.
Continuous dyeing methods for solid effects on nylon/cellulosic blends range
from low-cost padsteam dyeing with direct dyes or the padthermofix disperse/
reactive process, to much more elaborate and costly two-bath sequences for high
all-round fastness performance. Premetallised and milling acid dyes by pad
steam are mostly used to colour the nylon but the class preferred on the cellulosic
fibre may be direct, reactant-fixable, reactive, sulphur or vat dyes (Table 8.2).
Table 8.2 Dye selections for continuous dyeing of nylon/cellulosic blends
Blend
Nylon/
cellulosic
Colour
effect
Dyeing
method
Dye
selection
Solid
Paddrysteam
Salt-controllable direct dyes

and salt-controllable direct dyes
and reactant-fixable dyes
Contents
Paddrythermofix
Low-energy disperse dyes and

reactive dyes
Paddrythermofix
acid shock
Selected premetallised or milling

acid dyes and reactive dyes
Paddrythermofix
padbatch
Unsulphonated 1:2 metal-complex

dyes and reactive dyes
Paddrythermofix
chemical padsteam
Selected premetallised dyes, then

pre-reduced sulphur dyes
Paddrysteam,
paddrychemical
padsteam
Selected 1:2 metal-complex dyes,

then vat dyes
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118
8.5 REFERENCES
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
12.
13.
14.
15.
16.
17.
18.
19.
20.
21.
22.
23.
24.
25.
26.
27.
28.
J A Hook and A C Welham, J.S.D.C., 104 (1988) 329.

R L Stone, R H Wang and G P Morton, Text. Chem. Colorist, 18 (Aug 1986) 11.
T P Nevell in Cellulosics dyeing, Ed. J Shore (Bradford: SDC, 1995) 6.
M M Muratova, T Y Rosinskaya, L I Belenkii and L L Vidrevich, Tekstil. Prom., 12 (Dec 1980)
48.
N E Houser, AATCC Nat. Tech. Conf., (Oct 1985) 116.
K Imada, M Sasakura and T Yoshida, Text. Chem. Colorist, 22 (Nov 1990) 18.
A N Lee, Dyer, 178 (Apr 1993) 30.
D Hildebrand, Proc. 7th Int. Wool Text. Res. Conf., (Tokyo), Vol. V (1985) 239.
H Putze and G Dillmann, Textilveredlung, 15 (1980) 457.
M Matsui, U Meyer and H Zollinger, J.S.D.C., 104 (1988) 425.
H Zahn, I Steeken and U Altenhofen, Chemiefasern und Textilind., 31/83 (1981) 684.
I Steenken, I Souren, U Altenhofen and H Zahn, Textil Praxis, 39 (1984) 1146.
U Altenhofen, I Souren and H Zahn, Textilveredlung, 20 (1985) 144.
J M Cardamone, AATCC International Conference and Exhibition, (Oct 1994) 7.
J M Cardamone, W N Marmer, E J Blanchard, A H Lambert and J Bulan-Brady, Text. Chem.
Colorist, 28 (Nov 1996) 19.
I Steenken, I Funken and G Blankenburg, Textilveredlung, 21 (1986) 128.
J Haarer, H Thomas and H Hcker, Melliand Textilber., 76 (1995) 1003.
G Kratz, A Funder, H Thomas and H Hcker, Melliand Textilber., 70 (1989) 128.
H Putze, Textil Praxis, 39 (1984) 1051.
B Vogt, U Altenhofen and H Zahn, Textilveredlung, 20 (1985) 90.
R M Hoffman and R W Peterson, J. Text. Inst., 49 (1958) 418.
G Wnsch, Textilveredlung, 24 (1989) 57.
D R Wallwork, Textile Technology Internat., (1990) 229.
A N Lee, Dyer, 179 (Apr 1994) 29.
Brazzoli SpA, Dyer, 179 (Aug 1994) 31.
O Annen, F Somm and R Buser, Textilveredlung, 22 (1987) 19.
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119
CHAPTER 9
Cellulosic/acrylic and other CB blends
9.1 EXHAUST DYEING OF CELLULOSIC/ACRYLIC BLENDS

Cellulosic/acrylic blends are the most important of the acrylic fibre blends. The
cellulosic fibre contributes economy, moisture regain and antistatic properties. In
apparel outlets, the acrylic component is included for heat insulation, crease
recovery and abrasion resistance. Important characteristics of cellulosic/acrylic
fibre blends in upholstery, pile fabrics and tufted carpets are appearance
retention, resilience and wear resistance.
Cotton/acrylic blends are widely used in the rapidly expanding sportswear
and leisurewear sectors. Fine-spun 20:80 to 50:50 cotton/acrylic yarns are used
in lightweight woven suiting, dresswear and sportswear, or knitted underwear,
leisurewear and swimwear. Blends of viscose and acrylic fibres are used in skirts,
dresswear, linings and hosiery yarns. It may be desirable to insert durable pleats
in dresswear garments with the aid of a reactant resin finish. Modacrylic fibres in
blends with cotton or viscose (20:80 to 50:50) have been exploited for
underwear, hosiery, leisure clothing and dresswear, particularly pleated skirts.
High-bulk acrylic and modal fibre long-staple yarns are suitable for dresswear
and suitings with a wool-like appearance. Fleece fabrics are made from woollenspun acrylic fibre pile in a cotton backing. Fancy high-bulk acrylic jersey
knitgoods containing linen or viscose slubs are of interest for furnishing fabrics
as well as apparel. Viscose/acrylic staple yarns have proved effective as high-twist
pile for non-crush carpets, as they are significantly cheaper than all-wool or
wool/viscose carpets.
Package dyeing of cotton/acrylic yarns is important. Careful prescouring of
the cotton is essential using trisodium phosphate at 6070C and an alkanol
polyoxyethylene detergent. This is necessary to remove residual lubricants and,
in the case of unrelaxed yarns containing high-bulk acrylic, to avoid fixation of
contaminants during relaxation by steaming. Good whiteness is achieved on the
cellulosic component by bleaching with silicate-stabilised hydrogen peroxide at
70C and pH 910. Careful control is necessary to avoid yellowing of the acrylic
fibre.
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CELLULOSIC/ACRYLIC AND OTHER CB BLENDS
The selection of dyes for cellulosic/acrylic blends is complicated by the fact

that disperse dyes show poor build-up and limited fastness on the acrylic
component, so that basic dyes must be used in most instances. Problems of
incompatibility between these dyes and the various classes of anionic dyes
required to meet appropriate fastness demands on the cellulosic fibre (sections
4.2 and 4.3) are therefore characteristic of such blends, in contrast to those of
cellulosics with other synthetic fibres. Cross-staining is less of a problem,
however, and a good reserve can be obtained on either component, although
solid effects are most often required.
The choice of best dyeing method is determined by the colour effect and
gamut required, as well as the wet fastness specification. Cellulosic/acrylic blends
can be readily dyed to reserve the acrylic fibre by pretreating with a syntan at 60
70C and then dyeing with salt-controllable direct dyes at 70C and pH 78. It is
less convenient to reserve the cellulosic component because staining by basic dyes
may be troublesome, particularly with regenerated cellulosic fibres or with
cotton that has suffered oxidative damage during scouring or bleaching. The
carboxyl groups formed as a result of alkaline oxidation of cellulose provide
anionic sites for the sorption of basic dyes. Basic dyes are applied to the acrylic
component with a cationic retarder at the boil. The rates of exhaustion of basic
dyes of various types on acrylic fibres have been analysed in self shades and
combination recipes using high-pressure liquid chromatography [1]. The
preferred dyes for reserving the cellulosic component are mainly of the localisedcharge monoazo or anthraquinone types. Any basic dye staining of the cellulosic
fibre can be removed using sodium dithionite and a nonionic detergent at 60C.
Solidity or contrast effects can be easily obtained by one-bath methods. The
most economical approach for pale depths is one-bath application of disperse
and direct dyes. Wet fastness is seldom acceptable at intermediate depths, but the
levelling properties of disperse dyes are much superior to those of basic dyes on
acrylic fibres. The disperse dyes recommended for pale depths on cellulosic/
acrylic blends are mainly low- and intermediate-energy dyes of Mr 230350,
particularly nitro, monoazo and anthraquinone types. The preferred direct dyes
are almost all salt-controllable disazo, polyazo or stilbene types with three or
four anionic groups.
The blend is dyed at the boil and pH 45 in the presence of an anionic
dispersing agent. Disperse dyes are partly absorbed by the cellulosic component
in the early stage of dyeing, but transfer in favour of the acrylic fibre proceeds as
the dyeing temperature approaches the boil. The acrylic component is dyed first,
then the dyebath temperature is lowered to 80C, Glaubers salt added and the
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EXHAUST DYEING OF CELLULOSIC/ACRYLIC BLENDS
121
cellulosic fibre filled in with the direct dyes. It is not difficult to remove the
residual stain from the cellulosic fibre by subsequent scouring.
Cellulosic/acrylic blends can be dyed in pale or medium depths by a one-bath
process with direct and basic dyes, but there is a risk of co-precipitation of these
dyes. Careful selection of basic dyes and the addition of a nonionic antiprecipitant are necessary. Problems of incompatibility can be virtually overcome
by the selection of basic dyes of small molecular size and the relatively
hydrophilic multisulphonated direct dyes with a low tendency to aggregate in the
absence of electrolyte [2].
The cellulosic fibre is dyed first at 80C and pH 56 (acetateacetic buffer)
with the direct dyes, Glaubers salt and an alkanol polyoxyethylene antiprecipitant. The basic dyes and an anionic retarder are then added and the
temperature raised to the boil to approach target depth on the acrylic
component. If necessary, more Glaubers salt may be added to improve
exhaustion of the direct dyes. The acidic dyebath is important to avoid
aggregation and possible precipitation of the dyes. The direct dyes must show
satisfactory exhaustion under these mildly acidic conditions that are preferred for
applying basic dyes. The direct dyes tend to retard the uptake of the basic dyes by
the acrylic component and may give restraining of final exhaustion in heavy
depths. An advantage of dyeing under mildly acidic conditions is to avoid the
risk of reductive decomposition of some direct dyes under alkaline conditions at
elevated temperatures.
Medium or heavy depths may be dyed by a more lengthy procedure that
minimises any risk of incompatibility. In the two-stage sequence, the basic dyes
are applied with an alkanol polyoxyethylene anti-precipitant at pH 56, raising
the temperature slowly from 80C to the boil. When dyeing of the acrylic fibre is
complete, the temperature is lowered again to 80C, the direct dyes and
Glaubers salt are added and dyeing of the cellulosic component is completed at
this temperature. A two-bath method is similar, except that the basic dyes are
applied at pH 45 with a cationic retarder and the direct dyeing is commenced at
40C and pH 7, after an intermediate clear with a nonionic detergent.
Better fastness of the cellulosic fibre is given by reactive, reactant-fixable or vat
dyes. Basic dyes and reactive dyes are preferred for bright hues of high wet
fastness. Basic dyes would be restrained by the presence of reactive dyes and they
tend to be unstable to the conditions of alkaline fixation, so that two-bath
methods are normally necessary. Full depths are usually achieved by dyeing the
acrylic fibre first with basic dyes. The temperature of the reactive dyeing stage
must not exceed the glass-transition temperature of the dyed acrylic fibre in order
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to avoid possible desorption of basic dyes [3]. Data have been given on the
stability to cross-dyeing of basic dyes tested over the pH range 2 to 9 [2]. There is
a risk of change in hue of basic dyeings during the alkaline fixation and soaping
of reactive dyeings on the cellulosic component. The vinylsulphone reactive dyes
are stable to cross-dyeing with basic dyes at pH 5. Advantage may be taken of
this in a two-stage sequence, in which the alkaline fixation bath for the reactive
dyeing is subsequently adjusted to pH 5 with acetic acid in order to dye the
acrylic fibre with the basic dyes.
A two-stage process with reactant-fixable copper-complex direct dyes and
basic dyes is suitable to achieve high wet fastness in pale and medium depths [4].
The reactant-fixable dyes are applied first to the cellulosic component at pH 56
(acetateacetic buffer) and 70C in the presence of electrolyte. The basic dyes are
then added with an alkylamine polyoxyethylene as anti-precipitant and mildly
cationic retarder, and the acrylic fibre is dyed at the boil. An appropriate cationic
fixing agent is used to aftertreat the dyeings. Advantages of this process include a
short dyeing time, good level dyeing behaviour and high standards of
reproducibility and fastness performance [5].
When dyeing yarn in package form it is usual to select vat dyes for the
cellulosic fibre. Problems of incompatibility are more evident when vat dyes are
used with basic dyes. A two-bath sequence is necessary because the anionic
dispersing agents in the vat dye formulations would restrain uptake of the basic
dyes and promote staining of the cellulose, at the same time causing instability of
the vat dye dispersion. If the cellulosic fibre were dyed first, the vat dye would act
as a mordant and the basic dyes would stain the strongly anionic fibre surface.
This stain would not be removed completely by soaping [2]. Thus it is preferable
to dye the acrylic component first, because the basic dyes are fast to cross-dyeing,
and the reducing conditions of vat dyeing at 5060C help to remove the basic
dye stain from the cellulosic fibre. Some vat dyes stain the acrylic fibre
significantly and allowance for this must be made in shade matching. The
preferred vat dyes for minimum staining of the acrylic fibre are mainly the
polycyclic quinones and their halogenated derivatives, including the
dibromopyranthrones, indanthrones, dichloro- and dibromoiso-violanthrones,
and alkoxyviolanthrones [6].
9.2 CONTINUOUS DYEING OF CELLULOSIC/ACRYLIC BLENDS
These are the only acrylic blends produced in sufficient quantity to justify
continuous dyeing. The principles of dye selection in relation to compatibility
and fastness requirements are essentially similar to the analogous batchwise
methods, but the application techniques have much in common with the
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CONTINUOUS DYEING OF CELLULOSIC/ACRYLIC BLENDS
123
continuous dyeing of polyester/cellulosic blends. Blends of acrylic fibres with

either cotton or viscose can be processed satisfactorily on continuous ranges after
singeing, desizing and scouring in open width.
For blends containing a high proportion of acrylic fibre with cotton, it is often
possible to obtain an acceptably solid appearance and moderate fastness in pale
depths by dyeing the acrylic fibre only using disperse dyes applied by paddry
thermofix. Higher fastness in pale or medium depths is attainable on these
acrylic-rich blends using basic dyes by padsteam, leaving the cellulosic fibre
undyed. The fabric is padded at 70C with the basic dyes, the liquor being
adjusted to pH 5 with citric acid. The fabric is then steamed at 100103C, but it
may be necessary to give a prolonged steaming with certain basic dyes. If reserve
of the cellulosic fibre is desired, this may require a clearing treatment in an
anionic detergent solution at 90C, or in a reduction clearing bath at 70C in the
case of deeper shades.
For pale depths of outstanding fastness, selected vat dyes can be applied to
give reasonable solidity on both fibres. These are applied by pigment padding
from dispersion and drying, followed by chemical padding. Salt (100 g l1) is
added to the alkaline dithionite solution to minimise transfer from the acrylic
fibre to the cellulose during subsequent steaming. Halogenated vat dyes of the
pyranthrone, indanthrone and isoviolanthrone types, as well as alkoxy
derivatives of violanthrone, are especially suitable [6].
Solid dyeings on cotton/acrylic blends can also be obtained using liquid brands
of sulphur dyes to colour both fibres. Advantages of this approach over
alternative two-stage systems are the lower costs of dyes and chemicals, a shorter
and simpler dyeing cycle, satisfactory fastness and improved coverage of
immature cotton [7]. On the other hand, of course, sulphur dyes are much more
restricted to a gamut of relatively dull hues.
Basic and direct dyes may be applied together in the padsteam process, using
an alkanol polyoxyethylene sulphate to complex with the basic dyes and an
alkanol polyoxyethylene to disperse the complex in the pad liquor (section 4.3),
but there are serious limitations. The depth on the acrylic fibre is limited by the
stability of the dyeagent complex and the restraining influence of the anionic
agent and the direct dyes. A fixation accelerator is also required to promote yield
and penetration of the basic dyes into the acrylic component during steaming.
These agents are usually water-insoluble aryl ethers containing halogeno or
cyano substituents [8]. A product of this type is emulsified in the pad liquor
together with an anti-precipitant system. Selection of the direct dyes is restricted
by their limited solubility in the pad liquor at pH 5, slow diffusion into the
cellulosic fibre during steaming and only moderate wet fastness.
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Conventional basic dyes are not compatible with vat dye dispersions but
selected basic dyes have been marketed in complex form as liquids stabilised with
anionic dispersing agents. These are compatible with liquid brands of vat dyes
for continuous dyeing. Before dyeing with these complexes, the anionic groups in
the acrylic fibre must be converted to the ammonium salt form by pretreatment
with an ammonium salt at 80C. If these basic dye complexes are applied to
untreated acrylic fibres with anionic groups in their usual sodium salt form, the
complexes do not dissociate and give relatively low yields with poor fastness.
The pretreated cellulosic/acrylic fabric is padded with the complexed basic
dyes together with selected vat dyes at 50C and pH 89 (phosphate buffer).
During thermofixation at 200C the complexes are transferred from the
cellulosic to the acrylic fibre and also dissociate to give the parent basic dyes.
These blends show high wet fastness after the residual basic dye stain has been
cleared from the cellulosic fibre during conventional chemical padsteam
fixation of the vat dyes. Optimum fastness in full depths on untreated cellulosic/
acrylic blends can be achieved by padsteam dyeing with conventional basic
dyes, followed by the usual pigment paddrychemical padsteam sequence for
vat dyeing of the cellulosic fibre. This relatively costly process gives a wide range
of shades of high fastness to light and wet treatments. The application of vat dyes
is instrumental in removing any basic dye that may have stained the cellulosic
fibre in the first stage.
Basic and reactive dyes are generally incompatible at only moderate
concentrations in the pad liquor, especially the localised-charge basic dyes
with the most highly sulphonated members of the reactive class.
Nevertheless, these two classes yield exceptionally bright hues for deep
contrast effects of excellent fastness, applied by a two-bath sequence of
conventional padsteam processes. If a resin finish is required for the
cellulosic component, the fabric should be treated under conditions that
minimise discoloration of the acrylic fibres, particularly with regard to
curing temperature. The amount of resin applied should be determined by
the cellulosic content of the blend. Fabrics containing more than 50% of
acrylic fibre do not normally require a resin finish.
9.3 BLENDS OF CELLULOSIC FIBRES WITH MODACRYLIC OR ACIDDYEABLE ACRYLIC VARIANTS
Dynel (Union Carbide) modacrylic fibre is used in 20:80 to 50:50 blends with
cotton or viscose for half-hose, underwear and nightwear. The modacrylic
component contributes dimensional stability, improved handle and good
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BLENDS OF CELLULOSIC FIBRES WITH ACRYLIC VARIANTS
125
launderability. Woven goods include pile fabrics with a cotton warp and a 70:30
cotton/Dynel weft. Dynel is resistant to mercerising and peroxide bleaching of
the cotton. It is usual to dye solid shades on these blends but a wide range of
colour contrasts is possible because the dyes preferred for Dynel do not normally
stain the cellulosic fibre.
Shades of moderate fastness (light 56 and mild washing tests) are obtained
with disperse and direct dyes by a one-bath method. Higher wet fastness requires
vat, sulphur or reactive dyes for the cotton and basic dyes for Dynel but a twostage process is unavoidable. The general approach is to dye the Dynel at the boil
and pH 5 with basic dyes and then to fill in the cotton under normal conditions
for the cellulosic dyes chosen.
Verel modacrylic fibre is blended with cotton for sportswear and underwear,
typically as 25:75 blends. Flannel-type fabrics can be made from 75:25 Verel/
viscose yarns. No resin finish is necessary for this modacrylic-rich blend. Solid
shades can be obtained on Verel/cellulosic blends using disperse or 1:2 metalcomplex dyes on Verel and direct dyes on the cotton or viscose. Either fibre can
be reserved and contrast or shadow effects are also possible if desired.
A full range of dyed effects can be produced on blends of acid-dyeable acrylic
variants with cellulosic fibres. Several techniques are available to dye the acrylic
and reserve the cellulosic component:
(1) The acrylic fibre is dyed with basic dyes by the urea method. The dyes
should be dissolved in hot water and either methanol or a nonionic
surfactant, rather than acetic acid. Dyeing takes place in the presence of 3%
urea and the dyebath pH gradually rises from slightly acidic to slightly
alkaline during the course of dyeing. The dyed material is rinsed well and
given a mild scour with sodium hypochlorite at 40C to clear the cellulosic
fibres.
(2) Selected chrome dyes may be applied from an acidic dyebath. It is essential
to scour with a nonionic detergent and tetrasodium pyrophosphate after
chroming is complete. These dyes have satisfactory fastness to perspiration
and steam pleating.
(3) The acid-dyeable acrylic fibre is dyed with selected levelling acid dyes from
phosphoric acid solution, followed by a neutralising scouring treatment as
for chrome dyeings. The light fastness of these dyes may be lower when
dyed with phosphoric acid. Preferred dyes include selected monoazo or
anthraquinone disulphonates of Mr 400600. The fastness of levelling acid
dyes is generally lower than that of basic or chrome dyes, so this approach is
usually confined to bright shades on lower-quality goods.
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126
It is less convenient to dye the cellulosic fibre and reserve the acid-dyeable acrylic
variant because of the affinity of the latter for most classes of dyes. Selected saltcontrollable direct dyes of the multisulphonated type can be applied after the
material has been pretreated at 6070C with a weakly cationic surfactant. The
best reserve of the acid-dyeable acrylic fibre is achieved by dyeing at pH 8 and
70C. The wet fastness is improved by finishing with a crease-resist resin. If solid
shades are required a two-bath method is preferred, first dyeing the acrylic
variant with basic or chrome dyes and then filling in the cellulosic fibre with
direct dyes at pH 8.
9.4 BLENDS OF BASIC-DYEABLE POLYESTER WITH COTTON
Knitted fabrics made from cotton and basic-dyeable polyester fibres can be
dyed in contrasting colours using direct and basic dyes applied together with
a nonionic anti-precipitant by a one-bath method at 120C in a jet or
overflow machine. Aftertreatment with a cationic fixing agent or a reactant
resin is advisable to attain satisfactory wet fastness on the cotton. Improved
fastness without resin treatment is possible using reactive and basic dyes. A
two-bath method is necessary because of the problems of interaction [9]. The
basic dyes may be applied first, followed by aminochlorotriazine dyes under
conventional conditions at 80C. An inverse process is preferred for
vinylsulphone dyes and basic dyes, because these reactive dyeings are stable
to the mildly acidic conditions necessary for dyeing the basic-dyeable
polyester component.
9.5 DYEING METHODS AND DYE SELECTION FOR CB BLENDS
Reserve of the basic-dyeable component in these blends can be readily obtained
using salt-controllable direct dyes, but it is less convenient to reserve the
cellulosic fibre because of potential staining by basic dyes. Solid or contrast
effects are attainable in various ways (Table 9.1), according to the fastness
performance required and the processing costs that can be tolerated. One-bath
methods with direct dyes and disperse or basic dyes offer the simplest approach
in pale or medium depths. Various two-stage or two-bath sequences are available
using reactive, reactant-fixable, sulphur or vat dyes before or after basic dyeing
of the non-cellulosic component.
Continuous dyeing methods for solid effects on cellulosic/acrylic blends range
from low-cost coloration of the acrylic fibre only, using disperse or basic dyes
especially on acrylic-rich materials, to elaborate two-bath sequences entailing
double steaming operations. The more costly processes necessary for high all-
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DYEING METHODS AND DYE SELECTION FOR CB BLENDS
127
Table 9.1 Dye selections for exhaust dyeing of CB blends

Blend
Colour effect
Dyeing method
Dye selection
Cellulosic/
acrylic
Acrylic
reserve
Single-class
Syntan pretreatment, then

salt-controllable direct dyes
Cellulosic
reserve
Single-class
Localised-charge basic dyes
Solid or
contrast
One-bath
(pale depths)
Direct dyes and disperse dyes at

pH 45
One-bath
Multisulphonated direct dyes and

migrating basic dyes with
anti-precipitant
Two-stage
Basic dyes at the boil, then direct

dyes at 80C
Reactant-fixable dyes at 70C, then
basic dyes at the boil
Vinylsulphone reactive dyes, then
basic dyes at pH 5
Two-bath
Basic dyes at the boil, then

aminochlorotriazine dyes at 80C
Basic dyes at the boil, then vat dyes
at 50C
Cellulosic/
modacrylic
Cellulosic/aciddyeable acrylic
Solid
One-bath
Direct dyes and disperse dyes
Two-stage or
two-bath
Basic dyes at the boil, then vat,

sulphur or reactive dyes
Acrylic
reserve
Single-class
Multisulphonated salt-controllable
direct dyes at pH 8 and 70C
Cellulosic
reserve
Single-class
Basic dyes with 3% urea

Chrome dyes at pH 45
Levelling acid dyes from phosphoric
acid solution
Cotton/basicdyeable
polyester
Solid
Two-bath
Basic dyes or chrome dyes, then

salt-controllable direct dyes at pH 8
Solid or
contrast
One-bath
Direct dyes and basic dyes with

anti-precipitant at 120C
Two-bath
Basic dyes, then aminochlorotriazine

reactive dyes at 80C
basic dyes at pH 5
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Table 9.2 Dye selections for continuous dyeing of cellulosic/acrylic blends

Blend
Colour effect
Dyeing method
Dye selection
Cellulosic/
acrylic
Solid
Paddrythermofix
(pale depths)
Disperse dyes
Paddrysteam
Basic dyes with citric acid

Direct dyes and basic dyes
with anti-precipitant and
fixation accelerator
Paddrychemical
padsteam
Halogenated vat dyes or

sulphur dyes
Paddrythermofix
chemical padsteam
Ammonium salt pretreatment,

then vat dye liquids and
stabilised basic dyes at pH 89
Paddrysteam,
paddrychemical
padsteam
Conventional basic dyes,

then vat dyes
Paddrysteam,
paddrysteam
Conventional basic dyes,

then reactive dyes
round fastness require reactive or vat dyes for the cellulosic component and basic
dyes for the acrylic fibre (Table 9.2).
9.6 REFERENCES
1.
2.
3.
4.
5.
6.
7.
8.
9.
M White, F Schlaeppi, N E Houser and J T Larkins, AATCC Nat. Tech. Conf. (Oct 1983) 280.
A Laeppli and R Jenny, Textilveredlung, 23 (1988) 248.
W Haertl, Textil Praxis, 44 (1989) 285; Melliand Textilber., 70 (1989) 354; Textilveredlung, 24
(1989) 214.
Anon, Chemiefasern und Textilind., 34/86 (1984) 752.
F R Latham in Cellulosic dyeing, Ed. J Shore (Bradford: SDC 1995) 246.
H M Tobin, Am. Dyestuff Rep., 70 (Sep 1981) 32.
H Fischer, Textilveredlung, 13 (1978) 449.
M A Herlant, Text. Chem. Colorist, 17 (June 1985) 117; Am. Dyestuff Rep., 74 (Sep 1985) 55,
(Oct 1985) 37.
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CHAPTER 10
Cotton/viscose and other CC blends
10.1 PROPERTIES AND PERFORMANCE OF CELLULOSIC FIBRES IN

THEIR BLENDS
Bast fibres consist of bundles of thick-walled cells held together by non-cellulosic
material. The ultimate fibres in flax and ramie are about 30 m in diameter. Flax
fibres are about 30 mm in length but those of ramie are unusually long (ca. 150
mm). In the bast bundles the ends of these individual fibres overlap. Flax and
ramie are separated into their ultimate fibres before spinning into fine yarns.
Separation of flax fibre bundles from the harvested stems is time-consuming.
During prolonged retting or soaking in water, the effect of bacterial action on
the intercellular material loosens the fibres sufficiently for mechanical separation
by scutching and hackling. The mechanical decortication of ramie can be
achieved without preliminary retting.
Bast fibres contain far less cellulose than does cotton (Table 10.1). The
intercellular material includes pectins, hemicelluloses and lignins. Much of this is
removed when flax or ramie is scoured. Inadequately scoured goods are difficult
to dye level because the bast fibre and the non-cellulosic impurities differ in
dyeability.
Table 10.1 Composition of typical natural cellulosic fibres [1]

