JP7024706B2 - Curable compositions and optics - Google Patents
Curable compositions and optics Download PDFInfo
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- JP7024706B2 JP7024706B2 JP2018504356A JP2018504356A JP7024706B2 JP 7024706 B2 JP7024706 B2 JP 7024706B2 JP 2018504356 A JP2018504356 A JP 2018504356A JP 2018504356 A JP2018504356 A JP 2018504356A JP 7024706 B2 JP7024706 B2 JP 7024706B2
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- Prior art keywords
- meth
- acrylate
- curable composition
- compound
- mass
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- 239000000203 mixture Substances 0.000 title claims description 59
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 114
- 150000001875 compounds Chemical class 0.000 claims description 51
- 239000002245 particle Substances 0.000 claims description 44
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 claims description 33
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 24
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 24
- 239000000047 product Substances 0.000 claims description 20
- 125000006187 phenyl benzyl group Chemical group 0.000 claims description 18
- 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 claims description 14
- 239000003822 epoxy resin Substances 0.000 claims description 12
- 229920000647 polyepoxide Polymers 0.000 claims description 12
- 230000003287 optical effect Effects 0.000 claims description 9
- 239000007795 chemical reaction product Substances 0.000 claims description 8
- 239000004593 Epoxy Substances 0.000 claims description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 4
- -1 acryloyloxy Chemical group 0.000 description 68
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 40
- 239000004305 biphenyl Substances 0.000 description 23
- 235000010290 biphenyl Nutrition 0.000 description 23
- 238000000034 method Methods 0.000 description 21
- 239000006185 dispersion Substances 0.000 description 16
- 239000006087 Silane Coupling Agent Substances 0.000 description 15
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 15
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 14
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical class O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- 239000000758 substrate Substances 0.000 description 11
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- IJVHTTITHMXYTG-UHFFFAOYSA-N benzhydryl prop-2-enoate Chemical compound C=1C=CC=CC=1C(OC(=O)C=C)C1=CC=CC=C1 IJVHTTITHMXYTG-UHFFFAOYSA-N 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- 229920005989 resin Polymers 0.000 description 8
- 239000011347 resin Substances 0.000 description 8
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000002270 dispersing agent Substances 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000000654 additive Substances 0.000 description 6
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 6
- 229920000193 polymethacrylate Polymers 0.000 description 6
- 229930185605 Bisphenol Natural products 0.000 description 5
- 239000010419 fine particle Substances 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- 239000012044 organic layer Substances 0.000 description 5
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 5
- 239000007870 radical polymerization initiator Substances 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 125000003118 aryl group Polymers 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 4
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 4
- 150000002596 lactones Chemical group 0.000 description 4
- 239000004973 liquid crystal related substance Substances 0.000 description 4
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 4
- 229910052753 mercury Inorganic materials 0.000 description 4
- 229920005862 polyol Polymers 0.000 description 4
- MSTBNCRDGMNFOU-UHFFFAOYSA-N 1-[4-[4-(2-oxobut-3-enyl)phenyl]phenyl]but-3-en-2-one Chemical group C1=CC(CC(=O)C=C)=CC=C1C1=CC=C(CC(=O)C=C)C=C1 MSTBNCRDGMNFOU-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- KBQVDAIIQCXKPI-UHFFFAOYSA-N 3-trimethoxysilylpropyl prop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C=C KBQVDAIIQCXKPI-UHFFFAOYSA-N 0.000 description 3
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 3
- HTVITOHKHWFJKO-UHFFFAOYSA-N Bisphenol B Chemical compound C=1C=C(O)C=CC=1C(C)(CC)C1=CC=C(O)C=C1 HTVITOHKHWFJKO-UHFFFAOYSA-N 0.000 description 3
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 239000011324 bead Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000010894 electron beam technology Methods 0.000 description 3
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 235000011187 glycerol Nutrition 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229910000039 hydrogen halide Inorganic materials 0.000 description 3
- 239000012433 hydrogen halide Substances 0.000 description 3
- 239000002609 medium Substances 0.000 description 3
- 229920003986 novolac Polymers 0.000 description 3
- 239000003504 photosensitizing agent Substances 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 238000007493 shaping process Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- 229910052726 zirconium Inorganic materials 0.000 description 3
- QBECDXJGYFRACA-UHFFFAOYSA-N (4-phenylphenyl)methyl prop-2-enoate Chemical compound C1=CC(COC(=O)C=C)=CC=C1C1=CC=CC=C1 QBECDXJGYFRACA-UHFFFAOYSA-N 0.000 description 2
- 0 *[n]1c(ccc(-c2c3[n](*)c(cccc4)c4c3ccc2)c2)c2c2c1cccc2 Chemical compound *[n]1c(ccc(-c2c3[n](*)c(cccc4)c4c3ccc2)c2)c2c2c1cccc2 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-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
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 2
- 229930040373 Paraformaldehyde Natural products 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000003377 acid catalyst Substances 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 229910052783 alkali metal Inorganic materials 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
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- JXTHNDFMNIQAHM-UHFFFAOYSA-N dichloroacetic acid Chemical compound OC(=O)C(Cl)Cl JXTHNDFMNIQAHM-UHFFFAOYSA-N 0.000 description 2
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 2
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000000499 gel Substances 0.000 description 2
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 2
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 2
- 230000001678 irradiating effect Effects 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- PCILLCXFKWDRMK-UHFFFAOYSA-N naphthalene-1,4-diol Chemical compound C1=CC=C2C(O)=CC=C(O)C2=C1 PCILLCXFKWDRMK-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229920002866 paraformaldehyde Polymers 0.000 description 2
- FZUGPQWGEGAKET-UHFFFAOYSA-N parbenate Chemical compound CCOC(=O)C1=CC=C(N(C)C)C=C1 FZUGPQWGEGAKET-UHFFFAOYSA-N 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000005056 polyisocyanate Substances 0.000 description 2
- 229920001228 polyisocyanate Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 description 1
- QNODIIQQMGDSEF-UHFFFAOYSA-N (1-hydroxycyclohexyl)-phenylmethanone Chemical compound C=1C=CC=CC=1C(=O)C1(O)CCCCC1 QNODIIQQMGDSEF-UHFFFAOYSA-N 0.000 description 1
- VKTQADPEPIVMHK-UHFFFAOYSA-N (2-phenylphenyl)methanol Chemical compound OCC1=CC=CC=C1C1=CC=CC=C1 VKTQADPEPIVMHK-UHFFFAOYSA-N 0.000 description 1
- PKMSXGVLJHFQHJ-UHFFFAOYSA-N (2-phenylphenyl)methyl prop-2-enoate Chemical compound C=CC(=O)OCC1=CC=CC=C1C1=CC=CC=C1 PKMSXGVLJHFQHJ-UHFFFAOYSA-N 0.000 description 1
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- LTQBNYCMVZQRSD-UHFFFAOYSA-N (4-ethenylphenyl)-trimethoxysilane Chemical compound CO[Si](OC)(OC)C1=CC=C(C=C)C=C1 LTQBNYCMVZQRSD-UHFFFAOYSA-N 0.000 description 1
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 1
- BGJSXRVXTHVRSN-UHFFFAOYSA-N 1,3,5-trioxane Chemical compound C1OCOCO1 BGJSXRVXTHVRSN-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- BOKGTLAJQHTOKE-UHFFFAOYSA-N 1,5-dihydroxynaphthalene Chemical compound C1=CC=C2C(O)=CC=CC2=C1O BOKGTLAJQHTOKE-UHFFFAOYSA-N 0.000 description 1
- SEXZHJJUKFXNDY-UHFFFAOYSA-N 1-(bromomethyl)-2-phenylbenzene Chemical group BrCC1=CC=CC=C1C1=CC=CC=C1 SEXZHJJUKFXNDY-UHFFFAOYSA-N 0.000 description 1
- QEFMDEFYYCMJPY-UHFFFAOYSA-N 1-(chloromethyl)-2-phenylbenzene Chemical group ClCC1=CC=CC=C1C1=CC=CC=C1 QEFMDEFYYCMJPY-UHFFFAOYSA-N 0.000 description 1
- CRXWFDHIWZFCTR-UHFFFAOYSA-N 1-[2-[2-(2-oxobut-3-enyl)phenyl]phenyl]but-3-en-2-one Chemical group C=CC(=O)CC1=CC=CC=C1C1=CC=CC=C1CC(=O)C=C CRXWFDHIWZFCTR-UHFFFAOYSA-N 0.000 description 1
- CPNDWRWNUGOQGV-UHFFFAOYSA-N 1-[3-(2-oxobut-3-enyl)-2-phenylphenyl]but-3-en-2-one Chemical group C=CC(=O)CC1=CC=CC(CC(=O)C=C)=C1C1=CC=CC=C1 CPNDWRWNUGOQGV-UHFFFAOYSA-N 0.000 description 1
- QFIROYAYCOLNFE-UHFFFAOYSA-N 1-[4-[2-(2-oxobut-3-enyl)phenyl]phenyl]but-3-en-2-one Chemical group C1=CC(CC(=O)C=C)=CC=C1C1=CC=CC=C1CC(=O)C=C QFIROYAYCOLNFE-UHFFFAOYSA-N 0.000 description 1
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 1
- ALLIZEAXNXSFGD-UHFFFAOYSA-N 1-methyl-2-phenylbenzene Chemical group CC1=CC=CC=C1C1=CC=CC=C1 ALLIZEAXNXSFGD-UHFFFAOYSA-N 0.000 description 1
- DVWQNBIUTWDZMW-UHFFFAOYSA-N 1-naphthalen-1-ylnaphthalen-2-ol Chemical compound C1=CC=C2C(C3=C4C=CC=CC4=CC=C3O)=CC=CC2=C1 DVWQNBIUTWDZMW-UHFFFAOYSA-N 0.000 description 1
- KWVGIHKZDCUPEU-UHFFFAOYSA-N 2,2-dimethoxy-2-phenylacetophenone Chemical compound C=1C=CC=CC=1C(OC)(OC)C(=O)C1=CC=CC=C1 KWVGIHKZDCUPEU-UHFFFAOYSA-N 0.000 description 1
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 description 1
- JMVZGKVGQDHWOI-UHFFFAOYSA-N 2-(2-methylpropoxy)-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OCC(C)C)C(=O)C1=CC=CC=C1 JMVZGKVGQDHWOI-UHFFFAOYSA-N 0.000 description 1
- YSUQLAYJZDEMOT-UHFFFAOYSA-N 2-(butoxymethyl)oxirane Chemical compound CCCCOCC1CO1 YSUQLAYJZDEMOT-UHFFFAOYSA-N 0.000 description 1
- BXGYYDRIMBPOMN-UHFFFAOYSA-N 2-(hydroxymethoxy)ethoxymethanol Chemical compound OCOCCOCO BXGYYDRIMBPOMN-UHFFFAOYSA-N 0.000 description 1
- CWNOEVURTVLUNV-UHFFFAOYSA-N 2-(propoxymethyl)oxirane Chemical compound CCCOCC1CO1 CWNOEVURTVLUNV-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 description 1
- UHFFVFAKEGKNAQ-UHFFFAOYSA-N 2-benzyl-2-(dimethylamino)-1-(4-morpholin-4-ylphenyl)butan-1-one Chemical compound C=1C=C(N2CCOCC2)C=CC=1C(=O)C(CC)(N(C)C)CC1=CC=CC=C1 UHFFVFAKEGKNAQ-UHFFFAOYSA-N 0.000 description 1
- SVIQBUBNVYWIDV-UHFFFAOYSA-N 2-methoxy-2-(2-methoxyphenyl)-1-phenylethanone Chemical compound C=1C=CC=C(OC)C=1C(OC)C(=O)C1=CC=CC=C1 SVIQBUBNVYWIDV-UHFFFAOYSA-N 0.000 description 1
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- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
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- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
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- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- PXQLVRUNWNTZOS-UHFFFAOYSA-N sulfanyl Chemical class [SH] PXQLVRUNWNTZOS-UHFFFAOYSA-N 0.000 description 1
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- 238000003786 synthesis reaction Methods 0.000 description 1
- MUTNCGKQJGXKEM-UHFFFAOYSA-N tamibarotene Chemical compound C=1C=C2C(C)(C)CCC(C)(C)C2=CC=1NC(=O)C1=CC=C(C(O)=O)C=C1 MUTNCGKQJGXKEM-UHFFFAOYSA-N 0.000 description 1
- ADXGNEYLLLSOAR-UHFFFAOYSA-N tasosartan Chemical compound C12=NC(C)=NC(C)=C2CCC(=O)N1CC(C=C1)=CC=C1C1=CC=CC=C1C=1N=NNN=1 ADXGNEYLLLSOAR-UHFFFAOYSA-N 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- GQIUQDDJKHLHTB-UHFFFAOYSA-N trichloro(ethenyl)silane Chemical compound Cl[Si](Cl)(Cl)C=C GQIUQDDJKHLHTB-UHFFFAOYSA-N 0.000 description 1
- HKFSBKQQYCMCKO-UHFFFAOYSA-N trichloro(prop-2-enyl)silane Chemical compound Cl[Si](Cl)(Cl)CC=C HKFSBKQQYCMCKO-UHFFFAOYSA-N 0.000 description 1
- YNJBWRMUSHSURL-UHFFFAOYSA-N trichloroacetic acid Chemical compound OC(=O)C(Cl)(Cl)Cl YNJBWRMUSHSURL-UHFFFAOYSA-N 0.000 description 1
- UMFJXASDGBJDEB-UHFFFAOYSA-N triethoxy(prop-2-enyl)silane Chemical compound CCO[Si](CC=C)(OCC)OCC UMFJXASDGBJDEB-UHFFFAOYSA-N 0.000 description 1
- NBXZNTLFQLUFES-UHFFFAOYSA-N triethoxy(propyl)silane Chemical compound CCC[Si](OCC)(OCC)OCC NBXZNTLFQLUFES-UHFFFAOYSA-N 0.000 description 1
- VTHOKNTVYKTUPI-UHFFFAOYSA-N triethoxy-[3-(3-triethoxysilylpropyltetrasulfanyl)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCSSSSCCC[Si](OCC)(OCC)OCC VTHOKNTVYKTUPI-UHFFFAOYSA-N 0.000 description 1
- LFRDHGNFBLIJIY-UHFFFAOYSA-N trimethoxy(prop-2-enyl)silane Chemical compound CO[Si](OC)(OC)CC=C LFRDHGNFBLIJIY-UHFFFAOYSA-N 0.000 description 1
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
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- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
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- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
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- 235000005074 zinc chloride Nutrition 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- C—CHEMISTRY; METALLURGY
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Description
本発明は、高屈折率かつ低粘度の硬化性組成物とその硬化物、及び光学部材に関する。 The present invention relates to a curable composition having a high refractive index and a low viscosity, a cured product thereof, and an optical member.
