CN111801770A - Photocurable composition for imprinting comprising polymer - Google Patents
Photocurable composition for imprinting comprising polymer Download PDFInfo
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- CN111801770A CN111801770A CN201980015183.5A CN201980015183A CN111801770A CN 111801770 A CN111801770 A CN 111801770A CN 201980015183 A CN201980015183 A CN 201980015183A CN 111801770 A CN111801770 A CN 111801770A
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- component
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- photocurable composition
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- 239000000203 mixture Substances 0.000 title claims abstract description 93
- 229920000642 polymer Polymers 0.000 title claims abstract description 27
- -1 acryloyloxy group Chemical group 0.000 claims abstract description 73
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical class O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 37
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 26
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 19
- 125000002723 alicyclic group Chemical group 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 17
- 239000000178 monomer Substances 0.000 claims abstract description 14
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000011164 primary particle Substances 0.000 claims abstract description 13
- 239000004593 Epoxy Substances 0.000 claims abstract description 12
- 239000003999 initiator Substances 0.000 claims abstract description 9
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 6
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 5
- 238000010438 heat treatment Methods 0.000 claims description 26
- 238000004519 manufacturing process Methods 0.000 claims description 25
- 150000001875 compounds Chemical class 0.000 claims description 12
- 239000003960 organic solvent Substances 0.000 claims description 12
- 238000000016 photochemical curing Methods 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 11
- 239000011347 resin Substances 0.000 claims description 10
- 229920005989 resin Polymers 0.000 claims description 10
- 238000000465 moulding Methods 0.000 claims description 8
- 239000003963 antioxidant agent Substances 0.000 claims description 7
- 230000003078 antioxidant effect Effects 0.000 claims description 7
- 238000004140 cleaning Methods 0.000 claims description 7
- 125000005842 heteroatom Chemical group 0.000 claims description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000011049 filling Methods 0.000 claims description 6
- 239000002530 phenolic antioxidant Substances 0.000 claims description 6
- 150000003568 thioethers Chemical class 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 5
- 125000005647 linker group Chemical group 0.000 claims description 4
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 claims description 3
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 3
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims description 3
- 125000005073 adamantyl group Chemical group C12(CC3CC(CC(C1)C3)C2)* 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 2
- 125000000962 organic group Chemical group 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 28
- 239000000758 substrate Substances 0.000 description 19
- 239000000243 solution Substances 0.000 description 17
- 239000011521 glass Substances 0.000 description 14
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 12
- 230000003287 optical effect Effects 0.000 description 12
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- 238000005227 gel permeation chromatography Methods 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 238000004383 yellowing Methods 0.000 description 8
- 239000006185 dispersion Substances 0.000 description 7
- 238000002834 transmittance Methods 0.000 description 7
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 6
- 239000004615 ingredient Substances 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 239000010453 quartz Substances 0.000 description 5
- 239000004793 Polystyrene Substances 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 4
- 229910052753 mercury Inorganic materials 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 229920002223 polystyrene Polymers 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 4
- 230000037303 wrinkles Effects 0.000 description 4
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 3
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 3
- 239000012975 dibutyltin dilaurate Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 3
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 3
- 238000001552 radio frequency sputter deposition Methods 0.000 description 3
- 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
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 description 2
- 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
- 235000002597 Solanum melongena Nutrition 0.000 description 2
- 244000061458 Solanum melongena Species 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- JOBBTVPTPXRUBP-UHFFFAOYSA-N [3-(3-sulfanylpropanoyloxy)-2,2-bis(3-sulfanylpropanoyloxymethyl)propyl] 3-sulfanylpropanoate Chemical compound SCCC(=O)OCC(COC(=O)CCS)(COC(=O)CCS)COC(=O)CCS JOBBTVPTPXRUBP-UHFFFAOYSA-N 0.000 description 2
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 2
- 239000002318 adhesion promoter Substances 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
- 238000005336 cracking Methods 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- 239000002612 dispersion medium Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 230000002093 peripheral effect Effects 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 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
- KWVGIHKZDCUPEU-UHFFFAOYSA-N 2,2-dimethoxy-2-phenylacetophenone Chemical compound C=1C=CC=CC=1C(OC)(OC)C(=O)C1=CC=CC=C1 KWVGIHKZDCUPEU-UHFFFAOYSA-N 0.000 description 1
- CNDCQWGRLNGNNO-UHFFFAOYSA-N 2-(2-sulfanylethoxy)ethanethiol Chemical compound SCCOCCS CNDCQWGRLNGNNO-UHFFFAOYSA-N 0.000 description 1
- QSOFJLDXOMMNNK-UHFFFAOYSA-N 2-(hydroxymethyl)-2-methylpropane-1,3-diol 3-sulfanylbutanoic acid Chemical compound CC(S)CC(O)=O.CC(S)CC(O)=O.CC(S)CC(O)=O.OCC(C)(CO)CO QSOFJLDXOMMNNK-UHFFFAOYSA-N 0.000 description 1
- GJKGAPPUXSSCFI-UHFFFAOYSA-N 2-Hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone Chemical compound CC(C)(O)C(=O)C1=CC=C(OCCO)C=C1 GJKGAPPUXSSCFI-UHFFFAOYSA-N 0.000 description 1
- BXYWKXBAMJYTKP-UHFFFAOYSA-N 2-[2-[2-[2-(3-sulfanylpropanoyloxy)ethoxy]ethoxy]ethoxy]ethyl 3-sulfanylpropanoate Chemical compound SCCC(=O)OCCOCCOCCOCCOC(=O)CCS BXYWKXBAMJYTKP-UHFFFAOYSA-N 0.000 description 1
- VFBJXXJYHWLXRM-UHFFFAOYSA-N 2-[2-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]ethylsulfanyl]ethyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCCSCCOC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 VFBJXXJYHWLXRM-UHFFFAOYSA-N 0.000 description 1
- UHFFVFAKEGKNAQ-UHFFFAOYSA-N 2-benzyl-2-(dimethylamino)-1-(4-morpholin-4-ylphenyl)butan-1-one Chemical compound C=1C=C(N2CCOCC2)C=CC=1C(=O)C(CC)(N(C)C)CC1=CC=CC=C1 UHFFVFAKEGKNAQ-UHFFFAOYSA-N 0.000 description 1
- 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
- LWRBVKNFOYUCNP-UHFFFAOYSA-N 2-methyl-1-(4-methylsulfanylphenyl)-2-morpholin-4-ylpropan-1-one Chemical compound C1=CC(SC)=CC=C1C(=O)C(C)(C)N1CCOCC1 LWRBVKNFOYUCNP-UHFFFAOYSA-N 0.000 description 1
- HXIQYSLFEXIOAV-UHFFFAOYSA-N 2-tert-butyl-4-(5-tert-butyl-4-hydroxy-2-methylphenyl)sulfanyl-5-methylphenol Chemical compound CC1=CC(O)=C(C(C)(C)C)C=C1SC1=CC(C(C)(C)C)=C(O)C=C1C HXIQYSLFEXIOAV-UHFFFAOYSA-N 0.000 description 1
- PFANXOISJYKQRP-UHFFFAOYSA-N 2-tert-butyl-4-[1-(5-tert-butyl-4-hydroxy-2-methylphenyl)butyl]-5-methylphenol Chemical compound C=1C(C(C)(C)C)=C(O)C=C(C)C=1C(CCC)C1=CC(C(C)(C)C)=C(O)C=C1C PFANXOISJYKQRP-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
- BUZICZZQJDLXJN-UHFFFAOYSA-N 3-azaniumyl-4-hydroxybutanoate Chemical compound OCC(N)CC(O)=O BUZICZZQJDLXJN-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
- 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
- 238000004438 BET method Methods 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- GHKOFFNLGXMVNJ-UHFFFAOYSA-N Didodecyl thiobispropanoate Chemical compound CCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCC GHKOFFNLGXMVNJ-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 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
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-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
- MOLCWHCSXCKHAP-UHFFFAOYSA-N adamantane-1,3-diol Chemical compound C1C(C2)CC3CC1(O)CC2(O)C3 MOLCWHCSXCKHAP-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
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- 238000004458 analytical method Methods 0.000 description 1
- 230000003667 anti-reflective effect Effects 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
- 125000004429 atom Chemical group 0.000 description 1
- CHIHQLCVLOXUJW-UHFFFAOYSA-N benzoic anhydride Chemical class 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
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- TUGLVWDSALSXCF-UHFFFAOYSA-N decane;methanol Chemical compound OC.OC.CCCCCCCCCC TUGLVWDSALSXCF-UHFFFAOYSA-N 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
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 239000000113 methacrylic resin Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 1
- MBAUOPQYSQVYJV-UHFFFAOYSA-N octyl 3-[4-hydroxy-3,5-di(propan-2-yl)phenyl]propanoate Chemical compound OC1=C(C=C(C=C1C(C)C)CCC(=O)OCCCCCCCC)C(C)C MBAUOPQYSQVYJV-UHFFFAOYSA-N 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 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
- 239000011342 resin composition Substances 0.000 description 1
- 239000011163 secondary particle Substances 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
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- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
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- B29D11/00—Producing optical elements, e.g. lenses or prisms
- B29D11/00009—Production of simple or compound lenses
