JP6306296B2 - Photosensitive thermosetting resin composition and flexible printed wiring board - Google Patents
Photosensitive thermosetting resin composition and flexible printed wiring board Download PDFInfo
- Publication number
- JP6306296B2 JP6306296B2 JP2013144034A JP2013144034A JP6306296B2 JP 6306296 B2 JP6306296 B2 JP 6306296B2 JP 2013144034 A JP2013144034 A JP 2013144034A JP 2013144034 A JP2013144034 A JP 2013144034A JP 6306296 B2 JP6306296 B2 JP 6306296B2
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- JP
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- Prior art keywords
- bis
- resin composition
- dianhydride
- resin
- thermosetting resin
- Prior art date
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- 229920001187 thermosetting polymer Polymers 0.000 title claims description 85
- 239000011342 resin composition Substances 0.000 title claims description 79
- 229920005989 resin Polymers 0.000 claims description 78
- 239000011347 resin Substances 0.000 claims description 78
- -1 cyclic ether compound Chemical class 0.000 claims description 49
- 229920001721 polyimide Polymers 0.000 claims description 45
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 42
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 39
- 239000009719 polyimide resin Substances 0.000 claims description 39
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 36
- 239000003513 alkali Substances 0.000 claims description 21
- 238000010438 heat treatment Methods 0.000 claims description 20
- 238000007259 addition reaction Methods 0.000 claims description 8
- 239000002585 base Substances 0.000 claims description 7
- 239000003054 catalyst Substances 0.000 claims description 4
- 125000005462 imide group Chemical group 0.000 claims 4
- 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 47
- 238000000034 method Methods 0.000 description 43
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 33
- 239000010408 film Substances 0.000 description 29
- 150000003949 imides Chemical group 0.000 description 29
- 239000003822 epoxy resin Substances 0.000 description 28
- 229920000647 polyepoxide Polymers 0.000 description 28
- 230000018109 developmental process Effects 0.000 description 25
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 24
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 22
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- 150000001412 amines Chemical class 0.000 description 15
- 150000001875 compounds Chemical class 0.000 description 14
- 239000000203 mixture Substances 0.000 description 12
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 12
- 239000002253 acid Substances 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 9
- 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 9
- 229910000679 solder Inorganic materials 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000004805 Cyclohexane-1,2-dicarboxylic acid Substances 0.000 description 8
- 238000001723 curing Methods 0.000 description 8
- QSAWQNUELGIYBC-UHFFFAOYSA-N cyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCCCC1C(O)=O QSAWQNUELGIYBC-UHFFFAOYSA-N 0.000 description 8
- 150000004985 diamines Chemical class 0.000 description 8
- 239000012948 isocyanate Substances 0.000 description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 7
- 150000002513 isocyanates Chemical class 0.000 description 7
- 239000000758 substrate Substances 0.000 description 7
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 6
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 6
- 239000004642 Polyimide Substances 0.000 description 6
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000013007 heat curing Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 6
- 150000003457 sulfones Chemical class 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 125000005442 diisocyanate group Chemical group 0.000 description 5
- 238000011156 evaluation 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
- 239000011256 inorganic filler Substances 0.000 description 5
- 229910003475 inorganic filler Inorganic materials 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000003086 colorant Substances 0.000 description 4
- UKJLNMAFNRKWGR-UHFFFAOYSA-N cyclohexatrienamine Chemical group NC1=CC=C=C[CH]1 UKJLNMAFNRKWGR-UHFFFAOYSA-N 0.000 description 4
- 125000003700 epoxy group Chemical group 0.000 description 4
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 4
- 150000002576 ketones Chemical class 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 229920003986 novolac Polymers 0.000 description 4
- 239000005011 phenolic resin Substances 0.000 description 4
- 239000002952 polymeric resin Substances 0.000 description 4
- 229920003002 synthetic resin Polymers 0.000 description 4
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 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 3
- LJGHYPLBDBRCRZ-UHFFFAOYSA-N 3-(3-aminophenyl)sulfonylaniline Chemical compound NC1=CC=CC(S(=O)(=O)C=2C=C(N)C=CC=2)=C1 LJGHYPLBDBRCRZ-UHFFFAOYSA-N 0.000 description 3
- ICNFHJVPAJKPHW-UHFFFAOYSA-N 4,4'-Thiodianiline Chemical compound C1=CC(N)=CC=C1SC1=CC=C(N)C=C1 ICNFHJVPAJKPHW-UHFFFAOYSA-N 0.000 description 3
- 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 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 3
- 150000008065 acid anhydrides Chemical class 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 230000001588 bifunctional effect Effects 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 230000001678 irradiating effect Effects 0.000 description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 238000010030 laminating Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000001294 propane Substances 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 150000003462 sulfoxides Chemical class 0.000 description 3
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 2
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 2
- HEQOJEGTZCTHCF-UHFFFAOYSA-N 2-amino-1-phenylethanone Chemical class NCC(=O)C1=CC=CC=C1 HEQOJEGTZCTHCF-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
- UHFFVFAKEGKNAQ-UHFFFAOYSA-N 2-benzyl-2-(dimethylamino)-1-(4-morpholin-4-ylphenyl)butan-1-one Chemical compound C=1C=C(N2CCOCC2)C=CC=1C(=O)C(CC)(N(C)C)CC1=CC=CC=C1 UHFFVFAKEGKNAQ-UHFFFAOYSA-N 0.000 description 2
- JWAZRIHNYRIHIV-UHFFFAOYSA-N 2-naphthol Chemical compound C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-UHFFFAOYSA-N 0.000 description 2
- NUIURNJTPRWVAP-UHFFFAOYSA-N 3,3'-Dimethylbenzidine Chemical compound C1=C(N)C(C)=CC(C=2C=C(C)C(N)=CC=2)=C1 NUIURNJTPRWVAP-UHFFFAOYSA-N 0.000 description 2
- UENRXLSRMCSUSN-UHFFFAOYSA-N 3,5-diaminobenzoic acid Chemical compound NC1=CC(N)=CC(C(O)=O)=C1 UENRXLSRMCSUSN-UHFFFAOYSA-N 0.000 description 2
- LXJLFVRAWOOQDR-UHFFFAOYSA-N 3-(3-aminophenoxy)aniline Chemical compound NC1=CC=CC(OC=2C=C(N)C=CC=2)=C1 LXJLFVRAWOOQDR-UHFFFAOYSA-N 0.000 description 2
- ZBMISJGHVWNWTE-UHFFFAOYSA-N 3-(4-aminophenoxy)aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=CC(N)=C1 ZBMISJGHVWNWTE-UHFFFAOYSA-N 0.000 description 2
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 2
- KHYXYOGWAIYVBD-UHFFFAOYSA-N 4-(4-propylphenoxy)aniline Chemical compound C1=CC(CCC)=CC=C1OC1=CC=C(N)C=C1 KHYXYOGWAIYVBD-UHFFFAOYSA-N 0.000 description 2
- MQAHXEQUBNDFGI-UHFFFAOYSA-N 5-[4-[2-[4-[(1,3-dioxo-2-benzofuran-5-yl)oxy]phenyl]propan-2-yl]phenoxy]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(OC2=CC=C(C=C2)C(C)(C=2C=CC(OC=3C=C4C(=O)OC(=O)C4=CC=3)=CC=2)C)=C1 MQAHXEQUBNDFGI-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- 125000004018 acid anhydride group Chemical group 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 239000012670 alkaline solution Substances 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- 150000003934 aromatic aldehydes Chemical class 0.000 description 2
- 150000004984 aromatic diamines Chemical class 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 150000001555 benzenes Chemical class 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
- VHRGRCVQAFMJIZ-UHFFFAOYSA-N cadaverine Chemical compound NCCCCCN VHRGRCVQAFMJIZ-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- DMEGYFMYUHOHGS-UHFFFAOYSA-N cycloheptane Chemical group C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 2
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical class C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005194 fractionation Methods 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 description 2
- 229910001507 metal halide Inorganic materials 0.000 description 2
- 150000005309 metal halides Chemical class 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 150000000000 tetracarboxylic acids Chemical class 0.000 description 2
- 150000003627 tricarboxylic acid derivatives Chemical class 0.000 description 2
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 description 2
- OLQWMCSSZKNOLQ-ZXZARUISSA-N (3s)-3-[(3r)-2,5-dioxooxolan-3-yl]oxolane-2,5-dione Chemical compound O=C1OC(=O)C[C@H]1[C@@H]1C(=O)OC(=O)C1 OLQWMCSSZKNOLQ-ZXZARUISSA-N 0.000 description 1
- HFROTQKOFJESPY-CMDGGOBGSA-N (e)-3-(2-hydroxyphenyl)-1-piperidin-1-ylprop-2-en-1-one Chemical compound OC1=CC=CC=C1\C=C\C(=O)N1CCCCC1 HFROTQKOFJESPY-CMDGGOBGSA-N 0.000 description 1
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 1
- LUYHWJKHJNFYGV-UHFFFAOYSA-N 1,2-diisocyanato-3-phenylbenzene Chemical compound O=C=NC1=CC=CC(C=2C=CC=CC=2)=C1N=C=O LUYHWJKHJNFYGV-UHFFFAOYSA-N 0.000 description 1
- ZXHZWRZAWJVPIC-UHFFFAOYSA-N 1,2-diisocyanatonaphthalene Chemical compound C1=CC=CC2=C(N=C=O)C(N=C=O)=CC=C21 ZXHZWRZAWJVPIC-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
- PWGJDPKCLMLPJW-UHFFFAOYSA-N 1,8-diaminooctane Chemical compound NCCCCCCCCN PWGJDPKCLMLPJW-UHFFFAOYSA-N 0.000 description 1
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 1
- JRHNUZCXXOTJCA-UHFFFAOYSA-N 1-fluoropropane Chemical compound CCCF JRHNUZCXXOTJCA-UHFFFAOYSA-N 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical group C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-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
- VOZKAJLKRJDJLL-UHFFFAOYSA-N 2,4-diaminotoluene Chemical compound CC1=CC=C(N)C=C1N VOZKAJLKRJDJLL-UHFFFAOYSA-N 0.000 description 1
- UONVFNLDGRWLKF-UHFFFAOYSA-N 2,5-diaminobenzoic acid Chemical compound NC1=CC=C(N)C(C(O)=O)=C1 UONVFNLDGRWLKF-UHFFFAOYSA-N 0.000 description 1
- RLYCRLGLCUXUPO-UHFFFAOYSA-N 2,6-diaminotoluene Chemical compound CC1=C(N)C=CC=C1N RLYCRLGLCUXUPO-UHFFFAOYSA-N 0.000 description 1
- PGZXVWMZYVIVRK-UHFFFAOYSA-N 2-[2-(2-hydroxyphenoxy)phenoxy]phenol Chemical class OC1=CC=CC=C1OC1=CC=CC=C1OC1=CC=CC=C1O PGZXVWMZYVIVRK-UHFFFAOYSA-N 0.000 description 1
- XPNZGOXGWANTBW-UHFFFAOYSA-N 2-[2-[2-(2-carboxyphenoxy)phenyl]sulfonylphenoxy]benzoic acid Chemical class OC(=O)C1=CC=CC=C1OC1=CC=CC=C1S(=O)(=O)C1=CC=CC=C1OC1=CC=CC=C1C(O)=O XPNZGOXGWANTBW-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
- 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 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
- 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
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 125000004573 morpholin-4-yl group Chemical group N1(CCOCC1)* 0.000 description 1
- OBKARQMATMRWQZ-UHFFFAOYSA-N naphthalene-1,2,5,6-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 OBKARQMATMRWQZ-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
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- SXJVFQLYZSNZBT-UHFFFAOYSA-N nonane-1,9-diamine Chemical compound NCCCCCCCCCN SXJVFQLYZSNZBT-UHFFFAOYSA-N 0.000 description 1
- 150000002923 oximes Chemical class 0.000 description 1
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical compound NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 1
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- UMSVUULWTOXCQY-UHFFFAOYSA-N phenanthrene-1,2,7,8-tetracarboxylic acid Chemical compound OC(=O)C1=CC=C2C3=CC=C(C(=O)O)C(C(O)=O)=C3C=CC2=C1C(O)=O UMSVUULWTOXCQY-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 239000013034 phenoxy resin Substances 0.000 description 1
- 229920006287 phenoxy resin Polymers 0.000 description 1
- CCDXIADKBDSBJU-UHFFFAOYSA-N phenylmethanetriol Chemical compound OC(O)(O)C1=CC=CC=C1 CCDXIADKBDSBJU-UHFFFAOYSA-N 0.000 description 1
- 238000000206 photolithography Methods 0.000 description 1
- 230000036211 photosensitivity Effects 0.000 description 1
- CLYVDMAATCIVBF-UHFFFAOYSA-N pigment red 224 Chemical compound C=12C3=CC=C(C(OC4=O)=O)C2=C4C=CC=1C1=CC=C2C(=O)OC(=O)C4=CC=C3C1=C42 CLYVDMAATCIVBF-UHFFFAOYSA-N 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000007261 regionalization Effects 0.000 description 1
- 238000006798 ring closing metathesis reaction Methods 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 150000003335 secondary amines Chemical class 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
- 238000005476 soldering Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical group S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 150000003553 thiiranes Chemical class 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- 125000003258 trimethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- KLNPWTHGTVSSEU-UHFFFAOYSA-N undecane-1,11-diamine Chemical compound NCCCCCCCCCCCN KLNPWTHGTVSSEU-UHFFFAOYSA-N 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Images
Classifications
-
- 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
-
- 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
- G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
-
- 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
- G03F7/0387—Polyamides or polyimides
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/22—Secondary treatment of printed circuits
- H05K3/28—Applying non-metallic protective coatings
- H05K3/285—Permanent coating compositions
- H05K3/287—Photosensitive compositions
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0393—Flexible materials
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/0011—Working of insulating substrates or insulating layers
- H05K3/0017—Etching of the substrate by chemical or physical means
- H05K3/0026—Etching of the substrate by chemical or physical means by laser ablation
- H05K3/0032—Etching of the substrate by chemical or physical means by laser ablation of organic insulating material
- H05K3/0035—Etching of the substrate by chemical or physical means by laser ablation of organic insulating material of blind holes, i.e. having a metal layer at the bottom
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Engineering & Computer Science (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Manufacturing & Machinery (AREA)
- Materials For Photolithography (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Non-Metallic Protective Coatings For Printed Circuits (AREA)
- Optics & Photonics (AREA)
Description
本発明は、感光性熱硬化性樹脂組成物およびフレキシブルプリント配線板に関し、詳しくは、アルカリによる現像が可能であり、耐熱性および屈曲性に優れ、かつ、光照射後加熱硬化時の温度・時間管理が容易な感光性熱硬化性樹脂組成物および該感光性熱硬化性樹脂組成物の硬化物を備えたフレキシブルプリント配線板に関する。 The present invention relates to a photosensitive thermosetting resin composition and a flexible printed wiring board, and in particular, development with an alkali is possible, heat resistance and flexibility are excellent, and temperature and time during heat curing after light irradiation. The present invention relates to a photosensitive thermosetting resin composition that can be easily managed and a flexible printed wiring board including a cured product of the photosensitive thermosetting resin composition.
近年、スマートフォンやタブレット端末の普及と性能の向上が急速に進行している。これらに代表される情報機器端末は、小型化、薄型化への消費者の要求が高く、その要求に応えるべく、製品内部の回路基板の高密度化、省スペース化が必要となっている。そのため、折り曲げての収納が可能で、回路配置の自由度を高めることのできるフレキシブルプリント配線板の用途が拡大しており、フレキシブルプリント配線板に対する信頼性もこれまで以上に高いものが求められている。 In recent years, the spread of smartphones and tablet terminals and the improvement of performance are progressing rapidly. Information equipment terminals represented by these are highly demanded by consumers for downsizing and thinning, and in order to meet these demands, it is necessary to increase the density of circuit boards inside the products and save space. Therefore, the use of flexible printed wiring boards that can be folded and stored and that can increase the degree of freedom of circuit arrangement is expanding, and the reliability for flexible printed wiring boards is required to be higher than ever. Yes.
