JP7386896B2 - Photocurable adhesive compositions, photocurable adhesives, polarizing plates and optical equipment - Google Patents
Photocurable adhesive compositions, photocurable adhesives, polarizing plates and optical equipment Download PDFInfo
- Publication number
- JP7386896B2 JP7386896B2 JP2021564394A JP2021564394A JP7386896B2 JP 7386896 B2 JP7386896 B2 JP 7386896B2 JP 2021564394 A JP2021564394 A JP 2021564394A JP 2021564394 A JP2021564394 A JP 2021564394A JP 7386896 B2 JP7386896 B2 JP 7386896B2
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- JP
- Japan
- Prior art keywords
- component
- methacrylate
- acrylate
- group
- photocurable adhesive
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 230000001070 adhesive effect Effects 0.000 title claims description 94
- 239000000853 adhesive Substances 0.000 title claims description 92
- 239000000203 mixture Substances 0.000 title claims description 48
- 230000003287 optical effect Effects 0.000 title claims description 19
- 239000000178 monomer Substances 0.000 claims description 52
- 230000001681 protective effect Effects 0.000 claims description 27
- 150000001875 compounds Chemical class 0.000 claims description 19
- -1 oxetane compound Chemical class 0.000 claims description 18
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 14
- 238000006116 polymerization reaction Methods 0.000 claims description 14
- 125000003700 epoxy group Chemical group 0.000 claims description 13
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- 125000003118 aryl group Chemical group 0.000 claims description 11
- 229920000642 polymer Polymers 0.000 claims description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 9
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 9
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 8
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical group COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 6
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 claims description 6
- 150000002430 hydrocarbons Chemical group 0.000 claims description 5
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 5
- 229920002554 vinyl polymer Polymers 0.000 claims description 5
- 125000006267 biphenyl group Chemical group 0.000 claims description 4
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 claims description 4
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 4
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 claims description 4
- 125000001624 naphthyl group Chemical group 0.000 claims description 4
- 229920005862 polyol Polymers 0.000 claims description 4
- 150000003077 polyols Chemical class 0.000 claims description 4
- UWFRVQVNYNPBEF-UHFFFAOYSA-N 1-(2,4-dimethylphenyl)propan-1-one Chemical compound CCC(=O)C1=CC=C(C)C=C1C UWFRVQVNYNPBEF-UHFFFAOYSA-N 0.000 claims description 3
- LMAUULKNZLEMGN-UHFFFAOYSA-N 1-ethyl-3,5-dimethylbenzene Chemical compound CCC1=CC(C)=CC(C)=C1 LMAUULKNZLEMGN-UHFFFAOYSA-N 0.000 claims description 3
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 claims description 3
- HDPLHDGYGLENEI-UHFFFAOYSA-N 2-[1-(oxiran-2-ylmethoxy)propan-2-yloxymethyl]oxirane Chemical compound C1OC1COC(C)COCC1CO1 HDPLHDGYGLENEI-UHFFFAOYSA-N 0.000 claims description 3
- RQZUWSJHFBOFPI-UHFFFAOYSA-N 2-[1-[1-(oxiran-2-ylmethoxy)propan-2-yloxy]propan-2-yloxymethyl]oxirane Chemical compound C1OC1COC(C)COC(C)COCC1CO1 RQZUWSJHFBOFPI-UHFFFAOYSA-N 0.000 claims description 3
- SEFYJVFBMNOLBK-UHFFFAOYSA-N 2-[2-[2-(oxiran-2-ylmethoxy)ethoxy]ethoxymethyl]oxirane Chemical compound C1OC1COCCOCCOCC1CO1 SEFYJVFBMNOLBK-UHFFFAOYSA-N 0.000 claims description 3
- SHKUUQIDMUMQQK-UHFFFAOYSA-N 2-[4-(oxiran-2-ylmethoxy)butoxymethyl]oxirane Chemical compound C1OC1COCCCCOCC1CO1 SHKUUQIDMUMQQK-UHFFFAOYSA-N 0.000 claims description 3
- WTYYGFLRBWMFRY-UHFFFAOYSA-N 2-[6-(oxiran-2-ylmethoxy)hexoxymethyl]oxirane Chemical compound C1OC1COCCCCCCOCC1CO1 WTYYGFLRBWMFRY-UHFFFAOYSA-N 0.000 claims description 3
- OKRCJGMWAZBSSR-UHFFFAOYSA-N 2-[9-(oxiran-2-ylmethoxy)nonoxymethyl]oxirane Chemical compound C1OC1COCCCCCCCCCOCC1CO1 OKRCJGMWAZBSSR-UHFFFAOYSA-N 0.000 claims description 3
- KUAUJXBLDYVELT-UHFFFAOYSA-N 2-[[2,2-dimethyl-3-(oxiran-2-ylmethoxy)propoxy]methyl]oxirane Chemical compound C1OC1COCC(C)(C)COCC1CO1 KUAUJXBLDYVELT-UHFFFAOYSA-N 0.000 claims description 3
- FSYPIGPPWAJCJG-UHFFFAOYSA-N 2-[[4-(oxiran-2-ylmethoxy)phenoxy]methyl]oxirane Chemical compound C1OC1COC(C=C1)=CC=C1OCC1CO1 FSYPIGPPWAJCJG-UHFFFAOYSA-N 0.000 claims description 3
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 claims description 3
- UUODQIKUTGWMPT-UHFFFAOYSA-N 2-fluoro-5-(trifluoromethyl)pyridine Chemical compound FC1=CC=C(C(F)(F)F)C=N1 UUODQIKUTGWMPT-UHFFFAOYSA-N 0.000 claims description 3
- RUMACXVDVNRZJZ-UHFFFAOYSA-N 2-methylpropyl 2-methylprop-2-enoate Chemical compound CC(C)COC(=O)C(C)=C RUMACXVDVNRZJZ-UHFFFAOYSA-N 0.000 claims description 3
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 claims description 3
- MECNWXGGNCJFQJ-UHFFFAOYSA-N 3-piperidin-1-ylpropane-1,2-diol Chemical compound OCC(O)CN1CCCCC1 MECNWXGGNCJFQJ-UHFFFAOYSA-N 0.000 claims description 3
- NQSLZEHVGKWKAY-UHFFFAOYSA-N 6-methylheptyl 2-methylprop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C(C)=C NQSLZEHVGKWKAY-UHFFFAOYSA-N 0.000 claims description 3
- XFZOHDFQOOTHRH-UHFFFAOYSA-N 7-methyloctyl 2-methylprop-2-enoate Chemical compound CC(C)CCCCCCOC(=O)C(C)=C XFZOHDFQOOTHRH-UHFFFAOYSA-N 0.000 claims description 3
- CUXGDKOCSSIRKK-UHFFFAOYSA-N 7-methyloctyl prop-2-enoate Chemical compound CC(C)CCCCCCOC(=O)C=C CUXGDKOCSSIRKK-UHFFFAOYSA-N 0.000 claims description 3
- GDUZPNKSJOOIDA-UHFFFAOYSA-N 7-oxabicyclo[4.1.0]heptan-4-yl 2-methylprop-2-enoate Chemical compound C1C(OC(=O)C(=C)C)CCC2OC21 GDUZPNKSJOOIDA-UHFFFAOYSA-N 0.000 claims description 3
- VAYCBEIMJNGBGH-UHFFFAOYSA-N 7-oxabicyclo[4.1.0]heptan-4-yl prop-2-enoate Chemical compound C1C(OC(=O)C=C)CCC2OC21 VAYCBEIMJNGBGH-UHFFFAOYSA-N 0.000 claims description 3
- YXALYBMHAYZKAP-UHFFFAOYSA-N 7-oxabicyclo[4.1.0]heptan-4-ylmethyl 7-oxabicyclo[4.1.0]heptane-4-carboxylate Chemical compound C1CC2OC2CC1C(=O)OCC1CC2OC2CC1 YXALYBMHAYZKAP-UHFFFAOYSA-N 0.000 claims description 3
- COCLLEMEIJQBAG-UHFFFAOYSA-N 8-methylnonyl 2-methylprop-2-enoate Chemical compound CC(C)CCCCCCCOC(=O)C(C)=C COCLLEMEIJQBAG-UHFFFAOYSA-N 0.000 claims description 3
- LVGFPWDANALGOY-UHFFFAOYSA-N 8-methylnonyl prop-2-enoate Chemical compound CC(C)CCCCCCCOC(=O)C=C LVGFPWDANALGOY-UHFFFAOYSA-N 0.000 claims description 3
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 3
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 3
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 3
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 3
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 claims description 3
- 239000004793 Polystyrene Substances 0.000 claims description 3
- ORLQHILJRHBSAY-UHFFFAOYSA-N [1-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1(CO)CCCCC1 ORLQHILJRHBSAY-UHFFFAOYSA-N 0.000 claims description 3
- 150000001252 acrylic acid derivatives Chemical class 0.000 claims description 3
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 claims description 3
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 claims description 3
- AOJOEFVRHOZDFN-UHFFFAOYSA-N benzyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC1=CC=CC=C1 AOJOEFVRHOZDFN-UHFFFAOYSA-N 0.000 claims description 3
- GCTPMLUUWLLESL-UHFFFAOYSA-N benzyl prop-2-enoate Chemical compound C=CC(=O)OCC1=CC=CC=C1 GCTPMLUUWLLESL-UHFFFAOYSA-N 0.000 claims description 3
- KBLWLMPSVYBVDK-UHFFFAOYSA-N cyclohexyl prop-2-enoate Chemical compound C=CC(=O)OC1CCCCC1 KBLWLMPSVYBVDK-UHFFFAOYSA-N 0.000 claims description 3
- GTBGXKPAKVYEKJ-UHFFFAOYSA-N decyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCOC(=O)C(C)=C GTBGXKPAKVYEKJ-UHFFFAOYSA-N 0.000 claims description 3
- FWLDHHJLVGRRHD-UHFFFAOYSA-N decyl prop-2-enoate Chemical compound CCCCCCCCCCOC(=O)C=C FWLDHHJLVGRRHD-UHFFFAOYSA-N 0.000 claims description 3
- FKIRSCKRJJUCNI-UHFFFAOYSA-N ethyl 7-bromo-1h-indole-2-carboxylate Chemical compound C1=CC(Br)=C2NC(C(=O)OCC)=CC2=C1 FKIRSCKRJJUCNI-UHFFFAOYSA-N 0.000 claims description 3
- LNCPIMCVTKXXOY-UHFFFAOYSA-N hexyl 2-methylprop-2-enoate Chemical compound CCCCCCOC(=O)C(C)=C LNCPIMCVTKXXOY-UHFFFAOYSA-N 0.000 claims description 3
- LNMQRPPRQDGUDR-UHFFFAOYSA-N hexyl prop-2-enoate Chemical compound CCCCCCOC(=O)C=C LNMQRPPRQDGUDR-UHFFFAOYSA-N 0.000 claims description 3
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical class I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 3
- 239000003999 initiator Substances 0.000 claims description 3
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 claims description 3
