JP2005004052A - Photosensitive silicone resin composition, its hardened product and method for forming negative-type fine pattern - Google Patents
Photosensitive silicone resin composition, its hardened product and method for forming negative-type fine pattern Download PDFInfo
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- JP2005004052A JP2005004052A JP2003169200A JP2003169200A JP2005004052A JP 2005004052 A JP2005004052 A JP 2005004052A JP 2003169200 A JP2003169200 A JP 2003169200A JP 2003169200 A JP2003169200 A JP 2003169200A JP 2005004052 A JP2005004052 A JP 2005004052A
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- Prior art keywords
- silicone resin
- resin composition
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- mol
- alkali
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- 229920002050 silicone resin Polymers 0.000 title claims abstract description 93
- 239000011342 resin composition Substances 0.000 title claims abstract description 44
- 238000000034 method Methods 0.000 title abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 24
- 125000000962 organic group Chemical group 0.000 claims abstract description 23
- 238000009833 condensation Methods 0.000 claims abstract description 20
- 230000005494 condensation Effects 0.000 claims abstract description 20
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 14
- 150000002118 epoxides Chemical class 0.000 claims abstract description 13
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 13
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 11
- 150000001875 compounds Chemical class 0.000 claims abstract description 8
- 150000004756 silanes Chemical class 0.000 claims abstract description 8
- -1 acryl functional groups Chemical group 0.000 claims description 36
- 125000004432 carbon atom Chemical group C* 0.000 claims description 30
- 239000002904 solvent Substances 0.000 claims description 24
- 239000003054 catalyst Substances 0.000 claims description 23
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 21
- 229910000077 silane Inorganic materials 0.000 claims description 19
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 9
- 239000004793 Polystyrene Substances 0.000 claims description 7
- 239000003085 diluting agent Substances 0.000 claims description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 7
- 229920002223 polystyrene Polymers 0.000 claims description 7
- 239000000758 substrate Substances 0.000 claims description 7
- 239000004593 Epoxy Substances 0.000 claims description 6
- 239000006096 absorbing agent Substances 0.000 claims description 4
- 239000000049 pigment Substances 0.000 claims description 4
- 239000002518 antifoaming agent Substances 0.000 claims description 3
- 239000003963 antioxidant agent Substances 0.000 claims description 3
- 239000003112 inhibitor Substances 0.000 claims description 3
- 238000006116 polymerization reaction Methods 0.000 claims description 3
- 229910052809 inorganic oxide Inorganic materials 0.000 claims description 2
- 239000003504 photosensitizing agent Substances 0.000 claims description 2
- 239000003495 polar organic solvent Substances 0.000 claims description 2
- 239000010419 fine particle Substances 0.000 claims 1
- 238000000206 photolithography Methods 0.000 abstract description 15
- 239000003513 alkali Substances 0.000 abstract description 12
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 8
- 230000035945 sensitivity Effects 0.000 abstract description 8
- 238000003860 storage Methods 0.000 abstract description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 abstract description 6
- 125000000524 functional group Chemical group 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 4
- 239000003999 initiator Substances 0.000 abstract 1
- 230000015572 biosynthetic process Effects 0.000 description 17
- 238000003786 synthesis reaction Methods 0.000 description 17
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 14
- 238000000576 coating method Methods 0.000 description 13
- 239000011248 coating agent Substances 0.000 description 12
- 238000001723 curing Methods 0.000 description 12
- 239000000047 product Substances 0.000 description 11
- 229920005989 resin Polymers 0.000 description 11
- 239000011347 resin Substances 0.000 description 11
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 10
- 230000005540 biological transmission Effects 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 238000012643 polycondensation polymerization Methods 0.000 description 8
- 229920001296 polysiloxane Polymers 0.000 description 8
- 238000005259 measurement Methods 0.000 description 7
- 238000006068 polycondensation reaction Methods 0.000 description 7
- 239000010703 silicon Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- KBQVDAIIQCXKPI-UHFFFAOYSA-N 3-trimethoxysilylpropyl prop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C=C KBQVDAIIQCXKPI-UHFFFAOYSA-N 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 239000003377 acid catalyst Substances 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 6
- 230000018109 developmental process Effects 0.000 description 5
- 239000000975 dye Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- 230000003287 optical effect Effects 0.000 description 5
- 238000000059 patterning Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 4
- VVBLNCFGVYUYGU-UHFFFAOYSA-N 4,4'-Bis(dimethylamino)benzophenone Chemical compound C1=CC(N(C)C)=CC=C1C(=O)C1=CC=C(N(C)C)C=C1 VVBLNCFGVYUYGU-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 4
- 150000001298 alcohols Chemical class 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- ZYGHJZDHTFUPRJ-UHFFFAOYSA-N coumarin Chemical compound C1=CC=C2OC(=O)C=CC2=C1 ZYGHJZDHTFUPRJ-UHFFFAOYSA-N 0.000 description 4
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 150000002923 oximes Chemical class 0.000 description 4
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 125000003342 alkenyl group Chemical group 0.000 description 3
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 3
- 239000012965 benzophenone Substances 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 3
- 150000002576 ketones Chemical class 0.000 description 3
- 238000000016 photochemical curing Methods 0.000 description 3
- 238000007142 ring opening reaction Methods 0.000 description 3
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical group [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 3
- 238000004528 spin coating Methods 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 description 3
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 2
- BTJPUDCSZVCXFQ-UHFFFAOYSA-N 2,4-diethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(CC)=CC(CC)=C3SC2=C1 BTJPUDCSZVCXFQ-UHFFFAOYSA-N 0.000 description 2
- 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 description 2
- FLFWJIBUZQARMD-UHFFFAOYSA-N 2-mercapto-1,3-benzoxazole Chemical compound C1=CC=C2OC(S)=NC2=C1 FLFWJIBUZQARMD-UHFFFAOYSA-N 0.000 description 2
- RIWRBSMFKVOJMN-UHFFFAOYSA-N 2-methyl-1-phenylpropan-2-ol Chemical compound CC(C)(O)CC1=CC=CC=C1 RIWRBSMFKVOJMN-UHFFFAOYSA-N 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- ALYNCZNDIQEVRV-UHFFFAOYSA-N 4-aminobenzoic acid Chemical compound NC1=CC=C(C(O)=O)C=C1 ALYNCZNDIQEVRV-UHFFFAOYSA-N 0.000 description 2
- ZWMAYLMVFSCMMS-UHFFFAOYSA-N 4-ethynyl-n,n-dimethylaniline Chemical group CN(C)C1=CC=C(C#C)C=C1 ZWMAYLMVFSCMMS-UHFFFAOYSA-N 0.000 description 2
- FXFYOPQLGGEACP-UHFFFAOYSA-N 6-methylcoumarin Chemical compound O1C(=O)C=CC2=CC(C)=CC=C21 FXFYOPQLGGEACP-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- 239000004342 Benzoyl peroxide Substances 0.000 description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- DQFBYFPFKXHELB-UHFFFAOYSA-N Chalcone Natural products C=1C=CC=CC=1C(=O)C=CC1=CC=CC=C1 DQFBYFPFKXHELB-UHFFFAOYSA-N 0.000 description 2
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 2
- GUUVPOWQJOLRAS-UHFFFAOYSA-N Diphenyl disulfide Chemical compound C=1C=CC=CC=1SSC1=CC=CC=C1 GUUVPOWQJOLRAS-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 2
- 150000004056 anthraquinones Chemical class 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 235000006708 antioxidants Nutrition 0.000 description 2
- 125000003710 aryl alkyl group Chemical group 0.000 description 2
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 description 2
