JP5672827B2 - Photosensitive resin composition and use thereof - Google Patents
Photosensitive resin composition and use thereof Download PDFInfo
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- JP5672827B2 JP5672827B2 JP2010174199A JP2010174199A JP5672827B2 JP 5672827 B2 JP5672827 B2 JP 5672827B2 JP 2010174199 A JP2010174199 A JP 2010174199A JP 2010174199 A JP2010174199 A JP 2010174199A JP 5672827 B2 JP5672827 B2 JP 5672827B2
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- carbon atoms
- structural unit
- resin composition
- photosensitive resin
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- 239000011342 resin composition Substances 0.000 title claims description 56
- 125000004432 carbon atom Chemical group C* 0.000 claims description 47
- -1 fumaric acid diester Chemical class 0.000 claims description 44
- 239000000178 monomer Substances 0.000 claims description 44
- 229920001577 copolymer Polymers 0.000 claims description 36
- 239000003795 chemical substances by application Substances 0.000 claims description 25
- 125000000217 alkyl group Chemical group 0.000 claims description 24
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 19
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 16
- 239000004065 semiconductor Substances 0.000 claims description 16
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 14
- 150000002989 phenols Chemical class 0.000 claims description 14
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 13
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 13
- WTQZSMDDRMKJRI-UHFFFAOYSA-N 4-diazoniophenolate Chemical group [O-]C1=CC=C([N+]#N)C=C1 WTQZSMDDRMKJRI-UHFFFAOYSA-N 0.000 claims description 11
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Natural products OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 11
- 239000001530 fumaric acid Substances 0.000 claims description 11
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 11
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 claims description 10
- 125000003700 epoxy group Chemical group 0.000 claims description 10
- 150000007934 α,β-unsaturated carboxylic acids Chemical class 0.000 claims description 10
- 229920002554 vinyl polymer Polymers 0.000 claims description 8
- 239000003504 photosensitizing agent Substances 0.000 claims description 7
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims description 5
- 125000002723 alicyclic group Chemical group 0.000 claims description 4
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 claims description 4
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 1
- 239000010408 film Substances 0.000 description 88
- 238000000034 method Methods 0.000 description 25
- 238000011161 development Methods 0.000 description 21
- 239000011229 interlayer Substances 0.000 description 20
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 16
- 239000002904 solvent Substances 0.000 description 15
- 239000010409 thin film Substances 0.000 description 15
- 239000000758 substrate Substances 0.000 description 13
- 239000002253 acid Substances 0.000 description 12
- 230000008569 process Effects 0.000 description 11
- 229920005989 resin Polymers 0.000 description 11
- 239000011347 resin Substances 0.000 description 11
- 230000015572 biosynthetic process Effects 0.000 description 10
- 238000000576 coating method Methods 0.000 description 9
- 238000005886 esterification reaction Methods 0.000 description 9
- 238000002834 transmittance Methods 0.000 description 9
- 239000011248 coating agent Substances 0.000 description 8
- 229940116333 ethyl lactate Drugs 0.000 description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 8
- 150000002430 hydrocarbons Chemical group 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 8
- 238000004090 dissolution Methods 0.000 description 7
- 230000032050 esterification Effects 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 238000000206 photolithography Methods 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- 230000035945 sensitivity Effects 0.000 description 6
- 239000004094 surface-active agent Substances 0.000 description 6
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000010790 dilution Methods 0.000 description 5
- 239000012895 dilution Substances 0.000 description 5
- 229920002120 photoresistant polymer Polymers 0.000 description 5
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 5
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 4
- WXYSZTISEJBRHW-UHFFFAOYSA-N 4-[2-[4-[1,1-bis(4-hydroxyphenyl)ethyl]phenyl]propan-2-yl]phenol Chemical compound C=1C=C(C(C)(C=2C=CC(O)=CC=2)C=2C=CC(O)=CC=2)C=CC=1C(C)(C)C1=CC=C(O)C=C1 WXYSZTISEJBRHW-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- MTHSVFCYNBDYFN-UHFFFAOYSA-N anhydrous diethylene glycol Natural products OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 4
- 239000007869 azo polymerization initiator Substances 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- 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 4
- XLLIQLLCWZCATF-UHFFFAOYSA-N ethylene glycol monomethyl ether acetate Natural products COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- CATSNJVOTSVZJV-UHFFFAOYSA-N heptan-2-one Chemical compound CCCCCC(C)=O CATSNJVOTSVZJV-UHFFFAOYSA-N 0.000 description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 230000035699 permeability Effects 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000003505 polymerization initiator Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 4
- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 3
- 229910004205 SiNX Inorganic materials 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- PMBXCGGQNSVESQ-UHFFFAOYSA-N 1-Hexanethiol Chemical compound CCCCCCS PMBXCGGQNSVESQ-UHFFFAOYSA-N 0.000 description 2
- RRQYJINTUHWNHW-UHFFFAOYSA-N 1-ethoxy-2-(2-ethoxyethoxy)ethane Chemical compound CCOCCOCCOCC RRQYJINTUHWNHW-UHFFFAOYSA-N 0.000 description 2
- CNJRPYFBORAQAU-UHFFFAOYSA-N 1-ethoxy-2-(2-methoxyethoxy)ethane Chemical compound CCOCCOCCOC CNJRPYFBORAQAU-UHFFFAOYSA-N 0.000 description 2
- JOLQKTGDSGKSKJ-UHFFFAOYSA-N 1-ethoxypropan-2-ol Chemical compound CCOCC(C)O JOLQKTGDSGKSKJ-UHFFFAOYSA-N 0.000 description 2
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 2
- NKTOLZVEWDHZMU-UHFFFAOYSA-N 2,5-xylenol Chemical compound CC1=CC=C(C)C(O)=C1 NKTOLZVEWDHZMU-UHFFFAOYSA-N 0.000 description 2
- NXXYKOUNUYWIHA-UHFFFAOYSA-N 2,6-Dimethylphenol Chemical compound CC1=CC=CC(C)=C1O NXXYKOUNUYWIHA-UHFFFAOYSA-N 0.000 description 2
- MAQOZOILPAMFSW-UHFFFAOYSA-N 2,6-bis[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenol Chemical compound CC1=CC=C(O)C(CC=2C(=C(CC=3C(=CC=C(C)C=3)O)C=C(C)C=2)O)=C1 MAQOZOILPAMFSW-UHFFFAOYSA-N 0.000 description 2
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 2
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 2
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 2
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 2
- WFCQTAXSWSWIHS-UHFFFAOYSA-N 4-[bis(4-hydroxyphenyl)methyl]phenol Chemical compound C1=CC(O)=CC=C1C(C=1C=CC(O)=CC=1)C1=CC=C(O)C=C1 WFCQTAXSWSWIHS-UHFFFAOYSA-N 0.000 description 2
- OECTYKWYRCHAKR-UHFFFAOYSA-N 4-vinylcyclohexene dioxide Chemical compound C1OC1C1CC2OC2CC1 OECTYKWYRCHAKR-UHFFFAOYSA-N 0.000 description 2
- LPEKGGXMPWTOCB-UHFFFAOYSA-N 8beta-(2,3-epoxy-2-methylbutyryloxy)-14-acetoxytithifolin Natural products COC(=O)C(C)O LPEKGGXMPWTOCB-UHFFFAOYSA-N 0.000 description 2
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- MOYAFQVGZZPNRA-UHFFFAOYSA-N Terpinolene Chemical compound CC(C)=C1CCC(C)=CC1 MOYAFQVGZZPNRA-UHFFFAOYSA-N 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- GQFYYVLLULHPCZ-FOCLMDBBSA-N bis(4-tert-butylcyclohexyl) (e)-but-2-enedioate Chemical compound C1CC(C(C)(C)C)CCC1OC(=O)\C=C\C(=O)OC1CCC(C(C)(C)C)CC1 GQFYYVLLULHPCZ-FOCLMDBBSA-N 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 229940019778 diethylene glycol diethyl ether Drugs 0.000 description 2
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 2
- ODQWQRRAPPTVAG-GZTJUZNOSA-N doxepin Chemical compound C1OC2=CC=CC=C2C(=C/CCN(C)C)/C2=CC=CC=C21 ODQWQRRAPPTVAG-GZTJUZNOSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 150000002596 lactones Chemical class 0.000 description 2
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229940057867 methyl lactate Drugs 0.000 description 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 2
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- 239000007870 radical polymerization initiator Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000004904 shortening Methods 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 2
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- FVQMJJQUGGVLEP-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOOC(C)(C)C FVQMJJQUGGVLEP-UHFFFAOYSA-N 0.000 description 1
- HCNHNBLSNVSJTJ-UHFFFAOYSA-N 1,1-Bis(4-hydroxyphenyl)ethane Chemical compound C=1C=C(O)C=CC=1C(C)C1=CC=C(O)C=C1 HCNHNBLSNVSJTJ-UHFFFAOYSA-N 0.000 description 1
- OWEYKIWAZBBXJK-UHFFFAOYSA-N 1,1-Dichloro-2,2-bis(4-hydroxyphenyl)ethylene Chemical compound C1=CC(O)=CC=C1C(=C(Cl)Cl)C1=CC=C(O)C=C1 OWEYKIWAZBBXJK-UHFFFAOYSA-N 0.000 description 1
- YAJYJWXEWKRTPO-UHFFFAOYSA-N 2,3,3,4,4,5-hexamethylhexane-2-thiol Chemical compound CC(C)C(C)(C)C(C)(C)C(C)(C)S YAJYJWXEWKRTPO-UHFFFAOYSA-N 0.000 description 1
- UVGWILQZMJFWSY-UHFFFAOYSA-N 2,4,6-tris[(2-hydroxy-3,5-dimethylphenyl)methyl]benzene-1,3-diol Chemical compound CC1=CC(C)=C(O)C(CC=2C(=C(CC=3C(=C(C)C=C(C)C=3)O)C(O)=C(CC=3C(=C(C)C=C(C)C=3)O)C=2)O)=C1 UVGWILQZMJFWSY-UHFFFAOYSA-N 0.000 description 1
- KUFFULVDNCHOFZ-UHFFFAOYSA-N 2,4-xylenol Chemical compound CC1=CC=C(O)C(C)=C1 KUFFULVDNCHOFZ-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- OUFBXQDOWIOHMD-UHFFFAOYSA-N 2-[(2-hydroxy-4,6-dimethylphenyl)-(2-hydroxyphenyl)methyl]-3,5-dimethylphenol Chemical compound OC1=CC(C)=CC(C)=C1C(C=1C(=CC(C)=CC=1C)O)C1=CC=CC=C1O OUFBXQDOWIOHMD-UHFFFAOYSA-N 0.000 description 1
- NXMFPYRNSNUSNW-UHFFFAOYSA-N 2-[(2-hydroxy-4,6-dimethylphenyl)-(4-hydroxyphenyl)methyl]-3,5-dimethylphenol Chemical compound OC1=CC(C)=CC(C)=C1C(C=1C(=CC(C)=CC=1C)O)C1=CC=C(O)C=C1 NXMFPYRNSNUSNW-UHFFFAOYSA-N 0.000 description 1
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- WADSJYLPJPTMLN-UHFFFAOYSA-N 3-(cycloundecen-1-yl)-1,2-diazacycloundec-2-ene Chemical class C1CCCCCCCCC=C1C1=NNCCCCCCCC1 WADSJYLPJPTMLN-UHFFFAOYSA-N 0.000 description 1
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 description 1
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 description 1
- DZYOPRUWTOQPPW-UHFFFAOYSA-N 4-[(4-hydroxy-2-methylphenyl)-(2-hydroxyphenyl)methyl]-3-methylphenol Chemical compound CC1=CC(O)=CC=C1C(C=1C(=CC=CC=1)O)C1=CC=C(O)C=C1C DZYOPRUWTOQPPW-UHFFFAOYSA-N 0.000 description 1
