KR20200068649A - Photocurable composition for imprint - Google Patents
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- KR20200068649A KR20200068649A KR1020207007402A KR20207007402A KR20200068649A KR 20200068649 A KR20200068649 A KR 20200068649A KR 1020207007402 A KR1020207007402 A KR 1020207007402A KR 20207007402 A KR20207007402 A KR 20207007402A KR 20200068649 A KR20200068649 A KR 20200068649A
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- KR
- South Korea
- Prior art keywords
- component
- formula
- mass
- photocurable composition
- parts
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- 239000000203 mixture Substances 0.000 title claims abstract description 98
- -1 acrylate compound Chemical class 0.000 claims abstract description 86
- 229910000077 silane Inorganic materials 0.000 claims abstract description 44
- 238000010438 heat treatment Methods 0.000 claims abstract description 26
- 125000002723 alicyclic group Chemical group 0.000 claims abstract description 13
- 230000007062 hydrolysis Effects 0.000 claims abstract description 11
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 11
- 239000004593 Epoxy Substances 0.000 claims abstract description 9
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000003999 initiator Substances 0.000 claims abstract description 9
- 239000000047 product Substances 0.000 claims description 69
- 238000000034 method Methods 0.000 claims description 37
- 229920001296 polysiloxane Polymers 0.000 claims description 17
- 125000004432 carbon atom Chemical group C* 0.000 claims description 16
- 238000004519 manufacturing process Methods 0.000 claims description 14
- 239000011347 resin Substances 0.000 claims description 12
- 229920005989 resin Polymers 0.000 claims description 12
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 8
- 238000000016 photochemical curing Methods 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 6
- 125000005842 heteroatom Chemical group 0.000 claims description 6
- 239000002530 phenolic antioxidant Substances 0.000 claims description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 5
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 5
- 239000003963 antioxidant agent Substances 0.000 claims description 5
- 230000003078 antioxidant effect Effects 0.000 claims description 5
- 229910052710 silicon Inorganic materials 0.000 claims description 5
- 125000002947 alkylene group Chemical group 0.000 claims description 4
- 239000007859 condensation product Substances 0.000 claims description 4
- 125000003709 fluoroalkyl group Chemical group 0.000 claims description 3
- 150000004756 silanes Chemical class 0.000 claims description 3
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 125000001153 fluoro group Chemical group F* 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 125000000962 organic group Chemical group 0.000 claims description 2
- 230000003287 optical effect Effects 0.000 abstract description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 64
- 229910052802 copper Inorganic materials 0.000 description 64
- 239000010949 copper Substances 0.000 description 64
- 239000000758 substrate Substances 0.000 description 34
- 239000011521 glass Substances 0.000 description 33
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 15
- 238000003756 stirring Methods 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 11
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 10
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- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 238000000465 moulding Methods 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
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- 238000011156 evaluation Methods 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
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- 239000002904 solvent Substances 0.000 description 4
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 3
- 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 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
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- 239000007795 chemical reaction product Substances 0.000 description 3
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- 239000004615 ingredient Substances 0.000 description 3
- 239000003112 inhibitor Substances 0.000 description 3
- 239000003456 ion exchange resin Substances 0.000 description 3
- 229920003303 ion-exchange polymer Polymers 0.000 description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 3
- 229910052753 mercury Inorganic materials 0.000 description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 3
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- 239000010703 silicon Substances 0.000 description 3
- 229920002379 silicone rubber Polymers 0.000 description 3
- 239000004945 silicone rubber Substances 0.000 description 3
- 125000006850 spacer group Chemical group 0.000 description 3
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 3
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 3
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 description 3
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 102100027123 55 kDa erythrocyte membrane protein Human genes 0.000 description 2
- 101001057956 Homo sapiens 55 kDa erythrocyte membrane protein Proteins 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-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
- NJSVDVPGINTNGX-UHFFFAOYSA-N [dimethoxy(propyl)silyl]oxymethanamine Chemical compound CCC[Si](OC)(OC)OCN NJSVDVPGINTNGX-UHFFFAOYSA-N 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
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 2
- 239000011342 resin composition Substances 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- JLGNHOJUQFHYEZ-UHFFFAOYSA-N trimethoxy(3,3,3-trifluoropropyl)silane Chemical compound CO[Si](OC)(OC)CCC(F)(F)F JLGNHOJUQFHYEZ-UHFFFAOYSA-N 0.000 description 2
- BVQYIDJXNYHKRK-UHFFFAOYSA-N trimethoxy(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)silane Chemical compound CO[Si](OC)(OC)CCC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F BVQYIDJXNYHKRK-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
- VYMPLPIFKRHAAC-UHFFFAOYSA-N 1,2-ethanedithiol Chemical compound SCCS VYMPLPIFKRHAAC-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
- 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
- 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
- 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
- NULJCQIIEHDLEU-UHFFFAOYSA-N 3-(3-sulfanylpropoxy)-2,2-bis(3-sulfanylpropoxymethyl)propan-1-ol Chemical compound SCCCOCC(CO)(COCCCS)COCCCS NULJCQIIEHDLEU-UHFFFAOYSA-N 0.000 description 1
- SKKHNUKNMQLBTJ-UHFFFAOYSA-N 3-bicyclo[2.2.1]heptanyl 2-methylprop-2-enoate Chemical compound C1CC2C(OC(=O)C(=C)C)CC1C2 SKKHNUKNMQLBTJ-UHFFFAOYSA-N 0.000 description 1
- KBQVDAIIQCXKPI-UHFFFAOYSA-N 3-trimethoxysilylpropyl prop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C=C KBQVDAIIQCXKPI-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
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- WQZGKKKJIJFFOK-CBPJZXOFSA-N D-Gulose Chemical compound OC[C@H]1OC(O)[C@H](O)[C@H](O)[C@H]1O WQZGKKKJIJFFOK-CBPJZXOFSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 101100389975 Mus musculus Ezhip gene Proteins 0.000 description 1
- YDGMGEXADBMOMJ-LURJTMIESA-N N(g)-dimethylarginine Chemical compound CN(C)C(\N)=N\CCC[C@H](N)C(O)=O YDGMGEXADBMOMJ-LURJTMIESA-N 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 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
- 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
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 description 1
- 125000003670 adamantan-2-yl group Chemical group [H]C1([H])C(C2([H])[H])([H])C([H])([H])C3([H])C([*])([H])C1([H])C([H])([H])C2([H])C3([H])[H] 0.000 description 1
- MOLCWHCSXCKHAP-UHFFFAOYSA-N adamantane-1,3-diol Chemical compound C1C(C2)CC3CC1(O)CC2(O)C3 MOLCWHCSXCKHAP-UHFFFAOYSA-N 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- YDGMGEXADBMOMJ-UHFFFAOYSA-N asymmetrical dimethylarginine Natural products CN(C)C(N)=NCCCC(N)C(O)=O YDGMGEXADBMOMJ-UHFFFAOYSA-N 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- CHIHQLCVLOXUJW-UHFFFAOYSA-N benzoic anhydride Chemical compound C=1C=CC=CC=1C(=O)OC(=O)C1=CC=CC=C1 CHIHQLCVLOXUJW-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 150000008366 benzophenones Chemical class 0.000 description 1
- HECGKCOICWUUJU-UHFFFAOYSA-N bis(diphenylphosphanylmethyl)-phenylphosphane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)CP(C=1C=CC=CC=1)CP(C=1C=CC=CC=1)C1=CC=CC=C1 HECGKCOICWUUJU-UHFFFAOYSA-N 0.000 description 1
- FGUUNXDRMVKHCF-UHFFFAOYSA-N bis(hydroxymethyl)tricyclo[5.2.1.0(2,6)]decane Chemical compound C12CCCC2(CO)C2(CO)CC1CC2 FGUUNXDRMVKHCF-UHFFFAOYSA-N 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
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- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
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- VJYNTADJZPKUAF-UHFFFAOYSA-N diethoxy-methyl-(3,3,3-trifluoropropyl)silane Chemical compound CCO[Si](C)(OCC)CCC(F)(F)F VJYNTADJZPKUAF-UHFFFAOYSA-N 0.000 description 1
- DIJRHOZMLZRNLM-UHFFFAOYSA-N dimethoxy-methyl-(3,3,3-trifluoropropyl)silane Chemical compound CO[Si](C)(OC)CCC(F)(F)F DIJRHOZMLZRNLM-UHFFFAOYSA-N 0.000 description 1
- REQPQFUJGGOFQL-UHFFFAOYSA-N dimethylcarbamothioyl n,n-dimethylcarbamodithioate Chemical class CN(C)C(=S)SC(=S)N(C)C REQPQFUJGGOFQL-UHFFFAOYSA-N 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
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- 238000010894 electron beam technology Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- SBRXLTRZCJVAPH-UHFFFAOYSA-N ethyl(trimethoxy)silane Chemical compound CC[Si](OC)(OC)OC SBRXLTRZCJVAPH-UHFFFAOYSA-N 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
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- 238000001914 filtration Methods 0.000 description 1
- CZWLNMOIEMTDJY-UHFFFAOYSA-N hexyl(trimethoxy)silane Chemical compound CCCCCC[Si](OC)(OC)OC CZWLNMOIEMTDJY-UHFFFAOYSA-N 0.000 description 1
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- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 125000005641 methacryl group Chemical group 0.000 description 1
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- MSRJTTSHWYDFIU-UHFFFAOYSA-N octyltriethoxysilane Chemical compound CCCCCCCC[Si](OCC)(OCC)OCC MSRJTTSHWYDFIU-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
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- ZJLMKPKYJBQJNH-UHFFFAOYSA-N propane-1,3-dithiol Chemical compound SCCCS ZJLMKPKYJBQJNH-UHFFFAOYSA-N 0.000 description 1
- 239000007870 radical polymerization initiator Substances 0.000 description 1
- 238000001552 radio frequency sputter deposition Methods 0.000 description 1
- 238000012552 review Methods 0.000 description 1
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- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- 229920001169 thermoplastic Polymers 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
- ZLGWXNBXAXOQBG-UHFFFAOYSA-N triethoxy(3,3,3-trifluoropropyl)silane Chemical compound CCO[Si](OCC)(OCC)CCC(F)(F)F ZLGWXNBXAXOQBG-UHFFFAOYSA-N 0.000 description 1
- NYIKUOULKCEZDO-UHFFFAOYSA-N triethoxy(3,3,4,4,5,5,6,6,6-nonafluorohexyl)silane Chemical compound CCO[Si](OCC)(OCC)CCC(F)(F)C(F)(F)C(F)(F)C(F)(F)F NYIKUOULKCEZDO-UHFFFAOYSA-N 0.000 description 1
- DENFJSAFJTVPJR-UHFFFAOYSA-N triethoxy(ethyl)silane Chemical compound CCO[Si](CC)(OCC)OCC DENFJSAFJTVPJR-UHFFFAOYSA-N 0.000 description 1
- WUMSTCDLAYQDNO-UHFFFAOYSA-N triethoxy(hexyl)silane Chemical compound CCCCCC[Si](OCC)(OCC)OCC WUMSTCDLAYQDNO-UHFFFAOYSA-N 0.000 description 1
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
- NBXZNTLFQLUFES-UHFFFAOYSA-N triethoxy(propyl)silane Chemical compound CCC[Si](OCC)(OCC)OCC NBXZNTLFQLUFES-UHFFFAOYSA-N 0.000 description 1
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 description 1
- IJROHELDTBDTPH-UHFFFAOYSA-N trimethoxy(3,3,4,4,5,5,6,6,6-nonafluorohexyl)silane Chemical compound CO[Si](OC)(OC)CCC(F)(F)C(F)(F)C(F)(F)C(F)(F)F IJROHELDTBDTPH-UHFFFAOYSA-N 0.000 description 1
- NMEPHPOFYLLFTK-UHFFFAOYSA-N trimethoxy(octyl)silane Chemical compound CCCCCCCC[Si](OC)(OC)OC NMEPHPOFYLLFTK-UHFFFAOYSA-N 0.000 description 1
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 1
- 150000003673 urethanes Chemical class 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
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Abstract
[과제] 광학특성이 우수하며, 임프린트 후의 지지체의 휨량이 종래보다 훨씬 작은 경화물(성형체)을 형성할 수 있음과 함께, 열처리에 의해 이 경화물(성형체)의 상층의 반사방지층에 크랙이 발생하지 않는, 광경화성 조성물을 제공한다.
[해결수단] (a)지환식 (메트)아크릴레이트 화합물, (b)우레탄(메트)아크릴레이트 화합물 또는 에폭시(메트)아크릴레이트 화합물, (c)중합성기로서 (메트)아크릴로일옥시기를 갖는 실란 화합물 또는 이 실란 화합물을 포함하는 적어도 1종의 실란 화합물의 가수분해 중축합물, 및 (d)광라디칼개시제를 포함하는 임프린트용 광경화성 조성물.[Task] The optical properties are excellent, and the amount of warpage of the support after imprinting can form a much smaller cured product (formed body) than before, and cracks are generated in the antireflection layer on the upper layer of the cured product (formed body) by heat treatment. A photocurable composition is provided.
[Solutions] (a) an alicyclic (meth)acrylate compound, (b) a urethane (meth)acrylate compound or an epoxy (meth)acrylate compound, (c) having a (meth)acryloyloxy group as a polymerizable group A photocurable composition for imprints comprising a silane compound or a hydrolysis polycondensate of at least one silane compound containing the silane compound, and (d) a photoradical initiator.
Description
본 발명은, 지환식 (메트)아크릴레이트 화합물, 우레탄(메트)아크릴레이트 화합물 또는 에폭시(메트)아크릴레이트 화합물, 중합성기로서 (메트)아크릴로일옥시기를 갖는 실란 화합물 또는 이 실란 화합물을 포함하는 적어도 1종의 실란 화합물의 가수분해 중축합물, 및 광라디칼개시제를 포함하는 임프린트용 광경화성 조성물에 관한 것이다. 상세하게는, 광학특성(투명성, 고굴절률, 고아베수)이 우수하며, 임프린트 후의 지지체의 휨량이 종래보다 훨씬 작은 경화물 및 성형체를 형성할 수 있음과 함께, 이 경화물 및 성형체의 상층에 반사방지층(AR층)을 성막 후, 열처리를 거쳐도 이 반사방지층에 크랙이 발생하지 않는, 광경화성 조성물에 관한 것이다.The present invention includes an alicyclic (meth)acrylate compound, a urethane (meth)acrylate compound or an epoxy (meth)acrylate compound, a silane compound having a (meth)acryloyloxy group as a polymerizable group, or a silane compound containing the same. The present invention relates to a photocurable composition for imprints comprising a hydrolysis polycondensation product of at least one silane compound, and a photoradical initiator. Specifically, the optical properties (transparency, high refractive index, high Abbe number) are excellent, and the amount of warpage of the support after imprinting can form a cured product and a molded body much smaller than the conventional one. It relates to a photocurable composition in which a crack does not occur in the antireflection layer even after heat treatment after forming the antireflection layer (AR layer).