現在、フレキシブルプリント配線板の絶縁信頼性を確保するための絶縁膜として、折り曲げ部(屈曲部)には、ポリイミドをベースとしたカバーレイが用いられ、実装部(非屈曲部)には、感光性樹脂組成物を用いた混載プロセスが広く採用されている(特許文献1、2参照)。ポリイミドは、耐熱性および屈曲性などの機械的特性に優れ、一方、実装部に用いられる感光性樹脂組成物は、電気絶縁性やはんだ耐熱性などに優れ微細加工が可能であるという特性を有する。 Currently, a polyimide-based coverlay is used for the bent part (bent part) as an insulating film to ensure the insulation reliability of the flexible printed wiring board, and the mounting part (non-bent part) is photosensitive. A mixed loading process using a conductive resin composition is widely employed (see Patent Documents 1 and 2). Polyimide is excellent in mechanical properties such as heat resistance and flexibility, while the photosensitive resin composition used in the mounting part has characteristics such as excellent electrical insulation and solder heat resistance and can be finely processed. .
従来のポリイミドをベースとしたカバーレイでは、金型打ち抜きによる加工を必要とするため、微細配線には不向きである。そのため、微細配線が必要となるチップ実装部には、フォトリソグラフィーによる加工ができるアルカリ現像型の感光性樹脂組成物(ソルダーレジスト)を部分的に併用することが行われている。フレキシブルプリント配線板の製造においてこのような樹脂組成物の部分的な使い分けをする場合、カバーレイを貼り合わせる工程とソルダーレジストを形成する工程の2つの工程を経ることになり、コストと作業性に劣るという問題があった。 Conventional polyimide-based coverlays are not suitable for fine wiring because they require processing by die punching. For this reason, an alkali-developable photosensitive resin composition (solder resist) that can be processed by photolithography is partially used together in a chip mounting portion that requires fine wiring. When partially using such a resin composition in the production of a flexible printed wiring board, two processes, a process of bonding a cover lay and a process of forming a solder resist, are performed, resulting in cost and workability. There was a problem of being inferior.
そこで従来から、混載プロセスによらないフレキシブルプリント配線板の絶縁膜の検討がなされている。例えば、ソルダーレジスト用の感光性樹脂組成物をフレキシブルプリント配線板のカバーレイとして適用することが検討されているが、ソルダーレジスト用の樹脂組成物では、カバーレイとしての耐衝撃性や屈曲性などの信頼性が不十分である。ソルダーレジスト用の樹脂組成物では、アクリル系の光重合による硬化収縮も伴うため、フレキシブルプリント配線板の反りなど寸法安定性にも課題があった。 Therefore, conventionally, an insulating film of a flexible printed wiring board that does not depend on a mixed mounting process has been studied. For example, application of a photosensitive resin composition for a solder resist as a coverlay for a flexible printed wiring board has been studied. However, in a resin composition for a solder resist, impact resistance, flexibility, etc. as a coverlay The reliability is insufficient. Since the resin composition for solder resist is accompanied by curing shrinkage due to acrylic photopolymerization, there is a problem in dimensional stability such as warping of the flexible printed wiring board.
また、アルカリ溶解性と機械特性が両立できる感光性ポリイミドとして、ポリイミド前駆体を利用し、パターニングした後に熱閉環する方法も提案されているが、高温処理を必要とするなど作業性に問題があった。 In addition, as a photosensitive polyimide that can achieve both alkali solubility and mechanical properties, a method of using a polyimide precursor and performing thermal ring closure after patterning has been proposed. However, there is a problem in workability such as requiring high-temperature treatment. It was.
そこで本発明の目的は、耐衝撃性や屈曲性などの信頼性と加工精度、作業性に優れ、フレキシブルプリント配線板の絶縁膜、特に折り曲げ部(屈曲部)と実装部(非屈曲部)の一括形成プロセスに好適な感光性熱硬化性樹脂組成物を提供することにある。 Therefore, the object of the present invention is excellent in reliability such as impact resistance and flexibility, processing accuracy, and workability. Insulating films of flexible printed wiring boards, particularly bent portions (bending portions) and mounting portions (non-bending portions). It is providing the photosensitive thermosetting resin composition suitable for a batch formation process.
本発明者らは、上記課題を解決すべく鋭意検討した結果、カルボキシル基を有するポリイミド樹脂、光塩基発生剤および熱硬化成分を含む樹脂組成物が上記課題を解決しうることを見出した。
即ち、光照射によって光塩基発生剤が活性化し、発生した塩基を触媒としてカルボキシル基を有するポリイミド樹脂と熱硬化成分とを、加熱によって付加反応させることにより、未露光部分のみをアルカリ溶液によって除去することが可能となることが見出された。これによって、アルカリ現像による微細加工が可能となる一方、信頼性に優れた硬化物を得ることが期待できる。
As a result of intensive studies to solve the above problems, the present inventors have found that a resin composition containing a polyimide resin having a carboxyl group, a photobase generator and a thermosetting component can solve the above problems.
That is, a photobase generator is activated by light irradiation, and a polyimide resin having a carboxyl group and a thermosetting component are subjected to an addition reaction by heating using the generated base as a catalyst, whereby only an unexposed portion is removed with an alkaline solution. It has been found that this is possible. As a result, fine processing by alkali development becomes possible, and it can be expected to obtain a cured product having excellent reliability.
一方、光照射後の加熱硬化反応において、加熱温度や加熱時間の幅を広げることができれば、より作業性に優れた樹脂組成物となることから、本発明者らは、さらなる検討を重ねた結果、以下のことを見出し本発明を完成するに至った。即ち、イミド環、カルボキシル基およびフェノール性水酸基を有するポリイミド樹脂を含む感光性熱硬化性樹脂組成物とするか、もしくは、イミド環、カルボキシル基を有するポリイミド樹脂と、フェノール性水酸基を有する樹脂とを含む感光性熱硬化性樹脂組成物とすることにより、上記特性に加えて、より作業性に優れた感光性熱硬化性樹脂組成物を得ることができる。 On the other hand, in the heat curing reaction after light irradiation, if the range of the heating temperature and the heating time can be widened, the resin composition is more excellent in workability. The present inventors have found the following and completed the present invention. That is, a photosensitive thermosetting resin composition containing a polyimide resin having an imide ring, a carboxyl group and a phenolic hydroxyl group, or a polyimide resin having an imide ring and a carboxyl group, and a resin having a phenolic hydroxyl group. By setting it as the photosensitive thermosetting resin composition to be included, in addition to the above characteristics, a photosensitive thermosetting resin composition having more excellent workability can be obtained.
本発明は、以下の[1]〜[8]である。
[1](A)イミド環およびカルボキシル基を有するポリイミド樹脂、(B)フェノール性水酸基を有する樹脂、(C)光塩基発生剤、および、(D)熱硬化成分を含むことを特徴とする感光性熱硬化性樹脂組成物。
[2]前記樹脂(B)がさらにイミド環を有することを特徴とする[1]の感光性熱硬化性樹脂組成物。
[3]前記樹脂(B)がさらにカルボキシル基を有することを特徴とする[2]の感光性熱硬化性樹脂組成物。
[4](E)イミド環、フェノール性水酸基およびカルボキシル基を有するポリイミド樹脂、(C)光塩基発生剤、および、(D)熱硬化成分、を含むことを特徴とする感光性熱硬化性樹脂組成物。
[5]前記熱硬化成分(D)が環状エーテル化合物である[1]〜[4]のいずれかの感光性熱硬化性樹脂組成物。
[6]前記樹脂組成物がフレキシブルプリント配線板用であることを特徴とする[1]〜[5]のいずれかの感光性熱硬化性樹脂組成物。
[7][1]〜[6]のいずれかの感光性熱硬化性樹脂組成物からなる樹脂層を有することを特徴とするドライフィルム。
[8][1]〜[6]のいずれかの感光性熱硬化性樹脂組成物、または、[7]のドライフィルムを用いて形成される硬化物を備えることを特徴とするプリント配線板。
The present invention includes the following [1] to [8].
[1] A photosensitive resin comprising (A) a polyimide resin having an imide ring and a carboxyl group, (B) a resin having a phenolic hydroxyl group, (C) a photobase generator, and (D) a thermosetting component. Thermosetting resin composition.
[2] The photosensitive thermosetting resin composition according to [1], wherein the resin (B) further has an imide ring.
[3] The photosensitive thermosetting resin composition according to [2], wherein the resin (B) further has a carboxyl group.
[4] A photosensitive thermosetting resin comprising (E) a polyimide resin having an imide ring, a phenolic hydroxyl group and a carboxyl group, (C) a photobase generator, and (D) a thermosetting component. Composition.
[5] The photosensitive thermosetting resin composition according to any one of [1] to [4], wherein the thermosetting component (D) is a cyclic ether compound.
[6] The photosensitive thermosetting resin composition according to any one of [1] to [5], wherein the resin composition is for a flexible printed wiring board.
[7] A dry film comprising a resin layer made of the photosensitive thermosetting resin composition according to any one of [1] to [6].
[8] A printed wiring board comprising the photosensitive thermosetting resin composition according to any one of [1] to [6] or a cured product formed using the dry film according to [7].
本発明により、アルカリによる現像が可能であり、耐熱性および屈曲性に優れ、かつ、光照射後加熱硬化時の温度・時間管理が容易な感光性熱硬化性樹脂組成物、および、該感光性熱硬化性樹脂組成物からなる樹脂層を有するドライフィルム、該感光性熱硬化性樹脂組成物の硬化物を備えたフレキシブルプリント配線板を提供することが可能となる。本発明の感光性熱硬化性樹脂組成物は、フレキシブルプリント配線板の絶縁膜、特に折り曲げ部(屈曲部)と実装部(非屈曲部)の一括形成プロセスに好適である。 According to the present invention, a photosensitive thermosetting resin composition capable of developing with an alkali, excellent in heat resistance and flexibility, and easy in temperature and time management at the time of heat curing after light irradiation, and the photosensitivity It is possible to provide a dry film having a resin layer made of a thermosetting resin composition and a flexible printed wiring board provided with a cured product of the photosensitive thermosetting resin composition. The photosensitive thermosetting resin composition of the present invention is suitable for a process for forming an insulating film of a flexible printed wiring board, particularly a bent part (bent part) and a mounting part (non-bent part).
本発明の第一の感光性熱硬化性樹脂組成物は、(A)イミド環およびカルボキシル基を有するポリイミド樹脂、(B)フェノール性水酸基を有する樹脂、(C)光塩基発生剤、および、(D)熱硬化成分を含むことを特徴とするものである。本発明の第二の感光性熱硬化性樹脂組成物は、(E)イミド環、フェノール性水酸基およびカルボキシル基を有するポリイミド樹脂、(C)光塩基発生剤、および、(D)熱硬化成分、を含むことを特徴とするものである。
いずれも、光塩基発生剤から生じる塩基を触媒として、カルボキシル基を有するポリイミド樹脂と熱硬化成分とを露光後の加熱によって付加反応をさせ、未露光部分をアルカリ溶液によって除去することによって現像が可能となる樹脂組成物である点で共通する。また、いずれの感光性熱硬化性樹脂組成物も、フェノール性水酸基を系内に有するものである。
後述するように、フェノール性水酸基が存在すると、存在しない場合に比べて、露光後の加熱硬化反応時(下記PEB工程時)において同一の加熱温度下での、付加反応によりアルカリ耐性となるまでの時間を長くすることができる。また、加熱硬化反応時(下記PEB工程時)の加熱温度の選択幅を広げることができる。これらのことから、樹脂組成物の作業性、取扱性が向上する。未露光部がアルカリ耐性となる、いわゆるかぶりの発生を抑制することもできる。
The first photosensitive thermosetting resin composition of the present invention comprises (A) a polyimide resin having an imide ring and a carboxyl group, (B) a resin having a phenolic hydroxyl group, (C) a photobase generator, and ( D) A thermosetting component is included. The second photosensitive thermosetting resin composition of the present invention comprises (E) a polyimide resin having an imide ring, a phenolic hydroxyl group and a carboxyl group, (C) a photobase generator, and (D) a thermosetting component. It is characterized by including.
Both can be developed by using a base generated from the photobase generator as a catalyst, causing the polyimide resin having a carboxyl group and the thermosetting component to undergo an addition reaction by heating after exposure, and removing the unexposed portion with an alkaline solution. This is common in that it is a resin composition. Any photosensitive thermosetting resin composition has a phenolic hydroxyl group in the system.
As will be described later, when a phenolic hydroxyl group is present, compared to the case where it does not exist, it becomes alkali resistance by addition reaction at the same heating temperature in the heat curing reaction after exposure (at the time of the following PEB process). The time can be lengthened. Moreover, the selection range of the heating temperature at the time of thermosetting reaction (at the time of the following PEB process) can be expanded. From these things, the workability | operativity and handleability of a resin composition improve. It is also possible to suppress the occurrence of so-called fogging in which the unexposed part becomes alkali resistant.
本発明の感光性熱硬化性樹脂組成物は、フレキシブルプリント配線板の樹脂絶縁層、例えば、カバーレイ、ソルダーレジスト、に好適である。
本発明の感光性熱硬化性樹脂組成物を用いてフレキシブルプリント配線板の樹脂絶縁層を形成する場合、好適な製造方法は、下記のようになる。即ち、フレキシブルプリント配線板上に本発明の感光性熱硬化性樹脂組成物からなる樹脂層を形成する工程、パターン状に光を樹脂層に照射する工程、樹脂層を加熱する工程(Post Exposure Bake;PEBとも称する)、及び、樹脂層をアルカリ現像して、パターンを有する樹脂絶縁層を形成する工程を含む製造方法である。必要に応じて、アルカリ現像後、さらなる光照射や加熱硬化(ポストキュア)を行い、樹脂組成物を完全硬化させて信頼性の高い樹脂絶縁層を得る。
このように、本発明の感光性熱硬化性樹脂組成物は、好適には、選択的な光照射後の加熱処理により、カルボキシル基と熱硬化成分とが付加反応することによって、アルカリ現像によるネガ型のパターン形成が可能となるものである。
得られる硬化物が耐熱性および屈曲性に優れ、かつ、アルカリ現像により微細加工が可能であることから、ポリイミドに対してアルカリ現像型の感光性樹脂組成物を部分的に併用する必要がなく、フレキシブルプリント配線板の折り曲げ部(屈曲部)と実装部(非屈曲部)のいずれにも用いることができ、折り曲げ部(屈曲部)と実装部(非屈曲部)の一括形成プロセスに好適である。
The photosensitive thermosetting resin composition of the present invention is suitable for resin insulating layers of flexible printed wiring boards, such as coverlays and solder resists.
When forming the resin insulation layer of a flexible printed wiring board using the photosensitive thermosetting resin composition of this invention, a suitable manufacturing method is as follows. That is, a step of forming a resin layer comprising the photosensitive thermosetting resin composition of the present invention on a flexible printed wiring board, a step of irradiating the resin layer with light in a pattern, and a step of heating the resin layer (Post Exposure Bake) And also referred to as PEB), and a process of alkali-developing the resin layer to form a resin insulating layer having a pattern. If necessary, after alkali development, further light irradiation or heat curing (post-cure) is performed to completely cure the resin composition to obtain a highly reliable resin insulating layer.
As described above, the photosensitive thermosetting resin composition of the present invention is preferably a negative by alkaline development by an addition reaction between a carboxyl group and a thermosetting component by selective heat treatment after light irradiation. Mold pattern formation is possible.
Since the resulting cured product is excellent in heat resistance and flexibility and can be finely processed by alkali development, it is not necessary to partially use an alkali development type photosensitive resin composition for polyimide, It can be used for both the bent part (bent part) and the mounting part (non-bent part) of the flexible printed wiring board, and is suitable for the batch formation process of the bent part (bent part) and the mounting part (non-bent part). .
