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2004 10:52 Seite 42

Radiation curing

UV coatings for plastics

Stefan Smeets
Egbert Boerrigter
Stephan Peeters

Rapid curing, no or very low VOC content ,

high performance properties - UV-tech-
nology offers a number of advantages. On
plastics, though, UV curable coatings
have been difficult to achieve, mainly be-
cause of inferior adhesion to the sub-
strate compared to solvent borne sys-
tems. Optimisation of existing binder/re-
active diluent systems, however, can pro-
vide coatings for plastics with very good
performances.

UV-curing technology for industrial coat-

ings has been established for decades.
The advantages in terms of processing
(high speed, smaller equipment), per-
formance (scratch resistance, stain resist-
ance, etc) and environmental friendliness
Figure 1: Effect of diluting acrylates on adhesion to several substrates.
are well known. The use of UV-technology
Blue regions: highly preferred. Green regions: optional in balance with other properties
for coating plastics has been limited.
However, as this article aims to show, the
translation of the advantages of UV-tech-
nology into the field of plastic coatings
has lead to an optimisation of existing UV-
resins as well as the development of new
UV-binders.

Tailor made solutions required

The increasing use of plastics as construc-
tion materials in automotive, electronic and
telecommunication fields implies that their
coatability is becoming very important.
However, finding a universal coating for
all types of plastics is still a utopia. Their
low surface energies and sensitivity to
temperature and solvent make many plas-
tics difficult to coat. The number of differ-
ent materials comprising homopolymers
or blends of different polymers is enor-
mous and most substrates require tailor-
made solutions.
Moreover, due to different intrinsic prop-
erties within a polymer family, different
properties are targeted. Optimisation and Figure 2: UV-adhesion promoters for plastics. Blue regions: main component;
fine-tuning of well-known plastics materi- green regions: optional additive; white region: optional diluting acrylate

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Radiation curing

als by blending or using additives to ob-

tain better properties requires simultane-
ous adjustment of the corresponding coat-
ing formulations. The current trend to-
wards cheaper polymers is primarily driv-
en by their coatability, which allows to ob-
tain the required surface aesthetics.
Figure 3: A schematic representation of a UV-PUD
With UV-technology, one is no longer limit-
ed to coat plastics with solvent-based
products. Solvent coatings are inhibited
by their high VOC-emissions, the space-
consuming, long thermal drying tunnels
required and their limited curing speed.

Not only does UV-technology overcome these

problems, it also offers other advantages
such as the ability to coat heat-sensitive sub-
strates as well as a performance improve- Figure 4:
ment e.g. in scratch and stain resistance, Monitoring of
which are becoming increasingly important. the colour b val-
ues in Xenon-
testing. The
UV Curing Technology marks denote
the appearance
UV-resins are well established for surface
of first cracks
protection and decoration in many appli-
cations such as furniture, wood flooring,
construction, graphic arts and electronics
however, their use on plastic substrates is The chemistry used in UV-polymerisation • Photoinitiators, which under exposure to
still limited. Despite the advantages of the is almost entirely based on acrylate func- UV-light form radicals that initiate a poly-
UV-technology, equipment manufacturers, tionalised materials. A UV formulation al- merisation reaction between diluting
formulators and raw material suppliers ways contains the following ingredients: acrylates and acrylated oligomers.
face new challenges when attempting to • Diluting acrylates and acrylated oligomers, • Fillers and additives, which mostly do not
introduce this technology further into the which, as reactive materials, form the back- participate in the polymerisation reaction
field of plastic coatings. bone of the coating after drying. and remain embedded in the cured network.

Table 1: Molecular weight, shrinkage, and surface tension of diluting acrylates

Diluting Acrylate Description Molecular Shrinkage Surface tension
weight (%) at 25°C (mN/m)
IBOA Isobornyl acrylate 208 5.2 32
“Ebecryl 114” Oxyethylated phenol acrylate 236 6.8 39
ODA Octadecyl acrylate 200 8.3 30
“Ebecryl 1039” Urethane monoacrylate 33
TCDA Tricyclodecane diol diacrylate 304 5.9 40
“Ebecryl 145” Propoxylated neopentyl glycol diacrylate 328 9.0 31
DPGDA Dipropylene glycol diacrylate 242 13.0 35
TPGDA Tripropylene glycol diacrylate 300 18.1 34
HDDA Hexane diol diacrylate 226 19.0 36
“Ebecryl 160” Trimethylolpropane ethoxy triacrylate 428 14.1 39
“OTA 480” Propoxylated glycerol triacrylate 480 15.1 36
TMPTA Trimethylolpropane triacrylate 296 25.1 38
“Ebecryl 40” Alkoxylated pentaerythritol tetraacrylate 571 8.7 40
“Ebecryl 140” Ditrimethylol propane tetraacrylate 438 10.0 38

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Radiation curing

Diluting acrylates
UV-coatings are, by their nature, solvent
free, so they have to be formulated in a
way which compensates for the lack of sol-
vent in the adhesion on plastics sub-
strates. This adhesion is difficult because
of the inherent polymerisation process of
the UV-resins.

