JP5459590B2 - Photosensitive resin composition, polyimide resin film using the same, and flexible printed wiring board - Google Patents
Photosensitive resin composition, polyimide resin film using the same, and flexible printed wiring board Download PDFInfo
- Publication number
- JP5459590B2 JP5459590B2 JP2009173788A JP2009173788A JP5459590B2 JP 5459590 B2 JP5459590 B2 JP 5459590B2 JP 2009173788 A JP2009173788 A JP 2009173788A JP 2009173788 A JP2009173788 A JP 2009173788A JP 5459590 B2 JP5459590 B2 JP 5459590B2
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- JP
- Japan
- Prior art keywords
- resin composition
- film
- polyimide
- photosensitive resin
- diamine
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 229920001721 polyimide Polymers 0.000 title claims description 98
- 239000011342 resin composition Substances 0.000 title claims description 54
- 239000009719 polyimide resin Substances 0.000 title claims description 47
- 239000000178 monomer Substances 0.000 claims description 50
- 150000004985 diamines Chemical class 0.000 claims description 38
- 239000004642 Polyimide Substances 0.000 claims description 36
- 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 claims description 33
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 26
- 239000011347 resin Substances 0.000 claims description 26
- 229920005989 resin Polymers 0.000 claims description 26
- 239000002243 precursor Substances 0.000 claims description 18
- 125000006158 tetracarboxylic acid group Chemical group 0.000 claims description 17
- 239000000758 substrate Substances 0.000 claims description 16
- 125000003118 aryl group Chemical group 0.000 claims description 15
- 239000004305 biphenyl Substances 0.000 claims description 15
- 235000010290 biphenyl Nutrition 0.000 claims description 13
- 239000003999 initiator Substances 0.000 claims description 13
- LFBALUPVVFCEPA-UHFFFAOYSA-N 4-(3,4-dicarboxyphenyl)phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C(C(O)=O)=C1 LFBALUPVVFCEPA-UHFFFAOYSA-N 0.000 claims description 12
- 230000001681 protective effect Effects 0.000 claims description 11
- 239000000725 suspension Substances 0.000 claims description 11
- UHUUYVZLXJHWDV-UHFFFAOYSA-N trimethyl(methylsilyloxy)silane Chemical group C[SiH2]O[Si](C)(C)C UHUUYVZLXJHWDV-UHFFFAOYSA-N 0.000 claims description 7
- 125000003277 amino group Chemical group 0.000 claims description 6
- 230000008033 biological extinction Effects 0.000 claims description 6
- WKDNYTOXBCRNPV-UHFFFAOYSA-N bpda Chemical compound C1=C2C(=O)OC(=O)C2=CC(C=2C=C3C(=O)OC(C3=CC=2)=O)=C1 WKDNYTOXBCRNPV-UHFFFAOYSA-N 0.000 claims 1
- 230000005494 condensation Effects 0.000 claims 1
- 238000009833 condensation Methods 0.000 claims 1
- 239000010408 film Substances 0.000 description 87
- 239000007787 solid Substances 0.000 description 26
- 238000011161 development Methods 0.000 description 24
- 239000002966 varnish Substances 0.000 description 24
- -1 aromatic tetracarboxylic acid Chemical class 0.000 description 20
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 18
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 17
- 229910052751 metal Inorganic materials 0.000 description 16
- 239000002184 metal Substances 0.000 description 16
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 15
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 15
- 239000010410 layer Substances 0.000 description 15
- 229920005575 poly(amic acid) Polymers 0.000 description 15
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 14
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 description 13
- 150000001732 carboxylic acid derivatives Chemical group 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 13
- 239000012299 nitrogen atmosphere Substances 0.000 description 13
- 239000003505 polymerization initiator Substances 0.000 description 13
- HMLSBRLVTDLLOI-UHFFFAOYSA-N 1-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)C(C)OC(=O)C(C)=C HMLSBRLVTDLLOI-UHFFFAOYSA-N 0.000 description 12
- 229920001577 copolymer Polymers 0.000 description 12
- 238000003756 stirring Methods 0.000 description 12
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 239000010936 titanium Substances 0.000 description 10
- 229910052719 titanium Inorganic materials 0.000 description 10
- GPXCORHXFPYJEH-UHFFFAOYSA-N 3-[[3-aminopropyl(dimethyl)silyl]oxy-dimethylsilyl]propan-1-amine Chemical compound NCCC[Si](C)(C)O[Si](C)(C)CCCN GPXCORHXFPYJEH-UHFFFAOYSA-N 0.000 description 9
- QYIMZXITLDTULQ-UHFFFAOYSA-N 4-(4-amino-2-methylphenyl)-3-methylaniline Chemical group CC1=CC(N)=CC=C1C1=CC=C(N)C=C1C QYIMZXITLDTULQ-UHFFFAOYSA-N 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 238000002156 mixing Methods 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- NVKGJHAQGWCWDI-UHFFFAOYSA-N 4-[4-amino-2-(trifluoromethyl)phenyl]-3-(trifluoromethyl)aniline Chemical group FC(F)(F)C1=CC(N)=CC=C1C1=CC=C(N)C=C1C(F)(F)F NVKGJHAQGWCWDI-UHFFFAOYSA-N 0.000 description 8
- 239000011889 copper foil Substances 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- 239000004020 conductor Substances 0.000 description 7
- 229910052802 copper Inorganic materials 0.000 description 6
- 239000010949 copper Substances 0.000 description 6
- 238000001723 curing Methods 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 229910001220 stainless steel Inorganic materials 0.000 description 5
- 239000010935 stainless steel Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000011888 foil Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- XAUGWFWQVYXATQ-UHFFFAOYSA-N n-phenylbenzenesulfonamide Chemical compound C=1C=CC=CC=1S(=O)(=O)NC1=CC=CC=C1 XAUGWFWQVYXATQ-UHFFFAOYSA-N 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- 238000007747 plating Methods 0.000 description 3
- 238000012643 polycondensation polymerization Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- NSGXIBWMJZWTPY-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropane Chemical compound FC(F)(F)CC(F)(F)F NSGXIBWMJZWTPY-UHFFFAOYSA-N 0.000 description 2
- HDGLPTVARHLGMV-UHFFFAOYSA-N 2-amino-4-(1,1,1,3,3,3-hexafluoropropan-2-yl)phenol Chemical compound NC1=CC(C(C(F)(F)F)C(F)(F)F)=CC=C1O HDGLPTVARHLGMV-UHFFFAOYSA-N 0.000 description 2
- BEKFRNOZJSYWKZ-UHFFFAOYSA-N 4-[2-(4-aminophenyl)-1,1,1,3,3,3-hexafluoropropan-2-yl]aniline Chemical compound C1=CC(N)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(N)C=C1 BEKFRNOZJSYWKZ-UHFFFAOYSA-N 0.000 description 2
- ZGFPUTOTEJOSAY-UHFFFAOYSA-N FC1=C([Ti])C(F)=CC=C1N1C=CC=C1 Chemical compound FC1=C([Ti])C(F)=CC=C1N1C=CC=C1 ZGFPUTOTEJOSAY-UHFFFAOYSA-N 0.000 description 2
- 206010034972 Photosensitivity reaction Diseases 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- ABBZJHFBQXYTLU-UHFFFAOYSA-N but-3-enamide Chemical compound NC(=O)CC=C ABBZJHFBQXYTLU-UHFFFAOYSA-N 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical group [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 2
- 238000013007 heat curing Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- BVSPJPNNLDIUFE-UHFFFAOYSA-N n,n-dimethylbenzenesulfonamide Chemical compound CN(C)S(=O)(=O)C1=CC=CC=C1 BVSPJPNNLDIUFE-UHFFFAOYSA-N 0.000 description 2
- WNSXUAGCWVZDQC-UHFFFAOYSA-N n-ethylbenzenesulfonamide Chemical compound CCNS(=O)(=O)C1=CC=CC=C1 WNSXUAGCWVZDQC-UHFFFAOYSA-N 0.000 description 2
- YPHQUSNPXDGUHL-UHFFFAOYSA-N n-methylprop-2-enamide Chemical compound CNC(=O)C=C YPHQUSNPXDGUHL-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000000059 patterning Methods 0.000 description 2
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 230000036211 photosensitivity Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 230000035882 stress Effects 0.000 description 2
- JJRVRELEASDUMY-JXMROGBWSA-N (5e)-5-[[4-(dimethylamino)phenyl]methylidene]-2-sulfanylidene-1,3-thiazolidin-4-one Chemical compound C1=CC(N(C)C)=CC=C1\C=C\1C(=O)NC(=S)S/1 JJRVRELEASDUMY-JXMROGBWSA-N 0.000 description 1
- PVPBBTJXIKFICP-UHFFFAOYSA-N (7-aminophenothiazin-3-ylidene)azanium;chloride Chemical compound [Cl-].C1=CC(=[NH2+])C=C2SC3=CC(N)=CC=C3N=C21 PVPBBTJXIKFICP-UHFFFAOYSA-N 0.000 description 1
- VMEZXMFPKOMWHR-UHFFFAOYSA-N (dimethylamino)methyl prop-2-enoate Chemical compound CN(C)COC(=O)C=C VMEZXMFPKOMWHR-UHFFFAOYSA-N 0.000 description 1
- XYLJOGVVSQGQIY-ONEGZZNKSA-N (e)-n-methylbut-2-enamide Chemical compound CNC(=O)\C=C\C XYLJOGVVSQGQIY-ONEGZZNKSA-N 0.000 description 1
- PMYOYDPRILKMKB-SNAWJCMRSA-N (e)-n-propan-2-ylbut-2-enamide Chemical compound C\C=C\C(=O)NC(C)C PMYOYDPRILKMKB-SNAWJCMRSA-N 0.000 description 1
- KUQNCHZOCSYKOR-UHFFFAOYSA-N 1,1-dioxospiro[2,1$l^{6}-benzoxathiole-3,9'-xanthene]-3',4',5',6'-tetrol Chemical compound O1S(=O)(=O)C2=CC=CC=C2C21C1=CC=C(O)C(O)=C1OC1=C(O)C(O)=CC=C21 KUQNCHZOCSYKOR-UHFFFAOYSA-N 0.000 description 1
- QOSTVEDABRQTSU-UHFFFAOYSA-N 1,4-bis(methylamino)anthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C(NC)=CC=C2NC QOSTVEDABRQTSU-UHFFFAOYSA-N 0.000 description 1
- NLXFWUZKOOWWFD-UHFFFAOYSA-N 1-(2-hydroxyethylamino)-4-(methylamino)anthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C(NCCO)=CC=C2NC NLXFWUZKOOWWFD-UHFFFAOYSA-N 0.000 description 1
- XLPJNCYCZORXHG-UHFFFAOYSA-N 1-morpholin-4-ylprop-2-en-1-one Chemical compound C=CC(=O)N1CCOCC1 XLPJNCYCZORXHG-UHFFFAOYSA-N 0.000 description 1
- RESPXSHDJQUNTN-UHFFFAOYSA-N 1-piperidin-1-ylprop-2-en-1-one Chemical compound C=CC(=O)N1CCCCC1 RESPXSHDJQUNTN-UHFFFAOYSA-N 0.000 description 1
- LFEXGBPVZBXATF-UHFFFAOYSA-N 2,3-dimethylbenzenesulfonamide Chemical compound CC1=CC=CC(S(N)(=O)=O)=C1C LFEXGBPVZBXATF-UHFFFAOYSA-N 0.000 description 1
- SJIXRGNQPBQWMK-UHFFFAOYSA-N 2-(diethylamino)ethyl 2-methylprop-2-enoate Chemical compound CCN(CC)CCOC(=O)C(C)=C SJIXRGNQPBQWMK-UHFFFAOYSA-N 0.000 description 1
- DPBJAVGHACCNRL-UHFFFAOYSA-N 2-(dimethylamino)ethyl prop-2-enoate Chemical compound CN(C)CCOC(=O)C=C DPBJAVGHACCNRL-UHFFFAOYSA-N 0.000 description 1
- ZGDMDBHLKNQPSD-UHFFFAOYSA-N 2-amino-5-(4-amino-3-hydroxyphenyl)phenol Chemical group C1=C(O)C(N)=CC=C1C1=CC=C(N)C(O)=C1 ZGDMDBHLKNQPSD-UHFFFAOYSA-N 0.000 description 1