수지렌즈는, 휴대전화, 디지털카메라, 차재카메라 등의 전자기기에 이용되고 있으며, 그 전자기기의 목적에 따른, 우수한 광학특성을 갖는 것이 요구된다. 또한, 사용태양에 맞춰, 높은 내구성, 예를 들어 내열성 및 내후성, 그리고 수율좋게 성형할 수 있는 높은 생산성이 요구되고 있다. 이러한 요구를 만족하는 수지렌즈용의 재료로는, 예를 들어, 폴리카보네이트수지, 시클로올레핀폴리머, 메타크릴수지 등의 열가소성의 투명수지가 사용되어 왔다.Resin lenses are used in electronic devices such as mobile phones, digital cameras, and in-vehicle cameras, and it is required to have excellent optical properties according to the purpose of the electronic devices. In addition, according to the use mode, high durability, for example, heat resistance and weather resistance, and high productivity that can be molded with high yield are required. As a material for a resin lens satisfying these demands, thermoplastic transparent resins such as polycarbonate resins, cycloolefin polymers, and methacryl resins have been used, for example.
또한, 고해상도 카메라모듈에는 복수매의 렌즈가 이용되는데, 파장분산성이 낮은, 즉 고아베수를 갖는 렌즈가 주로 사용되고 있으며, 이것을 형성하는 광학재료가 요구되고 있다. 나아가, 수지렌즈의 제조에 있어서, 수율이나 생산효율의 향상, 더 나아가서는 렌즈적층시의 광축어긋남의 억제를 위해, 열가소성 수지의 사출성형으로부터, 실온에서 액상인 경화성 수지를 사용한 압착(押し付け)성형에 의한 웨이퍼레벨성형으로의 이행이 활발히 검토되고 있다. 웨이퍼레벨성형에서는, 생산성의 관점으로부터, 유리기판 등의 지지체 상에 렌즈를 형성하는 하이브리드렌즈방식이 일반적이다.In addition, a plurality of lenses are used in the high-resolution camera module, and a lens having a low wavelength dispersion property, that is, a high Abbe number is mainly used, and an optical material for forming the lens is required. Furthermore, in the production of a resin lens, in order to improve the yield and production efficiency, and further suppress the optical axis displacement during lens lamination, compression molding using a curable resin that is liquid at room temperature from injection molding of a thermoplastic resin. The transition to wafer-level molding by is actively being investigated. In wafer-level molding, from the viewpoint of productivity, a hybrid lens method in which a lens is formed on a support such as a glass substrate is generally used.
웨이퍼레벨성형이 가능한 광경화성 수지로는, 종래, 고투명성, 내열황변색성 및 금형으로부터의 이형성의 관점으로부터, 라디칼경화성 수지 조성물이 이용되고 있다(특허문헌 1).As a photocurable resin capable of wafer-level molding, a radically curable resin composition has been conventionally used from the viewpoint of high transparency, heat yellowing resistance, and mold release from a mold (Patent Document 1).
또한, 실란 화합물로 표면수식된 실리카입자, 분산제로 표면수식된 산화지르코늄입자 등의, 표면수식된 산화물입자를 함유함으로써, 높은 아베수의 경화물이 얻어지는 경화성 조성물이 알려져 있다(예를 들어, 특허문헌 2 및 특허문헌 3).Further, curable compositions are known in which a cured product of high Abbe number is obtained by containing surface-modified oxide particles, such as silica particles surface-modified with a silane compound and zirconium oxide particles surface-modified with a dispersant (for example, a patent) Document 2 and Patent Document 3).
최근, 카메라모듈의 박화에 대한 시장요구에 수반하여, 하이브리드렌즈방식에 이용되는 지지체의 두께가 박화되고 있다. 이에 따라, 특허문헌 1에 기재되어 있는 라디칼경화성 수지 조성물을 이용하면, 열처리를 수반하는 실장프로세스 후에, 렌즈 등의 성형체가 형성된 지지체가 쉽게 휜다는 과제가 현재화(顯在化)되고 있다. 상기 과제를 해결하기 위해, 사용하는 광경화성 수지의 탄성율을 낮추는 대책이 채용되고 있다. 그러나, 성형체가 렌즈인 경우, 그의 상층에 산화규소, 산화티탄 등의 무기물로 이루어지는 반사방지층이 형성된다. 이에 따라, 휨량이 작은 지지체 상에 형성되며, 반사방지층으로 피복된 렌즈를 열처리함으로써, 그 반사방지층에 크랙이 발생한다는 과제를 갖고 있다.In recent years, with the market demand for thinning of the camera module, the thickness of the support used in the hybrid lens method is thinning. Accordingly, when the radical curable resin composition described in Patent Literature 1 is used, the problem that a support body formed with a molded body such as a lens easily peels off after a mounting process involving heat treatment has been presented. In order to solve the above problems, measures to lower the modulus of elasticity of the photocurable resin used are employed. However, when the molded body is a lens, an antireflection layer made of an inorganic material such as silicon oxide or titanium oxide is formed on its upper layer. Accordingly, it is formed on a support having a small amount of warpage, and has a problem that cracks are generated in the antireflection layer by heat treatment of the lens coated with the antireflection layer.
또한, 특허문헌 2 또는 특허문헌 3에 기재된 표면수식된 산화물입자를 함유하는 경화성 조성물로부터 얻어지는 경화물은, 이 산화물입자의 편석, 투명성이 낮고, 무르고 내크랙성이 뒤떨어진다는 문제가 염려된다. 그리고, 이 문제는, 표면수식된 산화물입자의 함유량이 증가할수록 현저해진다.In addition, the cured product obtained from the curable composition containing the surface-modified oxide particles described in Patent Literature 2 or Patent Literature 3 is concerned with the problem that segregation and transparency of these oxide particles are low, soft and poor in crack resistance. And, this problem becomes remarkable as the content of the surface-modified oxide particles increases.
이에 따라, 고아베수(예를 들어 53 이상) 및 높은 투명성을 가지며, 하이브리드렌즈방식으로 유리기판 등의 지지체의 휨량이 작은, 고해상도 카메라모듈용 렌즈로서 사용할 수 있는 경화물 및 성형체가 얻어지고, 더 나아가서는 그 후의 열처리에 의해 이 경화물 및 성형체의 상층에 성막된 반사방지층에 크랙이 발생하지 않는, 경화성 수지재료는 아직 없어, 그 개발이 요망되고 있었다. 본 발명은, 이러한 사정을 감안하여 이루어진 것으로, 고아베수, 고굴절률, 고투명성 및 내열황변성을 나타내는 경화물 및 성형체를 형성할 수 있고, 또한 지지체의 휨량이 종래보다 작기 때문에 하이브리드렌즈방식으로 이 경화물 및 성형체를 제작하기에 호적하며, 또한 열처리에 의해 이 경화물 및 성형체의 상층의 반사방지층에 크랙이 발생하지 않는, 광경화성 조성물을 제공하는 것을 과제로 한다.Accordingly, a cured product and a molded body that can be used as a lens for a high-resolution camera module having a high Abbe number (for example, 53 or more) and high transparency, and having a small amount of warpage of a support such as a glass substrate in a hybrid lens method are obtained. Furthermore, there is no curable resin material that does not generate cracks in the antireflection layer formed on the upper layer of the cured product and the molded body by subsequent heat treatment, and its development has been desired. The present invention has been made in view of the above circumstances, and it is possible to form a cured product and a molded body exhibiting high Abbe number, high refractive index, high transparency, and heat resistance to yellowness, and also, since the amount of bending of the support is smaller than that of the conventional hybrid lens method. An object of the present invention is to provide a photocurable composition that is suitable for manufacturing this cured product and a molded body, and does not crack in the antireflection layer of the upper layer of the cured product and the molded body by heat treatment.
본 발명자들은, 상기의 과제를 해결하기 위해 예의검토를 행한 결과, (메트)아크릴로일옥시기를 갖는 실란 화합물 또는 이 실란 화합물을 포함하는 적어도 1종의 실란 화합물의 가수분해 중축합물을, 광경화성 조성물에 소정의 비율로 배합함으로써, 이 광경화성 조성물로부터 얻어지는 경화물 및 성형체는, 높은 아베수νD(53 이상)를 가지며, 파장 410nm에 있어서 90% 이상의 높은 투과율을 나타냄과 함께, 지지체의 휨량이 매우 작고(0μm 이상 1.5μm 미만), 175℃에서의 열처리에 의해 이 경화물 및 성형체의 상층의 반사방지층에 크랙이 발생하지 않는 것을 발견하여, 본 발명을 완성하였다.The present inventors conducted a courtesy review to solve the above-described problems, and as a result, a hydrolysis polycondensation product of a silane compound having a (meth)acryloyloxy group or at least one silane compound containing the silane compound is photocurable. By blending the composition in a predetermined ratio, the cured product and the molded product obtained from the photocurable composition have a high Abbe number ν D (53 or more), exhibit a high transmittance of 90% or more at a wavelength of 410 nm, and warp the support. The amount was very small (0 μm or more and less than 1.5 μm), and the present invention was completed by discovering that cracks did not occur in the antireflection layer on the upper layer of the cured product and the molded body by heat treatment at 175°C.
즉 본 발명의 제1 태양은, 하기 (a)성분, 하기 (b)성분, 하기 (c)성분, 및 하기 (d)성분을 포함하며, 이 (a)성분 및 이 (b)성분의 합 100질량부에 대해, 이 (b)성분이 30질량부 내지 90질량부 및 이 (c)성분이 1질량부 내지 100질량부이고, 이 (a)성분, 이 (b)성분 및 이 (c)성분의 합 100질량부에 대해 이 (d)성분이 0.1질량부 내지 5질량부인, 임프린트용 광경화성 조성물이다.That is, the first aspect of the present invention includes the following (a) component, the following (b) component, the following (c) component, and the following (d) component, and the sum of this (a) component and this (b) component With respect to 100 parts by mass, the component (b) is 30 parts by mass to 90 parts by mass, and the component (c) is 1 part by mass to 100 parts by mass, and the component (a), the component (b), and the component (c) ) It is the photocurable composition for imprints whose component (d) is 0.1 mass part-5 mass parts with respect to 100 mass parts of component sum.
(a): 1분자 중에 (메트)아크릴로일옥시기를 적어도 1개 갖는 지환식 (메트)아크릴레이트 화합물(단, (b)성분의 화합물을 제외한다.)(a): An alicyclic (meth)acrylate compound having at least one (meth)acryloyloxy group in one molecule (however, the compound of component (b) is excluded.)
(b): 우레탄(메트)아크릴레이트 화합물 또는 에폭시(메트)아크릴레이트 화합물(b): Urethane (meth)acrylate compound or epoxy (meth)acrylate compound
(c): 하기 식(1)로 표시되는 실란 화합물, 또는 이 식(1)로 표시되는 실란 화합물을 포함하는 적어도 1종의 실란 화합물의 가수분해 중축합물(c): Hydrolyzed polycondensate of at least one silane compound comprising a silane compound represented by the following formula (1) or a silane compound represented by this formula (1)
(d): 광라디칼개시제(d): Photo radical initiator
[화학식 1][Formula 1]
(식 중, R1은 수소원자 또는 메틸기를 나타내고, R2는 탄소원자수 1 내지 8의 알킬렌기를 나타내고, R3은 각각 독립적으로 수소원자 또는 탄소원자수 1 내지 4의 알킬기를 나타내고, R4는 탄소원자수 1 내지 4의 알킬기를 나타내고, a는 2 또는 3을 나타낸다.)(In the formula, R 1 represents a hydrogen atom or a methyl group, R 2 represents an alkylene group having 1 to 8 carbon atoms, R 3 each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R 4 is Represents an alkyl group having 1 to 4 carbon atoms, and a represents 2 or 3.)
상기 지환식 (메트)아크릴레이트 화합물이, 1분자 중에 (메트)아크릴로일옥시기를 예를 들어 1개 또는 2개 갖는다.The alicyclic (meth)acrylate compound has, for example, one or two (meth)acryloyloxy groups in one molecule.
상기 가수분해 중축합물이, 예를 들어, 하기 식(1a)로 표시되는 구조단위 또는 하기 식(1b)로 표시되는 구조단위를 갖는 오르가노폴리실록산이다.The hydrolyzed polycondensate is, for example, an organopolysiloxane having a structural unit represented by the following formula (1a) or a structural unit represented by the following formula (1b).
[화학식 2][Formula 2]
(식 중, R1, R2 및 R4는 상기 식(1)에 있어서의 정의와 동의이다.)(In the formula, R 1 , R 2 and R 4 are the same as the definition in the formula (1).)
상기 (c)성분이, 상기 식(1)로 표시되는 실란 화합물과 하기 식(2)로 표시되는 실란 화합물을 포함하는 적어도 2종의 실란 화합물의 가수분해 중축합물일 수도 있다.The component (c) may be a hydrolysis-condensation product of at least two silane compounds comprising a silane compound represented by the formula (1) and a silane compound represented by the following formula (2).
[화학식 3][Formula 3]
(식 중, Rf는 탄소원자수 1 내지 12의 플루오로알킬기를 나타내고, R5는 각각 독립적으로 수소원자 또는 탄소원자수 1 내지 4의 알킬기를 나타내고, R6은 탄소원자수 1 내지 4의 알킬기를 나타내고, b는 2 또는 3을 나타낸다.)(Wherein, Rf represents a fluoroalkyl group having 1 to 12 carbon atoms, R 5 each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R 6 represents an alkyl group having 1 to 4 carbon atoms, b represents 2 or 3.)
상기 식(2)에 있어서 Rf가, 예를 들어, 하기 식(3)으로 표시되는 기이다.In the formula (2), Rf is, for example, a group represented by the following formula (3).
[화학식 4][Formula 4]
(식 중, Y는 수소원자 또는 불소원자를 나타내고, c는 0 내지 2의 정수를 나타내고, d는 1 내지 6의 정수를 나타내고, *은 규소원자와의 결합손(結合手)을 나타낸다.)(In the formula, Y represents a hydrogen atom or a fluorine atom, c represents an integer from 0 to 2, d represents an integer from 1 to 6, and * represents a bond with a silicon atom.)
상기 가수분해 중축합물이, 예를 들어, 하기 식(1a)로 표시되는 구조단위 및 하기 식(2a)로 표시되는 구조단위를 갖는 오르가노폴리실록산, 또는 하기 식(1b)로 표시되는 구조단위 및 하기 식(2b)로 표시되는 구조단위를 갖는 오르가노폴리실록산이다.The hydrolysis-condensation product, for example, an organopolysiloxane having a structural unit represented by the following formula (1a) and a structural unit represented by the following formula (2a), or a structural unit represented by the following formula (1b), and It is an organopolysiloxane having a structural unit represented by the following formula (2b).
[화학식 5][Formula 5]
(식 중, R1, R2 및 R4는 상기 식(1)에 있어서의 정의와 동의이고, R6 및 Rf는 상기 식(2)에 있어서의 정의와 동의이다.)(Wherein, R 1 , R 2 and R 4 are synonymous with the definition in the formula (1), and R 6 and Rf are synonymous with the definition in the formula (2).)
본 발명의 임프린트용 광경화성 조성물은 추가로, 상기 (a)성분, 상기 (b)성분 및 상기 (c)성분의 합 100질량부에 대해 0.05질량부 내지 3질량부의 하기 (e)성분 및/또는 상기 (a)성분, 상기 (b)성분 및 상기 (c)성분의 합 100질량부에 대해 0.1질량부 내지 3질량부의 하기 (f)성분을 함유할 수도 있다.The photocurable composition for imprints of the present invention further comprises: 0.05 parts by mass to 3 parts by mass of the following components (e) and/or 100 parts by mass of the components (a), (b) and (c). Alternatively, the following components (f) may be contained in an amount of 0.1 to 3 parts by mass based on 100 parts by mass of the components (a), (b) and (c).
