TWI708808B - Active energy ray curable resin composition, cured product and optical sheet for optical articles - Google Patents
Active energy ray curable resin composition, cured product and optical sheet for optical articles Download PDFInfo
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- TWI708808B TWI708808B TW106108626A TW106108626A TWI708808B TW I708808 B TWI708808 B TW I708808B TW 106108626 A TW106108626 A TW 106108626A TW 106108626 A TW106108626 A TW 106108626A TW I708808 B TWI708808 B TW I708808B
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- active energy
- energy ray
- meth
- acrylate
- polymerizable compound
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- 230000003287 optical effect Effects 0.000 title claims abstract description 53
- 239000011342 resin composition Substances 0.000 title abstract description 41
- 150000001875 compounds Chemical class 0.000 claims abstract description 70
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims abstract description 47
- 239000000203 mixture Substances 0.000 claims abstract description 21
- 239000003999 initiator Substances 0.000 claims abstract description 11
- 229920000193 polymethacrylate Polymers 0.000 claims description 24
- 125000003118 aryl group Chemical group 0.000 claims description 16
- 125000000466 oxiranyl group Chemical group 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- XNHJPNPNLMENTO-OKILXGFUSA-N C(C(C)(C)C)[C@@]([C@](CO)(O)CC(C)(C)C)(O)CO Chemical compound C(C(C)(C)C)[C@@]([C@](CO)(O)CC(C)(C)C)(O)CO XNHJPNPNLMENTO-OKILXGFUSA-N 0.000 claims description 3
- 239000004593 Epoxy Substances 0.000 abstract description 14
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 abstract description 2
- 230000005855 radiation Effects 0.000 abstract 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 105
- -1 neopentylerythritol Ethane Chemical compound 0.000 description 49
- 229920005989 resin Polymers 0.000 description 15
- 239000011347 resin Substances 0.000 description 15
- LLEMOWNGBBNAJR-UHFFFAOYSA-N biphenyl-2-ol Chemical compound OC1=CC=CC=C1C1=CC=CC=C1 LLEMOWNGBBNAJR-UHFFFAOYSA-N 0.000 description 14
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 14
- 238000001723 curing Methods 0.000 description 13
- 239000000178 monomer Substances 0.000 description 12
- 239000000758 substrate Substances 0.000 description 12
- 238000000034 method Methods 0.000 description 11
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 10
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 10
- 239000003822 epoxy resin Substances 0.000 description 10
- 229920000647 polyepoxide Polymers 0.000 description 10
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 9
- 238000006116 polymerization reaction Methods 0.000 description 9
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 8
- 229920003023 plastic Polymers 0.000 description 8
- 239000004033 plastic Substances 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 8
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- 238000004132 cross linking Methods 0.000 description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 7
- 235000010292 orthophenyl phenol Nutrition 0.000 description 7
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- 239000003963 antioxidant agent Substances 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 6
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 5
- 229940106691 bisphenol a Drugs 0.000 description 5
- 239000004205 dimethyl polysiloxane Substances 0.000 description 5
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 5
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 4
- VVBLNCFGVYUYGU-UHFFFAOYSA-N 4,4'-Bis(dimethylamino)benzophenone Chemical compound C1=CC(N(C)C)=CC=C1C(=O)C1=CC=C(N(C)C)C=C1 VVBLNCFGVYUYGU-UHFFFAOYSA-N 0.000 description 4
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 125000004122 cyclic group Chemical group 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000001294 propane Substances 0.000 description 4
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 4
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 3
- CZZVAVMGKRNEAT-UHFFFAOYSA-N 2,2-dimethylpropane-1,3-diol;3-hydroxy-2,2-dimethylpropanoic acid Chemical compound OCC(C)(C)CO.OCC(C)(C)C(O)=O CZZVAVMGKRNEAT-UHFFFAOYSA-N 0.000 description 3
- 239000004925 Acrylic resin Substances 0.000 description 3
- 229920000178 Acrylic resin Polymers 0.000 description 3
- XDUZWPPSSHEDFK-VVXQKDJTSA-N C(C(C)(C)C)C([C@H](O)[C@H](O)CO)O Chemical compound C(C(C)(C)C)C([C@H](O)[C@H](O)CO)O XDUZWPPSSHEDFK-VVXQKDJTSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 239000004721 Polyphenylene oxide Substances 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 125000002947 alkylene group Chemical group 0.000 description 3
- YXVFYQXJAXKLAK-UHFFFAOYSA-N biphenyl-4-ol Chemical compound C1=CC(O)=CC=C1C1=CC=CC=C1 YXVFYQXJAXKLAK-UHFFFAOYSA-N 0.000 description 3
- 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 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 125000004386 diacrylate group Chemical group 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 3
- 125000003709 fluoroalkyl group Chemical group 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 125000004435 hydrogen atom Chemical class [H]* 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
- 229910001507 metal halide Inorganic materials 0.000 description 3
- 150000005309 metal halides Chemical class 0.000 description 3
- 229920003986 novolac Polymers 0.000 description 3
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 3
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- 239000010703 silicon Substances 0.000 description 3
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- 238000003860 storage Methods 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- HGCMSCWGVAYWHR-UHFFFAOYSA-N 1,3,5-trimethyl-2-[[phenyl-[(2,4,6-trimethylphenyl)methyl]phosphoryl]methyl]benzene Chemical compound CC1=CC(C)=CC(C)=C1CP(=O)(C=1C=CC=CC=1)CC1=C(C)C=C(C)C=C1C HGCMSCWGVAYWHR-UHFFFAOYSA-N 0.000 description 2
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- GJKGAPPUXSSCFI-UHFFFAOYSA-N 2-Hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone Chemical compound CC(C)(O)C(=O)C1=CC=C(OCCO)C=C1 GJKGAPPUXSSCFI-UHFFFAOYSA-N 0.000 description 2
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 description 2
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- 241000208340 Araliaceae Species 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 2
- 208000032544 Cicatrix Diseases 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
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- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
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- 235000005035 Panax pseudoginseng ssp. pseudoginseng Nutrition 0.000 description 2
- 235000003140 Panax quinquefolius Nutrition 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
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- 150000001412 amines Chemical class 0.000 description 2
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 2
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 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
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- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
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- 230000007423 decrease Effects 0.000 description 2
- QMMFVYPAHWMCMS-UHFFFAOYSA-N dimethyl monosulfide Natural products CSC QMMFVYPAHWMCMS-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
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- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical group 0.000 description 2
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 2
- 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 2
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- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 150000002596 lactones Chemical class 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
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- 239000010452 phosphate Substances 0.000 description 2
- 239000003504 photosensitizing agent Substances 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
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- 125000004079 stearyl 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])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])[H] 0.000 description 2
- 150000003440 styrenes Chemical class 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
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- JNELGWHKGNBSMD-UHFFFAOYSA-N xanthone Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3OC2=C1 JNELGWHKGNBSMD-UHFFFAOYSA-N 0.000 description 2
- 150000007964 xanthones Chemical class 0.000 description 2
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 2
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- QNODIIQQMGDSEF-UHFFFAOYSA-N (1-hydroxycyclohexyl)-phenylmethanone Chemical compound C=1C=CC=CC=1C(=O)C1(O)CCCCC1 QNODIIQQMGDSEF-UHFFFAOYSA-N 0.000 description 1
- CNLVUQQHXLTOTC-UHFFFAOYSA-N (2,4,6-tribromophenyl) prop-2-enoate Chemical compound BrC1=CC(Br)=C(OC(=O)C=C)C(Br)=C1 CNLVUQQHXLTOTC-UHFFFAOYSA-N 0.000 description 1
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- KHXKESCWFMPTFT-UHFFFAOYSA-N 1,1,1,2,2,3,3-heptafluoro-3-(1,2,2-trifluoroethenoxy)propane Chemical compound FC(F)=C(F)OC(F)(F)C(F)(F)C(F)(F)F KHXKESCWFMPTFT-UHFFFAOYSA-N 0.000 description 1
- RRZIJNVZMJUGTK-UHFFFAOYSA-N 1,1,2-trifluoro-2-(1,2,2-trifluoroethenoxy)ethene Chemical class FC(F)=C(F)OC(F)=C(F)F RRZIJNVZMJUGTK-UHFFFAOYSA-N 0.000 description 1
- BLTXWCKMNMYXEA-UHFFFAOYSA-N 1,1,2-trifluoro-2-(trifluoromethoxy)ethene Chemical compound FC(F)=C(F)OC(F)(F)F BLTXWCKMNMYXEA-UHFFFAOYSA-N 0.000 description 1
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 1
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- MLKIVXXYTZKNMI-UHFFFAOYSA-N 1-(4-dodecylphenyl)-2-hydroxy-2-methylpropan-1-one Chemical compound CCCCCCCCCCCCC1=CC=C(C(=O)C(C)(C)O)C=C1 MLKIVXXYTZKNMI-UHFFFAOYSA-N 0.000 description 1
- HUDYANRNMZDQGA-UHFFFAOYSA-N 1-[4-(dimethylamino)phenyl]ethanone Chemical compound CN(C)C1=CC=C(C(C)=O)C=C1 HUDYANRNMZDQGA-UHFFFAOYSA-N 0.000 description 1
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- YRTNMMLRBJMGJJ-UHFFFAOYSA-N 2,2-dimethylpropane-1,3-diol;hexanedioic acid Chemical compound OCC(C)(C)CO.OC(=O)CCCCC(O)=O YRTNMMLRBJMGJJ-UHFFFAOYSA-N 0.000 description 1
- SDJHPPZKZZWAKF-UHFFFAOYSA-N 2,3-dimethylbuta-1,3-diene Chemical compound CC(=C)C(C)=C SDJHPPZKZZWAKF-UHFFFAOYSA-N 0.000 description 1
- BTJPUDCSZVCXFQ-UHFFFAOYSA-N 2,4-diethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(CC)=CC(CC)=C3SC2=C1 BTJPUDCSZVCXFQ-UHFFFAOYSA-N 0.000 description 1
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- HLIQLHSBZXDKLV-UHFFFAOYSA-N 2-(2-hydroxyethoxy)-1-phenoxyethanol Chemical compound OCCOCC(O)OC1=CC=CC=C1 HLIQLHSBZXDKLV-UHFFFAOYSA-N 0.000 description 1
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- WCVRQHFDJLLWFE-UHFFFAOYSA-N pentane-1,2-diol Chemical compound CCCC(O)CO WCVRQHFDJLLWFE-UHFFFAOYSA-N 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 239000013034 phenoxy resin Substances 0.000 description 1
- 229920006287 phenoxy resin Polymers 0.000 description 1
- 125000000286 phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920001748 polybutylene Polymers 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- RSVDRWTUCMTKBV-UHFFFAOYSA-N sbb057044 Chemical compound C12CC=CC2C2CC(OCCOC(=O)C=C)C1C2 RSVDRWTUCMTKBV-UHFFFAOYSA-N 0.000 description 1
- 235000020637 scallop Nutrition 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 1
- 229960002447 thiram Drugs 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
- C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
- C08F20/10—Esters
- C08F20/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F20/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Polymerisation Methods In General (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
提供於模再現性、耐刮性優良、且就尺寸安定性或捲曲性而言為優良之光學物品用活性能量射線硬化型樹脂組成物、硬化物、及光學片。一種光學物品用活性能量射線硬化性組成物，將該光學物品用活性能量射線硬化性組成物藉由活性能量射線使其硬化而得之硬化物，及光學片，該光學物品用活性能量射線硬化性組成物含有活性能量射線聚合性化合物及光聚合起始劑，且： (1) 含有具2個以上之活性能量射線聚合性基且具有環氧乙烷基的聚合性化合物，且該環氧乙烷基之重量濃度相對於該活性能量射線聚合性化合物之全部量為6.0~15.0重量%； (2) 具2個以上之活性能量射線聚合性基之聚合性化合物之含量相對於該活性能量射線聚合性化合物之全部量為30~70重量%。It provides active energy ray-curable resin compositions, cured products, and optical sheets for optical articles that have excellent mold reproducibility, scratch resistance, and excellent dimensional stability or curling properties. An active energy ray hardenable composition for optical articles, a hardened product obtained by curing the active energy ray hardenable composition for optical articles by active energy rays, and an optical sheet in which the optical article is hardened by active energy rays The composition contains an active energy ray polymerizable compound and a photopolymerization initiator, and: (1) It contains a polymerizable compound having two or more active energy ray polymerizable groups and an ethylene oxide group, and the epoxy The weight concentration of the ethylene group relative to the total amount of the active energy ray polymerizable compound is 6.0 to 15.0% by weight; (2) The content of the polymerizable compound having two or more active energy ray polymerizable groups relative to the active energy The total amount of the radiation polymerizable compound is 30 to 70% by weight.
