KR101796133B1 - Curable composition for uv nano-imprint, and cured film obtained from curable composition - Google Patents
Curable composition for uv nano-imprint, and cured film obtained from curable composition Download PDFInfo
- Publication number
- KR101796133B1 KR101796133B1 KR1020110080616A KR20110080616A KR101796133B1 KR 101796133 B1 KR101796133 B1 KR 101796133B1 KR 1020110080616 A KR1020110080616 A KR 1020110080616A KR 20110080616 A KR20110080616 A KR 20110080616A KR 101796133 B1 KR101796133 B1 KR 101796133B1
- Authority
- KR
- South Korea
- Prior art keywords
- polymerizable monomer
- curable composition
- acrylate
- nanoimprint
- meth
- Prior art date
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- 239000000203 mixture Substances 0.000 title claims abstract description 118
- 239000000178 monomer Substances 0.000 claims abstract description 86
- 150000001875 compounds Chemical class 0.000 claims abstract description 49
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 39
- 239000000758 substrate Substances 0.000 claims abstract description 32
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 25
- 239000003999 initiator Substances 0.000 claims abstract description 22
- 239000004094 surface-active agent Substances 0.000 claims abstract description 21
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 61
- -1 2-hydroxypropyl Chemical group 0.000 claims description 38
- 238000000034 method Methods 0.000 claims description 29
- 150000003254 radicals Chemical class 0.000 claims description 26
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims description 9
- 239000005977 Ethylene Substances 0.000 claims description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 8
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 8
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- 238000000576 coating method Methods 0.000 claims description 7
- 239000007983 Tris buffer Substances 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 125000002947 alkylene group Chemical group 0.000 claims description 6
- 125000004122 cyclic group Chemical group 0.000 claims description 6
- 239000011248 coating agent Substances 0.000 claims description 5
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 claims description 4
- 125000003700 epoxy group Chemical group 0.000 claims description 4
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 claims description 4
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims description 4
- MYWOJODOMFBVCB-UHFFFAOYSA-N 1,2,6-trimethylphenanthrene Chemical compound CC1=CC=C2C3=CC(C)=CC=C3C=CC2=C1C MYWOJODOMFBVCB-UHFFFAOYSA-N 0.000 claims description 3
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 claims description 3
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 150000002431 hydrogen Chemical class 0.000 claims description 3
- SXIFAEWFOJETOA-UHFFFAOYSA-N 4-hydroxy-butyl Chemical group [CH2]CCCO SXIFAEWFOJETOA-UHFFFAOYSA-N 0.000 claims description 2
- 230000001678 irradiating effect Effects 0.000 claims description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 2
- KUDUQBURMYMBIJ-UHFFFAOYSA-N 2-prop-2-enoyloxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC(=O)C=C KUDUQBURMYMBIJ-UHFFFAOYSA-N 0.000 claims 2
- 239000004065 semiconductor Substances 0.000 abstract description 13
- 239000011521 glass Substances 0.000 abstract description 12
- 229910052751 metal Inorganic materials 0.000 abstract description 11
- 239000002184 metal Substances 0.000 abstract description 11
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 230000001681 protective effect Effects 0.000 abstract description 5
- 230000008961 swelling Effects 0.000 abstract description 3
- 150000003014 phosphoric acid esters Chemical class 0.000 abstract 1
- 239000010408 film Substances 0.000 description 39
- 239000002904 solvent Substances 0.000 description 14
- 230000003287 optical effect Effects 0.000 description 13
- 239000003112 inhibitor Substances 0.000 description 11
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 10
- 239000000463 material Substances 0.000 description 9
- 238000006116 polymerization reaction Methods 0.000 description 9
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 8
- 239000003086 colorant Substances 0.000 description 8
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 7
- 229920001214 Polysorbate 60 Polymers 0.000 description 6
- 239000010949 copper Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 6
- 239000010410 layer Substances 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- 238000001723 curing Methods 0.000 description 5
- 235000014113 dietary fatty acids Nutrition 0.000 description 5
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 5
- 239000000194 fatty acid Substances 0.000 description 5
- 229930195729 fatty acid Natural products 0.000 description 5
- 229910052750 molybdenum Inorganic materials 0.000 description 5
- 239000011733 molybdenum Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- NDWUBGAGUCISDV-UHFFFAOYSA-N 4-hydroxybutyl prop-2-enoate Chemical compound OCCCCOC(=O)C=C NDWUBGAGUCISDV-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 3
- 239000012965 benzophenone Substances 0.000 description 3
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 238000011282 treatment Methods 0.000 description 3
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 3
- CNJRPYFBORAQAU-UHFFFAOYSA-N 1-ethoxy-2-(2-methoxyethoxy)ethane Chemical compound CCOCCOCCOC CNJRPYFBORAQAU-UHFFFAOYSA-N 0.000 description 2
- LIPRQQHINVWJCH-UHFFFAOYSA-N 1-ethoxypropan-2-yl acetate Chemical compound CCOCC(C)OC(C)=O LIPRQQHINVWJCH-UHFFFAOYSA-N 0.000 description 2
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 2
- JONNRYNDZVEZFH-UHFFFAOYSA-N 2-(2-butoxypropoxy)propyl acetate Chemical compound CCCCOC(C)COC(C)COC(C)=O JONNRYNDZVEZFH-UHFFFAOYSA-N 0.000 description 2
- FPZWZCWUIYYYBU-UHFFFAOYSA-N 2-(2-ethoxyethoxy)ethyl acetate Chemical compound CCOCCOCCOC(C)=O FPZWZCWUIYYYBU-UHFFFAOYSA-N 0.000 description 2
- CKCGJBFTCUCBAJ-UHFFFAOYSA-N 2-(2-ethoxypropoxy)propyl acetate Chemical compound CCOC(C)COC(C)COC(C)=O CKCGJBFTCUCBAJ-UHFFFAOYSA-N 0.000 description 2
- DRLRGHZJOQGQEC-UHFFFAOYSA-N 2-(2-methoxypropoxy)propyl acetate Chemical compound COC(C)COC(C)COC(C)=O DRLRGHZJOQGQEC-UHFFFAOYSA-N 0.000 description 2
- QTUVQQKHBMGYEH-UHFFFAOYSA-N 2-(trichloromethyl)-1,3,5-triazine Chemical compound ClC(Cl)(Cl)C1=NC=NC=N1 QTUVQQKHBMGYEH-UHFFFAOYSA-N 0.000 description 2
- GJKGAPPUXSSCFI-UHFFFAOYSA-N 2-Hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone Chemical compound CC(C)(O)C(=O)C1=CC=C(OCCO)C=C1 GJKGAPPUXSSCFI-UHFFFAOYSA-N 0.000 description 2
- VHSHLMUCYSAUQU-UHFFFAOYSA-N 2-hydroxypropyl methacrylate Chemical compound CC(O)COC(=O)C(C)=C VHSHLMUCYSAUQU-UHFFFAOYSA-N 0.000 description 2
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- IYFATESGLOUGBX-YVNJGZBMSA-N Sorbitan monopalmitate Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O IYFATESGLOUGBX-YVNJGZBMSA-N 0.000 description 2
- HVUMOYIDDBPOLL-XWVZOOPGSA-N Sorbitan monostearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O HVUMOYIDDBPOLL-XWVZOOPGSA-N 0.000 description 2
- LFOXEOLGJPJZAA-UHFFFAOYSA-N [(2,6-dimethoxybenzoyl)-(2,4,4-trimethylpentyl)phosphoryl]-(2,6-dimethoxyphenyl)methanone Chemical compound COC1=CC=CC(OC)=C1C(=O)P(=O)(CC(C)CC(C)(C)C)C(=O)C1=C(OC)C=CC=C1OC LFOXEOLGJPJZAA-UHFFFAOYSA-N 0.000 description 2
- URLYGBGJPQYXBN-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methyl prop-2-enoate Chemical compound OCC1CCC(COC(=O)C=C)CC1 URLYGBGJPQYXBN-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 2
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000010538 cationic polymerization reaction Methods 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 description 2
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- 229940105990 diglycerin Drugs 0.000 description 2
- GPLRAVKSCUXZTP-UHFFFAOYSA-N diglycerol Chemical compound OCC(O)COCC(O)CO GPLRAVKSCUXZTP-UHFFFAOYSA-N 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
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- 230000001965 increasing effect Effects 0.000 description 2
- 238000001459 lithography Methods 0.000 description 2
- BHIWKHZACMWKOJ-UHFFFAOYSA-N methyl isobutyrate Chemical compound COC(=O)C(C)C BHIWKHZACMWKOJ-UHFFFAOYSA-N 0.000 description 2
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
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- 239000007870 radical polymerization initiator Substances 0.000 description 2
- 239000011342 resin composition Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
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- 229920001187 thermosetting polymer Polymers 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- QNODIIQQMGDSEF-UHFFFAOYSA-N (1-hydroxycyclohexyl)-phenylmethanone Chemical compound C=1C=CC=CC=1C(=O)C1(O)CCCCC1 QNODIIQQMGDSEF-UHFFFAOYSA-N 0.000 description 1
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- LGPAKRMZNPYPMG-UHFFFAOYSA-N (3-hydroxy-2-prop-2-enoyloxypropyl) prop-2-enoate Chemical compound C=CC(=O)OC(CO)COC(=O)C=C LGPAKRMZNPYPMG-UHFFFAOYSA-N 0.000 description 1
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- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- MSAHTMIQULFMRG-UHFFFAOYSA-N 1,2-diphenyl-2-propan-2-yloxyethanone Chemical compound C=1C=CC=CC=1C(OC(C)C)C(=O)C1=CC=CC=C1 MSAHTMIQULFMRG-UHFFFAOYSA-N 0.000 description 1
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 description 1
- DKEGCUDAFWNSSO-UHFFFAOYSA-N 1,8-dibromooctane Chemical compound BrCCCCCCCCBr DKEGCUDAFWNSSO-UHFFFAOYSA-N 0.000 description 1
- WQQZMYRVHZZOEW-UHFFFAOYSA-N 1-benzyl-4-(2-methylphenyl)sulfanylbenzene Chemical compound CC1=CC=CC=C1SC(C=C1)=CC=C1CC1=CC=CC=C1 WQQZMYRVHZZOEW-UHFFFAOYSA-N 0.000 description 1
- RWNUSVWFHDHRCJ-UHFFFAOYSA-N 1-butoxypropan-2-ol Chemical compound CCCCOCC(C)O RWNUSVWFHDHRCJ-UHFFFAOYSA-N 0.000 description 1
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 1
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- HFZLSTDPRQSZCQ-UHFFFAOYSA-N 1-pyrrolidin-3-ylpyrrolidine Chemical compound C1CCCN1C1CNCC1 HFZLSTDPRQSZCQ-UHFFFAOYSA-N 0.000 description 1
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- PIZHFBODNLEQBL-UHFFFAOYSA-N 2,2-diethoxy-1-phenylethanone Chemical compound CCOC(OCC)C(=O)C1=CC=CC=C1 PIZHFBODNLEQBL-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
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- AHLLKHCTFAQHSJ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol;1-methoxy-2-(2-methoxyethoxy)ethane Chemical compound COCCOCCOC.CCCCOCCOCCO AHLLKHCTFAQHSJ-UHFFFAOYSA-N 0.000 description 1
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- QRHHZFRCJDAUNA-UHFFFAOYSA-N 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine Chemical compound C1=CC(OC)=CC=C1C1=NC(C(Cl)(Cl)Cl)=NC(C(Cl)(Cl)Cl)=N1 QRHHZFRCJDAUNA-UHFFFAOYSA-N 0.000 description 1
- RVGLEPQPVDUSOJ-UHFFFAOYSA-N 2-Methyl-3-hydroxypropanoate Chemical compound COC(=O)CCO RVGLEPQPVDUSOJ-UHFFFAOYSA-N 0.000 description 1
- WMYINDVYGQKYMI-UHFFFAOYSA-N 2-[2,2-bis(hydroxymethyl)butoxymethyl]-2-ethylpropane-1,3-diol Chemical compound CCC(CO)(CO)COCC(CC)(CO)CO WMYINDVYGQKYMI-UHFFFAOYSA-N 0.000 description 1
- LCZVSXRMYJUNFX-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)CO LCZVSXRMYJUNFX-UHFFFAOYSA-N 0.000 description 1
- ZJRNXDIVAGHETA-UHFFFAOYSA-N 2-[2-(3,4-dimethoxyphenyl)ethenyl]-4,6-bis(trichloromethyl)-1,3,5-triazine Chemical compound C1=C(OC)C(OC)=CC=C1C=CC1=NC(C(Cl)(Cl)Cl)=NC(C(Cl)(Cl)Cl)=N1 ZJRNXDIVAGHETA-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or 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 of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C59/00—Surface shaping of articles, e.g. embossing; Apparatus therefor
- B29C59/16—Surface shaping of articles, e.g. embossing; Apparatus therefor by wave energy or particle radiation, e.g. infrared heating
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
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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
유리·금속과의 밀착성이 높은 경화막이 요구되고 있다. 또한, 예를 들면, 반도체 집적 회로에 형성된 경화막으로서, 가열되어도, 기판 계면에서의 부풀어짐이나 박리를 방지할 수 있는 경화막이 요구되고 있다. 예를 들면, 반도체 집적 회로의 제조에서의 보호막의 형성에 소요되는 수고나 시간을 단축하고, 소모품도 삭감하는 것이 요구되고 있다.
인산 에스테르를 가지는 화합물(A)과, 실란 커플링제(B)와, 하이드록시기를 가지는 라디칼 중합성 모노머(C)와, 광중합 개시제(D)와, 하이드록시기를 가지는 라디칼 중합성 모노머(C) 이외의 라디칼 중합성 모노머(E)와 계면활성제(F)를 포함하는 광 나노임프린트용 경화성 조성물에 의해 전술한 과제를 해결한다.A cured film having high adhesion to glass and metal is required. Further, for example, as a cured film formed in a semiconductor integrated circuit, a cured film capable of preventing swelling and peeling at the substrate interface is demanded even when heated. For example, it has been required to shorten the time and labor required for forming a protective film in the manufacture of a semiconductor integrated circuit, and to reduce consumables.