本発明の第一の感光性熱硬化性樹脂組成物は、(A)イミド環およびカルボキシル基を有するポリイミド樹脂、(B)フェノール性水酸基を有する樹脂、(C)光塩基発生剤、および、(D)熱硬化成分を含むことを特徴とするものである。イミド環およびカルボキシル基を有するポリイミド樹脂の他に、フェノール性水酸基を有する樹脂を含む。後述するように、このフェノール性水酸基を有する樹脂もイミド環を有する事が好ましく、また、カルボキシル基を有していてもよい。以下、各成分について詳述する。 The first photosensitive thermosetting resin composition of the present invention comprises (A) a polyimide resin having an imide ring and a carboxyl group, (B) a resin having a phenolic hydroxyl group, (C) a photobase generator, and ( D) A thermosetting component is included. In addition to the polyimide resin having an imide ring and a carboxyl group, a resin having a phenolic hydroxyl group is included. As will be described later, the resin having a phenolic hydroxyl group also preferably has an imide ring, and may have a carboxyl group. Hereinafter, each component will be described in detail.
[(A)イミド環およびカルボキシル基を有するポリイミド樹脂]
本発明において、(A)イミド環およびカルボキシル基を有するポリイミド樹脂は、カルボキシル基とイミド環を有する樹脂である。
(A)成分であるポリイミド樹脂は、イミド環として下記式(1)で表される部分構造を有することが好ましい。式(1)中、Rが芳香環を含むものであることが好ましい。
上記式(1)で表される部分構造は、下記式(2)または(3)で表されるものであることがより好ましい。
カルボキシル基の位置は特に限定されない。上記イミド環もしくはそれと結合する基の置換基としてカルボキシル基が存在してもよく、アミン成分やイソシアネート成分として、カルボキシル基を有するものを用いて合成することによってカルボキシル基をポリイミド樹脂に導入してもよい。
[(A) Polyimide resin having imide ring and carboxyl group]
In the present invention, (A) a polyimide resin having an imide ring and a carboxyl group is a resin having a carboxyl group and an imide ring.
The polyimide resin as component (A) preferably has a partial structure represented by the following formula (1) as an imide ring. In formula (1), it is preferable that R contains an aromatic ring.
The partial structure represented by the above formula (1) is more preferably one represented by the following formula (2) or (3).
The position of the carboxyl group is not particularly limited. A carboxyl group may be present as a substituent of the imide ring or a group bonded thereto, and the carboxyl group may be introduced into a polyimide resin by synthesis using an amine component or an isocyanate component having a carboxyl group. Good.
(A)成分であるポリイミド樹脂の合成には公知慣用の手法を用いることができる。例えば、カルボン酸無水物成分とアミン成分及び/又はイソシアネート成分とを反応させて得られる樹脂が挙げられる。イミド化は熱イミド化で行っても、化学イミド化で行ってもよく、またこれらを併用して製造してもよい。 A well-known and usual method can be used for the synthesis | combination of the polyimide resin which is (A) component. For example, the resin obtained by making a carboxylic anhydride component react with an amine component and / or an isocyanate component is mentioned. Imidization may be performed by thermal imidization, chemical imidization, or a combination thereof.
カルボン酸無水物成分としては、テトラカルボン酸無水物やトリカルボン酸無水物などが挙げられるが、これらの酸無水物に限定されるものではなく、アミノ基やイソシアネート基と反応する酸無水物基およびカルボキシル基を有する化合物であれば、その誘導体を含め用いることができる。また、これらのカルボン酸無水物成分は、1種を単独で用いてもよく、2種以上を組み合わせて使用してもよい。 Examples of the carboxylic acid anhydride component include tetracarboxylic acid anhydrides and tricarboxylic acid anhydrides, but are not limited to these acid anhydrides, and acid anhydride groups that react with amino groups and isocyanate groups, and Any compound having a carboxyl group can be used, including derivatives thereof. Moreover, these carboxylic anhydride components may be used individually by 1 type, and may be used in combination of 2 or more type.
テトラカルボン酸無水物としては、例えば、ピロメリット酸二無水物、3−フルオロピロメリット酸二無水物、3,6−ジフルオロピロメリット酸二無水物、3,6−ビス(トリフルオロメチル)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、2,2’−ジフルオロ−3,3’,4,4’−ビフェニルテトラカルボン酸二無水物、5,5’−ジフルオロ−3,3’,4,4’−ビフェニルテトラカルボン酸二無水物、6,6’−ジフルオロ−3,3’,4,4’−ビフェニルテトラカルボン酸二無水物、2,2’,5,5’,6,6’−ヘキサフルオロ−3,3’,4,4’−ビフェニルテトラカルボン酸二無水物、2,2’−ビス(トリフルオロメチル)−3,3’,4,4’−ビフェニルテトラカルボン酸二無水物、5,5’−ビス(トリフルオロメチル)−3,3’,4,4’−ビフェニルテトラカルボン酸二無水物、6,6’−ビス(トリフルオロメチル)−3,3’,4,4’−ビフェニルテトラカルボン酸二無水物、2,2’,5,5’−テトラキス(トリフルオロメチル)−3,3’,4,4’−ビフェニルテトラカルボン酸二無水物、2,2’,6,6’−テトラキス(トリフルオロメチル)−3,3’,4,4’−ビフェニルテトラカルボン酸二無水物、5,5’,6,6’−テトラキス(トリフルオロメチル)−3,3’,4,4’−ビフェニルテトラカルボン酸二無水物、および2,2’,5,5’,6,6’−ヘキサキス(トリフルオロメチル)−3,3’,4,4’−ビフェニルテトラカルボン酸二無水物、1,2,3,4−ベンゼンテトラカルボン酸二無水物、3,3”,4,4”−テルフェニルテトラカルボン酸二無水物、3,3’”,4,4’”−クァテルフェニルテトラカルボン酸二無水物、3,3””,4,4””−キンクフェニルテトラカルボン酸二無水物、メチレン−4,4’−ジフタル酸二無水物、1,1−エチニリデン−4,4’−ジフタル酸二無水物、2,2−プロピリデン−4,4’−ジフタル酸二無水物、1,2−エチレン−4,4’−ジフタル酸二無水物、1,3−トリメチレン−4,4’−ジフタル酸二無水物、1,4−テトラメチレン−4,4’−ジフタル酸二無水物、1,5−ペンタメチレン−4,4’−ジフタル酸二無水物、2,2−ビス(3,4−ジカルボキシフェニル)−1,1,1,3,3,3−へキサフルオロプロパン二無水物、ジフルオロメチレン−4,4’−ジフタル酸二無水物、1,1,2,2−テトラフルオロ−1,2−エチレン−4,4’−ジフタル酸二無水物、1,1,2,2,3,3−ヘキサフルオロ−1,3−トリメチレン−4,4’−ジフタル酸二無水物、1,1,2,2,3,3,4,4−オクタフルオロ−1,4−テトラメチレン−4,4’−ジフタル酸二無水物、1,1,2,2,3,3,4,4,5,5−デカフルオロ−1,5−ペンタメチレン−4,4’−ジフタル酸二無水物、チオ−4,4’−ジフタル酸二無水物、スルホニル−4,4’−ジフタル酸二無水物、1,3−ビス(3,4−ジカルボキシフェニル)−1,1,3,3−テトラメチルシロキサン二無水物、1,3−ビス(3,4−ジカルボキシフェニル)ベンゼン二無水物、1,4−ビス(3,4−ジカルボキシフェニル)ベンゼン二無水物、1,3−ビス(3,4−ジカルボキシフェノキシ)ベンゼン二無水物、1,4−ビス(3,4−ジカルボキシフェノキシ)ベンゼン二無水物、1,3−ビス〔2−(3,4−ジカルボキシフェニル)−2−プロピル〕ベンゼン二無水物、1,4−ビス〔2−(3,4−ジカルボキシフェニル)−2−プロピル〕ベンゼン二無水物、ビス〔3−(3,4−ジカルボキシフェノキシ)フェニル〕メタン二無水物、ビス〔4−(3,4−ジカルボキシフェノキシ)フェニル〕メタン二無水物、2,2−ビス〔3−(3,4−ジカルボキシフェノキシ)フェニル〕プロパン二無水物、2,2−ビス〔4−(3,4−ジカルボキシフェノキシ)フェニル〕プロパン二無水物、2,2−ビス〔3−(3,4−ジカルボキシフェノキシ)フェニル〕−1,1,1,3,3,3−ヘキサフルオロプロパン二無水物、2,2−ビス〔4−(3,4−ジカルボキシフェノキシ)フェニル〕プロパン二無水物、ビス(3,4−ジカルボキシフェノキシ)ジメチルシラン二無水物、1,3−ビス(3,4−ジカルボキシフェノキシ)−1,1,3,3−テトラメチルジシロキサン二無水物、2,3,6,7−ナフタレンテトラカルボン酸二無水物、1,2,5,6−ナフタレンテトラカルボン酸二無水物、3,4,9,10−ペリレンテトラカルボン酸二無水物、2,3,6,7−アントラセンテトラカルボン酸二無水物、1,2,7,8−フェナントレンテトラカルボン酸二無水物、1,2,3,4−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、シクロペンタンテトラカルボン酸二無水物、シクロヘキサン−1,2,3,4−テトラカルボン酸二無水物、シクロヘキサン−1,2,4,5−テトラカルボン酸二無水物、3,3’,4,4’−ビシクロヘキシルテトラカルボン酸二無水物、カルボニル−4,4’−ビス(シクロヘキサン−1,2−ジカルボン酸)二無水物、メチレン−4,4’−ビス(シクロヘキサン−1,2−ジカルボン酸)二無水物、1,2−エチレン−4,4’−ビス(シクロヘキサン−1,2−ジカルボン酸)二無水物、1,1−エチニリデン−4,4’−ビス(シクロヘキサン−1,2−ジカルボン酸)二無水物、2,2−プロピリデン−4,4’−ビス(シクロヘキサン−1,2−ジカルボン酸)二無水物、1,1,1,3,3,3−ヘキサフルオロ−2,2−プロピリデン−4,4’−ビス(シクロヘキサン−1,2−ジカルボン酸)二無水物、オキシ−4,4’−ビス(シクロヘキサン−1,2−ジカルボン酸)二無水物、チオ−4,4’−ビス(シクロヘキサン−1,2−ジカルボン酸)二無水物、スルホニル−4,4’−ビス(シクロヘキサン−1,2−ジカルボン酸)二無水物、3,3’−ジフルオロオキシ−4,4’−ジフタル酸二無水物、5,5’−ジフルオロオキシ−4,4’−ジフタル酸二無水物、6,6’−ジフルオロオキシ−4,4’−ジフタル酸二無水物、3,3’,5,5’,6,6’−ヘキサフルオロオキシ−4,4’−ジフタル酸二無水物、3,3’−ビス(トリフルオロメチル)オキシ−4,4’−ジフタル酸二無水物、5,5’−ビス(トリフルオロメチル)オキシ−4,4’−ジフタル酸二無水物、6,6’−ビス(トリフルオロメチル)オキシ−4,4’−ジフタル酸二無水物、3,3’,5,5’−テトラキス(トリフルオロメチル)オキシ−4,4’−ジフタル酸二無水物、3,3’,6,6’−テトラキス(トリフルオロメチル)オキシ−4,4’−ジフタル酸二無水物、5,5’,6,6’−テトラキス(トリフルオロメチル)オキシ−4,4’−ジフタル酸二無水物、3,3’,5,5’,6,6’−ヘキサキス(トリフルオロメチル)オキシ−4,4’−ジフタル酸二無水物、3,3’−ジフルオロスルホニル−4,4’−ジフタル酸二無水物、5,5’−ジフルオロスルホニル−4,4’−ジフタル酸二無水物、6,6’−ジフルオロスルホニル−4,4’−ジフタル酸二無水物、3,3’,5,5’,6,6’−ヘキサフルオロスルホニル−4,4’−ジフタル酸二無水物、3,3’−ビス(トリフルオロメチル)スルホニル−4,4’−ジフタル酸二無水物、5,5’−ビス(トリフルオロメチル)スルホニル−4,4’−ジフタル酸二無水物、6,6’−ビス(トリフルオロメチル)スルホニル−4,4’−ジフタル酸二無水物、3,3’,5,5’−テトラキス(トリフルオロメチル)スルホニル−4,4’−ジフタル酸二無水物、3,3’,6,6’−テトラキス(トリフルオロメチル)スルホニル−4,4’−ジフタル酸二無水物、5,5’,6,6’−テトラキス(トリフルオロメチル)スルホニル−4,4’−ジフタル酸二無水物、3,3’,5,5’,6,6’−ヘキサキス(トリフルオロメチル)スルホニル−4,4’−ジフタル酸二無水物、3,3’−ジフルオロ−2,2−パーフルオロプロピリデン−4,4’−ジフタル酸二無水物、5,5’−ジフルオロ−2,2−パーフルオロプロピリデン−4,4’−ジフタル酸二無水物、6,6’−ジフルオロ−2,2−パーフルオロプロピリデン−4,4’−ジフタル酸二無水物、3,3’,5,5’,6,6’−ヘキサフルオロ−2,2−パーフルオロプロピリデン−4,4’−ジフタル酸二無水物、3,3’−ビス(トリフルオロメチル)−2,2−パーフルオロプロピリデン−4,4’−ジフタル酸二無水物、5,5’−ビス(トリフルオロメチル)−2,2−パーフルオロプロピリデン−4,4’−ジフタル酸二無水物、6,6’−ジフルオロ−2,2−パーフルオロプロピリデン−4,4’−ジフタル酸二無水物、3,3’,5,5’−テトラキス(トリフルオロメチル)−2,2−パーフルオロプロピリデン−4,4’−ジフタル酸二無水物、3,3’,6,6’−テトラキス(トリフルオロメチル)−2,2−パーフルオロプロピリデン−4,4’−ジフタル酸二無水物、5,5’,6,6’−テトラキス(トリフルオロメチル)−2,2−パーフルオロプロピリデン−4,4’−ジフタル酸二無水物、3,3’,5,5’,6,6’−ヘキサキス(トリフルオロメチル)−2,2−パーフルオロプロピリデン−4,4’−ジフタル酸二無水物、9−フェニル−9−(トリフルオロメチル)キサンテン−2,3,6,7−テトラカルボン酸二無水物、9,9−ビス(トリフルオロメチル)キサンテン−2,3,6,7−テトラ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、9,9−ビス〔4−(3,4−ジカルボキシ)フェニル〕フルオレン二無水物、9,9−ビス〔4−(2,3−ジカルボキシ)フェニル〕フルオレン二無水物、エチレングリコールビストリメリテート二無水物、1,2−(エチレン)ビス(トリメリテート無水物)、1,3−(トリメチレン)ビス(トリメリテート無水物)、1,4−(テトラメチレン)ビス(トリメリテート無水物)、1,5−(ペンタメチレン)ビス(トリメリテート無水物)、1,6−(ヘキサメチレン)ビス(トリメリテート無水物)、1,7−(ヘプタメチレン)ビス(トリメリテート無水物)、1,8−(オクタメチレン)ビス(トリメリテート無水物)、1,9−(ノナメチレン)ビス(トリメリテート無水物)、1,10−(デカメチレン)ビス(トリメリテート無水物)、1,12−(ドデカメチレン)ビス(トリメリテート無水物)、1,16−(ヘキサデカメチレン)ビス(トリメリテート無水物)、1,18−(オクタデカメチレン)ビス(トリメリテート無水物)などが挙げられる。 Examples of the tetracarboxylic acid anhydride include pyromellitic dianhydride, 3-fluoropyromellitic dianhydride, 3,6-difluoropyromellitic dianhydride, 3,6-bis (trifluoromethyl) pyro Merit acid dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 4,4′-oxydiphthalic acid Anhydride, 2,2′-difluoro-3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 5,5′-difluoro-3,3 ′, 4,4′-biphenyltetracarboxylic acid Anhydride, 6,6′-difluoro-3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,2 ′, 5,5 ′, 6,6′-hexafluoro-3,3 ′ , 4,4'-biphenyltet Carboxylic dianhydride, 2,2′-bis (trifluoromethyl) -3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 5,5′-bis (trifluoromethyl) -3, 3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 6,6′-bis (trifluoromethyl) -3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,2 ′ , 5,5′-tetrakis (trifluoromethyl) -3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,2 ′, 6,6′-tetrakis (trifluoromethyl) -3, 3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 5,5 ′, 6,6′-tetrakis (trifluoromethyl) -3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride , And 2,2 ', 5,5', 6,6 -Hexakis (trifluoromethyl) -3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, 3,3 ", 4,4 "-Terphenyltetracarboxylic dianhydride, 3,3 '", 4,4' "-quaterphenyltetracarboxylic dianhydride, 3,3" ", 4,4" "-kinkphenyltetracarboxylic acid Dianhydride, methylene-4,4′-diphthalic dianhydride, 1,1-ethynylidene-4,4′-diphthalic dianhydride, 2,2-propylidene-4,4′-diphthalic dianhydride 1,2-ethylene-4,4′-diphthalic dianhydride, 1,3-trimethylene-4,4′-diphthalic dianhydride, 1,4-tetramethylene-4,4′-diphthalic acid Anhydride, 1,5-pentamethylene-4,4'-diph Talic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride, difluoromethylene-4,4′-diphthal Acid dianhydride, 1,1,2,2-tetrafluoro-1,2-ethylene-4,4′-diphthalic dianhydride, 1,1,2,2,3,3-hexafluoro-1, 3-trimethylene-4,4′-diphthalic