JP5735341B2 - Positive photosensitive resin composition - Google Patents
Positive photosensitive resin composition Download PDFInfo
- Publication number
- JP5735341B2 JP5735341B2 JP2011102111A JP2011102111A JP5735341B2 JP 5735341 B2 JP5735341 B2 JP 5735341B2 JP 2011102111 A JP2011102111 A JP 2011102111A JP 2011102111 A JP2011102111 A JP 2011102111A JP 5735341 B2 JP5735341 B2 JP 5735341B2
- Authority
- JP
- Japan
- Prior art keywords
- polyimide
- diamine
- bis
- carboxyl group
- acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000011342 resin composition Substances 0.000 title claims description 28
- 229920001721 polyimide Polymers 0.000 claims description 67
- 239000004642 Polyimide Substances 0.000 claims description 65
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 55
- 229920005989 resin Polymers 0.000 claims description 42
- 239000011347 resin Substances 0.000 claims description 42
- 150000004985 diamines Chemical class 0.000 claims description 41
- -1 silicon diamine Chemical class 0.000 claims description 30
- 239000002253 acid Substances 0.000 claims description 23
- 239000000178 monomer Substances 0.000 claims description 20
- 239000003822 epoxy resin Substances 0.000 claims description 16
- 229920000647 polyepoxide Polymers 0.000 claims description 16
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 15
- 229910052710 silicon Inorganic materials 0.000 claims description 15
- 239000010703 silicon Substances 0.000 claims description 15
- 229920001187 thermosetting polymer Polymers 0.000 claims description 8
- 150000002430 hydrocarbons Chemical class 0.000 claims description 5
- 239000004215 Carbon black (E152) Substances 0.000 claims description 4
- 229930195733 hydrocarbon Natural products 0.000 claims description 4
- 235000013311 vegetables Nutrition 0.000 claims 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 45
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 35
- 239000000243 solution Substances 0.000 description 28
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 24
- 238000010438 heat treatment Methods 0.000 description 19
- 239000000203 mixture Substances 0.000 description 18
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 16
- 239000002244 precipitate Substances 0.000 description 16
- 238000000034 method Methods 0.000 description 15
- 150000001875 compounds Chemical class 0.000 description 12
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 11
- 239000007864 aqueous solution Substances 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 10
- 230000008569 process Effects 0.000 description 10
- 238000003786 synthesis reaction Methods 0.000 description 10
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 9
- 238000002156 mixing Methods 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- 239000007788 liquid Substances 0.000 description 8
- 239000012299 nitrogen atmosphere Substances 0.000 description 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 8
- 239000002243 precursor Substances 0.000 description 8
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 description 7
- 229920003986 novolac Polymers 0.000 description 7
- NVKGJHAQGWCWDI-UHFFFAOYSA-N 4-[4-amino-2-(trifluoromethyl)phenyl]-3-(trifluoromethyl)aniline Chemical group FC(F)(F)C1=CC(N)=CC=C1C1=CC=C(N)C=C1C(F)(F)F NVKGJHAQGWCWDI-UHFFFAOYSA-N 0.000 description 6
- QQGYZOYWNCKGEK-UHFFFAOYSA-N 5-[(1,3-dioxo-2-benzofuran-5-yl)oxy]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(OC=2C=C3C(=O)OC(C3=CC=2)=O)=C1 QQGYZOYWNCKGEK-UHFFFAOYSA-N 0.000 description 6
- 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 6
- 239000011248 coating agent Substances 0.000 description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 6
- 125000006158 tetracarboxylic acid group Chemical group 0.000 description 6
- 150000000000 tetracarboxylic acids Chemical class 0.000 description 6
- RKFCDGOVCBYSEW-AUUKWEANSA-N tmeg Chemical compound COC=1C(OC)=CC(C(OC(C=2OC)=C34)=O)=C3C=1OC(=O)C4=CC=2O[C@@H]1O[C@H](CO)[C@@H](O)[C@H](O)[C@H]1O RKFCDGOVCBYSEW-AUUKWEANSA-N 0.000 description 6
- 238000011161 development Methods 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
- 239000003960 organic solvent Substances 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000001723 curing Methods 0.000 description 4
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 4
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 229920002577 polybenzoxazole Polymers 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 230000035945 sensitivity Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 150000003457 sulfones Chemical class 0.000 description 4
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 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
- 125000003277 amino group Chemical group 0.000 description 3
- 150000004984 aromatic diamines Chemical class 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 230000035699 permeability Effects 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- 238000006798 ring closing metathesis reaction Methods 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-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
- NARCYYCAXRVBGS-UHFFFAOYSA-N 2-[4-[4-(2-hydroxyphenoxy)phenyl]phenoxy]phenol Chemical group OC1=CC=CC=C1OC1=CC=C(C=2C=CC(OC=3C(=CC=CC=3)O)=CC=2)C=C1 NARCYYCAXRVBGS-UHFFFAOYSA-N 0.000 description 2
- BXUSJTNZBBPMHY-UHFFFAOYSA-N 2-amino-5-[4-[4-(4-amino-3-hydroxyphenoxy)phenyl]phenoxy]phenol Chemical group C1=C(O)C(N)=CC=C1OC1=CC=C(C=2C=CC(OC=3C=C(O)C(N)=CC=3)=CC=2)C=C1 BXUSJTNZBBPMHY-UHFFFAOYSA-N 0.000 description 2
- JEAQJTYJUMGUCD-UHFFFAOYSA-N 3,4,5-triphenylphthalic acid Chemical compound C=1C=CC=CC=1C=1C(C=2C=CC=CC=2)=C(C(O)=O)C(C(=O)O)=CC=1C1=CC=CC=C1 JEAQJTYJUMGUCD-UHFFFAOYSA-N 0.000 description 2
- 125000004203 4-hydroxyphenyl group Chemical group [H]OC1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 229930185605 Bisphenol Natural products 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- VHRGRCVQAFMJIZ-UHFFFAOYSA-N cadaverine Chemical compound NCCCCCN VHRGRCVQAFMJIZ-UHFFFAOYSA-N 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- QILSFLSDHQAZET-UHFFFAOYSA-N diphenylmethanol Chemical compound C=1C=CC=CC=1C(O)C1=CC=CC=C1 QILSFLSDHQAZET-UHFFFAOYSA-N 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000010894 electron beam technology Methods 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 229940116333 ethyl lactate Drugs 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- DUWWHGPELOTTOE-UHFFFAOYSA-N n-(5-chloro-2,4-dimethoxyphenyl)-3-oxobutanamide Chemical compound COC1=CC(OC)=C(NC(=O)CC(C)=O)C=C1Cl DUWWHGPELOTTOE-UHFFFAOYSA-N 0.000 description 2
- QVEIBLDXZNGPHR-UHFFFAOYSA-N naphthalene-1,4-dione;diazide Chemical group [N-]=[N+]=[N-].[N-]=[N+]=[N-].C1=CC=C2C(=O)C=CC(=O)C2=C1 QVEIBLDXZNGPHR-UHFFFAOYSA-N 0.000 description 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 2
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical compound NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 description 2
- 229920002120 photoresistant polymer Polymers 0.000 description 2
- 229920005575 poly(amic acid) Polymers 0.000 description 2
- 239000009719 polyimide resin Substances 0.000 description 2
- 235000019260 propionic acid Nutrition 0.000 description 2
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 2
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- 125000005409 triarylsulfonium group Chemical group 0.000 description 2
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- NSGXIBWMJZWTPY-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropane Chemical compound FC(F)(F)CC(F)(F)F NSGXIBWMJZWTPY-UHFFFAOYSA-N 0.000 description 1
- AVQQQNCBBIEMEU-UHFFFAOYSA-N 1,1,3,3-tetramethylurea Chemical compound CN(C)C(=O)N(C)C AVQQQNCBBIEMEU-UHFFFAOYSA-N 0.000 description 1
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- SBHHKGFHJWTZJN-UHFFFAOYSA-N 1,3-dimethylcyclobutane-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C1(C)C(C(O)=O)C(C)(C(O)=O)C1C(O)=O SBHHKGFHJWTZJN-UHFFFAOYSA-N 0.000 description 1
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- PWGJDPKCLMLPJW-UHFFFAOYSA-N 1,8-diaminooctane Chemical compound NCCCCCCCCN PWGJDPKCLMLPJW-UHFFFAOYSA-N 0.000 description 1
- CGSKOGYKWHUSLC-UHFFFAOYSA-N 1-(4-aminophenyl)-1,3,3-trimethyl-2h-inden-5-amine Chemical compound C12=CC=C(N)C=C2C(C)(C)CC1(C)C1=CC=C(N)C=C1 CGSKOGYKWHUSLC-UHFFFAOYSA-N 0.000 description 1
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 description 1
- RRQYJINTUHWNHW-UHFFFAOYSA-N 1-ethoxy-2-(2-ethoxyethoxy)ethane Chemical compound CCOCCOCCOCC RRQYJINTUHWNHW-UHFFFAOYSA-N 0.000 description 1
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 1
- UXOXUHMFQZEAFR-UHFFFAOYSA-N 2,2',5,5'-Tetrachlorobenzidine Chemical group C1=C(Cl)C(N)=CC(Cl)=C1C1=CC(Cl)=C(N)C=C1Cl UXOXUHMFQZEAFR-UHFFFAOYSA-N 0.000 description 1
- KKTUQAYCCLMNOA-UHFFFAOYSA-N 2,3-diaminobenzoic acid Chemical class NC1=CC=CC(C(O)=O)=C1N KKTUQAYCCLMNOA-UHFFFAOYSA-N 0.000 description 1
- PCAXITAPTVOLGL-UHFFFAOYSA-N 2,3-diaminophenol Chemical class NC1=CC=CC(O)=C1N PCAXITAPTVOLGL-UHFFFAOYSA-N 0.000 description 1
- WIOZZYWDYUOMAY-UHFFFAOYSA-N 2,5-diaminoterephthalic acid Chemical compound NC1=CC(C(O)=O)=C(N)C=C1C(O)=O WIOZZYWDYUOMAY-UHFFFAOYSA-N 0.000 description 1
- SSOVVTOURMQUSM-UHFFFAOYSA-N 2-[(4-propylphenoxy)methyl]oxirane Chemical compound C1=CC(CCC)=CC=C1OCC1OC1 SSOVVTOURMQUSM-UHFFFAOYSA-N 0.000 description 1
- OROIWZWHCJQKOA-UHFFFAOYSA-N 2-[2-[2-(2-hydroxyphenoxy)phenyl]sulfonylphenoxy]phenol Chemical class OC1=CC=CC=C1OC1=CC=CC=C1S(=O)(=O)C1=CC=CC=C1OC1=CC=CC=C1O OROIWZWHCJQKOA-UHFFFAOYSA-N 0.000 description 1
- YYHRJJWMKQMOFN-UHFFFAOYSA-N 2-amino-4-(3-amino-4-carboxyphenyl)benzoic acid Chemical group C1=C(C(O)=O)C(N)=CC(C=2C=C(N)C(C(O)=O)=CC=2)=C1 YYHRJJWMKQMOFN-UHFFFAOYSA-N 0.000 description 1
- UTYHQSKRFPHMQQ-UHFFFAOYSA-N 2-amino-4-(3-amino-4-hydroxyphenoxy)phenol Chemical compound C1=C(O)C(N)=CC(OC=2C=C(N)C(O)=CC=2)=C1 UTYHQSKRFPHMQQ-UHFFFAOYSA-N 0.000 description 1
- KZLDGFZCFRXUIB-UHFFFAOYSA-N 2-amino-4-(3-amino-4-hydroxyphenyl)phenol Chemical group C1=C(O)C(N)=CC(C=2C=C(N)C(O)=CC=2)=C1 KZLDGFZCFRXUIB-UHFFFAOYSA-N 0.000 description 1
- KECOIASOKMSRFT-UHFFFAOYSA-N 2-amino-4-(3-amino-4-hydroxyphenyl)sulfonylphenol Chemical compound C1=C(O)C(N)=CC(S(=O)(=O)C=2C=C(N)C(O)=CC=2)=C1 KECOIASOKMSRFT-UHFFFAOYSA-N 0.000 description 1
- KCFVSHSJPIVGCG-UHFFFAOYSA-N 2-amino-4-[(3-amino-4-hydroxyphenyl)methyl]phenol Chemical compound C1=C(O)C(N)=CC(CC=2C=C(N)C(O)=CC=2)=C1 KCFVSHSJPIVGCG-UHFFFAOYSA-N 0.000 description 1
- GPWZWWICAGSVPI-UHFFFAOYSA-N 2-amino-4-[2-(3-amino-4-carboxyphenyl)-1,1,1,3,3,3-hexafluoropropan-2-yl]benzoic acid Chemical compound C1=C(C(O)=O)C(N)=CC(C(C=2C=C(N)C(C(O)=O)=CC=2)(C(F)(F)F)C(F)(F)F)=C1 GPWZWWICAGSVPI-UHFFFAOYSA-N 0.000 description 1
- DLLQVJOXCPRYAP-UHFFFAOYSA-N 2-amino-4-[2-(3-amino-4-carboxyphenyl)propan-2-yl]benzoic acid Chemical compound C=1C=C(C(O)=O)C(N)=CC=1C(C)(C)C1=CC=C(C(O)=O)C(N)=C1 DLLQVJOXCPRYAP-UHFFFAOYSA-N 0.000 description 1