Shrinkage, solubility and surface

tension have to be considered
Figure 5: Gloss
The speed of the UV-polymerisation process monitoring in
produces internal stress in the coating the Xenon test
which is not found in conventional thermal
drying processes. When exposed to UV-
light, the photoinitiator starts a chain reac-
tion leading to polymerisation of the liquid Table 2: Viscosity of UV resins for adhesion on plastic substrates
coating accompanied by a decrease in vol- Resin Description Hoppler Viscosity, mPa s
ume and thus shrinkage. The liquid coating (T in °C)
consists mainly of highly viscous oligomers
and low viscosity monomers. The purpose “Ebecryl 740-40TP” Acrylic oligomer in TPGDA 8500 (60)
of the diluting acrylates or monomers is the
“Ebecryl 767” Acrylic oligomer in IBOA 8500 (60)
reduction of the viscosity of the total UV for-
mulation. These diluting acrylates play the “Ebecryl 745” Acrylic oligomer in blend TPGDA/HDDA 20,000 (25)
role of "reactive" solvents within conven-
tional formulations. But as they react in the “Ebecryl 303” Polymeric resin in HDDA 900 (25)
final polymer, they influence the final prop- “Ebecryl 436” Chlorinated polyester resin in TMPTA 1500 (60)
erties as well. Low viscosity acrylates with
high functionality and low molecular weight “Ebecryl 438” Chlorinated polyester resin in “OTA 480” 1500 (60)
will give high reactivity, high cross link den-
“Ebecryl 584” Chlorinated polyester resin in HDDA 2000 (60)
sity but also high shrinkage. Thus, they will
decrease the adhesion of a UV-coating. Low “Ebecryl 7100” Amine functional acrylate 1200 (25)
viscosity acrylates with low functionality will
give low reactivity, low cross link density “Ebecryl 168” Methacrylated acidic derivative 1350 (25)
and a high flexibility. “Ebecryl 170” Acrylated acidic derivative 3000 (25)

The shrinkage of some diluting acrylates is

shown in Table 1. The shrinkage is ex-
pressed as the change in density during
Another important parameter to consider Different substrates demand
curing of a formulation containing 100%
is the surface tension of the substrate. different solutions
resin and 5% photoinitiator. Although
Good adhesion is obtained when the sur-
these values give a good indication of the A formulation leading to a good adhesion
face tension of the substrate is higher
intrinsic properties of a diluting acrylates, on a particular plastic may not deliver
than that of the coating, giving an optimal
the behaviour in a final formulation de- good performance on another member of
wetting of the substrate. The surface ten-
pends on the other components as well. the same plastic family. The ability of sev-
sion of typical diluting acrylates is also
shown in Table 1. The surface tension of eral diluting acrylates to serve as an adhe-
The solubility parameters of both polymer- common plastic substrates may vary from sion promoter in a coating is shown in Fig-
ic substrate and formulation indicate 20 mN/m ("Teflon") to 44 mN/m (PET). In ure 1. In the blue region one can find the
whether adhesion is expected to be diffi- addition, a wide range of surface tensions preferred diluting acrylates for given sub-
cult or not. Generally, a diluting acrylate may be encountered for one specific sub- strate materials, whereas the products in
which can attack or swell a substrate will strate material, due to different surface the green region are used in balance with
form an interpenetrating polymer network treatments. For example, untreated other properties such as diluting power
between substrate and coating, leading to polypropylene may have a surface tension and reactivity.
an excellent adhesion. Thus, diluting acry- of 28 mN/m whereas corona treated PP can
lates such as oxyethylated phenol acry- go up to 40 mN/m. A surface treatment with Due to its capacity to swell the plastic sur-
late, DPGDA or HDDA are able to attack corona or flame results in the formation of face, HDDA is an interesting adhesion pro-
and swell polycarbonate. polar groups on the substrate. moter. In the case of PC or impact resistant

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Radiation curing

Table 3: Adhesion performance of some “Ucecoat” UV-PUD's. 5B = perfect adhesion

Dispersions Persoz Solvent resistance Flexibility PVC PC PP
hardness (s) (ADR), 12 µm on PC (impact, cm) (Corona)
DW 7770 311 > 100 > 100 5B 5B 0B
DW 7773 352 > 100 < 20 5B 5B 5B
DW 7825 295 50 > 100 5B 5B 0B
DW 7772 312 > 100 < 20 5B 5B 5B
DW 7849 263 30 > 100 5B 5B 0B

