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Radiation curing

UV coatings for plastics


Stefan Smeets Egbert Boerrigter Stephan Peeters
Rapid curing, no or very low VOC content , high performance properties - UV-technology offers a number of advantages. On plastics, though, UV curable coatings have been difficult to achieve, mainly because of inferior adhesion to the substrate compared to solvent borne systems. Optimisation of existing binder/reactive diluent systems, however, can provide coatings for plastics with very good performances.

UV-curing technology for industrial coatings has been established for decades. The advantages in terms of processing (high speed, smaller equipment), performance (scratch resistance, stain resistance, etc) and environmental friendliness are well known. The use of UV-technology for coating plastics has been limited. However, as this article aims to show, the translation of the advantages of UV-technology into the field of plastic coatings has lead to an optimisation of existing UVresins as well as the development of new UV-binders.

Figure 1: Effect of diluting acrylates on adhesion to several substrates. Blue regions: highly preferred. Green regions: optional in balance with other properties

Tailor made solutions required


The increasing use of plastics as construction 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 plastics difficult to coat. The number of different materials comprising homopolymers or blends of different polymers is enormous and most substrates require tailormade solutions. Moreover, due to different intrinsic properties within a polymer family, different properties are targeted. Optimisation and fine-tuning of well-known plastics materi-

Figure 2: UV-adhesion promoters for plastics. Blue regions: main component; green regions: optional additive; white region: optional diluting acrylate

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als by blending or using additives to obtain better properties requires simultaneous adjustment of the corresponding coating formulations. The current trend towards cheaper polymers is primarily driven by their coatability, which allows to obtain the required surface aesthetics. With UV-technology, one is no longer limited to coat plastics with solvent-based products. Solvent coatings are inhibited by their high VOC-emissions, the spaceconsuming, 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 substrates as well as a performance improvement e.g. in scratch and stain resistance, which are becoming increasingly important.

Figure 3: A schematic representation of a UV-PUD

UV Curing Technology
UV-resins are well established for surface protection and decoration in many applications such as furniture, wood flooring, construction, graphic arts and electronics however, their use on plastic substrates is still limited. Despite the advantages of the UV-technology, equipment manufacturers, formulators and raw material suppliers face new challenges when attempting to introduce this technology further into the field of plastic coatings.

Figure 4: Monitoring of the colour b values in Xenontesting. The marks denote the appearance of first cracks

The chemistry used in UV-polymerisation is almost entirely based on acrylate functionalised materials. A UV formulation always contains the following ingredients: Diluting acrylates and acrylated oligomers, which, as reactive materials, form the backbone of the coating after drying.

Photoinitiators, which under exposure to UV-light form radicals that initiate a polymerisation reaction between diluting acrylates and acrylated oligomers. Fillers and additives, which mostly do not participate in the polymerisation reaction and remain embedded in the cured network.

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


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

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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 solvent in the adhesion on plastics substrates. This adhesion is difficult because of the inherent polymerisation process of the UV-resins.

Shrinkage, solubility and surface tension have to be considered


The speed of the UV-polymerisation process produces internal stress in the coating which is not found in conventional thermal drying processes. When exposed to UVlight, the photoinitiator starts a chain reaction leading to polymerisation of the liquid coating accompanied by a decrease in volume and thus shrinkage. The liquid coating consists mainly of highly viscous oligomers and low viscosity monomers. The purpose of the diluting acrylates or monomers is the reduction of the viscosity of the total UV formulation. These diluting acrylates play the role of "reactive" solvents within conventional formulations. But as they react in the final polymer, they influence the final properties as well. Low viscosity acrylates with high functionality and low molecular weight will give high reactivity, high cross link density but also high shrinkage. Thus, they will decrease the adhesion of a UV-coating. Low viscosity acrylates with low functionality will give low reactivity, low cross link density and a high flexibility. The shrinkage of some diluting acrylates is shown in Table 1. The shrinkage is expressed as the change in density during curing of a formulation containing 100% resin and 5% photoinitiator. Although these values give a good indication of the intrinsic properties of a diluting acrylates, the behaviour in a final formulation depends on the other components as well. The solubility parameters of both polymeric substrate and formulation indicate whether adhesion is expected to be difficult or not. Generally, a diluting acrylate which can attack or swell a substrate will form an interpenetrating polymer network between substrate and coating, leading to an excellent adhesion. Thus, diluting acrylates such as oxyethylated phenol acrylate, DPGDA or HDDA are able to attack and swell polycarbonate.

