USOO5972O88A

United States Patent (19) 11 Patent Number: 5,972,088

Krishnan et al. (45) Date of Patent: Oct. 26, 1999
54) WATER-BASED GRAVURE PRINTING INK 4.543,102 9/1985 Defago et al. .............................. 8/471
4,854,969 8/1989 Bassemir et al. ........................... 106/2
75 Inventors: Ramasamy Krishnan, Colonia; 4.954,556 9/1990 Bull et al. ....... 524/378
Marilyn C. Yamat; Sabino Apostol, 5,039,339 8/1991 Phan et al. .............................. 428/481
5,098,478 3/1992 Krishnan et al. .................... 106/31.86
both of Bergenfield, all of N.J. 5,174.815 12/1992 Kondo et al. ... ... 106/31.6
rr. A 5,370,906 12/1994 Dankert ................................... 427/261
73 Assignee: Sun Chemical Corporation, Fort Lee, 5,389,130 2/1995 Batlaw et al. .. . . 106/31.26
N.J. 5,417,749 5/1995 Krishnan et al. .................... 106/31.26
5,429,841 7/1995 Batlaw et al. .. ... 106/31.26
21 Appl. No.: 09/178,621 5,573,578 11/1996 Okuda ............. ... 106/31.26
5,725,646 3/1998 Krishnan et al. .................... 106/31.73
22 Filed: Oct. 26, 1998 FOREIGN PATENT DOCUMENTS
Related U.S. Application Data O 473 450 A2 8/1991 European Pat. Off. ........ CO8L 93/04
41 19348 Al 12/1992 Germany ............... ... B41F 7/02
63 Siya
2
Rif application St. E. Ny.
, abandoned, which is a continuation-in-part o
WO 97/33750 9/1997 WIPO ............................. B41F 13/22
application No. 08/614,587, Mar. 13, 1996, Pat. No. 5,725, WO 97/33757 9/1997 WIPO ............................ B41D 13/22
646. OTHER PUBLICATIONS
51) Int. Cl. ........................... C09D 11/08; CO9D 11/10; R.H. Leach and R.J. Pierce, “The Printing Ink Manual.”
C09D 11/14 Fifth Edition (1993), pp. 571-576, no month available.
52 U.S. Cl. ..................................... 106(31.73 106/31.69
52) f s 8.7375 Primary Examiner Helene Klemanski
58 Field of Search ................................ losio. 7s. Attorney, Agent, or Firm-Sidney Persley
106/31.69, 31.75 57 ABSTRACT
56) References Cited A Single fluid water-based gravure printing ink comprising
water, a macromolecular resin binder comprised of resins
U.S. PATENT DOCUMENTS soluble in water regardless of the pH of the water; resins
3,356,030 12/1967 Greubel ................................... 101,452 water Soluble at water pH value ranging from 7.5 to 10, and
3877,372 4/1975 Leeds. 101/465 aqueous emulsion resins, pigment; and a hydroxyethyl eth
4,104,219 8/1978 Peters et al. .................... 260/29.6 RB ylene urea re-wetting agent.
4,173,554 11/1979 Sulzberg ....... ... 260/29.2 EP
4.278,467 7/1981 Fadner ........................................ 106/2 11 Claims, No Drawings
 5,972,088
1 2
WATER-BASED GRAVURE PRINTING INK vents Such as 2-ethyloxyethanol and the corresponding
acetate. These have been replaced with glycol ethers and
This application is a Continuation-In-Part of application esters and Solvents based on propylene glycol. The most
Ser. No. 08/977,531, filed Nov. 25, 1997, now abandoned common Solvents used in gravure ink formulations include
which is a Continuation-In-Part of application Ser. No. ethyl, iso-propyl and n-propyl alcohols, acetone, ethyl, iso
08/614,587, filed Mar. 13, 1996, now U.S. Pat. No. 5,725, propyl and n-propyl acetates, methoxy and ethoxy
646. propanols, aliphatic hydrocarbons, toluene, aliphatic hydro
carbon Solvents, primarily aromatic, aliphatic and naph
FIELD OF THE INVENTION thenic hydrocarbons, alcohols, ketones, esters, ethers and
halogenated compounds.
