JP6281188B2 - Urethane (meth) acrylate and photocurable resin composition containing the same - Google Patents
Urethane (meth) acrylate and photocurable resin composition containing the same Download PDFInfo
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- JP6281188B2 JP6281188B2 JP2013069011A JP2013069011A JP6281188B2 JP 6281188 B2 JP6281188 B2 JP 6281188B2 JP 2013069011 A JP2013069011 A JP 2013069011A JP 2013069011 A JP2013069011 A JP 2013069011A JP 6281188 B2 JP6281188 B2 JP 6281188B2
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- Prior art keywords
- group
- acrylate
- meth
- urethane
- general formula
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- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 title claims description 43
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 title claims description 24
- 239000011342 resin composition Substances 0.000 title claims description 21
- AVWRKZWQTYIKIY-UHFFFAOYSA-N urea-1-carboxylic acid Chemical group NC(=O)NC(O)=O AVWRKZWQTYIKIY-UHFFFAOYSA-N 0.000 claims description 41
- 125000002723 alicyclic group Chemical group 0.000 claims description 24
- 125000001931 aliphatic group Chemical group 0.000 claims description 16
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 14
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 claims description 11
- 125000004432 carbon atom Chemical group C* 0.000 claims description 10
- 125000005702 oxyalkylene group Chemical group 0.000 claims description 9
- 239000003999 initiator Substances 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 51
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 44
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 39
- -1 carboxymethylpentamethylene group Chemical group 0.000 description 37
- 238000000034 method Methods 0.000 description 20
- 125000006353 oxyethylene group Chemical group 0.000 description 19
- 150000001875 compounds Chemical class 0.000 description 18
- 229920005989 resin Polymers 0.000 description 15
- 239000011347 resin Substances 0.000 description 15
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 14
- 230000015572 biosynthetic process Effects 0.000 description 13
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 13
- 238000007664 blowing Methods 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 12
- 238000003786 synthesis reaction Methods 0.000 description 12
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 10
- 239000005056 polyisocyanate Substances 0.000 description 10
- 229920001228 polyisocyanate Polymers 0.000 description 10
- 238000000576 coating method Methods 0.000 description 9
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 238000000465 moulding Methods 0.000 description 6
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 5
- 229920003023 plastic Polymers 0.000 description 5
- 239000004033 plastic Substances 0.000 description 5
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 4
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 238000005452 bending Methods 0.000 description 4
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 description 4
- 238000001723 curing Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 231100000241 scar Toxicity 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 208000032544 Cicatrix Diseases 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 3
- 235000000126 Styrax benzoin Nutrition 0.000 description 3
- 244000028419 Styrax benzoin Species 0.000 description 3
- 235000008411 Sumatra benzointree Nutrition 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 229960002130 benzoin Drugs 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 235000019382 gum benzoic Nutrition 0.000 description 3
- 230000001678 irradiating effect Effects 0.000 description 3
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical group OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 3
- 229910052753 mercury Inorganic materials 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- 229920001451 polypropylene glycol Polymers 0.000 description 3
- 230000037387 scars Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- QNODIIQQMGDSEF-UHFFFAOYSA-N (1-hydroxycyclohexyl)-phenylmethanone Chemical compound C=1C=CC=CC=1C(=O)C1(O)CCCCC1 QNODIIQQMGDSEF-UHFFFAOYSA-N 0.000 description 2
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229920002284 Cellulose triacetate Polymers 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- 239000012975 dibutyltin dilaurate Substances 0.000 description 2
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 description 2
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 230000004927 fusion Effects 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 2
- MSAHTMIQULFMRG-UHFFFAOYSA-N 1,2-diphenyl-2-propan-2-yloxyethanone Chemical compound C=1C=CC=CC=1C(OC(C)C)C(=O)C1=CC=CC=C1 MSAHTMIQULFMRG-UHFFFAOYSA-N 0.000 description 1
- LCHAFMWSFCONOO-UHFFFAOYSA-N 2,4-dimethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(C)=CC(C)=C3SC2=C1 LCHAFMWSFCONOO-UHFFFAOYSA-N 0.000 description 1
- FGTYTUFKXYPTML-UHFFFAOYSA-N 2-benzoylbenzoic acid Chemical compound OC(=O)C1=CC=CC=C1C(=O)C1=CC=CC=C1 FGTYTUFKXYPTML-UHFFFAOYSA-N 0.000 description 1
- OFYFURKXMHQOGG-UHFFFAOYSA-J 2-ethylhexanoate;zirconium(4+) Chemical compound [Zr+4].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O OFYFURKXMHQOGG-UHFFFAOYSA-J 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- BQZJOQXSCSZQPS-UHFFFAOYSA-N 2-methoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OC)C(=O)C1=CC=CC=C1 BQZJOQXSCSZQPS-UHFFFAOYSA-N 0.000 description 1
- KTALPKYXQZGAEG-UHFFFAOYSA-N 2-propan-2-ylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(C(C)C)=CC=C3SC2=C1 KTALPKYXQZGAEG-UHFFFAOYSA-N 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- 229920002799 BoPET Polymers 0.000 description 1
- 229910001369 Brass Inorganic materials 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920000298 Cellophane Polymers 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 description 1
- GUCYFKSBFREPBC-UHFFFAOYSA-N [phenyl-(2,4,6-trimethylbenzoyl)phosphoryl]-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C(=O)C1=C(C)C=C(C)C=C1C GUCYFKSBFREPBC-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 150000008365 aromatic ketones Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 238000007611 bar coating method Methods 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 238000007756 gravure coating Methods 0.000 description 1
- 238000007646 gravure printing Methods 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- WKGDNXBDNLZSKC-UHFFFAOYSA-N oxido(phenyl)phosphanium Chemical compound O=[PH2]c1ccccc1 WKGDNXBDNLZSKC-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 229920013716 polyethylene resin Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 238000006748 scratching Methods 0.000 description 1
- 230000002393 scratching effect Effects 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 239000013008 thixotropic agent Substances 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- 125000005628 tolylene group Chemical group 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 125000006839 xylylene group Chemical group 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Landscapes
- Polyurethanes Or Polyureas (AREA)
- Paints Or Removers (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Description
本発明は、ウレタン（メタ）アクリレート及びこれを含有する光硬化型樹脂組成物に関する。 The present invention relates to urethane (meth) acrylate and a photocurable resin composition containing the same.
現在、種々のプラスチック成形品は、その透明性や加工性に加え、軽量かつ安価といった利点から、自動車関連部品や電子・電気製品をはじめとする様々な分野で利用されている。しかし、これらプラスチック成形品は、一般的に硬度が低く柔軟であるため、その表面に傷が付き易い欠点がある。そのため、表面に耐擦傷性に優れる塗料・コーティング剤を塗工して、被膜を形成する手法がなされている。 At present, various plastic molded products are used in various fields including automobile-related parts and electronic / electrical products because of their advantages of light weight and low cost in addition to their transparency and workability. However, since these plastic molded products are generally low in hardness and flexible, there is a drawback that the surface is easily scratched. Therefore, a technique for forming a film by applying a paint / coating agent having excellent scratch resistance to the surface has been used.
近年、被膜を形成する材料としては、活性エネルギー線硬化型樹脂組成物が主流となっている。これは、紫外線等の活性エネルギー線を照射することによって直ちに硬化するため、従来の熱硬化型樹脂と比較して熱などのエネルギーを必要とせず、加工速度が速いため生産性が非常に高いことに加え、その被膜は表面硬度、耐擦傷性、耐薬品性等に優れるためである。 In recent years, an active energy ray-curable resin composition has become mainstream as a material for forming a film. Because it cures immediately by irradiating active energy rays such as ultraviolet rays, it does not require heat and other energy compared to conventional thermosetting resins, and the processing speed is fast, so the productivity is very high. In addition, the film is excellent in surface hardness, scratch resistance, chemical resistance, and the like.
前記の活性エネルギー線硬化型樹脂組成物としては、架橋密度を高くすることによって表面硬度を高めたハードコート層を形成する手法が、一般的に普及している。例えば、ペンタエリスリトールトリアクリレート等の分子内に少なくとも２個以上の（メタ）アクリロイル基と水酸基を有する多官能（メタ）アクリレートと、イソホロンジイソシアネート等のポリイソシアネートを反応させた多官能ウレタン（メタ）アクリレートを含有する硬化皮膜が報告されている（特許文献１参照）。特許文献１の硬化皮膜は表面硬度が高く耐擦傷性が良好であり、ハードコートの課題であった硬化収縮に起因するカールは改善されたものの、塗工後のカールが未だに大きく実用上十分ではなかった。また、破断伸度や耐屈曲性の面でも満足のいくものではなく、三次元曲面への成形加工時における追随性（加工性）が求められる用途への適用は困難であった。 As said active energy ray hardening-type resin composition, the method of forming the hard-coat layer which raised surface hardness by making a crosslinking density high generally has prevailed. For example, a polyfunctional urethane (meth) acrylate obtained by reacting a polyfunctional (meth) acrylate having at least two (meth) acryloyl groups and a hydroxyl group in a molecule such as pentaerythritol triacrylate and a polyisocyanate such as isophorone diisocyanate. Has been reported (see Patent Document 1). The cured film of Patent Document 1 has high surface hardness and good scratch resistance, and curl due to curing shrinkage, which was a problem of hard coating, has been improved, but the curl after coating is still large and practically sufficient. There wasn't. In addition, it is not satisfactory in terms of breaking elongation and bending resistance, and it has been difficult to apply to applications that require followability (workability) during molding into a three-dimensional curved surface.
表面硬度が高く、成形加工時おける追随性（加工性）に優れる皮膜を形成することを目的として、イソシアヌレート環を有するポリイソシアネートと、２−ヒドロキシエチル（メタ）アクリレート等の水酸基含有（メタ）アクリレートを反応させたウレタン（メタ）アクリレートを含有する活性エネルギー線硬化型加飾積層フィルム用組成物が報告されている（特許文献２参照）。しかしながら、特許文献２の組成物は、金属ブラシ等の引掻きによる細かい擦り傷に対しては傷付きやすく、かつ、一旦付いた傷は、経時的に復元して消失することがないため、長期的に美観を保持することができないという課題があった。 Polyisocyanate having an isocyanurate ring and hydroxyl group-containing (meth) such as 2-hydroxyethyl (meth) acrylate for the purpose of forming a film having high surface hardness and excellent followability (workability) during molding. An active energy ray-curable decorative laminated film composition containing urethane (meth) acrylate reacted with acrylate has been reported (see Patent Document 2). However, the composition of Patent Document 2 is easily scratched by fine scratches caused by scratching a metal brush and the like, and scratches once attached are not restored and lost over time. There was a problem that aesthetics could not be maintained.
