WO2013161627A1 - インプリント材料 - Google Patents
インプリント材料 Download PDFInfo
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- WO2013161627A1 WO2013161627A1 PCT/JP2013/061286 JP2013061286W WO2013161627A1 WO 2013161627 A1 WO2013161627 A1 WO 2013161627A1 JP 2013061286 W JP2013061286 W JP 2013061286W WO 2013161627 A1 WO2013161627 A1 WO 2013161627A1
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- WIPO (PCT)
- Prior art keywords
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- comparative example
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- 239000000463 material Substances 0.000 title claims abstract description 274
- 150000001875 compounds Chemical class 0.000 claims abstract description 56
- 238000000576 coating method Methods 0.000 claims abstract description 51
- 239000002904 solvent Substances 0.000 claims abstract description 50
- 239000011248 coating agent Substances 0.000 claims abstract description 47
- 238000012360 testing method Methods 0.000 claims abstract description 29
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 26
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 15
- 239000003999 initiator Substances 0.000 claims abstract description 12
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 11
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 102
- 239000000758 substrate Substances 0.000 claims description 72
- 239000007787 solid Substances 0.000 claims description 59
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 41
- -1 acryloyloxy group Chemical group 0.000 claims description 41
- 238000000034 method Methods 0.000 claims description 30
- 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 claims description 21
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 20
- 230000003287 optical effect Effects 0.000 claims description 17
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 15
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 11
- 239000012528 membrane Substances 0.000 claims description 10
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 9
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 9
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- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims description 7
- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 claims description 7
- 238000011156 evaluation Methods 0.000 claims description 7
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 7
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 7
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- 150000001925 cycloalkenes Chemical class 0.000 claims description 6
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 5
- 239000004065 semiconductor Substances 0.000 claims description 5
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 claims description 4
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 4
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 4
- 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 claims description 4
- 238000003384 imaging method Methods 0.000 claims description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 4
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 claims description 3
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- 230000000052 comparative effect Effects 0.000 description 207
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- 102000004232 Mitogen-Activated Protein Kinase Kinases Human genes 0.000 description 64
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- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 18
- MPIAGWXWVAHQBB-UHFFFAOYSA-N [3-prop-2-enoyloxy-2-[[3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propoxy]methyl]-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical class C=CC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C MPIAGWXWVAHQBB-UHFFFAOYSA-N 0.000 description 17
- 235000019439 ethyl acetate Nutrition 0.000 description 14
- 238000000016 photochemical curing Methods 0.000 description 14
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 11
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- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 description 9
- 230000008569 process Effects 0.000 description 8
- 238000001723 curing Methods 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
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- QQZOPKMRPOGIEB-UHFFFAOYSA-N 2-Oxohexane Chemical compound CCCCC(C)=O QQZOPKMRPOGIEB-UHFFFAOYSA-N 0.000 description 4
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical class OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 4
- SYBYTAAJFKOIEJ-UHFFFAOYSA-N 3-Methylbutan-2-one Chemical compound CC(C)C(C)=O SYBYTAAJFKOIEJ-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 235000002597 Solanum melongena Nutrition 0.000 description 4
- 244000061458 Solanum melongena Species 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 239000003963 antioxidant agent Substances 0.000 description 4
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 4
- 239000003504 photosensitizing agent Substances 0.000 description 4
- 229920001451 polypropylene glycol Polymers 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 3
- QPRQEDXDYOZYLA-UHFFFAOYSA-N 2-methylbutan-1-ol Chemical compound CCC(C)CO QPRQEDXDYOZYLA-UHFFFAOYSA-N 0.000 description 3
- MSXVEPNJUHWQHW-UHFFFAOYSA-N 2-methylbutan-2-ol Chemical compound CCC(C)(C)O MSXVEPNJUHWQHW-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
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- 230000003078 antioxidant effect Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 125000004386 diacrylate group Chemical group 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000005096 rolling process Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 2
- XLLIQLLCWZCATF-UHFFFAOYSA-N 2-methoxyethyl acetate Chemical compound COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 description 2
- PFNHSEQQEPMLNI-UHFFFAOYSA-N 2-methyl-1-pentanol Chemical compound CCCC(C)CO PFNHSEQQEPMLNI-UHFFFAOYSA-N 0.000 description 2
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 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 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229920002799 BoPET Polymers 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- FHLPGTXWCFQMIU-UHFFFAOYSA-N [4-[2-(4-prop-2-enoyloxyphenyl)propan-2-yl]phenyl] prop-2-enoate Chemical class C=1C=C(OC(=O)C=C)C=CC=1C(C)(C)C1=CC=C(OC(=O)C=C)C=C1 FHLPGTXWCFQMIU-UHFFFAOYSA-N 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical class C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 2
- QUZSUMLPWDHKCJ-UHFFFAOYSA-N bisphenol A dimethacrylate Chemical class C1=CC(OC(=O)C(=C)C)=CC=C1C(C)(C)C1=CC=C(OC(=O)C(C)=C)C=C1 QUZSUMLPWDHKCJ-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
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- 230000008859 change Effects 0.000 description 2
- VPUGDVKSAQVFFS-UHFFFAOYSA-N coronene Chemical compound C1=C(C2=C34)C=CC3=CC=C(C=C3)C4=C4C3=CC=C(C=C3)C4=C2C3=C1 VPUGDVKSAQVFFS-UHFFFAOYSA-N 0.000 description 2
- 150000004775 coumarins Chemical class 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000010894 electron beam technology Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- CATSNJVOTSVZJV-UHFFFAOYSA-N heptan-2-one Chemical compound CCCCCC(C)=O CATSNJVOTSVZJV-UHFFFAOYSA-N 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
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- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
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- 229920001223 polyethylene glycol Polymers 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 2
- YKYONYBAUNKHLG-UHFFFAOYSA-N propyl acetate Chemical compound CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 2
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-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
- RIPYNJLMMFGZSX-UHFFFAOYSA-N (5-benzoylperoxy-2,5-dimethylhexan-2-yl) benzenecarboperoxoate Chemical compound C=1C=CC=CC=1C(=O)OOC(C)(C)CCC(C)(C)OOC(=O)C1=CC=CC=C1 RIPYNJLMMFGZSX-UHFFFAOYSA-N 0.000 description 1
- NALFRYPTRXKZPN-UHFFFAOYSA-N 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane Chemical compound CC1CC(C)(C)CC(OOC(C)(C)C)(OOC(C)(C)C)C1 NALFRYPTRXKZPN-UHFFFAOYSA-N 0.000 description 1
- NNNLYDWXTKOQQX-UHFFFAOYSA-N 1,1-di(prop-2-enoyloxy)propyl prop-2-enoate Chemical compound C=CC(=O)OC(CC)(OC(=O)C=C)OC(=O)C=C NNNLYDWXTKOQQX-UHFFFAOYSA-N 0.000 description 1
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- DXBHBZVCASKNBY-UHFFFAOYSA-N 1,2-Benz(a)anthracene Chemical compound C1=CC=C2C3=CC4=CC=CC=C4C=C3C=CC2=C1 DXBHBZVCASKNBY-UHFFFAOYSA-N 0.000 description 1
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- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- OEJAVRRJJOMQER-UHFFFAOYSA-N 1,4-bis(2-tert-butylperoxypropan-2-yloxy)benzene Chemical compound CC(C)(C)OOC(C)(C)OC1=CC=C(OC(C)(C)OOC(C)(C)C)C=C1 OEJAVRRJJOMQER-UHFFFAOYSA-N 0.000 description 1
- ALVZNPYWJMLXKV-UHFFFAOYSA-N 1,9-Nonanediol Chemical compound OCCCCCCCCCO ALVZNPYWJMLXKV-UHFFFAOYSA-N 0.000 description 1
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- FLYKCFXKXMGETI-UHFFFAOYSA-N 1-(2-hydroperoxypropan-2-yl)-2-propan-2-ylbenzene Chemical compound CC(C)C1=CC=CC=C1C(C)(C)OO FLYKCFXKXMGETI-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
- BOCJQSFSGAZAPQ-UHFFFAOYSA-N 1-chloroanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2Cl BOCJQSFSGAZAPQ-UHFFFAOYSA-N 0.000 description 1
- RRQYJINTUHWNHW-UHFFFAOYSA-N 1-ethoxy-2-(2-ethoxyethoxy)ethane Chemical compound CCOCCOCCOCC RRQYJINTUHWNHW-UHFFFAOYSA-N 0.000 description 1
- JOLQKTGDSGKSKJ-UHFFFAOYSA-N 1-ethoxypropan-2-ol Chemical compound CCOCC(C)O JOLQKTGDSGKSKJ-UHFFFAOYSA-N 0.000 description 1
- CSZZMFWKAQEMPB-UHFFFAOYSA-N 1-methoxybutan-2-ol Chemical compound CCC(O)COC CSZZMFWKAQEMPB-UHFFFAOYSA-N 0.000 description 1
- RHNJVKIVSXGYBD-UHFFFAOYSA-N 10-prop-2-enoyloxydecyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCCCCCOC(=O)C=C RHNJVKIVSXGYBD-UHFFFAOYSA-N 0.000 description 1
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- DZVCFNFOPIZQKX-LTHRDKTGSA-M merocyanine Chemical class [Na+].O=C1N(CCCC)C(=O)N(CCCC)C(=O)C1=C\C=C\C=C/1N(CCCS([O-])(=O)=O)C2=CC=CC=C2O\1 DZVCFNFOPIZQKX-LTHRDKTGSA-M 0.000 description 1
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- YLHXLHGIAMFFBU-UHFFFAOYSA-N methyl phenylglyoxalate Chemical compound COC(=O)C(=O)C1=CC=CC=C1 YLHXLHGIAMFFBU-UHFFFAOYSA-N 0.000 description 1
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- 125000000962 organic group Chemical group 0.000 description 1
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- AHHWIHXENZJRFG-UHFFFAOYSA-N oxetane Chemical compound C1COC1 AHHWIHXENZJRFG-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
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- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 1
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- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
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- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
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- 229920002647 polyamide Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
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- 238000006116 polymerization reaction Methods 0.000 description 1
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- 238000004904 shortening Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
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- 239000007921 spray Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 125000005504 styryl group Chemical group 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 1
- BSYVTEYKTMYBMK-UHFFFAOYSA-N tetrahydrofurfuryl alcohol Chemical compound OCC1CCCO1 BSYVTEYKTMYBMK-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- ANRHNWWPFJCPAZ-UHFFFAOYSA-M thionine Chemical class [Cl-].C1=CC(N)=CC2=[S+]C3=CC(N)=CC=C3N=C21 ANRHNWWPFJCPAZ-UHFFFAOYSA-M 0.000 description 1
- OKYDCMQQLGECPI-UHFFFAOYSA-N thiopyrylium Chemical class C1=CC=[S+]C=C1 OKYDCMQQLGECPI-UHFFFAOYSA-N 0.000 description 1
- 150000005075 thioxanthenes Chemical class 0.000 description 1
- 238000010023 transfer printing Methods 0.000 description 1
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Classifications
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- C08F222/10—Esters
- C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
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- B29C33/00—Moulds or cores; Details thereof or accessories therefor
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- B29C59/00—Surface shaping of articles, e.g. embossing; Apparatus therefor
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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- C08J7/04—Coating
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- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
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- G03F7/0002—Lithographic processes using patterning methods other than those involving the exposure to radiation, e.g. by stamping
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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
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- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L27/00—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
- H01L27/14—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation
- H01L27/144—Devices controlled by radiation
- H01L27/146—Imager structures
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- H01L27/14625—Optical elements or arrangements associated with the device
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
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- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0216—Coatings
- H01L31/02161—Coatings for devices characterised by at least one potential jump barrier or surface barrier
- H01L31/02167—Coatings for devices characterised by at least one potential jump barrier or surface barrier for solar cells
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24479—Structurally defined web or sheet [e.g., overall dimension, etc.] including variation in thickness
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
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- Y10T428/24479—Structurally defined web or sheet [e.g., overall dimension, etc.] including variation in thickness
- Y10T428/24612—Composite web or sheet
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
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- Y10T428/24802—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.]
Definitions
- the present invention relates to an imprint material (imprint film-forming composition) and a film produced from the material and having a pattern transferred thereto. More specifically, it relates to an imprint material in which the formed film has high adhesion to the film substrate and has low release force, and a film produced from the material and having a pattern transferred thereto. is there.
- Nanoimprint lithography is a method in which a mold having an arbitrary pattern is brought into contact with a substrate on which a resin film is formed, the resin film is pressurized, and heat or light is used as an external stimulus to cure the target pattern.
- This nanoimprint lithography has an advantage that nanoscale processing can be performed easily and inexpensively as compared with optical lithography or the like in conventional semiconductor device manufacturing. Therefore, nanoimprint lithography is a technology that is expected to be applied to the manufacture of semiconductor devices, opto-devices, displays, storage media, biochips, etc., instead of optical lithography technology.
- Various reports have been made on curable compositions (Patent Documents 2 and 3).
- a roll-to-roll method has been proposed as a method for mass-producing a film having a pattern transferred thereon with high efficiency.
- the roll-to-roll method proposed in optical nanoimprint lithography uses a flexible film as a base material, and uses a solvent-free type material that does not add a solvent so that the pattern dimensions are unlikely to change. The method has become mainstream.
- Patent Documents 4 and 5 there has been reported a method for obtaining sufficient adhesion with a film (base material) by adding a solvent.
- imprint material materials used in nanoimprint lithography
- imprint material materials used in nanoimprint lithography
- adhesion to a film substrate is provided.
- No specific study or report has been made on a material having a small release force, that is, a material having a characteristic that the mold can be easily peeled off from the cured resin film.
- the silicone compound as the above-described mold release improver is hindered by low compatibility with various components generally used in imprint materials.
- the present invention has been made based on the above circumstances, and the problem to be solved is that the components constituting the imprint material are sufficiently compatible with each other in a uniform form. Used to form an imprint material that has sufficient adhesion to the film substrate when forming a resin film and can be easily peeled off from the mold at the time of mold release, that is, a film having low release force It is to provide an imprint material that can be produced, and to provide a film made from the material and having a pattern transferred thereto.
- An object of the present invention is to provide an imprint material.
- the present inventors have found that a compound having an alkylene oxide unit having 2, 3 or 4 carbon atoms and having at least two polymerizable groups, photopolymerization initiation
- an agent a silicone compound that has been pointed out to have poor compatibility, and a material containing a solvent that has heretofore been refrained from being used because the pattern size is likely to change.
- the material is in the form of a transparent and uniform varnish and can form a uniform coating film.
- the cured film is applied to the film substrate and the pattern shape of the mold is transferred by light curing.
- the present invention provides, as a first aspect, component (A): a compound having at least one alkylene oxide unit having 2, 3, or 4 carbon atoms and having at least two polymerizable groups, and component (B):
- component (B): The present invention relates to an imprint material comprising a photopolymerization initiator, (C) component: a solvent that swells or dissolves the surface portion of the film substrate to which the imprint material is applied, and (D) component: a silicone compound.
