Subject Index

3D-UV curing pilot unit, 245 -cleavage-type photoinitiators, 24, 115 Abrasion resistance, 224 of ORMOCER coatings, 225 of parquet ooring coatings, 198 Absorbance, 42 Absorption spectra of different photoinitiators, 118 Accelerated weathering tests on UV resins, 134 Acid number, 127 Acrylate reactive diluents, 113 Acrylate resin type: effect on photoyellowing, 192 Acrylate terminated oligomers, 95 Acrylated polyacrylates, 101 Acrylates, 28 Adhesion, 211 Adhesion primer, 142 Adhesives, 281 Advantages and drawbacks of UV coatings, 11 of water-based UV coatings, 213 Advantages of UV coatings, 11 ecological, 11 economical, 11 performance, 11 Advantages of UV coatings for automotive clear coats, 256 Advantages of UV-curable powders, 215 Advantages of water-based coatings, 209211 Aluminum can, 57 Amine modication, 118 of acrylate resins, 101 synergist action, 118 Amine synergist action, 118 Amine synergists, 183 AmtecKistler test, 83, 271 Application determines substrate and properties, 20 Application elds of UV-curable formulations, 140 Application spectrum of UV-curable coatings, 253 Application viscosity, 66 303

Automotive applications, 252 Automotive clear coats, 159 Best available technique (BAT), 301 Blue ray disk with UV protective coating, 285 Brittleductile transition temperature, 79 C-radical scavengers, 111 Calculation of crosslink density, 73 Cantilever-beam method, 87 Car wash eld test, 269 Carbamato acrylates, 221 Cationic curing of epoxies, 121 Cationic metal coatings, 149 Cationic photoinitiators, 119, 121 avoiding the release of benzene, 121 Cationically curable systems, 120 Ceramiclear, 224 Chain type radical polymerization, 67 Challenges for exterior durable UV coatings, 229 Characterization of coatings, 74 Characterization of raw materials, 126 Chemical characterization, 90 Chemical methods to reduce oxygen inhibition, 183 Chemical resistance for automotive applications, 91 for wood applications, 91 Chemistry being determined by required properties, 21 Chemistry of typical automotive top coats, 255 Chromatographic characterization, 130 Classication of polymers duromers, 62 elastomers, 62 thermoplastics, 62 Classical UV applications, 195 in graphic arts, 199 on wooden surfaces, 195 Classication of the results of nanoscratch experiments, 274 Coating additives, 125

304

UV COATINGS BASICS, RECENT DEVELOPMENTS AND NEW APPLICATIONS Dissociation quantum yields of photoinitiators, 117 Donoracceptor mechanism, 31 Donoracceptor systems, 104, 105 Dosimeters, 55 Double bond conversion, 34 Drawbacks of UV coatings, 11, 179 Driving forces of UV technology, 14 Dual cure coatings, 218 adhesion improvement, 221 Dual cure dispersions, 108, 222 Dual cure powder coating hybrids, 221 Dual cure resins, 106 Dual cure systems, 186 Dual cure water-based coatings, 221 Durability tests, 253 Duromers, 62 DVD bonding, 283 Dynamic mechanical analysis, 77 Dynamic viscosity, 126 e-beam technology, 7, 8 E -modulus, 78 Easy matting, 210 Eco-efciency, 13 analysis, 258 of automotive primer/scaler, 258 of wooden door fronts, 13 portfolio, 263 Economic factors of UV curing, 19 Effect of crosslinking on coating properties, 172 Effect of crosslinking on mechanical properties, 162 Effective energy, 40, 43 Efciency of photoinitiation, 24 Elastic response, 268, 271274 Elastic response pattern, 273 Elasticity modulus, 75 Elasticity modulus as function of crosslink density, 78 Elastomers, 62 Electrical input power, 39 Electromagnetic spectrum, 7 Elongation at break, 76 Elongation at yield, 76 Energies as a function of wavelenght, 8 Energy density, 39, 41 Energy of a photon, 42 Energy output of a mercury bulb, 40 ENEs: structures and reactivities, 124 Environmental benet of UV-cured coatings, 260 Environmental impact assessment matrix, 296 Enzymatic esterication, 99