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- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
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- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
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- C08F220/343—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate in the form of urethane links
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
- C08F290/067—Polyurethanes; Polyureas
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G75/02—Polythioethers
- C08G75/04—Polythioethers from mercapto compounds or metallic derivatives thereof
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C—CHEMISTRY; METALLURGY
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- G—PHYSICS
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- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
Abstract
The present invention addresses the problem of providing a novel photocurable composition for imprinting, which contains a polymer. The solution is a photocurable composition for imprinting, which comprises the following component (a), the following component (b), the following component (c), the following component (d) and the following component (e). (a) The method comprises the following steps Surface-modified silica particles having a primary particle diameter of 1nm to 100nm, (b): 1 an alicyclic (meth) acrylate monomer having at least 1 (meth) acryloyloxy group in the molecule, (c): amino groupA urethane (meth) acrylate compound or an epoxy (meth) acrylate compound, (d): a polymer having a repeating structural unit represented by the following formula (1) and a repeating structural unit represented by the following formula (2), (e): photo radical initiator (in the formula, R)1And R2Each independently represents a methyl group or a hydrogen atom, A1Represents an alkyl group having 1 to 8 carbon atoms, A2Represents a single bond or an alkylene group having 1 to4 carbon atoms, X represents a polymerizable group having 1 or 2 or more (meth) acryloyloxy groups, Z1Represents a divalent group. )
Description
Technical Field
The present invention relates to a photocurable composition for imprinting, which contains an alicyclic (meth) acrylate monomer, a urethane (meth) acrylate compound or an epoxy (meth) acrylate compound, surface-modified silica particles, a polymer having a radical polymerizable group, and a photo-radical initiator. More specifically, the present invention relates to a photocurable composition which has excellent optical properties (transparency, high refractive index, and high abbe number), and in which an antireflection layer (AR layer) is formed on a cured product and a molded body, and then the antireflection layer is heat-treated, whereby cracks are not generated in the antireflection layer, and further cracks are not generated in the cured product after cleaning or development with an organic solvent.
Background
Resin lenses are used in electronic devices such as mobile phones, digital cameras, and vehicle-mounted cameras, and are required to have excellent optical characteristics according to the purpose of the electronic devices. In addition, depending on the form of use, high durability such as heat resistance and weather resistance, and high productivity enabling high-yield molding are required. As a material for a resin lens that satisfies such a demand, for example, thermoplastic transparent resins such as polycarbonate resin, cycloolefin polymer, and methacrylic resin are used.
In addition, although a plurality of lenses are used in a high-resolution camera module, a lens having low wavelength dispersion, that is, a high abbe number is mainly used, and an optical material for forming the lens is required. Further, in the production of resin lenses, in order to improve the yield and production efficiency and further suppress optical axis deviation in lens lamination, a shift from injection molding of a thermoplastic resin to wafer-level molding by extrusion molding using a curable resin that is liquid at room temperature has been actively studied. In wafer level molding, a hybrid lens system in which a lens is formed on a support such as a glass substrate is generally used from the viewpoint of productivity.
As a photocurable resin capable of being molded at a wafer level, a radical curable resin composition has been conventionally used from the viewpoint of high transparency, resistance to thermal yellowing, and mold releasability from a mold (patent document 1). Further, a curable composition is known which contains silica particles surface-modified with a silane compound, zirconia particles surface-modified with a dispersant, or other surface-modified oxide particles to obtain a cured product having a high abbe number (for example, patent documents 2 and 3).
Documents of the prior art
Patent document
Patent document 1: japanese patent No. 5281710 (International publication No. 2011/105473)
Patent document 2: japanese patent laid-open No. 2014-234458
Patent document 3: international publication No. 2016/104039
Disclosure of Invention
Problems to be solved by the invention
When the molded article is a lens, an antireflection layer made of an inorganic substance such as silicon oxide or titanium oxide is formed on the molded article. Therefore, there is a problem that cracks are generated in the antireflection layer by heat-treating the lens coated with the antireflection layer. In addition, the curable composition containing the surface-modified oxide particles has a problem that, in a developing step of cleaning uncured portions such as the outer peripheral portion of a wafer-shaped molded body having a plurality of lens patterns formed thereon after imprinting with an organic solvent, the organic solvent significantly attacks the wafer-shaped molded body, and cracks are generated in the wafer-shaped molded body.
There is still no curable resin material which can provide a molded article having a high abbe number (for example, 53 or more) and high transparency and usable as a lens for a high-resolution camera module, in which a crack does not occur in an antireflection layer formed as an upper layer of the molded article by a heat treatment thereafter, and further, in a developing step of cleaning an uncured portion such as an outer peripheral portion of the wafer-shaped molded article by an organic solvent, a crack does not occur in the wafer-shaped molded article, and development of the material has been desired. The present invention has been made in view of the above circumstances, and an object thereof is to provide a photocurable composition which can form a molded article having a high abbe number, a high refractive index, high transparency and thermal yellowing resistance, and which can form a molded article having a high cracking resistance in which an antireflection layer formed on an upper layer of the molded article does not crack when the molded article is subjected to a heat treatment and does not crack even when exposed to a developing step.
Means for solving the problems
The present inventors have intensively studied to solve the above problems, and as a result, they have found that a molded article obtained from a photocurable composition by blending surface-modified silica particles and a polymer having a radical polymerizable group in the photocurable composition at a predetermined ratio has a high refractive index nD(1.50 or more) and a high Abbe number vD(53 or more) and exhibits a high transmittance of 90% or more at a wavelength of 410nm, and the anti-reflective layer as an upper layer of the molded article is free from cracks and wrinkles by heat treatment at 175 ℃, and further free from cracks in a development step using an organic solvent, thereby completing the present invention.
That is, a first aspect of the present invention is a photocurable composition for imprinting, comprising 10 to 40 parts by mass of the component (a), 10 to 50 parts by mass of the component (b), 10 to 50 parts by mass of the component (c), 1 to 10 parts by mass of the component (d), and 0.1 to 5 parts by mass of the component (e), with respect to 100 parts by mass of the sum of the component (a), the component (b), the component (c), and the component (d).
(a) The components: surface-modified silica particles having a primary particle diameter of 1 to 100nm
(b) The components: 1 alicyclic (meth) acrylate monomer having at least 1 (meth) acryloyloxy group in the molecule (excluding the compound as the component (c))
(c) The components: urethane (meth) acrylate compound or epoxy (meth) acrylate compound (excluding the polymer as the component (d))
(d) The components: a polymer having a repeating structural unit represented by the following formula (1) and a repeating structural unit represented by the following formula (2)
(e) The components: photo-radical initiator
(in the formula, R1And R2Each independently represents a methyl group or a hydrogen atom, A1Represents an alkyl group having 1 to 8 carbon atoms, A2Represents a single bond or an alkylene group having 1 to4 carbon atoms, X represents a polymerizable group having 1 or 2 or more (meth) acryloyloxy groups, Z1Represents a divalent group represented by the following formula (a1), formula (a2), formula (a3) or formula (a 4). )
The photocurable composition for imprints of the present invention may further comprise 1 to 15 parts by mass of the following component (f) per 100 parts by mass of the sum of the components (a), (b), (c) and (d).
(f) The components: a polyfunctional thiol compound represented by the following formula (3)
(in the formula, A)3Represents a single bond or a linear or branched alkylene group having 1 to 6 carbon atoms, Z2Represents a single bond, an ester bond "-C (═ O) O-" or an ether bond "-O-", Q represents an organic group having 2 to 12 carbon atoms and containing at least 1 hetero atom or no hetero atom, or a hetero atom, and r represents an integer of 2 to 6. )
Here, the hetero atom means an atom other than a carbon atom and a hydrogen atom, and examples thereof include a nitrogen atom, an oxygen atom and a sulfur atom.