- the compound of the component (A) has at least two groups selected from the group consisting of an acryloyloxy group, a methacryloyloxy group, a vinyl group, and an allyl group as the polymerizable group.
- the imprint material according to the first aspect which is a compound.
- the imprint according to the first aspect wherein the compound of the component (A) is a compound having at least one selected from ethylene oxide, propylene oxide, and butylene oxide as an alkylene oxide unit.
- the component (B) is 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, 1-hydroxy-cyclohexyl-phenyl-ketone or 2-hydroxy-2-methyl-1-phenyl-propane-
- the present invention relates to the imprint material according to any one of the first to third aspects, including 1-one.
- the component (C) contains at least one selected from the group consisting of methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, cyclohexanone, and propylene glycol monomethyl ether.
- the imprint material according to any one of the aspects.
- the ratio of the solid content defined as the component excluding the component (C) from all components of the imprint material is 10% by mass to 80% by mass with respect to the total mass of the imprint material. It is related with the imprint material as described in any one of the 1st viewpoint thru
- the imprint material according to any one of the first to sixth aspects, wherein the film substrate is made of triacetyl cellulose, polyethylene terephthalate, polymethyl methacrylate, or cycloolefin (co) polymer.
- the adhesion between the cured film obtained when the imprint material is applied onto the film substrate and photocured and the film substrate are 100/100 in the evaluation of the test according to JIS K5400.
- the measured release force that is, the cured coating on the film substrate is removed from the surface having the pattern shape of the mold.
- a value obtained by converting a load at the time of peeling per 1 cm of the width of the film base material is greater than 0 g / cm and equal to or less than 0.5 g / cm.
- the present invention relates to the imprint method according to the ninth aspect, wherein the drying temperature in the drying step is selected from the range of 60 ° C to 150 ° C.
- the present invention relates to a film manufactured from the imprint material according to any one of the first to eighth aspects and having a pattern transferred thereto.
- a 12th viewpoint it is related with the optical member provided with the film
- the present invention relates to a solid-state imaging device provided on a substrate with a film to which the pattern described in the eleventh aspect is transferred.
- a 14th viewpoint it is related with the LED device provided with the film
- the present invention relates to a display including a film to which the pattern described in the eleventh aspect is transferred.
- an 18th viewpoint it is related with the electronic device provided with the film
- the imprint material of the present invention contains a compound containing an alkylene oxide unit having 2, 3, or 4 carbon atoms in the molecule and having at least two polymerizable groups, a photopolymerization initiator, a solvent, and a silicone compound. Therefore, the cured film produced from the imprint material can obtain sufficient adhesion to the film substrate, and the cured film can have low release force.
- the imprint material of the present invention can be photocured, and since a part of the pattern does not peel off when the mold is released, a film in which a desired pattern is accurately formed can be obtained. Therefore, it is possible to form a good optical imprint pattern.
- the imprint material of the present invention contains a silicone compound whose low compatibility is a problem with conventional imprint materials, the material can be obtained in the form of a transparent and uniform varnish, Generation of layer separation over time can be suppressed, and a material with high product stability can be obtained. For this reason, the imprint material of the present invention can form a homogeneous coating film, which leads to the supply of a highly stable product.
- membrane with which the pattern was transferred produced from the imprint material of this invention contains the silicone compound, it becomes a film
- the ability to suppress the release force to a low level not only suppresses adhesion of the imprint material to the mold that is the mold and the resulting deterioration of the mold, but also the mold release agent used in the mold release process imprints. It also leads to the solution of the problem of shortening the mold life caused by gradually shifting to the material.
- a film to which the pattern of the present invention having a low mold release force on the surface having the pattern shape of the mold is transferred leads to an extension of the mold life, which produces the target patterned substrate at low cost and high efficiency. Will lead to.
- the imprint material of the present invention is in the form of a uniform varnish as described above, there is no variation in the components even in the obtained cured film, and the roll-to-roll system line initial and late stages The optical characteristics of the film obtained in (1) are stabilized, which leads to an improvement in the yield in film production, and an improvement in production efficiency can be realized.
- the imprint material of the present invention can be formed on an arbitrary film substrate, and the formed film and the film substrate have sufficient adhesion, and the film has a low mold release. Have power. Therefore, a film to which a pattern formed after imprinting is transferred can be suitably used for manufacturing an optical member such as a solid-state imaging device, a solar cell, an LED device, or a display.
- the imprint material of the present invention has a compound having an alkylene oxide unit having 2, 3, or 4 carbon atoms as the component (A) and having at least two polymerizable groups and / or a silicone compound and / or
- the imprint material of the present invention can be designed suitably for the type of device to be manufactured, the type of exposure process and the type of baking process, and the process margin can be expanded. it can.
- the present invention includes (A) a compound containing an alkylene oxide unit having 2, 3 or 4 carbon atoms and having at least two polymerizable groups, (B) a photopolymerization initiator, (C) a solvent, and (D ) An imprint material characterized by containing a silicone compound, optionally having at least two polymerizable groups as component (E), and having 2, 3, or 4 carbon atoms in the molecule It is an imprint material which may contain (meth) acrylate and / or urethane (meth) acrylate having no alkylene oxide unit, and optionally other components.
- the cured film formed from the imprint material acquires high adhesion to the film substrate, and the cured film has low release force. It is characterized by achieving both.
- each component will be described in detail.
- the compound of the component (A) contains one or more alkylene oxide units having 2, 3, or 4 carbon atoms in one molecule alone or in combination, and at least two polymerizable groups, in short, a polymerizable group. Is at the end of the molecule.
- the component (A) included in the present invention increases the slipperiness of the film surface with respect to the film after pattern transfer, thereby contributing to a reduction in the release force generated when the mold is peeled off from the surface having the pattern shape. .
- the alkylene oxide unit includes ethylene oxide (—CH 2 CH 2 O—), propylene oxide (—CH (CH 3 ) CH 2 O—), (—CH 2 CH 2 CH 2 O—) or butylene oxide (—CH 2 CH 2 CH 2 CH 2 O—) is preferred.
- the polymerizable group include at least one organic group selected from the group consisting of an acryloyloxy group, a methacryloyloxy group, a vinyl group, and an allyl group.
- the acryloyloxy group may be expressed as an acryloxy group
- the methacryloyloxy group may be expressed as a methacryloxy group.
- ethylene oxide may be expressed as dimethylene oxide
- propylene oxide may be expressed as trimethylene oxide
- butylene oxide may be expressed as tetramethylene oxide.
- Examples of the compound (A) include ethylene glycol diacrylate, ethylene glycol dimethacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, ethoxylated bisphenol A diacrylate, ethoxylated bisphenol A dimethacrylate, and ethoxylated trimethylol.
- the compounds of the above component (A) can be used alone or in combination of two or more.
- the content of the alkylene oxide unit is not particularly limited as long as it is used within a range that does not impair the effect of the present invention.
- the photopolymerization initiator as the component (B) plays a role of generating radicals by light irradiation and initiating polymerization of photopolymerizable groups contained in the imprint material.
- the photopolymerization initiator as component (B) is not particularly limited as long as it has absorption in the light source used at the time of photocuring.
- tert-butylperoxy-iso-butrate 2, 5-dimethyl-2,5-bis (benzoyldioxy) hexane, 1,4-bis [ ⁇ - (tert-butyldioxy) -iso-propoxy] benzene, di-tert-butyl peroxide, 2,5-dimethyl-2 , 5-bis (tert-butyldioxy) hexene hydroperoxide, ⁇ - (iso-propylphenyl) -iso-propyl hydroperoxide, tert-butyl hydroperoxide, 1,1-bis (tert-butyldioxy) -3,3,5 -Trimethylcyclohexane, butyl-4,4-bis (tert-butyldioxy) bar Relate, cyclohexanone peroxide, 2,2 ′, 5,5′-tetra (tert-butylperoxycarbonyl) benzophenone, 3,3
- the imprint material of the present invention may undergo a process of photocuring through a film substrate.
- a part of the wavelength of the light irradiated from the light source will be cut by the film, and it is particularly limited if a photopolymerization initiator having absorption other than the wavelength region of the cut light is selected.
- 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, 1-hydroxy-cyclohexyl-phenyl-ketone from the viewpoint of good solubility in a solvent and good transmittance when formed into a film.
- 2-hydroxy-2-methyl-1-phenyl-propan-1-one is preferable, and 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide can be particularly preferably used.
- the above-mentioned compounds can be obtained as commercial products. Specific examples thereof include IRGACURE (registered trademark) 651, 184, 500, 2959, 127, 754, 907, 369, 379, 379EG, 819, 819DW, 1800, 1870, 784, OXE01, OXE02, 250, DAROCUR (registered trademark) 1173, MBF, 4265, Lucirin (registered trademark) TPO (above, BASF) Japan Co., Ltd.), KAYACURE (registered trademark) DETX, MBP, DMBI, EPA, OA (above, Nippon Kayaku Co., Ltd.), VISURE-10, 55 (above, STAUFFER Co.
- IRGACURE registered trademark
- DAROCUR
- ESACURE registered trademark
- KIP150, TZT 1001, KT 46, same KB1, same KL200, same KS300, same EB3, triazine-PMS, triazine A, triazine B (manufactured by Nippon Siebel Hegner), Adekaoptoma-N-1717, same N-1414, same N-1606 (stock) Company ADEKA).
- the above photopolymerization initiators can be used alone or in combination of two or more.
- the content of the component (B) in the imprint material of the present invention is preferably 0.1 phr to 30 phr, and more preferably 1 phr to 20 phr with respect to the mass of the component (A).
- this ratio is less than 0.1 phr, sufficient curability cannot be obtained, and patterning characteristics are deteriorated and a release force is increased.
- phr represents the mass of the photopolymerization initiator with respect to 100 g of the mass of the component (A).
- the solvent which swells or dissolves the surface portion of the film base material which is component (C) is a film base material which comes into contact with the coating film of the imprint material during the coating step and the drying step of the imprint material. It means a solvent that can swell or dissolve the outermost surface portion. The solvent swells or dissolves the surface portion of the film base material, thereby diffusing a part of the imprint material of the present invention into the film base material and photocuring the film base material and the cured film. It plays a role to improve the adhesion of the.
- the solvent also serves as a varnish homogenization aid for making the imprint material of the present invention containing the component (D), which is a silicone compound described later having poor solubility or compatibility, into a uniform varnish. .
- a film substrate described later particularly those which can obtain sufficient adhesion with a film substrate which is triacetyl cellulose, polyethylene terephthalate, polymethyl methacrylate or cycloolefin (co) polymer as a preferred example, That is, it is a solvent that can swell the outermost surface portion of the film base material or dissolve the outermost surface portion of the film base material but not the entire film base material, and is particularly compatible with the silicone compound.
- the solvent is not particularly limited as long as it can improve the solvent, but for example, acetone, methyl ethyl ketone, methyl isopropyl ketone, diethyl ketone, methyl isobutyl ketone, methyl n-butyl ketone, cyclohexanone, ethyl acetate, diacetone alcohol, furfuryl Alcohol, tetra Mud furfuryl alcohol, include propylene glycol monomethyl ether, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, cyclohexanone, propylene glycol monomethyl ether as particularly preferred.
- the said solvent can be used individually or in combination of 2 or more types.
- Particularly suitable film substrate and solvent combinations include methyl ethyl ketone, cyclohexanone and ethyl acetate when the film substrate is triacetyl cellulose, methyl ethyl ketone, cyclohexanone and ethyl acetate when polyethylene terephthalate, and methyl ethyl ketone when polymethyl methacrylate is used.
- Methyl ethyl ketone can be particularly suitably used from the viewpoints of good adhesion to the substrate, good solubility when used as a varnish, and good compatibility with other components when used as a varnish.
- solvents In addition to the solvent that swells or dissolves the surface portion of the film base material of component (C), other solvents can be used in combination.
- other solvents include toluene, p-xylene, o-xylene, ethylene glycol dimethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, and ethylene glycol methyl ether acetate.
- examples of combinations of component (C) with other solvents include methyl ethyl ketone and isopropanol, ethyl acetate and isopropanol, methyl ethyl ketone and methyl isobutyl ketone and isopropanol, acetic acid
- methyl ethyl ketone and isopropanol examples include methyl ethyl ketone and isopropanol, ethyl acetate and isopropanol, methyl ethyl ketone and methyl isobutyl ketone and isopropanol, acetic acid
- acetic acid A combination of ethyl and propylene glycol monomethyl ether can be mentioned.
- the content of the component (C) in the imprint material of the present invention depends on the thickness of the film base, the drying temperature after application to the film base, and the drying time, but the effect to be achieved by the present invention is impaired. In particular, if it is contained in a range that does not impair the effect of enhancing the compatibility of each component, while ensuring adhesion to the film substrate, but not too much dissolving the film substrate Not done.
- the solvent of the component (C) is removed from all the components of the imprint material of the present invention, that is, the above-mentioned components (A), (B), (D), and all components including other additives described later.
- the solvent is added in an amount such that the solid content defined as the amount is 10% to 80% by weight, more preferably 40% to 70% by weight, based on the imprint material. It is preferable to contain.
- the ratio of the solid content is less than 10% by mass, the target film thickness cannot be obtained, and when it exceeds 80% by mass, it may be difficult to ensure adhesion with the film substrate.
- the proportion of the solvent of the component (C) in the total solvent components is 10% by mass to 40% by mass.
- the silicone compound as component (D) is a compound having a silicone skeleton (siloxane skeleton) in the molecule, and preferably has a dimethyl silicone skeleton, and examples of such a compound include polyether-modified polydimethylsiloxane. It is done.
- the silicone compound of component (D) migrates to the outermost surface of the coating (cured film) during application to the film substrate of the imprint material of the present invention, during drying after application, and upon exposure, It plays a role of reducing the release force when the cured film on the material is peeled from the mold.
- silicone compound examples include X-22-164, X-22-164AS, X-22-164A, X-22-164B, X-22-164C, X-22-164E, X-22-163, KF-105, X-22-163A, X-22-163B, X-22-163C, X-22-169AS, X-22-174DX, X-22-1602, X-222-2404, X-22 2426, X-22-9002, X-22-2475, X-22-4952, KF-643, X-22-343, X-22-2046, X-24-8201, FL100-100cs, FL100-450cs ( (Shin-Etsu Chemical Co., Ltd.), BYK-302, BYK-307, BYK-322, BYK-323, BYK-330, BYK-333, B K-370, BYK-375, BYK-378, BYK-UV 3500, BYK-UV 3570 (above, manufactured by
- the above compounds having a silicone skeleton can be used alone or in combination of two or more.
- the content of the component (D) in the imprint material of the present invention is preferably 0.01 phr to 5 phr, and more preferably 0.1 phr to 3 phr with respect to the mass of the component (A).
- this ratio is less than 0.01 phr, the release force cannot be sufficiently reduced, and when it exceeds 5 phr, the compatibility of the imprint material in the varnish form may be deteriorated.