Proportion of dry weight (%)
Constituent
Raw
flax
Decorticated
ramie
Grey
cotton
Cellulose
Intercellular material
Wax
Ash
Residual material
80.1
10.5
2.6
1.5
5.3
83.3
7.5
0.2
2.1
6.9
94.0
2.5
0.6
1.2
1.7
129
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COTTON/VISCOSE AND OTHER CC BLENDS
Traditional viscose filaments have been produced by extruding a solution of

sodium cellulose xanthate dissolved in aqueous sodium hydroxide through a
spinneret into a coagulating bath containing sodium sulphate and sulphuric acid.
The filaments are stretched mechanically during regeneration and their
properties are determined by the concentration of the viscose solution, the rate of
coagulation and the rate of stretching. The coagulation process is controlled by
temperature and additives such as zinc sulphate or glucose. Regular viscose
differs from cotton in being non-fibrillar, having no central lumen and having a
much lower degree of polymerisation (DP). Although consisting wholly of
cellulose, the skin and core of viscose filaments differ somewhat in
supramolecular structure. The relative proportions of skin and core vary
according to the conditions of coagulation.
The presence of viscose in blends with cotton improves the appearance by
imparting more lustre and firmness of handle. The regenerated fibre provides
additional absorbency, which is useful in towelling constructions. Apparel uses
for cotton/viscose blends include poplin shirts, blouses, dresswear, knitwear,
leisure garments, T-shirts, underwear and childrens clothing. These blends offer
comfort appeal with good wear and laundering properties. The optimum blend
composition for wear resistance is approximately 70:30 cotton/viscose.
Terry towelling may be made from 50:50 or 65:35 cotton/viscose blends for
greater absorbency than all-cotton cloths. An important traditional use for
cotton/viscose unions is in brocade material for curtains and furnishings in which
the viscose appears on the surface in the form of floral designs. These
constructions often contain both filament and staple yarns. Pile fabrics are
sometimes made with a viscose pile in a cotton backing fabric. These are an
economical alternative to wool pile/cotton backing fabrics.
Hollow viscose fibres, such as Viloft (Courtaulds), have been produced in an
attempt to simulate the natural lumen of cotton. Sodium carbonate is
incorporated in the spinning dope. When this is extruded into the acidic
coagulating bath the carbon dioxide formed inside the filament creates a
continuous hollow central channel. Careful control of the conditions of the
carbonate decomposition reaction is necessary to obtain a reproducible product
[2]. The hollow structure of the fibre imparts high torsional rigidity leading to an
attractive handle with higher bulk and fabric cover than regular viscose at the
same fabric density. Hollow viscose fibres have a lower density (1.15 g cm3) and
higher water imbibition (130%) than regular viscose (1.52 g cm3 and 90%),
giving good insulation, extra absorbency and comfort.
These characteristics make an important contribution to the appeal of cotton/
Viloft and polyester/Viloft blends. These have been exploited successfully in
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PROPERTIES AND PERFORMANCE OF CELLULOSIC FIBRES IN THEIR BLENDS
131
knitted underwear, sportswear, leisure garments, dresswear and towelling. In

roller towels, for example, a polyester/Viloft warp yarn offers substantially
greater strength than traditional cotton yet contributes even higher absorbency to
the construction [2].
Compared with cotton, regular viscose suffers from the disadvantage of much
lower breaking strength, particularly when wet. This is seldom a problem in
apparel but it renders viscose unsuitable for more critical end uses. The term
modal was introduced to describe all regenerated cellulosic fibres having
tenacities in the conditioned state and wet moduli at 5% extension above certain
defined values [1]. Modal fibres are made with an above-normal concentration
of zinc sulphate in the coagulating bath and modifiers (such as dimethylamine
or cyclohexylamine) in the spinning dope. These fibres have a higher initial wet
modulus than regular viscose but lower than that of the polynosic fibres.
Polynosic fibres have been defined as having low wet extension even under
alkaline conditions, high knot strength and a higher DP than regular viscose. The
distinctive features of their method of production include:
(1) a xanthate solution of viscosity higher than that used in the manufacture of
regular viscose, achieved using an aged pulp of intrinsically higher DP rather
than a more concentrated solution;
(2) a coagulating bath of low salt concentration with no modifiers or other
additives;
(3) a lower temperature of extrusion than regular viscose.
Under these conditions, high stretch (up to 300%) can be achieved. Polynosic
fibres are highly oriented and have stressstrain curves closely similar to those of
cotton, rather than to other regenerated cellulosic fibres. They appear to be
fibrillar in structure and are largely unaffected by dilute solutions (up to 8%) of
sodium hydroxide, which will dissolve as much as 25% of regular viscose.
Polynosic fibres show improved laundering performance and give good yarn
strength in blends with cotton but they are generally less useful for blending with
polyester fibres [2].
Modal and polynosic fibres are finding increasing application in blends with
cotton for knitgoods. Vincel (Courtaulds) in a polynosic fibre that is used alone
or in blends with cotton, viscose or polyester staple fibres. A popular blend for
apparel fabrics is 50:50 cotton/Vincel. Blends of cotton with modal fibres are
particularly important in woven dresswear and lightweight suitings. These modalrich blends (80:20 to 55:45) are usually designed to exploit the lustre, drape and
softness of the regenerated fibre, whereas in cotton-rich mixtures the strength,
washability and durability of the natural fibre make important contributions.
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The degree of swelling of modal and polynosic fibres alone and in 50:50
blends with cotton was compared with an all-cotton control in solutions of
sodium hydroxide at concentrations up to 250 g l1 and temperatures in the
range 2080C. At ambient temperature the regenerated fibres were much
more swollen than cotton and the 50:50 blends showed the expected
intermediate degree of swelling. As the temperature of treatment increased
towards 80C, all fibre types and blends showed enhanced swelling, so that
the behaviour of the individual fibres and their blends became more closely
similar. Under mercerising conditions of high alkali concentration and low
temperature for a short time, the modal fibres and cotton control behaved
similarly [3].
The adverse effects of conventional viscose manufacturing plants on the
environment has been recognised for many years. Only recently, however, has
Courtaulds plc established commercial production of a regenerated cellulosic
fibre using a non-aqueous solvent method. Tencel (Courtaulds) is a lyocell fibre
obtained by continuous dissolution of wood pulp in mesomorphic Nmethylmorpholine-N-oxide (Figure 10.1) and extrusion into a dilute aqueous
solution of the amine oxide to precipitate the regenerated fibre [4]. The diluted
solvent is then purified and reused at the continuous dissolving stage, so that the
process is environmentally innocuous.
CH3
CH2 CH2
O
N
CH2 CH2
Figure 10.1 Solvent for manufacture of lyocell regenerated cellulosic fibres
Tencel has a bright lustre and a circular cross-section. The tenacity (wet
and dry) is markedly higher than that of cotton or any other type of
regenerated cellulosic fibre (Table 10.2). The wet tenacity is only about 15%
lower than the dry value and is markedly higher than that of cotton. The
exceptionally high wet modulus results in very low shrinkage, about 2% in
warp and weft [5]. Tencel is fibrillar in structure and resembles cotton even
more closely than modal fibres in its behaviour under stress and capacity for
absorbing liquid water. Because of the close similarity between the stress
strain curves of Tencel and cotton, it can contribute to the strength of the
blended yarn even at low blend levels. An interesting feature of Tencel is that
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PROPERTIES AND PERFORMANCE OF CELLULOSIC FIBRES IN THEIR BLENDS
133
Table 10.2 Typical physical properties of cellulosic fibre types [4]

Fibre tenacity (cN tex1)
Fibre type
Wet
Dry
Elongation
(%)
Viscose
Modal
Lyocell
Cotton
1015
1921
3438
2630
2226
3436
4042
2024
2025
1315
1315
79
Moisture
regain
(%)
Water
imbibition
(%)
13
12.5
11.5
8
90
75
65
50
the conversion of fibre strength to yarn strength is considerably higher than

for other cellulosic fibre types, because of the high cohesion between the
closely packed fibres of circular cross-section in the yarn. Tencel improves
the performance of blends with cotton by enhancing strength, lustre, yarn
regularity, spinning and wear performance.
10.2 DYEING BEHAVIOUR OF CELLULOSIC FIBRES IN THEIR BLENDS

Linen and its blends with cotton have been used traditionally in fine woven
apparel and household textiles, notably tablecloths, napkins, curtains and
furnishings. Ramie/cotton blends (60:40 to 50:50) are of interest for woven or
knitted leisure clothing. Linen fabrics and blends of linen or ramie with cotton
will withstand an alkaline scour at the boil, followed if necessary by a combined
peroxide/chlorite bleach. Dyeing in rope form with direct dyes is followed by
conventional resin finishing. Treatment with liquid ammonia at 20 m min1 can
be carried out before or after dyeing to enhance the performance of the final
finish. It is essential to carefully neutralise any retained ammonia by treatment in
rope form with acetic acid solution. Effective finishing is also important to
achieve optimum wet fastness of the direct dyes [6].
The traditional growing of flax has been resumed in Saxony since 1993.
Fabrics woven from open-end yarns spun from 40% short-staple linen and 60%
modal fibres are being produced. Various preparation sequences have been
evaluated, including enzymatic desizing in a jet machine and cold padbatch
bleaching, or continuous padsteam scour-bleach treatment with alkaline
peroxide. The preferred dyeing process is exhaust dyeing with reactive dyes,
which offer excellent reproducibility, levelness, penetration and fastness
performance [7].
Direct dyes usually dye viscose and mercerised cotton preferentially because a
greater surface area is available for sorption on these substrates than on
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unmercerised cotton. The order of increasing substantivity on various cellulosic

fibres does not differ significantly from dye to dye, except in the case of
phthalocyanine blues. These show higher substantivity for cotton than for
viscose or modal fibres. This is because their affinity for regenerated cellulose is
lower in spite of its greater accessibility [8].The higher dyeability of mercerised
cotton is attributable to the lower surface charge on this substrate. This
difference is less marked at higher electrolyte concentrations but under these
conditions direct dyes show slower migration and inferior levelling.
Solidity of shade with direct dyes on cotton/viscose blends varies considerably
with dye structure but it can be controlled by adjusting salt concentration and
dyeing temperature. The substantivity of direct dyes for cellulose is
approximately inversely related to their degree of sulphonation. Direct dyes
giving good solidity on cotton/viscose blends tend to be mainly disazo
tetrasulphonates, including some copper-complex types. Pale shades present little
difficulty when dyed in the absence of salt. Solidity in deeper shades is achieved
more readily with little or no salt present at the boil.
Where salt must be used for medium and full depths in order to attain
economical exhaustion, sometimes solidity can be ensured only by dyeing at a
temperature as low at 60C. The optimum conditions vary from one dye to
another and result in reduced penetration and lower wet fastness. Blends of
mercerised cotton and viscose, however, will often give good solidity in full
depths by dyeing at the boil with only low concentrations of salt (05 g l1)
because of the higher dyeability of mercerised cotton. The development of
viscose microfibres (section 1.4.2) has enabled colour yields and reflectance
values to be obtained with direct and reactive dyes that are close to those on
cotton. As a result, the attainment of solid effects on fabrics containing viscose
microfibres and cotton is now easier than on conventional cotton/viscose blends
[9].
Solidity of shade is normally aimed at in the dyeing of cotton/viscose blends
and it is not feasible to attempt reservation of either fibre. Vat or sulphur dyes are
often used because it is generally more difficult to achieve solidity with direct or
reactive dyes. Brocades and other furnishing fabrics woven into designs formed
by raised viscose wefts on a cotton warp ground are not as critical as intimate
blends where lack of solidity gives an objectionable skittery appearance. As with
direct dyes, the degree of solidity attainable with vat dyes depends on dye
selection and conditions of application. Preferred vat dyes include acridones,
carbazoles, indanthrone blues and violanthrone blues and greens. If conventional
dyeing conditions are applied, regular viscose will invariably be dyed more
heavily than the cotton. A decrease in dyeing temperature favours the cotton, so
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DYEING BEHAVIOUR OF CELLULOSIC FIBRES IN THEIR BLENDS
135
cold-dyeing vat dyes are more suitable in general. Pigment padding methods tend
to give better solidity than batchwise dyeing on the jig at 3050C.
The proportions of crystalline material in regenerated cellulosic fibres are
about 40% in regular viscose, 50% in modal fibres and 65% in polynosics,
compared with 70% in cotton. As crystallinity increases the water imbibition
and dyeability decrease accordingly. Thus direct dye uptake under a given set of
conditions generally increases in the order: cotton < polynosics < modal fibres <
regular viscose.
The uptake of selected direct dyes by the hollow viscose fibre Viloft
(Courtaulds) and two crimped modal fibres Avril (Avtex Fibers) and Prima (ITT
Rayonier) has been compared with cotton and regular viscose as controls (Table
10.3). CI Direct Red 80 is a tetrazo hexasulphonate of unusually high affinity,
whereas Blue 218 (a copper-complex disazo tetrasulphonate) and Yellow 106
have only moderate affinity for cellulose. The percentage exhaustion at
equilibrium was consistently lower on cotton than on any of the regenerated
cellulosic fibres, as expected. The dyeability of Viloft was closely similar to that
of regular viscose. Prima was consistently more dyeable than Avril, which was in
turn more dyeable than regular or hollow viscose.
Table 10.3 Differences in dyeability between various cellulosic

fibres [10]
Equilibrium exhaustion (%) of CI Direct
Fibre
Yellow 106
Red 80
Blue 218
Prima
Avril
Viscose
Viloft
Cotton
80
74
66
66
59
99
92
90
88
84
74
66
66
66
50
Methods of dyeing modal fibres and cotton/modal blends with direct, reactive
or vat dyes have been reviewed [11]. The selection of reactive dyes for the
production of shadow effects on 50:50 cotton/modal blends was outlined.
Exhaust dyeing systems for loose stock, yarn, knitted and woven fabrics were
described. Several padding methods on fabrics made from these blends were
detailed, including padbatch or padthermofix with reactive dyes, padjig or
padsteam with vat dyes, and paddevelop with vat leuco esters.
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The dye affinity of polynosic fibres such as Vincel (Courtaulds) can be

enhanced by pretreatment with sodium hydroxide solution. The concentration
should not exceed 60 g l1 or there may be a deterioration in physical properties.
Most dyes are absorbed more slowly and migrate less readily on Vincel than on
regular viscose. Blends of Vincel with either cotton or viscose can be dyed in solid
shades with carefully selected direct, reactive, vat or sulphur dyes, many dyes
being most suitable at specific depths of shade. The fastness properties of most of
these dyes are the same on Vincel and regular viscose. It is not practicable to dye
Vincel and reserve the other cellulosic fibre, although attractive shadow effects
can be produced with selected dyes and controlled dyeing conditions.
A minority of direct dyes, especially from the self-levelling and temperaturecontrollable classes, will give solid shades in pale depths on cotton/Vincel.
Selected high-reactivity dyes can also be used, either by padbatch or exhaust
application. Certain bright reactive dyes appear slightly duller on Vincel than on
cotton or viscose. Vat dyes are usually selected from those applicable at 50C or
higher temperatures and are preferably applied by pigment padding to improve
penetration and solidity of shade. Selected sulphur dyes can be used in medium
and full depths.
Any of the dye classes used for cotton can be applied to Tencel (Courtaulds)
lyocell fibre. Consistency of Tencel in terms of dyeability is routinely monitored
using dyes known to be sensitive to potential variations in this important
property [4]. In exhaust dyeing the colour yield on Tencel is similar to that on
viscose and greater than that on cotton. Thus care is required when dyeing
cotton/Tencel blends because of preferential uptake by Tencel. This makes
shadow effects much easier to achieve than solidity in exhaust dyeing. Viscose/
Tencel blends, on the other hand, readily give solid effects.
The yield of reactive dyes on Tencel is exceptional by all dyeing methods and
especially by printing. Thus alkaline treatment analogous to causticisation of
viscose or mercerisation of cotton is not necessary for Tencel. Blends of cotton
and Tencel can be mercerised, however. By careful modification of conventional
semi-continuous dyeing methods, solid dyeings with reactive dyes can be
achieved on 50:50 cotton/Tencel, using either padbatch application or a sodium
metasilicate development technique.
10.3 DYEING METHODS AND DYE SELECTION FOR CC BLENDS

Blends of cellulosic fibres with one other are ideally suitable for shadow effects,
especially those in which unmercerised cotton is the paler component and a
regenerated cellulosic fibre is the deeper one. A wide selection of dyes and dyeing
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DYEING METHODS AND DYE SELECTION FOR CC BLENDS
137
conditions yields satisfactory solidity on blends of mercerised cotton or regular

viscose with one another or with other regenerated cellulosics. Dye selection and
dyeing techniques are more restricted when dyeing solid effects on unmercerised
cotton blends (Table 10.4).
Table 10.4 Dye selections for CC blends

Blend
Colour effect
Dye selection
Cotton/linen
Cotton/ramie
Solid or shadow
Direct dyes or vat dyes
Mercerised
cotton/viscose
Solid
Direct dyes at low salt concentration

at the boil
Unmercerised
cotton/viscose
Solid
Disazo tetrasulphonated direct dyes

at 60C
Cotton/viscose
Solid or shadow
Selected vat dyes at 2030C
Cotton/viscose
microfibres
Solid or shadow
Direct or reactive dyes
Cotton/modal
Solid or shadow
Direct, reactive or vat dyes
Cotton/polynosic
Cotton/lyocell
Solid
Selected self-levelling and

temperature-controllable direct dyes
Selected vat dyes at 50C
Selected high-reactivity dyes by padbatch
Viscose/polynosic
Viscose/lyocell
Solid or shadow
Direct, reactive or vat dyes
10.4 REFERENCES
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.

R Aitken, J.S.D.C., 99 (1983) 150.
D Bechter, H Herlinger and E Pelz, Textil Praxis, 41 (1986) 59.
J M Taylor and P Mears, J.S.D.C., 107 (1991) 64; Chem. Brit. 30 (1994) 628.
I D Holme, Dyer, 178 (Oct 1993) 13.
G Kratz and A Funder, Melliand Textilber., 68 (1987) 775.
H Hellwich, Melliand Textilber., 78 (1997) 346.
O Annen, H Gerber and B Seuthe, Melliand Textilber., 72 (1991) 1015; J.S.D.C., 108 (1992) 215.
D Hildebrand and F Sthr, Melliand Textilber., 73 (1992) 281.
V Davis and R R King, J.S.D.C., 100 (1984) 342.
W Schaumann, Textilveredlung, 22 (1987) 15.
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POLYESTER/WOOL AND OTHER DA BLENDS
CHAPTER 11
Polyester/wool and other DA blends
11.1 DYEING OF POLYESTER/WOOL BLENDS

11.1.1 Properties and preparation of polyester/wool blends
The achievement of a desirable combination of physical properties is usually the
main justification for utilising a DA blend. Strength, abrasion resistance, crease
recovery and durable pleating characteristics are contributed by the polyester
fibre component. Virtually all goods made from polyester/wool blends are
intended for outerwear, typically suitings, dresses and skirts. Modified polyester
fibres with improved resistance to pilling have been blended with wool in knitted
jersey dresswear. This can eliminate the need to singe polyester/wool fabrics, a
treatment not usually available in wool processing. Singeing may also introduce
dyeability differences. Unlike all-wool jersey, polyester/wool fabrics can often be
dyed on the beam and these blends show better dimensional stability on washing.
Such blends were developed in the early 1950s and have been established in
woven suitings ever since. The important 55:45 polyester/wool blend arose from
the realisation that this is the minimum polyester content that allows durable
pleating of the blend fabric. Reducing the wool content lowers the aesthetic
appeal but decreasing the polyester proportion makes it no longer possible to
retain pleated effects after washing. The most important blend in the USA is an
80:20 fabric, composed of a textured filament polyester warp and a 55:45
polyester/wool blended staple weft. In Western Europe another luxurious fabric
is a 20:80 blend, containing a 55:45 blended staple warp and a pure wool weft.
Smaller market niches exist, e.g. a 40:60 polyester/wool blend for luxury
automotive fabrics. This specific outlet puts high demands on both fabric and
dye performance. To meet these demands the two fibres are usually dyed
separately as loose stock or tops and subsequently blended [1].
In recent years the re-discovery of natural fibres has given increased emphasis
to the aesthetic appeal of wool-rich blends, rather than the optimum balance of
comfort, wear and easy-care properties that is provided by the popular 55:45
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DYEING OF POLYESTER/WOOL BLENDS
139
blend. In these blends the content of polyester may be as low as 2030% and the
production of solid shades using conventional one-bath dyeing methods can be
quite difficult. The polyester component is often dyed much weaker in depth
than expected [2].
Polyester fibres will withstand the normal processes used to prepare wool
fabrics, such as carbonising and milling. The stentering temperature must not be
too high when carbonising polyester/wool fabrics, however, because appreciable
damage and yellowing of the polyester component may occur under such
conditions. Neutralised fabrics should have a slightly acidic pH to avoid possible
damage to the wool [3]. It is usual to give a crabbing treatment to polyester/wool
fabrics to minimise creasing during winch or jet scouring and subsequent dyeing.
Jet dyeing has a mild milling action on these goods and yields a softer handle
compared with the somewhat crisper feel characteristic of beam-dyed fabrics.
Careful preparation of the fabric prior to beam dyeing is most important.
Preshrinking is necessary to prevent any moir effect (water marking) that may
arise from differential shrinkage on the beam [4]. Presetting at 170190C
protects against rope creasing or possible shrinkage in beam dyeing. Higher
setting temperatures cause yellowing of the wool. Heat setting improves the
handle, resilience, crease resistance, dimensional stability, shrink resistance and
pilling performance of the goods. It does, however, reduce the dyeability of the
polyester component after setting. This may aggravate wool staining.
Scouring with an anionic detergent and soda ash eliminates the risk of residual
nonionic detergent being carried out into the dyebath and adversely affecting the
dispersion stability of disperse dyes. Polyester/wool knitted fabrics may be
scoured in the jet machine with ammonia at 40C before dyeing. Bright and/or
pastel shades may require a preliminary mild bleaching treatment. The wool may
be given either an oxidative or a reductive bleach, whereas the polyester only
requires treatment with a fluorescent brightening agent.
11.1.2 Stages at which dyeing may be carried out

The dyer of polyester/wool has three options:
(1) Dyeing each fibre type separately as loose stock or tops before blending.
(2) Dyeing as an intimately blended yarn.
(3) Dyeing as fabric in rope form or open width.
Dyeing separately prior to blending allows the choice of dyes of maximum
fastness, with level dyeing performance being of secondary importance. The
polyester can be dyed at 130C with high-energy disperse dyes of maximum
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sublimation fastness. Wool as loose stock or tops can be dyed with chrome
reactive, 1:2 metal-complex or milling acid dyes.
Dyeing in yarn or piece form allows greater flexibility with shorter lead times
in production and lower stockholding. The most important factor in polyester/
wool yarn dyeing is shrinkage of the yarn, for which 35% is considered
acceptable [5]. In contrast to polyester/wool fabrics, yarns blended from these
two fibres are not heat set before dyeing. Since disperse dyes show higher affinity
for unset polyester, high- or intermediate-energy dyes can be applied to the yarn
at 105C to give higher fastness to sublimation and less staining of the wool.
Dyeing at these later stages (especially as fabric) demands better level dyeing
behaviour from the dyes. This introduces constraints on the level of fastness
attainable from the disperse dyes, which must be low- or intermediate-energy
types in piece dyeing.
Beam dyeing is particularly suited to flat woven constructions and those
fabrics where felting could be a problem, i.e. wool-rich blends. Since the fabric is
held stationary and the liquor percolates through it, there is no mechanical action
on the cloth to induce felting shrinkage. The beam is less effective on structured
fabrics where the jet or overflow machine helps to retain fabric handle and bulk.
A specific problem associated with dyeing polyester/wool yarn or piece in
enclosed machinery at temperatures above the boil is control of dyebath pH.
Chemical changes brought about in wool by heat can cause the pH to rise. It if
rises above pH 7 the disperse dye dispersion can become unstable, as well as
causing further damage to the wool. Acetateacetic acid buffer systems are often
used for their economy and relative freedom from effluent problems.
11.1.3 Selection of dyes and carriers
The dyeing of polyester/wool is almost always directed towards solidity rather
than differential effects, because unfortunately the most troublesome of all crossstaining problems is the staining of wool by disperse dyes (section 3.4). This
blend is most frequently dyed using disperse dyes for the polyester and milling
acid or 1:2 metal-complex dyes for the wool. Matched formulations containing
both disperse and anionic dyes are commercially available. Since neutral to
slightly acidic conditions are required for both dye classes there are no conflicting
pH requirements. The critical parameter is that of temperature, since the top
temperature (130C) that would allow all disperse dyes to be used would also
cause unacceptable degradation of the wool. A compromise temperature within
the range 95120C is adopted and disperse dyes of low- or intermediate-energy
classes are selected to perform well at the chosen temperature.
The temperature at which the dyeing machine operates is the most important
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factor affecting the length of the dyeing process, the choice and colour yield of
the disperse dyes and the amount of carrier required. The two important factors
governing disperse dye selection are:
(1) the temperature at which the polyester/wool is to be dyed;
(2) the degree to which the disperse dye stains the wool.
The higher the dyebath temperature, the wider the choice of dyes, particularly for
medium or heavy depths of shade. Disperse dyes without carrier have virtually
no substantivity for polyester below 85C but above this point the dyeing rate
doubles for each 5C rise in temperature. The slow rate of diffusion of dyes into
the polyester is an indirect cause of the preferential staining of wool below the
boil. Even at low temperatures wool is rapidly penetrated by disperse dyes,
especially if dyed in the presence of a carrier. Some low-energy azo disperse dyes
are taken up by wool extremely rapidly.
High-energy dyes do not build up satisfactorily on polyester at the boil
even in the presence of a carrier, compared with low-energy dyes with better
levelling properties but lower fastness to heat. Only pale depths can be dyed
with intermediate-energy dyes at the boil. Medium depths with these dyes
require a dyeing temperature of 105C at least. Good carrier-dyeing
properties and low staining or ease of clearing from wool are given by
selected intermediate-energy dyes of the nitro, monoazo and especially
anthraquinone types. Many anthraquinone dyes are absorbed quickly onto
the polyester surface. Those blue and navy dyes that build up satisfactorily at
the boil tend to be anthraquinone-based and relatively expensive to
manufacture.
The inherently more cost-effective azo types will not build up to full depths at
the boil, showing inferior levelling and more staining of the wool. To gain the
benefit of this cost-effectiveness, it is necessary to dye at 105C or above. Full
navy or black shades are best dyed with intermediate-energy dyes at 110120C
using a wool protective agent. If maximum colour yield and fastness are
essential, high-energy dyes should be applied to the polyester at 130C before
blending with predyed wool. Even if the depth on the polyester is slightly heavier,
the blend may still give an appearance of solidity because of the higher lustre of
the synthetic fibre.
Several factors must be considered in selecting a suitable carrier for polyester/
wool dyeing. These include the types of dyeing equipment available, the degree
of staining of the wool and the relation between dye yield and applied
concentration of carrier. Carriers exert a plasticising influence on the polyester
structure and cause the glass-transition temperature to be lowered, although the
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enhanced swelling that accompanies carrier treatment is not necessarily

associated with acceleration of diffusion of the dyes into the fibre. An important
aspect of carrier dyeing is the concentrationefficiency profile, i.e. the range of
carrier concentrations within which maximum acceleration of dyeing takes
place. This occurs when the voids in the polyester fibre become saturated with
carrier [1]. Further additions of carrier above this saturation limit merely result in
a corresponding increase in carrier concentration in the dyebath. This is
accompanied by a restraining action on the disperse dyes present. This is
detrimental to colour yield and hence wastes both carrier and dye.
It is known that o-phenylphenol tends to accentuate wool staining more than
methylnaphthalene or phenolic esters like methyl cresotinate. These are in turn
inferior in this respect to diphenyl, trichlorobenzene and the inert esters like butyl
benzoate. Diphenyl, o-phenylphenol and trichlorobenzene tend to cause more
wool damage and yellowing on exposure to light than do ester carriers.
Nevertheless o-phenylphenol has been much used traditionally for polyester/
wool dyeing on ground of cost-effectiveness. Odour has been a problem with
methylnaphthalene or methyl salicylate and trichlorobenzene has been long
regarded as a serious toxic hazard. Diphenyl has tended to give localised carrier
spotting and the esters are inferior in cost-effectiveness.
There is relatively little cross-staining of the polyester fibre by anionic dyes for
wool. Levelling acid dyes give negligible staining and the reserve of polyester by
1:1 metal-complex or milling acid dyes is good to very good, with 1:2 metalcomplexes and chrome dyes moderate to good in general. Generally speaking,
unsulphonated 1:2 metal-complex dyes stain polyester more than their
sulphonated analogues and premetallised azo dyes more so than unmetallised
azo acid dyes. Anionic dyes begin to dye the wool at 4050C and dyebath
exhaustion is virtually complete after about 30 minutes at the boil. Dye selection
for wool is almost independent of dyeing temperature.
Wool dye selection can thus be made on grounds of wet fastness, since the
levelling and coverage is adequate under the conditions required to obtain a
satisfactory dyeing of the polyester fibre. Neutral dyeing of polyester/wool blends
is not recommended for three reasons:
(1) Damage of the wool is much less in the isoelectric region (pH 4.55) compared
with pH 68 conditions.
(2) The release of wool breakdown products causes the dyebath pH to rise,
resulting in instability of the disperse dye dispersion.
(3) Certain azo disperse dyes susceptible to reduction are adversely affected by
high temperature dyeing, as a result of the progressive hydrolysis of cystine
residues in wool.
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In the dyeing of these blends an optimum pH 55.5 should be maintained when

using sensitive azo disperse dyes and, if necessary, a reduction inhibitor such as
formaldehyde should be present in the dyebath [6].
Neutral-dyeing 1:2 metal-complex and milling acid dyes are preferred for
polyester/wool because 1:1 metal-complex and levelling acid dyes require
strongly acidic dyebaths where disperse dye staining is severe. Chrome dyes are
given an oxidative aftertreatment that can damage the wool and change the hue
of the dyed material [7]. A one-bath method for polyester/wool yarn using
disperse and chrome dyes allows full reduction clearing to eliminate loose
disperse dye without causing a significant shade change or loss of depth of the
wool dyeing [8].
Premetallised and milling acid dyes for wool tend to exhaust too rapidly at pH
4.55, especially the unsulphonated types and pale or medium depths of
monosulphonated 1:2 metal-complex dyes, resulting in unlevel dyeings. Disperse
dye staining is also more severe. For these reasons the dyebath is normally
buffered at pH 5.05.5, just above the ideal isoelectric zone, necessitating
careful control of treatment time. Most milling acid dyes show satisfactory
exhaustion and levelling after 10 minutes at 110C in this region of pH.
Thus premetallised dyes, supplemented by selected milling acid dyes in bright
shades, are widely used. The choice between unsulphonated, monosulphonated
or disulphonated 1:2 metal-complex types is related to dyebath conditions,
coverage and levelling requirements, as well as the target level of wet fastness in
subsequent tests. Unsulphonated premetallised dyes applied from a weakly acidic
bath show better levelling properties than sulphonated types but are more
expensive and lower in wet fastness, particularly in respect of staining of adjacent
nylon, a common lining material in polyester/wool garments.
Monosulphonated 1:2 metal-complex dyes have good coverage and levelling
properties at the high temperatures necessary for polyester/wool dyeing as well as
good wet fastness and better cost-effectiveness than unsulphonated analogues.
They are usually applied within the range of pH 56, according to depth of
shade. Disulphonated 1:2 premetallised dyes show more limited coverage,
although this is still adequate at high temperature. The wet fastness is the best of
the three types and these dyes are usually the most cost-effective. Disulphonated
dyes are typically used for full depths and are best applied at pH 5.
The choice between the one-bath and two-bath methods with disperse and
neutral-dyeing acid dyes depends on applied depth and target fastness
requirements. The one-bath method is more economical and gives satisfactory
fastness properties in pale or medium depths. The two-bath sequence gives more
reproducible solidity or brighter contrast effects as well as optimum fastness in
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full depths. In the one-bath process the disperse and acid dyes are applied
together at pH 56 with a dinaphthylmethanedisulphonate dispersing agent and
the selected type and concentration of carrier. The disperse dye stain is cleared
from the wool with a nonionic detergent at 6070C. Low-energy disperse dyes
of relatively low affinity for polyester tend to cause more staining in the one-bath
process than high-energy dyes, particularly at longer liquor ratios.
In the two-bath method the polyester component is dyed conventionally with
the disperse dyes alone under the conditions specified above. Surface deposition
on the polyester and the stain on the wool are removed by reduction clearing at
4550C with sodium dithionite, ammonia and nonionic detergent. The wool is
then cross-dyed at the boil with 1:2 metal-complex or milling acid dyes from an
ammonium acetateacetic acid bath containing an alkylamine polyoxyethylene
levelling agent. The disperse dyes selected for the two-bath method should show
minimum transfer from polyester to wool under these conditions. Dyes of high
fastness to sublimation do not transfer so readily as those of moderate fastness.
Quite recently, a series of new benzothienylazo disperse dyes (Figure 11.1) has
been evaluated [9]. These are capable of dyeing both components of a polyester/
wool blend to yield satisfactory exhaustion and fastness (Table 11.1). Dyeing
was carried out at pH 4.5 and the boil in the presence of methyl salicylate as
carrier. The wool was invariably dyed more deeply than the polyester,
presumably because all the coupling components selected were phenolic types
with some anionic character. Substituted aniline-type couplers are almost always
used in the synthesis of conventional monoazo disperse dyes. In view of the
limited range of relatively dull hues obtained, this approach is not of much
practical value so far unless dyes of brighter hue, especially blues, can be
discovered to augment them.
X
N
S
N R
Figure 11.1 Benzothienylazo dyes for single-class polyester/wool dyeing
11.1.4 Wool damage and wool protective agents