Description
本發明係關於應用了照射活性能量射線所致之硬化反應之使用於鑄模聚合的光學物品用活性能量射線硬化型樹脂組成物，及使該組成物硬化而得之光學片。The present invention relates to an active energy ray-curable resin composition for an optical article used for mold polymerization to which a curing reaction caused by active energy ray irradiation is applied, and an optical sheet obtained by curing the composition.
應用了照射活性能量射線所致之硬化反應的技術係廣泛地應用於塗料、光阻材料、印墨、黏著劑等。雖然以前一般而言有厚度數μm左右之膜厚的應用技術，於近年來利用了活性能量射線硬化型樹脂組成物可進行無溶劑塗布之優點，或藉由照射產生立即之硬化反應的優點，讓以數十μm以上之膜厚來製作特定之形狀的加工、塗布技術受到注目，且有人將光造型法或光鑄模聚合法等投入實際運用。 其中，光鑄模聚合法係例如對於經賦予微細形狀之母模填充(整批注入)活性能量射線硬化型樹脂組成物，介隔母模，藉由紫外線等使該樹脂組成物硬化之方法，可精密且大量地製造母模的複製。The technology that applies the hardening reaction caused by the irradiation of active energy rays is widely used in coatings, photoresist materials, printing inks, adhesives, etc. Although in the past there were generally application technologies with a thickness of about a few μm, in recent years, the advantages of active energy ray-curable resin compositions for solvent-free coating or the advantages of an immediate curing reaction by irradiation have been used. The processing and coating technology for making a specific shape with a film thickness of several tens of μm or more has attracted attention, and some people put the photo-molding method or photo-mold polymerization method into practical use. Among them, the photo-mold polymerization method is a method in which, for example, an active energy ray-curable resin composition is filled (bulk injection) with a finely shaped master mold, the master mold is interposed, and the resin composition is cured by ultraviolet rays. Precisely and mass-produce the reproduction of the master model.
伴隨著設備之小型化、輕量化，上述光鑄模聚合法係適用於在塑膠基材上具有由樹脂硬化物構成之微細且複雜之凹凸表現形狀的具形狀之光學片(例如，稜鏡透鏡片或菲涅耳透鏡片等)、透鏡、稜鏡等塑膠物品或光學物品之製造的方法。對於在藉由該光鑄模聚合法製造塑膠物品或光學物品時所使用之活性能量射線硬化型樹脂組成物要求優良之硬化性，且對於製造之硬化物要求模再現性(將硬化物從母模剝離時，從模轉印而得之微細形狀不會缺損或變形之性質)或耐刮性。此外，獲得之硬化物為光學片時，常常與擴散薄膜等其它薄膜進行疊層，此時也會要求尺寸安定性或減低捲曲性。然而，光鑄模聚合法等藉由光之聚合有聚合時的硬化收縮大，有就尺寸安定性或耐捲曲性為不良之情事。Along with the miniaturization and weight reduction of equipment, the above-mentioned photo-mold polymerization method is suitable for a shaped optical sheet (for example, a lens sheet) with a fine and complex concave-convex expression shape composed of a hardened resin on a plastic substrate. Or Fresnel lens sheet, etc.), lens, prism and other plastic objects or optical objects manufacturing methods. The active energy ray-curable resin composition used in the production of plastic articles or optical articles by the photo-mold polymerization method requires excellent curability, and mold reproducibility is required for the manufactured hardened product (the hardened product is removed from the master mold When peeling off, the fine shape transferred from the mold will not be damaged or deformed) or scratch resistance. In addition, when the obtained cured product is an optical sheet, it is often laminated with other films such as a diffusion film. In this case, dimensional stability or reduced curling properties are also required. However, polymerization by light such as the photo-mold polymerization method may cause large curing shrinkage during polymerization, and may have poor dimensional stability or curl resistance.
就硬化性優良，獲得之硬化物的模再現性也優良之光學物品用活性能量射線硬化型樹脂組成物而言，例如已有許多含有環氧(甲基)丙烯酸酯或胺甲酸乙酯(urethane)(甲基)丙烯酸酯之活性能量射線硬化型樹脂組成物之報告。具體而言，已知有例如含有雙酚A型環氧(甲基)丙烯酸酯、單官能(甲基)丙烯酸酯、2官能(甲基)丙烯酸酯及重量平均分子量為9.5萬之丙烯酸樹脂等聚合物成分，且硬化後之折射率為1.55以上的稜鏡透鏡用游離輻射線硬化型樹脂組成物(例如，參照專利文獻1)、或其含有：含有式(1)表示之化合物之具有聚合性不飽和雙鍵的單體、將聚合性不飽和單體聚合而得之重量平均分子量為2,000~100,000且聚合物結構中含有聚合性不飽和雙鍵之聚合物、及光聚合起始劑，且該單體與聚合物之含量為特定之比率(例如，參照專利文獻2)的一種光學物品用活性能量射線硬化型樹脂組成物。In terms of active energy ray-curable resin compositions for optical articles that have excellent curability and excellent mold reproducibility of the obtained cured product, for example, there are many containing epoxy (meth)acrylate or urethane ) Report on active energy ray-curable resin composition of (meth)acrylate. Specifically, there are known, for example, acrylic resins containing bisphenol A epoxy (meth)acrylate, monofunctional (meth)acrylate, bifunctional (meth)acrylate, and a weight average molecular weight of 95,000. A polymer component and an ionizing radiation-curable resin composition for a lens with a refractive index of 1.55 or more after curing (for example, refer to Patent Document 1), or a polymer containing a compound represented by formula (1) Monomers with unsaturated double bonds, polymers with a weight average molecular weight of 2,000 to 100,000 obtained by polymerizing polymerizable unsaturated monomers, and polymers containing polymerizable unsaturated double bonds in the polymer structure, and photopolymerization initiators, And the content of the monomer and the polymer is a specific ratio (for example, refer to Patent Document 2), an active energy ray-curable resin composition for optical articles.
【化1】
然而，在上述專利文獻1中記載之稜鏡透鏡用游離輻射線硬化型樹脂組成物，該聚合物成分不會鍵結至硬化反應所產生之交聯結構。因此，聚合物成分之含量多時有硬化性變差的傾向。此外，在專利文獻2中記載之光學物品用活性能量射線硬化型樹脂組成物，雖然模再現性優良但有時有就尺寸安定性或捲曲性而言為不良的情況。 [先前技術文獻] [專利文獻]However, in the ionizing radiation-curable resin composition for use in the lens described in Patent Document 1, the polymer component is not bonded to the crosslinked structure generated by the curing reaction. Therefore, when the content of the polymer component is large, the curability tends to deteriorate. In addition, the active energy ray-curable resin composition for optical articles described in Patent Document 2 has excellent mold reproducibility, but may be inferior in terms of dimensional stability or curling properties. [Prior Art Document] [Patent Document]
[專利文獻1] 日本特開平11-240926號公報 [專利文獻2] 日本特開2010-60890號公報[Patent Document 1] Japanese Patent Application Publication No. 11-240926 [Patent Document 2] Japanese Patent Application Publication No. 2010-60890
[發明所欲解決之課題] 本發明之課題係提供模再現性、耐刮性優良、且就尺寸安定性或捲曲性而言為優良之光學物品用活性能量射線硬化型樹脂組成物、硬化物、及使光學物品用活性能量射線硬化型樹脂組成物硬化而得之光學片。 [解決課題之手段][Problem to be solved by the present invention] The subject of the present invention is to provide an active energy ray-curable resin composition and cured product for optical articles that are excellent in mold reproducibility, scratch resistance, and excellent in terms of dimensional stability and curling properties , And an optical sheet obtained by curing an active energy ray-curable resin composition for optical articles. [Means to solve the problem]
一般而言，若降低組成物中之活性能量射線聚合性基的濃度，因為交聯密度下降，故硬化收縮減低，可抑制捲曲性。但在另一方面，耐刮性等機械物性也會下降。然而本案發明者們在深入研究之結果，發現藉由使組成物中之環氧乙烷濃度及具有2個以上之活性能量射線聚合性基的聚合性化合物的量為特定之範圍，可解決上述課題。 本案發明者們發現，藉由使用於結構中具有環氧乙烷骨架之具2個以上活性能量射線聚合性基的聚合性化合物，將柔軟之環氧乙烷基有效地導入至硬化物之主鏈，能減低在硬化時發生之內部應力也就是硬化收縮，結果可獲得維持了耐刮性且還抑制了捲曲性之硬化物。Generally speaking, if the concentration of the active energy ray polymerizable group in the composition is lowered, the crosslinking density is lowered, so the curing shrinkage is reduced, and the curling property can be suppressed. On the other hand, mechanical properties such as scratch resistance will also decrease. However, the inventors of the present case have conducted in-depth studies and found that the above can be solved by setting the concentration of ethylene oxide in the composition and the amount of polymerizable compound having two or more active energy ray polymerizable groups within a specific range. Subject. The inventors of the present case discovered that by using a polymerizable compound having two or more active energy ray polymerizable groups with an ethylene oxide skeleton in the structure, the soft ethylene oxide group can be effectively introduced into the main body of the cured product. The chain can reduce the internal stress that occurs during hardening, that is, hardening shrinkage. As a result, a hardened product that maintains scratch resistance and suppresses curling can be obtained.
也就是說，本發明係提供一種光學物品用活性能量射線硬化性組成物，該光學物品用活性能量射線硬化性組成物含有活性能量射線聚合性化合物及光聚合起始劑，且 (1) 含有具2個以上之活性能量射線聚合性基且具有環氧乙烷基的聚合性化合物，且該環氧乙烷基之重量濃度相對於該活性能量射線聚合性化合物之全部量為6.0~15.0重量%； (2) 具2個以上之活性能量射線聚合性基之聚合性化合物之含量相對於該活性能量射線聚合性化合物之全部量為30~70重量%。That is, the present invention provides an active energy ray curable composition for optical articles, the active energy ray curable composition for optical articles contains an active energy ray polymerizable compound and a photopolymerization initiator, and (1) contains A polymerizable compound having two or more active energy ray polymerizable groups and an ethylene oxide group, and the weight concentration of the ethylene oxide group relative to the total amount of the active energy ray polymerizable compound is 6.0 to 15.0 weight %; (2) The content of the polymerizable compound having two or more active energy ray polymerizable groups is 30 to 70% by weight relative to the total amount of the active energy ray polymerizable compound.