The photocurable composition for imprinting of the present invention may further comprise: 0.05 to 3 parts by mass of the following component (g) per 100 parts by mass of the sum of the components (a), (b), (c) and (d); and/or 0.1 to 3 parts by mass of the following component (h) per 100 parts by mass of the sum of the components (a), (b), (c) and (d).
(g) The components: phenolic antioxidant
(h) The components: thioether antioxidant
The surface-modified silica particles having a primary particle diameter of 1nm to 100nm as the component (a) are, for example, silica particles surface-modified by a (meth) acryloyloxy group bonded to a silicon atom via a divalent linking group. The divalent linking group is, for example, an alkylene group having 1 to 5 carbon atoms, preferably an alkylene group having 2 or 3 carbon atoms.
The urethane (meth) acrylate compound or the epoxy (meth) acrylate compound as the component (c) is a compound having, for example, 2 or 3 (meth) acryloyloxy groups in 1 molecule.
The polymer as the component (d) may further have a repeating structural unit represented by the following formula (4).
(in the formula, R3Represents a methyl group or a hydrogen atom, Z3Represents a single bondOr ethyleneoxy, A4An alicyclic hydrocarbon group having 5 to 13 carbon atoms. )
In the above-mentioned Z3Represents an ethyleneoxy group (-CH)2CH2O-group), the O atom of the ethyleneoxy group and A which represents the above-mentioned alicyclic hydrocarbon group4And (4) combining.
Examples of the alicyclic hydrocarbon group having 5 to 13 carbon atoms include cyclopentyl, cyclohexyl, isobornyl, tricyclo [5.2.1.02,6] dec-8-yl, tricyclodecenyl, and adamantyl groups which may have an alkyl group having 1 to 3 carbon atoms as a substituent.
The polymerizable group having 1 or 2 or more (meth) acryloyloxy groups is, for example, a group represented by the following formula (X0), formula (X1), formula (X2), formula (X3), formula (X4), formula (X5) or formula (X6), or a group obtained by replacing a part or all of acryloyloxy groups contained in these groups with methacryloyloxy groups.
The refractive index n at a wavelength of 589nm of a cured product of the photocurable composition for imprinting of the present inventionDIs 1.50 or more, and the Abbe number v of the cured productDIs 53 or more. The above refractive index nDThe Abbe number vDHigher values of both are preferred, but for example, the refractive index nDSo long as it is in the range of 1.50 to 1.55, Abbe number vDThe range of 53 to 60 may be used.
The second aspect of the present invention is a cured product of the photocurable composition for imprinting.
A third aspect of the present invention is a method for manufacturing a resin lens, including the steps of: and a step of subjecting the photocurable composition for imprinting to imprint molding.
A fourth aspect of the present invention is a method for producing a molded article of a photocurable composition for imprinting, the method including the steps of: a filling step of filling the photocurable composition for imprinting into a space between a support and a mold that are in contact with each other or into an internal space of a detachable mold; and a photocuring step of exposing the photocurable composition for imprinting filled in the space to light to cure the composition. The above-mentioned mold is also referred to as a mold.
The method for producing a molded article of the present invention may further comprise the steps of: a mold releasing step of taking out the photo-cured product obtained after the photo-curing step; and a heating step of heating the photo-cured product before, during, or after the releasing step. The method may further comprise the steps of: and a developing step of cleaning the uncured portion with an organic solvent after the releasing step and before the heating step. The photo-cured product after the development step may be photo-cured by exposure again.
In the method for producing a molded article of the present invention, the molded article is, for example, a lens for a camera module.
ADVANTAGEOUS EFFECTS OF INVENTION
The photocurable composition for imprinting of the present invention comprises the above-mentioned component (a) to component (e), and further optionally comprises the above-mentioned component (f), and the above-mentioned component (g) and/or the above-mentioned component (h), and therefore a cured product and a molded product obtained from the photocurable composition exhibit optical characteristics desired as an optical device, for example, a lens for a high-resolution camera module, that is, a high abbe number, a high refractive index, high transparency, and thermal yellowing resistance. Further, regarding the cured product and the molded product obtained from the photocurable composition of the present invention, neither cracks nor wrinkles are generated in the antireflection layer on the upper layer of the cured product and the molded product by the heat treatment at 175 ℃.
Detailed Description
[ (a) ingredient: surface-modified silica particles
The surface-modified silica particles that can be used as component (a) of the photocurable composition for imprinting of the present invention have a primary particle diameter of 1nm to 100 nm. Here, the primary particles are particles constituting a powder, and particles obtained by aggregating the primary particles are referred to as secondary particles. The primary particle diameter may be determined by a relational expression that holds between a specific surface area (surface area per unit mass) S of the surface-modified silica particle measured by a gas adsorption method (BET method), a density ρ of the surface-modified silica particle, and a primary particle diameter D: d is calculated as 6/(ρ S). The primary particle diameter calculated from the relational expression is an average particle diameter and is the diameter of the primary particle. The surface-modified silica particles are surface-modified with, for example, (meth) acryloyloxy groups bonded to silicon atoms via divalent linking groups. When the surface-modified silica particles are used, the surface-modified silica particles may be used as they are, or a colloidal substance (sol in which colloidal particles are dispersed in a dispersion medium) obtained by dispersing the surface-modified silica particles in an organic solvent as a dispersion medium in advance may be used. When the sol containing the surface-modified silica particles is used, the concentration of the solid content may be in the range of 10 to 60 mass%.
Examples of the sol containing the surface-modified silica particles include MEK-AC-2140Z, MEK-AC-4130Y, MEK-AC-5140Z, PGM-AC-2140Y, PGM-AC-4130Y, MIBK-AC-2140Z, MIBK-SD-L (manufactured by Nissan Chemicals Co., Ltd.), ELCOM (registered trademark) V-8802, and ELCOM V-8804 (manufactured by Nissan catalytic Chemicals Co., Ltd.).
The content of the component (a) in the photocurable composition for imprinting of the present invention is 10 to 40 parts by mass, preferably 15 to 35 parts by mass, based on 100 parts by mass of the sum of the component (a), the component (b) described later, the component (c) described later, and the component (d) described later. If the content of the component (a) is less than 10 parts by mass, cracks in the antireflection layer formed on the cured product obtained from the above-mentioned photocurable composition for imprinting and the molded article may not be suppressed. If the content of the component (a) is more than 40 parts by mass, haze may be generated in the cured product and the molded article, and the transmittance may be lowered.
The surface-modified silica particles of the component (a) may be used alone in 1 kind or in combination with 2 or more kinds.
[ (b) component: alicyclic (meth) acrylate monomer ]
The alicyclic (meth) acrylate monomer that can be used as the component (b) of the photocurable composition for imprinting of the present invention is a monomer compound having at least 1, for example, 1 or 2 (meth) acryloyloxy groups and 1 alicyclic hydrocarbon in 1 molecule of the monomer, and excluding the compound as the component (c) described later. Examples of the alicyclic (meth) acrylate monomer include cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 3, 5-trimethylcyclohexyl (meth) acrylate, 4-t-butylcyclohexyl (meth) acrylate, menthyl (meth) acrylate, isobornyl (meth) acrylate, norbornyl (meth) acrylate, 1-adamantyl (meth) acrylate, 2-methyladamantan-2-yl (meth) acrylate, 2-ethyladamantan-2-yl (meth) acrylate, tricyclo [5.2.1.0(2,6) ] decyl (meth) acrylate, tricyclo [5.2.1.0(2,6) ] decyloxyethyl (meth) acrylate, 1, 4-cyclohexanedimethanol di (meth) acrylate, a salt thereof, and a salt thereof, Tricyclo [5.2.1.0(2,6) ] decane dimethanol di (meth) acrylate, and 1, 3-adamantanediol di (meth) acrylate.
As the alicyclic (meth) acrylate monomer, commercially available ones can be used, and examples thereof include ビスコート #155, IBXA, ADMA (manufactured by Osaka organic chemical industry Co., Ltd., supra), NK エステル A-IB, NK エステル IB, NK エステル A-DCP, NK エステル DCP (manufactured by Newzhonghama chemical industry Co., Ltd., supra), and ファンクリル (registered trademark) FA-511AS, ファンクリル FA-512AS, ファンクリル FA-AS, ファンクリル FA-512M, ファンクリル FA-512MT, and ファンクリル FA-513M (manufactured by Hitachi chemical Co., Ltd.).