dianhydride, 1,1,2,2,3,3,4,4-octafluoro-1,4-tetramethylene-4,4′-diphthalic dianhydride 1,1,2,2,3,3,4,4,5,5-decafluoro-1,5-pentamethylene-4,4′-diphthalic dianhydride, thio-4,4′- Diphthalic dianhydride, sulfonyl-4,4′-diphthalic dianhydride, 1,3-bis (3,4-dicarboxyphene) ) -1,1,3,3-tetramethylsiloxane dianhydride, 1,3-bis (3,4-dicarboxyphenyl) benzene dianhydride, 1,4-bis (3,4-dicarboxyphenyl) ) Benzene dianhydride, 1,3-bis (3,4-dicarboxyphenoxy) benzene dianhydride, 1,4-bis (3,4-dicarboxyphenoxy) benzene dianhydride, 1,3-bis [ 2- (3,4-Dicarboxyphenyl) -2-propyl] benzene dianhydride, 1,4-bis [2- (3,4-dicarboxyphenyl) -2-propyl] benzene dianhydride, bis [ 3- (3,4-Dicarboxyphenoxy) phenyl] methane dianhydride, bis [4- (3,4-dicarboxyphenoxy) phenyl] methane dianhydride, 2,2-bis [3- (3,4 -Dicarboxyphenoxy Phenyl] propane dianhydride, 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride, 2,2-bis [3- (3,4-dicarboxyphenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane dianhydride, 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride, bis (3,4- Dicarboxyphenoxy) dimethylsilane dianhydride, 1,3-bis (3,4-dicarboxyphenoxy) -1,1,3,3-tetramethyldisiloxane dianhydride, 2,3,6,7-naphthalene Tetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 2,3,6,7-anthracenetetracarboxylic Acid dianhydride, 1,2,7,8-phenanthrenetetracarboxylic dianhydride, 1,2,3,4-butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic acid Anhydride, cyclopentanetetracarboxylic dianhydride, cyclohexane-1,2,3,4-tetracarboxylic dianhydride, cyclohexane-1,2,4,5-tetracarboxylic dianhydride, 3,3 ′ , 4,4′-bicyclohexyltetracarboxylic dianhydride, carbonyl-4,4′-bis (cyclohexane-1,2-dicarboxylic acid) dianhydride, methylene-4,4′-bis (cyclohexane-1, 2-dicarboxylic acid) dianhydride, 1,2-ethylene-4,4′-bis (cyclohexane-1,2-dicarboxylic acid) dianhydride, 1,1-ethynylidene-4,4′-bis (cyclohexane) San-1,2-dicarboxylic acid) dianhydride, 2,2-propylidene-4,4'-bis (cyclohexane-1,2-dicarboxylic acid) dianhydride, 1,1,1,3,3,3 -Hexafluoro-2,2-propylidene-4,4'-bis (cyclohexane-1,2-dicarboxylic acid) dianhydride, oxy-4,4'-bis (cyclohexane-1,2-dicarboxylic acid) dianhydride Thio-4,4′-bis (cyclohexane-1,2-dicarboxylic acid) dianhydride, sulfonyl-4,4′-bis (cyclohexane-1,2-dicarboxylic acid) dianhydride, 3,3 ′ -Difluorooxy-4,4'-diphthalic dianhydride, 5,5'-difluorooxy-4,4'-diphthalic dianhydride, 6,6'-difluorooxy-4,4'-diphthalic acid Anhydride, 3, 3 ', 5, 5', 6 6′-hexafluorooxy-4,4′-diphthalic dianhydride, 3,3′-bis (trifluoromethyl) oxy-4,4′-diphthalic dianhydride, 5,5′-bis (tri Fluoromethyl) oxy-4,4′-diphthalic dianhydride, 6,6′-bis (trifluoromethyl) oxy-4,4′-diphthalic dianhydride, 3,3 ′, 5,5′- Tetrakis (trifluoromethyl) oxy-4,4′-diphthalic dianhydride, 3,3 ′, 6,6′-tetrakis (trifluoromethyl) oxy-4,4′-diphthalic dianhydride, 5, 5 ', 6,6'-tetrakis (trifluoromethyl) oxy-4,4'-diphthalic dianhydride, 3,3', 5,5 ', 6,6'-hexakis (trifluoromethyl) oxy- 4,4'-diphthalic dianhydride, 3,3'-diflu Orosulfonyl-4,4′-diphthalic dianhydride, 5,5′-difluorosulfonyl-4,4′-diphthalic dianhydride, 6,6′-difluorosulfonyl-4,4′-diphthalic dianhydride 3,3 ′, 5,5 ′, 6,6′-hexafluorosulfonyl-4,4′-diphthalic dianhydride, 3,3′-bis (trifluoromethyl) sulfonyl-4,4′- Diphthalic dianhydride, 5,5′-bis (trifluoromethyl) sulfonyl-4,4′-diphthalic dianhydride, 6,6′-bis (trifluoromethyl) sulfonyl-4,4′-diphthalic acid Dianhydride, 3,3 ′, 5,5′-tetrakis (trifluoromethyl) sulfonyl-4,4′-diphthalic dianhydride, 3,3 ′, 6,6′-tetrakis (trifluoromethyl) sulfonyl -4,4'-diphthalate Dianhydride, 5,5 ′, 6,6′-tetrakis (trifluoromethyl) sulfonyl-4,4′-diphthalic dianhydride, 3,3 ′, 5,5 ′, 6,6′-hexakis ( Trifluoromethyl) sulfonyl-4,4′-diphthalic dianhydride, 3,3′-difluoro-2,2-perfluoropropylidene-4,4′-diphthalic dianhydride, 5,5′-difluoro -2,2-perfluoropropylidene-4,4'-diphthalic dianhydride, 6,6'-difluoro-2,2-perfluoropropylidene-4,4'-diphthalic dianhydride, 3, 3 ′, 5,5 ′, 6,6′-hexafluoro-2,2-perfluoropropylidene-4,4′-diphthalic dianhydride, 3,3′-bis (trifluoromethyl) -2, 2-perfluoropropylidene-4,4'-diphthalate Acid dianhydride, 5,5′-bis (trifluoromethyl) -2,2-perfluoropropylidene-4,4′-diphthalic dianhydride, 6,6′-difluoro-2,2-perfluoro Propylidene-4,4′-diphthalic dianhydride, 3,3 ′, 5,5′-tetrakis (trifluoromethyl) -2,2-perfluoropropylidene-4,4′-diphthalic dianhydride 3,3 ′, 6,6′-tetrakis (trifluoromethyl) -2,2-perfluoropropylidene-4,4′-diphthalic dianhydride, 5,5 ′, 6,6′-tetrakis ( Trifluoromethyl) -2,2-perfluoropropylidene-4,4′-diphthalic dianhydride, 3,3 ′, 5,5 ′, 6,6′-hexakis (trifluoromethyl) -2,2 -Perfluoropropylidene-4,4'-diph Talic dianhydride, 9-phenyl-9- (trifluoromethyl) xanthene-2,3,6,7-tetracarboxylic dianhydride, 9,9-bis (trifluoromethyl) xanthene-2,3 6,7-tetracarboxylic dianhydride, bicyclo [2,2,2] oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, 9,9-bis [4- (3 , 4-Dicarboxy) phenyl] fluorene dianhydride, 9,9-bis [4- (2,3-dicarboxy) phenyl] fluorene dianhydride, ethylene glycol bistrimellitic dianhydride, 1,2- ( Ethylene) bis (trimellitic anhydride), 1,3- (trimethylene) bis (trimellitic anhydride), 1,4- (tetramethylene) bis (trimellitic anhydride), 1,5- (pentamethylene) bis (trimetic anhydride) Retate anhydride), 1,6- (hexamethylene) bis (trimellitic anhydride), 1,7- (heptamethylene) bis (trimellitate anhydride), 1,8- (octamethylene) bis (trimellitic anhydride), 1,9- (nonamethylene) bis (trimellitic anhydride), 1,10- (decamethylene) bis (trimellitic anhydride), 1,12- (dodecamethylene) bis (trimellitic anhydride), 1,16- (hexadeca) Methylene) bis (trimellitate anhydride), 1,18- (octadecamethylene) bis (trimellitate anhydride), and the like.
トリカルボン酸無水物としては、例えば、トリメリット酸無水物や核水添トリメリット酸無水物などが挙げられる。 Examples of the tricarboxylic acid anhydride include trimellitic acid anhydride and nuclear hydrogenated trimellitic acid anhydride.
アミン成分としては、脂肪族ジアミンや芳香族ジアミンなどのジアミン、脂肪族ポリエーテルアミンなどの多価アミンを用いることができるが、これらのアミンに限定されるものではない。また、これらのアミン成分は、単独でまたは組み合わせて使用してもよい。 Examples of the amine component include diamines such as aliphatic diamines and aromatic diamines, and polyvalent amines such as aliphatic polyether amines, but are not limited to these amines. These amine components may be used alone or in combination.
ジアミンとしては、例えば、p−フェニレンジアミン(PPD)、1,3−ジアミノベンゼン、2,4−トルエンジアミン、2,5−トルエンジアミン、2,6−トルエンジアミンなどのベンゼン核1つのジアミン、4,4’−ジアミノジフェニルエーテル、3,3’−ジアミノジフェニルエーテル、3,4’−ジアミノジフェニルエーテルなどのジアミノジフェニルエーテル類、4,4’−ジアミノジフェニルメタン、3,3’−ジメチル−4,4’−ジアミノビフェニル、2,2’−ジメチル−4,4’−ジアミノビフェニル、2,2’−ビス(トリフルオロメチル)−4,4’−ジアミノビフェニル、3,3’−ジメチル−4,4’−ジアミノジフェニルメタン、3,3’,5,5’−テトラメチル−4,4’−ジアミノジフェニルメタン、ビス(4−アミノフェニル)スルフィド、4,4’−ジアミノベンズアニリド、3,3’−ジクロロベンジジン、3,3’−ジメチルベンジジン(o−トリジン)、2,2’−ジメチルベンジジン(m−トリジン)、3,3’−ジメトキシベンジジン、2,2’−ジメトキシベンジジン、3,3’−ジアミノジフェニルエーテル、3,4’−ジアミノジフェニルエーテル、4,4’−ジアミノジフェニルエーテル、3,3’−ジアミノジフェニルスルフィド、3,4’−ジアミノジフェニルスルフィド、4,4’−ジアミノジフェニルスルフィド、3,3’−ジアミノジフェニルスルホン、3,4’−ジアミノジフェニルスルホン、4,4’−ジアミノジフェニルスルホン、3,3’−ジアミノベンゾフェノン、3,3’−ジアミノ−4,4’−ジクロロベンゾフェノン、3,3’−ジアミノ−4,4’−ジメトキシベンゾフェノン、3,3’−ジアミノジフェニルメタン、3,4’−ジアミノジフェニルメタン、4,4’−ジアミノジフェニルメタン、2,2−ビス(3−アミノフェニル)プロパン、2,2−ビス(4−アミノフェニル)プロパン、2,2−ビス(3−アミノフェニル)−1,1,1,3,3,3−ヘキサフルオロプロパン、2,2−ビス(4−アミノフェニル)−1,1,1,3,3,3−ヘキサフルオロプロパン、3,3’−ジアミノジフェニルスルホキシド、3,4’−ジアミノジフェニルスルホキシド、4,4’−ジアミノジフェニルスルホキシド、3,3’−ジカルボキシ−4,4’−ジアミノジフェニルメタンなどのベンゼン核2つのジアミン、1,3−ビス(3−アミノフェニル)ベンゼン、1,3−ビス(4−アミノフェニル)ベンゼン、1,4−ビス(3−アミノフェニル)ベンゼン、1,4−ビス(4−アミノフェニル)ベンゼン、1,3−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、1,4−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)−4−トリフルオロメチルベンゼン、3,3’−ジアミノ−4−(4−フェニル)フェノキシベンゾフェノン、3,3’−ジアミノ−4,4’−ジ(4−フェニルフェノキシ)ベンゾフェノン、1,3−ビス(3−アミノフェニルスルフィド)ベンゼン、1,3−ビス(4−アミノフェニルスルフィド)ベンゼン、1,4−ビス(4−アミノフェニルスルフィド)ベンゼン、1,3−ビス(3−アミノフェニルスルホン)ベンゼン、1,3−ビス(4−アミノフェニルスルホン)ベンゼン、1,4−ビス(4−アミノフェニルスルホン)ベンゼン、1,3−ビス〔2−(4−アミノフェニル)イソプロピル〕ベンゼン、1,4−ビス〔2−(3−アミノフェニル)イソプロピル〕ベンゼン、1,4−ビス〔2−(4−アミノフェニル)イソプロピル〕ベンゼンなどのベンゼン核3つのジアミン、3,3’−ビス(3−アミノフェノキシ)ビフェニル、3,3’−ビス(4−アミノフェノキシ)ビフェニル、4,4’−ビス(3−アミノフェノキシ)ビフェニル、4,4’−ビス(4−アミノフェノキシ)ビフェニル、ビス〔3−(3−アミノフェノキシ)フェニル〕エーテル、ビス〔3−(4−アミノフェノキシ)フェニル〕エーテル、ビス〔4−(3−アミノフェノキシ)フェニル〕エーテル、ビス〔4−(4−アミノフェノキシ)フェニル〕エーテル、ビス〔3−(3−アミノフェノキシ)フェニル〕ケトン、ビス〔3−(4−アミノフェノキシ)フェニル〕ケトン、ビス〔4−(3−アミノフェノキシ)フェニル〕ケトン、ビス〔4−(4−アミノフェノキシ)フェニル〕ケトン、ビス〔3−(3−アミノフェノキシ)フェニル〕スルフィド、ビス〔3−(4−アミノフェノキシ)フェニル〕スルフィド、ビス〔4−(3−アミノフェノキシ)フェニル〕スルフィド、ビス〔4−(4−アミノフェノキシ)フェニル〕スルフィド、ビス〔3−(3−アミノフェノキシ)フェニル〕スルホン、ビス〔3−(4−アミノフェノキシ)フェニル〕スルホン、ビス〔4−(3−アミノフェノキシ)フェニル〕スルホン、ビス〔4−(4−アミノフェノキシ)フェニル〕スルホン、ビス〔3−(3−アミノフェノキシ)フェニル〕メタン、ビス〔3−(4−アミノフェノキシ)フェニル〕メタン、ビス〔4−(3−アミノフェノキシ)フェニル〕メタン、ビス〔4−(4−アミノフェノキシ)フェニル〕メタン、2,2−ビス〔3−(3−アミノフェノキシ)フェニル〕プロパン、2,2−ビス〔3−(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〕プロパン、2,2−ビス〔3−(3−アミノフェノキシ)フェニル〕−1,1,1,3,3,3−ヘキサフルオロプロパン、2,2−ビス〔3−(4−アミノフェノキシ)フェニル〕−1,1,1,3,3,3−ヘキサフルオロプロパン、2,2−ビス〔4−(3−アミノフェノキシ)フェニル〕−1,1,1,3,3,3−ヘキサフルオロプロパン、2,2−ビス〔4−(4−アミノフェノキシ)フェニル〕−1,1,1,3,3,3−ヘキサフルオロプロパンなどのベンゼン核4つのジアミンなどの芳香族ジアミン、1,2−ジアミノエタン、1,3−ジアミノプロパン、1,4−ジアミノブタン、1,5−ジアミノペンタン、1,6−ジアミノヘキサン、1,7−ジアミノヘプタン、1,8−ジアミノオクタン、1,9−ジアミノノナン、1,10−ジアミノデカン、1,11−ジアミノウンデカン、1,12−ジアミノドデカン、1,2−ジアミノシクロヘキサン等の脂肪族ジアミンが挙げられ、脂肪族ポリエーテルアミンとしては、エチレングリコール及び/又はプロピレングリコール系の多価アミン等が挙げられる。また、下記の様に、カルボキシル基を有するアミンを用いることもできる。カルボキシル基を有するアミンとしては、3,5−ジアミノ安息香酸、2,5−ジアミノ安息香酸、3,4−ジアミノ安息香酸等のジアミノ安息香酸類、3,5−ビス(3−アミノフェノキシ)安息香酸、3,5−ビス(4−アミノフェノキシ)安息香酸等のアミノフェノキシ安息香酸類、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、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]スルフォン化合物等を挙げることができる。 