此外，本發明提供將上述記載之光學物品用活性能量射線硬化性組成物藉由活性能量射線使其硬化而得之硬化物。In addition, the present invention provides a cured product obtained by curing the active energy ray curable composition for optical articles described above by active energy ray.
此外，本發明提供將上述記載之光學物品用活性能量射線硬化性組成物藉由活性能量射線使其硬化而得之光學片。 [發明之效果]In addition, the present invention provides an optical sheet obtained by curing the active energy ray curable composition for optical articles described above by active energy rays. [Effects of Invention]
藉由本發明，可獲得模再現性、耐刮性優良、且就尺寸安定性或耐捲曲性而言為優良之稜鏡透鏡片或菲涅耳透鏡片等具有微細之表面形狀的光學片。According to the present invention, it is possible to obtain an optical sheet having a fine surface shape, such as a fine lenticular lens sheet or a Fresnel lens sheet, which is excellent in mold reproducibility, scratch resistance, and excellent in dimensional stability or curl resistance.
(活性能量射線聚合性化合物) 於本發明使用之活性能量射線聚合性化合物係： (1) 含有具2個以上之活性能量射線聚合性基且具有環氧乙烷基之聚合性化合物作為必要成分；且 (2) 具2個以上之活性能量射線聚合性基之聚合性化合物之含量相對於該活性能量射線聚合性化合物之全部量為30~70重量%。(Active energy ray polymerizable compound) The active energy ray polymerizable compound used in the present invention: (1) A polymerizable compound having two or more active energy ray polymerizable groups and an ethylene oxide group is contained as an essential component ; And (2) The content of the polymerizable compound having two or more active energy ray polymerizable groups is 30 to 70% by weight relative to the total amount of the active energy ray polymerizable compound.
(1) 具有2個以上活性能量射線聚合性基且具有環氧乙烷基之聚合性化合物 就本發明中使用之具有2個以上活性能量射線聚合性基且具有環氧乙烷基之聚合性化合物而言，並沒有特別之限定，可使用公知者。 (其中，在本發明中，二(甲基)丙烯酸酯表示具有2個(甲基)丙烯醯基之化合物，三(甲基)丙烯酸酯表示具有3個(甲基)丙烯醯基之化合物，多(甲基)丙烯酸酯表示具有2個以上(甲基)丙烯醯基之化合物，(甲基)丙烯酸酯表示丙烯酸酯及甲基丙烯酸酯之總稱，(甲基)丙烯醯基表示丙烯醯基及甲基丙烯醯基之總稱。此外，有時會將環氧乙烷簡稱為EO)(1) A polymerizable compound having two or more active energy ray polymerizable groups and having an ethylene oxide group is used in the present invention, having two or more active energy ray polymerizable groups and having an ethylene oxide group polymerizable property The compound is not particularly limited, and known ones can be used. (In the present invention, di(meth)acrylate means a compound having 2 (meth)acrylic groups, and tri(meth)acrylate means a compound having 3 (meth)acrylic groups, Poly(meth)acrylate refers to a compound having two or more (meth)acrylic groups, (meth)acrylate refers to the general term of acrylate and methacrylate, and (meth)acrylic refers to acrylic And methacrylic acid group. In addition, sometimes ethylene oxide is abbreviated as EO)
可舉例如乙二醇二(甲基)丙烯酸酯、二乙二醇二(甲基)丙烯酸酯、三乙二醇二(甲基)丙烯酸酯、四乙二醇二(甲基)丙烯酸酯、七乙二醇二(甲基)丙烯酸酯等將具有環氧乙烷基之二醇與(甲基)丙烯酸進行反應而得之環氧乙烷基改性二(甲基)丙烯酸酯、或For example, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, Heptaethylene glycol di(meth)acrylate, etc., an oxirane-modified di(meth)acrylate obtained by reacting a glycol having an oxirane group with (meth)acrylic acid, or
三羥甲基丙烷之環氧乙烷改性多(甲基)丙烯酸酯、二(三羥甲基)丙烷之環氧乙烷改性多(甲基)丙烯酸酯、新戊四醇之環氧乙烷改性多(甲基)丙烯酸酯、二新戊四醇之環氧乙烷改性多(甲基)丙烯酸酯、四羥甲基甲烷之環氧乙烷改性多(甲基)丙烯酸酯等將具有環氧乙烷基之多元醇與(甲基)丙烯酸反應而得之環氧乙烷基改性多(甲基)丙烯酸酯、或Ethylene oxide modified poly(meth)acrylate of trimethylolpropane, ethylene oxide modified poly(meth)acrylate of di(trimethylol)propane, epoxy of neopentylerythritol Ethane modified poly(meth)acrylate, ethylene oxide modified poly(meth)acrylate of dineopentaerythritol, ethylene oxide modified poly(meth)acrylic acid of tetramethylolmethane Ester, etc., an oxirane-modified poly(meth)acrylate obtained by reacting a polyol having an oxirane group with (meth)acrylic acid, or
環氧乙烷基改性環氧多(甲基)丙烯酸酯、環氧乙烷基改性胺甲酸乙酯多(甲基)丙烯酸酯、環氧乙烷基改性聚酯多(甲基)丙烯酸酯等環氧乙烷改性多(甲基)丙烯酸酯寡聚物等。Ethylene oxide modified epoxy poly(meth)acrylate, ethylene oxide modified urethane poly(meth)acrylate, ethylene oxide modified polyester poly(meth) Ethylene oxide modified poly(meth)acrylate oligomers such as acrylates.
上述環氧乙烷基之重量濃度相對於上述活性能量射線聚合性化合物之全部量為6.0~15.0重量%。藉由使該重量濃度為該範圍，可兼具捲曲性及耐刮性等機械物性。其中，上述環氧乙烷基之重量濃度宜為6.5~10.0重量%，最好宜為7.0~9.0重量%。The weight concentration of the oxirane group is 6.0 to 15.0% by weight relative to the total amount of the active energy ray polymerizable compound. By setting the weight concentration in this range, mechanical properties such as curling and scratch resistance can be achieved. Among them, the weight concentration of the above-mentioned oxirane group is preferably 6.5 to 10.0% by weight, and most preferably 7.0 to 9.0% by weight.
在上述具2個以上之活性能量射線聚合性基且具有環氧乙烷基之聚合性化合物中，宜使用三羥甲基丙烷之環氧乙烷改性多(甲基)丙烯酸酯、二(三羥甲基)丙烷之環氧乙烷改性多(甲基)丙烯酸酯、新戊四醇之環氧乙烷改性多(甲基)丙烯酸酯、二新戊四醇之環氧乙烷改性多(甲基)丙烯酸酯、四羥甲基甲烷之環氧乙烷改性多(甲基)丙烯酸酯等之將具有環氧乙烷基之多元醇與(甲基)丙烯酸進行反應而得之環氧乙烷基改性多(甲基)丙烯酸酯，最好宜使用二新戊四醇之環氧乙烷改性多(甲基)丙烯酸酯。Among the above-mentioned polymerizable compounds having two or more active energy ray polymerizable groups and an ethylene oxide group, it is preferable to use trimethylolpropane ethylene oxide modified poly(meth)acrylate and di( Ethylene oxide modified poly(meth)acrylate of trimethylol)propane, ethylene oxide modified poly(meth)acrylate of neopentylerythritol, ethylene oxide of dineopentylerythritol Modified poly(meth)acrylate, ethylene oxide modified poly(meth)acrylate of tetramethylolmethane, etc. will react polyols with ethylene oxide groups with (meth)acrylic acid The obtained ethylene oxide modified poly (meth) acrylate is preferably the ethylene oxide modified poly (meth) acrylate of dineopentyl erythritol.
(2) 具有2個以上之活性能量射線聚合性基之聚合性化合物 就本發明中使用之具有2個以上之活性能量射線聚合性基之聚合性化合物而言，並沒有特別之限定，可使用公知之化合物。 可舉例如1,3-丁二醇二(甲基)丙烯酸酯、1,4-丁二醇二(甲基)丙烯酸酯、1,5-戊二醇二(甲基)丙烯酸酯、3-甲基-1,5-戊二醇二(甲基)丙烯酸酯、1,6-己二醇二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、1,8-辛二醇二(甲基)丙烯酸酯、1,9-壬二醇二(甲基)丙烯酸酯、三環癸烷二甲醇二(甲基)丙烯酸酯、乙二醇二(甲基)丙烯酸酯、或(2) The polymerizable compound having two or more active energy ray polymerizable groups. As for the polymerizable compound having two or more active energy ray polymerizable groups used in the present invention, there is no particular limitation and can be used Well-known compound. For example, 1,3-butanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,5-pentanediol di(meth)acrylate, 3- Methyl-1,5-pentanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,8-octane Glycol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, ethylene glycol di(meth)acrylate, or
具有2個以上活性能量射線聚合性基且具有環氧乙烷基之聚合性化合物、具有環氧乙烷基以外之環氧烷基之聚合性化合物，例如丙二醇二(甲基)丙烯酸酯、二丙二醇二(甲基)丙烯酸酯、三丙二醇二(甲基)丙烯酸酯、四丙二醇二(甲基)丙烯酸酯、聚丙二醇二(甲基)丙烯酸酯、1,3-丁二醇二(甲基)丙烯酸酯、1,4-丁二醇二(甲基)丙烯酸酯、1,6-己二醇二(甲基)丙烯酸酯、1,9-壬二醇二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、羥基三甲基乙酸新戊二醇二(甲基)丙烯酸酯、對於羥基三甲基乙酸新戊二醇加成己內酯而得之化合物之二(甲基)丙烯酸酯、新戊二醇己二酸二(甲基)丙烯酸酯、或A polymerizable compound having two or more active energy ray polymerizable groups and an ethylene oxide group, a polymerizable compound having an alkylene oxide group other than the ethylene oxide group, such as propylene glycol di(meth)acrylate, Propylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, tetrapropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, 1,3-butanediol di(meth)acrylate ) Acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, new Pentylene glycol di(meth)acrylate, hydroxytrimethylacetate neopentyl glycol di(meth)acrylate, and hydroxytrimethylacetate neopentyl glycol di(meth)acrylate, the second compound obtained by adding caprolactone to hydroxytrimethylacetate neopentyl glycol ( Meth) acrylate, neopentyl glycol adipate di(meth)acrylate, or
三羥甲基丙烷三(甲基)丙烯酸酯、新戊四醇三(甲基)丙烯酸酯、二新戊四醇之多(甲基)丙烯酸酯、對於三羥甲基丙烷、二(三羥甲基)丙烷、新戊四醇、二新戊四醇、四羥甲基甲烷加成了1~20莫耳之環氧乙烷以外的環氧烷而得之含羥基化合物等之具有3個以上羥基之化合物與(甲基)丙烯酸形成3分子以上之酯鍵結而得之化合物等、或Trimethylolpropane tri(meth)acrylate, neopentylerythritol tri(meth)acrylate, dineopentaerythritol as much as (meth)acrylate, for trimethylolpropane, di(trihydroxyl) (Methyl)propane, neopentylerythritol, dineopentylerythritol, tetramethylolmethane and 1-20 moles of ethylene oxide other than alkylene oxide, which have 3 hydroxyl-containing compounds The compound of the above hydroxyl group and (meth)acrylic acid form an ester bond of more than 3 molecules, etc., or
藉由將選自於由雙酚A型環氧樹脂、雙酚F型環氧樹脂、一部分經鹵素取代之雙酚A型環氧樹脂、一部分經鹵素取代之雙酚F型環氧樹脂、氫化雙酚A型環氧樹脂、及此等之混合物構成之群組中之1種以上的環氧樹脂與多莫耳之(甲基)丙烯酸反應而得之雙酚型的環氧(甲基)丙烯酸酯或苯酚酚醛清漆型之環氧(甲基)丙烯酸酯、甲酚酚醛清漆型之環氧(甲基)丙烯酸酯、萘骨架之環氧(甲基)丙烯酸酯或此等之混合物、或By selecting from bisphenol A type epoxy resin, bisphenol F type epoxy resin, part of bisphenol A type epoxy resin substituted by halogen, part of bisphenol F type epoxy resin substituted by halogen, hydrogenated Bisphenol-A type epoxy resins and mixtures of these epoxy resins are obtained by reacting at least one type of epoxy resins with Domol (meth)acrylic acid. Acrylate or phenol novolac type epoxy (meth)acrylate, cresol novolak type epoxy (meth)acrylate, naphthalene skeleton epoxy (meth)acrylate or a mixture of these, or
藉由多元醇與具有環狀結構之有機多異氰酸酯與多莫耳之含羥基(甲基)丙烯酸酯反應而得之胺甲酸乙酯(甲基)丙烯酸酯、藉由具有環狀結構之二醇與有機多異氰酸酯與多莫耳之含羥基(甲基)丙烯酸酯的反應而得之胺甲酸乙酯(甲基)丙烯酸酯、藉由具有環狀結構之有機多異氰酸酯與多莫耳之含羥基(甲基)丙烯酸酯之反應而得之胺甲酸乙酯(甲基)丙烯酸酯等。Urethane (meth)acrylate obtained by reacting a polyol with an organic polyisocyanate having a cyclic structure and a hydroxyl-containing (meth)acrylate of Domolar, and a diol having a cyclic structure Urethane (meth)acrylate obtained by the reaction of organic polyisocyanate and hydroxy-containing (meth)acrylate of Domol, through organic polyisocyanate having cyclic structure and hydroxy-containing Domol Urethane (meth)acrylate, etc. obtained by the reaction of (meth)acrylate.