The content of the component (b) in the photocurable composition for imprints of the present invention is 10 to 50 parts by mass, preferably 20 to 45 parts by mass, based on 100 parts by mass of the sum of the component (a), the component (b), the component (c) described later and the component (d) described later. If the content of the component (b) is less than 10 parts by mass, the refractive index of the cured product and the molded article obtained from the above photocurable composition for imprinting may be reduced to less than 1.50. If the content of the component (b) is more than 50 parts by mass, the amount of warpage of the support, which may form the cured product or the molded article, increases.
The alicyclic (meth) acrylate monomer as the component (b) may be used alone in 1 kind or in combination with 2 or more kinds.
[ (c) ingredient: urethane (meth) acrylate compound or epoxy (meth) acrylate compound ]
The urethane (meth) acrylate compound that can be used as the component (C) of the photocurable composition for imprinting of the present invention is a compound having a urethane structure represented by at least 2 (meth) acryloyloxy groups and at least 2 ″ -NH-C (═ O) O ″) in 1 molecule, and does not include a polymer as the component (d) described later. Examples of the urethane (meth) acrylate compound include EBECRYL (registered trademark) 230, EBECRYL 270, EBECRYL 280/15IB, EBECRYL 284, EBECRYL 4491, EBECRYL 4683, EBECRYL 4858, EBECRYL 8307, EBECRYL8402, EBECRYL 8411, EBECRYL4, EBECRYL 8807, EBECRYL 9270, EBECRYL 8800, EBECRYL294/25HD, EBECRYL 4100, EBECRYL 4220, EBECRYL 4513, EBECRYL 4738, EBECRRRYL 4740, EBECRYL 4820, EBECRYL 838311, EBECRYL 8465, EBECRYL 9260, EBECRYL 8701, KRM7735, KRM8667, KRM 8296 (see above, 5863 オルネクス, 27, 3218-3212000-33040), UV-364657-36463000-36463, UV-36567-36463-36567, UV-7461TE (manufactured by Nippon synthetic chemical Co., Ltd.), UA-306H, UA-306T, UA-306I, UA-510H, UF-8001G (manufactured by Kyowa chemical Co., Ltd.), M-1100, M-1200 (manufactured by Toyo synthetic Co., Ltd.), NK オリゴ U-2PPA, NK オリゴ U-6LPA, NK オリゴ U-200PA, NK オリゴ U-160TM, NK オリゴ U-290TM, NK オリゴ UA-4200, NK オリゴ UA-4400, NK オリゴ UA-122P, NK オリゴ UA-7100, and NK オリゴ UA-W2A (manufactured by Nippon kingdom chemical Co., Ltd.).
The epoxy (meth) acrylate compound that can be used as the component (c) of the photocurable composition for imprinting of the present invention is an ester obtained by reacting a compound having at least 2 epoxy rings in 1 molecule with (meth) acrylic acid, and does not include a polymer compound as the component (d) described later. Examples of the epoxy (meth) acrylate compound include EBECRYL (registered trademark) 645, EBECRYL 648, EBECRYL 860, EBECRYL 3500, EBECRYL 3608, EBECRYL 3702, EBECRYL 3708 (see above, manufactured by ダイセル, オルネクス), DA-911M, DA-920, DA-931, DA-314, DA-212 (see above, manufactured by ナガセケムテックス), HPEA-100 (see ケーエスエム), and ユニディック (registered trademark) V-5500, ユニディック V-5502, and ユニディック V-5508 (see above, manufactured by DIC (trademark)).
As the urethane (meth) acrylate compound or the epoxy (meth) acrylate compound as the component (c), a compound having 2 or 3 (meth) acryloyloxy groups in the molecule of the compound 1 is preferably used.
The content of the component (c) in the photocurable composition for imprints of the present invention is 10 to 50 parts by mass, preferably 30 to 50 parts by mass, based on 100 parts by mass of the sum of the component (a), the component (b), the component (c) and the component (d) described later. If the content of the component (c) is less than 10 parts by mass, the cured product and the molded product obtained from the above-mentioned photocurable composition for imprinting become brittle, and the cracking resistance of the cured product and the molded product may be lowered upon heating. If the content of the component (b) is more than 50 parts by mass, the change in the shape of the cured product and the molded article during heating may be increased due to the decrease in the crosslinking density.
The urethane (meth) acrylate compound or the epoxy (meth) acrylate compound as the component (c) may be used alone in 1 kind or in combination of 2 or more kinds.
[ (d) ingredient: polymer ]
The polymer that can be used as the component (d) of the photocurable composition for imprinting of the present invention is a copolymer containing a polymerizable group, and may have at least a repeating structural unit represented by the above formula (1) and a repeating structural unit represented by the above formula (2), and may further have a repeating structural unit represented by the above formula (4).
Examples of the repeating structural unit represented by the above formula (1) include repeating structural units represented by the following formulae (1-1) to (1-6).
Examples of the repeating structural unit represented by the above formula (2) include repeating structural units represented by the following formulae (2-1) to (2-44).
Examples of the repeating structural unit represented by the above formula (4) include repeating structural units represented by the following formulae (4-1) to (4-22).
Examples of the polymer of the component (D) include ヒタロイド (registered trademark) 7975, ヒタロイド 7975D, ヒタロイド 7988 (manufactured by Hitachi chemical Co., Ltd.), RP-274S, RP-310 (manufactured by ケーエスエム Co., Ltd.), アートキュア (registered trademark) RA-3602MI, アートキュア OPA-5000, アートキュア OPA-2511, and アートキュア RA-341 (manufactured by Industrial Co., Ltd.).
The content of the component (d) in the photocurable composition for imprints of the present invention is 1 to 10 parts by mass, preferably 3 to 7 parts by mass, based on 100 parts by mass of the sum of the component (a), the component (b), the component (c) and the component (d). If the content of the component (d) is less than 1 part by mass, the effect of suppressing the occurrence of cracks in the cured product in the developing step using a solvent is insufficient. If the content of the component (d) is more than 10 parts by mass, the viscosity of the photocurable composition for imprinting is greatly increased, and thus the workability is significantly reduced.
The component (d) may be a polymer of 1 kind alone or 2 or more kinds in combination.
[ (e) ingredient: photo radical initiator
Examples of the photo-radical initiator that can be used as the component (e) of the photocurable composition for imprint of the present invention include alkylbenzophenones, benzophenones, Michler's (Michler) ketones, acylphosphine oxides, benzoylbenzoates, oxime esters, tetramethylthiuram monosulfide, and thioxanthones, and particularly preferred is a photo-cleavage type photo-radical polymerization initiator. As the photo radical initiator, commercially available products such as IRGACURE (registered trademark) 184, IRGACURE369, IRGACURE 651, IRGACURE 500, IRGACURE 819, IRGACURE907, IRGACURE 784, IRGACURE 2959, IRGACURE CGI1700, IRGACURE CGI1750, IRGACURE CGI1850, IRGACUREC 24-61, IRGACURE TPO, IRGACURE 1116, IRGACURE 1173 (see above, manufactured by BASF ジャパン Co., Ltd.), and ESACURE KIP150, ESACURE KIP65LT, ESACURE KIP100F, ESACURE 37, ESURE 55, ESURE KTO46, ESACURE KIP75 (see above, manufactured by Lamberti Co., Ltd.) can be used.
The content of the component (e) in the photocurable composition for imprints of the present invention is 0.1 to 5 parts by mass, preferably 0.5 to 3 parts by mass, based on 100 parts by mass of the sum of the component (a), the component (b), the component (c) and the component (d). If the content of the component (e) is less than 0.1 part by mass, the strength of a cured product and a molded article obtained from the above-mentioned photocurable composition for imprinting may be reduced. If the content of the component (e) is more than 5 parts by mass, the heat yellowing resistance of the cured product and the molded article may be deteriorated.
The photo radical initiator as the component (e) may be used alone in 1 kind or in combination with 2 or more kinds.
[ (f) component: polyfunctional thiol Compound ]
The polyfunctional thiol compound that can be used as the component (f) of the photocurable composition for imprints of the present invention is a polyfunctional thiol compound represented by the above formula (3). Examples of the polyfunctional thiol compound represented by the formula (3) include 1, 2-ethanedithiol, 1, 3-propanedithiol, bis (2-mercaptoethyl) ether, trimethylolpropane tris (3-mercaptopropionate), tris- [ (3-mercaptopropionyloxy) -ethyl ] -isocyanurate, tetraethyleneglycol bis (3-mercaptopropionate), dipentaerythritol hexa (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptobutyrate), 1, 4-bis (3-mercaptobutyryloxy) butane, 1,3, 5-tris (3-mercaptobutyryloxyethyl) -1,3, 5-triazine-2, 4,6- (1H,3H,5H) -trione, trimethylolpropane tris (3-mercaptobutyrate), And trimethylolethane tris (3-mercaptobutyrate), pentaerythritol tris (3-mercaptopropyl) ether. As the polyfunctional thiol compound represented by the above formula (3), commercially available products such as カレンズ MT (registered trademark) PE1, カレンズ NR1, カレンズ BD1, TPMB, TEMB (manufactured by SHOWA DENKO K.K.), TMMP, TEMP, PEMP, EGMP-4, DPMP, TMMP II-20P, and PEMP II-20P, PEPT (manufactured by SC ORGANIC CHEMICAL CORPORATION Co., Ltd.) can be used.