The invention relates to water-based gravure printing ink. Since the solvent component typically constitutes from 30
DESCRIPTION OF RELATED ART to 70 wt.% of the gravure ink composition, the emission of
volatile organic compounds (VOCs) represents a significant
In an attempt to eliminate volatile organic compounds environmental concern. In order to comply with a myriad
(VOCs in the pressroom, water-based alternatives are being 15 federal, State and local environmental regulations, gravure
Sought for printing ink formulations. Water-based printing printers are been required to install Solvent recovery Systems
inkS for use in flexographic printing processes are known. which represent both a Substantial capital outlay and oper
This type of printing utilizes printing plates wherein the ating expense and a limit on production rates.
printing imageS Stand up in relief, i.e. the areas to be printed There are a number of other drawbacks associated with
are raised above the non-printing areas. Printing by the the water-base gravure inks of the prior art. For example, the
flexographic proceSS requires relatively low pressures Suf preSS handling characteristics of these water-base inks are
ficient to transfer the ink from the face of the image carrier uniquely different from organic Solvent base materials. Once
to the surface of the Substrate. Examples of useful water dry, aqueous based inks may be reluctant to redissolve in
based flexographic printing ink are described in U.S. Pat. water, depending upon the kind of resin System used in the
No. 4,173,554 and The Printing Ink Manual, edited by R. H. 25 ink. This could result in an increase in cylinder plugging and
Leach and R. J. Pierce, pages 571-576, 5th edition, number of preSS wash-ups. Conversely, the resin System may
(Blueprint, 1993). not be Sufficiently water resistant upon drying causing the
Water-based gravure printing processes have also been ink to be easily Smeared in the presence of moisture. The
developed to avoid the environmental impact and operating resin System used in water-based inkScan give rise to poor
expenses associated with the use of Solvents. For example, dot spread and increased skipped dots. These problems may
U.S. Pat. No. 4,104,219 discloses an ink containing a be difficult to overcome given the limited availability of
polyalkyl acrylate binder dispersed in a homogenous, aque resins for use in water-based Systems. Accordingly, the
ous phase. U.S. Pat. No. 4,543,102, describes a water-based adoption of a water-based systems may require changes in
ink composition containing up to 8% of a water miscible gravure cylinder engravings, press operating and housekeep
organic Solvent Such as polyvinyl alcohol. Water-based 35 ing procedures, higher press Speeds, and dryer modifica
gravure printing ink formulations are described in U.S. Pat. tions. Furthermore, the Substrate being printed upon may
Nos. 5,098,478; 4.954,556 and 5,389,130 wherein a Sub Strongly affect the performance of these water-based inkS. In
Stantial portion of Solvent is replaced with water. applications Such as printing on low Surface tension film and
The Solvent used in gravure ink is a temporary ingredient, publication gravure employing coated paper, organic Solvent
present purely as a means of applying the vehicle Solids to 40 Systems still give Superior performance. Even with uncoated
the Substrate by way of the printing unit. In theory, once the paper, water may cause dimensional distortion and curling.
vehicle Solids are applied, the Solvent is eliminated, mainly A comparison of the water-based and Solvent-based gra
by evaporation and/or absorption and takes no further part in Vure inks in the prior art shows that in a Solvent ink System
the properties of the printed film on the substrate. However, the Solvents are balanced So as to be Sufficiently non-volatile
in practice this is an over Simplification Since the Solvent 45 for minimal evaporation from the time the doctor blade
cannot always be eliminated easily and is Sometimes trapped removes the exceSS ink to the point of impression. After
in the lattices of the Substrate. impression, transfer of ink to the Substrate, and time to
In gravure printing Solvent Selection is typically governed achieve uniform lay, the Solvent must evaporate prior to
by the resin System employed; the press Speed; whether a rewind or Stacking. By comparison, in the water-based ink
direct or off-set gravure proceSS will be used; the design of 50 System of the prior art a percentage of the Solvent is replaced
the gravure cylinder; the Substrate; the desired end-use not just by water (which acts as the solvent) but also by a
properties of the print; and the pigment Selected. However, Volatile amine required to neutralize the acidic resin. Water,
the chemical nature of the resin System will, more often than while being non-volatile and not causing problems due to
not, severely restrict the choice of solvents. With most evaporation from the cell, can Still create difficulties at the
resins, a blend of Solvents will give a lower ink Viscosity 55 final drying Stage dependent on the amount of water present
than a Single Solvent. An incorrect Selection will produce a in the ink. Also, the Selection of amine and control of pH is
gravure ink having poor flow characteristics. as important as Viscosity control. Premature release of the
A gravure ink must remain fluid during the printing amine before the point of impression can result in a drop in
proceSS while the ink flows from the gravure cells onto the pH and Subsequent precipitation of the resin in the cells of
substrate. The solvent is then rapidly removed within the 60 the gravure cylinder. Furthermore, water-based Systems are
drying cycle. Hence, the evaporation rate of the Solvent must not as readily resolubilized as Solvent Systems. It is therefore
be geared to the length of time required to remove the exceSS possible that any precipitation will not be resolubilized
ink by the doctor blade and the elimination point of the within the next revolution of the cylinder in the ink duct.
