UV-Curing Coatings for Textiles:

Coatings with a Future

ERIK KRIJNEN, MARIELLE MARSMAN AND RONALD HOLWEG
TNO Centre for Textile Research
Schoemakerstraat 97
P.O. Box 6034
2600 JA Delft, The Netherlands

ABSTRACT: Radiation curing can offer many advantages in textile coating and
printing processes. In this paper some results are given of a study on UV-curable
coatings and the investigation of UV-curable binders for pigment printing.

INTRODUCTION

characteristics of a textile substrate can be changed

HE
t by PROPERTIES AND
the of
application a polymeric layer or coating[1,2]. Coatingsare ap-
plied to give textiles a more aesthetic outlook or to obtain a product with a
better performance, e.g., watertightness or a higher wear resistance. Coat-
ings used in the textile industry consist usually of plastisols (PVC) or solvent
and water based pastes of polymers. In the application of water based
systems considerable amounts of energy are consumed in the necessary re-
moval of water during a drying step prior to the actual curing of the coating.
The drying and curing steps in the application process need to be carefully
controlled in order to ensure an optimal quality of the final product. In most
cases the production speed is limited by the interplay of the drying and cur-

ing steps. The use of various types of organic solvents gives rise to toxic and
environmental problems; for this reason, water based systems are almost ex-
clusively used in the Dutch textile industry. UV-curable polymeric systems
circumvent the problems stated above by offering the following advantages
over conventional coating techniques:

0 no solvents or water needed

152 JOURNAL OF COATED FABRICS, Volume 24-October 1994

0093-4658/94/02 0152-10 $10.00/0
@1994 Technomic Publishmg Co., Inc.

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 153

. freedom in formulation
· low energy consumption
. enhanced process integration
· fast curing and processing
. short start-up times
· low environmental pollution
.
compact equipment with low fabric content
. heat-sensitive substrates can be coated

. thick coating layers can be applied in a one-step process

. double-sided
coatings can be applied in a single operation
UV-curing technology has already been introduced to a range of indus-
tries.UV-curing systems are used in coatings, inks and adhesives for wood,
paper, glass, synthetic materials, and metals. In the textile industry, however,
only little use has been made of this new technology because only a few
UV-curable materials can meet the requirements for textile coatings con-
cerning :
.
flexibility (hand)
.
strength
.
bonding
. chemical resistance

At the end of the 1970s, Walsh and co-workers started experimental work
on the application of UV-curing on textile substrates [3]. Other research
groups [4,5] have started projects since. The TNO Centre for Textile
Research started research on radiation curing in 1986 with a project on UV-
curable coatings [6]. Since then other projects have been carried out, e.g.,
UV-curable binders for pigment printing and breathability of UV-curable
coatings (TNO Plastics and Rubber Institute).
In this paper an overview of the results of the research projects on radia-
tion curable coatings and pigment binders is presented [ 7].

CHEMICAL BACKGROUND

A typical UV-curable coating or binder paste contains a high-molecular-

weight prepolymer (MW 700-5000), a monomer (MW < 500), and a photo-
initiator. The prepolymer and monomer contain reactive groups that can
polymerize. Figure 1 shows the structure of a diacrylate prepolymer and
monomer. Upon irradiation with ultraviolet light, the photoinitiator pro-

duces radicals, that start off the polymerization reaction, resulting in the for-
mation of a three-dimensional polymeric network. A schematic representa-
tion of the photochemically induced polymerization is given in Figure 2.

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154

FIGURE 1. Chemical structure of diacrylate prepolymer and monomer.

FIGURE 2. Radical polymenzation reaction.

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 155

FIGURE 3. Schematic representation of water/solvent based and UV process.

The UV-pastes which contain no water or solvent, can be cured imme-

diatley after application (Figure 3). Typical curing times are less than a sec-
ond.

Coating and Binder Properties

The properties of the coating or binder are strongly determined by the
choice of the starting materials. The use of low molecular weight prepoly-
mers and/or multi-functional (high reactivity) compounds will result in the

formation of a hard and brittle polymeric network. High molecular pre-

polymers with a mono- or difunctionality will give more flexible and elastic
polymeric films; however, the strength of these films is low. To ensure
strength as well as a good flexibility (hand) of the coating or binder film it
is often necessary to incorporate different types of prepolymers into the
coating as illustrated in Figure 4. Changing the prepolymer/monomer ratio
in the paste strongly influences the film properties, as is shown in Figure 5.
The viscosity of the paste is influenced by the prepolymer/monomer ratio
as well. High molecular weight materials tend to increase the initial viscosity

of the paste, whereas low molecular weight compounds (monomers) have an

opposite effect; therefore, monomers can be used as diluents. Taking into ac-
count the effects of the concentration and the reactivity of the monomer on
the hardness of the film, it is advisable to use monofunctional monomers to
lower the paste viscosity.

Blocking
UV-curing of coating and binder pastes are susceptable to inhibition by

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156

FIGURE 4. Strength and elasticity of a polyester/polyether/monomer coatmg film as a func-

tion of the percentage polyether prepolymer m the film.

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 157

FIGURE 5. Strength and elasticity of a polyester/polyether/monomer coating film as a func-

tion of the percentage monomer m the film

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158

oxygen. If the cure speed within the polymeric mixture is too slow, the

photoinitiated radicals in the polymerization reaction can be quenched by at-

mospheric oxygen resulting in blocking of the polymeric film. Mixtures of
high molecular weight and low functional prepolymers are especially prone
to this phenomenon. Because these types of materials are needed for flexible

coatings and binders, several investigations were made in order to avoid

blocking or to mask its results.
Blocking can be avoided by using a higher lamp intensity and a good
selection of the photoinitiator system, which will lead to an increase of the
cure speed. An alternative method is the exclusion of oxygen by using a

nitrogen blanket to create an inert atmosphere. Additives such as tertairy

amines and silicones can be used to mask the effects of blocking on the
coating or binder properties.