PS, only a small amount of HDDA is need-

ed in a formulation, whereas for harder PS
higher quantities are necessary. Because
of its low surface tension, ODA is a very
useful diluting acrylate for PP and PE. ODA
is mostly used in small amounts because
of its incompatibility with many acrylated
oligomers at high concentration. "Ebecryl
1039" is preferred over "Ebecryl 40" when
a higher flexibility is required. TCDA is a di-
functional diluting acrylate for rigid
SMC/BMC as it has a low shrinkage com-
bined with an excellent hardness. Table 4: Aliphatic urethane acrylates for exterior application

UV adhesion promoters
mers, the value of these resins has to be The amount of diluting acrylate must be
Diluting acrylates in a UV-formulation re- evaluated with experimental work on chosen depending on the required viscosi-
duce the viscosity and increase the adhe- each plastic. ty, but also the rigidity of the substrate. To
sion on several plastic substrates. Howev- increase the reactivity one can take a high-
er, they can reduce the high performance The ability of these resins to serve as an ad- er functional diluting acrylate, or one can
of an UV coating. Thus, in order to limit the hesion promoter in a primer and/or in a add "Ebecryl 7100", which is a low viscosi-
percentage of diluting acrylates in a UV coating is shown in Figure 2. As the adhe- ty amine functional acrylate. "Ebecryl 168"
formulation, one can switch from a one sion of UV-resins towards PC, PVC and PM- and "170" are methacrylated or acrylated
layer to a multi-layer approach with MA is mostly obtained with a small amount acidic components which are able to etch
primer, basecoat and topcoat. As the of diluting acrylate, no adhesion promoter is the surface of a filled plastic.
primer is responsible for the adhesion to required. Surface treatments, such as coro-
the substrate, both basecoat and topcoat na, flame, plasma or IPA cleaning are ad- The efficacy of the UV-resins to adhere to a
may contain less diluting oligomers. vised to activate the surface but also to re- plastic depends on the application process
move processing additives and contamina- and the contact and drying time. The best way
Almost all automotive paints use the tion. Figure 2 is composed of three areas to evaluate this is through industrial trials.
primer/basecoat/clearcoat build-up in or- (blue, green, white), and should serve as a
der to fulfil the high quality requirements. guideline to coat several plastic substrates. Low viscosity, high performance
The basecoat contains the colour pigment, The resins in the blue region represent the UV-resins
while the topcoat will provide the scratch- major component in a formulation, which
resistance etc. This multi-layer approach can be diluted with one of the diluting acry- The design of low viscosity, high perform-
makes it easy to switch from one colour to lates from the white region. Thus, "Ebecryl ance resins for spray application to coat
another without changing the primer and 740-40TP", "767" and "745" are acrylic acry- three-dimensional objects has led to a
topcoat. The use of one UV-primer for sev- lates which give good adhesion to many new generation of binders, radiation cur-
eral plastic parts could simplify the coat- plastics mainly due to their low functionality able polyurethane dispersions (UV-PUD)
ing process considerably. and thus shrinkage. "Ebecryl 303" is a poly- (Figure 3). The reaction of diisocyanates
meric resin diluted in HDDA that shows good (shown in blue in the diagram) with differ-
Several UV-resins (Table 2) provide a adhesion in combination with acrylic acry- ent polyols (polyester, polyether, polycar-
good adhesion to different plastic sub- lates. "Ebecryl 436", "438" and "584" are bonate) results in a polyurethane which
strates. In practice, however, as a plastic chlorinated polyester resins diluted in TMP- forms the basic chemistry of a UV-PUD.
can vary from one supplier to another, TA, “OTA 480” and HDDA, respectively. They Because of their relatively high molecular
can be filled or non-filled, can be a blend have a good reactivity combined with a very weight, UV-PUDs show almost no shrink-
of two miscible or compatibilised poly- low shrinkage (< 4 %). age after curing, resulting in an excellent