Solvent. This time span is clearly governed by preSS Speed. Therefore unless carefully controlled, fluctuations in pH can
In recent years, changes made to reduce the maximum 65 lead to packing in the etch of the gravure cylinder and
concentration of Solvent vapors allowable in the preSSroom ultimately to Screening. The Surface tension characteristics
atmosphere have resulted in the Virtual elimination of Sol of the water-based System must also be considered since
 5,972,088
3 4
generally they are totally different from those of solvent vehicle. The vehicle is a liquid carrier, which may be an
Systems. These differences can lead to poor Substrate wetting emulsion. In the present invention the vehicle is water which
which results in ink reticulation, crawling, and non-uniform replaces the volatile organic compound vehicle thereby
ink flow from the cells. Surface tension can be reduced, eliminating VOC emissions. The vehicle also contains
however, by careful Selection of Surface active agents or the binder resins which adhere the pigment to the Substrate
inclusion of Small quantities of alcohol. being printed. It has been Surprisingly found that the per
Despite extensive work in development of water-base formance of the gravure printing ink is not appreciably
gravure printing ink formulations, there remains a Strong affected by the complete elimination of solvent.
need in the gravure printing industry for an ink completely Many resin binder Systems require the addition of chemi
free of VOCs, while retaining the performance standards of cal plasticizers, in order to prevent ink drying in the cells of
conventional Solvent-based gravure inkS. the gravure cylinder on the preSS and to ensure Satisfactory
A Solvent-free water-based gravure printing ink would adhesion and flexibility on the Substrate. Water-based sys
eliminate the VOCs commonly emanating from solvent tems of the prior art will also contain resins which can be
based printing inkS. saponified, but must be sufficiently volatile to leave a
15 water-insoluble dried ink film. They will also contain addi
Therefore, it is an object of the present invention to tives to reduce Surface tension properties and So enhance lay
provide a Solvent-free gravure printing ink having no VOC characteristics. The Surface characteristics can be consider
emissions while preserving the principal advantages of
conventional Solvent-based gravure printing inkS. ably modified by additives which promote rub resistance and
slip.
Another object of the invention is to provide a gravure ink The following resins and mixtures may be incorporated
Suitable for use in a gravure printing process and compatible
with a wide variety of substrates. into the gravure ink of the present invention: rosin and
Another object of the invention is to provide a gravure ink modified rosins, Such as calcium, magnesium and Zinc
which retains the performance characteristics of conven metallic resinates, ester gum of rosin; maleic resins and
tional Solvent-based ink formulations and is compatible with 25
esters, dimerized and polymerized roSins, rosin modified
the Standard pigments and resin Systems used in gravure fumaric resins, shellac, asphalts, phenolic resins and roSin
printing. modified phenolic resins, alkyd resins, polystyrene resins
and copolymers thereof; terpene alkylated urea formalde
A further object of the present invention is to provide a hyde resins, alkylated urea formaldehyde resins, polyamide
more economical gravure ink from a raw material and Vinyl resins, Such as polyurethane resins, polyimide resins,
emission control cost Standpoint. polyvinyl acetate and polyvinyl alcohol, ketone resins,
Such objectives have been achieved by means of the acrylic resins, Such as polyacrylic acid and polymethacrylic
present invention. acid; epoxide resins, polyurethane resins, cellulosic resins,
Such as nitro- and ethyl-cellulose, ethyl cellulose, cellulose
SUMMARY OF THE INVENTION
35
acetate butyrate and carboxymethyl cellulose.
