Quelle/Publication: European Coatings Journal

Ausgabe/Issue: 02/2009
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Synthetic leather without solvents

Polyurethane synthetic leathers are normally produced corresponding efforts to achieve coating of textiles have at
in a multi-stage process which involves removing toxic best met with partial success. The attempts failed mainly
dimethyl formamide (DMF) from a solventborne layer, due to the inadequate thickness of the layers produced
then applying a solventborne wear layer. Solvent-free and the unsatisfactory mechanical and chemical resistance
waterborne PU dispersions with a very high solids properties of the resulting synthetic leather.
content of 60 % and excellent performance have now Bayer MaterialScience has now succeeded in developing
been produced for this application. high-solids, fine-particle polyurethane dispersions for the
formulation of synthetic leather with high resistance
Very high solids dispersions developed for textile coatings properties. These new aqueous dispersions with solids
Thomas Michaelis* contents of up to 60 % allow an economic and efficient
Holger Casselmann coating process to be performed on existing equipment.
Every year, more than 500 million square metres of textile In contrast to DMF coagulation, this process is entirely free
materials are coated with polyurethane (PU) to impart a of solvents and toxic substances. The process thus meets
leather-like character. The PU synthetic leather produced in the requirements imposed on new materials by leading
this manner is used, for example, in upholstered furniture manufacturers of upholstered furniture, sports goods, textile
and shoes. and automobiles.
The coating process typically used to date has a number
of disadvantages: it requires several steps, and most of Frothed foam replaces solvent displacement process
the raw materials for the production of the material are A fundamental characteristic of natural leather is its
based on solventborne resins formulated with toxic dimethyl microporosity. It has the ability to adsorb and later release
formamide (DMF). New high-solids PU dispersions now water vapour. With the conventional process for the
make the production of synthetic leather more efficient and production of synthetic leather, the mixing of DMF and
more environmentally friendly. water produces a voluminous, porous product as a result of
the coagulation process and the heat generated.A similarly
Different processes create‘feel’ and wear resistance porous layer can also be produced using the frothed foam
Synthetic materials have been competing with natural process (see Figure 1). During this process, air is intensively
leather for more than 30 years. The typical first step incorporated into a waterborne PU dispersion to produce
towards forming a PU synthetic leather is a coagulation foam, in a way very similar to that in which whipped cream
process: a woven or non-woven fabric is coated with a paste is made. Foams are produced at various densities (200800
preparation of polyurethane polymerised or dissolved in g/l) dependent on the amount of air entrapped. After drying,
DMF. It is then passed through water baths with decreasing these satisfy the demands for softness and resistance in the
DMF concentrations and finally through pure water. final material.
A phase transfer process with water converts the PU- Stabilisers, thickeners, crosslinking agents and pigments
based paste preparation into a microporous, sponge-like are added to the foam as needed. Until the development of
layer. The precipitation runs slowly from the outside in; the new PU dispersions with their increased solids content,
water penetrates into the layer and displaces the DMF however, it was not possible to apply sufficiently thick layers
solvent. Distillation is used to recover the toxic DMF from the with a relatively high density in a single step.
process water.The coagulation process results in products The advantages of this new technology are primarily
with volume and a pleasant handle, but not a leather-like economic: energy costs are reduced because smaller
appearance. To obtain a suitable high-quality surface, the amounts of water have to be evaporated. At the same time,
coagulated layer is coated with two or more additional layers machine capacity can be better utilised. Finally, the costs for
of solventborne PU raw materials. the storage and logistics of the raw materials are reduced.

Waterborne formulations have had major limitations Bimodal size distribution is the key to high solids
This conventional process cannot be sufficiently reconciled The challenge of producing a fine-particle PU dispersion
with the desire for the lowest possible VOC emissions, with a 60 % solids content quickly becomes apparent
since its polar character implies that residual amounts of when considering the following: even the closest theoretical
DMF will usually remain in the material. Legislative VOC packing of spheres, for example in a crystal, only fills 74 %
directives and the specifications of leading brand-name of the available space. Pouring spheres of equal size into
manufacturers in a variety of industries are expected to a loose pile will result in a density of only around 64 %, the
become increasingly stringent. Attempts have therefore experimental maximum for flowable materials.
been continuing for some time to produce porous, The new generation of polyurethane dispersions is
thick-layered flat fabrics as synthetic leathers without therefore very close to this physical limit. This minor
using solvents.Though waterborne coating systems are, masterpiece of research was achieved thanks to a clever
for example, expanding their presence in the wood bimodal distribution of the particles in the dispersion. Simply
and furniture industry and are becoming increasingly put: The dispersion contains small spheres that fit into the
established for the coating of metal industrial goods, gaps between the larger spheres.