- WHKJCZQKHJHUBB-UHFFFAOYSA-N 4-[(4-hydroxy-3,5-dimethylphenyl)-(3-hydroxyphenyl)methyl]-2,6-dimethylphenol Chemical compound CC1=C(O)C(C)=CC(C(C=2C=C(O)C=CC=2)C=2C=C(C)C(O)=C(C)C=2)=C1 WHKJCZQKHJHUBB-UHFFFAOYSA-N 0.000 description 1
- OHKTUDSKDILFJC-UHFFFAOYSA-N 4-[(4-hydroxy-3,5-dimethylphenyl)-(4-hydroxyphenyl)methyl]-2,6-dimethylphenol Chemical compound CC1=C(O)C(C)=CC(C(C=2C=CC(O)=CC=2)C=2C=C(C)C(O)=C(C)C=2)=C1 OHKTUDSKDILFJC-UHFFFAOYSA-N 0.000 description 1
- IJWIRZQYWANBMP-UHFFFAOYSA-N 4-[2-(4-hydroxy-3-propan-2-ylphenyl)propan-2-yl]-2-propan-2-ylphenol Chemical compound C1=C(O)C(C(C)C)=CC(C(C)(C)C=2C=C(C(O)=CC=2)C(C)C)=C1 IJWIRZQYWANBMP-UHFFFAOYSA-N 0.000 description 1
- GNAJJNNIQUTVBL-UHFFFAOYSA-N 4-[bis(4-hydroxy-2,3,5-trimethylphenyl)methyl]benzene-1,2-diol Chemical compound CC1=C(O)C(C)=CC(C(C=2C=C(O)C(O)=CC=2)C=2C(=C(C)C(O)=C(C)C=2)C)=C1C GNAJJNNIQUTVBL-UHFFFAOYSA-N 0.000 description 1
- NFWPZNNZUCPLAX-UHFFFAOYSA-N 4-methoxy-3-methylaniline Chemical compound COC1=CC=C(N)C=C1C NFWPZNNZUCPLAX-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- HTVITOHKHWFJKO-UHFFFAOYSA-N Bisphenol B Chemical compound C=1C=C(O)C=CC=1C(C)(CC)C1=CC=C(O)C=C1 HTVITOHKHWFJKO-UHFFFAOYSA-N 0.000 description 1
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- FVCPXLWAKNJIKK-UHFFFAOYSA-N Dimexano Chemical compound COC(=S)SSC(=S)OC FVCPXLWAKNJIKK-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 206010034972 Photosensitivity reaction Diseases 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000006149 azo coupling reaction Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- MWJNGKOBSUBRNM-BQYQJAHWSA-N dibutan-2-yl (e)-but-2-enedioate Chemical compound CCC(C)OC(=O)\C=C\C(=O)OC(C)CC MWJNGKOBSUBRNM-BQYQJAHWSA-N 0.000 description 1
- BLKQQTCUGZJWLN-VAWYXSNFSA-N dicyclohexyl (e)-but-2-enedioate Chemical compound C1CCCCC1OC(=O)/C=C/C(=O)OC1CCCCC1 BLKQQTCUGZJWLN-VAWYXSNFSA-N 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- DJOLQBLYDDQTSY-MDZDMXLPSA-N dipentan-2-yl (e)-but-2-enedioate Chemical compound CCCC(C)OC(=O)\C=C\C(=O)OC(C)CCC DJOLQBLYDDQTSY-MDZDMXLPSA-N 0.000 description 1
- FNMTVMWFISHPEV-AATRIKPKSA-N dipropan-2-yl (e)-but-2-enedioate Chemical compound CC(C)OC(=O)\C=C\C(=O)OC(C)C FNMTVMWFISHPEV-AATRIKPKSA-N 0.000 description 1
- MSVGHYYKWDQHFV-BQYQJAHWSA-N ditert-butyl (e)-but-2-enedioate Chemical compound CC(C)(C)OC(=O)\C=C\C(=O)OC(C)(C)C MSVGHYYKWDQHFV-BQYQJAHWSA-N 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000000219 ethylidene group Chemical group [H]C(=[*])C([H])([H])[H] 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 150000003903 lactic acid esters Chemical class 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- ZWWQICJTBOCQLA-UHFFFAOYSA-N o-propan-2-yl (propan-2-yloxycarbothioyldisulfanyl)methanethioate Chemical compound CC(C)OC(=S)SSC(=S)OC(C)C ZWWQICJTBOCQLA-UHFFFAOYSA-N 0.000 description 1
- KZCOBXFFBQJQHH-UHFFFAOYSA-N octane-1-thiol Chemical compound CCCCCCCCS KZCOBXFFBQJQHH-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 125000005375 organosiloxane group Chemical group 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- FFZANLXOAFSSGC-UHFFFAOYSA-N phosphide(1-) Chemical compound [P-] FFZANLXOAFSSGC-UHFFFAOYSA-N 0.000 description 1
- 238000007699 photoisomerization reaction Methods 0.000 description 1
- 230000036211 photosensitivity Effects 0.000 description 1
- 229920002432 poly(vinyl methyl ether) polymer Polymers 0.000 description 1
- 229920000151 polyglycol Polymers 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- 229920000259 polyoxyethylene lauryl ether Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- FZYCEURIEDTWNS-UHFFFAOYSA-N prop-1-en-2-ylbenzene Chemical compound CC(=C)C1=CC=CC=C1.CC(=C)C1=CC=CC=C1 FZYCEURIEDTWNS-UHFFFAOYSA-N 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000007717 redox polymerization reaction Methods 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 125000003003 spiro group Chemical group 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 125000005409 triarylsulfonium group Chemical group 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
Landscapes
- Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)
- Materials For Photolithography (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
本発明は、感光性を有し、ポジ型フォトレジスト等として用いられる感光性樹脂組成物に関する。さらに詳細には、フォトリソグラフィー技術を用いることによりパターン膜を形成することが可能な感光性樹脂組成物、さらにこれを用いて形成される層間絶縁膜又は平坦化膜を備えたフラットパネルディスプレイ（ＦＰＤ）又は半導体デバイスに関する。 The present invention relates to a photosensitive resin composition having photosensitivity and used as a positive photoresist or the like. More specifically, a photosensitive resin composition capable of forming a pattern film by using a photolithography technique, and a flat panel display (FPD) including an interlayer insulating film or a planarizing film formed using the photosensitive resin composition. ) Or a semiconductor device.
ＬＳＩなどの半導体集積回路や、ＦＰＤの表示面の製造、サーマルヘッドなどの回路基板の製造等を初めとする幅広い分野において、微細素子の形成或いは微細加工を行うために、従来からフォトリソグラフィー技術が利用されている。該フォトリソグラフィー技術においては、レジストパターンを形成するため、感光性樹脂組成物が用いられている。近年、これら感光性樹脂組成物の新たな用途として、半導体集積回路やＦＰＤなどの層間絶縁膜や平坦化膜の形成技術が注目されている。特に、ＦＰＤ表示面の高精細化や薄膜トランジスタ（ＴＦＴ）などに代表される半導体素子の製造プロセスの短縮化に対する市場の要望は強いものがある。 Conventionally, photolithography technology has been used to form or process microelements in a wide range of fields including semiconductor integrated circuits such as LSIs, FPD display surfaces, thermal heads and other circuit boards. It's being used. In the photolithography technique, a photosensitive resin composition is used to form a resist pattern. In recent years, as a new application of these photosensitive resin compositions, attention is paid to a technique for forming an interlayer insulating film and a planarizing film such as a semiconductor integrated circuit and an FPD. In particular, there is a strong market demand for higher definition of the FPD display surface and shortening of the manufacturing process of semiconductor elements typified by thin film transistors (TFTs).
このＦＰＤ表示面の高精細化を達成するためには、回路内において伝送損失を抑えることが重要であり、それには低誘電特性に優れた微細パターンを有する層間絶縁膜や平坦化膜が必須材料とされている。また、半導体素子の製造プロセスの短縮化については、ソースやゲート電極を保護する目的で、真空蒸着法にて窒化珪素（ＳｉＮｘ）などの無機層間絶縁膜を形成せず、ウェットプロセスで容易に形成可能な有機層間絶縁膜への代替が望まれている。そのため、有機層間絶縁膜は、ＳｉＮｘと同等の絶縁性が必須であり、比誘電率が３．０を下回るような、低誘電特性の層間絶縁膜が必要とされている。前記の低誘電特性を有する層間絶縁膜や平坦化膜を得るためには、感光性樹脂組成物におけるアルカリ可溶性樹脂の役割は多大であり、このような用途に用いられる感光性樹脂組成物に関して多くの研究がなされている。 In order to achieve high definition of the FPD display surface, it is important to suppress transmission loss in the circuit. For this purpose, an interlayer insulating film or a planarizing film having a fine pattern with excellent low dielectric properties is an essential material. It is said that. For shortening the manufacturing process of semiconductor elements, an inorganic interlayer insulating film such as silicon nitride (SiNx) is not formed by vacuum deposition for the purpose of protecting the source and gate electrodes, but easily formed by a wet process. An alternative to a possible organic interlayer dielectric is desired. Therefore, the organic interlayer insulating film must have an insulating property equivalent to that of SiNx, and an interlayer insulating film having a low dielectric property that has a relative dielectric constant of less than 3.0 is required. In order to obtain the interlayer insulating film and the planarizing film having the low dielectric properties, the role of the alkali-soluble resin in the photosensitive resin composition is great, and there are many related to the photosensitive resin composition used for such applications. Has been studied.
例えば特許文献１では、層間絶縁膜又は平坦化膜用の感光性樹脂組成物のアルカリ可溶性樹脂として不飽和カルボン酸とエポキシ基を有するラジカル重合性化合物とを用いることにより、良好な現像性を有しかつ高解像度のパターン膜が形成される技術が開示されている。しかしながら、前記アルカリ可溶性樹脂に含まれる構成単位は（メタ）アクリロイル基で構成されているため、十分な低誘電特性を得ることができないことが一般的に知られている。 For example, Patent Document 1 has good developability by using an unsaturated carboxylic acid and a radical polymerizable compound having an epoxy group as an alkali-soluble resin of a photosensitive resin composition for an interlayer insulating film or a planarizing film. In addition, a technique for forming a high-resolution pattern film is disclosed. However, since the structural unit contained in the alkali-soluble resin is composed of a (meth) acryloyl group, it is generally known that sufficient low dielectric properties cannot be obtained.
一方で特許文献２には、層間絶縁膜又は平坦化膜用の感光性樹脂組成物のアルカリ可溶性樹脂としてスチレン類、（メタ）アクリル酸及びヒドロキシアルキルエステルを構成単位として有する共重合体を用いることにより、良好な低誘電特性が得られることが開示されている。しかしながら、スチレン類を樹脂中に多量に導入した場合、樹脂の疎水性が高くなるため、現像時の残膜率を高く維持することはできるものの、現像残渣が多くなり、十分な現像性を得ることができないという問題がある。 On the other hand, Patent Document 2 uses a copolymer having styrenes, (meth) acrylic acid, and hydroxyalkyl esters as structural units as an alkali-soluble resin of a photosensitive resin composition for an interlayer insulating film or a planarizing film. Thus, it is disclosed that good low dielectric properties can be obtained. However, when a large amount of styrene is introduced into the resin, the hydrophobicity of the resin increases, so that the residual film ratio during development can be maintained high, but the development residue increases and sufficient developability is obtained. There is a problem that can not be.
また、特許文献３では、カラーフィルター用の保護膜、ＲＧＢ用画素、ブラックマトリックス又はスペーサーを形成するため、フマル酸ジエステルを有するアルカリ可溶性樹脂、光重合性多官能（メタ）アクリレート化合物及び光重合開始剤が含まれるネガ型感光性樹脂組成物を用い、良好な現像性が得られることが開示されている。しかしながら、ネガ型感光性樹脂組成物中に含まれる、光重合性多官能（メタ）アクリレートの比誘電率が高いため、組成物として十分な低誘電特性を得ることができないという問題がある。 Moreover, in patent document 3, in order to form the protective film for color filters, the pixel for RGB, a black matrix, or a spacer, alkali-soluble resin which has a fumaric acid diester, a photopolymerizable polyfunctional (meth) acrylate compound, and photopolymerization start It is disclosed that good developability can be obtained using a negative photosensitive resin composition containing an agent. However, since the relative permittivity of the photopolymerizable polyfunctional (meth) acrylate contained in the negative photosensitive resin composition is high, there is a problem that a low dielectric property sufficient as the composition cannot be obtained.
このような問題点を解決するために、ＦＰＤや半導体デバイスなどの層間絶縁膜又は平坦化膜に用いられる感光性樹脂組成物において、高い残膜率を維持したまま、現像残渣がなく、現像性が良く、低誘電特性に優れる高解像度のパターン膜を形成することが求められているのである。 In order to solve such problems, the photosensitive resin composition used for the interlayer insulating film or flattening film such as FPD and semiconductor device has no residual development and developability while maintaining a high residual film ratio. Therefore, it is required to form a pattern film with high resolution and excellent low dielectric properties.