- LKEDKQWWISEKSW-UHFFFAOYSA-N nonyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCOC(=O)C(C)=C LKEDKQWWISEKSW-UHFFFAOYSA-N 0.000 claims description 3
- MDYPDLBFDATSCF-UHFFFAOYSA-N nonyl prop-2-enoate Chemical compound CCCCCCCCCOC(=O)C=C MDYPDLBFDATSCF-UHFFFAOYSA-N 0.000 claims description 3
- NZIDBRBFGPQCRY-UHFFFAOYSA-N octyl 2-methylprop-2-enoate Chemical compound CCCCCCCCOC(=O)C(C)=C NZIDBRBFGPQCRY-UHFFFAOYSA-N 0.000 claims description 3
- 229940065472 octyl acrylate Drugs 0.000 claims description 3
- ANISOHQJBAQUQP-UHFFFAOYSA-N octyl prop-2-enoate Chemical compound CCCCCCCCOC(=O)C=C ANISOHQJBAQUQP-UHFFFAOYSA-N 0.000 claims description 3
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 claims description 3
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 3
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 3
- 229920002223 polystyrene Polymers 0.000 claims description 3
- BOQSSGDQNWEFSX-UHFFFAOYSA-N propan-2-yl 2-methylprop-2-enoate Chemical compound CC(C)OC(=O)C(C)=C BOQSSGDQNWEFSX-UHFFFAOYSA-N 0.000 claims description 3
- LYBIZMNPXTXVMV-UHFFFAOYSA-N propan-2-yl prop-2-enoate Chemical compound CC(C)OC(=O)C=C LYBIZMNPXTXVMV-UHFFFAOYSA-N 0.000 claims description 3
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 claims description 3
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 claims description 3
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 claims description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 2
- 238000012663 cationic photopolymerization Methods 0.000 claims description 2
- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-UHFFFAOYSA-N 0.000 claims description 2
- 229920002284 Cellulose triacetate Polymers 0.000 description 12
- 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 12
- 239000010410 layer Substances 0.000 description 10
- 125000000217 alkyl group Chemical group 0.000 description 9
- 229920005989 resin Polymers 0.000 description 9
- 239000011347 resin Substances 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 7
- 239000003505 polymerization initiator Substances 0.000 description 7
- 239000004372 Polyvinyl alcohol Substances 0.000 description 6
- 239000004973 liquid crystal related substance Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 229920002451 polyvinyl alcohol Polymers 0.000 description 6
- 125000002015 acyclic group Chemical group 0.000 description 5
- 125000005119 alkyl cycloalkyl group Chemical group 0.000 description 5
- 125000001316 cycloalkyl alkyl group Chemical group 0.000 description 5
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 5
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 150000002921 oxetanes Chemical class 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 3
- 125000002091 cationic group Chemical group 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
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- 238000000576 coating method Methods 0.000 description 3
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 125000002877 alkyl aryl group Chemical group 0.000 description 2
- 125000004448 alkyl carbonyl group Chemical group 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
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
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- 229910052736 halogen Inorganic materials 0.000 description 2
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- PLDLPVSQYMQDBL-UHFFFAOYSA-N 2-[[3-(oxiran-2-ylmethoxy)-2,2-bis(oxiran-2-ylmethoxymethyl)propoxy]methyl]oxirane Chemical compound C1OC1COCC(COCC1OC1)(COCC1OC1)COCC1CO1 PLDLPVSQYMQDBL-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
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- 238000000149 argon plasma sintering Methods 0.000 description 1
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- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- 125000001153 fluoro group Chemical group F* 0.000 description 1
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- 125000005843 halogen group Chemical group 0.000 description 1
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- 125000004356 hydroxy functional group Chemical group O* 0.000 description 1
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- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 229920000554 ionomer Polymers 0.000 description 1
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- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- AHHWIHXENZJRFG-UHFFFAOYSA-N oxetane Chemical compound C1COC1 AHHWIHXENZJRFG-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920005906 polyester polyol Polymers 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- GBXQPDCOMJJCMJ-UHFFFAOYSA-M trimethyl-[6-(trimethylazaniumyl)hexyl]azanium;bromide Chemical compound [Br-].C[N+](C)(C)CCCCCC[N+](C)(C)C GBXQPDCOMJJCMJ-UHFFFAOYSA-M 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
- C09J4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/062—Copolymers with monomers not covered by C09J133/06
- C09J133/068—Copolymers with monomers not covered by C09J133/06 containing glycidyl groups
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/10—Homopolymers or copolymers of methacrylic acid esters
- C09J133/12—Homopolymers or copolymers of methyl methacrylate
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
Landscapes
- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Nonlinear Science (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Mathematical Physics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Polarising Elements (AREA)
- Polyethers (AREA)
- Epoxy Resins (AREA)
Description
本発明は、光学材料分野に関し、具体的に、光硬化型接着剤組成物、光硬化型接着剤、偏光板及び光学設備に関する。 The present invention relates to the field of optical materials, and specifically relates to a photocurable adhesive composition, a photocurable adhesive, a polarizing plate, and optical equipment.
近年、液晶表示装置は、低消費電力、低電圧動作、軽量(light weight edness)と小型化等の特徴により、様々な表示装置に広く応用されている。液晶表示装置は、例えば液晶セル、偏光板、位相差フィルム、プリズムシート、光拡散フィルム、導光板、光反射シート等の多くの部品を含み得る。そのため、使用するフィルムの数を減少し、又はフィルムやシートを薄くすることにより、生産性と輝度を向上させ、液晶表示装置をより軽量化させるなど、積極的に改善を進めている。 In recent years, liquid crystal display devices have been widely applied to various display devices due to their characteristics such as low power consumption, low voltage operation, light weight edness, and miniaturization. A liquid crystal display device can include many components, such as a liquid crystal cell, a polarizing plate, a retardation film, a prism sheet, a light diffusion film, a light guide plate, and a light reflection sheet. Therefore, efforts are being made to improve productivity and brightness by reducing the number of films used or making films and sheets thinner, and by making liquid crystal display devices lighter.
偏光板は、二色性染料又はヨウ素が染色されたポリビニルアルコール(PVA)樹脂から製造される偏光子と、該偏光子の片側又は両側の表面に積層される保護フィルムとを含み、偏光子と保護フィルムとの間に接着剤を設置する。トリアセチルセルロース(TAC)フィルムは保護フィルムとして広く使用されている。しかし、TACフィルムは、高温と高湿の環境で変形してしまう欠点がある。そのため、TACフィルムの代わりに、各種の材料から製造される保護フィルムが開発され、また、ポリエチレンテレフタレート(PET)フィルム、シクロオレフィンポリマー(COP)フィルム、アクリル系フィルムを単独に使用する、又はこれらのフィルムの組み合わせの構想が次々と提案されている。 A polarizing plate includes a polarizer manufactured from polyvinyl alcohol (PVA) resin dyed with a dichroic dye or iodine, and a protective film laminated on one or both surfaces of the polarizer. Install adhesive between the protective film. Triacetyl cellulose (TAC) films are widely used as protective films. However, the TAC film has the drawback of being deformed in high temperature and high humidity environments. Therefore, instead of TAC film, protective films manufactured from various materials have been developed, and polyethylene terephthalate (PET) film, cycloolefin polymer (COP) film, and acrylic film are used alone or in combination with these films. Concepts for film combinations are being proposed one after another.
アクリル系接着剤、ポリウレタン樹脂溶液とポリイソシアネート樹脂溶液との混合により得られる乾式積層接着剤、スチレン・ブタジエン・ゴム接着剤、エポキシ接着剤、ポリビニルアルコール接着剤、ポリウレタン接着剤、ポリエステルイオノマー型ポリウレタン樹脂とグリシジル基を有する化合物を含む接着剤、熱硬化型接着剤等の接着剤が絶えず開発されている。しかし、これらの接着剤が異なるフィルムに対する接着力は問題として重点的に考慮すべき要因であり、また組成物の粘度、製造できる厚さ、耐酸性、耐アルカリ性、耐熱性も考慮すべき要因である。 Acrylic adhesives, dry lamination adhesives obtained by mixing polyurethane resin solutions and polyisocyanate resin solutions, styrene/butadiene/rubber adhesives, epoxy adhesives, polyvinyl alcohol adhesives, polyurethane adhesives, polyester ionomer type polyurethane resins Adhesives such as adhesives and thermosetting adhesives containing compounds having glycidyl and glycidyl groups are constantly being developed. However, the adhesion of these adhesives to different films is a factor that should be taken into consideration, as well as the viscosity of the composition, the thickness that can be produced, acid resistance, alkali resistance, and heat resistance. be.