- UHIDYCYNRPVZCK-UHFFFAOYSA-N 2-amino-4-[2-(3-amino-4-hydroxyphenyl)propan-2-yl]phenol Chemical compound C=1C=C(O)C(N)=CC=1C(C)(C)C1=CC=C(O)C(N)=C1 UHIDYCYNRPVZCK-UHFFFAOYSA-N 0.000 description 1
- XNMHGYOHNVQQEI-UHFFFAOYSA-N 2-amino-5-(4-amino-2,5-dicarboxyphenyl)terephthalic acid Chemical group C1=C(C(O)=O)C(N)=CC(C(O)=O)=C1C1=CC(C(O)=O)=C(N)C=C1C(O)=O XNMHGYOHNVQQEI-UHFFFAOYSA-N 0.000 description 1
- GOTHKMOMTHYAQH-UHFFFAOYSA-N 2-amino-5-(4-amino-2,5-dihydroxyphenyl)benzene-1,4-diol Chemical group C1=C(O)C(N)=CC(O)=C1C1=CC(O)=C(N)C=C1O GOTHKMOMTHYAQH-UHFFFAOYSA-N 0.000 description 1
- IIQLVLWFQUUZII-UHFFFAOYSA-N 2-amino-5-(4-amino-3-carboxyphenyl)benzoic acid Chemical group C1=C(C(O)=O)C(N)=CC=C1C1=CC=C(N)C(C(O)=O)=C1 IIQLVLWFQUUZII-UHFFFAOYSA-N 0.000 description 1
- ZGDMDBHLKNQPSD-UHFFFAOYSA-N 2-amino-5-(4-amino-3-hydroxyphenyl)phenol Chemical group C1=C(O)C(N)=CC=C1C1=CC=C(N)C(O)=C1 ZGDMDBHLKNQPSD-UHFFFAOYSA-N 0.000 description 1
- QRUWUSOUUMPANJ-UHFFFAOYSA-N 2-amino-5-[(4-amino-3-carboxyphenyl)methyl]benzoic acid Chemical compound C1=C(C(O)=O)C(N)=CC=C1CC1=CC=C(N)C(C(O)=O)=C1 QRUWUSOUUMPANJ-UHFFFAOYSA-N 0.000 description 1
- HSPUJPOVWDGDJF-UHFFFAOYSA-N 2-amino-5-[2-(4-amino-3-carboxyphenyl)propan-2-yl]benzoic acid Chemical compound C=1C=C(N)C(C(O)=O)=CC=1C(C)(C)C1=CC=C(N)C(C(O)=O)=C1 HSPUJPOVWDGDJF-UHFFFAOYSA-N 0.000 description 1
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- 238000011156 evaluation Methods 0.000 description 1
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- 239000007849 furan resin Substances 0.000 description 1
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- 239000007789 gas Substances 0.000 description 1
- 125000001188 haloalkyl group Chemical group 0.000 description 1
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- SSXMPWKNMJXRDH-UHFFFAOYSA-N heptane-1,4,4,7-tetramine Chemical compound NCCCC(N)(N)CCCN SSXMPWKNMJXRDH-UHFFFAOYSA-N 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical class I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
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- 238000011416 infrared curing Methods 0.000 description 1
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- ZDGGJQMSELMHLK-UHFFFAOYSA-N m-Trifluoromethylhippuric acid Chemical compound OC(=O)CNC(=O)C1=CC=CC(C(F)(F)F)=C1 ZDGGJQMSELMHLK-UHFFFAOYSA-N 0.000 description 1
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- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- CAAULPUQFIIOTL-UHFFFAOYSA-N methyl dihydrogen phosphate Chemical compound COP(O)(O)=O CAAULPUQFIIOTL-UHFFFAOYSA-N 0.000 description 1
- 229940057867 methyl lactate Drugs 0.000 description 1
- 238000011415 microwave curing Methods 0.000 description 1
- GNWCSWUWMHQEMD-UHFFFAOYSA-N naphthalene-1,2-dione diazide Chemical group [N-]=[N+]=[N-].[N-]=[N+]=[N-].C1=CC=C2C(=O)C(=O)C=CC2=C1 GNWCSWUWMHQEMD-UHFFFAOYSA-N 0.000 description 1
- KQSABULTKYLFEV-UHFFFAOYSA-N naphthalene-1,5-diamine Chemical compound C1=CC=C2C(N)=CC=CC2=C1N KQSABULTKYLFEV-UHFFFAOYSA-N 0.000 description 1
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical compound C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 description 1
- DOBFTMLCEYUAQC-UHFFFAOYSA-N naphthalene-2,3,6,7-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C=C2C=C(C(O)=O)C(C(=O)O)=CC2=C1 DOBFTMLCEYUAQC-UHFFFAOYSA-N 0.000 description 1
- UFWIBTONFRDIAS-UHFFFAOYSA-N naphthalene-acid Natural products C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 1
- YTVNOVQHSGMMOV-UHFFFAOYSA-N naphthalenetetracarboxylic dianhydride Chemical compound C1=CC(C(=O)OC2=O)=C3C2=CC=C2C(=O)OC(=O)C1=C32 YTVNOVQHSGMMOV-UHFFFAOYSA-N 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- GHLZUHZBBNDWHW-UHFFFAOYSA-N nonanamide Chemical compound CCCCCCCCC(N)=O GHLZUHZBBNDWHW-UHFFFAOYSA-N 0.000 description 1
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- UFOIOXZLTXNHQH-UHFFFAOYSA-N oxolane-2,3,4,5-tetracarboxylic acid Chemical compound OC(=O)C1OC(C(O)=O)C(C(O)=O)C1C(O)=O UFOIOXZLTXNHQH-UHFFFAOYSA-N 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 150000004714 phosphonium salts Chemical class 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 239000006187 pill Substances 0.000 description 1
- 229920003192 poly(bis maleimide) Polymers 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 235000013824 polyphenols Nutrition 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000004151 rapid thermal annealing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
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- 150000003462 sulfoxides Chemical class 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- LPSXSORODABQKT-UHFFFAOYSA-N tetrahydrodicyclopentadiene Chemical compound C1C2CCC1C1C2CCC1 LPSXSORODABQKT-UHFFFAOYSA-N 0.000 description 1
- QEMXHQIAXOOASZ-UHFFFAOYSA-N tetramethylammonium Chemical compound C[N+](C)(C)C QEMXHQIAXOOASZ-UHFFFAOYSA-N 0.000 description 1
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Description
本発明は、低温硬化可能な高感度ポジ型感光性樹脂組成物、該組成物を用いたパターン硬化膜の製造方法に関するものである。 The present invention relates to a high-sensitivity positive photosensitive resin composition that can be cured at low temperature, and a method for producing a patterned cured film using the composition.
半導体装置の表面保護膜、及び層間絶縁膜には、優れた耐熱性、電気特性、及び機械特性などを併せ持つポリイミド樹脂やポリベンズオキソザール樹脂が広く用いられている。半導体装置を製造する過程において、前駆体組成物をシリコンウエハ等の基板に塗布し、活性光線によるパターニングを行い、現像し、加熱処理を施すことで、該半導体装置の一部分となる表面保護膜または層間絶縁膜を形成できる。活性光線によってパターニングできる樹脂は一般的に感光性樹脂と称され、ポジ型感光性樹脂とネガ型感光性樹脂に大別される。ポジ型感光性樹脂は、ピンホールができにくい、正テーパーのパターンを形成できる、高解像度である、現像液が安全で環境にやさしいといった面で、ネガ型感光性樹脂よりも注目されている。近年の環境問題意識の高まりなどから、脱有機溶剤対策が求められており、フォトレジストと同様にアルカリ性水溶液で現像可能な耐熱性感光性樹脂材料が提案されつつある。中でも、アルカリ性水溶液可溶性であり且つ硬化後に耐熱性樹脂となるポリベンズオキサゾールの研究が盛んに行われている。しかしながら、感光性ポリベンズオキサゾール前駆体組成物は、感光性ポリイミド前駆体組成物に対し感度が低いという問題がある。それに対して、アルカリ水溶液可溶性重合体１００質量部に対して、光酸発生剤１〜５０質量部、スルホン酸無水物０．０１〜３０質量部及び架橋剤０．１〜７０質量部を含むことを特徴とするポジ型感光性樹脂組成物が提案されている（特許文献１）。前駆体は加熱によって重縮合する必要があり、高温プロセスが必要となる。これに対して、最近登場してきた次世代メモリとして有望なＭＲＡＭは高温プロセスに弱く、低温プロセスが望まれている。従って、表面保護膜剤においても従来の３５０℃前後というような高温ではなく、約２８０℃以下の低温で硬化できる材料が不可欠となってきた。しかしながらこのように低温で硬化できるポジ型感光性樹脂組成物が未だ得られていないという問題があった。 For surface protection films and interlayer insulating films of semiconductor devices, polyimide resins and polybenzoxozar resins having excellent heat resistance, electrical characteristics, mechanical characteristics and the like are widely used. In the process of manufacturing a semiconductor device, a precursor composition is applied to a substrate such as a silicon wafer, patterned with actinic rays, developed, and subjected to a heat treatment to form a surface protective film or a part of the semiconductor device. An interlayer insulating film can be formed. Resins that can be patterned by actinic rays are generally referred to as photosensitive resins, and are roughly divided into positive photosensitive resins and negative photosensitive resins. The positive photosensitive resin is attracting more attention than the negative photosensitive resin in that pinholes are difficult to form, a positive taper pattern can be formed, the resolution is high, and the developer is safe and environmentally friendly. Due to the recent increase in awareness of environmental problems, countermeasures for removing organic solvents have been demanded, and heat-resistant photosensitive resin materials that can be developed with an alkaline aqueous solution as well as photoresists are being proposed. In particular, research on polybenzoxazole, which is soluble in an alkaline aqueous solution and becomes a heat-resistant resin after curing, has been actively conducted. However, the photosensitive polybenzoxazole precursor composition has a problem that the sensitivity is low with respect to the photosensitive polyimide precursor composition. On the other hand, 1 to 50 parts by weight of a photoacid generator, 0.01 to 30 parts by weight of a sulfonic acid anhydride, and 0.1 to 70 parts by weight of a crosslinking agent are included with respect to 100 parts by weight of the aqueous alkali-soluble polymer. A positive photosensitive resin composition characterized by the above has been proposed (Patent Document 1). The precursor must be polycondensed by heating, and a high temperature process is required. On the other hand, MRAM, which is promising as a next-generation memory that has recently appeared, is vulnerable to high-temperature processes, and low-temperature processes are desired. Accordingly, a material that can be cured at a low temperature of about 280 ° C. or lower, not the high temperature of about 350 ° C. as in the past, has become indispensable for the surface protective film agent. However, there has been a problem that a positive photosensitive resin composition that can be cured at such a low temperature has not yet been obtained.
感光性樹脂組成物としては、ヒドロキシル基を有するポリイミド、ポリイミド前駆体、ポリベンゾオキサゾール前駆体などがあるが、ヒドロキシル基を有するポリイミドはヒドロキシを有するモノマーを多量に含む必要があり、モノマー組成比に制限がかかり、ポリイミド前駆体は重縮合のための高温加熱が必要であり、ポリベンゾオキサゾールはポリイミドに対して感度が低いという問題があった。本発明の目的は、低温硬化可能な高感度のポジ型感光性樹脂組成物、該組成物を用いた表面保護膜や絶縁膜の製造方法を提供することにある。 The photosensitive resin composition includes a hydroxyl group-containing polyimide, a polyimide precursor, a polybenzoxazole precursor, etc., but a hydroxyl group-containing polyimide needs to contain a large amount of a hydroxyl-containing monomer, and the monomer composition ratio There was a problem that the polyimide precursor had to be heated at a high temperature for polycondensation, and polybenzoxazole had a low sensitivity to polyimide. An object of the present invention is to provide a high-sensitivity positive photosensitive resin composition that can be cured at a low temperature, and a method for producing a surface protective film and an insulating film using the composition.
本発明者は、上記の課題に鑑み鋭意検討した結果、カルボキシル基を有するポリイミドを使用することで、パターニング性良好で低温硬化が可能なポジ型感光性樹脂組成物を実現できることを見出し、本発明を完成させるに至った。 As a result of intensive investigations in view of the above problems, the present inventors have found that by using a polyimide having a carboxyl group, it is possible to realize a positive photosensitive resin composition that has good patternability and can be cured at a low temperature. It came to complete.
即ち、本発明は、（Ａ）カルボキシル基を有するポリイミドと、（Ｂ）熱硬化性樹脂と、（Ｃ）光酸発生剤と、を含有してなるポジ型感光性樹脂組成物に関する。 That is, the present invention relates to a positive photosensitive resin composition comprising (A) a polyimide having a carboxyl group, (B) a thermosetting resin, and (C) a photoacid generator.
前記（Ｂ）熱硬化性樹脂がエポキシ樹脂であることが好ましい。 The (B) thermosetting resin is preferably an epoxy resin.
前記（Ａ）ポリイミドを構成するモノマーの酸成分の少なくとも一種が、エーテル結合を有する酸であることが好ましい。 It is preferable that at least one of the acid components of the monomer constituting the (A) polyimide is an acid having an ether bond.
前記（Ａ）ポリイミドを構成するモノマーの酸成分の少なくとも一種が直鎖炭化水素を有する酸であることが好ましい。 It is preferable that at least one of the acid components of the monomer constituting the (A) polyimide is an acid having a linear hydrocarbon.
前記（Ａ）ポリイミドを構成するモノマーのジアミン成分の少なくとも一種が、カルボキシル基を有するジアミンであることが好ましい。 It is preferable that at least one diamine component of the monomer constituting the (A) polyimide is a diamine having a carboxyl group.