本発明は上記実状を鑑みてなされたものであり、その第一の目的は、パターン膜を形成する現像工程において、高い残膜率を維持したまま、現像残渣がなく、高温ベーキング後においても平坦性、光透過率、耐溶剤性等の塗膜物性を損なうことなく、低誘電特性に優れた高解像度のパターン膜を形成することができる感光性樹脂組成物を提供することにある。 The present invention has been made in view of the above circumstances, and the first object thereof is to maintain a high residual film ratio in the development process for forming a pattern film, and there is no development residue and is flat even after high temperature baking. An object of the present invention is to provide a photosensitive resin composition capable of forming a high-resolution pattern film having excellent low dielectric properties without impairing coating film properties such as properties, light transmittance, and solvent resistance.
また、本発明の第二の目的は、前記の優れた感光性樹脂組成物により形成された平坦化膜又は層間絶縁膜を有するとともに、ＳｉＮｘなどの無機層間絶縁膜を形成することなく、ウェットプロセスで容易に形成可能な有機層間絶縁膜を有するＦＰＤ又は半導体デバイスを提供することにある。 The second object of the present invention is to provide a wet process without forming an inorganic interlayer insulating film such as SiNx while having a planarizing film or interlayer insulating film formed of the above-described excellent photosensitive resin composition. An FPD or a semiconductor device having an organic interlayer insulating film that can be easily formed is provided.
本発明における第１の発明の感光性樹脂組成物は、下記に示す成分（Ａ）、（Ｂ）及び（Ｃ）を含有し、各成分の構成割合が（Ａ）１００質量部に対して（Ｂ）５〜５０質量部及び（Ｃ）１〜７０質量部であることを特徴とする。
（Ａ）下記式（１）で表されるフマル酸ジエステル単量体から誘導される構成単位（ａ１）、下記式（２）で表される芳香族ビニル単量体から誘導される構成単位（ａ２）、下記式（３）で表されるα，β−不飽和カルボン酸単量体から誘導される構成単位（ａ３）及び下記式（４）で表される（メタ）アクリル酸エステル単量体から誘導される構成単位（ａ４）からなり、構成単位（ａ１）と構成単位（ａ２）の合計量が４０〜８５質量％であり、構成単位（ａ３）と構成単位（ａ４）の質量比（ａ４）／（ａ３）が０．２〜７．０である共重合体。
The photosensitive resin composition of the first invention in the present invention, the components shown below (A), containing (B) and (C), composition ratio of each component (A) with respect to 100 parts by weight ( B) 5 to 50 parts by mass and (C) 1 to 70 parts by mass.
(A) A structural unit derived from a fumaric acid diester monomer represented by the following formula (1) (a1), a structural unit derived from an aromatic vinyl monomer represented by the following formula (2) ( a2), a structural unit (a3) derived from an α, β-unsaturated carboxylic acid monomer represented by the following formula (3) and a (meth) acrylic acid ester single monomer represented by the following formula (4) It consists of a structural unit (a4) derived from the body, the total amount of the structural unit (a1) and the structural unit (a2) is 40 to 85% by mass, and the mass ratio of the structural unit (a3) to the structural unit (a4) A copolymer in which (a4) / (a3) is 0.2 to 7.0.
（Ｂ）水酸基を有するフェノール性化合物とキノンジアジド化合物とをエステル化反応させて得られる、キノンジアジド基を有する感光剤。
（Ｃ）下記式（５）で表されるエポキシ基を有する硬化剤。
(B) A photosensitizer having a quinonediazide group obtained by esterifying a phenolic compound having a hydroxyl group and a quinonediazide compound.
(C) A curing agent having an epoxy group represented by the following formula (5).
第２の発明のフラットパネルディスプレイは、第１の発明の感光性樹脂組成物を硬化した層を有するものである。
The flat panel display of the second invention has a layer obtained by curing the photosensitive resin composition of the first invention.
第３の発明の半導体デバイスは、第１の発明の感光性樹脂組成物を硬化した層を有するものである。 A semiconductor device of the third invention has a layer obtained by curing the photosensitive resin composition of the first invention.
本発明は、次のような効果を発揮することができる。
第１の発明の感光性樹脂組成物によれば、フォトリソグラフィー技術を用いたパターン膜を形成する現像工程において、高い残膜率を維持したまま、現像残渣がなく、ポストベイクなどの高温ベーキング後においても平坦性、光透過率、耐溶剤性等の塗膜物性を損なうことなく、低誘電特性に優れた高解像度のパターン膜を形成することができる。そして、該感光性樹脂組成物を用いることにより、優れた特性を有するＦＰＤ及び半導体デバイスを提供することができる。
The present invention can exhibit the following effects.
According to the photosensitive resin composition of the first invention, in the development step of forming a pattern film using a photolithography technique, there is no development residue while maintaining a high residual film ratio, and after high temperature baking such as post baking. In addition, a high-resolution pattern film having excellent low dielectric properties can be formed without impairing coating film properties such as flatness, light transmittance, and solvent resistance. And the FPD and semiconductor device which have the outstanding characteristic can be provided by using this photosensitive resin composition.
以下、本発明を具体化した実施形態について詳細に説明する。
本実施形態の感光性樹脂組成物は、下記に示す成分（Ａ）、（Ｂ）及び（Ｃ）を含有し、各成分の構成割合が（Ａ）１００質量部に対して（Ｂ）５〜５０質量部及び（Ｃ）１〜７０質量部に設定されたものである。
DESCRIPTION OF EMBODIMENTS Hereinafter, embodiments embodying the present invention will be described in detail.
The photosensitive resin composition of the present embodiment, components shown in the following (A), (B) and (C) containing, composition ratio of each component (A) with respect to 100 parts by weight of (B). 5 to It is set to 50 parts by mass and (C) 1 to 70 parts by mass.
成分（Ａ）：特定の共重合体。
成分（Ｂ）：特定のキノンジアジド基を有する感光剤。
成分（Ｃ）：特定のエポキシ基を有する硬化剤。
Component (A): a specific copolymer.
Component (B): Photosensitizer having a specific quinonediazide group.
Component (C): a curing agent having a specific epoxy group.
以下に各成分について順に説明する。
＜成分（Ａ）：特定の共重合体＞
成分（Ａ）の共重合体は、下記式（１）で表されるフマル酸ジエステル単量体から誘導される構成単位（ａ１）、下記式（２）で表される芳香族ビニル単量体から誘導される構成単位（ａ２）、下記式（３）で表されるα，β−不飽和カルボン酸単量体から誘導される構成単位（ａ３）及び下記式（４）で表される（メタ）アクリル酸エステル単量体から誘導される構成単位（ａ４）から構成されている。そして、前記構成単位（ａ１）と構成単位（ａ２）の合計量が４０〜８５質量％であり、構成単位（ａ３）と構成単位（ａ４）の質量比（ａ４）／（ａ３）が０．２〜７．０である。
Below, each component is demonstrated in order.
<Component (A): Specific copolymer>
The copolymer of component (A) is a structural unit (a1) derived from a fumaric acid diester monomer represented by the following formula (1), an aromatic vinyl monomer represented by the following formula (2) A structural unit derived from (a2), a structural unit derived from an α, β-unsaturated carboxylic acid monomer represented by the following formula (3), and a structural unit represented by the following formula (4) ( It is comprised from the structural unit (a4) induced | guided | derived from a meth) acrylic acid ester monomer. And the total amount of the said structural unit (a1) and a structural unit (a2) is 40-85 mass%, and mass ratio (a4) / (a3) of a structural unit (a3) and a structural unit (a4) is 0.00. 2 to 7.0.
前記式（１）〜（４）で表される構成単位はそれぞれ下記式（６）〜（９）で表される単量体（各構成単位用単量体）から誘導される。
The structural units represented by the formulas (1) to (4) are derived from monomers (monomers for each structural unit) represented by the following formulas (6) to (9), respectively.
〔フマル酸ジエステル単量体から誘導される構成単位（ａ１）〕
フマル酸ジエステル単量体から誘導される構成単位（ａ１）は、主鎖構造となる部分にメチレン基を有さず主鎖の炭素上に置換基が結合していることにより、フマル酸ジエステルで構成される重合体は剛直な主鎖構造を有する。そのため、主鎖の分子鎖熱運動性が抑制されることにより、特定の周波数帯域において熱エネルギーへの損失がないため、良好な低誘電特性を得ることができる。
[Structural Unit Derived from Fumaric Acid Diester Monomer (a1)]
The structural unit (a1) derived from the fumaric acid diester monomer is a fumaric acid diester because it has no methylene group in the main chain structure and a substituent is bonded to the carbon of the main chain. The constructed polymer has a rigid main chain structure. Therefore, since the thermal mobility of the molecular chain of the main chain is suppressed, there is no loss to thermal energy in a specific frequency band, so that a favorable low dielectric property can be obtained.
前記式（１）におけるＲ１及びＲ２は、それぞれ独立して炭素数３〜８の分岐アルキル基、炭素数４〜１２のシクロアルキル基又は置換分岐シクロアルキル基である。Ｒ１及びＲ２として好ましくは炭素数３〜６の分岐アルキル基、炭素数６〜１０のシクロアルキル基又は置換分岐シクロアルキル基である。より好ましくは３〜５の分岐アルキル基又は炭素数６〜８のシクロアルキル基である。 R 1 and R 2 in Formula (1) are each independently a branched alkyl group having 3 to 8 carbon atoms, a cycloalkyl group having 4 to 12 carbon atoms, or a substituted branched cycloalkyl group. R 1 and R 2 are preferably a branched alkyl group having 3 to 6 carbon atoms, a cycloalkyl group having 6 to 10 carbon atoms, or a substituted branched cycloalkyl group. More preferably, they are a 3-5 branched alkyl group or a C6-C8 cycloalkyl group.
分岐アルキル基の炭素数が８を超えると重合性が低下してしまい不都合な場合が生ずる。また、シクロアルキル基又は置換分岐シクロアルキル基の炭素数が１２を超えると、十分な現像性が得られないという問題がある。前記式（１）におけるＲ１及びＲ２は、同一の置換基であっても、異なる置換基であっても良いが、入手性の面から同一の構造であることが好ましい。
〔芳香族ビニル単量体から誘導される構成単位（ａ２）〕
構成単位（ａ２）を誘導する芳香族ビニル単量体は、重合時に構成単位（ａ１）を誘導するフマル酸ジエステル単量体との共重合反応性を向上させることができる。フマル酸ジエステル単量体は、電子受容性の強い単量体であるため、（メタ）アクリル酸エステルやアクリロニトリルのような極性のある単量体との共重合反応性は低いが、電子供与性の単量体との共重合性は比較的高い。構成単位（ａ２）を誘導する芳香族ビニル単量体は、フマル酸ジエステル単量体、α，β−不飽和カルボン酸単量体及び（メタ）アクリル酸エステル単量体の三者のいずれの単量体とも共重合性が良好である。このため、重合反応時に共重合性の異なる単量体から誘導される各構成単位を円滑に重合体中に導入することができ、共重合組成に分布の偏りがなく、均一な性質を有する共重合体を得ることができる。
If the branched alkyl group has more than 8 carbon atoms, the polymerizability is lowered, which may be inconvenient. Further, when the carbon number of the cycloalkyl group or the substituted branched cycloalkyl group exceeds 12, there is a problem that sufficient developability cannot be obtained. R 1 and R 2 in the formula (1) may be the same substituent or different substituents, but are preferably the same structure from the viewpoint of availability.
[Structural Unit Derived from Aromatic Vinyl Monomer (a2)]
The aromatic vinyl monomer that derives the structural unit (a2) can improve the copolymerization reactivity with the fumaric acid diester monomer that induces the structural unit (a1) during polymerization. The fumaric acid diester monomer is a highly electron-accepting monomer, so it has low copolymerization reactivity with polar monomers such as (meth) acrylic acid esters and acrylonitrile, but it has electron donating properties. The copolymerizability with the monomer is relatively high. The aromatic vinyl monomer for deriving the structural unit (a2) is any one of the three components of a fumaric acid diester monomer, an α, β-unsaturated carboxylic acid monomer, and a (meth) acrylic acid ester monomer. Both monomers have good copolymerizability. Therefore, each structural unit derived from monomers having different copolymerizability during the polymerization reaction can be smoothly introduced into the polymer, and the copolymer composition has no uniform distribution and has a uniform property. A polymer can be obtained.