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000006364 carbonyl oxy methylene group Chemical group [H]C([H])([*:2])OC([*:1])=O 0.000 description 2
- 235000005513 chalcones Nutrition 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- 235000001671 coumarin Nutrition 0.000 description 2
- 229960000956 coumarin Drugs 0.000 description 2
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 2
- 239000012024 dehydrating agents Substances 0.000 description 2
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 2
- OTARVPUIYXHRRB-UHFFFAOYSA-N diethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](C)(OCC)CCCOCC1CO1 OTARVPUIYXHRRB-UHFFFAOYSA-N 0.000 description 2
- PKTOVQRKCNPVKY-UHFFFAOYSA-N dimethoxy(methyl)silicon Chemical compound CO[Si](C)OC PKTOVQRKCNPVKY-UHFFFAOYSA-N 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 229940093915 gynecological organic acid Drugs 0.000 description 2
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 125000000555 isopropenyl group Chemical group [H]\C([H])=C(\*)C([H])([H])[H] 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 235000005985 organic acids Nutrition 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 239000002798 polar solvent Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 150000005622 tetraalkylammonium hydroxides Chemical class 0.000 description 2
- HJUGFYREWKUQJT-UHFFFAOYSA-N tetrabromomethane Chemical compound BrC(Br)(Br)Br HJUGFYREWKUQJT-UHFFFAOYSA-N 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- DQFBYFPFKXHELB-VAWYXSNFSA-N trans-chalcone Chemical compound C=1C=CC=CC=1C(=O)\C=C\C1=CC=CC=C1 DQFBYFPFKXHELB-VAWYXSNFSA-N 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- JNELGWHKGNBSMD-UHFFFAOYSA-N xanthone Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3OC2=C1 JNELGWHKGNBSMD-UHFFFAOYSA-N 0.000 description 2
- CNGTXGHYZBQUQS-UHFFFAOYSA-N ((1-(2-methoxyethoxy)ethoxy)methyl)benzene Chemical compound COCCOC(C)OCC1=CC=CC=C1 CNGTXGHYZBQUQS-UHFFFAOYSA-N 0.000 description 1
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- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- UOKUUKOEIMCYAI-UHFFFAOYSA-N trimethoxysilylmethyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)COC(=O)C(C)=C UOKUUKOEIMCYAI-UHFFFAOYSA-N 0.000 description 1
- PHPGKIATZDCVHL-UHFFFAOYSA-N trimethyl(propoxy)silane Chemical compound CCCO[Si](C)(C)C PHPGKIATZDCVHL-UHFFFAOYSA-N 0.000 description 1
- SIOVKLKJSOKLIF-HJWRWDBZSA-N trimethylsilyl (1z)-n-trimethylsilylethanimidate Chemical compound C[Si](C)(C)OC(/C)=N\[Si](C)(C)C SIOVKLKJSOKLIF-HJWRWDBZSA-N 0.000 description 1
- NLSXASIDNWDYMI-UHFFFAOYSA-N triphenylsilanol Chemical compound C=1C=CC=CC=1[Si](C=1C=CC=CC=1)(O)C1=CC=CC=C1 NLSXASIDNWDYMI-UHFFFAOYSA-N 0.000 description 1
- VUWVDNLZJXLQPT-UHFFFAOYSA-N tripropoxy(propyl)silane Chemical compound CCCO[Si](CCC)(OCCC)OCCC VUWVDNLZJXLQPT-UHFFFAOYSA-N 0.000 description 1
- GMTKSNCGYCTUCR-UHFFFAOYSA-N tris(ethenyl)-(2-methoxyethoxy)silane Chemical compound COCCO[Si](C=C)(C=C)C=C GMTKSNCGYCTUCR-UHFFFAOYSA-N 0.000 description 1
- FBGNFSBDYRZOSE-UHFFFAOYSA-N tris(ethenyl)-ethoxysilane Chemical compound CCO[Si](C=C)(C=C)C=C FBGNFSBDYRZOSE-UHFFFAOYSA-N 0.000 description 1
- 235000019156 vitamin B Nutrition 0.000 description 1
- 239000011720 vitamin B Substances 0.000 description 1
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- Materials For Photolithography (AREA)
- Silicon Polymers (AREA)
Abstract
Description
【0001】
【発明の属する技術分野】
本発明は、保存安定性に優れ、光開始剤を用いて光硬化することが可能であり、未硬化状態でアルカリ性水溶液やアルコール、ケトン、エーテルといった極性溶媒に可溶であり、硬化後はこれらの溶剤に難溶で、フォトリソグラフィーによるパターン形成ができ、感度、解像性に優れ、耐熱性、耐湿性、機械的特性、光透過性等に優れた硬化被膜を与える感光性シリコーン樹脂組成物、及びその硬化物、並びにこの組成物を用いたフォトリソグラフィーによるネガ型微細パターンの形成方法に関するものである。
【0002】
【従来の技術】
高分子材料であるシリコーン樹脂は、耐熱性、耐寒性、化学的安定性、接着性、電気特性、透明性などの優れた特性を有し、高精度製品が得られることからも、光部品、電気電子部品といった用途に多く用いられている。更に光硬化性を付与することで、フォトリソグラフィーを用いたパターニングを行うことができ、レジスト材料、光微細造形材料や光導波路の素材などとしても使用されている。
【0003】
しかし、シリコーン樹脂の場合、その樹脂の特徴から水溶液系で解像性に優れた材料は少ない。アルカリ可溶性シリコーン樹脂としては、高感度、高解像性を示すものとして、エポキシ変性シリコーンを酸加水分解させた例が挙げられる。特開平3−288857号、特開平4−070662号、特開平4−338958号公報(特許文献1〜3)に示されたネガ型シリコーンレジストの例では、光酸発生剤を使用してリソグラフィーを行っている。光酸発生剤は優れた触媒であるが、シロキサンの縮合触媒として優れているものは限られ、毒性の面から更に限られるため、高価である。また、現像前の加熱処理(PEB)により、露光からPEBまでの時間が長いと発生した酸が拡散して反応するため、解像性に影響を及ぼす。更に、樹脂の特性からアルカリ可溶性シリコーン樹脂と酸発生剤を混合した組成物の保存安定性は良好とは言えない。
【0004】
また、特開平5−100431号公報(特許文献4)では、アルカリ可溶性ポリシロキサンにアジド化合物を含有させてなる組成物が報告されているが、毒性の面からアジド化合物の種類や含有量が限られ、使用できる波長域も限られてくる。
【0005】
【特許文献1】
特開平3−288857号公報
【特許文献2】
特開平4−070662号公報
【特許文献3】
特開平4−338958号公報
【特許文献4】
特開平5−100431号公報
【0006】
【発明が解決しようとする課題】
本発明は、上記事情に鑑みなされたもので、経済的で、加工性の高いシリコーン樹脂を用い、保存安定性に優れ、光硬化前はアルカリ可溶であり、光硬化後にアルカリ不溶となり、光硬化において光酸発生剤を使用せずにフォトリソグラフィーによるネガ型のパターニングを行うことができ、高感度、高解像性を有し、耐熱性、耐湿性、耐薬品性、機械的強度に優れた硬化物となり得る感光性シリコーン樹脂組成物、及びその硬化物、並びに該組成物を用いたフォトリソグラフィーによるネガ型微細パターンの形成方法を提供することを目的とする。
【0007】
【課題を解決するための手段及び発明の実施の形態】
本発明者は、上記目的を達成するため鋭意検討を行った結果、特定量の一般式(1)で表されるエポキシ変性オルガノキシシラン及び特定量の一般式(2)で表される(メタ)アクリル変性オルガノキシシラン、又はこれらとオルガノキシシランとの混合物を共加水分解縮合して得られ、エポキシドの一部又は全部が開環して得られる水酸基及び(メタ)アクリル官能基を有する重量平均分子量が500〜50,000(GPCによるポリスチレン換算値)のアルカリ可溶性シリコーン樹脂、及び光開始剤を含有してなる感光性シリコーン樹脂組成物が、保存安定性に優れ、フォトリソグラフィーによるネガ型のパターニングをアルカリ現像で行うことができ、且つ高感度、高解像性であり、また、この硬化被膜が、耐熱性、耐湿性、機械的強度、透明性に優れることを見出した。
【0008】
即ち、上記アルカリ可溶性シリコーン樹脂と、光酸発生剤ではなく光開始剤と、この場合、好ましくは更に縮合触媒を使用することにより、現像前の加熱処理(PEB)を現像後に行うことで、解像性に影響を与えずに樹脂の硬化度を上げることができ、耐熱性、耐湿性、耐薬品性、機械的強度に優れる硬化物を得ることができることを知見し、本発明をなすに至ったものである。
【0009】
従って、本発明は、下記に示す感光性シリコーン樹脂組成物、及びその硬化物、並びにこの組成物を用いたフォトリソグラフィーによるネガ型微細パターンの形成方法を提供する。
[請求項1] (A)(i)下記一般式(1):
R1 XR2 YSi(OR3)4−X−Y (1)
(式中、R1は加水分解性のエポキシドを一つ以上有する炭素原子数2〜30の一価の有機基を示し、R2は炭素原子数1〜20の一価炭化水素基を示し、R3は水素原子、又は炭素原子数1〜10の非置換もしくは置換の一価炭化水素基を示す。Xは1〜3の整数であり、Yは0〜2の整数であり、1≦X+Y≦3を満足する。)
で表される1種又は2種以上のシラン化合物と、(ii)下記一般式(2):
R4 xR2 YSi(OR3)4−X−Y (2)
(式中、R4は(メタ)アクリル官能基を一つ以上有する炭素原子数3〜30の一価炭化水素基を示し、R2は炭素原子数1〜20の一価炭化水素基を示し、R3は水素原子、又は炭素原子数1〜10の非置換もしくは置換の一価炭化水素基を示す。Xは1〜3の整数であり、Yは0〜2の整数であり、1≦X+Y≦3を満足する。 )
で表される1種又は2種以上のシラン化合物との混合物、又はこれら(i),(ii)成分と、(iii)下記一般式(3):
R2 ZSi(OR3)4−Z (3)
(式中、R2は炭素原子数1〜20の一価炭化水素基を示し、R3は水素原子、又は炭素原子数1〜10の非置換もしくは置換の一価炭化水素基を示す。Zは0〜3の整数である。)
で表される1種又は2種以上のシラン化合物との混合物を、R1で表される有機基数がケイ素原子に結合したアルコキシ基を除く全有機基数に対して10モル%以上、且つR4で表される有機基数が同様にケイ素原子に結合したアルコキシ基を除く全有機基数に対して5モル%以上の割合で、更にモノオルガノトリオルガノキシシラン化合物とテトラオルガノキシシラン化合物との合計量が全シラン化合物の40モル%以上となる割合で共加水分解縮合することにより得られ、重量平均分子量が500〜50,000(GPCによるポリスチレン換算値)であるアルカリ可溶性シリコーン樹脂、及び(B)光開始剤を含有してなる感光性シリコーン樹脂組成物。
[請求項2] 更に、縮合触媒を含有することを特徴とする請求項1記載の感光性シリコーン樹脂組成物。
[請求項3] 更に、溶剤及び/又は反応性希釈剤を含有することを特徴とする請求項1又は2記載の感光性シリコーン樹脂組成物。
[請求項4] 更に、エポキシ硬化剤、光増感剤、光吸収剤、脱水剤、無機酸化物微粒子、重合禁止剤、酸化防止剤、消泡剤、レベリング剤及び顔料から選択される1種又は2種以上を含有することを特徴とする請求項1乃至3のいずれか1項に記載の感光性シリコーン樹脂組成物。
[請求項5] 請求項1乃至4のいずれか1項に記載の感光性シリコーン樹脂組成物の硬化物。
[請求項6] 基体上に請求項1乃至4のいずれか1項に記載の感光性シリコーン樹脂組成物の膜を形成し、この膜の所用部分を露光した後、この膜をアルカリ水溶液又は極性有機溶媒で処理して非露光部分を溶解除去し、上記露光部分に対応した形状の上記感光性シリコーン樹脂組成物の光硬化膜パターンを形成することを特徴とするネガ型微細パターンの形成方法。
【0010】
以下、本発明を詳細に説明する。
本発明の感光性シリコーン樹脂組成物は、(A)(i)加水分解可能なエポキシドを有するオルガノキシシランを含有するシラン及び(ii)光重合可能な(メタ)アクリル構造を有するオルガノキシシランを含有するシラン、又はこれらと(iii)オルガノキシシランとの混合物を共加水分解縮合して得られ、エポキシドの一部又は全部が開環して得られる水酸基及び(メタ)アクリル官能基を有する重量平均分子量が500〜50,000(GPCによるポリスチレン換算値)のアルカリ可溶性シリコーン樹脂、及び(B)光開始剤、好ましくは更に縮合触媒を含有するものである。
【0011】
アルカリ可溶性シリコーン樹脂
本発明のアルカリ可溶性シリコーン樹脂は、(i)下記一般式(1)で表される加水分解可能なエポキシドを1個又は2個以上有するエポキシ変性オルガノキシシランの1種又は2種以上、及び(ii)下記一般式(2)で表される光重合可能な(メタ)アクリル構造を1個又は2個以上有する(メタ)アクリル変性オルガノキシシランの1種又は2種以上、又はこれら(i),(ii)成分と、(iii)下記一般式(3)で表されるシラン化合物の共加水分解縮合物で、分岐した構造を有するシリコーン樹脂であるが、下記一般式(1)で表されるエポキシ変性オルガノキシシランの1種又は2種以上と、下記一般式(2)で表される(メタ)アクリル変性オルガノキシシランの1種又は2種以上と、下記一般式(3)で表されるシラン化合物の1種又は2種以上との共加水分解縮合物であることが好ましい。
【0012】
R1 XR2 YSi(OR3)4−X−Y (1)
R4 XR2 YSi(OR3)4−X−Y (2)
R2 ZSi(OR3)4−Z (3)
(式中、R1は加水分解性のエポキシドを一つ以上有する炭素原子数2〜30の一価の有機基を示し、R2は炭素原子数1〜20の一価炭化水素基を示し、R3は水素原子、又は炭素原子数1〜10の非置換もしくは置換の一価炭化水素基を示し、R4は(メタ)アクリル官能基を一つ以上有する炭素原子数3〜30の一価炭化水素基を示す。Xは1〜3の整数であり、Yは0〜2の整数であり、1≦X+Y≦3を満足する。Zは0〜3の整数である。)
【0013】
ここで、上記R1で表される炭素原子数2〜30、好ましくは炭素原子数3〜20、より好ましくは炭素原子数6〜12の加水分解性のエポキシドを1個又は2個以上含む一価の有機基としては、特に制限されるものではないが、具体的には、例えば、グリシジル基、グリシドキシメチル基、2−グリシドキシエチル基、3−グリシドキシプロピル基、2−(3,4−エポキシシクロヘキシル)エチル基、2−(2,3−エポキシシクロヘキシル)エチル基、3−(N−アリル−N−グリシジル)アミノプロピル基、3−(N,N−ジグリシジル)アミノプロピル基、3−(N−グリシジル)アミノプロピル基、3−(N−メチル−N−グリシジル)アミノプロピル基等が挙げられる。目的により重水素化した有機基も使用できる。
【0014】
上記R2で表される炭素原子数1〜20の一価炭化水素基としては、炭素原子数1〜10のアルキル基又はアルケニル基、炭素原子数6〜20のアリール基又はアラルキル基が好ましい。炭素原子数1〜10のアルキル基、アルケニル基としては、例えば、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、tert−ブチル基、ペンチル基、ネオペンチル基、ヘキシル基、ヘプチル基、シクロヘキシル基、シクロヘプチル基、オクチル基、α−エチルヘキシル基、ビニル基、アリル基、プロペニル基、イソプロペニル基、ブテニル基等が挙げられる。中でも好ましいのはメチル基、エチル基、ビニル基であり、重水素化したものも使用できる。また、炭素原子数6〜20のアリール基、アラルキル基としては、例えば、フェニル基、ベンジル基、トリル基、スチリル基等が挙げられる。中でも好ましいのはフェニル基であり、重水素化した芳香族炭化水素基も使用できる。