- phr represents the mass of the component (D) (silicone compound) with respect to 100 g of the mass of the component (A).
- ⁇ (E) component In the imprint material in the present invention, as the component (E), a (meth) acrylate having at least two polymerizable groups and not containing an alkylene oxide unit having 2, 3, or 4 carbon atoms in the molecule, and / Or urethane (meth) acrylate may be added.
- the said (E) component plays the role which adjusts the hardness of the cured film obtained by photoimprint.
- the polymerizable group include an acryloyloxy group, a methacryloyloxy group, a vinyl group, and an allyl group.
- (meth) acrylate refers to both acrylate and methacrylate.
- (meth) acrylic acid refers to acrylic acid and methacrylic acid.
- Examples of the compound (E) include 1,3-butanediol dimethacrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9- Nonanediol di (meth) acrylate, 1,10-decanediol diacrylate, 2-methyl-1,8-octanediol dimethacrylate, tricyclodecane dimethylol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 2-hydroxy-3-acryloyloxypropyl (meth) acrylate, bis (acryloyloxyethyl) hydroxyethyl isocyanurate, glycerin dimethacrylate, pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate , Pentaerythritol
- NK ester 701A A-DCP, A-DON-N, A-HD-N, A-NOD-N, DCP, DOD-N, HD-N, NOD-N, NPG, A-TMM-3, A-TMM-3L, A-TMM-3LMN, A-TMPT, TMPT, A-TMMT, AD-TMP, A-DPH, A-9550, A-9530, ADP-51EH, ATM-31EH, UA-7100 (manufactured by Shin-Nakamura Chemical Co., Ltd.), KAYARAD (Registered Trademark) T-1420, D-330, D-320, D-310, DPCA-20, DPCA-30, DPCA-60, DPCA-60, DPCA-120, TMPTA, PET-30 DPH , The DPHA-2C (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T,
- the compound (E) can be used alone or in combination of two or more.
- the ratio is preferably 1 phr to 100 phr, and more preferably 1 phr to 70 phr with respect to the mass of the component (A). If the component (E) is added in excess of 100 phr with respect to the component (A), the film hardness may increase excessively and the release force may increase.
- an epoxy compound As long as the imprint material of the present invention does not impair the effects of the present invention, an epoxy compound, a photoacid generator, a photosensitizer, an ultraviolet absorber, an antioxidant, an adhesion aid, or a mold release is used as necessary. A property improver can be contained.
- epoxy compound examples include Epolide (registered trademark) GT-401, PB3600, Celoxide (registered trademark) 2021P, 2000, 3000, EHPE3150, EHPE3150CE, Cyclomer (registered trademark) M100 (above, Inc.) Daicel), EPICLON (registered trademark) 840, 840-S, N-660, N-673-80M (above, manufactured by DIC Corporation).
- photoacid generator examples include IRGACURE (registered trademark) PAG103, PAG108, PAG121, PAG203, CGI725 (above, manufactured by BASF Japan Ltd.), WPAG-145, WPAG-170, WPAG-199, WPAG-281, WPAG-336, WPAG-367 (Wako Pure Chemical Industries, Ltd.), TFE triazine, TME-triazine, MP-triazine, dimethoxytriazine, TS-91, TS-01 (Sanwa Chemical Co., Ltd.) Manufactured).
- IRGACURE registered trademark
- PAG103, PAG108, PAG121, PAG203, CGI725 above, manufactured by BASF Japan Ltd.
- WPAG-145, WPAG-170, WPAG-199, WPAG-281, WPAG-336, WPAG-367 Wako Pure Chemical Industries, Ltd.
- TFE triazine TME-triazine
- photosensitizer examples include, for example, thioxanthene series, xanthene series, ketone series, thiopyrylium salt series, base styryl series, merocyanine series, 3-substituted coumarin series, 3,4-substituted coumarin series, cyanine series, acridine series. , Thiazine, phenothiazine, anthracene, coronene, benzanthracene, perylene, ketocoumarin, coumarin, and borate.
- the above photosensitizers can be used alone or in combination of two or more.
- the absorption wavelength in the UV region can be adjusted by using the photosensitizer.
- UV absorber examples include TINUVIN (registered trademark) PS, 99-2, 109, 328, 384-2, 400, 405, 460, 477, 479, 900, 928, 1130, 111FDL, 123, 144, 152, 292, 5100, 400-DW, 477-DW, 99-DW, 123-DW, 5050, 5060, 5151 (above, BASF Japan Ltd.).
- TINUVIN registered trademark
- PS 99-2, 109, 328, 384-2
- 400 405, 460, 477, 479, 900, 928, 1130, 111FDL, 123, 144, 152, 292, 5100, 400-DW, 477-DW, 99-DW, 123-DW, 5050, 5060, 5151 (above, BASF Japan Ltd.).
- the above ultraviolet absorbers can be used alone or in combination of two or more.
- the curing speed of the outermost surface of the film can be controlled during photocuring, and the mold release force can be reduced in some cases.
- antioxidants examples include IRGANOX (registered trademark) 1010, 1035, 1076, 1135, 1520L (above, BASF Japan Ltd.).
- the above antioxidants can be used alone or in combination of two or more. By using the antioxidant, it is possible to prevent the film from turning yellow due to oxidation.
- adhesion aid examples include 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, and the like. By using the adhesion aid, adhesion with the substrate is improved.
- the content of the adhesion assistant is preferably 5 phr to 50 phr, more preferably 10 phr to 50 phr, with respect to the mass of the component (A).
- the method for preparing the imprint material of the present invention is not particularly limited, but the (A) component, the (B) component, the (C) component and the (D) component, the optional component (E), and other additions as desired. It is only necessary that the agent is mixed and the imprint material is in a uniform state.
- the order of mixing the components (A) to (E) and other additives as required is not particularly limited as long as a uniform imprint material can be obtained.
- Examples of the preparation method include a method in which the component (A) is mixed with the component (B) at a predetermined ratio.
- the temperature of heating is not particularly limited as long as the temperature at which the imprint material is altered or decomposed is avoided, but the internal temperature of the imprint material can be heated in the range of 30 ° C to 120 ° C.
- the process of optical imprinting using the above imprinting material has the following steps a) to e): a) A step of applying the imprint material of the present invention to a film substrate to obtain a coating film, b) drying the coating film; c) A step of pressing and pressing a mold against the dried coating film, and applying heat as necessary. d) a step of forming a cured film by irradiating light for curing the coating film in a state where the coating film and the mold are in contact; and e) a step of peeling the formed cured film from the mold.
- the imprint material of the present invention can be applied to a film substrate and photocured to obtain a desired coating (cured film).
- a coating method a known or well-known method such as a spin coating method, a dip method, a flow coating method, an ink jet method, a spray method, a bar coating method, a gravure coating method, a slit coating method, a roll coating method, a transfer printing method, Examples thereof include brush coating, blade coating, and air knife coating.
- the substrate for applying the imprint material of the present invention may be a film substrate.
- the film base material is a polymer having flexibility and plasticity that can be deformed by an arbitrary force, and is also referred to as a film substrate, a flexible base material (substrate), and a flexible print base material (substrate).
- film base materials include triacetyl cellulose, polyethylene terephthalate, polymethyl methacrylate, cycloolefin (co) polymer, polyvinyl alcohol, polycarbonate, polystyrene, polyimide, polyamide, polyolefin, polypropylene, polyethylene, polyethylene naphthalate, and polyether.
- film base material examples include sulfone and copolymers obtained by combining these polymers.
- a triacetyl cellulose, a polyethylene terephthalate, a polymethyl methacrylate, or a cycloolefin (co) polymer is mentioned.
- the drying step is performed by baking for the purpose of evaporating the solvent on the coating film before the light irradiation, and the drying step (baking) is further performed on the coating film (cured film) after the light irradiation. good.
- the baking equipment is not particularly limited.
- the firing temperature is not particularly limited for the purpose of evaporating the solvent, the film base material is composed of a plastic polymer, and if the firing temperature is 200 ° C. or higher, the target pattern may not be obtained due to dissolution or deformation. Therefore, it is desirable that the upper limit of the firing temperature is 200 ° C. or less, particularly preferably 150 ° C. or less. Therefore, the firing temperature is preferably 40 ° C. to 200 ° C., and particularly preferably 60 ° C. to 150 ° C.
- the firing time is directly related to the tact time for obtaining the product, and may be short, but is preferably selected in the range of 10 seconds to 300 seconds, and more preferably in the range of 10 seconds to 180 seconds.
- the light source for curing the imprint material of the present invention is not particularly limited.
- the wavelength generally, a 436 nm G line, a 405 nm H line, a 365 nm I line, or a GHI mixed line can be used.
- the exposure dose is preferably 30 to 2000 mJ / cm 2 , more preferably 30 to 1000 mJ / cm 2 .
- the optical imprinting apparatus is not particularly limited as long as a target pattern can be obtained.
- ST50 manufactured by Toshiba Machine Co., Ltd.
- Sindre registered trademark
- NM-0801HB manufactured by Meisho Kiko Co., Ltd.
- a commercially available device such as a device, a method in which a base material and a mold are pressure-bonded to a roller and released after photocuring can be used.
- examples of the mold material used for the optical imprint used in the present invention include quartz, silicon, nickel, alumina, carbonylsilane, and glassy carbon.
- the target pattern it is particularly limited.
- the mold may be subjected to a mold release treatment for forming a thin film of a fluorine compound or the like on the surface thereof in order to improve the mold release property.
- examples of the mold release agent used for the mold release treatment include OPTOOL (registered trademark) HD and DSX manufactured by Daikin Industries, Ltd., but are not particularly limited as long as the target pattern can be obtained.
- the pattern size of the optical imprint is on the order of nanometers, specifically according to the pattern size of less than 1 micron.
- the adhesion between the cured film obtained and the film substrate is evaluated by a test according to JIS K5400, In the imprint material of the present invention, it is preferably 100/100.
- the adhesion test is also referred to as a substrate test, and a coating is cut (damaged) on a grid pattern (eg, 100 squares) in a grid pattern, and the substrate is tested to penetrate the substrate (substrate). The resistance of the coating against peeling is evaluated, and 100/100 indicates the result that 100 of 100 squares were not peeled off.
- the 90 ° peel test for evaluating the release force generally means that an adhesive (corresponding to a cured film formed from an imprint material in the present invention) is an adherend (in the present invention, a film substrate). It is a test to measure the resistance force (tension) generated when it is peeled off at a predetermined peeling speed in a 90 ° direction after a predetermined time. Usually, the measurement is performed by an evaluation method referring to JIS Z0237. To be implemented. A value obtained by converting the resistance force measured here per width of the adherend can be evaluated as a release force.
- the imprint material of this invention is apply
- the value obtained by converting the load when the film is completely peeled from the surface having the pattern shape of the mold into a width of 1 cm of the film substrate is preferably larger than 0 g / cm and not larger than 0.5 g / cm, more preferably 0.4 g / cm or less.
- the release force defined as described above is different from the evaluation of releasability such as microscopic observation of the mold shape pattern transfer rate as reported so far, and the film after photocuring from the mold. It is the value (g / cm) which quantified the force produced when peeling the film provided with. The force generated when the film is actually peeled increases with the expansion of the mold width and the film width.
- a film produced from the imprint material of the present invention and having a pattern transferred thereon, a semiconductor element comprising the film, an optical member comprising the film on a substrate, a solid-state imaging device, an LED device, a solar cell, and a display And electronic devices are also the subject of the present invention.
- each measuring apparatus used in the Example is as follows.
- Apparatus Electrode uniform irradiation device QRE-4016A manufactured by Oak Manufacturing Co., Ltd.
- [Ultraviolet visible spectrophotometer] Apparatus: SHIMADSU UV-3600 manufactured by Shimadzu Corporation
- Standard JIS K5400
- Apparatus KT-AB3120 manufactured by Co-Tech Co., Ltd.
- Example 1 [Preparation of imprint material] ⁇ Example 1> Weigh 10.00 g of A-200 (manufactured by Shin-Nakamura Chemical Co., Ltd.) into a 50 mL one-necked eggplant-shaped flask, then Lucirin TPO (registered trademark) (manufactured by BASF Japan Ltd. (hereinafter referred to as “TPO” in this specification). 0.25 g (2.5 phr with respect to the mass of A-200), and BYK-333 (manufactured by Big Chemie Japan Co., Ltd.) with 0.05 g (0.5 phr with respect to the mass of A-200).
- Example 2 Imprint material A2 (solid content: 50% MEK solution) was prepared in the same manner as in Example 1 except that A-200 in Example 1 was changed to A-400 (manufactured by Shin-Nakamura Chemical Co., Ltd.).
- Example 3 An imprint material A3 (solid content: 50% MEK solution) was prepared in the same manner as in Example 1 except that A-200 in Example 1 was changed to A-600 (manufactured by Shin-Nakamura Chemical Co., Ltd.).
- Example 4 An imprint material A4 (solid content: 50% MEK solution) was prepared in the same manner as in Example 1 except that A-200 in Example 1 was changed to A-1000 (manufactured by Shin-Nakamura Chemical Co., Ltd.).
- Example 5 Imprint material A5 (solid content: 50% MEK solution) in the same manner as in Example 1 except that A-200 of Example 1 was changed to KAYARAD (registered trademark) DPEA-12 (manufactured by Nippon Kayaku Co., Ltd.) Was prepared.
- Example 6 An imprint material A6 (solid content: 50% MEK solution) was prepared in the same manner as in Example 1 except that A-200 in Example 1 was changed to 1G (manufactured by Shin-Nakamura Chemical Co., Ltd.).
- Example 7 Imprint material A7 (solid content: 50% MEK solution) was prepared in the same manner as in Example 1 except that A-200 in Example 1 was changed to APG-100 (manufactured by Shin-Nakamura Chemical Co., Ltd.).
- Example 8 Imprint material A8 (solid content: 50% MEK solution) was prepared in the same manner as in Example 1, except that A-200 in Example 1 was changed to APG-200 (manufactured by Shin-Nakamura Chemical Co., Ltd.).
- Example 9 Imprint material A9 (solid content: 50% MEK solution) was prepared in the same manner as in Example 1 except that A-200 in Example 1 was changed to APG-400 (manufactured by Shin-Nakamura Chemical Co., Ltd.).
- Example 10 Imprint material A10 (solid content: 50% MEK solution) was prepared in the same manner as in Example 1, except that A-200 in Example 1 was changed to APG-700 (manufactured by Shin-Nakamura Chemical Co., Ltd.).
- Example 11 An imprint material A11 (solid content: 50% MEK solution) was prepared in the same manner as in Example 1 except that A-200 in Example 1 was changed to A-PTMG-65 (manufactured by Shin-Nakamura Chemical Co., Ltd.) did.
- Example 12 Weigh 5.00 g of A-1000 (manufactured by Shin-Nakamura Chemical Co., Ltd.) and 5.00 g of KAYARAD (registered trademark) DPEA-12 (manufactured by Nippon Kayaku Co., Ltd.) into a 50 mL one-necked eggplant-shaped flask, and then add TPO.