前記式（２）におけるＲ３は水素原子又はメチル基であり、Ｒ４は炭素数６〜１２の芳香族炭化水素基である。Ｒ３として好ましくは水素原子であり、Ｒ４として好ましくは炭素数６〜１０の芳香族炭化水素基である。Ｒ４の炭素数が１２を超えると、感光性樹脂組成物は十分な現像性を発揮することができなくなる。
〔（ａ１）＋（ａ２）の合計量〕
前記のフマル酸ジエステル単量体から誘導される構成単位（ａ１）と芳香族ビニル単量体から誘導される構成単位（ａ２）の共重合体中に含まれる合計量は、４０〜８５質量％、好ましくは４５〜８０質量％であり、さらに好ましくは５０〜７５質量％である。この合計量が４０質量％を下回ると、α，β−不飽和カルボン酸単量体から誘導される構成単位（ａ３）及び（メタ）アクリル酸エステル単量体から誘導される構成単位（ａ４）との共重合性に乏しくなり、かつ共重合体中に剛直なセグメントが少なくなることにより十分な低誘電特性が得られない。その一方、８５質量％を上回ると、共重合体の疎水性が高くなることにより、感光性樹脂組成物の現像性が得られず、パターン上に現像残渣が生ずる。
R 3 in the formula (2) is a hydrogen atom or a methyl group, and R 4 is an aromatic hydrocarbon group having 6 to 12 carbon atoms. R 3 is preferably a hydrogen atom, and R 4 is preferably an aromatic hydrocarbon group having 6 to 10 carbon atoms. When the carbon number of R 4 exceeds 12, the photosensitive resin composition cannot exhibit sufficient developability.
[Total amount of (a1) + (a2)]
The total amount contained in the copolymer of the structural unit (a1) derived from the fumaric acid diester monomer and the structural unit (a2) derived from the aromatic vinyl monomer is 40 to 85% by mass. , Preferably it is 45-80 mass%, More preferably, it is 50-75 mass%. When this total amount is less than 40% by mass, the structural unit (a3) derived from the α, β-unsaturated carboxylic acid monomer and the structural unit (a4) derived from the (meth) acrylic acid ester monomer As a result, the copolymer has poor copolymerizability, and there are few rigid segments in the copolymer, so that sufficient low dielectric properties cannot be obtained. On the other hand, when it exceeds 85% by mass, the hydrophobicity of the copolymer becomes high, so that the developability of the photosensitive resin composition cannot be obtained, and a development residue is generated on the pattern.
成分（Ａ）の（ａ１）＋（ａ２）合計量における（ａ１）及び（ａ２）の好ましい組成比率はモル分率で好ましくは（ａ１）：（ａ２）＝８０：２０〜１０：９０であり、さらに好ましくは７０：３０〜１５：８５である。（ａ１）が８０モル％を上回り、（ａ２）が２０モル％を下回ると、重合反応において（ａ１）の重合性が低下し、共重合性に問題がある。一方、（ａ２）が９０モル％を上回り、（ａ１）が１０モル％を下回ると、成分（Ａ）中における芳香族ビニル単量体から誘導される構成単位が多くなるため、共重合体の疎水性が高くなり、感光性樹脂組成物は十分な現像性を得られないおそれがある。
〔α，β−不飽和カルボン酸単量体から誘導される構成単位（ａ３）〕
α，β−不飽和カルボン酸単量体から誘導される構成単位（ａ３）は、現像工程において現像液に対する溶解性に寄与する成分である。前記式（３）におけるＲ５は水素原子、メチル基又はカルボキシメチル基である。好ましくは水素原子又はメチル基であり、前記以外の構成単位を用いると他の構成単位との共重合性が得られないという問題がある。
The preferred composition ratio of (a1) and (a2) in the total amount of (a1) + (a2) of component (A) is preferably (a1) :( a2) = 80: 20 to 10:90 in terms of mole fraction. More preferably, it is 70: 30-15: 85. When (a1) exceeds 80 mol% and (a2) is less than 20 mol%, the polymerizability of (a1) decreases in the polymerization reaction, and there is a problem in copolymerizability. On the other hand, when (a2) exceeds 90 mol% and (a1) is less than 10 mol%, the number of structural units derived from the aromatic vinyl monomer in component (A) increases, Hydrophobicity becomes high, and there is a possibility that the photosensitive resin composition cannot obtain sufficient developability.
[Structural Unit Derived from α, β-Unsaturated Carboxylic Acid Monomer (a3)]
The structural unit (a3) derived from the α, β-unsaturated carboxylic acid monomer is a component that contributes to solubility in the developer in the development process. R 5 in the formula (3) is a hydrogen atom, a methyl group or a carboxymethyl group. Preferably they are a hydrogen atom or a methyl group, and when a structural unit other than the above is used, there is a problem that copolymerizability with other structural units cannot be obtained.
このα，β−不飽和カルボン酸単量体から誘導される構成単位（ａ３）の含有量により成分（Ａ）の共重合体の酸価を調整することができる。酸価の範囲として好ましくは５０〜２００ｍｇＫＯＨ／ｇ、より好ましくは７０〜１５０ｍｇＫＯＨ／ｇとなるように構成単位（ａ３）の割合を調節する。この酸価が低すぎると現像液に対して十分な溶解性が得られず、その一方酸価が高すぎると現像時の残膜率が低下するおそれがある。
〔（メタ）アクリル酸エステル単量体から誘導される構成単位（ａ４）〕
（メタ）アクリル酸エステル単量体から誘導される構成単位（ａ４）は、現像性の調整、特に現像時の残膜率や解像度に寄与する成分である。前記式（４）におけるＲ６は水素原子又はメチル基、Ｒ７は炭素数６〜１２の芳香族炭化水素基、炭素数１〜１２のアルキル基、炭素数１〜１２の分岐アルキル基、炭素数２〜１２のヒドロキシアルキル基又は主環構成炭素数５〜１２の脂環式炭化水素基である。前記の主環構成炭素数５〜１２の脂環式炭化水素基は、付加的な構造、例えば環内二重結合、炭化水素基の側鎖、スピロ環の側鎖、環内架橋炭化水素基等を含んでいてもよい。Ｒ６として好ましくはメチル基であり、Ｒ７として好ましくは炭素数１〜６のアルキル基若しくは分岐アルキル基、炭素数６〜１０の芳香族炭化水素基、炭素数２〜４のヒドロキシアルキル基又はシクロヘキシル基、ジシクロペンタニル基である。Ｒ７の炭素数が１２を超えると、重合性が低下してしまい不都合な場合がある。構成単位（ａ４）を誘導するこれらの（メタ）アクリル酸エステル単量体は、現像性を調整する目的で１種のみ又は２種以上を組み合わせて用いることができる。
〔質量比（ａ４）／（ａ３）〕
α，β−不飽和カルボン酸単量体から誘導される構成単位（ａ３）と（メタ）アクリル酸エステル単量体から誘導される構成単位（ａ４）の質量比（ａ４）／（ａ３）は、０．２〜７．０であり、好ましくは０．３〜６．０であり、さらに好ましくは０．６〜４．０である。質量比（ａ４）／（ａ３）の値が０．２より低くなると、共重合体中にα，β−不飽和カルボン酸単量体から誘導される構成単位が多くなり、現像時の残膜率が低下するおそれがある。一方、質量比（ａ４）／（ａ３）の値が７．０より高くなると、（メタ）アクリル酸エステル単量体から誘導される構成単位が多くなり、十分な現像性が得られず、現像残渣の発生や、解像度の低下を招く。
The acid value of the copolymer of the component (A) can be adjusted by the content of the structural unit (a3) derived from the α, β-unsaturated carboxylic acid monomer. The proportion of the structural unit (a3) is adjusted so that the acid value is preferably 50 to 200 mgKOH / g, more preferably 70 to 150 mgKOH / g. If the acid value is too low, sufficient solubility in the developer cannot be obtained. On the other hand, if the acid value is too high, the residual film ratio during development may be reduced.
[Structural Unit Derived from (Meth) acrylic Acid Ester Monomer (a4)]
The structural unit (a4) derived from the (meth) acrylic acid ester monomer is a component that contributes to the adjustment of developability, particularly the remaining film ratio and resolution during development. In the formula (4), R 6 is a hydrogen atom or a methyl group, R 7 is an aromatic hydrocarbon group having 6 to 12 carbon atoms, an alkyl group having 1 to 12 carbon atoms, a branched alkyl group having 1 to 12 carbon atoms, carbon It is a C2-C12 hydroxyalkyl group or a main ring constituent C5-C12 alicyclic hydrocarbon group. The alicyclic hydrocarbon group having 5 to 12 carbon atoms constituting the main ring has an additional structure such as an intracyclic double bond, a side chain of a hydrocarbon group, a side chain of a spiro ring, an intracyclic bridged hydrocarbon group. Etc. may be included. R 6 is preferably a methyl group, and R 7 is preferably an alkyl group having 1 to 6 carbon atoms or a branched alkyl group, an aromatic hydrocarbon group having 6 to 10 carbon atoms, a hydroxyalkyl group having 2 to 4 carbon atoms, or A cyclohexyl group and a dicyclopentanyl group. When the number of carbon atoms in R 7 exceeds 12, the polymerizability may be lowered, which may be inconvenient. These (meth) acrylic acid ester monomers for inducing the structural unit (a4) can be used alone or in combination of two or more for the purpose of adjusting developability.
[Mass ratio (a4) / (a3)]
The mass ratio (a4) / (a3) of the structural unit (a3) derived from the α, β-unsaturated carboxylic acid monomer and the structural unit (a4) derived from the (meth) acrylate monomer is 0.2 to 7.0, preferably 0.3 to 6.0, and more preferably 0.6 to 4.0. When the value of the mass ratio (a4) / (a3) is lower than 0.2, the constitutional unit derived from the α, β-unsaturated carboxylic acid monomer in the copolymer increases, and the remaining film during development There is a risk that the rate will decrease. On the other hand, when the value of the mass ratio (a4) / (a3) is higher than 7.0, the number of structural units derived from the (meth) acrylic acid ester monomer increases, and sufficient developability cannot be obtained. Residue generation and resolution decrease.
成分（Ａ）の共重合体を得るために用いられる重合用溶剤としては、一般的に知られている溶剤を用いることができる。このような溶剤の具体的な例として、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル等のエチレングリコールモノアルキルエーテル類；エチレングリコールモノメチルエーテルアセテート、エチレングリコールモノエチルエーテルアセテート等のエチレングリコールモノアルキルエーテルアセテート類；ジエチレングリコールジメチルエーテル、ジエチレングリコールジエチルエーテル、ジエチレングリコールメチルエチルエーテル等のジエチレングリコールジアルキルエーテル類；プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル等のプロピレングリコールモノアルキルエーテル類；プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノエチルエーテルアセテート等のプロピレングリコールモノアルキルエーテルアセテート類；乳酸メチル、乳酸エチル等の乳酸エステル類；トルエン、キシレン等の芳香族炭化水素類；メチルエチルケトン、２−ヘプタノン、シクロヘキサノン等のケトン類；Ｎ，Ｎ−ジメチルアセトアミド、Ｎ−メチルピロリドン等のアミド類；γ−ブチロラクトン等のラクトン類等が挙げられる。これらの重合溶剤は、単独で又は２種以上を混合して使用することができる。 As the polymerization solvent used for obtaining the copolymer of component (A), generally known solvents can be used. Specific examples of such solvents include ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate and ethylene glycol monoethyl ether acetate. Diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether and diethylene glycol methyl ethyl ether; propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether and propylene glycol monoethyl ether; propylene glycol monomethyl ether acetate, propylene glycol mono Propylene glycol monoalkyl ether acetates such as tilether acetate; Lactic acid esters such as methyl lactate and ethyl lactate; Aromatic hydrocarbons such as toluene and xylene; Ketones such as methyl ethyl ketone, 2-heptanone and cyclohexanone; N, N -Amides such as dimethylacetamide and N-methylpyrrolidone; and lactones such as γ-butyrolactone. These polymerization solvents can be used alone or in admixture of two or more.