前記（Ａ）ポリイミドを構成するモノマーのジアミン成分が、少なくとも、カルボキシル基を有するジアミン及びカルボキシル基を有さないジアミンの２種を含むこと好ましい。 It is preferable that the diamine component of the monomer constituting the polyimide (A) includes at least two kinds of diamine having a carboxyl group and diamine having no carboxyl group.
前記（Ａ）ポリイミドを構成するモノマーのジアミン成分が、少なくとも、カルボキシル基を有するジアミン、カルボキシル基を有さないジアミン及びシリコンジアミンの３種を含むことが好ましい。 It is preferable that the diamine component of the monomer constituting the polyimide (A) includes at least three kinds of diamine having a carboxyl group, diamine having no carboxyl group, and silicon diamine.
前記（Ａ）ポリイミドのカルボキシル基１つに対する分子量が、５００〜１３００であることが好ましい。 (A) It is preferable that the molecular weight with respect to one carboxyl group of the said polyimide is 500-1300.
本発明のポジ型感光性樹脂組成物は、低温硬化可能で、高感度、高解像度といった優れたポジ型のリソグラフィー性能を有し、良好な形状のパターン硬化膜を得ることができる。さらに、低温プロセスで硬化できることにより、デバイスへのダメージが避けられ、信頼性の高い電子部品が得られる。 The positive photosensitive resin composition of the present invention can be cured at low temperature, has an excellent positive lithography performance such as high sensitivity and high resolution, and can obtain a cured pattern film having a good shape. Furthermore, since it can be cured by a low temperature process, damage to the device can be avoided and a highly reliable electronic component can be obtained.
以下、本発明にかかるポジ型感光性樹脂組成物の好適な実施形態について詳細に説明する。ただし、本発明は以下の実施形態に限定されるものではない。 Hereinafter, preferred embodiments of the positive photosensitive resin composition according to the present invention will be described in detail. However, the present invention is not limited to the following embodiments.
（Ａ）カルボキシル基を有するポリイミド
本発明におけるカルボキシル基を有するポリイミドとは、カルボキシル基を分子構造に有するポリイミドであり、アルカリ水溶液に可溶であることが好ましい。例えば、テトラカルボン酸とジアミンより誘導されるが、ジアミンの代わりにイソシアネートを使用してもよい。カルボキシル基は主鎖にあってもよく、側鎖にあってもよい。
(A) Polyimide having a carboxyl group The polyimide having a carboxyl group in the present invention is a polyimide having a carboxyl group in the molecular structure, and is preferably soluble in an alkaline aqueous solution. For example, it is derived from tetracarboxylic acid and diamine, but isocyanate may be used instead of diamine. The carboxyl group may be in the main chain or in the side chain.
本発明のポリイミドを合成する一例としてのテトラカルボン酸とジアミンとの反応は、当業者には理解されるように、公知の方法により行うことができる。例えば、有機溶媒中で、テトラカルボン酸とジアミンを等モル又はほぼ等モルの比率で投入し、反応温度７０℃以下、好ましくは０〜５０℃で付加反応させる。各成分の添加順序は任意である。反応が進行するにつれ反応液の粘度が徐々に上昇し、ポリイミドの前駆体であるポリアミド酸が生成する。生成したポリアミド酸を脱水閉環させることにより、ポリイミドが生成する。脱水閉環は、加熱による熱閉環法、又は脱水剤を使用する化学閉環法により行うことができる。 The reaction of tetracarboxylic acid and diamine as an example for synthesizing the polyimide of the present invention can be carried out by a known method as understood by those skilled in the art. For example, tetracarboxylic acid and diamine are added in an equimolar or nearly equimolar ratio in an organic solvent, and the addition reaction is performed at a reaction temperature of 70 ° C. or lower, preferably 0 to 50 ° C. The order of adding each component is arbitrary. As the reaction proceeds, the viscosity of the reaction solution gradually increases, and polyamic acid, which is a polyimide precursor, is generated. A polyimide is produced by dehydrating and ring-closing the produced polyamic acid. The dehydration ring closure can be performed by a thermal ring closure method by heating or a chemical ring closure method using a dehydrating agent.
本発明のポリイミドに用いるテトラカルボン酸としては特に限定されないが、例えば、２，２’−ヘキサフルオロプロピリデンジフタル酸二無水物、２，２−ビス（４−ヒドロキシフェニル）プロパンジベンゾエート−３，３’，４，４’−テトラカルボン酸二無水物、ブタンテトラカルボン酸二無水物、１，２，３，４−シクロブタンテトラカルボン酸二無水物、１，３−ジメチル−１，２，３，４−シクロブタンテトラカルボン酸、１，２，３，４−シクロペンタンテトラカルボン酸二無水物、２，３，５−トリカルボキシシクロペンチル酢酸二無水物、３，５，６−トリカルボキシノルボナン−２−酢酸二無水物、２，３，４，５−テトラヒドロフランテトラカルボン酸二無水物、５−（２，５−ジオキソテトラヒドロフラル）−３−メチル−３−シクロヘキセン−１，２−ジカルボン酸二無水物、ビシクロ［２，２，２］−オクト−７−エン−２，３，５，６−テトラカルボン酸二無水物等の脂肪族または脂環式テトラカルボン酸二無水物；ピロメリット酸二無水物、３，３’，４，４’−ベンゾフェノンテトラカルボン酸二無水物、３，３’，４，４’−ビフェニルスルホンテトラカルボン酸二無水物、１，４，５，８−ナフタレンテトラカルボン酸二無水物、２，３，６，７−ナフタレンテトラカルボン酸二無水物、３，３’，４，４’−ビフェニルエーテルテトラカルボン酸二無水物、３，３’，４，４’−ジメチルジフェニルシランテトラカルボン酸二無水物、３，３’，４，４’−テトラフェニルシランテトラカルボン酸二無水物、１，２，３，４−フランテトラカルボン酸二無水物、４，４’−ビス（３，４−ジカルボキシフェノキシ）ジフェニルスルフィド二無水物、４，４’−ビス（３，４−ジカルボキシフェノキシ）ジフェニルスルホン二無水物、４，４’−ビス（３，４−ジカルボキシフェノキシ）ジフェニルプロパン二無水物、３，３’，４，４’−パーフルオロイソプロピリデンジフタル酸二無水物、３，３’，４，４’−ビフェニルテトラカルボン酸二無水物、ビス（フタル酸）フェニルホスフィンオキサイド二無水物、ｐ−フェニレン−ビス（トリフェニルフタル酸）二無水物、ｍ−フェニレン−ビス（トリフェニルフタル酸）二無水物、ビス（トリフェニルフタル酸）−４，４’−ジフェニルエーテル二無水物、ビス（トリフェニルフタル酸）−４，４’−ジフェニルメタン二無水物等の芳香族テトラカルボン酸二無水物等、及びそれらの誘導体などが挙げられ、これらを単独で、または任意の割合で混合した混合物を好ましく用いることができる。 The tetracarboxylic acid used in the polyimide of the present invention is not particularly limited. For example, 2,2′-hexafluoropropylidenediphthalic dianhydride, 2,2-bis (4-hydroxyphenyl) propanedibenzoate-3 , 3 ′, 4,4′-tetracarboxylic dianhydride, butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2, 3,4-cyclobutanetetracarboxylic acid, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 3,5,6-tricarboxynorbonane 2-acetic acid dianhydride, 2,3,4,5-tetrahydrofurantetracarboxylic dianhydride, 5- (2,5-dioxotetrahydrofural) -3- Aliphatic such as til-3-cyclohexene-1,2-dicarboxylic dianhydride, bicyclo [2,2,2] -oct-7-ene-2,3,5,6-tetracarboxylic dianhydride or the like Alicyclic tetracarboxylic dianhydride; pyromellitic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenylsulfone tetracarboxylic acid Dianhydride, 1,4,5,8-naphthalene tetracarboxylic dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenyl ether tetracarboxylic Acid dianhydride, 3,3 ′, 4,4′-dimethyldiphenylsilane tetracarboxylic dianhydride, 3,3 ′, 4,4′-tetraphenylsilane tetracarboxylic dianhydride, 1,2,3 , 4-Franteto Carboxylic dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenyl sulfide dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenylsulfone dianhydride, 4, 4'-bis (3,4-dicarboxyphenoxy) diphenylpropane dianhydride, 3,3 ', 4,4'-perfluoroisopropylidenediphthalic dianhydride, 3,3', 4,4'- Biphenyltetracarboxylic dianhydride, bis (phthalic acid) phenylphosphine oxide dianhydride, p-phenylene-bis (triphenylphthalic acid) dianhydride, m-phenylene-bis (triphenylphthalic acid) dianhydride, Bis (triphenylphthalic acid) -4,4'-diphenyl ether dianhydride, bis (triphenylphthalic acid) -4,4'-diphenylmethane dianhydride Aromatic tetracarboxylic dianhydrides, etc., and derivatives thereof, and the like can be mentioned, and a mixture of these alone or in an arbitrary ratio can be preferably used.
中でも、有機溶媒への溶解性の高いポリイミドを得るためには、３，３’，４，４’−ビフェニルスルホンテトラカルボン酸二無水物、２，２’−ヘキサフルオロプロピリデンジフタル酸二無水物、２，３，３’，４’−ビフェニルテトラカルボン酸二無水物、４，４−（４，４’−イソプロピリデンジフェノキシ）ビスフタル酸無水物、２，２−ビス（４−ヒドロキシフェニル）プロパンジベンゾエート−３，３’，４，４’−テトラカルボン酸二無水物、３，３’，４，４’−ビフェニルエーテルテトラカルボン酸二無水物、３，３’，４，４’−テトラフェニルシランテトラカルボン酸二無水物、１，２−エタンジベンゾエート−３，３’，４，４’−テトラカルボン酸二無水物、４，４’−オキシジフタル酸二無水物、ｐ−フェニレンビス（トリメリット酸モノエステル酸無水物）、２，２−ビス（４−トリメリット酸モノエステル酸フェニル）プロパン酸二無水物からなる群より選ばれる少なくとも１種の酸二無水物を用いることが好ましい。 Among them, 3,3 ′, 4,4′-biphenylsulfonetetracarboxylic dianhydride, 2,2′-hexafluoropropylidenediphthalic dianhydride is used to obtain a polyimide having high solubility in an organic solvent. 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride, 4,4- (4,4′-isopropylidenediphenoxy) bisphthalic anhydride, 2,2-bis (4-hydroxyphenyl) ) Propanedibenzoate-3,3 ′, 4,4′-tetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenyl ether tetracarboxylic dianhydride, 3,3 ′, 4,4 ′ -Tetraphenylsilane tetracarboxylic dianhydride, 1,2-ethanedibenzoate-3,3 ', 4,4'-tetracarboxylic dianhydride, 4,4'-oxydiphthalic dianhydride, p-phenyle Use at least one acid dianhydride selected from the group consisting of bis (trimellitic acid monoester acid anhydride) and 2,2-bis (4-trimellitic acid monoester acid phenyl) propanoic acid dianhydride. Is preferred.
特に、（Ａ）ポリイミドを構成するモノマーの酸成分の少なくとも一種がエーテル結合を有する酸であることが有機溶剤への溶解性が高いことから好ましい。エーテル結合を有する酸としては、例えば１，２−エタンジベンゾエート−３，３’，４，４’−テトラカルボン酸二無水物、４，４’−オキシジフタル酸二無水物、ｐ−フェニレンビス（トリメリット酸モノエステル酸無水物）、２，２−ビス（４−トリメリット酸モノエステル酸フェニル）プロパン酸二無水物からなる群より選ばれる少なくとも１種の酸二無水物を用いることが好ましい。 In particular, it is preferable that at least one of the acid components of the monomer constituting the polyimide (A) is an acid having an ether bond because of its high solubility in an organic solvent. Examples of the acid having an ether bond include 1,2-ethanedibenzoate-3,3 ′, 4,4′-tetracarboxylic dianhydride, 4,4′-oxydiphthalic dianhydride, p-phenylenebis ( It is preferable to use at least one acid dianhydride selected from the group consisting of trimellitic acid monoester acid anhydride) and 2,2-bis (4-trimellitic acid monoester acid phenyl) propanoic acid dianhydride. .
また、（Ａ）ポリイミドを構成するモノマーの酸成分の少なくとも一種が、直鎖炭化水素を有する酸であることが有機溶剤への溶解性が高いことから好ましい。直鎖炭化水素を有する酸としては、例えば１，２−エタンジベンゾエート−３，３’，４，４’−テトラカルボン酸二無水物を用いることが好ましい。 Moreover, it is preferable that at least one of the acid components of the monomer constituting the polyimide (A) is an acid having a straight chain hydrocarbon because of its high solubility in an organic solvent. For example, 1,2-ethanedibenzoate-3,3 ', 4,4'-tetracarboxylic dianhydride is preferably used as the acid having a linear hydrocarbon.