When the photocurable composition for imprints of the present invention contains component (f), the content thereof is 1 to 15 parts by mass, preferably 3 to 10 parts by mass, based on 100 parts by mass of the sum of component (a), component (b), component (c) and component (d). If the content of the component (f) is more than 15 parts by mass, the mechanical properties of the cured product and the molded product obtained from the above-mentioned photocurable composition for imprint are deteriorated, and therefore the cured product and the molded product may be deformed in a mounting process accompanied by heat treatment.
The polyfunctional thiol compound as the component (f) may be used alone in 1 kind or in combination of 2 or more kinds.
[ (g) ingredient: phenol-based antioxidant
Examples of the phenolic antioxidant which can be used as the component (g) of the photocurable composition for imprinting of the present invention include IRGANOX (registered trademark) 245, IRGANOX 1010, IRGANOX 1035, IRGANOX 1076, IRGANOX 1135 (see above, manufactured by BASF ジャパン (Co.), SUMILIZER (registered trademark) GA-80, SUMILIZER GP, SUMILIZER MDP-S, SUMILIZER BBM-S, SUMILIZER WX-R (see above, manufactured by SUMITOMATIC CHEMICAL Co., Ltd.), and アデカスタブ (see registered trademarks) AO-20, アデカスタブ AO-30, アデカスタブ AO-40, アデカスタブ AO-50, アデカスタブ AO-60, アデカスタブ AO-80, アデカスタブ -330 (see above, manufactured by ADEKA).
When the photocurable composition for imprints of the present invention contains the component (g), the content thereof is 0.05 to 3 parts by mass, preferably 0.1 to 1 part by mass, based on 100 parts by mass of the sum of the component (a), the component (b), the component (c) and the component (d).
The phenolic antioxidant as the component (g) may be used singly in 1 kind or in combination of 2 or more kinds.
[ (h) ingredient: thioether-based antioxidant
Examples of the thioether-based antioxidant that can be used as the component (h) of the photocurable composition for imprint of the present invention include アデカスタブ (registered trademark) AO-412S, アデカスタブ AO-503 (available from ADEKA corporation), IRGANOX (registered trademark) PS802, IRGANOX PS800 (available from BASF corporation), and SUMILIZER (registered trademark) TP-D (available from sumitomo chemical corporation).
When the photocurable composition for imprints of the present invention contains the component (h), the content thereof is 0.1 to 3 parts by mass, preferably 0.1 to 1 part by mass, based on 100 parts by mass of the sum of the component (a), the component (b), the component (c) and the component (d).
The thioether antioxidant as the component (h) may be used singly or in combination of 1 or more.
< method for producing photocurable composition for imprinting >
The method for preparing the photocurable composition for imprinting of the present invention is not particularly limited. The preparation method includes, for example, a method of mixing the component (a), the component (b), the component (c), the component (d), the component (e), and if necessary, the component (f), the component (g), and/or the component (h) at a predetermined ratio to prepare a uniform solution.
The photocurable composition for imprinting of the present invention prepared into a solution is preferably used after being filtered using a filter or the like having a pore size of 0.1 to 5 μm.
< cured product >
The photocurable composition for imprinting of the present invention can be exposed to light (photocured) to obtain a cured product, and the cured product of the present invention is also an object. Examples of the light for exposure include ultraviolet rays, electron beams, and X-rays. As the light source used for the ultraviolet irradiation, for example, a solar ray, a chemical lamp, a low-pressure mercury lamp, a high-pressure mercury lamp, a metal halide lamp, a xenon lamp, and a UV-LED can be used. After exposure, post-baking may be performed to stabilize the physical properties of the cured product. The post-baking is not particularly limited, and is usually carried out at 50 to 260 ℃ for 1 minute to 24 hours using a hot plate, an oven or the like.
The cured product obtained by photocuring the photocurable composition for imprint of the present invention has an abbe number vDA refractive index n at a wavelength of 589nm (D line) of a cured product of 53 or moreDIs 1.50 or more, and yellowing due to heating is not observed. Therefore, the photocurable composition for imprints of the present invention can be suitably used for forming resin lenses.
< shaped body >
The photocurable composition for imprinting of the present invention can be used, for example, in an imprint molding method, whereby various molded articles can be easily produced simultaneously with the formation of a cured product. Examples of a method for producing a molded article include a method comprising the following steps: a filling step of filling the photocurable composition for imprinting of the present invention into a space between a support and a mold that are in contact with each other, or into an internal space of a detachable mold; a photocuring step of exposing the photocurable composition for imprinting filled in the space to light for photocuring; a mold releasing step of taking out the photo-cured product obtained in the photo-curing step; and a heating step of heating the photo-cured product before, during, or after the releasing step. In this case, the method may further include, after the step of releasing the photo-cured product obtained in the photo-curing step: and a developing step of cleaning and removing the uncured part with an organic solvent before the heating step. The method for producing the uncured portion is not particularly limited, but an unexposed portion, that is, an uncured portion can be produced by exposing only a predetermined position by mask exposure, projection exposure, or the like. Further, the photo-cured product after the development step may be subjected to photo-curing by re-exposure, if necessary.
The photocuring step of photocuring by exposure may be carried out under conditions for obtaining the cured product. Further, the conditions of the heating step for heating the photo-cured product are not particularly limited, and are appropriately selected from the range of 50 to 260 ℃ and 1 minute to 24 hours. The heating method is not particularly limited, and examples thereof include an electric heating plate and an oven. The molded article produced by such a method can be suitably used as a lens for a camera module.
Examples
The present invention will be described more specifically with reference to the following examples, but the present invention is not limited to the following examples. In the following examples and comparative examples, the apparatus and conditions used for preparation of the sample and analysis of the physical properties are as follows.
(1) Gel Permeation Chromatography (GPC)
The device comprises the following steps: GPC System manufactured by Shimadzu corporation
Column: shodex (registered trademark) GPC KF-804L, product of Shorey electric corporation, GPC KF-803L
Column temperature: 40 deg.C
Solvent: tetrahydrofuran (THF)
Standard sample: polystyrene
(2) Stirring defoaming machine
The device comprises the following steps: a rotation/revolution mixer あわとり Terra (registered trademark) ARE-310 (manufactured by Kabushiki Kaisha) シンキー
(3) UV exposure
The device comprises the following steps: アイグラフィックス intermittent UV irradiation device (high pressure mercury lamp 2kW X1 lamp)
(4) Transmittance of light
The device comprises the following steps: ultraviolet visible near infrared spectrophotometer V-670 made by Nippon spectral Kabushiki Kaisha
Reference: air (a)
(5) Refractive index nDAbbe number vD
The device comprises the following steps: アントンパール Multi-wavelength refractometer Abbemat MW
Measuring temperature: 23 deg.C
(6) Optical microscope (evaluation of crack resistance in developing step Using organic solvent)
The device comprises the following steps: MX61A, DP72 and BX-UCB manufactured by オリンパス Strain
Conditions are as follows: reflection (bright field), objective 5 times
(7) Formation of anti-reflection layer
The device comprises the following steps: サンユー electronic (strain) -made RF sputtering device SRS-700T/LL
The method comprises the following steps: RF sputtering/magnetron mode
Conditions are as follows: silicon target, 250W RF power,
the vertical distance between the target and the substrate is 100mm, the offset distance is 100mm,
ar flow rate of 45sccm, O2The flow rate is 2sccm,
the temperature is room temperature, and the sputtering time is 15 minutes
(8) Optical microscope (observation of antireflection film)
The device comprises the following steps: VHX-1000 and VH-Z1000R, manufactured by Strain キーエンス
Conditions are as follows: reflection (bright field), objective 500 times
(9) Lens molding
The device comprises the following steps: mingchang machine manufactured 6 inch corresponding nano printer
Light source: a high pressure mercury lamp was exposed to light through an i-ray band pass filter HB0365 (manufactured by Asahi-Chikusho Co., Ltd.)