成分（Ａ）の共重合体を得るために用いられる重合開始剤としては、一般的にラジカル重合開始剤として知られているものを使用することができる。その具体例としては、アゾ系重合開始剤特にシアノ基を有しないアゾ系重合開始剤又は有機過酸化物及び過酸化水素等を用いることができる。ラジカル重合開始剤として過酸化物を使用する場合には、これと還元剤とを組み合わせてレドックス型重合開始剤として使用してもよい。 As the polymerization initiator used for obtaining the copolymer of component (A), those generally known as radical polymerization initiators can be used. As a specific example thereof, an azo polymerization initiator, particularly an azo polymerization initiator having no cyano group or an organic peroxide and hydrogen peroxide can be used. When a peroxide is used as the radical polymerization initiator, it may be used as a redox polymerization initiator in combination with a reducing agent.
成分（Ａ）の共重合体を得る際の重量平均分子量を調節するために分子量調節剤を使用することができる。分子量調節剤としては、例えばｎ−ヘキシルメルカプタン、ｎ−オクチルメルカプタン、ｎ−ドデシルメルカプタン、ｔｅｒｔ−ドデシルメルカプタン、チオグリコール酸、メルカプトプロピオン酸等のメルカプタン類；ジメチルキサントゲンジスルフィド、ジイソプロピルキサントゲンジスルフィド等のキサントゲン類；ターピノーレン、α−メチルスチレンダイマー等が挙げられる。 In order to adjust the weight average molecular weight when obtaining the copolymer of the component (A), a molecular weight regulator can be used. Examples of molecular weight regulators include mercaptans such as n-hexyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, tert-dodecyl mercaptan, thioglycolic acid, mercaptopropionic acid, and xanthogens such as dimethylxanthogen disulfide and diisopropylxanthogen disulfide. A terpinolene, an α-methylstyrene dimer, and the like.
成分（Ａ）の共重合体の重量平均分子量として好ましくは５，０００〜６０，０００、より好ましくは５，０００〜３０，０００、さらに好ましくは８，０００〜２５，０００である。重量平均分子量が５，０００未満の場合にはポストベイク時にパターンフローが起こり、パターン膜の十分な解像度が得られないおそれがあり、６０，０００を超える場合には現像液に対する溶解性に乏しく、満足できる現像性が得られないおそれがある。
＜成分（Ｂ）：特定のキノンジアジド基を有する感光剤＞
特定の成分（Ｂ）のキノンジアジド基を有する感光剤は、フォトリソグラフィーによる露光工程においてフォトマスクを介して露光する際、露光部ではキノンジアジド基を有する感光剤の光異性化反応が起こることにより、カルボキシル基を生成し、その後の現像工程において現像液に対して露光部のレジスト膜を溶解させることができる。他方、未露光部は、カルボキシル基を生成しないため、レジスト膜の現像液に対する溶解を抑制することができ、その結果膜が残存し、パターン膜を形成することができる。
The weight average molecular weight of the component (A) copolymer is preferably 5,000 to 60,000, more preferably 5,000 to 30,000, and still more preferably 8,000 to 25,000. If the weight average molecular weight is less than 5,000, pattern flow may occur during post-baking, and sufficient resolution of the pattern film may not be obtained. If it exceeds 60,000, the solubility in the developer is poor and satisfactory. There is a possibility that developability that can be obtained is not obtained.
<Component (B): Photosensitizer having a specific quinonediazide group>
The photosensitive agent having a quinonediazide group of the specific component (B) is subjected to a photoisomerization reaction of the photosensitive agent having a quinonediazide group at the exposed portion when exposed through a photomask in an exposure process by photolithography. A group is generated, and the resist film in the exposed portion can be dissolved in the developer in the subsequent development process. On the other hand, since the unexposed portion does not generate a carboxyl group, dissolution of the resist film in the developer can be suppressed, and as a result, the film remains and a pattern film can be formed.
成分（Ｂ）のキノンジアジド基を有する感光剤は、水酸基を有するフェノール性化合物と、キノンジアジド化合物とをエステル化反応させて得ることができる。キノンジアジド化合物としては、１，２−ナフトキノンジアジド−５−スルフォニルクロライド、１，２−ナフトキノンジアジド−４−スルフォニルクロライド等に代表されるナフトキノンジアジドスルホン酸クロリドやベンゾキノンジアジドスルホン酸クロリドのようなキノンジアジドスルホン酸ハライドが用いられる。 The photosensitive agent having a quinonediazide group as component (B) can be obtained by esterifying a phenolic compound having a hydroxyl group and a quinonediazide compound. Examples of the quinonediazide compound include quinonediazidesulfonic acid such as naphthoquinonediazidesulfonic acid chloride and benzoquinonediazidesulfonic acid chloride represented by 1,2-naphthoquinonediazide-5-sulfonyl chloride, 1,2-naphthoquinonediazide-4-sulfonylchloride, and the like. Halides are used.
エステル化反応は、水酸基を有するフェノール性化合物とキノンジアジドスルホン酸ハライドとを、塩基性触媒例えば水酸化ナトリウム、炭酸ナトリウム、炭酸水素ナトリウム、トリエチルアミン等の存在下で、通常−２０〜６０℃程度の温度で反応させることにより行われる。エステル化率は、水酸基を有するフェノール性化合物の量とキノンジアジド化合物の量を調整することによって適宜のものとすることができる。このエステル化反応においては、エステル化数及びエステル化位置が種々異なる混合物が得られる。従って、エステル化率はこれら混合物の平均値として表わされる。また、これら反応生成物は、１種を単独で用いてもよく、２種以上を併用してもよい。 In the esterification reaction, a phenolic compound having a hydroxyl group and a quinonediazide sulfonic acid halide are usually reacted at a temperature of about -20 to 60 ° C in the presence of a basic catalyst such as sodium hydroxide, sodium carbonate, sodium hydrogen carbonate, triethylamine or the like. It is performed by making it react with. The esterification rate can be appropriately adjusted by adjusting the amount of the phenolic compound having a hydroxyl group and the amount of the quinonediazide compound. In this esterification reaction, mixtures with different esterification numbers and esterification positions are obtained. Accordingly, the esterification rate is expressed as an average value of these mixtures. Moreover, these reaction products may be used individually by 1 type, and may use 2 or more types together.
キノンジアジド基を有する感光剤のエステル化率は、好ましくは２０〜９５モル％、より好ましくは３５〜９０モル％である。エステル化率が２０モル％を下回ると感度の低下を招くおそれがあり、９５モル％を上回ると共重合体との相溶性が悪化してパターン膜が相分離し、白濁するおそれがある。 The esterification rate of the photosensitizer having a quinonediazide group is preferably 20 to 95 mol%, more preferably 35 to 90 mol%. If the esterification rate is less than 20 mol%, the sensitivity may be lowered. If the esterification rate is more than 95 mol%, the compatibility with the copolymer is deteriorated, and the pattern film may be phase-separated and cloudy.
キノンジアジド基を有する感光剤に使用できる水酸基を有するフェノール性化合物としては、下記式（１０）又は（１１）で表される化合物が好ましい。 As the phenolic compound having a hydroxyl group that can be used in a photosensitizer having a quinonediazide group, a compound represented by the following formula (10) or (11) is preferable.
前記式（１０）で示されるフェノール性化合物としては、例えば次のような化合物が挙げられる。
Examples of the phenolic compound represented by the formula (10) include the following compounds.
これらの一般式（１１）で表されるフェノール性化合物の中では、特に下記式（１６）又は下記式（１７）で表される化合物が好ましい。 Among the phenolic compounds represented by the general formula (11), a compound represented by the following formula (16) or the following formula (17) is particularly preferable.
＜成分（Ｃ）：特定のエポキシ基を有する硬化剤＞
本発明の感光性樹脂組成物に用いられる特定の硬化剤は前記式（５）に示される構造を有する。成分（Ｃ）のエポキシ基を有する硬化剤は、パターン膜を形成する際のフォトリソグラフィー工程において、露光部と未露光部のコントラストを向上させる効果が非常に高く、高い残膜率を維持したまま、現像残渣のないパターン膜を得ることができる。成分（Ｃ）のエポキシ基を有する硬化剤の構造は、シクロヘキシル基の末端が水酸基となっている。このため、未露光部ではシクロヘキシル基の高い結晶性によりアルカリ現像液の浸透を抑制し、露光部では末端の水酸基によりアルカリ現像液への溶解性が向上する。従って、成分（Ｃ）のエポキシ樹脂を有する硬化剤を多量に導入しても前記の特性を得ることができる。さらに、成分（Ｃ）のエポキシ樹脂を有する硬化剤はシクロヘキシル基の側鎖にエポキシ基を有しているため、共重合体（Ａ）の側鎖のカルボキシル基と高温ベーキング時に熱硬化反応を起こし、架橋膜を形成することができる。
<Component (C): Curing agent having specific epoxy group>
The specific hardening | curing agent used for the photosensitive resin composition of this invention has a structure shown by said Formula (5). The curing agent having an epoxy group as the component (C) has a very high effect of improving the contrast between the exposed area and the unexposed area in the photolithography process when forming the pattern film, and maintains a high residual film ratio. A pattern film having no development residue can be obtained. In the structure of the curing agent having an epoxy group of component (C), the terminal of the cyclohexyl group is a hydroxyl group. For this reason, penetration of the alkali developer is suppressed by the high crystallinity of the cyclohexyl group in the unexposed area, and solubility in the alkali developer is improved by the terminal hydroxyl group in the exposed area. Therefore, the above characteristics can be obtained even when a large amount of a curing agent having an epoxy resin as component (C) is introduced. Furthermore, since the curing agent having the epoxy resin of component (C) has an epoxy group in the side chain of the cyclohexyl group, it causes a thermosetting reaction with the carboxyl group in the side chain of the copolymer (A) during high temperature baking. A crosslinked film can be formed.
前記式（５）におけるＲ８は炭素数１〜１０の炭化水素基、ｓ及びｔはそれぞれ１〜３０及び１〜６の整数である。Ｒ８として好ましくは炭素数３〜８の炭化水素基、ｓ及びｔはそれぞれ３〜２０及び１〜５の整数であり、より好ましくは炭素数３〜６の炭化水素基、ｓ及びｔはそれぞれ５〜２０及び１〜４の整数である。 R 8 in the formula (5) is a hydrocarbon group having 1 to 10 carbon atoms, and s and t are integers of 1 to 30 and 1 to 6, respectively. R 8 is preferably a hydrocarbon group having 3 to 8 carbon atoms, s and t are each an integer of 3 to 20 and 1 to 5, more preferably a hydrocarbon group having 3 to 6 carbon atoms, and s and t are respectively It is an integer of 5-20 and 1-4.
前記式（５）で表されるエポキシ基を有する硬化剤の具体例として、例えば２，２−ビス（ヒドロキシメチル）−１−ブタノールの１，２−エポキシ−４−（２−オキシラニル）シクロヘキサン付加物（ダイセル化学工業（株）製、ＥＨＰＥ３１５０）などが挙げられる。 As a specific example of the curing agent having an epoxy group represented by the formula (5), for example, 1,2-epoxy-4- (2-oxiranyl) cyclohexane addition of 2,2-bis (hydroxymethyl) -1-butanol Products (Daicel Chemical Industries, Ltd., EHPE3150).