本発明のポリイミドに用いるジアミンとしては特に限定されないが、例えば、［ビス（４−アミノ−３−カルボキシ）フェニル］メタン、ｐ−フェニレンジアミン、ｍ−フェニレンジアミン、４，４’−ジアミノジフェニルメタン、４，４’−ジアミノフェニルエタン、４，４’−ジアミノフェニルエーテル、４，４’−ジジアミノフェニルスルフィド、４，４’−ジジアミノフェニルスルフォン、１，５−ジアミノナフタレン、３，３−ジメチル−４，４’−ジアミノビフェニル、５−アミノ−１−（４’−アミノフェニル）−１，３，３−トリメチルインダン、６−アミノ−１−（４’−アミノフェニル）−１，３，３−トリメチルインダン、４，４’−ジアミノベンズアニリド、３，５−ジアミノ−３’−トリフルオロメチルベンズアニリド、３，５−ジアミノ−４’−トリフルオロメチルベンズアニリド、３，４’−ジアミノジフェニルエーテル、２，７−ジアミノフルオレン、２，２−ビス（４−アミノフェニル）ヘキサフルオロプロパン、４，４’−メチレン−ビス（２−クロロアニリン）、２，２’，５，５’−テトラクロロ−４，４’−ジアミノビフェニル、２，２’−ジクロロ−４，４’−ジアミノ−５，５’−ジメトキシビフェニル、３，３’−ジメトキシ−４，４’−ジアミノビフェニル、４，４’−ジアミノ−２，２’−ビス（トリフルオロメチル）ビフェニル、２，２−ビス［４−（４−アミノフェノキシ）フェニル］プロパン、２，２−ビス［４−（３−アミノフェノキシ）フェニル］プロパン、２，２−ビス［４−（４−アミノフェノキシ）フェニル］スルフォン、２，２−ビス［４−（３−アミノフェノキシ）フェニル］スルフォン、２，２−ビス［４−（４−アミノフェノキシ）フェニル］ヘキサフルオロプロパン、１，４−ビス（４−アミノフェノキシ）ベンゼン、１，４−ビス（３−アミノフェノキシ）ベンゼン、４，４’−ビス（４−アミノフェノキシ）−ビフェニル、１，３’−ビス（４−アミノフェノキシ）ベンゼン、１，３’−ビス（３−アミノフェノキシ）ベンゼン、９，９−ビス（４−アミノフェニル）フルオレン、４，４’−（ｐ−フェニレンイソプロピリデン）ビスアニリン、４，４’−（ｍ−フェニレンイソプロピリデン）ビスアニリン、２，２’−ビス［４−（４−アミノ−２−トリフルオロメチルフェノキシ）フェニル］ヘキサフルオロプロパン、４，４’−ビス［４−（４−アミノ−２−トリフルオロメチル）フェノキシ］−オクタフルオロビフェニル等の芳香族ジアミン；ジアミノテトラフェニルチオフェン等の芳香環に結合された２個のアミノ基と当該アミノ基の窒素原子以外のヘテロ原子を有する芳香族ジアミン；１，１−メタキシリレンジアミン、１，３−プロパンジアミン、テトラメチレンジアミン、ペンタメチレンジアミン、オクタメチレンジアミン、ノナメチレンジアミン、４，４−ジアミノヘプタメチレンジアミン、１，４−ジアミノシクロヘキサン、イソフォロンジアミン、テトラヒドロジシクロペンタジエニレンジアミン、ヘキサヒドロ−４，７−メタノインダニレンジメチレンジアミン、トリシクロ［６，２，１，０２．７］−ウンデシレンジメチルジアミン、４，４’−メチレンビス（シクロヘキシルアミン）等の脂肪族ジアミンおよび脂環式ジアミン等及びそれらの誘導体などが挙げられ、これらを単独で、または任意の割合で混合した混合物を好ましく用いることができる。 The diamine used in the polyimide of the present invention is not particularly limited. For example, [bis (4-amino-3-carboxy) phenyl] methane, p-phenylenediamine, m-phenylenediamine, 4,4′-diaminodiphenylmethane, 4 , 4'-diaminophenyl ethane, 4,4'-diaminophenyl ether, 4,4'-didiaminophenyl sulfide, 4,4'-didiaminophenyl sulfone, 1,5-diaminonaphthalene, 3,3-dimethyl- 4,4′-diaminobiphenyl, 5-amino-1- (4′-aminophenyl) -1,3,3-trimethylindane, 6-amino-1- (4′-aminophenyl) -1,3,3 -Trimethylindane, 4,4'-diaminobenzanilide, 3,5-diamino-3'-trifluoromethylbenzanilide, 3,5 -Diamino-4'-trifluoromethylbenzanilide, 3,4'-diaminodiphenyl ether, 2,7-diaminofluorene, 2,2-bis (4-aminophenyl) hexafluoropropane, 4,4'-methylene-bis (2-chloroaniline), 2,2 ′, 5,5′-tetrachloro-4,4′-diaminobiphenyl, 2,2′-dichloro-4,4′-diamino-5,5′-dimethoxybiphenyl, 3,3′-dimethoxy-4,4′-diaminobiphenyl, 4,4′-diamino-2,2′-bis (trifluoromethyl) biphenyl, 2,2-bis [4- (4-aminophenoxy) phenyl ] Propane, 2,2-bis [4- (3-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] sulfone, 2,2-bis [4 -(3-aminophenoxy) phenyl] sulfone, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 1,4-bis (4-aminophenoxy) benzene, 1,4-bis ( 3-aminophenoxy) benzene, 4,4′-bis (4-aminophenoxy) -biphenyl, 1,3′-bis (4-aminophenoxy) benzene, 1,3′-bis (3-aminophenoxy) benzene, 9,9-bis (4-aminophenyl) fluorene, 4,4 ′-(p-phenyleneisopropylidene) bisaniline, 4,4 ′-(m-phenyleneisopropylidene) bisaniline, 2,2′-bis [4- (4-Amino-2-trifluoromethylphenoxy) phenyl] hexafluoropropane, 4,4′-bis [4- (4-amino-2-trifluoro) Aromatic diamine such as (romethyl) phenoxy] -octafluorobiphenyl; aromatic diamine having two amino groups bonded to an aromatic ring such as diaminotetraphenylthiophene and a hetero atom other than the nitrogen atom of the amino group; 1-metaxylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, octamethylenediamine, nonamethylenediamine, 4,4-diaminoheptamethylenediamine, 1,4-diaminocyclohexane, isophoronediamine, tetrahydrodicyclopentadiene cyclopentadienylide diamine, hexahydro-4,7-meth Noin mite range diamine, tricyclo [6,2,1,0 2.7] - undecylenate range methyl diamine, 4,4'-methylenebis (cyclohexylamine) etc Include such aliphatic diamines and alicyclic diamines, and the like, and their derivatives, it can be preferably used those mixtures alone or mixed in any proportion.
本発明のポリイミドは、アルカリ性の現像液に溶解することが好ましく、カルボキシル基を有することがアルカリ性の現像液への溶解を可能にする。更に、ポリイミド側鎖にカルボキシル基があるとアルカリ性の現像液への溶解性が増すことから、ポリイミド側鎖にカルボキシル基を与えられるジアミン、すなわちカルボキシル基を有するジアミンを使用することが好ましい。従って、（Ａ）ポリイミドを構成するモノマーのジアミン成分の少なくとも一種が、カルボキシル基を有するジアミンであることがアルカリ性の現像液への溶解を可能にする点において好ましい。カルボキシル基を有するジアミン類しては、カルボキシル基を有していれば特に限定されることはないが例えばカルボキシル基を２個有するジアミンとして以下の様なものが例示できる。 The polyimide of the present invention is preferably dissolved in an alkaline developer, and having a carboxyl group enables dissolution in an alkaline developer. Furthermore, since the solubility in an alkaline developer increases if a polyimide side chain has a carboxyl group, it is preferable to use a diamine that can give a carboxyl group to the polyimide side chain, that is, a diamine having a carboxyl group. Therefore, it is preferable that at least one of the diamine components of the monomer constituting the polyimide (A) is a diamine having a carboxyl group in terms of enabling dissolution in an alkaline developer. The diamine having a carboxyl group is not particularly limited as long as it has a carboxyl group. Examples of the diamine having two carboxyl groups include the following.
例えば、２，５−ジアミノテレフタル酸等のジアミノフタル酸類、３，３’−ジアミノ−４，４’−ジカルボキシビフェニル、４，４’−ジアミノ−３，３’−ジカルボキシビフェニル、４，４’−ジアミノ−２，２’−ジカルボキシビフェニル、４，４’−ジアミノ−２，２’，５，５’−テトラカルボキシビフェニル等のカルボキシビフェニル化合物類、３，３’−ジアミノ−４，４’−ジカルボキシジフェニルメタン、３，３’−ジカルボキシ−４，４’−ジアミノフェニルメタン、２，２−ビス［３−アミノ−４−カルボキシフェニル］プロパン、２，２−ビス［４−アミノ−３−カルボキシフェニル］プロパン、２，２−ビス［３−アミノ−４−カルボキシフェニル］ヘキサフルオロプロパン、４，４’−ジアミノ−２，２’，５，５’−テトラカルボキシジフェニルメタン等のカルボキシジフェニルメタン等のカルボキシジフェニルアルカン類、３，３’−ジアミノ−４，４’−ジカルボキシジフェニルエーテル、４，４’−ジアミノ−３，３’−ジカルボキシジフェニルエーテル、４，４’−ジアミノ−２，２’−ジカルボキシジフェニルエーテル、４，４’−ジアミノ−２，２’，５，５’−テトラカルボキシジフェニルエーテル等のカルボキシジフェニルエーテル化合物、３，３’−ジアミノ−４，４’−ジカルボキシジフェニルスルフォン、４，４’−ジアミノ−３，３’−ジカルボキシジフェニルスルフォン、４，４’−ジアミノ−２，２’−ジカルボキシジフェニルスルフォン、４，４’−ジアミノ−２，２’，５，５’−テトラカルボキシジフェニルスルフォン等のジフェニルスルフォン化合物、２，２−ビス［４−（４−アミノ−３−カルボキシフェノキシ）フェニル］プロパン等のビス［（カルボキシフェニル）フェニル］アルカン化合物類、２，２−ビス［４−（４−アミノ−３−カルボキシフェノキシ）フェニル］スルフォン等のビス［（カルボキシフェノキシ）フェニル］スルフォン化合物を挙げることができる。 For example, diaminophthalic acids such as 2,5-diaminoterephthalic acid, 3,3′-diamino-4,4′-dicarboxybiphenyl, 4,4′-diamino-3,3′-dicarboxybiphenyl, 4,4 Carboxyphenyl compounds such as '-diamino-2,2'-dicarboxybiphenyl, 4,4'-diamino-2,2', 5,5'-tetracarboxybiphenyl, 3,3'-diamino-4,4 '-Dicarboxydiphenylmethane, 3,3'-dicarboxy-4,4'-diaminophenylmethane, 2,2-bis [3-amino-4-carboxyphenyl] propane, 2,2-bis [4-amino- 3-carboxyphenyl] propane, 2,2-bis [3-amino-4-carboxyphenyl] hexafluoropropane, 4,4′-diamino-2,2 ′, 5 Carboxydiphenylalkanes such as carboxydiphenylmethane such as 5′-tetracarboxydiphenylmethane, 3,3′-diamino-4,4′-dicarboxydiphenyl ether, 4,4′-diamino-3,3′-dicarboxydiphenyl ether, 4 , 4′-diamino-2,2′-dicarboxydiphenyl ether, carboxydiphenyl ether compounds such as 4,4′-diamino-2,2 ′, 5,5′-tetracarboxydiphenyl ether, 3,3′-diamino-4, 4′-dicarboxydiphenyl sulfone, 4,4′-diamino-3,3′-dicarboxydiphenyl sulfone, 4,4′-diamino-2,2′-dicarboxydiphenyl sulfone, 4,4′-diamino-2 , 2 ', 5,5'-tetracarboxydiphenyls Diphenylsulfone compounds such as phonone, bis [(carboxyphenyl) phenyl] alkane compounds such as 2,2-bis [4- (4-amino-3-carboxyphenoxy) phenyl] propane, 2,2-bis [4- Bis [(carboxyphenoxy) phenyl] sulfone compounds such as (4-amino-3-carboxyphenoxy) phenyl] sulfone can be mentioned.