- A-1000 manufactured by Shin-Nakamura Chemical Co., Ltd.
- KAYARAD registered trademark
- DPEA-12 manufactured by Nippon Kayaku Co., Ltd.
- Example 13 An imprint material A13 (solid content: 50% MEK solution) was prepared in the same manner as in Example 12 except that A-1000 in Example 12 was changed to APG-700 (manufactured by Shin-Nakamura Chemical Co., Ltd.).
- Example 14 An imprint material A14 (solid content: 50% MEK solution) was prepared in the same manner as in Example 12 except that A-1000 in Example 12 was changed to A-PTMG-65 (manufactured by Shin-Nakamura Chemical Co., Ltd.) did.
- Example 15 Imprint material A15 (solid content: 50) as in Example 4 except that the TPO of Example 4 was changed to IRGACURE184 (manufactured by BASF Japan Ltd.) (hereinafter abbreviated as “184” in this specification). % MEK solution).
- Example 17> An imprint material A17 (solid content: 50% MEK solution) was prepared in the same manner as in Example 12, except that the TPO in Example 12 was changed to 184. ⁇ Example 18> Similarly, the imprint material A18 (solid content: 50% MEK solution) was used except that the TPO of Example 12 was changed to DAROCUR1173 (BASF Japan Ltd.) (hereinafter abbreviated as “1173” in this specification). Was prepared.
- Example 19 Imprint material A19 (solid content: 50% MIBK solution) was used in the same manner as in Example 5 except that MEK of Example 5 was changed to methyl isobutyl ketone (hereinafter abbreviated as “MIBK”). ) Prepared.
- Example 20 Imprint material A20 (solid content: 50% EtOAc solution) was used in the same manner as in Example 5 except that MEK of Example 5 was changed to ethyl acetate (hereinafter abbreviated as “EtOAc” in this specification). Prepared.
- Example 21 An imprint material A21 (solid content: 50% CHN solution) was prepared in the same manner as in Example 5 except that MEK of Example 5 was changed to cyclohexanone (hereinafter abbreviated as “CHN” in this specification). did.
- Example 22 Imprint material A22 (solid content: 50% PGME solution) as in Example 5 except that MEK of Example 5 was changed to propylene glycol monomethyl ether (hereinafter abbreviated as “PGME” in this specification). ) was prepared.
- Example 23 An imprint material A23 (solid content: 50% MEK solution) was prepared in the same manner as in Example 12 except that BYK-333 of Example 12 was changed to BYK-307 (manufactured by Big Chemie Japan Co., Ltd.).
- Imprint material A24 solid content: 50% MEK solution was prepared in the same manner as in Example 12, except that BYK-333 of Example 12 was changed to X-22-164AS (manufactured by Shin-Etsu Chemical Co., Ltd.). .
- Example 25 An imprint material A25 (solid content: 50% MEK solution) was prepared in the same manner as in Example 12 except that BYK-333 of Example 12 was changed to X-22-164E (manufactured by Shin-Etsu Chemical Co., Ltd.). .
- Example 26 An imprint material A26 (solid content: 50% MEK solution) was prepared in the same manner as in Example 12 except that BYK-333 of Example 12 was changed to X-22-1602 (manufactured by Shin-Etsu Chemical Co., Ltd.). .
- Example 27 An imprint material A27 (solid content: 50% MEK solution) was prepared in the same manner as in Example 12 except that BYK-333 of Example 12 was changed to X-22-2426 (manufactured by Shin-Etsu Chemical Co., Ltd.). .
- Imprint material A31 (solid content: 50% MEK solution) was prepared in the same manner as in Example 12 except that BYK-333 of Example 12 was changed to FL100-450cs (manufactured by Shin-Etsu Chemical Co., Ltd.).
- Example 32 Weigh 5.00 g of A-1000 (manufactured by Shin-Nakamura Chemical Co., Ltd.) and 5.00 g of KAYARAD (registered trademark) DPEA-12 (manufactured by Nippon Kayaku Co., Ltd.) into a 50 mL one-necked eggplant-shaped flask, and then add TPO.
- A-1000 manufactured by Shin-Nakamura Chemical Co., Ltd.
- KAYARAD registered trademark
- DPEA-12 manufactured by Nippon Kayaku Co., Ltd.
- Example 33 An imprint material A33 (solid content: 50% MEK solution) was prepared in the same manner as in Example 32 except that DPHA in Example 32 was changed to KAYARAD (registered trademark) PET-30 (manufactured by Nippon Kayaku Co., Ltd.). did.
- Example 34 An imprint material A34 (solid content: 50% MEK solution) was prepared in the same manner as in Example 32 except that DPHA in Example 32 was changed to A-DCP (manufactured by Shin-Nakamura Chemical Co., Ltd.).
- Example 35 Imprint material A35 (solid content: 50% MEK solution) was prepared in the same manner as in Example 32 except that DPHA in Example 32 was changed to UA-306H (manufactured by Kyoeisha Chemical Co., Ltd.).
- Example 36 Imprint material A36 (solid content: 50% MEK solution) was prepared in the same manner as in Example 32 except that DPHA of Example 32 was changed to UA-7100 (manufactured by Shin-Nakamura Chemical Co., Ltd.).
- Example 37 In a 50 mL one-necked eggplant type flask, 4.00 g of A-200 (manufactured by Shin-Nakamura Chemical Co., Ltd.) was weighed, and then 0.10 g of TPO (2.5 phr with respect to the mass of A-200), BYK-333 Add 0.02 g (Bicchemy Japan Co., Ltd.) (0.5 phr with respect to the mass of A-200) and 16.48 g of MEK, and stir using a magnetic stirrer to form a transparent and uniform varnish As an imprint material A37 (solid content: 20% MEK solution) was prepared.
- A37 solid content: 20% MEK solution
- Example 38 In a 50 mL single-necked flask, 14.00 g of A-200 (manufactured by Shin-Nakamura Chemical Co., Ltd.) was weighed, and then 0.35 g of TPO (2.5 phr with respect to the mass of A-200), BYK-333 0.07 g (by Big Chemie Japan Co., Ltd.) (0.5 phr with respect to the mass of A-200) and 6.18 g of MEK were added and stirred using a magnetic stirrer to form a transparent and uniform varnish As an imprint material A38 (solid content: 70% MEK solution) was prepared.
- Example 39 Imprint material A39 (solid content: 50% MEK solution) was prepared in the same manner as in Example 1 except that BYK-333 of Example 1 was changed to BYK-307 (manufactured by Big Chemie Japan Co., Ltd.).
- Example 40 An imprint material A40 (solid content: 50% MEK solution) was prepared in the same manner as in Example 1 except that BYK-333 of Example 1 was changed to X-22-164AS (manufactured by Shin-Etsu Chemical Co., Ltd.). .
- Example 41 Imprint material A41 (solid content: 50% MEK solution) was prepared in the same manner as in Example 1 except that BYK-333 of Example 1 was changed to X-22-164E (manufactured by Shin-Etsu Chemical Co., Ltd.). .
- Example 42 An imprint material A42 (solid content: 50% MEK solution) was prepared in the same manner as in Example 1 except that BYK-333 of Example 1 was changed to X-22-1602 (manufactured by Shin-Etsu Chemical Co., Ltd.). .
- Example 43 Imprint material A43 (solid content: 50% MEK solution) was prepared in the same manner as in Example 1 except that BYK-333 of Example 1 was changed to X-22-2426 (manufactured by Shin-Etsu Chemical Co., Ltd.). .
- Example 45 An imprint material A45 (solid content: 50% MEK solution) was prepared in the same manner as in Example 1 except that BYK-333 of Example 1 was changed to X-24-8201 (manufactured by Shin-Etsu Chemical Co., Ltd.). .
- Example 46 An imprint material A46 (solid content: 50% MEK solution) was prepared in the same manner as in Example 1 except that BYK-333 in Example 1 was changed to FL100-100cs (manufactured by Shin-Etsu Chemical Co., Ltd.).
- Imprint material A47 (solid content: 50% MEK solution) was prepared in the same manner as in Example 1 except that BYK-333 of Example 1 was changed to FL100-450cs (manufactured by Shin-Etsu Chemical Co., Ltd.).
- ⁇ Comparative Example 1> Weigh 10.00 g of A-200 (made by Shin-Nakamura Chemical Co., Ltd.) into a 50 mL one-necked eggplant-shaped flask, and then add 0.05 g (by mass of A-200) of BYK-333 (made by Big Chemie Japan Co., Ltd.). 0.5 phr) and 10.05 g of MEK were added and stirred using a magnetic stirrer to prepare imprint material B1 in the form of a transparent and uniform varnish.
- KAYARAD registered trademark
- DPEA-12 manufactured by Nippon Kayaku Co., Ltd.
- An imprint material B6 was prepared in the same manner as in Comparative Example 1 except that A-200 in Comparative Example 1 was changed to 1G (manufactured by Shin-Nakamura Chemical Co., Ltd.).
- An imprint material B14 was prepared in the same manner as in Comparative Example 12, except that A-200 in Comparative Example 12 was changed to A-600 (manufactured by Shin-Nakamura Chemical Co., Ltd.).
- ⁇ Comparative Example 21> An imprint material B21 was prepared in the same manner as in Comparative Example 12, except that A-200 in Comparative Example 12 was changed to APG-700 (manufactured by Shin-Nakamura Chemical Co., Ltd.).
- An imprint material B24 was prepared in the same manner as in Comparative Example 12, except that BYK-333 in Comparative Example 12 was changed to X-22-164AS (manufactured by Shin-Etsu Chemical Co., Ltd.). However, B24 was not obtained as a transparent and uniform varnish form.
- An imprint material B26 was prepared in the same manner as in Comparative Example 12 except that BYK-333 in Comparative Example 12 was changed to X-22-1602 (manufactured by Shin-Etsu Chemical Co., Ltd.).
- An imprint material B30 was prepared in the same manner as in Comparative Example 12, except that BYK-333 in Comparative Example 12 was changed to FL100-100cs (manufactured by Shin-Etsu Chemical Co., Ltd.).
- Imprint material B35 was prepared in the same manner as in No.32. However, B35 was not obtained as a transparent and uniform varnish form.
- ⁇ Comparative Example 37> In a 50 mL one-necked eggplant type flask, 10.00 g of A-200 (manufactured by Shin-Nakamura Chemical Co., Ltd.) is weighed, then 0.25 g of TPO (2.5 phr with respect to A-200 mass), and MEK of 10. 25 g was added and stirred using a magnetic stirrer to prepare imprint material B37.
- ⁇ Comparative Example 38> An imprint material B38 was prepared in the same manner as in Comparative Example 37 except that A-200 in Comparative Example 37 was changed to A-400 (manufactured by Shin-Nakamura Chemical Co., Ltd.).
- ⁇ Comparative Example 39> An imprint material B39 was prepared in the same manner as in Comparative Example 37 except that A-200 in Comparative Example 37 was changed to A-600 (manufactured by Shin-Nakamura Chemical Co., Ltd.).
- KAYARAD registered trademark
- DPEA-12 manufactured by Nippon Kayaku Co., Ltd.
- Imprint material B42 was prepared in the same manner as in Comparative Example 37 except that A-200 in Comparative Example 37 was changed to 1G (manufactured by Shin-Nakamura Chemical Co., Ltd.).
- ⁇ Comparative Example 46> An imprint material B46 was prepared in the same manner as in Comparative Example 37 except that A-200 in Comparative Example 37 was changed to APG-700 (manufactured by Shin-Nakamura Chemical Co., Ltd.).
- ⁇ Comparative Example 48> Weigh 5.00 g of A-1000 (manufactured by Shin-Nakamura Chemical Co., Ltd.) and 5.00 g of KAYARAD (registered trademark) DPEA-12 (manufactured by Nippon Kayaku Co., Ltd.) into a 50 mL one-necked eggplant-shaped flask, and then add TPO. 0.25 g (2.5 phr with respect to the total mass of A-1000 and DPEA-12), add 10.25 g of MEK, stir using a magnetic stirrer, and imprint material as a transparent and uniform varnish form B48 was prepared.
- A-1000 manufactured by Shin-Nakamura Chemical Co., Ltd.
- KAYARAD registered trademark
- DPEA-12 manufactured by Nippon Kayaku Co., Ltd.
- KAYARAD registered trademark
- DPHA manufactured by Nippon Kayaku Co., Ltd.
- 10.00 was weighed into a 50 mL one-necked eggplant-shaped flask, then 0.25 g of TPO (2.5 phr with respect to the mass of DPHA) and 10 MEKs. .25 g was added and stirred using a magnetic stirrer to prepare imprint material B49 in the form of a transparent and uniform varnish.
- KAYARAD registered trademark
- PET-30 manufactured by Nippon Kayaku Co., Ltd.
- An imprint material B51 was prepared in the same manner as in Comparative Example 49 except that DPHA in Comparative Example 49 was changed to A-DCP (manufactured by Shin-Nakamura Chemical Co., Ltd.).
- the imprint material is a transparent and uniform varnish. Whether it was obtained or not was evaluated visually as follows.
- ⁇ Transparent and uniform varnish form
- ⁇ Opaque or non-uniform form
- it is opaque or non-uniform form (transparent and non-uniform)
- the form of the varnish specifically refers to a state in which the entire varnish is clouded or white foreign matter is floating in the varnish.
- Example 43 When Example 43, Example 45, and Example 47 are compared, the result is that a uniform varnish can be obtained by addition of a solvent even though the type and amount of the silicone compound of component (D) are the same. It was. Further, in Comparative Examples 32 to 36, even when an acrylate compound or a urethane acrylate compound is added as another component, a uniform varnish is not formed, that is, the addition of these compounds alone does not lead to an improvement in compatibility. confirmed. The above results show that the silicone compound of component (D) is poorly compatible with other components in the absence of a solvent depending on the type, and even if an acrylate compound or a urethane acrylate compound is added as another component, the compatibility is improved.
- a photocurability test was performed using the imprint materials of Examples 1 to 47 and Comparative Examples 1 to 11.
- each imprint material obtained was wet on a triacetyl cellulose film (using Fujitac (registered trademark) manufactured by Fuji Film Co., Ltd.) (hereinafter abbreviated as “TAC film” in this specification).
- TAC film triacetyl cellulose film
- the film was applied using a film applicator so that the film thickness was 4 ⁇ m, and then dried in a clean oven at 110 ° C. for 30 seconds.
- the application side of the imprint material of the TAC film is roller-pressed onto the silicon substrate subjected to the above-described mold release treatment, and exposure of 350 mJ / cm 2 is performed from the TAC film side with an electrodeless uniform irradiation device. Curing was performed. Thereafter, the TAC film and the silicon substrate were peeled off, and in the imprint material applied and irradiated with light on the TAC film, it was confirmed whether photocuring proceeded depending on the presence or absence of the viscosity (tackiness) of the film surface after exposure. In addition, when photocuring is not progressing, the film surface remains viscous, and when touched by hand, the film surface is deformed. Therefore, when manufacturing a pattern transfer film by a roll-to-roll method, etc. When a product (film) is wound with a roll, a problem occurs, and it is determined that the product is not suitable as an imprint material.