上述具有2個以上活性能量射線聚合性基之聚合性化合物可使用1種亦可混合多種使用。The above-mentioned polymerizable compound having two or more active energy ray polymerizable groups may be used alone or in combination of multiple types.
如同前述，在本發明中，上述具有2個以上活性能量射線聚合性基之聚合性化合物相對於上述活性能量射線聚合性化合物之全部量必須為30~70重量%。在該範圍，尤其可獲得耐捲曲性、耐刮性等機械特性之平衡優良的硬化物。其中，具有2個以上活性能量射線聚合性基之聚合性化合物為40~60重量%較為理想。As mentioned above, in the present invention, the polymerizable compound having two or more active energy ray polymerizable groups must be 30 to 70% by weight relative to the total amount of the active energy ray polymerizable compound. In this range, a cured product having an excellent balance of mechanical properties such as curl resistance and scratch resistance can be obtained. Among them, the polymerizable compound having two or more active energy ray polymerizable groups is preferably 40 to 60% by weight.
(具有芳香族基之聚合性化合物) 在本發明中，使用具有芳香族基之聚合性化合物、具有環狀脂肪族結構之聚合性化合物、具有雜環結構之聚合性化合物、苯乙烯系化合物、具有直鏈狀脂肪族結構之聚合性化合物等，可獲得耐刮性或對於光學片為必要性能之高折射率而較為理想。例如，上述具有芳香族基之聚合性化合物之含量宜為使芳香族基之重量濃度相對於上述活性能量射線聚合性化合物之全部量為30~60重量%，其中宜為30~50重量%。(Polymerizable compound having an aromatic group) In the present invention, a polymerizable compound having an aromatic group, a polymerizable compound having a cyclic aliphatic structure, a polymerizable compound having a heterocyclic structure, a styrene compound, Polymerizable compounds having a linear aliphatic structure, etc., are ideal for obtaining scratch resistance or high refractive index which is necessary for optical sheets. For example, the content of the above-mentioned aromatic group-containing polymerizable compound is preferably such that the weight concentration of the aromatic group is 30-60% by weight relative to the total amount of the above-mentioned active energy ray polymerizable compound, and preferably 30-50% by weight.
就上述具有芳香族基之聚合性化合物而言，可舉例如具有芳香環之(甲基)丙烯酸酯類等。就具有芳香環之(甲基)丙烯酸酯類而言，可舉例如(甲基)丙烯酸苄醯氧基乙酯、(甲基)丙烯酸苄酯、(甲基)丙烯酸苯基乙酯、(甲基)丙烯酸苯氧基乙酯、苯氧基二乙二醇(甲基)丙烯酸酯、(甲基)丙烯酸2-羥基-3-苯氧基丙酯、2-苯基-2-(4-丙烯醯氧基苯基)丙烷、2-苯基-2-(4-丙烯醯氧基烷氧基苯基)丙烷、(甲基)丙烯酸2,4,6-三氯苯酯、(甲基)丙烯酸2,4,6-三溴苯酯、(甲基)丙烯酸2,4,6-三氯苄酯、(甲基)丙烯酸2,4,6-三溴苄酯、(甲基)丙烯酸2,4,6-三氯苯氧基乙酯、(甲基)丙烯酸2,4,6-三溴苯氧基乙酯、(甲基)丙烯酸鄰苯基苯酚(多)乙氧酯、(甲基)丙烯酸對苯基苯酚(多)乙氧酯等。Examples of the above-mentioned polymerizable compound having an aromatic group include (meth)acrylates having an aromatic ring. For (meth)acrylates having an aromatic ring, for example, benzyloxyethyl (meth)acrylate, benzyl (meth)acrylate, phenylethyl (meth)acrylate, (meth)acrylate Base) phenoxyethyl acrylate, phenoxydiethylene glycol (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, 2-phenyl-2-(4- Acrylic oxyphenyl) propane, 2-phenyl-2-(4-propenoxy alkoxy phenyl) propane, 2,4,6-trichlorophenyl (meth)acrylate, (methyl) ) 2,4,6-tribromophenyl acrylate, 2,4,6-trichlorobenzyl (meth)acrylate, 2,4,6-tribromobenzyl (meth)acrylate, (meth)acrylic acid 2,4,6-trichlorophenoxyethyl, (meth)acrylate 2,4,6-tribromophenoxyethyl, (meth)acrylate o-phenylphenol (poly)ethoxyester, ( Meth)acrylic acid p-phenylphenol (poly)ethoxyester and the like.
就上述具有環狀脂肪族結構之聚合性化合物而言，可舉例如具有環狀脂肪族之(甲基)丙烯酸酯類。就具有環狀脂肪族(甲基)丙烯酸酯類而言，可舉例如(甲基)丙烯酸環己酯、(甲基)丙烯酸異莰酯、(甲基)丙烯酸二環戊酯、(甲基)丙烯酸二環戊烯基氧基乙酯、(甲基)丙烯酸四氫糠(tetrahydrofurfuryl)酯、環氧丙基環碳酸酯(甲基)丙烯酸酯、二(甲基)丙烯酸三環癸烷二羥甲酯等。Examples of the polymerizable compound having a cycloaliphatic structure include (meth)acrylates having a cycloaliphatic structure. With regard to cycloaliphatic (meth)acrylates, for example, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentyl (meth)acrylate, (meth) )Dicyclopentenyloxyethyl acrylate, tetrahydrofurfuryl (meth)acrylate, glycidyl cyclocarbonate (meth)acrylate, tricyclodecane di(meth)acrylate Hydroxymethyl and so on.
就上述苯乙烯系化合物而言，可舉例如苯乙烯、α-甲基苯乙烯、氯苯乙烯等。Examples of the above-mentioned styrene compounds include styrene, α-methylstyrene, and chlorostyrene.
就上述雜環系化合物而言，可舉例如N-乙烯基吡咯啶酮、N-乙烯基己內酯、丙烯醯基𠰌啉、參(2-羥乙基)異氰尿酸酯(isocyanurate)、參(羥丙基)異氰尿酸酯及將1~20莫耳之環氧烷或ε己內酯對於此等進行開環加成而得之含羥基化合物等具有羥基之化合物與(甲基)丙烯酸形成酯鍵而得之具有異三聚氰酸結構的化合物等。The above heterocyclic compounds include, for example, N-vinylpyrrolidone, N-vinylcaprolactone, acryloyl 𠰌line, ginseng (2-hydroxyethyl) isocyanurate (isocyanurate) , Ginseng (hydroxypropyl) isocyanurate and the ring-opening addition of 1-20 mol of alkylene oxide or epsilon caprolactone to these hydroxyl-containing compounds and other compounds having hydroxyl groups and (former A compound having an isocyanuric acid structure obtained by forming an ester bond of acrylic acid.
(具2個以上活性能量射線聚合性基且具有環氧乙烷基，且具有芳香族基之聚合性化合物) 此外，當然也宜使用上述具2個以上活性能量射線聚合性基且具有環氧乙烷基，且具有芳香族基之聚合性化合物。就如此之聚合性化合物而言，可列舉為環氧乙烷基改性環氧多(甲基)丙烯酸酯之環氧乙烷改性雙酚A環氧多(甲基)丙烯酸酯、環氧乙烷改性雙酚F環氧多(甲基)丙烯酸酯、環氧乙烷改性雙酚S環氧多(甲基)丙烯酸酯等。此等之環氧乙烷基改性環氧多(甲基)丙烯酸酯所具有之環氧乙烷基係1分子中於平均值具有1~30個重複單元數較為理想。(Polymerizable compound having two or more active energy ray polymerizable groups, ethylene oxide group, and aromatic group) In addition, of course, it is also suitable to use the above-mentioned two or more active energy ray polymerizable groups and epoxy Ethyl group and a polymerizable compound having an aromatic group. For such polymerizable compounds, ethylene oxide modified bisphenol A epoxy poly(meth)acrylate, epoxy poly(meth)acrylate, epoxy Ethane modified bisphenol F epoxy poly(meth)acrylate, ethylene oxide modified bisphenol S epoxy poly(meth)acrylate, etc. The ethylene oxide group of these ethylene oxide-modified epoxy poly(meth)acrylates preferably has 1 to 30 repeating units on an average value per molecule.
上述具有環氧乙烷基及2個以上活性能量射線聚合性基之聚合性化合物可使用1種，也可混合多種使用。混合多種使用時，例如雙酚A之環氧乙烷加成之二丙烯酸酯與二新戊四醇之環氧乙烷加成物之丙烯酸酯的組合、或雙酚A之環氧乙烷加成之二丙烯酸酯與三羥甲基丙烷之環氧乙烷加成物之丙烯酸酯的組合較為理想。The above-mentioned polymerizable compound having an oxirane group and two or more active energy ray polymerizable groups may be used singly or in combination of multiple types. When mixing multiple types, for example, the combination of diacrylate of ethylene oxide adduct of bisphenol A and acrylate of ethylene oxide adduct of dineopentaerythritol, or ethylene oxide of bisphenol A The combination of the resulting diacrylate and the acrylate of the ethylene oxide adduct of trimethylolpropane is ideal.
