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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
1 15. graphic arts and electronics however. shrinkage. formulators and raw material suppliers face new challenges when attempting to introduce this technology further into the field of plastic coatings. form the backbone of the coating after drying. equipment manufacturers. With UV-technology. which allows to obtain the required surface aesthetics. • Fillers and additives. construction. which mostly do not participate in the polymerisation reaction and remain embedded in the cured network. Figure 4: Monitoring of the colour b values in Xenontesting.0 Molecular weight 208 236 200 Shrinkage (%) 5. which are becoming increasingly important. it also offers other advantages such as the ability to coat heat-sensitive substrates as well as a performance improvement e.de . The marks denote the appearance of first cracks The chemistry used in UV-polymerisation is almost entirely based on acrylate functionalised materials. 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. which.3 Surface tension at 25°C (mN/m) 32 39 30 33 40 31 35 34 36 39 36 38 40 38 44 06 04 ECJ www. as reactive materials. wood flooring. long thermal drying tunnels required and their limited curing speed. in scratch and stain resistance.0 18. • Photoinitiators. the spaceconsuming. Table 1: Molecular weight.0 13.0 14.1 19. 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. A UV formulation always contains the following ingredients: • Diluting acrylates and acrylated oligomers.9 9. Not only does UV-technology overcome these problems.8 8.g. their use on plastic substrates is still limited. Despite the advantages of the UV-technology. Solvent coatings are inhibited by their high VOC-emissions.1 8. which under exposure to UV-light form radicals that initiate a polymerisation reaction between diluting acrylates and acrylated oligomers.7 10.Radiation curing als by blending or using additives to obtain better properties requires simultaneous adjustment of the corresponding coating formulations.1 25. one is no longer limited to coat plastics with solvent-based products. The current trend towards cheaper polymers is primarily driven by their coatability.2 6.coatings.
a wide range of surface tensions may be encountered for one specific substrate material.de . Thus. Low viscosity acrylates with high functionality and low molecular weight will give high reactivity. 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.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. the behaviour in a final formulation depends on the other components as well. In addition. When exposed to UVlight. The surface tension of typical diluting acrylates is also shown in Table 1. These diluting acrylates play the role of "reactive" solvents within conventional formulations. Thus. mPa s (T in °C) 8500 (60) 8500 (60) 20. HDDA is an interesting adhesion promoter. they will decrease the adhesion of a UV-coating. The shrinkage of some diluting acrylates is shown in Table 1. The ability of several diluting acrylates to serve as an adhesion promoter in a coating is shown in Figure 1. DPGDA or HDDA are able to attack and swell polycarbonate. But as they react in the final polymer. low cross link density and a high flexibility. The surface tension of common plastic substrates may vary from 20 mN/m ("Teflon") to 44 mN/m (PET). In the blue region one can find the preferred diluting acrylates for given substrate materials.Radiation curing Diluting acrylates UV-coatings are. Shrinkage. solvent free. The liquid coating consists mainly of highly viscous oligomers and low viscosity monomers. 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. For example. Due to its capacity to swell the plastic surface. Good adhesion is obtained when the surface tension of the substrate is higher than that of the coating. high cross link density but also high shrinkage. diluting acrylates such as oxyethylated phenol acrylate.coatings. by their nature. In the case of PC or impact resistant 04 ECJ 06 45 www. 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. whereas the products in the green region are used in balance with other properties such as diluting power and reactivity. A surface treatment with corona or flame results in the formation of polar groups on the substrate. they influence the final properties as well. This adhesion is difficult because of the inherent polymerisation process of the UV-resins. The solubility parameters of both polymeric substrate and formulation indicate whether adhesion is expected to be difficult or not. untreated polypropylene may have a surface tension of 28 mN/m whereas corona treated PP can go up to 40 mN/m. The purpose of the diluting acrylates or monomers is the reduction of the viscosity of the total UV formulation. the photoinitiator starts a chain reaction leading to polymerisation of the liquid coating accompanied by a decrease in volume and thus shrinkage. Generally. due to different surface treatments. 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. a diluting acrylate which can attack or swell a substrate will form an interpenetrating polymer network between substrate and coating. so they have to be formulated in a way which compensates for the lack of solvent in the adhesion on plastics substrates. leading to an excellent adhesion. Low viscosity acrylates with low functionality will give low reactivity. giving an optimal wetting of the substrate.