【0015】
上記R3で表される炭素原子数1〜10の非置換もしくは置換の一価炭化水素基としては、炭素原子数1〜10のアルキル基又はアルケニル基が好ましく、またアルコキシ置換アルキル基であってもよい。具体的には、例えば、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、tert−ブチル基、ペンチル基、ネオペンチル基、ヘキシル基、ヘプチル基、シクロヘキシル基、シクロヘプチル基、オクチル基、α−エチルヘキシル基、ビニル基、アリル基、プロペニル基、イソプロペニル基、ブテニル基等が挙げられる。中でも好ましいのはメチル基、エチル基、ビニル基であり、重水素化したものも使用できる。
【0016】
上記式中のR4は、アクリル官能基又はメタクリル官能基を一つ以上含む炭素原子数3〜30、好ましくは5〜20、より好ましくは5〜10の一価炭化水素基であり、アクリル官能基又はメタクリル官能基の具体例としては、CH2=CHCOO−、CH2=C(CH3)COO−、CH2=CHCO−、CH2=C(CH3)CO−等が挙げられる。このような(メタ)アクリル官能基を含むR4の一価炭化水素基の具体例としては、特に制限されるものではないが、CH2=CHCOOCH2CH2−、CH2=C(CH3)COOCH2CH2−、[CH2=C(CH3)COOCH2]3C−CH2−、(CH2=CHCOOCH2)3C−CH2−、(CH2=CHCOOCH2)2CH(C2H5)CH2−等の、1個又は2個以上のアクリロイロキシ基又はメタクリロイロキシ基で置換されたアルキル基などが挙げられるが、好ましくはCH2=CHCOOCH2−、CH2=C(CH3)COOCH2−、CH2=CHCOOCH2CH2CH2−、CH2=C(CH3)COOCH2CH2CH2−である。目的により重水素化した有機基も使用できる。
【0017】
上記一般式(1)で表されるエポキシ変性オルガノキシシランの具体例としては、例えば、3−グリシドキシプロピルトリメトキシシラン、2−(3,4−エポキシシクロヘキシルエチル)トリメトキシシラン、3−グリシドキシプロピルトリエトキシシラン、ジメチルエトキシ−3−グリシドキシプロピルシラン、ジエトキシ−3−グリシドキシプロピルメチルシラン等が挙げられる。
【0018】
上記一般式(2)で表される(メタ)アクリル変性オルガノキシシランの具体例としては、例えば、3−メタクリロキシプロピルトリメトキシシラン、3−アクリロキシプロピルトリメトキシシラン、3−メタクリロキシプロピルトリエトキシシラン、3−アクリロキシプロピルトリエトキシシラン、メタクリロキシプロペニルトリメトキシシラン、メタクリロキシプロペニルトリエトキシシラン、メタクリロキシメチルトリメトキシシラン、メタクリロキシメチルトリエトキシシラン、メタクリロキシプロピルトリス(メトキシエトキシ)シラン、3−メタクリロキシプロピルジメトキシメチルシラン、3−メタクリロキシプロピルジエトキシメチルシラン等が挙げられる。
【0019】
上記一般式(3)で表されるシラン化合物の具体例としては、例えば、メチルトリメトキシシラン、メチルトリエトキシシラン、メチルトリプロポキシシラン、メチルトリブトキシシラン、エチルトリメトキシシラン、エチルトリエトキシシラン、エチルトリプロポキシシラン、エチルトリブトキシシラン、プロピルトリメトキシシラン、プロピルトリエトキシシラン、プロピルトリプロポキシシラン、プロピルトリブトキシシラン、ビニルトリエトキシシラン、ビニルトリ(メトキシエトキシ)シラン、フェニルトリメトキシシラン、フェニルトリエトキシシラン、フェニルトリプロポキシシラン、ベンジルトリメトキシシラン、ベンジルトリエトキシシラン、p−スチリルトリメトキシシラン等のモノオルガノトリオルガノキシシラン、ジメチルジメトキシシラン、ジメチルジエトキシシラン、ジメチルジプロポキシシラン、ジメチルジブトキシシラン、ジエチルジメトキシシラン、ジエチルジエトキシシラン、ジエチルジプロポキシシラン、ジエチルジブトキシシラン、ジプロピルジメトキシシラン、ジプロピルジエトキシシラン、ジプロピルジプロポキシシラン、ジプロピルジブトキシシラン、ジビニルジエトキシシラン、ジビニルジ(メトキシエトキシ)シラン、ジフェニルジヒドロキシシラン、3−メタクリロキシプロピルメチルジメトキシシラン、3−メタクリロキシプロピルメチルジエトキシシラン、3−(グリシドキシプロピル)メチルジメトキシシラン、3−(グリシドキシプロピル)メチルジエトキシシラン等のジオルガノジオルガノキシシラン、トリメチルメトキシシラン、トリメチルエトキシシラン、トリメチルプロポキシシラン、トリメチルブトキシシラン、トリエチルメトキシシラン、トリエチルエトキシシラン、トリエチルプロポキシシラン、トリエチルブトキシシラン、トリプロピルメトキシシラン、トリプロピルエトキシシラン、トリプロピルプロポキシシラン、トリプロピルブトキシシラン、トリビニルエトキシシラン、トリビニル(メトキシエトキシ)シラン、トリフェニルヒドロキシシラン、3−メタクリロキシプロピルジメチルメトキシシラン、3−メタクリロキシプロピルジメチルエトキシシラン、3−(グリシドキシプロピル)ジメチルメトキシシラン、3−(グリシドキシプロピル)ジメチルエトキシシラン等のトリオルガノモノオルガノキシシラン、テトラメトキシシラン、テトラエトキシシラン、テトラブトキシシラン等のテトラオルガノキシシランが挙げられる。
【0020】
本発明において、上記一般式(1),(2)及び(3)で表されるシラン化合物の混合割合としては、一般式(1)で表されるエポキシ変性オルガノキシシランのR1で表される有機基数がケイ素原子に結合したアルコキシ基を除く全有機基に対して10モル%以上、好ましくは20〜90モル%、更に好ましくは25〜75モル%、且つ一般式(2)で表される(メタ)アクリル変性オルガノキシシランのR4で表される有機基数が同様にケイ素原子に結合したアルコキシ基を除く全有機基に対して5モル%以上、好ましくは10〜80モル%、更に好ましくは20〜70モル%となる量である。ここで、R1で表される有機基数が10モル%未満であると、アルカリ可溶性が悪くなり、R4で表される有機基数が5モル%未満であると光硬化性に劣り、解像性が悪くなる。
【0021】
また、必要に応じて添加される一般式(3)で表されるシラン化合物において、モノオルガノトリオルガノキシシランは、全シラン量の0〜85モル%、特に20〜70モル%の割合で混合することが好ましく、またジオルガノジオルガノキシシランは、全シラン量の0〜40モル%、特に0〜20モル%で混合することが好ましく、更にトリオルガノモノオルガノキシシランは、一般式(1)のシラン化合物のモル量に対して0〜50モル%、特に0〜25モル%の割合で混合することが好ましい。一般式(3)のシランがテトラオルガノキシシランの場合は、全シラン量の0〜30モル%、特に0〜20モル%の割合で混合することが好ましい。
【0022】
更に、本発明においては、使用されるシラン化合物中のモノオルガノトリオルガノキシシラン化合物とテトラオルガノキシシラン化合物の合計量が40モル%以上、好ましくは50〜100モル%、より好ましくは60〜100モル%であることが必要である。40モル%未満であると、未硬化状態でのタックフリー性が悪くなる。
【0023】
アルカリ可溶性シリコーン樹脂の製造方法としては、特に限定されないが、例えば、一般式(1),(2)及び(3)で表されるシラン化合物を用いる場合、先ず一般式(1)で表されるエポキシ変性オルガノキシシランに、一般式(2)で表される(メタ)アクリル変性オルガノキシシランと、一般式(3)で表されるシラン化合物を混合し、酸触媒を必要に応じて溶媒と共に加え、酸性条件下での共加水分解及び縮重合により、エポキシドの一部又は全部が開環して得られる水酸基及び(メタ)アクリル官能基を有する共加水分解縮合物を得ることができる。
【0024】
本発明の共加水分解は、前述の通り、酸触媒の存在下に行う。酸触媒としては、公知の酸触媒である無機酸及び有機酸を用いることができ、具体的には、例えば、塩酸、硫酸、フッ酸等の無機酸や、酢酸、シュウ酸等の有機酸が挙げられる。中でも好ましいのは塩酸、酢酸、シュウ酸である。
【0025】
酸共加水分解は、通常、0〜50℃で60分間以上行うことが好ましい。このようにして得られる共加水分解物は、次に縮重合に供される。この縮重合反応の条件は、シリコーン樹脂の分子量をコントロールする上で重要である。加水分解速度は速いので、この加水分解反応時間中に縮重合反応も進行しているが、例えば重量平均分子量1,000以上(GPCによるポリスチレン換算値)の該シリコーン樹脂を得るためには、更に縮重合反応を進行させるため、溶媒及び生成するアルコール類を加熱留去しながら反応させる。この場合、縮重合反応は、通常溶媒の沸点より高い温度で120〜180分間行うことが好ましい。
【0026】
このようにして共加水分解及び縮重合を経て得られた共加水分解縮重合物には、アルコキシ基等のオルガノオキシ基及びシラノール、カルビノールが残存している。この場合、得られた共加水分解縮重合物に含まれる水酸基の一部のみをシリル化剤を用いてトリアルキルシロキシ基に転換することにより、保存安定性を向上させた共加水分解縮重合物を得ることもできる。シリル化剤としては、ヘキサメチルジシラザン、テトラメチルジブチルジシラザン、ヘキサエチルジシラザン、テトラメチルジビニルジシラザン、テトラビニルジメチルジシラザン、N−トリメチルシリルアセトアミド、N,O−ビス(トリメチルシリル)アセトアミド、N−トリメチルシリルイミダゾール等が挙げられるが、好ましくはヘキサアルキルジシラザンであり、特にヘキサメチルジシラザンが好ましい。
【0027】
上記の方法により、一般式(1),(2)及び(3)で表されるシラン化合物を共加水分解縮合して得られたアルカリ可溶性シリコーン樹脂において、一般式(1)で表されるシランが樹脂のアルカリ可溶性を高めている。
【0028】
上記一般式(1)のR1は、エポキシドを含有し、このエポキシドは加水分解縮合反応中に酸又はアルカリによって環開裂し、水酸基を生じるが、その水酸基は生成したシリコーン樹脂のアルカリ可溶性を高める働きをし、フォトリソグラフィーによるパターニング性能を向上させる。
【0029】
R1のエポキシドが開環した有機基は、具体的には、−CH(OH)CH(B)−(但し、Bは使用した酸(HB)の塩基部分もしくはOHを表す)で示される構造をしている。
【0030】
このR1で表される有機基中のエポキシドが開環した有機基は、ケイ素原子に結合したアルコキシ基を除く全有機基の10モル%以上、好ましくは15〜90モル%含まれていることが好ましい。10モル%未満では、アルカリ現像液に対する溶解性が悪くなる場合がある。
【0031】
該アルカリ可溶性シリコーン樹脂は、重量平均分子量がGPCによるポリスチレン換算値で500〜50,000であり、好ましくは1,000〜20,000である。平均分子量が小さすぎると耐熱性、耐湿性に優れた被膜が得られず、また大きすぎるとアルカリ可溶性が低下する。なお、アルカリ可溶性シリコーン樹脂の分子量は、縮重合反応の反応時間を変えることにより調整することができる。
【0032】
光開始剤
本発明に用いる光開始剤としては、通常光開始剤として使用されているものであれば特に制限はない。光開始剤の具体的な例として、ベンゾフェノン、2−クロロベンゾフェノン、p,p’−ビスジメチルアミノベンゾフェノン、o−ベンゾイル安息香酸メチル、4,4−ビス(ジメチルアミノ)ベンゾフェノン、4,4−ビス(ジエチルアミノ)ベンゾフェノン、4,4−ジクロロベンゾフェノン、4−ベンゾイル−4−メチルフェニルケトン、ジベンジルケトン、フルオレノン、2,2−ジメチル−2−ヒドロキシアセトフェノン、アセトフェノン、2,2−ジエトキシアセトフェノン、p−ジメチルアセトフェノン、2,3−ジエトキシアセトフェノン、2,2−ジメトキシ−2−フェニル−2−フェニルアセトフェノン、2−ヒドロキシ−2−メチルプロピオフェノン、p−t−ブチルジクロロアセトフェノン、p−ジメチルアミノプロピオフェノン、ジクロロアセトフェノン、トリクロロアセトフェノン、ミヒラーケトン、キサントン、p−tert−ブチルアセトフェノンチオキサントン、ベンジルジメチルケタール、チオキサンソン、2,4−ジエチルチオキサントン、2−メチルチオキサントン、2−クロロチオキサントン、2−イソプロピルチオキサントン、ジエチルチオキサントン、ベンジル、ベンジルジメチルケタール、ベンジルメトキシエチルアセタール、ベンゾイン、ベンゾインメチルエーテル、ベンゾインイソプロピルエーテル、ベンゾインブチルエーテル、2−エチルアントラキノン、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、2,3−ジフェニルアントラキノン、アントラキノン、2−t−ブチルアントラキノン、2−アミノアントラキノン、β−クロルアントラキノン、アントロン、ベンズアントロン、ジベンズスベロン、メチレンアントロン、2−フェニル−1,2−ブタジオン−2−(o−メトキシカルボニル)オキシム、1−フェニルプロパンジオン−2−(o−エトキシカルボニル)オキシム、1,3−ジフェニルプロパントリオン−2−(o−エトキシカルボニル)オキシム、1−フェニル−1,2−プロパンジオン−2−(o−ベンゾイル)オキシム、(2−アクリロイルオキシエチル)(4−ベンゾイルベンジル)ジメチル臭化アンモニウム、(4−ベンゾイルベンジル)塩化トリメチルアンモニウム、ベンゾイルパーオキサイド、クメンパーオキサイド、チオフェノール、2−ベンゾチアゾールチオール、2−ベンゾオキサゾールチオール、2−ベンズイミダゾールチオール、2−メルカプトベンゾイミダゾール、2−メルカプトベンゾオキサゾール、2−メルカプトベンゾチアゾール、2−メチル−[4−(メチルチオ)フェニル]−2−モルフォリノ−1−プロパノン、ナフタレンスルフォニルクロライド、キノリンスルホニルクロライド、N−フェニルチオアクリドン、4,4−アゾビスイソブチロニトリル、ジフェニルジスルフィド、ベンズチアゾールジスルフィド、ジフェニルスルフィド、デシルフェニルスルフィド、ジ−n−ブチルジスルフィド、ジベンジルスルフィド、ジベンゾイルジスルフィド、ジアセチルジスルフィド、ジボルニルジスルフィド、ジメトキシキサントゲンジスルフィド、テトラメチルチウラムモノスルフィド、テトラメチルチウラムテトラスルフィド、ベンジルジメチルジチオカーバメイトキノキサリン、1,3−ジオキソラン、N−ラウリルピリジニウム、トリフェニルホスフィン、カンファーキノン、四臭素化炭素、トリブロモフェニルスルホン、過酸化ベンゾイル等、及び3,3−カルボニルビス(7−ジエチルアミノクマリン)、6−メチルクマリンなどのクマリン系色素、エオシン、メチレンブルーなどの光還元性の色素とアスコルビン酸、トリエタノールアミンなどの還元剤の組み合わせなどが挙げられる。これらの中から、用いる光源の波長領域に吸収を持ち、使用する樹脂もしくは溶媒に溶解又は分散するものが好ましい。
【0033】
光開始剤の配合量としては、アルカリ可溶性シリコーン樹脂100質量部に対して、0.001〜20質量部が好ましく、より好ましくは0.01〜10質量部であり、更に好ましくは0.1〜5質量部である。0.001質量部より少ないと光重合開始能に支障をきたすおそれがあり、20質量部より多いと硬化深度が得にくくなるおそれがある。
【0034】
縮合触媒
本発明においては、更に縮合触媒を用いることができる。縮合触媒としては、通常、シラノール、アルコキシ基又は水酸基を縮合せしめる縮合触媒として使用されているものであれば特に制限はないが、例えば、テトラブチルチタネート、テトラプロピルチタネート、チタンテトラアセチルアセトナートなどのチタン系触媒、ジブチルスズジラウレート、ジブチルスズマレエート、ジブチルスズアセテート、オクチル酸スズ、ナフテン酸スズ、ジブチルスズアセチルアセトナートなどのスズ系触媒、アルミニウムトリスアセチルアセトナート、アルミニウムトリスエチルアセトアセテート、ジイソプロポキシアルミニウムエチルアセトアセテートなどのアルミニウム系触媒、ブチルアミン、オクチルアミン、ジブチルアミン、モノエタノールアミン、ジエタノールアミン、トリエタノールアミン、ジエチレントリアミン、トリエチレンテトラミン、オレイルアミン、シクロヘキシルアミン、ベンジルアミン、ジエチルアミノプロピルアミン、キシリレンジアミン、トリエチレンジアミン、グアニジン、ジフェニルグアニジン、2,4,6−トリス(ジメチルアミノメチル)フェノール、モルホリン、N−メチルモルホリン、2−エチル−4−メチルイミダゾール、DBUなどのアミン系触媒、γ−アミノプロピルトリメトキシシラン、N−(β−アミノエチル)アミノプロピルメチルジメトキシシランなどのアミノ基を有するシランカップリング剤などのシラノール縮合触媒、また、その他の酸性触媒、塩基性触媒などの公知のシラノール縮合触媒などが挙げられる。これらの触媒は単独又は2種以上併用してもよい。
【0035】
縮合触媒を用いる場合、その配合量は、アルカリ可溶性シリコーン樹脂100質量部に対して0.01〜20質量部であることが好ましく、より好ましくは0.1〜10質量部、更に好ましくは0.1〜3質量部である。縮合触媒の配合量が少なすぎると、硬化速度が遅くなるなど添加効果が得られないおそれがあり、一方多すぎると、得られる硬化物の強度などの物性が低下するおそれがある。
【0036】
溶剤及び反応性希釈剤
本発明の感光性シリコーン樹脂組成物には、溶剤及び反応性希釈剤を添加することができる。溶剤としては、上述したアルカリ可溶性シリコーン樹脂と相溶するものであれば特に制限はない。例えば、テトラヒドロフラン、ジグライム、トリグライムなどのエーテル類、メチルエチルケトン、メチルイソブチルケトンなどのケトン類、メタノール、エタノール、プロパノール、ブタノール、2−プロパノール、1−メトキシ−2−プロパノール、2−エトキシエタノール、2−エチルヘキシルアルコール、1,4−ブタンジオール、エチレングリコール、プロピレングリコールなどのアルコール類などが挙げられる。反応性希釈剤としては、ビニルエーテル類、ビニルアミド類、エポキシ樹脂、アクリル樹脂、変性シリコーン樹脂、オキセタン類、アリルフタレート類、アジピン酸ビニルなどが挙げられる。
【0037】
溶剤の使用量は、アルカリ可溶性シリコーン樹脂100質量部に対して1,000質量部以下(0〜1,000質量部)、特に10〜500質量部が好ましい。また、反応性希釈剤の使用量は、アルカリ可溶性シリコーン樹脂100質量部に対して100質量部以下(0〜100質量部)、特に10〜50質量部が好ましい。
【0038】
その他の成分
本発明の感光性シリコーン樹脂組成物には、フォトリソグラフィー特性を失わない範囲で必要により、その他の成分を均一に混合することもできる。
【0039】
例えば、エポキシ硬化剤として、アミン化合物類、イミダゾール化合物、カルボン酸類、フェノール類、第4級アンモニウム塩類等が挙げられる。これらのエポキシ基硬化剤の使用により、得られる被膜の耐熱性、耐湿性、耐溶剤性、耐酸性、耐メッキ性、密着性、電気特性及び機械的強度等を向上させることができる。エポキシ硬化剤の使用量は、アルカリ可溶性シリコーン樹脂100質量部に対し、通常、20質量部以下(即ち0〜20質量部)でよく、好ましくは0.01〜20質量部が好ましく、0.01〜10質量部がより好ましく、0.1〜5質量部が更に好ましい。