また、別途水酸基やカルボキシ基を１個有するジアミンを用いることもできる。例えば、２，４−ジアミノフェノール等のジアミノフェノール類、３，３’−ジアミノ−４，４’−ジヒドロキシビフェニル、４，４’−ジアミノ−３，３’−ジヒドロキシビフェニル、４，４’−ジアミノ−２，２’−ジヒドロキシビフェニル、４，４’−ジアミノ−２，２’，５，５’−テトラヒドロキシビフェニル等のヒドロキシビフェニル化合物類、３，３’−ジアミノ−４，４’−ジヒドロキシジフェニルメタン、４，４’−ジアミノ−３，３’−ジハイドロキシジフェニルメタン、４，４’−ジアミノ−２，２’−ジハイドロキシジフェニルメタン、２，２−ビス［３−アミノ−４−ヒドロキシフェニル］プロパン、２，２−ビス［４−アミノ−３−ヒドロキシフェニル］プロパン、２，２−ビス［３−アミノ−４−ヒドロキシフェニル］ヘキサフルオロプロパン、４，４’−ジアミノ−２，２’，５，５’−テトラヒドロキシジフェニルメタン等のヒドロキシジフェニルメタン等のヒドロキシジフェニルアルカン類、３，３’−ジアミノ−４，４’−ジヒドロキシジフェニルエーテル、４，４’−ジアミノ−３，３’−ジヒドロキシジフェニルエーテル、４，４’−ジアミノ−２，２’−ジヒドロキシジフェニルエーテル、４，４’−ジアミノ−２，２’，５，５’−テトラヒドロキシジフェニルエーテル等のヒドロキシジフェニルエーテル化合物、３，３’−ジアミノ−４，４’−ジヒドロキシジフェニルスルフォン、４，４’−ジアミノ−３，３’−ジヒドロキシジフェニルスルフォン、４，４’−ジアミノ−２，２’−ジヒドロキシジフェニルスルフォン、４，４’−ジアミノ−２，２’，５，５’−テトラヒドロキシジフェニルスルフォン等のジフェニルスルフォン化合物、２，２−ビス［４−（４−アミノ−３−ヒドロキシフェノキシ）フェニル］プロパン等のビス［（ヒドロキシフェニル）フェニル］アルカン化合物類、４，４’−ビス（４−アミノ−３−ヒドキシフェノキシ）ビフェニル等のビス（ヒドキシフェノキシ）ビフェニル化合物類、２，２−ビス［４−（４−アミノ−３−ヒドロキシフェノキシ）フェニル］スルフォン等のビス［（ヒドロキシフェノキシ）フェニル］スルフォン化合物、３，５−ジアミノ安息香酸等のジアミノ安息香酸類、４，４’−ジアミノ−３，３’−ジハイドロキシジフェニルメタン、４，４’−ジアミノ−２，２’−ジハイドロキシジフェニルメタン、２，２−ビス［３−アミノ−４−カルボキシフェニル］プロパン、４，４’−ビス（４−アミノ−３−ヒドキシフェノキシ）ビフェニル等のビス（ヒドキシフェノキシ）ビフェニル化合物類をあげることができる。 In addition, a diamine having one hydroxyl group or one carboxy group can also be used. For example, diaminophenols such as 2,4-diaminophenol, 3,3′-diamino-4,4′-dihydroxybiphenyl, 4,4′-diamino-3,3′-dihydroxybiphenyl, 4,4′-diamino -2,2'-dihydroxybiphenyl, hydroxybiphenyl compounds such as 4,4'-diamino-2,2 ', 5,5'-tetrahydroxybiphenyl, 3,3'-diamino-4,4'-dihydroxydiphenylmethane 4,4′-diamino-3,3′-dihydroxydiphenylmethane, 4,4′-diamino-2,2′-dihydroxydiphenylmethane, 2,2-bis [3-amino-4-hydroxyphenyl] propane, 2,2-bis [4-amino-3-hydroxyphenyl] propane, 2,2-bis [3-amino-4-hydroxy Nenyl] hexafluoropropane, hydroxydiphenylalkanes such as hydroxydiphenylmethane such as 4,4′-diamino-2,2 ′, 5,5′-tetrahydroxydiphenylmethane, 3,3′-diamino-4,4′-dihydroxy Diphenyl ether, 4,4′-diamino-3,3′-dihydroxydiphenyl ether, 4,4′-diamino-2,2′-dihydroxydiphenyl ether, 4,4′-diamino-2,2 ′, 5,5′-tetra Hydroxydiphenyl ether compounds such as hydroxydiphenyl ether, 3,3′-diamino-4,4′-dihydroxydiphenyl sulfone, 4,4′-diamino-3,3′-dihydroxydiphenyl sulfone, 4,4′-diamino-2,2 '-Dihydroxydiphenylsulfone, 4 Diphenyl sulfone compounds such as 4′-diamino-2,2 ′, 5,5′-tetrahydroxydiphenyl sulfone, and bis [2, such as 2,2-bis [4- (4-amino-3-hydroxyphenoxy) phenyl] propane (Hydroxyphenyl) phenyl] alkane compounds, bis (hydroxyphenoxy) biphenyl compounds such as 4,4′-bis (4-amino-3-hydroxyphenoxy) biphenyl, 2,2-bis [4- (4 -Amino-3-hydroxyphenoxy) phenyl] sulfone and other bis [(hydroxyphenoxy) phenyl] sulfone compounds, diaminobenzoic acids such as 3,5-diaminobenzoic acid, 4,4′-diamino-3,3′-di Hydroxydiphenylmethane, 4,4'-diamino-2,2'-dihydroxydiphenylmethane, 2 Bis (hydroxyphenoxy) biphenyl compounds such as 1,2-bis [3-amino-4-carboxyphenyl] propane and 4,4′-bis (4-amino-3-hydroxyphenoxy) biphenyl. .
また、本発明における（Ａ）ポリイミドを構成するモノマーのジアミン成分が、少なくとも、カルボキシル基を有するジアミン及びカルボキシル基を有さないジアミンの２種を含むことが好ましい。ポリイミドのジアミン成分としてカルボキシル基を有さないジアミンを含有することで、ポリイミドに含まれるカルボキシル基の量を制御することが可能となり、（Ａ）ポリイミドのカルボキシル基１つに対する分子量を制御することが可能となる。また、カルボキシル基を有さないジアミンとして芳香族ジアミンでｍ−位（３−）にアミノ基を持つジアミンを用いれば、ポリイミドの溶媒への溶解性が向上する傾向があり好ましい。 Moreover, it is preferable that the diamine component of the monomer which comprises (A) polyimide in this invention contains at least 2 types of the diamine which has a carboxyl group, and the diamine which does not have a carboxyl group. By containing a diamine having no carboxyl group as the diamine component of the polyimide, it becomes possible to control the amount of carboxyl groups contained in the polyimide, and (A) the molecular weight of one polyimide carboxyl group can be controlled. It becomes possible. In addition, it is preferable to use an aromatic diamine having an amino group at the m-position (3-) as a diamine having no carboxyl group, since the solubility of polyimide in a solvent tends to be improved.
更に、露光後の再接着性を高めるために、ジアミンの一部に、シリコンジアミンを選択することができる。この場合には、（Ａ）ポリイミドを構成するモノマーのジアミン成分が、少なくとも、カルボキシル基を有するジアミン、カルボキシル基を有さないジアミン及びシリコンジアミンの３種を含むことが好ましい。シリコンジアミンの例としては、ビス（４−アミノフェニル）ジメチルシラン、ビス（４−アミノフェニル）テトラメチルシロキサン、ビス（４−アミノフェニル）テトラメチルジシロキサン、ビス（γ−アミノプロピル）テトラメチルジシロキサン、１，４−ビス（γ−アミノプロピルジメチルシリル）ベンゼン、ビス（４−アミノブチル）テトラメチルジシロキサン、ビス（γ−アミノプロピル）テトラフェニルジシロキサン等が挙げられる。溶剤浸透性が向上し、低温で硬化させた場合にも溶剤が残りにくいという利点もある。これらの理由から、本発明の（Ａ）ポリイミドを構成するモノマーのジアミン成分が、少なくとも、カルボキシル基を有するジアミン、カルボキシル基を有さないジアミン及びシリコンジアミンの３種を含むことが好ましい。 Furthermore, in order to improve the re-adhesion after exposure, silicon diamine can be selected as a part of the diamine. In this case, it is preferable that the diamine component of the monomer constituting the polyimide (A) includes at least three kinds of diamine having a carboxyl group, diamine having no carboxyl group, and silicon diamine. Examples of silicon diamines include bis (4-aminophenyl) dimethylsilane, bis (4-aminophenyl) tetramethylsiloxane, bis (4-aminophenyl) tetramethyldisiloxane, bis (γ-aminopropyl) tetramethyldi Examples include siloxane, 1,4-bis (γ-aminopropyldimethylsilyl) benzene, bis (4-aminobutyl) tetramethyldisiloxane, and bis (γ-aminopropyl) tetraphenyldisiloxane. The solvent permeability is improved, and there is an advantage that the solvent hardly remains even when cured at a low temperature. For these reasons, it is preferable that the diamine component of the monomer constituting the polyimide (A) of the present invention contains at least three kinds of diamine having a carboxyl group, diamine having no carboxyl group, and silicon diamine.
本発明のポリイミドは、主鎖中にイミド骨格を有し、カルボキシル基を有する。ポリイミドのカルボキシル基１つに対する分子量が５００〜１３００であることが好ましい。ポリイミドのカルボキシル基当量が５００未満であると現像時に接着層が非着層から剥離してしまう可能性が高くなる傾向にある。逆にポリイミドのカルボキシル基等量が１３００より大きくなるとアルカリ現像液への溶解性が低下する傾向にある。なお、本発明における（Ａ）ポリイミドのカルボキシル基１つに対する分子量が、５００〜１３００であるとは、（Ａ）ポリイミドの分子構造から理論計算値で算出された値である。 The polyimide of the present invention has an imide skeleton in the main chain and a carboxyl group. It is preferable that the molecular weight with respect to one carboxyl group of a polyimide is 500-1300. If the carboxyl group equivalent of polyimide is less than 500, the adhesive layer tends to be peeled off from the non-adhering layer during development. On the other hand, when the equivalent amount of the carboxyl group of the polyimide is larger than 1300, the solubility in an alkali developer tends to be lowered. In addition, the molecular weight with respect to one carboxyl group of (A) polyimide in the present invention is 500 to 1300, which is a value calculated by theoretical calculation from the molecular structure of (A) polyimide.
本発明のポリイミドはテトラカルボン酸とカルボキシル基を有するジアミンとの反応により得ることができる。これにより、ポリイミドにはジアミンに由来するカルボキシル基が導入される。モノマーの種類及びその仕込み比、反応条件等を適宜調整することにより、ポリイミドのカルボキシル基当量を５００〜１３００とすることができる。ポジ型感光性樹脂組成物の現像液浸透性によって好ましいカルボキシル基当量は変化する。例えば、現像液水溶液浸透性の大きい組成となる場合はカルボキシル等量は大きい方へ調製することが好ましい。逆に、アルカリ水溶液浸透性の小さい組成となる場合はカルボキシル等量を小さい方へ調整することが好ましい。また、カルボキシル基を有するモノマーを使用することで、ヒドロキシル基を有するモノマーを使用するよりも、モノマー組成比の自由度が増し、最終的な硬化膜の特性を制御しやすい。更に、ポジ型感光性樹脂組成物として使用される酸発生剤は、通常カルボキシル基を生成しアルカリ水溶液に溶解する。本発明にかかる（Ａ）カルボキシル基を有するポリイミドもカルボキシル基を有しており、ヒドロキシ基を有する樹脂と比較して、アルカリ水溶への溶解性速度ムラが抑制されることも利点となる。 The polyimide of this invention can be obtained by reaction with tetracarboxylic acid and the diamine which has a carboxyl group. Thereby, the carboxyl group derived from diamine is introduce | transduced into a polyimide. The carboxyl group equivalent of polyimide can be set to 500-1300 by adjusting suitably the kind of monomer, its charging ratio, reaction conditions, etc. The preferred carboxyl group equivalent varies depending on the developer permeability of the positive photosensitive resin composition. For example, in the case of a composition having a large aqueous solution solution penetrability, it is preferable to prepare the carboxyl equivalent in the larger one. On the contrary, when it becomes a composition with small alkaline aqueous solution permeability, it is preferable to adjust a carboxyl equivalent to the smaller one. Moreover, by using the monomer which has a carboxyl group, the freedom degree of a monomer composition ratio increases rather than using the monomer which has a hydroxyl group, and it is easy to control the characteristic of a final cured film. Furthermore, the acid generator used as a positive photosensitive resin composition usually generates a carboxyl group and dissolves in an alkaline aqueous solution. (A) The polyimide which has a carboxyl group concerning this invention also has a carboxyl group, and also compared with resin which has a hydroxyl group, it also becomes an advantage that the solubility rate nonuniformity to alkaline water solution is suppressed.
（Ｂ）熱硬化性樹脂
本発明のポジ型感光性樹脂組成物に含まれる熱硬化性樹脂は、加熱することにより硬化反応が進行する化合物のことであり、具体的には炭素−炭素２重結合を有する化合物・エポキシ化合物・イソシアネート化合物・シアン酸エステル化合物等である。熱により（Ａ）カルボキシル基を有するポリイミドと架橋しうる、あるいはそれ自身が重合しうる化合物を含むことが好ましい。塗布、露光、現像後に加熱処理する工程において、カルボキシル基を有するポリイミドと反応、架橋する。又は、前記加熱処理する工程において、当該樹脂自身が重合する。これによって、比較的低い温度、例えば２００℃以下の硬化において懸念される膜の脆さを防ぎ、機械特性を向上させることができる。また、ポリイミドが有するカルボキシル基と反応することで、電気信頼性を向上させることができる。また、当該樹脂が架橋しうる温度としては、ポジ型感光性樹脂組成物の塗布、乾燥、露光、現像の各工程で架橋が進行しないように１５０℃以上であることが好ましい。
(B) Thermosetting resin The thermosetting resin contained in the positive photosensitive resin composition of the present invention is a compound that undergoes a curing reaction when heated, and specifically, a carbon-carbon double layer. Examples thereof include a compound having a bond, an epoxy compound, an isocyanate compound, and a cyanate ester compound. It is preferable to include a compound that can be cross-linked with (A) a polyimide having a carboxyl group by heat, or that itself can be polymerized. In the step of heat treatment after coating, exposure and development, it reacts and crosslinks with the polyimide having a carboxyl group. Alternatively, the resin itself polymerizes in the heat treatment step. Thereby, the brittleness of the film, which is a concern at curing at a relatively low temperature, for example, 200 ° C. or less, can be prevented, and the mechanical properties can be improved. Moreover, electrical reliability can be improved by reacting with the carboxyl group which a polyimide has. In addition, the temperature at which the resin can be crosslinked is preferably 150 ° C. or higher so that crosslinking does not proceed in each step of coating, drying, exposure, and development of the positive photosensitive resin composition.
本発明のポジ型感光性樹脂組成物に含まれる熱硬化性樹脂は、例えば、エポキシ樹脂、不飽和ポリエステル樹脂、メラミン樹脂、尿素樹脂、ジアリルフタレート樹脂、ビスマレイミド樹脂、トリアジン樹脂、ポリウレタン樹脂、フェノール樹脂、シアノアクリレート樹脂、ポリイソシアネート樹脂、フラン樹脂、レゾルシノール樹脂、キシレン樹脂、ベンゾグアナミン樹脂、シリコーン樹脂、シロキサン変性エポキシ樹脂及びシロキサン変性ポリアミドイミド樹脂が挙げられる。これらは単独で又は２種以上を混合して使用することができる。耐熱性及び接着性を向上する観点から、エポキシ樹脂を含有することが好ましい。 Examples of the thermosetting resin included in the positive photosensitive resin composition of the present invention include epoxy resins, unsaturated polyester resins, melamine resins, urea resins, diallyl phthalate resins, bismaleimide resins, triazine resins, polyurethane resins, and phenols. Examples thereof include resins, cyanoacrylate resins, polyisocyanate resins, furan resins, resorcinol resins, xylene resins, benzoguanamine resins, silicone resins, siloxane-modified epoxy resins, and siloxane-modified polyamideimide resins. These can be used alone or in admixture of two or more. From the viewpoint of improving heat resistance and adhesiveness, it is preferable to contain an epoxy resin.