そのため、各種のオキセタン類モノマーが開発され、これらのオキセタン類化合物は、一般的に低粘度、弱毒性、重合速度が速く、熱安定性、及び優れた機械特性などの特性を備え、カチオン硬化システムに応用されると、重合速度を向上させ、硬化後の生成物の性能を向上させることができる。しかしながら、該種類のモノマーは、実際の応用中に、市販の化合物の種類が少なく、硬化速度や硬度等の総合的な特性のバランスが取りにくい方面で依然として明らかな欠点があり、特に偏光板に応用される場合、オキセタン類化合物の導入後にシステム全体の接着性が問題となり、さらに最適化する必要がある。 Therefore, various oxetane monomers have been developed, and these oxetane compounds generally have properties such as low viscosity, weak toxicity, fast polymerization rate, thermal stability, and excellent mechanical properties, and are suitable for cationic curing systems. When applied, it can increase the polymerization rate and improve the performance of the cured product. However, this type of monomer still has obvious shortcomings in practical applications in that there are only a few types of commercially available compounds and it is difficult to balance the overall properties such as curing speed and hardness, especially in polarizing plates. In applications, the adhesion of the entire system becomes a problem after the introduction of oxetanes and requires further optimization.
本発明は、光硬化型接着剤組成物、光硬化型接着剤、偏光板及び光学設備を提供し、従来技術における光硬化型接着剤の接着性が不十分な問題を解決することを目的とする。 The present invention provides a photocurable adhesive composition, a photocurable adhesive, a polarizing plate, and an optical equipment, and aims to solve the problem of insufficient adhesion of photocurable adhesives in the prior art. do.
前記目的を達成するために、本発明の一つの局面によれば、成分(A)、成分(B)と成分(C)を含む光硬化型接着剤組成物が提供され、前記成分(A)は、式(aa)で示される構造を含有するオキセタン化合物であり、
[式(aa)中、Rがフェニル基、ビフェニル基、ナフチル基を表す。0≦n≦4である。]
前記成分(B)は、エポキシ基を有する化合物であり、
前記成分(C)は、光カチオン重合開始剤である。
In order to achieve the above object, one aspect of the present invention provides a photocurable adhesive composition comprising a component (A), a component (B), and a component (C), wherein the component (A) is an oxetane compound containing a structure represented by formula (aa),
[In formula (aa), R represents a phenyl group, a biphenyl group, or a naphthyl group. 0≦n≦4. ]
The component (B) is a compound having an epoxy group,
The component (C) is a photocationic polymerization initiator.
さらに、前記成分(A)は、
である。
Furthermore, the component (A) is
It is.
さらに、前記成分(B)は、炭素数が2~10であるポリオールのポリグリシジルエーテルである成分(B1)と、エポキシ基を有するポリマーである成分(B2)とを含む。 Further, the component (B) includes a component (B1) which is a polyglycidyl ether of a polyol having 2 to 10 carbon atoms, and a component (B2) which is a polymer having an epoxy group.
さらに、前記成分(B1)は、エチレングリコールジグリシジルエーテル、プロピレングリコールジグリシジルエーテル、1,4-ブタンジオールジグリシジルエーテル、ネオペンチルグリコールジグリシジルエーテル、1,6-ヘキサンジオールジグリシジルエーテル、ジメチロールシクロヘキサンジグリシジルエーテル、1,9-ノナンジオールジグリシジルエーテル、ジエチレングリコールジグリシジルエーテル、ジプロピレングリコールジグリシジルエーテル、ハイドロキノンジグリシジルエーテル、レゾルシノールジグリシジルエーテル、トリメチロールプロパントリグリシジルエーテル、ペンタエリスリトールトリ又はテトラグリシジルエーテル、及びイソシアヌル酸のエチレンオキシド付加物のジ又はトリグリシジルエーテルからなる群より選ばれるいずれか一種又は多種である。 Furthermore, the component (B1) includes ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, dimethylol Cyclohexane diglycidyl ether, 1,9-nonanediol diglycidyl ether, diethylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, hydroquinone diglycidyl ether, resorcinol diglycidyl ether, trimethylolpropane triglycidyl ether, pentaerythritol tri- or tetraglycidyl It is one or more selected from the group consisting of ethers and di- or triglycidyl ethers of ethylene oxide adducts of isocyanuric acid.
さらに、前記成分(B2)は、Tgが20℃以上であり、Mwが1000~30000、好ましくは3000~20000、さらに好ましくは5000~15000であり、前記Mwは、GPCで測定された分子量をポリスチレン換算して得られた重量平均分子量である。 Furthermore, the component (B2) has a Tg of 20° C. or higher and a Mw of 1,000 to 30,000, preferably 3,000 to 20,000, more preferably 5,000 to 15,000, and the Mw is the molecular weight measured by GPC of polystyrene. This is the weight average molecular weight obtained by conversion.
前記成分(B2)は、モノマー(b1)と、モノマー(b2)と、任意に使用するモノマー(b3)とから重合により得られる。前記モノマー(b1)は、エポキシ基及びエチレン性不飽和基を有する化合物であり、前記エチレン性不飽和基は、ビニル基又はアクリロイル基であり、好ましくは、前記モノマー(b1)は、グリシジルアクリレート、グリシジルメタクリレート、3,4-エポキシシクロヘキシルアクリレート、又は3,4-エポキシシクロヘキシルメタクリレートである。前記モノマー(b2)は、炭素数1~10個の炭化水素基を有する単官能性メタクリレートであり、好ましくは、前記モノマー(b2)は、メチルメタクリレート、エチルメタクリレート、プロピルメタクリレート、イソプロピルメタクリレート、ブチルメタクリレート、sec-ブチルメタクリレート、tert-ブチルメタクリレート、イソブチルメタクリレート、ヘキシルメタクリレート、シクロヘキシルメタクリレート、2-エチルへキシルメタクリレート、オクチルメタクリレート、イソオクチルメタクリレート、ノニルメタクリレート、イソノニルメタクリレート、デシルメタクリレート、イソデシルメタクリレート、及びベンジルメタクリレートからなる群より選ばれるいずれか一種又は多種である。前記モノマー(b3)は、モノマー(b1)とは異なるアルケニル化合物であり、好ましくは、前記モノマー(b3)は、芳香族基含有ビニル化合物、単官能性アクリレート、アクリロニトリル、メタクリロニトリル、アクリルアミド、及びメタクリルアミドからなる群より選ばれるいずれか一種であり、前記芳香族基含有ビニル化合物はスチレン又はα-メチルスチレンであり、前記単官能性アクリレートはメチルアクリレート、エチルアクリレート、プロピルアクリレート、イソプロピルアクリレート、ブチルアクリレート、sec-ブチルアクリレート、tert-ブチルアクリレート、イソブチルアクリレート、ヘキシルアクリレート、シクロヘキシルアクリレート、2-エチルヘキシルアクリレート、オクチルアクリレート、イソオクチルアクリレート、ノニルアクリレート、イソノニルアクリレート、デシルアクリレート、イソデシルアクリレート、ベンジルアクリレートからなる群より選ばれるいずれか一種又は多種である。 The component (B2) is obtained by polymerization from monomer (b1), monomer (b2), and optionally used monomer (b3). The monomer (b1) is a compound having an epoxy group and an ethylenically unsaturated group, and the ethylenically unsaturated group is a vinyl group or an acryloyl group. Preferably, the monomer (b1) is a glycidyl acrylate, Glycidyl methacrylate, 3,4-epoxycyclohexyl acrylate, or 3,4-epoxycyclohexyl methacrylate. The monomer (b2) is a monofunctional methacrylate having a hydrocarbon group having 1 to 10 carbon atoms, and preferably the monomer (b2) is methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, butyl methacrylate. , sec-butyl methacrylate, tert-butyl methacrylate, isobutyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, 2-ethylhexyl methacrylate, octyl methacrylate, isooctyl methacrylate, nonyl methacrylate, isononyl methacrylate, decyl methacrylate, isodecyl methacrylate, and benzyl One or more types selected from the group consisting of methacrylates. The monomer (b3) is an alkenyl compound different from the monomer (b1), and preferably the monomer (b3) is an aromatic group-containing vinyl compound, a monofunctional acrylate, acrylonitrile, methacrylonitrile, acrylamide, and one selected from the group consisting of methacrylamide, the aromatic group-containing vinyl compound is styrene or α-methylstyrene, and the monofunctional acrylate is methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl From acrylate, sec-butyl acrylate, tert-butyl acrylate, isobutyl acrylate, hexyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, isooctyl acrylate, nonyl acrylate, isononyl acrylate, decyl acrylate, isodecyl acrylate, benzyl acrylate One or more types selected from the group consisting of:
さらに、前記成分(B2)は、重量%で、前記モノマー(b1)を10~60重量%、前記モノマー(b2)を10~70重量%、及び前記モノマー(b3)を0~60重量%含む。 Furthermore, the component (B2) contains, in weight percent, 10 to 60% by weight of the monomer (b1), 10 to 70% by weight of the monomer (b2), and 0 to 60% by weight of the monomer (b3). .
さらに、前記成分(C)は、ヨードニウム塩、スルホニウム塩、アリールフェロセン塩からなる群より選ばれる一種又は多種の組み合わせである。 Furthermore, the component (C) is one type or a combination of various types selected from the group consisting of iodonium salts, sulfonium salts, and arylferrocene salts.