- AKVUWTYSNLGBJY-UHFFFAOYSA-N 2-methyl-1-morpholin-4-ylprop-2-en-1-one Chemical compound CC(=C)C(=O)N1CCOCC1 AKVUWTYSNLGBJY-UHFFFAOYSA-N 0.000 description 1
- RASDUGQQSMMINZ-UHFFFAOYSA-N 2-methyl-1-piperidin-1-ylprop-2-en-1-one Chemical compound CC(=C)C(=O)N1CCCCC1 RASDUGQQSMMINZ-UHFFFAOYSA-N 0.000 description 1
- RRPOJJQFMPCHBE-UHFFFAOYSA-N 2-methyl-n,n-bis(3-methylphenyl)benzenesulfonamide Chemical compound CC1=CC=CC(N(C=2C=C(C)C=CC=2)S(=O)(=O)C=2C(=CC=CC=2)C)=C1 RRPOJJQFMPCHBE-UHFFFAOYSA-N 0.000 description 1
- LOECBMNQVDQYQZ-UHFFFAOYSA-N 2-methyl-n,n-bis(4-methylphenyl)benzenesulfonamide Chemical compound C1=CC(C)=CC=C1N(S(=O)(=O)C=1C(=CC=CC=1)C)C1=CC=C(C)C=C1 LOECBMNQVDQYQZ-UHFFFAOYSA-N 0.000 description 1
- BIRVTMAYQAJZFX-UHFFFAOYSA-N 2-methyl-n,n-diphenylbenzenesulfonamide Chemical compound CC1=CC=CC=C1S(=O)(=O)N(C=1C=CC=CC=1)C1=CC=CC=C1 BIRVTMAYQAJZFX-UHFFFAOYSA-N 0.000 description 1
- KLWUWNHLZITTHU-UHFFFAOYSA-N 2-methyl-n-phenylbenzenesulfonamide Chemical compound CC1=CC=CC=C1S(=O)(=O)NC1=CC=CC=C1 KLWUWNHLZITTHU-UHFFFAOYSA-N 0.000 description 1
- YQIGLEFUZMIVHU-UHFFFAOYSA-N 2-methyl-n-propan-2-ylprop-2-enamide Chemical compound CC(C)NC(=O)C(C)=C YQIGLEFUZMIVHU-UHFFFAOYSA-N 0.000 description 1
- YCMLQMDWSXFTIF-UHFFFAOYSA-N 2-methylbenzenesulfonimidic acid Chemical compound CC1=CC=CC=C1S(N)(=O)=O YCMLQMDWSXFTIF-UHFFFAOYSA-N 0.000 description 1
- IXPWKHNDQICVPZ-UHFFFAOYSA-N 2-methylhex-1-en-3-yne Chemical compound CCC#CC(C)=C IXPWKHNDQICVPZ-UHFFFAOYSA-N 0.000 description 1
- JMADMUIDBVATJT-UHFFFAOYSA-N 2-methylprop-2-enamide;propan-2-one Chemical compound CC(C)=O.CC(C)=O.CC(=C)C(N)=O JMADMUIDBVATJT-UHFFFAOYSA-N 0.000 description 1
- NDXGRHCEHPFUSU-UHFFFAOYSA-N 3-(3-aminophenyl)aniline Chemical group NC1=CC=CC(C=2C=C(N)C=CC=2)=C1 NDXGRHCEHPFUSU-UHFFFAOYSA-N 0.000 description 1
- WWJCRUKUIQRCGP-UHFFFAOYSA-N 3-(dimethylamino)propyl 2-methylprop-2-enoate Chemical compound CN(C)CCCOC(=O)C(C)=C WWJCRUKUIQRCGP-UHFFFAOYSA-N 0.000 description 1
- UFQHFMGRRVQFNA-UHFFFAOYSA-N 3-(dimethylamino)propyl prop-2-enoate Chemical compound CN(C)CCCOC(=O)C=C UFQHFMGRRVQFNA-UHFFFAOYSA-N 0.000 description 1
- ZSPPPAFDNHYXNW-UHFFFAOYSA-N 3-[n-ethyl-4-[(4-nitrophenyl)diazenyl]anilino]propanenitrile Chemical compound C1=CC(N(CCC#N)CC)=CC=C1N=NC1=CC=C([N+]([O-])=O)C=C1 ZSPPPAFDNHYXNW-UHFFFAOYSA-N 0.000 description 1
- LJMPOXUWPWEILS-UHFFFAOYSA-N 3a,4,4a,7a,8,8a-hexahydrofuro[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1C2C(=O)OC(=O)C2CC2C(=O)OC(=O)C21 LJMPOXUWPWEILS-UHFFFAOYSA-N 0.000 description 1
- XTEBLARUAVEBRF-UHFFFAOYSA-N 4-(1,1,1,3,3,3-hexafluoropropan-2-yl)aniline Chemical compound NC1=CC=C(C(C(F)(F)F)C(F)(F)F)C=C1 XTEBLARUAVEBRF-UHFFFAOYSA-N 0.000 description 1
- UNBOSJFEZZJZLR-UHFFFAOYSA-N 4-(4-nitrophenylazo)aniline Chemical compound C1=CC(N)=CC=C1N=NC1=CC=C([N+]([O-])=O)C=C1 UNBOSJFEZZJZLR-UHFFFAOYSA-N 0.000 description 1
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 1
- FWTBRYBHCBCJEQ-UHFFFAOYSA-N 4-[(4-phenyldiazenylnaphthalen-1-yl)diazenyl]phenol Chemical compound C1=CC(O)=CC=C1N=NC(C1=CC=CC=C11)=CC=C1N=NC1=CC=CC=C1 FWTBRYBHCBCJEQ-UHFFFAOYSA-N 0.000 description 1
- PHBWSCCOVCLKFB-UHFFFAOYSA-N 4-methyl-n,n-bis(3-methylphenyl)benzenesulfonamide Chemical compound C1=CC(C)=CC=C1S(=O)(=O)N(C=1C=C(C)C=CC=1)C1=CC=CC(C)=C1 PHBWSCCOVCLKFB-UHFFFAOYSA-N 0.000 description 1
- YGXPIWIUZCEBHN-UHFFFAOYSA-N 4-methyl-n,n-bis(4-methylphenyl)benzenesulfonamide Chemical compound C1=CC(C)=CC=C1N(S(=O)(=O)C=1C=CC(C)=CC=1)C1=CC=C(C)C=C1 YGXPIWIUZCEBHN-UHFFFAOYSA-N 0.000 description 1
- VLYSRNWCIRFSSM-UHFFFAOYSA-N 4-methyl-n,n-diphenylbenzenesulfonamide Chemical compound C1=CC(C)=CC=C1S(=O)(=O)N(C=1C=CC=CC=1)C1=CC=CC=C1 VLYSRNWCIRFSSM-UHFFFAOYSA-N 0.000 description 1
- VLVCWODDMDGANW-UHFFFAOYSA-N 4-methyl-n-phenylbenzenesulfonamide Chemical compound C1=CC(C)=CC=C1S(=O)(=O)NC1=CC=CC=C1 VLVCWODDMDGANW-UHFFFAOYSA-N 0.000 description 1
- HOOIIRHGHALACD-UHFFFAOYSA-N 5-(2,5-dioxooxolan-3-yl)-3-methylcyclohex-3-ene-1,2-dicarboxylic acid Chemical compound C1C(C(O)=O)C(C(O)=O)C(C)=CC1C1C(=O)OC(=O)C1 HOOIIRHGHALACD-UHFFFAOYSA-N 0.000 description 1
- 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 1
- ZHBXLZQQVCDGPA-UHFFFAOYSA-N 5-[(1,3-dioxo-2-benzofuran-5-yl)sulfonyl]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(S(=O)(=O)C=2C=C3C(=O)OC(C3=CC=2)=O)=C1 ZHBXLZQQVCDGPA-UHFFFAOYSA-N 0.000 description 1
- JVERADGGGBYHNP-UHFFFAOYSA-N 5-phenylbenzene-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C(C(=O)O)=CC(C=2C=CC=CC=2)=C1C(O)=O JVERADGGGBYHNP-UHFFFAOYSA-N 0.000 description 1
- ALJHHTHBYJROOG-UHFFFAOYSA-N 7-(dimethylamino)phenothiazin-3-one Chemical compound C1=CC(=O)C=C2SC3=CC(N(C)C)=CC=C3N=C21 ALJHHTHBYJROOG-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- RGCKGOZRHPZPFP-UHFFFAOYSA-N Alizarin Natural products C1=CC=C2C(=O)C3=C(O)C(O)=CC=C3C(=O)C2=C1 RGCKGOZRHPZPFP-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Photosensitive Polymer And Photoresist Processing (AREA)
- Materials For Photolithography (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Non-Metallic Protective Coatings For Printed Circuits (AREA)
Description
本発明は、フレキシブルプリント配線板の保護膜の形成等に好適に用いられる感光性樹脂組成物、及びこれを用いたポリイミド樹脂膜、フレキシブルプリント配線板に関する。 The present invention relates to a photosensitive resin composition suitably used for forming a protective film of a flexible printed wiring board, a polyimide resin film using the same, and a flexible printed wiring board.
ポリイミド樹脂は耐熱性に優れ、また良好な電気絶縁性を示すことよりプリント配線板の基材、層間接着剤、カバーレイ（保護膜）等として使用されている。また配線の微細化に伴い、保護膜としてのポリイミド樹脂を微細加工するために感光性を持たせることが検討されている。配線形成した基材上に、ポリイミド樹脂を含む感光性樹脂組成物の塗膜を形成した後、マスクを介して紫外線等を照射して露光部を変質させることで、露光部のみ（ポジ型）又は非露光部のみ（ネガ型）を除去することができ、パターン形成が可能となる。 Polyimide resins are used as a substrate for printed wiring boards, interlayer adhesives, coverlays (protective films) and the like because of their excellent heat resistance and good electrical insulation. Further, with the miniaturization of wiring, it has been studied to provide photosensitivity in order to finely process a polyimide resin as a protective film. After forming a coating film of a photosensitive resin composition containing a polyimide resin on the substrate on which the wiring is formed, the exposed portion is altered by irradiating ultraviolet rays or the like through a mask, so that only the exposed portion (positive type) Alternatively, only the non-exposed portion (negative type) can be removed, and the pattern can be formed.
このような感光性樹脂組成物として、特許文献１にはポリイミド前駆体（ポリアミド酸）と、化学線により２量化又は重合可能な炭素−炭素二重結合及びアミノ基又はその四級化塩を含む化合物（光重合性モノマー）と、必要に応じて加える増感剤、光開始剤、共重合モノマーとからなるネガ型の感光材料が開示されている。この感光材料にパターンを介して化学線を照射すると、露光部では、光重合性モノマーが重合すると共に、光重合性モノマーのアミノ基とポリイミド前駆体のカルボキシル基がイオン的に結合して、溶剤溶解性が低下する。その後未露光部を現像液で溶解除去してパターン形成し、加熱、硬化してポリイミド膜が得られる。 As such a photosensitive resin composition, Patent Document 1 includes a polyimide precursor (polyamic acid), a carbon-carbon double bond that can be dimerized or polymerized by actinic radiation, and an amino group or a quaternized salt thereof. A negative photosensitive material comprising a compound (photopolymerizable monomer) and a sensitizer, a photoinitiator, and a copolymerization monomer added as necessary is disclosed. When this photosensitive material is irradiated with actinic radiation through a pattern, the photopolymerizable monomer is polymerized in the exposed area, and the amino group of the photopolymerizable monomer and the carboxyl group of the polyimide precursor are ionically bonded to form a solvent. Solubility decreases. Thereafter, the unexposed portion is dissolved and removed with a developer to form a pattern, and heated and cured to obtain a polyimide film.
一方、特許文献２にはネガ型の感光性ポリイミド樹脂を保護膜として用いた回路基板及び回路付きサスペンション基板が開示されている。回路付きサスペンション基板は、ステンレス等の金属箔基材上に絶縁層を有し、その上に銅などの金属からなる導体層のパターン回路、及びこれを被覆する絶縁層を有する。特許文献２では、金属箔基材上の絶縁層及び導体層を被覆する絶縁層としてネガ型の感光性ポリイミド樹脂を使用している。 On the other hand, Patent Document 2 discloses a circuit board using a negative photosensitive polyimide resin as a protective film and a suspension board with circuit. The suspension board with circuit has an insulating layer on a metal foil base material such as stainless steel, and has a pattern circuit of a conductor layer made of a metal such as copper, and an insulating layer covering the insulating layer. In Patent Document 2, a negative photosensitive polyimide resin is used as an insulating layer covering the insulating layer and the conductor layer on the metal foil base material.
一般にポリイミドの熱膨張係数はシリコンや金属に比べると大きい。従って、金属やシリコンからなる基材及び導体層とポリイミドとを組み合わせたフレキシブルプリント配線板では、ポリイミドと金属との熱膨張係数の差に起因して基板に反りが生じることがある。ハードディスクドライブに使用されるサスペンション用の基板は、ステンレス（ＳＵＳ）等の金属基板上にポリイミドからなる絶縁層を形成し、その上に銅箔を積層した構造をとっている。このようなサスペンション用基板では、他の一般的なフレキシブルプリント配線板と比べて基板の反りの影響は大きく、例えば基板の反りによりハードディスク読み取り誤差を招きやすくなったり、ポリイミド層と金属層との間に残留応力が蓄積することでクラックや層間剥離などを生じたりするという問題がある。そこで、金属との熱膨張係数の差を少なくするために、熱膨張係数の小さいポリイミドが求められている。 In general, the thermal expansion coefficient of polyimide is larger than that of silicon or metal. Therefore, in a flexible printed wiring board in which a base material or conductor layer made of metal or silicon and a polyimide are combined with a polyimide, the substrate may be warped due to a difference in thermal expansion coefficient between the polyimide and the metal. A suspension substrate used in a hard disk drive has a structure in which an insulating layer made of polyimide is formed on a metal substrate such as stainless steel (SUS) and a copper foil is laminated thereon. In such a suspension substrate, the influence of the warp of the substrate is larger than that of other general flexible printed circuit boards. For example, the warp of the substrate is likely to cause a hard disk reading error, or between the polyimide layer and the metal layer. There is a problem that cracks and delamination occur due to accumulation of residual stress. Therefore, in order to reduce the difference in thermal expansion coefficient from metal, polyimide having a low thermal expansion coefficient is required.