Examples of the diamine include one diamine nucleus diamine such as p-phenylenediamine (PPD), 1,3-diaminobenzene, 2,4-toluenediamine, 2,5-toluenediamine, and 2,6-toluenediamine. , 4′-diaminodiphenyl ether, 3,3′-diaminodiphenyl ether, diaminodiphenyl ethers such as 3,4′-diaminodiphenyl ether, 4,4′-diaminodiphenylmethane, 3,3′-dimethyl-4,4′-diaminobiphenyl 2,2′-dimethyl-4,4′-diaminobiphenyl, 2,2′-bis (trifluoromethyl) -4,4′-diaminobiphenyl, 3,3′-dimethyl-4,4′-diaminodiphenylmethane 3,3 ′, 5,5′-tetramethyl-4,4′-diaminodiphenylme , Bis (4-aminophenyl) sulfide, 4,4′-diaminobenzanilide, 3,3′-dichlorobenzidine, 3,3′-dimethylbenzidine (o-tolidine), 2,2′-dimethylbenzidine (m -Toridine), 3,3'-dimethoxybenzidine, 2,2'-dimethoxybenzidine, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,3'-diamino Diphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 3, 3'-diaminobenzophenone, 3,3'-diamino- , 4′-dichlorobenzophenone, 3,3′-diamino-4,4′-dimethoxybenzophenone, 3,3′-diaminodiphenylmethane, 3,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylmethane, 2,2- Bis (3-aminophenyl) propane, 2,2-bis (4-aminophenyl) propane, 2,2-bis (3-aminophenyl) -1,1,1,3,3,3-hexafluoropropane, 2,2-bis (4-aminophenyl) -1,1,1,3,3,3-hexafluoropropane, 3,3′-diaminodiphenyl sulfoxide, 3,4′-diaminodiphenyl sulfoxide, 4,4 ′ -Two diamine diamines such as diaminodiphenyl sulfoxide, 3,3'-dicarboxy-4,4'-diaminodiphenylmethane 1,3-bis (3-aminophenyl) benzene, 1,3-bis (4-aminophenyl) benzene, 1,4-bis (3-aminophenyl) benzene, 1,4-bis (4-aminophenyl) ) Benzene, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (3-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (3- Aminophenoxy) -4-trifluoromethylbenzene, 3,3′-diamino-4- (4-phenyl) phenoxybenzophenone, 3,3′-diamino-4,4′-di (4-phenylphenoxy) benzophenone, 1 , 3-bis (3-aminophenyl sulfide) benzene, 1,3-bis (4-aminophenyl sulfide) benzene, 1,4-bis (4-aminophenyl) Rufido) benzene, 1,3-bis (3-aminophenylsulfone) benzene, 1,3-bis (4-aminophenylsulfone) benzene, 1,4-bis (4-aminophenylsulfone) benzene, 1,3- Bis [2- (4-aminophenyl) isopropyl] benzene, 1,4-bis [2- (3-aminophenyl) isopropyl] benzene, 1,4-bis [2- (4-aminophenyl) isopropyl] benzene, etc. Benzene nucleus of three diamines, 3,3′-bis (3-aminophenoxy) biphenyl, 3,3′-bis (4-aminophenoxy) biphenyl, 4,4′-bis (3-aminophenoxy) biphenyl, 4 , 4′-bis (4-aminophenoxy) biphenyl, bis [3- (3-aminophenoxy) phenyl] ether, bis [3- ( -Aminophenoxy) phenyl] ether, bis [4- (3-aminophenoxy) phenyl] ether, bis [4- (4-aminophenoxy) phenyl] ether, bis [3- (3-aminophenoxy) phenyl] ketone, Bis [3- (4-aminophenoxy) phenyl] ketone, bis [4- (3-aminophenoxy) phenyl] ketone, bis [4- (4-aminophenoxy) phenyl] ketone, bis [3- (3-amino Phenoxy) phenyl] sulfide, bis [3- (4-aminophenoxy) phenyl] sulfide, bis [4- (3-aminophenoxy) phenyl] sulfide, bis [4- (4-aminophenoxy) phenyl] sulfide, bis [ 3- (3-aminophenoxy) phenyl] sulfone, bis [3- (4-aminophenoxy) ) Phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [3- (3-aminophenoxy) phenyl] methane, bis [3 -(4-aminophenoxy) phenyl] methane, bis [4- (3-aminophenoxy) phenyl] methane, bis [4- (4-aminophenoxy) phenyl] methane, 2,2-bis [3- (3- Aminophenoxy) phenyl] propane, 2,2-bis [3- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (3-aminophenoxy) phenyl] propane, 2,2-bis [4 -(4-aminophenoxy) phenyl] propane, 2,2-bis [3- (3-aminophenoxy) phenyl] -1,1,1,3,3,3-he Safluoropropane, 2,2-bis [3- (4-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, 2,2-bis [4- (3-aminophenoxy) ) Phenyl] -1,1,1,3,3,3-hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl] -1,1,1,3,3,3-hexa Aromatic diamines such as four diamines of benzene nucleus such as fluoropropane, 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane, 1 It includes aliphatic diamines of 2-diaminocyclohexane, etc., the aliphatic polyether amines, polyvalent amines ethylene glycol and / or propylene glycol and the like. Moreover, the amine which has a carboxyl group can also be used as follows. Examples of the amine having a carboxyl group include 3,5-diaminobenzoic acid, 2,5-diaminobenzoic acid, diaminobenzoic acids such as 3,4-diaminobenzoic acid, and 3,5-bis (3-aminophenoxy) benzoic acid. Aminophenoxybenzoic acids such as 3,5-bis (4-aminophenoxy) benzoic acid, 3,3′-diamino-4,4′-dicarboxybiphenyl, 4,4′-diamino-3,3′-di Carboxybiphenyl compounds such as carboxybiphenyl, 4,4′-diamino-2,2′-dicarboxybiphenyl, 4,4′-diamino-2,2 ′, 5,5′-tetracarboxybiphenyl, 3,3 ′ -Diamino-4,4'-dicarboxydiphenylmethane, 3,3'-dicarboxy-4,4'-diaminodiphenylmethane, 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- Carboxydiphenylalkanes such as carboxydiphenylmethane such as 2,2 ′, 5,5′-tetracarboxydiphenylmethane, 3,3′-diamino-4,4′-dicarboxydiphenyl ether, 4,4′-diamino-3,3 Carboxydiphenyl ether compounds such as '-dicarboxydiphenyl ether, 4,4'-diamino-2,2'-dicarboxydiphenyl ether, 4,4'-diamino-2,2', 5,5'-tetracarboxydiphenyl ether, 3, 3'-diamino-4,4'-dicarboxydiphenylsulfur 4,4′-diamino-3,3′-dicarboxydiphenyl sulfone, 4,4′-diamino-2,2′-dicarboxydiphenyl sulfone, 4,4′-diamino-2,2 ′, 5 Diphenyl sulfone compounds such as 5′-tetracarboxydiphenyl sulfone, bis [(carboxyphenyl) phenyl] alkane compounds such as 2,2-bis [4- (4-amino-3-carboxyphenoxy) phenyl] propane, 2, Examples thereof include bis [(carboxyphenoxy) phenyl] sulfone compounds such as 2-bis [4- (4-amino-3-carboxyphenoxy) phenyl] sulfone.
イソシアネート成分としては、芳香族ジイソシアネート及びその異性体や多量体、脂肪族ジイソシアネート類、脂環式ジイソシアネート類及びその異性体などのジイソシアネートやその他汎用のジイソシアネート類を用いることができるが、これらのイソシアネートに限定されるものではない。また、これらのイソシアネート成分は、単独でまたは組み合わせて使用してもよい。
ジイソシアネートとして、例えば4,4’−ジフェニルメタンジイソシアネート、トリレンジイソシアネート、ナフタレンジイソシアネート、キシリレンジイソシアネート、ビフェニルジイソシアネート、ジフェニルスルホンジイソシアネート、ジフェニルエーテルジイソシアネートなどの芳香族ジイソシアネート及びその異性体、多量体、ヘキサメチレンジイソシアネート、イソホロンジイソシアネート、ジシクロヘキシルメタンジイソシアネートなどの脂肪族ジイソシアネート類、あるいは前記芳香族ジイソシアネートを水添した脂環式ジイソシアネート類及び異性体、もしくはその他汎用のジイソシアネート類が挙げられる。
Diisocyanates such as aromatic diisocyanates and isomers and multimers, aliphatic diisocyanates, alicyclic diisocyanates and isomers thereof, and other general-purpose diisocyanates can be used as the isocyanate component. It is not limited. These isocyanate components may be used alone or in combination.
Examples of diisocyanates include aromatic diisocyanates such as 4,4′-diphenylmethane diisocyanate, tolylene diisocyanate, naphthalene diisocyanate, xylylene diisocyanate, biphenyl diisocyanate, diphenyl sulfone diisocyanate, diphenyl ether diisocyanate, and isomers, multimers, hexamethylene diisocyanate, isophorone. Aliphatic diisocyanates such as diisocyanate and dicyclohexylmethane diisocyanate, alicyclic diisocyanates and isomers obtained by hydrogenation of the aromatic diisocyanate, or other general-purpose diisocyanates can be mentioned.
(A)成分であるポリイミド樹脂はアミド結合を有していてもよい。これはイソシアネートとカルボン酸を反応させて得られるアミド結合であってもよく、それ以外の反応によるものでもよい。さらにその他の付加および縮合からなる結合を有していてもよい。 The polyimide resin as component (A) may have an amide bond. This may be an amide bond obtained by reacting an isocyanate and a carboxylic acid, or may be caused by other reaction. Furthermore, you may have the coupling | bonding which consists of another addition and condensation.
(A)成分であるポリイミド樹脂の合成には、公知慣用のカルボキシル基及び/又は酸無水物基を有するアルカリ溶解性ポリマー、オリゴマー、モノマーを用いてもよく、例えばこれらの公知慣用のアルカリ溶解性樹脂類を単独でもしくは上記のカルボン酸無水物成分と組み合わせて、上記のアミン/イソシアネート類と反応させて得られる樹脂であってもよい。 For the synthesis of the polyimide resin as the component (A), a publicly known and commonly used alkali-soluble polymer, oligomer or monomer having a carboxyl group and / or an acid anhydride group may be used. Resins obtained by reacting with the above amines / isocyanates alone or in combination with the above carboxylic anhydride component may also be used.
(A)成分であるポリイミド樹脂は、アルカリ現像工程に対応するために、その酸価が20〜200mgKOH/gであることが好ましく、より好適には60〜150mgKOH/gであることが好ましい。この酸価が20mgKOH/g以上の場合、アルカリに対する溶解性が増加し、現像性が良好となり、さらには、光照射後の熱硬化成分との架橋度が高くなるため、十分な現像コントラストを得ることができる。また、この酸価が200mgKOH/g以下の場合には、後述する光照射後のPEB(POST EXPOSURE BAKE)工程でのいわゆる熱かぶりを抑制でき、プロセスマージンが大きくなる。 The polyimide resin as component (A) preferably has an acid value of 20 to 200 mgKOH / g, more preferably 60 to 150 mgKOH / g in order to correspond to the alkali development step. When the acid value is 20 mgKOH / g or more, the solubility in alkali increases, the developability becomes good, and further, the degree of crosslinking with the thermosetting component after light irradiation becomes high, so that sufficient development contrast is obtained. be able to. When the acid value is 200 mgKOH / g or less, so-called heat fogging in a PEB (POST EXPOSURE BAKE) step after light irradiation described later can be suppressed, and the process margin is increased.
また、(A)成分であるポリイミド樹脂の分子量は、現像性と硬化塗膜特性を考慮すると、質量平均分子量1,000〜100,000が好ましく、さらに2,000〜50,000がより好ましい。
この分子量が1,000以上の場合、露光・PEB後に十分な耐現像性と硬化物性を得ることができる。また、分子量が100,000以下の場合、アルカリ溶解性が増加し、現像性が向上する。
The molecular weight of the polyimide resin as component (A) is preferably 1,000 to 100,000, more preferably 2,000 to 50,000, considering developability and cured coating film characteristics.
When the molecular weight is 1,000 or more, sufficient development resistance and cured properties can be obtained after exposure and PEB. On the other hand, when the molecular weight is 100,000 or less, alkali solubility increases and developability improves.
[(B)フェノール性水酸基を有する樹脂]
(B)フェノール性水酸基を有する樹脂としては、主鎖もしくは側鎖にフェノール性水酸基、即ちベンゼン環に結合した水酸基を有していれば特に制限されない。フェノール性水酸基もカルボキシル基と同様、熱硬化成分と付加反応することができる。
好ましくは1分子中に2個以上のフェノール性水酸基を有する化合物である。
1分子中に2個以上のフェノール性水酸基を有する化合物としては、ノボラック型フェノール樹脂、ノボラック型アルキルフェノール樹脂、ビスフェノールAのノボラック樹脂、ジシクロペンタジエン型フェノール樹脂、ザイロック(Xylok)型フェノール樹脂、テルペン変性フェノール樹脂、ポリビニルフェノール類、フェノール類とフェノール性水酸基を有する芳香族アルデヒドとの縮合物、1−ナフトール又は2−ナフトールと芳香族アルデヒド類との縮合物などを挙げることができるが、これらに限られるものではない。これらのフェノール性水酸基含有化合物は、単独で又は2種類以上を混合して用いることができる。
[(B) Resin having phenolic hydroxyl group]
(B) The resin having a phenolic hydroxyl group is not particularly limited as long as it has a phenolic hydroxyl group in the main chain or side chain, that is, a hydroxyl group bonded to a benzene ring. Similarly to the carboxyl group, the phenolic hydroxyl group can undergo an addition reaction with the thermosetting component.