Coating application processes equipment advances, 37 roll and curtain coating, 37 spray coating, 37 UV robots, 37 Coating line examples aluminum cans, 57 hardwood panels, 57 plastic components, 57 printing press, 58 Coating markets, 2 Coil coating process, 279 Coil coatings, 278 Combinatorial application testing, 155 Comparison of UV coatings to standard 1K and 2K clears, 268 Components of UV formulations, 22 Composition of a water-based adhesion primer, 142 Composition of wood coatings, 141 Compositions of UV curable coatings, 9 Confocal Raman Microscopy, 34 Considerations for selection of starting formulations, 151 Conversion limitation by Tg , 165 Conversion limitation due to vitrication, 80 Copolymerization, 28 Correlation of coating performance with crosslink density, 174 E -modulus with crosslink density, 175 scratch resistance with crosslink density, 175 Crockmeter, 83 Crosslink density: correlation with modulus, 73 Crosslink density, 68, 71, 72, 78, 81, 173 Crosslinking reaction of AcResin adhesives, 282 CSM-Nanoscratch, 83 Cure conversion in the presence of HALS radical scavenger, 230 of UV absorber, 230 Cure extent, 33, 36 Curing and hardness gradient, 90 Curing under inert conditions, 185 Curing under nitrogen and carbon dioxide, 238 Current R&D topics, 15 E value, 134 Deep UV photoresists, 202 Degree of crosslinking, 71 Dendritic acrylate oligomers, 104 Dendritic resins, 103 Depth prole of acrylate conversion, 36 Differential scanning calorimetry (DSC), 130 Differential thermal analysis (DTA), 130 Discolouration, 110

SUBJECT INDEX Epoxy acrylates, 9597 synthesis, 97 Equipment, 37 Equipment suppliers, 58 Evaluation of scratch resistance, 158 Excimer lamps, 47 Explanation of initial photoyellowness, 193 Exposure parameter measurement, 48 Exposure process, 38 Exposure prole, 52 Exterior applications, 135 Exterior durable UV coatings: challenges, 229 Falling sand test, 83 Fe-added mercury lamp spectrum, 47 Fe-additive, 47 Field test car wash, 273 Field test scratch performance, 270, 273, 274 Film coating instead of painting, 286 Film coating technology, 286 Film formation, 65 Fischerscope , 83 Fischerscope measurements, 154 Flash light curing, vi Flexibility, 81 Flexibility as a function of Tg , 167 Flexographic printing plate, 200 Foil coating process, 288 Foil coating technology, 287 Food contact, 300 Formulation robot, 155 Formulation screening for new applications, 149 Formulations, 140 Formulations for graphic inks, 144, 145 overprint varnish, 147 pigmented UV ink, 145 UV exo ink, 146 UV offset ink, 145 UV screen ink, 148 Formulations for wood coatings, 141 Fracture response, 268, 271, 272, 274 Frontal polymerization, 32 Function of UV absorbers, 227 Functions of a coating, 1 Furniture foil coatings, 286 Furniture wood coatings, 197 Future coating technologies, 3 advantages, 3 drawbacks, 3 Ga-added mercury lamp spectrum, 47 Ga-additive, 47 Gelpoint, 71 Glass region, 63