Molding conditions are as follows: the pressing pressure is 100N, 20mW/cm2X 300 seconds
(10) Lens height determination
The device comprises the following steps: three eagle optical instrument (trunk) system non-contact surface character determination device PF-60
The supply sources of the compounds used in the respective production examples, examples and comparative examples are as follows.
A-DCP: trade name manufactured by shinkamura chemical industry (ltd.): NK エステル A-DCP
MEK-AC-2140Z: trade name manufactured by Nissan chemical Co., Ltd.: オルガノシリカゾル MEK-AC-2140Z
AOI: trade name manufactured by showa electrician (strain): カレンズ AOI (registered trademark)
BEI: trade name manufactured by showa electrician (strain): カレンズ BEI (registered trademark)
FA-513 AS: trade name manufactured by Hitachi chemical Co., Ltd.: ファンクリル (registered trademark) FA-513AS
UA-4200: trade name manufactured by shinkamura chemical industry (ltd.): NK オリゴ UA-4200
DA-212: ナガセケムテックス trade name: デナコールアクレート DA-212
NR 1: trade name manufactured by showa electrician (strain): カレンズ (registered trademark) MT NR1
I184: trade name manufactured by BASF ジャパン (strain): irgacure (registered trademark) 184
I245: trade name manufactured by BASF ジャパン (strain): irganox (registered trademark) 245
AO-503: trade name of ADEKA: アデカスタブ (registered trademark) AO-503
Production example 1
In a 500mL eggplant type flask, 120g of A-DCP as the alicyclic (meth) acrylate monomer (b) was weighed and dissolved in 120g of methyl ethyl ketone (hereinafter, abbreviated as MEK in the present specification). Then, 260.3g of MEK-AC-2140Z (silica particles having a primary particle diameter of 10 to 15nm surface-modified with (meth) acryloyloxy group, MEK dispersion containing 46 mass% of solid content) was added to the surface-modified silica particles (a), followed by stirring and homogenization. Then, MEK was distilled off at 50 ℃ and under a reduced pressure of 133.3Pa or less using an evaporator to obtain an A-DCP dispersion of the surface-modified silica particles (the surface-modified silica particle content: 50% by mass).
Production example 2
112.5g of A-DCP as the alicyclic (meth) acrylate monomer (b) was weighed in a 500mL eggplant type flask and dissolved in 112.5g of methyl ethyl ketone (hereinafter, abbreviated as MEK in the present specification). Then, as (a) the surface-modified silica particles described above, 305g of MEK-AC-2140Z (silica particles having a primary particle diameter of 10nm to 15nm surface-modified with (meth) acryloyloxy group, MEK dispersion containing 46 mass% of solid content) was added, and the mixture was stirred and homogenized. Then, MEK was distilled off at 50 ℃ and under a reduced pressure of 133.3Pa or less using an evaporator to obtain an A-DCP dispersion of the surface-modified silica particles (the surface-modified silica particles content: 55% by mass).
Production example 3
Into a 4-necked flask equipped with a dropping funnel, 45.2g of propylene glycol monomethyl ether acetate (hereinafter, abbreviated as PGMEA in the present specification) was charged, and into the dropping funnel, 50.0g of methyl methacrylate, 29.7g of isobornyl acrylate, 9.28g of 2-hydroxyethyl methacrylate, and 5.86g of 2, 2' -azobisisobutyronitrile were dissolved in 176.2g of PGMEA. After the atmosphere in the 4-neck flask was replaced with nitrogen, the temperature in the 4-neck flask was raised to 80 ℃ and the solution in the dropping funnel was added dropwise to the 4-neck flask over 3 hours. After completion of the dropwise addition, the reaction was carried out for 12 hours, and after stirring at 110 ℃ for 1 hour, the temperature in the 4-neck flask was lowered to 60 ℃. To the resulting reaction solution were added 0.266g of p-methoxyphenol, 0.451g of dibutyltin dilaurate, and 15.1g of AOI, and the mixture was stirred at 60 ℃ for 3 hours. The reaction solution was returned to room temperature, and reprecipitated/dried using methanol cooled to 10 ℃ to obtain 53.0g of polymer 1 having a repeating structural unit represented by the following formula (a). The weight average molecular weight Mw of the obtained polymer 1, as measured by GPC in terms of polystyrene, was 12,900.
Production example 4
26.5g of PGMEA was placed in a 4-neck flask equipped with a dropping funnel, and a solution prepared by dissolving 45.0g of methyl methacrylate, 6.50g of 2-hydroxyethyl methacrylate, and 4.10g of 2, 2' -azobisisobutyronitrile in 103.3g of PGMEA was placed in the dropping funnel. After the atmosphere in the 4-neck flask was replaced with nitrogen, the temperature in the 4-neck flask was raised to 80 ℃ and the solution in the dropping funnel was added dropwise to the 4-neck flask over 3 hours. After completion of the dropwise addition, the reaction was carried out for 12 hours, and after stirring at 110 ℃ for 1 hour, the temperature in the 4-neck flask was lowered to 60 ℃. To the resulting reaction solution were added 0.186g of p-methoxyphenol, 0.315g of dibutyltin dilaurate, and 10.6g of AOI, and the mixture was stirred at 60 ℃ for 3 hours. The reaction solution was returned to room temperature, and reprecipitated/dried using methanol cooled to 10 ℃ to obtain 27.7g of polymer 2 having a structural unit represented by the following formula (B). The weight average molecular weight Mw of the polymer 2 thus obtained was 10,200 in terms of polystyrene as measured by GPC.
Production example 5
33.1g of PGMEA was placed in a 4-neck flask equipped with a dropping funnel, and 25.0g of methyl methacrylate, 20.8g of isobornyl acrylate, 19.5g of 2-hydroxyethyl methacrylate, and 4.10g of 2, 2' -azobisisobutyronitrile dissolved in 128.9g of PGMEA were further placed in the dropping funnel. After the atmosphere in the 4-neck flask was replaced with nitrogen, the temperature in the 4-neck flask was raised to 80 ℃ and the solution in the dropping funnel was added dropwise to the 4-neck flask over 3 hours. After completion of the dropwise addition, the reaction was carried out for 12 hours, and after stirring at 110 ℃ for 1 hour, the temperature in the 4-neck flask was lowered to 60 ℃. To the resulting reaction solution were added 0.558g of p-methoxyphenol, 0.946g of dibutyltin dilaurate, and BEI53.8g, and the mixture was stirred at 60 ℃ for 3 hours. The reaction solution was returned to room temperature, and reprecipitated/dried using methanol cooled to 10 ℃ to obtain 4.36g of polymer 3 having a structural unit represented by the following formula (C). The weight average molecular weight Mw of the obtained polymer 3 was 17,000 as measured by GPC in terms of polystyrene.
[ example 1]
Solid components of the a-DCP dispersion obtained in production example 1as (a) the surface-modified silica particles, a-DCP as (b) the alicyclic (meth) acrylate monomer, UA-4200 as (c) the urethane (meth) acrylate compound, polymer 1 obtained in production example 3as (d) the polymer, I184 as (e) the photo radical initiator, I245 as (g) the phenolic antioxidant, and AO-503 as (h) the thioether antioxidant were blended at ratios described in table 1 below, respectively. The proportions of A-DCP shown in Table 1 below contain the A-DCP components contained in the above-mentioned A-DCP dispersion. Then, the complex was shaken at 50 ℃ for 3 hours and mixed, and then NR 1as the (f) polyfunctional thiol compound was added and mixed by stirring using the stirring and defoaming machine for 30 minutes. This apparatus was further used to prepare a photocurable composition for imprinting 1 by stirring and defoaming for 10 minutes. In table 1 below, "part" means "part by mass".
Examples 2 to 8 and comparative examples 1 to 3
By mixing the components (a) to (h) at the ratios shown in the following table 1 in the same manner as in example 1, photocurable compositions for imprints 2 to 11 were prepared. However, example 4 does not use component (f), comparative example 1 does not use components (a) and (d) and component (f), comparative example 2 does not use components (a) and (f), and comparative example 3 does not use components (d) and (f).