The present invention is a Solvent free, water-based, The resin may be soluble or dispersible in either the water
Single fluid gravure printing ink comprising (a) water; (b) a or aqueous emulsion, depending on the resins hydrophobic/
macromolecular resin binder comprised of (i) binders hydrophilic character. In a preferred embodiment, the resin
soluble in water regardless of the pH of the water, (ii) rosin is soluble in the water. The resin binder may be emulsified
salt binders soluble in water at a pH ranging from about 7.5 40
by mechanical energy being imparted by, for example,
to about 10, and (iii) aqueous emulsions binders; (c) pig pumping the components together in the ink reservoir of a
ment; and (d) a hydroxyethyl ethylene urea re-wetting agent. Standard gravure printing press. Emulsifiers, Such as
According to the present invention, VOC emissions of Surfactants, may be added to increase the Stability of the
gravure inks are reduced by 100% relative to standard emulsion. Generally, the emulsion will remain Stable during
Solvent based and water-based gravure printing inks while 45 printing by circulation of the ink in the printing well.
the rigid requirements of gravure printing, e.g., tone Scale It is unusual to find a resin that will impart all the desired
density, gloSS, rub resistance, Viscosity and adhesion con properties to a gravure ink. Therefore, a formulator will
tinue to be met. Select two or possibly three resins to achieve a resin com
bination giving the required ink characteristics which
DESCRIPTION OF THE INVENTION 50 include: adequate adhesion to the Substrate; good Solubility
in the water, combination release properties with the ability
Currently, the ink System for Surface packaging gravure is to dry and give tack-free ink films, capability of providing
rich in VOCs. Nevertheless, chronic problems like hazing the necessary level of gloss; good pigment-wetting proper
and resolubility were reported. Several waterbased formu ties, toughness, adequate rub resistance; and flexibility, to
lations have been attempted to replace the existing System, 55 ensure non-cracking of the final printed product.
but to no avail. GloSS and open-time appeared to be the Examples of Suitable macromolecular resin binders which
major drawbackS. are soluble in the water regardless of the pH of the water
The advent of 2-hydroxyethylethylene urea have allowed include: carboxymethyl-cellulose, hydroxyethylcellulose,
the aforementioned problems to be overcome. For example, hydroxypropyl-cellulose, hydroxybutylmethylcellulose,
adding only 0.5 wt.% 2-hydroxyethylethylene urea over 60 poly(C-C) alkylene oxides, polyethyleneimine, polyvinyl
comes the problems existing with prior art formulations and alcohol, polyvinyl acetate, polyvinylpyrollidone, polyvinyl
increases gloSS from 6 to 9 points. Improved resolubility and Oxazolidone and polyacrylamide polymers.
open-time were also acheived using the Solvent-free and Preferably, the macromolecular resin rosin salt binders
highly water washable gravure printing inks of the present present in the ink are only those which are Soluble in the
invention that contain 2-hydroxyethylethylene urea. 65 water at pH value ranging from about 7.5 to about 10 and
In its broadest Sense, the gravure printing ink composition more preferably from about 2.5 to about 6.5 pH. Suitable
of the present invention is made up of a pigment and a examples of Such binders include methacrylic resin rosin
 5,972,088
S 6
Salts, Styrene-acrylic resin roSin Salts, resin rosin Salts, and acid amides, Surfactants, defoaming agents, catalysts,
polystyrene-Sulfonic acid resin rosin Salts. antioxidants, corrosion inhibitors, biocides and deodorants.
