CN113195547B - Photocurable composition for imprinting - Google Patents
Photocurable composition for imprinting Download PDFInfo
- Publication number
- CN113195547B CN113195547B CN201980084213.8A CN201980084213A CN113195547B CN 113195547 B CN113195547 B CN 113195547B CN 201980084213 A CN201980084213 A CN 201980084213A CN 113195547 B CN113195547 B CN 113195547B
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- China
- Prior art keywords
- ext
- component
- meth
- photocurable composition
- imprinting
- Prior art date
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- 239000000203 mixture Substances 0.000 title claims abstract description 108
- -1 acrylate compound Chemical class 0.000 claims abstract description 86
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 35
- 125000000524 functional group Chemical group 0.000 claims abstract description 15
- 239000011164 primary particle Substances 0.000 claims abstract description 14
- 239000003999 initiator Substances 0.000 claims abstract description 10
- 238000004519 manufacturing process Methods 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 17
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 15
- 229920005989 resin Polymers 0.000 claims description 14
- 239000011347 resin Substances 0.000 claims description 13
- 150000001252 acrylic acid derivatives Chemical class 0.000 claims description 11
- 239000004593 Epoxy Substances 0.000 claims description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims description 10
- 238000000016 photochemical curing Methods 0.000 claims description 9
- 239000003963 antioxidant agent Substances 0.000 claims description 8
- 238000000465 moulding Methods 0.000 claims description 8
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 6
- 125000002947 alkylene group Chemical group 0.000 claims description 6
- 125000005842 heteroatom Chemical group 0.000 claims description 6
- 239000002530 phenolic antioxidant Substances 0.000 claims description 6
- 125000005647 linker group Chemical group 0.000 claims description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000011161 development Methods 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 238000011049 filling Methods 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 2
- 125000000962 organic group Chemical group 0.000 claims description 2
- 239000002245 particle Substances 0.000 abstract description 8
- 239000000377 silicon dioxide Substances 0.000 abstract 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 72
- 241000206607 Porphyra umbilicalis Species 0.000 description 26
- 125000004122 cyclic group Chemical group 0.000 description 23
- 239000000758 substrate Substances 0.000 description 23
- 239000011521 glass Substances 0.000 description 18
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 17
- 239000000126 substance Substances 0.000 description 17
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- 239000006185 dispersion Substances 0.000 description 16
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- 230000000903 blocking effect Effects 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 12
- 230000003287 optical effect Effects 0.000 description 8
- 229920000858 Cyclodextrin Polymers 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 239000007788 liquid Substances 0.000 description 6
- 150000003254 radicals Chemical class 0.000 description 6
- 238000002834 transmittance Methods 0.000 description 6
- 230000003078 antioxidant effect Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 229920001223 polyethylene glycol Polymers 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 5
- 125000006850 spacer group Chemical group 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 239000002202 Polyethylene glycol Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000005336 cracking Methods 0.000 description 4
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 230000003667 anti-reflective effect Effects 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- FOTKYAAJKYLFFN-UHFFFAOYSA-N decane-1,10-diol Chemical compound OCCCCCCCCCCO FOTKYAAJKYLFFN-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- AICOOMRHRUFYCM-ZRRPKQBOSA-N oxazine, 1 Chemical compound C([C@@H]1[C@H](C(C[C@]2(C)[C@@H]([C@H](C)N(C)C)[C@H](O)C[C@]21C)=O)CC1=CC2)C[C@H]1[C@@]1(C)[C@H]2N=C(C(C)C)OC1 AICOOMRHRUFYCM-ZRRPKQBOSA-N 0.000 description 3
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 description 3
- 229920002379 silicone rubber Polymers 0.000 description 3
- 239000004945 silicone rubber Substances 0.000 description 3
- DCTMXCOHGKSXIZ-UHFFFAOYSA-N (R)-1,3-Octanediol Chemical compound CCCCCC(O)CCO DCTMXCOHGKSXIZ-UHFFFAOYSA-N 0.000 description 2
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 2
- 102100027123 55 kDa erythrocyte membrane protein Human genes 0.000 description 2
- 229920001450 Alpha-Cyclodextrin Polymers 0.000 description 2
- 101001057956 Homo sapiens 55 kDa erythrocyte membrane protein Proteins 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- JOBBTVPTPXRUBP-UHFFFAOYSA-N [3-(3-sulfanylpropanoyloxy)-2,2-bis(3-sulfanylpropanoyloxymethyl)propyl] 3-sulfanylpropanoate Chemical compound SCCC(=O)OCC(COC(=O)CCS)(COC(=O)CCS)COC(=O)CCS JOBBTVPTPXRUBP-UHFFFAOYSA-N 0.000 description 2
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 2
- 125000005073 adamantyl group Chemical group C12(CC3CC(CC(C1)C3)C2)* 0.000 description 2
- IHUNBGSDBOWDMA-AQFIFDHZSA-N all-trans-acitretin Chemical compound COC1=CC(C)=C(\C=C\C(\C)=C\C=C\C(\C)=C\C(O)=O)C(C)=C1C IHUNBGSDBOWDMA-AQFIFDHZSA-N 0.000 description 2
- HFHDHCJBZVLPGP-RWMJIURBSA-N alpha-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO HFHDHCJBZVLPGP-RWMJIURBSA-N 0.000 description 2
- 229940043377 alpha-cyclodextrin Drugs 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 229940097362 cyclodextrins Drugs 0.000 description 2
- 239000002612 dispersion medium Substances 0.000 description 2
- GHLKSLMMWAKNBM-UHFFFAOYSA-N dodecane-1,12-diol Chemical compound OCCCCCCCCCCCCO GHLKSLMMWAKNBM-UHFFFAOYSA-N 0.000 description 2
- GJBXIPOYHVMPQJ-UHFFFAOYSA-N hexadecane-1,16-diol Chemical compound OCCCCCCCCCCCCCCCCO GJBXIPOYHVMPQJ-UHFFFAOYSA-N 0.000 description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920001281 polyalkylene Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 2
- 238000001552 radio frequency sputter deposition Methods 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- HCEPYODGJFPWOI-UHFFFAOYSA-N tridecane-1,13-diol Chemical compound OCCCCCCCCCCCCCO HCEPYODGJFPWOI-UHFFFAOYSA-N 0.000 description 2
- XSMIOONHPKRREI-UHFFFAOYSA-N undecane-1,11-diol Chemical compound OCCCCCCCCCCCO XSMIOONHPKRREI-UHFFFAOYSA-N 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
- VYMPLPIFKRHAAC-UHFFFAOYSA-N 1,2-ethanedithiol Chemical compound SCCS VYMPLPIFKRHAAC-UHFFFAOYSA-N 0.000 description 1
- 229940043375 1,5-pentanediol Drugs 0.000 description 1
- ALVZNPYWJMLXKV-UHFFFAOYSA-N 1,9-Nonanediol Chemical compound OCCCCCCCCCO ALVZNPYWJMLXKV-UHFFFAOYSA-N 0.000 description 1
- XUIXZBXRQFZHIT-UHFFFAOYSA-N 1-[1-(1-hydroxypropan-2-yloxy)propan-2-yloxy]-3-methoxypropan-2-ol Chemical compound COCC(O)COC(C)COC(C)CO XUIXZBXRQFZHIT-UHFFFAOYSA-N 0.000 description 1
- CSCSROFYRUZJJH-UHFFFAOYSA-N 1-methoxyethane-1,2-diol Chemical compound COC(O)CO CSCSROFYRUZJJH-UHFFFAOYSA-N 0.000 description 1
- OEYNWAWWSZUGDU-UHFFFAOYSA-N 1-methoxypropane-1,2-diol Chemical compound COC(O)C(C)O OEYNWAWWSZUGDU-UHFFFAOYSA-N 0.000 description 1
- IMQFZQVZKBIPCQ-UHFFFAOYSA-N 2,2-bis(3-sulfanylpropanoyloxymethyl)butyl 3-sulfanylpropanoate Chemical compound SCCC(=O)OCC(CC)(COC(=O)CCS)COC(=O)CCS IMQFZQVZKBIPCQ-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
- OJRJDENLRJHEJO-UHFFFAOYSA-N 2,4-diethylpentane-1,5-diol Chemical compound CCC(CO)CC(CC)CO OJRJDENLRJHEJO-UHFFFAOYSA-N 0.000 description 1
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 1
- ZUAURMBNZUCEAF-UHFFFAOYSA-N 2-(2-phenoxyethoxy)ethanol Chemical compound OCCOCCOC1=CC=CC=C1 ZUAURMBNZUCEAF-UHFFFAOYSA-N 0.000 description 1
- CNDCQWGRLNGNNO-UHFFFAOYSA-N 2-(2-sulfanylethoxy)ethanethiol Chemical compound SCCOCCS CNDCQWGRLNGNNO-UHFFFAOYSA-N 0.000 description 1
- QSOFJLDXOMMNNK-UHFFFAOYSA-N 2-(hydroxymethyl)-2-methylpropane-1,3-diol 3-sulfanylbutanoic acid Chemical compound CC(S)CC(O)=O.CC(S)CC(O)=O.CC(S)CC(O)=O.OCC(C)(CO)CO QSOFJLDXOMMNNK-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
- LCZVSXRMYJUNFX-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)CO LCZVSXRMYJUNFX-UHFFFAOYSA-N 0.000 description 1
- BXYWKXBAMJYTKP-UHFFFAOYSA-N 2-[2-[2-[2-(3-sulfanylpropanoyloxy)ethoxy]ethoxy]ethoxy]ethyl 3-sulfanylpropanoate Chemical compound SCCC(=O)OCCOCCOCCOCCOC(=O)CCS BXYWKXBAMJYTKP-UHFFFAOYSA-N 0.000 description 1
- VFBJXXJYHWLXRM-UHFFFAOYSA-N 2-[2-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]ethylsulfanyl]ethyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCCSCCOC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 VFBJXXJYHWLXRM-UHFFFAOYSA-N 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
- OGKIRQFIEJXGOL-UHFFFAOYSA-N 2-diethoxysilylethyl prop-2-enoate Chemical compound CCO[SiH](CCOC(=O)C=C)OCC OGKIRQFIEJXGOL-UHFFFAOYSA-N 0.000 description 1
- RPGSLKIRAVVCNK-UHFFFAOYSA-N 2-dimethoxysilylethyl prop-2-enoate Chemical compound CO[SiH](CCOC(=O)C=C)OC RPGSLKIRAVVCNK-UHFFFAOYSA-N 0.000 description 1
- WBEKRAXYEBAHQF-UHFFFAOYSA-N 2-ethyl-2-(hydroxymethyl)propane-1,3-diol;3-sulfanylbutanoic acid Chemical compound CC(S)CC(O)=O.CC(S)CC(O)=O.CC(S)CC(O)=O.CCC(CO)(CO)CO WBEKRAXYEBAHQF-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- LWRBVKNFOYUCNP-UHFFFAOYSA-N 2-methyl-1-(4-methylsulfanylphenyl)-2-morpholin-4-ylpropan-1-one Chemical compound C1=CC(SC)=CC=C1C(=O)C(C)(C)N1CCOCC1 LWRBVKNFOYUCNP-UHFFFAOYSA-N 0.000 description 1
- PSLRXNFNXYNXEK-UHFFFAOYSA-N 2-triethoxysilylethyl prop-2-enoate Chemical compound CCO[Si](OCC)(OCC)CCOC(=O)C=C PSLRXNFNXYNXEK-UHFFFAOYSA-N 0.000 description 1
- BUJVPKZRXOTBGA-UHFFFAOYSA-N 2-trimethoxysilylethyl prop-2-enoate Chemical compound CO[Si](OC)(OC)CCOC(=O)C=C BUJVPKZRXOTBGA-UHFFFAOYSA-N 0.000 description 1
- HNVMCAHOYIOFAQ-UHFFFAOYSA-N 3-dimethoxysilylpropyl prop-2-enoate Chemical compound CO[SiH](OC)CCCOC(=O)C=C HNVMCAHOYIOFAQ-UHFFFAOYSA-N 0.000 description 1
- SXFJDZNJHVPHPH-UHFFFAOYSA-N 3-methylpentane-1,5-diol Chemical compound OCCC(C)CCO SXFJDZNJHVPHPH-UHFFFAOYSA-N 0.000 description 1
- XDQWJFXZTAWJST-UHFFFAOYSA-N 3-triethoxysilylpropyl prop-2-enoate Chemical compound CCO[Si](OCC)(OCC)CCCOC(=O)C=C XDQWJFXZTAWJST-UHFFFAOYSA-N 0.000 description 1