さらに、前記光硬化型接着剤組成物を基準とする時、前記成分(A)の含有量は25~55重量%、好ましくは25~45重量%であり、前記成分(B1)の含有量は10~45重量%であり、前記成分(B2)の含有量は20~80重量%であり、前記成分(C)の含有量は3~5重量%である。 Furthermore, when based on the photocurable adhesive composition, the content of the component (A) is 25 to 55% by weight, preferably 25 to 45% by weight, and the content of the component (B1) is The content of component (B2) is 20 to 80% by weight, and the content of component (C) is 3 to 5% by weight.
本発明の他の局面によれば、光硬化型接着剤組成物から重合により得られる光硬化型接着剤を提供する。該光硬化型接着剤組成物は、前記光硬化型接着剤組成物のいずれか一種である。 According to another aspect of the present invention, there is provided a photocurable adhesive obtained by polymerization from a photocurable adhesive composition. The photocurable adhesive composition is any one of the photocurable adhesive compositions described above.
本発明の他の局面によれば、偏光子と、接着剤を介して前記偏光子に接着された保護フィルムとを含む偏光板を提供する。該接着剤は、前記光硬化型接着剤である。 According to another aspect of the present invention, there is provided a polarizing plate including a polarizer and a protective film adhered to the polarizer via an adhesive. The adhesive is the photocurable adhesive described above.
本発明の他の局面によれば、偏光板を含む光学設備を提供する。該偏光板は前記偏光板である。 According to another aspect of the invention, an optical equipment including a polarizing plate is provided. The polarizing plate is the polarizing plate described above.
本発明の技術案によれば、特定のオキキタン化合物を選択して、エポキシ基を有する化合物及び光カチオン重合開始剤と配合して使用することにより、得られた光硬化型接着剤の付着力、硬化性、及び偏光子と保護フィルムに対する接着性が改善される。 According to the technical proposal of the present invention, by selecting a specific oxiquitane compound and using it in combination with a compound having an epoxy group and a photocationic polymerization initiator, the adhesive strength of the resulting photocurable adhesive, Curability and adhesion to polarizers and protective films are improved.
なお、矛盾がなければ、本発明における実施例及び実施例における特徴は、互いに組み合わせることができる。以下、実施例により、本発明を詳しく説明する。 Note that, unless there is a contradiction, the embodiments of the present invention and the features in the embodiments can be combined with each other. Hereinafter, the present invention will be explained in detail with reference to Examples.
本発明の背景技術に分析されるように、従来技術におけるオキセタン類化合物は、一般的に低粘度、弱毒性、重合速度が速く、熱安定性、及び優れた機械特性などの特性を備えているが、実際の応用中に、硬化性における硬化速度と硬度とのバランスが取りにくい方面では依然として問題がある。特に偏光板に応用される場合、オキセタン類化合物の導入後に接着剤の全体的な接着効果が理想的ではない。この問題を解決するために、本発明は、光硬化型接着剤組成物、光硬化型接着剤、偏光板及び光学設備を提供する。 As analyzed in the background art of the present invention, oxetane compounds in the prior art generally have characteristics such as low viscosity, weak toxicity, fast polymerization rate, thermal stability, and excellent mechanical properties. However, during actual application, there is still a problem in that it is difficult to balance curing speed and hardness. Especially when applied to polarizing plates, the overall adhesion effect of the adhesive is not ideal after the introduction of oxetane compounds. In order to solve this problem, the present invention provides a photocurable adhesive composition, a photocurable adhesive, a polarizing plate, and optical equipment.
本発明の一つの典型的な実施形態では、成分(A)、成分(B)と成分(C)を含む光硬化型接着剤組成物が提供され、成分(A)は、式(aa)で示される構造を含有するオキセタン化合物であり、
[式(aa)中、Rがフェニル基、ビフェニル基、ナフチル基を表す。0≦n≦4である。]
成分(B)は、エポキシ基を有する化合物であり、成分(C)は、光カチオン重合開始剤である。
In one exemplary embodiment of the present invention, there is provided a photocurable adhesive composition comprising component (A), component (B) and component (C), wherein component (A) has the formula (aa): An oxetane compound containing the structure shown,
[In formula (aa), R represents a phenyl group, a biphenyl group, or a naphthyl group. 0≦n≦4. ]
Component (B) is a compound having an epoxy group, and component (C) is a cationic photopolymerization initiator.
本発明は、特定のオキキタン化合物を選択して、エポキシ基を有する化合物及び光カチオン重合開始剤と配合して使用することにより、得られた光硬化型接着剤の付着力、硬化性、及び偏光子と保護フィルムに対する接着性が改善される。 The present invention improves the adhesion, curability, and polarization of the resulting photocurable adhesive by selecting a specific oxiquitane compound and using it in combination with a compound having an epoxy group and a photocationic polymerization initiator. Improved adhesion to the child and protective film.
試験により検証した結果、前記成分(A)は、
である場合、効果がより明らかである。
As a result of testing, the component (A) is:
, the effect is more obvious.
本発明の一つの実施形態では、前記成分(B)は、成分(B1)と成分(B2)を含む。成分(B1)は、炭素数が2~10であるポリオールのポリグリシジルエーテルであり、成分(B2)は、エポキシ基を有するポリマーである。前記二種のエポキシ基含有化合物を配合し、更にオキセタン化合物と配合することにより、光硬化型接着剤の接着性をさらに向上させる。 In one embodiment of the present invention, the component (B) includes component (B1) and component (B2). Component (B1) is a polyglycidyl ether of a polyol having 2 to 10 carbon atoms, and component (B2) is a polymer having an epoxy group. By blending the above two types of epoxy group-containing compounds and further blending with an oxetane compound, the adhesiveness of the photocurable adhesive is further improved.
好ましくは、前記成分(B1)は、エチレングリコールジグリシジルエーテル、プロピレングリコールジグリシジルエーテル、1,4-ブタンジオールジグリシジルエーテル、ネオペンチルグリコールジグリシジルエーテル、1,6-ヘキサンジオールジグリシジルエーテル、ジメチロールシクロヘキサンジグリシジルエーテル、1,9-ノナンジオールジグリシジルエーテル、ジエチレングリコールジグリシジルエーテル、ジプロピレングリコールジグリシジルエーテル、ハイドロキノンジグリシジルエーテル、レゾルシノールジグリシジルエーテル、トリメチロールプロパントリグリシジルエーテル、ペンタエリスリトールトリ又はテトラグリシジルエーテル、及びイソシアヌル酸のエチレンオキシド付加物のジ又はトリグリシジルエーテルからなる群より選ばれるいずれか一種又は多種である。 Preferably, the component (B1) is ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, di- Methylolcyclohexane diglycidyl ether, 1,9-nonanediol diglycidyl ether, diethylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, hydroquinone diglycidyl ether, resorcinol diglycidyl ether, trimethylolpropane triglycidyl ether, pentaerythritol tri- or tetra One or more types selected from the group consisting of glycidyl ether and di- or triglycidyl ether of an ethylene oxide adduct of isocyanuric acid.
光硬化型接着剤の塗布の施工性を向上させ、また接着性を確保するためには、前記成分(B2)は、Tgが20℃以上(従来技術の一般的な測定方法と同様、すなわち、示差走査熱量計(DSC)を使用して、10℃/分の加熱速度で測定された値)であることが好ましく、Mwが1000~30000、好ましくは3000~20000、さらに好ましくは5000~15000である。ここで、Mwとは、GPCで測定された分子量をポリスチレン換算して得られる重量平均分子量である。前記成分(B2)のMwが1000未満である場合、偏光子と保護フィルムとの接着力を向上させる効果は明らかではなく、Mwが30000を超えると、塗布性が低下し、施工の困難性が増す。 In order to improve the workability of applying the photocurable adhesive and to ensure adhesiveness, the component (B2) must have a Tg of 20° C. or higher (same as the general measurement method of the prior art, that is, The value measured using a differential scanning calorimeter (DSC) at a heating rate of 10° C./min), and the Mw is preferably 1000 to 30000, preferably 3000 to 20000, more preferably 5000 to 15000. be. Here, Mw is the weight average molecular weight obtained by converting the molecular weight measured by GPC into polystyrene. When the Mw of the component (B2) is less than 1,000, the effect of improving the adhesive force between the polarizer and the protective film is not obvious, and when the Mw exceeds 30,000, the applicability decreases, making installation difficult. Increase.
