JP5526693B2 - Photosensitive resin composition and use thereof - Google Patents
Photosensitive resin composition and use thereof Download PDFInfo
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- JP5526693B2 JP5526693B2 JP2009235166A JP2009235166A JP5526693B2 JP 5526693 B2 JP5526693 B2 JP 5526693B2 JP 2009235166 A JP2009235166 A JP 2009235166A JP 2009235166 A JP2009235166 A JP 2009235166A JP 5526693 B2 JP5526693 B2 JP 5526693B2
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- 239000011342 resin composition Substances 0.000 title claims description 53
- 125000004432 carbon atom Chemical group C* 0.000 claims description 50
- 229920001577 copolymer Polymers 0.000 claims description 49
- 239000000178 monomer Substances 0.000 claims description 39
- -1 itaconic acid diester Chemical class 0.000 claims description 34
- 125000000217 alkyl group Chemical group 0.000 claims description 33
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 24
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 20
- 150000001875 compounds Chemical class 0.000 claims description 17
- 239000004065 semiconductor Substances 0.000 claims description 17
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 13
- 125000003700 epoxy group Chemical group 0.000 claims description 13
- 150000002989 phenols Chemical class 0.000 claims description 12
- WTQZSMDDRMKJRI-UHFFFAOYSA-N 4-diazoniophenolate Chemical group [O-]C1=CC=C([N+]#N)C=C1 WTQZSMDDRMKJRI-UHFFFAOYSA-N 0.000 claims description 11
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 9
- 229920002554 vinyl polymer Polymers 0.000 claims description 9
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 8
- 150000007934 α,β-unsaturated carboxylic acids Chemical class 0.000 claims description 8
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 125000002723 alicyclic group Chemical group 0.000 claims description 4
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 239000010408 film Substances 0.000 description 87
- 238000000034 method Methods 0.000 description 26
- 229920000647 polyepoxide Polymers 0.000 description 25
- 239000003822 epoxy resin Substances 0.000 description 23
- 238000011161 development Methods 0.000 description 22
- 239000011229 interlayer Substances 0.000 description 20
- 239000002904 solvent Substances 0.000 description 18
- 239000010409 thin film Substances 0.000 description 15
- 239000000758 substrate Substances 0.000 description 12
- 230000015572 biosynthetic process Effects 0.000 description 10
- 238000006116 polymerization reaction Methods 0.000 description 10
- 238000002834 transmittance Methods 0.000 description 10
- 238000000576 coating method Methods 0.000 description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
- 230000008569 process Effects 0.000 description 9
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 9
- 238000003786 synthesis reaction Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 230000000704 physical effect Effects 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000000206 photolithography Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 4
- 239000004593 Epoxy Substances 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- MTHSVFCYNBDYFN-UHFFFAOYSA-N anhydrous diethylene glycol Natural products OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 4
- 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 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000000470 constituent Substances 0.000 description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- 230000006866 deterioration Effects 0.000 description 4
- ZWWQRMFIZFPUAA-UHFFFAOYSA-N dimethyl 2-methylidenebutanedioate Chemical compound COC(=O)CC(=C)C(=O)OC ZWWQRMFIZFPUAA-UHFFFAOYSA-N 0.000 description 4
- IPKKHRVROFYTEK-UHFFFAOYSA-N dipentyl phthalate Chemical compound CCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCC IPKKHRVROFYTEK-UHFFFAOYSA-N 0.000 description 4
- 230000032050 esterification Effects 0.000 description 4
- 238000005886 esterification reaction Methods 0.000 description 4
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 4
- XLLIQLLCWZCATF-UHFFFAOYSA-N ethylene glycol monomethyl ether acetate Natural products COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 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
- 150000002978 peroxides Chemical class 0.000 description 4
- 239000003505 polymerization initiator Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 4
- 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 3
- 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 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 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
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- 229920003986 novolac Polymers 0.000 description 3
- 230000010287 polarization Effects 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 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 2
- 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
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-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
- 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
- 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
- 229930185605 Bisphenol Natural products 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
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 239000007869 azo polymerization initiator Substances 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 230000007547 defect Effects 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
- 238000004090 dissolution Methods 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
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229940116333 ethyl lactate Drugs 0.000 description 2
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000002401 inhibitory effect Effects 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
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-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
- 238000012545 processing Methods 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
- 238000004904 shortening Methods 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- 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 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
- 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 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
- 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 1
- BFSVOASYOCHEOV-UHFFFAOYSA-N 2-diethylaminoethanol Chemical compound CCN(CC)CCO BFSVOASYOCHEOV-UHFFFAOYSA-N 0.000 description 1
- VHSHLMUCYSAUQU-UHFFFAOYSA-N 2-hydroxypropyl methacrylate Chemical compound CC(O)COC(=O)C(C)=C VHSHLMUCYSAUQU-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- OELQSSWXRGADDE-UHFFFAOYSA-N 2-methylprop-2-eneperoxoic acid Chemical compound CC(=C)C(=O)OO OELQSSWXRGADDE-UHFFFAOYSA-N 0.000 description 1
- VCMRHBFMLZZCJR-UHFFFAOYSA-N 3-(3-ethyloctan-3-yloxycarbonyl)but-3-enoic acid Chemical compound CCCCCC(CC)(CC)OC(=O)C(=C)CC(=O)O VCMRHBFMLZZCJR-UHFFFAOYSA-N 0.000 description 1
- 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
- JEKBXKBRBLABQJ-UHFFFAOYSA-N 4,6-bis[(4-hydroxy-3,5-dimethylphenyl)methyl]benzene-1,2,3-triol Chemical compound CC1=C(O)C(C)=CC(CC=2C(=C(O)C(O)=C(CC=3C=C(C)C(O)=C(C)C=3)C=2)O)=C1 JEKBXKBRBLABQJ-UHFFFAOYSA-N 0.000 description 1
- HKZMZQQZDDNTIS-UHFFFAOYSA-N 4-[(4-hydroxy-2,3-dimethylphenyl)-(2-hydroxyphenyl)methyl]-2,3-dimethylphenol Chemical compound CC1=C(O)C=CC(C(C=2C(=CC=CC=2)O)C=2C(=C(C)C(O)=CC=2)C)=C1C HKZMZQQZDDNTIS-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
- XKDBWDVWKVZQIQ-UHFFFAOYSA-N 4-[bis(4-hydroxyphenyl)methyl]-2-ethoxyphenol Chemical compound C1=C(O)C(OCC)=CC(C(C=2C=CC(O)=CC=2)C=2C=CC(O)=CC=2)=C1 XKDBWDVWKVZQIQ-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
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 102100026735 Coagulation factor VIII Human genes 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
- 101000911390 Homo sapiens Coagulation factor VIII Proteins 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-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
- IXTOPTAHMFPHDG-UHFFFAOYSA-N OC1=CC=C(C=C1)C(C)(C)C1=CC=C(C=C1)C(C)(C1=CC=C(C=C1)O)C1=CC=C(C=C1)O.OC1=C(C=C(C=C1)C)CC1=C(C(=CC(=C1)C)CC1=C(C=CC(=C1)C)O)O Chemical compound OC1=CC=C(C=C1)C(C)(C)C1=CC=C(C=C1)C(C)(C1=CC=C(C=C1)O)C1=CC=C(C=C1)O.OC1=C(C=C(C=C1)C)CC1=C(C(=CC(=C1)C)CC1=C(C=CC(=C1)C)O)O IXTOPTAHMFPHDG-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
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- LEEBETSNAGEFCY-UHFFFAOYSA-N [N-]=[N+]=[N-].[N-]=[N+]=[N-].O=C1C=CC(=O)C=C1 Chemical compound [N-]=[N+]=[N-].[N-]=[N+]=[N-].O=C1C=CC(=O)C=C1 LEEBETSNAGEFCY-UHFFFAOYSA-N 0.000 description 1
- KVXNKFYSHAUJIA-UHFFFAOYSA-N acetic acid;ethoxyethane Chemical compound CC(O)=O.CCOCC KVXNKFYSHAUJIA-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000006149 azo coupling reaction Methods 0.000 description 1
- 230000005540 biological transmission Effects 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
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 1
- OGVXYCDTRMDYOG-UHFFFAOYSA-N dibutyl 2-methylidenebutanedioate Chemical compound CCCCOC(=O)CC(=C)C(=O)OCCCC OGVXYCDTRMDYOG-UHFFFAOYSA-N 0.000 description 1
- GFHMGSFDHKDJSG-UHFFFAOYSA-N dicyclohexyl 2-methylidenebutanedioate Chemical compound C1CCCCC1OC(=O)C(=C)CC(=O)OC1CCCCC1 GFHMGSFDHKDJSG-UHFFFAOYSA-N 0.000 description 1
- ZEFVHSWKYCYFFL-UHFFFAOYSA-N diethyl 2-methylidenebutanedioate Chemical compound CCOC(=O)CC(=C)C(=O)OCC ZEFVHSWKYCYFFL-UHFFFAOYSA-N 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 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
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 239000003999 initiator Substances 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
- 238000000691 measurement method Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000004767 nitrides Chemical class 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
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical compound NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 description 1
- 239000013500 performance material Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 238000007699 photoisomerization reaction Methods 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- 230000036211 photosensitivity Effects 0.000 description 1
- 229920002432 poly(vinyl methyl ether) polymer Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000007717 redox polymerization reaction Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007665 sagging Methods 0.000 description 1
- 150000003839 salts Chemical class 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
- 229910000029 sodium carbonate Inorganic materials 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
- 239000007921 spray Substances 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 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
- 238000001771 vacuum deposition Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/08—Styrene
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
- G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/022—Quinonediazides
- G03F7/0226—Quinonediazides characterised by the non-macromolecular additives
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/022—Quinonediazides
- G03F7/023—Macromolecular quinonediazides; Macromolecular additives, e.g. binders
- G03F7/0233—Macromolecular quinonediazides; Macromolecular additives, e.g. binders characterised by the polymeric binders or the macromolecular additives other than the macromolecular quinonediazides
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Medicinal Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Materials For Photolithography (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Computer Hardware Design (AREA)
- Manufacturing & Machinery (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
本発明は、感光性を有するポジ型の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または平坦化膜を備えたフラットパネルディスプレイ（ＦＰＤ）または半導体デバイスに関する。 The present invention relates to a positive photosensitive resin composition having photosensitivity. 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ＴＦＴ（薄膜トランジスタ）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 represented by TFT (Thin Film Transistor).