上記エポキシ樹脂としては、硬化して接着作用を有するものであれば特に限定されず、例えば、エポキシ樹脂ハンドブック（新保正樹編、日刊工業新聞社）等に記載されるエポキシ樹脂を広く使用することができる。具体的には、例えば、ビスフェノールＡ型エポキシ等の二官能エポキシ樹脂、フェノールノボラック型エポキシ樹脂やクレゾールノボラック型エポキシ樹脂等のノボラック型エポキシ樹脂、トリスフェノールメタン型エポキシ樹脂を使用することができる。また、多官能エポキシ樹脂、グリシジルアミン型エポキシ樹脂、複素環含有エポキシ樹脂又は脂環式エポキシ樹脂など、一般に知られているものを適用することができる。より具体的な例として以下のように例示することができる。エピコート８２８（油化シェル社製）等のビスフェノール樹脂、１８０Ｓ６５（油化シェル社製）等のオルソクレゾールノボラック樹脂、１５７Ｓ７０（油化シェル社製）等のビスフェノールＡノボラック樹脂、１０３２Ｈ６０（油化シェル社製）等のトリスヒドロキシフェニルメタンノボラック樹脂、ＥＳＮ３７５等のナフタレンアラルキルノボラック樹脂、テトラフェニロールエタン１０３１Ｓ（油化シェル社製）、ＹＧＤ４１４Ｓ（東都化成）、トリスヒドロキシフェニルメタンＥＰＰＮ５０２Ｈ（日本化薬）、特殊ビスフェノールＶＧ３１０１Ｌ（三井化学）、特殊ナフトールＮＣ７０００（日本化薬）、ＴＥＴＲＡＤ−Ｘ、ＴＥＴＲＡＤ−Ｃ（三菱瓦斯化学社製）等のグリシジルアミン型樹脂などがあげられる。 The epoxy resin is not particularly limited as long as it is cured and has an adhesive action. For example, a wide range of epoxy resins described in the epoxy resin handbook (edited by Masaki Shinbo, Nikkan Kogyo Shimbun) can be used. it can. Specifically, for example, bifunctional epoxy resins such as bisphenol A type epoxy, novolac type epoxy resins such as phenol novolac type epoxy resin and cresol novolac type epoxy resin, and trisphenolmethane type epoxy resin can be used. Moreover, what is generally known, such as a polyfunctional epoxy resin, a glycidyl amine type epoxy resin, a heterocyclic ring-containing epoxy resin, or an alicyclic epoxy resin, can be applied. More specific examples can be illustrated as follows. Bisphenol resin such as Epicoat 828 (manufactured by Yuka Shell), orthocresol novolak resin such as 180S65 (manufactured by Yuka Shell), bisphenol A novolak resin such as 157S70 (manufactured by Yuka Shell), 1032H60 (manufactured by Yuka Shell) Trishydroxyphenylmethane novolak resin such as ESN375, naphthalene aralkyl novolak resin such as ESN375, tetraphenylolethane 1031S (manufactured by Yuka Shell), YGD414S (Tohto Kasei), trishydroxyphenylmethane EPPN502H (Nippon Kayaku), special Examples thereof include glycidylamine type resins such as bisphenol VG3101L (Mitsui Chemicals), special naphthol NC7000 (Nippon Kayaku), TETRAD-X, and TETRAD-C (manufactured by Mitsubishi Gas Chemical Company).
（Ｂ）熱硬化性樹脂成分の配合量は、硬化後の接着剤の耐熱性、接着性を維持し、高信頼性を発現させるため、（Ａ）、（Ｂ）及び（Ｃ）成分の合計１００質量部に対して５〜７０質量部であることが好ましく、８〜５０質量部であることがより好ましく、１０〜４０質量部であることが更に好ましい。 The blending amount of the (B) thermosetting resin component is the sum of the components (A), (B) and (C) in order to maintain the heat resistance and adhesiveness of the cured adhesive and to exhibit high reliability. The amount is preferably 5 to 70 parts by mass, more preferably 8 to 50 parts by mass, and still more preferably 10 to 40 parts by mass with respect to 100 parts by mass.
（Ｃ）光酸発生剤
本発明のポジ型感光性樹脂組成物に含まれる光酸発生剤には、光により酸を発生する化合物が使用される。（Ｃ）成分は感光剤であり、酸を発生させ、光の照射部のアルカリ水溶液への可溶性を増大させる機能を有するものである。具体的にはナフトキノンジアジド構造を有する化合物、オニウム塩、ハロゲン含有化合物、などを用いることができるが、感光性ジアゾキノン化合物が好ましい。
(C) Photoacid generator The photoacid generator contained in the positive photosensitive resin composition of the present invention uses a compound that generates an acid by light. The component (C) is a photosensitizer and has a function of generating an acid and increasing the solubility of the light irradiated portion in an alkaline aqueous solution. Specifically, a compound having a naphthoquinonediazide structure, an onium salt, a halogen-containing compound, and the like can be used, and a photosensitive diazoquinone compound is preferable.
上記オニウム塩としては、ヨードニウム塩、スルホニウム塩、ホシホニウム塩、ホスホニウム塩、アンモニウム塩、及びジアゾニウム塩などが挙げられ、ジアリールヨードニウム塩、トリアリールスルホニウム塩、及びトリアリキルスルホニウム塩からなる群から選ばれるオニウム塩が好ましい。 Examples of the onium salt include an iodonium salt, a sulfonium salt, a fosiphonium salt, a phosphonium salt, an ammonium salt, and a diazonium salt, and an onium selected from the group consisting of a diaryl iodonium salt, a triaryl sulfonium salt, and a triarylsulfonium salt. Salts are preferred.
上記ハロゲン含有化合物としては、ハロアルキル基含有炭化水素化合物などが挙げられ、トリクロロメチルトリアジンが好ましい。 Examples of the halogen-containing compound include haloalkyl group-containing hydrocarbon compounds, and trichloromethyltriazine is preferred.
上記ナフトキノンジアジド構造を有する化合物は、１，２−ベンゾキノンジアジド構造あるいは１，２−ナフトキノンジアジド構造を有する化合物であり、米国特許明細書第２７７２９７５号、第２７９７２１３号、第３６６９６５８号により公知の物質である。それらの中で、特に好ましいのは、多価フェノール化合物と１，２−ナフトキノン−２−ジアジド−５−スルホン酸（６−ジアゾ−５，６−ジヒドロ−５−オキソ−ナフタレン−１−スルホン酸）または、１，２−ナフトキノン−２−ジアジド−４−スルホン酸とのエステルであるが、それらに限定されるものではない。 The compound having the naphthoquinonediazide structure is a compound having a 1,2-benzoquinonediazide structure or a 1,2-naphthoquinonediazide structure, and is a known substance according to US Pat. Nos. 2,727,975, 2,797,213 and 3,669,658. is there. Among them, polyphenol compounds and 1,2-naphthoquinone-2-diazide-5-sulfonic acid (6-diazo-5,6-dihydro-5-oxo-naphthalene-1-sulfonic acid are particularly preferable. ) Or an ester with 1,2-naphthoquinone-2-diazide-4-sulfonic acid, but is not limited thereto.
本発明で用いる（Ｃ）酸発生剤の添加量は、ポリイミド樹脂１００質量部に対して、１〜５０質量部が好ましく、３〜４３質量部がより好ましく、５〜３６質量部がさらにこの好ましく、５〜２９質量部が特に好ましい。１質量部未満だと良好なパターンが得られず、５０質量部を超えると感度が大幅に低下する。３６％質量部以下であると硬化後の膜の脆さが抑制され、２９質量部以下だと機械特性を向上させることができる。 The addition amount of the (C) acid generator used in the present invention is preferably 1 to 50 parts by mass, more preferably 3 to 43 parts by mass, and further preferably 5 to 36 parts by mass with respect to 100 parts by mass of the polyimide resin. 5 to 29 parts by mass are particularly preferable. If it is less than 1 part by mass, a good pattern cannot be obtained, and if it exceeds 50 parts by mass, the sensitivity is greatly reduced. When the amount is 36% by mass or less, the brittleness of the cured film is suppressed, and when it is 29% by mass or less, mechanical properties can be improved.
（溶媒）
本発明においては、これらの成分を溶媒に溶解してポジ型感光性樹脂組成物として使用することが好ましい。このような溶媒としては、Ｎ−メチルー２−ピロリドン、γブチロラクトン（以下、「ＧＢＬ」とも言う）、シクロペンタノン、シクロヘキサノン、イソホロン、Ｎ，Ｎ−ジメチルアセトアミド、ジメチルイミダゾリノン、テトラメチルウレア、ジメチルスルホキシド、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ジブチルエーテル、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、ジ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メチルエーテルアセテート、乳酸メチル、乳酸エチル、乳酸ブチル、メチルー１，３−ブチレングリコールアセテート、１，３−ブチレングリコールー３−モノメチルエーテル、ピルビン酸メチル、ピルビン酸エチル、メチルー３−メトキシプロピオネート等を単独または混合して使用できる。これらの溶媒のうち、これらの溶媒のうち、非アミド系溶媒がフォトレジストなどへの影響が少ない点から好ましい。具体的には、γブチロラクトン、乳酸エチル、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、プロピレングリコールモノメチルエーテルアセテートなどが好ましい。
(solvent)
In the present invention, these components are preferably dissolved in a solvent and used as a positive photosensitive resin composition. Examples of such solvents include N-methyl-2-pyrrolidone, γ-butyrolactone (hereinafter also referred to as “GBL”), cyclopentanone, cyclohexanone, isophorone, N, N-dimethylacetamide, dimethylimidazolinone, tetramethylurea, dimethyl. Sulfoxide, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, methyl lactate, ethyl lactate, butyl lactate, methyl-1,3- Butylene glycol acetate, 1,3-butylene glycol-3-monomethyl ether, pill Methyl phosphate, ethyl pyruvate, a-methyl-3-methoxy propionate or the like can be used alone or in combination. Of these solvents, among these solvents, non-amide solvents are preferred because they have little influence on the photoresist and the like. Specifically, γ-butyrolactone, ethyl lactate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate and the like are preferable.
（パターン硬化膜の製造方法）
本発明によるパターン硬化膜の製造方法は、上述したポジ型感光性樹脂組成物を支持体基板上に塗布し乾燥する工程、露光する工程、感光性樹脂膜の露光部を除去するためにアルカリ水溶液を用いて現像する工程、及び現像された感光性樹脂膜を加熱処理する工程を経て、所望の耐熱性高分子のパターンとすることができる。以下に各工程について説明する。
(Method for producing patterned cured film)
The process for producing a patterned cured film according to the present invention comprises a step of applying the positive photosensitive resin composition described above on a support substrate and drying, a step of exposing, and an alkaline aqueous solution for removing the exposed portion of the photosensitive resin film. A pattern of a desired heat-resistant polymer can be obtained through a step of developing using a heat treatment and a step of heat-treating the developed photosensitive resin film. Each step will be described below.
（塗布・乾燥工程）
本発明のポジ型感光性樹脂組成物を支持体上に塗布する。支持体としては例えば、シリコンウエハ、セラミック基板、アルミ基板、銅基板等が挙げられる。塗布方法としては、スピナーを用いた回転塗布、ダイコーター又はロールコーター等のコーターによる塗布が挙げられる。支持体への塗布後、ホットプレート、オーブン等を用いて乾燥する。これにより、ポジ型感光性樹脂組成物の被膜である感光性樹脂膜が形成される。
(Coating / drying process)
The positive photosensitive resin composition of the present invention is applied on a support. Examples of the support include a silicon wafer, a ceramic substrate, an aluminum substrate, and a copper substrate. Examples of the coating method include spin coating using a spinner and coating with a coater such as a die coater or a roll coater. After coating on the support, it is dried using a hot plate, oven or the like. Thereby, the photosensitive resin film which is a film of a positive photosensitive resin composition is formed.
（露光工程）
支持体上で被膜となった感光性樹脂膜にマスクを介して、コンタクトアライナー、ミラープロジェクションやステッパーを用いて化学線による露光を行うか、光線、電子線またはイオン線を直接照射する。該化学線としては、Ｘ線、電子線、紫外線、または可視光線などが使用できるが、２００〜５００ｎｍ波長のものが好ましい。パターンの解像度及び取扱い性の点で、その光源波長は水銀ランプのｇ線、ｈ線もしくはｉ線が好ましく、単独でも混合していても良い。
(Exposure process)
The photosensitive resin film formed on the support is exposed to actinic radiation through a mask using a contact aligner, mirror projection, or stepper, or directly irradiated with a light beam, an electron beam, or an ion beam. As the actinic radiation, X-rays, electron beams, ultraviolet rays, visible rays, or the like can be used, but those having a wavelength of 200 to 500 nm are preferable. From the viewpoint of pattern resolution and handleability, the light source wavelength is preferably a g-line, h-line or i-line of a mercury lamp, which may be used alone or in combination.