(C) having a hydroxyl group, a compound (A) having a phosphoric acid ester, a silane coupling agent (B), a radically polymerizable monomer (C) having a hydroxy group, a photopolymerization initiator The present invention solves the above-mentioned problems by a curable composition for a photo-nanoimprint comprising a radically polymerizable monomer (E) and a surfactant (F).
Description
본 발명은, 광 나노임프린트용 경화성 조성물, 광 나노임프린트용 경화성 조성물로부터 얻어진 경화막(패턴화된 경화막을 포함함) 및 그 형성 방법에 관한 것이다. 또한, 본 발명은, 광 나노임프린트용 경화성 조성물로부터 얻어진 경화막을 가지는 표시 소자 등에 관한 것이다.The present invention relates to a curable composition for a photo-nanoimprint, a cured film (including a patterned cured film) obtained from a curable composition for a photo-nanoimprint, and a method of forming the same. The present invention also relates to a display element having a cured film obtained from a curable composition for a photo-nanoimprint.
광 나노임프린트법은, 광디스크 제작에서는 잘 알려져 있는 엠보싱 기술을 발전시켜, 요철 패턴을 형성한 금형원기(金型原器)(일반적으로 몰드, 스탬퍼, 템플레이트라고 함)를, 레지스트에 프레스하여 역학적으로 변형시켜 미세 패턴을 정밀하게 전사(轉寫)하는 기술이다. 몰드를 한 번 제조하면, 나노 구조 등의 미세 구조를 간단하게 반복적으로 성형할 수 있으므로 경제적이며, 또한 유해한 폐기·배출물이 적은 나노 가공 기술이므로, 최근, 다양한 분야로의 응용이 기대되고 있다.In the optical nanoimprint method, a well-known embossing technique is developed in optical disc manufacturing, and a mold prototype (generally called a mold, a stamper, or a template) in which a concavo-convex pattern is formed is pressed into a resist and mechanically Thereby transferring the fine pattern precisely. Since the microstructure such as the nanostructure can be simply and repeatedly formed, it is economical and nano-processing technology with less harmful disposal and emission is expected to be applied to various fields.
포토리소그래피법에 비해, 광 나노임프린트법에 따른 패턴 형성은 공정이 간단하며, 재료 사용량의 삭감도 기대할 수 있으므로, 고밀도 반도체 집적 회로 제조에 사용하는 것이 제안되어 있다. 예를 들면, 특허 문헌 1, 특허 문헌 2에는 실리콘 웨이퍼를 몰드로서 사용하여, 25nm 이하의 미세 구조를 전사에 의해 형성하는 광 나노임프린트 기술이 개시되어 있다.Compared with the photolithography method, it is proposed that the pattern formation according to the photo-nanoimprint method is simple in process and the amount of material used can be reduced. Therefore, it is proposed to use it in the manufacture of a high-density semiconductor integrated circuit. For example, Patent Document 1 and Patent Document 2 disclose an optical nanoimprint technique for forming a microstructure of 25 nm or less by transfer using a silicon wafer as a mold.
또한, 특허 문헌 3에는, 반도체 마이크로 리소그래피 분야에 적용되는 광 나노임프린트를 사용한 복합(composite) 조성물이 개시되어 있다.Also, Patent Document 3 discloses a composite composition using a photo-nanoimprint applied to the field of semiconductor microlithography.
한편, 최근에는, 반도체 집적 회로를 구성하는 Si 등의 반도체 재료나, 반도체 탑재용 세라믹스(Al2O3 등) 기판의 열팽창 계수에 근접시키기 위하여, 몰리브덴(Mo)을 기재(基材)로 하고, 이 기재의 양측에 동(Cu) 또는 Cu 합금을 피복한 복합 재료가 제안되어 있다.On the other hand, in recent years, molybdenum (Mo) is used as a base material in order to bring it close to the thermal expansion coefficient of a semiconductor material such as Si constituting a semiconductor integrated circuit and a substrate for ceramics (Al 2 O 3 etc.) , And copper (Cu) or a Cu alloy is coated on both sides of the base material.
또한, Si 등의 기판 상에 TFT를 형성한 경우, 실리콘 웨이퍼를 사용하므로, 기판이 불투명하고, 면적도 웨이퍼의 크기 이하로 한정된다. 이를 해결하기 위하여, 유리 기판 상에 TFT를 형성하는 연구가 활발히 행해지고 있다.Further, when a TFT is formed on a substrate made of Si or the like, since the silicon wafer is used, the substrate is opaque and the area is limited to the size of the wafer or less. In order to solve this problem, studies for forming a TFT on a glass substrate have been actively conducted.
그러므로, 반도체 집적 회로를 제조하는 광 나노임프린트 재료는, 금속이나 유리와의 양호한 밀착성이 요구된다. 그러나, 종래에는, 어느 쪽 기판과도 밀착성이 양호한 재료가 없었다.Therefore, a photo-nanoimprint material for manufacturing a semiconductor integrated circuit is required to have good adhesion with metal or glass. However, conventionally, there was no material having good adhesion to either substrate.
전술한 상황 하에서, 유리·금속과의 밀착성이 높은 경화막이 요구되고 있다. 또한, 예를 들면, 반도체 집적 회로에 형성된 경화막으로서, 가열되어도, 기판 계면에서의 부풀어짐이나 박리를 방지할 수 있는 경화막이 요구되고 있다. 예를 들면, 반도체 집적 회로의 제조에 있어서 보호막의 형성에 소요되는 수고나 시간을 단축하고, 소모품도 삭감하는 것이 요구되고 있다.Under the above-described circumstances, there is a demand for a cured film having high adhesion to glass and metal. Further, for example, as a cured film formed in a semiconductor integrated circuit, a cured film capable of preventing swelling and peeling at the substrate interface is demanded even when heated. For example, in manufacturing a semiconductor integrated circuit, it is required to shorten the time and labor required for forming a protective film, and to reduce consumables.
본 발명자들은, 광 나노임프린트용 경화성 조성물에, 소정의 구조를 가지는 화합물(A)과 실란 커플링제(B)를 병용하는 것에 의해, 유리 기판 및 금속 기판과 높은 밀착성을 얻을 수 있는 것을 발견하고, 이 지견에 따라 화합물(A)과, 실란 커플링제(B)와, 하이드록시기를 가지는 라디칼 중합성 모노머(C)와, 광중합 개시제(D)와, 라디칼 중합성 모노머(C) 이외의 라디칼 중합성 모노머(E)와 계면활성제(F)를 포함하는 광 나노임프린트용 경화성 조성물에 관한 본 발명을 완성했다.The present inventors have found that high adhesion can be obtained with a glass substrate and a metal substrate by using a compound (A) having a predetermined structure and a silane coupling agent (B) in combination with a curable composition for a photo-nanoimprint, (A), a silane coupling agent (B), a radically polymerizable monomer (C) having a hydroxy group, a photopolymerization initiator (D) and a radically polymerizable monomer The present invention has been completed on a curable composition for a photo-nanoimprint comprising a monomer (E) and a surfactant (F).
본 발명은 하기와 같은 광 나노임프린트용 경화성 조성물, 광 나노임프린트용 경화성 조성물로부터 얻어진 경화막 및 그 형성 방법 등을 제공한다.The present invention provides a curable composition for a photo-nanoimprint, a cured film obtained from a curable composition for a photo-nanoimprint, and a method of forming the same.
[1] 일반식 (1)로 표시되는 화합물(A)과, 실란 커플링제(B)와, 하이드록시기를 가지는 라디칼 중합성 모노머(C)와, 광중합 개시제(D)와, 라디칼 중합성 모노머(C) 이외의 라디칼 중합성 모노머(E)와 계면활성제(F)를 포함하는 광 나노임프린트용 경화성 조성물.[1] A photopolymerizable composition comprising a compound (A) represented by the general formula (1), a silane coupling agent (B), a radically polymerizable monomer (C) having a hydroxy group, a photopolymerization initiator (D) (C) and a surfactant (F) other than the radical polymerizable monomer (E).
(식 (1) 중, R1은 각각 독립적으로 탄소수 1∼3의 알킬 또는 수소이며, R2는 각각 독립적으로 환상(環狀) 구조를 가질 수 있는 탄소수 2∼12의 알킬렌이며, m은 0∼2의 정수임.)(In the formula (1), R 1 is independently alkyl having 1 to 3 carbon atoms or hydrogen, R 2 is independently alkylene having 2 to 12 carbon atoms which may have a cyclic structure, m is An integer from 0 to 2.)
[2] R1은 각각 독립적으로 수소 또는 메틸이며, R2는 에틸렌인, 상기 [1]에 기재된 광 나노임프린트용 경화성 조성물.[2] The curable composition for a photo-nanoimprint according to [1], wherein R 1 is each independently hydrogen or methyl, and R 2 is ethylene.
[3] 실란 커플링제(B)가 에폭시기 함유 실란 커플링제인, 상기 [1] 또는 상기 [2]에 기재된 광 나노임프린트용 경화성 조성물.[3] The curable composition for a photo-nanoimprint as described in [1] or [2], wherein the silane coupling agent (B) is an epoxy group-containing silane coupling agent.
[4] 하이드록시기를 가지는 라디칼 중합성 모노머(C)가, 탄소간 이중 결합 또는 탄소간 삼중 결합을 하나 이상 가지는, 하이드록시기를 가지는 라디칼 중합성 모노머인, 상기 [1] ∼ 상기 [3] 중 어느 한 항에 기재된 광 나노임프린트용 경화성 조성물.[4] The thermosetting resin composition according to any one of [1] to [3], wherein the radically polymerizable monomer (C) having a hydroxy group is a radically polymerizable monomer having at least one carbon- A curable composition for a photo-nanoimprint as set forth in any one of claims 1 to 5.
[5] 하이드록시기를 가지는 라디칼 중합성 모노머(C)가, 일반식 (2)로 표시되는 화합물인, 상기 [1] ∼ 상기 [3] 중 어느 한 항에 기재된 광 나노임프린트용 경화성 조성물.[5] The curable composition for a photo-nanoimprint as described in any one of [1] to [3], wherein the radically polymerizable monomer (C) having a hydroxy group is a compound represented by the general formula (2).
(식 (2) 중, R11은 수소 또는 탄소수 1∼3의 알킬이며, R12는 각각 독립적으로 환상 구조를 가질 수 있는 탄소수 2∼12의 알킬렌이며, n은 1∼30의 정수임.)(In the formula (2), R 11 is hydrogen or alkyl having 1 to 3 carbon atoms, R 12 is independently alkylene having 2 to 12 carbon atoms which may have a cyclic structure, and n is an integer of 1 to 30)
[6] 하이드록시기를 가지는 라디칼 중합성 모노머(C)가 펜타에리트리톨트리(메타)아크릴레이트, 2-하이드록시에틸(메타)아크릴레이트, 2-하이드록시프로필(메타)아크릴레이트, 4-하이드록시부틸(메타)아크릴레이트 및 1,4-시클로헥산디메탄올모노(메타)아크릴레이트로 이루어지는 군으로부터 선택되는 1종 이상인, 상기 [1] ∼ 상기 [3] 중 어느 한 항에 기재된 광 나노임프린트용 경화성 조성물.[6] The composition according to any one of [1] to [5], wherein the radically polymerizable monomer (C) having a hydroxy group is at least one selected from the group consisting of pentaerythritol tri (meth) acrylate, 2-hydroxyethyl (meth) acrylate, (1) to (3) above, wherein the photo-polymerizable monomer is at least one selected from the group consisting of acryloxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate and 1,4-cyclohexanedimethanol mono Lt; / RTI >
[7] 라디칼 중합성 모노머(C) 이외의 라디칼 중합성 모노머(E)가, 에틸렌글리콜디메타크릴레이트, 1,6-헥산디올디(메타)아크릴레이트, 펜타에리트리톨테트라아크릴레이트, 트리스[(메타)아크릴옥시에틸]이소시아누레이트, 부틸(메타)아크릴레이트, 네오펜틸글리콜디(메타)아크릴레이트로 이루어지는 군으로부터 선택되는 1종 이상인, 상기 [1] ∼ 상기 [6] 중 어느 한 항에 기재된 광 나노임프린트용 경화성 조성물.[7] The thermosetting resin composition according to any one of [1] to [5], wherein the radical polymerizable monomer (E) other than the radical polymerizable monomer (C) is at least one selected from the group consisting of ethylene glycol dimethacrylate, 1,6-hexanediol di (meth) acrylate, pentaerythritol tetraacrylate, (1) to (6) above, which is at least one selected from the group consisting of (meth) acryloxyethyl] isocyanurate, butyl (meth) acrylate and neopentyl glycol di Wherein the curable composition for a photo-nanoimprint is a curable composition.
[8] 계면활성제(F)를 더 포함하는, 상기 [1] ∼ 상기 [7] 중 어느 한 항에 기재된 광 나노임프린트용 경화성 조성물.[8] The curable composition for a photo-nanoimprint as described in any one of [1] to [7], further comprising a surfactant (F).
[9] 계면활성제(F)가, 광 반응성기를 가지는 계면활성제인, 상기 [8]에 기재된 광 나노임프린트용 경화성 조성물.[9] The curable composition for a photo-nanoimprint as described in [8] above, wherein the surfactant (F) is a surfactant having a photoreactive group.
[10] 화합물(A)을 0.1∼20 중량%, 실란 커플링제(B)를 0.1∼20 중량%, 하이드록시기를 가지는 라디칼 중합성 모노머(C)를 1∼60 중량%, 광중합 개시제(D)를 0.2∼20 중량%, 라디칼 중합성 모노머(C) 이외의 라디칼 중합성 모노머(E)를 5∼80 중량%, 계면활성제(F)를 0.01∼10 중량% 포함하는, 상기 [8] 또는 상기 [9]에 기재된 광 나노임프린트용 경화성 조성물.(10) A photopolymerization initiator composition comprising 0.1 to 20% by weight of a compound (A), 0.1 to 20% by weight of a silane coupling agent (B), 1 to 60% by weight of a radically polymerizable monomer (C) , The surfactant (F) is contained in an amount of from 0.2 to 20% by weight, the radically polymerizable monomer (E) other than the radical polymerizable monomer (C) in an amount of from 5 to 80% The curable composition for a photo-nanoimprint as described in [9].