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、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 with a dielectric constant lower 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、層間絶縁膜また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、層間絶縁膜また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）アクリル酸およ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.
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また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。 In order to solve such problems, a photosensitive resin composition used for an interlayer insulating film or a planarizing film such as an FPD or a semiconductor device has no development residue and maintains developability while maintaining a high residual film ratio. Therefore, it is required to form a high-resolution pattern film having excellent low dielectric properties.
本発明は上記実状に鑑みてなされたものであり、その目的は、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 object thereof is to maintain a high residual film rate in the development process for forming a pattern film, without developing residue, and light transmittance even after high temperature baking, An object of the present invention is to provide a photosensitive resin composition capable of forming a pattern film excellent in low dielectric properties without impairing physical properties of a coating film such as 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または層間絶縁膜を有するＦＰＤまたは半導体デバイスを提供することにある。
さらに、本発明の第三の目的は、前記の優れた感光性樹脂組成物により、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また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 an FPD or a semiconductor device having a planarizing film or an interlayer insulating film formed of the above-described excellent photosensitive resin composition.
Furthermore, the third object of the present invention is to provide an FPD having an organic interlayer insulating film that can be easily formed by a wet process without forming an inorganic interlayer insulating film such as SiNx by the above-described excellent photosensitive resin composition. Another object is to provide a semiconductor device.
上記の目的を達成するために、第１の発明の感光性樹脂組成物は成分（Ａ）、下記に示す成分（Ｂ）および成分（Ｃ）からなり、各成分の構成割合が成分（Ａ）１００質量部に対して成分（Ｂ）５〜５０質量部および成分（Ｃ）１〜５０質量部である。そして、前記成分（Ａ）は下記式（１）で表されるイタコン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）および下記式（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を有する共重合体であり、構成単位（ａ１）と構成単位（ａ２）の合計量に対して構成単位（ａ１）が１５〜９５質量％、構成単位（ａ２）が５〜８５質量％であると共に、構成単位（ａ１）と構成単位（ａ２）の合計量１００質量部に対して構成単位（ａ３）が５〜１５０質量部であることを特徴とする。 In order to achieve the above object, the photosensitive resin composition of the first invention comprises the component (A), the component (B) and the component (C) shown below, and the constituent ratio of each component is the component (A). It is 5-50 mass parts of component (B) and 1-50 mass parts of component (C) with respect to 100 mass parts. The component (A) is derived from a structural unit (a1) derived from an itaconic acid diester monomer represented by the following formula (1) and an aromatic vinyl monomer represented by the following formula (2). And a copolymer having a structural unit derived from an α, β-unsaturated carboxylic acid monomer represented by the following formula (3): the structural unit (a1) and the structural unit The structural unit (a1) is 15 to 95% by mass and the structural unit (a2) is 5 to 85% by mass with respect to the total amount of (a2), and the total amount of the structural unit (a1) and the structural unit (a2). A structural unit (a3) is 5-150 mass parts with respect to 100 mass parts.
成分（Ｂ）：多官能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エステル化物。
Component (B): An esterified product having a quinonediazide group, obtained by esterifying a polyfunctional phenolic compound and a quinonediazide compound.
成分（Ｃ）：エポキシ基を有する架橋性化合物。
第２の発明の感光性樹脂組成物は、第１の発明において、前記成分（Ａ）は、構成単位（ａ１）、構成単位（ａ２）および構成単位（ａ３）に加えて下記式（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）を、構成単位（ａ１）と構成単位（ａ２）の合計量１００質量部に対して５〜１４０質量部有する共重合体であることを特徴とする。
Component (C): a crosslinkable compound having an epoxy group.
In the photosensitive resin composition of the second invention, in the first invention, the component (A) is represented by the following formula (4) in addition to the structural unit (a1), the structural unit (a2) and the structural unit (a3). 5 to 140 parts by mass of the structural unit (a4) derived from the (meth) acrylic acid ester monomer represented by the formula (100) with respect to 100 parts by mass of the total amount of the structural unit (a1) and the structural unit (a2). It is a copolymer.
第３の発明のフラットパネルディスプレイは、第１または第２の発明の感光性樹脂組成物から得られるパターン膜を有するものである。
The flat panel display of 3rd invention has a pattern film obtained from the photosensitive resin composition of 1st or 2nd invention.
第４の発明の半導体デバイスは、第１または第２の発明の感光性樹脂組成物から得られるパターン膜を有するものである。 The semiconductor device of 4th invention has a pattern film obtained from the photosensitive resin composition of 1st or 2nd invention.
本発明は、次のような効果を発揮することができる。
本発明の感光性樹脂組成物は、成分（Ａ）が現像性（アルカリ溶解性）および低誘電特性に寄与し、成分（Ｂ）が現像性に寄与し、さらに成分（Ｃ）が耐溶剤性等の塗膜物性を高めることができ、特に成分（Ａ）の構成単位（ａ１）が低誘電特性に寄与し、構成単位（ａ３）および（ａ４）が現像性に寄与することができる。従って、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、その用途として優れた特性を有するＦＰＤおよ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.
In the photosensitive resin composition of the present invention, the component (A) contributes to developability (alkali solubility) and low dielectric properties, the component (B) contributes to developability, and the component (C) is solvent resistant. In particular, the structural unit (a1) of the component (A) can contribute to low dielectric properties, and the structural units (a3) and (a4) can contribute to developability. Therefore, in the development process of forming a pattern film using photolithography technology, there is no development residue while maintaining a high residual film ratio, and the coating film has light transmittance, solvent resistance, etc. even after high temperature baking such as post baking. A pattern film having excellent low dielectric properties can be formed without impairing physical properties. And the FPD and semiconductor device which have the characteristic outstanding as the use 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（ポジ型）感光性樹脂組成物は、下記に示す成分（Ａ）、（Ｂ）および（Ｃ）からなり、各成分の構成割合が成分（Ａ）１００質量部に対して成分（Ｂ）５〜５０質量部および成分（Ｃ）１〜５０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 (positive type) photosensitive resin composition of the present embodiment comprises the following components (A), (B), and (C), and the constituent ratio of each component is a component with respect to 100 parts by mass of the component (A). (B) 5 to 50 parts by mass and component (C) 1 to 50 parts by mass are set.