液晶表示装置などのバックライトには、輝度を向上させるためのプリズムフィルムやマイクロレンズフィルム等の輝度向上シートが設置されている。輝度向上フィルムは主に、金型を用いて樹脂材料を賦形する方法により製造されることから、輝度向上フィルム用樹脂材料は溶剤を含まず、かつ、賦形に適した低粘度である必要がある。また、輝度向上効果を高めるために硬化物における屈折率が高く透明性が高いこと、傷が付き難いことなども重要な要求性能となっている。 A brightness improving sheet such as a prism film or a microlens film for improving the brightness is installed in a backlight of a liquid crystal display device or the like. Since the brightness-improving film is mainly manufactured by a method of shaping a resin material using a mold, the resin material for a brightness-improving film needs to be solvent-free and have a low viscosity suitable for shaping. There is. Further, in order to enhance the effect of improving the brightness, high refractive index and high transparency of the cured product and scratch resistance are also important required performances.
輝度向上フィルム用樹脂材料として、酸化ジルコニウム微粒子とフェニルフェノールポリエトキシアクリレート等を含有する硬化性組成物が知られている（特許文献１参照）。このような無機微粒子配合型の樹脂材料は屈折率が高い特徴を有する一方で、無機微粒子を配合することにより高粘度化する傾向にあり、無機微粒子を含有しながらも粘度の低い樹脂材料の開発が求められていた。 As a resin material for a brightness-improving film, a curable composition containing zirconium oxide fine particles, phenylphenol polyethoxyacrylate and the like is known (see Patent Document 1). While such a resin material containing inorganic fine particles has a high refractive index, it tends to have a high viscosity by adding inorganic fine particles, and development of a resin material containing inorganic fine particles but having a low viscosity. Was sought after.
したがって、本発明が解決しようとする課題は、高屈折率かつ低粘度の硬化性組成物とその硬化物、及び光学部材を提供することにある。 Therefore, an object to be solved by the present invention is to provide a curable composition having a high refractive index and a low viscosity, a cured product thereof, and an optical member.
本発明者らは上記課題を解決するため鋭意検討を行った結果、酸化ジルコニウム粒子とフェニルベンジル（メタ）アクリレートとを組み合わせることにより、粘度と屈折率とのバランスに非常に優れる硬化性組成物が得られることを見出し、本発明に至った。 As a result of diligent studies to solve the above problems, the present inventors have obtained a curable composition having an extremely excellent balance between viscosity and refractive index by combining zirconium oxide particles and phenylbenzyl (meth) acrylate. It was found that it could be obtained, and the present invention was reached.
即ち、本発明は、酸化ジルコニウム粒子（Ａ）と（メタ）アクリロイル基含有化合物（Ｂ）とを含有し、前記（メタ）アクリロイル基含有化合物（Ｂ）がフェニルベンジル（メタ）アクリレート（Ｂ１）を必須の成分とすることを特徴とする硬化性組成物に関する。 That is, the present invention contains zirconium oxide particles (A) and a (meth) acryloyl group-containing compound (B), and the (meth) acryloyl group-containing compound (B) contains phenylbenzyl (meth) acrylate (B1). The present invention relates to a curable composition characterized by being an essential component.
本発明はさらに、前記硬化性組成物を硬化して得られる硬化物、及び光学部材に関する。 The present invention further relates to a cured product obtained by curing the curable composition and an optical member.
本発明によれば、高屈折率かつ低粘度の硬化性組成物とその硬化物、及び光学部材を提供することができる。 According to the present invention, it is possible to provide a curable composition having a high refractive index and a low viscosity, a cured product thereof, and an optical member.
以下、本発明を詳細に説明する。
本発明の硬化性組成物は、酸化ジルコニウム粒子（Ａ）と（メタ）アクリロイル基含有化合物（Ｂ）とを含有し、前記（メタ）アクリロイル基含有化合物（Ｂ）がフェニルベンジル（メタ）アクリレート（Ｂ１）を必須の成分とすることを特徴とする。Hereinafter, the present invention will be described in detail.
The curable composition of the present invention contains zirconium oxide particles (A) and a (meth) acryloyl group-containing compound (B), and the (meth) acryloyl group-containing compound (B) is a phenylbenzyl (meth) acrylate (meth) acrylate. It is characterized in that B1) is an essential component.
本発明の硬化性組成物が含有する酸化ジルコニウム粒子（Ａ）は、原料の酸化ジルコニウム粒子（ａ）を（メタ）アクリロイル基含有化合物（Ｂ）を必須とする分散媒中に分散させて得られるものである。硬化性組成物中の酸化ジルコニウム粒子（Ａ）の平均粒子径は、屈折率が高く光透過性にも優れる硬化物となることから、２０～１００ｎｍの範囲であることが好ましい。 The zirconium oxide particles (A) contained in the curable composition of the present invention are obtained by dispersing the raw material zirconium oxide particles (a) in a dispersion medium requiring a (meth) acryloyl group-containing compound (B). It is a thing. The average particle size of the zirconium oxide particles (A) in the curable composition is preferably in the range of 20 to 100 nm because it is a cured product having a high refractive index and excellent light transmission.
なお、本願発明において前記酸化ジルコニウム粒子（Ａ）の平均粒子径は硬化性組成物中の粒子径を以下の条件で測定した値である。
粒子径測定装置：大塚電子株式会社製「ＥＬＳＺ－２」
粒子径測定サンプル：硬化性組成物を不揮発分０．６質量％のメチルイソブチルケトン溶液としたもの。In the present invention, the average particle size of the zirconium oxide particles (A) is a value obtained by measuring the particle size in the curable composition under the following conditions.
Particle size measuring device: "ELSZ-2" manufactured by Otsuka Electronics Co., Ltd.
Particle size measurement sample: A curable composition prepared as a methyl isobutyl ketone solution having a non-volatile content of 0.6% by mass.
原料として用いる酸化ジルコニウム粒子（ａ）は、一般に市販されているものなど公知のものが使用できる。粒子の形状は特に限定されるものではないが、例えば、球状、中空状、多孔質状、棒状、板状、繊維状、又は不定形のいずれでも良い。中でも、分散安定性に優れ、屈折率の高い硬化物が得られることから球状であることが好ましい。前記酸化ジルコニウム粒子（ａ）の平均一次粒子径は、分散安定性に優れ、光透過率及び屈折率の高い硬化物が得られることから１～５０ｎｍものが好ましく、特に１～３０ｎｍのものが好ましい。前記酸化ジルコニウム粒子（ａ）の結晶構造も特に限定されないが、分散安定性に優れ、屈折率の高い硬化物が得られることから単斜晶系が好ましい。また、本発明では、各種シランカップリング剤（Ｃ）等を用いて前記酸化ジルコニウム粒子（ａ）の微粒子表面に官能基を導入しても良い。 As the zirconium oxide particles (a) used as a raw material, known particles such as those generally available on the market can be used. The shape of the particles is not particularly limited, but may be, for example, spherical, hollow, porous, rod-shaped, plate-shaped, fibrous, or amorphous. Above all, a spherical shape is preferable because a cured product having excellent dispersion stability and a high refractive index can be obtained. The average primary particle diameter of the zirconium oxide particles (a) is preferably 1 to 50 nm, and particularly preferably 1 to 30 nm, because a cured product having excellent dispersion stability and high light transmittance and refractive index can be obtained. .. The crystal structure of the zirconium oxide particles (a) is not particularly limited, but a monoclinic crystal system is preferable because a cured product having excellent dispersion stability and a high refractive index can be obtained. Further, in the present invention, a functional group may be introduced on the surface of the fine particles of the zirconium oxide particles (a) using various silane coupling agents (C) or the like.
前記シランカップリング剤（Ｃ）は、例えば下記のものを挙げることができる。 Examples of the silane coupling agent (C) include the following.
（メタ）アクリロイルオキシ系のシランカップリング剤としては、３－（メタ）アクリロイルオキシプロピルトリメチルシラン、３－（メタ）アクリロイルオキシプロピルメチルジメトキシシラン、３－（メタ）アクリロイルオキシプロピルトリメトキシシラン、３－（メタ）アクリロイルオキシプロピルメチルジエトキシシラン、３－（メタ）アクリロイルオキシプロピルトリエトキシシランが例示される。アクリロキシ系のシランカップリング剤としては、３－アクリロキシプロピルトリメトキシシランが例示される。 Examples of the (meth) acryloyloxy-based silane coupling agent include 3- (meth) acryloyloxypropyltrimethylsilane, 3- (meth) acryloyloxypropylmethyldimethoxysilane, and 3- (meth) acryloyloxypropyltrimethoxysilane, 3 Examples thereof include- (meth) acryloyloxypropylmethyldiethoxysilane and 3- (meth) acryloyloxypropyltriethoxysilane. Examples of the acryloxy-based silane coupling agent include 3-acryloxypropyltrimethoxysilane.
ビニル系のシランカップリング剤としては、アリルトリクロロシラン、アリルトリエトキシシラン、アリルトリメトキシシラン、ジエトキシメチルビニルシラン、トリクロロビニルシラン、ビニルトリクロルシラン、ビニルトリメトキシシラン、ビニルトリエトキシシラン、ビニルトリス（２－メトキシエトキシ）シランが例示される。 Examples of the vinyl-based silane coupling agent include allyltrichlorosilane, allyltriethoxysilane, allyltrimethoxysilane, diethoxymethylvinylsilane, trichlorovinylsilane, vinyltricrolsilane, vinyltrimethoxysilane, vinyltriethoxysilane, and vinyltris (2-). Methoxyethoxy) silane is exemplified.