[11] 기판 상에, 상기 [1] ∼ 상기 [10] 중 어느 한 항에 기재된 광 나노임프린트용 경화성 조성물을 도포하고, 그 도막 상에 몰드를 탑재하고, 여기에 광을 조사하여 경화막을 형성하고, 몰드를 박리함으로써, 미세 요철 패턴을 가지는 경화막을 형성하는 방법.[11] A curable composition for a photo-nanoimprint as described in any one of [1] to [10] above is applied onto a substrate, a mold is mounted on the coated film, light is irradiated thereon to form a cured film And peeling the mold to form a cured film having a fine uneven pattern.
[12] 광 나노임프린트용 경화성 조성물의 도막에 광을 조사하여 얻어진 경화막을, 가열하는, 상기 [11]에 기재된 미세 요철 패턴을 가지는 경화막을 형성하는 방법.[12] A method for forming a cured film having a fine concavo-convex pattern according to [11], wherein the cured film obtained by irradiating the coating film of the curable composition for photo-nano imprint with light is heated.
[13] 상기 [11] 또는 상기 [12]에 기재된 방법으로 얻어진 미세 요철 패턴을 가지는 경화막.[13] A cured film having a fine uneven pattern obtained by the method described in [11] or [12] above.
[14] 상기 [13]에 기재된 미세 요철 패턴을 가지는 경화막을 가지는 표시 소자.[14] A display element having a cured film having a fine uneven pattern described in [13] above.
그리고, 본 명세서 중, 아크릴레이트와 메타크릴레이트의 양자를 나타내기 위해 "(메타)아크릴레이트"와 같이 표기하는 경우가 있다.In the present specification, the term "(meth) acrylate" may be used to denote both of acrylate and methacrylate.
본 발명의 바람직한 태양에 따른 광 나노임프린트용 경화성 조성물로부터 얻어지는 경화막은, 예를 들면, 금속·유리와의 밀착성이 높은 경화막을 제공할 수 있다. 본 발명의 바람직한 태양에 따른 광 나노임프린트용 경화성 조성물로부터 얻어지는 경화막은 반도체 집적 회로의 표면에 형성된 경우, 가열되어도, 기판 계면에서의 부풀어짐이나 박리를 방지할 수 있다.The cured film obtained from the curable composition for a photo-nanoimprint according to a preferred embodiment of the present invention can provide a cured film having high adhesion with, for example, a metal and a glass. When the cured film obtained from the curable composition for a photo-nanoimprint according to a preferred embodiment of the present invention is formed on the surface of a semiconductor integrated circuit, it is possible to prevent swelling and peeling at the substrate interface even when heated.
또한, 본 발명의 바람직한 태양에 따른 광 나노임프린트용 경화성 조성물은, 높은 투명성을 가진다.In addition, the curable composition for a photo-nanoimprint according to a preferred embodiment of the present invention has high transparency.
또한, 본 발명의 바람직한 태양에 따른 광 나노임프린트용 경화성 조성물을 사용함으로써, 반도체 집적 회로의 제조에 있어서의 보호막의 형성에 소요되는 수고나 시간을 단축할 수 있어 소모품도 삭감할 수 있다.Further, by using the curable composition for a photo-nanoimprint according to the preferred embodiment of the present invention, time and time required for forming a protective film in the production of a semiconductor integrated circuit can be shortened and consumables can be reduced.
1. 본 발명의 광 나노임프린트용 경화성 조성물1. The curable composition for a photo-nanoimprint of the present invention
본 발명의 광 나노임프린트용 경화성 조성물은, 일반식 (1-1)∼(1-3) 중 어느 하나로 표시되는 화합물(A)과, 실란 커플링제(B)와, 하이드록시기를 가지는 라디칼 중합성 모노머(C)와, 광중합 개시제(D)와, 라디칼 중합성 모노머(B) 이외의 라디칼 중합성 모노머(E)와 계면활성제(F)를 포함하는 경화성 조성물이다.The curable composition for a photo-nanoimprint of the present invention comprises a compound (A) represented by any one of the general formulas (1-1) to (1-3), a silane coupling agent (B), a radical polymerizable Is a curing composition comprising a monomer (C), a photopolymerization initiator (D), a radical polymerizable monomer (E) other than the radical polymerizable monomer (B) and a surfactant (F).
본 발명의 광 나노임프린트용 경화성 조성물은, 화합물(A)과, 실란 커플링제(B)와, 하이드록시기를 가지는 라디칼 중합성 모노머(C)와, 광중합 개시제(D)와, 라디칼 중합성 모노머(B) 이외의 라디칼 중합성 모노머(E)와, 계면활성제(F) 외에, 열경화성 화합물, 용매, 첨가제, 중합 금지제, 착색제 등을 임의로 더 포함할 수 있다.The curable composition for a photo-nanoimprint of the present invention comprises a compound (A), a silane coupling agent (B), a radically polymerizable monomer (C) having a hydroxy group, a photopolymerization initiator (D), a radically polymerizable monomer A solvent, an additive, a polymerization inhibitor, a colorant, and the like in addition to the radical polymerizable monomer (E) other than the radical polymerizable monomer (B) and the surfactant (F)
본 발명의 광 나노임프린트용 경화성 조성물은, E형 점도계로 측정한, 25℃에서의 점도가 2∼500 mPa·s이면, 광 나노임프린트용 경화성 조성물과 몰드와의 박리성이 양호하게 되므로 바람직하다.The curable composition for a photo-nanoimprint of the present invention preferably has a viscosity of 2 to 500 mPa · s at 25 ° C, as measured by an E-type viscometer, since the releasability between the curable composition for the photo-nanoimprint and the mold becomes satisfactory .
1.1 화합물(A)1.1 Compound (A)
화합물(A)은, 상기 일반식 (1)로 표시되는 화합물이며, 일반식 (1)을 구체적으로 나타낸 일반식 (1-1)∼(1-3) 중 어느 하나로 표시되는 화합물이다.The compound (A) is a compound represented by the general formula (1) and represented by any one of the general formulas (1-1) to (1-3) shown in the general formula (1).
식 (1-1)∼(1-3) 중의 R1은 탄소수 1∼3의 알킬 또는 수소이며, R2는 환상 구조를 가질 수 있는 탄소수 2∼12의 알킬렌이지만, 이들 중에서도, R1은 탄소수 1 또는 수소인 것이 바람직하며, R2는 에틸렌인 것이 바람직하다.Equation (1-1) to (1-3) of R 1 is hydrogen or alkyl having a carbon number of 1~3, R 2 is alkylene having a carbon number of 2 to 12, but the alkyl which may have a cyclic structure, among these, R 1 is It is preferably 1 carbon atom or hydrogen, and R 2 is preferably ethylene.
화합물(A)은, 식 (1-1)∼(1-3)으로 표시되는 화합물로부터 선택되는 1종의 화합물일 수도 있고, 이들의 혼합물일 수도 있다.The compound (A) may be a single compound selected from the compounds represented by the formulas (1-1) to (1-3), or a mixture thereof.
화합물(A)이 식 (1-1)∼(1-3)으로 표시되는 화합물로부터 선택되는 2종 이상의 혼합물인 경우, 주성분이 (1-1) 또는 (1-2)로 표시되는 화합물인 것이 바람직하다.When the compound (A) is a mixture of two or more compounds selected from the compounds represented by the formulas (1-1) to (1-3), the main component is a compound represented by (1-1) or (1-2) desirable.
이들 중에서도, R1이 메틸이며, R2가 에틸렌인 식 (1-1)로 표시되는 화합물이 주성분이며, R1이 메틸이며, R2가 에틸렌인 식 (1-2) 또는 식 (1-3)으로 표시되는 화합물이 부성분인 혼합물[(도호화학공업주식회사) PPME(상품명)], 및 R1이 수소 또는 메틸이며, R2가 에틸렌인 식 (1-2)로 표시되는 화합물이 주성분이며, R1이 수소 또는 메틸이며, R2가 에틸렌인 식 (1-1) 또는 식 (1-3)으로 표시되는 화합물이 부성분인 혼합물[(다이셀·사이텍주식회사) EBECRYL168(상품명)]이 바람직하다.Among these, R 1 is a methyl, R 2 is a main component the compound represented by the ethylene in the formula (1-1), R 1 is a methyl, R 2 is ethylene in the formula (1-2) or (1 (PPME (trade name)), which is a subcomponent of a compound represented by the formula (3), and a compound represented by the formula (1-2) in which R 1 is hydrogen or methyl and R 2 is ethylene (EBECRYL 168 (trade name)) in which R 1 is hydrogen or methyl, and R 2 is ethylene and the compound represented by the formula (1-1) or (1-3) is a subcomponent Do.
광 나노임프린트용 경화성 조성물 중에 화합물(A)이 0.1∼20 중량% 포함되면 경화성 조성물을 경화하여 얻어지는 경화막의 금속에 대한 밀착성이 높아지므로 바람직하고, 광 나노임프린트용 경화성 조성물 중에 화합물(A)이 0.5∼10 중량% 포함되면 더욱 바람직하며, 1.5∼6 중량%이면 가장 바람직하다.When the compound (A) is contained in an amount of 0.1 to 20% by weight in the curable composition for a photo-nanoimprint, the adhesion of the cured film obtained by curing the curable composition to a metal is increased, By weight to 10% by weight, and most preferably 1.5 to 6% by weight.
1.2 실란 커플링제(B)1.2 Silane coupling agent (B)
본 발명의 광 나노임프린트용 경화성 조성물은, 실란 커플링제(B)를 포함한다. 본 발명의 광 나노임프린트용 경화성 조성물에 포함되는 실란 커플링제로서는, 에폭시기 함유 실란 커플링제를 사용하는 것이 바람직하다.The curable composition for a photo-nanoimprint of the present invention comprises a silane coupling agent (B). As the silane coupling agent contained in the curable composition for a photo-nanoimprint of the present invention, it is preferable to use an epoxy group-containing silane coupling agent.
에폭시기 함유 실란 커플링제의 구체예로서는, 3-글리시독시프로필디메틸에톡시실란, 3-글리시독시프로필메틸디에톡시실란, 3-글리시독시프로필트리메톡시실란을 들 수 있다. 이들 중에서도, 3-글리시독시프로필트리메톡시실란이, 밀착성을 향상시키는 효과가 크기 때문에 바람직하다.Specific examples of the epoxy group-containing silane coupling agent include 3-glycidoxypropyldimethylethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-glycidoxypropyltrimethoxysilane. Among them, 3-glycidoxypropyltrimethoxysilane is preferable because it has a large effect of improving adhesion.
실란 커플링제(B)는, 1종의 화합물이라도 되고, 2종 이상의 화합물의 혼합물이라도 된다.The silane coupling agent (B) may be one kind of compound or a mixture of two or more kinds of compounds.
본 발명의 광 나노임프린트용 경화성 조성물에 있어서, 실란 커플링제(B)가 광 나노임프린트용 경화성 조성물 중에 0.1∼20 중량% 포함되면, 얻어지는 경화막과 기판의 밀착성을 향상시키는 효과가 크기 때문에 바람직하고, 경화성 조성물 전체의 1∼10 중량% 포함되면 더욱 바람직하며, 3∼6 중량%인 것이 가장 바람직하다.In the curable composition for a photo-nanoimprint of the present invention, when the silane coupling agent (B) is contained in an amount of 0.1 to 20 wt% in the curable composition for a photo-nanoimprint, the effect of improving the adhesion between the obtained cured film and the substrate is great , More preferably from 1 to 10 wt%, and most preferably from 3 to 6 wt% of the entire curable composition.
1.3 하이드록시기를 가지는 라디칼 중합성 모노머(C)1.3 Radically polymerizable monomer (C) having hydroxy group
하이드록시기를 가지는 라디칼 중합성 모노머(C)는, 하이드록시기를 가지는 라디칼 중합성의 화합물이면 특별히 한정되지 않는다.The radically polymerizable monomer (C) having a hydroxy group is not particularly limited as long as it is a radically polymerizable compound having a hydroxy group.
하이드록시기를 가지는 라디칼 중합성 모노머(C)는, 중합성 관능기(탄소간 이중 결합, 탄소간 삼중 결합을 포함함)를 적어도 1개 가지는 것이 바람직하다.The radically polymerizable monomer (C) having a hydroxy group preferably has at least one polymerizable functional group (including a carbon-carbon double bond and a carbon-carbon triple bond).
그리고, 본 발명의 바람직한 태양의 광 나노임프린트용 경화성 조성물에서의 하이드록시기를 가지는 라디칼 중합성 모노머(C)는, 광 나노임프린트용 경화성 조성물 중에 포함되는 다른 성분과의 상용성(相溶性)을 높이는 효과를 가진다.The radically polymerizable monomer (C) having a hydroxy group in the curable composition for a photo-nanoimprint of the preferred embodiment of the present invention is excellent in compatibility with other components contained in the curable composition for light nanoimprint Effect.
하이드록시기를 가지는 라디칼 중합성 모노머(C)의 바람직한 예로서는, 하이드록시와 1개의 탄소간 이중 결합을 가지는 중합성 모노머, 하이드록시와 2개의 탄소간 이중 결합을 가지는 중합성 모노머, 하이드록시와 3개 이상의 탄소간 이중 결합을 가지는 중합성 모노머를 들 수 있다.Preferable examples of the radically polymerizable monomer (C) having a hydroxy group include a polymerizable monomer having hydroxy and one carbon-carbon double bond, a polymerizable monomer having hydroxy and two carbon-carbon double bonds, Or more of carbon-carbon double bonds.
하이드록시기를 가지는 라디칼 중합성 모노머(C)에서, 하이드록시와 1개의 탄소간 이중 결합을 가지는 중합성 모노머의 구체예로서는, 2-하이드록시에틸(메타)아크릴레이트, 2-하이드록시프로필(메타)아크릴레이트, 4-하이드록시부틸(메타)아크릴레이트, 1,4-시클로헥산디메탄올모노(메타)아크릴레이트를 들 수 있다.Specific examples of the polymerizable monomer having hydroxy and one carbon-carbon double bond in the radically polymerizable monomer (C) having a hydroxy group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) Acrylate, 4-hydroxybutyl (meth) acrylate, and 1,4-cyclohexanedimethanol mono (meth) acrylate.