(e): 페놀계 산화방지제(e): Phenolic antioxidant
(f): 설파이드계 산화방지제(f): sulfide-based antioxidant
본 발명의 임프린트용 광경화성 조성물은 추가로, 상기 (a)성분, 상기 (b)성분 및 상기 (c)성분의 합 100질량부에 대해, 1질량부 내지 20질량부의 하기 (g)성분을 함유할 수도 있다.The photocurable composition for imprints of the present invention further comprises 1 part by mass to 20 parts by mass of the following (g) component based on 100 parts by mass of the components (a), (b), and (c). It may contain.
(g): 하기 식(4)로 표시되는 다관능티올 화합물(g): Multifunctional thiol compound represented by the following formula (4)
[화학식 6][Formula 6]
(식 중, R7은 단결합 또는 탄소원자수 1 내지 6의 직쇄상 혹은 분지쇄상의 알킬렌기를 나타내고, X는 단결합 또는 에스테르결합을 나타내고, A는 헤테로원자를 적어도 1개 포함하거나 혹은 헤테로원자를 포함하지 않는 탄소원자수 2 내지 12의 유기기 또는 헤테로원자를 나타내고, r1은 2 내지 6의 정수를 나타낸다.)(Wherein, R 7 represents a single bond or a linear or branched alkylene group having 1 to 6 carbon atoms, X represents a single bond or an ester bond, and A contains at least one heteroatom or a heteroatom. Represents an organic group or a hetero atom having 2 to 12 carbon atoms, and r 1 represents an integer of 2 to 6.)
본 발명의 임프린트용 광경화성 조성물은, 그의 경화물의 파장 589nm에 있어서의 굴절률nD가 1.48 이상 1.55 이하이고, 또한 이 경화물의 아베수νD가 53 이상 60 이하이다.In the photocurable composition for imprints of the present invention, the refractive index n D of the cured product at a wavelength of 589 nm is 1.48 or more and 1.55 or less, and the Abbe number ν D of this cured product is 53 or more and 60 or less.
본 발명의 제2 태양은, 상기 임프린트용 광경화성 조성물의 경화물이다.The 2nd aspect of this invention is a hardened|cured material of the said photocurable composition for imprints.
본 발명에 제3 태양은, 상기 임프린트용 광경화성 조성물을 임프린트성형하는 공정을 포함하는, 수지렌즈의 제조방법이다.A third aspect of the present invention is a method of manufacturing a resin lens comprising a step of imprinting the photocurable composition for imprinting.
본 발명의 제4 태양은, 임프린트용 광경화성 조성물의 성형체의 제조방법으로서, 상기 임프린트용 광경화성 조성물을, 맞닿은(接し合う) 지지체와 주형 사이의 공간, 또는 분할가능한 주형의 내부의 공간에 충전하는 공정, 및 이 공간에 충전된 임프린트용 광경화성 조성물을 노광하여 광경화하는 공정을 포함하는, 성형체의 제조방법이다. 상기 주형은 몰드라고도 칭한다.A fourth aspect of the present invention is a method of manufacturing a molded body of a photocurable composition for imprint, wherein the photocurable composition for imprint is filled in a space between a support and a mold that is in contact with each other, or a space inside a dividable mold. And a step of exposing and photocuring the photocurable composition for imprint filled in the space. The mold is also referred to as a mold.
본 발명의 성형체의 제조방법에 있어서, 상기 광경화하는 공정의 후, 얻어진 광경화물을 취출하여 이형하는 공정, 그리고, 이 광경화물을, 이 이형하는 공정의 전, 중도 또는 후에 있어서 가열하는 공정을 추가로 포함할 수도 있다.In the manufacturing method of the molded article of the present invention, after the photocuring step, a step of taking out and releasing the obtained photocured product, and a step of heating the photocured product before, during, or after the step of releasing the photocured product It may further include.
본 발명의 성형체의 제조방법에 있어서, 이 성형체는, 예를 들어 카메라모듈용 렌즈이다.In the manufacturing method of the molded object of this invention, this molded object is a lens for camera modules, for example.
본 발명의 임프린트용 광경화성 조성물은, 상기 (a)성분 내지 상기 (d)성분을 포함하며, 추가로 임의로, 상기 (e)성분 및/또는 상기 (f)성분, 그리고 상기 (g)성분을 포함하므로, 이 광경화성 조성물로부터 얻어지는 경화물 및 성형체가, 광학디바이스, 예를 들어, 고해상도 카메라모듈용의 렌즈로서 바람직한 광학특성, 즉 고아베수, 고굴절률, 고투명성 및 내열황변성을 나타낸다. 또한, 상기 경화물 및 성형체가 형성된 지지체의 휨량이 매우 작고(0μm 이상 1.5μm 미만), 또한 175℃에서의 열처리에 의해 이 경화물 및 성형체의 상층의 반사방지층에 크랙이 발생하지 않는다.The photocurable composition for imprints of the present invention includes the components (a) to (d), and further optionally, the components (e) and/or the components (f) and (g). Since it contains, the cured product and molded product obtained from this photocurable composition exhibit optical properties desirable as an optical device, for example, a lens for a high-resolution camera module, that is, high Abbe number, high refractive index, high transparency, and heat yellowing resistance. In addition, the cured product and the molded body have a very small amount of warpage (0 µm or more and less than 1.5 µm), and no cracks are generated in the antireflection layer of the cured product and the molded body by heat treatment at 175°C.
도 1은 유리기판의 휨량의 평가방법을 나타내는 모식도이다.1 is a schematic view showing a method for evaluating a warpage amount of a glass substrate.
[(a)성분: 지환식 (메트)아크릴레이트 화합물][(a) component: alicyclic (meth)acrylate compound]
본 발명의 임프린트용 광경화성 조성물의 (a)성분으로서 사용가능한 지환식 (메트)아크릴레이트 화합물은, 1분자 중에 (메트)아크릴로일옥시기를 적어도 1개 및 지환식 탄화수소기를 1개 가지며, 또한 후술하는 (b)성분의 화합물을 제외하는 것이다. 이 지환식 (메트)아크릴레이트 화합물로서, 예를 들어, 시클로펜틸(메트)아크릴레이트, 시클로헥실(메트)아크릴레이트, 3,3,5-트리메틸시클로헥실(메트)아크릴레이트, 4-tert-부틸시클로헥실(메트)아크릴레이트, 멘틸(메트)아크릴레이트, 이소보닐(메트)아크릴레이트, 노보닐(메트)아크릴레이트, 1-아다만틸(메트)아크릴레이트, 2-아다만틸(메트)아크릴레이트, 2-메틸아다만탄-2-일(메트)아크릴레이트, 2-에틸아다만탄-2-일(메트)아크릴레이트, 1,3-아다만탄디올디(메트)아크릴레이트, 트리시클로[5.2.1.0(2,6)]데카닐(메트)아크릴레이트, 트리시클로[5.2.1.0(2,6)]데카닐옥시에틸(메트)아크릴레이트, 1,4-시클로헥산디메탄올디(메트)아크릴레이트, 트리시클로[5.2.1.0(2,6)]데칸디메탄올디(메트)아크릴레이트, 및 1,3-아다만탄디올디(메트)아크릴레이트를 들 수 있다.The alicyclic (meth)acrylate compound that can be used as the component (a) of the photocurable composition for imprints of the present invention has at least one (meth)acryloyloxy group and one alicyclic hydrocarbon group in one molecule, and It excludes the compound of (b) component mentioned later. As this alicyclic (meth)acrylate compound, for example, cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, 3,3,5-trimethylcyclohexyl (meth)acrylate, 4-tert- Butylcyclohexyl (meth)acrylate, menthyl (meth)acrylate, isobornyl (meth)acrylate, norbornyl (meth)acrylate, 1-adamantyl (meth)acrylate, 2-adamantyl (meth) )Acrylate, 2-methyladamantan-2-yl(meth)acrylate, 2-ethyladamantan-2-yl(meth)acrylate, 1,3-adamantanedioldi(meth)acrylate , Tricyclo[5.2.1.0(2,6)]decanyl(meth)acrylate, tricyclo[5.2.1.0(2,6)]decanyloxyethyl(meth)acrylate, 1,4-cyclohexanedi Methanol di(meth)acrylate, tricyclo[5.2.1.0(2,6)]decane dimethanol di(meth)acrylate, and 1,3-adamantanediol di(meth)acrylate.
상기 지환식 (메트)아크릴레이트 화합물로서 시판품을 이용할 수도 있고, 예를 들어, 비스코트#155, IBXA, ADMA(이상, 오사카유기화학공업(주)제), NK에스테르A-IB, 동(同) IB, 동 A-DCP, 동 DCP(이상, 신나카무라화학공업(주)제), 및 판크릴(등록상표) FA-511AS, 동 FA-512AS, 동 FA-513AS, 동 FA-512M, 동 FA-512MT, 동 FA-513M(이상, 히타치화성(주)제)을 들 수 있다.Commercially available products can also be used as the alicyclic (meth)acrylate compound, for example, BisCoat #155, IBXA, ADMA (above, manufactured by Osaka Organic Chemical Industry Co., Ltd.), NK Ester A-IB, Copper (identical) ) IB, copper A-DCP, copper DCP (above, manufactured by Shin-Nakamura Chemical Co., Ltd.), and Pancryl (registered trademark) FA-511AS, copper FA-512AS, copper FA-513AS, copper FA-512M, copper FA-512MT, copper FA-513M (above, Hitachi Chemical Co., Ltd. product) are mentioned.
상기 (a)성분의 지환식 (메트)아크릴레이트 화합물은, 1종 단독으로 또는 2종 이상을 조합하여 사용할 수 있다.The alicyclic (meth)acrylate compound of the component (a) can be used alone or in combination of two or more.
[(b)성분: 우레탄(메트)아크릴레이트 화합물 또는 에폭시(메트)아크릴레이트 화합물][(b) component: urethane (meth)acrylate compound or epoxy (meth)acrylate compound]
본 발명의 임프린트용 광경화성 조성물의 (b)성분으로서 사용가능한 우레탄(메트)아크릴레이트 화합물은, 1분자 중에 (메트)아크릴로일옥시기를 적어도 2개 및 “-NH-C(=O)O-”로 표시되는 우레탄구조를 적어도 2개 갖는 화합물이다. 이 우레탄(메트)아크릴레이트 화합물로서, 예를 들어, EBECRYL(등록상표) 230, 동 270, 동 280/15IB, 동 284, 동 4491, 동 4683, 동 4858, 동 8307, 동 8402, 동 8411, 동 8804, 동 8807, 동 9270, 동 8800, 동 294/25HD, 동 4100, 동 4220, 동 4513, 동 4738, 동 4740, 동 4820, 동 8311, 동 8465, 동 9260, 동 8701, KRM7735, 동 8667, 동 8296(이상, 다이셀·올넥스(주)제), 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(이상, 일본합성화학(주)제), UA-306H, UA-306T, UA-306I, UA-510H, UF-8001G(이상, 공영사화학(주)제), M-1100, M-1200(이상, 동아합성(주)제), 및 NK올리고 U-2PPA, 동 U-6LPA, 동 U-200PA, U-200PA, 동 U-160TM, 동 U-290TM, 동 UA-4200, 동 UA-4400, 동 UA-122P, 동 UA-7100, 동 UA-W2A(이상, 신나카무라화학공업(주)제)를 들 수 있다.The urethane (meth)acrylate compound that can be used as the component (b) of the photocurable composition for imprints of the present invention contains at least two (meth)acryloyloxy groups in one molecule and “-NH-C(=O)O. -” is a compound having at least two urethane structures. As this urethane (meth)acrylate compound, for example, EBECRYL (trademark) 230, copper 270, copper 280/15IB, copper 284, copper 4491, copper 4683, copper 4858, copper 8307, copper 8402, copper 8411, East 8804, East 8807, East 9270, East 8800, East 294/25HD, East 4100, East 4220, East 4513, East 4738, East 4740, East 4820, East 8311, East 8465, East 9260, East 8701, KRM7735, East 8667, Copper 8296 (above, manufactured by Daicel Allnex), 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 (above, manufactured by Japan Synthetic Chemical Co., Ltd.), UA-306H, UA-306T, UA-306I , UA-510H, UF-8001G (above, manufactured by Gongyoung Chemical Co., Ltd.), M-1100, M-1200 (above, manufactured by Dong-A Synthetic Co., Ltd.), and NK Oligo U-2PPA, copper U-6LPA, Copper U-200PA, Copper U-200PA, Copper U-160TM, Copper U-290TM, Copper UA-4200, Copper UA-4400, Copper UA-122P, Copper UA-7100, Copper UA-W2A (above, Shin-Nakamura Chemical Industry And manufactured by Co., Ltd.).
본 발명의 임프린트용 광경화성 조성물의 (b)성분으로서 사용가능한 에폭시(메트)아크릴레이트 화합물은, 1분자 중에 에폭시환을 적어도 2개 갖는 화합물과 (메트)아크릴산을 반응시킨 에스테르이다. 이 에폭시(메트)아크릴레이트 화합물로서, 예를 들어, EBECRYL(등록상표) 645, 동 648, 동 860, 동 3500, 동 3608, 동 3702, 동 3708(이상, 다이셀·올넥스(주)제), DA-911M, DA-920, DA-931, DA-314, DA-212(이상, 나가세켐텍스(주)제), HPEA-100(케이에스엠(주)제), 및 유니딕(등록상표) V-5500, 동 V-5502, 동 V-5508(DIC(주)제)을 들 수 있다.The epoxy (meth)acrylate compound which can be used as the component (b) of the photocurable composition for imprints of the present invention is an ester obtained by reacting a compound having at least two epoxy rings in one molecule and (meth)acrylic acid. As the epoxy (meth)acrylate compound, for example, EBECRYL (registered trademark) 645, copper 648, copper 860, copper 3500, copper 3608, copper 3702, copper 3708 (above, manufactured by Daicel Allnex Co., Ltd.) ), DA-911M, DA-920, DA-931, DA-314, DA-212 (above, manufactured by Nagase Chemtex Co., Ltd.), HPEA-100 (manufactured by KSM Co., Ltd.), and Unidic (registered) Trademark) V-5500, copper V-5502, copper V-5508 (made by DIC Corporation).
본 발명의 임프린트용 광경화성 조성물의 (b)성분의 함유량은, 상기 (a)성분 및 이 (b)성분의 합 100질량부에 대해, 30질량부 내지 90질량부, 바람직하게는 50질량부 내지 90질량부이다. 이 (b)성분의 함유량이 30질량부보다 적으면, 상기 임프린트용 광경화성 조성물로부터 얻어진 경화물 및 성형체가 형성된 지지체의 휨이 증가할 우려가 있다. 또한 이 (b)성분의 함유량이 90질량부보다 많으면, 이 임프린트용 광경화성 조성물로부터 얻어진 경화물 및 성형체의 굴절률이 1.48 미만으로 저하될 우려가 있다.The content of the component (b) of the photocurable composition for imprint of the present invention is 30 parts by mass to 90 parts by mass, preferably 50 parts by mass with respect to 100 parts by mass of the component (a) and the component (b). To 90 parts by mass. When the content of the component (b) is less than 30 parts by mass, there is a fear that the cured product obtained from the photocurable composition for imprint and the support body on which the molded body is formed increases. Moreover, when content of this (b) component is more than 90 mass parts, there exists a possibility that the refractive index of the hardened|cured material and molded object obtained from this photocurable composition for imprints may fall to less than 1.48.