Figure 5: Gloss monitoring in the Xenon test

Table 2: Viscosity of UV resins for adhesion on plastic substrates


Resin Ebecryl 740-40TP Ebecryl 767 Ebecryl 745 Ebecryl 303 Ebecryl 436 Ebecryl 438 Ebecryl 584 Ebecryl 7100 Ebecryl 168 Ebecryl 170 Description Acrylic oligomer in TPGDA Acrylic oligomer in IBOA Acrylic oligomer in blend TPGDA/HDDA Polymeric resin in HDDA Chlorinated polyester resin in TMPTA Chlorinated polyester resin in OTA 480 Chlorinated polyester resin in HDDA Amine functional acrylate Methacrylated acidic derivative Acrylated acidic derivative Hoppler Viscosity, mPa s (T in C) 8500 (60) 8500 (60) 20,000 (25) 900 (25) 1500 (60) 1500 (60) 2000 (60) 1200 (25) 1350 (25) 3000 (25)

Another important parameter to consider is the surface tension of the substrate. Good adhesion is obtained when the surface tension of the substrate is higher than that of the coating, giving an optimal wetting of the substrate. The surface tension of typical diluting acrylates is also shown in Table 1. The surface tension of common plastic substrates may vary from 20 mN/m ("Teflon") to 44 mN/m (PET). In addition, a wide range of surface tensions may be encountered for one specific substrate material, due to different surface treatments. For example, untreated polypropylene may have a surface tension of 28 mN/m whereas corona treated PP can go up to 40 mN/m. A surface treatment with corona or flame results in the formation of polar groups on the substrate.

Different substrates demand different solutions


A formulation leading to a good adhesion on a particular plastic may not deliver good performance on another member of the same plastic family. The ability of several diluting acrylates to serve as an adhesion promoter in a coating is shown in Figure 1. In the blue region one can find the preferred diluting acrylates for given substrate materials, whereas the products in the green region are used in balance with other properties such as diluting power and reactivity. Due to its capacity to swell the plastic surface, HDDA is an interesting adhesion promoter. In the case of PC or impact resistant

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


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

PS, only a small amount of HDDA is needed 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 difunctional diluting acrylate for rigid SMC/BMC as it has a low shrinkage combined with an excellent hardness.

Table 4: Aliphatic urethane acrylates for exterior application

UV adhesion promoters
Diluting acrylates in a UV-formulation reduce the viscosity and increase the adhesion on several plastic substrates. However, they can reduce the high performance of an UV coating. Thus, in order to limit the percentage of diluting acrylates in a UV formulation, one can switch from a one layer to a multi-layer approach with primer, basecoat and topcoat. As the primer is responsible for the adhesion to the substrate, both basecoat and topcoat may contain less diluting oligomers. Almost all automotive paints use the primer/basecoat/clearcoat build-up in order to fulfil the high quality requirements. The basecoat contains the colour pigment, while the topcoat will provide the scratchresistance etc. This multi-layer approach makes it easy to switch from one colour to another without changing the primer and topcoat. The use of one UV-primer for several plastic parts could simplify the coating process considerably. Several UV-resins (Table 2) provide a good adhesion to different plastic substrates. In practice, however, as a plastic can vary from one supplier to another, can be filled or non-filled, can be a blend of two miscible or compatibilised poly-

mers, the value of these resins has to be evaluated with experimental work on each plastic. The ability of these resins to serve as an adhesion promoter in a primer and/or in a coating is shown in Figure 2. As the adhesion of UV-resins towards PC, PVC and PMMA is mostly obtained with a small amount of diluting acrylate, no adhesion promoter is required. Surface treatments, such as corona, flame, plasma or IPA cleaning are advised to activate the surface but also to remove processing additives and contamination. Figure 2 is composed of three areas (blue, green, white), and should serve as a guideline to coat several plastic substrates. The resins in the blue region represent the major component in a formulation, which can be diluted with one of the diluting acrylates from the white region. Thus, "Ebecryl 740-40TP", "767" and "745" are acrylic acrylates which give good adhesion to many plastics mainly due to their low functionality and thus shrinkage. "Ebecryl 303" is a polymeric resin diluted in HDDA that shows good adhesion in combination with acrylic acrylates. "Ebecryl 436", "438" and "584" are chlorinated polyester resins diluted in TMPTA, OTA 480 and HDDA, respectively. They have a good reactivity combined with a very low shrinkage (< 4 %).

The amount of diluting acrylate must be chosen depending on the required viscosity, but also the rigidity of the substrate. To increase the reactivity one can take a higher functional diluting acrylate, or one can add "Ebecryl 7100", which is a low viscosity amine functional acrylate. "Ebecryl 168" and "170" are methacrylated or acrylated acidic components which are able to etch the surface of a filled plastic. The efficacy of the UV-resins to adhere to a plastic depends on the application process and the contact and drying time. The best way to evaluate this is through industrial trials.