【0040】
増感剤は、感度を向上させるために添加されるものである。増感剤の具体例としては、2,4−ジエチルチオキサントン、イソプロピルチオキサントン、2,3−ビス(4−ジエチルアミノベンザル)シクロペンタノン、2,6−ビス(4−ジメチルアミノベンザル)シクロヘキサノン、2,6−ビス(4−ジメチルアミノベンザル)−4−メチルシクロヘキサノン、ミヒラーケトン、4,4−ビス(ジエチルアミノ)ベンゾフェノン、4,4−ビス(ジメチルアミノ)カルコン、4,4−ビス(ジエチルアミノ)カルコン、p−ジメチルアミノシンナミリデンインダノン、p−ジメチルアミノベンジリデンインダノン、2−(p−ジメチルアミノフェニルビニレン)イソナフトチアゾール、1,3−ビス(4−ジメチルアミノフェニルビニレン)イソナフトチアゾール、1,3−ビス(4−ジメチルアミノベンザル)アセトン、1,3−カルボニルビス(4−ジエチルアミノベンザル)アセトン、3,3−カルボニルビス(7−ジエチルアミノクマリン)、N−フェニル−N−エチルエタノールアミン、N−フェニルエタノールアミン、N−トリルジエタノールアミン、ジメチルアミノ安息香酸イソアミル、ジエチルアミノ安息香酸イソアミル、3−フェニル−5−ベンゾイルチオテトラゾール、1−フェニル−5−エトキシカルボニルチオテトラゾールなどが挙げられ、これらを1種又は2種以上使用することができる。
【0041】
増感剤の添加量は、アルカリ可溶性シリコーン樹脂100質量部に対し、通常10質量部以下(即ち、0〜10質量部)でよく、好ましくは0.01〜10質量部、より好ましくは0.1〜5質量部である。増感剤の量が少ないと、高感度化の効果が得られない場合があり、増感剤の量が多いと、解像性が低くなるおそれがある。
【0042】
光吸収剤としては、具体的には、アゾ系、ベンゾフェノン系、アミノケトン系、キノリン系、アントラキノン系、ジフェニルシアノアクリレート系、トリアジン系、p−アミノ安息香酸系染料などが使用でき、有機系染料がよく用いられる。これらの中でも、アゾ系及びベンゾフェノン系染料が好ましい。
【0043】
有機染料の添加量は、アルカリ可溶性シリコーン樹脂100質量部に対し、通常、10質量部以下(即ち、0〜10質量部)でよく、好ましくは0.01〜10質量部、より好ましくは0.1〜3質量部である。添加量が少なすぎると、添加効果が得られない場合があり、添加量が多すぎると、硬化後の膜特性に影響するおそれがある。
【0044】
紫外線及び可視光線の吸収効果が高い光吸収剤は、高アスペクト比、高解像度を得るために有用である。また、酸無水物など有機系の脱水剤をアルカリ可溶性シリコーン樹脂100質量部に対して20質量部以下(0〜20質量部)配合することや、シリカ、アルミナ、チタニア、ジルコニア、炭酸カルシウムといった無機系酸化物の微粒子(<1μm)をアルカリ可溶性シリコーン樹脂100質量部に対して100質量部以下(0〜100質量部)配合することができる。
【0045】
また、重合禁止剤としては、例えば、ハイドロキノン、ハイドロキノンモノメチルエーテル、ピロガロール、tert−ブチルカテコール、フェノチアジンなど、酸化防止剤としては、例えば、BHT、ビタミンBなど、消泡剤、レベリング剤としては、例えば、シリコーン系界面活性剤、フッソ系界面活性剤、アクリル系樹脂など、また顔料としては、フタロシアニン・ブルー、フタロシアニン・グリーン、酸化チタン、カーボンブラックなどの公知の着色用顔料等を添加することもできる。また、接着性付与剤、可塑剤等の各種添加剤を適宜添加することもできる。
【0046】
感光性シリコーン樹脂組成物
本発明の感光性シリコーン樹脂組成物は、前記アルカリ可溶性シリコーン樹脂に、光開始剤、必要に応じて縮合触媒、溶剤、反応性希釈剤、エポキシ硬化剤や増感剤などのその他の必要な成分を加え、均一に混合することにより得ることができ、ネガ型のフォトリソグラフィー用樹脂組成物として使用することができる。
【0047】
このようにして得られた本発明の感光性シリコーン樹脂組成物は、未硬化状態でアルカリ性水溶液やアルコール、ケトン、エーテルといった極性溶媒に可溶であり、硬化後はこれらの溶剤に難溶で、フォトリソグラフィーにより精細なパターンを形成することができ、例えば次のように用いられる。即ち、スピンナー等の塗布装置を用いて所定の基体、例えばシリコーンウェハー、ガラス板、金属板、プラスチック板などに塗布し、組成物に溶剤が含まれる場合は溶剤を加熱、風乾などにより除去して、好ましくは100μm以下(溶剤乾燥後の厚さ)、より好ましくは0.5〜50μmの組成物被膜を形成した後、マスクアライナー等を用い、これに直接、或いはフォトマスクで組成物被膜表面を遮蔽してから、光を照射する。照射する光としては、例えば、遠紫外線(波長:例えば193nm,253nm等)、i線(波長:365nm)、g線(波長:436nm)、h線(波長:405nm)等の紫外線が挙げられる。
【0048】
前記フォトマスクで遮蔽された未硬化部分(非露光部分)の組成物被膜は、例えば、水酸化カリウム、炭酸ナトリウム、アンモニア水等の無機アルカリ類、エチルアミン等の第一級アミン類、ジエチルアミン等の第二級アミン類、トリエチルアミン等の第三級アミン類、テトラメチルアンモニウムハイドロオキサイド、トリメチルヒドロキシエチルアンモニウムハイドロオキサイドなどの非置換又はヒドロキシ置換テトラアルキルアンモニウムハイドロオキサイド等の第四級アンモニウム塩の水溶液よりなるアルカリ現像液等を単独又は混合して用いて溶解除去することにより、前記フォトマスクに応じたパターン、即ち精細なパターンを得ることができる。なお、好ましくは、アルカリ水溶液としては、0.1〜5質量%、好ましくは1〜3質量%のテトラメチルアンモニウムハイドロオキサイドなどの非置換又はヒドロキシ置換テトラアルキルアンモニウムハイドロオキサイド等のアルカリ水溶液が好ましい。もしくは、メタノール、THFなどの極性有機溶媒を用いても同様に解像することができる。硬化後、加熱処理、好ましくは100℃以上、特に好ましくは120〜150℃の温度で1〜2時間加熱することにより、硬化させた被膜中に残存する溶剤等の揮発分が完全に飛散し、更に硬化反応が進行し、耐熱性、耐湿性、機械的特性、密着性等に優れた被膜が得られる。
【0049】
本発明の感光性シリコーン樹脂組成物は、オニウム塩、スルホニウム塩などの光酸発生剤を用いたフォトリソグラフィーにおいても、精細なパターンを形成する。
【0050】
【実施例】
以下、合成例と実施例及び比較例を示して本発明を更に具体的に説明するが、本発明は下記の実施例に限定されるものではない。なお、下記例中、平均分子量は、GPC(ゲルパーミエーションクロマトグラフ)によるポリスチレン換算値であり、また記号Mwは重量平均分子量を意味し、Meはメチル基であり、Etはエチル基である。
【0051】
[合成例1]
2−(3,4−エポキシシクロヘキシルエチル)トリメトキシシラン0.15mol、3−アクリロキシプロピルトリメトキシシラン0.05mol、及びフェニルトリメトキシシラン0.10mol(シラン混合物中におけるケイ素原子に結合したアルコキシ基を除く全有機基数に対するR1、R4の割合(以下、同様)はそれぞれ50モル%、17モル%)をメタノール溶媒中に仕込み、これに純水及び酸触媒としての濃塩酸を混合した溶液を攪拌下で滴下し、25℃で加水分解反応を行った。次に、反応混合物を1時間加熱還流して縮重合反応させたのち、溶媒及び生成したアルコール類を留去しながら、更に縮重合反応を2時間行った。次に、得られた加水分解縮合物を水洗したのち、テトラヒドロフランに溶解した。その溶液を穴径0.8μmのフィルターで濾過した。濾液中の溶剤を80℃/2mmHgで減圧留去し、更に、室温で24時間真空乾燥させ、粉末状の固形物としてアルカリ可溶性シリコーン樹脂を得た。GPC測定の結果、アルカリ可溶性シリコーン樹脂は、Mw2,800であった。
【0052】
[合成例2]
2−(3,4−エポキシシクロヘキシルエチル)トリメトキシシラン0.06mol、3−アクリロキシプロピルトリメトキシシラン0.03mol、及びフェニルトリメトキシシラン0.21mol(R1、R4の割合はそれぞれ20モル%、10モル%)を用いて合成例1と同様の操作を行い、アルカリ可溶性シリコーン樹脂を得た。GPC測定の結果、アルカリ可溶性シリコーン樹脂は、Mw2,000であった。
【0053】
[合成例3]
2−(3,4−エポキシシクロヘキシルエチル)トリメトキシシラン0.12mol、3−アクリロキシプロピルトリメトキシシラン0.06mol、及びメチルトリメトキシシラン0.12mol(R1、R4の割合はそれぞれ40モル%、20モル%)を用いて合成例1と同様の操作を行い、アルカリ可溶性シリコーン樹脂を得た。GPC測定の結果、アルカリ可溶性シリコーン樹脂は、Mw3,200であった。
【0054】
[合成例4]
2−(3,4−エポキシシクロヘキシルエチル)トリメトキシシラン0.12mol、3−アクリロキシプロピルトリメトキシシラン0.03mol、フェニルトリメトキシシラン0.12mol、及びテトラエトキシシラン0.03mol(R1、R4の割合はそれぞれ44モル%、11モル%)を用いて合成例1と同様の操作を行い、アルカリ可溶性シリコーン樹脂を得た。GPC測定の結果、アルカリ可溶性シリコーン樹脂は、Mw1,500であった。
【0055】
[合成例5]
2−(3,4−エポキシシクロヘキシルエチル)トリメトキシシラン0.15mol、3−アクリロキシプロピルトリメトキシシラン0.15mol(R1、R4の割合はそれぞれ50モル%、50モル%)を用いて合成例1と同様の操作を行い、アルカリ可溶性シリコーン樹脂を得た。GPC測定の結果、アルカリ可溶性シリコーン樹脂は、Mw4,800であった。
【0056】
[合成例6]
合成例1と同様の仕込組成、操作で、縮合時間を3時間行い、アルカリ可溶性シリコーン樹脂を得た。GPC測定の結果、アルカリ可溶性シリコーン樹脂は、Mw10,800であった。
【0057】
[調製例1]感光性シリコーン樹脂組成物の調製
合成例1〜6で得られたアルカリ可溶性シリコーン樹脂100質量部に対し、光開始剤(Darocure1173)1質量部を溶解したジグライム100質量部を均一に混ぜ、本発明の感光性シリコーン樹脂組成物を得た。
【0058】
[実施例1]
上記で得られた感光性シリコーン樹脂組成物をシリコンウェハー上に、スピンコート法により乾燥後の膜厚が20〜25μmになるように回転数を調整して塗布し、80℃乾燥機で10分乾燥させた。この組成物被膜は、未硬化の状態で粘着性はなかった。被膜のアルカリ可溶性を試験した結果を表1にまとめた。なお、表1の樹脂溶解時間とは、作製した被膜がディップ法で完全に2.38%のMe4NOH水溶液に溶解するまでの時間を計測したものである。
【表1】
【0059】
これらの感光性シリコーン樹脂組成物群は、30日後(25℃)も表1と同等のアルカリ可溶性を示した。
【0060】
[実施例2]
上記で得られた感光性シリコーン樹脂組成物をシリコンウェハー上に、スピンコート法により膜厚が5μm及び25μmになるように回転数を調整して塗布し、80℃乾燥機で10分乾燥させた。これらの組成物被膜は、未硬化の状態で粘着性はなかった。この組成物被膜をマスクアライナーで露光(100mJ/cm2)した後、ディップ法により2.38%のMe4NOH水溶液で未露光部分の樹脂を溶解し、純水にて洗浄し、シリコンウェハー上に5μmL/Sの解像パターン(膜厚5μm)及び25μmL/Sの解像パターン(膜厚25μm)を得た。これらの被膜を150℃乾燥機で60分加熱した。被膜の硬さは、いずれも鉛筆硬度で4Hに相当した。
【0061】
得られた被膜を250℃で24時間処理したが、基板からの剥離、パターンの崩れ、クラックの発生はなかった。また、得られた被膜は、熱サイクル試験(−20℃/120℃)を100回行った後も、基板からの剥離、パターンの崩れ、クラックの発生はなかった。更に、得られた被膜は、85℃/85%RHで1,000時間処理した後も、基板からの剥離、パターンの崩れ、クラックの発生はなかった。
【0062】
[実施例3]
合成例1及び合成例2で合成したアルカリ可溶性シリコーン樹脂100質量部に光開始剤(Darocure1173)1質量部を溶解したジグライム100質量部をそれぞれ均一に混ぜた感光性シリコーン樹脂組成物を溶融して中空ファイバーに詰め、UV硬化させた後、カットバック法により伝送損失を測定した。伝送損失は633nmにおいて0.05dB/cm以下であり、熱サイクル試験(−20℃/120℃)を100回行った後も、伝送損失に変化は見られなかった。また、85℃/85%RHで1,000時間処理した後も、伝送損失に変化は見られなかった。なお、合成例1の樹脂の光硬化後の屈折率は633nmにおいて1.529であり、合成例2の樹脂は1.546であった。
【0063】
[実施例4]
上記で得られた感光性シリコーン樹脂組成物100質量部に対し、更に、シリコーン縮合触媒である錫触媒(ジラウリン酸ジノルマルブチル錫)0.1質量部を均一に混ぜ、本発明の感光性シリコーン樹脂組成物を得た。
【0064】
実施例2と同様にして、得られた縮合触媒を含む感光性シリコーン樹脂組成物をシリコンウェハー上に塗布し、乾燥、露光、現像し、シリコンウェハー上に5μmL/Sの解像パターンを得た。
【0065】
更に、この被膜を150℃乾燥機で60分加熱することにより、シリコーンの縮合反応を行い、強固な被膜を得た。被膜の硬さは、鉛筆硬度で5Hに相当した。
【0066】
実施例2と同様に得られた被膜を試験した。熱処理(250℃で24時間)、熱サイクル試験(−20℃/120℃を100回)、耐湿試験(85℃/85%RHで1,000時間)のそれぞれの試験後に基板からの剥離、パターンの崩れ、クラックの発生はなかった。
【0067】
実施例3と同様にカットバック法により伝送損失を測定した。伝送損失は633nmにおいて0.05dB/cm以下であり、熱サイクル試験(−20℃/120℃)を100回行った後も、伝送損失に変化は見られなかった。また、85℃/85%RHで1,000時間処理した後も、伝送損失に変化は見られなかった。
【0068】
[比較例1]
2−(3,4−エポキシシクロヘキシルエチル)トリメトキシシラン0.15mol、及びフェニルトリメトキシシラン0.15mol(R1、R4の割合はそれぞれ50モル%、0モル%)をメタノール溶媒中に仕込み、これに純水及び酸触媒としての濃塩酸を混合した溶液を攪拌下で滴下し、25℃で加水分解反応を行った。次に、反応混合物を1時間加熱還流して縮重合反応させたのち、溶媒及び生成したアルコール類を留去しながら、更に縮重合反応を2時間行った。次に、得られた加水分解縮合物を水洗したのち、テトラヒドロフランに溶解した。その溶液を穴径0.8μmのフィルターで濾過した。濾液中の溶剤を80℃/2mmHgで減圧留去し、更に、室温で24時間真空乾燥させ、粉末状の固形物としてアルカリ可溶性シリコーン樹脂を得た。GPC測定の結果、アルカリ可溶性シリコーン樹脂は、Mw2,700であった。
【0069】
上記アルカリ可溶性シリコーン樹脂10質量部に対し、光酸発生剤(アデカオプトマーSP−172)0.3質量部を溶解したジエチレングリコール10質量部を均一に混ぜ、アルカリ可溶性シリコーン樹脂組成物(ネガ型感光性樹脂組成物)を得た。
【0070】
得られた樹脂組成物をシリコンウェハー上に、スピンコート法により膜厚が5μmになるように回転数を調整して塗布し、80℃乾燥機で15分乾燥させた。この組成物被膜は、未硬化の状態で粘着性はなかった。この組成物被膜をマスクアライナーで露光(200mJ/cm2)した後、ディップ法によりEt4NOH水溶液で未露光部分の樹脂を溶解し、純水にて洗浄し、シリコンウェハー上に5μmL/Sの解像パターンを得ることができた。被膜の硬さは、鉛筆硬度で4Hに相当した。
【0071】
このアルカリ可溶性シリコーン樹脂組成物は、30日後(25℃)にはアルカリ可溶性を示さなかった。
【0072】
【発明の効果】
本発明のアルカリ可溶性シリコーン樹脂を用いた感光性シリコーン樹脂組成物は、フォトリソグラフィーによるパターン形成において、有機溶剤を用いず、アルカリ性水溶液で解像することができ、光酸発生剤を使用しないことで現像前のポストキュアを省略することが可能となり、感度、解像性に優れており、精細なパターニングを行うことができ、また保存安定性にも優れるものであり、この硬化被膜は、耐熱性、耐寒性、耐湿性、機械的特性、耐溶剤性、耐メッキ性、光透過性に優れるものである。
よって、本発明の感光性シリコーン樹脂組成物は、レジスト材料や光微細造形用素材、パターンを型に利用した微細型取り材料として、また被膜の光透過性や容易に屈折率を制御することができることから、光伝送体、例えば光回路形成材料など、また液晶表示装置、例えばフォトスペーサー、カラーフィルターとその保護膜、反射防止膜などにも使用できる。[0001]
BACKGROUND OF THE INVENTION
The present invention is excellent in storage stability, can be photocured using a photoinitiator, is soluble in polar solvents such as an alkaline aqueous solution, alcohol, ketone, and ether in an uncured state. Photosensitive silicone resin composition that is difficult to dissolve in any solvent, can be patterned by photolithography, has excellent sensitivity and resolution, and provides a cured film with excellent heat resistance, moisture resistance, mechanical properties, light transmission, etc. And a cured product thereof, and a method for forming a negative fine pattern by photolithography using this composition.
[0002]
[Prior art]