하이드록시기를 가지는 라디칼 중합성 모노머(C)에서, 하이드록시와 2개의 탄소간 이중 결합을 가지는 중합성 모노머의 구체예로서는, 이소시아눌산 에틸렌옥시드 변성 디(메타)아크릴레이트, 글리세롤디아크릴레이트, 펜타에리트리톨디(메타)아크릴레이트, 펜타에리트리톨디(메타)아크릴레이트모노스테어레이트, 트리메틸올프로판디(메타)아크릴레이트, 디펜타에리트리톨디(메타)아크릴레이트를 들 수 있다.In the radically polymerizable monomer (C) having a hydroxy group, specific examples of the polymerizable monomer having hydroxy and two carbon-carbon double bonds include isocyanuric acid ethylene oxide-modified di (meth) acrylate, glycerol diacrylate, Acrylate, pentaerythritol di (meth) acrylate, pentaerythritol di (meth) acrylate monostearate, trimethylol propane di (meth) acrylate and dipentaerythritol di (meth) acrylate.
하이드록시기를 가지는 라디칼 중합성 모노머(C)에서, 하이드록시와 3개 이상의 탄소간 이중 결합을 가지는 중합성 모노머의 구체예로서는, 펜타에리트리톨트리(메타)아크릴레이트, 디펜타에리트리톨펜타(메타)아크릴레이트, 알킬 변성 디펜타에리트리톨펜타(메타)아크릴레이트, 알킬 변성 디펜타에리트리톨테트라(메타)아크릴레이트, 알킬 변성 디펜타에리트리톨트리(메타)아크릴레이트를 들 수 있다.Specific examples of the polymerizable monomer having hydroxy and at least three carbon-carbon double bonds in the radically polymerizable monomer (C) having a hydroxy group include pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, Acrylate, alkyl-modified dipentaerythritol penta (meth) acrylate, alkyl-modified dipentaerythritol tetra (meth) acrylate, and alkyl-modified dipentaerythritol tri (meth) acrylate.
이들 중에서도, 광 나노임프린트용 경화성 조성물에 응용한 경우의 도포 안정성의 관점에서, 하이드록시기를 가지는 라디칼 중합성 모노머(C)는, 2-하이드록시에틸메타크릴레이트, 2-하이드록시프로필메타아크릴레이트, 4-하이드록시부틸아크릴레이트, 1,4-시클로헥산디메탄올모노아크릴레이트, 펜타에리트리톨트리(메타)아크릴레이트가 바람직하다.Among these, from the viewpoint of coating stability when applied to a curable composition for a photo-nanoimprint, the radically polymerizable monomer (C) having a hydroxy group is preferably selected from the group consisting of 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate , 4-hydroxybutyl acrylate, 1,4-cyclohexanedimethanol monoacrylate, and pentaerythritol tri (meth) acrylate are preferable.
또한, 하이드록시기를 가지는 라디칼 중합성 모노머(C)는, 상기 일반식 (2)로 표시되는 화합물인 것이 바람직하다. 일반식 (2) 중, R12는 각각 독립적으로 환상 구조를 가질 수 있는 탄소수 2∼12의 알킬렌이지만, 이들 중에서도, 에틸렌, 프로필렌, 부틸렌 또는 하기 식 (20)의 구조로 표시되는 기가 바람직하다.The radically polymerizable monomer (C) having a hydroxy group is preferably a compound represented by the above general formula (2). In the general formula (2), R 12 is an alkylene group having 2 to 12 carbon atoms which may independently have a cyclic structure. Of these, ethylene, propylene, butylene, or a group represented by the following formula (20) Do.
또한, 상기 일반식 (2)의 n은 1∼30의 정수이며, 바람직하게는 1∼10, 더욱 바람직하게는 1∼3, 가장 바람직하게는 1이다.In the general formula (2), n is an integer of 1 to 30, preferably 1 to 10, more preferably 1 to 3, and most preferably 1.
하이드록시기를 가지는 라디칼 중합성 모노머(C)로서 사용하는 화합물은, 25℃에서의 점도가 100 mPa·s 이하이면, 예를 들면, 얻어지는 경화성 조성물의 점도를 저하시킬 수 있으므로 바람직하다.The compound used as the radically polymerizable monomer (C) having a hydroxy group is preferable because the viscosity at 25 캜 of 100 mPa 이하 or less can lower the viscosity of the obtained curable composition, for example.
하이드록시기를 가지는 라디칼 중합성 모노머(C)는, 1종의 화합물이라도 되고, 2종 이상의 화합물의 혼합물이라도 된다.The radically polymerizable monomer (C) having a hydroxy group may be a single compound or a mixture of two or more compounds.
광 나노임프린트용 경화성 조성물 중에 하이드록시기를 가지는 라디칼 중합성 모노머(C)가 1∼60 중량% 포함되면 광 나노임프린트 경화성 조성물의 도포성의 면에서 바람직하고, 5∼50 중량% 포함되면 더욱 바람직하며, 10∼35 중량%이면 가장 바람직하다.When the radically polymerizable monomer (C) having a hydroxy group is contained in an amount of 1 to 60% by weight in the curable composition for a photo-nanoimprint, it is preferable in view of coatability of the photo-nanoimprint curable composition, more preferably 5 to 50% Most preferably 10 to 35% by weight.
1.4 광중합 개시제(D)1.4 Photopolymerization initiator (D)
본 발명의 광 나노임프린트 경화성 조성물에는, 광중합 개시제를 포함한다. 본 발명에 사용되는 광중합 개시제는, 광 조사에 의해 전술한 중합성 화합물을 중합하는 활성종(活性種)을 발생하는 화합물이면 어느 것이라도 사용할 수 있다. 광중합 개시제로서는, 광 조사에 의해 라디칼을 발생하는 라디칼 중합 개시제, 광 조사에 의해 산을 발생하는 양이온 중합 개시제가 바람직하고, 보다 바람직하게는 라디칼 중합 개시제이지만, 상기 중합성 화합물의 중합성 기의 종류에 따라 적절하게 결정된다. 즉, 본 발명의 광중합 개시제는, 사용하는 광원의 파장에 대하여 활성을 가지는 것이 배합되고, 반응 형식의 차이(예를 들면, 라디칼 중합이나 양이온 중합 등)에 따라 적절한 활성종을 발생시키는 것을 사용할 필요가 있다. 또한, 본 발명에서, 광중합 개시제는 복수 종류를 병용해도 된다.The photo-nanoimprint curable composition of the present invention contains a photopolymerization initiator. The photopolymerization initiator used in the present invention may be any compound that generates active species (active species) that polymerize the above-mentioned polymerizable compound by light irradiation. As the photopolymerization initiator, a radical polymerization initiator that generates a radical by light irradiation and a cation polymerization initiator that generates an acid by light irradiation are preferable, and a radical polymerization initiator is more preferable. However, the kind of the polymerizable group . ≪ / RTI > That is, the photopolymerization initiator of the present invention is required to be one which has an activity with respect to the wavelength of a light source to be used and which generates an appropriate active species in accordance with a difference in reaction type (for example, radical polymerization or cation polymerization) . In the present invention, a plurality of types of photopolymerization initiators may be used in combination.
본 발명에 사용되는 광중합 개시제는, 예를 들면, 시판되고 있는 개시제를 사용할 수 있다. 이들의 예로서는, Irgacure2959(1-[4-(2-하이드록시에톡시)페닐]-2-하이드록시-2-메틸-1-프로판-1-온), Irgacure184(1-하이드록시시클로헥실페닐케톤), Irgacure500(1-하이드록시시클로헥실페닐케톤, 벤조페논), Irgacure651(2,2-디메톡시-1,2-디페닐에탄-1-온), Irgacure369(2-벤질-2-디메틸아미노-1-(4-모르폴리노페닐)부타논-1), Irgacure907(2-메틸-1-[4-메틸티오페닐]-2-모르폴리노프로판-1-온), Irgacure819(비스(2,4,6-트리메틸벤조일)-페닐포스핀옥사이드), Irgacure1800(비스(2,6-디메톡시벤조일)-2,4,4-트리메틸펜틸포스핀옥사이드, 1-하이드록시-시클로헥실-페닐-케톤), Irgacure1800(비스(2,6-디메톡시벤조일)-2,4,4-트리메틸펜틸포스핀옥사이드, 2-하이드록시-2-메틸-1-페닐-1-프로판-1-온), IrgacureOXE01(1,2-옥탄디온, 1-[4-(페닐티오)페닐]-2-(O-벤조일옥심)), Darocur1173(2-하이드록시-2-메틸-1-페닐-1-프로판-1-온), Darocur1116, 1398, 1174 및 1020, CGI242(에타논, 1-[9-에틸-6-(2-메틸벤조일)-9H-카르바졸-3-일]-1-(O-아세틸옥심)), DarocurTPO(2,4,6-트리메틸벤조일-디페닐포스핀옥사이드)(이상 모두 상품명, BASF재팬 주식회사); ESACURE 1001M(1-[4-벤조일페닐설파닐]페닐]-2-메틸-2-(4-메틸페닐설포닐)프로판-1-온)(이상 모두 상품명, DKSH 재팬 주식회사); 아데카옵토머N-1414(카르바졸·페논계), 아데카옵토머N-1717(아크리딘계), 아데카옵토머N-1606(트리아진계)(이상 모두 상품명, 주식회사 ADEKA); TFE-트리아진(2-[2-(퓨란-2-일)비닐]-4,6-비스(트리클로로메틸)-1,3,5-트리아진), TME-트리아진(2-[2-(5-메틸퓨란-2-일)비닐]-4,6-비스(트리클로로메틸)-1,3,5-트리아진), MP-트리아진(2-(4-메톡시페닐)-4,6-비스(트리클로로메틸)-1,3,5-트리아진)(이상 모두 상품명, 산와 케미컬 주식회사); TAZ-113(2-[2-(3,4-디메톡시페닐)에테닐]-4,6-비스(트리클로로메틸)-1,3,5-트리아진), TAZ-108(2-(3,4-디메톡시페닐)-4,6-비스(트리클로로메틸)-1,3,5-트리아진)(이상 모두 상품명, 미도리화학 주식회사);As the photopolymerization initiator used in the present invention, for example, commercially available initiators can be used. Examples of these include Irgacure2959 (1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propan-1-one), Irgacure 184 (1-hydroxycyclohexyl phenyl ketone ), Irgacure 500 (1-hydroxycyclohexyl phenyl ketone, benzophenone), Irgacure 651 (2,2-dimethoxy-1,2-diphenylethane- Irgacure 907 (2-methyl-1- [4-methylthiophenyl] -2-morpholinopropane-1-one) 4,6-trimethylbenzoyl) -phenylphosphine oxide), Irgacure 1800 (bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, 1 -hydroxy-cyclohexyl- ), Irgacure 1800 (bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, 2-hydroxy-2-methyl- (2-hydroxy-2-methyl-1-phenyl-1-propane-1-ene) -On), (9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O- acetyloxime), Darocur TPO (2,4,6-trimethylbenzoyl-diphenylphosphine oxide) (all trade names, BASF Japan Co., Ltd.); ESACURE 1001M (1- [4-benzoylphenylsulfanyl] phenyl] -2-methyl-2- (4-methylphenylsulfonyl) propan-1-one) (all trade names, DKSH Japan KK); ADEKA OPTOMER N-1414 (carbazole-phenone type), ADEKA OPTOMER N-1717 (ACRYLINE type), ADEKA OPTOMER N-1606 (triazine type) (all trade names, ADEKA Co., Ltd.); (Trichloromethyl) -1,3,5-triazine), TME-triazine (2- [2 (furan-2-yl) vinyl] (Trichloromethyl) -1,3,5-triazine), MP-triazine (2- (4-methoxyphenyl) - 4,6-bis (trichloromethyl) -1,3,5-triazine) (all trade names, Sanwa Chemical Co., Ltd.); TAZ-113 (2- [2- (3,4-dimethoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -1,3,5-triazine), TAZ- 3,4-dimethoxyphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine) (all trade names, Midori Kagaku Co., Ltd.);
그 외에, 벤조페논, 4,4'-비스디에틸아미노벤조페논, 4,4'-비스디메틸아미노벤조페논, 메틸-2-벤조페논, 4-벤조일-4'-메틸디페닐설피드, 4-페닐벤조페논, 2-클로로티옥산톤, 2-메틸티옥산톤, 2-이소프로필티옥산톤, 4-이소프로필티옥산톤, 2,4-디에틸티옥산톤, 1-클로로-4-프로폭시티옥산톤, 2-메틸티옥산톤, 티옥산톤암모늄염, 벤조인, 4,4'-디메톡시벤조인, 벤조인메틸에테르, 벤조인에틸에테르, 벤조인이소프로필에테르, 벤조인이소부틸에테르, 벤질디메틸케탈, 1,1,1-트리클로로아세토페논, 디에톡시아세토페논 및 디벤조수베론, o-벤조일벤조산 메틸, 2-벤조일나프탈렌, 4-벤조일비페닐, 4-벤조일디페닐에테르, 1,4-벤조일벤젠, 벤질, 10-부틸-2-클로로아크리돈, [4-(메틸페닐티오)페닐]페닐메탄, 2-에틸안트라퀴논, 2,2-비스(2-클로로페닐)4,5,4',5'-테트라키스(3,4,5-트리메톡시페닐)1,2'-비이미다졸, 2,2-비스(o-클로로페닐)4,5,4',5'-테트라페닐-1,2'-비이미다졸, 트리스(4-디메틸아미노페닐)메탄, 에틸-4-(디메틸아미노)벤조에이트, 2-(디메틸아미노)에틸벤조에이트, 부톡시에틸-4-(디메틸아미노)벤조에이트를 들 수 있다.In addition to the above, there may be mentioned benzophenone, 4,4'-bisdiethylaminobenzophenone, 4,4'-bisdimethylaminobenzophenone, methyl-2-benzophenone, 4-benzoyl- 2-chlorothioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 1- 2-methylthioxanthone, thioxanthone ammonium salt, benzoin, 4,4'-dimethoxybenzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin Isobutyl ether, benzyl dimethyl ketal, 1,1,1-trichloroacetophenone, diethoxyacetophenone and dibenzosuberone, methyl o-benzoylbenzoate, 2-benzoylnaphthalene, 4-benzoylbiphenyl, 4- Benzoylbenzene, benzyl, 10-butyl-2-chloroacridone, [4- (methylphenylthio) phenyl] phenylmethane, 2- ethyl anthraquinone, 2,2- Phenyl) 4,5,4 ', 5'-tetrakis (3,4,5-tri Methoxyphenyl) 1,2'-biimidazole, 2,2-bis (o-chlorophenyl) 4,5,4 ', 5'-tetraphenyl- (Dimethylamino) benzoate, butoxyethyl-4- (dimethylamino) benzoate, and the like.