- LABQKWYHWCYABU-UHFFFAOYSA-N 4-(3-sulfanylbutanoyloxy)butyl 3-sulfanylbutanoate Chemical compound CC(S)CC(=O)OCCCCOC(=O)CC(C)S LABQKWYHWCYABU-UHFFFAOYSA-N 0.000 description 1
- SXIFAEWFOJETOA-UHFFFAOYSA-N 4-hydroxy-butyl Chemical group [CH2]CCCO SXIFAEWFOJETOA-UHFFFAOYSA-N 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- 102100026735 Coagulation factor VIII Human genes 0.000 description 1
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- GHKOFFNLGXMVNJ-UHFFFAOYSA-N Didodecyl thiobispropanoate Chemical compound CCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCC GHKOFFNLGXMVNJ-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 239000001116 FEMA 4028 Substances 0.000 description 1
- 101000911390 Homo sapiens Coagulation factor VIII Proteins 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229920002367 Polyisobutene Polymers 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 235000002597 Solanum melongena Nutrition 0.000 description 1
- 244000061458 Solanum melongena Species 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- YPCHGLDQZXOZFW-UHFFFAOYSA-N [2-[[4-methyl-3-[[3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propoxy]carbonylamino]phenyl]carbamoyloxymethyl]-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound CC1=CC=C(NC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C)C=C1NC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C YPCHGLDQZXOZFW-UHFFFAOYSA-N 0.000 description 1
- VSVVZZQIUJXYQA-UHFFFAOYSA-N [3-(3-dodecylsulfanylpropanoyloxy)-2,2-bis(3-dodecylsulfanylpropanoyloxymethyl)propyl] 3-dodecylsulfanylpropanoate Chemical compound CCCCCCCCCCCCSCCC(=O)OCC(COC(=O)CCSCCCCCCCCCCCC)(COC(=O)CCSCCCCCCCCCCCC)COC(=O)CCSCCCCCCCCCCCC VSVVZZQIUJXYQA-UHFFFAOYSA-N 0.000 description 1
- VTLHIRNKQSFSJS-UHFFFAOYSA-N [3-(3-sulfanylbutanoyloxy)-2,2-bis(3-sulfanylbutanoyloxymethyl)propyl] 3-sulfanylbutanoate Chemical compound CC(S)CC(=O)OCC(COC(=O)CC(C)S)(COC(=O)CC(C)S)COC(=O)CC(C)S VTLHIRNKQSFSJS-UHFFFAOYSA-N 0.000 description 1
- YAAUVJUJVBJRSQ-UHFFFAOYSA-N [3-(3-sulfanylpropanoyloxy)-2-[[3-(3-sulfanylpropanoyloxy)-2,2-bis(3-sulfanylpropanoyloxymethyl)propoxy]methyl]-2-(3-sulfanylpropanoyloxymethyl)propyl] 3-sulfanylpropanoate Chemical compound SCCC(=O)OCC(COC(=O)CCS)(COC(=O)CCS)COCC(COC(=O)CCS)(COC(=O)CCS)COC(=O)CCS YAAUVJUJVBJRSQ-UHFFFAOYSA-N 0.000 description 1
- MZVQCMJNVPIDEA-UHFFFAOYSA-N [CH2]CN(CC)CC Chemical group [CH2]CN(CC)CC MZVQCMJNVPIDEA-UHFFFAOYSA-N 0.000 description 1
- RMKZLFMHXZAGTM-UHFFFAOYSA-N [dimethoxy(propyl)silyl]oxymethyl prop-2-enoate Chemical compound CCC[Si](OC)(OC)OCOC(=O)C=C RMKZLFMHXZAGTM-UHFFFAOYSA-N 0.000 description 1
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
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- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
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- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
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- 239000004611 light stabiliser Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
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- ZBPYFGWSQQFVCJ-UHFFFAOYSA-N pentadecane-1,15-diol Chemical compound OCCCCCCCCCCCCCCCO ZBPYFGWSQQFVCJ-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
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- 239000004431 polycarbonate resin Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
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- 229920001155 polypropylene Polymers 0.000 description 1
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- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- ZJLMKPKYJBQJNH-UHFFFAOYSA-N propane-1,3-dithiol Chemical compound SCCCS ZJLMKPKYJBQJNH-UHFFFAOYSA-N 0.000 description 1
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- 239000007870 radical polymerization initiator Substances 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
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- 239000011163 secondary particle Substances 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 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 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- XLKZJJVNBQCVIX-UHFFFAOYSA-N tetradecane-1,14-diol Chemical compound OCCCCCCCCCCCCCCO XLKZJJVNBQCVIX-UHFFFAOYSA-N 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
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- 239000004416 thermosoftening plastic Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- WDUXKFKVDQRWJN-UHFFFAOYSA-N triethoxysilylmethyl prop-2-enoate Chemical compound CCO[Si](OCC)(OCC)COC(=O)C=C WDUXKFKVDQRWJN-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- JLGLQAWTXXGVEM-UHFFFAOYSA-N triethylene glycol monomethyl ether Chemical compound COCCOCCOCCO JLGLQAWTXXGVEM-UHFFFAOYSA-N 0.000 description 1
- HBZPRQCNASJKHW-UHFFFAOYSA-N trimethoxysilyl prop-2-enoate Chemical compound CO[Si](OC)(OC)OC(=O)C=C HBZPRQCNASJKHW-UHFFFAOYSA-N 0.000 description 1
- JPPHEZSCZWYTOP-UHFFFAOYSA-N trimethoxysilylmethyl prop-2-enoate Chemical compound CO[Si](OC)(OC)COC(=O)C=C JPPHEZSCZWYTOP-UHFFFAOYSA-N 0.000 description 1
- 125000002221 trityl group Chemical group [H]C1=C([H])C([H])=C([H])C([H])=C1C([*])(C1=C(C(=C(C(=C1[H])[H])[H])[H])[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
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- 238000005406 washing Methods 0.000 description 1
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- 229910052724 xenon Inorganic materials 0.000 description 1
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- 238000004383 yellowing Methods 0.000 description 1
Classifications
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- 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
- C08F251/00—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof
-
- 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
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
-
- 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
- C08F220/00—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
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
-
- 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
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/37—Thiols
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/37—Thiols
- C08K5/372—Sulfides, e.g. R-(S)x-R'
-
- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
-
- 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
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- 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
- G02B1/041—Lenses
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F9/00—Registration or positioning of originals, masks, frames, photographic sheets or textured or patterned surfaces, e.g. automatically
- G03F9/70—Registration or positioning of originals, masks, frames, photographic sheets or textured or patterned surfaces, e.g. automatically for microlithography
- G03F9/7003—Alignment type or strategy, e.g. leveling, global alignment
- G03F9/7042—Alignment for lithographic apparatus using patterning methods other than those involving the exposure to radiation, e.g. by stamping or imprinting
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Exposure Of Semiconductors, Excluding Electron Or Ion Beam Exposure (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Polymerisation Methods In General (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
- Shaping Of Tube Ends By Bending Or Straightening (AREA)
Abstract
The invention provides a novel photocurable composition for imprinting. The solution is an imprinting photocurable composition comprising a component (a), a component (b), a component (c), a component (d) and a component (e). Component (a): a silica particle (b) component having a primary particle diameter of 1nm to 100nm and surface-modified with a functional group having an ethylenically unsaturated group: a polyfunctional (meth) acrylate compound having an ethylenically unsaturated group (c) component: a polyrotaxane (d) component having an ethylenically unsaturated group: a photoradical initiator (e) component: specific polyfunctional thiol compounds.
Description
Technical Field
The present invention relates to a photocurable composition for imprinting, which comprises silica particles surface-modified with a functional group having an ethylenically unsaturated group, a polyfunctional (meth) acrylate compound having an ethylenically unsaturated group, a polyrotaxane having an ethylenically unsaturated group, a photo-radical initiator, and a polyfunctional thiol compound. More specifically, the present invention relates to a photocurable composition for producing a cured product and a molded article having the following characteristics. The cured product and the molded article are characterized by excellent adhesion without peeling from the support even after a thermal shock test continuously exposed to a low temperature of-20 ℃ or lower and a high temperature of 80 ℃ or higher, and by the fact that the antireflection layer (AR layer) is formed on the upper layer and then no cracks are generated even after heat treatment.
Background
Resin lenses are used for electronic devices such as mobile phones, digital cameras, and in-vehicle cameras, and are required to have excellent optical characteristics that meet the purpose of the electronic devices. In addition, depending on the use form, high durability such as heat resistance and weather resistance, and high productivity that can be molded with good yield are required. As a material for resin lenses satisfying such a demand, for example, thermoplastic transparent resins such as polycarbonate resins, cycloolefin polymers, and methacrylic resins are used.
In addition, although a plurality of lenses are used in a high-resolution camera module, a lens having low wavelength dispersion, that is, a lens having a high abbe number is mainly used, and an optical material for forming the lens is required. Further, in order to improve the yield and the production efficiency in the production of resin lenses and to further suppress the optical axis shift in the lamination of lenses, a transition from injection molding of thermoplastic resins to wafer-level molding by press molding using curable resins that are liquid at room temperature has been actively studied. In the wafer level molding, a hybrid lens system is generally used in which lenses are formed on a support such as a glass substrate from the viewpoint of productivity.