[ Table 1]
[ production of cured film ]
Each of the photocurable compositions for imprinting prepared in examples 1 to 8 and comparative examples 1 to 3 was sandwiched between 2 glass substrates subjected to mold release treatment by coating NOVEC (registered trademark) 1720 (manufactured by ス リ ー エ ム ジャパン corporation) and drying the coating layer together with a silicone rubber spacer having a thickness of 500 μm. The sandwiched photocurable composition for imprinting was irradiated with the UV irradiation device through an i-ray band pass filter (manufactured by Nichisu corporation) at 20mW/cm2A 300 second UV exposure was performed. After exposure, the obtained cured product was peeled off from the glass substrate subjected to the release treatment, and then heated on a hot plate at 100 ℃ for 10 minutes to produce a cured film having a diameter of 3cm and a thickness of 0.5 mm.
[ evaluation of transmittance and thermal yellowing resistance ]
The transmittance at a wavelength of 410nm of the cured film produced by the above method was measured using the above ultraviolet-visible near infrared spectrophotometer. The results are shown in table 2 below. The cured film was further placed on a silicon wafer, and heated on a hot plate heated to 175 ℃ for 2 minutes and 30 seconds through the silicon wafer, to perform a heat resistance test. The transmittance at a wavelength of 410nm of the cured film after the heat resistance test was measured using the above 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.
[ refractive index nDAbbe number vDEvaluation of]
The refractive index n at a wavelength of 589nm of the cured film produced by the above method was measured using the above multi-wavelength refractometerDAnd Abbe number vD. The results are shown in Table 2 below.
[ evaluation of crack resistance in developing step Using organic solvent ]
Each of the photocurable imprint compositions prepared in examples 1 to 8 and comparative examples 1 to 3 was dropped on a photomask substrate (opening 1cm square) subjected to a mold release treatment by coating NOVEC (registered trademark) 1720 (manufactured by ス リ ー エ ム ジャパン corporation) and drying. Then, an adhesive aid (product name: KBM-5103) made by shin-Etsu chemical Co., Ltd.) was diluted with PGMEA to a 5 mass% solution and dried to sandwich a 4-inch glass wafer (0.7mm thick) subjected to an adhesion treatment with a silicone rubber spacer having a thickness of 500 μm. The sandwiched photocurable composition was irradiated with the UV irradiation device via an i-ray band pass filter (manufactured by Nichisu corporation) at 62mW/cm2A 5 second UV exposure was performed. After exposure, the obtained cured product was peeled off from the glass substrate subjected to the release treatment, and then immersed (developed) in a stirred PGMEA, followed by rinsing with PGMEA to remove the unexposed portion, thereby producing a cured film having a thickness of 0.5mm in a 1cm square on the 4-inch glass wafer subjected to the adhesion treatment. The side surface of the cured film obtained was observed with an optical microscope (manufactured by オリンパス K) to determine that a crack was observed as "x" and that no crack was observed as "o". The results are shown in Table 2 below.
[ formation of antireflection layer and evaluation of crack resistance ]
0.020g of each of the photocurable compositions for imprints prepared in examples 1 to 8 and comparative examples 1 to 3 was weighed on a glass substrate subjected to a mold release treatment by coating NOVEC (registered trademark) 1720 (manufactured by ス リ ー エ ム ジャパン, Inc.) and drying. Then, a photo-curable composition for imprinting on the glass substrate was sandwiched between spacers made of silicone rubber having a thickness of 300 μm and a quartz substrate (6cm square, 1mm thick) which was subjected to an adhesion treatment by coating a solution prepared by diluting an adhesion promoter (product name: KBM-5103) made by shin-Etsu chemical Co., Ltd.) with PGMEA to 5 mass% and drying the solution. The sandwiched photocurable composition was irradiated with the UV irradiation device through an i-ray band pass filter (manufactured by Nichisu corporation) at 20mW/cm2A 300 second UV exposure was performed. After exposure, the cured product obtained was peeled off from the glass substrate, and then heated on a hot plate at 100 ℃ for 10 minutes to form a cured film having a diameter of 1cm, a thickness of 0.3mm and a mass of 0.020g on the quartz substrate.
A silicon oxide layer having a thickness of 200nm was formed as an antireflection layer on the cured film formed on the quartz substrate under the above-described film formation conditions by using the above-described RF sputtering apparatus. After the presence or absence of cracks was confirmed by observing the antireflection layer on the cured film using an optical microscope (manufactured by the company (ltd) キーエンス), the quartz substrate was heated for 2 minutes and 30 seconds at 175 ℃. The quartz substrate after the heat resistance test was also observed for the presence or absence of cracks in the antireflection layer on the cured film using an optical microscope (manufactured by the company "キーエンス"), and the crack resistance of the antireflection layer was determined. The case where cracks were observed in the anti-reflection layer on the cured film was judged as x, and the case where neither cracks nor wrinkles were observed in the anti-reflection layer on the cured film was judged as o. The results of the respective are shown in table 2 below.
[ Table 2]
TABLE 2
The antireflection layer formed on the cured films produced from the photocurable composition for imprints of comparative example 1 not containing the component (a) and the component (d) and the photocurable composition for imprints of comparative example 2 not containing the component (a) resulted in the occurrence of cracks after the heat resistance test. Further, the cured film produced from the photocurable composition for imprints of comparative example 3 containing the component (a) but not the component (d) was a result of cracks occurring on the side wall of the cured film after the development step of cleaning the uncured portion with an organic solvent. From the above results, the cured film obtained from the photocurable composition for imprinting of the present invention exhibited high abbe number, high refractive index, high transparency, and resistance to thermal yellowing, and exhibited the characteristics desired for a lens for a high-resolution camera module, in which neither cracks nor wrinkles were generated in the antireflection layer having the upper layer of the cured film by heat treatment at 175 ℃.
[ production of lens ]
The photocurable composition for imprint 1 prepared in example 1, the photocurable composition for imprint 4 prepared in example 4, and the photocurable composition for imprint 8 prepared in example 8 were molded into a lens shape on a glass substrate as a support by the above-mentioned method for producing a molded body using a nickel mold (a total of 15 lens molds each having a diameter of 2mm and a depth of 300 μm were arranged in 3 columns by 5 columns) and a nano printer, respectively. The mold used was subjected to mold release treatment in advance with NOVEC (registered trademark) 1720 (manufactured by ス リ ー エ ム ジャパン corporation). The glass substrate used was subjected to adhesion treatment by coating a solution prepared by diluting an adhesion promoter (product name: KBM-5103) made by shin-Etsu chemical Co., Ltd.) with PGMEA in a concentration of 5 mass% and drying the solution. After removing the cured product from the mold, the cured product was heated with a hot plate at 100 ℃ for 10 minutes to produce a convex lens on the glass substrate subjected to the adhesion treatment.
The convex lenses obtained on the glass substrate were measured for the lens height (thickness) before and after the heat test by the non-contact surface property measuring apparatus, and the change rate thereof was calculated from the following formula "[ (lens height before heating-lens height after heating)/lens height before heating ] × 100", and the dimensional stability by heating was evaluated. Further, the presence or absence of the occurrence of cracks in the convex lens after the heat test was observed with a microscope attached to the non-contact surface property measuring apparatus. The heating test is a test in which the convex lens obtained on the glass substrate is heated on a hot plate at 175 ℃ for 2 minutes and 30 seconds, and then cooled to room temperature (about 23 ℃). The results are shown in table 3 below.
[ Table 3]
TABLE 3
As shown in Table 3, the convex lens obtained from the photocurable composition for imprints of the present invention exhibited small changes in lens height (change rate of 0.20% or less) and high dimensional stability even after a thermal history of 2 minutes and 30 seconds at 175 ℃.
Claims (15)
1. A photocurable composition for imprinting, comprising a component (a) 10 to 40 parts by mass, a component (b) 10 to 50 parts by mass, a component (c) 10 to 50 parts by mass, a component (d) 1 to 10 parts by mass, and a component (e) 0.1 to 5 parts by mass, with respect to 100 parts by mass of the sum of the component (a), the component (b), the component (c), and the component (d),
(a) the components: surface-modified silica particles having a primary particle diameter of 1 to 100nm,
(b) the components: 1 an alicyclic (meth) acrylate monomer having at least 1 (meth) acryloyloxy group in the molecule, excluding a compound as the component (c),
(c) the components: a urethane (meth) acrylate compound or an epoxy (meth) acrylate compound, excluding a polymer as the component (d),
(d) the components: a polymer having a repeating structural unit represented by the following formula (1) and a repeating structural unit represented by the following formula (2),
(e) the components: a photo-radical initiator, which is a compound of formula (I),
in the formula, R1And R2Each independently represents a methyl group or a hydrogen atom, A1Represents an alkyl group having 1 to 8 carbon atoms, A2Represents a single bond or an alkylene group having 1 to4 carbon atoms, X represents a polymerizable group having 1 or 2 or more (meth) acryloyloxy groups, Z1Represents a divalent group represented by the following formula (a1), formula (a2), formula (a3) or formula (a4)The radical(s) is (are),
2. the photocurable composition for imprints of claim 1, further comprising 1 to 15 parts by mass of the following component (f) per 100 parts by mass of the sum of the components (a), (b), (c) and (d),
(f) the components: a polyfunctional thiol compound represented by the following formula (3),
in the formula, A3Represents a single bond or a linear or branched alkylene group having 1 to 6 carbon atoms, Z2Represents a single bond, an ester bond or an ether bond, Q represents an organic group having 2 to 12 carbon atoms and containing at least 1 hetero atom or no hetero atom, or a hetero atom, and r represents an integer of 2 to 6.