광중합 개시제(D)는, 광 나노임프린트용 경화성 조성물 중에 0.2∼20 중량% 포함되면, 광 나노임프린트용 경화성 조성물로 만든 경우에 고감도가 되므로 바람직하고, 0.5∼15 중량%이면 더욱 바람직하고, 3∼10 중량%이면 가장 바람직하다.When the photopolymerization initiator (D) is contained in an amount of 0.2 to 20 wt% in the curable composition for a photo-nanoimprint, it is preferable that the photopolymerization initiator (D) is highly sensitized when it is made into a curable composition for a photo-nanoimprint, more preferably 0.5 to 15 wt% Most preferably 10% by weight.
1.5 라디칼 중합성 모노머(C) 이외의 라디칼 중합성 모노머(E)1.5 Radically polymerizable monomer (E) other than the radically polymerizable monomer (C)
본 발명의 광 나노임프린트용 경화성 조성물은, 라디칼 중합성 모노머(C) 이외의 라디칼 중합성 모노머(E)를 포함한다.The curable composition for a photo-nanoimprint of the present invention comprises a radically polymerizable monomer (E) other than the radical polymerizable monomer (C).
라디칼 중합성 모노머(C) 이외의 라디칼 중합성 모노머(E)는, 광 감도를 높이는 면에서 유용하다. 본 발명의 라디칼 중합성 모노머(C) 이외의 라디칼 중합성 모노머(E)는, 내(耐)도금액성이나 내약품성의 관점에서, 하이드록시를 가지고 있지 않은 다관능(메타)아크릴레이트인 것이 바람직하다.Radically polymerizable monomers (E) other than the radical polymerizable monomer (C) are useful in increasing the light sensitivity. The radically polymerizable monomer (E) other than the radically polymerizable monomer (C) of the present invention is preferably a polyfunctional (meth) acrylate having no hydroxy from the viewpoint of plating resistance and chemical resistance Do.
라디칼 중합성 모노머(C) 이외의 라디칼 중합성 모노머(E)의 구체예로서는, 에틸렌글리콜디(메타)아크릴레이트, 디에틸렌글리콜디(메타)아크릴레이트, 트리에틸렌글리콜디(메타)아크릴레이트, 테트라에틸렌글리콜디(메타)아크릴레이트, 폴리에틸렌글리콜디(메타)아크릴레이트, 프로필렌글리콜디(메타)아크릴레이트, 디프로필렌글리콜디(메타)아크릴레이트, 트리프로필렌글리콜디(메타)아크릴레이트, 테트라프로필렌글리콜디(메타)아크릴레이트, 폴리프로필렌글리콜디(메타)아크릴레이트, 비스페놀 A 에틸렌옥시드 변성 디(메타)아크릴레이트, 비스페놀 F 에틸렌옥시드 변성 디(메타)아크릴레이트, 트리메틸올프로판트리(메타)아크릴레이트, 에틸렌옥시드 변성 트리메틸올프로판트리(메타)아크릴레이트, 프로필렌옥시드 변성 트리메틸올프로판트리(메타)아크릴레이트, 디트리메틸올프로판테트라(메타)아크릴레이트, 글리세롤트리(메타)아크릴레이트, 1,6-헥산디올디(메타)아크릴레이트, 메톡시화 시클로헥실디(메타)아크릴레이트, 네오펜틸글리콜디(메타)아크릴레이트, 디글리세린테트라(메타)아크릴레이트, 펜타에리트리톨테트라(메타)아크릴레이트, 디펜타에리트리톨헥사(메타)아크릴레이트, 카프로락톤 변성 디펜타에리트리톨헥사(메타)아크릴레이트, 1,4-부탄디올디(메타)아크릴레이트, 1,3-부틸렌글리콜디(메타)아크릴레이트, 디시클로펜타닐디(메타)아크릴레이트, 트리스[(메타)아크릴옥시에틸]이소시아누레이트, 카프로락톤 변성 트리스[(메타)아크릴옥시에틸]이소시아누레이트가 있다.Specific examples of the radical polymerizable monomer (E) other than the radical polymerizable monomer (C) include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) Acrylates such as ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di Di (meth) acrylate, dipropylene glycol di (meth) acrylate, bisphenol A ethylene oxide modified di (meth) acrylate, bisphenol F ethylene oxide modified di (meth) acrylate, trimethylolpropane tri Acrylate, ethylene oxide-modified trimethylolpropane tri (meth) acrylate, propylene oxide-modified trimethylolpropane tri (Meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, glycerol tri (meth) acrylate, 1,6-hexanediol di (meth) acrylate, methoxylated cyclohexyl di Acrylate, dipentaerythritol hexa (meth) acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate, glycol di (meth) acrylate, diglycerin tetra (Meth) acrylate, dicyclopentanyl di (meth) acrylate, tris [(meth) acryloxyethyl] isocyanurate, And caprolactone-modified tris [(meth) acryloxyethyl] isocyanurate.
이들 중에서도, 라디칼 중합성 모노머(C) 이외의 라디칼 중합성 모노머(E)로서, 1,6-헥산디올디(메타)아크릴레이트, 비스페놀 F 에틸렌옥시드 변성 디(메타)아크릴레이트, 펜타에리트리톨테트라아크릴레이트, 디펜타에리트리톨헥사아크릴레이트, 카프로락톤 변성 디펜타에리트리톨헥사(메타)아크릴레이트, 트리스[(메타)아크릴옥시에틸]이소시아누레이트, 카프로락톤 변성 트리스[(메타)아크릴옥시에틸]이소시아누레이트로부터 선택되는 하나 이상을 함유하고 있으면, 본 발명의 광 나노임프린트용 경화성 조성물로부터 얻어지는 경화막의 내약품성이 높아지므로 바람직하다.Among them, as the radically polymerizable monomer (E) other than the radical polymerizable monomer (C), 1,6-hexanediol di (meth) acrylate, bisphenol F ethylene oxide modified di (meth) acrylate, pentaerythritol (Meth) acrylate, dipentaerythritol hexaacrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate, tris [(meth) acryloxyethyl] isocyanurate, caprolactone- Ethyl] isocyanurate, it is preferable that the cured film obtained from the curable composition for a photo-nanoimprint of the present invention has high chemical resistance.
라디칼 중합성 모노머(C) 이외의 라디칼 중합성 모노머(E)로서 사용하는 화합물은, 25℃에서의 점도가 3000 mPa·s 이하이면, 예를 들면, 얻어지는 경화성 조성물의 점도를 저하시킬 수 있으므로 바람직하다.The compound used as the radically polymerizable monomer (E) other than the radical polymerizable monomer (C) has a viscosity at 25 ° C of 3,000 mPa · s or less, for example, because it can lower the viscosity of the obtained curable composition Do.
라디칼 중합성 모노머(C) 이외의 라디칼 중합성 모노머(E)는, 1종의 화합물이라도 되고, 2종 이상의 화합물의 혼합물이라도 된다.The radically polymerizable monomer (E) other than the radical polymerizable monomer (C) may be a single compound or a mixture of two or more compounds.
라디칼 중합성 모노머(C) 이외의 라디칼 중합성 모노머(E)가, 광 나노임프린트용 경화성 조성물 중에 5∼80 중량% 포함되면, 광 나노임프린트용 경화성 조성물이 광에 대하여 고감도로 되므로 바람직하고, 30∼80 중량% 포함되면 광 나노임프린트용 경화성 조성물로부터 얻어지는 경화막의 내약품성이 높아지므로, 더욱 바람직하고, 50∼75 중량%이면 가장 바람직하다.When the radically polymerizable monomer (E) other than the radically polymerizable monomer (C) is contained in the curable composition for photo-nanoimprinting in an amount of 5 to 80% by weight, the curable composition for optical nanoimprint is highly sensitive to light, By weight to 80% by weight, the chemical resistance of the cured film obtained from the curable composition for a photo-nanoimprint increases, and more preferably from 50 to 75% by weight.
1.6 계면활성제(F)1.6 Surfactant (F)
본 발명의 광 나노임프린트용 경화성 조성물은, 계면활성제(F)를 포함한다.The curable composition for a photo-nanoimprint of the present invention comprises a surfactant (F).
이와 같은 계면활성제로서는, 폴리플로우 No.45, 폴리플로우 KL-245, 폴리플로우 No.75, 폴리플로우 No.90, 폴리플로우 No.95(이상 모두 상품명, 교에이샤화학공업 주식회사), 디스퍼베이크(Disperbyk) 161, 디스퍼베이크 162, 디스퍼베이크 163, 디스퍼베이크 164, 디스퍼베이크 166, 디스퍼베이크 170, 디스퍼베이크 180, 디스퍼베이크 181, 디스퍼베이크 182, BYK300, BYK306, BYK310, BYK320, BYK330, BYK344, BYK346, BYK-UV3500, BYK-UV3570(이상 모두 상품명, 빅케미·재팬주식회사), KP-341, KP-358, KP-368, KF-96-50CS, KF-50-100CS(이상 모두 상품명, 신에쓰화학공업주식회사), 서플론 SC-101, 서플론 KH-40(이상 모두 상품명, 세이미케미칼 주식회사), 프타젠트 222F, 프타젠트 251, FTX-218(이상 모두 상품명, 주식회사 네오스), EFTOP EF-351, EFTOP EF-352, EFTOP EF-601, EFTOP EF-801, EFTOP EF-802(이상 모두 상품명, 미쓰비시머티리얼 주식회사), 메가팩 F-171, 메가팩 F-177, 메가팩 F-475, 메가팩 F-556, 메가팩 F-477, 메가팩 R-30, 메가팩 RS-72-K(이상 모두 상품명, DIC 주식회사), TEGO Rad 2200N, TEGO Rad 2250N(이상 모두 상품명, 에보닉 테고 케미 주식회사), 플루오로알킬벤젠술폰산염, 플루오로알킬카르복시산염, 플루오로알킬폴리옥시에틸렌에테르, 요오드화 플루오로알모늄, 플루오로알킬베타인, 플루오로알킬술폰산염, 디글리세린테트라키스(플루오로알킬폴리옥시에틸렌에테르), 플루오로알킬트리메틸암모늄염, 플루오로알킬아미노술폰산염, 폴리옥시에틸렌노닐페닐에테르, 폴리옥시에틸렌옥틸페닐에테르, 폴리옥시에틸렌알킬에테르, 폴리옥시에틸렌라우릴에테르, 폴리옥시에틸렌올레일에테르, 폴리옥시에틸렌트리데실에테르, 폴리옥시에틸렌세틸에테르, 폴리옥시에틸렌스테아릴에테르, 폴리옥시에틸렌라우레이트, 폴리옥시에틸렌라우레이트, 폴리옥시에틸렌스테아레이트, 폴리옥시에틸렌라우릴아민, 소르비탄라우레이트, 소르비탄팔미테이트, 소르비탄스테아레이트, 소르비탄올레이트, 소르비탄지방산 에스테르, 폴리옥시에틸렌소르비탄라우레이트, 폴리옥시에틸렌소르비탄팔미테이트, 폴리옥시에틸렌소르비탄스테아레이트, 폴리옥시에틸렌소르비탄올레이트, 폴리옥시에틸렌나프틸에테르, 알킬벤젠술폰산염, 또는 알킬디페닐에테르디술폰산염을 예로 들 수 있다.Examples of such surfactants include Polyflow No. 45, Polyflow KL-245, Polyflow No. 75, Polyflow No. 90, Polyflow No. 95 (all trade names, Kyowa Chemical Industry Co., Ltd.) Disperbyk 161, Disper Bake 162, Disper Bake 163, Disper Bake 164, Disper Bake 166, Disper Bake 170, Disper Bake 180, Disper Bake 181, Disper Bake 182, BYK 300, BYK 306, BYK310, BYK320, BYK330, BYK344, BYK346, BYK-UV3500 and BYK-UV3570 (all trade names, Big Chemie Japan KK), KP-341, KP-358, KP-368, KF- 10000CS (all trade names, manufactured by Shin-Etsu Chemical Co., Ltd.), Surfron SC-101, Surfron KH-40 (all trade names, all of which are trade names, Seifo Chemical Co., Ltd.), PtGent 222F, PtGent 251 and FTX- EFTOP EF-351, EFTOP EF-601, EFTOP EF-801 and EFTOP EF-802 (all trade names, all of which are trademarks of Mitsubishi Materials Corporation) Mega pack F-177, mega pack F-475, mega pack F-556, mega pack F-477, mega pack R-30, megapack RS-72-K (Trade names, manufactured by DIC Co., Ltd.), TEGO Rad 2200N and TEGO Rad 2250N (all trade names, Ebonic Tegochemistry Co., Ltd.), fluoroalkylbenzenesulfonic acid salts, fluoroalkylcarboxylic acid salts, fluoroalkylpolyoxyethylene ethers, , Fluoroalkyl betaine, fluoroalkyl sulfonic acid salt, diglycerin tetrakis (fluoroalkyl polyoxyethylene ether), fluoroalkyltrimethylammonium salt, fluoroalkylaminosulfonic acid salt, polyoxyethylene nonylphenyl ether, polyoxyethylene Octyl phenyl ether, polyoxyethylene alkyl ether, polyoxyethylene lauryl ether, polyoxyethylene oleyl ether, polyoxyethylene tridecyl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, poly Polyoxyethylene stearate, polyoxyethylene laurylamine, sorbitan laurate, sorbitan palmitate, sorbitan stearate, sorbitan fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, Polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, oxyethylene sorbitan laurate, polyoxyethylene sorbitan palmitate, polyoxyethylene sorbitan stearate, polyoxyethylene sorbitan oleate, polyoxyethylene naphthyl ether, alkylbenzenesulfonic acid salt, Salts are examples.