As a photocurable resin capable of wafer level molding, a radically curable resin composition has been conventionally used from the viewpoints of high transparency, heat resistance Huang Bianse and mold releasability (patent document 1).
Further, curable compositions are known which contain oxide particles surface-modified with a silane compound, zirconia particles surface-modified with a dispersant, or the like, to obtain cured products having a high abbe number (for example, patent documents 2 and 3).
On the other hand, there is known a polyrotaxane having a cyclic molecule having an opening, a linear molecule, and a blocking group (stopper), wherein the blocking group is disposed at both ends of a string-like pseudo-polyrotaxane which is formed by wrapping the opening of the cyclic molecule with the linear molecule, and the cyclic molecule has a (meth) acryloyl group (for example, patent document 4). The linear molecule penetrates through the opening of the cyclic molecule, and the blocking group is provided so that the cyclic molecule does not separate from the linear molecule. The term "inclusion" refers to the introduction of another molecule into the space of the opening of the cyclic molecule, and the term "pseudo-polyrotaxane" refers to polyrotaxane having no blocking group. The photocurable composition containing the polyrotaxane can produce a photocurable article having high strength, high elastic modulus and excellent toughness.
Prior art literature
Patent literature
Patent document 1: japanese patent No. 5281710 (International publication No. 2011/105473)
Patent document 2: japanese patent laid-open publication No. 2014-234458
Patent document 3: international publication No. 2016/104039
Patent document 4: international publication No. 2016/072356
Disclosure of Invention
Problems to be solved by the invention
In the case where the molded article produced by wafer level molding is a lens, an antireflection layer made of an inorganic material such as silicon oxide or titanium oxide is formed on the upper layer. Accordingly, there is a problem that the antireflection layer is cracked by heat-treating the lens coated with the antireflection layer. Further, if a cured product of the curable composition containing the surface-modified oxide particles is subjected to a thermal shock test continuously exposed to a low temperature of-20 ℃ or lower and a high temperature of 80 ℃ or higher, the cured product has a problem of peeling from the support.
A molded article having a high abbe number (for example, 53 or more) which can be used as a lens for a high-resolution camera module can be obtained, and further, a curable resin material which is not peeled off from a support even when the molded article is exposed to a thermal shock test is not yet available, and development of such a curable resin material is desired, because an antireflection layer formed on an upper layer of the molded article does not cause cracking by a subsequent heat treatment. The present invention has been made in view of such circumstances. That is, the object of the present invention is to provide a photocurable composition which can form a molded article having a high Abbe number, and which can form a molded article having a high thermal shock resistance in which the molded article is not peeled off from a support even when exposed to a thermal shock test without causing cracking of an upper antireflective layer of the molded article by heat treatment of the molded article.
Means for solving the problems
A first aspect of the present invention is a photocurable composition for imprinting, which comprises the following component (a), the following component (b), the following component (c), the following component (d), and the following component (e).
(a) The components are as follows: silica particles having primary particle diameter of 1nm to 100nm and surface-modified with functional group having ethylenic unsaturated group
(b) The components are as follows: polyfunctional (meth) acrylate compounds having ethylenically unsaturated groups
(c) The components are as follows: polyrotaxane having ethylenically unsaturated group
(d) The components are as follows: photo radical initiator
(e) The components are as follows: a polyfunctional thiol compound represented by the following formula (1)
(wherein R is 1 Represents a single bond or a linear or branched alkylene group having 1 to 6 carbon atoms, Z 1 Represents a single bond, an ester bond or an ether bond, Q 1 An organic group having 2 to 12 carbon atoms containing at least 1 heteroatom or no heteroatom, or a heteroatom, and s represents an integer of 2 to 6. )
The photocurable composition for imprinting of the present invention may further contain the following component (f) and/or the following component (g).
(f) The components are as follows: phenolic antioxidants
(g) The components are as follows: sulfide-based antioxidants
The photocurable composition for imprinting of the present invention may further contain the following component (h).
(h) The components are as follows: monofunctional (meth) acrylate compounds having ethylenically unsaturated groups
The component (b) includes at least one of the following component (b 1) and the following component (b 2).
(b1) The components are as follows: difunctional (meth) acrylate compounds represented by the following formula (2)
(b2) The components are as follows: urethane (meth) acrylate compounds (excluding polyrotaxane having an ethylenically unsaturated group as the component (c)) or epoxy (meth) acrylate compounds
(wherein R is 2 Represents a hydrogen atom or a methyl group, Q 2 Represents a linear or branched hydrocarbon group having 2 to 16 carbon atoms. )
The component (b) includes, for example, the component (b 1) and the component (b 2).
The silica particles having a surface modified with a functional group having an ethylenically unsaturated group as the component (a) are, for example, silica particles having a surface modified with a (meth) acryloyloxy group bonded to a silicon atom via a divalent linking group. The divalent linking group is, for example, an alkylene group having 1 to 5 carbon atoms, preferably an alkylene group having 2 or 3 carbon atoms.
A second aspect of the present invention is a cured product of the photocurable composition for imprinting.
A third aspect of the present invention is a method for manufacturing a resin lens, comprising the steps of: and a step of subjecting the photocurable composition for imprinting to imprinting molding.
A fourth aspect of the present invention is a method for producing a molded article of an imprint photocurable composition, comprising the steps of: filling the space between the support and the mold, which are in contact with each other, or the space inside the mold, which is detachable, with the photocurable composition for imprinting; and exposing the imprint photocurable composition filled in the space to light to perform photocuring. The above-mentioned casting mould is also called a model.
The method for producing a molded article of the present invention may further comprise the steps of: a step of taking out the obtained photo-cured product after the photo-curing step and releasing the photo-cured product; and heating the photocurable product before, during, or after the demolding step.
The step of releasing the mold may further include a development step using an organic solvent after the step of heating.
In the method for producing a molded article of the present invention, the molded article is, for example, a lens for a camera module.
ADVANTAGEOUS EFFECTS OF INVENTION
The photocurable composition for imprinting of the present invention comprises the component (a) to the component (e), and further optionally comprises the component (f) and/or the component (g), and the component (h). Accordingly, the cured product and the molded article obtained from the photocurable composition exhibit optical characteristics, i.e., a high abbe number, which are desired as optical devices such as lenses for high-resolution camera modules. Further, regarding the cured product and the molded article obtained from the photocurable composition of the present invention, the antireflective layer on the upper layer of the cured product and the molded article did not develop cracks by heat treatment at 175 ℃, and the cured product and the molded article did not peel off from the support even when exposed to a thermal shock test.
Drawings
Fig. 1 is a digital microscopic photograph showing the corner of a cured film made of the imprint photocurable composition 6 of example 6.
Fig. 2 is a digital microscopic photograph showing the corner of the cured film made of the imprint photocurable composition 14 of comparative example 2.
Detailed Description
The components of the photocurable composition for imprinting of the present invention will be described in more detail. In the present invention, the ethylenically unsaturated group is a group having a double bond between 2 carbon atoms, and examples thereof include (CH) 2 =ch) -group and [ CH 2 ＝C(CH 3 )]-a radical. The invention is characterized in thatThe ethylenically unsaturated group-containing compound contained in the photocurable composition for imprinting is selected from the group consisting of components (a) to (c) and component (h).
[ (a) component: silica particles surface-modified with functional group having ethylenically unsaturated group
The silica particles having been surface-modified with a functional group having an ethylenically unsaturated group, which can be used as the component (a) of the photocurable composition for imprinting of the present invention, have a primary particle diameter of 1nm to 100nm. The primary particles are particles constituting a powder, and particles obtained by agglomerating the primary particles are referred to as secondary particles. The primary particle diameter may be represented by a relationship between a specific surface area (surface area per unit mass) S of the surface-modified silica particles having an ethylenically unsaturated group, a density ρ of the surface-modified silica particles, and a primary particle diameter D, which are measured by a gas adsorption method (BET method): d=6/(ρs) is calculated. The primary particle diameter calculated from the relational expression is the average particle diameter, and is the diameter of the primary particles. The silica particles having the surface modified with the functional group having an ethylenically unsaturated group are surface modified with, for example, (meth) acryloyloxy groups bonded to silicon atoms via a divalent linking group. When the surface-modified silica particles having an ethylenically unsaturated group are used, the surface-modified silica particles may be used as they are, or a colloidal substance obtained by dispersing the surface-modified silica particles in an organic solvent as a dispersion medium (a sol in which colloidal particles are dispersed in a dispersion medium) may be used. When the sol containing the surface-modified silica particles is used, the sol may be used in which the concentration of the solid content is in the range of 10 to 60 mass%.
As the sol containing the silica particles surface-modified with the functional group having an ethylenically unsaturated group, for example, MEK-AC-2140Z, MEK-AC-4130Y, MEK-AC-5140Z, PGM-AC-2140Y, PGM-AC-4130Y, MIBK-AC-2140Z, MIBK-SD-L (above, manufactured by Nissan chemical Co., ltd.), ELCOM (registered trademark) V-8802, ELCOM V-8804 (above, manufactured by Nissan catalyst Co., ltd.) can be used.
The content of the component (a) in the photocurable composition for imprinting of the present invention is 10 to 40 parts by mass, preferably 10 to 30 parts by mass, based on 100 parts by mass of the sum of the component (a), the component (b), the component (c), the component (e) and the component (h) contained in the composition. If the content of the component (a) is less than 10 parts by mass, cracks in the antireflection layer formed on the upper layer of the cured product and the molded article obtained from the above-mentioned photocurable composition for imprinting may not be suppressed. If the content of the component (a) is more than 40 parts by mass, haze (high) may be generated between the cured product and the molded article, and the transmittance may be lowered.
The silica particles having been surface-modified with a functional group having an ethylenically unsaturated group as the component (a) may be used alone or in combination of 1 or more than 2 kinds.
[ (b) component: polyfunctional (meth) acrylate Compound having an ethylenically unsaturated group ]
The polyfunctional (meth) acrylate compound having an ethylenically unsaturated group which can be used as the component (b) of the photocurable composition for imprinting of the present invention is a compound having 2 or more ethylenically unsaturated groups in the molecule of the polyfunctional (meth) acrylate compound 1. Examples of the polyfunctional (meth) acrylate compound include urethane (meth) acrylate compounds, epoxy (meth) acrylate compounds, and other difunctional (meth) acrylate compounds. In the present specification, a compound represented by the following formula (2) among the other difunctional (meth) acrylate compounds is referred to as a (b 1) component, and the urethane (meth) acrylate compound or the epoxy (meth) acrylate compound is referred to as a (b 2) component. When the photocurable composition for imprinting of the present invention contains the component (b 1), the composition has excellent compatibility with a polyrotaxane having an ethylenically unsaturated group as the component (c) described later.