Ammonia, organic amines Such as monoethanolamine or Ammonia or other Volatile amines may also be added in
N,N-diethanolamine, mineral acid and organic acid Such as trace amounts to aid in dissolving the resin.
acetic acid may be added to the water in order to adjust its In a particularly preferred embodiment of the present
pH in the preferred range. invention, up to 5 wt.% of non-ionic Surfactant is used to
Suitable examples of the macromolecular resin binders reduce Surface tension and Stabilize the pigment resin dis
comprising aqueous emulsions include acrylic or vinyl persions. Suitable Surfactants include, for example, acety
emulsion polymers prepared from monomerS Selected from lenic glycols, ethoxylated glycols and Sorbitan esters. It is
the group consisting of acrylic acid esters, methacrylic acid also well known in the art to incorporate miscellaneous
esters, acrylic acid esters of polyhydric alcohols, methyl additives into the ink composition to enhance performance
methacrylate, Styrene, Vinyl Styrene and Vinyl acetate. with regard to gloSS, rub resistance, uniform density of the
The pigment, as in all colored gravure inkS, is the most print flexibility and adhesion.
expensive part of the formulation. Therefore, the economics 15
In the gravure ink formulations of the present invention
of pigment Selection is vitally important. In many areas of the water is preferably present in an amount of 25 to 60 wt.
gravure printing, pigments need specific properties to meet % of the ink; and more preferably 35 to 50 wt.%. It is also
the demands made on them during the printing proceSS and preferred that the macromolecular resin binder be present in
in the end use of the printed material, e.g. printing of an amount of 10 to 70 wt.%; and more preferably 30 to 60
polyvinyl chloride wallcoverings, deep-freeze polyethylene wt.%; and most preferably the macromolecular resin binder
bags. The normal practice is to have a preferred Standard is a composite having up to 5 wt.% of a resin binder soluble
range of pigments against which alternatives can be in water regardless of the pH of the water; and 10 to 70 wt.
assessed. In addition, consideration should be given to the % of a resin binder soluble in water at a pH ranging from 7.5
pigment's tinctorial Strength, ease of dispersion and gloSS to 10; and up to 20 wt.% of an aqueous emulsion resin
characteristics. Where it is envisaged that the pigment will 25
binder. At press Viscosity, the maximum pigmentation for
be used in a concentrated base Scheme, it must have good organic pigments typically does not exceed 15 wt.%, more
flow properties at high pigmentation. In comparison with preferably 5-10 wt.% of pigment is used. However, with
flexographic, offset and letterpreSS, printing the gravure inorganic pigments Such as titanium dioxide, pigment levels
process can, when required, deposit fairly heavy film as high as 25-35 wt.% are used. Therefore, the pigment is
weights of ink, which are governed by depth of engraving on preferably present in an amount of 2 to 35 wt.%. Finally, it
the gravure cylinder and hence the volume of ink held by the is preferred that the hydroxyethyl ethylene urea rewetting
cells of the cylinder. agent be used in an amount of 0.5 to 10 wt.%.
Pigments Suitable for formulating the gravure ink of the The Viscosity requirements of gravure inkS dramatically
present invention are Selected from the group consisting of distinguish them from paste-like inks, Such as lithographic
CI Pigment Yellows 1,3,4, 5, 12, 13, 14, 17,55, 65,73, 83, 35 inkS. Ink Viscosity must be adjusted to meet Several critical
97 and 98; CI Pigment Oranges 13, 16 and 46; CI Pigment factors. Too high a Viscosity results in an inadequate flow of
Reds 2, 3, 4, 10, 12, 48, 48:1, 48:2, 53, 57:2, 81, 104,146, ink from the cells of the cylinder and causes a phenomenon
170 and 176; CI Pigment Greens 2, 7 and 36; CI Pigment commonly known as “Screening”. Too low a Viscosity
Blues 1, 15:1, 15:2, 15:3, 15:6, 16, 29, 56 and 61; CI results in a “slur-Out' or "halo' occurring on the trailing
Pigment Violets 3, 23 and 37, CI Pigment Blacks 6 and 7; 40 edge of the print, appearing as a thin film of ink printing
and CI Pigment Whites 6, 7, 18 and 26. beyond the limits of the design. With this in mind, the final
Optionally, extenderS Such as china clay and precipitated Strength and shade adjustments to a gravure ink should be
calcium carbonate may be used in the gravure ink formu made when the proper Viscosity and printing Speed have
lations of the present invention. Extenders help control gloSS been determined. The viscosity of the gravure ink of the
levels and improve the lay characteristics in ink formula 45 present invention will fall between 14 and 90 seconds at 25
tions having high binder/pigment ratios. Due to their low C. (measured using a Shell Cup #2) and more preferably is
cost, extenders can be used to effectively cheapen the cost of between 16 and 50 seconds at 25 C. The present gravure
gravure inkS. For example, extenders can be used in publi inks can, however, be used at temperatures of up to 75 C.