ポリイミドの熱膨張係数を小さくするために、特許文献２では剛直なポリマー骨格を持つネガ型の感光性ポリイミドが提案されている。このようなポリイミドは、熱膨張係数は小さくなるが、感光性を付与した際にパターニング精度が悪くなったり、また基板との接着性が弱くなったりするという問題がある。この理由として、ネガ型の感光性ポリイミドは、構造上、露光・現像後に膜として残る現像液不溶部も溶媒と相互作用しやすく、現像時に膨張しやすいことが考えられる。 In order to reduce the thermal expansion coefficient of polyimide, Patent Document 2 proposes a negative photosensitive polyimide having a rigid polymer skeleton. Although such a polyimide has a small thermal expansion coefficient, there are problems that patterning accuracy is deteriorated when the photosensitivity is imparted, and adhesion to the substrate is weakened. As a reason for this, it is conceivable that the negative photosensitive polyimide has a structure in which a developer-insoluble portion remaining as a film after exposure and development is likely to interact with the solvent and easily expand during development.
上記の問題に鑑み、本発明は、熱膨張係数を低くできるとともに、基材との接着性に優れたネガ型感光性樹脂組成物及びそれを用いた絶縁性保護膜、フレキシブルプリント配線板を提供することを課題とする。 In view of the above problems, the present invention provides a negative photosensitive resin composition that has a low coefficient of thermal expansion and excellent adhesion to a substrate, an insulating protective film using the same, and a flexible printed wiring board. The task is to do.
本発明は、ポリイミド前駆体樹脂、光重合性モノマー、及び光重合開始剤を含有するネガ型感光性樹脂組成物であって、前記ポリイミド前駆体樹脂は、芳香族テトラカルボン酸二無水物と２種類以上のジアミンとを縮合重合したものであり、前記ジアミン又は前記芳香族テトラカルボン酸二無水物として、ビフェニル骨格を持つモノマーを２種類以上含有すると共に、該ビフェニル骨格を持つモノマーの含有量は、芳香族テトラカルボン酸二無水物とジアミンとの合計量に対して５０モル％以上であり、前記ジアミンとして、テトラメチルジシロキサン骨格を持つジアミンを、ジアミン合計量に対して０．５モル％以上５モル％以下含有し、前記ジアミンとして、フッ素化モノマーをジアミン合計量に対して３０モル％以上７０モル％以下含有することを特徴とする、感光性樹脂組成物である。 The present invention is a negative photosensitive resin composition containing a polyimide precursor resin, a photopolymerizable monomer, and a photopolymerization initiator, wherein the polyimide precursor resin comprises an aromatic tetracarboxylic dianhydride and 2 Condensation polymerization of two or more kinds of diamines, and the diamine or the aromatic tetracarboxylic dianhydride contains two or more monomers having a biphenyl skeleton, and the content of the monomer having the biphenyl skeleton is , 50 mol% or more based on the total amount of aromatic tetracarboxylic dianhydride and diamine, and diamine having a tetramethyldisiloxane skeleton as the diamine is 0.5 mol% based on the total amount of diamine. more than 5 mole% containing less, as the diamine, containing 30 mol% to 70 mol% relative to diamine total amount of fluorinated monomer Characterized in that it is a photosensitive resin composition.
剛直な成分であるビフェニル骨格を持つモノマーを２種類以上用い、その含有量を５０モル％以上とすることで、熱膨張係数を低くすることができ、かつ良好な現像性を得ることができる。同時に、また柔軟なテトラメチルジシロキサン骨格を持つジアミンを少量用い、ジシロキサン骨格をポリマー主鎖に導入することによって、基板との密着性を向上できると共に、ポリイミド樹脂の透明性（ｉ線透過性）を向上できる。尚、ビフェニル骨格を持つモノマーは芳香族テトラカルボン酸二無水物、ジアミンのいずれであっても良いが、芳香族テトラカルボン酸二無水物、ジアミンの両方にビフェニル骨格を持つモノマーを使用することが好ましい。 By using two or more monomers having a biphenyl skeleton that is a rigid component and making the content 50 mol% or more, the thermal expansion coefficient can be lowered and good developability can be obtained. At the same time, by using a small amount of a diamine having a flexible tetramethyldisiloxane skeleton and introducing the disiloxane skeleton into the polymer main chain, the adhesion to the substrate can be improved and the transparency of the polyimide resin (i-line permeability) ) Can be improved. The monomer having a biphenyl skeleton may be either an aromatic tetracarboxylic dianhydride or a diamine, but a monomer having a biphenyl skeleton may be used for both the aromatic tetracarboxylic dianhydride and the diamine. preferable.
前記ジアミンとして、フッ素化モノマーをジアミン合計量に対して３０モル％以上７０モル％以下含有することが好ましい。フッ素化モノマーを適量使用することで、ポリイミドの透明性を向上することができるとともにパターニング（現像）時の溶解速度もコントロールすることができる。 As said diamine, it is preferable to contain a fluorinated monomer 30 mol% or more and 70 mol% or less with respect to the total amount of diamine . By using an appropriate amount of the fluorinated monomer, the transparency of the polyimide can be improved and the dissolution rate during patterning (development) can also be controlled.
前記芳香族テトラカルボン酸二無水物として少なくとも３，４，３’，４’−ビフェニルテトラカルボン酸二無水物（ＢＰＤＡ）を、芳香族テトラカルボン酸二無水物合計量に対して５０モル％以上含有することが好ましい。このようなモノマー構成とすることで剛直な成分であるビフェニル骨格を持つモノマーの含有量を多くすることができ、ポリイミドの熱膨張係数を低くすることができる。 As the aromatic tetracarboxylic dianhydride, at least 3,4,3 ′, 4′-biphenyltetracarboxylic dianhydride (BPDA) is 50 mol% or more based on the total amount of the aromatic tetracarboxylic dianhydride. It is preferable to contain. By setting it as such a monomer structure, content of the monomer with the biphenyl skeleton which is a rigid component can be increased, and the thermal expansion coefficient of a polyimide can be made low.
また、光重合開始剤として、波長３６５ｎｍでのモル吸光係数が１０００以上である光重合開始剤と、波長４３６ｎｍでのモル吸光係数が１０以上である光重合開始剤を含有することが好ましい。露光の際にはｉ線（波長３６５ｎｍ）とｇ線（波長４３６ｎｍ）の２種類の線が主に使用される。ｇ線吸収タイプの光重合開始剤とｉ線吸収タイプの光重合開始剤とを併用することで光重合性モノマーの反応性を高めることができ、露光部／非露光部の溶解速度差を大きくすることができる。 The photopolymerization initiator preferably contains a photopolymerization initiator having a molar extinction coefficient of 1000 or more at a wavelength of 365 nm and a photopolymerization initiator having a molar extinction coefficient of 10 or more at a wavelength of 436 nm . In the exposure, two types of lines, i-line (wavelength 365 nm) and g-line (wavelength 436 nm), are mainly used. By using a g-line absorption type photopolymerization initiator and an i-line absorption type photopolymerization initiator in combination, the reactivity of the photopolymerizable monomer can be increased, and the difference in dissolution rate between exposed and non-exposed areas is increased. can do.
光重合性モノマーとして、アミノ基を有するモノマーが好ましい。光重合性モノマーのアミノ基がポリイミド前駆体（ポリアミド酸）のカルボン酸部分とイオン的に結合することで、ポリイミド前駆体に光反応性官能基を導入することができる。 As the photopolymerizable monomer, a monomer having an amino group is preferable . A photoreactive functional group can be introduced into the polyimide precursor by ionically bonding the amino group of the photopolymerizable monomer with the carboxylic acid moiety of the polyimide precursor (polyamide acid).
また本発明は、上記いずれかの感光性樹脂組成物を基材上に塗布して製膜し、加熱硬化して得られるポリイミド樹脂膜を提供する。感光性樹脂組成物の製膜後、加熱硬化する前にマスクを通して露光して現像液で現像すれば、任意のパターンを形成したポリイミド樹脂膜を得ることもできる。この加熱硬化の過程で、ポリイミド前駆体（ポリアミック酸）樹脂がポリイミド樹脂となる。 Moreover, this invention provides the polyimide resin film obtained by apply | coating one of the said photosensitive resin compositions on a base material, forming into a film, and heat-hardening. If the photosensitive resin composition is formed and then exposed to light through a mask before being cured by heating and developed with a developer, a polyimide resin film having an arbitrary pattern can be obtained. In this heat curing process, the polyimide precursor (polyamic acid) resin becomes a polyimide resin.
さらに本発明は上記製造方法によって得られ、熱膨張係数が１０ｐｐｍ／℃以上２０ｐｐｍ／℃以下であることを特徴とするポリイミド樹脂膜、及び該ポリイミド樹脂膜を保護膜として有するフレキシブルプリント配線板を提供する。 Furthermore, the present invention provides a polyimide resin film obtained by the above production method and having a thermal expansion coefficient of 10 ppm / ° C. or more and 20 ppm / ° C. or less, and a flexible printed wiring board having the polyimide resin film as a protective film. To do.
ポリイミド樹脂膜の熱膨張係数を１０ｐｐｍ／℃以上２０ｐｐｍ／℃以下とすることで、ステンレス、銅などの金属とポリイミド樹脂膜の熱膨張係数を近づけることができ、温度変化による反りの少ないフレキシブルプリント配線板が得られる。 By setting the thermal expansion coefficient of the polyimide resin film to 10 ppm / ° C. or more and 20 ppm / ° C. or less, it is possible to bring the thermal expansion coefficient of the polyimide resin film closer to metals such as stainless steel and copper, and flexible printed wiring with less warping due to temperature changes. A board is obtained.
本発明の感光性樹脂組成物によれば、熱膨張係数が低く、かつ基材との接着力に優れたポリイミド樹脂膜を得ることができる。また本発明のポリイミド樹脂膜は、その熱膨張係数が、金属の熱膨張係数により近いため、残留応力の少ないフレキシブルプリント配線板が得られる。 According to the photosensitive resin composition of the present invention, it is possible to obtain a polyimide resin film having a low thermal expansion coefficient and excellent adhesive strength with a substrate. Moreover, since the thermal expansion coefficient of the polyimide resin film of the present invention is closer to that of the metal, a flexible printed wiring board with less residual stress can be obtained.
本発明の感光性樹脂組成物の原料であるポリイミド前駆体樹脂（ポリアミック酸溶液）は、芳香族テトラカルボン酸二無水物とジアミンとの縮合重合によって得られる。この縮合重合反応は、従来のポリイミドの合成と同様な条件にて行うことができる。 The polyimide precursor resin (polyamic acid solution) that is a raw material of the photosensitive resin composition of the present invention is obtained by condensation polymerization of an aromatic tetracarboxylic dianhydride and a diamine. This condensation polymerization reaction can be performed under the same conditions as in the conventional synthesis of polyimide.
芳香族テトラカルボン酸二無水物としては、３，４，３’，４’−ビフェニルテトラカルボン酸二無水物（ＢＰＤＡ）、ピロメリット酸二無水物（ＰＭＤＡ）、３，３’，４，４’−ベンゾフェノン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、３，３’，４，４’−ジフェニルスルホン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、１，２，４，５−シクロヘキサンテトラカルボン酸二無水物、２，２−ビス（３，４−ジカルボンキシフェニル）ヘキサフルオロプロパン二無水物、５−（２，５−ジオキソテトラヒドロフリル）−３−メチル−３−シクロヘキセン−１，２−ジカルボン酸二無水物等が例示される。 Examples of aromatic tetracarboxylic dianhydrides include 3,4,3 ′, 4′-biphenyltetracarboxylic dianhydride (BPDA), pyromellitic dianhydride (PMDA), 3,3 ′, 4,4. '-Benzophenone tetracarboxylic dianhydride, 4,4'-oxydiphthalic dianhydride, 3,3', 4,4'-diphenylsulfone tetracarboxylic dianhydride, bicyclo (2,2,2) -oct -7-ene-2,3,5,6-tetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxylicoxyphenyl) Examples include hexafluoropropane dianhydride, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride, and the like.
中でも、下記式（Ｉ）で表される３，４，３’，４’−ビフェニルテトラカルボン酸二無水物（ＢＰＤＡ）はビフェニル骨格を持つ剛直な構造であり、ポリイミド樹脂の熱膨張係数を低くできる点で好ましい。 Among them, 3,4,3 ′, 4′-biphenyltetracarboxylic dianhydride (BPDA) represented by the following formula (I) has a rigid structure having a biphenyl skeleton, and has a low thermal expansion coefficient of polyimide resin. It is preferable in that it can be performed.
ジアミンとしては、２，２’−ジメチル４，４’−ジアミノビフェニル（ｍＴＢＨＧ）、２，２’−ビス（トリフルオロメチル）４，４’−ジアミノビフェニル（ＴＦＭＢ）、２，２’−ビス（４−アミノフェニル）ヘキサフルオロプロパン（Ｂｉｓ−Ａ−ＡＦ）パラフェニレンジアミン（ＰＰＤ）、４，４’−ジアミノジフェニルエーテル（ＯＤＡ）、３，３’−ジヒドロキシ４，４’−ジアミノビフェニル、４、４’−ジヒドロキシ３，３’−ジアミノビフェニル等が例示できる。 Examples of the diamine include 2,2′-dimethyl 4,4′-diaminobiphenyl (mTBHG), 2,2′-bis (trifluoromethyl) 4,4′-diaminobiphenyl (TFMB), 2,2′-bis ( 4-Aminophenyl) hexafluoropropane (Bis-A-AF) paraphenylenediamine (PPD), 4,4′-diaminodiphenyl ether (ODA), 3,3′-dihydroxy 4,4′-diaminobiphenyl, 4, 4 Examples include '-dihydroxy 3,3'-diaminobiphenyl.