상기 (b)성분의 우레탄(메트)아크릴레이트 화합물 또는 에폭시(메트)아크릴레이트 화합물은, 1종 단독으로 또는 2종 이상을 조합하여 사용할 수 있다.The urethane (meth)acrylate compound or the epoxy (meth)acrylate compound of the component (b) may be used alone or in combination of two or more.
[(c)성분: 실란 화합물, 또는 이 실란 화합물을 포함하는 적어도 1종의 실란 화합물의 가수분해 중축합물][Component (c): a silane compound, or a hydrolysis polycondensate of at least one silane compound containing the silane compound]
본 발명의 임프린트용 광경화성 조성물의 (c)성분으로서 사용가능한 실란 화합물은, (메트)아크릴로일옥시기를 갖는 상기 식(1)로 표시되는 실란 화합물이다. 이 식(1)로 표시되는 실란 화합물로서, 예를 들어, (메트)아크릴로일옥시프로필트리메톡시실란, (메트)아크릴로일옥시프로필트리에톡시실란, (메트)아크릴로일옥시옥틸트리메톡시실란, (메트)아크릴로일옥시옥틸트리에톡시실란, (메트)아크릴로일옥시프로필메틸디메톡시실란, 및 (메트)아크릴로일옥시프로필메틸디에톡시실란을 들 수 있다.The silane compound that can be used as the component (c) of the photocurable composition for imprints of the present invention is a silane compound represented by the formula (1) having a (meth)acryloyloxy group. As a silane compound represented by this formula (1), for example, (meth)acryloyloxypropyl trimethoxysilane, (meth)acryloyloxypropyl triethoxysilane, (meth)acryloyloxyox Tiltrimethoxysilane, (meth)acryloyloxyoctyltriethoxysilane, (meth)acryloyloxypropylmethyldimethoxysilane, and (meth)acryloyloxypropylmethyldiethoxysilane.
본 발명의 임프린트용 광경화성 조성물의 (c)성분으로서 사용가능한 가수분해 중축합물은, 상기 식(1)로 표시되는 실란 화합물의 가수분해 중축합물, 플루오로알킬기를 갖는 상기 식(2)로 표시되는 실란 화합물과 이 식(1)로 표시되는 실란 화합물과의 가수분해 중축합물, 이 식(2)로 표시되는 실란 화합물과 이 식(1)로 표시되는 실란 화합물과 기타 실란 화합물과의 가수분해 중축합물, 또는 이 식(1)로 표시되는 실란 화합물과 이 기타 실란 화합물과의 가수분해 중축합물이다. 이 식(2)로 표시되는 실란 화합물로서, 예를 들어, 3,3,3-트리플루오로프로필트리메톡시실란, 3,3,3-트리플루오로프로필메틸디메톡시실란, 3,3,3-트리플루오로프로필트리에톡시실란, 3,3,3-트리플루오로프로필메틸디에톡시실란, 트리메톡시(1H,1H,2H,2H-노나플루오로헥실)실란, 메틸디메톡시(1H,1H,2H,2H-노나플루오로헥실)실란, 트리에톡시(1H,1H,2H,2H-노나플루오로헥실)실란, 메틸디에톡시(1H,1H,2H,2H-노나플루오로헥실)실란, 트리메톡시(1H,1H,2H,2H-트리데카플루오로-n-옥틸)실란, 및 트리에톡시(1H,1H,2H,2H-트리데카플루오로-n-옥틸)실란을 들 수 있다. 상기 기타 실란 화합물은, 상기 식(1)로 표시되는 실란 화합물, 상기 식(2)로 표시되는 실란 화합물의 어느 것에도 해당하지 않는 실란 화합물이다. 이 기타 실란 화합물로서, 예를 들어, 메틸트리메톡시실란, 메틸트리에톡시실란, 에틸트리메톡시실란, 에틸트리에톡시실란, n-프로필트리메톡시실란, n-프로필트리에톡시실란, n-헥실트리메톡시실란, n-헥실트리에톡시실란, n-옥틸트리메톡시실란, n-옥틸트리에톡시실란, 테트라메톡시실란, 및 테트라에톡시실란을 들 수 있다.The hydrolysis polycondensate usable as the component (c) of the photocurable composition for imprints of the present invention is represented by the formula (2) having a hydrolysis polycondensation product of the silane compound represented by the formula (1) and a fluoroalkyl group. Hydrolysis of silane compound represented by this formula (1) and silane compound represented by this formula (1), Hydrolysis of silane compound represented by this formula (2) and silane compound represented by this formula (1), and other silane compounds It is a polycondensation product or a hydrolysis polycondensation product of the silane compound represented by this formula (1) with this other silane compound. As the silane compound represented by the formula (2), for example, 3,3,3-trifluoropropyltrimethoxysilane, 3,3,3-trifluoropropylmethyldimethoxysilane, 3,3, 3-trifluoropropyltriethoxysilane, 3,3,3-trifluoropropylmethyldiethoxysilane, trimethoxy(1H,1H,2H,2H-nonafluorohexyl)silane, methyldimethoxy(1H ,1H,2H,2H-nonafluorohexyl)silane, triethoxy(1H,1H,2H,2H-nonafluorohexyl)silane, methyldiethoxy(1H,1H,2H,2H-nonafluorohexyl) Silane, trimethoxy(1H,1H,2H,2H-tridecafluoro-n-octyl)silane, and triethoxy(1H,1H,2H,2H-tridecafluoro-n-octyl)silane Can be. The said other silane compound is a silane compound which does not correspond to either of the silane compound represented by said formula (1) and the silane compound represented by said formula (2). As this other silane compound, for example, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, and n-hexyltrimethoxysilane, n-hexyltriethoxysilane, n-octyltrimethoxysilane, n-octyltriethoxysilane, tetramethoxysilane, and tetraethoxysilane.
본 발명의 임프린트용 광경화성 조성물의 (c)성분의 함유량은, 상기 (a)성분 및 상기 (b)성분의 합 100질량부에 대해 1질량부 내지 100질량부, 바람직하게는 5질량부 내지 80질량부이다. 이 (c)성분의 함유량이 1질량부보다 적으면, 상기 임프린트용 광경화성 조성물로부터 얻어지는 경화물 및 성형체의 상층의 반사방지층은 열처리에 의해 크랙이 발생한다. 또한 이 (c)성분의 함유량이 100질량부보다 많으면, 이 임프린트용 광경화성 조성물로부터 얻어지는 경화물 및 성형체는, 굴절률이 저하되므로, 고해상도 카메라모듈용 렌즈에는 적합하지 않다.The content of the component (c) of the photocurable composition for imprint of the present invention is 1 part by mass to 100 parts by mass, preferably 5 parts by mass to 100 parts by mass of the sum of the components (a) and (b) 80 parts by mass. When the content of the component (c) is less than 1 part by mass, the antireflection layer of the cured product obtained from the photocurable composition for imprint and the upper layer of the molded body is cracked by heat treatment. In addition, when the content of the component (c) is more than 100 parts by mass, the cured product and the molded product obtained from the photocurable composition for imprint are not suitable for a lens for a high-resolution camera module because the refractive index decreases.
상기 (c)성분의 실란 화합물 또는 가수분해 중축합물은, 1종 단독으로 또는 2종 이상을 조합하여 사용할 수 있다.The silane compound or hydrolysis polycondensate of the component (c) can be used alone or in combination of two or more.
[(d)성분: 광라디칼개시제][(d) Ingredient: Photo radical initiator]
본 발명의 임프린트용 광경화성 조성물의 (d)성분으로서 사용가능한 광라디칼개시제로서, 예를 들어, 알킬페논류, 벤조페논류, 미힐러(Michler)의 케톤류, 아실포스핀옥사이드류, 벤조일벤조에이트류, 옥심에스테르류, 테트라메틸티우람모노설파이드류 및 티옥산톤류를 들 수 있고, 특히, 광개열형의 광라디칼중합개시제가 바람직하다. 상기 광라디칼개시제로서 시판품, 예를 들어, IRGACURE(등록상표) 184, 동 369, 동 651, 동 500, 동 819, 동 907, 동 784, 동 2959, 동 CGI1700, 동 CGI1750, 동 CGI1850, 동 CG24-61, 동 TPO, 동 1116, 동 1173(이상, BASF재팬(주)제), 및 ESACURE KIP150, 동 KIP65LT, 동 KIP100F, 동 KT37, 동 KT55, 동 KTO46, 동 KIP75(이상, Lamberti사제)를 채용할 수 있다.As a photo radical initiator usable as the component (d) of the photocurable composition for imprint of the present invention, for example, alkylphenones, benzophenones, Michler's ketones, acylphosphine oxides, benzoylbenzoate And oxime esters, tetramethylthiuram monosulfides, and thioxanthones. Particularly preferred is a photo-thermal photo-radical polymerization initiator. Commercially available products as the photo-radical initiator, for example, IRGACURE (registered trademark) 184, copper 369, copper 651, copper 500, copper 819, copper 907, copper 784, copper 2959, copper CGI1700, copper CGI1750, copper CGI1850, copper CG24 -61, Copper TPO, Copper 1116, Copper 1173 (above, BASF Japan Co., Ltd.), and ESACURE KIP150, Copper KIP65LT, Copper KIP100F, Copper KT37, Copper KT55, Copper KTO46, Copper KIP75 (above, manufactured by Lamberti) Can be employed.
본 발명의 임프린트용 광경화성 조성물의 (d)성분의 함유량은, 상기 (a)성분, 상기 (b)성분 및 상기 (c)성분의 합 100질량부에 대해 0.1질량부 내지 5질량부, 바람직하게는 0.5질량부 내지 3질량부이다. 이 (d)성분의 함유량이 0.1질량부보다 적으면, 상기 임프린트용 광경화성 조성물로부터 얻어지는 경화물 및 성형체의 강도가 저하될 우려가 있다. 또한 이 (d)성분의 함유량이 5질량부보다 많으면, 이 임프린트용 광경화성 조성물로부터 얻어지는 경화물 및 성형체의 내열황변성이 악화될 우려가 있다.The content of the component (d) of the photocurable composition for imprint of the present invention is preferably 0.1 parts by mass to 5 parts by mass, based on 100 parts by mass of the components (a), (b), and (c). It is 0.5 to 3 parts by mass. When the content of the component (d) is less than 0.1 parts by mass, the strength of the cured product and the molded body obtained from the photocurable composition for imprint may be lowered. Moreover, when content of this (d) component is more than 5 mass parts, there exists a possibility that the heat-resistant yellowing property of the hardened|cured material and molded object obtained from this photocurable composition for imprinting may deteriorate.
상기 (d)성분의 광라디칼개시제는, 1종 단독으로 또는 2종 이상을 조합하여 사용할 수 있다.The photoradical initiator of the component (d) can be used alone or in combination of two or more.
[(e)성분: 페놀계 산화방지제][(e) Ingredient: Phenolic antioxidant]
본 발명의 임프린트용 광경화성 조성물의 (e)성분으로서 사용가능한 페놀계 산화방지제로서, 예를 들어, IRGANOX(등록상표) 245, 동 1010, 동 1035, 동 1076, 동 1135(이상, BASF재팬(주)제), SUMILIZER(등록상표) GA-80, 동 GP, 동 MDP-S, 동 BBM-S, 동 WX-R(이상, 스미토모화학(주)제), 및 아데카스타브(등록상표) AO-20, 동 AO-30, 동 AO-40, 동 AO-50, 동 AO-60, 동 AO-80, 동 AO-330(이상, (주)ADEKA제)을 들 수 있다.As a phenolic antioxidant which can be used as component (e) of the photocurable composition for imprints of the present invention, for example, IRGANOX (registered trademark) 245, copper 1010, copper 1035, copper 1076, copper 1135 (above, BASF Japan ( Note), SUMILIZER (registered trademark) GA-80, copper GP, copper MDP-S, copper BBM-S, copper WX-R (above, Sumitomo Chemical Co., Ltd.), and Adekastab (registered trademark) And AO-20, copper AO-30, copper AO-40, copper AO-50, copper AO-60, copper AO-80 and copper AO-330 (above, manufactured by ADEKA Corporation).
본 발명의 임프린트용 광경화성 조성물의 (e)성분의 함유량은, 상기 (a)성분, 상기 (b)성분 및 상기 (c)성분의 합 100질량부에 대해, 0.05질량부 내지 3질량부, 바람직하게는 0.1질량부 내지 1질량부이다.Content of (e) component of the photocurable composition for imprint of this invention is 0.05 mass part-3 mass parts with respect to 100 mass parts of sum of said (a) component, said (b) component, and said (c) component, It is preferably 0.1 parts by mass to 1 part by mass.
상기 (e)성분의 페놀계 산화방지제는, 1종 단독으로 또는 2종 이상을 조합하여 사용할 수 있다.The phenolic antioxidant of the component (e) may be used alone or in combination of two or more.
[(f)성분: 설파이드계 산화방지제][(f) Ingredient: sulfide-based antioxidant]
본 발명의 임프린트용 광경화성 조성물의 (f)성분으로서 사용가능한 설파이드계 산화방지제로서, 예를 들어, 아데카스타브(등록상표) AO-412S, 동 AO-503(이상, (주)ADEKA제), IRGANOX(등록상표) PS802, 동 PS800(이상, BASF재팬(주)제), 및 SUMILIZER(등록상표) TP-D(스미토모화학(주)제)를 들 수 있다.As a sulfide-based antioxidant that can be used as the component (f) of the photocurable composition for imprints of the present invention, for example, Adekastab (registered trademark) AO-412S, copper AO-503 (above, manufactured by ADEKA Corporation) , IRGANOX (registered trademark) PS802, copper PS800 (above, BASF Japan Co., Ltd.), and SUMILIZER (registered trademark) TP-D (Sumitomo Chemical Co., Ltd.).
본 발명의 임프린트용 광경화성 조성물의 (f)성분의 함유량은, 상기 (a)성분, 상기 (b)성분 및 상기 (c)성분의 합 100질량부에 대해, 0.1질량부 내지 3질량부, 바람직하게는 0.1질량부 내지 1질량부이다.The content of the component (f) of the photocurable composition for imprint of the present invention is 0.1 parts by mass to 3 parts by mass, based on 100 parts by mass of the components (a), (b), and (c). It is preferably 0.1 parts by mass to 1 part by mass.
상기 (f)성분의 설파이드계 산화방지제는, 1종 단독으로 또는 2종 이상을 조합하여 사용할 수 있다.The sulfide-based antioxidant of the component (f) may be used alone or in combination of two or more.
본 발명의 임프린트용 광경화성 조성물은, 상기 (e)성분 및 상기 (f)성분 중 어느 일방을 함유하고 있으면 되는데, 양방을 함유할 수도 있다. 이 (e)성분 및/또는 이 (f)성분의 함유량이 상기 범위의 하한값보다 적으면, 열처리를 수반하는 실장프로세스 전후로, 상기 광경화성 조성물로부터 얻어지는 경화물 및 성형체의 투과율이 변화할 우려가 있다. 또한 이 (e)성분 및/또는 이 (f)성분의 함유량이 상기 범위의 상한값보다 많으면, 이 광경화성 조성물로부터 얻어지는 경화물 및 성형체는 취화(脆化)되고, 또한 사용환경에서 태양광 등의 강한 광에 노출될 때에 녹색으로 변색될 우려가 있다.The photocurable composition for imprints of the present invention may contain either one of the components (e) and (f), but may also contain both. When the content of the component (e) and/or the component (f) is less than the lower limit of the range, the transmittance of the cured product and the molded body obtained from the photocurable composition may change before and after the mounting process involving heat treatment. . In addition, when the content of the component (e) and/or the component (f) is greater than the upper limit of the above range, the cured product and molded product obtained from the photocurable composition become embrittled, and in the use environment, such as sunlight. When exposed to strong light, there is a risk of discoloration to green.