Silicone resin, which is a polymer material, has excellent properties such as heat resistance, cold resistance, chemical stability, adhesiveness, electrical properties, transparency, and high precision products. It is widely used for applications such as electrical and electronic parts. Furthermore, by imparting photocurability, patterning using photolithography can be performed, and it is also used as a resist material, an optical microfabrication material, an optical waveguide material, and the like.
[0003]
However, in the case of a silicone resin, few materials are excellent in resolution in an aqueous solution system due to the characteristics of the resin. Examples of the alkali-soluble silicone resin include an acid-hydrolyzed example of epoxy-modified silicone, which exhibits high sensitivity and high resolution. In the examples of negative silicone resists disclosed in JP-A-3-288857, JP-A-4-070662, and JP-A-4-338958 (Patent Documents 1 to 3), lithography is performed using a photoacid generator. Is going. Photoacid generators are excellent catalysts, but they are expensive because they are limited as siloxane condensation catalysts and are more limited in terms of toxicity. Further, due to the heat treatment (PEB) before development, if the time from exposure to PEB is long, the generated acid diffuses and reacts, which affects the resolution. Furthermore, the storage stability of a composition in which an alkali-soluble silicone resin and an acid generator are mixed cannot be said to be good due to the characteristics of the resin.
[0004]
Japanese Patent Application Laid-Open No. 5-100431 (Patent Document 4) reports a composition in which an azide compound is contained in an alkali-soluble polysiloxane, but the type and content of the azide compound are limited from the viewpoint of toxicity. Therefore, the usable wavelength range is also limited.
[0005]
[Patent Document 1]
JP-A-3-288857
[Patent Document 2]
JP-A-4-070662
[Patent Document 3]
JP-A-4-338958
[Patent Document 4]
Japanese Patent Laid-Open No. 5-100431
[0006]
[Problems to be solved by the invention]
The present invention has been made in view of the above circumstances, uses an economical and highly workable silicone resin, has excellent storage stability, is alkali-soluble before photocuring, becomes alkali-insoluble after photocuring, It is possible to perform negative patterning by photolithography without using a photoacid generator for curing, and has high sensitivity and high resolution, and excellent heat resistance, moisture resistance, chemical resistance, and mechanical strength. It is an object of the present invention to provide a photosensitive silicone resin composition that can be a cured product, a cured product thereof, and a method for forming a negative fine pattern by photolithography using the composition.
[0007]
Means for Solving the Problem and Embodiment of the Invention
As a result of intensive studies to achieve the above object, the present inventor has obtained a specific amount of an epoxy-modified organoxysilane represented by the general formula (1) and a specific amount of the general formula (2) (meta ) Weight obtained by cohydrolyzing and condensing acryl-modified organoxysilane or a mixture of these with organoxysilane, and having a hydroxyl group and a (meth) acryl functional group obtained by ring opening of a part or all of the epoxide A photosensitive silicone resin composition comprising an alkali-soluble silicone resin having an average molecular weight of 500 to 50,000 (polystyrene converted value by GPC) and a photoinitiator is excellent in storage stability and is of a negative type by photolithography. Patterning can be performed by alkali development, and it has high sensitivity and resolution, and this cured film is heat resistant, moisture resistant, mechanical Every time, it was found that excellent in transparency.
[0008]
That is, the alkali-soluble silicone resin, the photoinitiator, not the photoacid generator, and in this case, preferably by using a condensation catalyst, the heat treatment (PEB) before development is performed after development. It was found that the degree of cure of the resin can be increased without affecting the image properties, and a cured product having excellent heat resistance, moisture resistance, chemical resistance, and mechanical strength can be obtained, and the present invention has been made. It is a thing.
[0009]
Accordingly, the present invention provides a photosensitive silicone resin composition shown below, a cured product thereof, and a method for forming a negative fine pattern by photolithography using this composition.
[Claim 1] (A) (i) The following general formula (1):
R1 XR2 YSi (OR3)4-XY (1)
(Wherein R1Represents a monovalent organic group having 2 to 30 carbon atoms having at least one hydrolyzable epoxide, R2Represents a monovalent hydrocarbon group having 1 to 20 carbon atoms, R3Represents a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms. X is an integer of 1 to 3, Y is an integer of 0 to 2, and satisfies 1 ≦ X + Y ≦ 3. )
And (ii) the following general formula (2):
R4 xR2 YSi (OR3)4-XY (2)
(Wherein R4Represents a monovalent hydrocarbon group having 3 to 30 carbon atoms having at least one (meth) acryl functional group, and R2Represents a monovalent hydrocarbon group having 1 to 20 carbon atoms, R3Represents a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms. X is an integer of 1 to 3, Y is an integer of 0 to 2, and satisfies 1 ≦ X + Y ≦ 3. )
A mixture with one or two or more silane compounds represented by: or (i) and (ii) components; and (iii) the following general formula (3):
R2 ZSi (OR3)4-Z (3)
(Wherein R2Represents a monovalent hydrocarbon group having 1 to 20 carbon atoms, R3Represents a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms. Z is an integer of 0-3. )
A mixture with one or more silane compounds represented by1The number of organic groups represented by the formula is 10 mol% or more based on the total number of organic groups excluding the alkoxy group bonded to the silicon atom, and R4Similarly, the total number of monoorganotriorganoxysilane compounds and tetraorganoxysilane compounds in a proportion of 5 mol% or more with respect to the total number of organic groups excluding alkoxy groups bonded to silicon atoms. Is obtained by cohydrolytic condensation at a ratio of 40 mol% or more of the total silane compound, and an alkali-soluble silicone resin having a weight average molecular weight of 500 to 50,000 (polystyrene equivalent value by GPC), and (B) A photosensitive silicone resin composition comprising a photoinitiator.
[Claim 2] The photosensitive silicone resin composition according to claim 1, further comprising a condensation catalyst.
[Claim 3] The photosensitive silicone resin composition according to claim 1 or 2, further comprising a solvent and / or a reactive diluent.
[Claim 4] Furthermore, one kind selected from an epoxy curing agent, a photosensitizer, a light absorber, a dehydrating agent, fine inorganic oxide particles, a polymerization inhibitor, an antioxidant, an antifoaming agent, a leveling agent and a pigment. Or the photosensitive silicone resin composition of any one of Claims 1 thru | or 3 containing 2 or more types.
[Claim 5] A cured product of the photosensitive silicone resin composition according to any one of claims 1 to 4.
[Claim 6] A film of the photosensitive silicone resin composition according to any one of claims 1 to 4 is formed on a substrate, and a desired portion of the film is exposed. A method for forming a negative fine pattern, comprising treating with an organic solvent to dissolve and remove a non-exposed portion, and forming a photocured film pattern of the photosensitive silicone resin composition having a shape corresponding to the exposed portion.
[0010]
Hereinafter, the present invention will be described in detail.
The photosensitive silicone resin composition of the present invention comprises (A) (i) a silane containing an organoxysilane having a hydrolyzable epoxide and (ii) an organoxysilane having a photopolymerizable (meth) acrylic structure. Silanes contained, or obtained by cohydrolytic condensation of a mixture of these and (iii) organoxysilane, and having a hydroxyl group and a (meth) acryl functional group obtained by ring-opening part or all of the epoxide An alkali-soluble silicone resin having an average molecular weight of 500 to 50,000 (polystyrene converted value by GPC) and (B) a photoinitiator, preferably further containing a condensation catalyst.