この中でも、式（ＩＩ）で表される２，２’−ジメチル４，４’−ジアミノビフェニル（ｍＴＢＨＧ）や式（ＩＩＩ）で表される２，２’−ビス（トリフルオロメチル）４，４’−ジアミノビフェニル（ＴＦＭＢ）は、ビフェニル骨格を持つ剛直な構造であり、ポリイミド樹脂の熱膨張係数を低くできる点で好ましい。 Among these, 2,2′-dimethyl 4,4′-diaminobiphenyl (mTBHG) represented by the formula (II) and 2,2′-bis (trifluoromethyl) 4,4 represented by the formula (III) '-Diaminobiphenyl (TFMB) is a rigid structure having a biphenyl skeleton, and is preferable in that the thermal expansion coefficient of the polyimide resin can be lowered.
ビフェニル骨格を持つモノマーは、芳香族テトラカルボン酸二無水物であってもジアミンであっても良く、モノマー成分全体（芳香族テトラカルボン酸とジアミンの合計量）に対して５０モル％以上とする必要がある。５０モル％未満ではポリイミド樹脂の低熱膨張係数と現像性とを両立することができない。さらに好ましいビフェニル骨格を持つモノマーの含有率は、７０％以上である。 The monomer having a biphenyl skeleton may be an aromatic tetracarboxylic dianhydride or a diamine, and is 50 mol% or more based on the entire monomer component (total amount of aromatic tetracarboxylic acid and diamine). There is a need. If it is less than 50 mol%, the low thermal expansion coefficient and developability of the polyimide resin cannot be compatible. The content of the monomer having a more preferable biphenyl skeleton is 70% or more.
また、ジアミンとしてテトラメチルジシロキサン骨格を持つジアミンを、ジアミン成分全体に対して０．５モル％以上５モル％以下含有する必要がある。テトラメチルジシロキサン骨格を持つジアミンを少量含有することでポリイミド樹脂の接着性が向上する。テトラメチルジシロキサン骨格を持つジアミンの量が０．５モル％未満では上記の効果を充分に得ることができない。一方、５モル％を超えるとポリイミド樹脂の熱膨張係数が大きくなる。 Moreover, it is necessary to contain 0.5 mol% or more and 5 mol% or less of diamine having a tetramethyldisiloxane skeleton as the diamine with respect to the entire diamine component. By containing a small amount of a diamine having a tetramethyldisiloxane skeleton, the adhesion of the polyimide resin is improved. If the amount of the diamine having a tetramethyldisiloxane skeleton is less than 0.5 mol%, the above effect cannot be obtained sufficiently. On the other hand, when it exceeds 5 mol%, the thermal expansion coefficient of the polyimide resin increases.
テトラメチルジシロキサン骨格を持つジアミンとは、シロキサン骨格を有しその末端に一級アミノ基を２つ有する化合物である。例えば下記式（ＩＶ）で表される物が広く採用されている。 A diamine having a tetramethyldisiloxane skeleton is a compound having a siloxane skeleton and two primary amino groups at its ends. For example, a product represented by the following formula (IV) is widely used.
上記の他に、下記構造式で表される物も例示される。 In addition to the above, those represented by the following structural formulas are also exemplified.
さらに、ジアミン又は芳香族テトラカルボン酸二無水物として、フッ素化モノマーをジアミン成分全体に対して３０モル％以上７０モル％以下含有すると好ましい。フッ素化モノマーを含有することでポリイミド樹脂の透明性（光透過性）を向上することができる。さらに、ポリイミド樹脂の現像液への溶解性が高まることから厚膜での現像性が向上する。ただしフッ素化モノマーの含有量が多くなりすぎるとコスト高となり、また絶縁膜の機械物性が低下するため、フッ素化モノマーの含有量は７０モル％以下とすることが好ましい。 Furthermore, it is preferable to contain a fluorinated monomer as a diamine or aromatic tetracarboxylic dianhydride in an amount of 30 mol% or more and 70 mol% or less with respect to the entire diamine component. By containing the fluorinated monomer, the transparency (light transmittance) of the polyimide resin can be improved. Furthermore, since the solubility of the polyimide resin in the developer is increased, the developability with a thick film is improved. However, if the content of the fluorinated monomer is excessively high, the cost is increased and the mechanical properties of the insulating film are lowered. Therefore, the content of the fluorinated monomer is preferably 70 mol% or less.
フッ素化モノマーとしては上記の２，２’−ビス（トリフルオロメチル）４，４’−ジアミノビフェニル（ＴＦＭＢ）や、式（ＶＩ）で表される２，２’−ビス（４−アミノフェニル）ヘキサフルオロプロパン（ＢＩＳ−Ａ−ＡＦ）等が例示できる。ビフェニル骨格を持つＴＦＭＢを選択すると、熱膨張係数を低くすることができ、好ましい。 Examples of the fluorinated monomer include 2,2′-bis (trifluoromethyl) 4,4′-diaminobiphenyl (TFMB) and 2,2′-bis (4-aminophenyl) represented by the formula (VI). Examples include hexafluoropropane (BIS-A-AF). Selecting TFMB having a biphenyl skeleton is preferable because the thermal expansion coefficient can be lowered.
本発明の感光性樹脂組成物を構成するポリイミド前駆体樹脂のＧＰＣ測定による重量平均分子量は２００００〜４０００００の範囲が好ましい。重量平均分子量がこの範囲を超える場合は組成物の印刷性の低下、現像時の抜け残り等を発生しやすくなる。一方、重量平均分子量がこの範囲未満の場合は現像時に膜劣化が生じる、皮膜の機械強度が不十分になる、等の問題を生じる場合がある。さらに好ましい重量平均分子量の範囲は２００００〜１０００００である。 The weight average molecular weight by GPC measurement of the polyimide precursor resin constituting the photosensitive resin composition of the present invention is preferably in the range of 20,000 to 400,000. When the weight average molecular weight exceeds this range, the printability of the composition is liable to be lowered, and the remaining residue during development is likely to occur. On the other hand, if the weight average molecular weight is less than this range, problems such as film deterioration during development and insufficient mechanical strength of the film may occur. Furthermore, the range of a preferable weight average molecular weight is 20000-100,000.
本発明の感光性樹脂組成物を構成する光重合性モノマーは、Ｘ線、電子線、紫外線等を照射（露光）することで架橋する光反応性官能基を持つモノマーであり、不飽和二重結合等の光反応性官能基とアミノ基とを含有することが好ましい。このような化合物として、メタクリル酸Ｎ，Ｎ−ジメチルアミノエチル、アクリル酸Ｎ，Ｎ−ジメチルアミノエチル、メタクリル酸Ｎ，Ｎ−ジエチルアミノエチル、アクリル酸Ｎ，Ｎ−ジエチルアミノエチル、メタクリル酸Ｎ，Ｎ−ジメチルアミノメチル、メタクリル酸Ｎ，Ｎ−ジメチルアミノプロピル、アクリル酸Ｎ，Ｎ−ジメチルアミノメチル、アクリル酸Ｎ，Ｎ−ジメチルアミノプロピル、アクリルアミド、メタクリルアミド、Ｎ−メチルメタクリルアミド、Ｎ−メチルアクリルアミド、Ｎ−エチルメタクリルアミド、Ｎ−エチルアクリルアミド、Ｎ−イソプロピルメタクリルアミド、Ｎ−イソプロピルアクリルアミド、Ｎ−ブチルメタクリルアミド、Ｎ−ブチルアクリルアミド、ジアセトンアクリルアミド、ジアセトンメタクリルアミド、Ｎ−シクロヘキシルメタクリルアミド、Ｎ−シクロヘキシルアクリルアミド、Ｎ−メチロ−ルアクリルアミド、アクリロイルモルホリン、メタクリロイルモルホリン、アクリロイルピペリジン、メタクリロイルピペリジン、クロトンアミド、Ｎ−メチルクロトンアミド、Ｎ−イソプロピルクロトンアミド、Ｎ−ブチルクロトンアミド、酢酸アリルアミド、プロピオン酸アリルアミドなどが例示される。光重合性モノマーはポリイミド前駆体樹脂のカルボキシル基に対して１〜１．５当量の範囲で配合することが好ましい。 The photopolymerizable monomer constituting the photosensitive resin composition of the present invention is a monomer having a photoreactive functional group that is cross-linked by irradiation (exposure) with X-rays, electron beams, ultraviolet rays or the like. It preferably contains a photoreactive functional group such as a bond and an amino group. Such compounds include N, N-dimethylaminoethyl methacrylate, N, N-dimethylaminoethyl acrylate, N, N-diethylaminoethyl methacrylate, N, N-diethylaminoethyl acrylate, N, N-methacrylate. Dimethylaminomethyl, N, N-dimethylaminopropyl methacrylate, N, N-dimethylaminomethyl acrylate, N, N-dimethylaminopropyl acrylate, acrylamide, methacrylamide, N-methylmethacrylamide, N-methylacrylamide, N-ethyl methacrylamide, N-ethyl acrylamide, N-isopropyl methacrylamide, N-isopropyl acrylamide, N-butyl methacrylamide, N-butyl acrylamide, diacetone acrylamide, diacetone methacrylamide N-cyclohexylmethacrylamide, N-cyclohexylacrylamide, N-methylacrylamide, acryloylmorpholine, methacryloylmorpholine, acryloylpiperidine, methacryloylpiperidine, crotonamide, N-methylcrotonamide, N-isopropylcrotonamide, N-butyl Examples include crotonamide, acetic acid allylamide, propionic acid allylamide, and the like. The photopolymerizable monomer is preferably blended in the range of 1 to 1.5 equivalents relative to the carboxyl group of the polyimide precursor resin.
本発明の感光性樹脂組成物を構成する光重合開始剤としては、ｉ線（波長３６５ｎｍ）吸収タイプとしてはα−アミノケトン型のもの、ｇ線（波長４３６ｎｍ）吸収タイプとしてはチタノセン化合物等のメタロセン系のものがそれぞれ好ましく用いられる。いずれの開始剤も、ポリイミド前駆体樹脂固形分に対して０．１〜１０重量％配合することによって良好な現像性が得られる。光重合開始剤は単独で使用しても複数を併用しても良い。複数の光重合開始剤を併用することで良好な結果が得られる場合もある。 The photopolymerization initiator constituting the photosensitive resin composition of the present invention includes an α-aminoketone type as the i-line (wavelength 365 nm) absorption type and a metallocene such as a titanocene compound as the g-line (wavelength 436 nm) absorption type. Those of the system are preferably used. When any initiator is blended in an amount of 0.1 to 10% by weight based on the solid content of the polyimide precursor resin, good developability can be obtained. A photoinitiator may be used individually or may be used together. Good results may be obtained by using a plurality of photopolymerization initiators in combination.