305

Glass transition region, 63 Glass transition temperature (Tg ), 64, 160, 162 determines mechanical properties, 171 inuence of crosslink density, 164 inuence of cure conversion, 164 inuence on exibility, 167 inuence on hardness, 167 structural inuencing factors, 163 Gloss and haze measurement, 84 Graphic application requirements, 132 Graphic arts industry, 199 Gravure printing plates, 200 Guidelines for classication and labelling of UV acrylates eurymeric acrylates, 292 stenomeric acrylates, 292 Guides for the safe use of UV technologies, 291 H-abstraction type photoinitiators, 24, 115 HALS radical scavengers, 227, 230, 231 Hardness, 80 Hardness and exibility as a function of Tg , 166 Hardness as a function of Tg , 167 Hardness at the surface as a function of UV exposure atmosphere, 176 Hardness-exibility balance, 177 Hardwood panels, 57 Hazard classes, 292 Health, safety and environmental (HSE) aspects, 291 Heat of polymerization, 32 High performance liquid chromatography (HPLC), 130 High-throughput screening (HTS), 153, 154 Homogeneity of polymer networks, 79 Hybrid-Cure systems, 218 Hydrogen abstraction type photoinitiators type II, 115 Hydroperoxide decomposers, 109, 111 Hyperbranched resins, 103 Illumination, 41 Imaging applications, 199, 202 Indentation hardness, 81 Industrial parquet coating, 142 Inert atmosphere, 182 Inuence of curing conditions, 240 Inuence of Mc (molecular weight between crosslinks) on exibility, 169 Inuence of resin/diluent functionality on polymerization process and properties, 161 Inuence of the oxygen content on curing reaction, 240

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UV COATINGS BASICS, RECENT DEVELOPMENTS AND NEW APPLICATIONS Matching the spectral output of the lamp with the absorption characteristics of the photoinitiators, 52 Matt formulations, 143 Matting process, 198 Measurement of exposure parameters, 52 Measures to decrease detrimental oxygen effect, 181 Mechanical properties of coatings, 162 Mechanical properties of materials, 63 Mechanical properties of UV cured coatings brittleductile transition (Tb ), 170 effect of crosslinking on Tb , 170 effect of Tg (hard or soft), 171 measures to obtain hard and exible coatings, 172 Mechanical response, 271 Mechanism of monomer inhibition and stabilization possibilities, 109 Mercury based lamps, 45 Metal containing monomers, 105 Methacrylates, 28 Microgel formation, 68 Microwave powered mercury lamps, 45 Modulus as a function of temperature, 64 Modulus of elasticity, 63 Molecular weight between crosslinks, 71 Molecular weight build-up during curing, 66 Monitoring lm formation and curing, 73 Monitoring of optimized UV process, 50 Monomers, 111 Multifunctional monomers, 113 Nano-indentation, 176 Nano-Scratch Tester, 84 Nano-scratching, 176 Nanocoatings, 223 Nanocomposites, 223 Nanoindentation measurements correlation to laboratory tests, 272 correlation with eld tests, 274 principle, 85 Nanoparticles, 226 Near-infrared (NIR) spectroscopy, 35 Network characterization, 74 Network formation, 62, 66, 68 Network formation by chain connections, 70 Network structures, 65, 71 Network types, 69 New applications for radiation curable coatings, 252 Norrish type I photoinitiators, 115 Novel routes to urethane acrylates, 99 Nuclear magnetic resonance (NMR), 129

Infrared spectroscopy, 128 Inhibition under aerobic conditions, 109 Inhibition under anaerobic (inert) conditions, 111 Initial photoyellowing, 186 decay of yellowing, 187, 188 effect of photoinitiator content, 191 effect of photoinitiator type, 189 effect of resin type, 192 Initial yellowing, 179 Inks, 202 Interaction of UV process parameters, 20, 21 Internal stress, 84, 87 as a function of shrinkage, 89 as a function of Tg , 88 as a function of temperature, 88 Interpenetrating networks, 68 Iodine value, 127 Irradiance, 39, 40 Isocyanato acrylates, 106, 219 Jablonsky-type diagram, 23 Key exposure parameters, 49 Kinematic viscosity, 126 Kinetic chain length, 27 Kinetics of the photopolymerization, 26 Labelling guide, 291 Labelling recommendations in case of incomplete data, 294 Laboratory scratch tests, 271 LambertBeer law, 42 Larolux , 239 process, 185 UV inert curing, 244 Layer composition of parquet ooring coating, 142 LED based light sources, 47 Letterpress printing plates, 200 Light stabilizers, 227 Lithographic printing plates, 201 Low emission photoinitiators, 119 Low yellowing photoinitiators, 118 Lower extractables, 209 MacoskoMiller theory, 69, 72 Maleimides, 31 Mar resistance, 267 Market development of industrial coatings, 2 Market UV acrylate resins, 196 Market of UV coatings, 4, 5 Mass spectrometry, 129