成分（Ａ）：特定の共重合体。
成分（Ｂ）：キノンジアジド基を有するエステル化物。
成分（Ｃ）：エポキシ基を有する架橋性化合物。
Component (A): a specific copolymer.
Component (B): esterified product having a quinonediazide group.
Component (C): a crosslinkable compound having an 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）は、下記式（１）で表されるイタコン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）および下記式（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を有する共重合体により構成されている。共重合体中の構成単位（ａ１）と構成単位（ａ２）の合計量に対して構成単位（ａ１）は１５〜９５質量％、構成単位（ａ２）は５〜８５質量％、および構成単位（ａ３）は構成単位（ａ１）と構成単位（ａ２）の合計量１００質量部に対して５〜１５０質量部である。
Below, each component is demonstrated in order.
<Component (A): Specific copolymer>
The component (A) is derived from a structural unit (a1) derived from an itaconic acid diester monomer represented by the following formula (1) and an aromatic vinyl monomer represented by the following formula (2). It is composed of a copolymer having a structural unit derived from a structural unit (a2) and an α, β-unsaturated carboxylic acid monomer represented by the following formula (3). The structural unit (a1) is 15 to 95% by mass, the structural unit (a2) is 5 to 85% by mass, and the structural unit (a) based on the total amount of the structural unit (a1) and the structural unit (a2) in the copolymer. a3) is 5-150 mass parts with respect to 100 mass parts of total amounts of a structural unit (a1) and a structural unit (a2).
さらに、成分（Ａ）の共重合体は、構成単位（ａ１）、構成単位（ａ２）および構成単位（ａ３）に加えて、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）を、構成単位（ａ１）と構成単位（ａ２）の合計量１００質量部に対して５〜１４０質量部有していることが好ましい。 Furthermore, the copolymer of component (A) is a (meth) acrylic acid ester monomer represented by the following formula (4) in addition to the structural unit (a1), the structural unit (a2) and the structural unit (a3). The structural unit (a4) derived from the body preferably has 5 to 140 parts by mass with respect to 100 parts by mass of the total amount of the structural unit (a1) and the structural unit (a2).
前記式（１）〜（４）で表される各構成単位はそれぞれ下記式（１）´〜（４）´で表される単量体（各構成単位用単量体）から誘導される。
Each structural unit represented by the formulas (1) to (4) is derived from a monomer (monomer for each structural unit) represented by the following formulas (1) ′ to (4) ′.
〔イタコン酸ジエステル単量体から誘導される構成単位（ａ１）〕
イタコン酸ジエステル単量体から誘導される構成単位（ａ１）は、主鎖に対して対称的な位置にエステル基が存在することから誘電分極が相殺される。このため共重合体全体としての誘電分極が非常に小さくなるため、良好な低誘電特性を得ることができる。
[Structural Unit Derived from Itaconic Acid Diester Monomer (a1)]
In the structural unit (a1) derived from the itaconic acid diester monomer, the dielectric polarization is offset because the ester group is present at a symmetrical position with respect to the main chain. For this reason, since the dielectric polarization as a whole copolymer becomes very small, a favorable low dielectric property can be obtained.
前記式（１）におけるＲ１およびＲ２は、それぞれ独立して炭素数１〜８の直鎖アルキル基、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である。Ｒ１およびＲ２として、現像性の面から好ましくは炭素数１〜６の直鎖アルキル基および炭素数３〜６の分岐アルキル基、炭素数６〜１０のシクロアルキル基であり、より好ましくは炭素数１〜４の直鎖アルキル基、炭素数３〜４の分岐アルキル基または炭素数６〜８のシクロアルキル基である。 R 1 and R 2 in the formula (1) are each independently a linear alkyl group having 1 to 8 carbon atoms, a branched alkyl group having 3 to 8 carbon atoms, or a cycloalkyl group having 4 to 12 carbon atoms. R 1 and R 2 are preferably a linear alkyl group having 1 to 6 carbon atoms, a branched alkyl group having 3 to 6 carbon atoms, and a cycloalkyl group having 6 to 10 carbon atoms, more preferably from the viewpoint of developability. It is a C1-C4 linear alkyl group, a C3-C4 branched alkyl group, or a C6-C8 cycloalkyl group.
直鎖アルキル基および分岐アルキル基の炭素数が８、また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ず、現像残渣が発生する場合がある。前記式（１）におけるＲ１および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、低誘電特性の面から同一の構造であることが好ましい。 If the straight-chain alkyl group and the branched alkyl group have 8 carbon atoms and the cycloalkyl group has more than 12 carbon atoms, sufficient developability may not be obtained, and a development residue may be generated. R 1 and R 2 in the formula (1) may be the same or different substituents, but are preferably the same structure from the viewpoint of low dielectric properties.
構成単位（ａ１）は、構成単位（ａ１）と構成単位（ａ２）の合計量に対して１５〜９５質量％含まれ、現像性と低誘電特性の両立の面から好ましくは２０〜９０質量％、より好ましくは２５〜７５質量％含まれる。構成単位（ａ１）の含有量が１５質量％を下回ると共重合体中の誘電分極が大きくなり、十分な低誘電特性が得られない場合が生じる。一方、構成単位（ａ１）の含有量が９５質量％を超えると、現像性が低下し現像残渣が発生するおそれがある。
〔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）を誘導するイタコン酸ジエステル単量体と構成単位（ａ３）を誘導するα，β−不飽和カルボン酸単量体および構成単位（ａ４）を誘導する（メタ）アクリル酸エステル単量体との共重合性を向上させることができる。構成単位（ａ２）を誘導する芳香族ビニル単量体は、前記式（１）′のイタコン酸ジエステル単量体、式（３）′のα，β−不飽和カルボン酸単量体および式（４）′の（メタ）アクリル酸エステル単量体の３者のいずれの単量体とも共重合性が良好であるため、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共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。
The structural unit (a1) is contained in an amount of 15 to 95% by mass with respect to the total amount of the structural unit (a1) and the structural unit (a2), and preferably 20 to 90% by mass in terms of both developability and low dielectric properties. More preferably, the content is 25 to 75% by mass. When the content of the structural unit (a1) is less than 15% by mass, the dielectric polarization in the copolymer increases, and sufficient low dielectric properties may not be obtained. On the other hand, when the content of the structural unit (a1) exceeds 95% by mass, developability may be deteriorated and a development residue may be generated.
[Structural Unit Derived from Aromatic Vinyl Monomer (a2)]
The aromatic vinyl monomer that derives the structural unit (a2) includes an itaconic acid diester monomer that induces the structural unit (a1) during polymerization and an α, β-unsaturated carboxylic acid monomer that induces the structural unit (a3). The copolymerizability with the (meth) acrylic acid ester monomer which induces the monomer and the structural unit (a4) can be improved. The aromatic vinyl monomer from which the structural unit (a2) is derived includes the itaconic acid diester monomer of the formula (1) ′, the α, β-unsaturated carboxylic acid monomer of the formula (3) ′, and the formula ( 4) Since each of the three monomers of (meth) acrylic acid ester monomer has good copolymerizability, each structural unit derived from monomers having different copolymerizability during the polymerization reaction Can be smoothly introduced into the copolymer, and a copolymer having uniform properties can be obtained without uneven distribution of the copolymer composition.