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Radiation curing

adhesion to many substrates. The combi- THE AUTHORS acrylates, were tested in a mixture with
nation of this property together with the "Ebecryl 284" (20% addition of "Ebecryl
very low viscosity and the advantages of
➤ Stefan Smeets, PhD, is Manager Technical 1290" and "Ebecryl 5129".)
Service & Development Industrial Coatings Europe
UV-technology make these structures very at Surface Specialties UCB, responsible for
suitable for either primer or topcoat. Plastics Coatings. Figure 4 illustrates the monitoring of the
colour b value in the Xenon test for the 6
This urethane technology provides versa- ➤ Ir. Egbert Boerrigter, MBA, is Market Manager urethane acrylates. The colour retention is
Radcure Europe at Surface Specialties UCB.
tile solutions combining different chain excellent - after a relaxation phase (b de-
structures. Such polymers combine hard creasing), b values increase only very
➤ Stephan Peeters, PhD, is Manager Global New slightly. The visual appearance of the first
segments which could be urethane, urea, Technology Development Radcure at Surface
allophanates and soft segments such as Specialties UCB. crack formation is also indicated for each
polyester, polyether, polycarbonate. When product. Pictorial standards are used to
compared to traditional 100% UV systems, note degradation with cracking (ASTM
the UV-PUD's morphology could be adjust- Extensive test experience has been gained D660). "Ebecryl 284", "294/25 HD",
ed depending on the degree of cross link- with different types of accelerated tests "1290" and "8402", which were also test-
ing needed and the desired stiffness. and cycling conditions. This paper only ed by natural exposure in Belgium and
concentrates on the Xenon test, using a Florida, are still free of cracks after three
Xenon “WeatherOMeter”, according to the years.
The adhesion of different radiation curable
ASTM G26 method.
PUDs on different substrates has been test-
ed. In addition to adhesion (12 µm dry coat- Figure 5 illustrates the monitoring of the
Because of the huge variety of plastics, it gloss in the Xenon test. In general the
ing), the Persoz hardness (50 µm dry film on
was decided to test the UV clearcoats on gloss retention is excellent up to 2000 h of
glass), flexibility (impact resistance of a 12
weather stable white thermoset polymer Xenon exposure. Upon prolonged expo-
µm film on aluminium) and solvent resist-
coated panels at 20 µm coating thickness. sure the gloss decreases.
ance (Acetone Double Rubs of a 12 µm film
A visual evaluation was carried out along
on PC) is shown in Table 3.
with colour and gloss monitoring during
the tests.
UV resins for exterior
applications Aliphatic urethane acrylates in general
outperform other oligomer types in both
Damage of common plastics by solar radi- accelerated and natural weathering tests.
ation depends on the susceptibility of the Aromatic polymers, on the other hand, are
polymer type to solar UV-radiation as well inherently not stable to light and tend to
as the complexity of the weathering envi- yellow and degrade rapidly. Also conven-
ronment to which it is exposed. tional polyether and polyester acrylates Results at a glance
The magnitude of the damage can be con- are more sensitive to degradation.
trolled using stabilizers in the plastic com- • With UV-technology, one is no longer
position. Expansion of the use of radia- UV-resins suitable for formulation of coat- limited to coat plastics with solvent-
tion-cured coatings on plastics in exterior ings for exterior application were identi- based products.
applications depends on the development fied (Table 4). These include aliphatic ure-
of binders which combine excellent weath- thane acrylates based on chemical back- • Diluting power, solubility, shrinkage
ering performance with other increasingly bones that are stable towards degradation and surface tension of diluting acry-
more stringent requirements. under the influence of light and moisture. lates have to be considered when
Accelerated weathering tests are widely These resins have excellent colour and preparing UV coatings for plastics.
used to assess the weatherability of poly- gloss retention properties. Di- and trifunc-
mers. The most important parameter gov- tional products result in relatively low • Several UV-resins provide a good ad-
erning the reliability of the various meth- cross link densities and are, in general, hesion to different plastic substrates.
ods is the nature of the light source em- less sensitive to crack formation than
ployed. The short wavelength emission of higher functional products which result in • Radiation curable polyurethane dis-
UV-B lamps can cause unnatural accelera- more densely cross linked systems. Never- persions are suitable as primer and
tion or degradation whereas UV-A lamps theless, hexafunctional urethane acrylates topcoat to coat three-dimensional
have no output below the normal solar are indispensable in providing superior plastic objects.
cut-off of 295 nm and may allow enhanced scratch resistance.
correlation with actual outdoor weather- • Several aliphatic urethane acrylates
ing. With appropriate filters, the Xenon arc In a comparative study, all the products, are suitable to coat exterior plastics.
spectral light distribution corresponds except "Ebecryl 1290" and "Ebecryl 5129", They are stable to degradation by
well to sunlight in both the UV and the vis- were diluted with 30% HDDA. HDDA is one light or moisture and have also ex-
ible range. In combination with humidity of the best performing diluting acrylates cellent colour and gloss retention
control features, this makes the Xenon for exterior use. "Ebecryl 1290" and "Ebe- properties.
test the most widely accepted standard. cryl 5129", both hexa-functional urethane

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