本発明の一つの実施形態では、前記成分(B2)は、モノマー(b1)と、モノマー(b2)と、任意に使用するモノマー(b3)とから重合により得られる。成分(B2)は、低Mwのポリマーである。通常の重合法によりこのようなポリマーを製造することが望まれる場合、通常、連鎖移動剤及び/又は重合開始剤を増す必要がある。大量の連鎖移動剤を使用してポリマーを形成する場合、組成物のカチオン硬化性及び/又は接着力が低下しやすくなり、また、組成物の保存安定性も低下しやすくなる。そのため、好ましくは、モノマー(b1)は、エポキシ基及びエチレン性不飽和基を有する化合物であり、エチレン性不飽和基は、ビニル基又はアクリロイル基である。好ましくは、モノマー(b1)は、グリシジルアクリレート、グリシジルメタクリレート、3,4-エポキシシクロヘキシルアクリレート、又は3,4-エポキシシクロヘキシルメタクリレートである。モノマー(b2)は、炭素数1~10個の炭化水素基を有する単官能性メタクリレートであり、好ましくは、メチルメタクリレート、エチルメタクリレート、プロピルメタクリレート、イソプロピルメタクリレート、ブチルメタクリレート、sec-ブチルメタクリレート、tert-ブチルメタクリレート、イソブチルメタクリレート、ヘキシルメタクリレート、シクロヘキシルメタクリレート、2-エチルへキシルメタクリレート、オクチルメタクリレート、イソオクチルメタクリレート、ノニルメタクリレート、イソノニルメタクリレート、デシルメタクリレート、イソデシルメタクリレート、及びベンジルメタクリレートからなる群より選ばれるいずれか一種又は多種である。モノマー(b3)は、モノマー(b1)とは異なるアルケニル化合物であり、好ましくは、芳香族基含有ビニル化合物、単官能性アクリレート、アクリロニトリル、メタクリロニトリル、アクリルアミド、及びメタクリルアミドからなる群より選ばれるいずれか一種である。芳香族基含有ビニル化合物は、スチレン又はα-メチルスチレンである。単官能性アクリレートは、メチルアクリレート、エチルアクリレート、プロピルアクリレート、イソプロピルアクリレート、ブチルアクリレート、sec-ブチルアクリレート、tert-ブチルアクリレート、イソブチルアクリレート、ヘキシルアクリレート、シクロヘキシルアクリレート、2-エチルヘキシルアクリレート、オクチルアクリレート、イソオクチルアクリレート、ノニルアクリレート、イソノニルアクリレート、デシルアクリレート、イソデシルアクリレート、ベンジルアクリレートからなる群より選ばれるいずれか一種又は多種である。これにより、大量の連鎖移動剤及び/又は重合開始剤を採用する高温重合による問題を回避することができる。 In one embodiment of the invention, component (B2) is obtained by polymerization from monomer (b1), monomer (b2) and optionally used monomer (b3). Component (B2) is a low Mw polymer. If it is desired to make such polymers by conventional polymerization methods, it is usually necessary to increase the chain transfer agent and/or polymerization initiator. When forming a polymer using a large amount of chain transfer agent, the cationic curability and/or adhesive strength of the composition tends to decrease, and the storage stability of the composition also tends to decrease. Therefore, preferably, the monomer (b1) is a compound having an epoxy group and an ethylenically unsaturated group, and the ethylenically unsaturated group is a vinyl group or an acryloyl group. Preferably, monomer (b1) is glycidyl acrylate, glycidyl methacrylate, 3,4-epoxycyclohexyl acrylate, or 3,4-epoxycyclohexyl methacrylate. Monomer (b2) is a monofunctional methacrylate having a hydrocarbon group having 1 to 10 carbon atoms, preferably methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, sec-butyl methacrylate, tert- Any member selected from the group consisting of butyl methacrylate, isobutyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, 2-ethylhexyl methacrylate, octyl methacrylate, isooctyl methacrylate, nonyl methacrylate, isononyl methacrylate, decyl methacrylate, isodecyl methacrylate, and benzyl methacrylate. or one or more types. Monomer (b3) is an alkenyl compound different from monomer (b1), and is preferably selected from the group consisting of aromatic group-containing vinyl compounds, monofunctional acrylates, acrylonitrile, methacrylonitrile, acrylamide, and methacrylamide. Either one is one of them. The aromatic group-containing vinyl compound is styrene or α-methylstyrene. Monofunctional acrylates include methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, sec-butyl acrylate, tert-butyl acrylate, isobutyl acrylate, hexyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, isooctyl It is one or more selected from the group consisting of acrylate, nonyl acrylate, isononyl acrylate, decyl acrylate, isodecyl acrylate, and benzyl acrylate. This avoids problems with high temperature polymerizations that employ large amounts of chain transfer agents and/or polymerization initiators.
前記モノマー(b1)とモノマー(b2)は必須のモノマー単位として、カチオン硬化性化合物である成分(B1)及び成分(A)と共重合する。また前記モノマー(b1)は、特に好ましくは、グリシジルメタクリレートであり、前記モノマー(b2)は、特に好ましくは、メチルメタクリレート、エチルメタクリレート、シクロヘキシルメタクリレート及びベンジルメタクリレートからなる群より選ばれる一種又は多種である。反応性とシステム粘度等の調整の観点から、モノマー(b3)をさらに添加することができる。 The monomer (b1) and monomer (b2) are copolymerized as essential monomer units with component (B1) and component (A), which are cationic curable compounds. Furthermore, the monomer (b1) is particularly preferably glycidyl methacrylate, and the monomer (b2) is particularly preferably one or more selected from the group consisting of methyl methacrylate, ethyl methacrylate, cyclohexyl methacrylate, and benzyl methacrylate. . From the viewpoint of adjusting reactivity, system viscosity, etc., monomer (b3) can be further added.
好ましくは、重量%で、成分(B2)は、モノマー(b1)を10~60重量%、モノマー(b2)を10~70重量%とモノマー(b3)を0~60重量%含む。モノマー(b3)がスチレンを含む場合、成分(B2)中、スチレンの含有量は5~45重量%、好ましくは10~40重量%である。モノマー(b3)が単官能性アクリレートを含む場合、成分(B2)中、単官能性アクリレートの含有量は1~30重量%、好ましくは5~25重量%である。好ましくは、成分(B2)は、モノマー(b2)として、含有量が10~70重量%であるメチルメタクリレートを含み、且つモノマー(b3)として、含有量が1~50重量%であるスチレンを含む。好ましくは、成分(B2)は、モノマー(b1)として、含有量が10~60重量%であるグリシジルメタクリレート、モノマー(b2)として、含有量が10~70重量%であるメチルメタクリレート、及びモノマー(b3)として、含有量が1~30重量%である炭素数1~10個の炭化水素基を有する単官能性アクリレートを含む。前記スチレンや単官能性アクリレートの使用量の調整で、組成物を含む反応系の活性、粘度、体積収縮率、及び形成された接着剤の安定性をさらに調整する。 Preferably, in % by weight, component (B2) comprises 10 to 60 % by weight of monomer (b1), 10 to 70 % by weight of monomer (b2) and 0 to 60 % by weight of monomer (b3). When monomer (b3) contains styrene, the content of styrene in component (B2) is 5 to 45% by weight, preferably 10 to 40% by weight. When the monomer (b3) contains a monofunctional acrylate, the content of the monofunctional acrylate in component (B2) is 1 to 30% by weight, preferably 5 to 25% by weight. Preferably, component (B2) contains methyl methacrylate as monomer (b2) with a content of 10 to 70% by weight, and contains styrene as monomer (b3) with a content of 1 to 50% by weight. . Preferably, component (B2) comprises glycidyl methacrylate having a content of 10 to 60% by weight as monomer (b1), methyl methacrylate having a content of 10 to 70% by weight as monomer (b2), and monomer (b2) having a content of 10 to 70% by weight. b3) contains a monofunctional acrylate having a hydrocarbon group having 1 to 10 carbon atoms in a content of 1 to 30% by weight. By adjusting the amount of styrene or monofunctional acrylate used, the activity, viscosity, volume shrinkage rate of the reaction system containing the composition, and stability of the formed adhesive can be further adjusted.
本発明の一つの実施形態では、前記成分(C)は、ヨードニウム塩、スルホニウム塩、アリールフェロセン塩からなる群より選ばれる一種又は多種の組み合わせである。好ましくは、前記成分(C)は、以下の式(I)及び/又は(II)に示される構造を有する化合物である。
[ここで、
R1とR2は、それぞれ独立的に水素、C1-C20の直鎖又は分岐アルキル基、C4-C20のシクロアルキルアルキル基又はアルキルシクロアルキル基を表し、また、これらの基における非環式-CH2-は、-O-、-S-又は1,4-フェニレン基で置換されてもよい。
R3とR4は、それぞれ独立的に水素、C1-C20の直鎖又は分岐アルキル基、C4-C20のシクロアルキルアルキル基又はアルキルシクロアルキル基、C6-C20の置換又は非置換アリール基を表し、また、これらの基における非環式-CH2-は、-O-、-S-又は1,4-フェニレン基で置換されてもよい。
R5は、C6-C20の置換又は非置換アリール基、C6-C20の置換又は非置換アルキルアリール基、C1-C20の直鎖又は分岐アルキル基、C4-C20のシクロアルキルアルキル基又はアルキルシクロアルキル基、置換又は非置換のフェニルチオフェニル基を表し、また、これらの基における非環式-CH2-は、カルボニル基、-O-、-S-又は1,4-フェニレン基で置換されてもよい。
R6とR7は、それぞれ独立的にアルキル基、ヒドロキシ基、アルコキシ基、アルキルカルボニル基、アリールカルボニル基、アルコキシカルボニル基、アリールオキシカルボニル基、アリールチオカルボニル基、アシルオキシ基、アリールチオ基、アリール基、複素環式炭化水素基、アリールオキシ基、アルキルスルフィニル基、アリールスルフィニル基、アルキルスルホニル基、アリールスルホニル基、ヒドロキシ(ポリ)アルキレンオキシ基、置換してもよいアミノ基、シアノ基、ニトロ基又はハロゲン原子を表す。
m1、m2は、それぞれ独立的に、R6とR7の個数を表し、0、1、2、3、又は4から選ばれる。
X-は、それぞれ独立的に、M-、ClO4
-、CN-、HSO4
-、NO3
-、CF3COO-、(BM4) -、(SbM6) -、(AsM6) -、(PM6) -、Al[OC(CF3)3]4
-、スルホン酸イオン、B(C6M5)4
-、又は[(Rf)bPF6-b] -を表す。その中、Mはハロゲンであり、Rfはそれぞれ独立的に水素原子の80%以上がフッ素原子に置換されたアルキル基を表し、bは1~5の整数を表す。]
In one embodiment of the present invention, the component (C) is one or a combination of various selected from the group consisting of iodonium salts, sulfonium salts, and arylferrocene salts. Preferably, the component (C) is a compound having a structure represented by the following formula (I) and/or (II).