前記式（２）におけるＲ３およびＲ４は、それぞれ独立して水素原子またはメチル基であり、現像性の面からＲ３およびＲ４は水素原子が好ましい。
構成単位（ａ２）は、構成単位（ａ１）と構成単位（ａ２）の合計量に対して５〜８５質量％含まれ、現像性の面から好ましくは１０〜８０質量％、より好ましくは１５〜８０質量％含まれる。構成単位（ａ２）の含有量が５質量％を下回る、または８５質量％を超えると共重合性のバランスが崩れ、所望とする共重合体が得られなくなる。また構成単位（ａ２）の含有量が８５質量％を超えると現像性が低下し、現像残渣が発生するおそれがある。
〔構成単位（ａ１）と構成単位（ａ２）の合計量〕
前記のイタコン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４０〜９５質量％であることが好ましく、現像性と低誘電特性の両立の面から５０〜７５質量％であることがさらに好ましい。この合計量が４０質量％を下回ると、現像液への溶解性が高くなり過ぎるため残膜率の低下やパターン不良を生じる場合がある。その一方、合計量が９５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発生するおそれがある。
〔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、またはメチル基である。耐熱性の面からＲ５として好ましくはメチル基である。
R 3 and R 4 in the formula (2) are each independently a hydrogen atom or a methyl group, and R 3 and R 4 are preferably a hydrogen atom from the viewpoint of developability.
The structural unit (a2) is contained in an amount of 5 to 85% by mass with respect to the total amount of the structural unit (a1) and the structural unit (a2), and is preferably 10 to 80% by mass, more preferably 15 to 50% from the viewpoint of developability. 80% by mass is contained. When the content of the structural unit (a2) is less than 5% by mass or exceeds 85% by mass, the balance of copolymerization is lost, and a desired copolymer cannot be obtained. On the other hand, if the content of the structural unit (a2) exceeds 85% by mass, the developability is lowered and a development residue may be generated.
[Total amount of structural unit (a1) and structural unit (a2)]
The total amount contained in the copolymer of the structural unit (a1) derived from the itaconic acid diester monomer and the structural unit (a2) derived from the aromatic vinyl monomer is 40 to 95% by mass. It is preferable that it is 50 to 75% by mass from the viewpoint of achieving both developability and low dielectric properties. When this total amount is less than 40% by mass, the solubility in the developer becomes too high, and thus the remaining film ratio may be reduced and pattern defects may occur. On the other hand, if the total amount exceeds 95% 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 may be generated on the pattern.
[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 contributing to developability in the development process. R 5 in the formula (3) is a hydrogen atom or a methyl group. From the viewpoint of heat resistance, R 5 is preferably a methyl group.
構成単位（ａ３）は、構成単位（ａ１）と構成単位（ａ２）の合計量１００質量部に対して５〜１５０質量部含まれ、現像性と低誘電特性の両立の面から好ましくは１０〜１００質量部含まれる。構成単位（ａ３）の含有量が５質量部を下回ると、現像液への溶解性が得られず現像残渣が発生する場合がある。一方、構成単位（ａ３）の含有量が１５０質量部を上回ると、現像液への溶解性が高くなり過ぎるため残膜率の低下やパターン不良を生じる場合がある。
〔（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の調整を目的として加えることができる。前記式（４）におけるＲ６は水素原子またはメチル基、Ｒ７は炭素数１〜１２のアルキル基、炭素数３〜１２の分岐アルキル基、炭素数６〜１２のアリール基、ベンジル基、炭素数１〜１２のヒドロキシアルキル基または主環構成炭素数３〜１２の脂環式炭化水素基である。耐熱性の面からＲ６として好ましくはメチル基であり、現像性の面からＲ７として好ましくは炭素数１〜６のアルキル基、炭素数３〜６の分岐アルキル基、炭素数６〜８のアリール基、炭素数1〜４のヒドロキシアルキル基、シクロヘキシル基である。Ｒ７の炭素数が１２を超えると、共重合性が低下し問題となる。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種のみまたは２種以上を組み合わせて用いることができる。
The structural unit (a3) is included in an amount of 5 to 150 parts by mass with respect to 100 parts by mass of the total amount of the structural unit (a1) and the structural unit (a2), and preferably 10 to 10 from the viewpoint of both developability and low dielectric properties. 100 parts by mass are included. If the content of the structural unit (a3) is less than 5 parts by mass, solubility in the developer may not be obtained and a development residue may be generated. On the other hand, when the content of the structural unit (a3) exceeds 150 parts by mass, the solubility in the developer becomes excessively high, which may cause a decrease in the remaining film rate and a pattern defect.
[Structural Unit Derived from (Meth) acrylic Acid Ester Monomer (a4)]
The structural unit (a4) derived from the (meth) acrylic acid ester monomer can be added for the purpose of adjusting the developability, in particular, adjusting 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 alkyl group having 1 to 12 carbon atoms, a branched alkyl group having 3 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, a benzyl group, carbon It is a C1-C12 hydroxyalkyl group or a main ring constituent C3-C12 alicyclic hydrocarbon group. From the viewpoint of heat resistance, R 6 is preferably a methyl group, and from the viewpoint of developability, R 7 is preferably an alkyl group having 1 to 6 carbon atoms, a branched alkyl group having 3 to 6 carbon atoms, or 6 to 8 carbon atoms. An aryl group, a hydroxyalkyl group having 1 to 4 carbon atoms, and a cyclohexyl group. If the number of carbon atoms in R 7 exceeds 12, the copolymerizability will be lowered, causing a problem. 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.
構成単位（ａ４）は、構成単位（ａ１）と構成単位（ａ２）の合計量１００質量部に対して好ましくは５〜１４０質量部含まれ、現像性、透明性の面からさらに好ましくは１０〜９０質量部含まれる。構成単位（ａ４）の含有量が５質量部を下回ると、構成単位（ａ４）に基づく効果が十分に発揮されなくなる。一方、１４０質量部を上回ると、共重合体（Ａ）の耐熱性が低下し、ポストベイク時にパターンの熱ダレによる残渣の発生や透明性の低下を招くおそれがある。 The structural unit (a4) is preferably included in an amount of 5 to 140 parts by mass with respect to 100 parts by mass of the total amount of the structural unit (a1) and the structural unit (a2), and more preferably 10 to 10 in terms of developability and transparency. 90 parts by mass are included. When content of a structural unit (a4) is less than 5 mass parts, the effect based on a structural unit (a4) will not fully be exhibited. On the other hand, when the amount exceeds 140 parts by mass, the heat resistance of the copolymer (A) is lowered, and there is a possibility that generation of a residue due to thermal sagging of the pattern or reduction in transparency may occur during post-baking.
成分（Ａ）は上記に示した構成単位(ａ１)、（ａ２）および（ａ３）または(ａ１)、（ａ２）、（ａ３）および（ａ４）からなる共重合体であることにより、誘電率、現像性、残膜率、透明性および耐溶剤性に優れた感光性樹脂組成物を提供することができる。なお、成分（Ａ）にその他の構成単位として、例えば酢酸ビニルに代表される脂肪族ビニル単量体から誘導される構成単位を含有すると上記物性のバランスが崩れる結果を招く。
〔共重合体（Ａ）の合成法〕
共重合体（Ａ）を合成するに際しては、公知のラジカル重合法を適用することができる。その際、共重合成分である(ａ１)´、（ａ２）´、（ａ３）´、（ａ４）´は重合釜に一括で仕込むことも、分割で反応系中に滴下しても良い。
Component (A) is a copolymer comprising the structural units (a1), (a2) and (a3) or (a1), (a2), (a3) and (a4) shown above, so that the dielectric constant It is possible to provide a photosensitive resin composition excellent in developability, residual film ratio, transparency and solvent resistance. In addition, when the component (A) contains, for example, a structural unit derived from an aliphatic vinyl monomer typified by vinyl acetate as the other structural unit, the balance of the above physical properties is lost.
[Synthesis Method of Copolymer (A)]
In synthesizing the copolymer (A), a known radical polymerization method can be applied. At that time, the copolymerization components (a1) ′, (a2) ′, (a3) ′, and (a4) ′ may be charged all at once into the polymerization kettle or may be dropped into the reaction system in a divided manner.