他方、最近では、特許文献１のように表面硬度を高めて耐擦傷性を改善する発想とは反対に、弾性を高くすることによって外力を吸収し、傷を経時的に復元して消失させる機能を持つ被膜を形成する手法が要望されており、１分子中に３個以上のイソシアネート基を有する有機イソシアネートと、ポリアルキレングリコールモノ（メタ）アクリレートを反応させたウレタン（メタ）アクリレートが報告されている（特許文献３参照）。しかしながら、特許文献３に記載のイソシアヌレート変性体を原料として用いたウレタン（メタ）アクリレートは、傷が経時的に復元して消失するものの、硬化収縮に起因するカールが僅かながら生じ、かつ、イソシアヌレート骨格が剛直であるため、破断伸度がいまだ十分ではなく改良の余地があった。また、トリメチロールプロパンのアダクト変性体を原料として用いたウレタン（メタ）アクリレートは、傷が経時的に復元して消失するものの、復元力が低いため、傷の付き方や荷重によっては傷が残ってしまうという課題があった。 On the other hand, recently, as opposed to the idea of increasing surface hardness and improving scratch resistance as in Patent Document 1, a function of absorbing external force by increasing elasticity and restoring and erasing the scratch over time There is a demand for a method for forming a coating film having a urethane (meth) acrylate obtained by reacting an organic isocyanate having three or more isocyanate groups in one molecule with a polyalkylene glycol mono (meth) acrylate. (See Patent Document 3). However, the urethane (meth) acrylate using the isocyanurate-modified product described in Patent Document 3 as a raw material recovers with time and disappears, but slightly curls due to cure shrinkage occur, and isocyania Since the nurate skeleton is rigid, the elongation at break is still insufficient and there is room for improvement. In addition, the urethane (meth) acrylate using a trimethylolpropane adduct modified as a raw material disappears as the scratches are restored over time, but the resilience is low, so the scratches may remain depending on how the scratches are applied and the load. There was a problem that it would end up.
さらに、ウレタン（メタ）アクリレートを含有する活性エネルギー線硬化型樹脂組成物としては、２−ヒドロキシエチル（メタ）アクリレート等の水酸基含有（メタ）アクリレートと、アロファネート基含有ポリイソシアネートを反応させたウレタン（メタ）アクリレートが報告されている（特許文献４参照）。特許文献４では、表面硬度については良く検討されているものの、傷復元性に関しては検討されていなかった。 Furthermore, as the active energy ray-curable resin composition containing urethane (meth) acrylate, a hydroxyl group-containing (meth) acrylate such as 2-hydroxyethyl (meth) acrylate and an allophanate group-containing polyisocyanate are reacted ( (Meth) acrylate has been reported (see Patent Document 4). In Patent Document 4, although the surface hardness is well studied, the flaw resilience has not been studied.
本発明が解決しようとする課題は、一旦付いた傷が経時的に復元して消失する特性を有し、成形加工時における追随性や密着性に優れ、かつ、寸法安定性や耐屈曲性にも優れるウレタン（メタ）アクリレート、及びそれを含有する光硬化型樹脂組成物を提供することである。 The problem to be solved by the present invention is that scratches once attached are restored over time and disappear, excellent followability and adhesion during molding, and dimensional stability and flex resistance. It is providing the urethane (meth) acrylate which is excellent also, and the photocurable resin composition containing it.
本発明者は、上記課題を解決するために鋭意検討した結果、特定構造のウレタン（メタ）アクリレートが、上記課題解決に適した化合物であることを見出した。
すなわち、本発明は以下のとおりである。
［１］ 下記一般式（１）で表される、アロファネート基含有ウレタン（メタ）アクリレート。
As a result of intensive studies to solve the above problems, the present inventors have found that urethane (meth) acrylate having a specific structure is a compound suitable for solving the above problems.
That is, the present invention is as follows.
[1] Allophanate group-containing urethane (meth) acrylate represented by the following general formula (1).
（式中、Ｒ１及びＲ４は、それぞれ同一でも異なっていてもよく水素原子又はメチル基、Ｒ２は、炭素数１〜２０の２価の脂肪族、脂環式又は芳香族炭化水素基、Ｒ３は、炭素数１〜２０の脂肪族、脂環式又は芳香族炭化水素基、Ａ１Ｏ及びＡ２Ｏは、それぞれ同一でも異なっていてもよく炭素数２〜４のオキシアルキレン基、ｍ及びｎは、同一でも異なっていてもよく、オキシアルキレン基の繰り返し単位数を表す２〜１０の数である。）
［２］ 上記一般式（１）において、Ｒ２が脂環式炭化水素基であり、かつ、ｍ及びｎが５〜９の数である、［１］に記載のアロファネート基含有ウレタン（メタ）アクリレート。
［３］ 前記［１］又は［２］に記載のアロファネート基含有ウレタン（メタ）アクリレート及び光重合開始剤を含有する、光硬化型樹脂組成物。
(In the formula, R 1 and R 4 may be the same or different and each represents a hydrogen atom or a methyl group; R 2 is a divalent aliphatic, alicyclic or aromatic hydrocarbon group having 1 to 20 carbon atoms; , R 3 is an aliphatic, alicyclic or aromatic hydrocarbon group having 1 to 20 carbon atoms, and A 1 O and A 2 O may be the same as or different from each other, and an oxyalkylene group having 2 to 4 carbon atoms. , M and n may be the same or different, and are 2 to 10 numbers representing the number of repeating units of the oxyalkylene group.
[2] The allophanate group-containing urethane (meth) according to [1], wherein R 2 is an alicyclic hydrocarbon group in the general formula (1), and m and n are numbers from 5 to 9. Acrylate.
[3] A photocurable resin composition comprising the allophanate group-containing urethane (meth) acrylate according to [1] or [2] and a photopolymerization initiator.
本発明のアロファネート基含有ウレタン（メタ）アクリレートの硬化物は、成形加工時における追随性、寸法安定性や耐屈曲性、密着性に優れ、かつ表面に一旦傷が付いても経時的消失して復元し、長期的に美観を保持することができるなど、被膜形成用の素材として極めて適した特性を有する。したがって、本発明のアロファネート基含有ウレタン（メタ）アクリレート及びこれを含有する光硬化型樹脂組成物は、各種プラスチック成形品やフィルムの被膜形成材として有用である。 The cured product of the allophanate group-containing urethane (meth) acrylate of the present invention is excellent in followability at the time of molding, dimensional stability, flex resistance, adhesion, and disappears with time even if the surface is scratched once. It has characteristics that are extremely suitable as a material for film formation, such as being able to be restored and retain its aesthetics for a long period of time. Therefore, the allophanate group-containing urethane (meth) acrylate of the present invention and the photocurable resin composition containing the same are useful as film forming materials for various plastic molded products and films.
以下に本発明の詳細について説明する。
上記一般式（１）で表される本発明のアロファネート基含有ウレタン（メタ）アクリレート（Ａ）において、Ｒ１及びＲ４は水素原子又はメチル基であるが、硬化速度の観点から水素原子が好ましい。これらＲ１及びＲ４はそれぞれ同一でも異なっていてもよい。
Ｒ２は炭素数１〜２０の２価の脂肪族、脂環式又は芳香族炭化水素基である。
脂肪族炭化水素基としては、テトラメチレン基、カルボキシメチルペンタメチレン基、ヘキサメチレン基、オクタメチレン基等が挙げられる。脂環式炭化水素基としては、メチルシクロへキシレン基、シクロヘキサンジイルビスメチレン基、下記一般式（２）で表される基等が挙げられる。
Details of the present invention will be described below.
In the allophanate group-containing urethane (meth) acrylate (A) of the present invention represented by the above general formula (1), R 1 and R 4 are a hydrogen atom or a methyl group, but a hydrogen atom is preferable from the viewpoint of curing speed. . R 1 and R 4 may be the same or different.
R 2 is a C 1-20 divalent aliphatic, alicyclic or aromatic hydrocarbon group.
Examples of the aliphatic hydrocarbon group include a tetramethylene group, a carboxymethylpentamethylene group, a hexamethylene group, and an octamethylene group. Examples of the alicyclic hydrocarbon group include a methylcyclohexylene group, a cyclohexanediyl bismethylene group, and a group represented by the following general formula (2).
芳香族炭化水素基としては、トリレン基、キシリレン基等が挙げられる。Ｒ２が脂肪族又は脂環式炭化水素基であることによって、傷復元性と破断伸度を両立しながらも耐候性及び耐黄変性に優れ、さらに、脂環式炭化水素基であることによって、破断伸度が特に高いため、成形加工時における追随性（加工性）に優れる。これらの中でも、テトラメチレン基、ヘキサメチレン基等の脂肪族炭化水素基、シクロヘキサンジイルビスメチレン基、上記一般式（２）で表される基等の脂環式炭化水素基が好ましく、ヘキサメチレン基及び上記一般式（２）で表される基がより好ましい。 Examples of the aromatic hydrocarbon group include a tolylene group and a xylylene group. By being an aliphatic or alicyclic hydrocarbon group, R 2 is excellent in weather resistance and yellowing resistance while achieving both flaw resilience and elongation at break, and further, by being an alicyclic hydrocarbon group Since the elongation at break is particularly high, the followability (workability) during molding is excellent. Among these, an aliphatic hydrocarbon group such as a tetramethylene group and a hexamethylene group, a cyclohexanediyl bismethylene group, and an alicyclic hydrocarbon group such as a group represented by the above general formula (2) are preferable, and a hexamethylene group And a group represented by the general formula (2) is more preferred.
Ｒ３は炭素数１〜２０の脂肪族、脂環式又は芳香族炭化水素基である。脂肪族炭化水素基としては、メチル基、エチル基、プロピル基、ブチル基、ヘキシル基、オクチル基、デシル基等が挙げられる。脂環式炭化水素基としては、シクロペンチル基、シクロヘキシル基等が挙げられる。芳香族炭化水素基としては、フェニル基、ベンジル基等が挙げられる。これらの中でも、炭素数１〜１０の脂肪族炭化水素基が好ましく、炭素数２〜６の脂肪族炭化水素基がよりさらに好ましい。 R 3 is an aliphatic, alicyclic or aromatic hydrocarbon group having 1 to 20 carbon atoms. Examples of the aliphatic hydrocarbon group include a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group, and a decyl group. Examples of the alicyclic hydrocarbon group include a cyclopentyl group and a cyclohexyl group. Examples of the aromatic hydrocarbon group include a phenyl group and a benzyl group. Among these, a C1-C10 aliphatic hydrocarbon group is preferable, and a C2-C6 aliphatic hydrocarbon group is still more preferable.