Preferably, it is a compound having two or more phenolic hydroxyl groups in one molecule.
Examples of compounds having two or more phenolic hydroxyl groups in one molecule include novolak-type phenol resins, novolak-type alkylphenol resins, bisphenol A novolak resins, dicyclopentadiene-type phenol resins, xylok-type phenol resins, and terpene-modified. Examples thereof include phenol resins, polyvinylphenols, condensates of phenols and aromatic aldehydes having a phenolic hydroxyl group, 1-naphthol or condensates of 2-naphthol and aromatic aldehydes. Is not something These phenolic hydroxyl group-containing compounds can be used alone or in admixture of two or more.
(B)成分である樹脂としては、イミド環を有するものが好ましい。イミド環は上記したものと同様のものを挙げることができる。イミド環、フェノール性水酸基を有する樹脂としては、例えば、上記のようなカルボン酸無水物に対して、フェノール性水酸基を有するジアミンを用いて合成したポリイミド樹脂が好ましい。フェノール性水酸基を有するジアミンとしては、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、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等のカルボキシジフェニルアルカン類、4,4’−ジアミノ−2,2’−ジハイドロキシジフェニルメタン、4,4’−ビス(4−アミノ−3−ヒドロキシフェノキシ)ビフェニル等のビス(ヒドロキシフェノキシ)ビフェニル化合物類、1,3−ビス(3−アミノ−4−ヒドロキシフェノキシ)ベンゼン、1,3−ビス(4−アミノ−3−ヒドロキシフェノキシ)ベンゼン等のビス(ヒドロキシフェノキシ)ベンゼン化合物類等が挙げられる。
フェノール性水酸基を有する樹脂の分子量は、露光・PEB後の現像性、耐現像性および硬化塗膜特性を考慮すると、質量平均分子量1,000〜100,000が好ましく、さらに2,000〜50,000がより好ましい。
As resin which is (B) component, what has an imide ring is preferable. Examples of the imide ring are the same as those described above. As the resin having an imide ring and a phenolic hydroxyl group, for example, a polyimide resin synthesized using a diamine having a phenolic hydroxyl group with respect to the carboxylic acid anhydride as described above is preferable. Examples of the diamine having a phenolic hydroxyl group include diaminophenols such as 2,4-diaminophenol, 3,3′-diamino-4,4′-dihydroxybiphenyl, 4,4′-diamino-3,3′-. Hydroxybiphenyl compounds such as dihydroxybiphenyl, 4,4′-diamino-2,2′-dihydroxybiphenyl, 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-hydroxyphenyl] hexafluoropropane, hydroxydiphenylalkanes such as hydroxydiphenylmethane such as 4,4′-diamino-2,2 ′, 5,5′-tetrahydroxydiphenylmethane, 3,3′-diamino-4 , 4′-dihydroxydiphenyl ether, 4,4′-diamino-3,3′-dihydroxydiphenyl ether, 4,4′-diamino-2,2′-dihydroxydiphenyl ether, 4,4′-diamino-2,2 ′, 5 , 5′-tetrahydroxydiphenyl ether, etc., 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 -Bis [(hydroxyphenoxy) phenyl] sulfone compounds such as amino-3-hydroxyphenoxy) phenyl] sulfone, 4,4′-diamino-3,3′-dihydroxydiphenylmethane, 4,4′-diamino-2,2 Carboxydiphenylalkanes such as '-dihydroxydiphenylmethane, 4,4'-diamino-2,2' Bis (hydroxyphenoxy) biphenyl compounds such as dihydroxydiphenylmethane, 4,4′-bis (4-amino-3-hydroxyphenoxy) biphenyl, 1,3-bis (3-amino-4-hydroxyphenoxy) benzene, 1 Bis (hydroxyphenoxy) benzene compounds such as 3-bis (4-amino-3-hydroxyphenoxy) benzene.
The molecular weight of the resin having a phenolic hydroxyl group is preferably a mass average molecular weight of 1,000 to 100,000, more preferably 2,000 to 50, in consideration of developability after exposure and PEB, development resistance and cured coating film properties. 000 is more preferable.
[(C)光塩基発生剤]
(C)光塩基発生剤は、紫外線や可視光等の光照射により分子構造が変化するか、または、分子が開裂することにより、カルボキシル基を有するポリイミド樹脂と熱硬化成分との付加反応の触媒として機能しうる1種以上の塩基性物質を生成する化合物である。塩基性物質として、例えば2級アミン、3級アミンが挙げられる。
光塩基発生剤として、例えば、α−アミノアセトフェノン化合物、オキシムエステル化合物や、アシルオキシイミノ基,N−ホルミル化芳香族アミノ基、N−アシル化芳香族アミノ基、ニトロベンジルカーバメイト基、アルコオキシベンジルカーバメート基等の置換基を有する化合物等が挙げられる。なかでも、オキシムエステル化合物、α−アミノアセトフェノン化合物が好ましい。α−アミノアセトフェノン化合物としては、特に、2つ以上の窒素原子を有するものが好ましい。
[(C) Photobase generator]
(C) The photobase generator is a catalyst for an addition reaction between a polyimide resin having a carboxyl group and a thermosetting component by changing the molecular structure upon irradiation with light such as ultraviolet light or visible light, or by cleaving the molecule. Is a compound that produces one or more basic substances that can function as Examples of basic substances include secondary amines and tertiary amines.
Examples of photobase generators include α-aminoacetophenone compounds, oxime ester compounds, acyloxyimino groups, N-formylated aromatic amino groups, N-acylated aromatic amino groups, nitrobenzyl carbamate groups, and alkoxyoxybenzyl carbamates. And compounds having a substituent such as a group. Of these, oxime ester compounds and α-aminoacetophenone compounds are preferred. As the α-aminoacetophenone compound, those having two or more nitrogen atoms are particularly preferable.
その他の光塩基発生剤として、WPBG-018(商品名:9-anthrylmethylN,N’-diethylcarbamate),WPBG-027(商品名:(E)-1-[3-(2-hydroxyphenyl)-2-propenoyl]piperidine),WPBG-082(商品名:guanidinium2-(3-benzoylphenyl)propionate), WPBG-140 (商品名:1-(anthraquinon-2-yl)ethyl imidazolecarboxylate)等を使用することもできる。 Other photobase generators include WPBG-018 (trade name: 9-anthrylmethylN, N'-diethylcarbamate), WPBG-027 (trade name: (E) -1- [3- (2-hydroxyphenyl) -2-propenoyl ] piperidine), WPBG-082 (trade name: guanidinium2- (3-benzoylphenyl) propionate), WPBG-140 (trade name: 1- (anthraquinon-2-yl) ethyl imidazolecarboxylate), and the like can also be used.
α―アミノアセトフェノン化合物は、分子中にベンゾインエーテル結合を有し、光照射を受けると分子内で開裂が起こり、硬化触媒作用を奏する塩基性物質(アミン)が生成する。α−アミノアセトフェノン化合物の具体例としては、(4−モルホリノベンゾイル)−1−ベンジル−1−ジメチルアミノプロパン(イルガキュア369、商品名、BASFジャパン社製)や4−(メチルチオベンゾイル)−1−メチル−1−モルホリノエタン(イルガキュア907、商品名、BASFジャパン社製)、2−(ジメチルアミノ)−2−[(4−メチルフェニル)メチル]−1−[4−(4−モルホリニル)フェニル]−1−ブタノン(イルガキュア379、商品名、BASFジャパン社製)などの市販の化合物またはその溶液を用いることができる。 The α-aminoacetophenone compound has a benzoin ether bond in the molecule, and when irradiated with light, cleavage occurs in the molecule to produce a basic substance (amine) that exhibits a curing catalytic action. Specific examples of the α-aminoacetophenone compound include (4-morpholinobenzoyl) -1-benzyl-1-dimethylaminopropane (Irgacure 369, trade name, manufactured by BASF Japan Ltd.) and 4- (methylthiobenzoyl) -1-methyl. -1-morpholinoethane (Irgacure 907, trade name, manufactured by BASF Japan Ltd.), 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl]- A commercially available compound such as 1-butanone (Irgacure 379, trade name, manufactured by BASF Japan Ltd.) or a solution thereof can be used.
オキシムエステル化合物としては、光照射により塩基性物質を生成する化合物であればいずれをも使用することができる。かかるオキシムエステル化合物としては、市販品として、BASFジャパン社製のCGI−325、イルガキュアーOXE01、イルガキュアーOXE02、アデカ社製N−1919、NCI−831などが挙げられる。また、特許第4344400号公報に記載された、分子内に2個のオキシムエステル基を有する化合物も好適に用いることができる。 Any oxime ester compound can be used as long as it is a compound that generates a basic substance by light irradiation. Examples of such oxime ester compounds include CGI-325, Irgacure OXE01, Irgacure OXE02 manufactured by BASF Japan, N-1919, and NCI-831 manufactured by Adeka. Moreover, the compound which has two oxime ester groups in the molecule | numerator described in the patent 4344400 gazette can also be used suitably.
その他、特開2004−359639号公報、特開2005−097141号公報、特開2005−220097号公報、特開2006−160634号公報、特開2008−094770号公報、特表2008−509967号公報、特表2009−040762号公報、特開2011−80036号公報記載のカルバゾールオキシムエステル化合物等を挙げることができる。 In addition, JP-A-2004-359639, JP-A-2005-097141, JP-A-2005-220097, JP-A-2006-160634, JP-A-2008-094770, JP-A-2008-509967, Specific examples include carbazole oxime ester compounds described in JP2009-040762A and JP2011-80036A.
このような光塩基発生剤は、1種を単独で用いてもよく、2種以上を組み合わせて用いてもよい。アルカリ現像型熱硬化性樹脂組成物中の光塩基発生剤の配合量は、好ましくは熱硬化成分100質量部に対して0.1〜40質量部であり、さらに好ましくは、0.1〜30質量部である。0.1質量部以上の場合、光照射部/未照射部の耐現像性のコントラストを良好に得ることができる。また、40質量部以下の場合、硬化物特性が向上する。 Such a photobase generator may be used individually by 1 type, and may be used in combination of 2 or more type. The blending amount of the photobase generator in the alkali development type thermosetting resin composition is preferably 0.1 to 40 parts by mass, more preferably 0.1 to 30 parts by mass with respect to 100 parts by mass of the thermosetting component. Part by mass. In the case of 0.1 part by mass or more, the development resistance contrast of the light irradiated part / non-irradiated part can be obtained satisfactorily. Moreover, in 40 mass parts or less, hardened | cured material characteristic improves.
[(D)熱硬化成分]
(D)熱硬化成分は、熱によって、カルボキシル基もしくはフェノール性水酸基と付加反応が可能な官能基を有するものである。熱硬化成分としては、例えば、環状(チオ)エーテル基を有する化合物が好ましく、エポキシ樹脂、多官能オキセタン化合物等が挙げられる。
[(D) Thermosetting component]
(D) The thermosetting component has a functional group capable of addition reaction with a carboxyl group or a phenolic hydroxyl group by heat. As the thermosetting component, for example, a compound having a cyclic (thio) ether group is preferable, and examples thereof include an epoxy resin and a polyfunctional oxetane compound.
上記エポキシ樹脂は、エポキシ基を有する樹脂であり、公知のものをいずれも使用できる。分子中にエポキシ基を2個有する2官能性エポキシ樹脂、分子中にエポキシ基を多数有する多官能エポキシ樹脂等が挙げられる。なお、水素添加された2官能エポキシ化合物であってもよい。 The epoxy resin is a resin having an epoxy group, and any known one can be used. Examples thereof include a bifunctional epoxy resin having two epoxy groups in the molecule, and a polyfunctional epoxy resin having many epoxy groups in the molecule. In addition, a hydrogenated bifunctional epoxy compound may be used.
多官能エポキシ化合物としては、ビスフェノールA型エポキシ樹脂、ブロム化エポキシ樹脂、ノボラック型エポキシ樹脂、ビスフェノールF型エポキシ樹脂、水添ビスフェノールA型エポキシ樹脂、グリシジルアミン型エポキシ樹脂、ヒダントイン型エポキシ樹脂、脂環式エポキシ樹脂、トリヒドロキシフェニルメタン型エポキシ樹脂、ビキシレノール型もしくはビフェノール型エポキシ樹脂又はそれらの混合物;ビスフェノールS型エポキシ樹脂、ビスフェノールAノボラック型エポキシ樹脂、テトラフェニロールエタン型エポキシ樹脂、複素環式エポキシ樹脂、ジグリシジルフタレート樹脂、テトラグリシジルキシレノイルエタン樹脂、ナフタレン基含有エポキシ樹脂、ジシクロペンタジエン骨格を有するエポキシ樹脂、グリシジルメタアクリレート共重合系エポキシ樹脂、シクロヘキシルマレイミドとグリシジルメタアクリレートの共重合エポキシ樹脂、CTBN変性エポキシ樹脂等が挙げられる。 Polyfunctional epoxy compounds include bisphenol A type epoxy resin, brominated epoxy resin, novolac type epoxy resin, bisphenol F type epoxy resin, hydrogenated bisphenol A type epoxy resin, glycidylamine type epoxy resin, hydantoin type epoxy resin, alicyclic ring Epoxy resin, trihydroxyphenylmethane type epoxy resin, bixylenol type or biphenol type epoxy resin or a mixture thereof; bisphenol S type epoxy resin, bisphenol A novolak type epoxy resin, tetraphenylolethane type epoxy resin, heterocyclic epoxy Resin, diglycidyl phthalate resin, tetraglycidyl xylenoyl ethane resin, naphthalene group-containing epoxy resin, epoxy resin having dicyclopentadiene skeleton, glycidyl meta Acrylate copolymer epoxy resins, copolymerized epoxy resins of cyclohexylmaleimide and glycidyl methacrylate, and a CTBN modified epoxy resin.
その他の液状2官能性エポキシ樹脂としては、ビニルシクロヘキセンジエポキシド、(3’,4’−エポキシシクロヘキシルメチル)−3,4−エポキシシクロヘキサンカルボキシレート、(3’,4’−エポキシ−6’−メチルシクロヘキシルメチル)−3,4−エポキシ−6−メチルシクロヘキサンカルボキシレート等の脂環族エポキシ樹脂を挙げることができる。これらのエポキシ樹脂は、1種を単独で用いてもよく、2種以上を併用してもよい。 Other liquid bifunctional epoxy resins include vinylcyclohexene diepoxide, (3 ′, 4′-epoxycyclohexylmethyl) -3,4-epoxycyclohexanecarboxylate, and (3 ′, 4′-epoxy-6′-methyl). And alicyclic epoxy resins such as (cyclohexylmethyl) -3,4-epoxy-6-methylcyclohexanecarboxylate. These epoxy resins may be used individually by 1 type, and may use 2 or more types together.
なお、(D)熱硬化成分として、マレイミド化合物、ブロックイソシアネート化合物、アミノ樹脂、ベンゾオキサジン樹脂、カルボジイミド樹脂、シクロカーボネート化合物、エピスルフィド樹脂などの公知慣用の化合物を配合してもよい。 In addition, you may mix | blend well-known and usual compounds, such as a maleimide compound, a block isocyanate compound, an amino resin, a benzoxazine resin, a carbodiimide resin, a cyclocarbonate compound, an episulfide resin, as (D) thermosetting component.
(D)熱硬化成分の配合量としては、(A)成分であるポリイミド樹脂との当量比(カルボキシル基:エポキシ基などの熱反応性基)が1:0.1〜1:10であることが好ましい。このような配合比の範囲とすることにより、現像性が良好となり、容易に微細パターンを形成できる。上記当量比は、1:0.2〜1:5であることがさらに好ましい。 (D) As a compounding quantity of a thermosetting component, equivalence ratio (a carboxyl group: thermoreactive groups, such as an epoxy group) with the polyimide resin which is (A) component is 1: 0.1-1: 10. Is preferred. By making it the range of such a mixture ratio, developability becomes favorable and a fine pattern can be formed easily. The equivalent ratio is more preferably 1: 0.2 to 1: 5.