cation gravure inks to assist tack reduction and control in this Viscosity range.
colour strength. 50 The gravure ink of the present invention can be printed on
Rewetting agents are also employed in the present gravure a wide range of Substrates Such as paper, films and foils and
ink formulation to reduce Screening which occurs when the can also be used for sheet-fed printing of rigid Surfaces Such
ink in a cell of a Second color combines with the dried ink as board. It should be noted, however, that absorbent Sub
of a first color. To off-set the effects of Screening, a rewetting Strates require lower ink Viscosities than non-porous
agent is employed. The rewetting agent Suitable for use in 55 Surfaces, in fact Some Substrates require the addition of
the present invention is hydroxyethyl ethylene urea. While retarding Solvents to enable an acceptable print to be
not wishing to be bound by theory, it is believed that the achieved.
hydroxyethyl ethylene urea rewetting agent also Serves as a Printing at high Speeds demands fast drying gravure inkS
plasticizer by providing Surface continuity to the dry film on and hence low Viscosities, to enable the ink to flow rapidly
the Substrate. 60 out of the cells at the point of impression. Although water
The water-based gravure ink of the present invention may based, the drying Speed for the water-based gravure ink of
optionally contain other conventional additives, the effects the present invention is Surprisingly rapid. It should be borne
of which must be evaluated, and if necessary, compensated in mind, however, that the drying rate of a gravure ink will
for in the printing process. These adjuvants will include greatly depend on the drying technique employed. For
plasticizerS Such as Sucrose acetate iso-butyrate, triethyl 65 example, Slow-Speed sheet-fed machines have no drying
citrate, and epoxidised Soy bean oil, and waxes Such as systems other than cold air blowers. High-speed web
polyethylene waxes, halogenated hydrocarbon waxes, fatty machines, on the other hand, may have a Sophisticated
 5,972,088
7 8
drying System between each unit providing a high-velocity EXAMPLE 4
hot air Stream. Steam heated drums are also be used to heat
the web while cold chill rollers are used to cool the web on The Single fluid, water-based red gravure printing ink
exit. prepared in Example 2 was run at the Chestnut preSS using
The following example further illustrates Specific aspects a carrier board Substrate. The print quality was a better than
of the water-based gravure ink of the present invention and that of a comparative Solvent based ink System and provided
is not intended to limit the Scope thereof in any respect and 20-25% higher gloss.
should not be So construed. Throughout this specification, all EXAMPLE 5
parts and percentages shown, unless otherwise noted, are by
weight. The Single fluid, water-based red gravure printing ink
EXAMPLE 1. prepared in Example 4 was run for “Teabag printability.
A Single fluid, water-based gravure ink was prepared from The print quality observed was comparable to that of the
the following components: The water present in the ink was existing Solvent based ink System containing 7-12 wt.%
VOCS.
Supplied by the water contained in the acrylic resin latex, 15
hydroxypropyl cellulose, hydroxyethyl ethylene urea and EXAMPLE 6
maleated rosin ester components.
Single fluid, water-based red and blue gravure printing
inks were prepared from the following formulations:
Amount
Component (wt.%)
pigment 9-10 Amount (wt.%
ammonia 2-3
water 55-58
Component Red Blue
hydroxyethylethylene urea (75% solids in water) .5-2.3 blue base (SunChemical 52-1339) 27.0
polyester resin 7-9 25
red base (SunChemical RCD-9017) 27.0
acrylic resin 24-26 polyester (Trigloss RD0110) 22.78 22.78
ethylene glycol surfactant 1.2-2.3 acrylic emulsion (Neocryl XA-5048) 45.55 45.55
Total 1OO.OO
hydroxyethylethylene urea (SR-511) O.51 O.51
defoamer (Foamex 805 & 3.062, (a1:1)() O.O7 O.O7
ethylene glycol surfactant 2.04 2.04
(Surfonyl 420)
EXAMPLE 2 acrylic resin (Joncryl 67) O.8 O.80
water 2.05 2.05
A Single fluid, water-based red gravure printing ink was
prepared from the following formulation: Total 1OOOO 1OO.OO

35 (SunChemical (R) is a trademark of the Sun Chemical Corporation.