本發明之硬化性組成物推測是藉由於交聯結構中納入環氧乙烷鏈，而可獲得就捲曲性而言為優良且兼具機械物性(耐刮性等)之硬化物者。使用於交聯結構中未納入環氧乙烷鏈，具有如懸吊於側鏈之環氧乙烷骨架的單官能聚合性化合物時，因為交聯密度下降，雖然捲曲性受到抑制但有可能無法獲得兼具機械物性之硬化物。 考慮此等情事，具2個以上活性能量射線聚合性基且具有環氧乙烷基之聚合性化合物係在多個活性能量射線聚合性基之間存在有環氧乙烷鏈如此之結構較為理想。The curable composition of the present invention is presumably obtained by incorporating an ethylene oxide chain in the cross-linked structure to obtain a cured product that is excellent in curling properties and has mechanical properties (scratch resistance, etc.). When used in a monofunctional polymerizable compound that does not include an ethylene oxide chain in the cross-linked structure and has an ethylene oxide skeleton suspended from the side chain, the cross-linking density decreases, although the curling property is suppressed, but it may not be possible Obtain a hardened product with both mechanical properties. Considering these circumstances, it is preferable that a polymerizable compound having two or more active energy ray polymerizable groups and an ethylene oxide group has an ethylene oxide chain between multiple active energy ray polymerizable groups. .
(其他之聚合性化合物) 在本發明中，併用具有1個活性能量射線聚合性基之聚合性化合物(有時稱為單官能單體)較為理想。就單官能單體而言並沒有特別之限定，可使用公知之單體。(Other polymerizable compounds) In the present invention, it is preferable to use a polymerizable compound having one active energy ray polymerizable group (sometimes referred to as a monofunctional monomer). The monofunctional monomer is not particularly limited, and known monomers can be used.
可使用例如(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丙酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸己酯、(甲基)丙烯酸庚酯、(甲基)丙烯酸辛酯、(甲基)丙烯酸壬酯、(甲基)丙烯酸癸酯、(甲基)丙烯酸十二烷酯、(甲基)丙烯酸十四烷酯、(甲基)丙烯酸十六烷酯、(甲基)丙烯酸硬脂酯、(甲基)丙烯酸十八烷酯、(甲基)丙烯酸二十二烷酯等具有碳數1~22之烷基的(甲基)丙烯酸酯類；(甲基)丙烯酸羥乙酯、(甲基)丙烯酸羥丙酯、(甲基)丙烯酸甘油酯、内酯改性(甲基)丙烯酸羥乙酯、(甲基)丙烯酸聚乙二醇酯、(甲基)丙烯酸聚丙二醇酯等具有羥烷基之丙烯酸酯類等之具有烷基之(甲基)丙烯酸酯類、或For example, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate can be used , Octyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, dodecyl (meth)acrylate, tetradecyl (meth)acrylate, (meth)acrylic acid Cetyl ester, stearyl (meth)acrylate, stearyl (meth)acrylate, behenyl (meth)acrylate, etc. (meth)acrylic acid having an alkyl group with 1 to 22 carbon atoms Esters; hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, glycerol (meth)acrylate, lactone modified hydroxyethyl (meth)acrylate, polyethylene (meth)acrylate Alkyl esters, polypropylene glycol (meth)acrylates, etc., acrylates with hydroxyalkyl groups, etc. (meth)acrylates with alkyl groups, or
(甲基)丙烯酸環氧丙酯、α-乙基(甲基)丙烯酸環氧丙酯、α-正丙基(甲基)丙烯酸環氧丙酯、α-正丁基(甲基)丙烯酸環氧丙酯、(甲基)丙烯酸-3,4-環氧丁酯、(甲基)丙烯酸-4,5-環氧戊酯、(甲基)丙烯酸-6,7-環氧戊酯、α-乙基(甲基)丙烯酸-6,7-環氧戊酯、(甲基)丙烯酸β-甲基環氧丙酯、(甲基)丙烯酸-3,4-環氧基環己酯、內酯改性(甲基)丙烯酸-3,4-環氧基環己酯、乙烯基環氧己烯氧化物等具有聚合性不飽和雙鍵及環氧基之聚合性化合物、(Meth) glycidyl acrylate, α-ethyl (meth) glycidyl acrylate, α-n-propyl (meth) glycidyl acrylate, α-n-butyl (meth) acrylate ring Propylene oxide, 3,4-epoxybutyl (meth)acrylate,-4,5-epoxypentyl (meth)acrylate, 6,7-epoxypentyl (meth)acrylate, α -Ethyl (meth)acrylate-6,7-epoxypentyl ester, (meth)acrylate β-methylglycidyl ester, (meth)acrylate-3,4-epoxycyclohexyl ester, internal Ester-modified (meth)acrylic acid-3,4-epoxycyclohexyl, vinyl epoxyhexene oxide and other polymerizable compounds having polymerizable unsaturated double bonds and epoxy groups,
(甲基)丙烯酸、(甲基)丙烯酸β-羧基乙酯、2-丙烯醯氧基乙基琥珀酸、2-丙烯醯氧基乙基鄰苯二甲酸、2-丙烯醯氧基乙基六氫鄰苯二甲酸及此等之內酯改性物等具有酯鍵之不飽和單羧酸、馬來酸等具有聚合性不飽和雙鍵及羧基之聚合性單體、(Meth) acrylic acid, β-carboxyethyl (meth)acrylate, 2-propenyloxyethyl succinic acid, 2-propenyloxyethyl phthalic acid, 2-propenyloxyethyl hexa Unsaturated monocarboxylic acids with ester bonds such as hydrogen phthalic acid and modified lactones, and polymerizable monomers with polymerizable unsaturated double bonds and carboxyl groups such as maleic acid,
富馬酸二甲酯、富馬酸二乙酯、富馬酸二丁酯、伊康酸二甲酯、伊康酸二丁酯、富馬酸甲基乙酯、富馬酸甲基丁酯、伊康酸甲基乙酯等不飽和二羧酸酯類、Dimethyl Fumarate, Diethyl Fumarate, Dibutyl Fumarate, Dimethyl Iconate, Dibutyl Iconate, Methyl Ethyl Fumarate, Methyl Butyl Fumarate , Unsaturated dicarboxylic acid esters such as methyl ethyl itconate,
苯乙烯、α-甲基苯乙烯、氯苯乙烯等苯乙烯衍生物類；丁二烯、異戊二烯、戊二烯、二甲基丁二烯等二烯系化合物類；氯乙烯、溴乙烯等鹵化乙烯和鹵化亞乙烯類；甲基乙烯基酮、丁基乙烯基酮等不飽和酮類；乙酸乙烯酯、丁酸乙烯酯等乙烯酯類；甲基乙烯基醚、丁基乙烯基醚等乙烯基醚類；丙烯腈、甲基丙烯腈、氰化亞乙烯等氰化乙烯類；丙烯醯胺或其酸醇取代醯胺類；N-苯基馬來醯亞胺、N-環己基馬來醯亞胺等N-取代馬來醯亞胺類；Styrene derivatives such as styrene, α-methylstyrene and chlorostyrene; diene compounds such as butadiene, isoprene, pentadiene, dimethylbutadiene, etc.; vinyl chloride, bromine Halogenated vinyl and halogenated vinylenes such as ethylene; unsaturated ketones such as methyl vinyl ketone and butyl vinyl ketone; vinyl esters such as vinyl acetate and vinyl butyrate; methyl vinyl ether and butyl vinyl Vinyl ethers such as ether; vinyl cyanide such as acrylonitrile, methacrylonitrile, vinylene cyanide; acrylamide or its acid alcohol substituted amides; N-phenylmaleimide, N-ring N-substituted maleimines such as hexyl maleimines;
氟化乙烯、偏二氟乙烯、三氟乙烯、氯三氟乙烯、溴三氟乙烯、五氟丙烯或六氟丙烯等含氟α-烯烴類；或三氟甲基三氟乙烯基醚、五氟乙基三氟乙烯基醚或七氟丙基三氟乙烯基醚等(全)氟烷基之碳數為1至18之(全)氟烷基・全氟乙烯基醚類；(甲基)丙烯酸2,2,2-三氟乙酯、(甲基)丙烯酸2,2,3,3-四氟丙酯、(甲基)丙烯酸1H,1H,5H-八氟戊酯、(甲基)丙烯酸1H,1H,2H,2H-十七氟癸酯或(甲基)丙烯酸全氟乙氧基乙酯等(全)氟烷基之碳數為1至18的(甲基)丙烯酸(全)氟烷酯類等含氟之乙烯性不飽和單體類；Fluorinated α-olefins such as fluorinated ethylene, vinylidene fluoride, trifluoroethylene, chlorotrifluoroethylene, bromotrifluoroethylene, pentafluoropropylene or hexafluoropropylene; or trifluoromethyl trifluorovinyl ether, five Fluoroethyl trifluorovinyl ether or heptafluoropropyl trifluorovinyl ether and other (per)fluoroalkyl (per)fluoroalkyl and perfluorovinyl ethers with carbon numbers of 1 to 18; (methyl ) 2,2,2-trifluoroethyl acrylate, 2,2,3,3-tetrafluoropropyl (meth)acrylate, 1H,1H,5H-octafluoropentyl (meth)acrylate, (methyl) )Acrylic 1H, 1H, 2H, 2H-heptadecafluorodecyl or perfluoroethoxyethyl (meth)acrylate and other (per)fluoroalkyl (meth)acrylic acid with carbon number of 1 to 18 (all ) Fluorine-containing ethylenically unsaturated monomers such as fluoroalkyl esters;
γ-甲基丙烯醯氧基丙基三甲氧基矽烷等含矽基之(甲基)丙烯酸酯類；(甲基)丙烯酸N,N-二甲基胺基乙酯、(甲基)丙烯酸N,N-二乙基胺基乙酯或(甲基)丙烯酸N,N-二乙基胺基丙酯等(甲基)丙烯酸N,N-二烷基胺基烷酯；γ-methacryloxypropyltrimethoxysilane and other silicon-containing (meth)acrylates; (meth)acrylic acid N,N-dimethylaminoethyl, (meth)acrylic acid N , N,N-dialkylaminoethyl (meth)acrylate or N,N-diethylaminopropyl (meth)acrylate, etc.;
(甲基)丙烯酸磷乙酯(phosphoethyl (meth)acrylate)、(甲基)丙烯酸N,N-二甲基胺基乙酯、(甲基)丙烯酸N,N-二乙基胺基乙酯或(甲基)丙烯酸N,N-二乙基胺基丙酯、二[(甲基)丙烯醯氧基乙基]磷酸酯、三[(甲基)丙烯醯氧基乙基]磷酸酯等。Phosphoethyl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylate, N,N-diethylaminoethyl (meth)acrylate or (Meth)acrylic acid N,N-diethylaminopropyl ester, bis[(meth)acryloxyethyl]phosphate, tris[(meth)acryloxyethyl]phosphate, etc.
其中，就理想之單官能單體而言，可舉例如式(1)表示之1官能(甲基)丙烯酸酯。Among them, as an ideal monofunctional monomer, for example, monofunctional (meth)acrylate represented by formula (1) can be mentioned.