(A)Wherein R is 2 Represents a hydrogen atom or a methyl group, Q 2 Represents a linear or branched hydrocarbon group having 2 to 16 carbon atoms. )
Among the other difunctional (meth) acrylate compounds, as compounds not represented by the above formula (2), diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, polytetramethylene glycol di (meth) acrylate, and EO-modified hydrogenated bisphenol a di (meth) acrylate may be mentioned, for example. Ext>ext>ext>ext> examplesext>ext>ext>ext> ofext>ext>ext>ext> theext>ext>ext>ext> compoundsext>ext>ext>ext> thatext>ext>ext>ext> canext>ext>ext>ext> beext>ext>ext>ext> usedext>ext>ext>ext> includeext>ext>ext>ext> thoseext>ext>ext>ext> commerciallyext>ext>ext>ext> availableext>ext>ext>ext> productsext>ext>ext>ext> suchext>ext>ext>ext> asext>ext>ext>ext> 2ext>ext>ext>ext> Gext>ext>ext>ext>,ext>ext>ext>ext> 3ext>ext>ext>ext> Gext>ext>ext>ext>,ext>ext>ext>ext> 4ext>ext>ext>ext> Gext>ext>ext>ext>,ext>ext>ext>ext> 9ext>ext>ext>ext> Gext>ext>ext>ext>,ext>ext>ext>ext> 14ext>ext>ext>ext> Gext>ext>ext>ext>,ext>ext>ext>ext> 23ext>ext>ext>ext> Gext>ext>ext>ext>,ext>ext>ext>ext> Aext>ext>ext>ext> -ext>ext>ext>ext> 200ext>ext>ext>ext>,ext>ext>ext>ext> Aext>ext>ext>ext> -ext>ext>ext>ext> 400ext>ext>ext>ext>,ext>ext>ext>ext> Aext>ext>ext>ext> -ext>ext>ext>ext> 600ext>ext>ext>ext>,ext>ext>ext>ext> Aext>ext>ext>ext> -ext>ext>ext>ext> 1000ext>ext>ext>ext>,ext>ext>ext>ext> APGext>ext>ext>ext> -ext>ext>ext>ext> 100ext>ext>ext>ext>,ext>ext>ext>ext> APGext>ext>ext>ext> -ext>ext>ext>ext> 200ext>ext>ext>ext>,ext>ext>ext>ext> APGext>ext>ext>ext> -ext>ext>ext>ext> 400ext>ext>ext>ext>,ext>ext>ext>ext> APGext>ext>ext>ext> -ext>ext>ext>ext> 700ext>ext>ext>ext>,ext>ext>ext>ext> 3ext>ext>ext>ext> PGext>ext>ext>ext>,ext>ext>ext>ext> 9ext>ext>ext>ext> PGext>ext>ext>ext>,ext>ext>ext>ext> andext>ext>ext>ext> Aext>ext>ext>ext> -ext>ext>ext>ext> PTMGext>ext>ext>ext> -ext>ext>ext>ext> 65ext>ext>ext>ext> (ext>ext>ext>ext> aboveext>ext>ext>ext>,ext>ext>ext>ext> manufacturedext>ext>ext>ext> byext>ext>ext>ext> Xinzhongcunext>ext>ext>ext> chemicalext>ext>ext>ext> industryext>ext>ext>ext> (ext>ext>ext>ext> productext>ext>ext>ext>)ext>ext>ext>ext>,ext>ext>ext>ext> Larelativeext>ext>ext>ext> 3ext>ext>ext>ext> EGext>ext>ext>ext> -ext>ext>ext>ext> Aext>ext>ext>ext>,ext>ext>ext>ext> Larelativeext>ext>ext>ext> 4ext>ext>ext>ext> EGext>ext>ext>ext> -ext>ext>ext>ext> Aext>ext>ext>ext> theext>ext>ext>ext> stepsext>ext>ext>ext> ofext>ext>ext>ext> theext>ext>ext>ext> methodext>ext>ext>ext> includeext>ext>ext>ext> theext>ext>ext>ext> stepsext>ext>ext>ext> ofext>ext>ext>ext> theext>ext>ext>ext> sleeveext>ext>ext>ext> 9ext>ext>ext>ext> EGext>ext>ext>ext> -ext>ext>ext>ext> Aext>ext>ext>ext>,ext>ext>ext>ext> sleeveext>ext>ext>ext> 14ext>ext>ext>ext> EGext>ext>ext>ext> -ext>ext>ext>ext> Aext>ext>ext>ext>,ext>ext>ext>ext> sleeveext>ext>ext>ext> PTMGext>ext>ext>ext> -ext>ext>ext>ext> 250ext>ext>ext>ext> (ext>ext>ext>ext> aboveext>ext>ext>ext>,ext>ext>ext>ext> fromext>ext>ext>ext> coext>ext>ext>ext> -ext>ext>ext>ext> grongext>ext>ext>ext>,ext>ext>ext>ext> chemicalext>ext>ext>ext> companyext>ext>ext>ext>,ext>ext>ext>ext> incext>ext>ext>ext>.ext>ext>ext>ext>)ext>ext>ext>ext>,ext>ext>ext>ext> brusselext>ext>ext>ext> コext>ext>ext>ext> strainext>ext>ext>ext> #ext>ext>ext>ext> 310ext>ext>ext>ext> hpext>ext>ext>ext>,ext>ext>ext>ext> brusselext>ext>ext>ext> コext>ext>ext>ext> strainext>ext>ext>ext> #ext>ext>ext>ext> 335ext>ext>ext>ext> hpext>ext>ext>ext> (ext>ext>ext>ext> aboveext>ext>ext>ext>,ext>ext>ext>ext> fromext>ext>ext>ext> osakaext>ext>ext>ext> organicext>ext>ext>ext> chemicalext>ext>ext>ext> industryext>ext>ext>ext>,ext>ext>ext>ext> incext>ext>ext>ext>.ext>ext>ext>ext>)ext>ext>ext>ext>,ext>ext>ext>ext> andext>ext>ext>ext> hbpeext>ext>ext>ext> -ext>ext>ext>ext> 4ext>ext>ext>ext> (ext>ext>ext>ext> fromext>ext>ext>ext> firstext>ext>ext>ext> industryext>ext>ext>ext>,ext>ext>ext>ext> incext>ext>ext>ext>.ext>ext>ext>ext>)ext>ext>ext>ext>.ext>ext>ext>ext>
[ (b 1) component: difunctional (meth) acrylate Compound represented by the above formula (2)
The difunctional (meth) acrylate compound represented by the above formula (2) that can be used as the component (b 1) of the photocurable composition for imprinting of the present invention is a compound having 2 (meth) acryloyloxy groups in the molecule of the compound 1. Examples of the difunctional (meth) acrylate compound include ethylene glycol di (meth) acrylate, 1, 3-propylene glycol di (meth) acrylate, 1, 4-butanediol di (meth) acrylate, 1, 5-pentanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 3-methyl-1, 5-pentanediol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, 1, 7-heptanediol di (meth) acrylate, 1, 8-hexanediol di (meth) acrylate, 1, 9-nonanediol di (meth) acrylate, 1, 10-decanediol di (meth) acrylate, 1, 11-undecanediol di (meth) acrylate, 1, 12-dodecanediol di (meth) acrylate, 1, 13-tridecanediol di (meth) acrylate, 1, 14-tetradecanediol di (meth) acrylate, 1, 15-pentadecanediol di (meth) acrylate, 1, 16-hexadecanediol di (meth) acrylate, 1, 3-octanediol di (meth) acrylate, 1, 8-decanediol di (meth) acrylate, 1, 10-decanediol di (meth) acrylate, 1, 3-decanediol di (meth) acrylate, 1, 10-decanediol di (meth) acrylate, 2, 4-trimethyl-1, 6-hexanediol di (meth) acrylate, 2, 4-diethyl-1, 5-pentanediol di (meth) acrylate, and 2, 9-tetramethyl-1, 10-decanediol di (meth) acrylate.
Examples of the difunctional (meth) acrylate compound that can be used include, for example, brand #195, brand #230, brand # コ (manufactured by Osaka organic chemical industries, inc.), BD, NPG, A-NPG, HD-N, A-HD-N, NOD-N, A-NOD-N, DOD-N, A-DOD-N (manufactured by Santa Clara chemical industries, inc.), and brand-brand EG, brand-name chemical industries, inc.
[ (b 2) component: urethane (meth) acrylate compound or epoxy (meth) acrylate compound ]
The urethane (meth) acrylate compound that can be used as the (b 2) component of the photocurable composition for imprinting of the present invention is a compound having a urethane structure represented by at least 2 (meth) acryloyloxy groups and at least 2 "-nh—c (=o) O-" in 1 molecule. Wherein the urethane (meth) acrylate compound is a compound other than a polyrotaxane having an ethylenically unsaturated group as the component (c) described later. Examples of the urethane (meth) acrylate compound include EBECRYL (registered trademark) 230, EBECRYL 270, EBECRYL 280/15IB, EBECRYL 284, EBECRYL 4491, EBECRYL 4683, EBECRYL 4858, EBECRYL 8307, EBECRYL 8402, EBECRYL 8411, EBECRYL 8804, EBECRYL 8807, EBECRYL 9270, EBECRYL 8800, EBECRYL294/25HD, EBECRYL 4100, EBECRYL 4220, EBECRYL 4513, EBECRYL 4738, EBECL 4740, EBECRYL 4820, EBECRYL 8311, EBECRYL 8465, ECRYL 9260, EBECECL 8701, KRM7735, KRM8667, KRM 8296 (above, the materials include, but are not limited to, seama, manufactured by Waxwell, uv-2000B, UV-2750B, UV-3000B, UV-3200B, UV-3210EA, UV-3300B, UV-3310B, UV-3500B, UV-3520EA, UV-3700B, UV-6640B, UV-6630B, UV-7000B, UV-7510B, UV-7461TE (manufactured by Japanese synthetic chemical Co., ltd.), UA-306H, UA-306T, UA-306I, UA-510H, UF-8001G (manufactured by Kabushiki Kaisha chemical Co., ltd.), M-1100, M-1200 (above, and NK-on, U-2PPA, NK-off, U-6LPA, NK-on, U-200PA, NK-on, U-160TM, NK-on, U-290TM, NK-on, U-4200, NK-on, U-4400, NK-on, U-122P, NK-on, line-of-care UA-7100, NK-on, U-W2A (manufactured by New Zhongcun chemical industry, inc.) respectively.
The epoxy (meth) acrylate compound that can be used as the component (b 2) of the photocurable composition for imprinting of the present invention is an ester obtained by reacting a compound having at least 2 epoxy rings in 1 molecule with (meth) acrylic acid. Examples of the epoxy (meth) acrylate compound include EBECRYL (registered trademark) 645, EBECRYL 648, EBECRYL 860, EBECRYL3500, EBECRYL 3608, EBECRYL 3702, EBECRYL 3708 (manufactured by the above-mentioned division of the family of the chinese names), DA-911M, DA-920, DA-931, DA-314, DA-212 (the above, the hucky cell, HPEA-100, V-5500, tikuku V-5502, tiku V-5508 (above, DIC (strain)), and tiku (registered trademark), respectively.