Trigloss is a trademark of R&A Auxiliaries.
Component Neocryl (R) is a trademark of ICI Industries.
(SR-511 is a trademark of the Sartomer Corp.
Pigment Red 57:2 9 Foamex 805 & 3.062 are trademarks of the Tego Chemie Corp.
polyester resin (Trigloss RD O110)(a) 7-9 Surfynol (R) 420 is a trademark of the Air Products Corp.
acrylic resin (Johncryl 68) 24.5-26.0 40 Joncryl (R) 67 is a trademark of the S.C. Johnson Corp.
ethylene gylcol surfactant (Surfynol 1.2-2.3
420)(e) Both printing inks were run on a Chestnut preSS using a
aqueous ammonia 2.0-3.0 carrier board Substrate. The print quality was better than that
water 55-58 of a comparative solvent based ink and provided a 20–25%
hydroxyethylethylene urea (SR-511) 0.5-2.3 increase in gloSS.
45
Total 1OOOO
EXAMPLE 7
Trigloss is a trademark of R&A Auxiliaries.
Joncryl (R) 68 is a trademark of S.C. Johnson Corp. A color matched single fluid, water-based gravure ink was
Surfynol (R) 420 is a trademark of the Air Products Corp. prepared having the following formulation:
(SR-511 is a trademark of the Sartomer Corp. 50

EXAMPLE 3 Amount
Component (wt.%)
A printed coated paper Sample containing an ink formu
lated according to Example 1 was produced on a Chestnut acrylic resin (Vancryl 68SN) 1.O.O
gravure printing press at a print Speed of approximately 55 water 13.0

1,000 feet per minute (fpm) to demonstrate the use of the zinc sulfide (sachtolith grade HDS) 36.5
CaCOs 1.O.O
water-based gravure printing inks of present invention on synthetic silica flattening agent 2.5
coated paper. The printing press run was carried out at polyethlene wax (AquaPoly 250) 1.O
temperatures ranging from 15-20 C. The print Samples polyester varnish (Trigloss Vehicle) 1.2
obtained from the press run were fast drying, clear and Sharp 60 acrylic emulsion (Neocryl XA-5048) 22.5
hydroxyethylethylene urea (SR-511) 1.O
with stable tack. There was no discernible toning in the ethylene glycol surfactant (Surfynol 420) 1.O
non-image area. Optical photomicrographs of the print black base (PMA-900) 0.4
Samples showed a Smoother Surface than print Samples blue base (PMA-525)(8) O.3
printed with gravure inks formulated without hydroxyeth yellow base (PMA-220)(8) O.6
ylethylene urea. These print Samples were brittle and had a 65 Total 1OO.OO
more rigid as Seen from numerous cracks on the print film
Surface.
 5,972,088
9 10
-continued What is claimed is:
1. A Single fluid water-based gravure printing ink com
Component
Amount
(wt.%)
prising:
(Vancryl (R) 68SN is a trademark of Air Products Corp. (a) water; (b) a macromolecular resin binder that com
AquaPoly (E 250 is a trademark of Micro Powders, Inc. prises: (i) resins Soluble in water regardless of the pH
'Trigloss is a trademark of R&A Auxiliaries. of the water, (ii) resin rosin Salts Soluble in water at a
Neocryl (R) is a trademark of ICI Industries. pH ranging from about 7.5 to about 10, and (iii) of
(SR-511 is a trademark of the Sartomer Corp. aqueous emulsion resins; (c) pigment; and (d) a
Surfynol (R) 420 is a trademark of the Air Products Corp.
PMA is a trademark of Sun Chemical Corp. hydroxyethylethylene urea re-wetting agent.
The ink was printed on the rough side of SBS board 2. The ink of claim 1 wherein the water is present in an
(available from James River Corp.) The print quality amount of from 35-50 wt.% based on the weight of the ink.
3. The ink of claim 1 wherein the macromolecular resin
observed was comparable to a comparative Solvent based
ink. binder is present in an amount of from 30-60 wt.% based
15 on the weight of the ink.