[0011]
Alkali-soluble silicone resin
The alkali-soluble silicone resin of the present invention comprises (i) one or more epoxy-modified organoxysilanes having one or more hydrolyzable epoxides represented by the following general formula (1), and ( ii) One or more of (meth) acryl-modified organoxysilanes having one or more photopolymerizable (meth) acrylic structures represented by the following general formula (2), or these (i) , (Ii) and (iii) a co-hydrolyzed condensate of a silane compound represented by the following general formula (3), which is a silicone resin having a branched structure, represented by the following general formula (1) 1 type or 2 or more types of epoxy-modified organoxysilane, 1 type or 2 or more types of (meth) acryl-modified organoxysilane represented by the following general formula (2), and the following general formula (3) Silane It is preferably a co-hydrolysis-condensation product of one or more compounds.
[0012]
R1 XR2 YSi (OR3)4-XY (1)
R4 XR2 YSi (OR3)4-XY (2)
R2 ZSi (OR3)4-Z (3)
(Wherein R1Represents a monovalent organic group having 2 to 30 carbon atoms having at least one hydrolyzable epoxide, R2Represents a monovalent hydrocarbon group having 1 to 20 carbon atoms, R3Represents a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms;4Represents a monovalent hydrocarbon group having 3 to 30 carbon atoms having at least one (meth) acrylic functional group. X is an integer of 1 to 3, Y is an integer of 0 to 2, and satisfies 1 ≦ X + Y ≦ 3. Z is an integer of 0-3. )
[0013]
Where R1As a monovalent organic group containing 1 or 2 or more hydrolyzable epoxides having 2 to 30 carbon atoms, preferably 3 to 20 carbon atoms, more preferably 6 to 12 carbon atoms, represented by Although not particularly limited, specifically, for example, glycidyl group, glycidoxymethyl group, 2-glycidoxyethyl group, 3-glycidoxypropyl group, 2- (3,4-epoxy (Cyclohexyl) ethyl group, 2- (2,3-epoxycyclohexyl) ethyl group, 3- (N-allyl-N-glycidyl) aminopropyl group, 3- (N, N-diglycidyl) aminopropyl group, 3- (N -Glycidyl) aminopropyl group, 3- (N-methyl-N-glycidyl) aminopropyl group and the like. Depending on the purpose, deuterated organic groups can also be used.
[0014]
R above2As the monovalent hydrocarbon group having 1 to 20 carbon atoms represented by the formula, an alkyl group or alkenyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group is preferable. Examples of the alkyl group or alkenyl group having 1 to 10 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, neopentyl, hexyl, and heptyl. Group, cyclohexyl group, cycloheptyl group, octyl group, α-ethylhexyl group, vinyl group, allyl group, propenyl group, isopropenyl group, butenyl group and the like. Of these, a methyl group, an ethyl group, and a vinyl group are preferable, and deuterated ones can also be used. Moreover, as a C6-C20 aryl group and an aralkyl group, a phenyl group, a benzyl group, a tolyl group, a styryl group etc. are mentioned, for example. Of these, a phenyl group is preferable, and a deuterated aromatic hydrocarbon group can also be used.
[0015]
R above3The unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms is preferably an alkyl or alkenyl group having 1 to 10 carbon atoms, and may be an alkoxy-substituted alkyl group. Specifically, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group, heptyl group, cyclohexyl group, cycloheptyl group, octyl Group, α-ethylhexyl group, vinyl group, allyl group, propenyl group, isopropenyl group, butenyl group and the like. Of these, a methyl group, an ethyl group, and a vinyl group are preferable, and deuterated ones can also be used.
[0016]
R in the above formula4Is a monovalent hydrocarbon group having 3 to 30, preferably 5 to 20, more preferably 5 to 10 carbon atoms containing at least one acrylic functional group or methacryl functional group. As a specific example, CH2= CHCOO-, CH2= C (CH3) COO-, CH2= CHCO-, CH2= C (CH3) CO- and the like. R containing such (meth) acrylic functional groups4Specific examples of the monovalent hydrocarbon group are not particularly limited, but CH2= CHCOOCH2CH2-, CH2= C (CH3) COOCH2CH2-, [CH2= C (CH3) COOCH2]3C-CH2-, (CH2= CHCOOCH2)3C-CH2-, (CH2= CHCOOCH2)2CH (C2H5) CH2An alkyl group substituted with one or two or more acryloyloxy groups or methacryloyloxy groups such as-, etc., preferably CH2= CHCOOCH2-, CH2= C (CH3) COOCH2-, CH2= CHCOOCH2CH2CH2-, CH2= C (CH3) COOCH2CH2CH2-. Depending on the purpose, deuterated organic groups can also be used.
[0017]
Specific examples of the epoxy-modified organoxysilane represented by the general formula (1) include 3-glycidoxypropyltrimethoxysilane, 2- (3,4-epoxycyclohexylethyl) trimethoxysilane, 3- Examples thereof include glycidoxypropyltriethoxysilane, dimethylethoxy-3-glycidoxypropylsilane, diethoxy-3-glycidoxypropylmethylsilane, and the like.
[0018]
Specific examples of the (meth) acryl-modified organoxysilane represented by the general formula (2) include, for example, 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropyltri Ethoxysilane, 3-acryloxypropyltriethoxysilane, methacryloxypropenyltrimethoxysilane, methacryloxypropenyltriethoxysilane, methacryloxymethyltrimethoxysilane, methacryloxymethyltriethoxysilane, methacryloxypropyltris (methoxyethoxy) silane, Examples include 3-methacryloxypropyldimethoxymethylsilane and 3-methacryloxypropyldiethoxymethylsilane.
[0019]
Specific examples of the silane compound represented by the general formula (3) include, for example, methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, Ethyltripropoxysilane, ethyltributoxysilane, propyltrimethoxysilane, propyltriethoxysilane, propyltripropoxysilane, propyltributoxysilane, vinyltriethoxysilane, vinyltri (methoxyethoxy) silane, phenyltrimethoxysilane, phenyltriethoxy Monoorganotriorganoxysilanes such as silane, phenyltripropoxysilane, benzyltrimethoxysilane, benzyltriethoxysilane, p-styryltrimethoxysilane, Methyldimethoxysilane, dimethyldiethoxysilane, dimethyldipropoxysilane, dimethyldibutoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diethyldipropoxysilane, diethyldibutoxysilane, dipropyldimethoxysilane, dipropyldiethoxysilane, di Propyl dipropoxysilane, dipropyldibutoxysilane, divinyldiethoxysilane, divinyldi (methoxyethoxy) silane, diphenyldihydroxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3- (gly Diorganodiorganoxysilanes such as sidoxypropyl) methyldimethoxysilane, 3- (glycidoxypropyl) methyldiethoxysilane, trimethyl Methoxysilane, trimethylethoxysilane, trimethylpropoxysilane, trimethylbutoxysilane, triethylmethoxysilane, triethylethoxysilane, triethylpropoxysilane, triethylbutoxysilane, tripropylmethoxysilane, tripropylethoxysilane, tripropylpropoxysilane, tripropylbutoxysilane , Trivinylethoxysilane, trivinyl (methoxyethoxy) silane, triphenylhydroxysilane, 3-methacryloxypropyldimethylmethoxysilane, 3-methacryloxypropyldimethylethoxysilane, 3- (glycidoxypropyl) dimethylmethoxysilane, 3- (Glycidoxypropyl) triorganomonoorganoxysilane such as dimethylethoxysilane, tetramethoxy Tetraorganoxysilanes such as silane, tetraethoxysilane, tetrabutoxysilane and the like can be mentioned.
[0020]
In the present invention, the mixing ratio of the silane compounds represented by the general formulas (1), (2) and (3) is R of the epoxy-modified organoxysilane represented by the general formula (1).1The number of organic groups represented by the formula (2) is 10 mol% or more, preferably 20 to 90 mol%, more preferably 25 to 75 mol%, and general formula (2) with respect to all organic groups excluding the alkoxy group bonded to the silicon atom. R of (meth) acryl-modified organoxysilane represented by4Similarly, the amount of the organic group represented by the formula is 5 mol% or more, preferably 10 to 80 mol%, more preferably 20 to 70 mol%, based on all organic groups excluding the alkoxy group bonded to the silicon atom. . Where R1When the number of organic groups represented by the formula is less than 10 mol%, the alkali solubility becomes poor, and R4When the number of organic groups represented by is less than 5 mol%, the photocurability is inferior and the resolution is deteriorated.
[0021]
In addition, in the silane compound represented by the general formula (3) added as necessary, the monoorganotriorganoxysilane is mixed in a proportion of 0 to 85 mol%, particularly 20 to 70 mol% of the total amount of silane. The diorganodiorganoxysilane is preferably mixed in an amount of 0 to 40 mol%, particularly 0 to 20 mol% of the total amount of silane, and the triorganomonoorganoxyxysilane is preferably represented by the general formula (1). It is preferable to mix in a proportion of 0 to 50 mol%, particularly 0 to 25 mol%, relative to the molar amount of the silane compound. When the silane of the general formula (3) is tetraorganoxysilane, it is preferably mixed in a proportion of 0 to 30 mol%, particularly 0 to 20 mol% of the total silane amount.
[0022]
Furthermore, in the present invention, the total amount of the monoorganotriorganoxysilane compound and the tetraorganoxysilane compound in the silane compound to be used is 40 mol% or more, preferably 50 to 100 mol%, more preferably 60 to 100. It must be mol%. If it is less than 40 mol%, the tack-free property in an uncured state will deteriorate.
[0023]
Although it does not specifically limit as a manufacturing method of alkali-soluble silicone resin, For example, when using the silane compound represented by General formula (1), (2) and (3), it is first represented by General formula (1). The epoxy-modified organoxysilane is mixed with the (meth) acryl-modified organoxysilane represented by the general formula (2) and the silane compound represented by the general formula (3), and the acid catalyst is used together with a solvent as necessary. In addition, a cohydrolysis condensate having a hydroxyl group and a (meth) acryl functional group obtained by ring opening of a part or all of the epoxide can be obtained by cohydrolysis and condensation polymerization under acidic conditions.
[0024]
As described above, the co-hydrolysis of the present invention is performed in the presence of an acid catalyst. As the acid catalyst, inorganic acids and organic acids which are known acid catalysts can be used. Specifically, for example, inorganic acids such as hydrochloric acid, sulfuric acid and hydrofluoric acid, and organic acids such as acetic acid and oxalic acid are used. Can be mentioned. Of these, hydrochloric acid, acetic acid and oxalic acid are preferred.
[0025]
The acid cohydrolysis is usually preferably performed at 0 to 50 ° C. for 60 minutes or more. The cohydrolyzate thus obtained is then subjected to condensation polymerization. The conditions for this polycondensation reaction are important for controlling the molecular weight of the silicone resin. Since the hydrolysis rate is fast, the polycondensation reaction also proceeds during this hydrolysis reaction time. For example, in order to obtain the silicone resin having a weight average molecular weight of 1,000 or more (GPC polystyrene conversion value), In order to advance the polycondensation reaction, the reaction is carried out while distilling off the solvent and the alcohol to be produced. In this case, the polycondensation reaction is usually preferably performed at a temperature higher than the boiling point of the solvent for 120 to 180 minutes.
[0026]
Thus, organooxy groups such as alkoxy groups, silanol and carbinol remain in the cohydrolyzed polycondensation product obtained through cohydrolysis and condensation polymerization. In this case, the cohydrolysis polycondensation product having improved storage stability by converting only a part of the hydroxyl groups contained in the obtained cohydrolysis polycondensation product to a trialkylsiloxy group using a silylating agent. You can also get Examples of silylating agents include hexamethyldisilazane, tetramethyldibutyldisilazane, hexaethyldisilazane, tetramethyldivinyldisilazane, tetravinyldimethyldisilazane, N-trimethylsilylacetamide, N, O-bis (trimethylsilyl) acetamide, N -Trimethylsilylimidazole and the like can be mentioned, and hexaalkyldisilazane is preferable, and hexamethyldisilazane is particularly preferable.
[0027]
In the alkali-soluble silicone resin obtained by cohydrolyzing and condensing the silane compounds represented by the general formulas (1), (2) and (3) by the above method, the silane represented by the general formula (1) Increases the alkali solubility of the resin.
[0028]
R in the above general formula (1)1Contains an epoxide, and this epoxide undergoes ring cleavage by acid or alkali during the hydrolysis condensation reaction to produce a hydroxyl group, which acts to enhance the alkali solubility of the generated silicone resin, and provides patterning performance by photolithography. To improve.
[0029]
R1Specifically, the organic group in which the epoxide was opened has a structure represented by —CH (OH) CH (B) — (wherein B represents the base part of the acid (HB) used or OH). ing.
[0030]
This R1The organic group in which the epoxide in the organic group represented by the formula is opened is contained in an amount of 10 mol% or more, preferably 15 to 90 mol% of all organic groups excluding the alkoxy group bonded to the silicon atom. If it is less than 10 mol%, the solubility in an alkali developer may be deteriorated.
[0031]
The alkali-soluble silicone resin has a weight average molecular weight of 500 to 50,000 in terms of polystyrene by GPC, preferably 1,000 to 20,000. When the average molecular weight is too small, a film excellent in heat resistance and moisture resistance cannot be obtained, and when it is too large, alkali solubility is lowered. The molecular weight of the alkali-soluble silicone resin can be adjusted by changing the reaction time of the condensation polymerization reaction.