エポキシ系のシランカップリング剤としては、ジエトキシ（グリシディルオキシプロピル）メチルシラン、２－（３、４エポキシシクロヘキシル）エチルトリメトキシシラン、３－グリシドキシプロピルトリメトキシシラン、３－グリシドキシプロピルメチルジエトキシシラン、３－ブリシドキシプロピルトリエトキシシランが例示される。スチレン系のシランカップリング剤としては、ｐ－スチリルトリメトキシシランが例示される。 Examples of the epoxy-based silane coupling agent include diethoxy (glycidyloxypropyl) methylsilane, 2- (3,4 epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, and 3-glycidoxypropylmethyl. Examples thereof include diethoxysilane and 3-bricidoxypropyltriethoxysilane. Examples of the styrene-based silane coupling agent include p-styryltrimethoxysilane.
アミノ系のシランカップリング剤としては、Ｎ－２（アミノエチル）３－アミノプロピルメチルジメトキシシラン、Ｎ－２（アミノエチル）３－アミノプロピルトリメトキシシラン、Ｎ－２（アミノエチル）３－アミノプロピルトリエトキシシラン、３－アミノプロピルトリメトキシシラン、３－アミノプロピルトリエトキシシラン、３－トリエトキシシリル－Ｎ－（１、３－ジメチル－ブチリデン）プロピルアミン、Ｎ－フェニル－３－アミノプロピルトリメトキシシランが例示される。 Examples of the amino-based silane coupling agent include N-2 (aminoethyl) 3-aminopropylmethyldimethoxysilane, N-2 (aminoethyl) 3-aminopropyltrimethoxysilane, and N-2 (aminoethyl) 3-amino. Propyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, N-phenyl-3-aminopropyltri An example is methoxysilane.
ウレイド系のシランカップリング剤としては、３－ウレイドプロピルトリエトキシシランが例示される。クロロプロピル系のシランカップリング剤としては、３－クロロプロピルトリメトキシシランが例示される。メルカプト系のシランカップリング剤としては、３－メルカプトプロピルメチルジメトキシシラン、３－メルカプトプロピルトリメトキンシランが例示される。スルフィド系のシランカップリング剤としては、ビス（トリエトキシシリルプロピル）テトラスルファイドが例示される。イソシアネート系のシランカップリング剤としては、３－イソシアネートプロピルトリエトキシシランが例示される。アルミニウム系カップリング剤としては、アセトアルコキシアルミニウムジイソプロピレートが例示される。 Examples of the ureido-based silane coupling agent include 3-ureidopropyltriethoxysilane. Examples of the chloropropyl-based silane coupling agent include 3-chloropropyltrimethoxysilane. Examples of the mercapto-based silane coupling agent include 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethkinsilane. Examples of the sulfide-based silane coupling agent include bis (triethoxysilylpropyl) tetrasulfide. Examples of the isocyanate-based silane coupling agent include 3-isocyanatepropyltriethoxysilane. Examples of the aluminum-based coupling agent include acetalkoxyaluminum diisopropyrate.
これらのシランカップリング剤（Ｃ）は１種類を単独で用いても良いし、２種類以上を併用しても良い。中でも、（メタ）アクリロイルオキシ基、グリシジル基、エポキシシクロヘキシル基を有するものが好ましく、特に３－（メタ）アクリロイルオキシプロピルトリメトキシシランが最も好ましい。 One type of these silane coupling agents (C) may be used alone, or two or more types may be used in combination. Among them, those having a (meth) acryloyloxy group, a glycidyl group, and an epoxycyclohexyl group are preferable, and 3- (meth) acryloyloxypropyltrimethoxysilane is most preferable.
本発明では、前記酸化ジルコニウム粒子（Ａ）の分散安定性を一層高めるために、分散剤（Ｄ）を用いても良い。前記分散剤（Ｄ）は、前記酸化ジルコニウム粒子（Ａ）と親和性を有する官能基を含む化合物であれば特に限定されず、例えば、カルボン酸、硫酸、スルホン酸、リン酸、これら酸化合物の塩など、酸基を有するアニオン系の分散剤を挙げることができる。中でも、分散安定性が一層高い硬化性組成物となることから、リン酸エステル系分散剤が好ましく、ラクトン化合物由来の構造部位を有するものがより好ましい。また、その酸価が１００～３００ｍｇＫＯＨ/ｇの範囲であることがより好ましく、重量平均分子量（Ｍｗ）が１，０００～３，０００の範囲であることがより好ましい。 In the present invention, the dispersant (D) may be used in order to further enhance the dispersion stability of the zirconium oxide particles (A). The dispersant (D) is not particularly limited as long as it is a compound containing a functional group having an affinity with the zirconium oxide particles (A), and for example, carboxylic acid, sulfuric acid, sulfonic acid, phosphoric acid, and these acid compounds. Examples thereof include anionic dispersants having an acid group such as salts. Among them, a phosphoric acid ester-based dispersant is preferable, and one having a structural moiety derived from a lactone compound is more preferable, because the curable composition has higher dispersion stability. Further, the acid value thereof is more preferably in the range of 100 to 300 mgKOH / g, and the weight average molecular weight (Mw) is more preferably in the range of 1,000 to 3,000.
尚、本発明において、重量平均分子量（Ｍｗ）は、ゲルパーミエーションクロマトグラフ（ＧＰＣ）を用い、下記の条件により測定される値である。 In the present invention, the weight average molecular weight (Mw) is a value measured under the following conditions using a gel permeation chromatograph (GPC).
測定装置 ； 東ソー株式会社製 ＨＬＣ－８２２０
カラム ； 東ソー株式会社製ガードカラムＨＸＬ－Ｈ
＋東ソー株式会社製 ＴＳＫｇｅｌ Ｇ５０００ＨＸＬ
＋東ソー株式会社製 ＴＳＫｇｅｌ Ｇ４０００ＨＸＬ
＋東ソー株式会社製 ＴＳＫｇｅｌ Ｇ３０００ＨＸＬ
＋東ソー株式会社製 ＴＳＫｇｅｌ Ｇ２０００ＨＸＬ
検出器 ； ＲＩ（示差屈折計）
データ処理：東ソー株式会社製 ＳＣ－８０１０
測定条件： カラム温度 ４０℃
溶媒 テトラヒドロフラン
流速 １．０ｍｌ／分
標準 ；ポリスチレン
試料 ；樹脂固形分換算で０．４質量量％のテトラヒドロフラン溶液をマイクロフィルターでろ過したもの（１００μｌ）Measuring device; HLC-8220 manufactured by Tosoh Corporation
Column; Guard column HXL-H manufactured by Tosoh Corporation
+ TSKgel G5000HXL manufactured by Tosoh Corporation
+ TSKgel G4000HXL manufactured by Tosoh Corporation
+ TSKgel G3000HXL manufactured by Tosoh Corporation
+ TSKgel G2000HXL manufactured by Tosoh Corporation
Detector; RI (differential refractometer)
Data processing: SC-8010 manufactured by Tosoh Corporation
Measurement conditions: Column temperature 40 ° C
Solvent tetrahydrofuran
Flow velocity 1.0 ml / min Standard; Polystyrene sample; 0.4% by mass in terms of resin solid content Tetrahydrofuran solution filtered through a microfilter (100 μl)
本発明の硬化性組成物の調製において、前記分散剤（Ｄ）の使用量は特に限定されるものではないが、前記酸化ジルコニウム粒子（ａ）の総質量に対して、０．１～３０質量％の範囲であることが好ましく、０．５～１５質量％の範囲であることがより好ましい。 In the preparation of the curable composition of the present invention, the amount of the dispersant (D) used is not particularly limited, but is 0.1 to 30 mass with respect to the total mass of the zirconium oxide particles (a). It is preferably in the range of%, and more preferably in the range of 0.5 to 15% by mass.
本発明の硬化性組成物が含有する（メタ）アクリロイル基含有化合物（Ｂ）は、フェニルベンジル（メタ）アクリレート（Ｂ１）を必須の成分とする。フェニルベンジル（メタ）アクリレート（Ｂ１）は、オルソフェニルベンジル（メタ）アクリレート、メタフェニルベンジル（メタ）アクリレート、パラフェニルベンジル（メタ）アクリレートの何れでも良く、それぞれ単独で用いても良いし、２種類以上の混合物を用いても良い。このうち、オルトフェニルベンジル（メタ）アクリレート及びメタフェニルベンジル（メタ）アクリレートは、２５℃での液体の屈折率が１．５７以上であり、かつ、粘度が３０ｍＰａ・ｓ以下であり、比較的高屈折率でありながら、低粘度を示す点で好ましい。また、パラフェニルベンジルアクリレートは常温で固体であるが、４０℃での液体の屈折率が１．５９以上と非常に高い値を示す点で好ましい。 The (meth) acryloyl group-containing compound (B) contained in the curable composition of the present invention contains phenylbenzyl (meth) acrylate (B1) as an essential component. The phenylbenzyl (meth) acrylate (B1) may be any of orthophenylbenzyl (meth) acrylate, metaphenylbenzyl (meth) acrylate, and paraphenylbenzyl (meth) acrylate, and may be used alone or in two types. The above mixture may be used. Of these, orthophenylbenzyl (meth) acrylate and metaphenylbenzyl (meth) acrylate have a refractive index of 1.57 or more and a viscosity of 30 mPa · s or less at 25 ° C., which are relatively high. It is preferable in that it exhibits a low viscosity while having a refractive index. Further, although the paraphenylbenzyl acrylate is solid at room temperature, it is preferable in that the refractive index of the liquid at 40 ° C. is 1.59 or more, which is a very high value.
特に、高屈折率かつ低粘度の硬化性組成物となることから、オルトフェニルベンジル（メタ）アクリレート、メタフェニルベンジル（メタ）アクリレート及びパラフェニルベンジル（メタ）アクリレートを併用することが好ましく、その際の配合比は、オルトフェニルベンジル（メタ）アクリレート及びメタフェニルベンジル（メタ）アクリレートの合計と、パラフェニルベンジル（メタ）アクリレートとのモル比［｛〔オルトフェニルベンジル（メタ）アクリレート〕＋〔メタフェニルベンジル（メタ）アクリレート〕｝／〔パラフェニルベンジル（メタ）アクリレート〕］が５５／４５～１０／９０の範囲となるように用いることが好ましい。 In particular, since it is a curable composition having a high refractive index and low viscosity, it is preferable to use orthophenylbenzyl (meth) acrylate, metaphenylbenzyl (meth) acrylate and paraphenylbenzyl (meth) acrylate in combination, in which case. The compounding ratio of is the molar ratio of the total of orthophenylbenzyl (meth) acrylate and metaphenylbenzyl (meth) acrylate to paraphenylbenzyl (meth) acrylate [{[orthophenylbenzyl (meth) acrylate] + [metaphenyl]. It is preferable to use benzyl (meth) acrylate]} / [paraphenylbenzyl (meth) acrylate]] in the range of 55/45 to 10/90.
また、オルトフェニルベンジル（メタ）アクリレートとパラフェニルベンジル（メタ）アクリレートは、製造が簡便である点でも好ましい。これら２成分を用いる場合の配合比は、高屈折率かつ低粘度の硬化性組成物となることから、オルトフェニルベンジル（メタ）アクリレートと、パラフェニルベンジル（メタ）アクリレートとのモル比［〔オルトフェニルベンジル（メタ）アクリレート〕／〔パラフェニルベンジル（メタ）アクリレート〕］が、５５／４５～１０／９０の範囲であることが好ましい。 Further, orthophenylbenzyl (meth) acrylate and paraphenylbenzyl (meth) acrylate are also preferable in that they are easy to produce. When these two components are used, the compounding ratio is a curable composition having a high refractive index and a low viscosity. Therefore, the molar ratio of orthophenylbenzyl (meth) acrylate and paraphenylbenzyl (meth) acrylate [[Ortho Phenylbenzyl (meth) acrylate] / [paraphenylbenzyl (meth) acrylate]] is preferably in the range of 55/45 to 10/90.