本発明の感光性樹脂組成物は、上記のポリイミド前駆体樹脂と光重合性モノマー、重合開始剤を混合することで得ることができる。また本発明の感光性樹脂組成物には、必要に応じて、種々の添加剤を含有していても良い。例えば、現像時の視認性向上のための染料、顔料として、フェノールフタレイン、フェノールレッド、ニールレッド、ピロガロールレッド、ピロガロールバイレット、ディスパースレッド１、ディスパースレッド１３、ディスパースレッド１９、ディスパースオレンジ１、ディスパースオレンジ３、ディスパースオレンジ１３、ディスパースオレンジ２５、ディスパースブルー３、ディスパースブルー１４、エオシンＢ、ロダミンＢ、キナリザリン、５−（４−ジメチルアミノベンジリデン）ロダニン、アウリントリカルボキシアシド、アルミノン、アリザリン、パラローザニリン、エモジン、チオニン、メチレンバイオレット、ピグメントブルー、ピグメントレッド等が例示される。また非露光部の溶解促進を向上するための添加剤として、ベンゼンスルホンアミド、Ｎ−メチルベンゼンスルホンアミド、Ｎ−エチルベンゼンスルホンアミド、Ｎ，Ｎ−ジメチルベンゼンスルホンアミド、Ｎ−ｎ−ブチルベンゼンスルホンアミド、Ｎ−ｔ−ブチルベンゼンスルホンアミド、Ｎ，Ｎ−ジ−ｎ−ブチルベンゼンスルホンアミド、ベンゼンスルホンアニリド、Ｎ，Ｎ−ジフェニルベンゼンスルホンアミド、Ｎ−ｐ−トリルベンゼンスルホンアミド、Ｎ−ｏ−トリルベンゼンスルホンアミド、Ｎ−ｍ−トリルベンゼンスルホンアミド、Ｎ，Ｎ−ジ−ｐ−トリルベンゼンスルホンアミド、ｐ−トルエンスルホンアミド、Ｎ−メチル−ｐ−トルエンスルホンアミド、Ｎ−エチル−ｐ−トルエンスルホンアミド、Ｎ，Ｎ−ジメチル−ｐ−トルエンスルホンアミド、Ｎ−ｎ−ブチル−ｐ−トルエンスルホンアミド、Ｎ−ｔ−ブチル−ｐ−トルエンスルホンアミド、Ｎ，Ｎ−ジ−ｎ−ブチル−ｐ−トルエンスルホンアミド、Ｎ−フェニル−ｐ−トルエンスルホンアミド、Ｎ，Ｎ−ジフェニル−ｐ−トルエンスルホンアミド、Ｎ−ｐ−トリル−ｐ−トルエンスルホンアミド、Ｎ−ｍ−トリル−ｐ−トルエンスルホンアミド、Ｎ，Ｎ−ジ−ｐ−トリル−ｐ−トルエンスルホンアミド、Ｎ，Ｎ−ジ−ｍ−トリル−ｐ−トルエンスルホンアミド、ｏ−トルエンスルホンアミド、Ｎ−メチル−ｏ−トルエンスルホンアミド、Ｎ−エチル−ｏ−トルエンスルホンアミド、Ｎ，Ｎ−ジメチル−ｏ−トルエンスルホンアミド、Ｎ−ｎ−ブチル−ｏ−トルエンスルホンアミド、Ｎ−ｔ−ブチル−ｏ−トルエンスルホンアミド、Ｎ，Ｎ−ジ−ｎ−ブチル−ｏ−トルエンスルホンアミド、Ｎ−フェニル−ｏ−トルエンスルホンアミド、Ｎ，Ｎ−ジフェニル−ｏ−トルエンスルホンアミド、Ｎ−ｐ−トリル−ｏ−トルエンスルホンアミド、Ｎ−ｍ−トリル−ｏ−トルエンスルホンアミド、Ｎ，Ｎ−ジ−ｐ−トリル−ｏ−トルエンスルホンアミド、Ｎ，Ｎ−ジ−ｍ−トリル−ｏ−トルエンスルホンアミド、ナフタレンスルホンアミド、Ｎ−メチルナフタレンスルホンアミド、Ｎ−エチルナフタレンスルホンアミド、Ｎ，Ｎ−ジメチルナフタレンスルホンアミド、Ｎ−ｎ−ブチルナフタレンスルホンアミド、Ｎ−ｔ−ブチルナフタレンスルホンアミド、Ｎ，Ｎ−ジ−ｎ−ブチルナフタレンスルホンアミド、Ｎ−フェニルナフタレンスルホンアミド、Ｎ，Ｎ−ジフェニルナフタレンスルホンアミド、Ｎ−ｐ−トリルナフタレンスルホンアミド、Ｎ−ｏ−トリルナフタレンスルホンアミド、Ｎ−ｍ−トリルナフタレンスルホンアミド、Ｎ，Ｎ−ジ−ｐ−トリルナフタレンスルホンアミド、Ｎ，Ｎ−ジ−ｍ−トリルナフタレンスルホンアミド、２，３−ジメチルベンゼンスルホンアミド、Ｎ−メチル−２，３−ジメチルベンゼンスルホンアミド、Ｎ−ｎ−ブチル−２，３−ジメチルベンゼンスルホンアミド、ｐ−エチルベンゼンスルホンアミド、Ｎ−メチル−ｐ−エチルベンゼンスルホンアミド、Ｎ−エチルベンゼンスルホンアミド、Ｎ，Ｎ−ジメチルベンゼンスルホンアミド、Ｎ−ｎ−ブチル−ｐ−エチルベンゼンスルホンアミド等が例示できる。また基材との密着力向上のために、各種のシランカップリング剤やベンゾトリアゾール類、ベンゾチアゾール類、チアジアゾール類などの化合物を添加しても良い。 The photosensitive resin composition of this invention can be obtained by mixing said polyimide precursor resin, a photopolymerizable monomer, and a polymerization initiator. Moreover, the photosensitive resin composition of this invention may contain various additives as needed. For example, as dyes and pigments for improving visibility during development, phenolphthalein, phenol red, neil red, pyrogallol red, pyrogallol billet, disperse thread 1, disper thread 13, disper thread 19, disperse orange 1, Disperse orange 3, disperse orange 13, disperse orange 25, disperse blue 3, disperse blue 14, eosin B, rhodamine B, quinalizarin, 5- (4-dimethylaminobenzylidene) rhodanine, aurintricarboxyacid, aluminon , Alizarin, pararosaniline, emodin, thionine, methylene violet, pigment blue, pigment red and the like. Further, as an additive for improving the dissolution promotion in the non-exposed area, benzenesulfonamide, N-methylbenzenesulfonamide, N-ethylbenzenesulfonamide, N, N-dimethylbenzenesulfonamide, Nn-butylbenzenesulfonamide Nt-butylbenzenesulfonamide, N, N-di-n-butylbenzenesulfonamide, benzenesulfonanilide, N, N-diphenylbenzenesulfonamide, Np-tolylbenzenesulfonamide, N-o-tolyl Benzenesulfonamide, Nm-tolylbenzenesulfonamide, N, N-di-p-tolylbenzenesulfonamide, p-toluenesulfonamide, N-methyl-p-toluenesulfonamide, N-ethyl-p-toluenesulfone Amide, N, N-dimethyl-p-to Ensulfonamide, Nn-butyl-p-toluenesulfonamide, Nt-butyl-p-toluenesulfonamide, N, N-di-n-butyl-p-toluenesulfonamide, N-phenyl-p- Toluenesulfonamide, N, N-diphenyl-p-toluenesulfonamide, Np-tolyl-p-toluenesulfonamide, Nm-tolyl-p-toluenesulfonamide, N, N-di-p-tolyl- p-toluenesulfonamide, N, N-di-m-tolyl-p-toluenesulfonamide, o-toluenesulfonamide, N-methyl-o-toluenesulfonamide, N-ethyl-o-toluenesulfonamide, N, N-dimethyl-o-toluenesulfonamide, Nn-butyl-o-toluenesulfonamide, Nt-butyl-o-toluene Sulfonamide, N, N-di-n-butyl-o-toluenesulfonamide, N-phenyl-o-toluenesulfonamide, N, N-diphenyl-o-toluenesulfonamide, Np-tolyl-o- Toluenesulfonamide, Nm-tolyl-o-toluenesulfonamide, N, N-di-p-tolyl-o-toluenesulfonamide, N, N-di-m-tolyl-o-toluenesulfonamide, naphthalenesulfone Amide, N-methylnaphthalenesulfonamide, N-ethylnaphthalenesulfonamide, N, N-dimethylnaphthalenesulfonamide, Nn-butylnaphthalenesulfonamide, Nt-butylnaphthalenesulfonamide, N, N-di-n -Butylnaphthalenesulfonamide, N-phenylnaphthalenesulfonamide, N, N- Diphenylnaphthalenesulfonamide, Np-tolylnaphthalenesulfonamide, No-tolylnaphthalenesulfonamide, Nm-tolylnaphthalenesulfonamide, N, N-di-p-tolylnaphthalenesulfonamide, N, N-di -M-Tolylnaphthalenesulfonamide, 2,3-dimethylbenzenesulfonamide, N-methyl-2,3-dimethylbenzenesulfonamide, Nn-butyl-2,3-dimethylbenzenesulfonamide, p-ethylbenzenesulfonamide N-methyl-p-ethylbenzenesulfonamide, N-ethylbenzenesulfonamide, N, N-dimethylbenzenesulfonamide, Nn-butyl-p-ethylbenzenesulfonamide and the like. In addition, various silane coupling agents and compounds such as benzotriazoles, benzothiazoles, and thiadiazoles may be added to improve adhesion to the substrate.
上記の感光性樹脂組成物を基材上に塗布して製膜する工程、得られた膜を加熱して溶媒を除去する工程、溶媒を除去した膜に対して、マスクを通して露光する工程、現像液を用いて現像する工程、現像後の膜を加熱硬化する工程により、ポリイミド樹脂膜が得られる。 A step of coating the above photosensitive resin composition on a substrate to form a film, a step of heating the obtained film to remove the solvent, a step of exposing the film from which the solvent has been removed through a mask, development A polyimide resin film is obtained by a step of developing using a liquid and a step of heat-curing the film after development.
感光性樹脂組成物の塗布は、スクリーン印刷やスピンコート等一般的な方法を用いることができる。またその後の工程についても従来のネガ型感光性樹脂組成物を使用する場合と同様に行うことができる。 Application | coating of the photosensitive resin composition can use general methods, such as screen printing and a spin coat. Moreover, it can carry out similarly to the case where the conventional negative photosensitive resin composition is used also about a subsequent process.
このようにして得られたポリイミド樹脂膜は厚膜成形が可能であり現像時の膜厚を２０μｍ以上にできる。更に熱膨張係数を１０ｐｐｍ／℃以上２０ｐｐｍ／℃以下とすることができる。ステンレスの熱膨張係数は約１７ｐｐｍ／℃、銅の熱膨張係数は約１９ｐｐｍ／℃であるため、本発明のポリイミド樹脂膜の熱膨張係数はこれらの金属の熱膨張係数に近く、両者を組み合わせた場合に、温度変化による反りの少ない製品を得ることができる。 The polyimide resin film thus obtained can be formed into a thick film, and the film thickness during development can be 20 μm or more. Furthermore, the thermal expansion coefficient can be 10 ppm / ° C. or more and 20 ppm / ° C. or less. Since the thermal expansion coefficient of stainless steel is about 17 ppm / ° C. and the thermal expansion coefficient of copper is about 19 ppm / ° C., the thermal expansion coefficient of the polyimide resin film of the present invention is close to the thermal expansion coefficient of these metals. In some cases, a product with less warpage due to temperature change can be obtained.
なお、熱膨張係数は熱機械分析装置（ＴＭＡ）により測定することができ、５０℃から１５０℃までの平均値とする。 The thermal expansion coefficient can be measured by a thermomechanical analyzer (TMA), and is an average value from 50 ° C to 150 ° C.
また本発明は、上記のポリイミド樹脂膜を保護膜として有するフレキシブルプリント配線板を提供する。例えばポリイミド基材の片面に銅等の金属からなる導体配線を有し、その導体配線上に上記のポリイミド樹脂膜をカバーレイフィルム（保護膜）として有する片面フレキシブルプリント配線板が例示できる。またステンレス等の金属箔基材上にポリイミド等の絶縁層を有し、その上に銅等の金属からなる導体配線（回路）を有し、その導体配線上に該ポリイミド樹脂膜を保護膜として有する回路付きサスペンション基板も例示できる。この場合、本発明のポリイミド樹脂膜を金属箔基材上の絶縁層として使用することも可能である。この回路付きサスペンション基板は、ハードディスクドライブに使用されるサスペンション用の基板として用いられる。 Moreover, this invention provides the flexible printed wiring board which has said polyimide resin film as a protective film. For example, a single-sided flexible printed wiring board having conductor wiring made of a metal such as copper on one side of a polyimide base material and having the polyimide resin film as a coverlay film (protective film) on the conductor wiring can be exemplified. In addition, an insulating layer such as polyimide is provided on a metal foil base material such as stainless steel, conductor wiring (circuit) made of metal such as copper is provided thereon, and the polyimide resin film is used as a protective film on the conductor wiring. The suspension board with a circuit which has can also be illustrated. In this case, the polyimide resin film of the present invention can be used as an insulating layer on the metal foil substrate. This suspension board with circuit is used as a suspension board used in a hard disk drive.
次に発明を実施するための最良の形態を実施例により説明する。実施例は本発明の範囲を限定するものではない。 Next, the best mode for carrying out the invention will be described by way of examples. The examples are not intended to limit the scope of the invention.
（実施例１）
２，２’−ビス（トリフルオロメチル）４，４’−ジアミノビフェニル（ＴＦＭＢ）３５．５ｇ（１１１ｍｍｏｌ）、ｐ−フェニレンジアミン（ＰＰＤ）１９．４ｇ（１８０ｍｍｏｌ）、１，３−ビス（３−アミノプロピル）テトラメチルジシロキサン（ＡＰＤＳ）０．５６ｇ（２．２５ｍｍｏｌ）をＮ−メチルピロリドン７００ｇに溶解させた後、３，４，３’，４’−ビフェニルテトラカルボン酸二無水物（ＢＰＤＡ）４４．２ｇ（１５０ｍｍｏｌ）とピロメリット酸二無水物（ＰＭＤＡ）３２．７ｇ（１５０ｍｍｏｌ）を加えて窒素雰囲気下室温で１時間撹拌した。その後６０℃で２０時間撹拌し反応を終えた。合成した共重合ワニスの固形分は１６．５％であった。このワニスに光重合性モノマーであるメタクリル酸Ｎ，Ｎ−ジメチルアミノエチル（ＤＡＥＭ）をポリアミック酸のカルボン酸に対して１．２当量、また重合開始剤として２−ベンジル２−（ジメチルアミノジメチルアミノ）−１−［４−（４−モルフォリニル）フェニル］−１−ブタノン（波長３６５ｎｍでのモル吸光係数１５００）とビス（η５−２−，４−シクロペンタジエン−１−イル）−ビス（２，６−ジフルオロ−３−（１Ｈ−ピロール−１−イル）−フェニル）チタニウム（波長４３６ｎｍでのモル吸光係数２１）を樹脂固形分に対してそれぞれ４％と２％混合し、感光性樹脂組成物を作製した。
Example 1
2,2′-bis (trifluoromethyl) 4,4′-diaminobiphenyl (TFMB) 35.5 g (111 mmol), p-phenylenediamine (PPD) 19.4 g (180 mmol), 1,3-bis (3- Aminopropyl) tetramethyldisiloxane (APDS) 0.56 g (2.25 mmol) was dissolved in 700 g of N-methylpyrrolidone, and then 3,4,3 ′, 4′-biphenyltetracarboxylic dianhydride (BPDA). 44.2 g (150 mmol) and pyromellitic dianhydride (PMDA) 32.7 g (150 mmol) were added and stirred at room temperature for 1 hour in a nitrogen atmosphere. Thereafter, the reaction was completed by stirring at 60 ° C. for 20 hours. The synthesized copolymer varnish had a solid content of 16.5%. In this varnish, 1.2 equivalents of N, N-dimethylaminoethyl methacrylate (DAEM), which is a photopolymerizable monomer, with respect to the carboxylic acid of polyamic acid, and 2-benzyl 2- (dimethylaminodimethylamino) as a polymerization initiator. ) -1- [4- (4-Morpholinyl) phenyl] -1-butanone (molar extinction coefficient 1500 at a wavelength of 365 nm) and bis (η5-2,4-cyclopentadien-1-yl) -bis (2, 6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium (molar extinction coefficient 21 at a wavelength of 436 nm) was mixed with 4% and 2%, respectively, with respect to the resin solid content, and a photosensitive resin composition Was made.