[here,
R 1 and R 2 each independently represent hydrogen, a C 1 -C 20 linear or branched alkyl group, a C 4 -C 20 cycloalkylalkyl group or an alkylcycloalkyl group, and Acyclic -CH 2 - may be substituted with -O-, -S- or 1,4-phenylene group.
R 3 and R 4 are each independently hydrogen, a C 1 -C 20 linear or branched alkyl group, a C 4 -C 20 cycloalkylalkyl group or an alkylcycloalkyl group, a C 6 -C 20 substituted or It represents an unsubstituted aryl group, and the acyclic -CH 2 - in these groups may be substituted with -O-, -S- or 1,4-phenylene group.
R 5 is a C 6 -C 20 substituted or unsubstituted aryl group, a C 6 -C 20 substituted or unsubstituted alkylaryl group, a C 1 -C 20 linear or branched alkyl group, a C 4 -C 20 It represents a cycloalkylalkyl group or an alkylcycloalkyl group, a substituted or unsubstituted phenylthiophenyl group, and the acyclic -CH 2 - in these groups represents a carbonyl group, -O-, -S- or 1, It may be substituted with a 4-phenylene group.
R 6 and R 7 each independently represent an alkyl group, a hydroxy group, an alkoxy group, an alkylcarbonyl group, an arylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an arylthiocarbonyl group, an acyloxy group, an arylthio group, an aryl group , heterocyclic hydrocarbon group, aryloxy group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, hydroxy(poly)alkyleneoxy group, optionally substituted amino group, cyano group, nitro group, or Represents a halogen atom.
m1 and m2 each independently represent the number of R 6 and R 7 and are selected from 0, 1, 2, 3, or 4.
X − is each independently M − , ClO 4 − , CN − , HSO 4 − , NO 3 − , CF 3 COO − , (BM 4 ) − , (SbM 6 ) − , (AsM 6 ) − , (PM 6 ) − , Al[OC(CF 3 ) 3 ] 4 − , sulfonic acid ion, B(C 6 M 5 ) 4 − , or [(Rf) b PF 6-b ] − . Among them, M is a halogen, Rf each independently represents an alkyl group in which 80% or more of hydrogen atoms are substituted with fluorine atoms, and b represents an integer of 1 to 5. ]
前記物質を光カチオン重合開始剤として採用することにより、光硬化型接着剤組成物の硬化速率を高めることができる。 By employing the above substance as a photocationic polymerization initiator, the curing rate of the photocurable adhesive composition can be increased.
好ましい構造として、式(I)と(II)に示される化合物において、R1とR2は、それぞれ独立的に水素、C1-C12の直鎖又は分岐アルキル基、C4-C10のシクロアルキルアルキル基又はアルキルシクロアルキル基を表し、また、これらの基における非環式-CH2-は-O-で置換されてもよく;R3とR4は、それぞれ独立的に水素、C1-C10の直鎖又は分岐アルキル基、C4-C10のシクロアルキルアルキル基又はアルキルシクロアルキル基、C6-C12の置換又は非置換アリール基を表し、また、これらの基における非環式-CH2-は-O-、-S-又は1,4-フェニレン基で置換されてもよく;R5はC6-C10の置換又は非置換アリール基、C6-C10の置換又は非置換アルキルアリール基、置換又は非置換のフェニルチオフェニル基を表し、また、これらの基における非環式-CH2-はカルボニル基、-O-、-S-又は1,4-フェニレン基で置換されてもよく;R6とR7は、C1-C10の直鎖又は分岐アルキル基、C1-C10の直鎖又は分岐アルコキシ基、C1-C10のアルキルカルボニル基、及びハロゲンを表す。 As a preferred structure, in the compounds represented by formulas (I) and (II), R 1 and R 2 each independently represent hydrogen, a C 1 -C 12 linear or branched alkyl group, or a C 4 -C 10 alkyl group. Represents a cycloalkylalkyl group or an alkylcycloalkyl group, and the acyclic -CH 2 - in these groups may be substituted with -O-; R 3 and R 4 each independently represent hydrogen, C 1 -C 10 straight chain or branched alkyl group, C 4 -C 10 cycloalkylalkyl group or alkylcycloalkyl group, C 6 -C 12 substituted or unsubstituted aryl group; Cyclic -CH 2 - may be substituted with -O-, -S- or 1,4-phenylene; R 5 is a C 6 -C 10 substituted or unsubstituted aryl group, a C 6 -C 10 It represents a substituted or unsubstituted alkylaryl group, a substituted or unsubstituted phenylthiophenyl group, and the acyclic -CH 2 - in these groups represents a carbonyl group, -O-, -S- or 1,4-phenylene. may be substituted with a group; R 6 and R 7 are a C 1 -C 10 straight chain or branched alkyl group, a C 1 -C 10 straight chain or branched alkoxy group, a C 1 -C 10 alkylcarbonyl group , and represents a halogen.
同類の構造を有する市販の光カチオン開始剤も、本発明の成分(C)として用いられる。例えば(但し、これらに限らない)PAG20001、PAG20001s、PAG20002、PAG20002s、PAG30201、PAG30101(上記は、いずれも会社Trnoloy製)、Irgacure250(BASF製)等が挙げられる。 Commercially available photocationic initiators with similar structures can also be used as component (C) of the present invention. Examples include (but are not limited to) PAG20001, PAG20001s, PAG20002, PAG20002s, PAG30201, PAG30101 (all of the above are manufactured by the company Trnoloy), Irgacure 250 (manufactured by BASF), and the like.
本発明の光硬化型接着剤組成物において、各成分の使用量として、従来技術中の相応的な成分の使用量を参考することできる。好ましくは、光硬化型接着剤組成物を基準とする時、成分(A)の含有量は25~60重量%、好ましくは25~55重量%、さらに好ましくは25~45重量%であり;成分(B1)の含有量は10~45重量%、好ましくは10~35重量%であり;成分(B2)の含有量は15~80重量%、好ましくは20~80重量%、さらに好ましくは15~35重量%であり;成分(C)の含有量は3~5重量%、好ましくは5重量%である。 In the photocurable adhesive composition of the present invention, as the usage amount of each component, the usage amount of the corresponding component in the prior art can be referred to. Preferably, the content of component (A) is 25 to 60% by weight, preferably 25 to 55% by weight, more preferably 25 to 45% by weight, based on the photocurable adhesive composition; The content of (B1) is 10 to 45% by weight, preferably 10 to 35% by weight; the content of component (B2) is 15 to 80% by weight, preferably 20 to 80% by weight, more preferably 15 to 80% by weight. 35% by weight; the content of component (C) is 3 to 5% by weight, preferably 5% by weight.
製品の応用のニーズに応じて、本発明の光硬化型接着剤には、本分野で一般的に使用される有機及び/又は無機助剤、例えばレベリング剤、分散剤、硬化剤、界面活性剤、溶媒等を添加してもよいが、助剤がこれらに限定されない。これは当業者にとっては自明なことである。さらに、組成物の応用効果に悪影響を及ぼさないという前提で、他の増感剤及び/又は光開始剤も接着剤に添加して併用することができる。 Depending on the needs of the product application, the photocurable adhesive of the present invention may contain organic and/or inorganic auxiliaries commonly used in this field, such as leveling agents, dispersants, curing agents, surfactants. , a solvent, etc. may be added, but the auxiliary agent is not limited to these. This is obvious to those skilled in the art. Furthermore, other sensitizers and/or photoinitiators may also be added to the adhesive for use, provided that they do not adversely affect the application effectiveness of the composition.
応用のニーズに応じて、光硬化型接着剤には、応用性能を高めるように一種又は多種の大分子又は高分子化合物を選択的に添加することができ、また、反応性官能基を含まないポリマーを選択的に添加することができる。この大分子又は高分子化合物はポリオール又はポリエステルポリオールであってもよい。これらのポリマーは、通常、フェノール性水酸基、カルボキシル基などの酸性官能基を含む樹脂である。 According to application needs, one or more large molecules or polymer compounds can be selectively added to the photocurable adhesive to enhance the application performance, and it does not contain any reactive functional groups. Polymers can be added selectively. This large molecule or polymeric compound may be a polyol or polyester polyol. These polymers are usually resins containing acidic functional groups such as phenolic hydroxyl groups and carboxyl groups.
本発明の一つの典型的な実施形態では、光硬化型接着剤組成物から重合により得られた光硬化型接着剤を提供する。該光硬化型接着剤組成物は、前記光硬化型接着剤組成物のいずれか一種である。 One typical embodiment of the present invention provides a photocurable adhesive obtained by polymerization from a photocurable adhesive composition. The photocurable adhesive composition is any one of the photocurable adhesive compositions described above.
本発明の光硬化型接着剤組成物は、特定のオキセタン化合物を選択して、エポキシ基を有する化合物及び光カチオン重合開始剤と配合して使用するため、得られた光硬化型接着剤の付着力、硬化性、及び偏光子と保護フィルムに対する接着性が改善される。 In the photocurable adhesive composition of the present invention, a specific oxetane compound is selected and used in combination with a compound having an epoxy group and a photocationic polymerization initiator. Adhesion, curability, and adhesion to polarizers and protective films are improved.