前記フェニルベンジル（メタ）アクリレート（Ｂ１）の製造方法は、例えば、ビフェニルメタノールと（メタ）アクリル酸とをエステル化反応させる方法（方法１）や、クロロメチルビフェニル、ブロモメチルビフェニルのようなハロゲン化メチルビフェニルと、（メタ）アクリル酸のカリウム、ナトリウム、リチウムなどのアルカリ金属塩とを反応させる方法（方法２）、ビフェニル、ハロゲン化水素、及びホルムアルデヒド誘導体を反応させて得られる反応混合物を、更に、アクリル酸又はアクリル酸アルカリ金属塩と反応させる方法（方法３）等が挙げられる。 The method for producing the phenylbenzyl (meth) acrylate (B1) is, for example, a method of esterifying biphenylmethanol and (meth) acrylic acid (method 1), or a method of hydrohalizing chloromethylbiphenyl or bromomethylbiphenyl. A method for reacting methylbiphenyl with an alkali metal salt such as potassium, sodium, or lithium (meth) acrylic acid (method 2), a reaction mixture obtained by reacting biphenyl, hydrogen halide, and a formaldehyde derivative, further added. , A method of reacting with acrylic acid or an acrylic acid alkali metal salt (method 3) and the like.
前記方法３について、ビフェニルとホルムアルデヒドとの反応割合は、ビフェニル１モルに対し、ホルムアルデヒドを１～２５モルの範囲で用いることが好ましい。ホルムアルデヒドはホルマリン水溶液、パラホルムアルデヒド、トリオキサンなどいずれの形態で用いても良い。前記ハロゲン化水素は濃塩酸や塩化水素ガス等が挙げられ、ビフェニルに対して過剰のモル比で使用することが好ましい。反応は酸触媒条件下で行われることが好ましく、用いる酸触媒は、例えば、硫酸、リン酸、ポリリン酸、トリクロロ酢酸、ジクロロ酢酸、モノクロロ酢酸、メタンスルホン酸、ｐ－トルエンスルホン酸、塩化亜鉛などのルイス酸等が挙げられる。必要に応じてジメトキシエタン、ジオキサン、シクロペンチルメチルエーテル、酢酸等の有機溶媒中で反応させても良く、反応温度は６０～１８０℃の範囲であることが好ましい。 Regarding the above method 3, the reaction ratio between biphenyl and formaldehyde is preferably in the range of 1 to 25 mol of formaldehyde with respect to 1 mol of biphenyl. Formaldehyde may be used in any form such as formalin aqueous solution, paraformaldehyde, and trioxane. Examples of the hydrogen halide include concentrated hydrochloric acid and hydrogen chloride gas, and it is preferable to use the hydrogen halide in an excessive molar ratio with respect to biphenyl. The reaction is preferably carried out under acid catalyst conditions, and the acid catalyst used is, for example, sulfuric acid, phosphoric acid, polyphosphoric acid, trichloroacetic acid, dichloroacetic acid, monochloroacetic acid, methanesulfonic acid, p-toluenesulfonic acid, zinc chloride and the like. Lewis acid and the like can be mentioned. If necessary, the reaction may be carried out in an organic solvent such as dimethoxyethane, dioxane, cyclopentyl methyl ether and acetic acid, and the reaction temperature is preferably in the range of 60 to 180 ° C.
このような方法により前記フェニルベンジル（メタ）アクリレート（Ｂ１）を製造する場合、フェニルベンジル（メタ）アクリレート（Ｂ１）の他、ビス［（メタ）アクリロイルメチル］ビフェニル（Ｂ１’）やビフェニル構造がメチレンを介して結節された分子構造を有するビフェニル化合物（Ｂ１”）等が副生することがある。この場合、反応生成物１００質量部中のフェニルベンジル（メタ）アクリレート（Ｂ１）の含有量は３０～９５質量部の範囲であることが好ましく、３５～８５質量部の範囲であることがより好ましい。また、反応生成物１００質量部中のビス［（メタ）アクリロイルメチル］ビフェニル（Ｂ１’）の含有量は５～７０質量部の範囲であることが好ましく、１５～６５質量部の範囲であることがより好ましい。更に、反応生成物１００質量部中の前記ビフェニル構造がメチレンを介して結節された分子構造を有するビフェニル化合物（Ｂ１”）の含有量は０．５～３０質量部の範囲であることが好ましく、１～２５質量部の範囲であることがより好ましい。 When the phenylbenzyl (meth) acrylate (B1) is produced by such a method, in addition to the phenylbenzyl (meth) acrylate (B1), bis [(meth) acryloylmethyl] biphenyl (B1') and the biphenyl structure are methylene. A biphenyl compound (B1 ″) or the like having a molecular structure knotted via the above may be produced as a by-product. In this case, the content of phenylbenzyl (meth) acrylate (B1) in 100 parts by mass of the reaction product is 30. It is preferably in the range of ~ 95 parts by mass, more preferably in the range of 35 to 85 parts by mass, and of bis [(meth) acryloylmethyl] biphenyl (B1') in 100 parts by mass of the reaction product. The content is preferably in the range of 5 to 70 parts by mass, more preferably in the range of 15 to 65 parts by mass. Further, the biphenyl structure in 100 parts by mass of the reaction product is knotted via methylene. The content of the biphenyl compound (B1 ") having a molecular structure is preferably in the range of 0.5 to 30 parts by mass, and more preferably in the range of 1 to 25 parts by mass.
また、このような方法により前記フェニルベンジル（メタ）アクリレート（Ｂ１）を製造する場合、反応生成物中に未反応原料のビフェニルが残る場合がある。この場合、本願発明所望の効果である高屈折率かつ低粘度の組成物が得られることから、反応生成物１００質量部中のビフェニルの含有量は０．５～１５質量部の範囲であることが好ましく、１～１０質量部の範囲であることがより好ましい。 Further, when the phenylbenzyl (meth) acrylate (B1) is produced by such a method, biphenyl as an unreacted raw material may remain in the reaction product. In this case, the content of biphenyl in 100 parts by mass of the reaction product is in the range of 0.5 to 15 parts by mass because a composition having a high refractive index and a low viscosity, which is the desired effect of the present invention, can be obtained. Is preferable, and the range is more preferably in the range of 1 to 10 parts by mass.
反応生成物中の各成分の含有率を測定する方法は、例えば、ガスクロマトグラフ、液体クロマトグラフ、ゲルパーミネーションクロマトグラフなどが挙げられる。 Examples of the method for measuring the content of each component in the reaction product include a gas chromatograph, a liquid chromatograph, and a gel permeation chromatograph.
前記ビス［（メタ）アクリロイルメチル］ビフェニル（Ｂ１’）は、例えば、２，２’－ビス（アクリロイルメチル）－１，１’－ビフェニル、３，３’－ビス（アクリロイルメチル）－１，１’－ビフェニル、４，４’－ビス（アクリロイルメチル）－１，１’－ビフェニル、２，４’－ビス（アクリロイルメチル）－１，１’－ビフェニル、２，４－ビス（アクリロイルメチル）－１，１’－ビフェニル、２，６－ビス（アクリロイルメチル）－１，１’－ビフェニル等が挙げられる。 The bis [(meth) acryloylmethyl] biphenyl (B1') is, for example, 2,2'-bis (acryloylmethyl) -1,1'-biphenyl, 3,3'-bis (acryloylmethyl) -1,1. '-Biphenyl, 4,4'-bis (acryloylmethyl) -1,1'-biphenyl, 2,4'-bis (acryloylmethyl) -1,1'-biphenyl, 2,4-bis (acryloylmethyl)- Examples thereof include 1,1'-biphenyl and 2,6-bis (acryloylmethyl) -1,1'-biphenyl.
前記ビフェニル構造がメチレンを介して結節された分子構造を有するビフェニル化合物（Ｂ１”）は、分子構造中に含まれるビフェニル構造単位の数が２～５の範囲であることが好ましい。ビフェニル化合物（Ｂ１”）の重合度を同定する方法は、例えば、シリカゲルカラムクロマトグラフィーで反応生成物から前記フェニルベンジル（メタ）アクリレート（Ａ）や前記ビス（アクリロイルメチル）ビフェニル（Ｂ１’）を除いた成分を、ガスクロマトグラフ質量分析計（ＧＣ－ＭＳ）や高速液体クロマトグラフ質量分析計（ＬＣ―ＭＳ）を用いて分析する方法が挙げられる。 The biphenyl compound (B1 ") having a molecular structure in which the biphenyl structure is knotted via methylene preferably has a biphenyl compound (B1”) in which the number of biphenyl structural units contained in the molecular structure is in the range of 2 to 5. The method for identifying the degree of polymerization of ") is, for example, a component obtained by removing the phenylbenzyl (meth) acrylate (A) and the bis (acryloylmethyl) biphenyl (B1') from the reaction product by silica gel column chromatography. Examples thereof include a method of analysis using a gas chromatograph mass analyzer (GC-MS) or a high-speed liquid chromatograph mass analyzer (LC-MS).
本発明では、前記（メタ）アクリロイル基含有化合物（Ｂ）として前記フェニルベンジル（メタ）アクリレート（Ｂ１）以外の、その他の（メタ）アクリロイル基含有化合物（Ｂ２）を併用しても良い。前記その他の（メタ）アクリロイル基含有化合物（Ｂ２）は、例えば、エポキシ（メタ）アクリレート、ウレタン（メタ）アクリレート、フルオレン骨格含有（メタ）アクリレート、これら以外の単官能型或いは多官能型（メタ）アクリレート化合物等が挙げられる。 In the present invention, other (meth) acryloyl group-containing compound (B2) other than the phenylbenzyl (meth) acrylate (B1) may be used in combination as the (meth) acryloyl group-containing compound (B). The other (meth) acryloyl group-containing compound (B2) includes, for example, epoxy (meth) acrylate, urethane (meth) acrylate, fluorene skeleton-containing (meth) acrylate, and other monofunctional or polyfunctional (meth) compounds. Examples thereof include acrylate compounds.
前記エポキシ（メタ）アクリレートは、具体的には、エポキシ樹脂に（メタ）アクリル酸又はその無水物を反応させて得られるものであり、前記エポキシ樹脂は、例えば、ヒドロキノン、カテコール等の２価フェノールのジグリシジルエーテル；３，３’－ビフェニルジオール、４，４’－ビフェニルジオール等のビフェノール化合物のジグリシジルエーテル；ビスフェノールＡ型エポキシ樹脂、ビスフェノールＢ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、ビスフェノールＳ型エポキシ樹脂等のビスフェノール型エポキシ樹脂；１，４－ナフタレンジオール、１，５－ナフタレンジオール、１，６－ナフタレンジオール、２，６－ナフタレンジオール、２，７－ナフタレンジオール、ビナフトール、ビス（２，７－ジヒドロキシナフチル）メタン等のナフトール化合物のポリグリジシルエーテル；４，４’，４”－メチリジントリスフェノール等のトリグリシジルエーテル；フェノールノボラック型エポキシ樹脂、クレゾールノボラック樹脂等のノボラック型エポキシ樹脂 Specifically, the epoxy (meth) acrylate is obtained by reacting an epoxy resin with (meth) acrylic acid or an anhydride thereof, and the epoxy resin is, for example, a divalent phenol such as hydroquinone or catechol. Diglycidyl ether; Diglycidyl ether of biphenol compounds such as 3,3'-biphenyldiol and 4,4'-biphenyldiol; bisphenol A type epoxy resin, bisphenol B type epoxy resin, bisphenol F type epoxy resin, bisphenol S type Bisphenol type epoxy resin such as epoxy resin; 1,4-naphthalenediol, 1,5-naphthalenediol, 1,6-naphthalenediol, 2,6-naphthalenediol, 2,7-naphthalenediol, binaphthol, bis (2, 7-Dihydroxynaphthyl) Polyglycidyl ether of a naphthol compound such as methane; 4,4', 4 "-triglycidyl ether such as methylidine trisphenol; novolak type epoxy resin such as phenol novolac type epoxy resin and cresol novolak resin.