Ａ１Ｏ及びＡ２Ｏは炭素数２〜４の直鎖又は分岐状のオキシアルキレン基であり、例えば、オキシエチレン基、オキシプロピレン基、オキシブチレン基、オキシテトラメチレン基等が挙げられる。これらの中でも、破断伸度及びウレタン化反応性の観点から、オキシエチレン基及びオキシテトラメチレン基が好ましく、オキシエチレン基がより好ましい。これらＡ１Ｏ及びＡ２Ｏは、それぞれ同一でも異なっていてもよい。
ｍ及びｎはオキシアルキレン基の繰り返し単位数を表す２〜１０の数であり、Ｒ２が脂環式炭化水素基である場合は５〜９の範囲であることが好ましい。これらｍ及びｎは、それぞれ同一でも異なっていてもよく、オキシアルキレン基は、それぞれ二種類以上をランダム状やブロック状に含んでいてもよい。ｍ及びｎが２未満であると傷が復元せずに傷跡が残りやすく、かつ、寸法安定性や耐屈曲性に劣る。一方、ｍ及びｎが１０を超えると傷が復元せずに傷跡が残りやすく、かつ、強靭性が低いため破断伸度が低い。上記の範囲であることにより、一旦付いた傷が復元して消失し、破断伸度が格段に高いため、成形加工時における追随性に優れ、かつ、寸法安定性や耐屈曲性にも優れる。
A 1 O and A 2 O are linear or branched oxyalkylene groups having 2 to 4 carbon atoms, and examples thereof include an oxyethylene group, an oxypropylene group, an oxybutylene group, and an oxytetramethylene group. Among these, from the viewpoint of breaking elongation and urethanization reactivity, an oxyethylene group and an oxytetramethylene group are preferable, and an oxyethylene group is more preferable. These A 1 O and A 2 O may be the same or different.
m and n are numbers of 2 to 10 representing the number of repeating units of the oxyalkylene group, and when R 2 is an alicyclic hydrocarbon group, it is preferably in the range of 5 to 9. These m and n may be the same or different, and the oxyalkylene group may contain two or more types in a random or block form. If m and n are less than 2, scratches are not restored and scars are likely to remain, and dimensional stability and flex resistance are poor. On the other hand, when m and n exceed 10, scratches are not restored and scars are likely to remain, and because the toughness is low, the elongation at break is low. By being in the above range, the scratch once attached is restored and disappears, and the elongation at break is remarkably high. Therefore, the followability at the time of molding is excellent, and the dimensional stability and the bending resistance are also excellent.
本発明のアロファネート基含有ウレタン（メタ）アクリレート（Ａ）は、具体的には、下記一般式（３）で表されるアロファネート基含有ポリイソシアネート（ａ−１）と、下記一般式（４）で表されるポリオキシアルキレンモノ（メタ）アクリレート（ａ−２）を反応させることによって得られる化合物である。 The allophanate group-containing urethane (meth) acrylate (A) of the present invention is specifically an allophanate group-containing polyisocyanate (a-1) represented by the following general formula (3) and the following general formula (4). It is a compound obtained by reacting the polyoxyalkylene mono (meth) acrylate (a-2) represented.
（式中、Ｒ２は炭素数１〜２０の２価の脂肪族、脂環式又は芳香族炭化水素基、Ｒ３は炭素数１〜２０の脂肪族、脂環式又は芳香族炭化水素基である。） (Wherein R 2 is a divalent aliphatic, alicyclic or aromatic hydrocarbon group having 1 to 20 carbon atoms, and R 3 is an aliphatic, alicyclic or aromatic hydrocarbon group having 1 to 20 carbon atoms. .)
（式中、Ｒ５は上記一般式（１）におけるＲ１又はＲ４であり、水素原子又はメチル基、Ａ３Ｏは上記一般式（１）におけるＡ１Ｏ又はＡ２Ｏであり、炭素数２〜４のオキシアルキレン基、ｐは上記一般式（１）におけるｍ又はｎであり、オキシアルキレン基の繰り返し単位数を表す２〜１０の数である。） (In the formula, R 5 is R 1 or R 4 in the above general formula (1), a hydrogen atom or a methyl group, A 3 O is A 1 O or A 2 O in the above general formula (1), carbon (The oxyalkylene group of formula 2-4, p is m or n in the general formula (1), and is a number of 2-10 representing the number of repeating units of the oxyalkylene group.)
前記アロファネート基含有ポリイソシアネート（ａ−１）は、上記一般式（３）で表される化合物であれば、特に限定されない。一般的には公知の方法に従って、脂肪族、脂環式又は芳香族炭化水素基を有するモノアルコールと、該モノアルコール中の水酸基当量に対してイソシアネート当量が過剰となる量の脂肪族、脂環式又は芳香族ジイソシアネートを、２−エチルヘキサン酸ジルコニウム等のアロファネート化触媒の存在下でアロファネート化反応させることによって得られる化合物である。
一般に入手可能な市販品としては、例えば、上記一般式（１）におけるＲ２がヘキサメチレン基である住化バイエルウレタン（株）社製「デスモジュールＸＰ２５８０」、旭化成ケミカルズ（株）社製「デュラネートＡ２０１Ｈ」、日本ポリウレタン（株）社製「ＬＶＡ−２０９」、「ＬＶＡ−２１０」、「ＶＡ−２１１」や、Ｒ２が一般式（２）で表される脂環式炭化水素基である住化バイエルウレタン（株）社製「デスモジュールＸＰ２５６５」等が挙げられる。これら（ａ−１）成分は、単独でも二種類以上を併用してもよい。
The allophanate group-containing polyisocyanate (a-1) is not particularly limited as long as it is a compound represented by the general formula (3). In general, according to a known method, a monoalcohol having an aliphatic, alicyclic or aromatic hydrocarbon group, and an aliphatic or alicyclic in an amount in which an isocyanate equivalent is excessive with respect to a hydroxyl group equivalent in the monoalcohol It is a compound obtained by subjecting a formula or aromatic diisocyanate to an allophanatization reaction in the presence of an allophanatization catalyst such as zirconium 2-ethylhexanoate.
As commercially available products, for example, “Desmodur XP2580” manufactured by Sumika Bayer Urethane Co., Ltd., in which R 2 in the above general formula (1) is a hexamethylene group, “Duranate” manufactured by Asahi Kasei Chemicals Co., Ltd. A201H ”,“ LVA-209 ”,“ LVA-210 ”,“ VA-211 ”manufactured by Nippon Polyurethane Co., Ltd., and R 2 is an alicyclic hydrocarbon group represented by the general formula (2) "Death module XP2565" manufactured by Kabayer Urethane Co., Ltd. These components (a-1) may be used alone or in combination of two or more.
前記ポリオキシアルキレンモノ（メタ）アクリレート（ａ−２）は、上記一般式（４）で表される化合物であれば特に限定されず、一般的には公知の方法に従って、（メタ）アクリル酸又は水酸基含有（メタ）アクリレートに、三フッ化ホウ素・ジエチルエーテル錯体等の触媒の存在下で、炭素数２〜４のアルキレンオキサイド又はテトラヒドロフランを開環重合させることによって得られる化合物である。
具体的な化合物としては、例えば、ポリオキシエチレン（平均付加モル数２〜１０）モノ（メタ）アクリレート、ポリオキシプロピレン（平均付加モル数２〜１０）モノ（メタ）アクリレート、ポリオキシブチレン（平均付加モル数２〜１０）モノ（メタ）アクリレート、ポリオキシエチレン・ポリオキシプロピレン（平均付加モル数２〜１０）モノ（メタ）アクリレート、ポリオキシエチレン・ポリオキシテトラメチレン（平均付加モル数２〜１０）モノ（メタ）アクリレート、ポリオキシプロピレン・ポリオキシテトラメチレン（平均付加モル数２〜１０）モノ（メタ）アクリレート等が挙げられる。これら（ａ−２）成分は、単独でも二種類以上を併用してもよい。
The polyoxyalkylene mono (meth) acrylate (a-2) is not particularly limited as long as it is a compound represented by the general formula (4). Generally, according to a known method, (meth) acrylic acid or It is a compound obtained by ring-opening polymerization of a C2-C4 alkylene oxide or tetrahydrofuran to a hydroxyl group-containing (meth) acrylate in the presence of a catalyst such as boron trifluoride / diethyl ether complex.
Specific examples of the compound include polyoxyethylene (average addition mole number 2 to 10) mono (meth) acrylate, polyoxypropylene (average addition mole number 2 to 10) mono (meth) acrylate, polyoxybutylene (average Addition mole number 2 to 10) mono (meth) acrylate, polyoxyethylene / polyoxypropylene (average addition mole number 2 to 10) mono (meth) acrylate, polyoxyethylene / polyoxytetramethylene (average addition mole number 2 to 2) 10) Mono (meth) acrylate, polyoxypropylene / polyoxytetramethylene (average added mole number 2 to 10) mono (meth) acrylate, and the like. These components (a-2) may be used alone or in combination of two or more.
本発明のアロファネート基含有ウレタン（メタ）アクリレート（Ａ）は、前記アロファネート基含有ポリイソシアネート（ａ−１）と前記ポリオキシアルキレンモノ（メタ）アクリレート（ａ−２）をウレタン化反応させることによって得られる化合物である。
（ａ−１）成分と（ａ−２）成分の配合比率は、（ａ−１）成分中のイソシアネート基１当量に対して（ａ−２）成分の水酸基が通常０．１〜１０当量であり、０．５〜５当量が好ましく、０．９〜１．２当量がより好ましい。反応温度は通常１０〜１５０℃であり、３０〜１２０℃が好ましく、４０〜８０℃がより好ましい。反応の終点はイソシアネート基を示す２２７０ｃｍ−１の赤外吸収スペクトルの消失や、ＪＩＳ Ｋ ７３０１に記載の方法でイソシアネート基の含有量を求めることで確認することができる。なお、前記ウレタン化反応では反応速度を促進する目的としてジブチルスズジラウレート等のスズ化合物や、トリエチルアミン等のアミンを触媒として用いてもよい。
The allophanate group-containing urethane (meth) acrylate (A) of the present invention is obtained by subjecting the allophanate group-containing polyisocyanate (a-1) and the polyoxyalkylene mono (meth) acrylate (a-2) to a urethanization reaction. Compound.