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。このような重合用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、単独でまたは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 a solvent for polymerization include ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; ethylene glycol monoalkyl such as ethylene glycol monomethyl ether acetate and ethylene glycol monoethyl ether acetate. Ether acetates; 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 Propylene glycol monoalkyl ether acetates such as monoethyl ether 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, Examples thereof include amides such as N-dimethylacetamide and N-methylpyrrolidone; 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、シアノ基を有さないアゾ系重合開始剤または有機過酸化物およ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. Specific examples thereof include an azo polymerization initiator, an azo polymerization initiator having no cyano group, an organic peroxide, and hydrogen peroxide. 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（質量平均分子量）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等が挙げられる。 In order to adjust the weight average molecular weight (mass 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. Etc.
成分（Ａ）の共重合体の重量平均分子量は好ましくは５，０００〜６０，０００、現像性の面からより好ましくは５，０００〜３０，０００、特に好ましくは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、十分な現像性が得られず現像残渣が発生するおそれがある。
＜成分（Ｂ）：キノンジアジド基を有するエステル化物＞
成分（Ｂ）のキノンジアジド基を有するエステル化物（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エステル化物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溶解させることができる。一方、未露光部は、現像液に対して溶解抑止能を有しているため、膜を形成することができる。つまり、キノンジアジド基を有するエステル化物は、フォトマスクを介して露光することにより、その後の現像工程にて現像液に対する溶解性の差を発現することができるため、パターン膜を得ることができる。
The weight average molecular weight of the copolymer of the component (A) is preferably 5,000 to 60,000, more preferably 5,000 to 30,000, particularly preferably 8,000 to 25,000 from the viewpoint of developability. is there. 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 the weight average molecular weight exceeds 60,000, the solubility in the developer is poor and sufficient Development developability may not be obtained.
<Component (B): Esterified product having a quinonediazide group>
When the esterified product (photosensitive agent) having a quinonediazide group as component (B) is exposed through a photomask in an exposure process by photolithography, a photoisomerization reaction of the esterified product having a quinonediazide group occurs in the exposed portion. A carboxyl group can be generated and dissolved in a developer in a subsequent development step. On the other hand, since the unexposed part has a dissolution inhibiting ability with respect to the developer, a film can be formed. That is, since the esterified product having a quinonediazide group can be exposed through a photomask to exhibit a difference in solubility in a developing solution in a subsequent development step, a pattern film can be obtained.
キノンジアジド基を有するエステル化物のエステル化率は好ましくは２０〜９０モル％、残膜率の面からより好ましくは２５〜５０モル％である。ただし、エステル化率は多官能フェノール由来のヒドロキシル基に対するキノンジアジド化合物のモル％を表す。エステル化率が２０モル％を下回ると現像性の低下を招き、現像残渣が発生するおそれがあり、９０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、白濁や透明性の低下をまねくおそれがある。 The esterification rate of the esterified product having a quinonediazide group is preferably 20 to 90 mol%, and more preferably 25 to 50 mol% from the viewpoint of the remaining film ratio. However, the esterification rate represents the mol% of the quinonediazide compound with respect to the hydroxyl group derived from polyfunctional phenol. If the esterification rate is less than 20 mol%, the developability may be lowered, and a development residue may be generated. If the esterification rate is more than 90 mol%, the compatibility with the copolymer is deteriorated and the pattern film is phase-separated. There is a risk of cloudiness and loss of transparency.
成分（Ｂ）のキノンジアジド基を有するエステル化物は、キノンジアジド化合物とフェノール性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−スルフォニルクロリド、１，２−ナフトキノンジアジド−４−スルフォニルクロリド等に代表されるナフトキノンジアジドスルホン酸ハライドやベンゾキノンジアジドスルホン酸クロリドに代表されるベンゾキノンジアジドスルホン酸ハライドが用いられる。フェノール性化合物としては、下記式（５）または（６）で表される化合物が好ましい。 The esterified product having a quinonediazide group as component (B) can be obtained by esterifying a quinonediazide compound and a phenolic compound. Examples of the quinonediazide compound include 1,2-naphthoquinonediazide-5-sulfonyl chloride, benzoquinonediazide represented by naphthoquinonediazidesulfonic acid halide represented by 1,2-naphthoquinonediazide-4-sulfonylchloride, and benzoquinonediazidesulfonic acid chloride. Sulfonic acid halides are used. As the phenolic compound, a compound represented by the following formula (5) or (6) is preferable.
前記式（５）で示されるフェノール性化合物としては、例えば下記式（５ａ）〜（５ｃ）のような化合物が挙げられる。
Examples of the phenolic compound represented by the formula (5) include compounds represented by the following formulas (5a) to (5c).
＜成分（Ｃ）：エポキシ基を有する架橋性化合物＞
エポキシ基を有する架橋性化合物（エポキシ化合物または硬化剤）のエポキシ基は、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。エポキシ基を有する架橋性化合物の具体例としては、ビスフェノール型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、ナフタレン型エポキシ樹脂、脂環式エポキシ樹脂、グリシジルエーテル型エポキシ樹脂、グリシジルエステル型エポキシ樹脂、グリシジルアミン型エポキシ樹脂、複素環式エポキシ樹脂、シロキサン型エポキシ樹脂、フルオレン型エポキシ樹脂、テトラフェニロールエタン型エポキシ樹脂、ＤＰＰ（ジ−ｎ−ペンチルフタレート）型エポキシ樹脂、トリスヒドロキシフェニルメタン型エポキシ樹脂、ジシクロペンタジエンフェノール型エポキシ樹脂等が挙げられる。上記に挙げたエポキシ樹脂の中でも、下記式（８）〜（１１）で表されるエポキシ樹脂が特に好ましい。
<Component (C): Crosslinkable compound having an epoxy group>
The epoxy group of the crosslinkable compound (epoxy compound or curing agent) having an epoxy group can cause a thermosetting reaction with a carboxyl group in the side chain of the copolymer (A) during high temperature baking to form a crosslinked film. Specific examples of the crosslinkable compound having an epoxy group include bisphenol type epoxy resin, cresol novolac type epoxy resin, phenol novolac type epoxy resin, naphthalene type epoxy resin, alicyclic epoxy resin, glycidyl ether type epoxy resin, glycidyl ester type. Epoxy resin, glycidylamine type epoxy resin, heterocyclic epoxy resin, siloxane type epoxy resin, fluorene type epoxy resin, tetraphenylolethane type epoxy resin, DPP (di-n-pentylphthalate) type epoxy resin, trishydroxyphenylmethane Type epoxy resin, dicyclopentadienephenol type epoxy resin and the like. Among the epoxy resins listed above, epoxy resins represented by the following formulas (8) to (11) are particularly preferable.
式（８）で表されるエポキシ樹脂の中でも（株）プリンテック社製のＶＧ３１０１Ｌが好ましく、式（１０）で表されるエポキシ樹脂の中でもダイセル化学工業（株）社製のＥＨＰＥ−３１５０が好ましく、式（１１）で表されるエポキシ樹脂の中でもジャパンエポキシレジン（株）社製のエピコート８２８、エピコート８３４、エピコート１００１が好ましい。
Among epoxy resins represented by formula (8), VG3101L manufactured by Printec Co., Ltd. is preferable, and among epoxy resins represented by formula (10), EHPE-3150 manufactured by Daicel Chemical Industries, Ltd. is preferable. Among the epoxy resins represented by the formula (11), Epicoat 828, Epicoat 834 and Epicoat 1001 manufactured by Japan Epoxy Resins Co., Ltd. are preferable.