3. The photocurable composition for imprints of claim 1 or 2, further comprising: 0.05 to 3 parts by mass of the following component (g) per 100 parts by mass of the sum of the components (a), (b), (c) and (d); and/or 0.1 to 3 parts by mass of the following component (h) per 100 parts by mass of the sum of the components (a), (b), (c) and (d),
(g) the components: a phenolic antioxidant, which is a phenolic antioxidant,
(h) the components: a thioether-based antioxidant.
4. The photocurable composition for imprints of any one of claims 1 to 3, wherein the component (a) is a silica particle surface-modified with a (meth) acryloyloxy group bonded to a silicon atom via a divalent linking group.
5. The photocurable composition for imprinting according to any one of claims 1 to4, wherein the urethane (meth) acrylate compound or the epoxy (meth) acrylate compound as the component (c) is a compound having 2 or 3 (meth) acryloyloxy groups in 1 molecule.
6. The photocurable composition for imprinting according to any one of claims 1 to 5, wherein the polymer as the component (d) is a polymer further having a repeating structural unit represented by the following formula (4),
in the formula, R3Represents a methyl group or a hydrogen atom, Z3Represents a single bond or an ethyleneoxy group, A4An alicyclic hydrocarbon group having 5 to 13 carbon atoms.
7. The photocurable composition for imprints according to claim 6, wherein the alicyclic hydrocarbon group having 5 to 13 carbon atoms is a cyclopentyl group, a cyclohexyl group, an isobornyl group, a tricyclo [5.2.1.02,6] dec-8-yl group, a tricyclodecenyl group, or an adamantyl group which may have an alkyl group having 1 to 3 carbon atoms as a substituent.
8. The photocurable composition for imprinting according to any one of claims 1 to 7, wherein the polymerizable group having 1 or 2 or more (meth) acryloyloxy groups is a group represented by formula (X0), formula (X1), formula (X2), formula (X3), formula (X4), formula (X5) or formula (X6), or a group obtained by replacing a part or all of acryloyloxy groups contained in these groups with methacryloyloxy groups,
9. the photocurable composition for imprints of any one of claims 1 to 8,a refractive index n at a wavelength of 589nm of a cured product of the photocurable composition for imprintingDIs 1.50 or more, and the Abbe number v of the cured productDIs 53 or more.
10. A cured product of the photocurable composition for imprinting according to claim 9.
11. A method for manufacturing a resin lens, comprising the steps of: a step of subjecting the photocurable composition for imprinting according to any one of claims 1 to 9 to imprint molding.
12. A method for producing a molded article of a photocurable composition for imprinting, comprising the steps of: a filling step of filling the space between the support and the mold in contact with each other or the internal space of the detachable mold with the photocurable composition for imprinting according to any one of claims 1 to 9; and a photocuring step of exposing the photocurable composition for imprinting filled in the space to light to cure the composition.
13. The method for producing a molded article according to claim 12, comprising the steps of: a mold releasing step of taking out the obtained photo-cured product after the photo-curing step; and a heating step of heating the photo-cured product before, during, or after the releasing step.
14. The method for producing a molded article according to claim 13, further comprising the steps of: and a developing step of cleaning the uncured portion with an organic solvent after the mold releasing step and before the heating step.
15. The method for producing a molded article according to any one of claims 12 to 14, wherein the molded article is a lens for a camera module.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2018-033773 | 2018-02-27 | ||
| JP2018033773 | 2018-02-27 | ||
| PCT/JP2019/001392 WO2019167461A1 (en) | 2018-02-27 | 2019-01-18 | Polymer-containing photocurable composition for imprinting use |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111801770A true CN111801770A (en) | 2020-10-20 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201980015183.5A Pending CN111801770A (en) | 2018-02-27 | 2019-01-18 | Photocurable composition for imprinting comprising polymer |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JPWO2019167461A1 (en) |
| KR (1) | KR20200128404A (en) |
| CN (1) | CN111801770A (en) |
| TW (1) | TW201940602A (en) |
| WO (1) | WO2019167461A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114806225A (en) * | 2022-03-28 | 2022-07-29 | 浙江恒逸石化研究院有限公司 | Preparation method of liquid titanium dioxide |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP7280560B2 (en) * | 2019-11-15 | 2023-05-24 | 日産化学株式会社 | Manufacturing method of resin lens using developing solution and rinse solution, and its rinse solution |
| WO2022075162A1 (en) | 2020-10-08 | 2022-04-14 | Dic株式会社 | Active energy ray curable composition, cured product, lens, and camera module |
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| JP2012099638A (en) * | 2010-11-02 | 2012-05-24 | Fujifilm Corp | Curable composition for imprint |
| US20140309327A1 (en) * | 2011-11-17 | 2014-10-16 | Three Bond Fine Chemical Co., Ltd. | Acrylic resin composition |
| JP2015071741A (en) * | 2013-09-04 | 2015-04-16 | Jsr株式会社 | Curable composition, nano imprint material, cured film, laminate, method of producing cured film, pattern formation method, and semiconductor light-emitting element substrate |
| US20150249409A1 (en) * | 2012-11-22 | 2015-09-03 | Mitsubishi Electric Corporation | Control device for ac rotating machine, ac rotating machine drive system equipped with control device for ac rotating machine and electric power steering system |
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| US8853291B2 (en) | 2010-02-26 | 2014-10-07 | Nippon Steel & Sumikin Chemical Co., Ltd. | Curable resin composition, cured article thereof, and optical material |
| JP5932598B2 (en) * | 2012-10-16 | 2016-06-08 | 株式会社ブリヂストン | Photo-curable elastomer composition, sealing material, and apparatus |
| JP2014234458A (en) | 2013-06-03 | 2014-12-15 | 昭和電工株式会社 | Curable composition, and cured product thereof |
| JP2016121277A (en) | 2014-12-25 | 2016-07-07 | 日東電工株式会社 | Photocurable resin composition and optical material using the same |
-
2019
- 2019-01-18 KR KR1020207026632A patent/KR20200128404A/en unknown
- 2019-01-18 JP JP2020502853A patent/JPWO2019167461A1/en active Pending
- 2019-01-18 CN CN201980015183.5A patent/CN111801770A/en active Pending
- 2019-01-18 WO PCT/JP2019/001392 patent/WO2019167461A1/en active Application Filing
- 2019-01-30 TW TW108103417A patent/TW201940602A/en unknown
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012099638A (en) * | 2010-11-02 | 2012-05-24 | Fujifilm Corp | Curable composition for imprint |
| US20140309327A1 (en) * | 2011-11-17 | 2014-10-16 | Three Bond Fine Chemical Co., Ltd. | Acrylic resin composition |
| US20150249409A1 (en) * | 2012-11-22 | 2015-09-03 | Mitsubishi Electric Corporation | Control device for ac rotating machine, ac rotating machine drive system equipped with control device for ac rotating machine and electric power steering system |
| JP2015071741A (en) * | 2013-09-04 | 2015-04-16 | Jsr株式会社 | Curable composition, nano imprint material, cured film, laminate, method of producing cured film, pattern formation method, and semiconductor light-emitting element substrate |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114806225A (en) * | 2022-03-28 | 2022-07-29 | 浙江恒逸石化研究院有限公司 | Preparation method of liquid titanium dioxide |
| CN114806225B (en) * | 2022-03-28 | 2023-08-29 | 浙江恒逸石化研究院有限公司 | Preparation method of liquid titanium dioxide |
Also Published As
| Publication number | Publication date |
|---|---|
| JPWO2019167461A1 (en) | 2021-03-11 |
| KR20200128404A (en) | 2020-11-12 |
| TW201940602A (en) | 2019-10-16 |
| WO2019167461A1 (en) | 2019-09-06 |
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