厚み４０μｍの銅箔上に上記感光性樹脂組成物をスピンコート法によって塗布した後、９０℃で３０分間加熱乾燥して厚み２０μｍの感光性ポリイミド前駆体の被膜を形成した。次いでネガ型のテストパターンを介し露光量５００ｍＪ／ｃｍ２で紫外光を照射した後、１０５℃で１０分間ポストベークを行った。続いて有機溶剤系現像液を用いて３０℃で現像処理を行い、蒸留水で十分洗浄した後、窒素気流で強制風乾燥した。その後、窒素雰囲気下で１２０℃で３０分間、２２０℃で３０分間、３４０℃で６０分間の熱処理を行ってポリイミド前駆体のイミド化を行ったところ、膜減りもほぼなく良好な現像パターンを保ったポリイミド樹脂膜が得られた。得られた硬化後ポリイミド膜の熱膨張係数は１６ｐｐｍ／℃、残膜率は８９％であった。なお、熱膨張係数はセイコーインスツルメンツ（株）製熱応力歪測定装置「ＴＭＡ／ＳＳ１２０Ｃ」を用いたＴＭＡ測定（引張試験）で行い、温度範囲−５０℃→２００℃→−５０℃の温度上昇、下降の両方で測定して、５０℃から１５０℃までの温度範囲での平均値を求めた。 The photosensitive resin composition was applied onto a copper foil having a thickness of 40 μm by a spin coating method, and then heated and dried at 90 ° C. for 30 minutes to form a film of a photosensitive polyimide precursor having a thickness of 20 μm. Next, ultraviolet light was irradiated through a negative test pattern at an exposure amount of 500 mJ / cm 2 and then post-baked at 105 ° C. for 10 minutes. Subsequently, development processing was performed at 30 ° C. using an organic solvent-based developer, washed thoroughly with distilled water, and then forced-air dried with a nitrogen stream. Then, when the polyimide precursor was imidized by performing heat treatment at 120 ° C. for 30 minutes, 220 ° C. for 30 minutes, and 340 ° C. for 60 minutes in a nitrogen atmosphere, a good development pattern was maintained with almost no film loss. A polyimide resin film was obtained. The obtained cured polyimide film had a thermal expansion coefficient of 16 ppm / ° C. and a residual film ratio of 89%. The thermal expansion coefficient is measured by TMA measurement (tensile test) using a thermal stress strain measuring device “TMA / SS120C” manufactured by Seiko Instruments Inc., and the temperature rise is −50 ° C. → 200 ° C. → −50 ° C. The average value in the temperature range from 50 ° C. to 150 ° C. was determined by measuring both in descending.
（実施例２）
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（ＢＩＳ−Ａ−ＡＦ）４１．７ｇ（１１４ｍｍｏｌ）、２，２’−ジメチル４，４’−ジアミノビフェニル（ｍＴＢＨＧ）３８．２ｇ（１８０ｍｍｏｌ）、１，３−ビス（３−アミノプロピル）テトラメチルジシロキサン（ＡＰＤＳ）１．４９ｇ（６．０ｍｍｏｌ）をＮ−メチルピロリドン７００ｇに溶解させた後、３，４，３’，４’−ビフェニルテトラカルボン酸二無水物（ＢＰＤＡ）５７．４ｇ（１９５ｍｍｏｌ）とピロメリット酸二無水物（ＰＭＤＡ）２２．９ｇ（１０５ｍｍｏｌ）を加えて窒素雰囲気下室温で１時間撹拌した。その後６０℃で２０時間撹拌し反応を終えた。合成した共重合ワニスの固形分は１８．９％であった。このワニスに光重合性モノマーであるメタクリル酸Ｎ，Ｎ−ジメチルアミノエチル（ＤＡＥＭ）をポリアミック酸のカルボン酸に対して１．２当量、また重合開始剤として２−ベンジル２−（ジメチルアミノジメチルアミノ）−１−［４−（４−モルフォリニル）フェニル］−１−ブタノンとビス（η５−２−，４−シクロペンタジエン−１−イル）−ビス（２，６−ジフルオロ−３−（１Ｈ−ピロール−１−イル）−フェニル）チタニウムを樹脂固形分に対してそれぞれ４％と２％混合し、感光性樹脂組成物を作製した。
(Example 2)
2,2′-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (BIS-A-AF) 41.7 g (114 mmol), 2,2′-dimethyl 4,4′-diaminobiphenyl (mTBHG) 38 .2 g (180 mmol), 1,3-bis (3-aminopropyl) tetramethyldisiloxane (APDS) 1.49 g (6.0 mmol) was dissolved in 700 g of N-methylpyrrolidone, and then 3, 4, 3 ′ , 4′-biphenyltetracarboxylic dianhydride (BPDA) 57.4 g (195 mmol) and pyromellitic dianhydride (PMDA) 22.9 g (105 mmol) were added and stirred at room temperature for 1 hour under a nitrogen atmosphere. Thereafter, the reaction was completed by stirring at 60 ° C. for 20 hours. The solid content of the synthesized copolymer varnish was 18.9%. In this varnish, 1.2 equivalents of N, N-dimethylaminoethyl methacrylate (DAEM), which is a photopolymerizable monomer, with respect to the carboxylic acid of polyamic acid, and 2-benzyl 2- (dimethylaminodimethylamino) as a polymerization initiator. ) -1- [4- (4-Morpholinyl) phenyl] -1-butanone and bis (η5-2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrole) The photosensitive resin composition was prepared by mixing 4% and 2% of -1-yl) -phenyl) titanium with respect to the resin solid content.
得られた感光性樹脂組成物を用いて、実施例１と同様にプリベーク後の厚みが２０μｍである樹脂膜を作成した。膜減りもほぼなく良好な現像パターンを保ったポリイミド樹脂膜が得られた。得られた硬化後ポリイミド膜の熱膨張係数は１９ｐｐｍ／℃、残膜率は８８％であった。 Using the resulting photosensitive resin composition, a resin film having a thickness after pre-baking of 20 μm was prepared in the same manner as in Example 1. A polyimide resin film having almost no film reduction and maintaining a good development pattern was obtained. The obtained cured polyimide film had a thermal expansion coefficient of 19 ppm / ° C. and a residual film ratio of 88%.
（実施例３）
２，２’−ビス（トリフルオロメチル）４，４’−ジアミノビフェニル（ＴＦＭＢ）４３．２ｇ（１３５ｍｍｏｌ）、２，２’−ジメチル４，４’−ジアミノビフェニル（ｍＴＢＨＧ）３３．８ｇ（１５９ｍｍｏｌ）、１，３−ビス（３−アミノプロピル）テトラメチルジシロキサン（ＡＰＤＳ）１．４９ｇ（６．０ｍｍｏｌ）をＮ−メチルピロリドン７００ｇに溶解させた後、３，４，３’，４’−ビフェニルテトラカルボン酸二無水物（ＢＰＤＡ）４４．２ｇ（１５０ｍｍｏｌ）とピロメリット酸二無水物（ＰＭＤＡ）３２．７ｇ（１５０ｍｍｏｌ）を加えて窒素雰囲気下室温で１時間撹拌した。その後６０℃で２０時間撹拌し反応を終えた。合成した共重合ワニスの固形分は１８．２％であった。このワニスに光重合性モノマーであるメタクリル酸Ｎ，Ｎ−ジメチルアミノエチル（ＤＡＥＭ）をポリアミック酸のカルボン酸に対して１．２当量、また重合開始剤として２−ベンジル２−（ジメチルアミノジメチルアミノ）−１−［４−（４−モルフォリニル）フェニル］−１−ブタノンとビス（η５−２−，４−シクロペンタジエン−１−イル）−ビス（２，６−ジフルオロ−３−（１Ｈ−ピロール−１−イル）−フェニル）チタニウムを樹脂固形分に対してそれぞれ４％と２％混合し、感光性樹脂組成物を作製した。
(Example 3)
2,2′-bis (trifluoromethyl) 4,4′-diaminobiphenyl (TFMB) 43.2 g (135 mmol), 2,2′-dimethyl4,4′-diaminobiphenyl (mTBHG) 33.8 g (159 mmol) 1,3-bis (3-aminopropyl) tetramethyldisiloxane (APDS) 1.49 g (6.0 mmol) was dissolved in 700 g of N-methylpyrrolidone, and then 3,4,3 ′, 4′-biphenyl was dissolved. Tetracarboxylic dianhydride (BPDA) 44.2 g (150 mmol) and pyromellitic dianhydride (PMDA) 32.7 g (150 mmol) were added, and the mixture was stirred at room temperature for 1 hour in a nitrogen atmosphere. Thereafter, the reaction was completed by stirring at 60 ° C. for 20 hours. The solid content of the synthesized copolymer varnish was 18.2%. In this varnish, 1.2 equivalents of N, N-dimethylaminoethyl methacrylate (DAEM), which is a photopolymerizable monomer, with respect to the carboxylic acid of polyamic acid, and 2-benzyl 2- (dimethylaminodimethylamino) as a polymerization initiator. ) -1- [4- (4-Morpholinyl) phenyl] -1-butanone and bis (η5-2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrole) The photosensitive resin composition was prepared by mixing 4% and 2% of -1-yl) -phenyl) titanium with respect to the resin solid content.
得られた感光性樹脂組成物を用いて、実施例１と同様にプリベーク後の厚みが２０μｍである樹脂膜を作成した。膜減りもほぼなく良好な現像パターンを保ったポリイミド樹脂膜が得られた。得られた硬化後ポリイミド膜の熱膨張係数は１８ｐｐｍ／℃、残膜率は９０％であった。 Using the resulting photosensitive resin composition, a resin film having a thickness after pre-baking of 20 μm was prepared in the same manner as in Example 1. A polyimide resin film having almost no film reduction and maintaining a good development pattern was obtained. The obtained cured polyimide film had a thermal expansion coefficient of 18 ppm / ° C. and a residual film ratio of 90%.
（実施例４）
２，２’−ビス（トリフルオロメチル）４，４’−ジアミノビフェニル（ＴＦＭＢ）４６．１ｇ（１４４ｍｍｏｌ）、ｐ−フェニレンジアミン（ＰＰＤ）１６．２ｇ（１５０ｍｍｏｌ）、１，３−ビス（３−アミノプロピル）テトラメチルジシロキサン（ＡＰＤＳ）１．４９ｇ（６ｍｍｏｌ）をＮ−メチルピロリドン７００ｇに溶解させた後、３，４，３’，４’−ビフェニルテトラカルボン酸二無水物（ＢＰＤＡ）８８．３ｇ（３００ｍｍｏｌ）を加えて窒素雰囲気下室温で１時間撹拌した。その後６０℃で２０時間撹拌し反応を終えた。合成した共重合ワニスの固形分は１７．０％であった。このワニスに光重合性モノマーであるメタクリル酸Ｎ，Ｎ−ジメチルアミノエチル（ＤＡＥＭ）をポリアミック酸のカルボン酸に対して１．２当量、また重合開始剤として２−ベンジル２−（ジメチルアミノジメチルアミノ）−１−［４−（４−モルフォリニル）フェニル］−１−ブタノンとビス（η５−２−，４−シクロペンタジエン−１−イル）−ビス（２，６−ジフルオロ−３−（１Ｈ−ピロール−１−イル）−フェニル）チタニウムを樹脂固形分に対してそれぞれ４％と２％混合し、感光性樹脂組成物を作製した。
Example 4
2,2′-bis (trifluoromethyl) 4,4′-diaminobiphenyl (TFMB) 46.1 g (144 mmol), p-phenylenediamine (PPD) 16.2 g (150 mmol), 1,3-bis (3- Aminopropyl) tetramethyldisiloxane (APDS) 1.49 g (6 mmol) was dissolved in N-methylpyrrolidone 700 g, and then 3,4,3 ′, 4′-biphenyltetracarboxylic dianhydride (BPDA) 88. 3 g (300 mmol) was added and stirred at room temperature for 1 hour under a nitrogen atmosphere. Thereafter, the reaction was completed by stirring at 60 ° C. for 20 hours. The solid content of the synthesized copolymer varnish was 17.0%. In this varnish, 1.2 equivalents of N, N-dimethylaminoethyl methacrylate (DAEM), which is a photopolymerizable monomer, with respect to the carboxylic acid of polyamic acid, and 2-benzyl 2- (dimethylaminodimethylamino) as a polymerization initiator. ) -1- [4- (4-Morpholinyl) phenyl] -1-butanone and bis (η5-2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrole) The photosensitive resin composition was prepared by mixing 4% and 2% of -1-yl) -phenyl) titanium with respect to the resin solid content.
得られた感光性樹脂組成物を用いて、実施例１と同様にプリベーク後の厚みが２０μｍであるポリイミド樹脂膜を作製した。膜減りもほぼなく良好な現像パターンを保っていた。得られた硬化後ポリイミド膜の熱膨張係数は１７ｐｐｍ／℃、残膜率は９１％であった。 Using the obtained photosensitive resin composition, a polyimide resin film having a thickness after pre-baking of 20 μm was prepared in the same manner as in Example 1. There was almost no film loss and a good development pattern was maintained. The obtained cured polyimide film had a thermal expansion coefficient of 17 ppm / ° C. and a residual film ratio of 91%.