本発明の別の典型的な実施形態では、偏光子と、接着剤を介して該偏光子に接着された保護フィルムとを含む偏光板を提供する。該接着剤は前記の光硬化型接着剤である。本発明の光硬化型接着剤は、接着性が良好であり、耐酸性、耐アルカリ性、及び優れた熱安定性を有するため、それを接着剤とする偏光板の耐用年数が長く、光学性能が良好である。 Another exemplary embodiment of the invention provides a polarizing plate that includes a polarizer and a protective film adhered to the polarizer via an adhesive. The adhesive is the photocurable adhesive described above. The photocurable adhesive of the present invention has good adhesion, acid resistance, alkali resistance, and excellent thermal stability, so the polarizing plate using it as an adhesive has a long service life and good optical performance. In good condition.
本発明の光硬化型接着剤は、ポリビニルアルコール系樹脂フィルムからなる偏光子に保護フィルムを接着するために用いられることができ、例えば、一軸延伸され二色性色素が吸着・配向されたポリビニルアルコール系樹脂フィルムからなる偏光子に保護フィルムを接着するために用いられることができる。これにより、保護フィルムを偏光子に貼り付けることで偏光板を作製する。保護フィルムは、偏光子の片面に貼り付けられることもでき、偏光子の両面に貼り付けられることもできる。保護フィルムが偏光子の両面に貼り付けられる場合、各保護フィルムは、同じ種類の樹脂により得られる保護フィルムであってもよく、異なる種類の樹脂により得られる保護フィルムであってもよい。 The photocurable adhesive of the present invention can be used to adhere a protective film to a polarizer made of a polyvinyl alcohol resin film, such as polyvinyl alcohol that has been uniaxially stretched and has a dichroic dye adsorbed and oriented. It can be used to adhere a protective film to a polarizer made of a resin film. Thereby, a polarizing plate is produced by attaching the protective film to the polarizer. The protective film can be attached to one side of the polarizer, or can be attached to both sides of the polarizer. When the protective films are attached to both sides of the polarizer, each protective film may be made of the same type of resin or may be made of different types of resin.
本発明の前記応用に基づいて、本分野中の従来のプロセスにより偏光板を製造することができる。典型的には、製造方法は、光硬化型接着剤を介して偏光子の片側又は両側に保護フィルムを貼り付けること、光照射により光硬化型接着剤を硬化させることを含む。 Based on the above application of the invention, polarizing plates can be manufactured by conventional processes in the field. Typically, the manufacturing method includes attaching a protective film to one or both sides of a polarizer via a photocurable adhesive, and curing the photocurable adhesive by light irradiation.
具体的なプロセスは、以下の工程を含む。
(1) 塗布工程:光硬化型接着剤を未硬化状態で保護フィルムに塗布し、接着剤塗布面が形成される。
(2) 貼り付け工程:保護フィルムの接着剤塗布面に偏光子を貼り付ける。
(3) 硬化工程:光照射により光硬化型接着剤を硬化させ、接着剤層を形成する。
The specific process includes the following steps.
(1) Coating process: The photocurable adhesive is applied to the protective film in an uncured state to form the adhesive coated surface.
(2) Attaching process: Attach the polarizer to the adhesive-coated surface of the protective film.
(3) Curing process: The photocurable adhesive is cured by light irradiation to form an adhesive layer.
偏光板の製造過程中、保護フィルムを片面に貼り付けることも、保護フィルムを両面に貼り付けることもできる。好ましくは、両面の保護フィルムの少なくとも一者は、他の光学的機能も兼ね備える。 During the manufacturing process of the polarizing plate, a protective film can be attached to one side, or a protective film can be attached to both sides. Preferably, at least one of the protective films on both sides also has other optical functions.
偏光子として、本分野における一般的な種類、例えば、一軸延伸され、ヨウ素又は二色性染料が吸着・配向されたポリビニルアルコール系樹脂フィルムを使用することできる。 As the polarizer, it is possible to use a type commonly used in this field, such as a uniaxially stretched polyvinyl alcohol resin film on which iodine or dichroic dye is adsorbed and oriented.
本発明の別の典型的な実施形態では、偏光板を含む光学設備を提供する。該偏光板は前記の偏光板である。 Another exemplary embodiment of the invention provides an optical equipment that includes a polarizer. The polarizing plate is the polarizing plate described above.
実際の使用中、偏光板は、その片側に偏光機能以外の光学機能を示す光学層を積層して得られる光学部材として製造されてもよい。光学部材については、使用目的に応じて、偏光板と、前記反射層乃至半透過反射層、光散乱層、位相差板、集光板、輝度向上フィルム等から選択される一層又は二層以上の光学層とを組み合わせて、二層又は三層以上の積層体を作製することができる。光学部材を形成する各種光学層は、接着剤で偏光板と一体化される。以上の光学部材を液晶セルの片面又は両面に配置することにより、液晶表示装置を製造することができる。 In actual use, a polarizing plate may be manufactured as an optical member obtained by laminating an optical layer exhibiting an optical function other than a polarizing function on one side of the polarizing plate. Regarding optical members, depending on the purpose of use, one or more optical layers selected from a polarizing plate and the above-mentioned reflective layer or semi-transparent reflective layer, light scattering layer, retardation plate, light condensing plate, brightness enhancement film, etc. A laminate of two layers, three layers or more can be produced by combining the layers. Various optical layers forming an optical member are integrated with a polarizing plate using an adhesive. A liquid crystal display device can be manufactured by arranging the above optical members on one or both sides of a liquid crystal cell.
以下の実施例により、本発明をさらに詳しく説明するが、これらの実施例に限定されるものではない。 The present invention will be explained in more detail with reference to the following examples, but is not limited to these examples.
1.光硬化型接着剤の調製
表に示される処方を参照して、原料を均一に混合し、光硬化型接着剤組成物を得た(特記しない限り、記載されている「部」は全て「質量部」である)。
1. Preparation of photocurable adhesive Referring to the recipe shown in the table, the raw materials were mixed uniformly to obtain a photocurable adhesive composition (unless otherwise specified, all "parts" are "mass"). ).
2.性能評価
実施例と比較例で調製された光硬化型接着剤を消泡処理し、コーティングフィルムの厚さが10μmとなるように、バーコーターで厚さ80μmのトリアセチルセルロース(TAC)保護フィルム(商品名:Fujitech、富士フイルム会社)に塗布し、続いて、ポリビニルアルコール-ヨウ素偏光子の片側と貼り付けた。次に、コーティングフィルムの厚さが10μmとなるように、該偏光子の他の片側に同じ接着剤を塗布し、ノルボルネン系樹脂フィルム(商品名ZEONOR、OPTES会社)と貼り付けた。次に、水銀ランプ(露光機の品番RW-UV20101、累積で放射エネルギー2000mJ/cm2を受けた)により硬化を実施した。
2. Performance evaluation The photocurable adhesives prepared in Examples and Comparative Examples were subjected to defoaming treatment, and coated with a triacetyl cellulose (TAC) protective film (80 μm thick) using a bar coater so that the coating film thickness was 10 μm. (trade name: Fujitech, Fuji Film Company), and then attached to one side of a polyvinyl alcohol-iodine polarizer. Next, the same adhesive was applied to the other side of the polarizer so that the thickness of the coating film was 10 μm, and a norbornene resin film (trade name: ZEONOR, manufactured by OPTES Company) was attached. Next, curing was carried out using a mercury lamp (exposure machine part number RW-UV20101, which received a cumulative radiant energy of 2000 mJ/cm 2 ).
付着力、硬化性能と接着性能を評価し、具体的な評価方法と標準は以下の通りである。 Adhesion, curing performance and adhesive performance were evaluated, and the specific evaluation methods and standards are as follows.
(1)付着力
付着力はARCOTESTのダインペンで測定され、具体的に、線を均等に分布させ、3秒以内にインクが液滴状にならない最大番号のダインペンの番号は測定値とされた。表面ダイン値が小さいほど、付着する下層の表面張力が大きく、付着に有利である。
(1) Adhesion force The adhesion force was measured with an ARCOTEST dyne pen, and specifically, the number of the highest numbered dyne pen that distributed the lines evenly and did not cause the ink to form droplets within 3 seconds was taken as the measured value. The smaller the surface dyne value, the greater the surface tension of the lower layer to which it is attached, which is advantageous for adhesion.
(2)接着性
両面にあった不同の保護フィルム(すなわち、TACフィルムとノルボルネンフィルム)の接着性をそれぞれ評価し、次のように評価した。
A:界面で偏光子から保護フィルムを剥がすことができず、無理に剥がすとフィルムに損傷を与える。即ち、接着性が優れる。
B:界面で偏光子から保護フィルムを剥がすことができ、フィルムに損傷を与えない。即ち、接着性が良好である。
C:硬化した直後、浮いている、又は全く接着していない状態である。即ち、接着性が不良である。
(2) Adhesiveness The adhesiveness of different protective films on both sides (ie, TAC film and norbornene film) was evaluated as follows.
A: The protective film cannot be peeled off from the polarizer at the interface, and if it is forcibly removed, the film will be damaged. That is, the adhesive property is excellent.
B: The protective film can be peeled off from the polarizer at the interface without damaging the film. That is, the adhesive property is good.
C: Immediately after curing, the adhesive is floating or not adhered at all. That is, the adhesiveness is poor.
(3)硬化性
偏光子からTACフィルムとノルボルネンフィルムを剥がし、そして、GB1728-79の表面乾燥時間測定法-フィンガータッチ法を参照し、硬化フィルムの表面状況を観察し、以下のように評価した。
A:べたつきの状況がない。即ち、硬化性が良好である。
B:べたつきの状況がある。即ち、硬化性が不良である。
(3) Curability The TAC film and norbornene film were peeled off from the polarizer, and the surface condition of the cured film was observed with reference to the GB1728-79 surface drying time measurement method - finger touch method, and evaluated as follows. .