本発明の第二の感光性熱硬化性樹脂組成物は、(E)イミド環、フェノール性水酸基およびカルボキシル基を有するポリイミド樹脂、(C)光塩基発生剤、および、(D)熱硬化成分、を含むことを特徴とする。即ち、本発明においてカルボキシル基とフェノール性水酸基が同一の樹脂上に存在していてもよい。 The second photosensitive thermosetting resin composition of the present invention comprises (E) a polyimide resin having an imide ring, a phenolic hydroxyl group and a carboxyl group, (C) a photobase generator, and (D) a thermosetting component. It is characterized by including. That is, in the present invention, the carboxyl group and the phenolic hydroxyl group may be present on the same resin.
[(E)イミド環、フェノール性水酸基およびカルボキシル基を有するポリイミド樹脂]
(E)成分は、イミド環、フェノール性水酸基およびカルボキシル基を有するポリイミド樹脂である。具体的には、上記(A)成分であるポリイミド樹脂に、フェノール性水酸基が導入されたものを挙げることができる。例えば、ポリイミド樹脂を合成する際に、原料として、カルボキシル基の他、フェノール性水酸基を有するアミン成分やイソシアネート成分を用いることによって(E)成分を得ることができる。
(E)成分であるポリイミド樹脂の分子量は、露光・PEB後の現像性、耐現像性および硬化塗膜特性を考慮すると、質量平均分子量1,000〜100,000が好ましく、さらに2,000〜50,000がより好ましい。
[(E) Polyimide resin having imide ring, phenolic hydroxyl group and carboxyl group]
The component (E) is a polyimide resin having an imide ring, a phenolic hydroxyl group and a carboxyl group. Specific examples include those obtained by introducing a phenolic hydroxyl group into the polyimide resin as the component (A). For example, when synthesizing a polyimide resin, the component (E) can be obtained by using an amine component or an isocyanate component having a phenolic hydroxyl group in addition to a carboxyl group as a raw material.
The molecular weight of the polyimide resin as the component (E) is preferably a mass average molecular weight of 1,000 to 100,000, more preferably 2,000 to 10,000, considering developability after exposure / PEB, development resistance and cured coating film characteristics. 50,000 is more preferable.
(高分子樹脂)
本発明の感光性熱硬化性樹脂組成物には、得られる硬化物の可撓性、指触乾燥性の向上を目的に慣用公知の高分子樹脂を配合することができる。高分子樹脂としてはセルロース系、ポリエステル系、フェノキシ樹脂系ポリマー、ポリビニルアセタール系、ポリビニルブチラール系、ポリアミド系、ポリアミドイミド系バインダーポリマー、ブロック共重合体、エラストマー等が挙げられる。上記高分子樹脂は1種類を単独で用いてもよく、2種類以上を併用してもよい。
(Polymer resin)
The photosensitive thermosetting resin composition of the present invention can be blended with conventionally known polymer resins for the purpose of improving the flexibility and dryness of the touch of the resulting cured product. Examples of the polymer resin include cellulose, polyester, phenoxy resin, polyvinyl acetal, polyvinyl butyral, polyamide, polyamideimide binder polymer, block copolymer, elastomer and the like. The above polymer resins may be used alone or in combination of two or more.
(無機充填剤)
本発明の感光性熱硬化性樹脂組成物には、無機充填剤を配合することができる。無機充填剤は、感光性熱硬化性樹脂組成物の硬化物の硬化収縮を抑制し、密着性、硬度などの特性を向上させるために使用される。無機充填剤としては、例えば、硫酸バリウム、無定形シリカ、溶融シリカ、球状シリカ、タルク、クレー、炭酸マグネシウム、炭酸カルシウム、酸化アルミニウム、水酸化アルミニウム、窒化ケイ素、窒化アルミニウム、窒化ホウ素、ノイブルグシリシャスアース等が挙げられる。上記無機充填剤は1種類を単独で用いてもよく、2種類以上を併用してもよい。
(Inorganic filler)
An inorganic filler can be blended in the photosensitive thermosetting resin composition of the present invention. An inorganic filler is used in order to suppress the curing shrinkage of the cured product of the photosensitive thermosetting resin composition and to improve properties such as adhesion and hardness. Examples of the inorganic filler include barium sulfate, amorphous silica, fused silica, spherical silica, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, silicon nitride, aluminum nitride, boron nitride, and Neuburg Examples include rich earth. The said inorganic filler may be used individually by 1 type, and may use 2 or more types together.
(着色剤)
さらに、本発明の感光性熱硬化性樹脂組成物には、着色剤を配合することができる。着色剤としては、赤、青、緑、黄、白、黒などの慣用公知の着色剤を使用することができ、顔料、染料、色素のいずれでもよい。
(Coloring agent)
Furthermore, a coloring agent can be mix | blended with the photosensitive thermosetting resin composition of this invention. As the colorant, conventionally known colorants such as red, blue, green, yellow, white, and black can be used, and any of pigments, dyes, and pigments may be used.
(有機溶剤)
本発明の感光性熱硬化性樹脂組成物には、樹脂組成物の調製のためや、基材やキャリアフィルムに塗布するための粘度調整のために、有機溶剤を使用することができる。
このような有機溶剤としては、ケトン類、芳香族炭化水素類、グリコールエーテル類、グリコールエーテルアセテート類、エステル類、アルコール類、脂肪族炭化水素、石油系溶剤などを挙げることができる。このような有機溶剤は、1種を単独で用いてもよく、2種以上の混合物として用いてもよい。
(Organic solvent)
In the photosensitive thermosetting resin composition of the present invention, an organic solvent can be used for preparing the resin composition and adjusting the viscosity for application to a substrate or a carrier film.
Examples of such organic solvents include ketones, aromatic hydrocarbons, glycol ethers, glycol ether acetates, esters, alcohols, aliphatic hydrocarbons, petroleum solvents, and the like. Such an organic solvent may be used individually by 1 type, and may be used as a 2 or more types of mixture.
(その他の任意成分)
本発明の感光性熱硬化性樹脂組成物には、必要に応じてさらに、光重合性モノマー、メルカプト化合物、密着促進剤、酸化防止剤、紫外線吸収剤などの成分を配合することができる。これらは、電子材料の分野において公知の物を使用することができる。また、上記の感光性熱硬化性樹脂組成物には、微粉シリカ、ハイドロタルサイト、有機ベントナイト、モンモリロナイトなどの公知慣用の増粘剤、シリコーン系、フッ素系、高分子系などの消泡剤及び/又はレベリング剤、シランカップリング剤、防錆剤などのような公知慣用の添加剤類を配合することができる。
なお、光重合性モノマーの配合量は、(A)成分であるポリイミド樹脂100質量部に対して、15質量部以下であることが好ましく、10質量部以下であることがより好ましく、0質量部である(含まない)ことが最も好ましい。
(Other optional ingredients)
The photosensitive thermosetting resin composition of the present invention may further contain components such as a photopolymerizable monomer, a mercapto compound, an adhesion promoter, an antioxidant, and an ultraviolet absorber as necessary. As these, those known in the field of electronic materials can be used. The photosensitive thermosetting resin composition includes a known and commonly used thickener such as finely divided silica, hydrotalcite, organic bentonite, and montmorillonite, an antifoaming agent such as silicone, fluorine, and polymer. // Known additives such as a leveling agent, a silane coupling agent, and a rust preventive agent can be blended.
In addition, it is preferable that the compounding quantity of a photopolymerizable monomer is 15 mass parts or less with respect to 100 mass parts of polyimide resin which is (A) component, It is more preferable that it is 10 mass parts or less, 0 mass part Most preferably (not included).
〔ドライフィルム〕
本発明のドライフィルムは、本発明の感光性熱硬化性樹脂組成物からなる樹脂層を有することを特徴とする。
ドライフィルム化に際しては、例えば、本発明の感光性熱硬化性樹脂組成物を有機溶剤で希釈して適切な粘度に調整し、コンマコーター等の公知の手法でキャリアフィルム上に均一な厚さに塗布する。その後、通常、50〜130℃の温度で1〜30分間乾燥し、キャリアフィルム上に樹脂層を形成する。
[Dry film]
The dry film of the present invention is characterized by having a resin layer comprising the photosensitive thermosetting resin composition of the present invention.
In forming a dry film, for example, the photosensitive thermosetting resin composition of the present invention is diluted with an organic solvent to adjust to an appropriate viscosity, and a uniform thickness is formed on the carrier film by a known method such as a comma coater. Apply. Thereafter, drying is usually performed at a temperature of 50 to 130 ° C. for 1 to 30 minutes to form a resin layer on the carrier film.
キャリアフィルムとしては、プラスチックフィルムが用いられる。キャリアフィルムの厚さについては特に制限はないが、一般に、10〜150μmの範囲で適宜選択される。キャリアフィルム上に樹脂層を形成した後、さらに、樹脂層の表面に剥離可能なカバーフィルムを積層してもよい。 A plastic film is used as the carrier film. Although there is no restriction | limiting in particular about the thickness of a carrier film, Generally, it selects suitably in the range of 10-150 micrometers. After forming the resin layer on the carrier film, a peelable cover film may be further laminated on the surface of the resin layer.
〔フレキシブルプリント配線板及びその製造方法〕
本発明のフレキシブルプリント配線板は、感光性熱硬化性樹脂組成物、又は、ドライフィルムの樹脂層からなる硬化物を有することを特徴とするものである。
本発明のフレキシブルプリント配線板の製造方法は、フレキシブルプリント配線板上に感光性熱硬化性樹脂組成物からなる樹脂層を形成する工程、パターン状に光を樹脂層に照射する工程、樹脂層を加熱する工程、及び、樹脂層をアルカリ現像して、カバーレイ及びソルダーレジストのうちの少なくともいずれか一方を形成する工程を含む。
[Flexible printed wiring board and manufacturing method thereof]
The flexible printed wiring board of the present invention is characterized by having a cured product composed of a photosensitive thermosetting resin composition or a resin layer of a dry film.
The method for producing a flexible printed wiring board of the present invention includes a step of forming a resin layer made of a photosensitive thermosetting resin composition on a flexible printed wiring board, a step of irradiating the resin layer with light in a pattern, and a resin layer. A step of heating, and a step of alkali-developing the resin layer to form at least one of a coverlay and a solder resist.
[樹脂層形成工程]
この工程では、フレキシブルプリント配線板上にアルカリ現像型熱硬化性樹脂組成物からなる樹脂層を少なくとも一層形成する。
樹脂層の形成方法としては、塗布法と、ラミネート法が挙げられる。
塗布法の場合、スクリーン印刷等の方法により、アルカリ現像型熱硬化性樹脂組成物をフレキシブルプリント配線板上に塗布し、乾燥することにより樹脂層を形成する。
ラミネート法の場合、まずは、アルカリ現像型熱硬化性樹脂組成物を有機溶剤で希釈して適切な粘度に調整し、キャリアフィルム上に塗布、乾燥して樹脂層を有するドライフィルムを作成する。次に、ラミネーター等により樹脂層が、フレキシブルプリント配線板と接触するように貼り合わせた後、キャリアフィルムを剥離する。
[Resin layer forming step]
In this step, at least one resin layer made of an alkali development type thermosetting resin composition is formed on the flexible printed wiring board.
Examples of the method for forming the resin layer include a coating method and a laminating method.
In the case of the application method, the alkali development type thermosetting resin composition is applied onto the flexible printed wiring board by a method such as screen printing and dried to form a resin layer.
In the case of the laminating method, first, the alkali development type thermosetting resin composition is diluted with an organic solvent to adjust to an appropriate viscosity, applied onto a carrier film, and dried to prepare a dry film having a resin layer. Next, after bonding together so that a resin layer may contact a flexible printed wiring board with a laminator etc., a carrier film is peeled.
また、樹脂層とフレキシブルプリント配線板の間には、他の層を介在させることができる。他の層は、アルカリ現像型感光性樹脂組成物からなることが好ましい。アルカリ現像型感光性樹脂組成物としては、公知の組成物を使用することができ、例えば、カバーレイ用又はソルダーレジスト用の公知の組成物を使用できる。このように他の層を含めた積層構造とすることにより、さらに耐衝撃性と屈曲性に優れた硬化物を得ることができる。 Moreover, another layer can be interposed between the resin layer and the flexible printed wiring board. The other layer is preferably made of an alkali development type photosensitive resin composition. As an alkali development type photosensitive resin composition, a well-known composition can be used, For example, the well-known composition for coverlays or a soldering resist can be used. Thus, by setting it as the laminated structure including another layer, the hardened | cured material which was further excellent in impact resistance and flexibility can be obtained.
[光照射工程]
この工程は、ネガ型のパターン状に光照射にて樹脂層に含まれる光塩基発生剤を活性化して光照射部を硬化する。この工程では、光照射部で発生した塩基により、光塩基発生剤が不安定化し、塩基が化学的に増殖することにより、樹脂層の深部まで十分硬化できる。
[Light irradiation process]
This step activates the photobase generator contained in the resin layer by light irradiation in a negative pattern to cure the light irradiation part. In this step, the photobase generator is destabilized by the base generated in the light irradiation part, and the base is chemically proliferated, whereby the resin layer can be sufficiently cured to the deep part.
光照射機としては、直接描画装置、メタルハライドランプを搭載した光照射機などを用いることができる。パターン状の光照射用のマスクは、ネガ型のマスクである。
光照射に用いる活性エネルギー線としては、最大波長が350〜450nmの範囲にあるレーザー光又は散乱光を用いることが好ましい。最大波長をこの範囲とすることにより、効率よく光塩基発生剤を活性化させることができる。この範囲のレーザー光を用いていればガスレーザー、固体レーザーのいずれでもよい。また、その光照射量は膜厚等によって異なるが、一般には100〜1500mJ/cm2とすることができる。
As the light irradiator, a direct writer, a light irradiator equipped with a metal halide lamp, or the like can be used. The patterned light irradiation mask is a negative mask.
As the active energy ray used for light irradiation, it is preferable to use laser light or scattered light having a maximum wavelength in the range of 350 to 450 nm. By setting the maximum wavelength within this range, the photobase generator can be activated efficiently. If a laser beam in this range is used, either a gas laser or a solid laser may be used. Moreover, although the light irradiation amount changes with film thicknesses etc., it can generally be set as 100-1500 mJ / cm < 2 >.
[加熱工程]
この工程は、光照射後、樹脂層を加熱することにより光照射部を硬化する。この工程により、光照射工程で発生した塩基により深部まで硬化できる。加熱温度は、例えば、80〜140℃である。加熱時間は、例えば、10〜100分である。
本発明における感光性熱硬化性樹脂組成物の硬化は、例えば、熱反応によるエポキシ樹脂の開環反応であるため、光ラジカル反応で硬化が進行する場合と比べてひずみや硬化収縮を抑えることができる。
[Heating process]
In this step, after the light irradiation, the light irradiation part is cured by heating the resin layer. By this process, it is possible to cure to a deep part by the base generated in the light irradiation process. The heating temperature is, for example, 80 to 140 ° C. The heating time is, for example, 10 to 100 minutes.
Since the curing of the photosensitive thermosetting resin composition in the present invention is, for example, a ring-opening reaction of an epoxy resin by a thermal reaction, it can suppress distortion and curing shrinkage compared to the case where curing proceeds by a photoradical reaction. it can.
[現像工程]
現像工程は、アルカリ現像により、未照射部を除去して、ネガ型のパターン状の絶縁膜、特に、カバーレイ及びソルダーレジストを形成する。
現像方法としては、ディッピング等の公知の方法によることができる。また、現像液としては、水酸化カリウム、アミン類、水酸化テトラメチルアンモニウム水溶液(TMAH)等のアルカリ水溶液またはこれらの混合液を用いることができる。
なお、現像工程の後に、さらに、絶縁膜を光照射してもよい。また、例えば、150℃以上で加熱してもよい。
[Development process]
In the development step, the unirradiated portion is removed by alkali development to form a negative patterned insulating film, particularly a coverlay and a solder resist.