The dyeing of polyester/wool blends presents difficulties of severe damage of
wool at the top temperature normally used to dye polyester with high-energy
dyes. The range of disperse dyes performing adequately in carrier dyeing at
105C is limited. Some carriers are toxic (e.g. trichlorobenzene) and all carriers
are harmful in the working environment. There are considerable advantages to
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Table 11.1 Hue and fastness properties of benzothienylazo dyes [9]

Light fastness
Wash fastness
Substituent
(X)
Coupler
(R)
Hue on
polyester/wool
P/W W
P/W W
CN
CN
CN
CN
CN
COOEt
COOEt
COOEt
COOEt
COOEt
Resorcinol
Naphthalene-2,3-diol
8-Hydroxyquinoline
2-Naphthol
Resorcinol
8-Hydroxyquinoline
4-Chloro-1-naphthol
Yellowish orange
Reddish brown
Reddish orange
Reddish violet
Reddish orange
Reddish brown
Reddish violet
Reddish violet
Reddish brown
Reddish violet
7
7
6
7
7
6
6
6
7
7
6
7
7
6
7
7
6
7
7
7
4
4
5
4
4
4
4
5
4
4
5
5
4
5
4
5
4
5
5
5
6
6
7
7
7
6
7
6
6
6
5
5
5
5
5
5
5
5
5
4
P = polyester
W = wool
P/W = polyester/wool
be gained by dyeing at 110C or above, in terms of colour yield, levelling,

fastness and shorter processing cycles. Against this must be balanced the physical
and chemical degradation of the wool keratin when treated under these
conditions. Aqueous hydrolysis results in breakage of electrostatic linkages
between oppositely charged sidechains. Dyeing wool at the boil and pH 24
results mainly in hydrolysis of peptide bonds (depolymerisation). At pH 5 and
above the main effect is hydrolysis of the disulphide bonds in cystine units
(breaking of crosslinks). Damage is considerable at 120C and any pH.
These chemical changes result in lower strength and abrasion resistance,
accompanied by increased elongation, alkali solubility and yellowing. The extent
of damage to the wool depends on dyebath temperature, pH and treatment time.
The degree of yellowing of the wool is greater at 120C than at 110C but the
effect of yellowing is less critical when dyeing in dark shades. For these dyeings
the higher temperature favours higher exhaustion of intermediate-energy
disperse dyes. Such problems are especially acute with ultra-lightweight
dresswear made from polyester microfibres blended with exceptionally fine
wool.
In order to minimise wool damage, it is necessary to add a reagent that will
chemically modify the molecular structure of the wool keratin, stabilising certain
reactive sidechains and forming new crosslinks that replace those lost during
hydrolysis. For many years, formaldehyde was the only reagent to confer
effective protection in this way (Scheme 11.1). The crosslinking action of
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CH2S
[wool]
SCH2
H2O
[wool]
Cystine
(CH2)4
[wool]
CH2SH + HSCH2
[wool]
Cysteine (CYS)
[wool]
CH2SCH2SCH2
[wool]
CYS CYS link
HCHO
(CH2)4
HCHO
NH2
Lysine (LYS)
[wool]
[wool]
LYS
NHCH2OH
[wool]
(CH2)4NHCH2NH(CH2)4
LYS
Methylollysine
[wool]
LYS link
CH2OH
2HCHO
[wool] CH2
[wool] CH2
OH
Tyrosine (TYR)
OH
Dimethyloltyrosine
CH2OH
LYS
[wool] CH2
CH2OH
N
H
[wool] CH2
Tryptophan (TRY)
CH2NH(CH2)4
TYR
2HCHO
[wool]
OH
CH2
[wool]
[wool]
LYS link
CH2
LYS
HOCH2
HOCH2
N
CH2OH
CH2NH(CH2)4
Dimethyloltryptophan
TRY
[wool]
LYS link
Scheme 11.1
formaldehyde causes embrittlement of wool, slightly reducing the elongation at

break and markedly lowering the urea-bisulphite solubility. When dyeing in the
presence of 5% o.w.f. formaldehyde (30% solution), the treatment time should
not exceed 6090 minutes at 110C or 3040 minutes at 120C.
Several further precautions are necessary if formaldehyde is added:
(1) Careful dye selection is important because certain dyes undergo a colour
change in the presence of formaldehyde at 110120C.
(2) Treatment should be within the isoelectric region for wool (pH 4.55) and
the maximum permitted dyeing time should not be exceeded.
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(3) Ammonium salts for pH control should be replaced by an acetateacetic

acid or mixed phosphate buffer, because ammonia reacts with formaldehyde to form hexamethylene tetramine.
(4) Formaldehyde vapour is environmentally hazardous and this increasingly
restricts the circumstances in which it can be used. This trend favours
the replacement of formaldehyde by precursor compounds of the
N-methylolamide class. Disadvantages of this process include residual
odour, variations in fabric strength and harshness of handle, especially with
beam-dyed fabrics [10].
The leading formaldehyde precursor used for this purpose is
dimethylolethyleneurea (DMEU). This functions as a wool protective agent by
slow decomposition to release formaldehyde into the dyebath. There is little
release of the active species +CH2OH at pH 46 and 70C but at
110120C DMEU is almost completely dissociated into ethyleneurea and
formaldehyde (Scheme 11.2).
HOH2C N
N CH2OH
2H+
NH + 2 +CH2OH
HN
C
DMEU
EU
Scheme 11.2
HO
HOH2C N
HO
OH
N CH2OH
2H+
OH
HN
C
NH + 2 +CH2OH
DMDHEU
DHEU
Scheme 11.3
The addition of dimethyloldihydroxyethyleneurea (DMDHEU) when dyeing

polyester/wool permits treatment for up to one hour at 120C, resulting in
improved colour yields on the polyester component without detrimental effect on
the physical properties and structure of the wool. By a similar mechanism
(Scheme 11.3), DMDHEU acts as a stabiliser for the wool in pressure dyeing and
accelerates the rate of dyeing of the polyester fibre without adversely affecting the
equilibrium exhaustion of the acid dyes [11].
Reactive dyes also exert a protective effect on wool keratin. They are believed
to minimise damage by reacting with the cysteine residues formed by cystine
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148
hydrolysis (Scheme 11.1). This concept has been exploited to develop colourless
protective agents that imitate the behaviour of reactive dyes [12]. These more
sophisticated products are likely to be less cost-effective than formaldehyde
precursors but they do avoid the hazards of exposure to formaldehyde vapour.
In a recent investigation of this problem, botany wool fabrics were treated
with solutions of potential protective agents at 120C or 130C and pH 4. Wool
damage was assessed in terms of tear strength and wet bursting strength. The
addition of either potassium bromate (KBrO3), to counteract the reductive
hydrolysis of cystine disulphide crosslinks, or sodium hydrogen maleate
(HOOCCH=CHCOONa), to react with the thiol groups of the cysteine
formed, improved the strength retention. Both products caused stiffening of the
fabric but the handle of the bromate-treated wool was superior to that treated
with sodium hydrogen maleate [13]. Dimethylolethyleneurea and selected
vinylsulphone and bromoacrylamide reactive dyes gave some protection but
the wool damage was still substantial at 130C.
11.1.5 Future prospects for polyester/wool blends
The availability of deep-dye and basic-dyeable polyester yarns (section 5.1) has
widened the range of possibilities of fabric design in piece-dyed polyester/wool.
Deep-dye polyester staple fibres blended with wool can be dyed without the cost
or pollution problems associated with carriers and pressure-dyeing equipment is
not essential. The melting point and initial modulus of deep-dye polyester,
however, are lower than the normal fibre. Trevira 350 (HOE) is a low-pill staple
polyester of high dyeability but lower tensile strength and resistance to abrasion
than the standard homopolymer. Pretreatment of Trevira 350/wool blends entails
an emulsified solvent scour to remove oil stains, followed by drying and heat
setting. The dyebath is set at pH 56 with a levelling agent and a crease lubricant.
A sequestering agent is not normally required. The wool component is often
dyed with 1:2 metal-complex dyes. Dyeing is generally carried out on an
overflow machine at 105C. Under these conditions the colour yield on Trevira
350 is 510% higher than on standard polyester [14].
Carriers have been widely recognised to be injurious to the health of
operatives working with them. Carrier vapours are hazardous and pollute the
environment where they are used. Residual traces present in the dyed fabric may
be released on subsequent heat treatment. These products are being increasingly
restricted from use in sophisticated markets. Polyester/wool fabrics may still be
dyed with carriers in those developing countries where environmental laws are
less rigorous than in highly developed economies. This is typical of a general
trend in which harmful products or processes that have been abandoned in
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developed countries for environmental reasons may still be undertaken in lowwage or less-regulated industries.
Several possible options exist to minimise the future use of carriers by
polyester/wool dyers. These include:
(1) Improved carriers with no significant environmental problems may be
developed, such as ethylenediaminetetramethylphosphonic acid (EDTMP).
The surprising effectiveness of this compound (Figure 11.2) in enhancing the
uptake of disperse dyes by polyester fibres [15] has not yet been demonstrated
on a commercial scale.
(2) Improved wool protective agents may be developed for use in dyebaths at
120C. The existing products intended for this purpose are not impressively
effective (section 11.1.4).
(3) Improved deep-dye polyester fibres may be developed for dyeing in blends
with wool at 105C or lower temperatures. The existing variants of this type
are rather costly and show other disadvantages (section 5.1).
(4) Producer-coloured or stock-dyed polyester may be blended with scoured
wool that may be cross-dyed later in yarn or piece form. This approach is
less versatile than those listed above.
(5) Producer-coloured or stock-dyed polyester may be blended with wool
already predyed as loose stock or tops. This is even less versatile but there
are no restrictions on dye selection and this approach yields a product of
maximum fastness.
O
HO P
O
H2C
HO
H2C
P OH
OH
N CH2CH2 N
O
HO P
CH2
O
CH2
P OH
OH
HO
EDTMP
Figure 11.2 Potential carrier to enhance disperse dye uptake
11.2 BLENDS OF CELLULOSE ACETATE OR TRIACETATE WITH WOOL

Worsted-spun blends of cellulose acetate/wool are cheap and attractive for handknitting yarns. The full handle, elastic recovery and resilience of knitted wool are
not much affected by inclusion of 3040% cellulose acetate fibre. The acetate
component of the blend contributes improvements in crease recovery and
dimensional stability during washing. Blends of 70:30 wool/acetate became
important for a time in woven carpet constructions. Although more expensive
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than viscose, cellulose acetate offered better resilience and coverage compared
with wool/viscose blends [16]. Apparel end uses such as blouses, skirts and
suitings are made from blends of wool with cellulose acetate or triacetate.
Triacetate/wool is used for dresswear and leisure clothing, but this blend is less
important than acetate/wool or polyester/wool. Triacetate/wool fabrics have
good crease recovery and dimensional stability (Figure 1.1), but wool is degraded
by the S finish usually given to 100% triacetate fabrics. This is a surface
saponification in 3% sodium hydroxide solution at 8090C, often given as an
antistatic and antisoiling treatment. It is difficult to set triacetate/wool fabrics
without damaging the wool. Durable pleating can be introduced if the triacetate
content exceeds 60%, however, and triacetate/wool is more resistant than
acetate/wool to the boiling conditions necessary to dye the wool satisfactorily.
Cellulose acetate/wool fabrics will not withstand carbonising. The fabrics are
easily damaged and scouring or milling processes must be carried out with
minimum mechanical friction under mild conditions of alkalinity and temperature. A suitable sequence is:
(1) crabbing at pH 56 and 8085C with an alkylphenol polyoxyethylene;
(2) scouring at 4050C with ammonia and a nonionic detergent.
The staining of wool by disperse dyes increases with decreasing pH and becomes
particularly serious if the saturation limit of the cellulose acetate is exceeded. The
acid conditions at the boil required to apply 1:1 metal-complex or levelling acid
dyes to wool would damage cellulose acetate and cause more severe disperse dye
staining of the wool. Pale and medium depths are dyed at 8590C or below to
avoid loss of lustre by the acetate fibres. Full depths must be dyed at the boil to
achieve optimum fastness of the anionic dyes on the wool, but the decreased
lustre of the acetate component is less obvious in full depths.
Disperse dyes are absorbed mainly by the acetate component below the boil,
but migration in favour of the wool proceeds when the boil is reached. On
prolonged boiling some migration back to the cellulose acetate may occur if the
saturation limit has not been exceeded, but this is usually accompanied by
damage to the acetate fibre. Disperse dyes for cellulose acetate giving minimum
staining of wool are mainly low-energy (Mr 220300) monoazo, nitro or
quinoline yellows and oranges, together with intermediate-energy (Mr 300380)
monoazo reds and anthraquinone violets, blues and greens.
Knitting yarns normally require a one-bath method with disperse and acid
dyes to give either solidity of shade or contrast effects, or with acid dyes alone to
give reservation of the acetate. Colour contrast effects are often a feature of twofold acetate/wool yarns and these can usually be achieved by dyeing the fibres
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BLENDS OF CELLULOSE ACETATE OR TRIACETATE WITH WOOL
151
simultaneously. The dyes for wool can be milling acid or 1:2 metal-complex
types, according to brightness and wet fastness required. Neutral-dyeing milling
acid dyes of Mr 550850, mainly disulphonates of disazo, anthraquinone,
xanthene or triarylmethane chromogens are used for acetate reserve effects, or
for shadow and contrast effects in conjunction with disperse dyes.
The disperse and milling acid dyes are applied at pH 56 from an ammonium
acetateacetic acid bath with an alkanol polyoxyethylene dispersing agent.
Neutral-dyeing 1:2 metal-complex dyes are applied in a similar way at pH 67
(ammonium acetate) with a weakly cationic alkylamine polyoxyethylene
levelling agent. The surface staining of the wool can be cleared by scouring with
a nonionic detergent at 4050C. If necessary, sodium dithionite may be added
for more effective clearing, especially if azo disperse dyes are present. Brighter
contrast effects and better fastness in full depths are achieved by dyeing the
cellulose acetate first, giving an intermediate clear and then dyeing the wool at
pH 67 in a fresh bath. The disperse dyes on the acetate must be selected to
withstand these cross-dyeing conditions without migrating to the wool.
The tendency of cellulose acetate to delustre in aqueous treatments at
temperatures above 85C has always been a problem for the dyers of blends in
which the other fibre gives optimum dyeability under these conditions. This has
been overcome by the introduction in 1987 of Xtol (Courtaulds) fibre. This can
be dyed at the boil without delustring. The physical properties of Xtol are
identical with those of conventional cellulose acetate fibres. Thus it retains the
soft handle, rich lustre and comfort properties of traditional acetate apparel and
conventional scouring and finishing processes can still be used.
The stability at temperatures up to the boil allows a much wider selection of
disperse dyes to be used on Xtol. The restriction of conventional acetate to 85C
meant that only disperse dyes that exhausted well at that temperature, i.e. the
low-energy types with only moderate to poor wet fastness, could be used. Many
of the higher-energy dyes developed for polyester dyeing can be used on Xtol and
these dyeings show excellent fastness to washing at 50C [17].
Intimate blends of wool and cellulose triacetate are usually spun on the
worsted system and then piece-dyed for solidity, contrast or reserve effects.
The cross-staining of wool with disperse dyes is more pronounced in these
blends than in wool/acetate blends, because the dyeing rate on triacetate is
so much slower. Carriers will accelerate this rate but their use is deprecated
on environmental grounds. Before dyeing, triacetate/wool fabrics are
scoured at 5060C with ammonia and an anionic detergent. Triacetate is
more resistant than the secondary acetate to wool dyeing conditions, but to
ensure preferential dyeing of triacetate by the disperse dyes it is essential to
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dye this blend at 105C, or at the boil with a carrier. These conditions cause
more severe disperse dye staining than in cellulose acetate/wool blends at
8590C. Cross-staining of the wool can be minimised by including a
nonionic dispersant in the dyebath. Recommended disperse dyes of the
intermediate-energy class (Mr 300400) are mainly nitrodiphenylamine
yellows, monoazo reds and anthraquinone blues.
In a one-bath method with selected disperse and milling acid dyes in pale or
medium depths, both classes of dyes are applied together at the boil and pH 67
(ammonium acetate), with an anionic dispersing agent and butyl benzoate or
diethyl phthalate as carrier. A two-bath procedure entails dyeing the triacetate
first at 105C and the wool later in a fresh bath at the boil. The latter sequence is
preferred for full depths where 1:2 metal-complex dyes may be required and
wool staining is a particularly serious problem.
Migration in favour of the triacetate increases with temperature, dyeing time,
pH and concentration of carrier, so that relatively severe dyeing conditions are
preferred for optimum yield. The disperse dye stain is cleared from the wool
using an anionic detergent at 6070C. It may be necessary to add sodium
dithionite and ammonia but the physical properties of the wool may suffer. The
two-bath method for full depths on triacetate/wool is easier than on acetate/wool
because there is less tendency for disperse dyes to transfer from triacetate during
cross-dyeing of the wool at the boil.
11.3 DYEING OF POLYESTER/NYLON BLENDS

Polyester/nylon blends exhibit exceptional strength and durability in robust
outerwear and protective clothing. Half-hose is an important outlet for polyester/
nylon as staple yarns or filament unions. The two fibres may be intimately
blended in warp or weft yarns, or may be woven or knitted as separate yarns in
the form of designs that are usually coloured in distinctive hues. It is customary
to dye the intimate blends in solid shades.
Polyester became an important carpet fibre in the USA around 1970 because
of the popularity at that time of heavyweight shag-pile constructions. The
attractive appearance of polyester yarns was retained longer than that of nylon
because of their superior heat set retention. However, when polyester was used
later in lighter-weight semi-shag and saxony constructions it was found to have
inadequate abrasion performance and resistance to pile deformation. The
abrasion resistance of nylon is about three times that of polyester [18]. Blends of
50:50 polyester/nylon were used for lighter-weight carpets in the USA but an
80:20 polyester/nylon blend was introduced in the UK for the so-called splush
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DYEING OF POLYESTER/NYLON BLENDS
153
carpeting, mainly for bedrooms and bathrooms, and this has remained popular
for many years [16].
Most of the problems encountered with polyester/nylon carpet blends arise
with stock-dyed yarns at the heat-setting stage. During autoclave or continuous
steam setting, some low-energy disperse dyes migrate into the spinning lubricant
on the fibre surface and give a yarn with inferior fastness to rubbing. Highenergy disperse dyes, if dyed for too short a time at top temperature, yield ring
dyeings that give rise to unacceptable colour changes during setting as a result of
further dye diffusion within the fibre.
The affinity of disperse dyes for polyester is higher than for nylon, but the rate
of diffusion in nylon is much more rapid than in polyester. Most disperse dyes,
therefore, dye the nylon component of a polyester/nylon blend more heavily in
the absence of a carrier at the boil, but the polyester is favoured at higher
temperatures or when at dyeing at the boil with a carrier. Carriers of the aryl
ester or trichlorobenzene types have been preferred to o-phenylphenol or
diphenyl because they give a more satisfactory partition and relatively low
residual odour. The use of carriers, however, is seldom acceptable nowadays
because of their adverse environmental impact.
The principle of producing solid shades of moderate fastness on polyester/
nylon using disperse dyes alone is determined essentially by dye selection and
dyeing temperature. The most rapidly diffusing dyes are likely to give the best
results. Nylon absorbs almost all of the disperse dye present at 60C but as the
temperature is raised the rate of transfer to the polyester can be controlled by the
rate of temperature rise. In high-temperature dyeing at 120C or under carrierdyeing conditions at the boil most of the nitro and aminoketone (yellow),
monoazo (yellow to red) and anthraquinone (red to blue) disperse dyes colour
polyester more readily, but some disazo orange and aminonaphthoquinone blue
dyes still favour the nylon.
Shadow effects can be produced without difficulty but the best reserve is
with polyester, using acid dyes on the nylon. It is difficult to dye polyester
with complete reserve of the nylon. Many acid dyes give an excellent reserve
of polyester when applied at pH 4 and 9095C with the usual levelling
agents for nylon dyeing. Neutral-dyeing 1:2 metal-complex dyes can be
applied in a similar way at pH 78. Multisulphonated reactive dyes at
pH 34 give an outstanding reserve of the polyester, although both of these
classes of dyes are rather more sensitive to dye-affinity variations in the
nylon. The whiteness of the polyester can be enhanced by applying a
disperse-type fluorescent brightening agent at the boil after dyeing and
aftertreatment of the nylon.
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Patterned contrast effects are produced by cross-dyeing half-hose knitted from

nylon and polyester yarns. In the two-stage method, the darker colour is dyed on
the nylon with milling acid or 1:2 metal-complex dyes and the lighter colour is
then dyed on the polyester. Disperse dyes selected for their relatively low affinity
for nylon are mainly intermediate-energy monoazo or anthraquinone types of Mr
300380. The nylon is dyed with the anionic dyes at 70C from an ammonium
acetateacetic acid bath, then the disperse dyes are added, the temperature raised
and dyeing continued at 120C to achieve the target depth on the polyester.
Where a deep colour is required on the polyester, it is necessary to use a twobath process. More attractive independent contrasts are possible in this way by
dyeing the polyester first at 120C. The disperse dye stain is desorbed from the
nylon in an intermediate clear with a nonionic detergent or destructively stripped
with an alkaline dithionite treatment at 70C. The anionic dyes are applied from
a fresh bath at the same temperature, pH control being necessary to facilitate
exhaustion. Even so, the contrast is difficult to control owing to some transfer of
disperse dyes from the polyester during the second stage of the process [19]. A
syntan aftertreatment is given finally to improve wet fastness on the nylon.
11.4 BLENDS OF CELLULOSE ACETATE OR TRIACETATE
WITH NYLON
High tensile strength and abrasion resistance are important contributions made
by nylon to these blends. In woven or knitted dresswear, linings and
undergarments, the cellulose ester fibre usually predominates and blends ranging
from 85:15 to 65:35 are typical. Cellulose acetate/nylon has been used in staple
blends for hand-knitting yarns or as nylon warp/acetate weft woven filament
dresswear. Special effects are attainable using ply yarns, e.g. a crimped nylon
yarn twisted with a bright cellulose acetate filament yarn. Triacetate/nylon
fabrics often exhibit better elastic properties and abrasion resistance. These
blends are suitable for hosiery, knitwear and sportswear. Warp-knitted velvet
fabrics with a cellulose acetate or triacetate pile and a nylon backing are useful as
furnishing fabrics, outerwear, trimmings and lining fabrics, particularly on cost
grounds. Overprinting of dyed fabrics with metallic pigments is popular. Dyeing
and printing are completed prior to raising [20].
Cellulose acetate/nylon blends cannot be preset in steam or hot air because of
the sensitivity of the acetate fibre to heat, but the dyeing process exerts a
hydrosetting action to stabilise the material. Intimate blends of these fibres for
knitting yarns are dyed to a wide range of shades, mainly in pale depths. Selected
disperse dyes can be applied at 80C with a nonionic dispersing agent to give
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BLENDS OF CELLULOSE ACETATE OR TRIACETATE WITH NYLON
155
shadow effects. Owing to low wash fastness this method is only suitable for pale
or medium depths [19].
Whilst it is theoretically possible to use disperse dyes to colour both
components of a 50:50 blend, in practice it is found that most of the dye is
absorbed by the acetate component, especially at neutral or slightly alkaline pH.
Acceptable solidity on 80:20 blends is given by simple monoazo or
1,4-disubstituted anthraquinone dyes. The light fastness of many disperse dyes
varies appreciably between nylon and cellulose acetate.
Triacetate/nylon fabrics are usually prescoured at 70C with a nonionic
detergent, stenter set at 210C and then given an S finish. Solid dyeings can be
achieved using disperse dyes at the boil with an anionic dispersing agent and, if
necessary, addition of a butyl benzoate or diethyl phthalate carrier. Some dyes
show better solidity in the presence of a carrier, whereas others with lower
substantivity for nylon give a more solid effect without carrier. The concentration
of carrier can be adjusted to shift the balance of partition towards either fibre
when carrier dyeing at the boil.
High-temperature dyeing at 120C offers greater latitude in dye selection,
improved exhaustion and penetration of both fibres [21]. The best solidity is
given by certain low-energy monoazo and anthraquinone dyes. Several orange
and brown monoazo and disazo dyes of higher fastness tend to favour the nylon
component too much. If problems of solidity arise due to preferential dyeing of
the nylon at high temperature, this can be improved by pretreating the blend at
5060C with a carrier suitable for triacetate. The use of a carrier should be
regarded as a last resort, however, because of the adverse environmental impact
of these products.
Solidity is not easy to achieve on cellulose acetate/nylon or triacetate/nylon
because most disperse dyes show a marked bathochromic shift on nylon
compared with their respective hues on the cellulose acetate or triacetate
component: yellows appear redder, reds bluer, and blues greener on nylon. This
effect makes staple blends look skittery (lacking solidity) if a substantial
proportion of nylon is present. The difference in hue may be attributable to the
preferential absorption of the more bathochromic ionised species (Scheme 11.4)
of such dyes by the amine end groups in nylon. Both fibre components are
capable of hydrophobic interaction and hydrogen bonding with either charged
or uncharged forms of these dyes (Figure 11.3). The colour difference is of little
interest for contrast effects on filament unions because the hue on the nylon is
usually duller than that on the acetate or triacetate fibre.
A good reserve of cellulose acetate or triacetate is obtained using 1:2 metal-
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NO2
O2N
NO2
NH
OH
OH
H+
O2N
NH
Mid-yellow
Reddish yellow
CI Disperse Yellow 1
OH
NH2
OH
H+
NH2
Red
Violet
CI Disperse Red 15
Scheme 11.4
Reddish yellow
NO2
NO2
O2N
O2 N
NH
OH
NH
(CH2)6
NO2
O
O C
H2C
Mid-yellow
NH3
NH
O2N
NH
CH3
HC O
HC
CH
OH
O C
(CH2)4
Mid-yellow
Acetate fibre
O C
NH
Nylon fibre
Figure 11.3 Dyefibre bonding of CI Disperse Yellow 1 on acetate and nylon
complex or milling acid dyes on the nylon component at 80C (acetate/nylon) or