感光性樹脂組成物における、成分（Ｃ）の構成割合は、成分（Ａ）の共重合体１００質量部に対して１〜５０質量部であり、低誘電性の面から好ましくは５〜４５質量部、さらに好ましくは１０〜４０質量部である。この構成割合が１質量部を下回るとパターン膜（硬化膜）の溶剤耐性が不十分になり、５０質量部を上回ると、共重合体との相溶性が悪化し、パターン膜の相分離が起こり、白濁や透明性の低下を招くおそれがある。
＜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、密着性向上助剤、界面活性剤等の添加成分を配合することができる。
（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、単独でまたは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）のエポキシ基と成分（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ができる。硬化促進剤としては、例えば三新化学工業（株）製のサンエイドＳＩ−４５Ｌ、サンエイドＳＩ−６０Ｌ、サンエイドＳＩ−８０Ｌ、サンエイドＳＩ−１００Ｌ、サンエイドＳＩ−１１０Ｌ、サンエイドＳＩ−１５０Ｌ等の芳香族スルホニウム塩、サンアプロ（株）製のＵ−ＣＡＴ ＳＡ１０２、Ｕ−ＣＡＴ ＳＡ１０６、Ｕ−ＣＡＴ ＳＡ５０６、Ｕ−ＣＡＴ ＳＡ６０３、Ｕ−ＣＡＴ ５００２等のジアザビシクロウンデセン塩、サンアプロ（株）製のＣＰＩ−１００Ｐ、ＣＰＩ−１０１Ａ、ＣＰＩ−２００ｋ、ＣＰＩ−２１０ｓ等の光酸発生剤、四国化成工業（株）製のキュアゾール １Ｂ２ＰＺ等のイミダゾール類等が挙げられる。
The constituent ratio of the component (C) in the photosensitive resin composition is 1 to 50 parts by mass with respect to 100 parts by mass of the copolymer of the component (A), and preferably 5 to 45 mass from the viewpoint of low dielectric properties. Parts, more preferably 10 to 40 parts by mass. When this proportion is less than 1 part by mass, the solvent resistance of the pattern film (cured film) becomes insufficient, and when it exceeds 50 parts by mass, the compatibility with the copolymer deteriorates and phase separation of the pattern film occurs. There is a risk of causing cloudiness and a decrease in transparency.
<Other additive components>
Additive components such as a solvent, a curing accelerator, a contrast improver, an adhesion improving aid, and a surfactant can be blended in the photosensitive resin composition.
(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 can promote the crosslinking reaction between the epoxy group of the component (C) and the carboxyl group of the side chain of the component (A) copolymer. Examples of the curing accelerator include aromatic sulfoniums such as San-Aid SI-45L, Sun-Aid SI-60L, Sun-Aid SI-80L, Sun-Aid SI-100L, Sun-Aid SI-110L, and Sun-Aid SI-150L manufactured by Sanshin Chemical Industry Co., Ltd. Salt, diazabicycloundecene salts such as U-CAT SA102, U-CAT SA106, U-CAT SA506, U-CAT SA603, U-CAT 5002, etc. manufactured by San Apro Co., Ltd., and CPI-100P manufactured by San Apro Co., Ltd. Photoacid generators such as CPI-101A, CPI-200k, and CPI-210s, and imidazoles such as Curesol 1B2PZ manufactured by Shikoku Kasei Kogyo Co., Ltd.
硬化促進剤の構成割合は、成分（Ｃ）の１００質量部に対し、通常０．１〜１５質量部である。
（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（５）または（６）で表されるフェノール性化合物を配合することができる。これらのフェノール性化合物のフェノール基は光が照射されない未露光部において、成分（Ｂ）の感光剤のジアゾ基とアゾカップリング反応を起こして成分（Ｂ）の溶解抑止効果を高める。その結果、これらフェノール性化合物を用いない場合に比べ、露光部と未露光部のアルカリ現像液への溶解性の差を大きくする（コントラストを大きくする）ことができるため、残膜率、解像度の向上を図ることができる。
The composition ratio of the curing accelerator is usually 0.1 to 15 parts by mass with respect to 100 parts by mass of the component (C).
(Contrast improver)
In the photosensitive resin composition, a phenolic compound represented by the formula (5) or (6) can be blended for the purpose of improving contrast. The phenol group of these phenolic compounds causes an azo coupling reaction with the diazo group of the photosensitive agent of component (B) in the unexposed area where no light is irradiated, thereby enhancing the dissolution inhibiting effect of component (B). As a result, compared to the case where these phenolic compounds are not used, the difference in solubility between the exposed area and the unexposed area in the alkaline developer can be increased (the contrast is increased). Improvements can be made.
コントラスト向上剤として添加されるフェノール性化合物として好ましくは、前記式（５ａ）、（５ｂ）、（５ｃ）、（６ａ）または（６ｂ）で表される化合物であり、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。
（密着性向上助剤および界面活性剤）
感光性樹脂組成物には、必要に応じて密着性向上助剤、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、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、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、例えばモメンティブ・パフォーマンス・マテリアルズ・ジャパン製のＴＳＦ−４３１、ＴＳＦ−４３３、ＴＳＦ−４３７、住友３Ｍ（株）製の＜ノベック＞ＨＦＥ、大日本インキ化学工業（株）製のメガファックＦ−４７７、Ｆ−４８３、Ｆ−５５４、ＴＦ−１４３４、ＴＥＧＯ製のＧｌｉｄｅ−４１０、Ｇｌｉｄｅ−４４０、Ｇｌｉｄｅ−４５０、Ｇｌｉｄｅ−Ｂ１４８４等が挙げられる。
＜感光性樹脂組成物の調製法＞
感光性樹脂組成物を調製するに際しては、前記成分（Ａ）、（Ｂ）および（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および半導体デバイス＞
フラットパネルディスプレイおよび半導体デバイスは前記感光性樹脂組成物の有用な用途であり、感光性樹脂組成物を硬化したパターン膜、すなわち平坦化膜または層間絶縁膜を有する。平坦化膜およ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用また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。次いで、塗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５００ｍＪ／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。
The phenolic compound added as a contrast improver is preferably a compound represented by the formula (5a), (5b), (5c), (6a) or (6b), and usually 100 parts by mass of a copolymer. Is used in an amount of 1 to 20 parts by mass.
(Adhesion improvement aid and surfactant)
If necessary, the photosensitive resin composition may further contain an adhesion improving aid, a surfactant and the like. Examples of the adhesion improving aid include alkyl imidazoline, polyhydroxystyrene, polyvinyl methyl ether, t-butyl novolac, epoxy silane, silane coupling agent and the like. Examples of surfactants include, for example, TSF-431, TSF-433, TSF-437 manufactured by Momentive Performance Materials Japan, <Novec> HFE manufactured by Sumitomo 3M Co., Ltd., Dainippon Ink & Chemicals, Inc. ) Manufactured by MegaFuck F-477, F-483, F-554, TF-1434, TEGO-made Glide-410, Glide-440, Glide-450, Glide-B1484, and the like.
<Method for preparing photosensitive resin composition>
In preparing the photosensitive resin composition, the components including the components (A), (B) and (C) may be blended together, or the components may be blended sequentially after being dissolved in a solvent. May be. 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>
Flat panel displays and semiconductor devices are useful applications of the photosensitive resin composition, and have a pattern film obtained by curing the photosensitive resin composition, that is, a planarizing film or an interlayer insulating film. In forming the planarization film and the interlayer insulating film, a solution of the photosensitive resin composition is usually applied on the substrate and prebaked to form a coating 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. Next, after pattern exposure is performed on the coating film through a predetermined mask, development processing is performed using an alkaline developer, and rinsing processing 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 for the entire surface exposure is usually 500 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。なお、全面にパターン膜を形成する場合には、パターン露光、現像などは行わなくてよい。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. When a pattern film is formed on the entire surface, pattern exposure, development, etc. need not be performed. 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, as a method for applying the photosensitive resin composition, any method such as a spin coating method, a roll coating method, a land coating method, a spray method, a casting coating method, a dip coating method, and a slit coating method may be used. Use it. 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、実施例およ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」および「％」は、特に断りがない限り全て質量基準である。以下に各実施例および各比較例で用いた測定方法および評価方法を示す。
＜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、テトラヒドロフラン（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。
〔合成例１、共重合体Ａ−１の合成〕
温度計、攪拌機および冷却管を備えた１０００ｍＬの４つ口フラスコにプロピレングリコールモノメチルエーテルアセテート（ＰＧＭＥＡ）を２４９．５ｇ仕込み、窒素置換した後、オイルバスで液温が８０℃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 by using a gel permeation chromatography apparatus HLC-8220GPC manufactured by Tosoh Corporation, using SHODEX K801 manufactured by Showa Denko KK as a column, tetrahydrofuran (THF) as an eluent, and an RI detector. It calculated | required by conversion using the calibration curve obtained by a polystyrene standard with a known molecular weight.