[(g)성분: 다관능티올 화합물][(g) component: polyfunctional thiol compound]
본 발명의 임프린트용 광경화성 조성물의 (g)성분으로서 사용가능한 다관능티올 화합물은, 상기 식(4)로 표시되는 다관능티올 화합물이다. 이 식(4)로 표시되는 다관능티올 화합물로서, 예를 들어, 1,2-에탄디티올, 1,3-프로판디티올, 비스(2-메르캅토에틸)에테르, 트리메틸올프로판트리스(3-메르캅토프로피오네이트), 트리스-[(3-메르캅토프로피오닐옥시)-에틸]-이소시아누레이트, 테트라에틸렌글리콜비스(3-메르캅토프로피오네이트), 디펜타에리스리톨헥사키스(3-메르캅토프로피오네이트), 펜타에리스리톨테트라키스(3-메르캅토부티레이트), 1,4-비스(3-메르캅토부티릴옥시)부탄, 1,3,5-트리스(3-메르캅토부티릴옥시에틸)-1,3,5-트리아진-2,4,6-(1H,3H,5H)-트리온, 트리메틸올프로판트리스(3-메르캅토부티레이트), 및 트리메틸올에탄트리스(3-메르캅토부티레이트), 펜타에리스리톨트리스(3-메르캅토프로필)에테르를 들 수 있다. 상기 식(4)로 표시되는 다관능티올 화합물로서, 시판품, 예를 들어, 카렌즈MT(등록상표) PE1, 동 NR1, 동 BD1, TPMB, TEMB(이상, 쇼와덴코(주)제), 및 TMMP, TEMPIC, PEMP, EGMP-4, DPMP, TMMP II-20P, PEMP II-20P, PEPT(이상, SC유기화학(주)제)를 채용할 수 있다.The polyfunctional thiol compound which can be used as the component (g) of the photocurable composition for imprint of the present invention is a polyfunctional thiol compound represented by the formula (4). As a polyfunctional thiol compound represented by this formula (4), for example, 1,2-ethanedithiol, 1,3-propanedithiol, bis(2-mercaptoethyl) ether, trimethylolpropane tris (3 -Mercaptopropionate), tris-[(3-mercaptopropionyloxy)-ethyl]-isocyanurate, tetraethylene glycol bis(3-mercaptopropionate), dipentaerythritolhexakis(3 -Mercaptopropionate), pentaerythritol tetrakis (3-mercaptobutyrate), 1,4-bis (3-mercaptobutyryloxy) butane, 1,3,5-tris (3-mercaptobutyryl) Oxyethyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, trimethylolpropane tris (3-mercaptobutyrate), and trimethylol ethane tris (3- Mercaptobutyrate) and pentaerythritol tris (3-mercaptopropyl) ether. As a polyfunctional thiol compound represented by the formula (4), commercially available products, for example, Carens MT (registered trademark) PE1, copper NR1, copper BD1, TPMB, TEMB (above, Showa Denko Co., Ltd.), And TMMP, TEMPIC, PEMP, EGMP-4, DPMP, TMMP II-20P, PEMP II-20P, PEPT (above, SC Organic Chemical Co., Ltd.) can be employed.
본 발명의 임프린트용 광경화성 조성물의 (g)성분의 함유량은, 상기 (a)성분, 상기 (b)성분 및 상기 (c)성분의 합 100질량부에 대해, 1질량부 내지 25질량부, 바람직하게는 5질량부 내지 15질량부이다. 이 (g)성분의 함유량이 1질량부보다 적으면, 상기 임프린트용 광경화성 조성물로부터 얻어진 경화물 및 성형체가 형성된 지지체의 휨이 커질 우려가 있다. 또한 이 (g)성분의 함유량이 25질량부보다 많으면, 이 임프린트용 광경화성 조성물로부터 얻어진 경화물 및 성형체는 기계특성이 악화되기 때문에, 열처리를 수반하는 실장프로세스에서 이 경화물 및 성형체가 변형될 우려가 있다.Content of (g) component of the photocurable composition for imprints of this invention is 1 mass part-25 mass parts with respect to 100 mass parts of the sum of (a) component, (b) component, and (c) component, It is preferably 5 parts by mass to 15 parts by mass. When the content of the component (g) is less than 1 part by mass, there is a fear that the cured product obtained from the photocurable composition for imprinting and the support body on which the molded body is formed become large. In addition, when the content of the component (g) is more than 25 parts by mass, the cured product and the molded body obtained from the photocurable composition for imprint deteriorate mechanical properties, and thus the cured product and the molded body may be deformed in a mounting process involving heat treatment. I have a concern.
상기 (g)성분의 다관능티올 화합물은, 1종 단독으로 또는 2종 이상을 조합하여 사용할 수 있다.The polyfunctional thiol compound of the component (g) may be used alone or in combination of two or more.
<임프린트용 광경화성 조성물의 조제방법><Preparation method of photocurable composition for imprint>
본 발명의 임프린트용 광경화성 조성물의 조제방법은, 특별히 한정되지 않는다. 조제법으로는, 예를 들어, (a)성분, (b)성분, (c)성분 및 (d)성분, 그리고 필요에 따라 (e)성분 및/또는 (f)성분, 및 (g)성분을 소정의 비율로 혼합하여 혼합하고 균일한 용액으로 하는 방법을 들 수 있다.The preparation method of the photocurable composition for imprints of this invention is not specifically limited. As a preparation method, for example, (a) component, (b) component, (c) component and (d) component, and (e) component and/or (f) component, and (g) component as needed, And a method of mixing at a predetermined ratio to mix and form a uniform solution.
또한, 용액에 조제한 본 발명의 임프린트용 광경화성 조성물은, 구멍직경이 0.1μm 내지 5μm인 필터 등을 이용하여 여과한 후, 사용하는 것이 바람직하다.In addition, the photocurable composition for imprints of the present invention prepared in a solution is preferably used after filtration using a filter having a pore diameter of 0.1 μm to 5 μm.
<경화물><Light cargo>
본 발명의 임프린트용 광경화성 조성물을, 노광(광경화)하여, 경화물을 얻을 수 있으며, 본 발명은 이 경화물도 대상으로 한다. 노광하는 광선으로는, 예를 들어, 자외선, 전자선 및 X선을 들 수 있다. 자외선 조사에 이용하는 광원으로는, 예를 들어, 태양광선, 케미칼램프, 저압수은등, 고압수은등, 메탈할라이드램프, 크세논램프, 및 UV-LED를 사용할 수 있다. 또한, 노광 후, 경화물의 물성을 안정화시키기 위해 포스트베이크를 실시할 수도 있다. 포스트베이크의 방법으로는, 특별히 한정되지 않으나, 통상, 핫플레이트, 오븐 등을 사용하여, 50℃ 내지 260℃, 1분 내지 24시간의 범위에서 행해진다.The photocurable composition for imprint of the present invention can be exposed (photocured) to obtain a cured product, and the present invention also covers the cured product. Examples of the light rays to be exposed include ultraviolet rays, electron beams, and X-rays. As a light source used for ultraviolet irradiation, for example, sunlight, chemical lamp, low pressure mercury lamp, high pressure mercury lamp, metal halide lamp, xenon lamp, and UV-LED can be used. Further, after exposure, post-baking may be performed to stabilize the physical properties of the cured product. The method of post-baking is not particularly limited, but is usually performed in a range of 50°C to 260°C and 1 minute to 24 hours using a hot plate, oven, or the like.
본 발명의 임프린트용 광경화성 조성물을 광경화함으로써 얻어지는 경화물은, 아베수νD가 53 이상으로 높은 것이고, 파장 589nm(D선)에 있어서의 굴절률nD가 1.48 이상이며, 또한, 가열에 의한 황변도 보이지 않는다. 그러므로, 본 발명의 임프린트용 광경화성 조성물은, 수지렌즈 형성용으로서 호적하게 사용할 수 있다.The cured product obtained by photocuring the photocurable composition for imprints of the present invention has an Abbe number ν D of 53 or higher, a refractive index n D at a wavelength of 589 nm (D line) of 1.48 or more, and also by heating. No yellowing is visible. Therefore, the photocurable composition for imprints of the present invention can be suitably used for forming a resin lens.
<성형체><formed body>
본 발명의 임프린트용 광경화성 조성물은, 예를 들어 임프린트성형법을 사용함으로써, 경화물의 형성과 병행하여 각종 성형체를 용이하게 제조할 수 있다. 성형체를 제조하는 방법으로는, 예를 들어 맞닿은 지지체와 주형 사이의 공간, 또는 분할가능한 주형의 내부의 공간에 본 발명의 임프린트용 광경화성 조성물을 충전하는 공정, 이 공간에 충전된 임프린트용 광경화성 조성물을 노광하여 광경화하는 공정, 이 광경화하는 공정에 의해 얻어진 광경화물을 취출하여 이형하는 공정, 그리고, 이 광경화물을, 이 이형하는 공정의 전, 중도 또는 후에 있어서 가열하는 공정을 포함하는 방법을 들 수 있다.The photocurable composition for imprints of the present invention can easily produce various molded articles in parallel with the formation of a cured product, for example, by using an imprint molding method. As a method for manufacturing a molded body, for example, a process of filling the photocurable composition for imprints of the present invention in a space between abutting supports and a mold or an interior space of a dividable mold, the photocurability for imprints filled in this space A step of exposing the composition to photocuring, a step of taking out and releasing the photocured product obtained by the photocuring step, and a step of heating the photocured product before, during, or after the releasing step And a method.
상기 노광하여 광경화하는 공정은, 상기 서술한 경화물을 얻기 위한 조건을 적용하여 실시할 수 있다. 나아가, 상기 광경화물을 가열하는 공정의 조건으로는, 특별히 한정되지 않으나, 통상, 50℃ 내지 260℃, 1분 내지 24시간의 범위에서 적당히 선택된다. 또한, 가열수단으로는, 특별히 한정되지 않으나, 예를 들어, 핫플레이트 및 오븐을 들 수 있다. 이러한 방법에 의해 제조된 성형체는, 카메라모듈용 렌즈로서 호적하게 사용할 수 있다.The step of exposing and photocuring can be carried out by applying the conditions for obtaining the cured product described above. Further, the conditions for the process of heating the photocured product are not particularly limited, but are usually selected suitably in the range of 50°C to 260°C and 1 minute to 24 hours. Moreover, although it does not specifically limit as a heating means, For example, a hot plate and an oven are mentioned. The molded body manufactured by such a method can be suitably used as a lens for a camera module.
실시예Example
이하, 실시예를 들어, 본 발명을 보다 구체적으로 설명하나, 본 발명은 하기의 실시예로 한정되는 것은 아니다. 한편, 하기 실시예 및 비교예에 있어서, 시료의 조제 및 물성의 분석에 이용한 장치 및 조건은, 이하와 같다.Hereinafter, for example, the present invention will be described in more detail, but the present invention is not limited to the following examples. On the other hand, in the following Examples and Comparative Examples, the apparatus and conditions used for preparation of samples and analysis of physical properties are as follows.
(1) 교반탈포기(1) Stirring deaerator
장치: (주)싱키제 자전·공전믹서 아와토리렌타로(등록상표) ARE-310Apparatus: Akitori Rent-a-Rotor (registered trademark) ARE-310
(2) UV노광(2) UV exposure
장치: 아이그래픽스(주)제 배치식 UV조사장치(고압수은등 2kW×1등)Apparatus: Batch-type UV irradiator manufactured by iGraphics Co., Ltd.
(3) 투과율(3) transmittance
장치: 일본분광(주)제 자외가시근적외 분광광도계 V-670Apparatus: Ultraviolet-visible infrared spectrophotometer V-670 manufactured by Nippon Spectroscopic Co., Ltd.
레퍼런스: 공기Reference: Air
(4) 굴절률nD, 아베수νD (4) Refractive index n D , Abbe number ν D
장치: 안톤파사제 다파장굴절계 Abbemat MWApparatus: Multi-wavelength refractometer Abbemat MW manufactured by Anton Passage
측정온도: 23℃Measurement temperature: 23℃
(5) 휨량 측정, 렌즈높이 측정(5) Deflection measurement, lens height measurement
장치: 미타카코키(주)제 비접촉 표면성상 측정장치 PF-60Apparatus: Mitaka Koki Co., Ltd. non-contact surface property measuring device PF-60
(6) 반사방지층의 성막(6) Film formation of anti-reflection layer
장치: 삼유전자(주)제 RF스퍼터장치 SRS-700T/LLApparatus: RF sputter apparatus SRS-700T/LL manufactured by Samyu Electronics Co., Ltd.
방식: RF스퍼터·마그네트론방식Method: RF sputter magnetron method
조건: 타겟재=실리콘, RF파워=250W,Condition: Target material=silicon, RF power=250W,
타겟·기판간의 수직거리=100mm,Vertical distance between target and substrate = 100mm,
옵셋거리=100mm,Offset distance=100mm,
Ar유량=45sccm, O2유량=2sccm,Ar flow rate = 45 sccm, O 2 flow rate = 2 sccm,
온도=실온, 스퍼터시간=15분Temperature = room temperature, sputtering time = 15 minutes
(7) 광학현미경(7) Optical microscope
장치: (주)키엔스제 VHX-1000, VH-Z1000RDevice: VHX-1000, VH-Z1000R, manufactured by Keyence Co., Ltd.
조건: 반사(명시야), 대물 500배Condition: reflection (bright field), 500 times objective
(8) 렌즈성형(8) Lens molding
장치: 메이쇼기공(주)제 6인치대응 나노임프린터Apparatus: 6-inch compatible nanoimprinter manufactured by Meisho Engineering Co., Ltd.
광원: 고압수은등, i선 밴드패스필터 HB0365(아사히분광(주)제)를 통해 노광Light source: High-pressure mercury lamp, exposed through i-ray band pass filter HB0365 (manufactured by Asahi spectroscopy)
성형조건: 압착압 100N, 20mW/cm2×300초Forming conditions: Compression pressure 100N, 20mW/cm 2 ×300 seconds
나아가, 하기 합성예에서 나타내는 오르가노폴리실록산의 중량평균분자량Mw는, 겔퍼미에이션크로마토그래피(이하, 본 명세서에서는 GPC라 약칭한다.)에 의한 측정 결과이다. 측정에는, (주)시마즈제작소제 GPC시스템을 이용하였다. 해당 GPC시스템의 구성과, 측정조건은 하기와 같다.Furthermore, the weight average molecular weight Mw of the organopolysiloxane shown in the following Synthesis Example is a measurement result by gel permeation chromatography (hereinafter abbreviated as GPC in this specification). For the measurement, a GPC system manufactured by Shimadzu Corporation was used. The configuration and measurement conditions of the corresponding GPC system are as follows.