120C (triacetate/nylon) and pH 56 with ammonium acetateacetic acid.
Dependent colour contrasts with the nylon heavier in depth are given by disperse
dyes selected for minimum staining of nylon and neutral-dyeing acid dyes to fill
in the nylon component. When anionic dyes are used in these contrast dyeings,
careful pH control is necessary for reproducible results. The preferred milling
acid dyes are mainly disazo disulphonates (yellow to red) and monosulphonated
(violet to blue) and disulphonated (blue to green) anthraquinone dyes with
relatively high wet fastness performance.
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BLENDS OF CELLULOSE ACETATE OR TRIACETATE WITH NYLON
157
The two classes of dyes are compatible but a two-stage sequence may give
better control of solidity than does a one-bath process. A carrier may be
necessary to assist dyeing of the triacetate. Moderate or full depths of disperse
and anionic dyes are afterscoured at 5060C with a nonionic detergent, or if
necessary with sodium dithionite as a reduction clearing agent. Thorough
scouring is essential where good wet fastness is important, because the disperse
dyes have only low fastness on the nylon component.
11.5 BLENDS OF POLY(VINYL CHLORIDE) FIBRES WITH WOOL
OR NYLON
Much of the poly(vinyl chloride) or PVC fibre used for textile applications is
found in DA blends with wool or nylon. PVC fibre is an economical component
of staple blends and exhibits the unusual properties of inherent flame resistance
and a high degree of shrinkage when heated above 60C. Although the shrinkage
phenomenon limits the conditions of processing to some extent, it does enable
unique effects to be produced in speciality fabrics. It is essential to ensure that the
component fibres are thoroughly blended, as the PVC fibre may contract at the
boil to 50% of its original length. During processing of the blend the PVC fibres
tend to become concentrated in the interior of the yarn, so that dyeing of the
PVC component may be unnecessary if it is present only in a small proportion.
Solid pale or medium depths, shadow effects and PVC reserve are all possible in
blends with wool or nylon.
Staple PVC fibres blended with wool at the 1020% level contribute strength
and bulk to the yarn for hand-knitting or as a weft in blanket manufacture. If
latent-shrinkage properties are required without resorting to milling, 2025% of
the PVC fibre can be incorporated and the fabric shrunk by scouring or stenter
drying at 8090C. Owing to the heavyweight characteristics obtained, these
blends are of more interest for outerwear or uniforms rather than dressgoods or
light suitings.
Latent-shrinkage fibres are usually dyed as staple or combed tops at 5060C
with a trichlorobenzene carrier before blending with dyed wool. The preshrunk
PVC fibres can be dyed at 9095C as a blend with undyed wool. Selected lowenergy monoazo and anthraquinone disperse dyes give minimum cross-staining
of wool when applied with acid dyes in a one-bath method. Full depths may be
dyed by a two-bath sequence:
(1) PVC fibre dyed with disperse dyes at 9095C;
(2) wool stain cleared using nonionic detergent and ammonia at 5060C;
(3) wool dyed at the boil with premetallised or chrome dyes selected for
minimum staining of PVC fibre.
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Knitted interlock made from a 70:30 blend of nylon and PVC fibre for washable
apparel is relaxed in boiling water, desized, dyed and stenter dried. Such fabrics
are processed in open width throughout under minimum tension to allow
optimum shrinkage, giving a felt-like material that can be raised to give a sueded
appearance and handle. The PVC fibre migrates inwards to such an extent that
often only the nylon needs to be dyed.
Selected disperse dyes will give a similar depth on nylon and PVC fibre, but
light fastness on the PVC component is often a problem. Low-energy nitro,
monoazo and 1,4-disubstituted anthraquinone dyes give the best solidity in
general. Most of the other disperse dyes favour nylon or give different tones on
the two fibres, nylon again showing the more bathochromic hue. These blends
are dyed at the boil with a nonionic dispersing agent and a trichlorobenzene
carrier if necessary to promote uptake by the PVC fibre. Acid dyes can be used to
fill in the nylon. Full depths should be reduction cleared after dyeing using
sodium dithionite, soda ash and a nonionic dispersing agent.
Table 11.2 Dye selections for dyeing of DA blends
Blend
Polyester/wool
Colour
effect
Dyeing
method
Dye
selection
Polyester
reserve
Single-class
1:1 metal-complex or milling acid dyes at

appropriate pH
Solid
One-bath
Intermediate-energy disperse dyes and

monosulphonated 1:2 metal-complex
dyes at 105C with carrier
High-energy disperse dyes and
disulphonated 1:2 metal-complex dyes at
120C with wool protective agent
Acetate/wool
Triacetate/
wool
Contents
Two-bath
Selected disperse dyes at 120C, then

1:2 metal-complex or milling acid dyes
at the boil
Acetate
reserve
Single-class
Disulphonated milling acid dyes
Solid or
contrast
One-bath
Selected disperse dyes and neutral-dyeing

acid dyes at pH 6
Two-bath
(full depths)
Selected disperse dyes at 80C, then 1:2

One-bath

milling acid dyes at the boil with ester
carrier
Solid
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BLENDS OF POLY(VINYL CHLORIDE) FIBRES WITH WOOL OR NYLON
159
Table 11.2 Continued

Colour
effect
Dyeing
method
Dye
selection
Triacetate/
wool
Solid
Two-bath
(full depths)
Intermediate-energy disperse dyes at

105C, then 1:2 metal-complex dyes at
the boil
Polyester/
nylon
Polyester
reserve
Single-class
Acid dyes at pH 4 and 90C
Solid or
shadow
Single-class
Low-energy disperse dyes at 110120C
Solid or
contrast
Two-stage
Darker hue with neutral-dyeing acid dyes

at 70C, then intermediate-energy
disperse dyes at 120C
Two-bath
(full depths)
Intermediate-energy disperse dyes at

120C, then anionic dyes at 70C with
syntan aftertreatment
Acetate
reserve
Single-class
Premetallised or milling acid dyes at 80C
Solid or
shadow
Single-class
(pale depths)
Solid or
contrast
Two-stage
Selected disperse dyes, then milling acid

dyes at 80C
Triacetate
reserve
Single-class
Premetallised or milling acid dyes at 120C
Solid
Single-class
(pale depths)
Two-stage
Selected disperse dyes, then milling acid

dyes at 120C
PVC
reserve
Single-class
Premetallised acid dyes at the boil
Solid
One-bath
(pale depths)
Low-energy disperse dyes and acid dyes

at 9095C
Two-bath
(full depths)
Disperse dyes at 9095C, then

premetallised or chrome dyes at the boil
PVC
reserve
Single-class
Milling acid dyes at the boil
Solid
Single-class
(pale depths)
Low-energy disperse dyes at the boil
One-bath
Selected disperse dyes and milling acid

dyes at the boil
Blend
Acetate/nylon
Triacetate/
nylon
PVC/wool
PVC/nylon
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11.6 DYEING METHODS AND DYE SELECTION FOR DA BLENDS

In these blends a good reserve can invariably be achieved on the ester fibre or
PVC fibre using acid dyes at the appropriate pH and temperature for the aciddyeable component. Intermediate-energy disperse dyes and neutral-dyeing acid
dyes are compatible in one-bath processes for solid shades on blends of the ester
fibres with wool, although full depths require a two-bath sequence with an
intermediate clear to remove the disperse dye staining from the wool. Solidity
with low-energy disperse dyes in pale depths is possible on the other blends in the
DA category (Table 11.2) but more elaborate two-stage or two-bath procedures
are necessary for medium or full depths, the ester fibre or PVC fibre being dyed
first.
11.7 REFERENCES
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
12.
13.
14.
15.
16.
17.
18.
19.
20.
21.
S M Doughty, Rev. Prog. Coloration, 16 (1986) 25.

A F Doran, unpublished work.
M Brenner and H Zahn, Melliand Textilber., 64 (1983) 845.
H H Konrad and K Trschmann, Textile Praxis, 33 (1978) 932.
K H Rstermundt, Deutscher Frber Kalender, 80 (1976) 247.
P Rube and D Wegerle, Melliand Textilber., 57 (1976) 496.
T Balchin, Am. Dyestuff Rep., 72 (Sep 1983) 27.
M Drewniak, Am. Dyestuff Rep., 68 (Jun 1979) 45.
T H Afifi and A Z Sayed, J.S.D.C., 113 (1997) 256.
G Rmer, Textilveredlung, 14 (1979) 332.
E D Katcher and M P Neznakomova, Textil Praxis, 37 (1982) 637.
D M Lewis, Rev. Prog. Coloration, 19 (1989) 49.
C M Carr, J.S.D.C., 108 (1992) 531.
K H Rstermundt, Textil Praxis, 47 (1992) 649.
Y Riad, S M Hamza, H M El-Nahas and A A El-Bardan, J.S.D.C., 106 (1990) 25.
J M Taylor and P Mears, J.S.D.C., 107 (1991) 64.
T L Dawson and B P Roberts, J.S.D.C., 93 (1977) 83.
H W Partridge, Rev. Prog. Coloration, 6 (1975) 56.
G Wnsch, Textilveredlung, 24 (1989) 57.
P L Moriarty, Text. Chem. Colorist, 14 (Aug 1982) 148.
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161
CHAPTER 12
Polyester/acrylic and other DB blends
12.1 DYEING OF POLYESTER/ACRYLIC BLENDS

Cotton-spun blends of polyester and acrylic fibres (often 85:15 to 70:30), or
polyester fabrics containing acrylic effect yarns, are important in woven or
knitted upholstery and furnishings, outerwear, easy-care suiting, dressgoods,
sportswear and leisure clothing. As the major component, polyester confers
strength, easy-care properties, dimensional stability and high whiteness. Acrylic
fibre as the minor component contributes a soft, natural handle, high bulk and
cover, improved comfort in wear and versatility in coloration. Polyester/acrylic
fibre blends are usually piece-dyed and can be readily processed in garment form,
owing to their excellent shape retention, crease recovery and abrasion resistance.
Blending of polyester with modacrylic fibres is usually intended to take
advantage of the inherent flame resistance of the modacrylic component. The
relatively low abrasion resistance of the latter is greatly compensated by the
presence of polyester in the blend [1].
Polyester/acrylic fabrics are scoured at pH 4 with a nonionic detergent and
heat set at 185190C before dyeing. Pale or medium depths of selected disperse
dyes can be dyed on the polyester with satisfactory reserve of the acrylic fibre
using a methylnaphthalene carrier at the boil. Yellow to orange aminoketone or
disazo dyes give the best reserve, but selected low-energy red to blue
anthraquinone dyes are also acceptable under these conditions. An excellent
reserve of the polyester component is given at the boil and pH 5 with selected
basic dyes and a cationic retarder, e.g. cetyltrimethylammonium bromide.
The same method can be employed for solid, shadow or contrast effects by
adding an alkanol polyoxyethylene as anti-precipitant, appropriate disperse dyes
and a carrier formulated with a nonionic emulsifying system. Anionic dispersing
agents are best avoided because they may either complex with the cationic
retarder and increase staining of the acrylic fibre by the disperse dyes, or complex
with the basic dyes and cause unacceptable restraining. Anionic emulsifying
161
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POLYESTER/ACRYLIC AND OTHER DB BLENDS
systems for the carrier would also show these defects and may exhibit lower
emulsion stability in the presence of the cationic dyes or retarder.
Maximum brightness in contrast effects may be limited because of staining of
the acrylic fibre by the disperse dyes. The adverse effect of disperse dye staining
on the light fastness of basic dyes on the acrylic component has been quantified
[2]. The disperse dye stain should be cleared by treatment at 60C with sodium
dithionite, ammonia and a nonionic detergent.
An alternative two-stage approach is to use an anionic retarder for the basic
dyes. In the first stage the surface of the polyester is ring-dyed with disperse dyes
at pH 78 (sodium acetate) and 80C in a compatible system containing an
anionic retarder, a conventional anionic emulsion of the carrier and a nonionic
anti-precipitant. The pH is then adjusted to 5 with acetic acid, the basic dyes
added and the dyeing temperature increased to the boil to dye the acrylic fibre
and promote diffusion of the disperse dyes into the interior of the polyester. A
final scour at 60C with a nonionic detergent, ammonia and dithionite completes
the procedure.
Kayacryl ED (KYK) basic dyes contain as counter-ion an arylsulphonate that
acts as an anionic retarder and migrating agent. This facilitates compatibility
with conventional anionic formulations of disperse dyes and auxiliaries. No antiprecipitant is required and the fastness properties are equal to those of
conventional basic dyes. Superior levelling is shown without the customary use
of a cationic retarder. There is less staining of equipment and savings of time,
labour, water, energy and auxiliaries [3]. The Kayacryl ED dyes migrate much
more readily than conventional basic dyes and show good stability over a wide
range of pH.
These one-bath or two-bath dyeing methods on winch, jet or package dyeing
machines offer reproducible contrast effects at low cost [4]. In general, it is
preferable for the acrylic fibre to be dyed more deeply if reserve, shadow or
contrast effects at full depths are required. Solid or contrast dyeings in full depths
should be dyed by a two-bath method for optimum fastness and control of
colour matching. The polyester component is dyed first because a basic dyeing
on the acrylic fibre may show slight bleeding later in the disperse dyebath,
especially if treated at high temperature. For optimum solidity, the polyester
should be dyed slightly heavier than the target shade to allow for slight transfer
to the acrylic fibre in the second stage. Anionic dispersing agents (and an anionic
carrier emulsion if necessary) can be used in the first bath and a cationic retarder
selected for the basic dyes without restriction. An intermediate scour with a
nonionic detergent at 80C is necessary to clear the disperse dye stain and to
remove any residual carrier present.
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BLENDS OF CELLULOSE ACETATE OR TRIACETATE WITH ACRYLIC FIBRES
163
12.2 BLENDS OF CELLULOSE ACETATE OR TRIACETATE WITH

ACRYLIC FIBRES
Staple 50:50 or 60:40 blends of cellulose acetate or triacetate with acrylic fibres
are used in jersey dresswear, high-bulk sweaters, hand-knitting yarns, sportswear,
tropical suitings and woven furnishing fabrics. The cellulose ester fibre
contributes a smooth, silky handle, lustrous appearance and good dimensional
stability, giving an attractive combination of properties with the fuller handle,
easy-care performance and heat insulation contributed by the acrylic component.
Reserve and contrast effects are of relatively low interest on cellulose acetate/
acrylic fabrics because they are usually made from blended-staple yarns and
cross-staining is a problem. Solid effects in pale depths can be obtained with
disperse dyes applied at 7580C and shaded if necessary with basic dyes for the
acrylic component, although this fibre is only ring-dyed under these conditions.
Higher temperatures are best avoided because the lustre of the acetate fibre
would be impaired.
Full depths are achieved by a compromise two-bath method. The acrylic
fibre is dyed for the minimum time at the boil and pH 45 (acetic acid) with
the basic dyes and a cationic retarder. The dyebath is then cooled to 80C
and run to drain. The disperse dyes are then applied at 7080C and pH 6
from a fresh bath containing a nonionic dispersing agent to achieve the
target depth on the acetate fibre. This method does not give optimum
fastness in heavy depths on the acrylic fibre but the degree of damage to the
cellulose acetate is just about tolerable.
Much improved control of the dyeing of cellulose acetate/acrylic blends has
become possible with the introduction by Courtaulds in 1987 of Xtol cellulose
acetate fibre, which can be dyed at the boil without delustring. Fancy mixed-ply
yarns containing Xtol and Courtelle (Courtaulds) can be dyed in a wide range of
solid, shadow or contrast effects using selected disperse and basic dyes in a onebath method. Reserve effects are problematical, particularly alongside deep
shades, but acrylic reserve is probably the best choice.
Although acrylic fibres are readily dyeable with low-energy disperse dyes, the
high-energy dyes recommended for Xtol give little or no cross-staining of the
acrylic fibre in 50:50 blends with Xtol. Basic dyes for the acrylic fibre need more
care in selection because they tend to stain most fibres including Xtol [5]. It is
possible to achieve minimal cross-staining of Xtol by careful selection, however.
The highest possible dyeing temperature should be used and the dyeing time
should be sufficient to allow migration of the basic dyes from Xtol to Courtelle.
Reduction clearing after dyeing may assist in reducing the ultimate staining of the
acrylic fibre.
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164
Triacetate/acrylic blends can be dyed to solid shades, shadow (with the acrylic
as the heavier depth), contrast and triacetate reserve. It is not possible to dye the
triacetate with reserve of the acrylic fibre. A good reserve of the ester fibre in a
triacetate/acrylic fabric is obtained by dyeing with basic dyes selected for
minimum staining of triacetate using a nonionic dispersing agent. Any stain on
the triacetate is cleared with slightly acidified hypochlorite at ambient
temperature, followed by a sodium bisulphite rinse.
Solid and contrast effects are achieved by a one-bath method using selected
disperse and basic dyes. At temperatures below the boil the basic dyes tend to
stain the triacetate, but migration to the acrylic fibre proceeds at the boil. Dyes in
which the charge is delocalised (yellow to red methines and cyanines, oxazine
blues and triarylmethane greens) migrate more readily than dyes with a localised
charge (azo and anthraquinone derivatives).
When dyeing colour contrasts, the acrylic component should preferably be
dyed to a deeper colour than the triacetate in order to minimise undesirable
cross-staining of the acrylic fibre by the disperse dyes. Satisfactory one-bath
dyeing is achieved at the boil and pH 57 (phosphate buffer) with sodium
N-methyloleylaminoethanesulphonate as a weakly anionic retarding agent
(Figure 12.1). The basic dyes and disperse dyes are added separately in that
order, followed by an aryl ester carrier in an anionic emulsion. Full depths should
be scoured at 60C with a nonionic detergent to remove the residual basic dye
stain from the triacetate.
CH3(CH2)7CH
CH(CH2)7CO
N CH2CH2SO3 Na+
H3C
Figure 12.1 Anionic retarder for basic dyes
Solid or contrast effects can be produced on blends of cellulose acetate or

triacetate with acid-dyeable acrylic variants by two-stage methods using acid or
chrome dyes for the acrylic fibre first, then neutralising and applying selected
disperse dyes to the ester fibre at 70C (acetate) or at the boil with an aryl ester
carrier (triacetate). Dyes requiring only moderately acidic conditions should be
selected for the acrylic variant. The acrylic fibre can be reserved by applying
disperse dyes that have good affinity for the ester fibre at the appropriate dyeing
temperature. The ester fibre is reserved by applying levelling acid dyes at a
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BLENDS OF CELLULOSE ACETATE OR TRIACETATE WITH ACRYLIC FIBRES
165
moderately acidic pH, preferably using phosphoric acid. Chrome dyes may be
used for higher fastness but metal-complex types tend to stain the ester fibres.
12.3 DYEING OF NORMAL/BASIC-DYEABLE POLYESTER BLENDS
Polyester copolymer variant yarns of the basic-dyeable type (section 5.1) are used
in combination with the homopolymer for reserve, shadow and contrast effects.
The basic-dyeable copolymer is more accessible than the homopolymer and in
most instances shows higher yields and rates of dyeing with disperse dyes,
although some anthraquinone derivatives do not behave in this way. Basicdyeable polyester exhibits lower tensile strength than the homopolymer and
much lower abrasion resistance. It is more readily degraded by acid or alkali than
the homopolymer, so that it should be dyed at pH 56 and a temperature no
higher than 120C. Glaubers salt addition minimises degradation within these
limits. Caustic soda should be avoided and reduction clearing with ammonia and
dithionite should not be carried out above 60C.
Careful scouring with a nonionic detergent and soda ash at 6070C to
remove spinning oils is important. Presetting at 165C is also recommended.
Satisfactory reserve of the homopolymer is achieved at the boil and pH 5 using
basic dyes, Glaubers salt and a nonionic carrier emulsion. Aryl ester carriers
promote optimum reserve of the normal polyester when using basic dyes only.
The preferred basic dyes for this blend are mainly methine, cyanine, monoazo or
oxazine types. Practically all of them except certain orange to red monoazo dyes
reserve normal polyester well. The residual stain is cleared from the
homopolymer at 50C using sodium dithionite, ammonia, a nonionic detergent
and Glaubers salt to protect the basic-dyeable polyester from hydrolysis.
Pyrazoline fluorescent brightening agents cannot be used in reserve effects on the
homopolymer because they tend to promote damage of the basic-dyeable
variant. Compounds based on benzoxazolyl- and benzofuranyl-benzimidazole
derivatives (Figure 12.2) are preferred because they are resistant to chlorite
bleaching [6].
Shadow effects with disperse dyes on these blends show the sharpest
differentiation using slow-diffusing high-energy dyes from a long liquor at about
80C, if necessary with a low concentration of an ester carrier, but the normal
polyester is badly ring-dyed under these conditions. The best approach to solidity
is to use rapid-diffusing low-energy dyes at the boil with a diphenyl carrier, or at
120C with an ester carrier to assist levelling. Some subtle contrasts are possible
with selected low- and high-energy disperse dyes in mixtures, but the scope for
selection is extremely limited.
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166
N
R1
R2
Substituted 1,3-diphenylpyrazolines
CH3
N
R1
N
N
R2
CH3
Substituted benzoxazolyl-benzimidazoles
CH3
N
R1
R2
CH3
Substituted benzofuranyl-benzimidazoles
Figure 12.2 Structural types of fluorescent brightening agents
The most widely used disperse dyes for contrast effects with basic dyes are
mainly quinoline and anthraquinone derivatives. Cationic retarders may be used
especially in pale depths, but they tend to be less effective than on acrylic fibres
because the rate of diffusion of the dye is already much slower on basic-dyeable
polyester and restraining may be excessive in full depths. Weakly cationic
retarders of the alkylamine polyoxyethylene type promote levelling in the high
temperature method at 120C. Some useful azo and anthraquinone disperse dyes
show light fastness at least one blue-scale rating lower on basic-dyeable polyester
compared with the homopolymer. All basic dyes show lower light fastness on
basic-dyeable polyester than on acrylic fibres and this limits their selection for
pile fabrics, upholstery and carpets. In most cases, the monoazo types with a
localised charge tend to show better fastness to light than do dyes with a
delocalised charge on the molecule.
Anionic scouring or dispersing agents and carriers formulated with anionic
emulsifiers should be avoided. Diphenyl and aryl ester carriers in nonionic
emulsifying systems are preferred for their compatibility with basic dyes, ease of
removal from the fibre and minimal influence on light fastness. The disperse and
basic dyes are added separately to a solution of an alkanol polyoxyethylene antiprecipitant before the nonionic carrier emulsion. The ester carriers accelerate the
rate of uptake of basic as well as disperse dyes and they give better migration
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DYEING OF NORMAL/BASIC-DYEABLE POLYESTER BLENDS
167
Table 12.1 Dye selections for DB blends

Blend
Colour effect
Dyeing method
Dye selection
Polyester/
acrylic
Acrylic
reserve
Single-class
Low-energy disperse dyes with

methylnaphthalene carrier
Polyester
reserve
Single-class
Basic dyes with cationic retarder
Solid or
contrast
One-bath
Disperse dyes and basic dyes with

nonionic carrier system and
anti-precipitant
Two-stage
Disperse dyes at 80C, then basic

dyes at the boil with anionic retarder
and carrier
Two-bath
(full depths)
Disperse dyes at 120C, then basic

dyes with cationic retarder
Single-class
(pale depths)
Disperse dyes at 80C
Two-bath
(full depths)
Basic dyes briefly at the boil with

cationic retarder, then disperse
dyes at 80C
Acetate/
acrylic
Solid
Xtol/
Courtelle
(Courtaulds)
Solid or
contrast
One-bath
High-energy disperse dyes and

selected basic dyes at the boil
with anti-precipitant
Triacetate/
acrylic
Triacetate
reserve
Single-class
Basic dyes with nonionic dispersing

agent
Solid or
contrast
One-bath
Disperse dyes and delocalisedcharge basic dyes at the boil with

anionic retarder and carrier
Acetate
reserve
Single-class
Chrome or levelling acid dyes

at pH 4
Solid or
contrast
Two-stage
Chrome or levelling acid dyes, then

Triacetate
reserve
Single-class
Chrome or levelling acid dyes

at pH 4
Solid or
contrast
Two-stage
Chrome or levelling acid dyes, then

disperse dyes at the boil with aryl
ester carrier
Homopolymer
reserve
Single-class
Delocalised-charge basic dyes and

nonionic aryl ester carrier emulsion
at the boil
Shadow
Single-class
High-energy disperse dyes at 80C
Acetate/
acid-dyeable
acrylic
Triacetate/
acid-dyeable
acrylic
Normal/
basic-dyeable
polyester
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168

Blend
Colour effect
Dyeing method
Dye selection
Normal/
basic-dyeable
polyester
Solid
Single-class

with aryl ester carrier
Contrast
One-bath
Disperse dyes and basic dyes at

120C with nonionic aryl ester
carrier and anti-precipitant
under high temperature conditions. Diphenyl gives the most economical yields at
the boil and tends to favour the disperse dyes, so that this type of carrier is often
preferred for contrast effects in full depths. Where possible, however, it is
preferable to dye at high temperature and to use carriers sparingly, if at all. Full
depths are cleared with dithionite and ammonia as already described.
12.4 DYEING METHODS AND DYE SELECTION FOR DB BLENDS

The disperse-dyeable component of DB blends containing polyester or cellulose
triacetate can be readily reserved. Solid effects with disperse dyes only can be
achieved in pale depths on acetate/acrylic and normal/basic-dyeable polyester
blends, but better control of shade matching is possible using basic and disperse
dyes. One-bath methods for solid or contrast effects are available for polyester or
triacetate with acrylic fibres, as well as normal/basic-dyeable polyester. Twostage or two-bath sequences become necessary for full depths on the blends
containing conventional or acid-dyeable acrylic variants (Table 12.1).
12.5 REFERENCES
1.
2.
3.
4.
5.
6.
I R Hardin, Man-made fibres: their origin and development, Eds. R B Seymour and R S Porter
(London: Elsevier, 1993).
J Jeths, Chemiefasern und Textilind., 25/77 (1975) 356.
R Parkham, Am. Dyestuff Rep., 82 (Sep 1993) 79.
F T Wallenberger, Text. Research J., 50 (1980) 289.
T Martini, Chemiefasern und Textilind., 38/90 (1988) 827.
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169
CHAPTER 13
Polyester/cellulosic and other DC blends
13.1 EXHAUST DYEING OF POLYESTER/CELLULOSIC BLENDS

13.1.1 Properties and preparation of polyester/cellulosic blends
Blends of ester fibres with cotton or viscose are produced in greater quantity than
the corresponding blends with wool (section 1.3). Factors contributing to this
situation have been the relative ease of processing, effective clearing and
versatility of application, leading to a wide range of dyed and finished effects.
Without question the exploitation of polyester/cellulosic blends represents the
most successful compromise between the contrasting physical properties of
synthetic and natural fibres. Polyester/cellulosic yarns are used in sewing threads
and slub effects for apparel. Woven polyester/cellulosic fabrics are important in
shirting, sheeting, dressgoods, outerwear and workwear. Woven staple 67:33
polyester/cotton and 50:50 polyester/viscose blends in numerous constructions
form the well-established basis of this field and many of these fabrics are
produced in sufficient quantities to justify continuous dyeing.
Polyester/cellulosic knitgoods include fleece knits, interlocks and jerseys,
sportswear, T-shirts and dresswear. Knitted fabrics are less appropriate for
continuous dyeing owing to their lower dimensional stability but the
development of atmospheric jet machines has made it possible to dye these
fabrics satisfactorily. Presetting can often be avoided if there is no risk of creasing
in the jet dyeing machine and the brief dyeing cycle, short liquor ratio, high
degree of turbulence and vigorous washing conditions make this technique
highly efficient.
As the most important fibre blend, ranging in characteristics from lightweight
poplin shirting to heavy drill workwear fabric, polyester/cotton is sufficiently
familiar to require little description. Polyester/linen blends are noteworthy as a
luxury alternative to polyester/cotton in high-quality fashion goods, tableware
and bedlinen. Care must be taken not to mar the characteristic nature of the linen
texture.
169
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POLYESTER/CELLULOSIC AND OTHER DC BLENDS
The primary shortcoming of woven polyester/cotton blends in the late 1950s

was their inability to create fabrics that would retain creases once they had been
made into garments. The breakthrough was the development of the durable press
finish that allowed deferred curing of the garment. This was constructed and the
creases set in before complete reaction of the finish with the cotton component of
the blend. This procedure resulted in a garment that would retain its creases
through a prolonged series of washwear cycles. Initially, the process was applied
to all-cotton fabrics in the early 1960s but severe problems occurred because of
the adverse effect of the durable press finish on strength and abrasion resistance.
When it was later adopted for polyester/cotton blends, however, the durability
and crease resistance of the polyester made an impressive contribution to the
finish. Improvements were also made to the finish formulations, to blending of
the fibres in the yarn and to the garment pressing methods.
Polyester/viscose is an essential blend for apparel, replacing polyester to a
great extent over the last decade. The superior comfort of this blend over the
synthetic fibre alone is without question and it is this, together with the
capability to accept chemical finishes that produce fabric qualities
unrecognisable from the starting material, that has led to the outstanding
popularity of this blend in apparel [1]. Viscose fibres can be chemically crimped
in manufacture by selecting regeneration conditions after extrusion that give
filaments with an asymmetric cross-section, such as less acid in the spinning bath
and a higher bath temperature. The asymmetry causes the filaments to form
continuous helical curves that impart the crimp characteristics. Sarille
(Courtaulds) is a crimped viscose fibre that has been particularly successful with
polyester, including 65:35 Sarille-rich blends for dressgoods [2].
Blends of polyester with regular or crimped viscose, modal or polynosic fibres
are important in such outlets as lightweight tropical suiting, fashionwear,
raincoats, leisure clothing and sportswear. Blends with viscose, and especially
modal or polynosic fibres, are more suitable than cotton blends for knitgoods in
view of their higher lustre and softness. Polyester/polynosic fibre blends have
particularly good dimensional stability for use in tubular-knitted fabrics and
garments [3]. Polyester/Vincel blends with polyester as the main component are
of interest for rainwear, and for lightweight lawn constructions in summer
dresswear and blouses.
A valuable advantage for polyester in blends with cotton is its outstanding
resistance to the rather severe preparation necessary for raw cotton before
dyeing. Thorough preparation of polyester/cellulosic woven fabrics is the
essential prelude to successful dyeing, especially if a continuous method is to be
used. Any subsequent unlevelness or stains are almost always related to
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inadequate preparation. About 70% of typical dyeing faults are attributable to