이들 중에서도, 광 반응성기를 가지는 계면활성제인, BYK-UV3500, BYK-UV3570, 메가팩 RS-72-K, TEGO Rad 2200N, TEGO Rad 2250N은, 광 나노임프린트용 경화성 조성물의 광경화성을 높이는 관점에서 바람직하다.Of these, BYK-UV3500, BYK-UV3570, Megapack RS-72-K, TEGO Rad 2200N and TEGO Rad 2250N, which are photoreactive groups-having surfactants, are preferred from the viewpoint of enhancing the photocurability of the curable composition for optical nanoimprint Do.
계면활성제(F)는, 광 나노임프린트용 경화성 조성물 전체량에 대하여, 0.01∼10 중량% 포함되면, 광 나노임프린트용 경화성 조성물의 도포 균일성을 높이는 관점에서 바람직하고, 0.05∼3 중량%인 것이 더욱 바람직하고, 0.1∼1 중량%인 것이 가장 바람직하다.When the surfactant (F) is contained in an amount of 0.01 to 10% by weight based on the total amount of the curable composition for a photo-nanoimprint, the amount is preferably in the range of 0.05 to 3% by weight from the viewpoint of enhancing the coating uniformity of the curable composition for a light nanoimprint And most preferably 0.1 to 1% by weight.
1.7 그 외의 성분1.7 Other ingredients
광 나노임프린트용 경화성 조성물은, 보존 안정성이나, 형성되는 막의 내구성, 경화성 조성물의 도포 특성 등을 향상시키기 위해, 용매, 중합 금지제, 착색제 등을 더 포함해도 된다.The curable composition for a photo-nanoimprint may further contain a solvent, a polymerization inhibitor, a colorant, and the like in order to improve storage stability, durability of a film to be formed, and application properties of the curable composition.
광 나노임프린트용 경화성 조성물에, 이들 성분이 1종 포함되어도 되고, 2종 이상 포함되어도 된다.These components may be contained in the curable composition for optical nanoimprint, or two or more of these components may be contained.
1.7.1 용매(G)1.7.1 Solvent (G)
광 나노임프린트용 경화성 조성물은 경화성 조성물의 도포 특성을 향상시키기 위해 용매(G)를 포함해도 된다. 이 용매(G)로서는 비점(沸點)이 100℃ 이상인 용매가 바람직하다.The curable composition for a photo-nanoimprint may contain a solvent (G) for improving the application properties of the curable composition. The solvent (G) is preferably a solvent having a boiling point of 100 ° C or higher.
비점이 100℃ 이상인 용매(G)의 구체예로서는, 물, 아세트산 부틸, 프로피온산 부틸, 하이드록시아세트산 메틸, 하이드록시아세트산 에틸, 하이드록시아세트산 부틸, 메톡시아세트산 메틸, 메톡시아세트산 에틸, 메톡시아세트산 부틸, 에톡시아세트산 메틸, 에톡시아세트산 에틸, 3-하이드록시프로피온산 메틸, 3-하이드록시프로피온산 에틸, 3-메톡시프로피온산 메틸, 3-메톡시프로피온산 에틸, 3-에톡시프로피온산 메틸, 3-에톡시프로피온산 에틸, 2-하이드록시프로피온산 메틸, 2-하이드록시프로피온산 에틸, 2-하이드록시프로피온산 프로필, 2-메톡시프로피온산 메틸, 2-메톡시프로피온산 에틸, 2-메톡시프로피온산 프로필, 2-에톡시프로피온산 메틸, 2-에톡시프로피온산 에틸, 2-하이드록시-2-메틸프로피온산 메틸, 2-하이드록시-2-메틸프로피온산 에틸, 2-메톡시-2-메틸프로피온산 메틸, 2-에톡시-2-메틸프로피온산 에틸, 피루브산 메틸, 피루브산 에틸, 피루브산 프로필, 아세토아세트산 메틸, 아세토아세트산 에틸, 2-옥소부탄산메틸, 2-옥소부탄산에틸, 디옥산, 에틸렌글리콜, 디에틸렌글리콜, 트리에틸렌글리콜, 프로필렌글리콜, 디프로필렌글리콜, 트리프로필렌글리콜, 1,4-부탄디올, 에틸렌글리콜모노이소프로필에테르, 에틸렌글리콜모노부틸에테르, 프로필렌글리콜모노메틸에테르, 프로필렌글리콜모노메틸에테르아세테이트, 프로필렌글리콜모노에틸에테르아세테이트, 프로필렌글리콜모노프로필에테르아세테이트, 디프로필렌글리콜모노메틸에테르아세테이트, 디프로필렌글리콜모노에틸에테르아세테이트, 디프로필렌글리콜모노부틸에테르아세테이트, 에틸렌글리콜모노부틸에테르아세테이트, 시클로헥사논, 시클로펜타논, 디에틸렌글리콜모노메틸에테르, 디에틸렌글리콜모노메틸에테르아세테이트, 디에틸렌글리콜모노에틸에테르, 디에틸렌글리콜모노에틸에테르아세테이트, 디에틸렌글리콜모노부틸에테르, 디에틸렌글리콜모노부틸에테르아세테이트, 디에틸렌글리콜디메틸에테르, 디에틸렌글리콜디에틸에테르, 디에틸렌글리콜메틸에틸에테르, 톨루엔, 크실렌, 아니솔, γ-부티로락톤, N,N-디메틸아세트아미드, N-메틸-2-피롤리돈, 디메틸이미다졸리디논을 들 수 있다.Specific examples of the solvent (G) having a boiling point of 100 ° C or higher include water, butyl acetate, butyl propionate, methyl hydroxyacetate, ethyl hydroxyacetate, butyl hydroxyacetate, methyl methoxyacetate, methoxyacetate, , Methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, Hydroxypropionate, ethyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, propyl 2-hydroxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, Methyl, ethyl 2-ethoxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, Methyl 2-methylpropionate, methyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, Propylene glycol monobutyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether, diethylene glycol monobutyl ether, Propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene glycol monobutyl ether acetate, ethylene glycol monobutyl ether Acetate, cyclo Hexanone, cyclopentanone, diethylene glycol monomethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether Diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, toluene, xylene, anisole,? -Butyrolactone, N, N-dimethylacetamide, N-methyl- Pyrrolidone, and dimethylimidazolidinone.
이들 용매(G) 중에서도, 디프로필렌글리콜모노메틸에테르아세테이트, 디프로필렌글리콜모노에틸에테르아세테이트, 디프로필렌글리콜모노부틸에테르아세테이트, 프로필렌글리콜모노메틸에테르아세테이트, 프로필렌글리콜모노에틸에테르아세테이트, 3-메톡시프로피온산 메틸, 3-에톡시프로피온산 에틸, 디에틸렌글리콜모노에틸에테르아세테이트, 디에틸렌글리콜모노부틸에테르아세테이트, 디에틸렌글리콜디메틸에테르, 디에틸렌글리콜메틸에틸에테르 등을 사용하면, 경화성 조성물의 도포성이 안정되므로 바람직하다.Of these solvents (G), dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxypropionic acid Use of methyl, ethyl 3-ethoxypropionate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether or the like is preferable because the application property of the curable composition is stable desirable.
용매(G)는, 1종의 화합물이라도 되고, 2종 이상의 화합물의 혼합물이라도 된다.The solvent (G) may be a single compound or a mixture of two or more compounds.
용매(G)의 함유량은, 광 나노임프린트용 경화성 조성물 중에서, 3 중량% 이하인 것이 바람직하다. 즉, 본 발명의 조성물은, 바람직하게는 특정 1 관능 및 또는 2 관능의 단량체를 반응성 희석제로서 포함하므로, 본 발명의 조성물의 성분을 용해시키기 위한 유기 용제는, 반드시 함유할 필요는 없다. 또한, 유기 용제를 포함하지 않으면, 용제의 휘발을 목적으로 한 베이킹 공정이 불필요하게 되므로, 프로세스 간략화에 효과적인 점 등의 장점이 있다. 따라서, 용매(G)의 함유량은, 바람직하게는 3 중량% 이하, 더욱 바람직하게는 2 중량% 이하이며, 함유하지 않는 것이 특히 바람직하다. 이와 같이, 본 발명의 조성물은, 반드시, 유기 용제를 포함하는 것은 아니지만, 반응성 희석제에서는, 용해되지 않는 화합물 등을, 본 발명의 조성물로서 용해시키는 경우나 점도를 미세 조정할 때 등에, 임의로 첨가해도 된다.The content of the solvent (G) is preferably 3% by weight or less in the curable composition for a photo-nanoimprint. That is, since the composition of the present invention preferably contains a monofunctional or bifunctional monomer as a reactive diluent, the organic solvent for dissolving the components of the composition of the present invention need not always be contained. In addition, if an organic solvent is not included, a baking step for volatilizing the solvent is not required, which is advantageous in simplifying the process. Therefore, the content of the solvent (G) is preferably 3% by weight or less, more preferably 2% by weight or less, and it is particularly preferable that the solvent (G) is not contained. As described above, the composition of the present invention does not necessarily include an organic solvent, but may be optionally added, for example, when dissolving a compound or the like that is not dissolved in the reactive diluent in the composition of the present invention or when finely adjusting the viscosity .
1.7.2 중합 금지제(H)1.7.2 Polymerization inhibitor (H)
광 나노임프린트용 경화성 조성물은, 보존 안정성을 향상시키기 위해 중합 금지제(H)를 포함해도 된다.The curable composition for a photo-nanoimprint may contain a polymerization inhibitor (H) to improve storage stability.
중합 금지제(H)의 구체예로서는, 3,5-디부틸-4-하이드록시톨루엔, 4-메톡시페놀, 하이드로퀴논, 페노티아진을 들 수 있다. 이들 중에서도, 광 나노임프린트용 경화성 조성물의 점도 변화를 최소로 하는 관점에서, 중합 금지제(H)로서 페노티아진을 사용하는 것이 바람직하다.Specific examples of the polymerization inhibitor (H) include 3,5-dibutyl-4-hydroxytoluene, 4-methoxyphenol, hydroquinone and phenothiazine. Of these, phenothiazine is preferably used as the polymerization inhibitor (H) from the viewpoint of minimizing the viscosity change of the curable composition for photo-nanoimprint.
중합 금지제(H)는, 1종의 화합물이라도 되고, 2종 이상의 화합물의 혼합물이라도 된다.The polymerization inhibitor (H) may be a single compound or a mixture of two or more compounds.
중합 금지제(H)는, 광 나노임프린트용 경화성 조성물의 보존 안정성과 광에 대한 고감도성을 양립시키는 관점에서, 광 나노임프린트용 경화성 조성물 중에 0.01∼1 중량% 포함되는 것이 바람직하다.The polymerization inhibitor (H) is preferably contained in an amount of 0.01 to 1% by weight in the curable composition for a photo-nanoimprint, from the viewpoint of achieving both the storage stability of the curable composition for photo-nano imprint and the high sensitivity to light.
1.7.3 착색제(I)1.7.3 Colorant (I)
광 나노임프린트용 경화성 조성물은, 착색제(I)를 포함해도 되고, 이 경우, 예를 들면, 얻어지는 경화막 상태를 검사할 때 기판과의 식별을 용이하게 행할 수 있다.The curable composition for a photo-nanoimprint may contain a colorant (I). In this case, for example, when inspecting the state of the obtained cured film, it is possible to easily identify the substrate.
착색제(I)는, 1종의 화합물이라도 되고, 2종 이상의 화합물의 혼합물이라도 된다.The colorant (I) may be a single compound or a mixture of two or more compounds.
착색제(I)는, 광 나노임프린트용 경화성 조성물 중에 0.1∼10 중량% 정도, 바람직하게는 0.2∼5 중량% 정도 포함되어도 된다. 경화성 조성물 원료의 상용성의 관점에서, 착색제는 염료인 것이 바람직하다.The colorant (I) may be contained in an amount of about 0.1 to 10% by weight, preferably about 0.2 to 5% by weight, in the curable composition for a photo-nanoimprint. From the viewpoint of compatibility of the curable composition raw material, the colorant is preferably a dye.
2. 광 나노임프린트용 경화성 조성물2. Curable composition for optical nanoimprint
본 발명의 광 나노임프린트용 경화성 조성물은, 경화성 조성물을 구성하는 각 성분을 혼합함으로써 제조된다. 구체적으로는, 본 발명의 광 나노임프린트용 경화성 조성물은, 소정의 구조를 가지는 화합물(A)과, 실란 커플링제(B)와, 하이드록시기를 가지는 라디칼 중합성 모노머(C)와, 광중합 개시제(D)와, 라디칼 중합성 모노머(C) 이외의 라디칼 중합성 모노머(E)와 계면활성제(F)를 포함하는 광 나노임프린트용 경화성 조성물 및 임의로 포함되는 성분[용매(G), 중합 금지제(H), 착색제(I) 등]을 혼합하여 제조된다.The curable composition for a photo-nanoimprint of the present invention is prepared by mixing each component constituting the curable composition. Specifically, the curable composition for a photo-nanoimprint of the present invention comprises a compound (A) having a predetermined structure, a silane coupling agent (B), a radically polymerizable monomer (C) having a hydroxy group, a photopolymerization initiator (D), a radically polymerizable monomer (E) other than the radically polymerizable monomer (C) and a surfactant (F), and optionally a component [solvent (G), polymerization inhibitor H), colorant (I), etc.].