As the urethane (meth) acrylate compound or the epoxy (meth) acrylate compound of the component (b 2), a compound having 2 or 3 (meth) acryloyloxy groups in the molecule of the compound 1 is preferably used. The urethane (meth) acrylate compound or the epoxy (meth) acrylate compound of the component (b 2) may be used alone or in combination of 1 or more than 2.
When the photocurable composition for imprinting of the present invention contains at least one of the component (b 1) and the component (b 2) as the component (b), the content thereof satisfies all of the relationships represented by the following formulas (3) to (5), preferably all of the relationships represented by the following formulas (3 ') to (5'), with respect to 100 parts by mass of the sum of the component (a), the component (b), the component (c), the component (e) and the component (h) contained in the composition. Here, the content of the component (b 1) is defined as X parts by mass, and the content of the component (b 2) is defined as Y parts by mass.
Formula (3): 30 mass parts to less than or equal to (X+Y) to less than or equal to 85 mass parts
Formula (4): x is more than or equal to 0 mass part and less than or equal to 70 mass parts
Formula (5): y is more than or equal to 0 and less than or equal to 80 mass parts
Formula (3'): 30 to 80 mass parts of (X+Y)
Formula (4'): x is more than or equal to 0 mass part and less than or equal to 60 mass parts
Formula (5'): y is more than or equal to 0 mass part and less than or equal to 70 mass parts
If the content of the component (b 1) is more than 70 parts by mass, the cured product and the molded article obtained from the photocurable composition for imprinting may become brittle, and the crack resistance of the cured product and the molded article may be lowered. Further, if the content of the component (b 2) is more than 80 parts by mass, the crosslink density of the cured product and the molded article obtained from the photocurable composition for imprinting may decrease, and the shape change of the cured product and the molded article upon heating may increase.
[ (c) component: polyrotaxane having an ethylenically unsaturated group
The polyrotaxane having an ethylenically unsaturated group which can be used as the component (c) of the photocurable composition for imprinting of the present invention has a closed group disposed at both ends of a cyclic molecule, which has an ethylenically unsaturated group, so that the cyclic molecule does not separate, by wrapping the cyclic molecule into a string-like pseudo polyrotaxane. The cyclic molecule, the linear molecule and the blocking group, which are the constituent elements of the polyrotaxane having an ethylenically unsaturated group in the cyclic molecule, will be described.
< c-1. Cyclic molecule >)
The cyclic molecule of the polyrotaxane having an ethylenically unsaturated group as the component (c) is not particularly limited as long as it is cyclic and has an opening, and is formed into a string shape by wrapping a linear molecule. The ethylenically unsaturated group is preferably a cyclic molecule, and may be bonded directly to the cyclic molecule or may be bonded via a spacer. The spacer is not particularly limited, and examples thereof include an alkylene group, an oxyalkylene group, a hydroxyalkylene group, a carbamoyl group, an acrylate chain, a polyalkylene ether chain, and a polyalkylene carbonate chain. The cyclic molecule is preferably selected from, for example, α -cyclodextrin, β -cyclodextrin and γ -cyclodextrin.
< c-2. Straight chain molecule >
The linear molecule of the polyrotaxane having an ethylenically unsaturated group as the component (c) is not particularly limited as long as it can be included in a string form in the opening of the cyclic molecule to be used. For example, the linear molecule is exemplified by a compound (polymer) described in patent document 4, and among them, a polymer selected from polyethylene glycol, polyisoprene, polyisobutylene, polybutadiene, polypropylene glycol, polytetrahydrofuran, polydimethylsiloxane, polyethylene, polypropylene, polyvinyl alcohol and polyvinyl methyl ether is preferable, and polyethylene glycol is particularly preferable.
The weight average molecular weight of the linear molecule is 1,000 or more, preferably 3,000 ～ 100,000, and more preferably 6,000 to 50,000. In the polyrotaxane having an ethylenically unsaturated group as the component (c), the combination of (cyclic molecule, linear molecule) is preferably (derived from α -cyclodextrin, derived from polyethylene glycol).
< c-3. Blocking group >)
The blocking group of the polyrotaxane having an ethylenically unsaturated group as the component (c) is not particularly limited as long as it is a group which is disposed at both ends of the pseudo polyrotaxane and acts so that the cyclic molecule used is not detached. For example, among the blocking groups exemplified in patent document 4, preferred blocking groups are blocking groups selected from dinitrophenyl groups, cyclodextrins, adamantyl groups, trityl groups, luciferins, silsesquioxane groups, and pyrenes, and more preferred blocking groups are adamantyl groups and cyclodextrins. The blocking group is bonded to the linear molecule via, for example, an-NH-C (=O) -group.
The polyrotaxane having an ethylenically unsaturated group may be commercially available, and examples thereof include, the seta, the seta SA1303P, the seta SA1305P-10, the seta SA2403P, the seta, and the seta. The seta-back SA2405P-10, seta-back SA3403P, seta-back SA1303P, seta-back SM2403P, seta-back SA3403P (above, the cover is made of the company of the genus, and the cover is made of the genus.
The content of the component (c) in the photocurable composition for imprinting of the present invention is 1 to 15 parts by mass, preferably 3 to 10 parts by mass, based on 100 parts by mass of the sum of the component (a), the component (b), the component (c), the component (e) and the component (h) contained in the composition. If the content of the component (c) is less than 1 part by mass, the effect of suppressing the peeling of the cured product and the molded article obtained from the photocurable composition for imprinting from the support in the thermal shock test may become insufficient. If the content of the component (c) is more than 15 parts by mass, haze may be generated between the cured product and the molded article, and the transmittance may be lowered.
The polyrotaxane having an ethylenically unsaturated group as the component (c) may be used alone or in combination of 1 or more than 2.
[ (d) component: photo radical initiator ]
Examples of the photo-radical initiator that can be used as the component (d) of the photocurable composition for imprinting of the present invention include, for example, alkyl phenones, benzophenones, ketones of Michler's (Michler), acyl phosphinoxides, benzoyl benzoates, oxime esters, tetramethylthiurams monosulfide and thioxanthones, and particularly, photo-cleavage type photo-radical polymerization initiators are preferable. As the photo radical initiator, commercially available products such as OMNIRAD (registered trademark) 184, OMNIRAD 369, OMNIRAD 651, OMNIRAD 500, OMNIRAD 819, OMNIRAD 907, OMNIRAD 784, OMNIRAD 2959, OMNIRAD TPO, OMNIRAD 1173 (manufactured by IGM Resins Co., ltd.) [ old IRGACURE (registered trademark) 184, IRGACURE 369, IRGACURE 651, IRGACURE 500, IRGACURE 819, IRGACURE 907, IRGACURE 784, IRGACURE 2959, IRGACURE TPO, IRGACURE 1173 (manufactured by BASF Co., ltd.), IRGACURE CGI1700, IRGACURE CGI1850, IRGACURE CGI 1116-61, IRGACURE (manufactured by IRGACURE) and BASERE CGI-1116, IRGACURE (manufactured by BASF) and BASECURE-CGI-75, BASECURE-37, BASECURE-65, and KIACESP-60, HIZUK.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.K.can be used.
The content of the component (d) in the photocurable composition for imprinting of the present invention is 0.1 to 5 parts by mass, preferably 0.5 to 3 parts by mass, based on 100 parts by mass of the sum of the component (a), the component (b), the component (c), the component (e) and the component (h) contained in the composition. If the content of the component (d) is less than 0.1 part by mass, there is a possibility that the strength of the cured product and the molded article obtained from the above-mentioned photocurable composition for imprinting is lowered. If the content of the component (d) is more than 5 parts by mass, the heat yellowing resistance of the cured product and the molded article may be deteriorated.
The photo radical initiator as the component (d) may be used alone or in combination of 1 or more than 2.
[ (e) component: multifunctional thiol Compound represented by the above formula (1)
The polyfunctional thiol compound that can be used as the component (e) of the photocurable composition for imprinting of the present invention is a polyfunctional thiol compound represented by the above formula (1). Examples of the polyfunctional thiol compound represented by the formula (1) include 1, 2-ethanedithiol, 1, 3-propanedithiol, bis (2-mercaptoethyl) ether, trimethylolpropane tris (3-mercaptopropionate), tris- [ (3-mercaptopropionyloxy) -ethyl ] -isocyanurate, tetraethyleneglycol bis (3-mercaptopropionate), dipentaerythritol hexa (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptobutyrate), 1, 4-bis (3-mercaptobutyryloxy) butane, 1,3, 5-tris (3-mercaptobutyryloxyethyl) -1,3, 5-triazine-2, 4,6- (1H, 3H, 5H) -trione, trimethylolpropane tris (3-mercaptobutyrate), and trimethylolethane tris (3-mercaptobutyrate). As the polyfunctional thiol compound represented by the above formula (1), commercially available products such as, for example, takara Shuzo MT (registered trademark) PE1, takara Shuzo MT NR1, takara Shuzo BD1, takara Shuzo MB, teMB (manufactured by Showa electric Co., ltd.), and TMMP, TEMPIC, PEMP, EGMP-4, DPMP, TMMP II-20P, PEMP II-20P, PEPT (manufactured by SC organic chemical Co., ltd.) can be used.
The content of the component (e) in the photocurable composition for imprinting of the present invention is 1 to 15 parts by mass, preferably 3 to 10 parts by mass, based on 100 parts by mass of the sum of the component (a), the component (b), the component (c), the component (e) and the component (h) contained in the composition. If the content of the component (e) is less than 1 part by mass, there is a possibility that the adhesion between the molded article and the support and the cured product obtained from the photocurable composition for imprinting may be reduced. If the content of the component (e) is more than 15 parts by mass, the strength of the cured product and the molded article may be lowered, and the shape change of the cured product and the molded article upon heating may be increased.
The polyfunctional thiol compound represented by the formula (1) as the component (e) may be used alone or in combination of 1 or more than 2.
[ (f) component: phenolic antioxidants
Examples of phenolic antioxidants that can be used as component (f) of the imprinting photocurable composition of the present invention include IRGANOX (registered trademark) 245, IRGANOX 1010, IRGANOX 1035, IRGANOX 1076, IRGANOX 1135 (above, manufactured by BASF, a part of the world, sumizer (registered trademark) GA-80, sumizer GP, sumizer MDP-S, sumizer BBM-S, sumizer WX-R (above, manufactured by summonic chemical company), and _tarda (registered trademark) AO-20, _tarda AO-30, _tarda AO-40, _tarda AO-50, _tarda AO-60, _tarda AO-80, and _tarda AO-330.
When the photocurable composition for imprinting of the present invention contains the component (f), the content thereof is 0.05 to 3 parts by mass, preferably 0.1 to 1 part by mass, relative to 100 parts by mass of the sum of the components (a), (b), (c), (e) and (h) contained in the composition.