poor penetration [4].
The nature of the size used on warp yarns of woven goods should be identified
so that it can be effectively removed. Rapid identification of sizes is now much
more sophisticated than it was ten years ago [1]. Weavers often change size
formulations without prior notification and this can lead to serious dyeing
problems. Size removal outside the dyeing machine is greatly preferred to
minimise machine occupancy and avoid build-up of residual contaminants.
Neutral pH washing is the best for water-soluble sizes that respond well to
vigorous treatment, but complete removal may require enzyme desizing before
alkaline scouring. Hot- or cold-active enzymes are available for batchwise or
continuous desizing.
Cotton is usually the minor component in a polyester/cotton blend so that
alkaline scouring, peroxide bleaching and mercerising usually provide adequate
preparation. Most polyester/cellulosic fabrics may be winch scoured in anionic
detergent and soda ash at 7080C. Cold padbatch peroxide bleaching offers a
low-cost alternative to batchwise processes to increase the production rate and
quality of polyester/cotton knitgoods [5].
Cold mercerising after bleaching improves the absorbency, lustre and
dimensional stability of polyester/cotton and improves the colour yield of vat or
reactive dyeings. It is not recommended for viscose or modal fibre blends,
however. The dyeability of the cellulosic component in these blends can be
enhanced by cold causticising followed by thorough rinsing.
Crease recovery, dimensional stability and pilling resistance are all improved
by stenter setting of polyester/cellulosic fabrics. This is normally carried out at
180200C on a stenter either before or after dyeing. The higher temperature is
particularly relevant for closely woven poplins or similar constructions destined
for continuous dyeing. Heat setting before dyeing reduces the tendency to crease
if subsequently dyed in rope form. Dyeability variations arising from differences
in thermal history of the polyester may also be less evident. Sensitivity to these
differences is greater in batchwise dyeing. If heat setting is carried out before
preparation, care must be taken to ensure that there are no oil stains or other
contaminants that might become set into the material and prove more difficult to
remove later [6]. Heat setting after dyeing removes minor creases introduced in
rope dyeing and also stabilises the fabric structure at its finished width.
Singeing of both sides of the fabric is essential for polyester/cellulosic staple
blends, but this treatment should be carried out after batchwise dyeing. The
microscopic beads of fused polymer formed on the tips of the projecting
polyester fibres take up dye more readily than the intact fibres in the body of the
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fabric. Because of their amorphous character these produce an unacceptable

skittery or speckled appearance, especially after batchwise dyeing. Cropping to
sheer off the protruding fibre ends is an alternative that avoids this problem.
13.1.2 Disperse dyeing of the polyester component
Polyester/cellulosic yarns are mostly dyed as cones or cheeses, or on beams,
under high-temperature conditions. Fabrics are generally dyed on a beam, in a jet
or overflow machine, or on a continuous range. In circulating-liquor machines
the initial dye uptake should be uniform throughout the load to ensure that the
final dyeing is level. A rapid rate of dyeing and a slow rate of circulation of the
dye liquor may both contribute to unlevel dyeing problems. To ensure uniform
uptake the increment of exhaustion for each cycle of liquor through the machine
should be not greater than about 2% exhaustion per cycle. The drains of such
machines should be designed so that it is safe to release the exhausted liquor
while still under pressure but this technique is effectively limited to circulatingliquor machines.
Beam dyeing is unsuitable for polyester/cellulosic fabrics of very low
permeability, constructions with a sculptured surface and knitgoods that are
often difficult to wind evenly with suitable tension on to a beam. Jet dyeing
machines can cause crushing or creasing of fabrics with a sensitive surface,
such as velvet or corduroy. After jet dyeing it is desirable to cool the dyebath
slowly to about 80C in order to avoid the risk of creasing of the dyed
material. Certain lightweight cloths may also give difficulty in the jet
machine owing to the excessive length of an economical machine load. The
completely relaxed and tensionless dyeing conditions in a jet or overflow
machine allow relaxation, bulking and shrinkage that is physically prevented
in the beam machine. Thus the softer, bulkier handle and subdued lustre
provided by jet dyeing may be preferred for polyester/viscose knitgoods, for
example, whereas the firmer, flatter handle and stronger reflections from
beam-dyed goods are usually favoured for polyester/linen and many
polyester/cotton fabrics [6].
Many of the comments on wool staining by disperse dyes (section 3.4) are
applicable to the staining of cellulosic fibres, but these are less sensitive than wool
to the relatively severe conditions required to clear the stain. Staining is
aggravated by low pH and poor dispersion stability, as well as marginally by
nonionic agents and carrier chemicals. The disperse dye stain has low fastness to
light and wet treatments. On polyester/cellulosics the degree of staining is less
than on wool, prolonged boiling favours migration to polyester without severe
damage to the cellulose and the stain can be reduction cleared safely.
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Cotton staining in the dyebath at 130C with those dyes having low
substantivity for cotton is usually negligible. After the hold period at top
temperature, residual dye remains in solution at 130C and if the dyebath is
drained by blowing out under pressure, the deposition of loose dye on the
fibre surfaces is minimised. On the other hand, if the dyebath is cooled
slowly the dissolved dye will re-precipitate and undesirable deposition will
occur.
For the highest fastness the unfixed disperse dyes on the polyester surface and
the stain on the cellulosic component should be removed by a thorough soaping
with detergent or by a suitable reduction clearing. In many cases the clearing
treatment can be incorporated in the subsequent dyeing of the cellulosic fibre, as
in the reduction, reoxidation and soaping of vat or sulphur dyes. Where reactive
dyes are used and the highest fastness standard is required it may be necessary to
give a reduction clearing treatment separately before the reactive dyes are
applied. Disperse dyes tend to stain the lignin component of linen, so that
reduction clearing of the stain is more important than with cotton [6]. Vat or
reactive dyes are normally chosen for linen and it is dyed in open width to avoid
creasing. Clearing can be combined with the reduction stage of vat dyeing on this
blend.
Disperse dyes of all relevant chemical types have been used in the batchwise
dyeing of polyester/cellulosic blends but the trend has been in favour of the highenergy dyes, especially where durable press finishes are to be applied. Not only
have the levels of sublimation fastness in chemical finishing and end-use
requirements become more severe, but there have been improvements in the
design and operation of jet and overflow machines to process these blends. Highenergy dyes show optimum yield and levelling properties under these conditions.
Low-energy dyes are now only of marginal interest for excellent levelling in pale
depths. The affinity of disperse dyes for cellulose is a factor of practical
significance in selecting suitable dyes for either batchwise or continuous
methods. In continuous dyeing the selection has to take into account the rapidity
of clearing of the stained cellulosic component and the sensitivity of the staining
to variables arising during thermofixation [7].
Light fastness on polyester is usually adequate and after dyeing the dyes are
protected from chemical attack at moderate temperatures by the hydrophobic
nature and relative impermeability of the fibre. Nevertheless, some dyes are
sensitive to alkaline conditions or to the presence of heavy metal ions at relatively
low concentrations. Thus disperse dyes are normally applied under slightly acidic
conditions (pH 5) and a sequestering agent is normally used with those dyes
known to be sensitive to trace metals.
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The rate of exhaustion of a disperse dye by polyester is controlled by the

rate at which the temperature is raised. At some temperature between 80C
and 120C the dyeing rate for that dye reaches a maximum. The temperature
range over which the dyeing rate is at this maximum is known as the critical
dyeing temperature (CDT). Slow-diffusing high-energy dyes have a high
CDT, whereas more rapidly-diffusing dyes have a lower CDT. Specific values
of CDT depend on the rate of temperature rise, dye concentration, liquor
flow rate, liquor ratio and the substrate to be dyed. Rapid-dyeing procedures
depend on adding the disperse dyes at a temperature just below the CDT and
then raising the temperature slowly in the vicinity of the CDT to ensure that
the exhaustion rate that just permits level dyeing is not exceeded. The
temperature is then raised from just above the CDT to the top dyeing
temperature at the maximum rate.
In polyester/cellulosic dyeing the need for levelling agents with disperse dyes is
less critical than when dyeing polyester alone. In the early stage of a batchwise
dyeing, or in the first padding of a continuous process, the cellulosic fibres
absorb a substantial proportion of the disperse dyes applied. These subsequently
migrate to the polyester as the top dyeing temperature or the thermofixation step
is reached. The cellulosic component is thus, in a sense, acting as a retarding or
levelling agent for the disperse dyes [8].
Nevertheless, many dyers still prefer to add a levelling agent, especially for
pale depths. The efficiency of ethoxylated nonionic surfactants used as levelling
agents during accelerated heating in the early stage of exhaust dyeing of the
polyester component was studied with a trichromatic combination of low-energy
disperse dyes. Criteria for the selection of nonionic levelling agents include costeffectiveness, ease of handling, effect on dye yield, minimal foaming and ease of
removal from the substrate by rinsing [9].
Oligo-soaps are polyethylene glycol fatty acid esters of high Mr and general
formula: RCOO(CH2CH2O)nCH2CH2OH. These agents provide excellent dye
dispersing and solubilising characteristics. By forming a complex molecular
matrix with the polyester surface during dyeing, these compounds give excellent
dye levelling under a wide variety of conditions [10]. Their low-foaming
properties eliminate the need for mixtures of nonionic levelling agents, dispersing
agents and defoamers in jet dyeing systems.
Fastness to sublimation of disperse dyes is not a criterion for selecting
those that yield optimum wet fastness performance in finished polyester/
cellulosic fabrics. Those found suitable in this respect must show minimum
tendency to thermomigration or desorption in aqueous media after heat
treatment at temperatures above 140C. They should also have minimum
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substantivity for adjacent fibres, notably nylon, in wet fastness tests.

Selection of dyes that show minimum staining of the cellulosic fibres is also
advisable.
Unsatisfactory wash fastness of disperse dyes on the polyester fibre,
particularly with regard to staining of adjacent nylon, may arise from
aftertreatments such as soaping at the boil. These are normally necessary when
dyeing the cellulosic fibre with vat, sulphur, reactive or azoic dyes. Even if a
reduction clear is given after the boiling soap treatment, unfixed disperse dye
may still be present on the polyester surface. This problem can be minimised by
selecting disperse dyes that do not migrate readily to the fibre surface when the
fabric is soaped at the boil. An alternative approach is to use reactant-fixable
direct dyes on the cellulosic component that do not require a boiling soap
treatment [11].
Many disperse dyes show lower light fastness on polyester microfibres (section
1.4.2) compared with standard polyester, so this becomes a further factor in dye
selection [12]. The relatively higher amounts of disperse dyes needed on
microfibres have a significant influence on build-up. Small differences in build-up
between dyes on conventional polyester are exaggerated on polyester
microfibres. The high applied concentrations needed to achieve full depths on
microfibres play a critical part in the resultant limited wash fastness after poststentering. Traditionally acceptable dyes for conventional recipes can show
unacceptable results when applied to microfibres.
Major dyemakers have put considerable research effort into developing a
new generation of disperse dyes designed to optimise wash fastness and
minimise the cross-staining of the cellulosic fibre [13]. If the Dispersol XF
(BASF) dyes, for example, are compared with conventional monoazo and
anthraquinone disperse dyes, the differences in wash fastness and crossstaining performance are magnified when tested on polyester microfibres.
Diester-containing azo disperse dyes and certain azothiophene blues (Figure
13.1) that are capable of being rendered soluble by a mild alkaline
COCH3
HN
NO2
CH2CH2COOCH3
Ar1
N N
N
CH2CH2COOCH3
O 2N
N N Ar2
Figure 13.1 Azo disperse dye structures capable of solubilisation by alkali (Ar = aryl)
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aftertreatment offer considerable benefits when dyeing polyester microfibre/

cellulosic blends. These include:
(1) minimal cross-staining of the cellulosic fibre;
(2) minimal processing times because the alkaline fixation stage for reactive
dyes clears the disperse dye stain;
(3) avoidance of a reduction clear with dithionite;
(4) achieving good wash fastness standards after post-stentering.
13.1.3 Direct dyeing of the cellulosic component
Several possible batchwise dyeing methods are available for polyester/cellulosic
blends, based on the use of disperse dyes and the various classes of dyes for the
cellulosic fibre. The choice between these possibilities depends mainly on
requirements of hue, depth and fastness properties. Direct dyes are popular due
to their economy, compatibility, robustness and adequate fastness in pale depths.
Their major weakness is their poor wet fastness in depths above about halfstandard depth [1]. The wet fastness of direct dyeings can be enhanced
substantially, however, when finishing with a durable press reactant together
with a cationic fixing agent [14].
Most direct dyes give a good reserve of polyester. An economical one-bath
bleaching and direct dyeing system for achieving an excellent polyester reserve
effect entails treating the scoured polyester/cotton fabric with sodium carbonate,
hydrogen peroxide, silicate stabiliser and a hexametaphosphate sequestrant at
pH 10 and the boil to bleach the cotton in the presence of selected peroxidestable direct dyes [15]. After cooling to 85C, salt is added and the temperature
raised to 95C to achieve full exhaustion of the direct dyes.
Solidity on blended staple yarns is usually the colour effect required. Disperse
and direct dyes can be applied in a cheap and simple one-bath process, but the
relatively low fastness levels are inadequate for many polyester/cellulosic outlets.
Disperse/direct combinations are thus mostly used at the cheaper end of the
market. Because of the limited wet fastness of direct dyes, staining of the
cellulosic fibre by disperse dyes is less important than with other combinations.
The direct dyebath serves as a soaping bath to give a mild clearing of the disperse
dyeing.
A practical advantage that direct dyeing offers over reactive dyeing of these
blends is the markedly lower concentration of electrolyte necessary. The salt
concentration (1015 g l1) is rarely sufficient to adversely affect the dispersion
stability of the disperse dyes, although instability occasionally arises in shortliquor (package or beam) equipment. Similarly, neither the dispersing agents nor
any levelling agent required would normally interfere with the direct dyeing
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process. On the other hand, many direct dyes are adversely affected at the high
temperature (120130C) and acidic pH (4.55.5) usually preferred for disperse
dyeing. It is necessary to ensure that the direct dyes are sufficiently soluble and
chemically stable under these conditions. The influence of pH and additions of
electrolyte, carrier, levelling and sequestering agents on the stability and dyeing
behaviour of direct dyes selected for the one-bath method has been tabulated
[16]. The vulnerability of most direct dyes to alkaline reducing conditions
precludes conventional reduction clearing of the dyed polyester component [8].
General recommendations have been given for the package dyeing of
polyester/cotton yarns with direct and disperse dyes by the one-bath method,
either at high temperature [17] or using 12% of a mixture of diphenyl and
trichlorobenzene as carrier [18]. Disperse/direct recipes are important for blends
of polyester with viscose or other regenerated cellulosic variants for suiting
materials, where fast-to-light direct dyes can be used without the need for high
wash fastness. Aftertreatment and resin finishing of disperse/direct dyeings can
give materials of acceptable if still limited wet fastness.
In the one-bath method with disperse and direct dyes, the polyester fibre is
dyed at pH 6 with a disodium dinaphthylmethanedisulphonate dispersing agent
at 130C on the beam or in a jet machine. The dyebath is then cooled to 90C,
salt is added and dyeing continued until the cellulosic fibre reaches the target
depth. Aftertreatment with a cationic fixing agent is given where appropriate to
improve the fastness properties of the direct dyes. These are selected for stability
in the high-temperature dyebath and are mainly self-levelling or salt-controllable
disazo multisulphonated dyes. A wider choice of direct dyes can be used in the
two-bath method with intermediate reduction clearing. This alternative gives
moderately good fastness in pale or medium depths, provided the fabric is given
a durable resin finish.
13.1.4 Reactant-fixable direct dyes for the cellulosic component
Reactant-fixable dyes are those copper-complex direct dyes (Figure 8.5) that are
suitable for aftertreatment with certain Indosol (Clariant) cationic fixing agents,
yielding exceptionally good fastness to washing. Not all direct dyes respond in
acceptable ways to these treatments. In general, bright unmetallised direct dyes
show poor light fastness after treatments with Indosol agents. Selected
unmetallised reactive dyes have been used to provide bright hues that supplement
the limited shade gamut of the reactant-fixable range [11].
Substantial savings in processing time, labour costs, chemicals, water and
effluent treatment are claimed for reactant-fixable dyes, compared with vat or
reactive alternatives. These savings are even more significant when dyeing
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cellulosic blends than in the dyeing of all-cotton or all-viscose materials [19]. The
reasons for this arise from the fact that the dyeing of these blends can be
technically complex and time-consuming. In most cases the Indosol system
allows for one-bath dyeing, leading to specific savings over other conventional
cellulosic dyeing methods. Reduction clearing or soaping at the boil can be
avoided, leading to further reductions in time, energy and water consumption.
The soaping and rinsing of reactive dyeings are much more time-consuming than
cationic aftertreatment [1].
The cationic nature of Indosol E-50 (Clariant) is multifunctional and one
molecule of fixing agent can interact electrostatically with several sulphonate
groups in the same or different Indosol dye molecules. Furthermore, chelating
groups in the fixing agent are able to form coordination bonds with the copper
atoms in the dye molecules. These two features result in the formation of a much
more stable complex between dye and agent than when simple cationic fixing
agents are used to fix conventional direct dyes by electrostatic bonding only. The
fastness level achieved corresponds to that of domestic laundering at 50C.
Indosol E-50 is particularly suitable for treatment of knitted underwear,
sportswear and hosiery. In the case of Indosol EF (Clariant), the electrostatic and
coordination bonds formed as described above are further reinforced because
this agent is capable of reacting with a hydroxy group in cellulose to form a
covalent ether bond, similar to that produced in a typical reactive dyeing. This
additional fixation leads to high levels of colour fastness at all applied depths,
e.g. laundering at 60C. Although Indosol EF is applied by exhaustion at 40C
rather than the 60C used for Indosol E-50, a further alkaline treatment with
caustic soda, or alternatively a high-temperature cure at 150C, is necessary to
initiate the reaction of Indosol EF with cellulose.
Most woven cellulosic blend fabrics require at least a moderate degree of
crease recovery to exhibit satisfactory easy-care properties. Indosol CR
(Clariant) completely replaces the cellulose reactant resins that confer easycare properties by crosslinking. It can only be applied by a paddrybake
sequence. A cationic fixing agent of the Indosol E-50 type is reacted with a
conventional reactant of the dimethyloldihydroxyethyleneurea type to give
Indosol CR. Formation of the dyeIndosol E-50 complex occurs initially, but
on curing the reactant crosslinks the cellulose segments and forms a threedimensional matrix in which the dyeagent complex is held permanently.
Thus exceptionally high wash fastness is achieved, allowing full depths to
yield satisfactory fastness to washing tests at the boil. Microfibre blends of
polyester and viscose have been dyed successfully with disperse and reactantfixable dyes.
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The use of selected disperse dyes for the polyester allows for rapid rates of
temperature rise and short duration at 130C, minimising possible decomposition of the copper-complex reactant-fixable dyes. This process has clear
advantages:
(1) One-bath operation simplifies control and improves productivity [20].
(2) In-to-out times are reduced to between 3.5 hours (Indosol CR) and 4.5
hours (Indosol E-50/EF).
(3) Only 515 g l1 Glaubers salt is required, compared with 20100 g l1
electrolyte in reactive dyeing.
(4) The levelling power of the reactant-fixable dyes is excellent at 130C.
(5) Shading additions are easy to make before Indosol aftertreatment.
The most obvious drawback of this approach is the restricted gamut in
bright shades. A copper-specific sequestering agent Plexophor SFI (Clariant)
must be used to protect certain disperse blue dyes that are sensitive to copper
ions when dyeing in fully-flooded jet machines. Ethylenediaminetetra-acetic
acid is too powerful, causing demetallisation of the reactant-fixable dyes,
whereas phosphates have little ability to sequester copper [21]. Shading
additions to the aftertreated dyeing can be difficult because of the highly
cationic surface charge. Addition of anionic dyes results in rapid strike and
hence unlevelness. An anionic surfactant must be added before any shading
with the reactant-fixable dyes.
Two popular routes to black dyeings on polyester/viscose blends are based on
either CI Direct Black 22 (Figure 13.2) or the reactant-fixable system. Black 22
after resin treatment shows exceptional fastness on viscose and is a classic dye of
the ortho, para primary amino or hydroxy type where the molecules of dye can
condense with free formaldehyde or the N-methylol groups of the reactant. A
problem with Black 22 is the necessity for alkali to maintain solubility in dyeing
and this affects the stability of the disperse dyes adversely. A two-stage procedure
is necessary, dyeing the polyester at pH 5 and 130C and then cooling and
adjusting to an alkaline pH to dye the viscose. The use of reactant-fixable dyes
avoids the need for this pH swing [1].
In a more recent development, Clariant have introduced the Optisal/Optifix
system, supported by a computer program. This consists of a range of bright,
metal-free direct dyes with high exhaustion values and low salt content. These
features result in minimal contamination of waste waters. The stability of these
dyes at 130C allows them to be used in a one-bath method with disperse dyes
on polyester/cellulosic blends. Fixation of the Optisal dyes to cellulose occurs
during an alkaline aftertreatment with a cationic reactant, Optifix F Liquid
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H2N
NH2
NH2
N
H2N
SO3Na
N N
H O
O H
N
N
N
N
NaO3S
SO3Na
NaO3S
Figure 13.2 CI Direct Black 22
(Clariant), which does not release formaldehyde. These dyeings will meet
domestic laundering requirements up to 50C [22].
13.1.5 Reactive dyeing of the cellulosic component
Reactive dyeing is by far the most important technique adopted for exhaust
dyeing of the cellulosic portion of these blends. Reactive dyes can be used for a
full gamut of hues at virtually all depths. When dyeing a polyester-rich blend,
such as 70:30 for example, with reactive dyes at a typical liquor ratio of 15:1, the
effective liquor:cellulose ratio is 15:0.3 or 50:1. Hence it is essential to select for
batchwise dyeing reactive dyes that give high fixation at a long liquor ratio. The
use of reactive dyes of low substantivity for the exhaust dyeing of such blends is
inefficient, expensive and difficult to reproduce. Reactive dyes are almost
completely free from cross-staining of the polyester. The only exceptions are the
phthalocyanine-based blues and greens that may give slight staining in some
instances.
It is with this class of dyes on these particular blends, however, that the total
dyeing time can be the most prolonged. The original processing systems for these
blends usually consisted of:
(1) conventional high-temperature application of the disperse dyes;
(2) reduction clearing to remove any disperse dye staining from the cellulosic
fibre;
(3) conventional reactive dyeing in a fresh bath at the pH, temperature and
electrolyte concentration appropriate for the reactive system selected;
(4) rinsing and soaping at the boil as usual.
Total load-to-unload times could be as long as 12 hours and even then additional
shading corrections might be required. Detailed cost comparisons have shown
that the two-bath method with disperse and reactive dyes costs in labour, energy,
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dyes and chemicals about three times as much as the one-bath alternative with
disperse and direct dyes [23]. Traditionally, this two-bath sequence with
intermediate clearing was considered essential for optimum fastness of solid
dyeings or maximum brightness of contrast effects in full depths. There was
virtually no risk of interaction between the disperse and reactive dyes. The
selection of disperse dyes was unrestricted and common salt could be used freely
in the reactive dyeing bath.
Preparation of blends of microfibre polyester with viscose for sportswear by
scouring, drying and heat setting should be followed by a two-bath dyeing
sequence. The polyester is dyed first on the jet at 130C. This is followed by a
reduction clear, and then the viscose is dyed with vinylsulphone dyes [12].
Options have been presented for rationalising dyeing sequences on polyester/
cotton compared with the traditional bleach, polyester dyeing, reduction clear
and reactive dyeing. Novel concepts for relocating the bleaching step were considered and the savings attainable from rationalisation demonstrated [24].
During the 1980s, reactive dye manufacturers optimised exhaust dyeing
techniques for these blends with a view to reducing overall dyeing times and
limiting the number of soaping and rinsing steps. Developments were mainly
aimed at reducing the time and energy requirements without affecting the
fastness of the dyed goods. When dyeing in combination with conventional
alkali-fixing reactive dyes, some compromise in processing is required. Ideally,
alkali-sensitive disperse dyes should be fully absorbed by the polyester before
alkali is added to the dyebath. Likewise, the disperse dyes should not be
introduced until the reactive dyes are fully fixed and the dyebath neutralised,
otherwise lower or erratic yields may result [6]. The particular process chosen
also depends on the type and utilisation of the available machinery.
Opportunities for automation, short load-to-unload times, low energy
requirements and savings of water and chemicals are important [25].
Most of these developments followed either of two distinct approaches:
(1) Two-stage processes in which the polyester was dyed first and then alkali
added at a later stage to induce fixation of the reactive dyes, usually from
the low-reactivity ranges.
(2) The reverse two-stage or two-bath processes, in which the cellulosic fibre
was dyed first and then after an intermediate rinse the polyester was hightemperature dyed. This sequence was particularly suitable for vinylsulphone
dyes.
Although dyeing times can be reduced by up to 4 hours using these techniques,
there still remains the serious disadvantage of the high concentrations (50100
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g l1) of electrolytes required. This interferes with dispersion stability by

suppressing the essential ionising mechanism of the anionic polyelectrolyte
dispersing agents through a common-ion effect, thus decreasing the charge on
the dispersed particles and promoting agglomeration. The interference is
variable, frequently affecting one manufacturers formulation of a particular dye
more than anothers, or even varying between successive batches of the same
formulation. Dispersion stability depends on many parameters such as batch
quality of the dispersing agents and the physical form of the disperse dye, not
merely particle size distribution but also crystal form. This problem may be
alleviated by the judicious use of additional dispersing agents, of which the
ethoxylated phosphate type is particularly effective [8].
Another problem in disperse/reactive systems is the difficulty of reconciling the
different pH requirements of the two classes of dyes. Conventional reactive dyes
need alkaline conditions (pH 1012) for fixation. Although a few disperse dyes
will tolerate such alkalinity during dyeing, many containing vulnerable
heterocyclic rings or hydrolysable ester groups (Figure 13.1) must be dyed below
pH 6. Nevertheless, practically all disperse dyeings will withstand quite severe
alkalinity once the dyes have thoroughly penetrated the polyester fibre.
In the conventional two-stage approach, the initial disperse dyeing at high
temperature ensures uniform wetting out of the cellulosic fibres. Disperse dye
staining is normally removed during subsequent alkaline fixation of the lowreactivity dyes at 80100C, but disperse dyes with ester groups that can be
hydrolysed at pH 11 and 80C are preferred. Selection of the disperse dyes is
limited, however, to those with good dispersion stability in the presence of
electrolyte. For this reason, the use of Glaubers salt rather than common salt is
essential. The reactive groups in the low-reactivity dyes are sufficiently stable to
withstand the conditions of high-temperature dyeing of the polyester at pH 56
(phosphate buffer). High-reactivity dyes are generally unsuitable because of the
risk of interaction with the disperse dyes (section 4.1).
A mild oxidising agent such as sodium m-nitrobenzenesulphonate is added to
inhibit reduction of azo reactive dyes at 130C, especially when dyeing polyester/
viscose blends. This agent is less effective for azo disperse dyes or under acidic
conditions. The reducing action of viscose can be attributed to:
(1) high aldehyde end group content arising from oxidative damage in
bleaching;
(2) residual sulphur in the form of sodium sulphide or carbon disulphide from
xanthate regeneration in manufacture. Sulphide levels as low as 10 mg l1 in
enclosed systems can attack some azo direct or reactive dyes [1].
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In a more versatile alternative technique, the disperse and reactive dyes are
applied together at high temperature and pH 4.56. Salt, if added at the
start, would promote exhaustion of the reactive dyes but could then exert its
maximum deleterious effect on the dispersion stability. After exhausting the
disperse dyes at high temperature, the dyebath is cooled to 80C. This is the
best point at which to add the salt, since the residual concentration of
disperse dyes is too low for them to be adversely affected. After the lowreactivity dyes have been exhausted by the cellulosic fibre, alkali (usually
sodium carbonate) is added to bring about fixation. Good batch-to-batch
reproducibility of hue is related to the relative sensitivity of such systems to
process variables as demonstrated in the BASF process for the rapid dyeing
of these blends, which has been applied successfully to microfibre polyester/
viscose [25]. As with direct dyeings, reduction clearing of the disperse dyeing
must be avoided because of the sensitivity of azo reactive dyes to reduction.
Some clearing takes place, however, during the alkaline fixation and soaping
to desorb unfixed and hydrolysed reactive dyes.
In the Sumitomo RPD-Supra two-stage method, disperse dyes are applied to
the polyester in the first stage and Sumifix Supra (NSK) bifunctional reactive
dyes (Figure 8.1) are applied to the cellulosic fibre in the second stage. These
aminochlorotriazine-sulphatoethylsulphone dyes exhibit high substantivity and
reactivity, resulting in excellent fixation. They level well and show low sensitivity
to variations in time and temperature, giving highly reproducible dyeings [26].
The levelling of reactive dyes is closely related to substantivity, migration and
rate of fixation. In the case of Sumifix Supra structures, chromogens have been
selected from a wide range of chemical classes and optimised in substantivity and
reactivity to ensure a high degree of levelness. The reaction rate can be controlled
mainly by dyebath pH and temperature. Owing to the difference in reactivity
between the two functional groups, optimum dyeing conditions cover a relatively
wide range of conditions [27,28].
With the high-reactivity ranges of reactive dyes, it is necessary to complete
fixation on the cellulosic fibre before applying the disperse dyes to the polyester.
After dyeing with the high-reactivity dyes at the appropriate pH, temperature
and salt concentration in the presence of sodium m-nitrobenzenesulphonate,
followed by the relevant alkaline fixation conditions, the pH is adjusted to 66.5
with acetic acid. The disperse dyes and disodium dinaphthylmethanedisulphonate as dispersing agent are added and the polyester is dyed to the target
depth at 130C.
High-temperature dyeing is a highly efficient alternative to soaping at the boil
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as a means of desorbing the unfixed reactive dyes at a rapid rate of diffusion in