【化2】
(式(1)中，R1 係氫原子，R2 係氫原子或甲基，n之平均值係1~5之數。) 可藉由例如將對苯基苯酚或鄰苯基苯酚與環氧乙烷或環氧丙烷的反應物，和(甲基)丙烯酸反應來獲得式(1)表示之化合物。對苯基苯酚或鄰苯基苯酚與環氧乙烷或環氧丙烷的反應物可輕易地從市面上取得。可使用例如三洋化成(股)製，NEWPOL OPE-20(使2莫耳環氧乙烷對於1莫耳鄰苯基苯酚反應而得者。)、NEWPOL OPE-40(使4莫耳環氧乙烷對於1莫耳鄰苯基苯酚反應而得者。)等。(In formula (1), R 1 is a hydrogen atom, R 2 is a hydrogen atom or a methyl group, and the average value of n is a number from 1 to 5.) For example, p-phenylphenol or o-phenylphenol and ring The reactant of oxyethane or propylene oxide reacts with (meth)acrylic acid to obtain the compound represented by formula (1). The reactant of p-phenylphenol or o-phenylphenol with ethylene oxide or propylene oxide can be easily obtained from the market. For example, Sanyo Kasei Co., Ltd., NEWPOL OPE-20 (reacted by reacting 2 moles of ethylene oxide to 1 mole of o-phenylphenol.), NEWPOL OPE-40 (using 4 moles of ethylene oxide for 1 Mole of o-phenylphenol reaction.) and so on.
就上述單官能單體而言，可使用1種亦可混合多種使用。混合多種使用時，例如(甲基)丙烯酸鄰苯基苯酚(多)乙氧酯與(甲基)丙烯酸苯氧基(多)乙氧酯之組合，就確保高折射率及與基材薄膜的黏合性上較為理想。此外，(甲基)丙烯酸鄰苯基苯酚(多)乙氧酯與丙烯酸苯氧基苄酯的組合就賦予高折射率、低黏度及復原性(稜鏡)的方面較為理想。Regarding the above-mentioned monofunctional monomer, one type may be used, or multiple types may be mixed and used. When multiple types are used in combination, for example, the combination of ortho-phenylphenol (poly)ethoxy (meth)acrylate and phenoxy (poly)ethoxy (meth)acrylate can ensure high refractive index and good compatibility with the substrate film. The adhesion is ideal. In addition, the combination of ortho-phenylphenol (poly)ethoxy (meth)acrylate and phenoxybenzyl acrylate is ideal in terms of imparting high refractive index, low viscosity, and restoring properties.
在本發明中，上述單官能單體在不損害本發明之效果的範圍內使用較為理想。具體而言，在相對於上述活性能量射線聚合性化合物之全部量為30~70重量%之範圍內較為理想。其中，單官能單體為40~60重量%，就同時實現作業性(低黏度化)與機械物性兩者上較為理想。In the present invention, the above-mentioned monofunctional monomer is preferably used in a range that does not impair the effects of the present invention. Specifically, it is preferably within a range of 30 to 70% by weight relative to the total amount of the active energy ray polymerizable compound. Among them, the monofunctional monomer is 40 to 60% by weight, which is ideal for achieving both workability (lower viscosity) and mechanical properties.
(光聚合起始劑) 就本發明中使用之光聚合起始劑而言，可舉例如二苯基酮、3,3’-二甲基-4-甲氧基二苯基酮、4,4’-雙二甲基胺基二苯基酮、4,4’-雙二乙基胺基二苯基酮、4,4’-二氯二苯基酮、米其勒酮(Michler's ketone)、3,3’,4,4’-四(三級丁基過氧化羰基)二苯基酮等二苯基酮類；(Photopolymerization initiator) As the photopolymerization initiator used in the present invention, for example, benzophenone, 3,3'-dimethyl-4-methoxybenzophenone, 4, 4'-bis-dimethylamino benzophenone, 4,4'-bis-diethylamino benzophenone, 4,4'-dichloro benzophenone, Michler's ketone , 3,3',4,4'-tetra(tertiary butylperoxycarbonyl)diphenyl ketone and other diphenyl ketones;
氧雜蒽酮(xanthone)、噻吨酮(thioxanthone)、2-甲基噻吨酮、2-氯噻吨酮、2,4-二乙基噻吨酮等氧雜蒽酮、噻吨酮類；安息香(Benzoin)、安息香甲醚、安息香***、安息香異丙醚等醯偶姻醚(acyloin ether)類；Xanthones (xanthone), thioxanthone (thioxanthone), 2-methylthioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone and other xanthones, thioxanthones ; Benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether and other acyloin ethers;
二苯乙二酮(benzil)、聯乙醯等α-二酮類；二硫化四甲基秋蘭姆(tetramethylthiuram disulfide)、對甲苯二硫化物等硫化物類；4-二甲基胺基苯甲酸、4-二甲基胺基苯甲酸乙酯等苯甲酸類；Α-diketones such as benzil and biacetin; sulfides such as tetramethylthiuram disulfide and p-toluene disulfide; 4-dimethylaminobenzene Benzoic acids such as formic acid and ethyl 4-dimethylaminobenzoate;
3,3’-羰基-雙(7-二乙基胺基)香豆素、1-羥基環己基苯基酮、2,2’-二甲氧基-1,2-二苯基乙-1-酮、2-甲基-1-[4-(甲硫基)苯基]-2-𠰌啉基丙-1-酮、2-苄基-2-二甲基胺基-1-(4-𠰌啉基苯基)-丁-1-酮、2-羥基-2-甲基-1-苯基丙-1-酮、2,4,6-三甲基苯甲醯基二苯基氧化膦、雙(2,4,6-三甲基苯甲醯基)苯基氧化膦、1-[4-(2-羥基乙氧基)苯基]-2-羥基-2-甲基-1-丙-1-酮、1-(4-異丙基苯基)-2-羥基-2-甲基丙-1-酮、1-(4-十二烷基苯基)-2-羥基-2-甲基丙-1-酮、4-苯甲醯基-4’-甲基二甲基硫化物、2,2’-二乙氧基苯乙酮、苄基二甲基縮酮、苄基-β-甲氧基乙基縮醛、鄰苯甲醯基苯甲酸甲酯、雙(4-二甲基胺基苯基)酮、對二甲基胺基苯乙酮、α,α-二氯-4-苯氧基苯乙酮、戊基-4-二甲基胺基苯甲酸酯、2-(鄰氯苯基)-4,5-二苯基咪唑基二聚體、2,4-雙-三氯甲基-6-[二-(乙氧基羰基甲基)胺基]苯基-S-三氮雜苯、2,4-雙-三氯甲基-6-(4-乙氧基)苯基-S-三氮雜苯、2,4-雙-三氯甲基-6-(3-溴-4-乙氧基)苯基-S-三氮雜苯蔥醌、2-三級丁基蔥醌、2-戊基蔥醌、β-氯蔥醌等。3,3'-carbonyl-bis(7-diethylamino) coumarin, 1-hydroxycyclohexyl phenyl ketone, 2,2'-dimethoxy-1,2-diphenylethane-1 -Ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-𠰌olinylpropan-1-one, 2-benzyl-2-dimethylamino-1-(4 -𠰌linylphenyl)-butan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2,4,6-trimethylbenzyldiphenyl oxide Phosphine, bis(2,4,6-trimethylbenzyl)phenylphosphine oxide, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1 -Propan-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-(4-dodecylphenyl)-2-hydroxy- 2-methylpropan-1-one, 4-benzyl-4'-methyl dimethyl sulfide, 2,2'-diethoxy acetophenone, benzyl dimethyl ketal, benzyl -Β-methoxyethyl acetal, methyl phthalate, bis(4-dimethylaminophenyl) ketone, p-dimethylaminoacetophenone, α,α- Dichloro-4-phenoxyacetophenone, pentyl-4-dimethylaminobenzoate, 2-(o-chlorophenyl)-4,5-diphenylimidazolyl dimer, 2 ,4-Bis-trichloromethyl-6-[bis-(ethoxycarbonylmethyl)amino]phenyl-S-triazine, 2,4-bis-trichloromethyl-6-( 4-ethoxy)phenyl-S-triazine, 2,4-bis-trichloromethyl-6-(3-bromo-4-ethoxy)phenyl-S-triazine Quinone, 2-tertiary butyl onionquinone, 2-pentyl onionquinone, β-chloronionquinone, etc.
上述光聚合起始劑可使用1種亦可混合多種使用。其使用量雖然沒有特別之限制，為了保持感度良好，防止結晶析出、塗膜物性之劣化等，相對於本發明之光學物品用活性能量射線硬化型樹脂組成物100重量份宜使用0.05~20重量份，其中為0.1~10重量份特別理想。The above-mentioned photopolymerization initiator may be used singly or in combination of multiple types. Although the amount used is not particularly limited, in order to maintain good sensitivity, prevent crystal precipitation, deterioration of coating film properties, etc., it is preferable to use 0.05 to 20 parts by weight relative to 100 parts by weight of the active energy ray curable resin composition for optical articles of the present invention Parts, of which 0.1-10 parts by weight is particularly desirable.
其中，選自1-羥基環己基苯基酮、2-羥基-2-甲基-1-苯基丙-1-酮、1-[4-(2-羥基乙氧基)苯基]-2-羥基-2-甲基-1-丙-1-酮、噻吨酮及噻吨酮衍生物、2,2’-二甲氧基-1,2-二苯基乙-1-酮、2,4,6-三甲基苯甲醯基二苯基氧化膦、雙(2,4,6-三甲基苯甲醯基)苯基氧化膦、2-甲基-1-[4-(甲硫基)苯基]-2-𠰌啉基-1-丙烷酮、2-苄基-2-二甲基胺基-1-(4-𠰌啉基苯基)-丁-1-酮之群組中之1種或2種以上之混合系，就為了獲得硬化性高之光學物品用活性能量射線硬化型樹脂組成物而言特別理想。Among them, selected from 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-(2-hydroxyethoxy)phenyl]-2 -Hydroxy-2-methyl-1-propan-1-one, thioxanthone and thioxanthone derivatives, 2,2'-dimethoxy-1,2-diphenylethan-1-one, 2 ,4,6-Trimethylbenzyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzyl)phenylphosphine oxide, 2-methyl-1-[4-( (Methylthio)phenyl)-2-𠰌line-1-propanone, 2-benzyl-2-dimethylamino-1-(4-𠰌linephenyl)-butan-1-one One type or a mixture of two or more types in the group is particularly desirable in order to obtain an active energy ray-curable resin composition for optical articles with high curability.
進一步地，本發明之光學物品用活性能量射線硬化型樹脂組成物可於上述光聚合起始劑中併用各種光敏劑。就光敏劑而言，可舉例如胺類、尿素類、含硫化合物、含磷化合物、含氯化合物或腈類或其他含氮化合物等。Furthermore, the active energy ray-curable resin composition for optical articles of the present invention can use various photosensitizers in combination with the photopolymerization initiator. Examples of photosensitizers include amines, ureas, sulfur-containing compounds, phosphorus-containing compounds, chlorine-containing compounds, nitriles, or other nitrogen-containing compounds.
使用了本發明之光學物品用活性能量射線硬化型樹脂組成物的物品之製造中，紫外線等活性能量射線常常是通過為支撐體之透明基材面進行照射。因此，光聚合起始劑宜為在長波長區域具有吸光能力之起始劑，例如在紫外線為360~450nm之範圍發揮光起始功能之光聚合起始劑較為理想。In the manufacture of articles using the active energy ray-curable resin composition for optical articles of the present invention, active energy rays such as ultraviolet rays are often irradiated through the transparent substrate surface that is the support. Therefore, the photopolymerization initiator is preferably an initiator having light absorbing ability in the long wavelength region, for example, a photopolymerization initiator that functions as a photoinitiator in the range of 360 to 450 nm of ultraviolet rays is preferable.