The phenolic antioxidants as the component (f) may be used singly or in combination of 1 or 2 or more.
[ (g) ingredients: sulfide antioxidant ]
Examples of sulfide-based antioxidants that can be used as the component (g) of the imprinting photocurable composition of the present invention include, for example, a dyprodum AO-412S, a dyprodum AO-503 (manufactured by ADEKA, above), IRGANOX PS802, IRGANOX PS800 (manufactured by BASF, above), and a SUMILIZER TP-D (manufactured by SUMILIZER, above).
When the photocurable composition for imprinting of the present invention contains component (g), the content thereof is 0.05 to 3 parts by mass, preferably 0.1 to 1 part by mass, relative to 100 parts by mass of the sum of component (a), component (b), component (c), component (e) and component (h) contained in the composition.
The sulfide-based antioxidant as the component (g) may be used alone or in combination of 1 or more than 2.
[ (h) component: monofunctional (meth) acrylate Compound having an ethylenically unsaturated group ]
The monofunctional (meth) acrylate compound having an ethylenically unsaturated group that can be used as the component (h) of the photocurable composition for imprinting of the present invention is a compound having 1 ethylenically unsaturated group in the molecule of the monofunctional (meth) acrylate compound 1. Examples of the monofunctional (meth) acrylate compound include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, dodecyl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, 1-adamantyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxydiglycol (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl oxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, methoxyethylene glycol (meth) acrylate, methoxydiglycol (meth) acrylate, methoxytriglycol (meth) acrylate, methoxytetraglycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, methoxypropyleneglycol (meth) acrylate, and (meth) acrylate, methoxy tripropylene glycol (meth) acrylate, ethyl carbitol (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, (meth) acryloxymethyltrimethoxysilane, (meth) acryloxymethyldimethoxysilane, (meth) acryloxymethyltriethoxysilane, (meth) acryloxymethyldiethoxysilane, 2- (meth) acryloxyethyltrimethoxysilane, 2- (meth) acryloxyethyldimethoxysilane, 2- (meth) acryloxyethyltriethoxysilane, 2- (meth) acryloxyethyldiethoxysilane, 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyldimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, 8- (meth) acryloxytrimethoxysilane, 8- (meth) acryloxyoctylethoxysilane, and 8- (meth) acryloyloxy octyldiethoxysilane.
Examples of the monofunctional (meth) acrylate compounds include those commercially available AS examples, AIB, TBA, NOAA, IOAA, LA, STA, ISTA, IBXA, 1-ADA, 1-ADMA, falsy コ, falsy #150, falsy コ, falsy # コ, falsy #160, falsy コ, falsy #190, falsy # コ, falsy #192, falsy # コ, falsy # MTG, falsy # MPE400A, falsy # MPE # 500A, HEA, 4-HBA (above manufactured by Osaka organic chemical Co., ltd.), FA-BZM, FA-511AS, FA-512M, FA-512, FA-512AS, FA-M, FA-513AS (above), hitachi chemical Co., ltd.), LMA, LA, S, A-S, S-1800M, S-1800A, IB, A-IB, PHE-1G, AMP-10G, PHE-2G, AMP-20GY, M-20G, M-30G, AM-30G, M-40G, M-90G, AM-90G, M-130G, M-130G, M-230G, M-230G, M-30PG, AM-30PG, 702A (above, the method comprises the steps of (a) preparing the laver by the chemical industry of new China, namely, laver, wherein the laver is the laver, the laver is the laver E, the laver is the laver NB, the laver is the laver IB, the laver is the laver TB, the laver is the laver EH, the laver L, the laver is the laver, the laver (a kind of the laver, and the laver-hur-a kind, and the laver-industry (a kind). The method comprises the steps of a laver, a laver CH, a laver IB-X, a laver BZ, a laver P, a laver THF (1000), a laver 130MA, ext>se:Sup>Aext>housingext>POext>-ext>Aext>,ext>housingext>THFext>-ext>Aext>,ext>se:Sup>Aext>housingext>portionext>ofext>theext>housingext>portionext>se:Sup>Aext>housingext>MTGext>-ext>Aext>,ext>housingext>130ext>Aext>theext>backext>coverext>isext>madeext>ofext>se:Sup>Aext>materialext>selectedext>fromext>theext>groupext>consistingext>ofext>backext>POext>-ext>Aext>,ext>backext>THFext>-ext>Aext>,ext>backext>MTGext>-ext>Aext>,ext>backext>130ext>Aext>,ext>andext>backext>THFext>-ext>Aext>,ext>backext>MTGext>-ext>Aext>,ext>backext>MTAext>,ext>andext>backext>-ext>Aext>,ext>respectivelyext>se:Sup>Aext>laverext>DPMext>-ext>Aext>,ext>se:Sup>Aext>laverext>ECext>-ext>Aext>,ext>se:Sup>Aext>laverext>Mext>-ext>600ext>Aext>,ext>(ext>aboveext>)ext>,ext>KBMext>-ext>5103ext>,ext>KBMext>-ext>503ext>,ext>KBMext>-ext>502ext>,ext>KBEext>-ext>503ext>,ext>KBEext>-ext>502ext>,ext>KBMext>-ext>5803ext>(ext>manufacturedext>byext>Xinyueext>chemicalext>industriesext>,ext>tdext>.ext>)ext>.ext>
When the photocurable composition for imprinting of the present invention contains component (h), the content thereof is 0.5 to 20 parts by mass, preferably 1 to 10 parts by mass, relative to 100 parts by mass of the sum of component (a), component (b), component (c), component (e) and component (h) contained in the composition.
The monofunctional (meth) acrylate compound having an ethylenically unsaturated group as the component (h) may be used alone or in combination of 1 or more than 2.
< other additives >)
The photocurable composition for imprinting of the present invention may further contain, if necessary, a chain transfer agent, an antioxidant, an ultraviolet absorber, a light stabilizer, a leveling agent, a rheology modifier, an adhesion aid such as a silane coupling agent, a pigment, a dye, a defoaming agent, and the like, as long as the effects of the present invention are not impaired.
Method for preparing photocurable composition for imprinting
The method for preparing the photocurable composition for imprinting of the present invention is not particularly limited. As the preparation method, for example, a method of mixing the component (a), the component (b 1), the component (b 2), the component (c), the component (d) and the component (e), and if necessary, the component (f) and/or the component (g) and the component (h) in a predetermined ratio to prepare a uniform solution is exemplified.
The photocurable composition for imprinting of the present invention prepared as a solution is preferably used after filtration using a filter or the like having a pore size of 0.1 to 10. Mu.m.
< cured object >)
The photocurable composition for imprinting of the present invention can be exposed to light (photocured) to obtain a cured product, and the present invention also aims at the cured product. Examples of the light beam for exposure include ultraviolet rays, electron rays, and X-rays. As a light source used for ultraviolet irradiation, for example, solar rays, a chemical lamp, a low-pressure mercury lamp, a high-pressure mercury lamp, a metal halide lamp, a xenon lamp, and a UV-LED can be used. In addition, post baking may be performed after exposure in order to stabilize the physical properties of the cured product. The post-baking method is not particularly limited, and is usually performed at 50 to 260℃for 1 minute to 24 hours using a hot plate, an oven, or the like.
Abbe number v of a cured product obtained by photocuring the photocurable composition for imprinting of the present invention D Up to 53 or more. Therefore, the photocurable composition for imprinting of the present invention can be suitably used for forming a resin lens.
< shaped body >)
The photocurable composition for imprinting of the present invention can be used, for example, by an imprint molding method, whereby various molded articles can be easily produced simultaneously with the formation of the cured product. As a method for producing a molded article, for example, a method comprising the steps of: filling the space between the support and the mold, which are in contact with each other, or the space inside the mold, which is detachable from the support, with the photocurable composition for imprinting of the present invention; exposing the imprint photocurable composition filled in the space to light to perform photocuring; a step of taking out the photo-cured product obtained by the photo-curing step and releasing the photo-cured product; and heating the photocurable product before, during, or after the demolding step. In this case, after the step of taking out the photo-cured product obtained by the step of photo-curing and releasing the photo-cured product, the step of heating may further include a developing step of washing/removing the uncured portion with an organic solvent. The method for producing the uncured portion is not particularly limited, and an uncured portion, which is an unexposed portion, may be produced by exposing only a predetermined position by mask exposure, projection exposure, or the like. Further, the photo-cured product after the development step may be re-exposed to light to be photo-cured, if necessary.
The step of performing the photo-curing by the exposure may be performed by applying conditions for obtaining the cured product. Further, the conditions for the step of heating the above-mentioned photo-cured product are not particularly limited, but are usually appropriately selected from the range of 50 to 260 ℃ and 1 minute to 24 hours. The heating means is not particularly limited, and examples thereof include an electric heating plate and an oven. The molded article produced by such a method can be suitably used as a lens for a camera module.
Examples
The present invention will be described more specifically with reference to the following examples, but the present invention is not limited to the examples. In the following examples and comparative examples, the apparatus and conditions used for preparing the samples and analyzing the physical properties are as follows.
(1) Stirring deaeration machine
The device comprises: awamori of rotation/revolution mixer (product of the company) ARE ARE-310
(2) UV exposure
The device comprises: intermittent UV-LED irradiation device (wavelength 365 nm) made of one-side cover
(3) Abbe number v D
The device comprises: abbemat MW of multi-wavelength refractometer manufactured by Divan Seisakusho
Measuring temperature: 23 DEG C
(4) Thermal shock testing machine
The device comprises: falstein brand small thermal shock tester TSE-11-A manufactured by Kabushiki Kaisha
Conditions are as follows: exposure time = 30 minutes at-40 ℃/85 ℃, -40 ℃ and 85 ℃,50 cycles
(5) Digital microscope (peeling observation in thermal shock test)
The device comprises: a further strain of KH-7700, MXG-2500REZ, from the phylaxis system
Conditions are as follows: reflection (dark field), low-Range,100 times
(6) Transmittance measurement
The device comprises: ultraviolet visible near infrared spectrophotometer V-670 manufactured by Japan Spectrophy Co., ltd
Reference: air-conditioner
(7) Film formation of anti-reflection layer
The device comprises: SRV4300 series manufactured by Shengang refiner (plant)
The mode is as follows: RF sputtering/magnetron mode
Conditions are as follows: target = SiO 2 Vertical distance between target/substrate = 100mm,
temperature=room temperature, sputtering time=29 minutes
(8) Optical microscope (anti-reflection film observation)
The device comprises: VHX-1000, VH-Z1000R from Kyowa
Conditions are as follows: reflection (bright field), objective 500 times
Suppliers of the compounds used in each of the production examples, examples and comparative examples are as follows.