the absence of electrolyte. Shade reproducibility depends on the stability of the
dyefibre bonds in the reactive-dyed cellulosic fibre to the high-temperature
polyester dyeing stage. Any final shading of the cellulosic fibre requires a fresh
bath to be set after clearing of the disperse dyeing.
This two-stage method is particularly appropriate for vinylsulphone reactive
dyes because the dye-fibre bond formed by the nucleophilic addition mechanism
[29] is more resistant to acid hydrolysis than that formed by most other types of
reactive dyes. Thus vinylsulphone dyeings are not impaired by the mildly acidic
dyebath preferred for applying disperse dyes to the polyester fibre [30]. Soaping
after application of the vinylsulphone dyes is unnecessary because any unfixed
dye is readily removed in the final wash-off after the disperse dyeing stage.
This reverse approach is useful for piece dyeing on a jet machine, but is less
suitable for beam dyeing or package dyeing of yarn than the sequence in which
the polyester is dyed first, owing to greater aggregation of the unsorbed disperse
dyes in the high concentration of electrolyte present in the dyebath. Advantages
of the Then Airflow aerodynamic jet dyeing machine for this process are said to
be optimum fabric quality, freedom from creasing, no foaming, a high degree of
reproducibility and ease of cleaning of the machine after use [31].
Exhaust dyeing of the cellulosic fibre with Levafix E (DyStar) dichloroquinoxaline and Levafix E-A (DyStar) difluoropyrimidine dyes proceeds with
salt at 4060C, followed by fixation at pH 9.511.5. Dyeing of the polyester
with disperse dyes is completed at pH 46 and 130C. The principles and
practice of automatic metering of the chemicals have been detailed with special
reference to Levametering (DyStar) systems [32]. This ensures optimum fixation
conditions for both components of the blend, giving excellent reproducibility,
level dyeing and high colour yields. Full automation of the dyeing process
eliminates the dead time that occurs with manual control. The time savings
enhance productivity and lower the costs of labour and energy.
Kayacelon React (KYK) reactive dyes contain two aminonicotinotriazine
reactive groups per molecule (Figure 8.6). They readily react with cellulose,
eliminating the nicotino group to form a covalent bond that is identical with that
given by analogous dyes of the well-established bis(aminochlorotriazine) type.
The substitution reaction occurs with nonionised hydroxy groups in cellulose
under neutral dyeing conditions at high temperature, although if necessary the
reaction can be induced at lower temperatures under mildly alkaline conditions
[27,33]. A one-bath process for dyeing polyester/cotton blends with disperse dyes
and Kayacelon React dyes entails application at pH 7 and 130C with salt and a
nonionic levelling agent. After dyeing, the fabric is soaped at the boil and rinsed
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as in conventional reactive dyeing methods. The use of a fixing agent is not

recommended for pale depths, but a product of the long-chain alkylammonium
type is used for medium-depth dyeings and a polyamine auxiliary used for full
depths.
13.1.6 Water-insoluble colorants for polyester/cellulosic blends
Insoluble vat and sulphur dyes often show moderate to severe cross-staining of
the polyester component in these blends. In the case of vat dyes, this can
sometimes be exploited in using them to colour both fibres simultaneously. Some
of the benzamidoanthraquinone vat dyes of fairly low Mr dye polyester more
readily than the cellulosic fibre at 130C and can be used for solid effects on the
two fibres in pale depths. Certain olive green, khaki, brown and black dyes of
relatively complex structure give duller and more bathochromic hues on the
cellulosic fibre compared with the polyester.
Many polycyclic vat dyes give a good reserve of polyester fibres when applied
by the usual alkaline leuco methods. These are also useful when dyeing solid or
contrast effects with disperse dyes for the polyester. They include the halogenated
derivatives of anthanthrone or pyranthrone, the indanthrone and violanthrone
blues and greens, as well as most of the acridone and carbazole types. The colour
gamut is restricted in the bright orange, red and violet sectors, however.
Two-stage dyeing with disperse and vat dyes is a valuable method of achieving
excellent fastness to light and washing at all depths. The disperse and vat dyes
may be applied at pH 56 with an anionic dispersing agent. After dyeing the
polyester at 130C, the temperature is quickly lowered to 85C and the vat dyes
are reduced with alkaline dithionite. The cellulosic fibre is dyed to shade at an
appropriate
temperature
within
the
range
2060C, followed by reoxidation at 50C and soaping at the boil. Staining of
the polyester fibre by the vat dyes may complicate shade matching. The vat
dyeing conditions in the second stage act as a reduction clearing bath for the
disperse dyeing.
Selection of the vat dyes is restricted by problems of instability in hightemperature dyeing. This difficulty can be overcome by introducing the vat
pigment dispersion after cooling to 85C, but before adding the reducing system.
Owing to the rapid consumption of sodium dithionite, vat dyes are applied more
easily in machines completely filled with liquor, i.e. beams and fully-flooded jet
machines, rather than in only partly flooded jets or overflow machines. Only
selected vat dyes are sufficiently stable in the reduced form for addition at 85C,
including flavanthrone yellow, the indanthrone and violanthrone blues and
greens, as well as several of the carbazole types. In the case of the indanthrone
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blues, carbazole browns and olive greens, sodium nitrite should be added to
prevent over-reduction.
Well known drawbacks of vat dyeing processes include the difficulty of
maintaining satisfactory reducing conditions and the need to avoid over- or
under-reduction. These problems can lead to unlevelness, poor reproducibility of
shade and, in some cases, poor fastness to rubbing. Sodium dithionite is
especially unattractive from the environmental viewpoint. Ecologically
innocuous methods for reducing vat dyes currently under consideration include:
(1) electrochemical reduction using a mediator;
(2) organic reducing agents such as hydroxyacetone;
(3) iron pentacarbonyl or other Fe(II) complexes.
Iron complexes with ligands derived from triethanolamine or gluconic acid have
been investigated with selected Indanthren (BASF) dyes applied by exhaust
dyeing. Iron salt requirements, various molar ratios of Fe(II) salt to gluconic acid,
the influence of caustic soda concentration and the presence of Fe(III) ions,
levelling behaviour and over-reduction were investigated [34].
Two-bath methods of applying disperse dyes followed by vat or sulphur dyes
usually present no serious limitations. The reducing conditions in the second
dyebath are often sufficient to clear the surface deposition of disperse dyes
without an intermediate clear. Alkaline dithionite should be used to solubilise the
sulphur dyes because sodium sulphide may damage the polyester fibre.
The low cost of sulphur dyes makes disperse/sulphur dye recipes useful for
dull, heavy depths, but there are obvious limitations of shade. They are usually
satisfactory when the wash fastness requirements are less stringent than the
typical standards for disperse/vat dyeings. With certain heavy shades it may be
necessary to introduce an intermediate clearing step. Sulphur black dyeing is a
rather laborious procedure but it does produce dyeings of excellent bloom and
wash fastness. Either pre-reduced or solubilised sulphur dyes may be used. The
pre-reduced approach is more economical but it does cause more staining of the
dyeing vessel.
Pigment coloration of bleached polyester/cotton garments, e.g. knitted leisure
shirts, can be carried out after treating them with a suitable cationic binder.
Exhaust coloration with the dispersion of organic pigments and a compatible
anionic dispersing agent is followed by stonewashing with a surfactant, dry heat
fixation of the binder and finally a heat setting treatment to stabilise the fabric.
Colour yield, levelness of coloration and fastness to rubbing are all potential
problems [35]. Attention must be paid to the time and temperature of
pretreatment, binder concentration, pH and the effects of stonewashing on
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fastness to rubbing, yield and levelness. Single-class application to fibre blends is

a major advantage claimed for this process.
13.2 CONTINUOUS DYEING OF POLYESTER/CELLULOSIC BLENDS

13.2.1 Disperse dyeing of the polyester component
The continuous dyeing of woven polyester/cellulosic blend fabrics is a most
important sector of the textile dyeing industry. Statistics for the USA have shown
that more than half of the polyester fibre processed is destined for dyed polyester/
cellulosic fabrics, more than half of which are dyed con-tinuously by pad
thermofix processes. Continuous processing of long runs to a given colour
ensures consistently high yields and reproducible uniformity at a much more
economical price per metre than batchwise methods. The length of run to each
colour normally exceeds 5000 m, so a typical order in several colours will take
several hours to process through each stage. The trend, however, is for shorter
runs. Dyeing and heat setting of woven fabrics can be achieved simultaneously
without the risk of rope creasing. Crease formation, however, can still arise in
continuous processing and it is responsible for more seconds quality than any
other fault.
Thorough preparation is especially important before the continuous
dyeing of polyester/cotton. Each stage can be carried out continuously, i.e.
singeing, enzyme desizing, alkaline peroxide padsteam scour-bleach,
mercerising and heat setting before dyeing. Typical fabrics prepared in this
way include shirting, light suiting, rainwear, workwear, military and civilian
uniforms. This preparation sequence merely removes the surface impurities
from the polyester fibres, which are not significantly penetrated by the
alkaline peroxide liquor applied to the cotton. Mercerising enhances the
colour yield, lustre and dimensional stability of the fabric, as well as its
appearance by improving the coverage of immature cotton neps. The
crystalline structure of the cotton cellulose is modified [36], swelling the
fibres and eliminating their convolutions, but the polyester is not materially
affected. Heat setting is obligatory to minimise subsequent dimensional
changes at the high temper-atures reached in thermosol dyeing [37].
Polyester/cellulosic fabrics should be padded evenly with the dye
dispersion and a nonionic wetting agent at pH 56. A migration inhibitor of
the anionic polyelectrolyte type, e.g. sodium alginate, polyacrylamide,
poly(vinyl alcohol) or carboxymethylcellulose, is normally included and this
gels during drying to ultimately form a solid film in which much of the dye is
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entrapped. Migration inhibitors of the polyacrylamide type do not interfere

with dye transfer in thermofixation as much as does alginate [6]. Liquid
brands of disperse dyes are preferred to solid forms, as they are less prone to
migrate during drying and they give less staining of the cellulosic fibres.
Higher colour yields are attainable and the pad liquors are easier to prepare
in the large quantities normally required for continuous dyeing. On the other
hand, liquid dyes can settle on long storage and thus require thorough
agitation before weighing. When stored in partly used containers they may
vary in strength owing to loss of water or deposition of solids at the air/
liquid interface.
Prior to thermofixation the disperse dyes are present in the interstices of
the fabric in a highly aggregated state and are embedded, together with the
dispersants and wetting agent, in this solidified matrix of polyelectrolyte.
During drying and thermofixation the smaller aggregates release disperse dye
molecules that migrate to the fibre surfaces. Further disaggregation proceeds
and there is a build-up of dye near these surfaces [38]. Diffusion into the
interior of the polyester fibres can only take place when the disperse dyes are
in the monomolecular form and the temperature has reached that of the
thermofixation chamber.
A vertical infrared predrying zone minimises the tendency towards
streakiness or two-sided effects if insufficient migration inhibitor has been
used. This treatment should reduce the moisture content of the fabric from
5060% after padding to 2530%, so that drying can be completed in a hotflue machine at 100120C or on modulated drying cylinders (scaled from
80C to 140C) without significant migration [39]. Problems encountered
during padding and intermediate drying include the induction period while
the fabric is being heated up and staining of the cellulosic fibres by the
disperse dyes, which is greater than in batchwise dyeing. These factors are
both dependent on the type of drying unit, the fabric construction and the
composition of the pad liquor. The use of optimised dispersing systems
facilitates the transfer of disperse dyes from the surface of the cellulosic
fibres to the polyester during intermediate drying to give the highest
attainable yield on the polyester [40].
Migration during intermediate drying can cause many faults that are
difficult to rectify. It is particularly troublesome in the continuous dyeing of
knitted fabrics containing polyester/cellulosic yarns. Migration may occur as
a result of high liquor retention after padding, a slow initial rate of drying or
a high residual moisture content after the predrying step [41]. Faults arising
from dye migration include:
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CONTINUOUS DYEING OF POLYESTER/CELLULOSIC BLENDS
189
(1)
(2)
(3)
(4)
Ending: the drying rate and visual depth vary along the length of a run.
Streakiness: variable rates of drying over the fabric surface.
Frosting: dye migration from the interior to the surface of the fabric.
Two-sidedness: one surface of the fabric is hotter than the other during
drying, giving a visible difference in depth with the hotter side deeper.
(5) Dark selvedges: these regions hotter than the fabric centre.
(6) Light selvedges: these regions cooler than the fabric centre.
(7) Poor penetration: disturbance of the weave reveals undyed regions at the
crossovers and inside the threads.
With the exception of creasing, shading across the width of the fabric is the
biggest single cause of customer rejects [39]. Several tests are available to assess
migration, namely the sandwich, watch glass, glass plate, hot air and fold
tests [42].
Parameters that influence migration are dye class and constitution, physical
form of the dyes, dyebath additives and preparation of the substrate. In general,
disperse dyes in liquid form perform better in this respect than those formulated
as grains or powders. Quality control problems are more likely when handling
liquid brands, however, because of the risk of sedimentation on storage.
Differences in migration behaviour between equivalent disperse dyes with the
same CI generic name may arise because different formulating agents are present.
Even when the fabric is evenly and fully penetrated during padding, the final
dyeing may exhibit poor penetration because of migration or inadequate
thermofixation. During drying, water evaporates from the fabric surface and is
replaced by capillary flow of dye liquor from the interior. The dyed material will
show inferior fastness to washing and wear points of the garments, such as
collars, cuffs and elbows, will tend to develop into lightly coloured folds or
patches [6].
In a study of the behaviour of disperse dyes padded on to a 70:30 polyester/
cotton blend, the dye applied was found to be distributed with only 30% of the
total amount on the polyester and the remainder on the cotton. Thus the
concentration of disperse dye before thermofixation was more than five times
greater on the cotton than on the polyester. During thermofixation most of the
dye was found to be transferred from cotton to polyester by volatilisation into
the vapour phase [43]. Factors contributing to staining of the cotton include the
chemical nature and concentration of migration inhibitor present, the dyebath
pH and the chemical structure of the dyes used [44]. At unusually high
temperatures, or if the treatment time is unduly prolonged, dye is lost by
volatilisation and contamination of the interior surfaces of the thermofixation
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unit. Subsequent dyeings may be spoiled by volatilisation and redeposition of this

condensed dye on the new material.
Optimum fixation conditions depend on the design and efficiency of the
thermofixation equipment as well as the depth and sublimation fastness of the
dyeing, but the treatment temperature is usually within the range 205220C.
Although high-energy disperse dyes require somewhat critical conditions for
optimum transfer and fixation, they are the most widely used dyes for pad
thermofix methods, especially in full depths. The optimum temperature of
thermofixation is that at which the maximum amount of dye is transferred to the
polyester without significant loss by volatilisation or contamination. Treatment
at this temperature ensures optimum colour yield and fastness, high
reproducibility, low sensitivity to temperature variations and colour stability
during subsequent durable finishing. Too low a temperature of thermofixation or
time of treatment may prevent complete transfer of dye from cotton to polyester,
resulting in excessive staining of the cotton and poor yield on the polyester.
Listing arising from differential temperature distribution may be found after
thermosol treatment. Contact with the base-plates on a thermosol pin stenter
may cause off-shade selvedge marking [39].
The effective time of thermofixation at a given temperature is not the same as
the nominal duration of the treatment. Air is a poor heat-transfer medium and it
may take 4560 seconds before the fabric temperature is within a degree or two
of the air temperature in a conventional hot-air thermofixation unit. The time
taken also depends critically on the fabric weight and construction. The heavier
the fabric, the longer it takes to attain equilibrium temperature. It is important
that the material has been dried uniformly before entering the thermofixation
unit, otherwise the initial heating stage will be used to evaporate this residual
moisture rather than raising the cloth temperature to its maximum. This will
result in uneven and inadequate dye fixation [6].
Reduction clearing after the thermosol treatment is desirable to attain
optimum fastness on the polyester and to clear any disperse dye stain from the
cellulosic fibres. Reduction treatment must be avoided, however, if the cotton has
already been dyed. When vat dyes are applied the reducing conditions necessary
are often sufficient to clear the unfixed disperse dyes effectively, so that a separate
clearing treatment is unnecessary. Those disperse dyes that contain alkalihydrolysable groupings, or certain heterocyclic diazo components such as the
nitrothiophene blues (Figure 13.1) can be cleared by alkaline washing rather than
reduction clearing. Alkaline washing is substantially cheaper than reduction
clearing. It is applicable after dyeing with reactive dyes and it may be combined
with the washing-off of unfixed reactive dyes.
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Many dyed polyester/cellulosic fabrics are subjected to fairly severe heat treatments during subsequent durable finishing and garment manufacture. These
processes may induce further migration of low- or intermediate-energy disperse
dyes from the polyester to the cellulosic fibres or the resin film, resulting in possible colour changes or inferior fastness to rubbing and wet treatments. The
selection of high-energy disperse dyes helps to minimise these problems.
The severity of the thermomigration effect depends on several factors:
(1) constitution and applied depth of the dyes used;
(2) heat treatment history of the polyester fibres;
(3) degree of penetration of the polyester after thermofixation;
(4) degree of staining of the cellulosic fibres;
(5) temperature and duration of the heat treatment that causes the
thermomigration;
(6) presence of other contaminants on the surface of the fibre components.
Important counter measures [45,46] that can be taken include:
(1) careful dye selection to avoid dyes prone to thermomigration;
(2) adequate thermofixation conditions to ensure optimum penetration of the
polyester fibres;
(3) thorough post-clearing to minimise residual staining of the cellulosic fibres;
(4) lowering the curing temperature in subsequent resin finishing;
(5) minimal application of softeners and antistatic agents at the finishing stage.
13.2.2 Water-soluble dyes for the cellulosic component

The economically attractive one-bath batchwise process with disperse and direct
dyes cannot be adapted readily to continuous dyeing. Direct dyes exhibit only
limited solubility and are highly aggregated at padding concentrations. Their
high substantivity leads to shade matching problems because of rapid depletion
from the pad liquor (tailing). Steaming times would have to be prolonged
because direct dyes diffuse only slowly into the cellulosic fibres. The possibility of
padthermofix application of the disperse dyes, reduction clearing and then
batchwise dyeing with direct dyes is of no interest because of high processing cost
to achieve only moderate fastness.
Reactive and vat dyes are the main alternatives for dyeing the cellulosic
component. Reactive dyes give an excellent reserve of the polyester. Reserve of
the cellulosic component is much less desirable, especially in polyester/cotton
workwear fabrics or polyester/viscose blends in general, because the cellulosic
fibre is preferentially abraded during wear. One-bath or two-bath processes
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based on disperse and reactive dyes offer exceptional brightness and very good
fastness up to medium depths, especially for polyester/viscose dresswear or
shirting.
The simplest method of reserving the polyester fibre is to pad with highreactivity dyes, sodium bicarbonate and salt to minimise migration, followed by
drying at 90C. Urea is usually added to improve solubility during padding and
to enhance the colour yield. For maximum fixation in full depths or under
adverse drying conditions, a brief steaming treatment may be given before
soaping at the boil. In an alternative process, low-reactivity dyes are applied with
soda ash and urea, dried and reacted by thermofixation at
160200C. Improved results are obtained from either method on polyester/
viscose blends if the padded fabric is batched and stored for 12 hours before
drying. Better storage stability of the pad liquor is ensured if the fabric is padded
with the dyes in neutral solution and dried, then padded again in caustic soda
and salt solution, steamed, rinsed cold and soaped at the boil.
Selected disperse and reactive dyes can be fixed simultaneously by the simple
and economical one-bath paddrythermofix process. Dye selection is critical
because of the risk of interaction between disperse and reactive dyes under
alkaline conditions (section 4.1). Suitable disperse and high-reactivity dyes are
padded with urea, sodium bicarbonate and migration inhibitor. Sodium
m-nitrobenzenesulphonate is added to prevent reduction of certain azo reactive
dyes, particularly on polyester/viscose fabrics. After drying, the fabric is
thermofixed at 200220C and soaped at the boil.
Urea concentrations greater than about 50 g l1 induce excessive staining of
the cellulosic fibres under these conditions, resulting in unsatisfactory fastness
and inferior yield on the polyester. Another disadvantage of urea is that it
decomposes above 135C (Scheme 13.1) and the ammonia and cyanic acid
formed are objectionable. Although more costly, dicyandiamide (cyanoguanidine) and dicyanoguanidine (Figure 13.3) are preferable to urea, because
they are thermally stable and do not give rise to toxic by-products [47].
A more versatile selection of dyes is possible in two-stage methods using pad
drythermofix application of disperse dyes to the polyester, followed by pad
steam, alkalipad or alkalishock treatment to fix the reactive dyes on the
cellulosic fibre. Less productive, but giving the widest freedom in terms of dye
selection is the semi-continuous two-bath sequence of conventional paddry
thermofix to apply the disperse dyes and then cold padbatch dyeing with the
reactive dyes. High-reactivity dyes offer higher productivity than low-reactivity
types because of the short batching times required [48].
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193
NH2
H2N C O
HN C OH
N C OH + NH3
Urea
Cyanic acid
Scheme 13.1
NH2
HN C
NH CN
HN C
NH CN
Dicyandiamide
NH CN
Dicyanoguanidine
Figure 13.3 Alternatives to urea in thermosol dyeing
The advantages of semi-continuous dyeing methods for these blends include:

(1) suitability for lengths to a colour that are insufficient to justify fully
continuous processing;
(2) optimum use of readily available equipment;
(3) higher productivity and better uniformity at the padding stage than by
batchwise dyeing;
(4) continuity of colour over long runs compared with production of several
discrete batchwise dyeings;
(5) suitability for contrast effects with versatile control of shade matching.
Useful alternatives to the above semi-continuous process are the padbatch
beam and padbatchjet sequences, which are more productive with highreactivity dyes and especially suitable for vinylsulphone dyes. The blend fabric is
padded with the reactive dyes and the usual amounts of alkali and salt and then
batched for 224 hours according to dye reactivity. It is then transferred to a
high-temperature beam or jet machine, rinsed and soaped at the boil. After
addition of the disperse dyes, dispersing agent and acetic acid to pH 6, the
polyester component is dyed at 130C in the usual way. These processes offer the
advantages of optimum yields of the reactive dyes with minimum occupation of
the available pressure-dyeing equipment.
This approach is suitable for tubular-knit polyester/cellulosic fabrics by dyeing
the cellulosic component first using a padding unit (e.g. BeauTech, Calator or
Jawatex) designed specifically for padbatch processing of knitted fabrics. The
polyester component is then jet-dyed with disperse dyes. Significant savings over
traditional exhaust processes for knitgoods are claimed [49]. These semicontinuous techniques are particularly versatile for contrast effects since one run
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on the padbatch equipment can be divided into a series of batches for beam or
jet dyeing to different hues in the second stage.
13.2.3 Water-insoluble dyes for polyester/cellulosic blends

Selected members of the vat dye range will dye both components of a polyester/
cellulosic blend in most shades up to medium depth. At full depths the cellulosic
fibre is dyed more deeply and a skittery effect is evident. The target shade should
be matched with a single dye or binary mixture if possible. Trichromatic
combinations of dyes that differ widely in hue should be avoided. The best
solidity is given by selected indigoid and thioindigoid dyes but these have limited
fastness. Good solidity and better fastness are provided in the yellow to orange
sector by polycyclic quinone derivatives.
Suitable dyes are padded at 3040C with a wetting agent of the
sulphoricinoleate type and a migration inhibitor. After drying and
thermofixation at 200220C to promote diffusion of the vat dyes into the
polyester, the fabric is cooled in air and the dyes on the cellulosic component
reduced by padding in alkaline dithionite. Because of the previously high
temperature of the thermofixation stage, special attention must be given to
ensure that the fabric is adequately cooled before chemical padding and that the
pad liquor temperature is kept below 30C. After steaming, the dyeing is
reoxidised and soaped at the boil as usual.
The same process sequence is used to apply mixtures of selected disperse and
vat dyes at the initial padding stage. Matched mixtures of selected disperse and
vat dyes have been commercially available for many years. The critical factor is
the stability of the disperse dyes to reducing systems, once they have been fixed
on the polyester. The chemical padsteam stage is effective in clearing the
disperse dye stain from the cellulosic fibres as well as reducing the vat dyes
present. Only in unusually heavy depths is it necessary to apply the vat dyes from
a separate bath. The most severe requirements of fastness to rubbing, washing,
chlorine and dry heat in all depths for uniforms or workwear are met with
selected high-energy disperse dyes and vat dyes [50].
The disperse dyes are selected for stability under the reducing conditions of the
padsteam stage and the vat dyes should give only limited staining of the
polyester under thermofixation conditions. The higher the treatment temperature
is above 190C, the greater is the degree of staining. Minimal staining is shown
by the indanthrone blues and many of the acridone and carbazole types.
Satisfactory results can be achieved with dyes giving an intermediate degree of
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staining, if disperse dyes are used to adjust the hue on the polyester. Vat dyes of
this kind include violanthrone and isoviolanthrone derivatives, as well as most of
the benzamidoanthraquinones, oxazoles and thiazoles [51].
Vat leuco ester dyes will give a solid effect in pale depths on the two
components of a polyester/cellulosic blend. These dyes are padded at 6080C
with soda ash, sodium nitrite and a wetting agent. The dyeing on the cellulosic
fibre is developed on a jig or a continuous washing range by immersion of the
fabric in dilute sulphuric acid at 2040C, neutralisation with soda ash at 40C
and soaping at the boil. In this process the vat leuco esters dye the cellulose and
initially stain the surface of the polyester.
Final rinsing, drying and heat setting at 200210C achieves optimum fastness
and yield of the vat dyes on the polyester. The fabric must be completely free
from alkali at the thermofixation stage to avoid discoloration of the cellulosic
fibre. The oxidised forms of these dyes diffuse into the polyester during
thermofixation, which is an essential part of the dyeing process as it develops and
stabilises the colour. A hydrosetting treatment on the beam at 130C may be
given to achieve penetration of the polyester if no thermofixation equipment is
available.
In applications requiring high fastness in pale depths this method of dyeing
both fibre components simultaneously is elegant and easy to use. The only
drawbacks are that there is only a limited possibility of adjusting the proportions
of dye between the two fibres and the products are costly. In pale depths both of
these disadvantages are of minor significance.
The solubilised vat leuco esters can also be applied in combination with
disperse dyes. The blend fabric is padded at pH 56 with, in addition to the usual
migration inhibitor, a mixture of anionic and nonionic auxiliaries. Drying and
thermofixation to dye the polyester with the disperse dyes initiates preliminary
decomposition of the vat leuco esters. These are then fully fixed by padding in
the usual nitrite and sulphuric acid, then developing on a jig or washing range
[8].
Most disperse dyes in dispersion are unable to withstand the reducing systems
required for sulphur dyeing, but once they have been absorbed within the
polyester fibre they are quite stable. Disperse dyes are applied together with
dispersed or solubilised sulphur dyes by padding at pH 4.55.5 and drying,
followed by thermofixation at 190210C. Padding with alkaline dithionite,
steaming, reoxidation to fix the sulphur dyes and soaping at the boil completes
the process. Sodium sulphide or hydrosulphide reduction is avoided because it
has an adverse effect on the polyester fibres.
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An alternative process involves padding with disperse dyes, solubilised sulphur

dyes and the reducing agent thiourea dioxide at pH 56, followed by drying and
thermo-fixation to fix both classes of dyes. In this case, however, the thiourea
dioxide restricts the choice of disperse dyes since some azo dyes are attacked by it
[8].
Dyeing problems of various kinds may be associated with chemical padsteam
development of vat or sulphur dyes [52]. Inadequate yield may result from
incorrect formulation or subsequent decomposition of the chemical pad liquor.
Listing at the selvedges, foaming, shade variation or condensation spotting can
all arise in the steaming stage necessary to fix the dyes on the cellulosic
component. To obtain full development of shade, it is absolutely essential that
there should be no air in the steamer. Ineffective washing to remove chemical
residues, insufficient oxidising chemicals to reoxidise the leuco forms of the dyes
and deposition of unfixed dye on the surface of the fibres may lead to fastness
problems after final rinsing. Reoxidation of indanthrone blues above pH 9 may
result in over-oxidation, leading to greener and duller shades.
Azoic combinations still offer possibilities for colouring the cellulosic component
in certain bright shade areas. In red shades, for example, this approach is more
economical and gives higher fastness to chlorine than reactive dyeing. Continuing
interest in these products is attributable to the availability of stabilised liquid brands
for ease of handling, low costs of machinery and labour, high productivity and
flexibility of operation. Computer programs are available on disc for IBMcompatible systems. These supply complete recipes including precise application
procedures that ensure simple and reliable application in the dyehouse [53].
In a low-cost one-bath process, the fabric is padded at 40C with a stabilised
azoic diazo component (Fast Salt), an azoic coupler (Naphtol) and a matching
mixture of disperse dyes for the polyester, together with an acid donor (sodium
monochloroacetate) and urea or dicyandiamide to optimise coupling [54]. After
drying at 130C the fabric is thermofixed at 210C, rinsed and soaped at the
boil.
A versatile semi-continuous sequence entails conventional paddrythermofix
dyeing of the polyester with disperse dyes, followed by padding at 50C with an
azoic Fast Salt and a Naphtol dissolved in an alkaline solution containing
methylated spirit (formaldehyde must be excluded). After impregnation the
fabric is batched for 12 hours, developed in acetic acid solution and soaped at
the boil to remove unreacted azoic components [55].
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197
13.3 BLENDS OF CELLULOSE ACETATE OR TRIACETATE WITH