however. while the topcoat will provide the scratchresistance etc. the value of these resins has to be evaluated with experimental work on each plastic. ODA is mostly used in small amounts because of its incompatibility with many acrylated oligomers at high concentration. The reaction of diisocyanates (shown in blue in the diagram) with different polyols (polyester. ODA is a very useful diluting acrylate for PP and PE. radiation curable polyurethane dispersions (UV-PUD) (Figure 3).de . polycarbonate) results in a polyurethane which forms the basic chemistry of a UV-PUD. The best way to evaluate this is through industrial trials. Low viscosity. both basecoat and topcoat may contain less diluting oligomers. such as corona. Figure 2 is composed of three areas (blue. Surface treatments. whereas for harder PS higher quantities are necessary. PVC and PMMA is mostly obtained with a small amount of diluting acrylate. Thus. only a small amount of HDDA is needed in a formulation. and should serve as a guideline to coat several plastic substrates. resulting in an excellent 46 06 04 ECJ www. The amount of diluting acrylate must be chosen depending on the required viscosity. This multi-layer approach makes it easy to switch from one colour to another without changing the primer and topcoat. Several UV-resins (Table 2) provide a good adhesion to different plastic substrates. The resins in the blue region represent the major component in a formulation. "438" and "584" are chlorinated polyester resins diluted in TMPTA. 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. high performance resins for spray application to coat three-dimensional objects has led to a new generation of binders. They have a good reactivity combined with a very low shrinkage (< 4 %). "Ebecryl 740-40TP". "Ebecryl 168" and "170" are methacrylated or acrylated acidic components which are able to etch the surface of a filled plastic. "767" and "745" are acrylic acrylates which give good adhesion to many plastics mainly due to their low functionality and thus shrinkage. Almost all automotive paints use the primer/basecoat/clearcoat build-up in order to fulfil the high quality requirements. The ability of these resins to serve as an adhesion promoter in a primer and/or in a coating is shown in Figure 2. In practice. As the adhesion of UV-resins towards PC. "Ebecryl 436". green. The basecoat contains the colour pigment. polyether.coatings. As the primer is responsible for the adhesion to the substrate. as a plastic can vary from one supplier to another. The use of one UV-primer for several plastic parts could simplify the coating process considerably. "Ebecryl 303" is a polymeric resin diluted in HDDA that shows good adhesion in combination with acrylic acrylates. white). in order to limit the percentage of diluting acrylates in a UV formulation. 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). high performance UV-resins The design of low viscosity. which is a low viscosity amine functional acrylate. However. respectively. Thus.Radiation curing Table 3: Adhesion performance of some “Ucecoat” UV-PUD's. they can reduce the high performance of an UV coating. but also the rigidity of the substrate. no adhesion promoter is required. Because of its low surface tension. 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. 12 µm on PC > 100 > 100 50 > 100 30 Flexibility (impact. TCDA is a difunctional diluting acrylate for rigid SMC/BMC as it has a low shrinkage combined with an excellent hardness. To increase the reactivity one can take a higher functional diluting acrylate. or one can add "Ebecryl 7100". which can be diluted with one of the diluting acrylates from the white region. The efficacy of the UV-resins to adhere to a plastic depends on the application process and the contact and drying time. Because of their relatively high molecular weight. UV-PUDs show almost no shrinkage after curing. can be a blend of two miscible or compatibilised poly- mers. flame. "Ebecryl 1039" is preferred over "Ebecryl 40" when a higher flexibility is required. can be filled or non-filled. one can switch from a one layer to a multi-layer approach with primer. basecoat and topcoat. “OTA 480” and HDDA. plasma or IPA cleaning are advised to activate the surface but also to remove processing additives and contamination.