- the film surface after exposure did not exhibit a consistency and did not deform even when touched by hand.
- the film surface after exposure showed viscosity. From the above, it became clear that the photopolymerization initiator of component (B) is an essential component.
- PET film Cosmo Shine (registered trademark) A4100)
- PMMA film Using a company-made Technoloy (registered trademark) S001G) (hereinafter abbreviated as “PMMA film” in this specification), a wet film thickness of 4 ⁇ m was applied using a fully automatic film applicator, It was dried in a clean oven at 110 ° C. for 30 seconds.
- the application surface (coating film) of the imprint material of each film is roller-pressed onto the moth-eye pattern mold subjected to the above-described release treatment, and the coating film is 350 mJ from the film side with an electrodeless uniform irradiation apparatus. / Cm ⁇ 2 > exposure was performed and photocuring was performed. Then, a 90 ° peel test with reference to JIS Z0237 was performed, and the cured film formed on each film substrate adhered to the surface having the mold pattern shape was completely peeled from the surface having the mold pattern shape. The load was measured. The load per 1 cm width of the film was calculated and used as the release force (g / cm). The obtained results are shown in Table 2 (Tables 2-1 to 2-4). In addition, in the mold after the release force test, in any of the examples and comparative examples, the adhesion of organic matter cannot be confirmed visually, and the pattern forming film transferred from the mold is also visually peeled off. No defects were confirmed.
- the imprint materials of Examples 1 to 47 can be prepared in the form of a transparent and uniform varnish as shown in Table 1 above, and do not exhibit tackiness after photocuring in [Photocurability Test].
- 100/100 perfect adhesion was achieved in the cross-cut test, and a release force greater than 0 g / cm and 0.5 g / cm or less was achieved. That is, the result which showed that the material of Example 1 thru
- the imprint material of Comparative Example 12 to Comparative Example 14, Comparative Example 16 to Comparative Example 22, Comparative Example 26, Comparative Example 28, and Comparative Example 30, that is, the imprint material not containing the component (C) solvent
- it can be prepared in the form of a transparent and uniform varnish as shown in Table 1 above
- the evaluation of adhesion to a TAC film, PET film, and PMMA film by a cross-cut test was 0/100, and the adhesion was completely expressed. No results were obtained.
- the imprint materials of Comparative Examples 54 to 58 in which the proportion of the solvent of the component (C) was reduced and the solid content concentration was 90% by mass resulted in the lowering of the adhesion to each film substrate. became.
- the imprint materials of Comparative Example 59 and Comparative Example 60 using other solvents (IPA and Tol) instead of the solvent of component (C) no adhesion was exhibited (0/100). ).
- the film obtained from the imprint material of the present invention is a composition that achieves both high adhesion and low release force when producing a structure on a film substrate such as roll-to-roll. It can be suitably used for products such as devices, solar cells, LED devices, and displays.
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Abstract
Description
したがって、ナノインプリントリソグラフィは、光リソグラフィ技術に代わり、半導体デバイス、オプトデバイス、ディスプレイ、記憶媒体、バイオチップ等の製造への適用が期待されている技術であることから、ナノインプリントリソグラフィに用いる光ナノインプリントリソグラフィ用硬化性組成物について様々な報告がなされている(特許文献2、特許文献3)。
一方、光ナノインプリントリソグラフィとは異なる技術分野においては、溶剤を加えてフィルム(基材)との十分な密着を獲得する方法が報告されている(特許文献4、特許文献5)。
第2観点として、前記(A)成分の化合物は、前記重合性基として、アクリロイルオキシ基、メタアクリロイルオキシ基、ビニル基及びアリル基からなる群から選ばれる少なくとも1種の基を少なくとも2つ有する化合物である、第1観点に記載のインプリント材料に関する。
第3観点として、前記(A)成分の化合物は、アルキレンオキサイドユニットとして、エチレンオキサイド、プロピレンオキサイド及びブチレンオキサイドから選ばれる少なくとも1種を少なくとも1つ有する化合物である、第1観点に記載のインプリント材料に関する。
第4観点として、前記(B)成分が、2,4,6-トリメチルベンゾイル-ジフェニル-ホスフィンオキサイド、1-ヒドロキシ-シクロヘキシル-フェニル-ケトン又は2-ヒドロキシ-2-メチル-1-フェニル-プロパン-1-オンを含む、第1観点乃至第3観点のいずれか一つに記載のインプリント材料に関する。
第5観点として、前記(C)成分がメチルエチルケトン、メチルイソブチルケトン、酢酸エチル、シクロヘキサノン及びプロピレングリコールモノメチルエーテルからなる群から選ばれる少なくとも1種を含有することを特徴とする、第1観点乃至第4観点のいずれか一つに記載のインプリント材料に関する。
第6観点として、前記インプリント材料の全成分から(C)成分を除いたものとして定義される固形分の割合が、前記インプリント材料の総質量に対して10質量%乃至80質量%であることを特徴とする、第1観点乃至第5観点のいずれか一つに記載のインプリント材料に関する。
第7観点として、前記フィルム基材が、トリアセチルセルロース、ポリエチレンテレフタレート、ポリメタクリル酸メチル又はシクロオレフィン(コ)ポリマーからなる、第1観点乃至第6観点のいずれか一つに記載のインプリント材料に関する。
第8観点として、前記インプリント材料を前記フィルム基材上に塗布し、光硬化させた場合において得られた硬化膜と前記フィルム基材との密着性が、JIS K5400に従う試験の評価において100/100であり、かつ、前記インプリント材料を前記フィルム基材上に塗布し、該フィルム基材上の塗膜をモールドのパターン形状を有する面に接着させ、続いて該塗膜を光硬化させ、その後フィルム基材上の硬化被膜をモールドのパターン形状を有する面から90°剥離する試験において、計測された離型力、すなわち、該フィルム基材上の硬化被膜をモールドのパターン形状を有する面から剥離したときの荷重を該フィルム基材の横幅1cmあたりに換算した値が0g/cmより大きく0.5g/cm以下である、第1観点乃至第7観点のいずれか一つに記載のインプリント材料に関する。
第9観点として、第1観点乃至第8観点のいずれか一つに記載のインプリント材料をフィルム基材に塗布し塗膜を得る工程、前記塗膜を乾燥させる工程、前記乾燥させた塗膜にモールドを押し付け加圧する、又は該加圧と共に加熱する工程、前記塗膜と前記モールドとが接した状態で、該塗膜を硬化させる光を照射し、硬化膜を形成する工程、及び形成された前記硬化膜を前記モールドから剥離する工程、を有するインプリント方法に関する。
第10観点として、前記乾燥工程における乾燥温度が60℃乃至150℃の範囲から選択される、第9観点に記載のインプリント方法に関する。
第11観点として、第1観点乃至第8観点のうちいずれか一つに記載のインプリント材料から作製され、パターンが転写された膜に関する。
第12観点として、第11観点に記載のパターンが転写された膜を基材上に備えた光学部材に関する。
第13観点として、第11観点に記載のパターンが転写された膜を基材上に備えた固体撮像装置に関する。
第14観点として、第11観点に記載のパターンが転写された膜を基材上に備えたLEDデバイスに関する。
第15観点として、第11観点に記載のパターンが転写された膜を備えた半導体素子に関する。
第16観点として、第11観点に記載のパターンが転写された膜を備えた太陽電池に関する。
第17観点として、第11観点に記載のパターンが転写された膜を備えたディスプレイに関する。
第18観点として、第11観点に記載のパターンが転写された膜を備えた電子デバイスに関する。
また本発明のインプリント材料は、光硬化が可能であり、かつモールドの離型時にパターンの一部に剥がれが生じないため、所望のパターンが正確に形成された膜が得られる。したがって、良好な光インプリントのパターン形成が可能である。
さらに本発明のインプリント材料は、従来のインプリント材料では相溶性の低さが課題とされたシリコーン化合物を含有しているものの、透明且つ均一なワニスの形態にて材料を得ることができ、時間経過による層分離の発生を抑制でき、製品安定性の高い材料とすることができる。そしてそのため、本発明のインプリント材料は均質な塗膜を形成でき、ひいては安定性の高い製品の供給につながる。
また、本発明のインプリント材料は上述の通り均一なワニスの形態にあるため、得られた硬化膜においても面内での成分のばらつきがなく、ロール・ツー・ロール方式のライン初期と後期とで得られる膜の光学特性が安定し、これは膜作製における歩留まりの向上につながり、生産効率向上を実現可能となる。
さらに、本発明のインプリント材料は、上記(A)成分の炭素原子数2、3又は4のアルキレンオキサイドユニットを有し、且つ重合性基を少なくとも2つ有する化合物及び/又はシリコーン化合物及び/又は溶剤の種類及び割合を変更することで、硬化速度、動的粘度、膜厚、基材との密着性、離型力をコントロールすることができる。したがって、本発明のインプリント材料は、製造するデバイス種と露光プロセス及び焼成プロセスの種類に対応した材料の設計が可能であり、プロセスマージンを拡大できるため、光学部材の製造に好適に用いることができる。
本発明のインプリント材料は上述の構成を為すことで、インプリント材料から形成される硬化膜がフィルム基材に対して高い密着性を獲得し、且つ、該硬化膜は低い離型力性を実現することを両立させた点に特徴がある。
以下、各成分について詳細に説明する。
(A)成分の化合物は、一分子内に炭素原子数2、3又は4のアルキレンオキサイドユニットを単独、又は組み合わせて一つ以上含有し、且つ重合性基を少なくとも2つ以上、要するに重合性基を分子末端に有する化合物を指す。本発明に含まれる(A)成分は、パターン転写後の膜に対して、膜表面の滑り性を高め、これによりモールドのパターン形状を有する面との剥離時に生ずる離型力の低下に貢献する。
上記アルキレンオキサイドユニットは、エチレンオキサイド(-CH2CH2O-)、プロピレンオキサイド(-CH(CH3)CH2O-)、(-CH2CH2CH2O-)又はブチレンオキサイド(-CH2CH2CH2CH2O-)であることが好ましい。
上記重合性基としては、例えば、アクリロイルオキシ基、メタアクリロイルオキシ基、ビニル基及びアリル基からなる群から選ばれる少なくとも1種類の有機基のことを指す。ここで、アクリロイルオキシ基はアクリロキシ基と、メタアクリロイルオキシ基はメタアクリロキシ基と表現されることがある。また、エチレンオキサイドはジメチレンオキサイドと、プロピレンオキサイドはトリメチレンオキサイドと、ブチレンオキサイドはテトラメチレンオキサイドと表現されることがある。
(B)成分である光重合開始剤は、光照射によりラジカルを発生し、インプリント材料に含まれる光重合性基同士の重合を開始する役割を果たす。