前記ビフェノール化合物、ビスフェノールＡ、ビスフェノールＢ、ビスフェノールＦ、ビスフェノールＳ、ナフトール化合物と、エチレンオキシド、プロピレンオキシド、テトラヒドロフラン、エチルグリシジルエーテル、プロピルグリシジルエーテル、ブチルグリシジルエーテル、フェニルグリシジルエーテル、アリルグリシジルエーテル等の種々の環状エーテル化合物との開環重合によって得られるポリエーテル変性芳香族ポリオールのポリグリシジルエーテル； The biphenol compound, bisphenol A, bisphenol B, bisphenol F, bisphenol S, naphthol compound, and various types such as ethylene oxide, propylene oxide, tetrahydrofuran, ethyl glycidyl ether, propyl glycidyl ether, butyl glycidyl ether, phenyl glycidyl ether, and allyl glycidyl ether. Polyglycidyl ether of a polyether-modified aromatic polyol obtained by ring-open polymerization with a cyclic ether compound;
前記ビフェノール化合物、ビスフェノールＡ、ビスフェノールＢ、ビスフェノールＦ、ビスフェノールＳ、ナフトール化合物と、ε－カプロラクトン等のラクトン化合物との重縮合によって得られるラクトン変性芳香族ポリオールのポリグリシジルエーテル等が挙げられる。 Examples thereof include polyglycidyl ether, which is a lactone-modified aromatic polyol obtained by polycondensation of the biphenol compound, bisphenol A, bisphenol B, bisphenol F, bisphenol S, and naphthol compound with a lactone compound such as ε-caprolactone.
これらの中でも、最終的に得られる組成物が高屈折率なものとなることから、分子構造中に芳香環骨格を有するものが好ましい。とりわけ、より高い屈折率を示し、かつ、高温高湿条件下であっても、プラスチックフィルム基材に対し高い付着性を示す硬化塗膜が得られることから、前記ビスフェノール型エポキシ樹脂が特に好ましい。 Among these, those having an aromatic ring skeleton in the molecular structure are preferable because the finally obtained composition has a high refractive index. In particular, the bisphenol type epoxy resin is particularly preferable because a cured coating film that exhibits a higher refractive index and exhibits high adhesion to a plastic film substrate even under high temperature and high humidity conditions can be obtained.
また、ビスフェノール型エポキシ樹脂の中でも、より高屈折率かつ高硬度の硬化物が得られることから、エポキシ当量が１６０～１，０００ｇ／ｅｑの範囲であるものが好ましく、１６５～６００ｇ／ｅｑの範囲であるものがより好ましい。 Further, among the bisphenol type epoxy resins, those having an epoxy equivalent in the range of 160 to 1,000 g / eq are preferable, and the range of 165 to 600 g / eq, because a cured product having a higher refractive index and higher hardness can be obtained. Is more preferable.
前記ウレタン（メタ）アクリレートは、例えば、各種のポリイソシアネート化合物、水酸基含有（メタ）アクリレート化合物、及び必要に応じて各種のポリオール化合物を反応させて得られるものが挙げられる。前記ポリイソシアネート化合物は、例えば、ヘキサメチレンジイソシアネート、イソホロンジイソシアネート、トリレンジイソシアネート、キシリレンジイソシアネート、４，４′－ジフェニルメタンジイソシアネート等のジイソシアネート化合物或いはそのヌレート変性体、アダクト変性体、ビウレット変性体が挙げられる。前記水酸基含有（メタ）アクリレート化合物は、例えば、ヒドロキシエチル（メタ）アクリレート、ヒドロキシプロピル（メタ）アクリレート、トリメチロールプロパンジアクリレート、ペンタエリスリトールトリ（メタ）アクリレート、ジペンタエリスリトールペンタ（メタ）アクリレート、及びこれらのポリオキシアルキレン変性体、ポリラクトン変性体等が挙げられる。前記ポリオール化合物は、例えば、エチレングリコール、プロプレングリコール、ブタンジオール、ヘキサンジオール、ポリオキシエチレングリコール、ポリオキシプロピレングリコール、グリセリン、トリメチロールプロパン、ペンタエリスリトール、ビフェノール、ビスフェノール等が挙げられる。 Examples of the urethane (meth) acrylate include those obtained by reacting various polyisocyanate compounds, hydroxyl group-containing (meth) acrylate compounds, and various polyol compounds as needed. Examples of the polyisocyanate compound include a diisocyanate compound such as hexamethylene diisocyanate, isophorone diisocyanate, tolylene diisocyanate, xylylene diisocyanate, and 4,4'-diphenylmethane diisocyanate, or a nurate-modified product thereof, an adduct-modified product, and a biuret-modified product. .. The hydroxyl group-containing (meth) acrylate compound includes, for example, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, trimethylolpropane diacrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, and Examples thereof include these polyoxyalkylene modified products and polylactone modified products. Examples of the polyol compound include ethylene glycol, propylene glycol, butanediol, hexanediol, polyoxyethylene glycol, polyoxypropylene glycol, glycerin, trimethylolpropane, pentaerythritol, biphenol, and bisphenol.
前記フルオレン骨格含有（メタ）アクリレートは屈折率が特に高い特徴を有する。具体的には、下記構造式１～４の何れかで表される化合物等が挙げられる。 The fluorene skeleton-containing (meth) acrylate has a particularly high refractive index. Specific examples thereof include compounds represented by any of the following structural formulas 1 to 4.
その他の単官能型或いは多官能型（メタ）アクリレート化合物は、例えば、メチル（メタ）アクリレート、エチル（メタ）アクリレート、プロピル（メタ）アクリレート、ブチル（メタ）アクリレート、ペンチル（メタ）アクリレート、ヘキシル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレート、オクチル（メタ）アクリレート等の脂肪族モノ（メタ）アクリレート化合物；シクロヘキシル（メタ）アクリレート、イソボルニル（メタ）アクリレート、アダマンチルモノ（メタ）アクリレート等の脂環型モノ（メタ）アクリレート化合物；グリシジル（メタ）アクリレート、テトラヒドロフルフリルアクリレート等の複素環型モノ（メタ）アクリレート化合物；ベンジル（メタ）アクリレート、フェニル（メタ）アクリレート、フェノキシ（メタ）アクリレート、フェノキシエチル（メタ）アクリレート、フェノキシエトキシエチル（メタ）アクリレート、２－ヒドロキシ－３－フェノキシプロピル（メタ）アクリレート、フェノキシベンジル（メタ）アクリレート、ベンジルベンジル（メタ）アクリレート、フェニルフェノキシエチル（メタ）アクリレート等の芳香族モノ（メタ）アクリレート化合物；ヒドロキシエチル（メタ）アクリレート、ヒドロキシプロピル（メタ）アクリレート、ヒドロキシブチル（メタ）アクリレート等の水酸基含有モノ（メタ）アクリレート化合物；下記構造式（５） Other monofunctional or polyfunctional (meth) acrylate compounds include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, and hexyl (meth). Acrylic mono (meth) acrylate compounds such as meta) acrylate, 2-ethylhexyl (meth) acrylate and octyl (meth) acrylate; alicyclic such as cyclohexyl (meth) acrylate, isobornyl (meth) acrylate and adamantyl mono (meth) acrylate. Type mono (meth) acrylate compound; heterocyclic mono (meth) acrylate compound such as glycidyl (meth) acrylate, tetrahydrofurfuryl acrylate; benzyl (meth) acrylate, phenyl (meth) acrylate, phenoxy (meth) acrylate, phenoxyethyl Fragrances of (meth) acrylate, phenoxyethoxyethyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, phenoxybenzyl (meth) acrylate, benzylbenzyl (meth) acrylate, phenylphenoxyethyl (meth) acrylate, etc. Group mono (meth) acrylate compound; hydroxyl group-containing mono (meth) acrylate compound such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate; the following structural formula (5)
エチレングリコールジ（メタ）アクリレート、プロピレングリコールジ（メタ）アクリレート、ブタンジオールジ（メタ）アクリレート、ヘキサンジオールジ（メタ）アクリレート、ネオペンチルグリコールジ（メタ）アクリレート等の脂肪族ジ（メタ）アクリレート化合物；１，４－シクロヘキサンジメタノールジ（メタ）アクリレート、ノルボルナンジ（メタ）アクリレート、ノルボルナンジメタノールジ（メタ）アクリレート、ジシクロペンタニルジ（メタ）アクリレート、トリシクロデカンジメタノールジ（メタ）アクリレート等の脂環型ジ（メタ）アクリレート化合物；ビフェノールジ（メタ）アクリレート、ビスフェノールジ（メタ）アクリレート等の芳香族ジ（メタ）アクリレート化合物；グリセロールジ（メタ）アクリレート、トリメチロールプロパンジ（メタ）アクリレート等の水酸基含有ジ（メタ）アクリレート化合物；前記各種のジ（メタ）アクリレート化合物の分子構造中にポリオキシエチレン鎖、ポリオキシプロピレン鎖、ポリオキシテトラメチレン鎖等のポリオキシアルキレン鎖を導入したポリオキシアルキレン変性ジ（メタ）アクリレート化合物；前記各種のジ（メタ）アクリレート化合物の分子構造中に（ポリ）ラクトン構造を導入したラクトン変性ジ（メタ）アクリレート化合物； An aliphatic di (meth) acrylate compound such as ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, butanediol di (meth) acrylate, hexanediol di (meth) acrylate, and neopentyl glycol di (meth) acrylate. 1,4-Cyclohexanedimethanol di (meth) acrylate, norbornandi (meth) acrylate, norbornan dimethanol di (meth) acrylate, dicyclopentanyldi (meth) acrylate, tricyclodecanedimethanol di (meth) acrylate Alicyclic di (meth) acrylate compounds such as biphenol di (meth) acrylate, aromatic di (meth) acrylate compounds such as bisphenol di (meth) acrylate; glycerol di (meth) acrylate, trimethyl propandi (meth). A hydroxyl group-containing di (meth) acrylate compound such as acrylate; a polyoxyalkylene chain such as a polyoxyethylene chain, a polyoxypropylene chain, or a polyoxytetramethylene chain was introduced into the molecular structure of the various di (meth) acrylate compounds. Polyoxyalkylene-modified di (meth) acrylate compound; A lactone-modified di (meth) acrylate compound in which a (poly) lactone structure is introduced into the molecular structure of the various di (meth) acrylate compounds;
トリメチロールプロパントリ（メタ）アクリレート、グリセリントリ（メタ）アクリレート等の脂肪族トリ（メタ）アクリレート化合物；ペンタエリスリトールトリ（メタ）アクリレート、ジトリメチロールプロパントリ（メタ）アクリレート、ジペンタエリスリトールトリ（メタ）アクリレート等の水酸基含有トリ（メタ）アクリレート化合物；前記各種のトリ（メタ）アクリレート化合物の分子構造中にポリオキシエチレン鎖、ポリオキシプロピレン鎖、ポリオキシテトラメチレン鎖等のポリオキシアルキレン鎖を導入したポリオキシアルキレン変性トリ（メタ）アクリレート化合物；前記各種のトリ（メタ）アクリレート化合物の分子構造中に（ポリ）ラクトン構造を導入したラクトン変性トリ（メタ）アクリレート化合物； Adipose tri (meth) acrylate compounds such as trimethylolpropane tri (meth) acrylate and glycerin tri (meth) acrylate; pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, dipentaerythritol tri (meth). A hydroxyl group-containing tri (meth) acrylate compound such as acrylate; a polyoxyalkylene chain such as a polyoxyethylene chain, a polyoxypropylene chain, or a polyoxytetramethylene chain was introduced into the molecular structure of the various tri (meth) acrylate compounds. Polyoxyalkylene-modified tri (meth) acrylate compound; A lactone-modified tri (meth) acrylate compound in which a (poly) lactone structure is introduced into the molecular structure of the various tri (meth) acrylate compounds;
ペンタエリスリトールテトラ（メタ）アクリレート、ジトリメチロールプロパンテトラ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート等の４官能以上の脂肪族ポリ（メタ）アクリレート化合物；ジペンタエリスリトールテトラ（メタ）アクリレート、ジペンタエリスリトールペンタ（メタ）アクリレート等の４官能以上の水酸基含有ポリ（メタ）アクリレート化合物；前記各種のポリ（メタ）アクリレート化合物の分子構造中にポリオキシエチレン鎖、ポリオキシプロピレン鎖、ポリオキシテトラメチレン鎖等のポリオキシアルキレン鎖を導入した４官能以上のポリオキシアルキレン変性ポリ（メタ）アクリレート化合物；前記各種のポリ（メタ）アクリレート化合物の分子構造中に（ポリ）ラクトン構造を導入した４官能以上のラクトン変性ポリ（メタ）アクリレート化合物：下記構造式（６） Tetrafunctional or higher aliphatic poly (meth) acrylate compounds such as pentaerythritol tetra (meth) acrylate, ditrimethylolpropanetetra (meth) acrylate, and dipentaerythritol hexa (meth) acrylate; dipentaerythritol tetra (meth) acrylate, di. Pentaerythritol Penta (meth) acrylate or other tetrafunctional or higher hydroxyl group-containing poly (meth) acrylate compound; polyoxyethylene chain, polyoxypropylene chain, polyoxytetramethylene in the molecular structure of the various poly (meth) acrylate compounds. 4-functional or higher polyoxyalkylene-modified poly (meth) acrylate compound in which a polyoxyalkylene chain such as a chain is introduced; 4-functional or higher in which a (poly) lactone structure is introduced into the molecular structure of the various poly (meth) acrylate compounds. Lactone-modified poly (meth) acrylate compound of: The following structural formula (6)
前記その他の（メタ）アクリロイル基含有化合物（Ｂ２）の中でも、屈折率の高い硬化性組成物が得られることから、分子構造中に芳香環を有する化合物が好ましく、分子構造中にビスフェノール構造を有する化合物がより好ましい。 Among the other (meth) acryloyl group-containing compounds (B2), a compound having an aromatic ring in its molecular structure is preferable, and a compound having a bisphenol structure in its molecular structure is preferable because a curable composition having a high refractive index can be obtained. Compounds are more preferred.