The developing method can be a known method such as dipping. Moreover, as a developing solution, alkaline water solution, such as potassium hydroxide, amines, tetramethylammonium hydroxide aqueous solution (TMAH), or these liquid mixture can be used.
Note that the insulating film may be further irradiated with light after the development step. For example, you may heat at 150 degreeC or more.
次に、本発明の感光性熱硬化性樹脂組成物から本発明のフレキシブルプリント配線板を製造する方法の一例を図1の工程図に基づき説明する。なお、図1では、樹脂層が積層構造である場合を示すが、1層のみからなる場合でもよい。 Next, an example of a method for producing the flexible printed wiring board of the present invention from the photosensitive thermosetting resin composition of the present invention will be described based on the process diagram of FIG. FIG. 1 shows a case where the resin layer has a laminated structure, but it may be composed of only one layer.
図1の積層工程は、樹脂層3と樹脂層4からなる積層構造体を、銅回路2が形成されたフレキシブルプリント配線基材1に形成する。
樹脂層3は、カルボキシル基含有樹脂などを含むアルカリ現像型の感光性樹脂組成物からなる。
樹脂層4は、樹脂層3上に形成され、1分子中に1個以上のイミド環と1個以上のカルボキシル基とを有するポリイミド樹脂、光塩基発生剤、及び熱硬化成分を含む感光性熱硬化性樹脂組成物からなる。
In the laminating process of FIG. 1, a laminated structure composed of the resin layer 3 and the
The resin layer 3 is made of an alkali development type photosensitive resin composition containing a carboxyl group-containing resin or the like.
The
図1の光照射工程は、樹脂層4上にマスク5を配置し、ネガ型のパターン状に光照射することにより、感光性熱硬化性樹脂組成物に含まれる光塩基発生剤を活性化して光照射部を硬化する工程である。図1の加熱工程は、光照射工程の後、樹脂層を加熱することにより、光照射部を硬化する工程(PEB工程)である。図1の現像工程は、アルカリ性水溶液によって現像することにより、未照射部が除去され、ネガ型のパターン層を形成する工程である。
The light irradiation process of FIG. 1 activates the photobase generator contained in the photosensitive thermosetting resin composition by disposing a mask 5 on the
なお、図1の第2光照射工程は、必要に応じて、残った光塩基発生剤を活性化して塩基を発生させるための工程であり、熱硬化工程は、必要に応じて、パターン層を十分に熱硬化させるための工程である。 In addition, the 2nd light irradiation process of FIG. 1 is a process for activating the remaining photobase generator as needed, and generating a base, and a thermosetting process is a pattern layer as needed. This is a process for sufficient heat curing.
以下、実施例、比較例により本発明をさらに詳細に説明するが、本発明は、これら実施例、比較例によって制限されるものではない。 EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further in detail, this invention is not restrict | limited by these Examples and a comparative example.
(実施例1〜4、参考例1〜3、比較例1、2)
<イミド環及びカルボキシル基を有するポリイミド樹脂溶液の合成例>
撹拌機、窒素導入管、分留環、冷却環を取り付けたセパラブル3つ口フラスコに、3,5−ジアミノ安息香酸を12.5g、2,2’−ビス[4―(4―アミノフェノキシ)フェニル]プロパンを8.2g、NMPを30g、γ−ブチロラクトンを30g、4,4’オキシジフタル酸無水物を27.9g、トリメリット酸無水物を3.8g加え、窒素雰囲気下、室温、100rpmで4時間撹拌した。次いでトルエンを20g加え、シリコン浴温度180℃、150rpmでトルエン及び水を留去しながら4時間撹拌してイミド環およびカルボキシル基を有するポリイミド樹脂溶液(PI−1)を得た。
得られた樹脂(固形分)の酸価は85mgKOH、重量平均分子量(Mw)は10000であった。
(Examples 1-4, Reference Examples 1-3, Comparative Examples 1 and 2)
<Synthesis example of polyimide resin solution having imide ring and carboxyl group>
In a separable three-necked flask equipped with a stirrer, nitrogen inlet tube, fractional ring, and cooling ring, 12.5 g of 3,5-diaminobenzoic acid, 2,2′-bis [4- (4-aminophenoxy) Phenyl] propane (8.2 g), NMP (30 g), γ-butyrolactone (30 g), 4,4′-oxydiphthalic anhydride (27.9 g) and trimellitic anhydride (3.8 g) were added at room temperature under a nitrogen atmosphere at 100 rpm. Stir for 4 hours. Next, 20 g of toluene was added and stirred for 4 hours while distilling off toluene and water at a silicon bath temperature of 180 ° C. and 150 rpm to obtain a polyimide resin solution (PI-1) having an imide ring and a carboxyl group.
The acid value of the obtained resin (solid content) was 85 mgKOH, and the weight average molecular weight (Mw) was 10,000.
<イミド環及びフェノール性水酸基を有するポリイミド樹脂溶液の合成例>
撹拌機、窒素導入管、分留環、冷却環を取り付けたセパラブル3つ口フラスコに、3,3’−ジアミノ−4,4’−ジヒドロキシジフェニルスルホン22.4g、2,2’−ビス[4―(4―アミノフェノキシ)フェニル]プロパンを8.2g、NMPを30g、γ−ブチロラクトンを30g、4,4’−オキシジフタル酸無水物を27.9g、フタル酸無水物を3.0g加え、窒素雰囲気下、室温、100rpmで4時間撹拌した。次いでトルエンを20g加え、シリコン浴温度180℃、150rpmでトルエン及び水を留去しながら4時間撹拌してイミド環を有するイミド環及びフェノール性水酸基を有するアルカリ可溶性樹脂溶液(PI−2)を得た。
得られた樹脂(固形分)は水酸基当量384、Mwは10000であった。
<Synthesis example of polyimide resin solution having imide ring and phenolic hydroxyl group>
To a separable three-necked flask equipped with a stirrer, a nitrogen introduction tube, a fractionation ring, and a cooling ring, 22.4 g of 3,3′-diamino-4,4′-dihydroxydiphenylsulfone, 2,2′-bis [4 Add 8.2 g of (4-aminophenoxy) phenyl] propane, 30 g of NMP, 30 g of γ-butyrolactone, 27.9 g of 4,4′-oxydiphthalic anhydride, and 3.0 g of phthalic anhydride, and add nitrogen. It stirred at room temperature and 100 rpm for 4 hours under atmosphere. Next, 20 g of toluene was added and stirred for 4 hours while distilling off toluene and water at a silicon bath temperature of 180 ° C. and 150 rpm to obtain an alkali-soluble resin solution (PI-2) having an imide ring having an imide ring and a phenolic hydroxyl group. It was.
The obtained resin (solid content) had a hydroxyl group equivalent of 384 and Mw of 10,000.
<イミド環、フェノール性水酸基、カルボキシル基を有するポリイミド樹脂溶液の合成例>
撹拌機、窒素導入管、分留環、冷却環を取り付けたセパラブル3つ口フラスコに、3,3’−ジアミノ−4,4’−ジヒドロキシジフェニルスルホン22.4g、2,2’−ビス[4―(4―アミノフェノキシ)フェニル]プロパンを8.2g、NMPを30g、γ−ブチロラクトンを30g、4,4’−オキシジフタル酸無水物を27.9g、トリメリット酸無水物を3.8g加え、窒素雰囲気下、室温、100rpmで4時間撹拌した。次いでトルエンを20g加え、シリコン浴温度180℃、150rpmでトルエン及び水を留去しながら4時間撹拌してイミド環を有するアルカリ溶解性樹脂溶液(PI−3)を得た。
得られた樹脂(固形分)の酸価は18mgKOH、Mwは10000、水酸基当量は390であった。
<Synthesis example of polyimide resin solution having imide ring, phenolic hydroxyl group, carboxyl group>
To a separable three-necked flask equipped with a stirrer, a nitrogen introduction tube, a fractionation ring, and a cooling ring, 22.4 g of 3,3′-diamino-4,4′-dihydroxydiphenylsulfone, 2,2′-bis [4 -(4-aminophenoxy) phenyl] propane 8.2g, NMP 30g, γ-
The acid value of the obtained resin (solid content) was 18 mgKOH, Mw was 10,000, and the hydroxyl group equivalent was 390.
<感光性熱硬化性樹脂組成物の調製>
下記表1記載の配合に従って、各記載の材料をそれぞれ配合、攪拌機にて予備混合した後、3本ロールミルにて混練し、感光性熱硬化性樹脂組成物を調製した。表中の値は、特に断りが無い限り質量部である。
<Preparation of photosensitive thermosetting resin composition>
According to the composition shown in Table 1 below, the materials described in the following were blended, premixed with a stirrer, and then kneaded with a three-roll mill to prepare a photosensitive thermosetting resin composition. The values in the table are parts by mass unless otherwise specified.
<樹脂層の形成工程>
銅厚18μmで回路が形成されているフレキシブルプリント配線基材を用意し、メック社CZ−8100を使用して、前処理を行った。その後、前記前処理を行ったフレキシブルプリント配線板に、実施例1〜7、比較例1及び2の感光性熱硬化性樹脂組成物を液状塗布方法にて乾燥後で膜厚10μmになるようにコーティングを行った。その後、熱風循環式乾燥炉にて80℃、30分にて乾燥し、樹脂層を形成した。その後、ORC社HMW680GW(メタルハライドランプ、散乱光)にて500mJ/cm2の露光量でネガ型のパターン状に光照射した。
<Resin layer formation process>
A flexible printed wiring substrate in which a circuit was formed with a copper thickness of 18 μm was prepared, and pre-treatment was performed using MEC CZ-8100. Thereafter, the photosensitive thermosetting resin compositions of Examples 1 to 7 and Comparative Examples 1 and 2 were dried by the liquid coating method on the flexible printed wiring board subjected to the pretreatment so as to have a film thickness of 10 μm. Coating was performed. Then, it dried at 80 degreeC and 30 minutes with the hot-air circulation type drying furnace, and formed the resin layer. Thereafter, the film was irradiated with a negative pattern with an exposure amount of 500 mJ / cm 2 using ORC HMW680GW (metal halide lamp, scattered light).
<PEB工程の時間管理幅評価>
上記露光後の樹脂層を有する基板を、90℃でそれぞれ15分、20分、25分、30分、35分、40分、45分、50分、55分、又は60分間加熱処理を行った。その後30℃の1質量%の炭酸ナトリウム水溶液中に基材を浸漬して3分間現像を行い、現像性の可否を評価し、現像可能な加熱時間の幅(分)を評価した。
<Evaluation of time management width of PEB process>
The substrate having the resin layer after the exposure was subjected to heat treatment at 90 ° C. for 15 minutes, 20 minutes, 25 minutes, 30 minutes, 35 minutes, 40 minutes, 45 minutes, 50 minutes, 55 minutes, or 60 minutes, respectively. . Thereafter, the substrate was immersed in a 1% by mass sodium carbonate aqueous solution at 30 ° C., developed for 3 minutes, evaluated for developability, and evaluated for the width (minutes) of the developable heating time.
<PEB工程の温度による現像性評価>
上記露光後の樹脂層を有する基板を、80℃60分、90℃30分、100℃15分間加熱処理を行った。その後30℃の1質量%の炭酸ナトリウム水溶液中に基材を浸漬して3分間現像を行い、現像性の可否を評価した。
表中 ○:現像可能で、塗膜の状態も良好
※1:露光部が現像液に溶解するためパターン形成不可。
※2:未露光部が現像液に溶解しないためパターン形成不可。
<Developability evaluation by temperature of PEB process>
The substrate having the exposed resin layer was heat-treated at 80 ° C. for 60 minutes, 90 ° C. for 30 minutes, and 100 ° C. for 15 minutes. Thereafter, the substrate was immersed in a 1% by mass sodium carbonate aqueous solution at 30 ° C. and developed for 3 minutes to evaluate the developability.
In the table: ○: Development is possible and the state of the coating film is good * 1: The pattern cannot be formed because the exposed area is dissolved in the developer.
* 2: The pattern cannot be formed because the unexposed area does not dissolve in the developer.
評価の結果を下記表1に示す。 The evaluation results are shown in Table 1 below.
*1:フェノールノボラック樹脂 水酸基当量106 明和化成(株)製
*2:ビスフェノールA型エポキシ樹脂 三菱化学(株)製
*3:オキシム系光重合開始剤 BASF社製
* 1: Phenol novolac resin Hydroxyl equivalent 106 Made by Meiwa Kasei Co., Ltd. * 2: Bisphenol A type epoxy resin Mitsubishi Chemical Co., Ltd. * 3: Oxime photopolymerization initiator BASF
表1に示す評価結果から明らかなように、実施例1〜4の感光性熱硬化性樹脂組成物は、80℃、90℃、100℃のいずれの温度での露光後加熱処理であっても現像性が良好であった。また、90℃におけるPEB時間管理幅の評価から、比較例に比べて、露光後の加熱時間を長くとれることが確認できた。以上から、本発明にかかる感光性熱硬化性樹脂組成物は、比較例1、2の樹脂組成物に比較してPEB工程の温度管理性、時間管理幅について大幅に優れていることが分かる。 As is clear from the evaluation results shown in Table 1, the photosensitive thermosetting resin compositions of Examples 1 to 4 may be subjected to post-exposure heat treatment at any of 80 ° C., 90 ° C., and 100 ° C. The developability was good. Moreover, from the evaluation of the PEB time management width at 90 ° C., it was confirmed that the heating time after exposure could be made longer than in the comparative example. From the above, it can be seen that the photosensitive thermosetting resin composition according to the present invention is significantly superior in the temperature controllability and time management width of the PEB process as compared with the resin compositions of Comparative Examples 1 and 2.
1 フレキシブルプリント配線板
2 銅回路
3 樹脂層
4 樹脂層
5 マスク
DESCRIPTION OF SYMBOLS 1 Flexible printed
Claims (6)
(B)イミド環およびフェノール性水酸基を有するポリイミド樹脂、
(C)光塩基発生剤、および、
(D)熱硬化成分
を含む感光性熱硬化性樹脂組成物であって、
光照射によって前記(C)光塩基発生剤を活性化し、発生した塩基を触媒として前記(A)イミド環およびカルボキシル基を有するポリイミド樹脂並びに(B)イミド環を有するフェノール性水酸基を有するポリイミド樹脂と、熱硬化成分とを、加熱によって付加反応させることにより、アルカリ現像による微細加工が可能となる用途に用いられることを特徴とする感光性熱硬化性樹脂組成物。 (A) a polyimide resin having an imide ring and a carboxyl group,
(B) a polyimide resin having an imide ring and a phenolic hydroxyl group,
(C) a photobase generator, and
(D) a photosensitive thermosetting resin composition containing a thermosetting component,
And (C) a polyimide resin having a imide ring and a carboxyl group, and (B) a polyimide resin having a phenolic hydroxyl group having an imide ring, using the generated base as a catalyst to activate the (C) photobase generator by light irradiation; A photosensitive thermosetting resin composition, which is used for applications in which fine processing by alkali development is possible by addition reaction of a thermosetting component with heating.
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JP2013144034A JP6306296B2 (en) | 2013-07-09 | 2013-07-09 | Photosensitive thermosetting resin composition and flexible printed wiring board |
KR1020167003054A KR102372561B1 (en) | 2013-07-09 | 2014-06-17 | Photosensitive thermosetting resin composition and flexible printed circuit board |
PCT/JP2014/066078 WO2015005077A1 (en) | 2013-07-09 | 2014-06-17 | Photosensitive thermosetting resin composition and flexible printed circuit board |
CN201480039321.0A CN105378564B (en) | 2013-07-09 | 2014-06-17 | Photosensitive thermosetting resin composition and flexible printed circuit board |
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