本發明之光學物品用活性能量射線硬化型樹脂組成物就改良黏度或對於透明基板之黏著性等目的而言，亦可併用樹脂等。可舉例如甲基丙烯酸甲酯樹脂、甲基丙烯酸甲酯系共聚物等丙烯酸樹脂；聚苯乙烯、甲基丙烯酸甲酯-苯乙烯系共聚物；聚酯樹脂；聚氨酯(polyurethane)樹脂；聚丁二烯或丁二烯-丙烯腈系共聚物等聚丁二烯樹脂；雙酚型環氧樹脂、苯氧基樹脂或酚醛清漆型環氧樹脂等環氧樹脂等。The active energy ray-curable resin composition for optical articles of the present invention may also use a resin in combination for the purpose of improving viscosity or adhesion to a transparent substrate. For example, acrylic resins such as methyl methacrylate resin and methyl methacrylate copolymer; polystyrene, methyl methacrylate-styrene copolymer; polyester resin; polyurethane resin; polybutylene Polybutadiene resins such as diene or butadiene-acrylonitrile copolymers; epoxy resins such as bisphenol type epoxy resins, phenoxy resins, or novolac type epoxy resins.
本發明之光學物品用活性能量射線硬化型樹脂組成物的黏度為了可均勻地塗布至母模，進一步地使其可複製具有微細結構之母模，在25℃係100~30000mPa･s之範圍較為理想，其中係150~20000mPa･s特別理想。即使為上述範圍以外之黏度，只要採取控制樹脂組成物之溫度以調整黏度等之方法仍可以使用。The viscosity of the active energy ray-curable resin composition for optical articles of the present invention can be uniformly applied to the master mold and further make it possible to replicate the master mold with a fine structure. The range is 100~30000mPa･s at 25℃. Ideal, of which 150~20000mPa･s is particularly ideal. Even if the viscosity is outside the above range, it can still be used as long as the temperature of the resin composition is controlled to adjust the viscosity.
本發明之光學物品用活性能量射線硬化型樹脂組成物之酸價(將於樣本1g中存在之酸成分依循規定之方法進行中和時需要的氫氧化鉀的毫克數)為5.0mgKOH/g以下因為會成為可獲得環境安定性優良之硬化物的光學物品用活性能量射線硬化型樹脂組成物故較為理想，為0mgKOH/g~3.0mgKOH/g特別理想。The acid value of the active energy ray-curable resin composition for optical articles of the present invention (the number of milligrams of potassium hydroxide required to neutralize the acid component in the sample 1g according to the prescribed method) is 5.0 mgKOH/g or less Since it becomes an active energy ray-curable resin composition for optical articles that can obtain a cured product with excellent environmental stability, it is ideal, and it is particularly desirable that it is 0 mgKOH/g to 3.0 mgKOH/g.
本發明之光學物品用活性能量射線硬化型樹脂組成物在對於形成在基材上之硬化樹脂成形層更進一步要求耐光性的情況等，因應需求可添加紫外線吸收劑。進一步地，在塗膜之改質，或改善塗布適性、從母模之離模性的情況，也可添加抗氧化劑、矽系添加劑、氟系添加劑、流變控制劑、消泡劑、離模劑、矽烷偶聯劑、抗靜電劑、防霧劑、著色劑等。In the active energy ray-curable resin composition for optical articles of the present invention, in cases where light resistance is further required for the cured resin molded layer formed on the substrate, an ultraviolet absorber may be added as required. Further, in the modification of the coating film, or to improve the coating suitability, and the release from the master mold, antioxidants, silicon-based additives, fluorine-based additives, rheology control agents, defoamers, and mold release can also be added Agent, silane coupling agent, antistatic agent, antifogging agent, coloring agent, etc.
就紫外線吸收劑而言，可舉例如2-[4-{(2-羥基-3-十二烷氧基丙基)氧基}-2-羥基苯基]-4,6-雙(2,4-二甲基苯基)-1,3,5-三氮雜苯、2-[4-{(2-羥基-3-十三烷氧基丙基)氧基}-2-羥基苯基]-4,6-雙(2,4-二甲基苯基)-1,3,5-三氮雜苯等三氮雜苯衍生物、2-(2’-𠮿
就抗氧化劑而言，可舉例如受阻酚系抗氧化劑、受阻胺系抗氧化劑、有機硫系抗氧化劑、磷酸酯系抗氧化劑等。Examples of antioxidants include hindered phenol antioxidants, hindered amine antioxidants, organic sulfur antioxidants, and phosphoric ester antioxidants.
就矽系添加劑而言，可舉例如二甲基聚矽氧烷、甲基苯基聚矽氧烷、環狀二甲基聚矽氧烷、甲基氫聚矽氧烷、聚醚改性二甲基聚矽氧烷共聚物、聚酯改性二甲基聚矽氧烷共聚物、氟改性二甲基聚矽氧烷共聚物、胺基改性二甲基聚矽氧烷共聚物等具有烷基或苯基之聚有機矽氧烷類。As for the silicon-based additives, for example, dimethyl polysiloxane, methyl phenyl polysiloxane, cyclic dimethyl polysiloxane, methyl hydrogen polysiloxane, polyether modified two Methylpolysiloxane copolymer, polyester-modified dimethylpolysiloxane copolymer, fluorine-modified dimethylpolysiloxane copolymer, amine-modified dimethylpolysiloxane copolymer, etc. Polyorganosiloxanes with alkyl or phenyl groups.
就如上述之各種添加劑的使用量而言，考慮充分發揮其效果，且不妨害紫外線硬化之範圍，相對於該光學物品用活性能量射線硬化型樹脂組成物100重量份，各別為0.01~10重量份之範圍較為理想。Regarding the usage amount of various additives as mentioned above, considering that they can fully exert their effects without harming the range of ultraviolet curing, relative to 100 parts by weight of the active energy ray curable resin composition for optical articles, each is 0.01-10 The range of parts by weight is ideal.
本發明之光學物品用活性能量射線硬化型樹脂組成物雖然因應需求可含有溶劑，但因為溶劑含有率少者可獲得不容易污染作業環境之光學物品用活性能量射線硬化型樹脂組成物故較為理想。具體而言，本發明之光學物品用活性能量射線硬化型樹脂組成物中之溶劑含有率宜為1重量%以下。Although the active energy ray-curable resin composition for optical articles of the present invention may contain a solvent according to demand, it is preferable because the active energy ray-curable resin composition for optical articles that is less likely to pollute the working environment can be obtained with a low solvent content. Specifically, the solvent content in the active energy ray-curable resin composition for optical articles of the present invention is preferably 1% by weight or less.
本發明之光學物品用活性能量射線硬化型樹脂組成物係適用於薄膜狀、片狀、板狀之透明基材上設置了由樹脂硬化物構成之成形樹脂層之結構的各種物品的材料。其中，在使用於透鏡等透明性為必要之物品的製造中時，組合各樹脂組成物成分來使用使在厚度200±25μm之硬化物中400~900nm的波長區域之透光率成為80%以上，宜為85%以上較為理想。The active energy ray-curable resin composition for optical articles of the present invention is a material suitable for various articles having a structure in which a molded resin layer composed of a resin cured product is provided on a transparent substrate in a film, sheet, or plate shape. Among them, when used in the manufacture of items that require transparency such as lenses, the components of the resin composition are combined to make the light transmittance in the 400~900nm wavelength region of the cured product with a thickness of 200±25μm become 80% or more , It is better to be above 85%.
(硬化物) 本發明之硬化物係使本發明之光學物品用活性能量射線硬化型樹脂組成物硬化而得者。該硬化物為了具有在對於賦予了微細形狀之樹脂硬化層施加之壓力小的情況具有不會變形之程度的硬度，且在短時間施加強的壓力之情況形狀也不會崩壞(不會硬脆裂)，在25℃之動態黏彈性的彈性係數宜為2500~ 3000MPa，更宜為2700~2900MPa。 同樣地關於捲曲，因為彈性係數越高越容易展現硬化收縮造成之影響，考慮物性平衡設計為上述範圍內較為理想。(Cured product) The cured product of the present invention is obtained by curing the active energy ray-curable resin composition for optical articles of the present invention. The hardened product has a hardness that does not deform when the pressure applied to the resin hardened layer with a fine shape is small, and the shape does not collapse even when strong pressure is applied for a short time (not hard Embrittlement), the elastic coefficient of dynamic viscoelasticity at 25°C should be 2500~3000MPa, more preferably 2700~2900MPa. Similarly with regard to curling, because the higher the elastic modulus, the easier it is to exhibit the effects of hardening shrinkage. It is ideal to design the balance of physical properties within the above range.
就控制捲曲性之因素而言，也可列舉在動態黏彈性之tan δ max。Tan δ max之峰值係展示在交聯結構之交聯點間分子量的分布，峰值低且寬的情況，因為交聯點間分子量之分布廣，硬化收縮分散，故就捲曲性而言為良好，峰值高且尖銳之情況，因為交聯點間分子量之分布均勻，硬化時會一下子全部產生收縮，就捲曲性而言會惡化故較不理想。在該點，關於耐刮性，藉由使交聯點間分子量之分布變廣，因為可提高樹脂硬化物之韌性，在與強度、彈性係數維持平衡之範圍內設計使Tan δ max之峰值低更為理想。As far as the factors controlling curling are concerned, tan δ max of dynamic viscoelasticity can also be cited. The peak value of Tan δ max shows the distribution of molecular weight between the cross-linking points of the cross-linked structure. The peak value is low and wide. Because the molecular weight distribution between the cross-linking points is wide, the hardening shrinkage is dispersed, so it is good in terms of curling properties. If the peak is high and sharp, because the molecular weight distribution between the cross-linking points is uniform, all of the shrinkage will occur all at once during hardening, and the curlability will deteriorate, so it is not ideal. At this point, regarding the scratch resistance, by broadening the molecular weight distribution between the cross-linking points, the toughness of the cured resin can be improved, and the peak value of Tan δ max can be lowered within a range that maintains a balance between the strength and the coefficient of elasticity. More ideal.
其中，在本發明中，動態黏彈性係使用Rheometoric Scientific公司製之「RSAII」作為黏彈性測定裝置，測定條件為升溫速度3℃/Min，頻率3.5Hz之條件下測定而得之值。Among them, in the present invention, the dynamic viscoelasticity is a value obtained by using "RSAII" manufactured by Rheometoric Scientific Co., Ltd. as a viscoelasticity measuring device, and the measurement conditions are a temperature rise rate of 3°C/Min and a frequency of 3.5 Hz.
(硬化方法) 使本發明之光學物品用活性能量射線硬化型樹脂組成物硬化的活性能量射線係指電磁波或帶電粒子束中，具有可將分子聚合、交聯之能量量子者，可舉例如可見光、紫外線、X射線等電磁波、或電子束等帶電粒子束。此等之中，就實用上常使用的有可見光、紫外線。為紫外線時，可使用超高壓汞燈、高壓汞燈、低壓汞燈、碳弧、黑光燈、金屬鹵化物燈等光源。(Curing method) The active energy ray used to cure the active energy ray-curable resin composition for optical articles of the present invention refers to those having energy quantum capable of polymerizing and cross-linking molecules in electromagnetic waves or charged particle beams, such as visible light , Ultraviolet, X-ray and other electromagnetic waves, or electron beams and other charged particle beams. Among these, visible light and ultraviolet light are commonly used in practice. When it is ultraviolet light, light sources such as ultra-high pressure mercury lamp, high pressure mercury lamp, low pressure mercury lamp, carbon arc, black light lamp, metal halide lamp, etc. can be used.