[Synthesis Example 1, Synthesis of Copolymer A-1]
249.5 g of propylene glycol monomethyl ether acetate (PGMEA) was charged into a 1000 mL four-necked flask equipped with a thermometer, a stirrer, and a cooling tube, purged with nitrogen, and then heated up to 80 ° C. with an oil bath. .
他方、イタコン酸ジメチル（ＤＭＩ）３７．７ｇ、メタクリル酸（ＭＡＡ）２５．０ｇ、α−メチルスチレン（α−Ｓｔ）３７．３ｇ、ｔ−ブチルパーオキシ−２−エチルヘキサノエート〔日油（株）製の過酸化物重合開始剤〕３．０ｇおよびＰＧＭＥＡ４７．５ｇ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２〜１６、共重合体Ａ−２〜１６〕
表１または表２に記載した仕込み種および量、滴下およ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−１６の合成を行った。
〔比較合成例１〜３、共重合体Ａ−１７〜Ａ−１９〕
表２に記載した仕込み種および量、滴下およ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−１７〜Ａ−１９の合成を行った。
On the other hand, 37.7 g of dimethyl itaconate (DMI), 25.0 g of methacrylic acid (MAA), 37.3 g of α-methylstyrene (α-St), t-butylperoxy-2-ethylhexanoate [NOF ( Peroxide polymerization initiator manufactured by Kogyo Co., Ltd.] 3.0 g and 47.5 g of PGMEA mixed in advance (dropping component) were dropped at a constant rate from a dropping funnel over 2 hours, and then maintained at the same temperature for 8 hours. Copolymer A-1 was obtained.
[Synthesis Examples 2 to 16, Copolymer A-2 to 16]
Copolymers A-2 to A-16 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 or Table 2 were changed.
[Comparative Synthesis Examples 1 to 3 , Copolymers A- 17 to A- 19 ]
Copolymers A- 17 to A- 19 were synthesized in the same manner as in Synthesis Example 1 except that the charge type and amount, dropping, and polymerization temperature described in Table 2 were changed.
ＤＭＩ：イタコン酸ジメチル
ＤＥＩ：イタコン酸ジエチル
ＤＢＩ：イタコン酸ジブチル
ＤｃＨＩ：イタコン酸ジシクロヘキシル
ＤｅＨＩ：イタコン酸ジエチルヘキシル
Ｓｔ：スチレン
α−Ｓｔ：α−メチルスチレン
ＭＡＡ：メタクリル酸
ＡＡ：アクリル酸
ＨＥＭＡ：メタクリル酸ヒドロキシエチル
ＨＰＭＡ：メタクリル酸ヒドロキシプロピル
ＬＭＡ：メタクリル酸ラウリル
ＭＭＡ：メタクリル酸メチル
ＣＨＭＡ：メタクリル酸シクロヘキシル
パーヘキシル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
パーブチル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
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
＜実施例１−１＞
合成例１で得られた共重合体Ａ−１を１００ｇ、前記式（６ａ）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２５．０ｇ、ＥＨＰＥ−３１５０〔エポキシ樹脂、エポキシ基は平均１５個、ダイセル化学工業（株）製〕４０．０ｇ、コントラスト向上を目的に前記式（６ａ）で表される化合物１０．０ｇ、架橋促進剤としてＣＩＰ−２１０Ｓ〔サンアプロ（株）製〕１．０ｇ、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Ｆ−４８３〔ＤＩＣ（株）製〕を０．５ｇを適量のプロピレングリコールモノメチルエーテルアセテート（ＰＧＭＥＡ）に溶解させて攪拌した後、０．２μｍのフィルターで濾過して、感光性樹脂組成物を調製した。
（薄膜パターンの形成）
上記の感光性樹脂組成物を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、約３．３μｍ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およ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秒間現像することで、ラインとスペース幅が１：１のライン＆スペースパターンおよ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ーク処理を行い、約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より残膜率を算出した。
DMI: dimethyl itaconate DEI: diethyl itaconate DBI: dibutyl itaconate DcHI: dicyclohexyl itaconate DeHI: diethylhexyl itaconate St: styrene α-St: α-methylstyrene MAA: methacrylic acid AA: acrylic acid HEMA: hydroxymethacrylate Ethyl HPMA: hydroxypropyl methacrylate LMA: lauryl methacrylate MMA: methyl methacrylate CHMA: cyclohexyl methacrylate perhexyl O: t-hexylperoxy-2-ethylhexanoate, peroxide-based polymerization manufactured by NOF Corporation Initiator Perbutyl O: t-butylperoxy-2-ethylhexanoate, a peroxide-based polymerization initiator manufactured by NOF Corporation AIBN: 2,2′-azobisisobutyronitrile [azo-based polymerization start Agent, By Wako Pure Chemical Industries Co., Ltd.]
PGMEA: Propylene glycol monomethyl ether acetate <Example 1-1>
100 g of copolymer A-1 obtained in Synthesis Example 1, 25.0 g of an esterified product of the compound represented by the formula (6a) and 1,2-naphthoquinonediazide-5-sulfonyl chloride, EHPE-3150 [ Epoxy resin, 15 epoxy groups on average, manufactured by Daicel Chemical Industries, Ltd.] 40.0 g, 10.0 g of the compound represented by formula (6a) for the purpose of improving contrast, CIP-210S [Sanapuro as a crosslinking accelerator Manufactured by Co., Ltd.] 1.0 g, radial wrinkles formed on the resist film during spin coating, so-called striations, and a fluorosurfactant, Megafac F-483 [manufactured by DIC Corporation] Is dissolved in an appropriate amount of propylene glycol monomethyl ether acetate (PGMEA) and stirred, and then a 0.2 μm filter is added. In filtered to prepare a photosensitive resin composition.
(Formation of thin film pattern)
The 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 about 3.3 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. By developing with a 4% by mass tetramethylammonium hydroxide aqueous solution at 23 ° C. for 60 seconds, a thin film (B) having a line & space pattern and a contact hole pattern with a line and space width of 1: 1 was obtained. The entire surface of this thin film (B) was exposed with 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 about 3.0 μm. .
(Evaluation of remaining film rate)
The residual film ratio was calculated from the following formula 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、３、５、１０μｍのホールパターンをＳＥＭ（走査型電子顕微鏡）にて観察した。いずれのサイズのホール内部にも残渣が見られる場合には×、５および１０μｍのホール内部には残渣は見られないが、３μｍのホール内部における基板のホールの界面付近に残渣が見られる場合には△、いずれのサイズのホール内部にも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３〜表５に示した。
（誘電率の評価）
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誘電率を算出した。その結果を表３〜表５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。この薄膜の４００ｎｍにおける透過率を、紫外−可視光分光光度計ＣＡＲＹ４Ｅ（バリアン（株）製）を用いて測定した。その結果を表３〜表５に示した。
（耐溶剤性の評価）
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、ＲｅｍｏｖｅｒＮ−３２１〔ナガセケムテックス（株）製〕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２％未満のものについては○、透過率差が２〜４％のものについては△、透過率差が４％を超えるものを×として評価した。その結果を表３〜表５に示した。
＜実施例１−２、１−３および２−１〜２−２４＞
表３〜表５に示した成分（Ａ）の共重合体、成分（Ｂ）のエステル化物、成分（Ｃ）のエポキシ化合物およびその他添加剤等を用いること以外は実施例１−１と同様の操作を行うことにより、感光性樹脂組成物を調製した。この感光性樹脂組成物について、実施例１−１と同様の物性を評価し、それらの結果を表３〜表５に示した。表３〜表５中の略号を次に示す。
Residual film ratio (%) = [film thickness of thin film (B) (μm) / film thickness of thin film (A) (μm)] × 100
(Evaluation of developability)
Among the patterns produced above, hole patterns of 3, 5, and 10 μm were observed with a SEM (scanning electron microscope). When residues are found inside holes of any size, no residue is seen inside holes of 5 and 10 μm, but when residues are found near the interface of the holes in the substrate inside the 3 μm holes. △, and when no residue was found inside the hole of any size, the developability was evaluated as ◯. The results are shown in Tables 3-5.