感光性樹脂組成物における、成分（Ｃ）の硬化剤の構成割合は、成分（Ａ）の共重合体１００質量部に対して、１〜７０質量部、好ましくは５〜６５質量部、さらに好ましくは１０〜６０質量部である。この構成割合が１質量部を下回ると現像時の残膜率が不十分になり、７０質量部を上回ると、アルカリ現像液に対する溶解性が悪化し、現像残渣が発生するおそれがある。
＜その他の添加成分＞
感光性樹脂組成物には、溶剤、硬化促進剤、コントラスト向上剤、相溶化剤、密着性向上助剤、界面活性剤等の添加成分を添加して使用することができる。
（溶剤）
溶剤の具体例としては、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル等のエチレングリコールモノアルキルエーテル類、エチレングリコールモノメチルエーテルアセテート、エチレングリコールモノエチルエーテルアセテート等のエチレングリコールモノアルキルエーテルアセテート類、ジエチレングリコールジメチルエーテル、ジエチレングリコールジエチルエーテル、ジエチレングリコールメチルエチルエーテル等のジエチレングリコールジアルキルエーテル類、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル等のプロピレングリコールモノアルキルエーテル類、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノエチルエーテルアセテート等のプロピレングリコールモノアルキルエーテルアセテート類、乳酸メチル、乳酸エチル等の乳酸エステル類、トルエン、キシレン等の芳香族炭化水素類、メチルエチルケトン、２−ヘプタノン、シクロヘキサノン等のケトン類、Ｎ，Ｎ−ジメチルアセトアミド、Ｎ−メチルピロリドン等のアミド類、γ−ブチロラクトン等のラクトン類等が挙げられる。これらの溶剤は、単独で又は２種以上を混合して使用することができる。
（硬化促進剤）
硬化促進剤は、前記成分（Ｃ）の硬化剤と成分（Ａ）共重合体の側鎖のカルボキシル基との架橋反応を促進させることや前記成分（Ｃ）の硬化剤の単独硬化反応を促進させることができる。硬化促進剤としては、例えばＳＩ−４５Ｌ、ＳＩ−６０Ｌ、ＳＩ−８０Ｌ、ＳＩ−１００Ｌ、ＳＩ−１１０Ｌ、ＳＩ−１５０Ｌ〔以上、三新化学工業（株）製〕等の芳香族スルホニウム塩；Ｕ−ＣＡＴ ＳＡ１０２、Ｕ−ＣＡＴ ＳＡ１０６、Ｕ−ＣＡＴ ＳＡ５０６、Ｕ−ＣＡＴ ＳＡ６０３、Ｕ−ＣＡＴ ５００２〔以上、サンアプロ（株）製〕等のジアザビシクロウンデセン塩；ＣＰＩ−１００Ｐ、ＣＰＩ−１０１Ａ、ＣＰＩ−２１０Ｋ、ＣＰＩ−２１０Ｓ〔以上、サンアプロ（株）製〕等の光酸発生剤が挙げられる。さらに、イミダゾール系の硬化促進剤としては、キュアゾール １Ｂ２ＰＺ〔四国化成工業（株）製〕が挙げられる。
The composition ratio of the curing agent of component (C) in the photosensitive resin composition is 1 to 70 parts by weight, preferably 5 to 65 parts by weight, more preferably 100 parts by weight of the copolymer of component (A). Is 10-60 parts by mass. If this constituent ratio is less than 1 part by mass, the remaining film ratio during development becomes insufficient, and if it exceeds 70 parts by mass, the solubility in an alkaline developer is deteriorated, and a development residue may be generated.
<Other additive components>
The photosensitive resin composition can be used by adding additional components such as a solvent, a curing accelerator, a contrast improver, a compatibilizer, an adhesion improving aid, and a surfactant.
(solvent)
Specific examples of the solvent include ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether, ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate and ethylene glycol monoethyl ether acetate, and diethylene glycol dimethyl ether. , Diethylene glycol dialkyl ethers such as diethylene glycol diethyl ether and diethylene glycol methyl ethyl ether, propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether and propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether Propylene glycol monoalkyl ether acetates such as acetate, lactic esters such as methyl lactate and ethyl lactate, aromatic hydrocarbons such as toluene and xylene, ketones such as methyl ethyl ketone, 2-heptanone and cyclohexanone, N, N-dimethyl Examples include amides such as acetamide and N-methylpyrrolidone, and lactones such as γ-butyrolactone. These solvents can be used alone or in admixture of two or more.
(Curing accelerator)
The curing accelerator promotes the crosslinking reaction between the curing agent of the component (C) and the carboxyl group of the side chain of the component (A) copolymer, or promotes the single curing reaction of the curing agent of the component (C). Can be made. Examples of the curing accelerator include aromatic sulfonium salts such as SI-45L, SI-60L, SI-80L, SI-100L, SI-110L, SI-150L (manufactured by Sanshin Chemical Industry Co., Ltd.); U Diazabicycloundecene salts such as -CAT SA102, U-CAT SA106, U-CAT SA506, U-CAT SA603, U-CAT 5002 [manufactured by San Apro Co., Ltd.]; CPI-100P, CPI-101A, CPI -210K, CPI-210S [above, the San Apro Co., Ltd. product] photoacid generators etc. are mentioned. Furthermore, examples of the imidazole-based curing accelerator include Curesol 1B2PZ [manufactured by Shikoku Chemicals Co., Ltd.].
また、光を照射することによって塩基を発生する光塩基発生剤等も使用することができる。この光塩基発生剤はブリーチング工程時の条件を調整することにより、光照射時にアミンなどの塩基を発生し、その後のポストベイク工程において架橋促進剤として用いることができる。 Moreover, the photobase generator etc. which generate | occur | produce a base by irradiating light can also be used. This photobase generator generates a base such as an amine during light irradiation by adjusting the conditions during the bleaching step, and can be used as a crosslinking accelerator in the subsequent post-baking step.
硬化促進剤の構成割合は、成分（Ｃ）の硬化剤１００質量部に対し、０．１〜１５質量部が好ましく、１〜１０質量部がより好ましい。
（コントラスト向上剤）
感光性樹脂組成物には、コントラストの向上を目的として、前記式（１０）又は（１１）で示される水酸基を有するフェノール性化合物を配合することができる。水酸基を有するフェノール性化合物は低分子であるため、感光性樹脂組成物において通常溶解促進剤として溶解速度を調節するために、又は感光性樹脂組成物の感度の向上或いは感度の調節のために好適である。これらの溶解速度或いは感度の調節は、フェノール性化合物の添加量を調節することにより行われ、溶解速度及び感度を向上させる場合には添加量を多くすればよく、また逆の場合には添加量を少なくすればよい。これらのフェノール性化合物を用いることにより、用いない場合に比べ、感光剤とアゾカップリング反応を起こす溶解抑止される樹脂成分に低分子化合物が含まれることとなり、これによって露光部と未露光部の溶解速度の差を大きくする（コントラストを大きくする）ことができ、解像度を向上させることができる。
0.1-15 mass parts is preferable with respect to 100 mass parts of hardening | curing agents of a component (C), and, as for the structure ratio of a hardening accelerator, 1-10 mass parts is more preferable.
(Contrast improver)
In the photosensitive resin composition, a phenolic compound having a hydroxyl group represented by the formula (10) or (11) can be blended for the purpose of improving the contrast. Since the phenolic compound having a hydroxyl group is a low molecule, it is suitable for adjusting the dissolution rate as a normal dissolution accelerator in the photosensitive resin composition, or for improving the sensitivity of the photosensitive resin composition or adjusting the sensitivity. It is. The dissolution rate or sensitivity is adjusted by adjusting the addition amount of the phenolic compound. To improve the dissolution rate and sensitivity, the addition amount may be increased, and vice versa. Should be reduced. By using these phenolic compounds, compared to the case where they are not used, a low molecular weight compound is contained in the resin component that inhibits dissolution that causes an azo coupling reaction with the photosensitive agent. The difference in dissolution rate can be increased (contrast can be increased), and the resolution can be improved.
水酸基を有するフェノール性化合物として好ましくは、前記式（１３）、（１４）、（１５）、（１６）又は（１７）であり、通常共重合体１００質量部に対して、１〜２０質量部の量で用いられる。
（相溶化剤）
感光性樹脂組成物には、成分（Ａ）共重合体、成分（Ｂ）キノンジアジド基を有する感光剤及び成分（Ｃ）エポキシ基を有する硬化剤の相溶性を向上させる目的で、下記式（１８）に示す、２個以上のカルボキシル基の一部が高級アルコールでエステル化されたポリカルボン酸エステル化合物をさらに配合することができる。
The phenolic compound having a hydroxyl group is preferably the formula (13), (14), (15), (16) or (17), and usually 1 to 20 parts by mass with respect to 100 parts by mass of the copolymer. Used in the amount of.
(Compatibilizer)
The photosensitive resin composition has the following formula (18) for the purpose of improving the compatibility of the component (A) copolymer, the component (B) a photosensitizer having a quinonediazide group, and the component (C) a curing agent having an epoxy group. And a polycarboxylic acid ester compound in which some of the two or more carboxyl groups are esterified with a higher alcohol can be further blended.
ポリカルボン酸エステル化合物の含有量は、成分（Ａ）の共重合体１００質量部に対して好ましくは０．０１〜１０質量部、より好ましくは０．５〜５質量部である。ポリカルボン酸エステル化合物の含有量が１０質量部より多いと、形成される被膜の耐熱性が低下するおそれがある。
（密着性向上助剤及び界面活性剤）
感光性樹脂組成物には、必要に応じ密着性向上助剤及び界面活性剤等をさらに配合することができる。密着性向上助剤の例としては、アルキルイミダゾリン、酪酸、アルキル酸、ポリヒドロキシスチレン、ポリビニルメチルエーテル、ｔ−ブチルノボラック、エポキシシラン、エポキシポリマー、シランカップリング剤等が挙げられる。界面活性剤の例としては、非イオン系界面活性剤、例えばポリグリコール類とその誘導体、すなわちポリプロピレングリコール又はポリオキシエチレンラウリルエーテル、フッ素含有界面活性剤、例えばフロラード〔商品名、住友３Ｍ（株）製〕、メガファック〔商品名、大日本インキ化学工業（株）製〕、スルフロン〔商品名、旭ガラス（株）製〕又は有機シロキサン界面活性剤、例えばＫＰ３４１〔商品名、信越化学工業（株）製〕が挙げられる。
＜感光性樹脂組成物の調製法＞
感光性樹脂組成物又はその希釈物を調製するに際しては、前記成分（Ａ）、（Ｂ）及び（Ｃ）をはじめとする各成分を一括配合してもよいし、各成分を溶剤に溶解した後に逐次配合してもよい。また、配合する際の投入順序や作業条件は特に制約を受けない。例えば、全成分を同時に溶剤に溶解して樹脂組成物を調製してもよいし、必要に応じて各成分を適宜２つ以上の溶液としておいて、使用時（塗布時）にこれらの溶液を混合して感光性樹脂組成物として調製してもよい。
＜フラットパネルディスプレイ及び半導体デバイス＞
前述した感光性樹脂組成物の用途としてのフラットパネルディスプレイ及び半導体デバイスは、感光性樹脂組成物の硬化した層、すなわち平坦化膜又は層間絶縁膜を有する。平坦化膜及び層間絶縁膜の形成に際しては、通常感光性樹脂組成物の溶液を基板上に塗布し、プリベイクを行って感光性樹脂組成物の塗膜（ポジ型フォトレジスト膜）を形成する。このとき、感光性樹脂組成物が塗布される基板は、ガラス、シリコンなど従来ＦＰＤ用又は半導体デバイス形成用の基板など公知のいずれの基板であってもよい。基板はベアな基板でも、酸化膜、窒化膜、金属膜などが形成されていても、さらには回路パターン或いは半導体デバイスなどが形成されている基板であってもよい。また、プリベイクの温度は通常４０〜１４０℃で、時間は０〜１５分程度である。
The content of the polycarboxylic acid ester compound is preferably 0.01 to 10 parts by mass, more preferably 0.5 to 5 parts by mass with respect to 100 parts by mass of the copolymer of component (A). When there is more content of a polycarboxylic acid ester compound than 10 mass parts, there exists a possibility that the heat resistance of the film formed may fall.
(Adhesion improvement aid and surfactant)
If necessary, the photosensitive resin composition may further contain an adhesion improving aid and a surfactant. Examples of the adhesion improving aid include alkyl imidazoline, butyric acid, alkyl acid, polyhydroxystyrene, polyvinyl methyl ether, t-butyl novolac, epoxy silane, epoxy polymer, silane coupling agent and the like. Examples of the surfactant include nonionic surfactants such as polyglycols and derivatives thereof, that is, polypropylene glycol or polyoxyethylene lauryl ether, fluorine-containing surfactants such as Florard [trade name, Sumitomo 3M Co., Ltd. , Megafuck [trade name, manufactured by Dainippon Ink & Chemicals, Inc.], Sulflon [trade name, manufactured by Asahi Glass Co., Ltd.] or organosiloxane surfactants such as KP341 [trade name, Shin-Etsu Chemical Co., Ltd. ) Made].
<Method for preparing photosensitive resin composition>
In preparing the photosensitive resin composition or a diluted product thereof, the components including the components (A), (B) and (C) may be blended together, or each component may be dissolved in a solvent. You may mix | blend sequentially later. In addition, there are no particular restrictions on the charging order and working conditions when blending. For example, the resin composition may be prepared by dissolving all the components in a solvent at the same time, and if necessary, each component is appropriately made into two or more solutions, and these solutions are used at the time of use (at the time of application). You may mix and prepare as a photosensitive resin composition.