SUBJECT INDEX OH number, 128 One-component dual cure coatings, 221, 222 Onium salts, 121 Optical density, 43 ORMOCER coatings, 223 ORMOCER systems, 105 Overcoming the detrimental effects of oxygen inhibition, 184 Overprint varnishes (OPV), 146 application, 204 for inert exposure, 148 formulations, 148, 204 performance requirements, 204 Oxetane groups, 121 Oxygen diffusion, 184 Oxygen diffusion scheme, 179 Oxygen inhibition, 179 inuence of viscosity on polymerization rate, 184, 243 Oxygen inhibition as function of layer depth, 180 Oxygen inhibition reaction, 30 Oxygen penetration, 180 Oxygen scavenging by a dye, 184 Painted lm, 287 Parquet coatings, 197 Parquet ooring UV coatings: scratch resistance, 225 Particle size measurement, 131 Peak irradiance, 43, 44 Pendulum hardness, 81 Perception of scratches, 268 Performance requirements for automotive coatings, 252 Perspectives of UV curing technology, 17 Phases of process design, 50 Phenolic antioxidants, 109 Photo DSC, 36 Photo latent base, 265 Photochemical yellowing, 133 Photoinduced curing chemistry, 22 Photoinitiation, 23 Photoinitiator classes, 116 Photoinitiator content: effect on photoyellowing, 191 Photoinitiator-free polymerization, 104 Photoinitiators, 115 hydrogen abstraction type II, 115 Norrish type I, 115 Photoinitiators for, 119 cationic curing, 119, 121 pigmented coatings, 119

307

radical curing, 114 through cure, 119 UV-stabilized coating, 119 Photoinitiators used in combination with light stabilizer package (UV absorber/HALS), 232 Photopolymer printing plates, 199 Photopolymerization kinetic chain length, 27 propagation, 25 rate of initiation, 27 termination, 25 Photoresists, 200, 202 Photosensitization of cationic photopolymerisation, 122 Photoyellowing, 186 Physical methods to reduce oxygen inhibition, 181 Pigmented UV coating formulation absorption spectra, 51 Pigmented UV coatings, 246 Pigmented UV ink, 145 Pigmented UV-curable coatings, 280 Plastic applications in automotive, 276 Plastic components, 57 Plastic response, 268, 271, 272, 274 Polycarbonate headlamp lenses, 258 Polyenes, 106 Polyester acrylates, 100 property spectrum, 161 synthesis, 100 Polyester and polyether acrylates, 100 Polyether acrylates, 101 Polymer bound photoinitiators, 119 Polymer denition, 108 Polymerization behaviour of acrylates and methacrylates, 30 Polymerization rates, 28 acrylates, 28 methacrylates, 28 Polymerization shrinkage, 84 Polyurethane acrylate dispersions, 108 Printed circuit boards (PCB), 202 Printing ink formulation, 144 Printing inks, 145 Printing plates, 200 Printing press, 58 Printing techniques, 201 Process control, 49 Process design, 53 Process window, 49, 50 Processing of UV powders, 215 Propagation, 25 Properties of UV curable acrylate resins fundamental inuencing factors, 161

308

UV COATINGS BASICS, RECENT DEVELOPMENTS AND NEW APPLICATIONS Safe application of inks, 291 Safe application of UV-curable systems, 295 Safe handling of acrylates, 292 Scratch laboratory test methods, 267 Scratch resistance, 175, 224, 271, 275 coating response to impacts, 77 correlation of eld tests with nanoindentation measurements, 274 requirements coatings have to fulll, 274 Scratch resistance after Jacksonville testing, 275 Scratch resistance of automotive coatings correlation with mechanical response, 271 Scratch resistance of different clear coats, 275 Scratch resistance of weather-resistant UV coatings, 244 eld tests, 270 Scratch resistant coatings for automotive applications, 266 Scratch resistant top coat formulations, 144 Scratch resistant UV coatings, 258 Scratch resistant UV coatings for DVD/Blue ray, 284 Scratch tests, 267 Selection criteria for raw materials for exterior applications, 135 Selection of raw materials, 131 exterior applications, 131, 135 graphic applications, 132 wood applications, 131 Selection of resin types for outdoor use, 132 Self-initiating UV-curable resins, 104 Shadow areas, 179, 185, 249 Shrinkage, 84, 86 Shrinkage as a function of functionality, 86 Side reactions contributing to discolouration, 110 Side reactions during esterication, 113 Silicon based oligomers, 105 Single scratch tests, 83 Solgel technology, 223 Solvent-borne UV coatings, 206 Spectroradiometers, 55 Spray application, 206 Spray coating, 37 Stabilizer/inhibitors, 108 Standard mercury lamp, 46 spectrum, 47 Stenomeric acrylates, 293 Step type polyaddition/condensation, 67 Stress-strain analysis, 77, 162 Stress-strain curves, 76 Stress-strain experiments, 63 Structural adhesives, 283