(Evaluation of dielectric constant)
By performing the same operation as above except that the test pattern was not exposed with PLA-501F, a 3.0 μm-thick thin film without a pattern was obtained on a 4-inch silicon wafer. An electrode was formed on this thin film, and the dielectric constant was calculated from the capacitance obtained by 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 Tables 3-5.
(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. The transmittance of this thin film at 400 nm was measured using an ultraviolet-visible light spectrophotometer CARY4E (manufactured by Varian Inc.). The results are shown in Tables 3-5.
(Evaluation of solvent resistance)
A glass substrate obtained by performing the same operation as the evaluation of transmittance was immersed in Remover N-321 (manufactured by Nagase ChemteX Corporation) at 60 ° C. for 1 minute, then rinsed with pure water, 200 ° C., A rebaking process for 15 minutes was performed. The difference between the transmittance before immersion in the solvent and the transmittance after re-baking is less than 2%. The difference between the transmittance is 2 to 4%. The transmittance difference is more than 4%. Was evaluated as x. The results are shown in Tables 3-5.
<Examples 1-2, 1-3 and 2-1 to 2-24>
The same as Example 1-1 except that the copolymer of component (A), the esterified product of component (B), the epoxy compound of component (C) and other additives shown in Tables 3 to 5 are used. By carrying out the operation, a photosensitive resin composition was prepared. About this photosensitive resin composition, the physical property similar to Example 1-1 was evaluated, and those results were shown in Table 3-Table 5. The abbreviations in Tables 3 to 5 are shown below.
ＶＧ３１０１Ｌ：エポキシ樹脂（エポキシ基は３個、（株）プリンテック製）
エピコート８２８：エポキシ樹脂（エポキシ基は２個、ジャパンエポキシレジン（株）製）
＜比較例１〜３＞
表５に示した成分（Ａ）の共重合体、成分（Ｂ）のエステル化物、成分（Ｃ）のエポキシ化合物およびその他添加剤等を用いること以外は実施例１−１と同様の操作を行うことにより、感光性樹脂組成物を調製した。この感光性樹脂組成物について、実施例１−１と同様の物性を評価し、それらの結果を表５に示した。
VG3101L: Epoxy resin (3 epoxy groups, manufactured by Printec Co., Ltd.)
Epicoat 828: Epoxy resin (two epoxy groups, manufactured by Japan Epoxy Resin Co., Ltd.)
<Comparative Examples 1 to 3 >
The same operation as in Example 1-1 is performed except that the copolymer of component (A), the esterified product of component (B), the epoxy compound of component (C), and other additives shown in Table 5 are used. Thus, a photosensitive resin composition was prepared. About this photosensitive resin composition, the physical property similar to Example 1-1 was evaluated, and those results were shown in Table 5.
一方、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、現像性の悪化および低誘電特性の悪化が観られた。比較例２では、成分（Ａ）の共重合体に構成単位（ａ１）および（ａ２）が含まれていないことから、現像性の悪化および低誘電特性の悪化が観られた。比較例３では、構成単位（ａ１）が成分（Ａ）の共重合体中に過度に含有、構成単位（ａ３）が成分（Ａ）の共重合体中において過度に減量、（ａ１）＋（ａ２）が成分（Ａ）の共重合体中に過度に含有されるため、低誘電性には優れるものの、現像性の低下が観られた。 On the other hand, in Comparative Example 1, since the structural unit (a1) was not contained in the component (A) copolymer, deterioration in developability and deterioration in low dielectric properties were observed. In Comparative Example 2, since the structural unit (a1) and (a2) were not included in the copolymer of component (A), deterioration in developability and deterioration in low dielectric properties were observed. In Comparative Example 3, the structural unit (a1) is excessively contained in the component (A) copolymer, the structural unit (a3) is excessively reduced in the component (A) copolymer, (a1) + ( Since a2) is excessively contained in the copolymer of component (A), although the low dielectric property is excellent, a decrease in developability was observed .
Claims (4)
前記成分（Ａ）は下記式（１）で表されるイタコン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）および下記式（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を有する共重合体であり、構成単位（ａ１）と構成単位（ａ２）の合計量に対して構成単位（ａ１）が１５〜９５質量％、構成単位（ａ２）が５〜８５質量％であると共に、構成単位（ａ１）と構成単位（ａ２）の合計量１００質量部に対して構成単位（ａ３）が５〜１５０質量部であることを特徴とする感光性樹脂組成物。
成分（Ｂ）：多官能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エステル化物。
成分（Ｃ）：エポキシ基を有する架橋性化合物。 It consists of component (A), component (B) and component (C) shown below, and the component ratio of each component is 5 to 50 parts by mass of component (B) and component (C) with respect to 100 parts by mass of component (A). 1 to 50 parts by weight of a photosensitive resin composition,
The component (A) is derived from a structural unit (a1) derived from an itaconic acid diester monomer represented by the following formula (1) and an aromatic vinyl monomer represented by the following formula (2). A copolymer having a structural unit derived from a structural unit (a2) and an α, β-unsaturated carboxylic acid monomer represented by the following formula (3), the structural unit (a1) and the structural unit (a2) The structural unit (a1) is 15 to 95% by mass, the structural unit (a2) is 5 to 85% by mass, and the total amount of the structural unit (a1) and the structural unit (a2) is 100% by mass. The photosensitive resin composition, wherein the structural unit (a3) is 5 to 150 parts by mass with respect to parts.
Component (B): An esterified product having a quinonediazide group, obtained by esterifying a polyfunctional phenolic compound and a quinonediazide compound.
Component (C): a crosslinkable compound having an epoxy group.
前記成分（Ａ）は下記式（１）で表されるイタコン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）および下記式（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を有する共重合体であり、構成単位（ａ１）と構成単位（ａ２）の合計量に対して構成単位（ａ１）が１５〜９５質量％、構成単位（ａ２）が５〜８５質量％であると共に、構成単位（ａ１）と構成単位（ａ２）の合計量１００質量部に対して構成単位（ａ３）が５〜１５０質量部であり、
さらに前記成分（Ａ）は、構成単位（ａ１）、構成単位（ａ２）および構成単位（ａ３）に加えて下記式（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）を、構成単位（ａ１）と構成単位（ａ２）の合計量１００質量部に対して５〜１４０質量部有する共重合体であることを特徴とする感光性樹脂組成物。
成分（Ｂ）：多官能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エステル化物。
成分（Ｃ）：エポキシ基を有する架橋性化合物。 It consists of component (A), component (B) and component (C) shown below, and the component ratio of each component is 5 to 50 parts by mass of component (B) and component (C) with respect to 100 parts by mass of component (A). 1 to 50 parts by weight of a photosensitive resin composition,
The component (A) is derived from a structural unit (a1) derived from an itaconic acid diester monomer represented by the following formula (1) and an aromatic vinyl monomer represented by the following formula (2). A copolymer having a structural unit derived from a structural unit (a2) and an α, β-unsaturated carboxylic acid monomer represented by the following formula (3), the structural unit (a1) and the structural unit (a2) The structural unit (a1) is 15 to 95% by mass, the structural unit (a2) is 5 to 85% by mass, and the total amount of the structural unit (a1) and the structural unit (a2) is 100% by mass. The structural unit (a3) is 5 to 150 parts by mass with respect to parts.
Furthermore, the component (A) is derived from a (meth) acrylic acid ester monomer represented by the following formula (4) in addition to the structural unit (a1), the structural unit (a2) and the structural unit (a3). the structural unit (a4), the total amount copolymers to that sense light resin composition characterized by a having 5-140 parts by weight per 100 parts by weight of the structural unit (a1) and the structural unit (a2) .
Component (B): An esterified product having a quinonediazide group, obtained by esterifying a polyfunctional phenolic compound and a quinonediazide compound.
Component (C): a crosslinkable compound having an epoxy group.
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