The mixing ratio of the component (a-1) and the component (a-2) is such that the hydroxyl group of the component (a-2) is usually 0.1 to 10 equivalents with respect to 1 equivalent of the isocyanate group in the component (a-1). Yes, 0.5 to 5 equivalents are preferable, and 0.9 to 1.2 equivalents are more preferable. The reaction temperature is usually 10 to 150 ° C, preferably 30 to 120 ° C, more preferably 40 to 80 ° C. The end point of the reaction can be confirmed by disappearance of the infrared absorption spectrum at 2270 cm −1 indicating the isocyanate group, or by determining the isocyanate group content by the method described in JIS K 7301. In the urethanization reaction, a tin compound such as dibutyltin dilaurate or an amine such as triethylamine may be used as a catalyst for the purpose of accelerating the reaction rate.
本発明の光硬化型樹脂組成物に含有させる光重合開始剤としては、下記のような化合物が挙げられる。例えば、ベンゾイン、ベンゾインメチルエーテル、ベンゾインイソプロピルエーテル等のベンゾイン又はベンゾインアルキルエーテル；ベンゾフェノン、ベンゾイル安息香酸等の芳香族ケトン；ベンジルジメチルケタール、ベンジルジエチルケタール等のベンジルケタール；１−ヒドロキシシクロヘキシルフェニルケトン、２−ヒドロキシ−２−メチル−１−フェニル−１−プロパン−１−オン等のアセトフェノン；２，４，６−トリメチルベンゾイルジフェニルフォスフィンオキサイド、ビス（２，４，６−トリメチルベンゾイル）フェニルフォスフィンオキサイド等のアシルフォスフィンオキサイド；２，４−ジメチルチオキサントン、２−イソプロピルチオキサントン等のチオキサントンが挙げられる。これらの中でも、１−ヒドロキシシクロヘキシルフェニルケトン、２−ヒドロキシ−２−メチル−１−フェニル−１−プロパン−１−オン等のアセトフェノン、２，４，６−トリメチルベンゾイルジフェニルフォスフィンオキサイド、ビス（２，４，６−トリメチルベンゾイル）フェニルフォスフィンオキサイド等のアシルフォスフィンオキサイドが好ましく、１−ヒドロキシシクロヘキシルフェニルケトン等のアセトフェノンがより好ましい。
前記光重合開始剤の使用量は、アロファネート基含有ウレタン（メタ）アクリレート（Ａ）を含有する樹脂固形分の合計質量に対して０．１〜２０質量％の範囲が好ましく、０．５〜５質量％の範囲がより好ましい。０．１質量％未満では硬化が十分に進行せず、２０質量％を越えると樹脂固形分の質量が相対的に減少し、硬化物の目標とする物性が低下するため好ましくない。
Examples of the photopolymerization initiator contained in the photocurable resin composition of the present invention include the following compounds. For example, benzoin or benzoin alkyl ethers such as benzoin, benzoin methyl ether, benzoin isopropyl ether; aromatic ketones such as benzophenone and benzoylbenzoic acid; benzyl ketals such as benzyl dimethyl ketal and benzyl diethyl ketal; 1-hydroxycyclohexyl phenyl ketone; -Acetophenone such as hydroxy-2-methyl-1-phenyl-1-propan-1-one; 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide And acyl phosphine oxides such as 2,4-dimethylthioxanthone and 2-isopropylthioxanthone. Among these, acetophenone such as 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-1-propan-1-one, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2 Acylphosphine oxide such as 1,4,6-trimethylbenzoyl) phenylphosphine oxide is preferred, and acetophenone such as 1-hydroxycyclohexyl phenyl ketone is more preferred.
The amount of the photopolymerization initiator used is preferably in the range of 0.1 to 20% by mass with respect to the total mass of the resin solids containing the allophanate group-containing urethane (meth) acrylate (A), and is preferably 0.5 to 5%. A range of mass% is more preferred. If it is less than 0.1% by mass, curing does not proceed sufficiently. If it exceeds 20% by mass, the mass of the resin solids is relatively reduced, and the target physical properties of the cured product are undesirably reduced.
本発明の光硬化型樹脂組成物には、任意成分として本発明の効果を阻害しない範囲内で種々の添加剤を配合することができる。添加剤の具体例としては、例えば、レベリング剤、シランカップリング剤、充填剤、顔料、チキソトロピー性付与剤、帯電防止剤、消泡剤、酸化防止剤、紫外線吸収剤、光安定剤等が挙げられる。 In the photocurable resin composition of the present invention, various additives can be blended as optional components as long as the effects of the present invention are not impaired. Specific examples of the additive include, for example, a leveling agent, a silane coupling agent, a filler, a pigment, a thixotropic agent, an antistatic agent, an antifoaming agent, an antioxidant, an ultraviolet absorber, and a light stabilizer. It is done.
本発明の光硬化型樹脂組成物は、アロファネート基含有ウレタン（メタ）アクリレート（Ａ）、光重合開始剤及び必要に応じて種々の添加剤を、常法により均一に混合して得ることができる。
前記樹脂組成物は、各種のプラスチック成形品や基材フィルムに塗布することによって、保護被膜を形成するこができる。基材フィルムの材質としてはプラスチックが好ましく、熱可塑性プラスチックがより好ましい。例えば、ポリエチレン樹脂、ポリプロピレン樹脂、ポリブタジエン樹脂、ポリエチレンテレフタレート（ＰＥＴ）樹脂、ポリブチレンテレフタレート樹脂、ポリエチレンナフタレート樹脂、ポリメチルメタクリレート樹脂、ポリカーボネート樹脂、トリアセチルセルロース（ＴＡＣ）樹脂、ポリスチレン樹脂、ポリ塩化ビニル樹脂、ＡＢＳ樹脂、ＡＳ樹脂等のプラスチックフィルムが挙げられる。これらの中でも、透明性や強靭性の観点からＰＥＴ樹脂が好ましい。
塗布方法としては、グラビアコート法、ロールコート法、フローコート法、バーコート法等の塗工方法や、グラビア印刷、スクリーン印刷等の印刷方法を適用することが可能である。塗膜の厚さは通常１〜１００μｍであり、傷復元性の観点から３〜８０μｍが好ましく、５〜５０μｍがより好ましい。１００μｍを超えると硬化物の硬化性が低下し、傷復元性や破断伸度が低下する恐れがあり、膜厚が１μｍ未満では傷復元性等の性能が十分に得られない場合があるため好ましくない。
The photocurable resin composition of the present invention can be obtained by uniformly mixing an allophanate group-containing urethane (meth) acrylate (A), a photopolymerization initiator and various additives as required by a conventional method. .
The said resin composition can form a protective film by apply | coating to various plastic molded articles and a base film. The material for the base film is preferably plastic, and more preferably thermoplastic. For example, polyethylene resin, polypropylene resin, polybutadiene resin, polyethylene terephthalate (PET) resin, polybutylene terephthalate resin, polyethylene naphthalate resin, polymethyl methacrylate resin, polycarbonate resin, triacetyl cellulose (TAC) resin, polystyrene resin, polyvinyl chloride Examples thereof include plastic films such as resin, ABS resin, and AS resin. Among these, PET resin is preferable from the viewpoint of transparency and toughness.
As the coating method, it is possible to apply a coating method such as a gravure coating method, a roll coating method, a flow coating method or a bar coating method, or a printing method such as gravure printing or screen printing. The thickness of the coating film is usually from 1 to 100 μm, preferably from 3 to 80 μm, more preferably from 5 to 50 μm from the viewpoint of scratch restoration properties. If the thickness exceeds 100 μm, the curability of the cured product is lowered, and there is a risk that the flaw resilience and elongation at break may be lowered. If the film thickness is less than 1 μm, performance such as flaw resilience may not be sufficiently obtained, which is preferable Absent.
本発明の光硬化型樹脂組成物は、赤外線、可視光線、紫外線、Ｘ線、γ線及び電子線より選ばれる活性エネルギー線を照射することにより硬化させることができる。活性エネルギー線の照射方法は、通常の光硬化型樹脂組成物の硬化方法を用いることができる。活性エネルギー線照射装置としては、紫外線を用いる場合、波長が２００〜４５０ｎｍの領域にスペクトル分布を有するフュージョンＵＶシステムズ社製ＨバルブやＤバルブ等の無電極ランプ、低圧水銀ランプ、高圧水銀ランプ、超高圧水銀ランプ、キセノンランプ、ガリウムランプ、メタルハライドランプ等が挙げられる。活性エネルギー線の照射量は、積算光量として通常１０〜３０００ｍＪ／ｃｍ２であり、好ましくは５０〜１０００ｍＪ／ｃｍ２である。照射するときの雰囲気は、空気中でもよいし、窒素やアルゴンなどの不活性ガス中で硬化してもよい。 The photocurable resin composition of the present invention can be cured by irradiation with an active energy ray selected from infrared rays, visible rays, ultraviolet rays, X-rays, γ rays and electron beams. As a method of irradiating the active energy ray, a normal curing method of a photocurable resin composition can be used. As the active energy ray irradiation device, when using ultraviolet rays, electrodeless lamps such as H bulb and D bulb manufactured by Fusion UV Systems having a spectral distribution in a wavelength range of 200 to 450 nm, low pressure mercury lamp, high pressure mercury lamp, High pressure mercury lamps, xenon lamps, gallium lamps, metal halide lamps and the like can be mentioned. The irradiation amount of the active energy ray is usually 10 to 3000 mJ / cm 2 as an integrated light amount, and preferably 50 to 1000 mJ / cm 2 . The atmosphere for irradiation may be air or may be cured in an inert gas such as nitrogen or argon.
以下、実施例及び比較例を示して本発明をさらに詳細に説明するが、本発明は以下の実施例により限定されるものではない。なお、以下の記載において特に規定しない限り、「部」は「質量部」、「％」は「質量％」を示す。 EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated further in detail, this invention is not limited by a following example. In the following description, “part” means “part by mass” and “%” means “% by mass” unless otherwise specified.