(B)成分である光重合開始剤としては、光硬化時に使用する光源に吸収をもつものであれば、特に限定されるものではないが、例えば、tert-ブチルペルオキシ-iso-ブタレート、2,5-ジメチル-2,5-ビス(ベンゾイルジオキシ)ヘキサン、1,4-ビス[α-(tert-ブチルジオキシ)-iso-プロポキシ]ベンゼン、ジ-tert-ブチルペルオキシド、2,5-ジメチル-2,5-ビス(tert-ブチルジオキシ)ヘキセンヒドロペルオキシド、α-(iso-プロピルフェニル)-iso-プロピルヒドロペルオキシド、tert-ブチルヒドロペルオキシド、1,1-ビス(tert-ブチルジオキシ)-3,3,5-トリメチルシクロヘキサン、ブチル-4,4-ビス(tert-ブチルジオキシ)バレレート、シクロヘキサノンペルオキシド、2,2’,5,5’-テトラ(tert-ブチルペルオキシカルボニル)ベンゾフェノン、3,3’,4,4’-テトラ(tert-ブチルペルオキシカルボニル)ベンゾフェノン、3,3’,4,4’-テトラ(tert-アミルペルオキシカルボニル)ベンゾフェノン、3,3’,4,4’-テトラ(tert-ヘキシルペルオキシカルボニル)ベンゾフェノン、3,3’-ビス(tert-ブチルペルオキシカルボニル)-4,4’-ジカルボキシベンゾフェノン、tert-ブチルペルオキシベンゾエート、ジ-tert-ブチルジペルオキシイソフタレート等の有機過酸化物;9,10-アントラキノン、1-クロロアントラキノン、2-クロロアントラキノン、オクタメチルアントラキノン、1,2-ベンズアントラキノン等のキノン類;ベンゾインメチル、ベンゾインエチルエーテル、α-メチルベンゾイン、α-フェニルベンゾイン等のベンゾイン誘導体、2,2-ジメトキシ-1,2-ジフェニルエタン-1-オン、1-ヒドロキシ-シクロヘキシル-フェニル-ケトン、2-ヒドロキシ-2-メチル-1-フェニル-プロパン-1-オン、1-[4-(2-ヒドロキシエトキシ)-フェニル]-2-ヒドロキシ-2-メチル-1-プロパン-1-オン、2-ヒドロキシ-1-[4-{4-(2-ヒドロキシ-2-メチル-プロピオニル)ベンジル}-フェニル]-2-メチル-プロパン-1-オン、フェニルグリオキシリックアシッドメチルエステル、2-メチル-1-[4-(メチルチオ)フェニル]-2-モルホリノプロパン-1-オン、2-ベンジル-2-ジメチルアミノ-1-(4-モルホリノフェニル)-ブタン-1-オン、2-ジメチルアミノ-2-(4-メチル-ベンジル)-1-(4-モルホリン-4-イル-フェニル)-ブタン-1-オン等のアルキルフェノン系化合物;ビス(2,4,6-トリメチルベンゾイル)-フェニルホスフィンオキサイド、2,4,6-トリメチルベンゾイル-ジフェニル-ホスフィンオキサイド等のアシルホスフィンオキサイド系化合物;1,2-オクタンジオン,1-[4-(フェニルチオ)-,2-(O-ベンゾイルオキシム)]、エタノン,1-[9-エチル-6-(2-メチルベンゾイル)-9H-カルバゾール-3-イル]-,1-(O-アセチルオキシム)等のオキシムエステル系化合物が挙げられる。
(C)成分であるフィルム基材の表面部を膨潤させ又は溶解する溶剤とは、インプリント材料のフィルム基材への塗布工程及び乾燥工程時に、インプリント材料の塗膜と接触するフィルム基材の最表面部を膨潤させるか又は溶解することが可能な溶剤を意味する。該溶剤は、フィルム基材の表面部を膨潤させ又は溶解することにより、本発明のインプリント材料の一部をフィルム基材中へ拡散させ、光硬化させた後のフィルム基材と硬化膜との密着性を向上させる役割を担う。また該溶剤は、溶解性若しくは相溶性に乏しい後述するシリコーン化合物である(D)成分を含有する本発明のインプリント材料を均一なワニスにするためのワニス均一化助剤としての役割をも果たす。
特に好適なフィルム基材と溶剤との組み合わせは、フィルム基材がトリアセチルセルロースの場合、メチルエチルケトン、シクロヘキサノン及び酢酸エチル、ポリエチレンテレフタレートの場合、メチルエチルケトン、シクロヘキサノン及び酢酸エチル、ポリメタクリル酸メチルの場合、メチルエチルケトン、メチルイソプロピルケトン、ジエチルケトン、メチルイソブチルケトン、メチルn-ブチルケトン、シクロヘキサノン、酢酸エチル、ジアセトンアルコール、フルフリルアルコール、テトラヒドロフリフリルアルコール及びプロピレングリコールモノメチルエーテル、シクロオレフィンの場合、アセトン、メチルエチルケトン、シクロヘキサノン及び酢酸エチルが好適に使用できる。
このため、大気圧下(760mmHg)にて、200℃以下、特に好ましくは150℃以下の温度で蒸発し、十分な密着性を発現する上記溶剤として、メチルエチルケトン(沸点:79.5℃)、メチルイソブチルケトン(沸点:116.2℃)、酢酸エチル(沸点:77.1℃)、シクロヘキサノン(沸点:155.6℃)、プロピレングリコールモノメチルエーテル(沸点:121.0℃)が好適であり、フィルム基材との密着性が良好であり、ワニスとする際の溶解性及びワニスとした際の他成分との相溶性が良いという観点でメチルエチルケトンを特に好適に使用できる。
好ましくは、本発明のインプリント材料の全成分、すなわち前述の(A)成分、(B)成分、(D)成分、並びに後述するその他添加剤を含む全成分から(C)成分の溶剤を除いたものとして定義される固形分の割合が、前記インプリント材料に対して10質量%乃至80質量%となる量にて、より好ましくは40質量%乃至70質量%となる量にて、溶剤を含有することが好ましい。前記固形分の割合が10質量%を下回る場合は目的の膜厚を得ることができず、80質量%を超えるとフィルム基材との密着性を確保することが困難な場合がある。
また、溶剤として上述のその他の溶剤を併用する場合、全溶剤成分のうちの(C)成分の溶剤の割合は、10質量%乃至40質量%である。
(D)成分であるシリコーン化合物は、分子内にシリコーン骨格(シロキサン骨格)を有する化合物であり、特にジメチルシリコーン骨格を有することが好ましく、そのような化合物の例としてポリエーテル変性ポリジメチルシロキサンが挙げられる。
(D)成分のシリコーン化合物は、本発明のインプリント材料のフィルム基材への塗布時、塗布後の乾燥時、及び露光時に、被膜(硬化膜)の最表面へと表層移行し、フィルム基材上の硬化膜をモールドから剥離するときの離型力を低下させる役割を果たす。
本発明におけるインプリント材料には、(E)成分として、少なくとも2つの重合性基を有し、且つ、分子内に炭素原子数2、3又は4のアルキレンオキサイドユニットを含有しない(メタ)アクリレート及び/又はウレタン(メタ)アクリレートを添加しても良い。上記(E)成分は、光インプリントにより得られる硬化膜の硬度を調整する役割を果たす。
当該重合性基としては、例えば、アクリロイルオキシ基、メタアクリロイルオキシ基、ビニル基、アリル基が挙げられる。なお、本明細書では(メタ)アクリレートとは、アクリレートとメタクリレートの両方を指す。例えば(メタ)アクリル酸は、アクリル酸とメタクリル酸を指す。
本発明のインプリント材料は、本発明の効果を損なわない限りにおいて、必要に応じて、エポキシ化合物、光酸発生剤、光増感剤、紫外線吸収剤、酸化防止剤、密着補助剤又は離型性向上剤を含有することができる。
本発明のインプリント材料の調製方法は、特に限定されないが、(A)成分、(B)成分、(C)成分及び(D)成分、並びに任意成分である(E)成分並びに所望によりその他添加剤を混合し、インプリント材料が均一な状態となっていればよい。
また、(A)成分乃至(E)成分並びに所望によりその他添加剤を混合する際の順序は、均一なインプリント材料が得られるなら問題なく、特に限定されない。当該調製方法としては、例えば、(A)成分に(B)成分を所定の割合で混合する方法が挙げられる。また、これに更に(C)成分、(D)成分及び(E)成分を混合し、均一なインプリント材料とする方法も挙げられる。さらに、この調製方法の適当な段階において、必要に応じて、その他の添加剤を更に添加して混合する方法が挙げられる。
上記インプリント材料を用いた光インプリントのプロセスは、以下の工程a)~e)を有する:
a)本発明のインプリント材料をフィルム基材に塗布し塗膜を得る工程、
b)前記塗膜を乾燥させる工程、
c)前記乾燥させた塗膜にモールドを押し付け加圧する、その際必要に応じて熱を加える工程。
d)前記塗膜と前記モールドとが接した状態で、該塗膜を硬化させる光を照射し、硬化膜を形成する工程、及び
e)形成された前記硬化膜を前記モールドから剥離する工程。
なかでも、本発明における好適なフィルム基材として、トリアセチルセルロース、ポリエチレンテレフタレート、ポリメタクリル酸メチル又はシクロオレフィン(コ)ポリマーが挙げられる。
乾燥工程は、光照射前の塗膜に対して溶剤を蒸発させる目的で焼成することによって実施され、また光照射後の被膜(硬化膜)に対して更に乾燥工程(焼成)を実施しても良い。
焼成機器としては、特に限定されるものではなく、例えば、ホットプレート、オーブン、ファーネスを用いて、適切な雰囲気下、すなわち大気、窒素等の不活性ガス又は真空中で焼成することができるものであればよい。
焼成温度は、溶剤を蒸発させる目的では、特に限定されないものの、フィルム基材は可塑性高分子で構成されており、焼成温度が200℃以上では溶解又は変形が起こり目的のパターンが得られないおそれがあることから、焼成温度の上限は200℃以下、特に好ましくは150℃以下とすることが望ましい。したがって、焼成温度は、例えば、40℃乃至200℃が好ましく、特に好ましくは60℃乃至150℃である。
また焼成時間は製品を得るタクトタイムに直接関わるため、短ければ良いが、10秒乃至300秒の範囲で選択されることが好ましく、10秒乃至180秒の範囲がより好ましい。
上記密着性の試験は基板目試験とも呼ばれ、碁盤目状の直角の格子パターン(例:100マス)に被膜をカット(傷を入れる)し、素地(基板)まで貫通するときの素地からの剥離に対する被膜の耐性を評価するものであり、100/100とは100マスのうち100マスとも剥がれなかった結果を示すものである。
そして本発明のインプリント材料を前記フィルム基材上に塗布し、該フィルム基材上の塗膜をモールドのパターン形状を有する面に接着させ、続いて該塗膜を、モールドのパターン形状を有する面を接着させたまま光硬化させ、その後フィルム基材上の硬化被膜をモールドのパターン形状を有する面から90°剥離する試験において計測された離型力、すなわち、該フィルム基材上の硬化被膜をモールドのパターン形状を有する面から完全に剥離したときの荷重を該フィルム基材の横幅1cmあたりに換算した値が0g/cmより大きく0.5g/cm以下であることが好ましく、より好ましくは0.4g/cm以下である。
本発明において、上述の如く定義される離型力とは、これまで報告されているようなモールド形状のパターン転写率の顕微鏡観察といった離型性の評価とは異なり、モールドから光硬化後の膜を備えたフィルムを剥がすときに生じる力を定量化した値(g/cm)である。そして実際にフィルムを剥がすとき生じる力は、モールド幅及びフィルム幅の伸長に伴い増加する。
光ナノインプリントリソグラフィの現場において扱うロール・ツー・ロールプロセスでは、モールド及びフィルム幅が長いことが一般的であることから、モールドとフィルムとを引き剥がす力が増加する傾向にあり、モールドへのフィルム(樹脂)の付着やそれによるモールドの劣化が懸案となっている。このため、単位長さ当りの荷重(本発明でいうところの離型力)を小さくすることはモールドの寿命を伸ばし、フィルムを安定供給できると考えられ、すなわち、離型力が小さいことはインプリント材料における重要な性能の一つである。
[露光機]
装置:株式会社オーク製作所製 無電極均一照射装置 QRE-4016A
[紫外線可視分光光度計]
装置:株式会社島津製作所製 SHIMADSU UV-3600
[密着性試験]
規格:JIS K5400
[全自動フィルムアプリケーター]
装置:コーテック株式会社製 KT-AB3120
ニッケル製のピッチ250nm、高さ250nmのモスアイパターンモールド(株式会社イノックス製)及び後述する光硬化性試験で使用するシリコン基板を、オプツール(登録商標)DSX(ダイキン工業株式会社製)をノベック(登録商標)HFE-7100(ハイドロフルオロエーテル、住友スリーエム株式会社)(以下、本明細書では「ノベックHFE-7100」と略称する。)で0.1質量%に希釈した溶液へ浸漬し、温度が90℃、湿度が90RH%の高温高湿装置を用いて1時間処理し、ノベックHFE-7100でリンス後、エアーで乾燥させた。
<実施例1>
50mL一つ口ナス型フラスコにA-200(新中村化学工業株式会社製)10.00gを秤量し、次いでLucirin TPO(登録商標)(BASFジャパン株式会社製(以下、本明細書では「TPO」と略称する。)を0.25g(A-200の質量に対して2.5phr)、BYK-333(ビックケミー・ジャパン株式会社製)を0.05g(A-200の質量に対して0.5phr)、メチルエチルケトン(以下、本明細書では「MEK」と略称する。)を10.30g加え、マグネチックスターラーを用いて撹拌し、透明で且つ均一なワニスの形態としてインプリント材料A1(固形分:50%のMEK溶液)を調製した。
<実施例2>
実施例1のA-200をA-400(新中村化学工業株式会社製)に変更した以外は、実施例1と同様にインプリント材料A2(固形分:50%のMEK溶液)を調製した。
<実施例3>
実施例1のA-200をA-600(新中村化学工業株式会社製)に変更した以外は、実施例1と同様にインプリント材料A3(固形分:50%のMEK溶液)を調製した。
<実施例4>
実施例1のA-200をA-1000(新中村化学工業株式会社製)に変更した以外は、実施例1と同様にインプリント材料A4(固形分:50%のMEK溶液)を調製した。
<実施例5>
実施例1のA-200をKAYARAD(登録商標)DPEA-12(日本化薬株式会社製)に変更した以外は、実施例1と同様にインプリント材料A5(固形分:50%のMEK溶液)を調製した。
<実施例6>
実施例1のA-200を1G(新中村化学工業株式会社製)に変更した以外は、実施例1と同様にインプリント材料A6(固形分:50%のMEK溶液)を調製した。
<実施例7>
実施例1のA-200をAPG-100(新中村化学工業株式会社製)に変更した以外は、実施例1と同様にインプリント材料A7(固形分:50%のMEK溶液)を調製した。
<実施例8>
実施例1のA-200をAPG-200(新中村化学工業株式会社製)に変更した以外は、実施例1と同様にインプリント材料A8(固形分:50%のMEK溶液)を調製した。
<実施例9>
実施例1のA-200をAPG-400(新中村化学工業株式会社製)に変更した以外は、実施例1と同様にインプリント材料A9(固形分:50%のMEK溶液)を調製した。
<実施例10>
実施例1のA-200をAPG-700(新中村化学工業株式会社製)に変更した以外は、実施例1と同様にインプリント材料A10(固形分:50%のMEK溶液)を調製した。
<実施例11>
実施例1のA-200をA-PTMG-65(新中村化学工業株式会社製)に変更した以外は、実施例1と同様にインプリント材料A11(固形分:50%のMEK溶液)を調製した。
50mL一つ口ナス型フラスコにA-1000(新中村化学工業株式会社製)5.00g、KAYARAD(登録商標)DPEA-12(日本化薬株式会社製)5.00gを秤量し、次いでTPOを0.25g(A-1000とDPEA-12の総質量に対して2.5phr)、BYK-333(ビックケミー・ジャパン株式会社製)を0.05g(A-1000とDPEA-12の総質量に対して0.5phr)、MEKを10.30g加え、マグネチックスターラーを用いて撹拌し、透明で且つ均一なワニスの形態としてインプリント材料A12(固形分:50%のMEK溶液)を調製した。
<実施例13>
実施例12のA-1000をAPG-700(新中村化学工業株式会社製)に変更した以外は、実施例12と同様にインプリント材料A13(固形分:50%のMEK溶液)を調製した。
<実施例14>
実施例12のA-1000をA-PTMG-65(新中村化学工業株式会社製)に変更した以外は、実施例12と同様にインプリント材料A14(固形分:50%のMEK溶液)を調製した。
実施例4のTPOをIRGACURE184(BASFジャパン株式会社製)(以下、本明細書では「184」と略称する。)に変更した以外は、実施例4と同様にインプリント材料A15(固形分:50%のMEK溶液)を調製した。
<実施例16>
実施例5のTPOを184に変更した以外は、実施例5と同様にインプリント材料A16(固形分:50%のMEK溶液)を調製した。
実施例12のTPOを184に変更した以外は、実施例12と同様にインプリント材料A17(固形分:50%のMEK溶液)を調製した。
<実施例18>
実施例12のTPOをDAROCUR1173(BASFジャパン株式会社製)(以下、本明細書では「1173」と略称する。)に変更した以外は同様にインプリント材料A18(固形分:50%のMEK溶液)を調製した。
実施例5のMEKをメチルイソブチルケトン(以下、本明細書では「MIBK」と略称する。)に変更した以外は、実施例5と同様にインプリント材料A19を(固形分:50%のMIBK溶液)調製した。