UV-resins suitable for formulation of coatings for exterior application were identified (Table 4). one is no longer limited to coat plastics with solventbased products. Aliphatic urethane acrylates in general outperform other oligomer types in both accelerated and natural weathering tests. PhD. polycarbonate. Accelerated weathering tests are widely used to assess the weatherability of polymers.de . Aromatic polymers. • Diluting power. These include aliphatic urethane acrylates based on chemical backbones that are stable towards degradation under the influence of light and moisture. are still free of cracks after three years. all the products. Such polymers combine hard segments which could be urethane. flexibility (impact resistance of a 12 µm film on aluminium) and solvent resistance (Acetone Double Rubs of a 12 µm film on PC) is shown in Table 3. 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. In combination with humidity control features. PhD. Figure 5 illustrates the monitoring of the gloss in the Xenon test. This urethane technology provides versatile solutions combining different chain structures. These resins have excellent colour and gloss retention properties. Di. which were also tested by natural exposure in Belgium and Florida. Nevertheless. MBA. is Market Manager Radcure Europe at Surface Specialties UCB.after a relaxation phase (b decreasing). Also conventional polyether and polyester acrylates are more sensitive to degradation. In general the gloss retention is excellent up to 2000 h of Xenon exposure. This paper only concentrates on the Xenon test. using a Xenon “WeatherOMeter”. They are stable to degradation by light or moisture and have also excellent colour and gloss retention properties. The colour retention is excellent . is Manager Global New Technology Development Radcure at Surface Specialties UCB. The most important parameter governing the reliability of the various methods is the nature of the light source employed. When compared to traditional 100% UV systems. 48 06 04 ECJ www. both hexa-functional urethane Figure 4 illustrates the monitoring of the colour b value in the Xenon test for the 6 urethane acrylates. In a comparative study. "294/25 HD". The magnitude of the damage can be controlled using stabilizers in the plastic composition. • Several UV-resins provide a good adhesion to different plastic substrates. acrylates. urea.and trifunctional products result in relatively low cross link densities and are. • Radiation curable polyurethane dispersions are suitable as primer and topcoat to coat three-dimensional plastic objects. 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. Extensive test experience has been gained with different types of accelerated tests and cycling conditions.coatings. With appropriate filters. The visual appearance of the first crack formation is also indicated for each product. Results at a glance • With UV-technology. Egbert Boerrigter. this makes the Xenon test the most widely accepted standard. the UV-PUD's morphology could be adjusted depending on the degree of cross linking needed and the desired stiffness. hexafunctional urethane acrylates are indispensable in providing superior scratch resistance. it was decided to test the UV clearcoats on weather stable white thermoset polymer coated panels at 20 µm coating thickness. b values increase only very slightly. according to the ASTM G26 method.) ➤ Ir. shrinkage and surface tension of diluting acrylates have to be considered when preparing UV coatings for plastics. 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. on the other hand. except "Ebecryl 1290" and "Ebecryl 5129". less sensitive to crack formation than higher functional products which result in more densely cross linked systems. were tested in a mixture with "Ebecryl 284" (20% addition of "Ebecryl 1290" and "Ebecryl 5129". the Xenon arc spectral light distribution corresponds well to sunlight in both the UV and the visible range. in general. THE AUTHORS ➤ Stefan Smeets. is Manager Technical Service & Development Industrial Coatings Europe at Surface Specialties UCB. Pictorial standards are used to note degradation with cracking (ASTM D660). "Ebecryl 1290" and "Ebecryl 5129". the Persoz hardness (50 µm dry film on glass). are inherently not stable to light and tend to yellow and degrade rapidly. "Ebecryl 284". "1290" and "8402". HDDA is one of the best performing diluting acrylates for exterior use. In addition to adhesion (12 µm dry coating). A visual evaluation was carried out along with colour and gloss monitoring during the tests. • Several aliphatic urethane acrylates are suitable to coat exterior plastics. The adhesion of different radiation curable PUDs on different substrates has been tested.Radiation curing adhesion to many substrates. 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. allophanates and soft segments such as polyester. Upon prolonged exposure the gloss decreases. solubility. Because of the huge variety of plastics. were diluted with 30% HDDA. responsible for Plastics Coatings. polyether. ➤ Stephan Peeters.
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