MEK-AC-2140Z: trade name manufactured by Nissan chemical Co., ltd.: fee, fee-AC-2140Z
APG-200: trade name manufactured by Xinzhongcun chemical industry Co., ltd.): NK diethyl APG-200
V#260: trade name manufactured by osaka organic chemical industry (ltd): pruss コ strain #260
V#230: trade name manufactured by osaka organic chemical industry (ltd): pruss コ strain #230
SA1303P: the company, from the company, may use the company, from the company, as a brand name: set cover (registered trademark) cover SA1303P
UA-4200: trade name manufactured by Xinzhongcun chemical industry Co., ltd.): NK-on-line UA-4200
EBECRYL4513: the cover is manufactured by the company setal, trade name: EBECRYL4513
I184: trade name manufactured by IGM Resins: OMNIRAD 184 (registered trademark) and IRGACURE 184 (registered trademark)
I245: commercial name manufactured by BASF industrial scale: IRGANOX (registered trademark) 245
AO-503: trade name manufactured by ADEKA corporation: the awarvens (registered trademark) AO-503
BA: compound name manufactured by tokyo chemical industry (ltd): butyl acrylate
HEMA: compound name manufactured by tokyo chemical industry (ltd): methacrylic acid 2-hydroxy ethyl ester
KBM-503: trade name manufactured by Xinyue chemical industry Co., ltd: KBM-503
PEPT: trade name manufactured by SC organic chemistry (ltd): PEPT (PEPT)
Production example 1
200g of v#260 as the difunctional (meth) acrylate compound represented by the above formula (2) (b 1) was weighed into a 500mL eggplant-type flask, and dissolved with 200g of methyl ethyl ketone (hereinafter, abbreviated as mek in this specification). Then, 441g of MEK-AC-2140Z (MEK dispersion having a primary particle diameter of 10nm to 15nm and a solid content of 45 mass%) as the silica particles (a) surface-modified with the functional group having an ethylenically unsaturated group (the silica particles having a primary particle diameter of 10nm to 15nm and a (meth) acryloyloxy group) were added, followed by stirring and homogenization. Then, MEK was distilled off at 50℃under a reduced pressure of 133.3Pa or less using an evaporator to obtain a V#260 dispersion of the above-mentioned surface-modified silica particles having an ethylenically unsaturated group (the content of the surface-modified silica particles: 50 mass%) as described above.
PREPARATION EXAMPLE 2
In a 500mL eggplant-type flask, 50g of V#230 as the difunctional (meth) acrylate compound represented by the above formula (2) was weighed out as (b 1), and 50g of MEK was used to dissolve the compound. Then, 111g of MEK-AC-2140Z (MEK dispersion having a primary particle diameter of 10nm to 15nm and a solid content of 45 mass%) which is the silica particles having been surface-modified with the functional group having an ethylenically unsaturated group (a) was added thereto, and the mixture was stirred and homogenized. Then, MEK was distilled off at 50℃under a reduced pressure of 133.3Pa or less using an evaporator to obtain the V#230 dispersion of the above-mentioned surface-modified silica particles having an ethylenically unsaturated group (the content of the surface-modified silica particles: 50 mass%) as described above.
PREPARATION EXAMPLE 3
In a 500mL eggplant-type flask, 50.0g of UA-4200 as the urethane (meth) acrylate compound (b 2) was weighed and dissolved in 50.0g of MEK. Then, 111g of MEK-AC-2140Z (MEK dispersion having a primary particle diameter of 10nm to 15nm and a solid content of 45 mass%) which is the silica particles having been surface-modified with the functional group having an ethylenically unsaturated group (a) was added thereto, and the mixture was stirred and homogenized. Then, MEK was distilled off at 60℃under a reduced pressure of 133.3Pa or less using an evaporator to obtain the above-mentioned UA-4200 dispersion of surface-modified silica particles having an ethylenically unsaturated group (the content of the surface-modified silica particles: 50 mass%) as described above.
PREPARATION EXAMPLE 4
In a 500mL eggplant-type flask, 20.0g of V#260 as the difunctional (meth) acrylate compound represented by the above formula (2) as (b 1) was weighed. Then, 40.0g of SA1303P (polyrotaxane having an acryl group in a side chain of a cyclic molecule formed of cyclodextrin, MEK dispersion liquid having a solid content of 50% by mass) was added as the polyrotaxane (c), and the mixture was stirred and homogenized. Then, MEK was distilled off at 50℃under a reduced pressure of 133.3Pa or less using an evaporator to obtain the above-mentioned V#260 solution of the polyrotaxane having an ethylenically unsaturated group (the polyrotaxane having an ethylenically unsaturated group content: 50 mass%).
PREPARATION EXAMPLE 5
In a 500mL eggplant-type flask, 20.0g of V#230 as the difunctional (meth) acrylate compound represented by the above formula (2) as (b 1) was weighed. Then, 40.0g of SA1303P (polyrotaxane having an acryl group in a side chain of a cyclic molecule formed of cyclodextrin, MEK dispersion liquid having a solid content of 50% by mass) was added as the polyrotaxane (c), and the mixture was stirred and homogenized. Then, MEK was distilled off at 50℃under a reduced pressure of 133.3Pa or less using an evaporator to obtain the above-mentioned V#230 solution of the polyrotaxane having an ethylenically unsaturated group (the polyrotaxane having an ethylenically unsaturated group content: 50 mass%).
Production example 6
In a 500mL eggplant type flask, 11.0g of UA-4200 as the (b 2) urethane (meth) acrylate compound was weighed. Then, 18.0g of SA1303P (polyrotaxane having an acryl group in a side chain of a cyclic molecule formed of cyclodextrin, MEK dispersion liquid having a solid content of 50% by mass) was added as the polyrotaxane (c), and the mixture was stirred and homogenized. Then, MEK was distilled off at 50℃under a reduced pressure of 133.3Pa or less using an evaporator to obtain the above-mentioned solution UA-4200 of a polyrotaxane having an ethylenically unsaturated group (the polyrotaxane having an ethylenically unsaturated group content: 45 mass%).
Example 1
The solid content of the v#260 dispersion liquid obtained in production example 1 as (a) silica particles having a surface modified with an ethylenically unsaturated group, v#260 as (b 1) a difunctional (meth) acrylate compound represented by the formula (2), UA-4200 as (b 2) a urethane (meth) acrylate compound having an ethylenically unsaturated group, the solid content of the v#260 solution obtained in production example 4 as (c) a polyrotaxane having an ethylenically unsaturated group, I184 as (d) a photo radical initiator, I245 as (f) a phenol antioxidant, and AO-503 as (g) a sulfide antioxidant were mixed in the proportions described in the following table 1, respectively. The ratio of v#260 shown in table 1 below contains the v#260 dispersion liquid and the v#260 component contained in the v#260 solution. Then, the compound was mixed by shaking at 50 ℃ for 16 hours, and then PEPT as the polyfunctional thiol compound represented by the formula (1) was added as (e), and the mixture was stirred and defoamed for 10 minutes by using the stirring and defoamation machine, thereby preparing the photocurable composition for imprint 1. In table 1 below, "parts" means "parts by mass".
Examples 2 to 12, comparative examples 1 and 2
With respect to examples 2, 3, 5, 6 and 9, the photocurable compositions for imprinting 2, 3, 5, 6 and 9 were prepared by mixing the components (a) to (g) in the proportions shown in the following table 1 by the same procedure as in example 1. In example 4, the imprint photocurable composition 4 was prepared by mixing the components (a) to (g) in the same proportions shown in table 1 below, except that the solid component of the v#230 dispersion obtained in production example 2 was used as the component (a) and the solid component of the v#230 solution obtained in production example 5 was used as the component (c). Examples 7 and 8 were prepared by mixing components (a) to (g) in the same proportions as in example 1, except that the solid component of the UA-4200 dispersion obtained in production example 3 was used as component (a) and the solid component of the UA-4200 solution obtained in production example 6 was used as component (c), respectively, to prepare photocurable compositions 7 and 8 for imprinting. Examples 10, 11 and 12 were prepared by mixing components (a) to (d) and components (f) to (h) in the proportions described in table 1 below, shaking the mixture at 50 ℃ for 16 hours, adding component (e), and stirring and defoaming for 10 minutes using the stirring and defoaming machine, using the solid component of the v#230 dispersion obtained in production example 2 as component (a), and using the solid component of the v#230 solution obtained in production example 5 as component (c). In comparative example 1, the photocurable composition 13 for imprinting was prepared by mixing the components (a) in the same proportions as in example 1 except that the solid component of the v#230 dispersion obtained in production example 2 was used and the component (c) was not used. The photocurable composition 14 for imprinting was prepared by mixing the components (a) to (g) in the proportions shown in table 1 below, using the same procedure as in example 1, except that the component (e) was not used in comparative example 2.
TABLE 1
TABLE 1
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[ production of cured film ]
The photocurable compositions for imprinting prepared in examples 1 to 12 and comparative examples 1 to 2 were sandwiched between 2 sheets of glass substrate subjected to release treatment by coating NOVEC 1720 (registered trademark) and drying the same together with a 500 μm thick spacer made of silicone rubber. The sandwiched photocurable composition for imprinting was irradiated with the UV-LED irradiation apparatus at 30mW/cm 2 UV exposure was performed for 200 seconds. The cured product obtained after the exposure was peeled off from the glass substrate subjected to the release treatment, and then heated with a hot plate at 100℃for 10 minutes, whereby a cured film having a diameter of 1cm and a thickness of 0.5mm was produced.
[ transmittance evaluation ]
The transmittance of the cured film produced by the above method at a wavelength of 410nm was measured using the above spectrophotometer. Further, as a heat resistance test, the cured film was heated in an oven at 125℃for 94 hours, and the transmittance of the cured film cooled to room temperature was measured in the same manner. The results are shown in Table 2 below.
[ Abbe number v ] D Evaluation]
Cutting the cured film produced by the above method to about 6mm square with a cutter, and measuring Abbe number v of the cured film with the above multi-wavelength refractometer D . The results are shown in Table 2 below.