（現像工程）
露光部を現像液で除去することにより、パターン樹脂膜が得られる。現像液としては例えば、水酸化ナトリウム、水酸化カリウム、計算ナトリウム、アンモニア、エチルアミン、ジエチルアミン、トリエチルアミン、トリエタノールアミン、テトラメチルアンモニウムヒドロキシドなどのアルカリ水溶液が好ましい。これらの水溶液の塩基濃度は０．１〜１０ｗｔ％とされることが好ましい。現像方法としては、スプレー、パドル、ディップ、または超音波等の方式が挙げられる。
(Development process)
A pattern resin film is obtained by removing the exposed portion with a developer. As the developer, for example, an aqueous alkali solution such as sodium hydroxide, potassium hydroxide, calculated sodium, ammonia, ethylamine, diethylamine, triethylamine, triethanolamine, tetramethylammonium hydroxide is preferable. The base concentration of these aqueous solutions is preferably 0.1 to 10 wt%. Examples of the developing method include spray, paddle, dip, and ultrasonic methods.
（加熱処理工程）
得られたパターン樹脂膜に２５０℃以下、好ましくは２００℃以下、より好ましくは１８０℃以下の熱処理を行うことにより、耐熱性高分子のパターンになる。
(Heat treatment process)
By subjecting the obtained pattern resin film to a heat treatment at 250 ° C. or less, preferably 200 ° C. or less, more preferably 180 ° C. or less, a heat-resistant polymer pattern is obtained.
また、加熱処理は、石英チューブ炉、ホットプレート、ラピッドサーマルアニール、縦型拡散炉、赤外線硬化炉、電子線硬化炉、及びマイクロ波硬化炉等を用いて行う。大気中、又は窒素等の不活性雰囲気中いずれを選択することもできるが、窒素下で行う方が感光性樹脂膜の参加を防ぐことができるので好ましい。本発明にかかるポジ型感光性樹脂組成物は加熱処理に必要な温度が従来よりも低いため、支持体やデバイスへのダメージを小さく抑えることができる。したがって、本発明のポジ型感光性樹脂組成物を用いることで、デバイスが歩留まり良く製造でき、且つプロセスの省エネルギー化に繋がる。 The heat treatment is performed using a quartz tube furnace, a hot plate, rapid thermal annealing, a vertical diffusion furnace, an infrared curing furnace, an electron beam curing furnace, a microwave curing furnace, or the like. Either air or an inert atmosphere such as nitrogen can be selected. However, it is preferable to perform the treatment under nitrogen because the participation of the photosensitive resin film can be prevented. Since the positive photosensitive resin composition according to the present invention has a lower temperature required for the heat treatment than before, damage to the support and the device can be reduced. Therefore, by using the positive photosensitive resin composition of the present invention, the device can be manufactured with a high yield, and the process energy can be saved.
以下、実施例及び比較例に基づき、本発明について更に具体的に説明する。なお、本発明は下記実施例に限定されるものではない。 Hereinafter, based on an Example and a comparative example, it demonstrates still more concretely about this invention. In addition, this invention is not limited to the following Example.
（合成例１）
撹拌機、温度計を備えた３リットルのフラスコ中にＮ，Ｎ−ジメチルホルムアミド（以下、ＤＭＦと示す）を２９５．５３ｇ仕込み、１，２−エタンジベンゾエート−３，３’，４，４’−テトラカルボン酸二無水物（以下、ＴＭＥＧと示す） を５９．９１ｇ投入し、窒素雰囲気下で、液温３０℃以下で撹拌した。［ビス（４−アミノ−３−カルボキシ）フェニル］メタン（以下、ＭＢＡＡと示す）を２２．９９ｇ投入し、同条件で撹拌した。並行して、信越化学工業株式会社製シロキサンジアミン（商品名：Ｘ−２２−９４０９Ｓ）５４．４７ｇを５４．４７ｇのＤＭＦに溶解した。得られたシリコンジアミンの溶解した溶液を前述のフラスコに投入し、同条件で撹拌した。続いて、ビス［４−（３−アミノフェノキシ）フェニル］スルフォン（以下、ＢＡＰＳ−ｍと示す）を１２．６３ｇ投入し、同条件で６０分間撹拌した。並行して、ＤＭＦ５９．１ｇにピリジン４６．２０ｇ、無水酢酸４４．７３ｇを混合した溶液を作製した。該溶液を前述のフラスコに投入し、１１０℃に加熱しながら１２０分間撹拌した。常温に戻ってから、フラスコに１．５リットルのイソプロピルアルコール（以下、ＩＰＡと示す）を投入し、析出物を回収した。更に１．５リットルのＩＰＡでの洗浄を５回行い、得られた析出物を１１０℃で１２時間乾燥し、ポリイミドを得た。
(Synthesis Example 1)
In a 3 liter flask equipped with a stirrer and a thermometer, 295.53 g of N, N-dimethylformamide (hereinafter referred to as DMF) was charged, and 1,2-ethanedibenzoate-3,3 ′, 4,4 ′ -59.91g of tetracarboxylic dianhydride (hereinafter referred to as TMEG) was added and stirred at a liquid temperature of 30 ° C or lower in a nitrogen atmosphere. 22.99 g of [bis (4-amino-3-carboxy) phenyl] methane (hereinafter referred to as MBAA) was added and stirred under the same conditions. In parallel, 54.47 g of siloxane diamine (trade name: X-22-9409S) manufactured by Shin-Etsu Chemical Co., Ltd. was dissolved in 54.47 g of DMF. The obtained silicon diamine-dissolved solution was put into the above-mentioned flask and stirred under the same conditions. Subsequently, 12.63 g of bis [4- (3-aminophenoxy) phenyl] sulfone (hereinafter referred to as BAPS-m) was added and stirred for 60 minutes under the same conditions. In parallel, a solution was prepared by mixing 46.20 g of pyridine and 44.73 g of acetic anhydride with 59.1 g of DMF. The solution was put into the aforementioned flask and stirred for 120 minutes while heating to 110 ° C. After returning to room temperature, 1.5 liters of isopropyl alcohol (hereinafter referred to as IPA) was added to the flask, and the precipitate was collected. Further, washing with 1.5 liters of IPA was performed 5 times, and the resulting precipitate was dried at 110 ° C. for 12 hours to obtain a polyimide.
（合成例２）
撹拌機、温度計を備えた３リットルのフラスコ中にＤＭＦを３２３．５６ｇ仕込み、ＴＭＥＧ を７２．７１ｇ投入し、窒素雰囲気下で、液温３０℃以下で撹拌した。ＭＢＡＡを３５．５２ｇ投入し、同条件で撹拌した。並行して、信越化学工業株式会社製シロキサンジアミン（商品名：Ｘ−２２−９４０９Ｓ）２６．４４ｇを２６．４４ｇのＤＭＦに溶解した。得られたシリコンジアミンの溶解した溶液を前述のフラスコに投入し、同条件で撹拌した。続いて、ＢＡＰＳ−ｍを１５．３３ｇ投入し、同条件で６０分間撹拌した。並行して、ＤＭＦ３９．６０ｇにピリジン５６．０７ｇ、無水酢酸５４．２８ｇを混合した溶液を作製した。該溶液を前述のフラスコに投入し、１１０℃に加熱しながら１２０分間撹拌した。常温に戻ってから、フラスコに１．５リットルのＩＰＡを投入し、析出物を回収した。更に１．５リットルのＩＰＡでの洗浄を５回行い、得られた析出物を１１０℃で１２時間乾燥し、ポリイミドを得た。
(Synthesis Example 2)
323.56 g of DMF was charged into a 3 liter flask equipped with a stirrer and a thermometer, 72.71 g of TMEG was charged, and the mixture was stirred at a liquid temperature of 30 ° C. or lower in a nitrogen atmosphere. 35.52 g of MBAA was added and stirred under the same conditions. In parallel, 26.44 g of siloxane diamine (trade name: X-22-9409S) manufactured by Shin-Etsu Chemical Co., Ltd. was dissolved in 26.44 g of DMF. The obtained silicon diamine-dissolved solution was put into the above-mentioned flask and stirred under the same conditions. Subsequently, 15.33 g of BAPS-m was added and stirred for 60 minutes under the same conditions. In parallel, a solution was prepared by mixing 56.07 g of pyridine and 54.28 g of acetic anhydride with 39.60 g of DMF. The solution was put into the aforementioned flask and stirred for 120 minutes while heating to 110 ° C. After returning to room temperature, 1.5 liters of IPA was added to the flask, and the precipitate was collected. Further, washing with 1.5 liters of IPA was performed 5 times, and the resulting precipitate was dried at 110 ° C. for 12 hours to obtain a polyimide.
（合成例３）
撹拌機、温度計を備えた３リットルのフラスコ中にＤＭＦを２８８．２６ｇ仕込み、ＴＭＥＧ を５６．５９ｇ投入し、窒素雰囲気下で、液温３０℃以下で撹拌した。ＭＢＡＡを１９．７４ｇ投入し、同条件で撹拌した。並行して、信越化学工業株式会社製シロキサンジアミン（商品名：Ｘ−２２−９４０９Ｓ）６１．７４ｇを６１．７４ｇのＤＭＦに溶解した。得られたシリコンジアミンの溶解した溶液を前述のフラスコに投入し、同条件で撹拌した。続いて、ＢＡＰＳ−ｍを１１．９３ｇ投入し、同条件で６０分間撹拌した。並行して、ＤＭＦ６４．１ｇにピリジン４３．６４ｇ、無水酢酸４２．２５ｇを混合した溶液を作製した。該溶液を前述のフラスコに投入し、１１０℃に加熱しながら１２０分間撹拌した。常温に戻ってから、フラスコに１．５リットルのＩＰＡを投入し、析出物を回収した。更に１．５リットルのＩＰＡでの洗浄を５回行い、得られた析出物を１１０℃で１２時間乾燥し、ポリイミドを得た。
(Synthesis Example 3)
In a 3 liter flask equipped with a stirrer and a thermometer, 288.26 g of DMF was charged, 56.59 g of TMEG was charged, and the mixture was stirred at a liquid temperature of 30 ° C. or lower in a nitrogen atmosphere. 19.74 g of MBAA was added and stirred under the same conditions. In parallel, 61.74 g of siloxane diamine (trade name: X-22-9409S) manufactured by Shin-Etsu Chemical Co., Ltd. was dissolved in 61.74 g of DMF. The obtained silicon diamine-dissolved solution was put into the above-mentioned flask and stirred under the same conditions. Subsequently, 11.93 g of BAPS-m was added and stirred for 60 minutes under the same conditions. In parallel, a solution was prepared by mixing 43.64 g of pyridine and 42.25 g of acetic anhydride with 64.1 g of DMF. The solution was put into the aforementioned flask and stirred for 120 minutes while heating to 110 ° C. After returning to room temperature, 1.5 liters of IPA was added to the flask, and the precipitate was collected. Further, washing with 1.5 liters of IPA was performed 5 times, and the resulting precipitate was dried at 110 ° C. for 12 hours to obtain a polyimide.
（合成例４）
撹拌機、温度計を備えた３リットルのフラスコ中にＤＭＦを３５０．００ｇ仕込み、ＴＭＥＧ を９５．４８ｇ投入し、窒素雰囲気下で、液温３０℃以下で撹拌した。続いて、ピロメリット酸二無水物（以下、ＰＭＤＡと示す）を７．６１ｇ投入し、同条件で撹拌した。続いて、ＭＢＡＡを４０．５１ｇ投入し、同条件で撹拌した。続いて、２，２’−ジトリフルオロメチル−４，４’−ジアミノビフェニル（以下、ＴＦＭＢと示す）を２５．４９ｇ投入し、同条件で６０分間撹拌した。並行して、ＤＭＦ１２．３ｇにピリジン６９．９５ｇ、無水酢酸６７．７２ｇを混合した溶液を作製した。該溶液を前述のフラスコに投入し、１１０℃に加熱しながら１２０分間撹拌した。常温に戻ってから、フラスコに１．５リットルのＩＰＡを投入し、析出物を回収した。更に１．５リットルのＩＰＡでの洗浄を５回行い、得られた析出物を１１０℃で１２時間乾燥し、ポリイミドを得た。
(Synthesis Example 4)
In a 3 liter flask equipped with a stirrer and a thermometer, 350.00 g of DMF was charged, 95.48 g of TMEG was charged, and the mixture was stirred at a liquid temperature of 30 ° C. or lower in a nitrogen atmosphere. Subsequently, 7.61 g of pyromellitic dianhydride (hereinafter referred to as PMDA) was added and stirred under the same conditions. Subsequently, 40.51 g of MBAA was added and stirred under the same conditions. Subsequently, 25.49 g of 2,2′-ditrifluoromethyl-4,4′-diaminobiphenyl (hereinafter referred to as TFMB) was added and stirred for 60 minutes under the same conditions. In parallel, a solution was prepared by mixing 69.95 g of pyridine and 67.72 g of acetic anhydride with 12.3 g of DMF. The solution was put into the aforementioned flask and stirred for 120 minutes while heating to 110 ° C. After returning to room temperature, 1.5 liters of IPA was added to the flask, and the precipitate was collected. Further, washing with 1.5 liters of IPA was performed 5 times, and the resulting precipitate was dried at 110 ° C. for 12 hours to obtain a polyimide.