(光學片) 就製造本發明之光學片的方法而言，可列舉將本發明之光學物品用活性能量射線硬化型樹脂組成物填充至具有必要之微細形狀的母模上後，使空氣不會混入地將塑膠基材加壓疊層使其黏合至所填充之該樹脂組成物上，從塑膠基材側照射紫外線等活性能量射線使該樹脂組成物硬化後，從母模離模之方法等。此外還可舉例如將該樹脂組成物連續地填充至輥狀之母模後，使空氣不會混入地將塑膠基材連續地黏合至所填充之該樹脂組成物上，從塑膠基材側照射紫外線等活性能量射線使該樹脂組成物硬化後，從輥狀之母模離模之連續製造的方法等。(Optical sheet) The method for manufacturing the optical sheet of the present invention includes filling the active energy ray-curable resin composition for optical articles of the present invention on a master mold having a necessary fine shape to prevent air A method of laminating the plastic base material with mixing and bonding to the filled resin composition, irradiating active energy rays such as ultraviolet rays from the side of the plastic base material to harden the resin composition, and releasing it from the master mold, etc. . In addition, for example, after the resin composition is continuously filled in the roll-shaped master mold, the plastic substrate is continuously bonded to the filled resin composition without air mixing, and the plastic substrate is irradiated. After the active energy rays such as ultraviolet rays cure the resin composition, it is a continuous manufacturing method that is released from a roll-shaped master mold.
就此方式中可使用之薄膜狀、片狀、板狀之透明基材而言，可舉例如聚對苯二甲酸乙二酯(PET)、聚萘二甲酸乙二酯(PEN)等聚酯樹脂、三乙酸纖維素、聚碳酸酯樹脂、甲基丙烯酸甲酯系共聚物等丙烯酸樹脂、苯乙烯樹脂、聚碸樹脂、聚醚碸樹脂、氯化乙烯樹脂、聚甲基丙烯酸醯亞胺樹脂等。此外，雖然不是塑膠基材，但也可同樣地使用玻璃基材等無機基材。 [實施例]For transparent substrates in the form of films, sheets, and plates that can be used in this method, for example, polyester resins such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN) , Acrylic resins such as cellulose triacetate, polycarbonate resins, methyl methacrylate copolymers, styrene resins, polyether resins, polyether resins, chlorinated vinyl resins, polymethacrylate imide resins, etc. . In addition, although it is not a plastic substrate, an inorganic substrate such as a glass substrate can also be used in the same manner. [Example]
以下列舉實施例及比較例來更具體地說明本發明。例中的「份」及「%」若無特別指明之情況下，全部皆為重量基準。Examples and comparative examples are given below to explain the present invention more specifically. Unless otherwise specified, "parts" and "%" in the example are all based on weight.
(光學物品用活性能量射線硬化性組成物之調整) 藉由下列表1所示之摻合調整組成物。此外，各成分之該環氧乙烷基的重量濃度及芳香族基之重量濃度係藉由各結構成分之結構式算出。(Adjustment of active energy ray curable composition for optical articles) The composition is adjusted by blending as shown in Table 1 below. In addition, the weight concentration of the oxirane group of each component and the weight concentration of the aromatic group are calculated from the structural formula of each structural component.
【表1】
表中簡稱如同下述。 UNIDIC V-5500 (DIC公司製，BPA型環氧丙烯酸酯) 芳香環量：33.7%，EO鏈含量：0% TMP3EO-3A：三羥甲基丙烷之EO改性 (n=3) 三丙烯酸酯 芳香環量：0%，EO鏈含量：18% BPA4EO-2A：BPA之EO改性 (n=4) 二丙烯酸酯 芳香環量：30.5%，EO鏈含量：31.2% 丙烯酸鄰苯氧基苯基乙酯 芳香環量：58.2%，EO鏈含量：16.4% 丙烯酸苯氧基乙酯 芳香環量：40.6%，EO鏈含量：20.8% 丙烯酸苄酯 芳香環量：48.1%，EO鏈含量：0% DP6A/DP5A=6/4：二新戊四醇六丙烯酸酯/二新戊四醇五丙烯酸酯=6/4 芳香環量：0%，EO鏈含量：0% DP-EO-6A/DP-EO-5A=6/4：二新戊四醇之EO改性六丙烯酸酯/二新戊四醇之EO改性五丙烯酸酯=6/4 (EO聚合度：0.85) 芳香環量：0%，EO鏈含量：26.7% I-184：1-羥基-環己基苯基酮 (光起始劑) IRGACURE184 [BASF公司製]The abbreviations in the table are as follows. UNIDIC V-5500 (made by DIC, BPA type epoxy acrylate) Aromatic ring content: 33.7%, EO chain content: 0% TMP3EO-3A: EO modified trimethylolpropane (n=3) triacrylate Aromatic ring content: 0%, EO chain content: 18% BPA4EO-2A: EO modification of BPA (n=4) Aromatic ring content of diacrylate: 30.5%, EO chain content: 31.2% Acrylic o-phenoxy phenyl Ethyl aromatic ring content: 58.2%, EO chain content: 16.4% Phenoxyethyl acrylate aromatic ring content: 40.6%, EO chain content: 20.8% Benzyl acrylate aromatic ring content: 48.1%, EO chain content: 0% DP6A/DP5A=6/4: Dineopentaerythritol hexaacrylate/Dineopentaerythritol pentaacrylate=6/4 Aromatic ring content: 0%, EO chain content: 0% DP-EO-6A/DP- EO-5A=6/4: EO modified hexaacrylate of dineopentaerythritol / EO modified pentaacrylate of dineopentaerythritol=6/4 (EO polymerization degree: 0.85) Aromatic ring content: 0% , EO chain content: 26.7% I-184: 1-hydroxy-cyclohexyl phenyl ketone (photoinitiator) IRGACURE184 [made by BASF]
(硬化物之製作方法及評價方法) 硬化物之製作方法及評價方法係如以下之方式來進行。(Production method and evaluation method of hardened object) The production method and evaluation method of hardened object are carried out as follows.
＜動態黏彈性測定 Tg、儲存彈性模數、tan δ max(峰高度)之測定＞ (硬化物之製作方法) 於玻璃板滴加實施例或比較例之樹脂組成物，藉由旋轉塗布器塗布使膜厚成為100μm後，於氮氣環境下進行UV照射來製作硬化塗膜。照射條件係藉由EYE GRAPHICS Co., Ltd.製之金屬鹵化物燈以累積光量1000mJ/cm2 來進行。之後，從玻璃板剝離為硬化物之樹脂薄膜，裁切為3mm×50mm作為試驗片。<Dynamic viscoelasticity measurement Tg, storage elastic modulus, and tan δ max (peak height) measurement> (Method of making hardened product) Drop the resin composition of the example or comparative example on the glass plate, and apply it by a spin coater After the film thickness became 100 μm, UV irradiation was performed in a nitrogen atmosphere to produce a cured coating film. The irradiation conditions were carried out with a metal halide lamp manufactured by EYE GRAPHICS Co., Ltd. with a cumulative light quantity of 1000 mJ/cm 2 After that, the cured resin film was peeled from the glass plate, and cut into 3 mm×50 mm as a test piece.
(動態黏彈性測定) 樹脂薄膜之Tg、儲存彈性模數、及tan δ max(峰部高度)之測定係使用Rheometoric Scientific公司製之「RSAII」作為黏彈性測定裝置，以升溫速度：3℃/Min，頻率：3.5Hz之測定條件來進行。(Dynamic viscoelasticity measurement) The Tg, storage elastic modulus, and tan δ max (peak height) of the resin film are measured using "RSAII" manufactured by Rheometoric Scientific as a viscoelasticity measuring device, with a heating rate: 3℃/ Min, frequency: 3.5 Hz measurement conditions.
＜捲曲性評價＞ 將75μm之PET薄膜(東洋紡公司製：COSMOSINE A4300)作為基材，塗布實施例或比較例之樹脂組成物，在氮氣環境下進行UV照射(照射條件為藉由EYE GRAPHICS Co., Ltd.製之金屬鹵化物燈，累積光量1000mJ/cm2 )，製作稜鏡片(節距20μm)。 將製作而得之稜鏡片裁切為5cm方形，於室溫放置1天後，藉由捲尺以公厘(millimeter)單位量測4個角落之翹曲(捲曲)程度，將4個角落的合計值作為捲曲性之指標。值越低表示越沒有捲曲。在本評價中，只要是10mm以下便判定為合格。<Curlability evaluation> A 75μm PET film (manufactured by Toyobo Co., Ltd.: COSMOSINE A4300) was used as a base material, and the resin composition of the examples or comparative examples was coated, and UV irradiation was performed in a nitrogen atmosphere (irradiation conditions are by EYE GRAPHICS Co. The metal halide lamp manufactured by, Ltd., the cumulative light quantity is 1000mJ/cm 2 ), and the scallops are made (pitch 20μm). Cut the fabricated slices into 5cm squares. After standing at room temperature for 1 day, measure the warping (curl) degree of the 4 corners with a tape measure in millimeter units, and add the total of the 4 corners. The value is used as an indicator of curlability. The lower the value, the less curling. In this evaluation, as long as it is 10 mm or less, it is judged as a pass.
＜耐刮性＞ 在藉由與上述相同之條件所製得之稜鏡片上重疊偏光薄膜，並於其上放置砝碼。於該狀態僅拉動稜鏡片，以目視觀察對於稜鏡片表面造成傷痕之程度。 改變砝碼之重量進行試驗，將不會造成傷痕之最大重量(g)作為耐刮性之值。值越高，耐刮性越優良。在本評價中，只要是100g以上便判定為合格。<Scratch resistance> The polarizing film is superimposed on the sheet made under the same conditions as above, and a weight is placed on it. In this state, only pull the 稜鏡 piece to visually observe the degree of scars on the surface of the 稜鏡 piece. Change the weight of the weight for the test, and the maximum weight (g) that will not cause scars is used as the value of scratch resistance. The higher the value, the better the scratch resistance. In this evaluation, as long as it is 100 g or more, it is judged as a pass.
實施例及比較例之結果表示於表2。The results of the examples and comparative examples are shown in Table 2.
【表2】
該結果，實施例1~3之光學物品用活性能量射線硬化性組成物之硬化物就捲曲性及耐刮性而言為優良。尤其是使用了二新戊四醇之環氧乙烷改性多(甲基)丙烯酸酯的實施例1及實施例2於耐刮性非常地優良。反觀比較例1~3因為任一者之環氧乙烷基的濃度皆在6重量%以下，耐刮性差。此外，比較例3之DMA儲存彈性模數(25℃)為3000非常地高，可知其就捲曲性而言為不良。As a result, the cured products of the active energy ray curable composition for optical articles of Examples 1 to 3 are excellent in curling properties and scratch resistance. In particular, Example 1 and Example 2 using the ethylene oxide modified poly(meth)acrylate of dineopentaerythritol are very good in scratch resistance. In contrast, Comparative Examples 1 to 3 have poor scratch resistance because the concentration of ethylene oxide groups in any of them is below 6 wt%. In addition, the DMA storage elastic modulus (25°C) of Comparative Example 3 is very high at 3000, and it can be seen that it is inferior in terms of curling properties.
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