[ evaluation of peeling resistance of cured film in thermal shock test ]
The photocurable compositions for imprinting prepared in examples 1 to 12 and comparative examples 1 to 2 were applied dropwise to a photomask substrate (1 cm square of opening) subjected to a mold release treatment by coating NOVEC 1720 (registered trademark), manufactured by nun corporation) and drying. Then, the photocurable composition for imprinting on the photomask substrate subjected to the release treatment was sandwiched by an alkali-free glass substrate (10 cm square, 0.7mm thick) via a 500 μm thick spacer made of silicone rubber. The alkali-free glass substrate was subjected to adhesion treatment by applying a 10 mass% solution of a bonding aid (product name: KBM-5803) produced by Xinyue chemical industries, ltd.) diluted with propylene glycol monomethyl ether acetate (hereinafter abbreviated as PGMEA in the present specification) and dried. The sandwiched photocurable composition for imprinting was irradiated with the UV-LED irradiation apparatus at 115mW/cm 2 UV exposure was performed for 2.2 seconds. After exposure, the resulting cured product was peeled off from the above-mentioned photomask substrate subjected to the mold release treatment, immersed in (developed in) stirred PGMEA, and rinsed with PGMEA to remove the unexposed portion. As a result, a cured film having a thickness of 0.5mm and a square of 1cm was produced on the alkali-free glass substrate subjected to the adhesion treatment. The cured film was again irradiated with the above UV-LED irradiation apparatus at 30mW/cm 2 After being subjected to UV exposure for 191.7 seconds, the substrate was heated by a hot plate at 100℃for 10 minutes, and then put into the thermal shock tester of the above-mentioned strain of Fenghu. After the completion of 50 cycles of the thermal shock test, the cured film was taken out from the tester, and the corner of the cured film was observed by using the digital microscope of the haven system (strain). The case where the cured film was peeled off from the alkali-free glass substrate subjected to the adhesion treatment was judged as "x", the case where the cured film was not peeled off was judged as "o", and the results are shown in table 2 below. As an example, a photograph of the corner of the cured film made of the photocurable composition for imprint 6 of example 6, which was judged to be "o", was observed, and a photograph of the cured film, which was judged to be "x", was observed, as shown in fig. 1, and a photograph of the cured film, which was judged to be "x", was observed, from a comparative example2, a photograph of the corner of the cured film produced from the photocurable composition 14 for imprinting is shown in fig. 2.
[ evaluation of anti-reflection layer (AR layer) film formation and crack resistance ]
The photocurable composition for imprinting prepared in examples 3 and 4 and comparative example 1 was weighed 0.03g on a glass substrate subjected to release treatment by coating and drying a NOVEC 1720 (manufactured by the registered trademark). Then, the photocurable composition for imprinting on the release-treated glass substrate was sandwiched by alkali-free glass substrates (6 cm square, 0.7mm thick) via a 500 μm thick spacer made of silicone rubber. The alkali-free glass substrate was subjected to adhesion treatment by applying a bonding aid (product name: KBM-5103) manufactured by Xinyue chemical industries, ltd.) diluted with PGMEA to a 30 mass% solution and drying the solution. The sandwiched photocurable composition for imprinting was irradiated with the UV-LED irradiation apparatus at 30mW/cm 2 UV exposure was performed for 200 seconds. After the exposure, the obtained cured product was peeled off from the glass substrate subjected to the release treatment, and then heated with a hot plate at 100℃for 10 minutes. As a result, a cured film having a diameter of 1cm, a thickness of 0.5mm and a mass of 0.03g was produced on the alkali-free glass substrate.
On the cured film formed on the alkali-free glass substrate, a silicon oxide layer having a film thickness of 200nm was formed as an antireflection layer under the above-mentioned film formation conditions using the above-mentioned RF sputtering apparatus. After the presence or absence of a crack was confirmed by observing the antireflection layer on the cured film using the optical microscope of the above-mentioned strain, the alkali-free glass substrate was heated with a hot plate at 175 ℃ for 2 minutes and 30 seconds to conduct a heat resistance test. Regarding the alkali-free glass substrate after the heat resistance test, the presence or absence of cracking of the antireflection layer on the cured film was observed using an optical microscope of the strain, and the cracking resistance of the antireflection layer was determined. The results of the cases were shown in table 2 below, in which the case where the crack was visible in the anti-reflection layer on the cured film was judged as "x", and the case where the crack and the wrinkle were not visible in the anti-reflection layer on the cured film was judged as "o".
TABLE 2
TABLE 2
The cured film made of the photocurable composition for imprinting 13 of comparative example 1 containing no component (c) and the cured film made of the photocurable composition for imprinting 14 of comparative example 2 containing no component (e) were peeled off from the alkali-free glass substrate after the thermal shock test. On the other hand, cured films prepared from the photocurable compositions for imprinting of examples 1 to 12 containing the components (a) to (e) were not peeled off from the alkali-free glass substrate after the thermal shock test. Abbe number v of cured film obtained from the photocurable composition for imprinting of the present invention D And 53 or more. The cured film (molded body) obtained from the photocurable composition for imprinting of the present invention therefore exhibits the following characteristics: the cured film (molded article) has excellent adhesion to a support without peeling off the support even after thermal shock test, and the antireflective layer on the upper layer of the cured film (molded article) has desirable characteristics as a lens for a high-resolution camera module without generating cracks by heat treatment at 175 ℃.
Claims (11)
1. A photocurable composition for imprinting comprising the following component (a), the following component (b), the following component (c), the following component (d) and the following component (e),
(a) The components are as follows: silica particles having a primary particle diameter of 1nm to 100nm and surface-modified with a functional group having an ethylenically unsaturated group,
(b) The components are as follows: a polyfunctional (meth) acrylate compound having an ethylenically unsaturated group,
(c) The components are as follows: polyrotaxane having an ethylenically unsaturated group,
(d) The components are as follows: a photo-radical initiator, and a photo-radical initiator,
(e) The components are as follows: a polyfunctional thiol compound represented by the following formula (1),
wherein R is 1 Represents a single bond or a linear or branched alkylene group having 1 to 6 carbon atoms, Z 1 Represents a single bond, an ester bond or an ether bond, Q 1 Represents an organic group having 2 to 12 carbon atoms containing at least 1 heteroatom or not containing a heteroatom, or a heteroatom, s represents an integer of 2 to 6,
the component (b) comprises the following component (b 1) and the following component (b 2),
(b1) The components are as follows: a difunctional (meth) acrylate compound represented by the following formula (2),
(b2) The components are as follows: a urethane (meth) acrylate compound or an epoxy (meth) acrylate compound, wherein the urethane (meth) acrylate compound does not include a polyrotaxane having an ethylenically unsaturated group as the component (c),
wherein R is 2 Represents a hydrogen atom or a methyl group, Q 2 Represents a linear or branched alkylene group having 2 to 16 carbon atoms.
2. The photocurable composition for imprinting according to claim 1, further comprising the following component (f) and/or the following component (g),
(f) The components are as follows: a phenolic antioxidant, wherein the phenolic antioxidant,
(g) The components are as follows: sulfide antioxidants.
3. The photocurable composition for imprinting according to claim 1 or 2, which further comprises the following component (h),
(h) The components are as follows: monofunctional (meth) acrylate compounds having an ethylenically unsaturated group.
4. The photocurable composition for imprinting according to claim 1 or 2, wherein the silica particles having a surface modified with a functional group having an ethylenically unsaturated group as the component (a) are silica particles having a surface modified with a (meth) acryloyloxy group bonded to a silicon atom via a divalent linking group.
5. The photocurable composition for imprinting according to claim 3, wherein the silica particles having a surface modified with a functional group having an ethylenically unsaturated group as the component (a) are silica particles having a surface modified with a (meth) acryloyloxy group bonded to a silicon atom via a divalent linking group.
6. A cured product of the photocurable composition for imprinting according to any one of claims 1 to 5.
7. A method for manufacturing a resin lens, comprising the steps of: a process of imprint molding the photocurable composition for imprint according to any one of claims 1 to 5.
8. A method for producing a molded article from an imprint photocurable composition, comprising the steps of: a step of filling the photocurable composition for imprinting according to any one of claims 1 to 5 in a space between a support and a mold in contact with each other or in an internal space of a detachable mold; and exposing the imprint photocurable composition filled in the space to light to perform photocuring.
9. The method for producing a molded article according to claim 8, further comprising the steps of: a step of taking out the obtained photo-cured product after the photo-curing step and releasing the photo-cured product; and heating the photocurable product before, during, or after the demolding step.
10. The method for producing a molded article according to claim 9, further comprising a development step using an organic solvent after the step of releasing the mold and before the step of heating.
11. The method for producing a molded body according to any one of claims 8 to 10, which is a lens for a camera module.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2018-240319 | 2018-12-21 | ||
| JP2018240319 | 2018-12-21 | ||
| PCT/JP2019/049184 WO2020129902A1 (en) | 2018-12-21 | 2019-12-16 | Photocurable composition for imprinting |
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| CN113195547A CN113195547A (en) | 2021-07-30 |
| CN113195547B true CN113195547B (en) | 2023-08-11 |
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| JP (1) | JP7021710B2 (en) |
| KR (1) | KR102496908B1 (en) |
| CN (1) | CN113195547B (en) |
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| JP2023157024A (en) * | 2020-09-14 | 2023-10-26 | 日産化学株式会社 | Primer layer formation composition for imprint |
| JPWO2022210664A1 (en) * | 2021-03-30 | 2022-10-06 |
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| WO2016171187A1 (en) * | 2015-04-21 | 2016-10-27 | 住友化学株式会社 | Photocurable resin composition, method for manufacturing cured film using same, and laminate containing said cured film |
| WO2018155013A1 (en) * | 2017-02-22 | 2018-08-30 | 日産化学工業株式会社 | Photocurable composition for imprinting |
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| WO2009136618A1 (en) * | 2008-05-07 | 2009-11-12 | アドバンスト・ソフトマテリアルズ株式会社 | Polyrotaxane, crosslinked structure comprising polyrotaxane and polymer, and processes for producing these |
| JP2010000612A (en) * | 2008-06-18 | 2010-01-07 | Fujifilm Corp | Nanoimprinting curable composition and pattern forming method |
| KR101779531B1 (en) | 2010-02-26 | 2017-09-18 | 신닛테츠 수미킨 가가쿠 가부시키가이샤 | Curable resin composition, cured article thereof, and optical material |
| JP2014234458A (en) | 2013-06-03 | 2014-12-15 | 昭和電工株式会社 | Curable composition, and cured product thereof |
| JP2015071741A (en) * | 2013-09-04 | 2015-04-16 | Jsr株式会社 | Curable composition, nano imprint material, cured film, laminate, method of producing cured film, pattern formation method, and semiconductor light-emitting element substrate |
| US10266630B2 (en) | 2014-11-04 | 2019-04-23 | Advanced Softmaterials Inc. | Photocurable composition, cured product formed from photocurable composition, and method for manufacturing said cured product |
| JP2016121277A (en) | 2014-12-25 | 2016-07-07 | 日東電工株式会社 | Photocurable resin composition and optical material using the same |
| JPWO2018052008A1 (en) * | 2016-09-16 | 2019-08-15 | 住友精化株式会社 | Polyrotaxane-containing composition and cured product thereof |
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| WO2016171187A1 (en) * | 2015-04-21 | 2016-10-27 | 住友化学株式会社 | Photocurable resin composition, method for manufacturing cured film using same, and laminate containing said cured film |
| WO2018155013A1 (en) * | 2017-02-22 | 2018-08-30 | 日産化学工業株式会社 | Photocurable composition for imprinting |
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| JPWO2020129902A1 (en) | 2021-11-04 |
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| SG11202106695XA (en) | 2021-07-29 |
| CN113195547A (en) | 2021-07-30 |
| WO2020129902A1 (en) | 2020-06-25 |
| KR20210106459A (en) | 2021-08-30 |
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| TWI805881B (en) | 2023-06-21 |
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