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 Quelle/Publication: European Coatings Journal
Ausgabe/Issue: 02/2009
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are currently presenting synthetic materials based on these

Four products cover most application needs new high-solids dispersions to brand-name manufacturers
All of the new "60 percent dispersions" (see Table 1) are of finished goods.
free of organic cosolvents and external emulsifiers. The star
among these products is the aliphatic, high-performance Results at a glance
dispersion "Impranil DLU". It can be used to formulate »› Polyurethane synthetic leathers are normally
particularly high-quality coatings for upholstery, automobile manufactured in a multi-stage process in which a soft
seats, sports goods and other technical products and porous layer is produced by removing toxic dimethyl
is characterised by extremely good foamability, flexibility formamide (DMF) from a solventborne layer, then applying
and hydrolytic stability.The "Impranil" high-solids dispersion a solventborne wear layer.»› By using a bimodal particle
range includes three other products. "LP RSC 1554" size distribution, a range of solvent-free waterborne PU
gives textiles more volume and body, and is well suited dispersions with a very high solids content of 60% has
to mechanical foaming. This dispersion can be used to been produced. The soft layer can be produced by foaming
formulate fashionable and cost-effective coatings for such the dispersions with air, and the high solids means that
things as sports goods and interior furnishings. "LP RSC thick layers can be applied in a single step.»› Another
1380" is used in similar applications to make the textile solvent-free dispersion is available which provides a top
materials supple, and in particular to improve their haptic layer with excellent lightfastness and physical resistance
properties. properties. The finished materials also offer low fogging
"LP RSC 1537" is a speciality product for the transfer (residual emission) levels.
process, in which the top layer is first applied to a transfer
paper, which may or may not be grained. This product is * Corresponding Author:
extremely well suited to the creation of an adhesion layer, Thomas Michaelis
which is subsequently transferred to the textile together with Bayer MaterialScience AG
the top layer and is characterised by its extreme softness Tel. +49 214 30 74027
and flexibility. But like the other representatives of the thomas.michaelis@bayermaterialscience.com
"60 percent products," this dispersion can also be applied
using the direct process to produce soft and waterproof
materials.The high-solids dispersions can be used as a
compact intermediate coat in a four-coat system to produce
high-grade synthetic leather for upholstered furniture and
automotive interiors, for example. Such synthetic leathers
are extraordinarily scratch and impact-resistant in addition
to being resistant to abrasion and hydrolysis.
In addition to these products, the company has developed
a new aliphatic polyurethane dispersion for the topcoat.
This is similarly free of organic cosolvents and external
emulsifiers. The "DLC-F" grade makes the surface of
synthetic leathers resistant to abrasion and ageing.

Emissions reduced by a factor of ten

The waterborne PU dispersions can be used to produce
synthetic leather and textiles whose resistance to abrasion
and hydrolysis is similar to those coated with solventborne
PU raw materials (see Table 2). Emissions analyses
according to VDA 278, however, show that the new
dispersions help lower the VOC and fogging values of
the materials by a factor of ten. The same applies to
the fogging test according to DIN 75201, in which the
quantity of condensable substances is determined (see
Figure 2).Emissions from textile materials coated with
dispersions from this new range are also lower than those
of coatings formulated with waterborne PU dispersions
containing cosolvents. Many PU dispersions containing
NMP (N-methylpyrrolidone) are still currently on the market.

Application and environmental benefits

This new generation of waterborne products means that
the days in which environmentally friendly, waterborne
dispersions for the coating of textiles were dismissed
as offering poor productivity or inadequate resistance
properties can finally be relegated to history. For
the production of synthetic leather, the frothed foam
process offers ecological advantages over the conventional
coagulation process as well as economic advantages over
conventional PU dispersions.Synthetic leather producers

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 Quelle/Publication: European Coatings Journal
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Physical Impranil DLU Impranil LP Impranil LP Impranil LP

properties Polyether/ RSC 1537 RSC 1554 RSC 1380
polycarbonate- Polyester- Polyester- Polyester-
polyurethane polyurethane polyurethane polyurethane
Impranil LP
RSC 1554

100% modulus 2 - 3 1.2 3 1.0

[MPa]

Tensile 20 – 30 13 26 14
strength [Mpa]

Elongation at 600 – 800 1200 1300 1300

break [%]

Swelling in 500 120 300 400

ethyl acetate
[%]

Swelling in 13 10 7 10
water [%]

Hydrolysis ++ + 0 0

Melting point 200 – 230 200 - 210 210 215

[°C]

Shore A 60 55 65 55
hardness

Lightfastness 7 7 7 7

Ionic charge a a a a

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Test Solventborne Waterborne

Peel strength (kg/cm)dry 4.0 > 5.0

Peel strength (kg/cm)wet 3.8 > 5.0

Total VOC mg/kg (thermal > 500 < 50

desorption test)

Abrasion resistance Taber 28 mg 23mg

1000 revs/ H22 wheel,
10N weight

Hydrolysis resistance < 4 weeks 6 weeks

‘Jungle test’: 70 °C; 95 %
humidity

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