<Flat panel display and semiconductor device>
The flat panel display and semiconductor device used as the photosensitive resin composition described above have a cured layer of the photosensitive resin composition, that is, a planarization film or an interlayer insulating film. In forming the planarizing film and the interlayer insulating film, a solution of a photosensitive resin composition is usually applied on a substrate and prebaked to form a coating film (positive photoresist film) of the photosensitive resin composition. At this time, the substrate to which the photosensitive resin composition is applied may be any known substrate such as a conventional FPD substrate or a semiconductor device forming substrate such as glass or silicon. The substrate may be a bare substrate, may be formed with an oxide film, a nitride film, a metal film, or the like, or may be a substrate on which a circuit pattern or a semiconductor device is formed. Moreover, the temperature of prebaking is 40-140 degreeC normally, and time is about 0-15 minutes.
次いで、ポジ型フォトレジスト膜に所定のマスクを介してパターン露光を行った後、アルカリ現像液を用いて現像処理し、必要に応じリンス処理を行って、感光性樹脂組成物の膜を形成する。このようにして形成された膜は、全面露光された後、ポストベイクされてパターン膜が形成される。全面露光の際の露光量は、通常６００ｍＪ／ｃｍ２以上であればよい。また、ポストベイク温度は通常１５０〜２５０℃、好ましくは１８０〜２３０℃、ポストベイク時間は、通常３０〜９０分である。 Next, after pattern exposure is performed on the positive photoresist film through a predetermined mask, development processing is performed using an alkali developer, and rinsing is performed as necessary to form a film of the photosensitive resin composition. . The film thus formed is exposed to the entire surface and then post-baked to form a pattern film. The exposure amount during the entire surface exposure is usually 600 mJ / cm 2 or more. The post-baking temperature is usually 150 to 250 ° C., preferably 180 to 230 ° C., and the post-baking time is usually 30 to 90 minutes.
感光性樹脂組成物を用いて形成されたパターン膜は、半導体デバイスや液晶表示装置、プラズマディスプレイなどのＦＰＤの平坦化膜或いは層間絶縁膜などとして利用される。ここで平坦化膜と層間絶縁膜とは全く独立したものではなく、感光性樹脂組成物により形成されたパターン膜は、平坦化膜としても、層間絶縁膜としても利用し得るものである。そして、半導体デバイスなどにおいては、そのような膜は層間絶縁膜としても平坦化膜としても機能する。 The pattern film formed using the photosensitive resin composition is used as a flattening film or an interlayer insulating film of an FPD such as a semiconductor device, a liquid crystal display device, or a plasma display. Here, the planarizing film and the interlayer insulating film are not completely independent, and the pattern film formed of the photosensitive resin composition can be used as the planarizing film or the interlayer insulating film. In a semiconductor device or the like, such a film functions as both an interlayer insulating film and a planarizing film.
前記パターン膜の形成において、感光性樹脂組成物又はその希釈物の塗布方法としては、スピンコート法、ロールコート法、ランドコート法、スプレー法、流延塗布法、浸漬塗布法、スリット塗布法など任意の方法を用いればよい。また、露光に用いられる放射線としては、例えばｇ線、ｈ線、ｉ線などの紫外線、ＫｒＦエキシマレーザー光或いはＡｒＦエキシマレーザー光などの遠紫外線、Ｘ線、電子線などが挙げられる。 In the formation of the pattern film, the coating method of the photosensitive resin composition or dilution thereof includes spin coating, roll coating, land coating, spraying, casting coating, dip coating, slit coating, and the like. Any method may be used. Examples of radiation used for exposure include ultraviolet rays such as g-rays, h-rays, and i-rays, far ultraviolet rays such as KrF excimer laser light or ArF excimer laser light, X-rays, and electron beams.
現像法としては、パドル現像法、浸漬現像法、揺動浸漬現像法、シャワー式現像法など従来フォトレジストを現像する際に用いられている方法によればよい。また現像剤としては、水酸化ナトリウム、水酸化カリウム、炭酸ナトリウム、珪酸ナトリウムなどの無機アルカリ、アンモニア、エチルアミン、プロピルアミン、ジエチルアミン、ジエチルアミノエタノール、トリエチルアミンなどの有機アミン、テトラメチルアンモニウムヒドロキシドなどの第四級アミンなどを所定の濃度に調整した水溶液を用いることができる。 As a developing method, a method conventionally used for developing a photoresist, such as a paddle developing method, an immersion developing method, a swinging immersion developing method, or a shower type developing method may be used. Developers include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate and sodium silicate, organic amines such as ammonia, ethylamine, propylamine, diethylamine, diethylaminoethanol and triethylamine, and tetramethylammonium hydroxide. An aqueous solution in which a quaternary amine or the like is adjusted to a predetermined concentration can be used.
以下、合成例、実施例及び比較例を挙げて前記実施形態をさらに具体的に説明する。なお「部」及び「％」は、特に断りがない限り全て質量基準である。以下に各実施例及び各比較例で用いた測定方法及び評価方法を示す。
＜重量平均分子量＞
重量平均分子量（Ｍｗ）は、東ソー（株）製ゲルパーミエーションクロマトグラフィー装置ＨＬＣ−８２２０ＧＰＣを用い、カラムとして昭和電工（株）製ＳＨＯＤＥＸ Ｋ８０１を用い、ＴＨＦを溶離液とし、ＲＩ検出器により測定して分子量既知のポリスチレン標準体により得られる検量線を用いた換算により求めた。
＜加熱残分＞
加熱残分（質量％）は、樹脂の溶液１ｇを精秤し、熱風オーブンで１７０℃、１時間乾燥後に乾燥前後の質量変化から算出した残存率より算出した。
＜酸価＞
酸価（ｍｇＫＯＨ／ｇ）は、ＪＩＳ Ｋ００７０：１９９２「化学製品の酸価、けん化価、エステル価、よう素価、水酸基価及び不けん化物の試験方法」に準じて、テトラヒドロフラン（ＴＨＦ）溶液に、一定量の樹脂を溶解させ、フェノールフタレインを指示薬として水酸化カリウム／エタノール溶液にて滴定し、測定を行った。
〔合成例１、共重合体Ａ−１の合成〕
温度計、攪拌機及び冷却管を備えた１０００ｍＬの４つ口フラスコに乳酸エチル（ＥＬ）５４０．０ｇを仕込み、窒素置換した後、オイルバスで液温が９０℃になるまで昇温した。
Hereinafter, the embodiment will be described more specifically with reference to synthesis examples, examples, and comparative examples. “Part” and “%” are all based on mass unless otherwise specified. The measurement methods and evaluation methods used in the examples and comparative examples are shown below.
<Weight average molecular weight>
The weight average molecular weight (Mw) was measured with a RI detector using a gel permeation chromatography apparatus HLC-8220GPC manufactured by Tosoh Corporation, using SHODEX K801 manufactured by Showa Denko KK as a column, THF as an eluent. Thus, it was determined by conversion using a calibration curve obtained from a polystyrene standard having a known molecular weight.
<Remaining heating>
The heating residue (mass%) was calculated from the residual ratio calculated from the change in mass before and after drying after precisely weighing 1 g of the resin solution and drying in a hot air oven at 170 ° C. for 1 hour.
<Acid value>
The acid value (mgKOH / g) is determined according to JIS K0070: 1992 “Testing method for acid value, saponification value, ester value, iodine value, hydroxyl value and unsaponified product of chemical products” in tetrahydrofuran (THF) solution. Then, a certain amount of resin was dissolved, and titration was carried out with a potassium hydroxide / ethanol solution using phenolphthalein as an indicator for measurement.
[Synthesis Example 1, Synthesis of Copolymer A-1]
Into a 1000 mL four-necked flask equipped with a thermometer, a stirrer, and a condenser tube, 540.0 g of ethyl lactate (EL) was charged and purged with nitrogen, and then heated up to 90 ° C. in an oil bath.
他方、フマル酸ビス（４−ｔｅｒｔ−ブチルシクロヘキシル）（ＤｃＨｔＢＦ）７１．１ｇ、メタクリル酸（ＭＡＡ）３８．４ｇ、スチレン（Ｓｔ）１８．９ｇ、メタクリル酸２−ヒドロキシエチル（ＨＥＭＡ）７１．６ｇ、２，２’−アゾビスイソブチロニトリル〔アゾ系重合開始剤、和光純薬工業（株）製〕１０．０ｇ及びＥＬ６０．０ｇを予め均一混合したもの（滴下成分）を２時間かけて滴下ロートより等速滴下した後、同温度にて８時間維持し、共重合体Ａ−１を得た。
〔合成例２〜９、共重合体Ａ−２〜Ａ−９の合成〕
表１に記載した仕込み種及び量、滴下及び重合温度を変更した以外は合成例１と同様の手法にて共重合体Ａ−２〜Ａ−９の合成を行った。
On the other hand, 71.1 g of bis (4-tert-butylcyclohexyl) fumarate (DcHtBF), 38.4 g of methacrylic acid (MAA), 18.9 g of styrene (St), 71.6 g of 2-hydroxyethyl methacrylate (HEMA), 2,2′-azobisisobutyronitrile (azo polymerization initiator, manufactured by Wako Pure Chemical Industries, Ltd.) 10.0 g and EL 60.0 g previously mixed uniformly (dropping component) was dropped over 2 hours. After dropping at a constant rate from the funnel, the mixture was maintained at the same temperature for 8 hours to obtain a copolymer A-1.
[Synthesis Examples 2-9, Synthesis of Copolymers A-2 to A-9]
Copolymers A-2 to A-9 were synthesized in the same manner as in Synthesis Example 1 except that the preparation type and amount, dropping, and polymerization temperature described in Table 1 were changed.
ＤｃＨｔＢＦ：フマル酸ビス（４−ｔｅｒｔ−ブチルシクロヘキシル）
ＤｃＨＦ：フマル酸ジシクロヘキシル
ＤｉＰＦ：フマル酸ジイソプロピル
ＤｓＢＦ：フマル酸ジｓｅｃ−ブチル
ＤｔＢＦ：フマル酸ジｔｅｒｔ−ブチル
ＤｓＡＦ：フマル酸ジｓｅｃ−アミル
Ｓｔ：スチレン
αＭｅＳｔ：α−メチルスチレン
ＭＡＡ：メタクリル酸
ＡＡ：アクリル酸
ＨＥＭＡ：メタクリル酸２−ヒドロキシエチル
ＨＰＭＡ：メタクリル酸ヒドロキシプロピル
ＭＭＡ：メタクリル酸メチル
ＣＨＭＡ：メタクリル酸シクロヘキシル
Ｈｅｘ−Ｏ：ｔ−ヘキシルパーオキシ−２−エチルヘキサノエート、日油（株）製の過酸化物系重合開始剤「パーヘキシルＯ」
Ｂｕ−Ｏ：ｔ−ブチルパーオキシ−２−エチルヘキサノエート、日油（株）製の過酸化物系重合開始剤「パーブチルＯ」
ＡＩＢＮ：２，２’−アゾビスイソブチロニトリル〔アゾ系重合開始剤、和光純薬工業（株）製〕
ＰＧＭＥＡ：プロピレングリコールモノメチルエーテルアセテート
ＥＬ：乳酸エチル
＜実施例１＞
合成例１で得られた共重合体Ａ−１を１００ｇ、前記式（１６）で表される化合物と１，２−ナフトキノンジアジド−５−スルフォニルクロライドとのエステル化物６．２５ｇ、さらに式（１６）で表されるフェノール性化合物１．２５ｇ、２，２−ビス（ヒドロキシメチル）−１−ブタノールの１，２−エポキシ−４−（２−オキシラニル）シクロヘキサン付加物〔ダイセル化学工業（株）製、ＥＨＰＥ３１５０〕１２．５ｇ、リン系アニオンを有するトリアリールスルホニウム塩〔サンアプロ（株）製、ＣＰＩ−２１０Ｓ〕０．２５ｇを、プロピレングリコールモノメチルエーテルアセテート１０５．７５ｇ及び乳酸エチル０．２９ｇに溶解し、回転塗布の際にレジスト膜上にできる放射線状のしわ、いわゆるストリエーションを防止するため、さらにフッ素系界面活性剤、メガファックＲ−０８〔大日本インキ化学工業（株）製〕を０．０１ｇ添加して攪拌した後、０．２μｍのフィルターで濾過して、感光性樹脂組成物の希釈物を調製した。
（薄膜パターンの形成）
この感光性樹脂組成物の希釈物を４インチシリコンウエハー上に回転塗布し、１００℃、９０秒間ホットプレートにてベーク後、４．２μｍ厚の薄膜（Ａ）を得た。この薄膜にキヤノン（株）製ｇ＋ｈ＋ｉ線マスクアライナー（ＰＬＡ−５０１Ｆ）にてラインとスペース幅が１：１となった種々の線幅及びコンタクトホールのテストパターンを最適露光量で露光し、０．４質量％水酸化テトラメチルアンモニウム水溶液で２３℃、６０秒間現像を行った。その結果、ラインとスペース幅として１：１のライン＆スペースパターン及びコンタクトホールパターンが形成された薄膜（Ｂ）を得た。この薄膜（Ｂ）を上記ＰＬＡ−５０１Ｆにて全面露光した後、オーブン中で２２０℃、６０分間加熱することによりポストベイク処理を行い、３．０μｍ厚のパターン付き薄膜（パターン膜）を得た。
（残膜率の評価）
上記の手法にて得られた薄膜（Ａ）、薄膜（Ｂ）の膜厚より以下の式に基づいて残膜率を算出した。
DcHtBF: Bis (4-tert-butylcyclohexyl) fumarate
DcHF: Dicyclohexyl fumarate DiPF: Diisopropyl fumarate DsBF: Disec-butyl fumarate DtBF: Ditert-butyl fumarate DsAF: Disec-amyl fumarate St: Styrene αMeSt: α-methylstyrene MAA: Methacrylic acid AAA: Acrylic Acid HEMA: 2-hydroxyethyl methacrylate HPMA: hydroxypropyl methacrylate MMA: methyl methacrylate CHMA: cyclohexyl methacrylate Hex-O: t-hexylperoxy-2-ethylhexanoate, manufactured by NOF Corporation Oxide polymerization initiator "Perhexyl O"
Bu-O: t-butyl peroxy-2-ethylhexanoate, a peroxide polymerization initiator “Perbutyl O” manufactured by NOF Corporation
AIBN: 2,2′-azobisisobutyronitrile [azo polymerization initiator, manufactured by Wako Pure Chemical Industries, Ltd.]