[0032]
Photoinitiator
The photoinitiator used in the present invention is not particularly limited as long as it is usually used as a photoinitiator. Specific examples of the photoinitiator include benzophenone, 2-chlorobenzophenone, p, p′-bisdimethylaminobenzophenone, methyl o-benzoylbenzoate, 4,4-bis (dimethylamino) benzophenone, 4,4-bis. (Diethylamino) benzophenone, 4,4-dichlorobenzophenone, 4-benzoyl-4-methylphenylketone, dibenzylketone, fluorenone, 2,2-dimethyl-2-hydroxyacetophenone, acetophenone, 2,2-diethoxyacetophenone, p -Dimethylacetophenone, 2,3-diethoxyacetophenone, 2,2-dimethoxy-2-phenyl-2-phenylacetophenone, 2-hydroxy-2-methylpropiophenone, pt-butyldichloroacetophenone, p-dimethylamino The Piophenone, dichloroacetophenone, trichloroacetophenone, Michler ketone, xanthone, p-tert-butylacetophenone thioxanthone, benzyldimethyl ketal, thioxanthone, 2,4-diethylthioxanthone, 2-methylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, diethylthioxanthone Benzyl, benzyldimethyl ketal, benzylmethoxyethyl acetal, benzoin, benzoin methyl ether, benzoin isopropyl ether, benzoin butyl ether, 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-diphenylanthraquinone, anthraquinone, 2-t-butylanthraquinone, 2-amino Nthraquinone, β-chloroanthraquinone, anthrone, benzanthrone, dibenzsuberon, methyleneanthrone, 2-phenyl-1,2-butadion-2- (o-methoxycarbonyl) oxime, 1-phenylpropanedione-2- (o-ethoxycarbonyl) ) Oxime, 1,3-diphenylpropanetrione-2- (o-ethoxycarbonyl) oxime, 1-phenyl-1,2-propanedione-2- (o-benzoyl) oxime, (2-acryloyloxyethyl) (4 -Benzoylbenzyl) dimethylammonium bromide, (4-benzoylbenzyl) trimethylammonium chloride, benzoyl peroxide, cumene peroxide, thiophenol, 2-benzothiazolethiol, 2-benzoxazolethiol, 2-benzene Diimidazolethiol, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 2-methyl- [4- (methylthio) phenyl] -2-morpholino-1-propanone, naphthalenesulfonyl chloride, quinolinesulfonyl chloride N-phenylthioacridone, 4,4-azobisisobutyronitrile, diphenyl disulfide, benzthiazole disulfide, diphenyl sulfide, decylphenyl sulfide, di-n-butyl disulfide, dibenzyl sulfide, dibenzoyl disulfide, diacetyl disulfide , Dibornyl disulfide, dimethoxyxanthogen disulfide, tetramethylthiuram monosulfide, tetramethylthiuram tetrasulfide Benzyldimethyldithiocarbamate quinoxaline, 1,3-dioxolane, N-laurylpyridinium, triphenylphosphine, camphorquinone, carbon tetrabromide, tribromophenylsulfone, benzoyl peroxide, and 3,3-carbonylbis (7-diethylamino) Coumarin), coumarin-based dyes such as 6-methylcoumarin, combinations of photoreductive dyes such as eosin and methylene blue, and reducing agents such as ascorbic acid and triethanolamine. Among these, those having absorption in the wavelength region of the light source to be used and being dissolved or dispersed in the resin or solvent to be used are preferable.
[0033]
As a compounding quantity of a photoinitiator, 0.001-20 mass parts is preferable with respect to 100 mass parts of alkali-soluble silicone resins, More preferably, it is 0.01-10 mass parts, More preferably, it is 0.1-0.1 mass parts. 5 parts by mass. If the amount is less than 0.001 part by mass, the photopolymerization initiation ability may be hindered. If the amount is more than 20 parts by mass, the curing depth may be difficult to obtain.
[0034]
Condensation catalyst
In the present invention, a condensation catalyst can be further used. The condensation catalyst is not particularly limited as long as it is usually used as a condensation catalyst for condensing silanol, alkoxy group or hydroxyl group. For example, tetrabutyl titanate, tetrapropyl titanate, titanium tetraacetylacetonate, etc. Titanium-based catalysts, dibutyltin dilaurate, dibutyltin maleate, dibutyltin acetate, tin octylate, tin naphthenate, dibutyltin acetylacetonate, etc., tin-based catalysts, aluminum trisacetylacetonate, aluminum trisethylacetoacetate, diisopropoxyaluminum ethylacetate Aluminum catalysts such as acetate, butylamine, octylamine, dibutylamine, monoethanolamine, diethanolamine, triethanolamine, diethanolamine Tylene triamine, triethylenetetramine, oleylamine, cyclohexylamine, benzylamine, diethylaminopropylamine, xylylenediamine, triethylenediamine, guanidine, diphenylguanidine, 2,4,6-tris (dimethylaminomethyl) phenol, morpholine, N-methyl Silane coupling agents having amino groups such as morpholine, 2-ethyl-4-methylimidazole, DBU and other amine-based catalysts, γ-aminopropyltrimethoxysilane, N- (β-aminoethyl) aminopropylmethyldimethoxysilane, etc. And known silanol condensation catalysts such as other acidic catalysts and basic catalysts. These catalysts may be used alone or in combination of two or more.
[0035]
When a condensation catalyst is used, the blending amount is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, and still more preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the alkali-soluble silicone resin. 1 to 3 parts by mass. If the amount of the condensation catalyst is too small, the effect of addition may not be obtained, for example, the curing rate may be slow. On the other hand, if the amount is too large, the physical properties such as strength of the resulting cured product may be reduced.
[0036]
Solvents and reactive diluents
A solvent and a reactive diluent can be added to the photosensitive silicone resin composition of the present invention. The solvent is not particularly limited as long as it is compatible with the alkali-soluble silicone resin described above. For example, ethers such as tetrahydrofuran, diglyme and triglyme, ketones such as methyl ethyl ketone and methyl isobutyl ketone, methanol, ethanol, propanol, butanol, 2-propanol, 1-methoxy-2-propanol, 2-ethoxyethanol, 2-ethylhexyl Examples include alcohols, alcohols such as 1,4-butanediol, ethylene glycol, and propylene glycol. Examples of the reactive diluent include vinyl ethers, vinyl amides, epoxy resins, acrylic resins, modified silicone resins, oxetanes, allyl phthalates, and vinyl adipate.
[0037]
The amount of the solvent used is preferably 1,000 parts by mass or less (0 to 1,000 parts by mass), particularly 10 to 500 parts by mass with respect to 100 parts by mass of the alkali-soluble silicone resin. Moreover, the usage-amount of a reactive diluent is 100 mass parts or less (0-100 mass parts) with respect to 100 mass parts of alkali-soluble silicone resins, and 10-50 mass parts is especially preferable.
[0038]
Other ingredients
In the photosensitive silicone resin composition of the present invention, if necessary, other components can be mixed uniformly as long as the photolithography characteristics are not lost.
[0039]
For example, examples of the epoxy curing agent include amine compounds, imidazole compounds, carboxylic acids, phenols, and quaternary ammonium salts. Use of these epoxy group curing agents can improve the heat resistance, moisture resistance, solvent resistance, acid resistance, plating resistance, adhesion, electrical properties, mechanical strength, and the like of the resulting film. The amount of the epoxy curing agent used may normally be 20 parts by mass or less (that is, 0 to 20 parts by mass), preferably 0.01 to 20 parts by mass, with respect to 100 parts by mass of the alkali-soluble silicone resin. -10 mass parts is more preferable, and 0.1-5 mass parts is still more preferable.
[0040]
A sensitizer is added in order to improve sensitivity. Specific examples of the sensitizer include 2,4-diethylthioxanthone, isopropylthioxanthone, 2,3-bis (4-diethylaminobenzal) cyclopentanone, 2,6-bis (4-dimethylaminobenzal) cyclohexanone, 2,6-bis (4-dimethylaminobenzal) -4-methylcyclohexanone, Michler's ketone, 4,4-bis (diethylamino) benzophenone, 4,4-bis (dimethylamino) chalcone, 4,4-bis (diethylamino) Chalcone, p-dimethylaminocinnamylidene indanone, p-dimethylaminobenzylidene indanone, 2- (p-dimethylaminophenylvinylene) isonaphthothiazole, 1,3-bis (4-dimethylaminophenylvinylene) isonaphthothiazole 1,3-bis (4-dimethyl) Minobenzal) acetone, 1,3-carbonylbis (4-diethylaminobenzal) acetone, 3,3-carbonylbis (7-diethylaminocoumarin), N-phenyl-N-ethylethanolamine, N-phenylethanolamine, N- Examples include tolyldiethanolamine, isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate, 3-phenyl-5-benzoylthiotetrazole, 1-phenyl-5-ethoxycarbonylthiotetrazole, and the like. Can do.
[0041]
The addition amount of the sensitizer may be usually 10 parts by mass or less (that is, 0 to 10 parts by mass) with respect to 100 parts by mass of the alkali-soluble silicone resin, preferably 0.01 to 10 parts by mass, more preferably 0.8. 1 to 5 parts by mass. If the amount of the sensitizer is small, the effect of increasing the sensitivity may not be obtained. If the amount of the sensitizer is large, the resolution may be lowered.
[0042]
Specific examples of the light absorber include azo, benzophenone, aminoketone, quinoline, anthraquinone, diphenylcyanoacrylate, triazine, p-aminobenzoic acid dyes, and organic dyes. Often used. Among these, azo dyes and benzophenone dyes are preferable.
[0043]
The organic dye may be added in an amount of usually 10 parts by mass or less (that is, 0 to 10 parts by mass), preferably 0.01 to 10 parts by mass, more preferably 0.1 parts by mass with respect to 100 parts by mass of the alkali-soluble silicone resin. 1 to 3 parts by mass. If the amount added is too small, the effect of addition may not be obtained, and if the amount added is too large, the film properties after curing may be affected.
[0044]
A light absorber having a high ultraviolet and visible light absorption effect is useful for obtaining a high aspect ratio and high resolution. In addition, an organic dehydrating agent such as an acid anhydride is blended in an amount of 20 parts by mass or less (0 to 20 parts by mass) with respect to 100 parts by mass of the alkali-soluble silicone resin, or inorganic such as silica, alumina, titania, zirconia, or calcium carbonate. Fine oxide particles (<1 μm) can be blended in an amount of 100 parts by mass or less (0 to 100 parts by mass) with respect to 100 parts by mass of the alkali-soluble silicone resin.
[0045]
Examples of the polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, pyrogallol, tert-butylcatechol, and phenothiazine. Examples of the antioxidant include BHT and vitamin B. Examples of the antifoaming agent and leveling agent include: , Silicone-based surfactants, fluorine-based surfactants, acrylic resins and the like, and as pigments, known coloring pigments such as phthalocyanine blue, phthalocyanine green, titanium oxide, and carbon black can be added. . Moreover, various additives, such as an adhesive imparting agent and a plasticizer, can be appropriately added.
[0046]
Photosensitive silicone resin composition
The photosensitive silicone resin composition of the present invention comprises the alkali-soluble silicone resin, photoinitiator, if necessary, a condensation catalyst, a solvent, a reactive diluent, an epoxy curing agent, a sensitizer, and other necessary components. Can be obtained by uniformly mixing, and can be used as a negative-type resin composition for photolithography.
[0047]
The photosensitive silicone resin composition of the present invention thus obtained is soluble in a polar solvent such as an alkaline aqueous solution, alcohol, ketone, or ether in an uncured state, and is hardly soluble in these solvents after curing. A fine pattern can be formed by photolithography, and is used as follows, for example. That is, it is applied to a predetermined substrate such as a silicone wafer, a glass plate, a metal plate, or a plastic plate using a coating device such as a spinner. If the composition contains a solvent, the solvent is removed by heating, air drying, or the like. After forming a composition film of preferably 100 μm or less (thickness after solvent drying), more preferably 0.5 to 50 μm, the surface of the composition film is directly or photomasked using a mask aligner or the like. Light is irradiated after shielding. Examples of the light to be irradiated include ultraviolet rays such as far ultraviolet rays (wavelengths: 193 nm, 253 nm, etc.), i rays (wavelength: 365 nm), g rays (wavelength: 436 nm), h rays (wavelength: 405 nm), and the like.
[0048]
The composition film of the uncured portion (non-exposed portion) shielded by the photomask is, for example, inorganic alkalis such as potassium hydroxide, sodium carbonate, aqueous ammonia, primary amines such as ethylamine, diethylamine, etc. Consists of aqueous solutions of secondary amines, tertiary amines such as triethylamine, quaternary ammonium salts such as tetramethylammonium hydroxide, unsubstituted or hydroxy-substituted tetraalkylammonium hydroxide such as trimethylhydroxyethylammonium hydroxide A pattern corresponding to the photomask, that is, a fine pattern can be obtained by dissolving and removing an alkali developer or the like alone or in combination. Preferably, the alkaline aqueous solution is 0.1 to 5% by mass, preferably 1 to 3% by mass of an alkaline aqueous solution such as unsubstituted or hydroxy-substituted tetraalkylammonium hydroxide such as tetramethylammonium hydroxide. Alternatively, the same resolution can be achieved by using a polar organic solvent such as methanol or THF. After curing, heat treatment, preferably 100 ° C. or higher, particularly preferably by heating at a temperature of 120 to 150 ° C. for 1 to 2 hours, volatile components such as the solvent remaining in the cured film are completely scattered, Further, the curing reaction proceeds, and a film excellent in heat resistance, moisture resistance, mechanical properties, adhesion and the like can be obtained.
[0049]
The photosensitive silicone resin composition of the present invention forms a fine pattern even in photolithography using a photoacid generator such as an onium salt or a sulfonium salt.
[0050]
【Example】
EXAMPLES Hereinafter, although a synthesis example, an Example, and a comparative example are shown and this invention is demonstrated further more concretely, this invention is not limited to the following Example. In the following examples, the average molecular weight is a polystyrene conversion value by GPC (gel permeation chromatograph), the symbol Mw means a weight average molecular weight, Me is a methyl group, and Et is an ethyl group.