generalized property spectrum, 161 Property spectrum of standard acrylate resins, 102, 161 Propertyproperty relationships, 172 Radiachromic dosimeters, 55 Radiant ux, 42 Radiant power, 39, 40 Radiation attenuation throughout coating thickness, 43 Radiation cured coil coatings, 279 Radical initiated UV induced crosslinking, 23 photoinitiation, 23 propagation, 24 termination, 24 Radical photoinitiators, 114 Radical polymerization systems, 95 Radical scavengers, 227, 228 Radical types occurring during processing/storage, 109 Radiometers, 52, 54 Radiometric devices, 54 Radiometric methods, 52 Rate of initiation, 27 Rate of polymerization, 33 Raw material suppliers, 135 Raw materials for exterior applications, 131 Raw materials for UV coatings, 94 REACH (Registration, Evaluation and Authorisation of Chemicals), 297, 298 impact on production chain, 298 motivation, 298 registration obligation and timeline, 298 Reactive diluent types, 112 Reactive diluents, 111 Reactivity ratios of comonomers, 29 Real-time infrared (RT-IR) spectroscopy, 26, 33 Recovery, 271, 272 Recovery behaviour, 274 Reduction of oxygen inhibition, 243 by chemical methods, 183 by physical methods, 181 Reectors, 48 Registration, evaluation and authorization of chemicals (REACH), 297, 298 Relationship of scratch and acid etch resistance, 275 Resin types for UV curing systems, 94 Responsivity, 54 Risk assessment matrix, 296 Risk assessment of UV curing, 295 RotaHub, 83 Rubber-elastic plateau, 64

SUBJECT INDEX Structureproperty relationships, 160, 172 Structures of typical thiols, 125 Suitability of UV coatings for automotive applications, 254 Superuid chromatography (SFC), 130 Surface tension, 65, 66 Taber Abraser method, 82 Tangent , 78 Temperature dependence of mechanical properties, 79 Termination in radical polymerization reactions, 25, 26 Terminology, 39 Terminology related to emission of light, 38, 39 electrical input power, 38 energy density, 39, 41 irradiance, 39, 40 radiant power, 39, 40 Terms and SI units of light emission, 41 Test methods for abrasion resistance, 82 coatings, 75 scratch resistance, 83 AMTEC-Kistler, 83 Crockmeter, 83 Indentation, 83 RotaHub, 83 Thermal analysis, 130 Thermal stress, 86 Thermal yellowing, 133 Thermogravimetric analysis (TGA), 131 Thermoplastics, 62 Thiol-ENE systems, 123 general mechanism, 123 insensitivity to oxygen inhibition, 123 Thiols structures, 125 Time-temperature superpositioning, 76 Topcoat for glass, 149 Topcoat formulations, 143 Torsion modulus, 75 Traditional applications of UV-curable systems, 195 Transesterication, 99 Transmittance, 42 Trends in UV technology, 15 at coatings manufacturers, 16 at end-users, 16 at raw material suppliers, 16 TTT (time, temperature, transition)-diagram, 79 Two component dual cure coatings, 219 Unsaturated esters, 31