＜実施例１＞
［アロファネート基含有ウレタンアクリレート（Ａ−１）の合成］
攪拌装置、空気導入管、温度計を備えた四つ口フラスコに、（ａ−１）成分としてアロファネート基含有ポリイソシアネート（デスモジュールＸＰ２５８０，住化バイエルウレタン（株）社製，イソシアネート基含有率＝２０．０％，以下、「ＸＰ２５８０」という。）５４部、（ａ−２）成分としてポリオキシエチレンモノアクリレート（オキシエチレン基の繰り返し単位数＝２，水酸基価＝３２６ｍｇＫＯＨ／ｇ，以下、「ＰＥＧ９０ＭＡ」という。）４６部、ジブチルスズジラウレート（以下、「ＤＢＴＤＬ」という。）０．０２部、ハイドロキノンモノメチルエーテル（以下、「ＭＥＨＱ」という。）０．０４部を投入した。なお、このときのイソシアネート基／水酸基の当量比は１．０である。
次に、空気を吹き込みながら内温を６０℃に保持して５時間反応させた後、ＪＩＳ Ｋ ７３０１の方法でイソシアネート基含有量が０．１％以下となり、イソシアネート基が水酸基とほぼ全て反応してウレタン結合が形成されたことを確認して、アロファネート基含有ウレタンアクリレート（Ａ−１）を１００部得た。
得られたウレタンアクリレート（Ａ−１）は、一般式（１）においてＲ１及びＲ４が水素原子、Ｒ２がヘキサメチレン基、Ｒ３はブチル基、Ａ１Ｏ及びＡ２Ｏがオキシエチレン基、並びにｍ及びｎが２である化合物であり、２５℃における粘度は下表１に示すように１２Ｐａ・ｓ、ゲルパーミエーションクロマトグラフィーで測定した数平均分子量（標準ポリスチレン換算）は８００であった。
<Example 1>
[Synthesis of Allophanate Group-Containing Urethane Acrylate (A-1)]
In a four-necked flask equipped with a stirrer, an air introduction tube and a thermometer, allophanate group-containing polyisocyanate (Desmodur XP2580, manufactured by Sumika Bayer Urethane Co., Ltd., isocyanate group content = 20.0%, hereinafter referred to as “XP2580”) 54 parts, (a-2) As a component, polyoxyethylene monoacrylate (number of repeating units of oxyethylene group = 2, hydroxyl value = 326 mgKOH / g, hereinafter, “PEG90MA ) 46 parts, 0.02 part of dibutyltin dilaurate (hereinafter referred to as “DBTDL”) and 0.04 part of hydroquinone monomethyl ether (hereinafter referred to as “MEHQ”). At this time, the equivalent ratio of isocyanate group / hydroxyl group is 1.0.
Next, after reacting for 5 hours while maintaining the internal temperature at 60 ° C. while blowing air, the isocyanate group content becomes 0.1% or less by the method of JIS K 7301, and the isocyanate groups react with almost all the hydroxyl groups. As a result, 100 parts of allophanate group-containing urethane acrylate (A-1) was obtained.
In the obtained urethane acrylate (A-1), in general formula (1), R 1 and R 4 are hydrogen atoms, R 2 is a hexamethylene group, R 3 is a butyl group, and A 1 O and A 2 O are oxyethylene. And the viscosity at 25 ° C. is 12 Pa · s as shown in Table 1 below, and the number average molecular weight measured by gel permeation chromatography (in terms of standard polystyrene) is 800. It was.
＜実施例２＞
［アロファネート基含有ウレタンアクリレート（Ａ−２）の合成］
攪拌装置、空気導入管、温度計を備えた四つ口フラスコに、実施例１で使用したＸＰ２５８０を４７部、ポリオキシエチレンモノアクリレート（オキシエチレン基の繰り返し単位数＝３．５，水酸基価＝２５０ｍｇＫＯＨ／ｇ，以下、「ＰＥＧ１５０ＭＡ」という。）５３部、ＤＢＴＤＬを０．０２部、ＭＥＨＱを０．０４部投入した。なお、このときのイソシアネート基／水酸基の当量比は１．０である。
次に、空気を吹き込みながら内温を６０℃に保持して５時間反応させた後、ＪＩＳ Ｋ ７３０１の方法でイソシアネート基含有量が０．１％以下となり、イソシアネート基が水酸基とほぼ全て反応してウレタン結合が形成されたことを確認して、アロファネート基含有ウレタンアクリレート（Ａ−２）を１００部得た。得られたウレタンアクリレート（Ａ−２）は、一般式（１）においてＲ１及びＲ４が水素原子、Ｒ２がヘキサメチレン基、Ｒ３はブチル基、Ａ１Ｏ及びＡ２Ｏがオキシエチレン基、並びにｍ及びｎが３．５である化合物であり、２５℃における粘度は１０Ｐａ・ｓ、数平均分子量は１，１００であった。
<Example 2>
[Synthesis of Allophanate Group-Containing Urethane Acrylate (A-2)]
In a four-necked flask equipped with a stirrer, an air introduction tube, and a thermometer, 47 parts of XP2580 used in Example 1, polyoxyethylene monoacrylate (number of repeating units of oxyethylene group = 3.5, hydroxyl value = 250 mg KOH / g, hereinafter referred to as “PEG150MA”) 53 parts, 0.02 part of DBTDL, and 0.04 part of MEHQ were added. At this time, the equivalent ratio of isocyanate group / hydroxyl group is 1.0.
Next, after reacting for 5 hours while maintaining the internal temperature at 60 ° C. while blowing air, the isocyanate group content becomes 0.1% or less by the method of JIS K 7301, and the isocyanate groups react with almost all the hydroxyl groups. As a result, 100 parts of allophanate group-containing urethane acrylate (A-2) was obtained. In the obtained urethane acrylate (A-2), in the general formula (1), R 1 and R 4 are hydrogen atoms, R 2 is a hexamethylene group, R 3 is a butyl group, and A 1 O and A 2 O are oxyethylene. And a compound having m and n of 3.5, a viscosity at 25 ° C. of 10 Pa · s, and a number average molecular weight of 1,100.
＜実施例３＞
［アロファネート基含有ウレタンアクリレート（Ａ−３）の合成］
攪拌装置、空気導入管、温度計を備えた四つ口フラスコに、実施例１で使用したＸＰ２５８０を３７部、ポリオキシエチレンモノアクリレート（オキシエチレン基の繰り返し単位数＝６，水酸基価＝１６５ｍｇＫＯＨ／ｇ，以下、「ＰＥＧ２６０ＭＡ」という）６３部、ＤＢＴＤＬを０．０２部、ＭＥＨＱを０．０４部投入した。なお、このときのイソシアネート基／水酸基の当量比は１．０である。
次に、空気を吹き込みながら内温を６０℃に保持して５時間反応させた後、ＪＩＳ Ｋ ７３０１の方法でイソシアネート基含有量が０．１％以下となり、イソシアネート基が水酸基とほぼ全て反応してウレタン結合が形成されたことを確認して、アロファネート基含有ウレタンアクリレート（Ａ−３）を１００部得た。得られたウレタンアクリレート（Ａ−３）は、一般式（１）においてＲ１及びＲ４が水素原子、Ｒ２がヘキサメチレン基、Ｒ３はブチル基、Ａ１Ｏ及びＡ２Ｏがオキシエチレン基、並びにｍ及びｎが６である化合物であり、２５℃における粘度は９Ｐａ・ｓ、数平均分子量は１，４００であった。
<Example 3>
[Synthesis of Allophanate Group-Containing Urethane Acrylate (A-3)]
In a four-necked flask equipped with a stirrer, an air introduction tube, and a thermometer, 37 parts of XP2580 used in Example 1, polyoxyethylene monoacrylate (number of repeating units of oxyethylene group = 6, hydroxyl value = 165 mgKOH / g, hereinafter referred to as “PEG260MA”), 63 parts, 0.02 part of DBTDL, and 0.04 part of MEHQ were added. At this time, the equivalent ratio of isocyanate group / hydroxyl group is 1.0.
Next, after reacting for 5 hours while maintaining the internal temperature at 60 ° C. while blowing air, the isocyanate group content becomes 0.1% or less by the method of JIS K 7301, and the isocyanate groups react with almost all the hydroxyl groups. As a result, 100 parts of allophanate group-containing urethane acrylate (A-3) was obtained. In the obtained urethane acrylate (A-3), in general formula (1), R 1 and R 4 are hydrogen atoms, R 2 is a hexamethylene group, R 3 is a butyl group, and A 1 O and A 2 O are oxyethylene. Group, m and n are 6 compounds, the viscosity at 25 ° C. was 9 Pa · s, and the number average molecular weight was 1,400.
＜実施例４＞
［アロファネート基含有ウレタンアクリレート（Ａ−４）の合成］
攪拌装置、空気導入管、温度計を備えた四つ口フラスコに、アロファネート基含有ポリイソシアネート（デスモジュールＸＰ２５６５，住化バイエルウレタン（株）社製，イソシアネート基含有率＝１２．０％，樹脂固形分８０％（酢酸ブチル希釈），以下、「ＸＰ２５６５」という。）５０部、ポリオキシエチレンモノアクリレート（オキシエチレン基の繰り返し単位数＝６，水酸基価＝１６５ｍｇＫＯＨ／ｇ，以下、「ＰＥＧ２６０ＭＡ」という。）５０部、ＤＢＴＤＬを０．０２部、ＭＥＨＱを０．０４部投入した。なお、このときのイソシアネート基／水酸基の当量比は１．０である。
次に、空気を吹き込みながら内温を６０℃に保持して５時間反応させた後、ＪＩＳ Ｋ ７３０１の方法でイソシアネート基含有量が０．１％以下となり、イソシアネート基が水酸基とほぼ全て反応してウレタン結合が形成されたことを確認してアロファネート基含有ウレタンアクリレート（Ａ−４）を得た。得られたウレタンアクリレート（Ａ−４）は、一般式（１）においてＲ１及びＲ４が水素原子、Ｒ２が一般式（２）で表される脂環式炭化水素基、Ｒ３はブチル基、Ａ１Ｏ及びＡ２Ｏがオキシエチレン基、並びにｍ及びｎが６である化合物であり、２５℃における粘度は５０Ｐａ・ｓ、数平均分子量は１，３００であった。
<Example 4>
[Synthesis of Allophanate Group-Containing Urethane Acrylate (A-4)]
In a four-necked flask equipped with a stirrer, an air introduction tube, and a thermometer, allophanate group-containing polyisocyanate (Desmodur XP2565, manufactured by Sumika Bayer Urethane Co., Ltd., isocyanate group content = 12.0%, resin solid 80% min (diluted with butyl acetate), hereinafter referred to as “XP2565”) 50 parts, polyoxyethylene monoacrylate (number of repeating units of oxyethylene group = 6, hydroxyl value = 165 mgKOH / g, hereinafter referred to as “PEG260MA”). ) 50 parts, 0.02 part DBTDL and 0.04 part MEHQ were added. At this time, the equivalent ratio of isocyanate group / hydroxyl group is 1.0.