GPC시스템 구성GPC system composition
시스템컨트롤러: CBM-20A, 컬럼오븐: CTO-20A, 오토샘플러: SIL-10AF, 검출기: SPD-20A 및 RID-10A, 배기유닛: DGU-20A3System controller: CBM-20A, Column oven: CTO-20A, Autosampler: SIL-10AF, Detector: SPD-20A and RID-10A, Exhaust unit: DGU-20A3
GPC컬럼: Shodex(등록상표) KF-804L 및 KF-803LGPC column: Shodex (registered trademark) KF-804L and KF-803L
컬럼온도: 40℃Column temperature: 40℃
용매: 테트라하이드로푸란Solvent: Tetrahydrofuran
유량: 1mL/분Flow rate: 1 mL/min
표준시료: 상이한 중량평균분자량(197000, 55100, 12800, 3950, 1260)의 폴리스티렌 5종Standard sample: 5 kinds of polystyrene with different weight average molecular weights (197000, 55100, 12800, 3950, 1260)
각 합성예, 실시예 및 비교예에 있어서 사용한 화합물의 공급원은 이하와 같다.The source of the compound used in each of the synthesis examples, examples and comparative examples is as follows.
A-DCP: 신나카무라화학공업(주)제 상품명: NK에스테르 A-DCPA-DCP: Product made by Shin-Nakamura Chemical Co., Ltd. Product name: NK Ester A-DCP
FA513AS: 히타치화성(주)제 상품명: 판크릴(등록상표) FA-513ASFA513AS: Hitachi Chemical Co., Ltd. Product name: Pancryl (registered trademark) FA-513AS
UA-4200: 신나카무라화학공업(주)제 상품명: NK올리고 UA-4200UA-4200: Shinnakamura Chemical Industry Co., Ltd. Product name: NK Oligo UA-4200
APTMS: 아크릴로일옥시프로필트리메톡시실란, 신에쓰화학공업(주)제 상품명: KBM-5103APTMS: Acryloyloxypropyl trimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd. Product name: KBM-5103
MPTMS: 메타크릴로일옥시프로필트리메톡시실란, 신에쓰화학공업(주)제 상품명: KBM-503MPTMS: Methacryloyloxypropyl trimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd. Product name: KBM-503
TFPTMS: 3,3,3-트리플루오로프로필트리메톡시실란, 신에쓰화학공업(주)제 상품명: KBM-7103TFPTMS: 3,3,3-trifluoropropyl trimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd. Product name: KBM-7103
TDFOTMS: 트리메톡시(1H,1H,2H,2H-트리데카플루오로-n-옥틸)실란, 동경화성공업(주)제TDFOTMS: Trimethoxy(1H,1H,2H,2H-tridecafluoro-n-octyl)silane, manufactured by Tokyo Chemical Industry Co., Ltd.
NPTMS: n-프로필트리메톡시실란, 신에쓰화학공업(주)제 상품명: KBM-3033NPTMS: n-propyl trimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd. Product name: KBM-3033
NR1: 쇼와덴코(주)제 상품명: 카렌즈(등록상표) MT NR1NR1: Showa Denko Co., Ltd. trade name: CARENS (registered trademark) MT NR1
I184: BASF재팬(주)제 상품명: Irgacure(등록상표) 184I184: BASF Japan Co., Ltd. trade name: Irgacure (registered trademark) 184
I245: BASF재팬(주)제 상품명: Irganox(등록상표) 245I245: BASF Japan Co., Ltd. trade name: Irganox (registered trademark) 245
[합성예 1] 오르가노폴리실록산(AF-55)의 제조[Synthesis Example 1] Preparation of organopolysiloxane (AF-55)
응축기를 구비한 500mL의 반응플라스크에, 35질량%수산화테트라에틸암모늄 7.71g(18.3mmol), 이온교환수 24.7g(1371mmol), 및 테트라하이드로푸란(이하, 본 명세서에서는 THF라 약칭한다.) 165.9g을 투입하고, 질소벌룬을 이용하여 이 반응플라스크 중의 공기를 질소로 치환하였다. 그 후, 실온하, 적하깔때기를 이용하여, APTMS 107.4g(458mmol) 및 TFPTMS 100.0g(458mmol)의 혼합물을, 약 10분간에 걸쳐 상기 반응플라스크에 적하하였다. 이 반응플라스크 내의 혼합물을 40℃로 승온하고, 4시간 교반하였다.In a 500 mL reaction flask equipped with a condenser, 35 mass% tetraethylammonium hydroxide 7.71 g (18.3 mmol), ion-exchanged water 24.7 g (1371 mmol), and tetrahydrofuran (hereinafter abbreviated as THF in this specification) 165.9 g was added, and nitrogen in the reaction flask was replaced with nitrogen using a nitrogen balloon. Then, using a dropping funnel at room temperature, a mixture of 107.4 g (458 mmol) of APTMS and 100.0 g (458 mmol) of TFPTMS was added dropwise to the reaction flask over about 10 minutes. The mixture in the reaction flask was heated to 40°C and stirred for 4 hours.
교반종료 후, 얻어진 반응물을 실온(약 25℃)으로 냉각하고, 이온교환수지 앰버리스트(등록상표) 15JWET 20.7g 및 분말셀룰로오스 KC플록(등록상표) W-100GK(일본제지(주)제) 4.15g을 첨가하고, 1시간 교반함으로써 반응을 정지시켰다. 그 후, 0.5μm 멤브레인필터로 여과하고, 아세트산에틸 207.4g으로 여물을 세정하였다. 얻어진 여액에 중합금지제로서 4-메톡시페놀(동경화성공업(주)제) 0.144g을 첨가하고, 교반함으로써 용해시킨 후, 이배퍼레이터를 이용하여 용매를 유거함으로써, 목적으로 하는 오르가노폴리실록산(AF-55) 145.1g을 얻었다. 얻어진 오르가노폴리실록산(AF-55)을 GPC로 측정한 바, 폴리스티렌환산으로 중량평균분자량Mw는 2,200, 분산도: Mw/Mn은 1.1이었다.After completion of stirring, the obtained reaction product was cooled to room temperature (about 25°C), ion exchange resin Amberlist (registered trademark) 15JWET 20.7 g, and powdered cellulose KC floc (registered trademark) W-100GK (manufactured by Nippon Paper Co., Ltd.) 4.15 The reaction was stopped by adding g and stirring for 1 hour. Then, it was filtered through a 0.5 μm membrane filter, and the filtrate was washed with 207.4 g of ethyl acetate. To the obtained filtrate, 0.144 g of 4-methoxyphenol (manufactured by Tokyo Chemical Industry Co., Ltd.) was added as a polymerization inhibitor, dissolved by stirring, and then the solvent was distilled using an evaporator to remove the desired organopolysiloxane. (AF-55) 145.1 g was obtained. When the obtained organopolysiloxane (AF-55) was measured by GPC, the weight average molecular weight Mw in terms of polystyrene was 2,200 and the degree of dispersion: Mw/Mn was 1.1.
[합성예 2] 오르가노폴리실록산(MF-55)의 제조[Synthesis Example 2] Preparation of organopolysiloxane (MF-55)
응축기를 구비한 500mL의 반응플라스크에, 35질량%수산화테트라에틸암모늄 6.94g(16.5mmol), 이온교환수 22.2g(1234mmol), 및 THF 153.9g을 투입하고, 질소벌룬을 이용하여 이 반응플라스크 중의 공기를 질소로 치환하였다. 그 후, 실온하, 적하깔때기를 이용하여, MPTMS 102.4g(412mmol) 및 TFPTMS 90.0g(412mmol)의 혼합물을, 약 10분간에 걸쳐 상기 반응플라스크에 적하하였다. 이 반응플라스크 내의 혼합물을 40℃로 승온하고, 4시간 교반하였다.To a 500 mL reaction flask equipped with a condenser, 6.94 g (16.5 mmol) of 35% by mass tetraethylammonium hydroxide, 22.2 g (1234 mmol) of ion-exchanged water, and 153.9 g of THF were added, and a nitrogen balloon was used in the reaction flask. Air was replaced with nitrogen. Thereafter, a mixture of 102.4 g (412 mmol) of MPTMS and 90.0 g (412 mmol) of TFPTMS was added dropwise to the reaction flask over about 10 minutes at room temperature using a dropping funnel. The mixture in the reaction flask was heated to 40°C and stirred for 4 hours.
교반종료 후, 얻어진 반응물을 실온(약 25℃)으로 냉각하고, 이온교환수지 앰버리스트(등록상표) 15JWET 19.2g 및 분말셀룰로오스 KC플록(등록상표) W-100GK(일본제지(주)제) 3.85g을 첨가하고, 1시간 교반함으로써 반응을 정지시켰다. 그 후, 0.5μm 멤브레인필터로 여과하고, 아세트산에틸 192.4g으로 여물을 세정하였다. 얻어진 여액에 중합금지제로서 4-메톡시페놀(동경화성공업(주)제) 0.135g을 첨가하고, 교반함으로써 용해시킨 후, 이배퍼레이터를 이용하여 용매를 유거함으로써, 목적으로 하는 오르가노폴리실록산(MF-55) 134.1g을 얻었다. 얻어진 오르가노폴리실록산(MF-55)을 GPC로 측정한 바, 폴리스티렌환산으로 중량평균분자량Mw는 2,000, 분산도: Mw/Mn은 1.1이었다.After completion of stirring, the obtained reaction product was cooled to room temperature (about 25°C), and ion exchange resin Amberlist (registered trademark) 15JWET 19.2g and powdered cellulose KC floc (registered trademark) W-100GK (manufactured by Nippon Paper Co., Ltd.) 3.85 The reaction was stopped by adding g and stirring for 1 hour. Then, it was filtered through a 0.5 μm membrane filter, and the filtrate was washed with 192.4 g of ethyl acetate. To the obtained filtrate, 0.135 g of 4-methoxyphenol (manufactured by Tokyo Chemical Industry Co., Ltd.) was added as a polymerization inhibitor, dissolved by stirring, and then the solvent was distilled using an evaporator to remove the desired organopolysiloxane. (MF-55) 134.1 g were obtained. When the obtained organopolysiloxane (MF-55) was measured by GPC, the weight average molecular weight Mw in terms of polystyrene was 2,000 and the degree of dispersion: Mw/Mn was 1.1.
[합성예 3] 오르가노폴리실록산(M6FP-50545)의 제조[Synthesis Example 3] Preparation of organopolysiloxane (M6FP-50545)
응축기를 구비한 200mL의 반응플라스크에, 35질량%수산화테트라에틸암모늄 1.80g(4.27mmol), 이온교환수 5.76g(320mmol), 및 THF 37.8g을 투입하고, 질소벌룬을 이용하여 이 반응플라스크 중의 공기를 질소로 치환하였다. 그 후, 실온하, 적하깔때기를 이용하여, MPTMS 26.5g(107mmol), TDFOTMS 5.00g(10.7mmol), 및 NPTMS 15.8g(96.1mmol)의 혼합물을, 약 10분간에 걸쳐 상기 반응플라스크에 적하하였다. 이 반응플라스크 내의 혼합물을 40℃로 승온하고, 4시간 교반하였다.To a 200 mL reaction flask equipped with a condenser, 1.80 g (4.27 mmol) of 35% by mass tetraethylammonium hydroxide, 5.76 g (320 mmol) of ion-exchanged water, and 37.8 g of THF were added, and a nitrogen balloon was used in the reaction flask. Air was replaced with nitrogen. Thereafter, a mixture of 26.5 g (107 mmol) of MPTMS, 5.00 g (10.7 mmol) of TDFOTMS, and 15.8 g (96.1 mmol) of NPTMS was added dropwise to the reaction flask over about 10 minutes using a dropping funnel at room temperature. . The mixture in the reaction flask was heated to 40°C and stirred for 4 hours.
교반종료 후, 얻어진 반응물을 실온(약 25℃)으로 냉각하고, 이온교환수지 앰버리스트(등록상표) 15JWET 4.73g과 분말셀룰로오스 KC플록(등록상표) W-100GK(일본제지(주)제) 0.946g을 첨가하고, 1시간 교반함으로써 반응을 정지시켰다. 그 후, 0.5μm 멤브레인필터로 여과하고, 아세트산에틸 47.3g으로 여물을 세정하였다. 얻어진 여액에 중합금지제로서 4-메톡시페놀(동경화성공업(주)제) 0.0325g을 첨가하고, 교반함으로써 용해시킨 후, 이배퍼레이터를 이용하여 용매를 유거함으로써, 목적으로 하는 오르가노폴리실록산(M6FP-50545) 33.0g을 얻었다. 얻어진 오르가노폴리실록산(M6FP-50545)을 GPC로 측정한 바, 폴리스티렌환산으로 중량평균분자량Mw는 4,400, 분산도: Mw/Mn은 1.6이었다.After the completion of stirring, the obtained reaction product was cooled to room temperature (about 25°C), and ion exchange resin Amberlist (registered trademark) 15JWET 4.73 g and powdered cellulose KC floc (registered trademark) W-100GK (manufactured by Japan Paper Co., Ltd.) 0.946 The reaction was stopped by adding g and stirring for 1 hour. Then, it was filtered through a 0.5 μm membrane filter, and the filtrate was washed with 47.3 g of ethyl acetate. To the obtained filtrate, 0.0325 g of 4-methoxyphenol (manufactured by Tokyo Chemical Industry Co., Ltd.) was added as a polymerization inhibitor, dissolved by stirring, and then the solvent was distilled using an evaporator to remove the desired organopolysiloxane. (M6FP-50545) 33.0 g was obtained. When the obtained organopolysiloxane (M6FP-50545) was measured by GPC, the weight average molecular weight Mw in terms of polystyrene was 4,400, and the dispersion degree: Mw/Mn was 1.6.
[실시예 1][Example 1]
(a)상기 지환식 (메트)아크릴레이트 화합물로서 A-DCP, (b)우레탄(메트)아크릴레이트 화합물로서 UA-4200, (d)광라디칼개시제로서 I184, 및 (e)페놀계 산화방지제로서 I245를, 각각 하기 표 1에 기재된 비율로 배합하고, 50℃에서 3시간 진탕시켜, 혼합하였다. 그 후, (c)합성예 1에서 제조한 오르가노폴리실록산(AF-55), 및 (g)상기 식(4)로 표시되는 다관능티올 화합물로서 NR1을 첨가하고, 상기 교반탈포기를 이용하여 30분간, 교반혼합하였다. 추가로 동일장치를 이용하여 10분간 교반탈포함으로써 임프린트용 광경화성 조성물1을 조제하였다. 한편, 하기 표 1 중, 「부」는 「질량부」를 나타낸다.(a) A-DCP as the alicyclic (meth)acrylate compound, (b) UA-4200 as a urethane (meth)acrylate compound, (d) I184 as a photoradical initiator, and (e) as a phenolic antioxidant I245 was blended at the ratios shown in Table 1, respectively, and shaken at 50°C for 3 hours, and then mixed. Thereafter, (c) organopolysiloxane (AF-55) prepared in Synthesis Example 1, and (g) NR1 was added as a polyfunctional thiol compound represented by Formula (4) above, and using the stirred defoamer. Stir and mix for 30 minutes. In addition, a photocurable composition 1 for imprint was prepared by stirring and defoaming for 10 minutes using the same apparatus. In addition, in Table 1 below, "part" represents "part by mass".