EXAMPLE 8 4. The ink of claim 1 wherein the macromolecular resin
A Screen ink System for wallpaper was converted into binders soluble in the water regardless of the pH of the water
fleXO-gravure application, the blend vehicle was modified are Selected from the group consisting of
with hydroxyethylethylene urea. Four colors of single fluid, carboxymethylcellulose, hydroxyethylcellulose,
water-based gravure inks were prepared having the follow hydroxypropylcellulose, hydroxybutylmethylcellulose, poly
ing formulation: (C-C)alkylene oxides, polyethyleneimine, polyvinyl
alcohol, polyvinyl acetate, polyvinyl-pyrollidone, polyviny
Amount (wt.%
loxazolidone and polyacrylamide.
5. The ink of claim 1 wherein the macromolecular resin
25
Component RED YELLOW BLUE BLACK rosin salt binders soluble in water at a pH of 7.5 to 10 are
pigment 10.5 13.5 13.5 12.3
Selected from the group consisting of methacrylic resin rosin
acrylic resin (Joncryl 67) 1.2 Salts, Styrene-acrylic resin rosin Salts, resin rosin Salts, and
nonionic surfactant O.9 1.2O 18O 18O polystyrene-Sulfonic acid resin rosin Salts.
cationic surfactant O.60 6. The ink of claim 1 wherein the macromolecular resin
aqueous ammonia
water
O.42
38.0
O.84
35.48
O.84
34.88
O.42
35.9
binders comprising aqueous emulsions are Selected from the
acrylic emulsion 31.15 31.15 31.15 351
group consisting of acrylic or vinyl emulsion polymers
(Lucidene 351) prepared from monomerS Selected from the group consisting
hydroxyethyl ethylene urea 5.75 5.75 5.75 5.75 of acrylic acid esters, methacrylic acid esters, acrylic acid
(SR-511)(c) 35
esters of polyhydric alcohols, methyl methacrylate, Styrene,
ethylene glycol surfactant 1.03 1.03 1.03 1.03 Vinyl Styrene and vinyl acetate.
(Surfynol 420)
defoamer (L-493) O.2O O.2O O.2O O.2O 7. The ink of claim 1 wherein the pigment is present in an
thickner (RM2020 NPR)(f) 3.50 3.50 3.50 3.50 amount of from 5-35 wt.% based on the weight of the ink.
silica (LO-VEL 27)(8) 5.60 5.6 5.60 5.60 8. The ink of claim 1 wherein the pigment is selected from
hydrocarbon wax 1.75 1.75 1.75 1.75 the group consisting of CI Pigment Yellows 1, 3, 4, 5, 12, 13,
40
(Acumist 12) 14, 17, 55, 65, 73, 83,97 and 98; CI Pigment Oranges 13,
Total 1OO.OO 10O.OO 10O.OO 10O.OO 16 and 46; CI Pigment Reds 2, 3, 4, 10, 12, 48, 48:1, 48:2,
53, 57:2, 81, 104,146, 170 and 176; CI Pigment Greens 2,
(Joncryl (R) 67 is a trademark of the S.C. Johnson Corp. 7 and 36; CI Pigment Blues 1, 15:1, 15:2, 15:3, 15:6, 16, 29,
Lucidene is a trademark of Mobay Industries. 56 and 61; CI Pigment Violets 3, 23 and 37; CI Pigment
(SR-511 is a trademark of the Sartomer Corp. 45
Surfynol (R) 420 is a trademark of the Air Products Corp. Blacks 6 and 7; and CI Pigment Whites 6, 7, 18 and 26.
(L493 is a trademark of Drew Chemical. 9. The ink of claim 1 further comprising a non-ionic
(RM2020 NPR is a trademark of Rohm & Haas Corp. Surfactant.
(LO-VEL (E 27 is a trademark of PPG Industries.
(Acumist (R) is a trademark of Allied Signal Corp. 10. The ink of claim 9 wherein the non-ionic Surfactant is
50 present in an amount of up to 5 wt.% based on the weight
The present invention has been described in detail, includ of the ink.
ing the preferred embodiments thereof. However, it will be 11. The ink of claim 9 wherein the non-ionic Surfactant is
appreciated that those skilled in the art, upon consideration Selected from the group consisting of acetylenic glycols,
of the present disclosure, may make modifications and/or ethoxylated glycols and Sorbitan esters.
improvements on the invention that fall within the Scope and
Spirit of this invention as Set forth in the following claims.