CELLULOSIC FIBRES
When cellulose acetate yarns were introduced in the 1920s, they created
considerable interest because of their potential for cross-dyeing effects with
cellulosic yarns. In blends with viscose, the acetate fibres confer a
considerable improvement in crease recovery. Cellulose acetate is used in
cotton-spun blends for a range of apparel end uses, mainly dresswear.
Cellulose acetate/viscose woven fabrics made from intimate staple blends
and conventional viscose filament constructions with acetate filament effect
threads were formerly popular for crepe dresswear, gabardines, tropical
suitings, leisure shirts, underwear and childrens wear. Two-fold yarns for
colour contrast effects, and viscose filament warps with acetate or acetate/
viscose staple wefts, may also be encountered. Acetate/viscose fabrics are still
significant for tailored ladieswear and shot silk linings. Acetate/cotton
brocades have been used for many years in floral patterned curtains and
upholstery.
When cellulose triacetate was first introduced in the 1950s, it was recognised
as a cheaper alternative to polyester with strength and wearing properties
intermediate between those of secondary cellulose acetate and polyester. It is
quicker-drying and more stable to boiling dyebaths than the secondary acetate. It
has better pill resistance than polyester, but is inferior to polyester in abrasion
resistance and dimensional stability.
Triacetate/cellulosic blends are mainly of interest for dresswear, suiting and
skirts, many of the garments being designed with durable pleated effects. The
triacetate component contributes easy-care properties, durable pleating and
crease recovery. Triacetate/viscose, more important than blends with cotton, is
used for childrens clothing, leisure shirts, pleated dresswear and lightweight
suiting. Triacetate/polynosic blends have also proved interesting for woven and
knitted ladieswear fabrics. A resin finish is required if the proportion of viscose
or polynosic fibre exceeds 30%.
Intact cellulose acetate shows only slight staining by dyes for cellulose, but
acetate/cotton must be bleached carefully under mildly acidic conditions because
partial saponification of the ester groups greatly increases subsequent staining of
the acetate component. If it is necessary to bleach cellulose acetate/viscose fabrics
for reserve effects or pale bright dyeings, this can be carried out with silicatestabilised hydrogen peroxide and an anionic detergent at 70C. Normally it is
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198
only necessary to singe, open-width relax in boiling water and then scour with
anionic detergent and ammonia at 6070C.
Reserve of viscose using selected disperse dyes for the acetate may be difficult.
The effect depends on the origin of the viscose and the efficiency of desizing and
peroxide bleaching, as well as the dyeing conditions. It is important to desize
thoroughly, since any residual size in the warp yarns will accentuate staining by
disperse dyes and thus require a more severe clearing treatment after dyeing.
Viscose staining also depends on dyeing time and temperature, liquor ratio and
the selection of anionic dispersing agents. The preferred disperse dyes that give
optimum reserve of viscose are mainly low-energy dyes (Mr 230300), including
dinitrodiphenylamine (yellow), nitroaniline monoazo (yellow to red) or 1,4disubstituted anthraquinone (red to blue) types.
The stain on the viscose can usually be cleared by alkaline reduction at
ambient temperature. Sodium dithionite in trisodium orthophosphate solution is
satisfactory with most azo disperse dyes. However, an oxidative clear with
sodium hypochlorite at a mildly alkaline pH, followed by an antichlor treatment
with sodium bisulphite, is often more effective for anthraquinone disperse dyes.
Either type of clearing treatment must be carried out under ambient conditions
to avoid decomposition of the disperse dyes on the cellulose acetate. Where both
types of disperse dye chromogen are present, it may be necessary to give both
clearing treatments in sequence with the reduction clear first. The essential
mechanisms are azo fission and leuco-anthraquinonoid solubilisation in the
reductive process and destruction of the anthraquinone chromogen by oxidative
attack [8].
If a neutral scouring and bleaching sequence is given to avoid saponification
of the cellulose acetate, this component can be reserved using selected saltcontrollable direct dyes of the multisulphonated type with salt at 80C. Solid
effects on acetate/viscose are traditionally obtained by a one-bath method at 75
80C and pH 67 with the disperse and direct dyes, salt and disodium
dinaphthylmethanedisulphonate as the dispersing agent. Care is required because
some copper-complex direct dyes are able to modify the hue of certain disperse
dyeings and the salt addition may lower the dispersion stability of some disperse
dyes.
Acetate/viscose dresswear or suiting fabrics are often dyed in colour contrasts,
or either fibre may be reserved. These blends have been particularly important
also in shot silk contrast effects on filament viscose warp/acetate weft lining
fabrics, where the component yarns are dyed in complementary contrasts such as
redgreen or bluegold. Optimum contrast in full depths requires a two-bath
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BLENDS OF CELLULOSE ACETATE OR TRIACETATE WITH CELLULOSIC FIBRES
199
sequence in which the cellulose acetate is dyed first, an intermediate clear at

ambient temperature is given and then the cellulosic fibre is shaded to target with
direct dyes. Either dithionite reduction or hypochlorite oxidation may be
employed as necessary with these high-contrast effects in which the acetate fibre
is usually dyed to the heavier depth. It is easier to obtain clear bright shades on
the cellulosic fibre in these instances by clearing the disperse dye stain before
applying the direct dyes.
Acetate/viscose blend fabrics for apparel are dyed on the winch or jig
according to fabric construction. Winch dyeing is avoided if there is likely to be
serious rope creasing. Dresswear or leisure shirting is usually plain woven from
50:50 acetate/viscose staple blend yarns, or contains an acetate filament warp
and staple viscose weft that can be dyed in contrasting colours. The dyed fabric is
normally resin-treated to achieve the required dimensional stability and wet
fastness.
Acetate/cotton curtaining and furnishing fabrics are dyed with disperse and
direct dyes selected from those with adequate light fastness for these outlets. It
has also been possible to produce solid effects on these blends using selected vat
dyes applied by pigment padding in the presence of disodium
dinaphthylmethanedisulphonate as dispersing agent. After drying, the fabric is
developed at the boil in a solution of sodium sulphite and sodium formaldehydesulphoxylate, reoxidised and soaped. Woven fabrics prone to creasing are
developed on the jig and knitted constructions on the winch.
Traditionally, however, there has been little point in using dyes of high fastness
on the cellulosic component of an acetate/cellulosic blend because the wet
fastness attainable on the acetate using low-energy disperse dyes was relatively
poor. Furthermore, the acetate fibre would be delustred by the boiling soap
aftertreatment needed to develop optimum fastness with reactive dyes on the
cellulosic component. The introduction of Xtol (Courtaulds) acetate fibre in
1987 enabled all unfixed reactive dyes to be completely removed from the
cellulosic fibre at the boil without delustring of the acetate fibre [56]. Together
with the higher wet fastness attainable with high-energy disperse dyes on Xtol,
much improved performance can be achieved compared with what was
previously possible on such blends.
Solid shades are most common on triacetate/cellulosic blends but contrast
effects and reservation of either fibre type are practicable. Most triacetate blend
fabrics are dyed on the winch or jet and adequate preparation is essential. Fabrics
for reserve effects or pale dyeings are enzyme desized and peroxide bleached.
Triacetate is more resistant to saponification under alkaline conditions than the
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secondary acetate, and triacetate/cotton fabrics may be cold mercerised. They

should not be S finished (section 11.2) or boiled with alkali, however, as this
aggravates cross-staining of the triacetate by direct dyes.
Selected disperse dyes will give a satisfactory reserve of the cellulosic fibre.
These can be applied at the boil and pH 56 with an ester carrier and disodium
dinaphthylmethanedisulphonate as dispersing agent. Triacetate absorbs disperse
dyes more slowly than acetate and this increases the likelihood of cross-staining
of the cellulosic fibre. Adequate clearing should be attainable using an anionic
detergent at 70C. Carrier addition can be avoided by jet dyeing at 120C but it
may then be necessary to reduction clear the disperse dye stain using sodium
dithionite at 40C.
The preferred disperse dyes for reserving the cellulosic fibre and showing good
stability to subsequent cross-dyeing with direct dyes and salt are mainly
intermediate-energy dyes (Mr 300400) with adequate fastness to pleating,
particularly monoazo and disazo (yellow to orange), chloronitroaniline monoazo
(red) and tri- or tetra-substituted anthraquinone (red to blue) types. Undamaged
cellulose triacetate can be reserved with selected multi-sulphonated self-levelling
and salt-controllable direct dyes, particularly stilbene derivatives and disazo
tetrasulphonates, including copper-complex types and symmetrical derivatives of
diarylurea middle components. It is usual to give a cationic aftertreatment to
improve wet fastness and avoid marking-off onto the undyed triacetate
component. Resin treatment is then necessary to enhance crease recovery,
dimensional stability and colour fastness. Vat dyes are unsuitable for triacetate
reserve effects because the triacetate fibre is partially saponified and cross-stained
during vat dyeing.
Solid and contrast effects are readily obtained by a two-stage process based on
the method already described for cellulosic fibre reserve with disperse dyes.
Direct and disperse dyes are added initially and after dyeing of the triacetate the
dyebath is cooled to 60C, salt is added and dyeing continued at 8090C to
target depth on the cellulosic fibre. Full depths show better fastness or brighter
contrast effects from a two-bath sequence with an intermediate clear of the
disperse dye stain using alkaline dithionite at 4050C.
Better wet fastness is achieved on triacetate/cellulosic blends using disperse
and vat dyes applied by a two-bath method. Vat dyes withstand the conditions of
disperse dye application better than do direct dyes and therefore the cellulosic
fibre is dyed first in this case. Selected cold-dyeing vat dyes are applied at pH 9
and 45C. Some staining of the triacetate occurs as a result of partial
saponification, but the stain has good fastness and the triacetate can be filled in
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BLENDS OF CELLULOSE ACETATE OR TRIACETATE WITH CELLULOSIC FIBRES
201
with disperse dyes from a fresh bath. The preferred vat dyes [51] include
benzamidoanthraquinones, heterocyclic anthraquinone derivatives (acridones,
oxazoles and thiazoles) and halogenated polycyclic quinones (anthanthrone,
dibenzopyrenedione and indanthrone).
Bright dyeings with good wet fastness can be obtained from a three-stage
sequence with disperse dyes applied by the conventional ester carrier process,
then exhaustion of the reactive dyes on to the cellulosic fibre with salt and finally
an alkaline fixation stage, cold rinsing and soaping at the boil.
A limited range of specific shades can be achieved on triacetate/viscose blend
fabrics using selected azoic diazo and coupling components. Solidity and
levelness were claimed to be acceptable and fastness to various agencies,
including wet and dry rubbing, was satisfactory [57].
13.4 BLENDS OF POLY(VINYL CHLORIDE) FIBRES WITH CELLULOSIC
FIBRES
Jersey fabrics in this category are made by the controlled shrinkage, dyeing,
stenter drying and raising of interlock knitted from staple blends of poly(vinyl
chloride) or PVC fibres with viscose or modal fibres. These constructions are
suitable for swimwear, sportswear, outerwear and upholstery fabrics. Woven
cotton or modal fibre blends with PVC fibre are also of interest, including a
70:30 cotton/PVC staple blend for corduroy constructions and a cotton warp/
PVC filament weft fabric for car upholstery. Processing is usually in open width
to minimise creasing.
After desizing and scouring with caustic soda (cotton blends) or soda ash
(viscose or modal blends) and an anionic detergent, these fabrics can be dyed by
a one-bath method using disperse and direct dyes at 8095C with dispersing
agent and salt. Better wet fastness is achieved by applying disperse and vat dyes
in a two-bath sequence. The conventional vat dyebath in the second stage clears
the disperse dye stain from the cellulosic fibre.
13.5 DYEING METHODS AND DYE SELECTION FOR DC BLENDS

Reserve or contrast effects are seldom in demand on polyester/cellulosic fabrics,
but on blends of cellulosics with cellulose acetate or triacetate, especially on
acetate/viscose fabrics, they do make a significant contribution. The simple onebath process with disperse and direct dyes is important on cellulosic blends with
the cellulose ester fibres or PVC fibre, but is only used on low-quality goods in
the polyester/cellulosic sector. Two-stage techniques with disperse and reactive
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202
Table 13.1 Dye selections for exhaust dyeing of DC blends
Blend
Colour
effect
Dyeing
method
Dye
selection
Polyester/
cellulosic
Polyester
reserve
Single-class
Direct dyes stable to peroxide bleach;

selected polycyclic vat dyes
Solid
Single-class
(pale depths)
Benzamidoanthraquinone vat dyes of

relatively low M r
One-bath
Disperse dyes and disazo

multisulphonated direct dyes at pH 6
Disperse dyes and reactant-fixable
dyes with copper-specific sequesterant
Disperse dyes and nicotinotriazine
reactive dyes at 130C
Two-stage

low-reactivity dyes at 8095C
High-reactivity dyes at low
temperature, then disperse dyes
at 130C
Disperse dyes at 130C, then selected
vat dyes at 2060C
Two-bath
(full depths)
Disperse dyes at 130C, then sulphur

dyes with dithionite
Acetate
reserve
Single-class
Salt-controllable multisulphonated
direct dyes at 80C
Cellulosic
reserve
Single-class
Solid
One-bath
Low-energy disperse dyes and

salt-controllable direct dyes at pH 67
and 80C
Contrast
Two-bath
Disperse dyes at 80C, reductive or

oxidative clear at 20C, then direct
dyes at 80C
Xtol/
cellulosic
Solid or
contrast
Two-stage
High-energy disperse dyes at the boil,

then reactive dyes at appropriate
temperature
Triacetate/
cellulosic
Triacetate
reserve
Single-class
Selected multisulphonated direct dyes

with cationic aftertreatment
Cellulosic
reserve
Single-class
Intermediate-energy disperse dyes

at 120C
Solid or
contrast
Two-stage
Disperse dyes at 120C, then direct

dyes at 90C
Acetate/
cellulosic
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DYEING METHODS AND DYE SELECTION FOR DC BLENDS
203
Blend
Colour
effect
Dyeing
method
Dye
selection
Triacetate/
cellulosic
Solid or
contrast
Two-bath
Selected vat dyes at 45C, then

intermediate-energy disperse dyes
at 120C
PVC/
cellulosic
Solid
One-bath
Low-energy disperse dyes and direct

dyes at 95C
Two-bath

cold-dyeing vat dyes
Table 13.2 Dye selections for continuous dyeing of polyester/cellulosic blends
Blend
Colour
effect
Dyeing
method
Dye
selection
Polyester/
cellulosic
Polyester
reserve
Paddry
High-reactivity dyes with sodium

bicarbonate and urea
Paddry
thermofix
Low-reactivity dyes with sodium

Paddry
thermofix
Selected disperse dyes and

high-reactivity dyes with sodium
Solid
Disperse dyes and stabilised azoic

components with acid donor and
hydrotropic agent
Paddrythermofix
padbatch
Disperse dyes, then high-reactivity

dyes
Padbatchbeam
or jet

Padjig develop
drythermofix
Vat leuco esters for both fibres

(pale depths)
Paddrythermofix
padsteam
Disperse dyes, then low-reactivity

dyes
Selected vat dyes for both fibres
(pale or medium depths)
High-energy disperse dyes, then
selected vat dyes
High-energy disperse dyes, then
dispersed or solubilised sulphur
dyes
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204
dyes represent the most important exhaust dyeing approach on polyester/

cellulosic or Xtol (Courtaulds) acetate/cellulosic blends. Two-stage or two-bath
processes with disperse and vat dyes offer high standards of all-round fastness
performance on blends of polyester, cellulose triacetate or PVC fibre with the
various natural or regenerated cellulosic fibres (Table 13.1).
Excellent polyester reserve effects are attainable on polyester/cellulosic fabrics
using highly productive paddry or paddrythermofix application of reactive
dyes. Solidity on the two fibre components up to medium depths is attainable
using vat dyes or their leuco esters alone, or a simple paddrythermofix process
with selected disperse and reactive dyes. Higher all-round fastness and a wider
selection of dyes are offered by various two-stage sequences involving
thermofixation of the disperse dyes on polyester and then chemical padsteam
fixation of vat, sulphur or reactive dyes. Compromise semi-continuous methods
such as paddrythermofixpadbatch or padbatchbeam (or jet) have also
been found useful for disperse and reactive dyes (Table 13.2).
13.6 REFERENCES
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
12.
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14.
15.
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R Aitken, J.S.D.C., 99 (1983) 150.
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W S Hickman and R J Chisholm, Australian Text., 13 (MarApr 1993) 24.
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R T Norris, Textilveredlung, 12 (1977) 258.
F Schlaeppi, R D Wagner and J L McNeill, Text. Chem. Colorist, 14 (1982) 257.
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(Oct 1985) 37.
N E Houser, J C Martin and M White, Am. Dyestuff Rep., 70 (Sep 1981) 19.
N E Houser and M White, AATCC Nat. Tech. Conf., (Oct 1976) 105.
T D Fulmer, Americas Textiles Internat., 18 (Jan 1989) 54.
T A Waldrop, Am. Dyestuff Rep., 75 (Sep 1986) 22.
D Monney, Dyer, (Apr 1994) 32.
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REFERENCES
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35.
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S Abeta and K Imada, AATCC Nat. Tech. Conf., (Oct 1985) 112.
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G H Kenyon, Am. Dyestuff Rep., 68 (Mar 1979) 19.
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N Morimura and M Ojima, Am. Dyestuff Rep., 74 (Feb 1985) 28.
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TRIACETATE/POLYESTER AND OTHER DD BLENDS
CHAPTER 14
Triacetate/polyester and other DD blends
14.1 DYEING PROPERTIES OF DISPERSE-DYEABLE FIBRE BLENDS

Cellulose acetate, triacetate and polyester differ greatly in dyeability at a given
temperature. The low-energy dye 1,4-diaminoanthraquinone (CI Disperse Violet
1) yields a 50% exhaustion value at 40C on acetate, 70C on triacetate and over
100C on polyester. The dyeing rate is much more rapid on cellulose acetate, so
that it is virtually impossible to achieve solid effects on either acetate/triacetate or
acetate/polyester blends. Shadow and reserve effects have been of some interest
on mixed-ply yarns. Triacetate/polyester offers more scope for achieving solidity
and this blend has proved moderately useful in dresswear fabrics woven from
filament yarns. Shadow effects and a limited degree of reserve of polyester with
appropriate selections of dye and carrier are also possible. Triacetate/polyester is
therefore by far the most versatile of the DD blends.
It is usual to scour, stenter set and S finish as for 100% triacetate fabrics (section
11.2). The presetting treatment markedly lowers the dyeability of the triacetate
component without greatly affecting the polyester, so that solid effects become
easier to obtain. During dyeing the triacetate is dyed preferentially in the early
stage, but migration from triacetate to polyester occurs later as the dyes diffuse
slowly into the polyester. Eventually a solid effect is achieved, the time depending
on the recipe and depth of shade. It is easier to attain acceptable solidity at short
liquor ratios and in pale depths. At longer liquor ratios preferential absorption
by the triacetate component becomes more obvious and it is progressively more
difficult to transfer the dyes to the polyester [1].
Cellulose triacetate and polyester are therefore sufficiently close in dyeing
properties to give good solidity with selected dyes under controlled dyeing
conditions. There are four possible methods of obtaining good solidity on triacetate/
polyester blends by batchwise dyeing:
(1) Monoazo, disazo or anthraquinone disperse dyes of intermediate or high
fastness to sublimation (Mr 300450) are the most suitable for this purpose
in the conventional high-temperature process at 120C.
206
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DYEING PROPERTIES OF DISPERSE-DYEABLE FIBRE BLENDS
207
(2) A two-stage method, dyeing first at 130C to achieve satisfactory yield and
penetration on the polyester fibre, followed by a period at the boil without
carrier to bring the triacetate fibre to the same depth.
(3) Selected dyes will give good solidity in the presence of an aryl ester or diphenyl
carrier at the boil. Anthraquinone dyes of intermediate sublimation fastness
are particularly appropriate. Few azo dyes give adequate solidity under these
conditions.
(4) In an alternative carrier-dyeing method, selected dyes favouring polyester at
the boil are used together with others that favour triacetate. This results in
complicated recipes with up to six component dyes.
These blends are almost always dyed at high temperature nowadays. The
selection of intermediate- to high-energy dyes applied at 120C is the preferred
approach. The two-stage method is time-consuming but provides better control
from the viewpoint of shade matching. Carrier-dyeing methods are much more
unattractive because of the adverse effect of these products on the working
environment. Combinations of dyes that are partially selective for dyeing the
respective fibres do give more control of colour matching to achieve a solid
effect, however.
In high-temperature dyeing small quantities of carrier are still sometimes
added to shift the balance in favour of the polyester. Ester-based carriers, such as
methyl salicylate or butyl benzoate, are particularly effective [2]. Phenolic
carriers lower the light fastness, especially on the triacetate component, and are
difficult to remove without appreciable stripping of dye from the triacetate. In
addition to its toxicity, trichlorobenzene causes moderate swelling of the
triacetate fibres and is best avoided.
The dyes favouring polyester under carrier-dyeing conditions at the boil are
the high-energy azo and anthraquinone types. Low-energy monoazo and nitro
dyes generally favour the triacetate fibres. If those dyes showing a preference for
triacetate are applied alone at 90C with an ester carrier, shadow and polyester
reserve effects can be readily obtained.
Shadow effects represent the only possibility on cellulose acetate/triacetate
blends for dresswear. Solidity, reserve and contrast effects are all excluded. The
acetate is dyed more deeply and there may be differences in hue between the
component fibres when applying combination recipes in mode shades. Dyeing at
60C favours the acetate fibre to the greatest extent and as the dyeing
temperature is increased the difference in depth decreases, although even at 95C
solidity is not generally achieved and the acetate fibre is delustred above 85
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PAGE TITLE
90C. The introduction in 1987 of Xtol (Courtaulds) acetate fibre [3] has offered
the possibility of dyeing acetate/triacetate blends at the boil to achieve nearsolidity without delustring but this possibility does not widen the colouring
potential of these blends very much. Simple low-energy yellow, orange and red
dyes of the substituted p-nitrophenylazoaniline type give the best approach to
solidity. Ester carriers do promote uptake of dyes by the triacetate component,
but these agents cause unacceptable swelling of the acetate fibres.
Solidity is virtually impossible to attain on polyester/acetate blends because
the rate of dyeing is so much higher on the acetate. If a reserve of the polyester is
required the acetate can be dyed at 6070C with a nonionic dispersing agent
using mainly monoazo yellow to red dyes of relatively high energy
(Mr 330450) containing N-hydroxyethyl or N-acetoxyethyl substituents in the
coupling amine, as well as violets and blues of the 1,4-disubstituted
anthraquinone type.
Shadow effects on this blend require higher dyeing temperatures and longer
times. Unfortunately, such severe conditions tend to degrade conventional
acetate fibres badly, leading to delustring, fibre swelling and loss in tensile
strength of the blend fabric. Much better shadow dyeings are obtained on blends
of Xtol (Courtaulds) acetate fibre with polyester, since high-energy dyes can be
effectively absorbed by both components without delustring of the Xtol fibres.
It is sometimes possible to use combinations of slow- and rapid-diffusing
disperse dyes in the presence of a carrier to increase the rate of dyeing on the
polyester. It is particularly important, however, to check the effect of the
carrier on the tensile strength of the acetate fibres. Rapid-diffusing dyes are
low-energy (Mr 230270) monoazo and anthraquinone types. The slowdiffusing dyes are similar in structural types but higher in energy (Mr
270350). Carrier-dyeing methods, however, are becoming increasingly
objectionable for ecological reasons.
Shadow effects with low- and intermediate-energy disperse dyes are readily
controlled on fabrics woven from normal and deep-dye polyester yarns (section
5.1). Dyes with similar rates of exhaustion on these two fibre variants should be
selected for mode shades [4]. The rate of temperature rise should be slowed in the
critical region and an alkanol polyoxyethylene retarder used to minimise
unlevelness. Good liquor circulation or vigorous agitation of the fabric are
necessary. Unlevel dyeings can be corrected by treatment with an ester carrier
and a dispersing agent at pH 56 and the boil.
The light fastness of disperse dyes on deep-dye polyester variants designed for
dyeing at the boil without carrier is inferior to that on normal polyester. This
deficiency is attributed to the presence of alkylene ether groups in the main chain
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DYEING PROPERTIES OF DISPERSE-DYEABLE FIBRE BLENDS
209
of the copolymer (section 5.1). The addition of stabilisers to the dyebath has
been examined with a view to overcoming this drawback [5]. An antioxidant
Irganox 1010 (Ciba) and an ultraviolet absorber Tinuvin 328 (Ciba) of the
hindered phenol type were used (Figure 14.1).
OH
tBu
tBu
tBu
tAm
tBu
CH2
O H2C C CH2 O
HO
CH2
tBu
OH
OH
tAm
tBu
Ultraviolet absorber
tAm = tertiary amyl
tBu
tBu
OH
Antioxidant
tBu = tertiary butyl
Figure 14.1 Stabilising agents for disperse dyes on deep-dye polyester
CI Disperse Red 60
CI Disperse Red 82
NH2
CN
O
CH2CH2OCOCH3
O2N
N N
N
CH2CH2OCOCH3
OH
Dyes of high light fastness
Red
CH3
Orange
CH3
CH3
O2N
N N
N
CH3
O
Dyes of low light fastness
Figure 14.2 Disperse dyes evaluated with stabilising agents
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Two disperse dyes of high light fastness and two of inferior fastness (Figure
14.2) were applied at 130C in the presence of these additives to polyester fabrics
knitted from the two variant yarns. Improvements in xenon-arc light fastness
ratings of 0.5 to 1 point were obtained with each additive. The ultraviolet
absorber was marginally more effective than the antioxidant and in some cases a
synergistic effect was observed using them in combination.
14.2 DYEING METHODS AND DYE SELECTION FOR DD BLENDS

Among these blends a reserve effect can only be achieved on polyester in its
blends with cellulose acetate or triacetate. There are several methods for
attaining good solidity on triacetate/polyester blends (Table 14.1) but this is the
only DD blend on which this effect is practicable. The two methods that require
Table 14.1 Disperse dye selections for DD blends

Blend
Colour effect
Dyeing method
Dye selection
Triacetate/
polyester
Polyester
reserve or
shadow
One-stage
Low-energy monoazo and nitro

dyes at 90C with ester carrier
Solid
One-stage
Intermediate- or high-energy
dyes at 120C
Intermediate-energy
anthraquinone dyes with ester
carrier at the boil
High-energy dyes for polyester
and low-energy dyes for
triacetate with ester carrier
Two-stage
Polyester dyes at 130C, then

triacetate dyes at the boil
Acetate/
triacetate
Shadow
One-stage
Low-energy dyes at 6080C
Polyester/
acetate
Polyester
reserve
One-stage
High-energy monoazo and

low-energy anthraquinone dyes
at 6070C
Polyester/Xtol
(Courtaulds)
Shadow
One-stage
High energy dyes at the boil

without carrier
Normal/
deep-dye
polyester
Shadow
One-stage
Low- and intermediate-energy

dyes at 120C
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DYEING METHODS AND DYE SELECTION FOR DD BLENDS
211
the use of a carrier to achieve this are of little or no interest nowadays. All DD
blends will readily yield shadow effects, of course, this being the inevitable result
of the widely different rates of dyeing between these disperse-dyeable fibres.
14.3 REFERENCES
1.
2.
3.
4.
5.
V R Adomas, R R Zhyamaitaitene and V V Brazauskas, Issled. svoistv. syrya i pererab. ego v

shelkov. prom-sti., M (1984 ) 141.
J Hrter, Melliand Textilber., 63 (1982) 296.
B Kster and H Herlinger, Textil Praxis, 40 (1985) 406.
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DYEING PROPERTIES OF THREE-COMPONENT BLENDS
CHAPTER 15
Dyeing properties of three-component blends
15.1 INTRODUCTION
Extension of the classification scheme in Chapter 2 to the case of threecomponent blends follows logically to give categories such as those listed in
Table 15.1. Clearly, there are twenty possible combinations of three from four
fibre types that could be assembled but in practice not all of them are useful. The
ten categories included in Table 15.1 are those in which actual three-component
blends have been encountered. It is often advantageous to approach each of these
blends as a one-off set of requirements. Nevertheless, the general principles
adopted in dealing with the binary blends offer the best basis for developing a
coherent dyeing method for a three-way blend.
The selection of fibre blend components and their proportions is as critical for
three-component blends as it is for the more familiar binary blends, but the
addition of a third component offers no guarantee of producing a fabric with
enhanced characteristics overall. Apparel fabrics for blazers, outerwear, flannels
and velours, traditionally manufactured with a cotton warp and a wool weft,
may be made with a blended wool/viscose or nylon/viscose weft, for example, on
economic grounds. Four-component blends are occasionally encountered, too,
since dresswear or other items of apparel may be woven from dissimilar blended
staple yarns in both warp and weft.
An interesting account has appeared of pushing back the frontiers of what is
achievable in multicolour piece dyeing for the woven suitings sector by the Gibbs
Burge dyehouse in Australia [1]. Regular production was established of fourcolour designs on multifibre fabrics, sometimes including six man-made fibres
(acrylic, modacrylic, nylon, viscose, regular and modified polyester). Numerous
fancy yarns (marls, mlanges, slub yarns, boucls, donegals) were incorporated
in design styling. Initially these were included as stripe effects, but then gradually
introduced into more complex constructions to extend the versatility of
appearance, colour and texture effects.
At the outset, limitations were anticipated in fastness to light, washing,
perspiration and rubbing, cross-staining, differential abrasion, differential
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INTRODUCTION
Table 15.1 Classification of ternary blends
AAA blends
Nylon/wool/polyurethane
Pale-dye/normal/deep-dye nylon
Normal/deep-dye/ultra-deep nylon
AAB Blends
Nylon/wool/acrylic fibre
Polyurethane/wool/basic-dyeable
polyester
Nylon/modacrylic fibre/acrylic fibre
Nylon/acid-dyeable acrylic fibre/basicdyeable acrylic fibre
Modacrylic fibre/acid-dyeable acrylic
fibre/basic-dyeable acrylic fibre
Normal/deep-dye/basic-dyeable nylon
AAC blends
Nylon/wool/cotton
Nylon/wool/viscose
Nylon/polyurethane/cotton
Normal nylon/deep-dye nylon/cotton
Normal nylon/deep-dye nylon/viscose
CBA blends
Cotton/acrylic fibre/nylon
Cotton/basic-dyeable acrylic fibre/aciddyeable acrylic fibre
Cotton/modacrylic fibre/acrylic fibre
DAA blends
Cellulose acetate/nylon/wool
Cellulose triacetate/nylon/wool
Polyester/nylon/wool
Polyester/polyurethane/wool
DAC blends
Cellulose acetate/nylon/cotton
Cellulose triacetate/nylon/cotton
Polyester/nylon/cotton
Polyester/polyurethane/cotton
Cellulose acetate/wool/viscose
Cellulose acetate/wool/linen
Cellulose acetate/nylon/viscose
Cellulose triacetate/nylon/viscose
Polyester/nylon/viscose
DBA blends
Polyester/acrylic fibre/wool
Normal polyester/basic-dyeable
polyester/wool
polyester/nylon
Poly(vinyl chloride)/acrylic fibre/wool
Poly(vinyl chloride)/acrylic fibre/nylon
DBC blends
Polyester/acrylic fibre/cotton
Polyester/acrylic fibre/viscose
polyester/cotton
polyester/viscose
DDA blends
Cellulose acetate/polyester/nylon
Cellulose acetate/poly(vinyl chloride)/wool
DDC blends
Cellulose triacetate/polyester/cotton
Cellulose triacetate/polyester/viscose
shrinkage and cockling. These proved to be less critical than expected, providing
careful compromises in dye selection and dyeing conditions were reached. In
general, most customers were prepared to accept wider tolerances in order to
obtain novel effects with greater intrinsic appeal [1].
15.2 DYEING OF AAA BLENDS