前記その他の（メタ）アクリロイル基含有化合物（Ｂ２）を用いる場合、（メタ）アクリロイル基含有化合物（Ｂ）中の前記フェニルベンジル（メタ）アクリレート（Ｂ１）の割合は、屈折率と粘度とのバランスに優れる硬化性組成物となることから、２０質量部以上であることが好ましく、４０質量部以上であることがより好ましく、５０質量部以上であることが特に好ましい。他方、硬化物における柔軟性を重視し、分子構造中にポリオキシアルキレン構造を有する（メタ）アクリレート等を比較的多く用いる等の場合には、（メタ）アクリロイル基含有化合物（Ｂ）中の前記フェニルベンジル（メタ）アクリレート（Ｂ１）は２０質量部未満であってもよい。この場合であっても、フェニルベンジル（メタ）アクリレート（Ｂ１）を含有することにより、粘度が高すぎず、かつ、屈折率の高い硬化性組成物が得られる。 When the other (meth) acryloyl group-containing compound (B2) is used, the ratio of the phenylbenzyl (meth) acrylate (B1) in the (meth) acryloyl group-containing compound (B) is a balance between the refractive index and the viscosity. 20 parts by mass or more is preferable, 40 parts by mass or more is more preferable, and 50 parts by mass or more is particularly preferable. On the other hand, when the flexibility of the cured product is emphasized and a relatively large amount of (meth) acrylate having a polyoxyalkylene structure in the molecular structure is used, the above-mentioned compound (B) containing a (meth) acryloyl group is used. Phenylbenzyl (meth) acrylate (B1) may be less than 20 parts by mass. Even in this case, by containing the phenylbenzyl (meth) acrylate (B1), a curable composition having a high viscosity and a high refractive index can be obtained.
前記その他の（メタ）アクリロイル基含有化合物（Ｂ２）として前記エポキシ（メタ）アクリレートを用いる場合には、（メタ）アクリロイル基含有化合物（Ｂ）中５～３５質量部の範囲で用いることが好ましい。前記その他の（メタ）アクリロイル基含有化合物（Ｂ２）として前記ウレタン（メタ）アクリレートを用いる場合には、（メタ）アクリロイル基含有化合物（Ｂ）中５～３５質量部の範囲で用いることが好ましい。前記その他の（メタ）アクリロイル基含有化合物（Ｂ２）として前記フルオレン骨格含有（メタ）アクリレートを用いる場合には、（メタ）アクリロイル基含有化合物（Ｂ）中５～４５質量部の範囲で用いることが好ましい。前記（メタ）アクリロイル基含有化合物（Ｂ２）として前記単官能型或いは多官能型（メタ）アクリレート化合物を用いる場合には、（メタ）アクリロイル基含有化合物（Ｂ）中５～６０質量部の範囲で用いることが好ましい。 When the epoxy (meth) acrylate is used as the other (meth) acryloyl group-containing compound (B2), it is preferably used in the range of 5 to 35 parts by mass in the (meth) acryloyl group-containing compound (B). When the urethane (meth) acrylate is used as the other (meth) acryloyl group-containing compound (B2), it is preferably used in the range of 5 to 35 parts by mass in the (meth) acryloyl group-containing compound (B). When the fluorene skeleton-containing (meth) acrylate is used as the other (meth) acryloyl group-containing compound (B2), it may be used in the range of 5 to 45 parts by mass in the (meth) acryloyl group-containing compound (B). preferable. When the monofunctional or polyfunctional (meth) acrylate compound is used as the (meth) acryloyl group-containing compound (B2), the amount is in the range of 5 to 60 parts by mass in the (meth) acryloyl group-containing compound (B). It is preferable to use it.
前記（メタ）アクリロイル基含有化合物（Ｂ２）として分子構造中にポリオキシアルキレン構造を有する（メタ）アクリレートを用いる場合には、（メタ）アクリロイル基含有化合物（Ｂ）中５～４５質量部の範囲で用いることが好ましい。また、分子構造中にポリオキシアルキレン構造を有する（メタ）アクリレートが有するオキシアルキレン構造の繰り返し単位数は、一分子中１０～３０の範囲であることが好ましい。前記（メタ）アクリロイル基含有化合物（Ｂ２）として分子構造中にポリオキシアルキレン構造を有する（メタ）アクリレートを用いることにより、柔軟性が高く復元性等に優れる硬化物を得ることができる。 When a (meth) acrylate having a polyoxyalkylene structure in the molecular structure is used as the (meth) acryloyl group-containing compound (B2), the range is 5 to 45 parts by mass in the (meth) acryloyl group-containing compound (B). It is preferable to use in. Further, the number of repeating units of the oxyalkylene structure of the (meth) acrylate having a polyoxyalkylene structure in the molecular structure is preferably in the range of 10 to 30 in one molecule. By using (meth) acrylate having a polyoxyalkylene structure in the molecular structure as the (meth) acryloyl group-containing compound (B2), a cured product having high flexibility and excellent stability can be obtained.
本発明の効果性組成物において前記酸化ジルコニウム粒子（Ａ）前記（メタ）アクリロイル基含有化合物（Ｂ）との配合割合は、所望の粘度や屈折率により適宜調整することができるが、分散安定性に優れ、屈折率が十分に高い硬化性組成物となることから、両者の質量比［（Ａ）/（Ｂ）］が２５/７５～７５/２５の範囲であることが好ましく、４０/６０～７０/３０の範囲であることがより好ましい。 In the effective composition of the present invention, the blending ratio of the zirconium oxide particles (A) and the (meth) acryloyl group-containing compound (B) can be appropriately adjusted depending on the desired viscosity and refractive index, but the dispersion stability. The mass ratio [(A) / (B)] of the two is preferably in the range of 25/75 to 75/25, and 40/60, because the curable composition is excellent in quality and has a sufficiently high refractive index. More preferably, it is in the range of ~ 70/30.
本発明の硬化性組成物は、ラジカル重合開始剤を含有してもよい。該ラジカル重合開始剤は、例えば、１－ヒドロキシシクロヘキシルフェニルケトン、２－ヒドロキシ－２－メチル－１－フェニルプロパン－１－オン、１－〔４－（２－ヒドロキシエトキシ）フェニル〕－２－ヒドロキシ－２－メチル－１－プロパン－１－オン、チオキサントン及びチオキサントン誘導体、２，２′－ジメトキシ－１，２－ジフェニルエタン－１－オン、２，４，６－トリメチルベンゾイルジフェニルホスフィンオキシド、ビス（２，４，６－トリメチルベンゾイル）フェニルホスフィンオキシド、２－メチル－１－［４－（メチルチオ）フェニル］－２－モルホリノ－１－プロパノン、２－ベンジル－２－ジメチルアミノ－１－（４－モルホリノフェニル）－ブタン－１－オン等が挙げられる。 The curable composition of the present invention may contain a radical polymerization initiator. The radical polymerization initiator is, for example, 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy. -2-Methyl-1-propane-1-one, thioxanthone and thioxanthone derivatives, 2,2'-dimethoxy-1,2-diphenylethane-1-one, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis ( 2,4,6-trimethylbenzoyl) phenylphosphenyl oxide, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-1-propanol, 2-benzyl-2-dimethylamino-1- (4-) Morphorinophenyl) -butane-1-one and the like can be mentioned.
これらラジカル重合開始剤の市販品は、例えば、「イルガキュア－１８４」、「イルガキュア－１４９」、「イルガキュア－２６１」、「イルガキュア－３６９」、「イルガキュア－５００」、「イルガキュア－６５１」、「イルガキュア－７５４」、「イルガキュア－７８４」、「イルガキュア－８１９」、「イルガキュア－９０７」、「イルガキュア－１１１６」、「イルガキュア－１６６４」、「イルガキュア－１７００」、「イルガキュア－１８００」、「イルガキュア－１８５０」、「イルガキュア－２９５９」、「イルガキュア－４０４３」、「ダロキュア－１１７３」（チバスペシャルティーケミカルズ社製）、「ルシリンＴＰＯ」（ビーエーエスエフ社製）、「カヤキュア－ＤＥＴＸ」、「カヤキュア－ＭＢＰ」、「カヤキュア－ＤＭＢＩ」、「カヤキュア－ＥＰＡ」、「カヤキュア－ＯＡ」（日本化薬株式会社製）、「バイキュア－１０」、「バイキュア－５５」（ストウファ・ケミカル社製）、「トリゴナルＰ１」（アクゾ社製）、「サンドレイ１０００」（サンドズ社製）、「ディープ」（アプジョン社製）、「クオンタキュア－ＰＤＯ」、「クオンタキュア－ＩＴＸ」、「クオンタキュア－ＥＰＤ」（ワードブレンキンソップ社製）等が挙げられる。 Commercially available products of these radical polymerization initiators include, for example, "Irgacure-184", "Irgacure-149", "Irgacure-261", "Irgacure-369", "Irgacure-500", "Irgacure-651", and "Irgacure". -754, "Irgacure-784", "Irgacure-819", "Irgacure-907", "Irgacure-1116", "Irgacure-1664", "Irgacure-1700", "Irgacure-1800", "Irgacure-1850" , "Irgacure-2959", "Irgacure-4043", "DaroCure-1173" (manufactured by Ciba Specialty Chemicals), "Lucillin TPO" (manufactured by BASF), "Kayacure-DETX", "Kayacure-MBP" , "Kayacure-DMBI", "Kayacure-EPA", "Kayacure-OA" (manufactured by Nippon Kayaku Co., Ltd.), "Vicure-10", "Vicure-55" (manufactured by Stoufa Chemical Co., Ltd.), "Trigonal P1" (Akzo), "Sandray 1000" (Sands), "Deep" (Apjon), "Quantacure-PDO", "Quantacure-ITX", "Quantacure-EPD" (Word Brenkinsop) (Manufactured by the company) and the like.
前記ラジカル重合開始剤の添加量は、十分な硬化性を発現するために、本願発明の硬化性組成物１００質量部に対し、０．０５～２０質量部の範囲であることが好ましく、０．１～１０質量部の範囲であることがより好ましい。 The amount of the radical polymerization initiator added is preferably in the range of 0.05 to 20 parts by mass with respect to 100 parts by mass of the curable composition of the present invention in order to exhibit sufficient curability. It is more preferably in the range of 1 to 10 parts by mass.