Next, after reacting for 5 hours while maintaining the internal temperature at 60 ° C. while blowing air, the isocyanate group content becomes 0.1% or less by the method of JIS K 7301, and the isocyanate groups react with almost all the hydroxyl groups. Thus, it was confirmed that a urethane bond was formed, and an allophanate group-containing urethane acrylate (A-4) was obtained. In the obtained urethane acrylate (A-4), R 1 and R 4 in the general formula (1) are hydrogen atoms, R 2 is an alicyclic hydrocarbon group represented by the general formula (2), and R 3 is butyl. Group, A 1 O and A 2 O are oxyethylene groups, and m and n are 6 compounds, the viscosity at 25 ° C. was 50 Pa · s, and the number average molecular weight was 1,300.
＜実施例５＞
［アロファネート基含有ウレタンアクリレート（Ａ−５）の合成］
攪拌装置、空気導入管、温度計を備えた四つ口フラスコに、実施例４で使用したＸＰ２５６５を４７部、ポリオキシエチレンモノアクリレート（オキシエチレン基の繰り返し単位数＝７，水酸基価＝１４６ｍｇＫＯＨ／ｇ，以下、「ＰＥＧ３１０ＭＡ」という。）５３部、ＤＢＴＤＬを０．０２部、ＭＥＨＱを０．０４部投入した。なお、このときのイソシアネート基／水酸基の当量比は１．０である。
次に、空気を吹き込みながら内温を６０℃に保持して５時間反応させた後、ＪＩＳ Ｋ ７３０１の方法でイソシアネート基含有量が０．１％以下となり、イソシアネート基が水酸基とほぼ全て反応してウレタン結合が形成されたことを確認して、アロファネート基含有ウレタンアクリレート（Ａ−５）を得た。得られたウレタンアクリレート（Ａ−５）は、一般式（１）においてＲ１及びＲ４が水素原子、Ｒ２が一般式（２）で表される脂環式炭化水素基、Ｒ３はブチル基、Ａ１Ｏ及びＡ２Ｏがオキシエチレン基、並びにｍ及びｎが７である化合物であり、２５℃における粘度は２６Ｐａ・ｓ、数平均分子量は１，５００であった。
<Example 5>
[Synthesis of Allophanate Group-Containing Urethane Acrylate (A-5)]
In a four-necked flask equipped with a stirrer, an air introduction tube, and a thermometer, 47 parts of XP2565 used in Example 4, polyoxyethylene monoacrylate (number of repeating units of oxyethylene group = 7, hydroxyl value = 146 mgKOH / g, hereinafter referred to as “PEG310MA”) 53 parts, 0.02 part of DBTDL, and 0.04 part of MEHQ were added. At this time, the equivalent ratio of isocyanate group / hydroxyl group is 1.0.
Next, after reacting for 5 hours while maintaining the internal temperature at 60 ° C. while blowing air, the isocyanate group content becomes 0.1% or less by the method of JIS K 7301, and the isocyanate groups react with almost all the hydroxyl groups. Then, it was confirmed that a urethane bond was formed, and an allophanate group-containing urethane acrylate (A-5) was obtained. The obtained urethane acrylate (A-5) is an alicyclic hydrocarbon group in which R 1 and R 4 are hydrogen atoms, R 2 is represented by the general formula (2) in the general formula (1), and R 3 is butyl. Group, A 1 O and A 2 O are oxyethylene groups, and m and n are 7. The viscosity at 25 ° C. was 26 Pa · s, and the number average molecular weight was 1,500.
＜実施例６＞
［アロファネート基含有ウレタンアクリレート（Ａ−６）の合成］
攪拌装置、空気導入管、温度計を備えた四つ口フラスコに、実施例４で使用したＸＰ２５６５を４３部、ポリオキシエチレンモノアクリレート（オキシエチレン基の繰り返し単位数＝８，水酸基価＝１２９ｍｇＫＯＨ／ｇ，以下、「ＰＥＧ３６０ＭＡ」という）５７部、ＤＢＴＤＬを０．０２部、ＭＥＨＱを０．０４部投入した。なお、このときのイソシアネート基／水酸基の当量比は１．０である。
次に、空気を吹き込みながら内温を６０℃に保持して５時間反応させた後、ＪＩＳ Ｋ ７３０１の方法でイソシアネート基含有量が０．１％以下となり、イソシアネート基が水酸基とほぼ全て反応してウレタン結合が形成されたことを確認して、アロファネート基含有ウレタンアクリレート（Ａ−６）を得た。得られたウレタンアクリレート（Ａ−６）は、一般式（１）においてＲ１及びＲ４が水素原子、Ｒ２が一般式（２）で表される脂環式炭化水素基、Ｒ３はブチル基、Ａ１Ｏ及びＡ２Ｏがオキシエチレン基、並びにｍ及びｎが８である化合物であり、２５℃における粘度は１６Ｐａ・ｓ、数平均分子量は１，６５０であった。
<Example 6>
[Synthesis of Allophanate Group-Containing Urethane Acrylate (A-6)]
In a four-necked flask equipped with a stirrer, an air introduction tube, and a thermometer, 43 parts of XP2565 used in Example 4, polyoxyethylene monoacrylate (number of repeating units of oxyethylene group = 8, hydroxyl value = 129 mgKOH / g, hereinafter referred to as “PEG360MA”), 57 parts, 0.02 part of DBTDL, and 0.04 part of MEHQ were added. At this time, the equivalent ratio of isocyanate group / hydroxyl group is 1.0.
Next, after reacting for 5 hours while maintaining the internal temperature at 60 ° C. while blowing air, the isocyanate group content becomes 0.1% or less by the method of JIS K 7301, and the isocyanate groups react with almost all the hydroxyl groups. Then, it was confirmed that a urethane bond was formed, and an allophanate group-containing urethane acrylate (A-6) was obtained. The obtained urethane acrylate (A-6) is an alicyclic hydrocarbon group in which R 1 and R 4 are hydrogen atoms, R 2 is represented by the general formula (2) in the general formula (1), and R 3 is butyl. Group, A 1 O and A 2 O are oxyethylene groups, and m and n are 8. The viscosity at 25 ° C. was 16 Pa · s, and the number average molecular weight was 1,650.
＜比較例１＞
［アロファネート基含有ウレタンアクリレート（Ａ’−１）の合成］
攪拌装置、空気導入管、温度計を備えた四つ口フラスコに、実施例１で使用したＸＰ２５８０を６３部、（ａ’−２）成分として２−ヒドロキシエチルアクリレート（オキシエチレン基の繰り返し単位数＝１，水酸基価＝４８３ｍｇＫＯＨ／ｇ。以下、「ＨＥＡ」という。）３７部、ＤＢＴＤＬを０．０２部、ＭＥＨＱを０．０４部投入した。なお、このときのイソシアネート基／水酸基の当量比は１．０である。
次に、空気を吹き込みながら内温を６０℃に保持して５時間反応させた後、ＪＩＳ Ｋ ７３０１の方法でイソシアネート基含有量が０．１％以下となり、イソシアネート基が水酸基とほぼ全て反応してウレタン結合が形成されたことを確認して、アロファネート基含有ウレタンアクリレート（Ａ’−１）を得た。得られたウレタンアクリレート（Ａ’−１）は、一般式（１）においてＲ１及びＲ４が水素原子、Ｒ２がヘキサメチレン基、Ｒ３はブチル基、Ａ１Ｏ及びＡ２Ｏがオキシエチレン基、並びにｍ及びｎが１である化合物であり、２５℃における粘度は１１Ｐａ・ｓ、数平均分子量は７００であった。
<Comparative Example 1>
[Synthesis of Allophanate Group-Containing Urethane Acrylate (A′-1)]
In a four-necked flask equipped with a stirrer, an air introduction tube, and a thermometer, 63 parts of XP2580 used in Example 1, 2-hydroxyethyl acrylate (number of repeating units of oxyethylene group) as component (a′-2) = 1, hydroxyl value = 483 mg KOH / g, hereinafter referred to as "HEA") 37 parts, 0.02 part of DBTDL and 0.04 part of MEHQ were added. At this time, the equivalent ratio of isocyanate group / hydroxyl group is 1.0.
Next, after reacting for 5 hours while maintaining the internal temperature at 60 ° C. while blowing air, the isocyanate group content becomes 0.1% or less by the method of JIS K 7301, and the isocyanate groups react with almost all the hydroxyl groups. Thus, it was confirmed that a urethane bond was formed, and an allophanate group-containing urethane acrylate (A′-1) was obtained. The obtained urethane acrylate (A′-1) has the following general formula (1): R 1 and R 4 are hydrogen atoms, R 2 is a hexamethylene group, R 3 is a butyl group, and A 1 O and A 2 O are oxy The compound was an ethylene group and m and n were 1, the viscosity at 25 ° C. was 11 Pa · s, and the number average molecular weight was 700.
＜比較例２＞
［アロファネート基含有ウレタンアクリレート（Ａ’−２）の合成］
攪拌装置、空気導入管、温度計を備えた四つ口フラスコに、実施例４で使用したＸＰ２５６５を７４部、比較例１で使用したＨＥＡを２６部、ＤＢＴＤＬを０．０２部、ＭＥＨＱを０．０４部投入した。なお、このときのイソシアネート基／水酸基の当量比は１．０である。
次に、空気を吹き込みながら内温を６０℃に保持して５時間反応させた後、ＪＩＳ Ｋ ７３０１の方法でイソシアネート基含有量が０．１％以下となり、イソシアネート基が水酸基とほぼ全て反応してウレタン結合が形成されたことを確認して、アロファネート基含有ウレタンアクリレート（Ａ’−２）を得た。得られたウレタンアクリレート（Ａ’−２）は、一般式（１）においてＲ１及びＲ４が水素原子、Ｒ２が一般式（２）で表される脂環式炭化水素基、Ｒ３はブチル基、Ａ１Ｏ及びＡ２Ｏがオキシエチレン基、並びにｍ及びｎが１である化合物であり、２５℃における粘度は１００Ｐａ・ｓ以上、数平均分子量は８００であった。
<Comparative example 2>
[Synthesis of Allophanate Group-Containing Urethane Acrylate (A′-2)]
In a four-necked flask equipped with a stirrer, an air introduction tube, and a thermometer, 74 parts of XP2565 used in Example 4, 26 parts of HEA used in Comparative Example 1, 0.02 part of DBTDL, and 0 of MEHQ .04 copies were added. At this time, the equivalent ratio of isocyanate group / hydroxyl group is 1.0.
Next, after reacting for 5 hours while maintaining the internal temperature at 60 ° C. while blowing air, the isocyanate group content becomes 0.1% or less by the method of JIS K 7301, and the isocyanate groups react with almost all the hydroxyl groups. Thus, it was confirmed that a urethane bond was formed, and an allophanate group-containing urethane acrylate (A′-2) was obtained. In the obtained urethane acrylate (A′-2), R 1 and R 4 in the general formula (1) are hydrogen atoms, R 2 is an alicyclic hydrocarbon group represented by the general formula (2), and R 3 is It is a compound in which butyl group, A 1 O and A 2 O are oxyethylene groups, and m and n are 1, the viscosity at 25 ° C. is 100 Pa · s or more, and the number average molecular weight is 800.