（実施例５）
２，２−ビス（４−アミノフェニル）ヘキサフルオロプロパン（ＢＩＳ−Ａ−ＡＦ）３０．１ｇ（９０ｍｍｏｌ）、２，２’−ジメチル４，４’−ジアミノビフェニル（ｍＴＢＨＧ）４３．６ｇ（２０５．５ｍｍｏｌ）、１，３−ビス（３−アミノプロピル）テトラメチルジシロキサン（ＡＰＤＳ）１．１２ｇ（４．５ｍｍｏｌ）をＮ−メチルピロリドン７００ｇに溶解させた後、３，４，３’，４’−ビフェニルテトラカルボン酸二無水物（ＢＰＤＡ）２９．１ｇ（１００ｍｍｏｌ）とピロメリット酸二無水物（ＰＭＤＡ）４３．６ｇ（２００ｍｍｏｌ）を加えて窒素雰囲気下室温で１時間撹拌した。その後６０℃で２０時間撹拌し反応を終えた。合成した共重合ワニスの固形分は１６．５％であった。このワニスに光重合性モノマーであるメタクリル酸Ｎ，Ｎ−ジメチルアミノエチル（ＤＡＥＭ）をポリアミック酸のカルボン酸に対して１．２当量、また重合開始剤として２−ベンジル２−（ジメチルアミノジメチルアミノ）−１−［４−（４−モルフォリニル）フェニル］−１−ブタノンとビス（η５−２−，４−シクロペンタジエン−１−イル）−ビス（２，６−ジフルオロ−３−（１Ｈ−ピロール−１−イル）−フェニル）チタニウムを樹脂固形分に対してそれぞれ４％と２％混合し、感光性樹脂組成物を作製した。
(Example 5)
2,2-bis (4-aminophenyl) hexafluoropropane (BIS-A-AF) 30.1 g (90 mmol), 2,2′-dimethyl 4,4′-diaminobiphenyl (mTBHG) 43.6 g (205. 5 mmol), 1,3-bis (3-aminopropyl) tetramethyldisiloxane (APDS) 1.12 g (4.5 mmol) was dissolved in 700 g of N-methylpyrrolidone, and then 3,4,3 ′, 4 ′ -29.1 g (100 mmol) of biphenyltetracarboxylic dianhydride (BPDA) and 43.6 g (200 mmol) of pyromellitic dianhydride (PMDA) were added and stirred at room temperature for 1 hour in a nitrogen atmosphere. Thereafter, the reaction was completed by stirring at 60 ° C. for 20 hours. The synthesized copolymer varnish had a solid content of 16.5%. In this varnish, 1.2 equivalents of N, N-dimethylaminoethyl methacrylate (DAEM), which is a photopolymerizable monomer, with respect to the carboxylic acid of polyamic acid, and 2-benzyl 2- (dimethylaminodimethylamino) as a polymerization initiator. ) -1- [4- (4-Morpholinyl) phenyl] -1-butanone and bis (η5-2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrole) The photosensitive resin composition was prepared by mixing 4% and 2% of -1-yl) -phenyl) titanium with respect to the resin solid content.
得られた感光性樹脂組成物を用いて、実施例１と同様にプリベーク後の厚みが２０μｍであるポリイミド樹脂膜を作製した。膜減りもほぼなく良好な現像パターンを保っていた。得られた硬化後ポリイミド膜の熱膨張係数は１８ｐｐｍ／℃、残膜率は８９％であった。 Using the obtained photosensitive resin composition, a polyimide resin film having a thickness after pre-baking of 20 μm was prepared in the same manner as in Example 1. There was almost no film loss and a good development pattern was maintained. The resulting cured polyimide film had a thermal expansion coefficient of 18 ppm / ° C. and a residual film ratio of 89%.
（参考例１）
２，２’−ビス（トリフルオロメチル）４，４’−ジアミノビフェニル（ＴＦＭＢ）６２．４ｇ（１９５ｍｍｏｌ）、２，２’−ジメチル４，４’−ジアミノビフェニル（ｍＴＢＨＧ）２１．０ｇ（９９ｍｍｏｌ）、１，３−ビス（３−アミノプロピル）テトラメチルジシロキサン（ＡＰＤＳ）１．４９ｇ（６．０ｍｍｏｌ）をＮ−メチルピロリドン７００ｇに溶解させた後、３，４，３’，４’−ビフェニルテトラカルボン酸二無水物（ＢＰＤＡ）８８．３ｇ（３００ｍｍｏｌ）を加えて窒素雰囲気下室温で１時間撹拌した。その後６０℃で２０時間撹拌し反応を終えた。合成した共重合ワニスの固形分は１６．８％であった。このワニスに光重合性モノマーであるメタクリル酸Ｎ，Ｎ−ジメチルアミノエチル（ＤＡＥＭ）をポリアミック酸のカルボン酸に対して１．２当量、また重合開始剤として２−ベンジル２−（ジメチルアミノジメチルアミノ)−１−［４−（４−モルフォリニル)フェニル]−１−ブタノンとビス（η５−２−，４−シクロペンタジエン−１−イル）−ビス（２，６−ジフルオロ−３−（１Ｈ−ピロール−１−イル)−フェニル）チタニウムを樹脂固形分に対してそれぞれ４％と２％混合し、感光性樹脂組成物を作製した。
( Reference Example 1 )
2,2′-bis (trifluoromethyl) 4,4′-diaminobiphenyl (TFMB) 62.4 g (195 mmol), 2,2′-dimethyl4,4′-diaminobiphenyl (mTBHG) 21.0 g (99 mmol) 1,3-bis (3-aminopropyl) tetramethyldisiloxane (APDS) 1.49 g (6.0 mmol) was dissolved in 700 g of N-methylpyrrolidone, and then 3,4,3 ′, 4′-biphenyl was dissolved. Tetracarboxylic dianhydride (BPDA) 88.3 g (300 mmol) was added, and the mixture was stirred at room temperature for 1 hour in a nitrogen atmosphere. Thereafter, the reaction was completed by stirring at 60 ° C. for 20 hours. The solid content of the synthesized copolymer varnish was 16.8%. In this varnish, 1.2 equivalents of N, N-dimethylaminoethyl methacrylate (DAEM), which is a photopolymerizable monomer, with respect to the carboxylic acid of polyamic acid, and 2-benzyl 2- (dimethylaminodimethylamino) as a polymerization initiator. ) -1- [4- (4-Morpholinyl) phenyl] -1-butanone and bis (η5-2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrole) The photosensitive resin composition was prepared by mixing 4% and 2% of -1-yl) -phenyl) titanium, respectively, with respect to the resin solid content.
得られた感光性樹脂組成物を用いて、実施例１と同様にプリベーク後の厚みが２０μｍであるポリイミド樹脂膜を作製した。膜減りもほぼなく良好な現像パターンを保っていた。得られた硬化後ポリイミド膜の熱膨張係数は１９ｐｐｍ／℃、残膜率は９２％であった。 Using the obtained photosensitive resin composition, a polyimide resin film having a thickness after pre-baking of 20 μm was prepared in the same manner as in Example 1. There was almost no film loss and a good development pattern was maintained. The obtained cured polyimide film had a thermal expansion coefficient of 19 ppm / ° C. and a residual film ratio of 92%.
（参考例２）
２，２’−ジメチル４，４’−ジアミノビフェニル（ｍＴＢＨＧ）３０．６ｇ（１４４ｍｍｏｌ）、ｐ−フェニレンジアミン（ＰＰＤ）１６．２ｇ（１５０ｍｍｏｌ）、１，３−ビス（３−アミノプロピル）テトラメチルジシロキサン（ＡＰＤＳ）１．４９ｇ（６．０ｍｍｏｌ）をＮ−メチルピロリドン７００ｇに溶解させた後、３，４，３’，４’−ビフェニルテトラカルボン酸二無水物（ＢＰＤＡ）８８．３ｇ（３００ｍｍｏｌ）を加えて窒素雰囲気下室温で１時間撹拌した。その後６０℃で２０時間撹拌し反応を終えた。合成した共重合ワニスの固形分は１６．８％であった。このワニスに光重合性モノマーであるメタクリル酸Ｎ，Ｎ−ジメチルアミノエチル（ＤＡＥＭ）をポリアミック酸のカルボン酸に対して１．２当量、また重合開始剤として２−ベンジル２−（ジメチルアミノジメチルアミノ)−１−［４−（４−モルフォリニル)フェニル]−１−ブタノンとビス（η５−２−，４−シクロペンタジエン−１−イル）−ビス（２，６−ジフルオロ−３−（１Ｈ−ピロール−１−イル)−フェニル）チタニウムを樹脂固形分に対してそれぞれ４％と２％混合し、感光性樹脂組成物を作製した。
( Reference Example 2 )
2,2′-dimethyl 4,4′-diaminobiphenyl (mTBHG) 30.6 g (144 mmol), p-phenylenediamine (PPD) 16.2 g (150 mmol), 1,3-bis (3-aminopropyl) tetramethyl After dissolving 1.49 g (6.0 mmol) of disiloxane (APDS) in 700 g of N-methylpyrrolidone, 88.3 g (300 mmol) of 3,4,3 ′, 4′-biphenyltetracarboxylic dianhydride (BPDA) ) And stirred at room temperature for 1 hour under a nitrogen atmosphere. Thereafter, the reaction was completed by stirring at 60 ° C. for 20 hours. The solid content of the synthesized copolymer varnish was 16.8%. In this varnish, 1.2 equivalents of N, N-dimethylaminoethyl methacrylate (DAEM), which is a photopolymerizable monomer, with respect to the carboxylic acid of polyamic acid, and 2-benzyl 2- (dimethylaminodimethylamino) as a polymerization initiator. ) -1- [4- (4-Morpholinyl) phenyl] -1-butanone and bis (η5-2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrole) The photosensitive resin composition was prepared by mixing 4% and 2% of -1-yl) -phenyl) titanium, respectively, with respect to the resin solid content.
得られた感光性樹脂組成物を用いて、実施例１と同様にプリベーク後の厚みが２０μｍであるポリイミド樹脂膜を作製した。膜減りもほぼなく良好な現像パターンを保っていた。得られた硬化後ポリイミド膜の熱膨張係数は２３ｐｐｍ／℃、残膜率は９３％であった。 Using the obtained photosensitive resin composition, a polyimide resin film having a thickness after pre-baking of 20 μm was prepared in the same manner as in Example 1. There was almost no film loss and a good development pattern was maintained. The obtained cured polyimide film had a thermal expansion coefficient of 23 ppm / ° C. and a residual film ratio of 93%.
（実施例８）
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（ＢＩＳ−Ａ−ＡＦ）４１．７ｇ（１１４ｍｍｏｌ）、２，２’−ジメチル４，４’−ジアミノビフェニル（ｍＴＢＨＧ）３８．２ｇ（１８０ｍｍｏｌ）、１，３−ビス（３−アミノプロピル）テトラメチルジシロキサン（ＡＰＤＳ）１．４９ｇ（６．０ｍｍｏｌ）をＮ−メチルピロリドン７００ｇに溶解させた後、３，４，３’，４’−ビフェニルテトラカルボン酸二無水物（ＢＰＤＡ）５７．４ｇ（１９５ｍｍｏｌ）とピロメリット酸二無水物（ＰＭＤＡ）２２．９ｇ（１０５ｍｍｏｌ）を加えて窒素雰囲気下室温で１時間撹拌した。その後６０℃で２０時間撹拌し反応を終えた。合成した共重合ワニスの固形分は１８．９％であった。このワニスに光重合性モノマーであるメタクリル酸Ｎ，Ｎ−ジメチルアミノエチル（ＤＡＥＭ）をポリアミック酸のカルボン酸に対して１．２当量、また重合開始剤としてビス（η５−２−，４−シクロペンタジエン−１−イル）−ビス（２，６−ジフルオロ−３−（１Ｈ−ピロール−１−イル）−フェニル）チタニウムのみを樹脂固形分に対して３％混合し、感光性樹脂組成物を作製した。
(Example 8)
2,2′-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (BIS-A-AF) 41.7 g (114 mmol), 2,2′-dimethyl 4,4′-diaminobiphenyl (mTBHG) 38 .2 g (180 mmol), 1,3-bis (3-aminopropyl) tetramethyldisiloxane (APDS) 1.49 g (6.0 mmol) was dissolved in 700 g of N-methylpyrrolidone, and then 3, 4, 3 ′ , 4′-biphenyltetracarboxylic dianhydride (BPDA) 57.4 g (195 mmol) and pyromellitic dianhydride (PMDA) 22.9 g (105 mmol) were added and stirred at room temperature for 1 hour under a nitrogen atmosphere. Thereafter, the reaction was completed by stirring at 60 ° C. for 20 hours. The solid content of the synthesized copolymer varnish was 18.9%. In this varnish, 1.2 equivalents of N, N-dimethylaminoethyl methacrylate (DAEM), which is a photopolymerizable monomer, with respect to the carboxylic acid of polyamic acid, and bis (η5-2,4-cyclohexane) as a polymerization initiator. Only 3% of pentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium is mixed with the resin solids to produce a photosensitive resin composition. did.
得られた感光性樹脂組成物を用いて、実施例１と同様にプリベーク後の厚みが２０μｍである樹脂膜を作成した。得られた硬化後ポリイミド膜の残膜率は７０％と低めであったが、細部までパターニングできていた。また熱膨張係数は１８ｐｐｍ／℃、残膜率は８８％であった。 Using the resulting photosensitive resin composition, a resin film having a thickness after pre-baking of 20 μm was prepared in the same manner as in Example 1. Although the residual film ratio of the obtained polyimide film after curing was as low as 70%, it was possible to pattern the details. The thermal expansion coefficient was 18 ppm / ° C., and the remaining film rate was 88%.