309

Unsaturated polyesters, 95 Urethane acrylates, 96100, 135, 173, 256, 277 enzymatic esterication, 99 exterior applications, 98, 132135 exible, 99 hard, 99 novel routes to, 99 property spectrum, 161 property tuning, 98 synthesis, 98 transesterication, 99 UV absorbers, 227, 228 UV spectra, 229 UV clear coat, 287 UV clearcoat developments for automotive OEM coatings, 220 UV coated materials for food contact, 300 UV coating line examples, 56 UV coating markets, 4, 5 regional split, 4 sectorial split, 4 trends across the regions, 5, 6 UV coating of polycarbonate, 149 UV coatings application examples, 8 from traditional to new applications, 9 UV equipment setup, 54 UV exo ink, 146 UV inkjet, 284 UV inks for exographic printing, 203 for lithographic printing, 203 for screen-printing, 203 UV lamps, 45 UV line equipment, 44 UV offset ink, 145 UV plasma cure , 248, 249 UV plasma curing, 186, 246, 247 UV powder coating formulations, 216 UV powder coating process, 216 UV powder coatings, 213, 258 advantages, 215 applications, 214 chemistry, 216 processing, 215 why UV powder?, 214 UV powder coatings on MDF, 198 UV protocol, 294 UV Protocol of safe handling of coatings, 291 UV renish primer, 258, 265 UV robot, 37 UV screen ink, 147 UV spectra of photoinitiators, 128

310

UV COATINGS BASICS, RECENT DEVELOPMENTS AND NEW APPLICATIONS inuence of curing conditions, 240243 inuence of oxygen content, 240 inuence of viscosity, 243 UV-dual cure processing for automotive top coat application, 276 UVITECH Project, 291, 295 Vinyl ether reactive diluents, 114 Vinyl ether (VE) monomers, 31 Vinyl ether/maleimide systems, 104 Viscoelastic materials, 162 Viscoelastic properties, 75 Viscosity, 66, 126, 243 Viscosity changes, 67 Vitrication, 165 VOC regulation, 296 Water-based systems, 107 Water-based UV coating, 206 types of (soluble, emulsion, dispersion), 208, 209 why water-based UV?, 206 Water-soluble UV-curable resins, 208 Weathering performance of UV coatings, 234 aging followed with IR spectroscopy, 234 Florida tests of UV clear coats, 238 of water-based UV coatings, 234237 Weathering resistance of UV-cured acrylics, 227 Weathering resistance of water-based coatings, 234 Weathering stability of coatings, 232 Weathering stability of polyurethane dispersion, 236 Weathering stability of UV-cured clear coats, 238 Wood application requirements, 131 Wood coatings market in Europe, 196 Wooden door fronts: eco-efciency, 13 Years in Florida, 238 Yellowing, 186 Yellowness decay, 188

UV systems for dental applications, 285 UV technology, 7 UV wood coatings 100% liquid coatings, 197 UV powder coatings, 197 water-based UV coatings, 197 UV-A clearcoats, 265 UV-A curable coating, 266 UV-curable adhesives for optical disks and displays, 283 UV-curable clear coats, 256 UV-curable coatings, 275 for car renish, 264 for hard top coats on plastic, 277 key for lm technology, 286289 on automotive plastics, 254 UV-curable dispersions, 208 UV-curable emulsions, 208 UV-curable functional groups, 31 UV-curable inks, 202, 203 UV-curable ink-jet inks, 284 UV-curable nanocoatings, 223 UV-curable nanocomposites, 226 UV-curable ORMOCER coatings, 224 UV-curable polyurethane dispersions (PUD), 222 UV-curable primer/sealer, 254, 258 UV-curable renish primers, 258 UV-curable water-based systems, 207 UV-cured parts in automotive applications, 257 UV-curing adhesives, 281 UV-curing in the presence of UV absorbers and radical scavengers, 227, 230 UV-curing of highly exible coatings, 277 UV-curing of pigmented systems, 246 UV-curing pilot line for automotive bodies, 257 UV-curing process, 10, 19 application, 20 chemistry, 21 equipment, 37 UV-curing under inert atmosphere, 238 advantages of carbon dioxide, 239 comparison nitrogen versus carbon dioxide, 238