＜比較例３＞
［アロファネート基含有ウレタンアクリレート（Ａ’−３）の合成］
攪拌装置、空気導入管、温度計を備えた四つ口フラスコに、実施例１で使用したＸＰ２５８０を２７部、（ａ’−２）成分としてポリオキシエチレンモノアクリレート（オキシエチレン基の繰り返し単位数＝１１，水酸基価＝９８ｍｇＫＯＨ／ｇ，以下、「ＰＥＧ４８０ＭＡ」という）７３部、ＤＢＴＤＬを０．０２部、ＭＥＨＱを０．０４部投入した。なお、このときのイソシアネート基／水酸基の当量比は１．０である。
次に、空気を吹き込みながら内温を６０℃に保持して５時間反応させた後、ＪＩＳ Ｋ ７３０１の方法でイソシアネート基含有量が０．１％以下となり、イソシアネート基が水酸基とほぼ全て反応してウレタン結合が形成されたことを確認して、アロファネート基含有ウレタンアクリレート（Ａ’−３）を得た。得られたウレタンアクリレート（Ａ’−３）は、一般式（１）においてＲ１及びＲ４が水素原子、Ｒ２がヘキサメチレン基、Ｒ３はブチル基、Ａ１Ｏ及びＡ２Ｏがオキシエチレン基、並びにｍ及びｎが１１である化合物であり、２５℃における粘度は５Ｐａ・ｓ、数平均分子量は２，２００であった。
<Comparative Example 3>
[Synthesis of Allophanate Group-Containing Urethane Acrylate (A′-3)]
In a four-necked flask equipped with a stirrer, an air introduction tube, and a thermometer, 27 parts of XP2580 used in Example 1, and polyoxyethylene monoacrylate (number of repeating units of oxyethylene group) as component (a′-2) = 11, hydroxyl value = 98 mgKOH / g, hereinafter referred to as "PEG480MA") 73 parts, DBTDL 0.02 parts, and MEHQ 0.04 parts. At this time, the equivalent ratio of isocyanate group / hydroxyl group is 1.0.
Next, after reacting for 5 hours while maintaining the internal temperature at 60 ° C. while blowing air, the isocyanate group content becomes 0.1% or less by the method of JIS K 7301, and the isocyanate groups react with almost all the hydroxyl groups. Then, it was confirmed that a urethane bond was formed, and an allophanate group-containing urethane acrylate (A′-3) was obtained. The obtained urethane acrylate (A′-3) has the following general formula (1): R 1 and R 4 are hydrogen atoms, R 2 is a hexamethylene group, R 3 is a butyl group, and A 1 O and A 2 O are oxy The compound was an ethylene group and m and n of 11, the viscosity at 25 ° C. was 5 Pa · s, and the number average molecular weight was 2,200.
＜比較例４＞
［ウレタンアクリレート（Ａ’−４）の合成］
攪拌装置、空気導入管、温度計を備えた四つ口フラスコに、（ａ’−１）成分としてヘキサメチレンジイソシアネート（以下、「ＨＤＩ」という。）のイソシアヌレート変性ポリイソシアネート（デュラネートＴＰＡ−１００，旭化成ケミカルズ（株）社製，イソシアネート基含有率＝２３．１％）を３９部、ポリオキシエチレンモノアクリレート（オキシエチレン基の繰り返し単位数＝４．５，水酸基価＝２０３ｍｇＫＯＨ／ｇ，以下、「ＰＥＧ２００ＭＡ」という。）６１部、ＤＢＴＤＬを０．０２部、ＭＥＨＱを０．０４部投入した。なお、このときのイソシアネート基／水酸基の当量比は１．０である。
次に、空気を吹き込みながら内温を６０℃に保持して５時間反応させた後、ＪＩＳ Ｋ ７３０１の方法でイソシアネート基含有量が０．１％となり、イソシアネート基が水酸基とほぼ全て反応してウレタン結合が形成されたことを確認して、イソシアヌレート基含有ウレタンアクリレート（Ａ’−４）を得た。得られたウレタンアクリレート（Ａ’−４）は、１分子中に繰り返し単位数が４．５のポリオキシエチレン基を有するがアロファネート基は有さず、上記一般式（１）に含まれない化合物であり、２５℃における粘度は１６Ｐａ・ｓ、数平均分子量は２，３００であった。
<Comparative Example 4>
[Synthesis of Urethane Acrylate (A′-4)]
In a four-necked flask equipped with a stirrer, an air introduction tube, and a thermometer, isocyanurate-modified polyisocyanate (Duranate TPA-100, hexamethylene diisocyanate (hereinafter referred to as “HDI”) as component (a′-1). 39 parts by Asahi Kasei Chemicals Corporation, isocyanate group content = 23.1%, polyoxyethylene monoacrylate (number of repeating units of oxyethylene group = 4.5, hydroxyl value = 203 mgKOH / g, hereinafter “ PEG200MA ")) 61 parts, DBTDL 0.02 part, and MEHQ 0.04 part were added. At this time, the equivalent ratio of isocyanate group / hydroxyl group is 1.0.
Next, after reacting for 5 hours while maintaining the internal temperature at 60 ° C. while blowing air, the isocyanate group content becomes 0.1% by the method of JIS K 7301, and the isocyanate groups are almost completely reacted with the hydroxyl groups. After confirming that a urethane bond was formed, an isocyanurate group-containing urethane acrylate (A′-4) was obtained. The obtained urethane acrylate (A′-4) has a polyoxyethylene group having a repeating unit number of 4.5 in one molecule, but does not have an allophanate group and is not included in the general formula (1). The viscosity at 25 ° C. was 16 Pa · s, and the number average molecular weight was 2,300.
＜比較例５＞
［ウレタンアクリレート（Ａ’−５）の合成］
攪拌装置、空気導入管、温度計を備えた四つ口フラスコに、比較例４で使用したＴＰＡ−１００を６０部、ＨＥＡを４０部、ＤＢＴＤＬを０．０２部、ＭＥＨＱを０．０４部投入した。なお、このときのイソシアネート基／水酸基の当量比は１．０である。
次に、空気を吹き込みながら内温を６０℃に保持して５時間反応させた後、ＪＩＳ Ｋ ７３０１の方法でイソシアネート基含有量が０．１％となり、イソシアネート基が水酸基とほぼ全て反応してウレタン結合が形成されたことを確認して、イソシアヌレート基含有ウレタンアクリレート（Ａ’−５）を得た。得られたウレタンアクリレート（Ａ’−５）は、１分子中に繰り返し単位数が１のポリオキシエチレン基を有するがアロファネート基は有さず、上記一般式（１）に含まれない化合物であり、数平均分子量は１，６００であった。
<Comparative Example 5>
[Synthesis of Urethane Acrylate (A′-5)]
In a four-necked flask equipped with a stirrer, an air inlet tube, and a thermometer, 60 parts of TPA-100 used in Comparative Example 4, 40 parts of HEA, 0.02 part of DBTDL, and 0.04 part of MEHQ are charged. did. At this time, the equivalent ratio of isocyanate group / hydroxyl group is 1.0.
Next, after reacting for 5 hours while maintaining the internal temperature at 60 ° C. while blowing air, the isocyanate group content becomes 0.1% by the method of JIS K 7301, and the isocyanate groups are almost completely reacted with the hydroxyl groups. After confirming that a urethane bond was formed, an isocyanurate group-containing urethane acrylate (A′-5) was obtained. The obtained urethane acrylate (A′-5) has a polyoxyethylene group having 1 repeating unit in one molecule, but does not have an allophanate group and is not included in the general formula (1). The number average molecular weight was 1,600.
＜比較例６＞
［ウレタンアクリレート（Ａ’−６）の合成］
攪拌装置、空気導入管、温度計を備えた四つ口フラスコに、（ａ’−１）成分としてＨＤＩのアダクト変性ポリイソシアネート（デュラネートＡＥ７１０−１００，旭化成ケミカルズ（株）社製，イソシアネート基含有率１２．０％）７４部、ＨＥＡを２６部、ＤＢＴＤＬを０．０２部、ＭＥＨＱを０．０４部投入した。なお、このときのイソシアネート基／水酸基の当量比は１．０である。
次に、空気を吹き込みながら内温を６０℃に保持して５時間反応させた後、ＪＩＳ Ｋ ７３０１の方法でイソシアネート基含有量が０．１％となり、イソシアネート基が水酸基とほぼ全て反応してウレタン結合が形成されたことを確認して、ウレタンアクリレート（Ａ’−６）を得た。得られたウレタンアクリレート（Ａ’−６）は、１分子中に繰り返し単位数が１のポリオキシエチレン基を有するがアロファネート基は有さず、上記一般式（１）に含まれない化合物であり、２５℃における粘度は９Ｐａ・ｓ、数平均分子量は１，７００であった。
<Comparative Example 6>
[Synthesis of Urethane Acrylate (A′-6)]
In a four-necked flask equipped with a stirrer, an air introduction tube, and a thermometer, an adduct-modified polyisocyanate of HDI (Duranate AE710-100, manufactured by Asahi Kasei Chemicals Corporation) as a component (a′-1), isocyanate group content 12.0) 74 parts, HEA 26 parts, DBTDL 0.02 parts, and MEHQ 0.04 parts were added. At this time, the equivalent ratio of isocyanate group / hydroxyl group is 1.0.
Next, after reacting for 5 hours while maintaining the internal temperature at 60 ° C. while blowing air, the isocyanate group content becomes 0.1% by the method of JIS K 7301, and the isocyanate groups are almost completely reacted with the hydroxyl groups. After confirming that a urethane bond was formed, urethane acrylate (A′-6) was obtained. The obtained urethane acrylate (A′-6) has a polyoxyethylene group having 1 repeating unit in one molecule but does not have an allophanate group and is not included in the general formula (1). The viscosity at 25 ° C. was 9 Pa · s, and the number average molecular weight was 1,700.