本発明の硬化性組成物を光重合にて硬化させる場合には、前記ラジカル重合開始剤に併せて種々の光増感剤を添加しても良い。前記光増感剤は、例えば、アミン類、尿素類、含硫黄化合物、含燐化合物、含塩素化合物またはニトリル類もしくはその他の含窒素化合物等が挙げられ、これらは単独で使用しても二種類以上を併用しても良い。これら光増感剤を添加する場合の添加量は、本願発明の硬化性組成物１００質量部に対し、０．０１～１０質量部の範囲であることが好ましい。 When the curable composition of the present invention is cured by photopolymerization, various photosensitizers may be added in addition to the radical polymerization initiator. Examples of the photosensitizer include amines, ureas, sulfur-containing compounds, phosphorus-containing compounds, chlorine-containing compounds, nitriles, and other nitrogen-containing compounds, and these are two types even when used alone. The above may be used together. When these photosensitizers are added, the amount added is preferably in the range of 0.01 to 10 parts by mass with respect to 100 parts by mass of the curable composition of the present invention.
本発明の硬化性組成物は、必要に応じてその他各種の添加剤を含有しても良い。各種の添加剤としては、紫外線吸収剤、酸化防止剤、シリコーン系添加剤、フッ素系添加剤、レオロジーコントロール剤、脱泡剤、帯電防止剤、防曇剤等が挙げられる。これら添加剤を添加する場合の添加量は、添加剤の効果を十分発揮し、また紫外線硬化を阻害しない範囲で、本発明の硬化性組成物１００質量部に対し、０．０１～４０質量部の範囲であることが好ましい。 The curable composition of the present invention may contain various other additives, if necessary. Examples of various additives include ultraviolet absorbers, antioxidants, silicone-based additives, fluorine-based additives, rheology control agents, defoaming agents, antistatic agents, anti-fog agents and the like. When these additives are added, the amount added is 0.01 to 40 parts by mass with respect to 100 parts by mass of the curable composition of the present invention within a range that sufficiently exerts the effect of the additives and does not inhibit ultraviolet curing. It is preferably in the range of.
本発明の硬化性組成物の粘度は、例えば金型を用いた賦形用途に用いる場合に、高速塗工条件下であっても金型の細部にまで欠点なく行渡るものとなることから、６，０００ｍＰａ・ｓ以下であることが好ましい。 Since the viscosity of the curable composition of the present invention can be spread to the details of the mold without any defect even under high-speed coating conditions, for example, when it is used for shaping using a mold. It is preferably 6,000 mPa · s or less.
本発明の硬化性組成物の屈折率は１．５７以上であることが好ましく、１．６０以上であることがより好ましい。 The refractive index of the curable composition of the present invention is preferably 1.57 or more, more preferably 1.60 or more.
本発明の硬化性組成物の製造方法は特に限定されないが、例えば、前記酸化ジルコニウム粒子（ａ）、前記（メタ）アクリロイル基含有化合物（Ｂ）の他、前記分散剤（Ｄ）やその他の添加座等を含む原料を一括で分散する方法（方法１）や、前記酸化ジルコニウム粒子（ａ）を有機溶媒中に分散し、これにその他の成分を添加して混合した後、必要に応じて有機溶媒を減圧除去する方法（方法２）等により調製することができる。 The method for producing the curable composition of the present invention is not particularly limited, and for example, in addition to the zirconium oxide particles (a) and the (meth) acryloyl group-containing compound (B), the dispersant (D) and other additions are added. A method of collectively dispersing raw materials including a constellation (method 1), or the zirconium oxide particles (a) are dispersed in an organic solvent, other components are added thereto and mixed, and then organic as necessary. It can be prepared by a method of removing the solvent under reduced pressure (method 2) or the like.
前記方法１や２で用いる分散機は、メディア式湿式分散機等、通常公知のものを制限なく使用することができ、例えば、ビーズミル（アシザワファインテック株式会社製スターミルＬＭＺ－０１５、寿工業（株）製ウルトラアペックスミルＵＡＭ－０１５等）が挙げられる。 As the disperser used in the above methods 1 and 2, commonly known ones such as a media type wet disperser can be used without limitation. For example, a bead mill (Star Mill LMZ-015 manufactured by Ashizawa Finetech Co., Ltd., Kotobuki Kogyo Co., Ltd.) ) Ultra Apex Mill UAM-015 etc.).
分散機で使用されるメディアは、通常公知のビーズであれば特に制限はないが、好ましくは、ジルコニア、アルミナ、シリカ、ガラス、炭化珪素、窒化珪素が挙げられる。メディアの平均粒径は５０～５００μｍが好ましく、１００～２００μｍのメディアがより好ましい。粒子径が５０μｍ以上であれば、原料粉に対する衝撃力が適正であり、分散に過度な時間を要しない。一方、メディアの粒子径が５００μｍ以下であれば、原料粉に対する衝撃力が適正であることから、分散された粒子の表面エネルギーの増大を抑制でき、再凝集を防止できる。 The medium used in the disperser is not particularly limited as long as it is a commonly known bead, but preferred examples thereof include zirconia, alumina, silica, glass, silicon carbide, and silicon nitride. The average particle size of the media is preferably 50 to 500 μm, more preferably 100 to 200 μm. When the particle size is 50 μm or more, the impact force against the raw material powder is appropriate and the dispersion does not require an excessive time. On the other hand, when the particle size of the media is 500 μm or less, the impact force on the raw material powder is appropriate, so that the increase in the surface energy of the dispersed particles can be suppressed and reaggregation can be prevented.
また、分散の初工程では衝撃力の大きい大粒径のメディアを使用し、分散された粒子の粒径が小さくなってから、再凝集が生じ難い小粒径のメディアを使用する２段階の方法により、分散工程時間を短くすることもできる。 In addition, in the first step of dispersion, a medium with a large particle size having a large impact force is used, and after the particle size of the dispersed particles becomes small, a medium with a small particle size that is unlikely to cause reaggregation is used. Therefore, the dispersion process time can be shortened.
本発明の硬化性組成物は、例えば、活性エネルギー線を照射する、加熱する等により硬化させることができる。前記活性エネルギー線にて硬化させる場合、該活性エネルギー線は、例えば、電子線、紫外線、可視光線等が挙げられる。活性エネルギー線として電子線を用いる場合には、コックロフトワルトン型加速器、バンデグラフ型電子加速器、共振変圧器型加速器、絶縁コア変圧器型、ダイナミトロン型、リニアフィラメント型および高周波型などの電子線発生装置を用いて本発明の硬化性組成物を硬化させることができる。また、活性エネルギー線として紫外線を用いる場合は、超高圧水銀灯、高圧水銀灯、低圧水銀灯等の水銀灯、キセノンランプ、カーボンアーク、メタルハイトランプ等により照射し、硬化させることができる。この際の紫外線の露光量は０．１～１０００ｍＪ／ｃｍ２の範囲であることが好ましい。The curable composition of the present invention can be cured by, for example, irradiating with active energy rays, heating, or the like. When curing with the active energy ray, the active energy ray may be, for example, an electron beam, ultraviolet rays, visible light or the like. When an electron beam is used as the active energy ray, electron beam generation such as Cockloft Walton type accelerator, Van de Graaff type electron accelerator, Resonant transformer type accelerator, Insulated core transformer type, Dynamitron type, Linear filament type and High frequency type is generated. The curable composition of the present invention can be cured using the apparatus. When ultraviolet rays are used as active energy rays, they can be cured by irradiating them with a mercury lamp such as an ultra-high pressure mercury lamp, a high pressure mercury lamp, or a low pressure mercury lamp, a xenon lamp, a carbon arc, or a metal height lamp. The exposure amount of ultraviolet rays at this time is preferably in the range of 0.1 to 1000 mJ / cm 2 .
一方、加熱によって硬化させる場合には、６０～２５０℃の温度領域に加熱することによって硬化させることができる。 On the other hand, when it is cured by heating, it can be cured by heating it in a temperature range of 60 to 250 ° C.
本発明の本発明の硬化性組成物は、これまでにない高い屈折を示し、粘度も非常に低いことから、例えば、眼鏡レンズ、デジタルカメラ用レンズ、フレネルレンズ、及びプリズムレンズ等のプラスチックレンズ、光学用オーバーコート剤、ハードコート剤、反射防止膜、光ファイバー、光導波路、ホログラム、プリズムレンズ、ＬＥＤ封止材料、太陽光電池用コーティング材等の各種光学部材用途に好適に使用することができ、これらのなかでも特に、液晶基板用プリズムレンズ等のプラスチックレンズ用に適している。 Since the curable composition of the present invention exhibits an unprecedentedly high refraction and a very low viscosity, for example, a plastic lens such as an optical lens, a lens for a digital camera, a Fresnel lens, and a prism lens. It can be suitably used for various optical member applications such as optical overcoating agents, hard coating agents, antireflection films, optical fibers, optical waveguides, holograms, prism lenses, LED encapsulant materials, and coating materials for solar cells. Among them, it is particularly suitable for plastic lenses such as prism lenses for liquid crystal substrates.
前記液晶基板用プリズムレンズとは、シート状成形体の片面に微細なプリズム形状部を複数有するものであって、通常、液晶表示素子の背面（光源側）に、該素子側にプリズム面が向くように配設され、更に、その背面に導光シートが配設されるように用いられるシート状レンズ、或いは前記プリズムレンズがこの導光シートの機能を兼ねているシート状レンズである。 The prism lens for a liquid crystal substrate has a plurality of fine prism-shaped portions on one side of a sheet-shaped molded body, and usually, the prism surface faces the back surface (light source side) of the liquid crystal display element and the element side. The sheet-shaped lens is arranged so as to be arranged, and the light guide sheet is further arranged on the back surface thereof, or the prism lens is a sheet-like lens that also has the function of the light guide sheet.
ここで該プリズムレンズのプリズム部の形状は、プリズム頂角の角度θが７０～１１０°の範囲であることが、集光性に優れ輝度が向上する点から好ましく、特に７５～１００°の範囲、中でも８０～９５°の範囲であることが特に好ましい。 Here, the shape of the prism portion of the prism lens preferably has a prism apex angle θ in the range of 70 to 110 ° from the viewpoint of excellent light collection and improved brightness, and particularly in the range of 75 to 100 °. Above all, the range of 80 to 95 ° is particularly preferable.
また、プリズムのピッチは、１００μｍ以下であることが好ましく、特に７０μｍ以下の範囲であることが、画面のモアレ模様の発生防止や、画面の精細度がより向上する点から好ましい。また、プリズムの凹凸の高さは、プリズム頂角の角度θとプリズムのピッチの値によって決定されるが、好ましくは５０μｍ以下の範囲であることが好ましい。さらに、プリズムレンズのシート厚さは、強度面からは厚い方が好ましいが、光学的には光の吸収を抑えるため薄い方が好ましく、これらのバランスの点から５０μｍ～１０００μｍの範囲であることが好ましい。 Further, the pitch of the prism is preferably 100 μm or less, and particularly preferably 70 μm or less from the viewpoint of preventing the occurrence of moire patterns on the screen and further improving the fineness of the screen. The height of the unevenness of the prism is determined by the angle θ of the prism apex angle and the value of the pitch of the prism, but is preferably in the range of 50 μm or less. Further, the sheet thickness of the prism lens is preferably thick from the viewpoint of strength, but is preferably thin from the viewpoint of optically suppressing light absorption, and may be in the range of 50 μm to 1000 μm from the viewpoint of these balances. preferable.
本発明の硬化性組成物を用いて前記プリズムレンズを製造する方法は、例えば、該組成物をプリズムパターンが形成された金型あるいは樹脂型等の成形型に塗布し、組成物の表面を平滑化した後に透明基材を重ね合わせ、該透明基材側から活性エネルギー線を照射し、硬化させる方法が挙げられる。 In the method for producing the prism lens using the curable composition of the present invention, for example, the composition is applied to a mold such as a mold or a resin mold on which a prism pattern is formed to smooth the surface of the composition. Examples thereof include a method in which transparent substrates are superposed after the formation and the transparent substrates are irradiated with active energy rays to cure them.
ここで用いる透明基材は、アクリル樹脂、ポリカーボネート樹脂、ポリエステル樹脂、ポリスチレン樹脂、フッ素樹脂、ポリイミド樹脂からなるプラスチック基材や、ガラス等が挙げられる。 Examples of the transparent base material used here include a plastic base material made of an acrylic resin, a polycarbonate resin, a polyester resin, a polystyrene resin, a fluororesin, a polyimide resin, glass, and the like.