Ternary AAA blends of acid-dyeable nylon variants, e.g. pale-dye/normal/deepdye or normal/deep-dye/ultra-deep, are less versatile than the binary blends
(section 5.2) because the range of coloured effects attainable is limited mainly to
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PAGE TITLE
three-way shadow effects. The cost of manufacture is similar to that for AAB
nylon blends containing two acid-dyeable variants with a basic-dyeable yarn.
These offer considerably wider possibilities for contrast and reserve effects.
Control of pH is most important for reproducible results on ternary acid-dyeable
blends. A relatively slight change in total exhaustion may significantly alter the
distribution between the variant yarns.
Acid dyes for these blends differ in selectivity according to structural type. The
differentiation within the range pH 47 tends to increase with degree of
sulphonation. Levelling acid dyes with three or four sulpho groups show selective
behaviour even in pale depths, but monosulphonates give marked differences
only in full depths applied at pH 78. Premetallised dyes and the more
hydrophobic supermilling acid dyes with high wet fastness properties show
such poor differentiation that they are of little value for these blends.
Three-way shadow effects are given by a range of monoazo or monosulphonated anthraquinone dyes. The normal nylon component can be reserved
(if necessary at a slightly higher pH) using a similar series of dyes that are
preferentially absorbed by the deep-dye and ultra-deep variants. These are
mainly mono- or disulphonated anthraquinone dyes. Many disulphonates and
trisulphonates, especially monoazo and disazo types, will give a satisfactory
reserve of the normal and deep-dye yarns. These dyes are selectively absorbed by
the ultra-deep variant under neutral conditions where hydrophobic dyefibre
bonding predominates.
Four approaches to dye selection are available to exploit the colouring
possibilities with these groups of dyes:
(1) A short but versatile range of hues for three-way shadow effects contains a
red and a green that allow reserve of the normal nylon at a higher pH.
(2) The same range can be used in conjunction with more highly sulphonated
types that dye the ultra-deep variant selectively. Such selections yield a
shadow effect on the normal and deep-dye yarns with a much deeper
contrasting (but dependent) hue on the ultra-deep nylon.
(3) Selected dyes that reserve only normal nylon can be used with the more
highly sulphonated types to obtain a dependent contrast on the more
dyeable variants with the normal nylon reserved.
(4) Alternatively, selected disperse dyes can also be added to give a three-way
dependent colour contrast. The ultra-deep yarn is invariably dyed very
heavily to a dull hue in these effects. It absorbs all three dye types and the
disperse dyes often show some preference for the ultra-deep component.
This limits the attractiveness of the coloured design and the wet fastness that
can be achieved.
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DYEING OF AAA BLENDS
215
Polyurethane fibres are sometimes used in nylon/wool fabrics to provide

enhanced stretch properties. Fast dyeings on this ternary blend are best obtained
with 1:2 metal-complex dyes. Coverage of physical variations in the nylon
component is less serious than for nylon/polyurethane blends (section 6.3). As in
the application of these dyes to nylon/wool (section 6.1), a syntan is added to
retard uptake by the nylon component and an alkanol polyoxy-ethylene is used
to improve levelling.
15.3 DYEING OF AAB BLENDS

Core-spun polyurethane yarns are sometimes used to confer better stretch
characteristics in polyester/wool fabrics. The use of disperse dyes for the
polyester often results in low fastness of the dyed polyurethane to spotting
with chlorinated solvents. If basic-dyeable polyester is used in blends with
wool and polyurethane, however, this problem no longer arises since ionic
dyes can be applied to all three fibres. The dyebath is set with an alkanol
polyoxyethylene as anti-precipitant, an anionic retarder for the basic dyes,
an aryl ester carrier formulated with a nonionic emulsifier, acetic acid and
the basic dyes. These dyes are exhausted on to the basic-dyeable polyester at
the boil. The dyebath is then cooled to 70C and the two acid-dyeable
components dyed simultaneously using suitable neutral-dyeing anionic dyes
with an anionic agent to control the distribution between the wool and
polyurethane.
Knitted blends of basic-dyeable and acid-dyeable acrylic yarns are sometimes
physically strengthened by including nylon. The one-bath method with selected
basic and acid dyes at pH 45 already described for nylon/acrylic blends (section
7.2) will give attractive contrasts between nylon and the basic-dyeable acrylic
fibre while reserving the acid-dyeable acrylic fibre. At lower pH, the acid dyes
will give a shadow effect on the two acid-dyeable components. Under nearneutral conditions, the basic dyes will give a similar effect on the two acrylic
variants.
Blends of normal, deep-dye and basic-dyeable nylon provide a wider range
of colouring possibilities than either the ternary AAA combinations or the
binary AB blends. There are still limitations imposed by cross-staining,
however. The dyeing method is essentially that already described for normal/
basic-dyeable nylon, using a phosphate buffer at pH 6 (section 5.3). The
coloured effects are varied by dye selection. Certain monosulphonated acid
dyes will give a shadow effect on the acid-dyeable components and reserve
the basic-dyeable yarn. If basic dyes of the localised-charge type are added, a
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shadow and contrast effect is obtained. A dependent contrast with reserve of

the basic-dyeable nylon is given by selected mono- and disulphonated acid
dyes in combination (section 5.2). If the disulphonated acid dyes and basic
dyes are used together, the normal nylon can be reserved with an
independent contrast on the other two fibres, but there are limitations of
depth. Finally, a restricted gamut of dependent three-colour contrasts is
possible using both types of acid dyes together with basic dyes.
15.4 DYEING OF AAC BLENDS

Traditionally, the most important AAC blend was the nylon/wool/viscose
combination for carpet yarns but this is now seldom encountered. Blends of
the AAC type are sometimes found in decorative uniforms or blazer-cloth
designs, examples being a cotton or nylon/viscose warp with a nylon/wool
weft or a nylon staple warp and a wool/viscose weft. All of these may be
readily dyed by a one-bath method under neutral conditions using selected
metal-complex or acid dyes as discussed for nylon/wool (section 6.1),
together with salt-controllable direct dyes mainly of the disazo or trisazo
tetrasulphonate type. Salt addition promotes exhaustion of the direct dyes by
the cellulosic component and a syntan is required to minimise uptake of
these dyes by nylon.
Nylon/polyurethane/cotton blends containing 1020% of the elastomeric
fibre are important in knitted underwear. Stretch corduroy fabrics containing
these three components can be dyed semi-continuously by first dyeing the
cotton with reactive dyes by cold padbatch, sulphur dyes by padsteam, or
vat leuco esters by a paddevelop method [2]. The two acid-dyeable fibres
are then filled in by exhaust dyeing with 1:2 metal-complex or milling acid
dyes in the presence of an appropriate auxiliary agent to control the
distribution between the nylon and polyurethane components (section 3.3).
Normal and deep-dye nylon yarns have been used in blends with cotton
for upholstery fabrics. These can be dyed with selected direct and acid dyes
as already discussed for nylon/cellulosic blends (section 8.2). The preferred
acid dyes are those mono- and disulphonated types that show good reserve
of the cotton as well as satisfactory differentiation of the nylon variant
yarns. Suitable direct dyes are mainly of the salt-controllable type with up to
four sulphonate groups. These give acceptable reserve of the nylon variant
yarns when applied in the presence of a syntan. In this way a restricted
gamut of shadow with contrast effects is possible, but the wet fastness
properties are limited.
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DYEING OF CBA BLENDS
217
15.5 DYEING OF CBA BLENDS

Carpets and rugs are sometimes made with an acrylic/modacrylic pile, one of the
objectives being to use the modacrylic fibre to reduce the risk of flammability.
Such a blend of 60:40 acid-dyeable acrylic/Dynel (Union Carbide) may be used
as the pile on a cotton backing. The dyeing procedure is to use a one-bath
method, selecting basic dyes for the Dynel, 1:2 metal-complex dyes for the aciddyeable acrylic variant and salt-controllable direct dyes for the cotton. The use of
an anti-precipitant system and careful dye selection are essential. A butyl
benzoate carrier favours absorption of the basic dyes by Dynel and the dyebath
should be maintained at pH 6 with ammonium sulphate. Wet fastness of the
cotton backing can be improved by a conventional treatment with a cationic
fixing agent.
Carpets made from basic-dyeable and acid-dyeable acrylic fibres on a jute or
cotton backing fabric, however, are more difficult to dye in deep contrasting
hues. The need to dye at pH 2 to minimise basic dye staining of the acid-dyeable
component (section 7.3) degrades the cellulosic fibre backing. Staining of the
acid-dyeable fibre by lignin impurities from the jute (section 5.2) may also occur.
For these reasons it is preferable to employ more subtle muted contrasts on these
constructions.
15.6 DYEING OF DAA BLENDS

So-called booster blends of low-pill polyester staple with long-staple wool for
jersey-knitted suitings, outerwear and casual wear contain 10% nylon staple to
provide a favourable balance of pilling resistance and increased durability in
suitings [3]. These offer an interesting challenge to the attainment of acceptable
solidity. In a one-bath method for pale or medium depths, all three fibres are
dyed simultaneously using disperse and 1:2 metal-complex or milling acid dyes,
followed by soaping to remove disperse dye staining from the wool and from the
surface of the polyester.
The polyester, and to some extent the nylon, can be dyed first with disperse
dyes and carrier at the boil or under pressure at 105C in a two-bath method.
After reduction clearing, the wool and nylon components are dyed in a fresh
bath with the selected anionic dyes. Attainment of optimum solidity on this
blend requires:
(1) selection of disperse dyes that favour polyester rather than nylon (section
11.3);
(2) selection of 1:2 metal-complex and milling acid dyes showing a suitable
partition between wool and nylon at the target depth (section 6.1);
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(3) the use of a syntan as a retarding agent on the nylon when dyeing in pale
depths.
Nylon may be used to improve the tensile strength and abrasion resistance of
cellulose ester/wool blends, as in 33:33:33 cellulose acetate/wool/nylon or
65:30:5 triacetate/wool/nylon. Two-bath dyeing methods are preferred for these
blends. Disperse dyes in the low- to intermediate-energy range (Mr
220380) are selected for cellulose acetate to give minimum staining of wool at
80C (section 11.2). Preferred disperse dyes for triacetate are the intermediateenergy types (Mr 300400), including nitrodiphenylamine yellows, monoazo
reds and anthraquinone violets and blues. These are applied at the boil in the
presence of an ester carrier. In both instances the disperse dye stain is cleared
from the wool using a nonionic detergent at 50C. The nylon and wool
components are filled in with neutral-dyeing 1:2 metal-complex or milling acid
dyes using appropriate auxiliaries (section 3.2). Chrome dyes are also suitable for
deep shades. Fabrics of this type that are triacetate-rich can be heat set at 200C
after dyeing to enhance dimensional stability and improve the wet fastness of the
disperse dyes.
Core-spun polyurethane yarns may be included in the weft direction in woven
polyester/wool fabrics to give improved stretch properties in skiwear and
sportswear. The polyurethane fibre readily absorbs most disperse dyes and this
may result in low fastness to solvent spotting. Disperse dyes for use on these
blends, therefore, are selected for low solubility in dry cleaning solvents. Twostage or two-bath methods are necessary, applying these disperse dyes with a
carrier at the boil followed by 1:2 metal-complex or milling acid dyes for the
wool. These methods are analogous to the corresponding processes in the
absence of polyurethane (section 11.1). Carriers of the aryl ester or trichlorobenzene type are preferred, however, because o-phenylphenol may damage the
polyurethane fibre.
15.7 DYEING OF DAC BLENDS

Solidity is difficult to achieve on polyester/nylon/cotton blends. It is often
advisable to leave the cotton undyed or pastel dyed because of problems of
colour matching or differential abrasion of the cotton (section 1.5.4). The
synthetic components can then be dyed in solid or preferably contrasting hues by
the methods devised for polyester/nylon blends (section 11.3).
Such considerations do not apply to the dyeing of those polyester/cotton or
polyester/viscose outerwear fabrics containing 510% of core-spun polyurethane
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DYEING OF DAC BLENDS
219
weft yarns to impart enhanced stretch to the construction. However, disperse

dyes used on these blends should be selected for low solubility in chlorinated
organic solvents because of their limited fastness on the polyurethane
component. Conventional exhaust methods of applying these dyes, together with
direct dyes or followed by reactive dyes for the cellulosic fibre, are analogous to
the corresponding processes in the absence of polyurethane (section 13.1).
Cellulose acetate/wool/viscose blends are normally dyed by a two-bath
method. The acetate is dyed first at 80C and the stain on the other two
components is reduction cleared with dithionite and ammonia. Direct and
neutral-dyeing acid dyes are then applied from a fresh bath in the presence of
salt. Shirting and pleated dresswear woven from 60:20:20 or 55:15:30 triacetate/
nylon/viscose blends may be dyed by a one-bath method based on the selection
of disperse dyes for solidity on the triacetate and nylon compo-nents (section
11.4). Direct dyes of the self-levelling and salt-controllable disazo
multisulphonate types are used to fill in the viscose.
A problem of unlevel dyeing was encountered on a union fabric woven from a
linen warp and a triacetate/nylon blended-staple weft. It was found that the most
critical stage of processing was steaming, which could lead to irregular stripy
faults in the vat-dyed linen warps. A factorial design was used to establish the
optimum conditions for steam fixation in order to minimise the fault [4].
15.8 DYEING OF DBA BLENDS

Fabrics containing these three types of yarn are generally intended for threecolour contrast effects or two-colour contrast with the disperse-dyeable fibre
reserved. Solidity is not often required, but polyester/wool/acrylic blended-staple
yarns for overcoats or suitings are dyed in solid shades by a two-bath method
[5]. Bright contrasts in complementary hues can be obtained if only the two
ionic-dyeable fibres are dyed. If disperse dyes are used as well they tend to dye (or
stain) all three fibre types to some extent, giving a dependent hue (Table 1.5) on
the basic-dyeable fibre and a duller hue or clearing problems on the acid-dyeable
component, especially when this is wool.
Many disperse dyes will give three-way shadow effects on blends of nylon
with normal and basic-dyeable polyester, the distribution being controlled by
dyeing temperature and addition of carrier (section 12.3), but the low wet
fastness on the nylon is a limiting factor. Better fastness is given by two-way
shadow with reserve of the acid-dyeable component of this type of blend
using a carrier and selected disperse dyes to reserve nylon or wool, typically
low-energy anthraquinone dyes (Mr 220300). Better control of the nylon
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reserve and shadow or dependent contrast effects on the two polyester

variants is provided by the method already described using disperse and
basic dyes (section 12.3). Anthraquinone basic dyes are generally unsuitable,
the preferred types being mainly methine, monoazo, triarylmethane,
xanthene and oxazine.
All of these shadow or reserve effects based on disperse dyes are more
successful when the acid-dyeable fibre is nylon rather than wool, which is too
easily stained by disperse dyes and difficult to clear satisfactorily (section 3.4).
The method already described (section 7.6) for contrast effects on basic-dyeable
polyester and nylon or wool using basic and acid dyes with an alkanol
polyoxyethylene anti-precipitant can be used on these blends to reserve the
normal polyester fibre. Selected premetallised, milling acid or reactive dyes are
used on the acid-dyeable fibre.
Dependent three-colour contrasts (Table 1.5) on blends of nylon or wool
with normal and basic-dyeable polyester are obtained by a two-stage method
at pH 56 (ammonium acetateacetic acid). The acid-dyeable component is
dyed with acid dyes at 75C in the presence of an alkanol polyoxyethylene
dispersing agent as anti-precipitant and Glaubers salt to protect the basicdyeable variant from hydrolysis. The basic dyes are then added, followed by
the disperse dyes and a diphenyl or aryl ester carrier formulated with a
nonionic emulsifying system. The target shades on the normal and basicdyeable polyester are achieved at the boil. Possible incompatibility between
some basic dyes and anionic dispersing agents in the disperse dye
formulations can be minimised by adding the disperse dyes along with the
acid dyes at the lower temperature. However, this does increase the disperse
dye staining of the acid-dyeable fibre.
15.9 DYEING OF DBC BLENDS

A troublesome characteristic of dyed contrast effects on polyester/cellulosic
blends is for the cellulosic component to be partially lost by differential abrasion
on exposed edges of the garment. Resin treatments, particularly the severe curing
conditions necessary for durable press processes, accentuate the tendency for this
to occur. The fault is especially obvious when the polyester is less heavily dyed, so
that the abraded areas have a frosted appearance. An improvement in this
respect is shown by blends of normal and basic-dyeable polyester with a
cellulosic fibre. If the polyester homopolymer is dyed to the palest depth, the
basic-dyeable copolymer to the heaviest depth and the cellulosic component to
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DYEING OF DBC BLENDS
221
an intermediate level, preferential abrasion of the cellulosic fibre does not alter
the apparent balance of the design too drastically. Similar considerations apply to
blends of polyester and acrylic fibres with cotton or viscose.
Three-colour designs of limited fastness on these DBC blends are obtainable
by a simple one-bath method. Selected intermediate-energy disperse dyes and
salt-controllable direct dyes are applied at pH 4 and 70C in the presence of an
alkanol polyoxyethylene anti-precipitant, as well as Glaubers salt to protect the
basic-dyeable polyester and to promote exhaustion of the direct dyes on to the
cellulosic fibre. The basic dyes and a suitable carrier formulated with a nonionic
emulsifier are added and the basic-dyeable polyester is dyed to shade at the boil.
A brighter gamut of contrasts with much better wet fastness on the cellulosic
fibre is offered by a two-stage method. Selected disperse and reactive dyes are
added with Glaubers salt and an alkanol polyoxyethylene anti-precipitant. The
reactive dyes are exhausted on to the cellulosic fibre at 60C and then fixed at an
appropriate alkaline pH and temperature. The pH is adjusted to 5 with acetic
acid, basic dyes and a nonionic carrier emulsion are added and the dyeing of the
polyester variant yarns is completed at the boil.
A three-fibre blend of interest in household textiles has a 65:35 polyester/
cotton warp and an 80:20 acrylic/cotton weft. Multicoloured or reserve effects
can be produced but if all three fibre types are to be dyed to a solid shade a threebath process, applying disperse, vat and basic dyes in that order, may be
necessary. The cost of this sequence can only be justified to achieve exceptional
fastness demands. If the vat dyes can be replaced by direct dyes, a more
economical two-bath sequence of disperse and direct dyes followed by basic dyes
is practicable at a lower level of fastness.
15.10 DYEING OF DDA BLENDS

The attainment of acceptable solidity and fastness is often difficult on these
blends and cross-staining makes multicoloured effects of little interest. For
example, the components of a 25:50:25 cellulose acetate/polyester/nylon
dresswear fabric can be dyed acceptably solid up to medium depth with a
limited selection of low-energy disperse dyes applied at 8090C with carrier.
Adequate yield and fastness on the polyester, however, can only be attained
under conditions that damage the cellulose acetate. Similarly, a blend of
67:18:15 wool/PVC fibre/acetate formerly used in lightweight uniforms was
most difficult to dye in piece form because of the physical and chemical
sensitivities of the component fibres. Both the wool and PVC fibres are prone
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222
to shrinkage, but not necessarily to comparable extents, and the cellulose

acetate tends to become delustred at temperatures normally preferred for
dyeing wool. Both wool and cellulose acetate may suffer hydrolytic damage
if treated under alkaline conditions. Wool is badly stained by the disperse
dyes that must be used to dye the other two components.
15.11 DYEING OF DDC BLENDS
Dresswear fabrics made from 65:15:20 or 30:40:30 cellulose triacetate/
polyester/viscose blends can be dyed by a one-bath method. This depends on
the selection of disperse dyes for optimum solidity on triacetate/polyester
(section 14.1) and direct dyes that give the best reserve of unsaponified
triacetate without suffering significant decomposition in the hightemperature dyeing process at 120C (section 13.3). The preferred disperse
dyes are monoazo or disazo intermediate-energy types (Mr 300380) and the
most suitable direct dyes are of the self-levelling and salt-controllable disazo
multisulphonate types. An addition of sodium m-nitrobenzenesulphonate
assists in minimising the risk of slight decomposition of the direct dyes at
high temperature.
15.12 DYEING METHODS AND DYE SELECTION FOR THREECOMPONENT BLENDS
It is difficult to summarise the numerous and varied methods that have to be
adopted for the exhaust dyeing of blends containing three different fibre
types (Table 15.2). Solid effects are usually what is required on those blends
(AAA, AAB, AAC and DAA) that contain any two of the major acid-dyeable
fibres (wool, nylon or polyurethane). The same limitation is true for blends
that contain two ester fibres (DDA or DDC) and the DAC blends of an ester
fibre and an amide fibre with a cellulosic fibre.
The full versatility of colouring possibilities, i.e. three-way shadow,
shadow/reserve, contrast/reserve, shadow/contrast and three-way contrast
effects, is only offered by those blends that contain at least two dyeability
variants of the same synthetic fibre. These can be the differential-dyeing
nylon variants in AAA, AAB or AAC blends, acid-dyeable/basic-dyeable
acrylic fibres (AAB blends) or normal/basic-dyeable polyester (DBA or DBC
blends).
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DYEING METHODS AND DYE SELECTION FOR THREE-COMPONENT BLENDS
223
Table 15.2 Dye selections for three-component blends

Blend
Composition
Colour effect
Dye selection
AAA
Pale-dye/normal/
deep-dye nylon
Three-way
shadow
Monoazo or anthraquinone levelling

acid dyes
Normal/deep-dye/
ultra-deep nylon
Reserve (n)/
shadow
Monosulphonated or disulphonated
acid dyes
Shadow/
contrast
Disulphonated and multisulphonated

acid dyes
Reserve (n)/
contrast
Monosulphonated and multisulphonated

acid dyes
Three-way
contrast
Monosulphonated and multisulphonated

acid dyes with disperse dyes
Nylon/wool/
polyurethane
Solid
1:2 metal-complex dyes
Polyurethane/wool/
basic-dyeable
polyester
Solid
Basic dyes with anionic retarder, then

neutral-dyeing acid dyes
Nylon/acid-dyeable
acrylic/basicdyeable acrylic
Reserve (a-d)/
contrast
Acid dyes and basic dyes at pH 45
Shadow/
contrast
Acid dyes and basic dyes at pH 2 (acid

shadow) or pH 7 (basic shadow)
Shadow/
reserve (b-d)
Selected monosulphonated acid dyes
Shadow/
contrast
Monosulphonated acid dyes with

localised-charge basic dyes
Contrast/
reserve (b-d)
Selected monosulphonated and

disulphonated acid dyes
Reserve (n)/
contrast
Disulphonated acid dyes with localisedcharge basic dyes
Nylon/wool/
cellulosic
Solid
Selected 1:2 metal-complex or milling

acid dyes and salt-controllable direct
dyes with syntan
Nylon/polyurethane/
cotton
Solid
Reactive dyes by padbatch, then 1:2

Normal nylon/
deep-dye nylon/
cotton
Shadow/
contrast
Monosulphonated and disulphonated

acid dyes and salt-controllable direct
dyes with syntan
CBA
Cotton/modacrylic/
acrylic
Solid or
contrast
Salt-controllable direct dyes, basic dyes

and 1:2 metal-complex dyes with aryl
ester carrier and anti-precipitant
DAA
Polyester/nylon/
wool
Solid
Disperse dyes and 1:2 metal-complex or

milling acid dyes with syntan
AAB
Normal/deep-dye/
basic-dyeable
nylon
AAC
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224

Blend
Composition
Colour effect
Dye selection
DAA
Acetate/nylon/wool
Solid
Low- to intermediate-energy disperse

dyes at 80C, then 1:2 metal-complex or
milling acid dyes with syntan
Triacetate/nylon/
wool
Solid
Intermediate-energy disperse dyes with

carrier at the boil, then 1:2 metal-complex
or milling acid dyes with syntan
Polyester/wool/
polyurethane
Solid
Disperse dyes with carrier, then 1:2

Polyester/nylon/
cotton
Contrast/
reserve (c)
Neutral-dyeing acid dyes at 70C, then

intermediate-energy disperse dyes
at 120C
Polyester/
polyurethane/
cellulosic
Solid
Disperse dyes and disazo

multisulphonated direct dyes
Acetate/wool/
viscose
Solid
Low-energy disperse dyes at 80C, then

direct dyes and neutral-dyeing acid dyes
Triacetate/nylon/
viscose
Solid
Low-energy disperse dyes and disazo

multisulphonated direct dyes
at 120C
Normal polyester/
basic-dyeable
polyester/nylon
Three-way
shadow
Selected disperse dyes with carrier
Shadow/
reserve (n)
Low energy disperse dyes with carrier
Contrast/
reserve (n)
Selected disperse dyes and basic dyes

at 120C
Reserve (p)/
contrast
Basic dyes and neutral-dyeing acid dyes

with anti-precipitant
Three-way
contrast
Acid dyes at 75C, then basic dyes and

disperse dyes with carrier and
anti-precipitant
Three-way
contrast
Intermediate-energy disperse dyes,

basic dyes and salt-controllable direct
dyes with carrier and anti-precipitant
DAC
DBA
DBC
Normal polyester/
basic-dyeable
polyester/
cellulosic
Disperse dyes and reactive dyes with

anti-precipitant, then basic dyes with
nonionic carrier at the boil
DDA
Acetate/polyester/
nylon
Solid
(pale depths)
Selected low-energy disperse dyes at

80C with carrier
DDC
Triacetate/
polyester/viscose
Solid

disazo multisulphonated direct dyes
at 120C
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REFERENCES
225
15.13 REFERENCES
1.
2.
3.
4.
5.
A Lester, Australian Text., 2 (MayJune 1982) 18.

F Somm, Textilveredlung, 15 (1980) 7.
J B Timmis, Dyer, 153 (4 Apr 1975) 363.
L N Nazarenko, R D Efremov and L V Danileika, Kiev tekhnol. I legkoi prom.-sti., Kiev
(1988) 4.
M V Karve, Indian Text. J., 87 (1977) 123.
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Blends Dyeing

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Blends Dyeing

Classification of fibre types and their blends

Dynamic competition between fibre types

Classification of fibre types in terms of dyeability 21

Why blending is necessary

Blending from the dyers viewpoint 1

Minimising incompatibility between dyes

Interaction between disperse dyes and reactive dyes 46

Wool/acrylic and other AB blends

Dyeing of wool/acrylic blends 86

Nylon/wool and other AA blends

Dyeing of nylon/wool blends 77

Design of differential-dyeing variant synthetic-polymer

Principles of design and colouring of

Wool/cellulosic and other AC blends

Dyeing of wool/cellulosic blends 100

Cellulosic/acrylic and other CB blends

Exhaust dyeing of cellulosic/acrylic blends 119

Cotton/viscose and other CC blends

10.1 Properties and performance of cellulosic fibres in

Polyester/wool and other DA blends

11.1 Dyeing of polyester/wool blends 138

Polyester/acrylic and other DB blends

12.1 Dyeing of polyester/acrylic blends 161

Polyester/cellulosic and other DC blends

13.1 Exhaust dyeing of polyester/cellulosic blends 169

Triacetate/polyester and other DD blends

14.1 Dyeing properties of disperse-dyeable fibre blends 206

Dyeing properties of three-component

Why blending is necessary

1.1 BLENDING FROM THE DYERS VIEWPOINT

WHY BLENDING IS NECESSARY

THE COMPOSITION OF BLEND FABRICS

nylon/acrylic half-hose, as well as the differential-dyeing variants of these

1.3 THE RELATIVE IMPORTANCE OF INDIVIDUAL BLENDS

Table 1.1 Textile fibres available for coloration worldwide

WHY BLENDING IS NECESSARY

Table 1.2 Blends of fibres available for coloration worldwide

a Includes wool/polyurethane, wool/viscose, cellulose acetate/nylon, ...

THE RELATIVE IMPORTANCE OF INDIVIDUAL BLENDS

WHY BLENDING IS NECESSARY

REASONS FOR THE DEVELOPMENT OF FIBRE BLENDS

Table 1.3 Crease recovery of blended polyester and wool [9]

a Data obtained by the CSIRO multiple pleat test

The improvement in dimensional stability that takes place when wool is

Figure 1.1 Milling shrinkage of cellulose triacetate/wool

WHY BLENDING IS NECESSARY

1.4.2 Development of microfibre variants

REASONS FOR THE DEVELOPMENT OF FIBRE BLENDS

filament diameter. Thus another important difference between microfibres and

WHY BLENDING IS NECESSARY

COLOUR EFFECTS ACHIEVED BY BLENDING

Differences between fibre components A and B

Matching hue and depth

Figure 1.2 Diagrammatic representation of colour effects in blends

WHY BLENDING IS NECESSARY

properties. It is especially prevalent in blends of a natural fibre with a synthetic

COLOUR EFFECTS ACHIEVED BY BLENDING

WHY BLENDING IS NECESSARY

Table 1.4 Limitations of colour contrast on a disperse-dyeable/ionicdyeable blend