[0051]
[Synthesis Example 1]
2- (3,4-epoxycyclohexylethyl) trimethoxysilane 0.15 mol, 3-acryloxypropyltrimethoxysilane 0.05 mol, and phenyltrimethoxysilane 0.10 mol (alkoxy groups bonded to silicon atoms in the silane mixture) R for all organic radicals excluding1, R4The ratios (hereinafter the same) are 50 mol% and 17 mol%, respectively, in a methanol solvent, and a solution in which pure water and concentrated hydrochloric acid as an acid catalyst are mixed is added dropwise with stirring, followed by addition at 25 ° C. A decomposition reaction was performed. Next, the reaction mixture was heated to reflux for 1 hour to undergo a condensation polymerization reaction, and then the condensation polymerization reaction was further performed for 2 hours while distilling off the solvent and the generated alcohols. Next, the obtained hydrolysis condensate was washed with water and then dissolved in tetrahydrofuran. The solution was filtered through a filter having a hole diameter of 0.8 μm. The solvent in the filtrate was distilled off under reduced pressure at 80 ° C./2 mmHg and further vacuum-dried at room temperature for 24 hours to obtain an alkali-soluble silicone resin as a powdery solid. As a result of GPC measurement, the alkali-soluble silicone resin had a Mw of 2,800.
[0052]
[Synthesis Example 2]
2- (3,4-epoxycyclohexylethyl) trimethoxysilane 0.06 mol, 3-acryloxypropyltrimethoxysilane 0.03 mol, and phenyltrimethoxysilane 0.21 mol (R1, R4Were used in the same manner as in Synthesis Example 1 to obtain an alkali-soluble silicone resin. As a result of the GPC measurement, the alkali-soluble silicone resin was Mw 2,000.
[0053]
[Synthesis Example 3]
2- (3,4-epoxycyclohexylethyl) trimethoxysilane 0.12 mol, 3-acryloxypropyltrimethoxysilane 0.06 mol, and methyltrimethoxysilane 0.12 mol (R1, R4Were used in the same manner as in Synthesis Example 1 to obtain an alkali-soluble silicone resin. As a result of the GPC measurement, the alkali-soluble silicone resin was Mw 3,200.
[0054]
[Synthesis Example 4]
2- (3,4-epoxycyclohexylethyl) trimethoxysilane 0.12 mol, 3-acryloxypropyltrimethoxysilane 0.03 mol, phenyltrimethoxysilane 0.12 mol, and tetraethoxysilane 0.03 mol (R1, R4Were used in the same manner as in Synthesis Example 1 to obtain an alkali-soluble silicone resin. As a result of GPC measurement, the alkali-soluble silicone resin had a Mw of 1,500.
[0055]
[Synthesis Example 5]
2- (3,4-epoxycyclohexylethyl) trimethoxysilane 0.15 mol, 3-acryloxypropyltrimethoxysilane 0.15 mol (R1, R4Were used in the same manner as in Synthesis Example 1 to obtain alkali-soluble silicone resins. As a result of GPC measurement, the alkali-soluble silicone resin was Mw 4,800.
[0056]
[Synthesis Example 6]
With the same charging composition and operation as in Synthesis Example 1, the condensation time was 3 hours to obtain an alkali-soluble silicone resin. As a result of the GPC measurement, the alkali-soluble silicone resin was Mw 10,800.
[0057]
[Preparation Example 1] Preparation of photosensitive silicone resin composition
100 parts by mass of diglyme in which 1 part by mass of a photoinitiator (Darocur 1173) is uniformly mixed with 100 parts by mass of the alkali-soluble silicone resin obtained in Synthesis Examples 1 to 6, and the photosensitive silicone resin composition of the present invention is mixed. Obtained.
[0058]
[Example 1]
The photosensitive silicone resin composition obtained above was applied on a silicon wafer by spin coating so that the film thickness after drying was adjusted to 20 to 25 μm, and was applied for 10 minutes with an 80 ° C. dryer. Dried. This composition coating was not tacky in an uncured state. The results of testing the alkali solubility of the coating are summarized in Table 1. The resin dissolution time in Table 1 means that the produced film was completely 2.38% Me by the dipping method.4The time until dissolution in the NOH aqueous solution is measured.
[Table 1]
[0059]
These photosensitive silicone resin composition groups showed alkali solubility equivalent to Table 1 after 30 days (25 ° C.).
[0060]
[Example 2]
The photosensitive silicone resin composition obtained above was applied onto a silicon wafer by adjusting the number of revolutions so that the film thickness was 5 μm and 25 μm by spin coating, and dried for 10 minutes with an 80 ° C. dryer. . These composition films were not cured and were not tacky. The composition film was exposed with a mask aligner (100 mJ / cm2) And then 2.38% Me by dip method.4The unexposed resin is dissolved with an aqueous NOH solution and washed with pure water to obtain a 5 μmL / S resolution pattern (film thickness 5 μm) and a 25 μmL / S resolution pattern (film thickness 25 μm) on a silicon wafer. It was. These coatings were heated with a 150 ° C. dryer for 60 minutes. The hardness of the film was equivalent to 4H in pencil hardness.
[0061]
The obtained film was treated at 250 ° C. for 24 hours, but there was no peeling from the substrate, pattern collapse, or generation of cracks. Moreover, even after the obtained coating film was subjected to a thermal cycle test (−20 ° C./120° C.) 100 times, peeling from the substrate, pattern collapse, and generation of cracks were not observed. Furthermore, the obtained coating film was not peeled off from the substrate, collapsed, or cracked even after being treated at 85 ° C./85% RH for 1,000 hours.
[0062]
[Example 3]
A photosensitive silicone resin composition obtained by uniformly mixing 100 parts by mass of diglyme in which 1 part by mass of a photoinitiator (Darocur 1173) was dissolved in 100 parts by mass of the alkali-soluble silicone resin synthesized in Synthesis Example 1 and Synthesis Example 2 was melted. After filling in a hollow fiber and UV-curing, transmission loss was measured by a cutback method. The transmission loss was 0.05 dB / cm or less at 633 nm, and no change was observed in the transmission loss even after the thermal cycle test (−20 ° C./120° C.) was performed 100 times. In addition, no change was observed in the transmission loss even after the treatment at 85 ° C./85% RH for 1,000 hours. The refractive index of the resin of Synthesis Example 1 after photocuring was 1.529 at 633 nm, and the resin of Synthesis Example 2 was 1.546.
[0063]
[Example 4]
To 100 parts by mass of the photosensitive silicone resin composition obtained above, 0.1 parts by mass of a tin catalyst (dinormal butyltin dilaurate) as a silicone condensation catalyst is uniformly mixed to obtain the photosensitive silicone of the present invention. A resin composition was obtained.
[0064]
In the same manner as in Example 2, the obtained photosensitive silicone resin composition containing the condensation catalyst was applied onto a silicon wafer, dried, exposed and developed to obtain a resolution pattern of 5 μmL / S on the silicon wafer. .
[0065]
Furthermore, this coating film was heated for 60 minutes with a 150 ° C. drier to perform a silicone condensation reaction to obtain a strong coating film. The hardness of the coating corresponded to 5H in pencil hardness.
[0066]
The resulting coating was tested as in Example 2. After each test of heat treatment (250 ° C. for 24 hours), thermal cycle test (−20 ° C./120° C. 100 times), moisture resistance test (85 ° C./85% RH for 1,000 hours), peeling from the substrate, pattern There was no collapse or cracking.
[0067]
The transmission loss was measured by the cutback method in the same manner as in Example 3. The transmission loss was 0.05 dB / cm or less at 633 nm, and no change was observed in the transmission loss even after the thermal cycle test (−20 ° C./120° C.) was performed 100 times. In addition, no change was observed in the transmission loss even after the treatment at 85 ° C./85% RH for 1,000 hours.
[0068]
[Comparative Example 1]
2- (3,4-epoxycyclohexylethyl) trimethoxysilane 0.15 mol and phenyltrimethoxysilane 0.15 mol (R1, R4Were mixed in pure methanol and concentrated hydrochloric acid as an acid catalyst, and the mixture was added dropwise with stirring to conduct a hydrolysis reaction at 25 ° C. . Next, the reaction mixture was heated to reflux for 1 hour to undergo a condensation polymerization reaction, and then the condensation polymerization reaction was further performed for 2 hours while distilling off the solvent and the generated alcohols. Next, the obtained hydrolysis condensate was washed with water and then dissolved in tetrahydrofuran. The solution was filtered through a filter having a hole diameter of 0.8 μm. The solvent in the filtrate was distilled off under reduced pressure at 80 ° C./2 mmHg and further vacuum-dried at room temperature for 24 hours to obtain an alkali-soluble silicone resin as a powdery solid. As a result of the GPC measurement, the alkali-soluble silicone resin was Mw 2,700.
[0069]
To 10 parts by mass of the alkali-soluble silicone resin, 10 parts by mass of diethylene glycol in which 0.3 parts by mass of a photoacid generator (Adekaoptomer SP-172) is dissolved is uniformly mixed to obtain an alkali-soluble silicone resin composition (negative photosensitive resin). Resin composition).
[0070]
The obtained resin composition was applied onto a silicon wafer by adjusting the rotational speed so that the film thickness became 5 μm by spin coating, and dried for 15 minutes with an 80 ° C. dryer. This composition coating was not tacky in an uncured state. This composition film was exposed with a mask aligner (200 mJ / cm2), Then Et by the dip method4The unexposed resin was dissolved with an aqueous NOH solution and washed with pure water, and a resolution pattern of 5 μmL / S could be obtained on the silicon wafer. The hardness of the coating corresponded to 4H in pencil hardness.
[0071]
This alkali-soluble silicone resin composition did not show alkali-solubility after 30 days (25 ° C.).
[0072]
【The invention's effect】
The photosensitive silicone resin composition using the alkali-soluble silicone resin of the present invention can be resolved with an alkaline aqueous solution without using an organic solvent in pattern formation by photolithography, and without using a photoacid generator. It is possible to omit post-cure before development, excellent sensitivity and resolution, fine patterning, and excellent storage stability. It has excellent cold resistance, moisture resistance, mechanical properties, solvent resistance, plating resistance, and light transmittance.
Therefore, the photosensitive silicone resin composition of the present invention can be used as a resist material, a material for optical microfabrication, a micromolding material utilizing a pattern as a mold, and can control the light transmittance and the refractive index of a coating easily. Since it can be used, it can also be used for an optical transmission body, for example, an optical circuit forming material, and a liquid crystal display device, for example, a photospacer, a color filter and its protective film, and an antireflection film.
Claims (6)
R1 XR2 YSi(OR3)4−X−Y (1)
(式中、R1は加水分解性のエポキシドを一つ以上有する炭素原子数2〜30の一価の有機基を示し、R2は炭素原子数1〜20の一価炭化水素基を示し、R3は水素原子、又は炭素原子数1〜10の非置換もしくは置換の一価炭化水素基を示す。Xは1〜3の整数であり、Yは0〜2の整数であり、1≦X+Y≦3を満足する。)
で表される1種又は2種以上のシラン化合物と、(ii)下記一般式(2):
R4 xR2 YSi(OR3)4−X−Y (2)
(式中、R4は(メタ)アクリル官能基を一つ以上有する炭素原子数3〜30の一価炭化水素基を示し、R2は炭素原子数1〜20の一価炭化水素基を示し、R3は水素原子、又は炭素原子数1〜10の非置換もしくは置換の一価炭化水素基を示す。Xは1〜3の整数であり、Yは0〜2の整数であり、1≦X+Y≦3を満足する。 )
で表される1種又は2種以上のシラン化合物との混合物、又はこれら(i),(ii)成分と、(iii)下記一般式(3):
R2 ZSi(OR3)4−Z (3)
(式中、R2は炭素原子数1〜20の一価炭化水素基を示し、R3は水素原子、又は炭素原子数1〜10の非置換もしくは置換の一価炭化水素基を示す。Zは0〜3の整数である。)
で表される1種又は2種以上のシラン化合物との混合物を、R1で表される有機基数がケイ素原子に結合したアルコキシ基を除く全有機基数に対して10モル%以上、且つR4で表される有機基数が同様にケイ素原子に結合したアルコキシ基を除く全有機基数に対して5モル%以上の割合で、更にモノオルガノトリオルガノキシシラン化合物とテトラオルガノキシシラン化合物との合計量が全シラン化合物の40モル%以上となる割合で共加水分解縮合することにより得られ、重量平均分子量が500〜50,000(GPCによるポリスチレン換算値)であるアルカリ可溶性シリコーン樹脂、及び(B)光開始剤を含有してなる感光性シリコーン樹脂組成物。(A) (i) The following general formula (1):
R 1 X R 2 Y Si ( OR 3) 4-X-Y (1)
(Wherein R 1 represents a monovalent organic group having 2 to 30 carbon atoms having at least one hydrolyzable epoxide, R 2 represents a monovalent hydrocarbon group having 1 to 20 carbon atoms, R 3 represents a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, X is an integer of 1 to 3, Y is an integer of 0 to 2, and 1 ≦ X + Y ≦ 3 is satisfied.)
(Ii) the following general formula (2):
R 4 x R 2 Y Si ( OR 3) 4-X-Y (2)
(In the formula, R 4 represents a monovalent hydrocarbon group having 3 to 30 carbon atoms having one or more (meth) acryl functional groups, and R 2 represents a monovalent hydrocarbon group having 1 to 20 carbon atoms. , R 3 represents a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, X is an integer of 1 to 3, Y is an integer of 0 to 2, and 1 ≦ X + Y ≦ 3 is satisfied.)
Or a mixture with one or two or more silane compounds represented by the formula (3):
R 2 Z Si (OR 3 ) 4-Z (3)
(In the formula, R 2 represents a monovalent hydrocarbon group having 1 to 20 carbon atoms, R 3 represents a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms. Z Is an integer from 0 to 3.)
And a mixture with one or more silane compounds represented by the formula ( 1) , wherein the number of organic groups represented by R 1 is 10 mol% or more with respect to the total number of organic groups excluding the alkoxy group bonded to the silicon atom, and R 4 Similarly, the total number of monoorganotriorganoxysilane compounds and tetraorganoxysilane compounds in a proportion of 5 mol% or more with respect to the total number of organic groups excluding alkoxy groups bonded to silicon atoms. Is obtained by cohydrolytic condensation at a ratio of 40 mol% or more of the total silane compound, and an alkali-soluble silicone resin having a weight average molecular weight of 500 to 50,000 (polystyrene equivalent value by GPC), and (B) A photosensitive silicone resin composition comprising a photoinitiator.
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