前記方法で得たプリズムシートは、そのまま使用することもできるし、透明基材を剥離してプリズムレンズ単独の状態で使用してもよい。透明基材上にプリズム部を形成したまま使用する場合には、プリズムレンズと透明基材との接着性を高める目的で、透明基材表面にプライマー処理等の接着性向上処理を施しておくことが好ましい。 The prism sheet obtained by the above method can be used as it is, or the transparent base material may be peeled off and the prism lens may be used alone. When the prism portion is used with the prism portion formed on the transparent substrate, the surface of the transparent substrate should be subjected to an adhesiveness improving treatment such as a primer treatment for the purpose of improving the adhesiveness between the prism lens and the transparent substrate. Is preferable.
一方、透明基材を剥離して使用する場合には、該透明基材が容易に剥離できるように、透明基材の表面をシリコーンやフッ素系の剥離剤で処理をしておくことが好ましい。 On the other hand, when the transparent substrate is peeled off and used, it is preferable to treat the surface of the transparent substrate with a silicone or fluorine-based release agent so that the transparent substrate can be easily peeled off.
以下に、実施例および比較例をもって本発明をより詳しく説明する。
製造例や実施例で用いた各成分及び分散機の詳細は以下の通り。Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples.
Details of each component and disperser used in the production examples and examples are as follows.
製造例１ ジルコニウム分散液（１）の製造
酸化ジルコニウム粒子（ａ１）５０ｇ、シランカップリング剤（Ｃ１）７．５ｇ、メチルエチルケトン１８３．０ｇを混合し、分散攪拌機で３０分間攪拌し、粗分散を行った。得られた混合液を、メディア式湿式分散機で粒子径１００μｍのジルコニアビーズを用いて分散処理した。途中の粒子径を確認しながら、滞留時間１００分の分散処理を行った後、分散剤（Ｄ１）５ｇを添加混合して、更に２０分間の分散処理によりジルコニウム分散液（１）を得た。Production Example 1 Production of Zirconium Dispersion Liquid (1) 50 g of zirconium oxide particles (a1), 7.5 g of silane coupling agent (C1), and 183.0 g of methyl ethyl ketone are mixed and stirred with a dispersion stirrer for 30 minutes for coarse dispersion. rice field. The obtained mixed solution was dispersed by a media type wet disperser using zirconia beads having a particle diameter of 100 μm. After performing a dispersion treatment with a residence time of 100 minutes while checking the particle size on the way, 5 g of the dispersant (D1) was added and mixed, and the dispersion treatment was further carried out for 20 minutes to obtain a zirconium dispersion liquid (1).
製造例２ フェニルベンジルアクリレート組成物の製造
・クロロ中間体の合成
攪拌機、冷却管、温度計、塩化水素ガス導入装置を具備した５Ｌ４つ口フラスコに、ジフェニル７０９ｇ、パラホルムアルデヒド２７６ｇ、酢酸１３８１ｇ、濃塩酸９５８ｇを仕込み、８０℃まで昇温した。仕込み溶液が８０℃であることを確認後、木下式ガラスボールフィルターを使って塩化水素ガスを２０ｇ／ｈｒ速度で仕込み溶液に導入した。仕込み溶液への塩化水素ガスの溶解が飽和であることを確認後、リン酸１０６１ｇを１時間かけて滴下し、更に、３０時間反応を行った。反応終了後、直ちに反応溶液から下層を取り除き、有機層にトルエン２．３ｋｇを添加し、有機層を４００ｇの１２．５％水酸化ナトリウム水溶液、飽和炭酸水素ナトリウム水溶液、蒸留水で洗浄した。有機層を留去後、クロロ中間体を白色固体として９０８ｇ得た。
・アクリレート化
上記で得られた中間体９０８ｇを反応溶媒であるジメチルホルムアミド１６０３ｇに溶解し、炭酸カリウム３７２ｇおよびメトキノンを全量に対して３００ｐｐｍになるように添加した。中間体溶液を４０℃に昇温後、アクリル酸３２３ｇを１．５時間で中間体溶液に滴下した。滴下終了後、２時間かけて８０℃まで昇温し、８０℃にて３時間加熱撹拌した。得られた溶液に水３．４ｋｇおよびトルエン１．８ｋｇを添加し抽出を行った後、有機層を水層が中性になるまで洗浄した。有機層を濃縮して液状のフェニルベンジルアクリレート組成物を９９５ｇ得た。
・フェニルベンジルアクリレート組成物の分析
得られたフェニルベンジルアクリレート組成物の２５℃における液屈折率は１．５９２であり、粘度は３０ｍＰａ・ｓであった。フェニルベンジルアクリレート組成物１００質量部中に含まれる各成分の含有量を、ガスクロマトグラムを用いて測定したところ、フェニルベンジルアクリレートが６５．２質量部、ビス（アクリロイルメチル）ビフェニルが１８．６質量部、ビフェニル構造がメチレンを介して結節された分子構造を有するビフェニル化合物が２．３質量部、ビフェニルが５．８質量部含まれており、残りの８．１質量部にはビフェニル以外の未反応原料等が含まれていた。また、フェニルベンジルアクリレートの異性体の質量比（モル比も同等）［〔オルトフェニルベンジルアクリレート〕／〔メタフェニルベンジルアクリレート〕／〔パラフェニルベンジルアクリレート〕］は２０／１／７９であった。Production Example 2 Production of phenylbenzyl acrylate composition-Synthesis of chloro intermediate In a 5L 4-neck flask equipped with a stirrer, a cooling tube, a thermometer, and a hydrogen chloride gas introduction device, diphenyl 709 g, paraformaldehyde 276 g, acetic acid 1381 g, and concentrated hydrochloric acid 958 g was charged and the temperature was raised to 80 ° C. After confirming that the charged solution was at 80 ° C., hydrogen chloride gas was introduced into the charged solution at a rate of 20 g / hr using a Kinoshita type glass ball filter. After confirming that the dissolution of hydrogen chloride gas in the charging solution was saturated, 1061 g of phosphoric acid was added dropwise over 1 hour, and the reaction was further carried out for 30 hours. Immediately after completion of the reaction, the lower layer was removed from the reaction solution, 2.3 kg of toluene was added to the organic layer, and the organic layer was washed with 400 g of 12.5% aqueous sodium hydroxide solution, saturated aqueous sodium hydrogen carbonate solution and distilled water. After distilling off the organic layer, 908 g of a chloro intermediate was obtained as a white solid.
-Acrylation 908 g of the above-mentioned intermediate was dissolved in 1603 g of dimethylformamide as a reaction solvent, and 372 g of potassium carbonate and methquinone were added so as to be 300 ppm with respect to the total amount. After raising the temperature of the intermediate solution to 40 ° C., 323 g of acrylic acid was added dropwise to the intermediate solution in 1.5 hours. After completion of the dropping, the temperature was raised to 80 ° C. over 2 hours, and the mixture was heated and stirred at 80 ° C. for 3 hours. After adding 3.4 kg of water and 1.8 kg of toluene to the obtained solution and performing extraction, the organic layer was washed until the aqueous layer became neutral. The organic layer was concentrated to obtain 995 g of a liquid phenylbenzyl acrylate composition.
-Analysis of the phenylbenzyl acrylate composition The liquid refractive index of the obtained phenylbenzyl acrylate composition at 25 ° C. was 1.592, and the viscosity was 30 mPa · s. When the content of each component contained in 100 parts by mass of the phenylbenzyl acrylate composition was measured using a gas chromatogram, 65.2 parts by mass of phenylbenzyl acrylate and 18.6 parts by mass of bis (acryloylmethyl) biphenyl were measured. , 2.3 parts by mass of biphenyl compound having a molecular structure in which the biphenyl structure is knotted via methylene, 5.8 parts by mass of biphenyl is contained, and the remaining 8.1 parts by mass is unreacted other than biphenyl. Raw materials etc. were included. The mass ratio (same molar ratio) of the isomers of phenylbenzyl acrylate [[orthophenylbenzyl acrylate] / [methphenylbenzyl acrylate] / [paraphenylbenzyl acrylate]] was 20/1/79.
フェニルベンジルアクリレート組成物のガスクロマトグラム分析条件は以下の通り。
機器：島津社製「ＧＣ－２０１０」
カラム：島津社製「Ｚｅｂｒｏｎ ＺＢ－５」
条件：Ｈｅキャリアガス、流量１．４７ｍＬ／ｍｉｎ、カラムオーブン５０℃、気化室３００℃、昇温範囲５０℃から３００℃（２５℃／ｍｉｎ）The gas chromatogram analysis conditions for the phenylbenzyl acrylate composition are as follows.
Equipment: Shimadzu "GC-2010"
Column: "Zebron ZB-5" manufactured by Shimadzu
Conditions: He carrier gas, flow rate 1.47 mL / min, column oven 50 ° C, vaporization chamber 300 ° C, temperature rise range 50 ° C to 300 ° C (25 ° C / min)
実施例１
◆硬化性組成物（１）の調製
製造例１で得られたジルコニウム分散液（１）に、表２に示す割合で（メタ）アクリレート化合物を添加し、エバポレーターで揮発成分を減圧除去した。更に重合開始剤を添加し、硬化性組成物（１）を調製した。Example 1
◆ Preparation of Curable Composition (1) A (meth) acrylate compound was added to the zirconium dispersion (1) obtained in Production Example 1 at the ratio shown in Table 2, and the volatile components were removed under reduced pressure using an evaporator. Further, a polymerization initiator was added to prepare a curable composition (1).
◆酸化ジルコニウム粒子の粒子径測定
先で得た硬化性組成物（１）中の酸化ジルコニウム粒子の平均粒子径を下記条件で測定した。
粒子径測定装置：大塚電子株式会社製「ＥＬＳＺ－２」
粒子径測定サンプル：硬化性組成物を不揮発分０．６質量％のメチルイソブチルケトン溶液としたもの。◆ Measurement of particle size of zirconium oxide particles The average particle size of zirconium oxide particles in the curable composition (1) obtained above was measured under the following conditions.
Particle size measuring device: "ELSZ-2" manufactured by Otsuka Electronics Co., Ltd.
Particle size measurement sample: A curable composition prepared as a methyl isobutyl ketone solution having a non-volatile content of 0.6% by mass.
◆屈折率の測定
先で得た硬化性組成物について、アッベ屈折率計によって屈折率を測定した。結果を表２に示した。◆ Measurement of refractive index The refractive index of the curable composition obtained above was measured with an Abbe refractive index meter. The results are shown in Table 2.
◆粘度の測定
硬化性組成物の粘度を、Ｅ型回転粘度計（東機産業株式会社製「ＲＥ８０Ｕ」）を使用し、２５℃条件下で測定した。◆ Viscosity measurement The viscosity of the curable composition was measured under 25 ° C. conditions using an E-type rotational viscometer (“RE80U” manufactured by Toki Sangyo Co., Ltd.).
実施例２～８及び比較例１～４
実施例１と同じ要領で硬化性組成物及び硬化物を作成し、各種評価を行った。結果を表２又は３に示した。Examples 2 to 8 and Comparative Examples 1 to 4
A curable composition and a cured product were prepared in the same manner as in Example 1, and various evaluations were performed. The results are shown in Table 2 or 3.
Claims (4)
前記その他の（メタ）アクリロイル基含有化合物（Ｂ２）が、ビスフェノールＡ型エポキシ樹脂と（メタ）アクリル酸との反応物であるエポキシ（メタ）アクリレートを含むものであり、
前記酸化ジルコニウム（Ａ）と前記（メタ）アクリロイル基含有化合物（Ｂ）の質量比［（Ａ）／（Ｂ）］が２５／７５～７５／２５の範囲であることを特徴とする硬化性組成物。 The zirconium oxide particles (A) and the (meth) acryloyl group-containing compound (B) are contained, and the (meth) acryloyl group-containing compound (B) is phenylbenzyl (meth) acrylate (B1) and the phenylbenzyl (meth ). ) A curable composition containing a (meth) acryloyl group-containing compound (B2) other than the acrylate (B1) as an essential component.
The other (meth) acryloyl group-containing compound (B2) contains an epoxy (meth) acrylate which is a reaction product of a bisphenol A type epoxy resin and (meth) acrylic acid.
The curable composition is characterized in that the mass ratio [(A) / (B)] of the zirconium oxide (A) and the (meth) acryloyl group-containing compound (B) is in the range of 25/75 to 75/25. thing.
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