＜実施例７〜１２、比較例７〜１２＞
［光硬化型樹脂組成物の調製］
下表３及び４に示すように、上記で得られたウレタンアクリレート１００部に、光重合開始剤として１−ヒドロキシシクロヘキシルフェニルケトン（イルガキュア１８４，ＢＡＳＦジャパン（株）社製。以下、「Ｉｒｇａｃｕｒｅ１８４」という。）３部、添加剤としてポリエーテル変性ポリジメチルシロキサン（ＢＹＫ−３５７０，ビックケミー・ジャパン（株）社製。以下、「ＢＹＫ−３５７０」という。）０．２部、有機溶剤としてメチルエチルケトン（以下、「ＭＥＫ」という。）１５０部を均一に混合して、樹脂固形分４０％の光硬化型樹脂組成物を得た。
<Examples 7 to 12 and Comparative Examples 7 to 12>
[Preparation of Photocurable Resin Composition]
As shown in Tables 3 and 4 below, 100 parts of the urethane acrylate obtained above was used as a photopolymerization initiator with 1-hydroxycyclohexyl phenyl ketone (Irgacure 184, manufactured by BASF Japan Ltd., hereinafter referred to as “Irgacure 184”. .) 3 parts, polyether-modified polydimethylsiloxane (BYK-3570, manufactured by BYK Japan Japan Co., Ltd. as an additive, hereinafter referred to as “BYK-3570”) 0.2 part, methyl ethyl ketone (hereinafter, referred to as “BYC-3570”) as an organic solvent 150 parts of “MEK”) were uniformly mixed to obtain a photocurable resin composition having a resin solid content of 40%.
［光硬化型樹脂組成物の硬化膜層を有するフィルムの作製］
易接着ＰＥＴフィルム（コスモシャインＡ４３００，膜厚１００μｍ，東洋紡績（株）社製）上に、上記で得られた光硬化型樹脂組成物を、乾燥膜厚で２５μｍとなるよう塗工し、８０℃にて１分間乾燥して有機溶剤を蒸発させた。次に、紫外線照射装置（フュージョンＵＶシステムズジャパン（株）社製，光源：Ｈバルブ）を用いて、積算光量５００ｍＪ／ｃｍ２の紫外線を照射することで、光硬化型樹脂組成物の硬化膜層を有するフィルムを得た。作製したフィルムについて下記の評価を実施した結果を、下表３及び４に示す。
[Production of film having cured film layer of photocurable resin composition]
On the easily adhesive PET film (Cosmo Shine A4300, film thickness 100 μm, manufactured by Toyobo Co., Ltd.), the photocurable resin composition obtained above was applied to a dry film thickness of 25 μm. The organic solvent was evaporated by drying at 1 ° C. for 1 minute. Next, a cured film layer of the photocurable resin composition is irradiated by irradiating ultraviolet rays with an integrated light amount of 500 mJ / cm 2 using an ultraviolet irradiation device (manufactured by Fusion UV Systems Japan Co., Ltd., light source: H bulb). A film having was obtained. The following evaluation results are shown in Tables 3 and 4 below for the produced films.
＜密着性＞
ＪＩＳ Ｋ ５６００に準拠し、作製した硬化膜層を有するフィルムを、６０℃、９０ＲＨ％の条件下で１時間保管した後、２５℃に冷却してからカッターナイフで１ｍｍ四方の碁盤目を１００個作製し、市販のセロハンテープを表面に密着させた後に一気に剥がしたとき、剥離せずに残った碁盤目の個数を下記の基準により判定した。
◎：残存した碁盤目の個数が１００個である。
○：残存した碁盤目の個数が９０〜９９個である。
△：残存した碁盤目の個数が６０〜８９個である。
×：残存した碁盤目の個数が６０個未満である。
<Adhesion>
In accordance with JIS K 5600, the prepared film having a cured film layer was stored at 60 ° C. and 90 RH% for 1 hour, then cooled to 25 ° C. and then 100 100 mm squares with a cutter knife. When the produced cellophane tape was adhered to the surface and peeled at once, the number of grids remaining without peeling was determined according to the following criteria.
A: The number of remaining grids is 100.
A: The number of remaining grids is 90 to 99.
Δ: The number of remaining grids is 60 to 89.
X: The number of remaining grids is less than 60.
＜傷復元性＞
作製した硬化膜層を有するフィルムに、２３℃、６０ＲＨ％の条件下、真鍮ブラシにより５００ｇの荷重を掛けて５往復擦ったとき、硬化物の表面状態を目視によって下記の基準により判定した。
◎：傷が３分以内に復元する。
○：３分後に傷が認められるが、１０分経過後には復元する。
△：１時間後に傷跡が若干認められる。
×：１時間後も傷が全く復元しない。
<Scratch resilience>
When the film having the cured film layer thus prepared was rubbed 5 times with a brass brush under a condition of 23 ° C. and 60 RH% for 5 reciprocations, the surface state of the cured product was visually determined according to the following criteria.
A: The wound is restored within 3 minutes.
○: Scratches are observed after 3 minutes, but are restored after 10 minutes.
Δ: Some scars are observed after 1 hour.
X: Scratches are not restored at all even after 1 hour.
＜破断伸度＞
作製した硬化膜層を有するフィルムを１０ｍｍ×６０ｍｍサイズに裁断し、オートグラフを用いてチャック間距離が４０ｍｍとなるようセットした後、８０℃の条件下、５０ｍｍ／ｍｉｎの引張速度にて引張試験を行い、硬化膜にクラックが生じたときの伸度を決定した。なお、破断伸度の評価基準は下記のとおりである。
◎：破断伸度が４０％以上である。
○：破断伸度が３０〜４０％未満である。
△：破断伸度が２０〜３０％未満である。
×：破断伸度が２０％未満である。
<Elongation at break>
The prepared film having a cured film layer is cut to a size of 10 mm × 60 mm, set so that the distance between chucks is 40 mm using an autograph, and then subjected to a tensile test at 80 ° C. and a tensile speed of 50 mm / min. The elongation when a crack occurred in the cured film was determined. The evaluation criteria for the elongation at break are as follows.
A: Elongation at break is 40% or more.
A: The elongation at break is 30 to less than 40%.
(Triangle | delta): Breaking elongation is 20 to less than 30%.
X: The elongation at break is less than 20%.
＜耐屈曲性＞
ＪＩＳ Ｋ ５６００に準拠し、作製した硬化膜層を有するフィルムの硬化膜面が外側になるよう円筒に巻きつけたとき、硬化膜の状態を下記の基準より判定した。
○：直径１ｍｍの円筒でクラックが生じない。
△：直径１ｍｍの円筒ではクラックが発生するが、直径４ｍｍの円筒ではクラックが生じない。
×：直径４ｍｍの円筒でクラックが生じる。
<Flexibility>
In accordance with JIS K 5600, when the prepared film having a cured film layer was wound around a cylinder so that the cured film surface was on the outside, the state of the cured film was determined from the following criteria.
○: Cracks do not occur in a cylinder having a diameter of 1 mm.
Δ: A crack occurs in a cylinder having a diameter of 1 mm, but no crack occurs in a cylinder having a diameter of 4 mm.
X: A crack occurs in a cylinder having a diameter of 4 mm.
＜寸法安定性＞
１０ｃｍ×１０ｃｍにカットした硬化膜層を有するフィルムを、８０℃、６０ＲＨ％の条件下で１時間加熱した後、２５℃に冷却してから、水平な台に硬化膜面を上にして置いたとき、浮き上がった４辺それぞれの高さの平均値を計測し、寸法安定性を下記の基準により判定した。
◎：高さの平均値が２ｍｍ未満である。
○：高さの平均値が２ｍｍ〜５ｍｍ未満である。
△：高さの平均値が５ｍｍ〜９ｍｍ未満である。
×：高さの平均値が９ｍｍ以上である。
<Dimensional stability>
A film having a cured film layer cut to 10 cm × 10 cm was heated at 80 ° C. and 60 RH% for 1 hour, cooled to 25 ° C., and then placed on a horizontal table with the cured film surface facing upward. At that time, the average value of the height of each of the four sides that floated was measured, and the dimensional stability was determined according to the following criteria.
A: The average height is less than 2 mm.
(Circle): The average value of height is 2 mm-less than 5 mm.
(Triangle | delta): The average value of height is 5 mm-less than 9 mm.
X: The average value of height is 9 mm or more.
上表３に示したとおり、本発明の実施例７〜１２の光硬化型樹脂組成物は、一旦付いた傷が経時的に復元して消失する特性を有し、成形加工時における追随性や密着性に優れ（破断伸度）、かつ、寸法安定性や耐屈曲性にも優れていた。とくに、実施例１０〜１２のように、一般式（１）においてＲ２が脂環式炭化水素基、かつ、ｍ及びｎが６〜８の範囲である化合物を用いた場合、破断伸度が特に高い。
他方、上表４の比較例７〜９に示すように、一般式（１）においてｍ及びｎが本発明の範囲を外れる化合物を用いた場合、傷は復元性せずに傷跡が残り、かつ、耐屈曲性や密着性、寸法安定性に劣っていた。また、比較例１０〜１２のように、ウレタン（メタ）アクリレートの構造中にアロファネート基を有しない化合物を用いた場合にも、傷復元性、破断伸度、耐屈曲性及び寸法安定性のいずれかを満足しなかった。
As shown in Table 3 above, the photocurable resin compositions of Examples 7 to 12 of the present invention have the property that the scratches once attached are restored over time and disappeared, Excellent adhesion (breaking elongation) and excellent dimensional stability and bending resistance. In particular, as in Examples 10 to 12, when a compound in which R 2 is an alicyclic hydrocarbon group and m and n are in the range of 6 to 8 in the general formula (1), the elongation at break is Especially high.
On the other hand, as shown in Comparative Examples 7 to 9 in Table 4 above, when a compound in which m and n are outside the scope of the present invention is used in the general formula (1), the scar remains without being recoverable, and In addition, the bending resistance, adhesion, and dimensional stability were inferior. Moreover, even when a compound having no allophanate group is used in the structure of urethane (meth) acrylate as in Comparative Examples 10 to 12, any of flaw resilience, elongation at break, flex resistance and dimensional stability I was not satisfied.
Claims (3)
A photocurable resin composition comprising the allophanate group-containing urethane (meth) acrylate according to claim 1 or 2 and a photopolymerization initiator.
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| JP2005162908A (en) * | 2003-12-03 | 2005-06-23 | Natoko Kk | Active energy ray-curable urethane (meth)acrylate, active energy ray-curable composition containing the same and functional member using them |
| DE102004048873A1 (en) * | 2004-10-07 | 2006-04-13 | Bayer Materialscience Ag | Process for the preparation of low-viscosity allophanates with actinically curable groups |
| DE102005011231A1 (en) * | 2005-03-11 | 2006-09-14 | Bayer Materialscience Ag | Special allophanates containing modified polyurethanes |
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| DE102007040240A1 (en) * | 2007-08-25 | 2009-02-26 | Bayer Materialscience Ag | Process for the preparation of low-viscosity allophanates with actinically curable groups |
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