특히, 본 발명의 광 나노임프린트 경화성의 조성물 조성에 있어서는, 광 나노임프린트용 경화성 조성물 중에 화합물(A)을 0.1∼20 중량%, 실란 커플링제(B)를 0.1∼20 중량%, 하이드록시기를 가지는 라디칼 중합성 모노머(C)가 1∼60 중량%, 광중합 개시제(D)가 0.2∼20 중량%, 라디칼 중합성 모노머(C) 이외의 라디칼 중합성 모노머(E)가 5∼80 중량%, 계면활성제(F)가 0.01∼10 중량%로 되도록 구성하는 것이 바람직하다.Particularly, in the composition of the photo-nanoimprint curable composition of the present invention, the curable composition for a photo-nanoimprint preferably contains 0.1 to 20 wt% of the compound (A), 0.1 to 20 wt% of the silane coupling agent (B) (C), the photopolymerization initiator (D) is contained in an amount of 0.2 to 20 wt%, the radical polymerizable monomer (E) other than the radical polymerizable monomer (C) is contained in an amount of 5 to 80 wt% It is preferable that the active agent (F) is constituted by 0.01 to 10% by weight.
본 발명의 광 나노임프린트용 경화성 조성물에서, 하이드록시기를 가지는 라디칼 중합성 모노머(C) 이외의 중합성 모노머(E)로서 1,6-헥산디올디아크릴레이트, 에틸렌글리콜디메타크릴레이트, 네오펜틸글리콜디(메타)아크릴레이트 등의 2 관능의 화합물, 및 펜타에리트리톨트리/테트라아크릴레이트, 트리스[(메타)아크릴옥시에틸]이소시아누레이트 등의 3 관능의 화합물을 혼합하여 사용하는 경우, 성분(A)으로서 식 (1-1)을 주성분으로 하는 화합물을 사용하고, 하이드록시기를 가지는 라디칼 중합성 모노머(C)로서 2-하이드록시에틸메타크릴레이트, 2-하이드록시프로필메타크릴레이트, 4-하이드록시부틸아크릴레이트, 및 1,4-시클로헥산디메탄올모노아크릴레이트, 2-하이드록시-3-페녹시프로필아크릴레이트로 이루어지는 군으로부터 선택되는 적어도 하나를 사용하고, 광중합 개시제(D)로서 1,2-옥탄디온, 1-[4-(페닐티오)페닐]-2-(O-벤조일옥심), 2,4,6-트리메틸벤조일-디페닐포스핀옥사이드로부터 선택되는 적어도 하나를 사용하는 것이 바람직하다.In the curable composition for a photo-nanoimprint of the present invention, as the polymerizable monomer (E) other than the radically polymerizable monomer (C) having a hydroxy group, 1,6-hexanediol diacrylate, ethylene glycol dimethacrylate, neopentyl (Meth) acrylate and glycol di (meth) acrylate, and trifunctional compounds such as pentaerythritol tri / tetraacrylate and tris [(meth) acryloxyethyl] isocyanurate, As the radically polymerizable monomer (C) having a hydroxyl group, a compound having a hydroxy group, such as 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2- At least one selected from the group consisting of 4-hydroxybutyl acrylate, and 1,4-cyclohexanedimethanol monoacrylate, 2-hydroxy-3-phenoxypropyl acrylate, As the photopolymerization initiator (D), 1,2-octanedione, 1- [4- (phenylthio) phenyl] -2- (O-benzoyloxime), 2,4,6-trimethylbenzoyl- It is preferable to use at least one selected from the group consisting of titanium oxide and pin oxide.
전술한 조성의 광 나노임프린트용 경화성 조성물에서는, 경화성 조성물의 점도나 경화막으로 만들었을 때의 가교 밀도의 면에서, 각 성분의 함유량은, 광 나노임프린트용 경화성 조성물 중에 화합물(A)이 0.5∼10 중량%, 실란 커플링제(B)를 1∼10 중량%, 하이드록시기를 가지는 라디칼 중합성 모노머(C)가 5∼50 중량%, 광중합 개시제(D)가 0.5∼15 중량%, 하이드록시기를 가지는 라디칼 중합성 모노머(C) 이외의 라디칼 중합성 모노머(E)가 10∼70 중량%, 계면활성제(F)가 0.1∼5 중량%로 되도록 구성하는 것이 바람직하다.In the curable composition for a photo-nanoimprint of the above composition, the content of each component in terms of the viscosity of the curable composition or the cross-linking density when the curable composition is made into a cured film is such that the compound (A) (C) and 0.5 to 15% by weight of a photopolymerization initiator (D), 1 to 10% by weight of a silane coupling agent (B), 1 to 10% by weight of a silane coupling agent It is preferable that the radically polymerizable monomer (E) other than the radical polymerizable monomer (C) is 10 to 70% by weight and the surfactant (F) is 0.1 to 5% by weight.
3. 광 나노임프린트용 경화성 조성물을 사용한 패턴(특히 미세 요철 패턴) 형성 방법3. Method for forming pattern (especially fine uneven pattern) using curable composition for photo-nanoimprint
본 발명에서는, 상기 광 나노임프린트용 경화성 조성물을 도포하여 패턴을 형성한다. 구체적으로는, 기판, 또는, 지지체 상에 적어도 본 발명의 광경화성 조성물로 이루어지는 패턴 형성층을 도포하고, 필요에 따라 건조시켜 광경화성 조성물로 이루어지는 층(패턴 형성층)을 형성하여 패턴 수용체를 제조하고, 상기 패턴 수용체의 패턴 형성층 표면에 몰드를 압접(壓接)하고, 몰드 패턴을 전사(轉寫)하는 가공을 행하고, 미세 요철 패턴 형성층을 노광하여 경화시킨다. 본 발명의 패턴 형성 방법에 의한 광 나노임프린트 리소그래피는, 적층화나 다중 패터닝도 행할 수 있고, 통상의 열임프린트와 조합하여 사용할 수도 있다. 즉, 노광하여 형성한 미세 요철 패턴을 또한 가열할 수도 있다. 가열 공정은 몰드를 박리한 후에 행해도 되며, 가열 후에 몰드를 박리해도 된다.In the present invention, the curable composition for optical nanoimprint is applied to form a pattern. More specifically, a pattern-forming layer comprising at least the photocurable composition of the present invention is applied onto a substrate or a support and, if necessary, dried to form a layer (pattern-forming layer) comprising a photocurable composition, The mold is pressed against the surface of the pattern-forming layer of the pattern receptor to transfer the mold pattern, and the fine concavo-convex pattern-forming layer is exposed and cured. The photo-nanoimprint lithography according to the pattern forming method of the present invention can be laminated or multi-patterned, and can be used in combination with a normal thermal imprint. That is, the fine uneven pattern formed by exposure may also be heated. The heating step may be performed after the mold is peeled off, or the mold may be peeled off after heating.
상기 몰드는 폴리디메틸실록산, 폴리우레탄아크릴레이트, 또는 석영을 포함한다.The mold includes polydimethylsiloxane, polyurethane acrylate, or quartz.
본 발명의 광 나노임프린트용 경화성 조성물은, 일반적으로 잘 알려진 도포 방법, 예를 들면, 딥 코팅법, 에어 나이프 코팅법, 커텐 코팅법, 와이어 바 코팅법, 그라비아 코팅법, 압출 코팅(extrusion coating)법, 스핀 코팅법, 슬릿 코팅법 등에 의해, 도포함으로써 형성할 수 있다. 본 발명의 광 나노임프린트용 경화성 조성물로 이루어지는 층의 막 두께는, 사용하는 용도에 따라 상이하지만, 0.05㎛∼30㎛이다. 또한, 본 발명의 광 나노임프린트용 경화성 조성물은, 다중 도포해도 된다.The curable composition for a photo-nanoimprint of the present invention can be applied to a substrate by a well-known coating method such as a dip coating method, an air knife coating method, a curtain coating method, a wire bar coating method, a gravure coating method, A spin coating method, a slit coating method, or the like. The thickness of the layer made of the curable composition for a photo-nanoimprint of the present invention is 0.05 to 30 탆, though it varies depending on the application to be used. The curable composition for a photo-nanoimprint of the present invention may be applied multiple times.
기판은, 상기 광 나노임프린트용 경화성 조성물이 도포되는 대상이 될 수 있는 것이면 특별히 한정되지 않고, 그 형상은 평판형으로 한정되지 않고, 곡면형이라도 된다.The substrate is not particularly limited as long as it can be a target to which the curable composition for optical nanoimprint is applied, and its shape is not limited to a flat plate, but may be a curved surface.
또한, 기판의 재질은 특별히 한정되지 않지만, 예를 들면, 폴리에틸렌테레프탈레이트(PET), 폴리부틸렌테레프탈레이트(PBT) 등의 폴리에스테르계 수지, 폴리에틸렌, 폴리프로필렌 등의 폴리올레핀 수지, 폴리염화비닐, 불소 수지, 아크릴계 수지, 폴리아미드, 폴리카보네이트, 폴리이미드 등의 플라스틱 필름, 셀로판, 아세테이트, 금속박, 폴리이미드와 금속박의 적층 필름, 필링(filling) 효과가 있는 글라신지, 양피지, 또는 폴리에틸렌, 점토 바인더, 폴리비닐알코올, 전분, 카르복시메틸셀룰로오스(CMC) 등으로 필링 처리한 종이, 유리가 있다.The material of the substrate is not particularly limited, and examples thereof include polyester resins such as polyethylene terephthalate (PET) and polybutylene terephthalate (PBT); polyolefin resins such as polyethylene and polypropylene; polyolefin resins such as polyvinyl chloride, A plastic film such as a fluorine resin, an acrylic resin, a polyamide, a polycarbonate and a polyimide, a cellophane, an acetate, a metal foil, a laminated film of a polyimide and a metal foil, a glossy paper, a parchment paper or a polyethylene having a filling effect, , Polyvinyl alcohol, starch, paper peeled with carboxymethylcellulose (CMC), and glass.
이들 기판을 구성하는 물질에는, 본 발명의 효과에 악영향을 미치지 않는 범위 내에서, 안료, 염료, 산화 방지제, 열화(劣化) 방지제, 충전제, 자외선 흡수제, 대전 방지제 및/또는 전자파 방지제 등의 첨가제를 더 포함해도 된다. 또한, 기판의 표면의 일부는, 기판과는 상이한 재질로 형성되어 있어도 된다.The substances constituting these substrates may contain additives such as a pigment, a dye, an antioxidant, a deterioration inhibitor, a filler, an ultraviolet absorber, an antistatic agent and / or an electromagnetic wave inhibitor within a range not adversely affecting the effect of the present invention . A part of the surface of the substrate may be formed of a material different from that of the substrate.
기판의 용도도 특별히 한정되지 않지만, 본 발명의 광 나노임프린트용 경화성 조성물로부터 얻어지는 경화막은 유리·금속과의 밀착성이 높으므로, 기판 표면에 금속제의 회로나 유리를 가지는 반도체 집적 회로 등에 사용되는 것이 바람직하다. 회로를 형성하는 금속은, 특별히 한정되는 것은 아니지만, 금, 은, 동, 알루미늄, 몰리브덴 또는 ITO가 바람직하다.The use of the substrate is not particularly limited, but the cured film obtained from the curable composition for a photo-nanoimprint of the present invention is preferably used for a semiconductor integrated circuit having a metal circuit or glass on the substrate surface because of its high adhesion with glass and metal Do. The metal forming the circuit is not particularly limited, but gold, silver, copper, aluminum, molybdenum or ITO is preferable.
기판에서의 경화막을 형성하는 면에는, 필요에 따라 발수(撥水) 처리, 코로나 처리, 플라즈마 처리, 블라스트 처리 등의 용이한 접착을 위한 처리를 행하거나, 표면에 접착되기 용이한 층이나 컬러 필터용 보호막을 형성해도 된다.The surface on which the cured film is formed on the substrate may be subjected to a treatment for easy adhesion such as water repellent treatment, corona treatment, plasma treatment, blast treatment, or the like, A protective film for a protective layer may be formed.
본 발명을 사용하여 광 임프린트 리소그래피를 행하는 경우, 통상, 몰드의 압력이 10 기압 이하에서 행하는 것이 바람직하다. 몰드의 압력을 10 기압 이하로 함으로써, 몰드나 기판이 쉽게 변형되지 않아 패턴 정밀도가 향상되는 경향이 있고, 또한, 가압(加壓)이 낮기 때문에 장치를 축소할 수 있는 경향이 있어 바람직하다. 몰드의 압력은, 몰드 볼록부의 광경화성 조성물의 잔막이 적어지는 범위 내에서, 몰드 전사의 균일성을 확보할 수 있는 영역을 선택하는 것이 바람직하다.In the case of performing optical imprint lithography using the present invention, it is usually preferable that the pressure of the mold is set at 10 atm or less. When the pressure of the mold is 10 atm or less, the mold or the substrate is not easily deformed, and the pattern accuracy tends to be improved. Further, since the pressure is low, the apparatus tends to be reduced. The pressure of the mold is preferably selected so that the uniformity of the mold transfer can be ensured within a range in which the residual film of the photocurable composition of the convex portion of the mold becomes smaller.
본 발명의 광경화성 조성물을 경화시키는 광으로서는, 특별히 한정되지 않지만, 고에너지 전리 방사선, 근자외, 원자외, 가시, 적외 등의 영역의 파장의 광 또는 방사선을 예로 들 수 있다. 또한, 본 발명에서, 광 임프린트 리소그래피에서의 광 조사는, 경화에 필요한 조사량보다 충분히 크면 된다. 경화에 필요한 조사량은, 광경화성 조성물의 결합의 소비량이나 경화막의 택크(tackiness)를 조사하여 결정된다.The light for curing the photocurable composition of the present invention is not particularly limited, but examples thereof include light or radiation having a wavelength in a region of high energy ionizing radiation, extraordinary, non-atomic, visible, infrared, and the like. Further, in the present invention, the light irradiation in optical imprint lithography may be sufficiently larger than the irradiation amount required for curing. The irradiation amount required for curing is determined by examining the consumption of the bonding of the photo-curing composition and the tackiness of the cured film.