（合成例５）
撹拌機、温度計を備えた３リットルのフラスコ中にＤＭＦを２９４．６９ｇ仕込み、ＴＭＥＧ を６０．８４ｇ投入し、窒素雰囲気下で、液温３０℃以下で撹拌した。ＭＢＡＡを１４．８６ｇ投入し、同条件で撹拌した。並行して、信越化学工業株式会社製シロキサンジアミン（商品名：Ｘ−２２−９４０９Ｓ）５５．３１ｇを５５．３１ｇのＤＭＦに溶解した。得られたシリコンジアミンの溶解した溶液を前述のフラスコに投入し、同条件で撹拌した。続いて、ＴＦＭＢを１８．９９ｇ投入し、同条件で６０分間撹拌した。並行して、ＤＭＦ５７．７ｇにピリジン４６．９２ｇ、無水酢酸４５．４２ｇを混合した溶液を作製した。該溶液を前述のフラスコに投入し、１１０℃に加熱しながら１２０分間撹拌した。常温に戻ってから、フラスコに１．５リットルのＩＰＡを投入し、析出物を回収した。更に１．５リットルのＩＰＡでの洗浄を５回行い、得られた析出物を１１０℃で１２時間乾燥し、ポリイミドを得た。
(Synthesis Example 5)
In a 3 liter flask equipped with a stirrer and a thermometer, 294.69 g of DMF was charged, 60.84 g of TMEG was charged, and the mixture was stirred at a liquid temperature of 30 ° C. or lower in a nitrogen atmosphere. 14.86 g of MBAA was added and stirred under the same conditions. In parallel, 55.31 g of siloxane diamine (trade name: X-22-9409S) manufactured by Shin-Etsu Chemical Co., Ltd. was dissolved in 55.31 g of DMF. The obtained silicon diamine-dissolved solution was put into the above-mentioned flask and stirred under the same conditions. Subsequently, 18.99 g of TFMB was added and stirred for 60 minutes under the same conditions. In parallel, a solution was prepared by mixing 46.92 g of pyridine and 45.42 g of acetic anhydride with 57.7 g of DMF. The solution was put into the aforementioned flask and stirred for 120 minutes while heating to 110 ° C. After returning to room temperature, 1.5 liters of IPA was added to the flask, and the precipitate was collected. Further, washing with 1.5 liters of IPA was performed 5 times, and the resulting precipitate was dried at 110 ° C. for 12 hours to obtain a polyimide.
（合成例６）
撹拌機、温度計を備えた３リットルのフラスコ中にＤＭＦを３４０．００ｇ仕込み、４，４’−オキシジフタル酸二無水物（以下、ＯＤＰＡと示す） を７６．４９ｇ投入し、窒素雰囲気下で、液温３０℃以下で撹拌した。続いて、ＭＢＡＡを４５．８８ｇ投入し、同条件で撹拌した。続いて、ＴＦＭＢを２７．６３ｇ投入し、同条件で６０分間撹拌した。並行して、ＤＭＦ６．５ｇにピリジン７８．０１ｇ、無水酢酸７５．５２ｇを混合した溶液を作製した。該溶液を前述のフラスコに投入し、１１０℃に加熱しながら１２０分間撹拌した。常温に戻ってから、フラスコに１．５リットルのＩＰＡを投入し、析出物を回収した。更に１．５リットルのＩＰＡでの洗浄を５回行い、得られた析出物を１１０℃で１２時間乾燥し、ポリイミドを得た。
(Synthesis Example 6)
A 3 liter flask equipped with a stirrer and a thermometer was charged with 340.00 g of DMF, charged with 76.49 g of 4,4′-oxydiphthalic dianhydride (hereinafter referred to as ODPA), and under a nitrogen atmosphere, The mixture was stirred at a liquid temperature of 30 ° C. or lower. Subsequently, 45.88 g of MBAA was added and stirred under the same conditions. Subsequently, 27.63 g of TFMB was added and stirred for 60 minutes under the same conditions. In parallel, a solution was prepared by mixing 6.5 g of DMF with 78.01 g of pyridine and 75.52 g of acetic anhydride. The solution was put into the aforementioned flask and stirred for 120 minutes while heating to 110 ° C. After returning to room temperature, 1.5 liters of IPA was added to the flask, and the precipitate was collected. Further, washing with 1.5 liters of IPA was performed 5 times, and the resulting precipitate was dried at 110 ° C. for 12 hours to obtain a polyimide.
（合成例７）
撹拌機、温度計を備えた３リットルのフラスコ中にＤＭＦを３１１．７４ｇ仕込み、ＴＭＥＧ を７０．１４ｇ投入し、窒素雰囲気下で、液温３０℃以下で撹拌した。ＭＢＡＡを４１．６０ｇ投入し、同条件で撹拌した。並行して、信越化学工業株式会社製シロキサンジアミン（商品名：Ｘ−２２−９４０９Ｓ）３８．２６ｇを３８．２６ｇのＤＭＦに溶解した。得られたシリコンジアミンの溶解した溶液を前述のフラスコに投入し、同条件で６０分間撹拌した。並行して、ＤＭＦ４３．５ｇにピリジン５４．０９ｇ、無水酢酸５２．３６ｇを混合した溶液を作製した。該溶液を前述のフラスコに投入し、１１０℃に加熱しながら１２０分間撹拌した。常温に戻ってから、フラスコに１．５リットルのＩＰＡを投入し、析出物を回収した。更に１．５リットルのＩＰＡでの洗浄を５回行い、得られた析出物を１１０℃で１２時間乾燥し、ポリイミドを得た。
(Synthesis Example 7)
In a 3 liter flask equipped with a stirrer and a thermometer, 311.74 g of DMF was charged, 70.14 g of TMEG was charged, and the mixture was stirred at a liquid temperature of 30 ° C. or lower in a nitrogen atmosphere. 41.60 g of MBAA was added and stirred under the same conditions. In parallel, 38.26 g of siloxane diamine (trade name: X-22-9409S) manufactured by Shin-Etsu Chemical Co., Ltd. was dissolved in 38.26 g of DMF. The obtained silicon diamine-dissolved solution was put into the aforementioned flask and stirred for 60 minutes under the same conditions. In parallel, a solution was prepared by mixing 54.09 g of pyridine and 52.36 g of acetic anhydride with 43.5 g of DMF. The solution was put into the aforementioned flask and stirred for 120 minutes while heating to 110 ° C. After returning to room temperature, 1.5 liters of IPA was added to the flask, and the precipitate was collected. Further, washing with 1.5 liters of IPA was performed 5 times, and the resulting precipitate was dried at 110 ° C. for 12 hours to obtain a polyimide.
（合成例８）
撹拌機、温度計を備えた３リットルのフラスコ中にＤＭＦを３５０．００ｇ仕込み、４，４’−オキシジフタル酸二無水物（以下、ＯＤＰＡと示す） を６７．７８ｇ投入し、窒素雰囲気下で、液温３０℃以下で撹拌した。続いて、ＢＡＰＳを４７．２４ｇ投入し、同条件で撹拌した。続いて、ＴＦＭＢを３４．９８ｇ投入し、同条件で６０分間撹拌した。並行して、ＤＭＦ１４．０ｇにピリジン６９．１２ｇ、無水酢酸６６．９２ｇを混合した溶液を作製した。該溶液を前述のフラスコに投入し、１１０℃に加熱しながら１２０分間撹拌した。常温に戻ってから、フラスコに１．５リットルのＩＰＡを投入し、析出物を回収した。更に１．５リットルのＩＰＡでの洗浄を５回行い、得られた析出物を１１０℃で１２時間乾燥し、ポリイミドを得た。
(Synthesis Example 8)
In a 3 liter flask equipped with a stirrer and a thermometer, 350.00 g of DMF was charged, 67.78 g of 4,4′-oxydiphthalic dianhydride (hereinafter referred to as ODPA) was charged, and under a nitrogen atmosphere, The mixture was stirred at a liquid temperature of 30 ° C. or lower. Subsequently, 47.24 g of BAPS was added and stirred under the same conditions. Subsequently, 34.98 g of TFMB was added and stirred for 60 minutes under the same conditions. In parallel, a solution was prepared by mixing 69.12 g of pyridine and 66.92 g of acetic anhydride in 14.0 g of DMF. The solution was put into the aforementioned flask and stirred for 120 minutes while heating to 110 ° C. After returning to room temperature, 1.5 liters of IPA was added to the flask, and the precipitate was collected. Further, washing with 1.5 liters of IPA was performed 5 times, and the resulting precipitate was dried at 110 ° C. for 12 hours to obtain a polyimide.
上記合成例１〜８においてポリイミドの原料として使用した酸二無水物及びジアミンの種類とモル比、ならびにポリイミドのカルボキシル基１つに対する分子量であるカルボキシル基当量を表１に記載する。 Table 1 shows the types and molar ratios of acid dianhydride and diamine used as raw materials for polyimide in Synthesis Examples 1 to 8, and the carboxyl group equivalent which is the molecular weight for one carboxyl group of polyimide.
（実施例１〜３、参考例４〜７、比較例１〜２）
＜ポジ型感光性樹脂組成物の調製＞
上記合成例で得た（Ａ）ポリイミドをγブチロラクトンに溶解して、固形分濃度３８％の溶液を得た。また、（Ｃ）４，４’−［１−［４−［１−（４−ヒドロキシフェニル）−１−メチルエチル］フェニル］エチリデン］ビスフェノールと６−ジアゾ−５，６−ジヒドロ−５−オキソ−ナフタレン−１−スルホン酸とのジエステルをγブチロラクトンに溶解して、固形分濃度３８％の溶液を得た。上記２種の溶液と、（Ｂ）２，２’−ビス（４−グリシジルオキシフェニル）プロパン（エピコート８２８）とγブチロラクトンを混合し、表２に記載した実施例１〜３、参考例４〜７、及び比較例１〜２のポジ型感光性樹脂組成物を得た。
(Examples 1-3, Reference Examples 4-7 , Comparative Examples 1-2)
<Preparation of positive photosensitive resin composition>
The polyimide (A) obtained in the above synthesis example was dissolved in γ-butyrolactone to obtain a solution having a solid content concentration of 38%. Further, (C) 4,4 ′-[1- [4- [1- (4-hydroxyphenyl) -1-methylethyl] phenyl] ethylidene] bisphenol and 6-diazo-5,6-dihydro-5-oxo -A diester with naphthalene-1-sulfonic acid was dissolved in γ-butyrolactone to obtain a solution having a solid content of 38%. The above two solutions, (B) 2,2′-bis (4-glycidyloxyphenyl) propane (Epicoat 828) and γ-butyrolactone were mixed, and Examples 1 to 3 and Reference Examples 4 to 4 described in Table 2 were mixed . 7 and Comparative Examples 1-2 were obtained.
＜ポジ型感光性樹脂組成物の評価＞
上記実施例、参考例、及び比較例のポジ型感光性樹脂組成物をスピンコーター（ミカサ株式会社製、ＭＳ−Ａ２００）を用いて、４インチシリコンウエハにスピンコートした。オーブンにて６０℃、５分間プリベークを行った。この塗膜に、ライン幅／スペース幅＝２μｍ／２μｍ、５μｍ／５μｍ、１０μｍ／１０μｍのパターンを有するポジ型フォトマスクを置いて減圧下で紫外線を５００ｍＪ／ｃｍ ２ 露光して感光させた。この感光フィルムに対し、２．３８重量％テトラメチルアンモニウム水溶液を３０℃に保温した溶液を用いて、１．０ｋｇｆ／ｍｍ ２ の吐出圧でスプレー現像を行った。現像後、純水でリンスを行い、１９０℃のオーブン中で６０分加熱して硬化させ、樹脂パターンの形成された反りのないシリコンウエハを得た。ＳＥＭを用いて得られたサンプルの外観観察を行い、パターニング性の評価を行った。結果を表２に示す。
<Evaluation of positive photosensitive resin composition>
The positive photosensitive resin compositions of the above Examples, Reference Examples and Comparative Examples were spin-coated on a 4-inch silicon wafer using a spin coater (Mikasa Co., Ltd., MS-A200). Pre-baking was performed in an oven at 60 ° C. for 5 minutes. A positive type photomask having a pattern of line width / space width = 2 μm / 2 μm, 5 μm / 5 μm, 10 μm / 10 μm was placed on this coating film, and exposed to UV light at a pressure of 500 mJ / cm 2 under reduced pressure. This photosensitive film was spray-developed with a discharge pressure of 1.0 kgf / mm 2 using a 2.38 wt% tetramethylammonium aqueous solution kept at 30 ° C. After the development, rinsing was performed with pure water, followed by heating and curing in an oven at 190 ° C. for 60 minutes to obtain a silicon wafer having no warp on which a resin pattern was formed. The appearance of the sample obtained using SEM was observed and the patterning property was evaluated. The results are shown in Table 2.
Claims (3)
（Ｂ）熱硬化性樹脂と、
（Ｃ）光酸発生剤と、
を含有してなり、
前記（Ｂ）熱硬化性樹脂がエポキシ樹脂であり、
前記（Ａ）ポリイミドを構成するモノマーの酸成分の少なくとも一種が、直鎖炭化水素を有する酸であり、
前記（Ａ）ポリイミドを構成するモノマーのジアミン成分が、少なくとも、カルボキシル基を有するジアミン、カルボキシル基を有さないジアミン及びシリコンジアミンの３種を含むことを特徴とするポジ型感光性樹脂組成物。 (A) a polyimide having a carboxyl group;
(B) a thermosetting resin;
(C) a photoacid generator;
Ri vegetables contain,
The (B) thermosetting resin is an epoxy resin,
(A) At least one of the acid components of the monomer constituting the polyimide is an acid having a linear hydrocarbon,
(A) The positive photosensitive resin composition, wherein the diamine component of the monomer constituting the polyimide (A) includes at least three kinds of diamine having a carboxyl group, diamine having no carboxyl group, and silicon diamine .
(A) the molecular weight to the one carboxyl group of polyimide, positive photosensitive resin composition according to claim 1 or 2, characterized in that it is 500 to 1300.
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