<実施例20>
実施例5のMEKを酢酸エチル(以下、本明細書では「EtOAc」と略称する。)に変更した以外は、実施例5と同様にインプリント材料A20(固形分:50%のEtOAc溶液)を調製した。
<実施例21>
実施例5のMEKをシクロヘキサノン(以下、本明細書では「CHN」と略称する。)に変更した以外は、実施例5と同様にインプリント材料A21(固形分:50%のCHN溶液)を調製した。
<実施例22>
実施例5のMEKをプロピレングリコールモノメチルエーテル(以下、本明細書では「PGME」と略称する。)に変更した以外は、実施例5と同様にインプリント材料A22(固形分:50%のPGME溶液)を調製した。
実施例12のBYK-333をBYK-307(ビックケミー・ジャパン株式会社製)に変更した以外は、実施例12と同様にインプリント材料A23(固形分:50%のMEK溶液)を調製した。
<実施例24>
実施例12のBYK-333をX-22-164AS(信越化学工業株式会社製)に変更した以外は、実施例12と同様にインプリント材料A24(固形分:50%のMEK溶液)を調製した。
<実施例25>
実施例12のBYK-333をX-22-164E(信越化学工業株式会社製)に変更した以外は、実施例12と同様にインプリント材料A25(固形分:50%のMEK溶液)を調製した。
<実施例26>
実施例12のBYK-333をX-22-1602(信越化学工業株式会社製)に変更した以外は、実施例12と同様にインプリント材料A26(固形分:50%のMEK溶液)を調製した。
<実施例27>
実施例12のBYK-333をX-22-2426(信越化学工業株式会社製)に変更した以外は、実施例12と同様にインプリント材料A27(固形分:50%のMEK溶液)を調製した。
<実施例28>
実施例12のBYK-333をX-22-2404(信越化学工業株式会社製)に変更した以外は、実施例12と同様にインプリント材料A28(固形分:50%のMEK溶液)を調製した。
<実施例29>
実施例12のBYK-333をX-24-8201(信越化学工業株式会社製)に変更した以外は、実施例12と同様にインプリント材料A29(固形分:50%のMEK溶液)を調製した。
<実施例30>
実施例12のBYK-333をFL100-100cs(信越化学工業株式会社製)に変更した以外は、実施例12と同様にインプリント材料A30(固形分:50%のMEK溶液)を調製した。
<実施例31>
実施例12のBYK-333をFL100-450cs(信越化学工業株式会社製)に変更した以外は、実施例12と同様にインプリント材料A31(固形分:50%のMEK溶液)を調製した。
50mL一つ口ナス型フラスコにA-1000(新中村化学工業株式会社製)5.00g、KAYARAD(登録商標)DPEA-12(日本化薬株式会社製)5.00gを秤量し、次いでTPOを0.25g(A-1000とDPEA-12の総質量に対して2.5phr)、BYK-333(ビックケミー・ジャパン株式会社製)を0.05g(A-1000とDPEA-12の総質量に対して0.5phr)、KAYARAD(登録商標)DPHA(日本化薬株式会社製)を1.00g(A-1000とDPEA-12の総質量に対して10phr)、MEKを11.30g加え、マグネチックスターラーを用いて撹拌し、透明で且つ均一なワニスの形態としてインプリント材料A32(固形分:50%のMEK溶液)を調製した。
<実施例33>
実施例32のDPHAをKAYARAD(登録商標)PET-30(日本化薬株式会社製)に変更した以外は、実施例32と同様にインプリント材料A33(固形分:50%のMEK溶液)を調製した。
<実施例34>
実施例32のDPHAをA-DCP(新中村化学工業株式会社製)に変更した以外は、実施例32と同様にインプリント材料A34(固形分:50%のMEK溶液)を調製した。
<実施例35>
実施例32のDPHAをUA-306H(共栄社化学株式会社製)に変更した以外は、実施例32と同様にインプリント材料A35(固形分:50%のMEK溶液)を調製した。
<実施例36>
実施例32のDPHAをUA-7100(新中村化学工業株式会社製)に変更した以外は、実施例32と同様にインプリント材料A36(固形分:50%のMEK溶液)を調製した。
50mL一つ口ナス型フラスコにA-200(新中村化学工業株式会社製)4.00gを秤量し、次いでTPOを0.10g(A-200の質量に対して2.5phr)、BYK-333(ビックケミー・ジャパン株式会社製)を0.02g(A-200の質量に対して0.5phr)、MEKを16.48g加え、マグネチックスターラーを用いて撹拌し、透明で且つ均一なワニスの形態としてインプリント材料A37(固形分:20%のMEK溶液)を調製した。
<実施例38>
50mL一つ口ナス型フラスコにA-200(新中村化学工業株式会社製)14.00gを秤量し、次いでTPOを0.35g(A-200の質量に対して2.5phr)、BYK-333(ビックケミー・ジャパン株式会社製)を0.07g(A-200の質量に対して0.5phr)、MEKを6.18g加え、マグネチックスターラーを用いて撹拌し、透明で且つ均一なワニスの形態としてインプリント材料A38(固形分:70%のMEK溶液)を調製した。
実施例1のBYK-333をBYK-307(ビックケミー・ジャパン株式会社製)に変更した以外は、実施例1と同様にインプリント材料A39(固形分:50%のMEK溶液)を調製した。
<実施例40>
実施例1のBYK-333をX-22-164AS(信越化学工業株式会社製)に変更した以外は、実施例1と同様にインプリント材料A40(固形分:50%のMEK溶液)を調製した。
<実施例41>
実施例1のBYK-333をX-22-164E(信越化学工業株式会社製)に変更した以外は、実施例1と同様にインプリント材料A41(固形分:50%のMEK溶液)を調製した。
<実施例42>
実施例1のBYK-333をX-22-1602(信越化学工業株式会社製)に変更した以外は、実施例1と同様にインプリント材料A42(固形分:50%のMEK溶液)を調製した。
<実施例43>
実施例1のBYK-333をX-22-2426(信越化学工業株式会社製)に変更した以外は、実施例1と同様にインプリント材料A43(固形分:50%のMEK溶液)を調製した。
<実施例44>
実施例1のBYK-333をX-22-2404(信越化学工業株式会社製)に変更した以外は、実施例1と同様にインプリント材料A44(固形分:50%のMEK溶液)を調製した。
<実施例45>
実施例1のBYK-333をX-24-8201(信越化学工業株式会社製)に変更した以外は、実施例1と同様にインプリント材料A45(固形分:50%のMEK溶液)を調製した。
<実施例46>
実施例1のBYK-333をFL100-100cs(信越化学工業株式会社製)に変更した以外は、実施例1と同様にインプリント材料A46(固形分:50%のMEK溶液)を調製した。
<実施例47>
実施例1のBYK-333をFL100-450cs(信越化学工業株式会社製)に変更した以外は、実施例1と同様にインプリント材料A47(固形分:50%のMEK溶液)を調製した。
50mL一つ口ナス型フラスコにA-200(新中村化学工業株式会社製)10.00gを秤量し、次いでBYK-333(ビックケミー・ジャパン株式会社製)を0.05g(A-200の質量に対して0.5phr)、MEKを10.05g加え、マグネチックスターラーを用いて撹拌し、透明で且つ均一なワニスの形態としてインプリント材料B1を調製した。
<比較例2>
比較例1のA-200をA-400(新中村化学工業株式会社製)に変更した以外は、比較例1と同様にインプリント材料B2を調製した。
<比較例3>
比較例1のA-200をA-600(新中村化学工業株式会社製)に変更した以外は、比較例1と同様にインプリント材料B3を調製した。
<比較例4>
比較例1のA-200をA-1000(新中村化学工業株式会社製)に変更した以外は、比較例1と同様にインプリント材料B4を調製した。
<比較例5>
比較例1のA-200をKAYARAD(登録商標)DPEA-12(日本化薬株式会社製)に変更した以外は、比較例1と同様にインプリント材料B5を調製した。
<比較例6>
比較例1のA-200を1G(新中村化学工業株式会社製)に変更した以外は、比較例1と同様にインプリント材料B6を調製した。
<比較例7>
比較例1のA-200をAPG-100(新中村化学工業株式会社製)に変更した以外は、比較例1と同様にインプリント材料B7を調製した。
<比較例8>
比較例1のA-200をAPG-200(新中村化学工業株式会社製)に変更した以外は、比較例1と同様にインプリント材料B8を調製した。
<比較例9>
比較例1のA-200をAPG-400(新中村化学工業株式会社製)に変更した以外は、比較例1と同様にインプリント材料B9を調製した。
<比較例10>
比較例1のA-200をAPG-700(新中村化学工業株式会社製)に変更した以外は、比較例1と同様にインプリント材料B10を調製した。
<比較例11>
比較例1のA-200をA-PTMG-65(新中村化学工業株式会社製)に変更した以外は、比較例1と同様にインプリント材料B11を調製した。
50mL一つ口ナス型フラスコにA-200(新中村化学工業株式会社製)20.00gを秤量し、次いでTPOを0.05g(A-200質量に対して2.5phr)、BYK-333(ビックケミー・ジャパン株式会社製)を0.10g(A-200の質量に対して0.5phr)加え、マグネチックスターラーを用いて撹拌し、透明で且つ均一なワニスの形態としてインプリント材料B12を調製した。
<比較例13>
比較例12のA-200をA-400(新中村化学工業株式会社製)に変更した以外は、比較例12と同様にインプリント材料B13を調製した。
<比較例14>
比較例12のA-200をA-600(新中村化学工業株式会社製)に変更した以外は、比較例12と同様にインプリント材料B14を調製した。
<比較例15>
比較例12のA-200をA-1000(新中村化学工業株式会社製)に変更した以外は、比較例12と同様にインプリント材料B15を調製した。しかし、B15は透明で且つ均一なワニスの形態として得られなかった。
<比較例16>
比較例12のA-200をKAYARAD(登録商標)DPEA-12(日本化薬株式会社製)に変更した以外は、比較例12と同様にインプリント材料B16を調製した。
<比較例17>
比較例12のA-200を1G(新中村化学工業株式会社製)に変更した以外は、比較例12と同様にインプリント材料B17を調製した。
<比較例18>
比較例12のA-200をAPG-100(新中村化学工業株式会社製)に変更した以外は、比較例12と同様にインプリント材料B18を調製した。
<比較例19>
比較例12のA-200をAPG-200(新中村化学工業株式会社製)に変更した以外は、比較例12と同様にインプリント材料B19を調製した。
<比較例20>
比較例12のA-200をAPG-400(新中村化学工業株式会社製)に変更した以外は、比較例12と同様にインプリント材料B20を調製した。
<比較例21>
比較例12のA-200をAPG-700(新中村化学工業株式会社製)に変更した以外は、比較例12と同様にインプリント材料B21を調製した。
<比較例22>
比較例12のA-200をA-PTMG-65(新中村化学工業株式会社製)に変更した以外は、比較例12と同様にインプリント材料B22を調製した。
比較例12のBYK-333をBYK-307(ビックケミー・ジャパン株式会社製)に変更した以外は、比較例12と同様にインプリント材料B23を調製した。しかし、B23は透明で且つ均一なワニスの形態として得られなかった。
<比較例24>
比較例12のBYK-333をX-22-164AS(信越化学工業株式会社製)に変更した以外は、比較例12と同様にインプリント材料B24を調製した。しかし、B24は透明で且つ均一なワニスの形態として得られなかった。
<比較例25>
比較例12のBYK-333をX-22-164E(信越化学工株式会社製)に変更した以外は、比較例12と同様にインプリント材料B25を調製した。しかし、B25は透明で且つ均一なワニスの形態として得られなかった。
<比較例26>
比較例12のBYK-333をX-22-1602(信越化学工業株式会社製)に変更した以外は、比較例12と同様にインプリント材料B26を調製した。
<比較例27>
比較例12のBYK-333をX-22-2426(信越化学工業株式会社製)に変更した以外は、比較例12と同様にインプリント材料B27を調製した。しかし、B27は透明で且つ均一なワニスの形態として得られなかった。
<比較例28>
比較例12のBYK-333をX-22-2404(信越化学工業株式会社製)に変更した以外は、比較例12と同様にインプリント材料B28を調製した。
<比較例29>
比較例12のBYK-333をX-24-8201(信越化学工業株式会社製)に変更した以外は、比較例12と同様にインプリント材料B29を調製した。しかし、B29は透明で且つ均一なワニスの形態として得られなかった。
<比較例30>
比較例12のBYK-333をFL100-100cs(信越化学工業株式会社製)に変更した以外は、比較例12と同様にインプリント材料B30を調製した。
<比較例31>
比較例12のBYK-333を、比較例12とFL100-450cs(信越化学工業株式会社製)に変更した以外は同様にインプリント材料B31を調製した。しかし、B31は透明で且つ均一なワニスの形態として得られなかった。
50mL一つ口ナス型フラスコにA-200(新中村化学工業株式会社製)20.00gを秤量し、次いでTPOを0.50g(A-200質量に対して2.5phr)、X-22-164E(信越化学工業株式会社製)を0.10g(A-200の質量に対して0.5phr)、KAYARAD(登録商標)DPHA(日本化薬株式会社製)を2.00g(A-200の質量に対して10phr)加え、マグネチックスターラーを用いて撹拌し、インプリント材料B32を調製した。しかし、B32は透明で且つ均一なワニスの形態として得られなかった。
<比較例33>
比較例32のX-22-164EをX-22-2426(信越化学工業株式会社製)に変更し、KAYARAD(登録商標)DPHAをKAYARAD(登録商標)PET-30(日本化薬株式会社製)に変更した以外は、比較例32と同様にインプリント材料B33を調製した。しかし、B33は透明で且つ均一なワニスの形態として得られなかった。
<比較例34>
比較例32のX-22-164EをX-24-8201(信越化学工業株式会社製)に変更し、KAYARAD(登録商標)DPHAをA-DCP(新中村化学工業株式会社製)に変更した以外は、比較例32と同様にインプリント材料B34を調製した。しかし、B34は透明で且つ均一なワニスの形態として得られなかった。
<比較例35>
比較例32のX-22-164EをFL100-100cs(信越化学工業株式会社製)に変更し、KAYARAD(登録商標)DPHAをUA-306H(共栄社化学株式会社製)に変更した以外は、比較例32と同様にインプリント材料B35を調製した。しかし、B35は透明で且つ均一なワニスの形態として得られなかった。
<比較例36>
比較例32のX-22-164EをFL100-450cs(信越化学工業株式会社製)に変更し、KAYARAD(登録商標)DPHAをUA-7100(新中村化学工業株式会社製)に変更した以外は、比較例32と同様にインプリント材料B36を調製した。しかし、B36は透明で且つ均一なワニスの形態として得られなかった。
50mL一つ口ナス型フラスコにA-200(新中村化学工業株式会社製)10.00gを秤量し、次いでTPOを0.25g(A-200質量に対して2.5phr)、MEKを10.25g加え、マグネチックスターラーを用いて撹拌し、インプリント材料B37を調製した。
<比較例38>
比較例37のA-200をA-400(新中村化学工業株式会社製)に変更した以外は、比較例37と同様にインプリント材料B38を調製した。
<比較例39>
比較例37のA-200をA-600(新中村化学工業株式会社製)に変更した以外は、比較例37と同様にインプリント材料B39を調製した。
<比較例40>
比較例37のA-200をA-1000(新中村化学工業株式会社製)に変更した以外は、比較例37と同様にインプリント材料B40を調製した。