PGMEA: Propylene glycol monomethyl ether acetate EL: Ethyl lactate <Example 1>
100 g of copolymer A-1 obtained in Synthesis Example 1, 6.25 g of an esterified product of the compound represented by the formula (16) and 1,2-naphthoquinonediazide-5-sulfonyl chloride, and further the formula (16 ), A 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct of 2,2-bis (hydroxymethyl) -1-butanol [manufactured by Daicel Chemical Industries, Ltd.] , EHPE3150] 12.5 g, a triarylsulfonium salt having a phosphorus anion [San Apro Co., Ltd., CPI-210S] 0.25 g was dissolved in propylene glycol monomethyl ether acetate 105.75 g and ethyl lactate 0.29 g. Prevents radial wrinkles on the resist film during spin coating, so-called striations Therefore, after adding 0.01 g of a fluorosurfactant, MegaFac R-08 [Dainippon Ink Chemical Co., Ltd.] and stirring, the mixture was filtered through a 0.2 μm filter to obtain a photosensitive resin composition. Product dilutions were prepared.
(Formation of thin film pattern)
The diluted photosensitive resin composition was spin-coated on a 4-inch silicon wafer and baked on a hot plate at 100 ° C. for 90 seconds to obtain a thin film (A) having a thickness of 4.2 μm. The thin film was exposed to various line widths and contact hole test patterns having a line and space width of 1: 1 with a g + h + i line mask aligner (PLA-501F) manufactured by Canon Inc. at an optimum exposure amount. Development was carried out with a 4% by mass aqueous tetramethylammonium hydroxide solution at 23 ° C. for 60 seconds. As a result, a thin film (B) having a 1: 1 line & space pattern and contact hole pattern as the line and space width was obtained. The entire surface of this thin film (B) was exposed with the above PLA-501F, and then post-baked by heating in an oven at 220 ° C. for 60 minutes to obtain a patterned thin film (pattern film) having a thickness of 3.0 μm.
(Evaluation of remaining film rate)
Based on the following formula, the remaining film ratio was calculated from the film thicknesses of the thin film (A) and the thin film (B) obtained by the above method.
残膜率（％）＝〔薄膜（Ｂ）の膜厚（μｍ）／薄膜（Ａ）の膜厚（μｍ）〕×１００
（現像性の評価）
上記で作製したパターンの中で、１０μｍのホールパターンを走査型電子顕微鏡（ＳＥＭ）にて観察した。ホール部全面に残渣が見られる場合には×、ホールと基板の界面付近のみに残渣が見られる場合には△、ホール部全面に残渣が見られない場合には○として現像性を評価した。その結果を表２に示した。
（比誘電率の評価）
前記ＰＬＡ−５０１Ｆにてテストパターンを露光しない以外は上記と同様の操作を行うことにより、パターンのない、３．０μｍ厚の薄膜を４インチシリコンウエハー上に得た。この薄膜上に電極を形成し、室温、１０ｋＨｚにおける条件で、安藤電気（株）製ＬＣＲメータ（ＡＧ−４３１１）を用いて得られた静電容量から比誘電率を算出した。その結果を表２に示した。
（透過率の評価）
縦７０ｍｍ、横７０ｍｍサイズの石英ガラス基板を用い、テストパターンを露光しない以外は上記と同様の操作を行うことにより、パターンのない薄膜をガラス基板上に得た。そして、紫外−可視光分光光度計ＣＡＲＹ４Ｅ（バリアン社製）を用いて、この薄膜を有するガラス基板の光の波長４００ｎｍにおける透過率（％）を測定した。その結果を表２に示した。
（溶剤耐性の評価）
透過率の評価と同様の操作を行うことで得たガラス基板を、フォトレジスト剥離液〔ナガセケムテックス（株）製、ＲｅｍｏｖｅｒＮ−３２１〕中に６０℃、１分間浸漬した後、純水リンスを行い、２００℃、１５分間の再ベーク処理を行った。そして、溶剤浸漬前の透過率と再ベーク処理後の透過率差が３％未満のものについては○、透過率差が３％以上のものについては×として評価した。その結果を表２に示した。
＜実施例２＞
合成例２で得られた共重合体Ａ−２を用いること以外は実施例１と同様の操作を行うことにより、感光性樹脂組成物の希釈物を調製した。この感光性樹脂組成物について、実施例１と同様の物性を評価し、それらの結果を表２に示した。
＜実施例３〜１９＞
表２及び表３に示した成分（Ａ）の共重合体、成分（Ｂ）の感光剤、成分（Ｃ）の硬化剤等を用いること以外は実施例１と同様の操作を行うことにより、感光性樹脂組成物の希釈物を調製した。この感光性樹脂組成物について、実施例１と同様の物性を評価し、それらの結果を表２及び表３に示した。
＜比較例１及び２＞
表３に示した成分（Ａ）の共重合体、成分（Ｂ）の感光剤、成分（Ｃ）の硬化剤等を用いること以外は実施例１と同様の操作を行うことにより、感光性樹脂組成物の希釈物を調製した。この感光性樹脂組成物について、実施例１と同様の物性を評価し、それらの結果を表３に示した。
Residual film ratio (%) = [film thickness of thin film (B) (μm) / film thickness of thin film (A) (μm)] × 100
(Evaluation of developability)
Among the patterns prepared above, a 10 μm hole pattern was observed with a scanning electron microscope (SEM). The developability was evaluated as x when a residue was found over the entire hole part, Δ when the residue was found only near the interface between the hole and the substrate, and ◯ when no residue was found over the entire hole part. The results are shown in Table 2.
(Evaluation of relative dielectric constant)
A 3.0 μm-thick thin film without a pattern was obtained on a 4-inch silicon wafer by performing the same operation as described above except that the test pattern was not exposed with the PLA-501F. An electrode was formed on this thin film, and the relative dielectric constant was calculated from the capacitance obtained using an LCR meter (AG-4411) manufactured by Ando Electric Co., Ltd. under conditions of room temperature and 10 kHz. The results are shown in Table 2.
(Evaluation of transmittance)
A quartz glass substrate having a size of 70 mm in length and 70 mm in width was used, and a thin film having no pattern was obtained on the glass substrate by performing the same operation as above except that the test pattern was not exposed. And the transmittance | permeability (%) in wavelength 400nm of the light of the glass substrate which has this thin film was measured using the ultraviolet-visible light spectrophotometer CARY4E (made by a Varian company). The results are shown in Table 2.
(Evaluation of solvent resistance)
After immersing a glass substrate obtained by performing the same operation as the evaluation of transmittance in a photoresist stripping solution [Nagase Chemtex Co., Ltd., RemoverN-321] at 60 ° C. for 1 minute, rinse with pure water. And a rebaking process at 200 ° C. for 15 minutes was performed. And the thing of the transmittance | permeability before a solvent immersion and the transmittance | permeability after a rebaking process was evaluated as (circle), and the thing with a transmittance | permeability difference of 3% or more evaluated as x. The results are shown in Table 2.
<Example 2>
A dilution of the photosensitive resin composition was prepared by performing the same operation as in Example 1 except that the copolymer A-2 obtained in Synthesis Example 2 was used. About this photosensitive resin composition, the physical property similar to Example 1 was evaluated, and those results were shown in Table 2.
<Examples 3 to 19>
By performing the same operation as in Example 1 except that the copolymer of component (A), the photosensitive agent of component (B), the curing agent of component (C) and the like shown in Table 2 and Table 3 are used. A dilution of the photosensitive resin composition was prepared. About this photosensitive resin composition, the physical property similar to Example 1 was evaluated, and those results were shown in Table 2.
<Comparative Examples 1 and 2>
By performing the same operation as in Example 1 except that the copolymer of component (A), the photosensitive agent of component (B), the curing agent of component (C), etc. shown in Table 3 are used, a photosensitive resin is obtained. A dilution of the composition was prepared. About this photosensitive resin composition, the physical property similar to Example 1 was evaluated, and those results were shown in Table 3.
一方、表３に示した結果より、比較例１では成分（Ａ）共重合体に構成単位（ａ１）が含まれていないことから、現像性が悪化した。比較例２では、共重合体に構成単位（ａ１）及び（ａ２）が含まれていないことから、比誘電率が悪くなる結果を示した。 On the other hand, from the results shown in Table 3, in Comparative Example 1, since the component (A) copolymer does not contain the structural unit (a1), the developability deteriorated. In the comparative example 2, since the structural unit (a1) and (a2) were not included in the copolymer, the result that the dielectric constant deteriorated was shown.
Claims (3)
（Ａ）下記式（１）で表されるフマル酸ジエステル単量体から誘導される構成単位（ａ１）、下記式（２）で表される芳香族ビニル単量体から誘導される構成単位（ａ２）、下記式（３）で表されるα，β−不飽和カルボン酸単量体から誘導される構成単位（ａ３）及び下記式（４）で表される（メタ）アクリル酸エステル単量体から誘導される構成単位（ａ４）からなり、構成単位（ａ１）と構成単位（ａ２）の合計量が４０〜８５質量％であり、構成単位（ａ３）と構成単位（ａ４）の質量比（ａ４）／（ａ３）が０．２〜７．０である共重合体。
（Ｂ）水酸基を有するフェノール性化合物とキノンジアジド化合物とをエステル化反応させて得られる、キノンジアジド基を有する感光剤。
（Ｃ）下記式（５）で表されるエポキシ基を有する硬化剤。
(A) A structural unit derived from a fumaric acid diester monomer represented by the following formula (1) (a1), a structural unit derived from an aromatic vinyl monomer represented by the following formula (2) ( a2), a structural unit (a3) derived from an α, β-unsaturated carboxylic acid monomer represented by the following formula (3) and a (meth) acrylic acid ester single monomer represented by the following formula (4) It consists of a structural unit (a4) derived from the body, the total amount of the structural unit (a1) and the structural unit (a2) is 40 to 85% by mass, and the mass ratio of the structural unit (a3) to the structural unit (a4) A copolymer in which (a4) / (a3) is 0.2 to 7.0.
(B) A photosensitizer having a quinonediazide group obtained by esterifying a phenolic compound having a hydroxyl group and a quinonediazide compound.
(C) A curing agent having an epoxy group represented by the following formula (5).
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