[실시예 2 내지 실시예 7][Examples 2 to 7]
상기 실시예 1과 동일한 수순으로, (a)성분 내지 (e)성분 및 (g)성분을 하기 표 1에 나타내는 비율로 혼합함으로써, 임프린트용 광경화성 조성물2 내지 7을 조제하였다.Photocurable compositions 2 to 7 for imprint were prepared by mixing (a) component to (e) component and (g) component at the ratio shown in Table 1 in the same procedure as in Example 1 above.
[실시예 8 및 실시예 9][Example 8 and Example 9]
상기 실시예 1과 동일한 수순으로, (a)성분 내지 (e)성분을 하기 표 1에 나타내는 비율로 혼합함으로써, 임프린트용 광경화성 조성물8 및 9를 조제하였다.Photocurable compositions 8 and 9 for imprint were prepared by mixing the components (a) to (e) at the ratios shown in Table 1 in the same procedure as in Example 1 above.
[비교예 1][Comparative Example 1]
상기 실시예 1과 동일한 수순으로, (a)성분, (b)성분, (d)성분 및 (e)성분을 하기 표 1에 나타내는 비율로 혼합함으로써, 임프린트용 광경화성 조성물10을 조제하였다.In the same procedure as in Example 1, the photocurable composition 10 for imprint was prepared by mixing (a) component, (b) component, (d) component, and (e) component in the ratio shown in Table 1 below.
[비교예 2][Comparative Example 2]
상기 실시예 1과 동일한 수순으로, (a)성분, (b)성분, (d)성분 및 (e)성분, 그리고 (c)성분에 해당하지 않는 실란 화합물로서 TFPTMS를 하기 표 1에 나타내는 비율로 혼합함으로써, 임프린트용 광경화성 조성물11을 조제하였다.In the same procedure as in Example 1, (a) component, (b) component, (d) component and (e) component, and (c) component does not correspond to the silane compound in the ratio shown in Table 1 TFPTMS By mixing, a photocurable composition 11 for imprinting was prepared.
[비교예 3][Comparative Example 3]
상기 실시예 1과 동일한 수순으로, (b)성분 내지 (e)성분을 하기 표 1에 나타내는 비율로 혼합함으로써, 임프린트용 광경화성 조성물12를 조제하였다.In the same procedure as in Example 1, the photocurable composition 12 for imprint was prepared by mixing the components (b) to (e) at the ratios shown in Table 1 below.
[표 1][Table 1]
[경화막의 제작][Production of hard film]
실시예 1 내지 실시예 9 및 비교예 1 내지 비교예 3에서 조제한 각 임프린트용 광경화성 조성물을, 500μm두께의 실리콘고무제 스페이서와 함께, NOVEC(등록상표) 1720(쓰리엠재팬(주)제)을 도포하고 건조함으로써 이형처리한 유리기판 2매로 끼워 넣었다. 이 끼워 넣은 임프린트용 광경화성 조성물을, 상기 UV조사장치를 이용하여 i선 밴드패스필터(아사히분광(주)제)를 개재하여 20mW/cm2로 300초간 UV노광하였다. 노광 후 얻어진 경화물을, 상기 이형처리한 유리기판으로부터 박리한 후, 100℃의 핫플레이트에서 10분간 가열함으로써, 직경 3cm, 두께 0.5mm의 경화막을 제작하였다.The photocurable compositions for each imprint prepared in Examples 1 to 9 and Comparative Examples 1 to 3, together with a spacer made of silicone rubber of 500 μm thickness, NOVEC (registered trademark) 1720 (manufactured by 3M Japan) It was sandwiched by two sheets of glass substrate which had been molded by coating and drying. The interposed imprinted photocurable composition was exposed to UV at 20 mW/cm 2 for 300 seconds using an i-ray band pass filter (manufactured by Asahi spectroscopy Co., Ltd.) using the UV irradiation device. A cured film having a diameter of 3 cm and a thickness of 0.5 mm was produced by peeling the cured product obtained after exposure from the release-treated glass substrate for 10 minutes on a hot plate at 100°C.
[투과율 및 내열황변성 평가][Evaluation of transmittance and heat yellowness]
상기의 방법으로 제작한 경화막의 파장 410nm의 투과율을, 상기 자외가시근적외 분광광도계를 이용하여 측정하였다. 결과를 하기 표 2에 나타낸다. 다시 상기 경화막을 실리콘웨이퍼 상에 놓고, 이 실리콘웨이퍼를 개재하여, 175℃로 가열한 핫플레이트 상에서 2분 30초간 가열하고, 내열성 시험을 행하였다. 내열성 시험 후의 경화막의 파장 410nm의 투과율을, 상기 자외가시근적외 분광광도계를 이용하여 측정하고, 가열 전후의 투과율변화로부터 내열황변성을 평가하였다. 결과를 하기 표 2에 함께 나타낸다.The transmittance of the wavelength of 410 nm of the cured film produced by the above method was measured using the ultraviolet visible near infrared spectrophotometer. The results are shown in Table 2 below. The cured film was again placed on a silicon wafer, and heated on a hot plate heated to 175°C for 2 minutes and 30 seconds through the silicon wafer, and subjected to a heat resistance test. The transmittance of the 410 nm wavelength of the cured film after the heat resistance test was measured using the ultraviolet visible near-infrared spectrophotometer, and the heat yellowing resistance was evaluated from the change in transmittance before and after heating. The results are shown in Table 2 below.
[굴절률nD·아베수νD 평가][Refractive index n D · Abbe number ν D evaluation]
상기의 방법으로 제작한 경화막의 파장 589nm에 있어서의 굴절률nD, 및 아베수νD를, 상기 다파장굴절계를 이용하여 측정하였다. 결과를 하기 표 2에 함께 나타낸다.The refractive index n D and Abbe number ν D at a wavelength of 589 nm of the cured film produced by the above method were measured using the multi-wavelength refractometer. The results are shown in Table 2 below.
[휨량의 평가][Evaluation of warpage amount]
실시예 1 내지 실시예 9 및 비교예 1 내지 비교예 3에서 조제한 각 임프린트용 광경화성 조성물 0.010g을, NOVEC(등록상표) 1720(쓰리엠재팬(주)제)을 도포하고 건조함으로써 이형처리한 제1의 유리기판 상에 칭량하였다. 그 후, 500μm두께의 실리콘고무제 스페이서를 개재하여, 신에쓰화학공업(주)제 접착보조제(제품명: KBM-5103)를 프로필렌글리콜모노메틸에테르아세테이트로 1질량%로 희석한 용액을 도포하고 건조함으로써 밀착처리한 제2의 유리기판(1.0cm가로세로, 0.5mm두께)으로, 상기 제1의 유리기판 상의 광경화성 조성물을 끼워 넣었다. 이 끼워 넣은 광경화성 조성물을, 상기 UV조사장치를 이용하여 i선 밴드패스필터(아사히분광(주)제)를 개재하여 20mW/cm2로 300초간 UV노광하였다. 노광 후 얻어진 경화물을, 상기 제1의 유리기판으로부터 박리한 후, 100℃의 핫플레이트에서 10분간 가열함으로써, 상기 제2의 유리기판 상에, 직경 0.5cm, 두께 0.5mm 및 질량 0.01g의 경화막을 제작하였다. 그 후, 상기 경화막이 제작된 제2의 유리기판을, 175℃의 핫플레이트에서 2분 30초간 가열함으로써 내열성 시험을 행하였다.A release agent obtained by coating and drying 0.010 g of the photocurable composition for each imprint prepared in Examples 1 to 9 and Comparative Examples 1 to 3 and NOVEC (registered trademark) 1720 (manufactured by 3M Japan Co., Ltd.) and drying them. Weighed on the glass substrate of 1. Subsequently, a solution diluted with propylene glycol monomethyl ether acetate in 1 mass% of the adhesive aid (product name: KBM-5103) manufactured by Shin-Etsu Chemical Industry Co., Ltd. through a spacer made of silicone rubber having a thickness of 500 μm was applied and dried. By doing so, the photocurable composition on the first glass substrate was sandwiched by a second glass substrate (1.0 cm width, 0.5 mm thick) that was adhered. The sandwiched photocurable composition was exposed to UV for 300 seconds at 20 mW/cm 2 through an i-ray band pass filter (manufactured by Asahi spectroscopy Co., Ltd.) using the UV irradiation device. The cured product obtained after exposure was peeled from the first glass substrate, and then heated on a hot plate at 100° C. for 10 minutes to form a diameter of 0.5 cm, a thickness of 0.5 mm, and a mass of 0.01 g on the second glass substrate. A cured film was produced. Then, the heat resistance test was performed by heating the 2nd glass substrate in which the said cured film was produced on the hot plate of 175 degreeC for 2 minutes 30 seconds.
상기 경화막이 제작된 제2의 유리기판을, 상기 비접촉 표면성상 측정장치의 스테이지에 이 제2의 유리기판이 상면이 되도록 배치하였다. 상기 제2의 유리기판의 중심을 측정개시점으로 하고, 이 제2의 유리기판의 4개의 정점을 향해 상기 스테이지에 대해 수직방향(Z축)의 변위를 측정하였다. 측정데이터로부터, 상기 제2의 유리기판의 중심과 이 제2의 유리기판의 각 정점 사이의 수직방향(Z축)의 변위량을 산출하여, 이들 평균값을 휨량으로 정의하였다. 도 1에 유리기판의 휨량 평가방법을 모식도로 나타낸다. 결과를 하기 표 2에 함께 나타낸다.The second glass substrate on which the cured film was prepared was placed on the stage of the non-contact surface property measuring device such that the second glass substrate was the top surface. The center of the second glass substrate was taken as the measurement start point, and displacement in the vertical direction (Z axis) was measured with respect to the stage toward the four vertices of the second glass substrate. From the measurement data, the displacement amount in the vertical direction (Z axis) between the center of the second glass substrate and each vertex of the second glass substrate was calculated, and these average values were defined as the amount of warpage. 1 is a schematic diagram showing a method for evaluating the amount of warpage of a glass substrate. The results are shown in Table 2 below.
[반사방지층의 성막과 내크랙성 평가][Evaluation of film formation and crack resistance of the antireflection layer]
실시예 1 내지 실시예 9 및 비교예 1 내지 비교예 3에서 조제한 각 임프린트용 광경화성 조성물 0.040g을, NOVEC(등록상표) 1720(쓰리엠재팬(주)제)을 도포하고 건조함으로써 이형처리한 제1의 유리기판 상에 칭량하였다. 그 후, 500μm두께의 실리콘고무제 스페이서를 개재하여, 신에쓰화학공업(주)제 접착보조제(제품명: KBM-5103)를 프로필렌글리콜모노메틸에테르아세테이트로 1질량%로 희석한 용액을 도포하고 건조함으로써 밀착처리한 제2의 유리기판(6cm가로세로, 0.7mm두께)으로, 상기 제1의 유리기판 상의 임프린트용 광경화성 조성물을 끼워 넣었다. 이 끼워 넣은 광경화성 조성물을, 상기 UV조사장치를 이용하여 i선 밴드패스필터(아사히분광(주)제)를 개재하여 20mW/cm2로 300초간 UV노광하였다. 노광 후 얻어진 경화물을, 상기 제1의 유리기판으로부터 박리한 후, 100℃의 핫플레이트에서 10분간 가열함으로써, 상기 제2의 유리기판 상에, 직경 1cm, 두께 0.5mm 및 질량 0.040g의 경화막을 제작하였다. 동일한 조작을 반복하여, 상기 제2의 유리기판 상에 3개의 이 경화막을 제작하였다.A release agent obtained by applying 0.040 g of the photocurable composition for each imprint prepared in Examples 1 to 9 and Comparative Examples 1 to 3, and NOVEC (registered trademark) 1720 (manufactured by 3M Japan Co., Ltd.) and drying to release the agent. Weighed on the glass substrate of 1. Subsequently, a solution diluted with propylene glycol monomethyl ether acetate in 1 mass% of the adhesive aid (product name: KBM-5103) manufactured by Shin-Etsu Chemical Industry Co., Ltd. through a spacer made of silicone rubber having a thickness of 500 μm was applied and dried. By doing so, the photocurable composition for imprint on the first glass substrate was sandwiched by a second glass substrate (6 cm width, 0.7 mm thick) that was adhered. The sandwiched photocurable composition was exposed to UV for 300 seconds at 20 mW/cm 2 through an i-ray band pass filter (manufactured by Asahi Spectrum Co., Ltd.) using the UV irradiation device. The cured product obtained after exposure was peeled from the first glass substrate, and then heated on a hot plate at 100° C. for 10 minutes to cure the second glass substrate with a diameter of 1 cm, a thickness of 0.5 mm, and a mass of 0.040 g. A membrane was produced. By repeating the same operation, three cured films were produced on the second glass substrate.
상기 제2의 유리기판 상에 제작된 3개의 경화막 상에, 상기 RF스퍼터장치를 이용하여 상기 성막조건으로, 막두께 200nm의 산화규소층을 반사방지층으로서 성막하였다. 상기 광학현미경을 이용하여, 상기 3개의 경화막 상의 반사방지층을 관찰하여 크랙의 유무를 확인한 후, 상기 제2의 유리기판을 175℃의 핫플레이트에서 2분 30초간 가열함으로써 내열성 시험을 행하였다. 내열성 시험 후의 상기 제2의 유리기판에 대해서도, 상기 광학현미경을 이용하여 상기 3개의 경화막 상의 반사방지층의 크랙의 유무를 관찰하고, 이 반사방지층의 내크랙성을 판정하였다. 이 3개의 경화막 상의 반사방지층 전체에서 크랙을 시인할 수 있는 경우를 ×, 이 3개의 경화막 상의 반사방지층 중 1개 또는 2개만 크랙을 시인할 수 있는 경우를 △, 이 3개의 경화막 상의 반사방지층 전체에서 크랙을 시인할 수 없는 경우를 ○로 판정하였다. 각각의 결과를 하기 표 2에 함께 나타낸다.On the three cured films fabricated on the second glass substrate, a silicon oxide layer having a film thickness of 200 nm was formed as an antireflection layer under the film forming conditions using the RF sputtering device. Using the optical microscope, the anti-reflection layers on the three cured films were observed to confirm the presence or absence of cracks, and then the heat resistance test was conducted by heating the second glass substrate on a hot plate at 175°C for 2 minutes 30 seconds. Also about the second glass substrate after the heat resistance test, the presence or absence of cracks in the antireflection layers on the three cured films was observed using the optical microscope, and the crack resistance of the antireflection layers was determined. When the crack can be visually recognized in the entire antireflection layer on the three cured films, △ when only one or two of the antireflection layers on the three cured films can be cracked, △, It was determined that the case where cracks could not be visually recognized in the entire antireflection layer was judged as ○. Each result is shown together in Table 2 below.