USE OF ADDITIVES

The use of two specific additives in UV-curable coatings have been in-
vestigated :
.

Flame Retardants in UV-Coatings

In a recent project, the possibilities and properties of flame retardant UV-
curable coatings were investigated using several types of phosphor and/or
nitrogen containing flame retardant additives. The additives had little or no
effect on the strength and flexibility of the coating film. In some cases, small
effects were observed on the transparency of the film and the viscosity of the
coating paste. A satisfactory flame retardant effect was displayed by most of
the additives.
When the cured coatings were subjected to a heat and/or washing treat-
ment, part of its flame retardant capacity was lost. This effect was ascribed
to a loss of additive, which is correlated to its chemical nature. Especially
salts and ether group containing compounds displayed this effect. No clear
relationship between the decrease in flame retardation and weight loss upon
the treatment could be established. Flame retardant additives possessing an
unsaturated double carbon-carbon bond, e.g. a vinyl group, do not display
the above effect because the additive can participate in the photoinitiated
radical polymerication reaction, through which it becomes fully immobi-
lized in the coating film.

Pigments in UV-Coatings
UV-curing of pigmented systems is hindered by the absorption and
reflectance of the incident UV-light by the pigments in the coating formula-
tion. Especially the inner polymer layers, which are remote from the surface,

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 159

FIGURE 6. Absorption versus absorbance m UV-coatings.

are prone to insufficient curing and bonding will be affected (Figure 6). Ex-

periments showed that the bonding of pigmented coatings is less compared

to the bonding between unpigmented coatings and substrate.

Using pigmented systems, it is important to select a pigment and photo-

initiator system that have different absorption characteristics. Here the ini-
tiator can absorb light in the absorption &dquo;gap&dquo; of the pigment and polymer-
ization will take place. An alternative solution is irradiation with UV-light
on both sides of the substrate to obtain complete curing.

UV-CURABLE BINDERS FOR PIGMENT PRINTING

In the conventional pigment printing of textile substrates, polymeric dis-

persions in water are used as binders. After application of the printing paste,
water needs to be evaporated and subsequent curing is necessary to cross-
link the binder, which is a time and energy consuming process. In an alter-
native UV-curing process the drying step can be omitted. Using 100%

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160

binder systems, which are free of solvent or water, a reduction of the energy
consumption and an increase in production speed can be obtained.
100% UV-Curable Binders
As in the case of conventional binders, in most cases polyacrylic, the
rheological featuers of the printing paste need to be shear-thinning, which is
necessary to obtain a good sharpness of the print and little strike through. In
the case of UV-curable binders, the rheological properties which are Newto-
nian, have to be modified in order to get a shear thinning effect. The initial
viscosity of the printing paste has to be of the same viscosity as the conven-
tional pigment printing pastes so that the same equipment can be used.
Initial investigations concentrated on modifying the rheology of the
100% binder by using several types of rheology modifiers, such as cellulose
acetate butyrate and silicon oxides. Unfortunately, no or little shear

thinning was observed and the initial viscosity remained to high for practical
use.

Water Based UV-Curable Binders

Reduction of the viscosity of 100% binder systems can be achieved by us-
ing more low molecular weight compounds in the binder formulation. In-
crease of the monomer/prepolymer ratio in the binder paste, however,
resulted in a sharp decrease in flexibility (’hand’) of the print. In order to ob-
tain an appropriate paste viscosity and an acceptable print, experiments were
carried out using water-based binders.
UV-curable prepolymers and monomers can be dispersed into water to
yield stable oil-in-water emulsions. Thickening of these emulsions and addi-
tion of pigments resulted in a paste suitable for screen-printing. Printing ex-
periments using a flat screen on various textile substrates gave satifying
results. Sharpness and hand of the prints are the same as or better than those
of conventional prints. The strike through can be considered acceptable. Rub
fastness of the prints is close to the rub fastness of conventional systems.

ACKNOWLEDGEMENTS

We would like to express our thanks to the members of the &dquo;Coating&dquo;

group of the Textile Research Association &dquo;De Voorzorg&dquo; and the members
of the &dquo;UV-binders&dquo; group for their contributions to the discussio; the Tex-
tile Research Association &dquo;De Voorzorg,&dquo; the Ministry of Economic Affairs,
NOVEM, and TNO for their financial support. We thank our collegues for
their contributions to the projects.

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REFERENCES

1. Wypych, J. 1988. Polymer Modified Textile Materials. New York: Wiley Interscience.
2. Van Parys, M. 1994. Coating. Guimaraes: Eurotex.
3. (a) Oraby, W. and Walsh, W. K. 1979.
J. Applied Polymer Science, 23:3227: (b)
Walsh, W. K. et al. 1983. "Water-Free, Low Energy Coloration Processes for Tex-
tiles ; Part I: Radiation Curing of Pigment Prints," Raleigh: University of North
Dakota.
4. Wisniewski, O. 1985. "Formulation de pates d’impression pigmentaires photo-
reticulables et tentatives d’optimation de leurs conditions d’application dans le
domaine textile," thesis University of Haute Alsace.
5. Einsele, U. and H. Herlinger. 1988. Textil Praxis International, 43:497.
6. Luiken, A. 1989. "Radiation Curable Coatings for Textile Substrates," Radtech
Europe 1989, Florence, Conference papers, 207.
7. Part of this presentation A. H. Luiken, M. P. W. Marsman, R. B. M. Holweg.
J. Coated Fabrics, 21:268.
1992.

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