상기 패턴의 표면의 막 강도를 높이기 위하여, 필요에 따라 광의 조사에 의해 경화한 상기 경화막을 가열·소성해도 되고, 120℃∼250℃에서 10∼60 분간 전체면을 가열하는 것이 바람직하다.In order to increase the film strength of the surface of the pattern, the cured film that has been cured by light irradiation may be heated or baked if necessary, and it is preferable to heat the entire surface at 120 to 250 DEG C for 10 to 60 minutes.
[실시예][Example]
이하, 실시예에 의해 본 발명을 더 설명하지만, 본 발명은 이들에 의해 한정되는 것은 아니다. 그리고, 이하에서 특별히 언급하지 않는 한, "부"는 중량부를 의미하는 것으로 한다.Hereinafter, the present invention will be further described by way of examples, but the present invention is not limited thereto. Unless specifically stated below, "part (s) " means " part (s) by weight ".
표 1에 기재된 비율로 배합하고, 혼합 용해하여 불소 수지제 멤브레인 필터(0.2㎛)로 여과하여, 각각의 광 나노임프린트용 경화성 조성물을 조제(調製)했다.Were mixed in the proportions shown in Table 1, mixed and dissolved, and filtered with a membrane filter made of fluororesin (0.2 mu m) to prepare each of the curable compositions for optical nanoimprint.
[표 1][Table 1]
표 1의 각 성분은 이하에 나타낸 바와 같다.Each component in Table 1 is as follows.
화합물(A)The compound (A)
A1: PPMEA1: PPME
A2: EBECRYL168A2: EBECRYL168
실란 커플링제(B)The silane coupling agent (B)
B1: 3-글리시독시프로필트리메톡시실란B1: 3-glycidoxypropyltrimethoxysilane
하이드록시기를 가지는 라디칼 중합성 모노머(C)The radically polymerizable monomer (C) having a hydroxy group
C1: 4-하이드록시부틸아크릴레이트C1: 4-hydroxybutyl acrylate
C2: 펜타에리트리톨트리아크릴레이트C2: pentaerythritol triacrylate
광중합 개시제(D)Photopolymerization initiator (D)
D1: Irgacure OXE01D1: Irgacure OXE01
D2: Darocur TPOD2: Darocur TPO
라디칼 중합성 모노머(C) 이외의 라디칼 중합성 모노머(E)The radical polymerizable monomer (E) other than the radical polymerizable monomer (C)
E1: 부틸메타아크릴레이트E1: butyl methacrylate
E2: 1,6-헥산디올디아크릴레이트E2: 1,6-hexanediol diacrylate
E3: 에틸렌글리콜디메타크릴레이트E3: Ethylene glycol dimethacrylate
E4: 네오펜틸글리콜디아크릴레이트E4: Neopentyl glycol diacrylate
E5: 트리스(아크릴옥시에틸)이소시아누레이트E5: Tris (acryloxyethyl) isocyanurate
E6: 펜타에리트리톨테트라아크릴레이트E6: Pentaerythritol tetraacrylate
계면활성제(F)Surfactant (F)
F1: TEGO Rad 2200NF1: TEGO Rad 2200N
F2: KP-341F2: KP-341
(1) 시험 기판의 제작(1) Fabrication of Test Substrate
유리 기판, 몰리브덴 기판, 동 기판 상에 얻어진 각 광 나노임프린트용 경화성 조성물을 400∼3,000 rpm의 임의의 회전수로 10초간 스핀 코팅하였다. 스핀 코팅한 도포 기판 상에 도트 패턴을 가지는 우레탄을 재질로 하는 몰드(질량: 15.3g, 접지 부분의 크기: 100mm × 100mm)를 탑재하고, 주식회사 탑콘 제품인 플록시미티 노광기 TME-150PRC를 사용하여, 노광량 1000 mJ/cm2로 전체면을 노광하였다. 노광량은 우시오전기 주식회사 제품인 적산 광량계 UIT-102, 수광기 UVD-365PD로 측정하였다. 노광 후, 몰드를 제거하고, 오븐 중 230℃에서 30분 포스트 베이킹하여, 레지스트 패턴을 형성하였다.A glass substrate, a molybdenum substrate, and each curable composition for a photo-nanoimprint obtained on the copper substrate were spin-coated for 10 seconds at an arbitrary number of revolutions of 400 to 3,000 rpm. A mold (mass: 15.3 g, ground size: 100 mm x 100 mm) having a dot pattern made of urethane having a dot pattern was mounted on a spin-coated coated substrate, and using a floccity exposing machine TME-150PRC, The entire surface was exposed with an exposure dose of 1000 mJ / cm 2 . The amount of exposure was measured by a UV detector UIT-102, manufactured by Ushio Electric Co., Ltd., and UVD-365PD, a photoreceptor. After the exposure, the mold was removed and post-baked in an oven at 230 캜 for 30 minutes to form a resist pattern.
(2) 패턴 형상의 관찰(2) Observation of pattern shape
상기 (1)에서 얻어진 포스트 베이킹 후의 레지스트 패턴 기판을 광학 현미경으로 1000배로 관찰하여, 패턴 형상을 관찰했다. 레지스트 패턴이, 몰드의 패턴 형상의 틀이 되는 원판의 패턴과 대략 동일한 경우에는 양호(G: Good), 몰드의 패턴 형상의 틀이 되는 원판의 패턴과 분명하게 상이한 경우에는 불량(NG: No Good)으로 하였다.The post-baked resist pattern substrate obtained in the above (1) was observed with an optical microscope at 1,000 times, and the pattern shape was observed. When the resist pattern is substantially the same as the pattern of the original plate serving as the frame of the pattern of the mold, the pattern is clearly different from the pattern of the original plate which is a good (G: Good) ).
(3) 경화막의 유리·몰리브덴·동과의 밀착성 평가(3) Evaluation of adhesion between glass, molybdenum and copper of cured film
이와 같이 하여 제조된 시험 기판에서, 경화막과 유리·몰리브덴·동과의 밀착성을 조사하였다.The adhesiveness between the cured film and glass, molybdenum, and copper was examined on the thus prepared test substrate.
밀착성을 평가하기 위하여, 크로스커트법(JIS K 5600-5-6: 1999)에 준하여, 박리가 생겼는지의 여부를 조사하였다. 전술한 시험은, 온도 25℃, 습도 65%의 조건하에서 행하였다. 박리가 생기지 않은 경우를 "○", 박리가 생긴 경우를 "×"로 표시하였으며, 결과는 표 2에 나타낸 바와 같다.In order to evaluate the adhesion, it was examined whether peeling occurred in accordance with the cross-cut method (JIS K 5600-5-6: 1999). The above-described test was performed under the conditions of a temperature of 25 DEG C and a humidity of 65%. The case where no peeling occurred was indicated by "? &Quot;, and the case where peeling occurred was indicated by" x ".
[표 2][Table 2]
본 발명은, 예를 들면, 반도체 집적 회로에 사용되는 보호막 또는 절연막에 사용할 수 있다.The present invention can be used, for example, in a protective film or an insulating film used in a semiconductor integrated circuit.
Claims (14)
식 (1) 중, R1은 각각 독립적으로 탄소수 1∼3의 알킬 또는 수소이며, R2는 각각 독립적으로 환상(環狀) 구조를 가질 수 있는 탄소수 2∼12의 알킬렌이며, m은 0∼2의 정수임.(A), a silane coupling agent (B), a radically polymerizable monomer (C) having a hydroxy group, a photopolymerization initiator (D) and a radically polymerizable monomer (C) other than the compound Of a radically polymerizable monomer (E) and a surfactant (F):
In formula (1), R 1 is independently alkyl having 1 to 3 carbon atoms or hydrogen, R 2 is independently alkylene having 2 to 12 carbon atoms which may have a cyclic structure, m is 0 An integer of ~ 2.
R1은 각각 독립적으로 수소 또는 메틸이며, R2는 에틸렌인, 광 나노임프린트용 경화성 조성물.The method according to claim 1,
R 1 is each independently hydrogen or methyl, and R 2 is ethylene.
실란 커플링제(B)가 에폭시기 함유 실란 커플링제인, 광 나노임프린트용 경화성 조성물.3. The method according to claim 1 or 2,
Wherein the silane coupling agent (B) is an epoxy group-containing silane coupling agent.
하이드록시기를 가지는 라디칼 중합성 모노머(C)가, 탄소간 이중 결합 또는 탄소간 삼중 결합을 하나 이상 가지는, 하이드록시기를 가지는 라디칼 중합성 모노머인, 광 나노임프린트용 경화성 조성물.3. The method according to claim 1 or 2,
Wherein the radically polymerizable monomer (C) having a hydroxy group is a radically polymerizable monomer having at least one carbon-carbon double bond or a carbon-carbon triple bond and having a hydroxy group.
하이드록시기를 가지는 라디칼 중합성 모노머(C)가, 일반식 (2)로 표시되는 화합물인, 광 나노임프린트용 경화성 조성물:
식 (2) 중, R11은 수소 또는 탄소수 1∼3의 알킬이며, R12는 각각 독립적으로 환상 구조를 가질 수 있는 탄소수 2∼12의 알킬렌이며, n은 1∼30의 정수임.3. The method according to claim 1 or 2,
A curable composition for a photo-nanoimprint, wherein the radically polymerizable monomer (C) having a hydroxy group is a compound represented by the general formula (2)
In the formula (2), R 11 is hydrogen or alkyl having 1 to 3 carbon atoms, R 12 is independently alkylene having 2 to 12 carbon atoms which may have a cyclic structure, and n is an integer of 1 to 30.
하이드록시기를 가지는 라디칼 중합성 모노머(C)가 펜타에리트리톨트리(메타)아크릴레이트, 2-하이드록시에틸(메타)아크릴레이트, 2-하이드록시프로필(메타)아크릴레이트, 4-하이드록시부틸(메타)아크릴레이트 및 1,4-시클로헥산디메탄올모노(메타)아크릴레이트로 이루어지는 군으로부터 선택되는 1종 이상인, 광 나노임프린트용 경화성 조성물.3. The method according to claim 1 or 2,
The radical polymerizable monomer (C) having a hydroxy group is selected from the group consisting of pentaerythritol tri (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (Meth) acrylate, and 1, 4-cyclohexanedimethanol mono (meth) acrylate.
라디칼 중합성 모노머(C) 이외의 라디칼 중합성 모노머(E)가, 에틸렌글리콜디메타크릴레이트, 1,6-헥산디올디(메타)아크릴레이트, 펜타에리트리톨테트라아크릴레이트, 트리스[(메타)아크릴옥시에틸]이소시아누레이트, 부틸(메타)아크릴레이트, 네오펜틸글리콜디(메타)아크릴레이트로 이루어지는 군으로부터 선택되는 1종 이상인, 광 나노임프린트용 경화성 조성물.3. The method according to claim 1 or 2,
Wherein the radical polymerizable monomer (E) other than the radical polymerizable monomer (C) is at least one selected from the group consisting of ethylene glycol dimethacrylate, 1,6-hexanediol di (meth) acrylate, pentaerythritol tetraacrylate, tris [ (Meth) acrylate, neopentyl glycol di (meth) acrylate, and the like. The curable composition for a photo-nanoimprint of the present invention is at least one selected from the group consisting of acryloxyethyl acrylate, acryloxyethyl acrylate,
계면활성제(F)가, 광 반응성기를 가지는 계면활성제인, 광 나노임프린트용 경화성 조성물.The method according to claim 1,
A curable composition for a photo-nanoimprint, wherein the surfactant (F) is a surfactant having a photoreactive group.
화합물(A)을 0.1∼20 중량%, 실란 커플링제(B)를 0.1∼20 중량%, 하이드록시기를 가지는 라디칼 중합성 모노머(C)를 1∼60 중량%, 광중합 개시제(D)를 0.2∼20 중량%, 라디칼 중합성 모노머(C) 이외의 라디칼 중합성 모노머(E)를 5∼80 중량%, 계면활성제(F)를 0.01∼10 중량% 포함하는, 광 나노임프린트용 경화성 조성물.The method according to claim 1 or 8,
(A), 0.1 to 20% by weight of a silane coupling agent (B), 1 to 60% by weight of a radically polymerizable monomer (C) having a hydroxy group, And 5 to 80% by weight of a radically polymerizable monomer (E) other than the radical polymerizable monomer (C) and 0.01 to 10% by weight of a surfactant (F).
광 나노임프린트용 경화성 조성물의 도막에 광을 조사하여 얻어진 경화막을, 더 가열하는, 미세 요철 패턴을 가지는 경화막을 형성하는 방법.11. The method of claim 10,
A method for forming a cured film having a fine concavo-convex pattern for further heating a cured film obtained by irradiating a coating film of a curable composition for a photo-nanoimprint with light.
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| JP6460672B2 (en) * | 2013-09-18 | 2019-01-30 | キヤノン株式会社 | Film manufacturing method, optical component manufacturing method, circuit board manufacturing method, and electronic component manufacturing method |
| JP6029558B2 (en) * | 2013-09-30 | 2016-11-24 | 富士フイルム株式会社 | Curable composition for optical imprint, pattern formation method, fine pattern, and method for manufacturing semiconductor device |
| KR101650740B1 (en) * | 2014-09-15 | 2016-08-24 | 한국화학연구원 | Photopolymerizable composition for nanoimprint and method of preparing nanopatterned film using the same |
| JP6856020B2 (en) * | 2015-06-17 | 2021-04-07 | 株式会社ニコン | Wiring pattern manufacturing method, transistor manufacturing method, and transfer member |
| KR20170033618A (en) | 2015-09-17 | 2017-03-27 | 에스케이이노베이션 주식회사 | Battery System |
| JP6881567B2 (en) | 2017-03-23 | 2021-06-02 | Ａｇｃ株式会社 | Curable composition for imprint, replica mold and its manufacturing method |
| JP2018178064A (en) * | 2017-04-21 | 2018-11-15 | 株式会社カネカ | Acrylic adhesive composition |
| JP7175092B2 (en) * | 2018-03-16 | 2022-11-18 | 東京応化工業株式会社 | Photocurable composition and pattern forming method |
| KR20200020279A (en) | 2018-08-17 | 2020-02-26 | 에스케이이노베이션 주식회사 | Secondary battery with improved storage characteristics and method for prevnting storage characteristics |
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