[표 2][Table 2]
표 1 및 표 2가 나타내는 바와 같이, (c)성분을 포함하지 않는 비교예 1 및 비교예 2의 임프린트용 광경화성 조성물로부터 제작한 경화막 상에 성막한 반사방지층은, 내열성 시험 후에 크랙이 발생하는 결과가 되었다. 또한, (a)성분을 포함하지 않는 비교예 3의 광경화성 조성물로부터 제작한 경화막은, 내열황변성 및 유리기판의 휨량은 양호한 특성을 나타내며, 이 경화막 상에 성막한 반사방지층은 내크랙성을 나타내지만, 굴절률nD가 1.48 미만으로 낮은 결과가 되었다. 이 결과는, 비교예 3의 광경화성 조성물로부터 제작한 경화막이, 고화소 카메라모듈용 렌즈에 호적하지 않은 것을 시사하고 있다. 이에 반해 본 발명의 광경화성 조성물로부터 제작한 경화막은, 초기투과율, 내열황변성, 휨량, 및 이 경화막 상에 성막한 반사방지층의 내크랙성의 모든 특성에서 양호한 특성을 나타내고, 또한 고아베수를 갖는 렌즈로서 호적한 굴절률nD 및 아베수νD를 나타내어, 본 발명의 우위성이 확인되었다.As shown in Table 1 and Table 2, the antireflection layer formed on the cured films prepared from the photocurable compositions for imprints of Comparative Examples 1 and 2 that do not contain component (c), cracks occurred after the heat resistance test. It became the result. In addition, the cured film prepared from the photocurable composition of Comparative Example 3 that does not contain the component (a) exhibits good properties of heat yellowing resistance and warpage amount of the glass substrate, and the antireflection layer formed on the cured film is crack resistant. However, it was found that the refractive index n D was lower than 1.48. This result suggests that the cured film produced from the photocurable composition of Comparative Example 3 is not suitable for a lens for a high-pixel camera module. On the other hand, the cured film produced from the photocurable composition of the present invention exhibits good properties in all characteristics of initial transmittance, heat yellowing resistance, warpage amount, and crack resistance of the antireflection layer formed on the cured film, and also has a high Abbe number. The refractive index n D and the Abbe number ν D which are suitable as the lens to be possessed were shown, and the superiority of the present invention was confirmed.
[렌즈의 제작][Production of lens]
실시예 5에서 조제한 임프린트용 광경화성 조성물5를, 니켈제의 주형(2mm직경×300μm깊이의 렌즈형을, 세로 3열×가로 5열의 계 15개 배치) 및 나노임프린터를 이용하고, 상기 서술한 성형체의 제조방법에 따라서, 지지체인 유리기판 상에서 렌즈형상으로 성형하였다. 한편, 사용한 주형은, 미리 NOVEC(등록상표) 1720(쓰리엠재팬(주)제)으로 이형처리하였다. 또한, 사용한 유리기판은, 미리 신에쓰화학공업(주)제 접착보조제(제품명: KBM-503)로 밀착처리하였다. 상기 주형으로부터 경화물을 분리한 후, 이 경화물을 100℃의 핫플레이트에서 10분간 가열함으로써, 상기 밀착처리한 유리기판 상에 볼록렌즈를 제작하였다.Using the photocurable composition 5 for imprint prepared in Example 5, a nickel mold (2 mm diameter x 300 μm depth lens type, 15 columns in 3 rows x 5 rows in total) and a nanoimprinter were described above. According to the manufacturing method of one molded body, it was molded into a lens shape on a glass substrate as a support. On the other hand, the mold used was previously mold-treated with NOVEC (registered trademark) 1720 (manufactured by 3M Japan). In addition, the used glass substrate was previously adhered with an adhesive adjuvant (product name: KBM-503) manufactured by Shin-Etsu Chemical Co., Ltd. After separating the cured product from the mold, the cured product was heated on a hot plate at 100° C. for 10 minutes to produce a convex lens on the adhered glass substrate.
상기 유리기판 상에 얻어진 볼록렌즈에 대하여, 가열시험 전후의 렌즈높이(두께)를 상기 비접촉 표면성상 측정장치로 측정하고, 그 변화율을 다음식 “[(가열 전의 렌즈높이-가열 후의 렌즈높이)/가열 전의 렌즈높이]×100”으로부터 산출하고, 가열에 의한 치수안정성을 평가하였다. 또한, 가열시험 후의 볼록렌즈에 있어서의 크랙의 발생의 유무를, 상기 비접촉 표면성상 측정장치에 부속된 마이크로스코프로 관찰하였다. 한편, 가열시험이란, 유리기판 상에 얻어진 볼록렌즈를 175℃의 핫플레이트에서 2분 30초간 가열한 후, 실온(약 23℃)까지 방랭하는 시험이다. 결과를 하기 표 3에 나타낸다.For the convex lens obtained on the glass substrate, the lens height (thickness) before and after the heating test was measured with the non-contact surface property measuring apparatus, and the rate of change was expressed by the following equation “((lens height before heating-lens height after heating)/ Lens height before heating]×100”, and dimensional stability by heating was evaluated. The presence or absence of cracks in the convex lens after the heating test was observed with a microscope attached to the non-contact surface property measuring apparatus. On the other hand, the heating test is a test in which the convex lens obtained on the glass substrate is heated on a hot plate at 175°C for 2 minutes and 30 seconds, and then cooled to room temperature (about 23°C). The results are shown in Table 3 below.
[표 3][Table 3]
표 3에 나타내는 바와 같이, 본 발명의 임프린트용 광경화성 조성물로부터 얻어진 볼록렌즈는, 175℃, 2분 30초간의 열이력을 거쳐도 렌즈높이의 변화가 작고, 치수안정성이 높다는 결과가 얻어졌다.As shown in Table 3, the convex lens obtained from the photocurable composition for imprint of the present invention obtained a small change in lens height and high dimensional stability even after a heat history of 175°C for 2 minutes 30 seconds.
Claims (14)
(a): 1분자 중에 (메트)아크릴로일옥시기를 적어도 1개 갖는 지환식 (메트)아크릴레이트 화합물(단, (b)성분의 화합물을 제외한다.)
(b): 우레탄(메트)아크릴레이트 화합물 또는 에폭시(메트)아크릴레이트 화합물
(c): 하기 식(1)로 표시되는 실란 화합물, 또는 이 식(1)로 표시되는 실란 화합물을 포함하는 적어도 1종의 실란 화합물의 가수분해 중축합물
(d): 광라디칼개시제
[화학식 1]
(식 중, R1은 수소원자 또는 메틸기를 나타내고, R2는 탄소원자수 1 내지 8의 알킬렌기를 나타내고, R3은 각각 독립적으로 수소원자 또는 탄소원자수 1 내지 4의 알킬기를 나타내고, R4는 탄소원자수 1 내지 4의 알킬기를 나타내고, a는 2 또는 3을 나타낸다.)The following (a) component, the following (b) component, the following (c) component, and the following (d) component are included. ) Component is 30 parts by mass to 90 parts by mass and (c) component is 1 part by mass to 100 parts by mass, and (a) component, this (b) component and the sum of 100 parts by mass of component (c) The photocurable composition for imprints whose component (d) is 0.1 parts by mass to 5 parts by mass.
(a): An alicyclic (meth)acrylate compound having at least one (meth)acryloyloxy group in one molecule (however, the compound of component (b) is excluded.)
(b): Urethane (meth)acrylate compound or epoxy (meth)acrylate compound
(c): Hydrolyzed polycondensate of at least one silane compound comprising a silane compound represented by the following formula (1) or a silane compound represented by this formula (1)
(d): Photo radical initiator
[Formula 1]
(In the formula, R 1 represents a hydrogen atom or a methyl group, R 2 represents an alkylene group having 1 to 8 carbon atoms, R 3 each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R 4 is Represents an alkyl group having 1 to 4 carbon atoms, and a represents 2 or 3.)
상기 지환식 (메트)아크릴레이트 화합물이 1분자 중에 (메트)아크릴로일옥시기를 1개 또는 2개 갖는, 임프린트용 광경화성 조성물.According to claim 1,
The said alicyclic (meth)acrylate compound has one or two (meth)acryloyloxy groups in 1 molecule, The photocurable composition for imprints.
상기 가수분해 중축합물이 하기 식(1a)로 표시되는 구조단위 또는 하기 식(1b)로 표시되는 구조단위를 갖는 오르가노폴리실록산인, 임프린트용 광경화성 조성물.
[화학식 2]
(식 중, R1, R2 및 R4는 상기 식(1)에 있어서의 정의와 동의이다.)The method according to claim 1 or 2,
A photocurable composition for imprinting, wherein the hydrolysis-condensation product is an organopolysiloxane having a structural unit represented by the following formula (1a) or a structural unit represented by the following formula (1b).
[Formula 2]
(In the formula, R 1 , R 2 and R 4 are the same as the definition in the formula (1).)
상기 (c)성분이, 상기 식(1)로 표시되는 실란 화합물과 하기 식(2)로 표시되는 실란 화합물을 포함하는 적어도 2종의 실란 화합물의 가수분해 중축합물인, 임프린트용 광경화성 조성물.
[화학식 3]
(식 중, Rf는 탄소원자수 1 내지 12의 플루오로알킬기를 나타내고, R5는 각각 독립적으로 수소원자 또는 탄소원자수 1 내지 4의 알킬기를 나타내고, R6은 탄소원자수 1 내지 4의 알킬기를 나타내고, b는 2 또는 3을 나타낸다.)The method according to any one of claims 1 to 3,
The photocurable composition for imprinting, wherein the component (c) is a hydrolysis-condensation product of at least two silane compounds containing a silane compound represented by the formula (1) and a silane compound represented by the following formula (2).
[Formula 3]
(Wherein, Rf represents a fluoroalkyl group having 1 to 12 carbon atoms, R 5 each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R 6 represents an alkyl group having 1 to 4 carbon atoms, b represents 2 or 3.)
상기 식(2)에 있어서 Rf가 하기 식(3)으로 표시되는 기인, 임프린트용 광경화성 조성물.
[화학식 4]
(식 중, Y는 수소원자 또는 불소원자를 나타내고, c는 0 내지 2의 정수를 나타내고, d는 1 내지 6의 정수를 나타내고, *은 규소원자와의 결합손을 나타낸다.)The method of claim 4,
In the formula (2), Rf is a group represented by the following formula (3), the photocurable composition for imprint.
[Formula 4]
(In the formula, Y represents a hydrogen atom or a fluorine atom, c represents an integer from 0 to 2, d represents an integer from 1 to 6, and * represents a bond with a silicon atom.)
상기 가수분해 중축합물이, 하기 식(1a)로 표시되는 구조단위 및 하기 식(2a)로 표시되는 구조단위를 갖는 오르가노폴리실록산, 또는 하기 식(1b)로 표시되는 구조단위 및 하기 식(2b)로 표시되는 구조단위를 갖는 오르가노폴리실록산인, 임프린트용 광경화 조성물.
[화학식 5]
(식 중, R1, R2 및 R4는 상기 식(1)에 있어서의 정의와 동의이고, R6 및 Rf는 상기 식(2)에 있어서의 정의와 동의이다.)The method of claim 4 or 5,
The hydrolysis polycondensate is an organopolysiloxane having a structural unit represented by the following formula (1a) and a structural unit represented by the following formula (2a), or a structural unit represented by the following formula (1b) and the following formula (2b) Organopolysiloxane having a structural unit represented by), a photocurable composition for imprint.
[Formula 5]
(Wherein, R 1 , R 2 and R 4 are synonymous with the definition in the formula (1), and R 6 and Rf are synonymous with the definition in the formula (2).)
추가로, 상기 (a)성분, 상기 (b)성분 및 상기 (c)성분의 합 100질량부에 대해 0.05질량부 내지 3질량부의 하기 (e)성분 및/또는
상기 (a)성분, 상기 (b)성분 및 상기 (c)성분의 합 100질량부에 대해 0.1질량부 내지 3질량부의 하기 (f)성분을 함유하는, 임프린트용 광경화성 조성물.
(e): 페놀계 산화방지제
(f): 설파이드계 산화방지제The method according to any one of claims 1 to 6,
Further, the following components (e) and/or 0.05 parts by mass to 3 parts by mass based on 100 parts by mass of the components (a), (b) and (c)
The photocurable composition for imprints containing 0.1 mass parts to 3 mass parts of the following (f) components with respect to 100 mass parts of the sum of the components (a), (b) and (c).
(e): Phenolic antioxidant
(f): sulfide-based antioxidant
추가로, 상기 (a)성분, 상기 (b)성분 및 상기 (c)성분의 합 100질량부에 대해, 1질량부 내지 20질량부의 하기 (g)성분을 포함하는, 임프린트용 광경화성 조성물.
(g): 하기 식(4)로 표시되는 다관능티올 화합물
[화학식 6]
(식 중, R7은 단결합 또는 탄소원자수 1 내지 6의 직쇄상 혹은 분지쇄상의 알킬렌기를 나타내고, X는 단결합 또는 에스테르결합을 나타내고, A는 헤테로원자를 적어도 1개 포함하거나 혹은 헤테로원자를 포함하지 않는 탄소원자수 2 내지 12의 유기기 또는 헤테로원자를 나타내고, r1은 2 내지 6의 정수를 나타낸다.)The method according to any one of claims 1 to 7,
In addition, the photocurable composition for imprints comprising 1 part by mass to 20 parts by mass of the following (g) component based on 100 parts by mass of the component (a), the component (b), and the component (c).
(g): Multifunctional thiol compound represented by the following formula (4)
[Formula 6]
(Wherein, R 7 represents a single bond or a linear or branched alkylene group having 1 to 6 carbon atoms, X represents a single bond or an ester bond, and A contains at least one heteroatom or a heteroatom. Represents an organic group or a hetero atom having 2 to 12 carbon atoms, and r 1 represents an integer of 2 to 6.)
상기 임프린트용 광경화성 조성물은, 그의 경화물의 파장 589nm에 있어서의 굴절률nD가 1.48 이상 1.55 이하이고, 또한 이 경화물의 아베수νD가 53 이상 60 이하인, 임프린트용 광경화성 조성물.The method according to any one of claims 1 to 8,
The photocurable composition for imprints has a refractive index n D of 1.48 or more and 1.55 or less at a wavelength of 589 nm of the cured product, and the Abbe number ν D of this cured product is 53 or more and 60 or less.
상기 광경화하는 공정의 후, 얻어진 광경화물을 취출하여 이형하는 공정, 그리고, 이 광경화물을, 이 이형하는 공정의 전, 중도 또는 후에 있어서 가열하는 공정을 포함하는, 성형체의 제조방법.The method of claim 12,
After the photocuring step, a step of taking out and releasing the obtained photocured product, and a step of heating the photocured product before, during, or after the releasing process.
상기 성형체가 카메라모듈용 렌즈인, 성형체의 제조방법.The method of claim 12 or 13,
A method of manufacturing a molded body, wherein the molded body is a lens for a camera module.
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| JP2018005581 | 2018-01-17 | ||
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| JP2014234458A (en) | 2013-06-03 | 2014-12-15 | 昭和電工株式会社 | Curable composition, and cured product thereof |
| WO2015190544A1 (en) * | 2014-06-13 | 2015-12-17 | 東亞合成株式会社 | Curable composition |
| WO2016104039A1 (en) | 2014-12-25 | 2016-06-30 | 日東電工株式会社 | Photocurable resin composition and optical material using same |
| JP2017049461A (en) * | 2015-09-02 | 2017-03-09 | 日産化学工業株式会社 | Polymerizable composition for imprinting molding comprising reactive siloxane compound |
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| JP2012214716A (en) * | 2011-03-30 | 2012-11-08 | Kyoritsu Kagaku Sangyo Kk | Photocurable resin composition for imprint molding, imprint molding cured body and method for manufacturing them |
| JP2014234458A (en) | 2013-06-03 | 2014-12-15 | 昭和電工株式会社 | Curable composition, and cured product thereof |
| WO2015190544A1 (en) * | 2014-06-13 | 2015-12-17 | 東亞合成株式会社 | Curable composition |
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