A: There is no sticky situation. That is, the curability is good.
B: There is a sticky situation. That is, the curability is poor.
3.具体的な処方及び評価結果
実施例1
成分(A)におけるRがフェニル基である時の異なる組成物の調製
成分(B1):3,4-エポキシシクロヘキシルメチル-3,4-エポキシシクロヘキシルカルボキシレート35質量部
成分(B2):グリシジルメタクリレート/メチルメタクリレート/アクリル酸ヒドロキシエチルから加熱重合により得られたもの(質量比30:40:30、Mwは12000)35質量部
成分(C):
Preparation of different compositions when R in component (A) is a phenyl group
表1の結果から、n=1である場合、硬化効果が良く、付着性が良く、TACフィルムやノルボルネンフィルムとの接着性が優れることがわかる。 From the results in Table 1, it can be seen that when n=1, the curing effect is good, the adhesion is good, and the adhesion to the TAC film and norbornene film is excellent.
実施例2
成分(A)におけるRがビフェニル基である時の異なる組成物の調製
成分(B1):3,4-エポキシシクロヘキシルメチル-3,4-エポキシシクロヘキシルカルボキシレート25質量部
成分(B2):グリシジルメタクリレート/メチルメタクリレート/アクリル酸ヒドロキシエチルから加熱重合により得られたもの(質量比30:40:30、Mwは12000)35質量部
成分(C):
Preparation of different compositions when R in component (A) is a biphenyl group
表2の結果から、n=1である場合、硬化効果が良く、付着性が良く、TACフィルムやノルボルネンフィルムとの接着性が優れていることがわかる。 From the results in Table 2, it can be seen that when n=1, the curing effect is good, the adhesion is good, and the adhesion to the TAC film and norbornene film is excellent.
実施例3
成分(A)におけるRがナフチル基である時の異なる組成物の調製
成分(A)(具体的に表3を参照) 40質量部
成分(B1):ペンタエリスリトールテトラグリシジルエーテル 30質量部
成分(B2):グリシジルメタクリレート/メチルメタクリレート/アクリル酸ヒドロキシエチルから加熱重合により得られたもの(質量比30:40:30、Mwは12000) 25質量部
成分(C):
Preparation of different compositions when R in component (A) is a naphthyl group
Component (A) (see Table 3 for details) 40 parts by mass Component (B1): Pentaerythritol tetraglycidyl ether 30 parts by mass Component (B2): Obtained from glycidyl methacrylate/methyl methacrylate/hydroxyethyl acrylate by heating polymerization (mass ratio 30:40:30, Mw 12000) 25 parts by mass Component (C):
表3の結果から、n=1である場合、硬化効果が良く、付着性が良く、TACフィルムやノルボルネンフィルムとの接着性が優れていることがわかる。 From the results in Table 3, it can be seen that when n=1, the curing effect is good, the adhesion is good, and the adhesion to the TAC film and norbornene film is excellent.
他のn=1である化合物を選択し、接着剤組成物中の重量比を変更して、応用性能を評価した。その結果を表4に示した。 Other compounds where n=1 were selected and their weight ratios in the adhesive composition were changed to evaluate their application performance. The results are shown in Table 4.
表1~3、表5の性能評価結果から、本発明の接着剤組成物は、硬化効果が良く、付着力が良く、TACフィルムやノルボルネンフィルムとの接着性が優れることが分かる。その理由として、本発明の組成物を含有する処方において、オキセタン化合物が単官能性酸素複素環を含み、適切な粘度を有し、且つ基におけるベンジル基が硬化速度を速めるため、優れた総合応用性能を有すると推測する。 From the performance evaluation results in Tables 1 to 3 and Table 5, it can be seen that the adhesive composition of the present invention has good curing effect, good adhesion, and excellent adhesion to TAC film and norbornene film. The reason is that in the formulation containing the composition of the present invention, the oxetane compound contains a monofunctional oxygen heterocycle, has an appropriate viscosity, and the benzyl group in the group accelerates the curing rate, so it has excellent overall application. It is assumed that it has the performance.
以上の記載は、本発明の好ましい実施例に過ぎず、本発明を制限するものではない。本分野の当業者にとって、本発明を様々に変更や変化することが可能である。本発明の趣旨や原則の範囲内でのすべての変更、均等変換、改進等が本発明の保護範囲内に含まれることが意図される。 The above description is only a preferred embodiment of the invention and is not intended to limit the invention. Various modifications and variations of the present invention will occur to those skilled in the art. All changes, equivalent conversions, improvements, etc. within the spirit and principles of the present invention are intended to be included within the protection scope of the present invention.
Claims (16)
前記成分(A)が、式(aa)で示される構造を含有するオキセタン化合物であり、
前記成分(B)が、エポキシ基を有する化合物であり、かつ
前記成分(C)が、光カチオン重合開始剤であり、
前記成分(B)が、
炭素数が2~10であるポリオールのポリグリシジルエーテル、又は、3,4-エポキシシクロヘキシルメチル-3,4-エポキシシクロヘキシルカルボキシレートである成分(B1)、および
エポキシ基を有するポリマーである成分(B2)(ただし、前記成分(B1)を除く)
を含み、
前記光硬化型接着剤組成物を基準とする時、
前記成分(A)の含有量が25~55重量%であり、
前記成分(B1)の含有量が10~45重量%であり、
前記成分(B2)の含有量が20~80重量%であり、かつ
前記成分(C)の含有量が3~5重量%である、
光硬化型接着剤組成物。 A photocurable adhesive composition comprising a component (A), a component (B), and a component (C),
The component (A) is an oxetane compound containing a structure represented by formula (aa),
The component (B) is a compound having an epoxy group, and the component (C) is a cationic photopolymerization initiator,
The component (B) is
A component (B1) which is a polyglycidyl ether of a polyol having 2 to 10 carbon atoms or 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate, and
Component (B2) which is a polymer having an epoxy group (excluding the above component (B1))
including;
When based on the photocurable adhesive composition,
The content of the component (A) is 25 to 55% by weight,
The content of the component (B1) is 10 to 45% by weight,
The content of the component (B2) is 20 to 80% by weight, and
The content of the component (C) is 3 to 5% by weight,
Photocurable adhesive composition.
前記Mwが、GPCで測定された分子量をポリスチレン換算して得られた重量平均分子量であることを特徴とする、請求項1に記載の光硬化型接着剤組成物。 The component (B2) has a Tg of 20°C or higher and a Mw of 1000 to 30000,
The photocurable adhesive composition according to claim 1 , wherein the Mw is a weight average molecular weight obtained by converting the molecular weight measured by GPC into polystyrene.
前記モノマー(b1)が、エポキシ基及びエチレン性不飽和基を有する化合物であり、前記エチレン性不飽和基が、ビニル基又はアクリロイル基であり、
前記モノマー(b2)が、炭素数1~10個の炭化水素基を有する単官能性メタクリレートであり、
前記モノマー(b3)が、前記モノマー(b1)とは異なるアルケニル化合物である、光硬化型接着剤組成物。 The photocurable adhesive composition according to claim 1 , characterized in that the component (B2) is obtained by polymerization from monomer (b1), monomer (b2), and optionally used monomer (b3). And,
The monomer (b1) is a compound having an epoxy group and an ethylenically unsaturated group, and the ethylenically unsaturated group is a vinyl group or an acryloyl group,
The monomer (b2) is a monofunctional methacrylate having a hydrocarbon group having 1 to 10 carbon atoms,
A photocurable adhesive composition, wherein the monomer (b3) is an alkenyl compound different from the monomer (b1).
前記芳香族基含有ビニル化合物が、スチレン又はα-メチルスチレンであり、かつ
前記単官能性アクリレートがメチルアクリレート、エチルアクリレート、プロピルアクリレート、イソプロピルアクリレート、ブチルアクリレート、sec-ブチルアクリレート、tert-ブチルアクリレート、イソブチルアクリレート、ヘキシルアクリレート、シクロヘキシルアクリレート、2-エチルヘキシルアクリレート、オクチルアクリレート、イソオクチルアクリレート、ノニルアクリレート、イソノニルアクリレート、デシルアクリレート、イソデシルアクリレート、ベンジルアクリレートからなる群より選ばれる一種以上であることを特徴とする、請求項7に記載の光硬化型接着剤組成物。 The monomer (b3) is any one selected from the group consisting of aromatic group-containing vinyl compounds, monofunctional acrylates, acrylonitrile, methacrylonitrile, acrylamide, and methacrylamide,
The aromatic group-containing vinyl compound is styrene or α-methylstyrene, and the monofunctional acrylate is methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, sec-butyl acrylate, tert-butyl acrylate, It is characterized by being one or more selected from the group consisting of isobutyl acrylate, hexyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, isooctyl acrylate, nonyl acrylate, isononyl acrylate, decyl acrylate, isodecyl acrylate, and benzyl acrylate. The photocurable adhesive composition according to claim 7 .
前記成分(A)の含有量が25~45重量%であることを特徴とする、請求項1に記載の光硬化型接着剤組成物。 When based on the photocurable adhesive composition,
The photocurable adhesive composition according to claim 1 , characterized in that the content of the component (A) is 25 to 45% by weight.
前記接着剤が請求項14に記載の光硬化型接着剤であることを特徴とする偏光板。 A polarizing plate comprising a polarizer and a protective film adhered to the polarizer via an adhesive,
A polarizing plate, wherein the adhesive is the photocurable adhesive according to claim 14 .
前記偏光板が請求項15に記載の偏光板であることを特徴とする光学設備。 Optical equipment including a polarizing plate,
An optical equipment characterized in that the polarizing plate is the polarizing plate according to claim 15 .
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