<比較例41>
比較例37のA-200をKAYARAD(登録商標)DPEA-12(日本化薬株式会社製)に変更した以外は、比較例37と同様にインプリント材料B41を調製した。
<比較例42>
比較例37のA-200を1G(新中村化学工業株式会社製)に変更した以外は、比較例37と同様にインプリント材料B42を調製した。
<比較例43>
比較例37のA-200をAPG-100(新中村化学工業株式会社製)に変更した以外は、比較例37と同様にインプリント材料B43を調製した。
<比較例44>
比較例37のA-200をAPG-200(新中村化学工業株式会社製)に変更した以外は、比較例37と同様にインプリント材料B44を調製した。
<比較例45>
比較例37のA-200をAPG-400(新中村化学工業株式会社製)に変更した以外は、比較例37と同様にインプリント材料B45を調製した。
<比較例46>
比較例37のA-200をAPG-700(新中村化学工業株式会社製)に変更した以外は、比較例37と同様にインプリント材料B46を調製した。
<比較例47>
比較例37のA-200をA-PTMG-65(新中村化学工業株式会社製)に変更した以外は、比較例37と同様にインプリント材料B47を調製した。
50mL一つ口ナス型フラスコにA-1000(新中村化学工業株式会社製)5.00g、KAYARAD(登録商標)DPEA-12(日本化薬株式会社製)5.00gを秤量し、次いでTPOを0.25g(A-1000とDPEA-12の総質量に対して2.5phr)、MEKを10.25g加え、マグネチックスターラーを用いて撹拌し、透明で且つ均一なワニスの形態としてインプリント材料B48を調製した。
50mL一つ口ナス型フラスコにKAYARAD(登録商標)DPHA(日本化薬株式会社製)10.00を秤量し、次いでTPOを0.25g(DPHAの質量に対して2.5phr)、MEKを10.25g加え、マグネチックスターラーを用いて撹拌し、透明で且つ均一なワニスの形態としてインプリント材料B49を調製した。
<比較例50>
比較例49のDPHAをKAYARAD(登録商標)PET-30(日本化薬株式会社製)に変更した以外は、比較例49と同様にインプリント材料B50を調製した。
<比較例51>
比較例49のDPHAをA-DCP(新中村化学工業株式会社製)に変更した以外は、比較例49と同様にインプリント材料B51を調製した。
<比較例52>
比較例49のDPHAをUA-306H(共栄社化学株式会社製)に変更した以外は、比較例49と同様にインプリント材料B52を調製した。
<比較例53>
比較例49のDPHAをUA-7100(新中村化学工業株式会社製)に変更した以外は、比較例49と同様にインプリント材料B53を調製した。
50mL一つ口ナス型フラスコにA-200(新中村化学工業株式会社製)18.00gを秤量し、次いでTPOを0.45g(A-200の質量に対して2.5phr)、BYK-333(ビックケミー・ジャパン株式会社製)を0.09g(A-200の質量に対して0.5phr)、MEKを2.06g加え、マグネチックスターラーを用いて撹拌し、透明で且つ均一なワニスの形態としてインプリント材料B54(固形分:90%のMEK溶液)を調製した。
<比較例55>
比較例54のMEKをMIBKに変更した以外は、比較例54と同様にインプリント材料B55(固形分:90%のMIBK溶液)を調製した。
<比較例56>
比較例54のMEKをEtOAcに変更した以外は、比較例54と同様にインプリント材料B56(固形分:90%のEtOAc溶液)を調製した。
<比較例57>
比較例54のMEKをCHNに変更した以外は、比較例54と同様にインプリント材料B57(固形分:90%のCHN溶液)を調製した。
<比較例58>
比較例54のMEKをPGMEに変更した以外は、比較例54と同様にインプリント材料B58(固形分:90%のPGME溶液)を調製した。
実施例1のMEKをイソプロピルアルコール(以下、「IPA」と略す)に変更した以外は、実施例1と同様にインプリント材料B59(固形分:50%のIPA溶液)を調製した。
<比較例60>
実施例1のMEKをトルエン(以下、「Tol」と略す)に変更した以外は同様にインプリント材料B60(固形分:50%のTol溶液)を調製した。
実施例1乃至実施例47及び比較例15、比較例23乃至比較例25、比較例27、比較例29、比較例31乃至比較例36において、インプリント材料が透明で且つ均一なワニスの形態として得られたかどうかを目視にて以下のように評価した。
○:透明であり、且つ均一なワニスの形態である
×:不透明である、或いは、不均一な形態である
なお、不透明である、あるいは、不均一な形態である(透明で且つ均一とならない)ワニスの形態とは、具体的にはワニス全体が白濁したり、ワニス中に白色の異物が浮遊している状態を指す。このように透明で且つ均一なワニスの形態とならない材料は、時間が経過すると層分離を引き起こし、塗膜ひいては硬化膜の性能にばらつきが発生することから、製品を安定供給することができないため、インプリント材料として不適格と判定される。
得られた結果並びにインプリント材料の成分(A)~(E)について表1(表1-1~表1-3)に示す。なお、表1(表1-1~表1-3)において、その対応する成分を加えていない場合は「-(ハイフン)」で示した。
一方、比較例1乃至比較例60において、成分(D)のシリコーン化合物を含有するが、成分(C)の溶剤を含有しないインプリント材料では、透明で且つ均一なワニスの形態として得られない材料もあった(比較例15、比較例23乃至比較例25、比較例27、比較例29、比較例31乃至比較例36)。
詳細には、比較例15、比較例23乃至比較例25、比較例27、比較例29、比較例31と、溶剤を含有する点だけが異なる実施例4、実施例39乃至実施例41、実施例43、実施例45、実施例47とを比較すると、成分(D)のシリコーン化合物の種類、添加量が同じにも関わらず、溶剤の添加により且つ均一なワニスが得られるとする結果が得られた。また、比較例32乃至比較例36においては、他成分としてアクリレート化合物若しくはウレタンアクリレート化合物を加えても均一のワニスの形態とならず、すなわちこれら化合物の添加だけでは相溶性の改善に至らないことが確認された。
以上の結果は、成分(D)のシリコーン化合物は、その種類によっては溶剤が存在しないと他の成分との相溶性が悪く、他成分としてアクリレート化合物若しくはウレタンアクリレート化合物を加えても相溶性が改善せず(比較例32乃至比較例36)、透明で且つ均一なワニスの形態とならない場合があること、すなわち、成分(D)のシリコーン化合物を配合した場合に透明で且つ均一なワニスの形態のインプリント材料を確実に得るために成分(C)の溶剤の存在が重要である点が確認された。
実施例1乃至実施例47及び比較例1乃至比較例11のインプリント材料を用いて光硬化性試験を行った。光硬化性試験は得られた各インプリント材料をトリアセチルセルロースフィルム(富士フイルム株式会社製 フジタック(登録商標)を使用)(以下、本明細書では「TACフィルム」と略称する。)上にウェット膜厚が4μmとなるようにフィルムアプリケーターを用いて塗布し、次いで、110℃のクリーンオーブンで30秒間乾燥させた。その後、TACフィルムのインプリント材料の塗布側を、前述の離型処理をしたシリコン基板上へローラー圧着させ、TACフィルム側から無電極均一照射装置にて、350mJ/cm2の露光を施し、光硬化を行った。その後、TACフィルムとシリコン基板とを剥がし、TACフィルム上に塗布・光照射したインプリント材料において、露光後の膜表面の粘稠性(タッキネス)の有無により光硬化が進行したかを確認した。なお、光硬化が進行していない場合、膜表面に粘稠性が残り、手で触れた際に膜表面が変形してしまうため、ロール・ツー・ロール方式などでパターン転写膜を製造する際、製品(膜)をロールで巻き取る際に不具合を生じ、インプリント材料として不適格と判定される。
以上のことから、成分(B)の光重合開始剤が必須成分であることが明らかとなった。
実施例1乃至実施例47及び比較例12乃至比較例14、比較例16乃至比較例22、比較例26、比較例28、比較例30、比較例37乃至比較例60で得られた各インプリント材料を、TACフィルム、ポリエチレンテレフタレートフィルム(東洋紡績株式会社 コスモシャイン(商標登録)A4100を使用)(以下、本明細書では「PETフィルム」と略称する。)、ポリメタクリル酸メチルフィルム(住友化学株式会社製 テクノロイ(商標登録)S001Gを使用)(以下、本明細書では「PMMAフィルム」と略称する。)上にウェット膜厚が4μmとなるように全自動フィルムアプリケーターを用いて塗布し、次いで、110℃のクリーンオーブンで30秒間乾燥させた。続いて各フィルムのインプリント材料の塗布面(塗膜)を、前述の離型処理を施したモスアイパターンモールド上へローラー圧着させ、フィルム側から該塗膜を無電極均一照射装置にて、350mJ/cm2の露光を施し、光硬化を行った。そしてJIS Z0237を参考にした90°剥離試験を行い、モールドのパターン形状を有する面と接着している各フィルム基材上に形成された硬化膜が、モールドのパターン形状を有する面から完全に剥がれたときの荷重を測定した。そしてフィルムの幅1cm当たりの荷重を算出し、離型力(g/cm)とした。得られた結果を表2(表2-1~表2-4)に示す。
なお、離型力試験をした後のモールドにおいて、いずれの実施例・比較例においても目視で有機物の付着は確認できず、また、モールドから転写されたパターン形成膜においても目視にて、剥がれ及び欠陥は一切確認できなかった。
前述の[光インプリント及び離型力試験]の実施後、各フィルム基材とパターン形成膜との密着性試験を行った。密着性試験はJIS K5400に従い、以下の手順にて行った。
まず、パターン形成膜を、カッターを用いてフィルム基材に達する碁盤目状の切り傷を1mm間隔にて100マス付けた。約50mmの長さのテープを碁盤目の上に粘着し、膜に対して90°の角度で瞬間的に引き剥がした。
テープ剥離後のマス目を観察し、100マスに対して剥離しなかったマス目数をxとし、密着性をx/100として評価した。本密着性試験を3回繰り返し、各評価の平均値を算出した。得られた結果を表2(表2-1~表2-4)に示す。
また、成分(C)の溶剤の割合を少なくし、固形分濃度を90質量%とした比較例54乃至比較例58のインプリント材料は、各フィルム基材への密着性がかえって低下する結果となった。
そして成分(C)の溶剤の代わりに、その他の溶剤(IPA及びTol)を用いた比較例59及び比較例60のインプリント材料にあっては、密着性が全く発現しなかった(0/100)。
また、成分(A)を含有せず、任意成分である成分(E)のみを単体で含有させた比較例49乃至比較例53のインプリント材料にあっても0.5g/cm以下の離型力を達成できず、最大で0.85g/cmにも達する非常に大きな離型力を発現するという結果となった。
Claims (18)
- (A)成分:炭素原子数2、3又は4のアルキレンオキサイドユニットを少なくとも1つ有し、且つ重合性基を少なくとも2つ有する化合物、
(B)成分:光重合開始剤、
(C)成分:インプリント材料が適用されるフィルム基材の表面部を膨潤させ又は溶解する溶剤、及び
(D)成分:シリコーン化合物、
を含むインプリント材料。 - 前記(A)成分の化合物は、前記重合性基として、アクリロイルオキシ基、メタアクリロイルオキシ基、ビニル基及びアリル基からなる群から選ばれる少なくとも1種の基を少なくとも2つ有する化合物である、請求項1に記載のインプリント材料。
- 前記(A)成分の化合物は、アルキレンオキサイドユニットとして、エチレンオキサイド、プロピレンオキサイド及びブチレンオキサイドから選ばれる少なくとも1種を少なくとも1つ有する化合物である、請求項1に記載のインプリント材料。
- 前記(B)成分が、2,4,6-トリメチルベンゾイル-ジフェニル-ホスフィンオキサイド、1-ヒドロキシ-シクロヘキシル-フェニル-ケトン又は2-ヒドロキシ-2-メチル-1-フェニル-プロパン-1-オンを含む、請求項1乃至請求項3のいずれか一項に記載のインプリント材料。
- 前記(C)成分がメチルエチルケトン、メチルイソブチルケトン、酢酸エチル、シクロヘキサノン及びプロピレングリコールモノメチルエーテルからなる群から選ばれる少なくとも1種を含有することを特徴とする、請求項1乃至請求項4のいずれか一項に記載のインプリント材料。
- 前記インプリント材料の全成分から(C)成分を除いたものとして定義される固形分の割合が、前記インプリント材料の総質量に対して10質量%乃至80質量%であることを特徴とする、請求項1乃至請求項5のいずれか一項に記載のインプリント材料。
- 前記フィルム基材が、トリアセチルセルロース、ポリエチレンテレフタレート、ポリメタクリル酸メチル又はシクロオレフィン(コ)ポリマーからなる、請求項1乃至請求項6のいずれか一項に記載のインプリント材料。
- 前記インプリント材料を前記フィルム基材上に塗布し、光硬化させた場合において得られた硬化膜と前記フィルム基材との密着性が、JIS K5400に従う試験の評価において100/100であり、かつ、
前記インプリント材料を前記フィルム基材上に塗布し、該フィルム基材上の塗膜をモールドのパターン形状を有する面に接着させ、続いて該塗膜を光硬化させ、その後フィルム基材上の硬化被膜をモールドのパターン形状を有する面から90°剥離する試験において、計測された離型力、すなわち、該フィルム基材上の硬化被膜をモールドのパターン形状を有する面から剥離したときの荷重を該フィルム基材の横幅1cmあたりに換算した値が0g/cmより大きく0.5g/cm以下である、
請求項1乃至請求項7のいずれか一項に記載のインプリント材料。 - 請求項1乃至請求項8のいずれか一項に記載のインプリント材料をフィルム基材に塗布し塗膜を得る工程、
前記塗膜を乾燥させる工程、
前記乾燥させた塗膜にモールドを押し付け加圧する、又は該加圧と共に加熱する工程、
前記塗膜と前記モールドとが接した状態で、該塗膜を硬化させる光を照射し、硬化膜を形成する工程、及び
形成された前記硬化膜を前記モールドから剥離する工程、
を有するインプリント方法。 - 前記乾燥工程における乾燥温度が60℃乃至150℃の範囲から選択される、請求項9に記載のインプリント方法。
- 請求項1乃至請求項8のうちいずれか一項に記載のインプリント材料から作製され、パターンが転写された膜。
- 請求項11に記載のパターンが転写された膜を基材上に備えた光学部材。
- 請求項11に記載のパターンが転写された膜を基材上に備えた固体撮像装置。
- 請求項11に記載のパターンが転写された膜を基材上に備えたLEDデバイス。
- 請求項11に記載のパターンが転写された膜を備えた半導体素子。
- 請求項11に記載のパターンが転写された膜を備えた太陽電池。
- 請求項11に記載のパターンが転写された膜を備えたディスプレイ。
- 請求項11に記載のパターンが転写された膜を備えた電子デバイス。
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JP7021856B2 (ja) * | 2016-03-14 | 2022-02-17 | 中国塗料株式会社 | 光硬化性樹脂組成物、硬化被膜、被膜付き基材およびその製造方法、ならびに基材に対する防曇処理方法 |
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TWI503365B (zh) | 2015-10-11 |
JPWO2013161627A1 (ja) | 2015-12-24 |
US20140216538A1 (en) | 2014-08-07 |
CN103503115A (zh) | 2014-01-08 |
JP5534282B2 (ja) | 2014-06-25 |
US9631081B2 (en) | 2017-04-25 |
KR20150004245A (ko) | 2015-01-12 |
CN103503115B (zh) | 2016-01-13 |
KR101592997B1 (ko) | 2016-02-11 |
TW201404818A (zh) | 2014-02-01 |
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