Low viscosity, high performance UV-resins


The design of low viscosity, high performance resins for spray application to coat three-dimensional objects has led to a new generation of binders, radiation curable polyurethane dispersions (UV-PUD) (Figure 3). The reaction of diisocyanates (shown in blue in the diagram) with different polyols (polyester, polyether, polycarbonate) results in a polyurethane which forms the basic chemistry of a UV-PUD. Because of their relatively high molecular weight, UV-PUDs show almost no shrinkage after curing, resulting in an excellent

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adhesion to many substrates. The combination of this property together with the very low viscosity and the advantages of UV-technology make these structures very suitable for either primer or topcoat. This urethane technology provides versatile solutions combining different chain structures. Such polymers combine hard segments which could be urethane, urea, allophanates and soft segments such as polyester, polyether, polycarbonate. When compared to traditional 100% UV systems, the UV-PUD's morphology could be adjusted depending on the degree of cross linking needed and the desired stiffness. The adhesion of different radiation curable PUDs on different substrates has been tested. In addition to adhesion (12 m dry coating), the Persoz hardness (50 m dry film on glass), flexibility (impact resistance of a 12 m film on aluminium) and solvent resistance (Acetone Double Rubs of a 12 m film on PC) is shown in Table 3.

THE AUTHORS Stefan Smeets, PhD, is Manager Technical


Service & Development Industrial Coatings Europe at Surface Specialties UCB, responsible for Plastics Coatings.

acrylates, were tested in a mixture with "Ebecryl 284" (20% addition of "Ebecryl 1290" and "Ebecryl 5129".)

Ir. Egbert Boerrigter, MBA, is Market Manager


Radcure Europe at Surface Specialties UCB.

Stephan Peeters, PhD, is Manager Global New


Technology Development Radcure at Surface Specialties UCB.

Extensive test experience has been gained with different types of accelerated tests and cycling conditions. This paper only concentrates on the Xenon test, using a Xenon WeatherOMeter, according to the ASTM G26 method. Because of the huge variety of plastics, it was decided to test the UV clearcoats on weather stable white thermoset polymer coated panels at 20 m coating thickness. A visual evaluation was carried out along with colour and gloss monitoring during the tests. Aliphatic urethane acrylates in general outperform other oligomer types in both accelerated and natural weathering tests. Aromatic polymers, on the other hand, are inherently not stable to light and tend to yellow and degrade rapidly. Also conventional polyether and polyester acrylates are more sensitive to degradation. UV-resins suitable for formulation of coatings for exterior application were identified (Table 4). These include aliphatic urethane acrylates based on chemical backbones that are stable towards degradation under the influence of light and moisture. These resins have excellent colour and gloss retention properties. Di- and trifunctional products result in relatively low cross link densities and are, in general, less sensitive to crack formation than higher functional products which result in more densely cross linked systems. Nevertheless, hexafunctional urethane acrylates are indispensable in providing superior scratch resistance. In a comparative study, all the products, except "Ebecryl 1290" and "Ebecryl 5129", were diluted with 30% HDDA. HDDA is one of the best performing diluting acrylates for exterior use. "Ebecryl 1290" and "Ebecryl 5129", both hexa-functional urethane

Figure 4 illustrates the monitoring of the colour b value in the Xenon test for the 6 urethane acrylates. The colour retention is excellent - after a relaxation phase (b decreasing), b values increase only very slightly. The visual appearance of the first crack formation is also indicated for each product. Pictorial standards are used to note degradation with cracking (ASTM D660). "Ebecryl 284", "294/25 HD", "1290" and "8402", which were also tested by natural exposure in Belgium and Florida, are still free of cracks after three years. Figure 5 illustrates the monitoring of the gloss in the Xenon test. In general the gloss retention is excellent up to 2000 h of Xenon exposure. Upon prolonged exposure the gloss decreases.

UV resins for exterior applications


Damage of common plastics by solar radiation depends on the susceptibility of the polymer type to solar UV-radiation as well as the complexity of the weathering environment to which it is exposed. The magnitude of the damage can be controlled using stabilizers in the plastic composition. Expansion of the use of radiation-cured coatings on plastics in exterior applications depends on the development of binders which combine excellent weathering performance with other increasingly more stringent requirements. Accelerated weathering tests are widely used to assess the weatherability of polymers. The most important parameter governing the reliability of the various methods is the nature of the light source employed. The short wavelength emission of UV-B lamps can cause unnatural acceleration or degradation whereas UV-A lamps have no output below the normal solar cut-off of 295 nm and may allow enhanced correlation with actual outdoor weathering. With appropriate filters, the Xenon arc spectral light distribution corresponds well to sunlight in both the UV and the visible range. In combination with humidity control features, this makes the Xenon test the most widely accepted standard.

Results at a glance
With UV-technology, one is no longer limited to coat plastics with solventbased products. Diluting power, solubility, shrinkage and surface tension of diluting acrylates have to be considered when preparing UV coatings for plastics. Several UV-resins provide a good adhesion to different plastic substrates. Radiation curable polyurethane dispersions are suitable as primer and topcoat to coat three-dimensional plastic objects. Several aliphatic urethane acrylates are suitable to coat exterior plastics. They are stable to degradation by light or moisture and have also excellent colour and gloss retention properties.

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