（比較例１）
２，２−ビス（４−アミノフェニル）ヘキサフルオロプロパン（ＢＩＳ−Ａ−ＡＦ）５０．１ｇ（１５０ｍｍｏｌ）、ｐ−フェニレンジアミン（ＰＰＤ）１５．６ｇ（１４４ｍｍｏｌ）、１，３−ビス（３−アミノプロピル）テトラメチルジシロキサン（ＡＰＤＳ）１．４９ｇ（６．０ｍｍｏｌ）をＮ−メチルピロリドン７００ｇに溶解させた後、ピロメリット酸二無水物（ＰＭＤＡ）６５．４ｇ（３００ｍｍｏｌ）を加えて窒素雰囲気下室温で１時間撹拌した。その後６０℃で２０時間撹拌し反応を終えた。合成した共重合ワニスの固形分は１５．９％であった。このワニスに光重合性モノマーであるメタクリル酸Ｎ，Ｎ−ジメチルアミノエチル（ＤＡＥＭ）をポリアミック酸のカルボン酸に対して１．２当量、また重合開始剤として２−ベンジル２−（ジメチルアミノジメチルアミノ）−１−［４−（４−モルフォリニル）フェニル］−１−ブタノンとビス（η５−２−，４−シクロペンタジエン−１−イル）−ビス（２，６−ジフルオロ−３−（１Ｈ−ピロール−１−イル）−フェニル）チタニウムを樹脂固形分に対してそれぞれ４％と２％混合し、感光性樹脂組成物を作製した。
(Comparative Example 1)
2,2-bis (4-aminophenyl) hexafluoropropane (BIS-A-AF) 50.1 g (150 mmol), p-phenylenediamine (PPD) 15.6 g (144 mmol), 1,3-bis (3- Aminopropyl) tetramethyldisiloxane (APDS) 1.49 g (6.0 mmol) was dissolved in 700 g of N-methylpyrrolidone, and then 65.4 g (300 mmol) of pyromellitic dianhydride (PMDA) was added to the nitrogen atmosphere. The mixture was stirred at room temperature for 1 hour. Thereafter, the reaction was completed by stirring at 60 ° C. for 20 hours. The synthesized copolymer varnish had a solid content of 15.9%. In this varnish, 1.2 equivalents of N, N-dimethylaminoethyl methacrylate (DAEM), which is a photopolymerizable monomer, with respect to the carboxylic acid of polyamic acid, and 2-benzyl 2- (dimethylaminodimethylamino) as a polymerization initiator. ) -1- [4- (4-Morpholinyl) phenyl] -1-butanone and bis (η5-2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrole) The photosensitive resin composition was prepared by mixing 4% and 2% of -1-yl) -phenyl) titanium with respect to the resin solid content.
得られた感光性樹脂組成物を用いて、実施例１と同様にプリベーク後の厚みが２０μｍであるポリイミド樹脂膜を作製した。硬化後の膜には若干の剥離が見られた。得られた硬化後ポリイミド膜の熱膨張係数は２５ｐｐｍ／℃、残膜率は７１％であった。ジアミン成分として使用したＰＰＤとＰＭＤＡはベンゼン環一つの構造で、これらを使用すると分子が剛直になって熱膨張係数は低下するが、現像液への溶解性が悪くなる。その結果残膜率が低下したものと推測される。 Using the obtained photosensitive resin composition, a polyimide resin film having a thickness after pre-baking of 20 μm was prepared in the same manner as in Example 1. Some peeling was observed in the cured film. The obtained cured polyimide film had a thermal expansion coefficient of 25 ppm / ° C. and a residual film ratio of 71%. The PPD and PMDA used as the diamine component have a single benzene ring structure. When these are used, the molecule becomes rigid and the thermal expansion coefficient is lowered, but the solubility in the developer is deteriorated. As a result, it is presumed that the remaining film rate has decreased.
（比較例２）
２，２’−ビス（トリフルオロメチル）４，４’−ジアミノビフェニル（ＴＦＭＢ）４８．０ｇ（１５０ｍｍｏｌ）、ｐ−フェニレンジアミン（ＰＰＤ）１６．２ｇ（１５０ｍｍｏｌ）、をＮ−メチルピロリドン７００ｇに溶解させた後、３，４，３’，４’−ビフェニルテトラカルボン酸二無水物（ＢＰＤＡ）８８．３ｇ（３００ｍｍｏｌ）を加えて窒素雰囲気下室温で１時間撹拌した。その後６０℃で２０時間撹拌し反応を終えた。合成した共重合ワニスの固形分は１６．２％であった。このワニスに光重合性モノマーであるメタクリル酸Ｎ，Ｎ−ジメチルアミノエチル（ＤＡＥＭ）をポリアミック酸のカルボン酸に対して１．２当量、また重合開始剤として２−ベンジル２−（ジメチルアミノジメチルアミノ）−１−［４−（４−モルフォリニル）フェニル］−１−ブタノンとビス（η５−２−，４−シクロペンタジエン−１−イル）−ビス（２，６−ジフルオロ−３−（１Ｈ−ピロール−１−イル）−フェニル）チタニウムを樹脂固形分に対してそれぞれ４％と２％混合し、感光性樹脂組成物を作製した。
(Comparative Example 2)
Dissolve 48.0 g (150 mmol) of 2,2′-bis (trifluoromethyl) 4,4′-diaminobiphenyl (TFMB) and 16.2 g (150 mmol) of p-phenylenediamine (PPD) in 700 g of N-methylpyrrolidone. Then, 88.3 g (300 mmol) of 3,4,3 ′, 4′-biphenyltetracarboxylic dianhydride (BPDA) was added and stirred at room temperature for 1 hour under a nitrogen atmosphere. Thereafter, the reaction was completed by stirring at 60 ° C. for 20 hours. The solid content of the synthesized copolymer varnish was 16.2%. In this varnish, 1.2 equivalents of N, N-dimethylaminoethyl methacrylate (DAEM), which is a photopolymerizable monomer, with respect to the carboxylic acid of polyamic acid, and 2-benzyl 2- (dimethylaminodimethylamino) as a polymerization initiator. ) -1- [4- (4-Morpholinyl) phenyl] -1-butanone and bis (η5-2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrole) The photosensitive resin composition was prepared by mixing 4% and 2% of -1-yl) -phenyl) titanium with respect to the resin solid content.
得られた感光性樹脂組成物を用いて、実施例１と同様にプリベーク後の厚みが２０μｍであるポリイミド樹脂膜を作製した。硬化後、ポリイミド膜細部に剥がれが見られ、銅箔との接着力が充分に得られなかった。得られた硬化後ポリイミド膜の熱膨張係数は１５ｐｐｍ／℃、残膜率は９３％であった。 Using the obtained photosensitive resin composition, a polyimide resin film having a thickness after pre-baking of 20 μm was prepared in the same manner as in Example 1. After curing, peeling was observed in the details of the polyimide film, and sufficient adhesive strength with the copper foil was not obtained. The obtained cured polyimide film had a thermal expansion coefficient of 15 ppm / ° C. and a residual film ratio of 93%.
以上の結果を表１、表２にまとめる。なお、残膜率は未現像の最終硬化後サンプルの膜厚と、現像・硬化後サンプルの露光部（残膜部）膜厚とを比較して求めた。本発明の感光性樹脂組成物（実施例１〜８）では膜厚２０μｍでも良好に現像が行え、さらに硬化後のポリイミド樹脂膜の熱膨張係数を低くすることができることがわかる。 The above results are summarized in Tables 1 and 2. The remaining film ratio was obtained by comparing the film thickness of the undeveloped final cured sample with the exposed portion (residual film portion) film thickness of the developed / cured sample. It can be seen that the photosensitive resin compositions (Examples 1 to 8) of the present invention can be developed satisfactorily even with a film thickness of 20 μm, and the thermal expansion coefficient of the cured polyimide resin film can be lowered.
（実施例９）
２，２’−ビス（トリフルオロメチル）４，４’−ジアミノビフェニル（ＴＦＭＢ）４６．１ｇ（１４４ｍｍｏｌ）、ｐ−フェニレンジアミン（ＰＰＤ）１６．２ｇ（１５０ｍｍｏｌ）、１，３−ビス（３−アミノプロピル）テトラメチルジシロキサン（ＡＰＤＳ）１．４９ｇ（６ｍｍｏｌ）をＮ−メチルピロリドン７００ｇに溶解させた後、３，４，３’，４’−ビフェニルテトラカルボン酸二無水物（ＢＰＤＡ）８８．３ｇ（３００ｍｍｏｌ）を加えて窒素雰囲気下室温で１時間撹拌した。その後６０℃で２０時間撹拌し反応を終えた。合成した共重合ワニスの固形分は１７．０％であった。このワニスに光重合性モノマーであるメタクリル酸Ｎ，Ｎ−ジメチルアミノエチル（ＤＡＥＭ）をポリアミック酸のカルボン酸に対して１．２当量、また重合開始剤として２−ベンジル２−（ジメチルアミノジメチルアミノ）−１−［４−（４−モルフォリニル）フェニル］−１−ブタノンとビス（シクロペンタジエニル）−ビス［２，６−ジフルオロ−３−（ピリ−Ｉ−イル）フェニル］チタンを樹脂固形分に対してそれぞれ４％と２％混合し、さらにベンゼンスルホンアニリドを樹脂固形分に対して１０％配合し、感光性樹脂組成物を作製した。
Example 9
2,2′-bis (trifluoromethyl) 4,4′-diaminobiphenyl (TFMB) 46.1 g (144 mmol), p-phenylenediamine (PPD) 16.2 g (150 mmol), 1,3-bis (3- Aminopropyl) tetramethyldisiloxane (APDS) 1.49 g (6 mmol) was dissolved in N-methylpyrrolidone 700 g, and then 3,4,3 ′, 4′-biphenyltetracarboxylic dianhydride (BPDA) 88. 3 g (300 mmol) was added and stirred at room temperature for 1 hour under a nitrogen atmosphere. Thereafter, the reaction was completed by stirring at 60 ° C. for 20 hours. The solid content of the synthesized copolymer varnish was 17.0%. In this varnish, 1.2 equivalents of N, N-dimethylaminoethyl methacrylate (DAEM), which is a photopolymerizable monomer, with respect to the carboxylic acid of polyamic acid, and 2-benzyl 2- (dimethylaminodimethylamino) as a polymerization initiator. ) -1- [4- (4-morpholinyl) phenyl] -1-butanone and bis (cyclopentadienyl) -bis [2,6-difluoro-3- (pyri-I-yl) phenyl] titanium 4% and 2% were mixed with respect to each component, and further 10% of benzenesulfonanilide was blended with respect to the resin solid content to prepare a photosensitive resin composition.
得られた感光性樹脂組成物を用いて、実施例１と同様にプリベーク後の厚みが２０μｍであるポリイミド樹脂膜を作製した。膜減りもほぼなく良好な現像パターンを保っていた。得られた硬化後ポリイミド膜の熱膨張係数は１７ｐｐｍ／℃、残膜率は９０％であった。
表面Ｎｉめっきの銅箔上に同様に塗工し、全面露光硬化のサンプルを作製して、ピール試験を実施したところ、密着力は、０．５ｋｇｆ／ｃｍと良好であった。
Using the obtained photosensitive resin composition, a polyimide resin film having a thickness after pre-baking of 20 μm was prepared in the same manner as in Example 1. There was almost no film loss and a good development pattern was maintained. The obtained cured polyimide film had a thermal expansion coefficient of 17 ppm / ° C. and a residual film ratio of 90%.
Coating was similarly performed on a surface Ni-plated copper foil, and a sample for whole surface exposure curing was prepared. When a peel test was performed, the adhesion was as good as 0.5 kgf / cm.
（比較例３）
２，２’−ジメチル−４，４’−ジアミノビフェニル（ｍＴＢＨＧ）１２．７ｇ（６０ｍｍｏｌ）、ｐ−フェニレンジアミン（ＰＰＤ）２６．０ｇ（２４０ｍｍｏｌ）、をＮ−メチルピロリドン７００ｇに溶解させた後、３，４，３’，４’−ビフェニルテトラカルボン酸二無水物（ＢＰＤＡ）８８．３ｇ（３００ｍｍｏｌ）を加えて窒素雰囲気下室温で１時間撹拌した。その後６０℃で２０時間撹拌し反応を終えた。合成した共重合ワニスの固形分は１６．２％であった。このワニスに光重合性モノマーであるメタクリル酸Ｎ，Ｎ−ジメチルアミノエチル（ＤＡＥＭ）をポリアミック酸のカルボン酸に対して１．２当量、また重合開始剤として２−ベンジル２−（ジメチルアミノジメチルアミノ）−１−［４−（４−モルフォリニル）フェニル］−１−ブタノンとビス（η５−２−，４−シクロペンタジエン−１−イル）−ビス［２，６−ジフルオロ−３−（１Ｈ−ピロール−１−イル）−フェニル］チタニウムを樹脂固形分に対してそれぞれ４％と２％混合し、さらにベンゼンスルホンアニリドを樹脂固形分に対して１０％混合し、感光性樹脂組成物を作製した。
(Comparative Example 3)
2,2′-dimethyl-4,4′-diaminobiphenyl (mTBHG) 12.7 g (60 mmol) and p-phenylenediamine (PPD) 26.0 g (240 mmol) were dissolved in N-methylpyrrolidone 700 g, 8,8.3 g (300 mmol) of 3,4,3 ′, 4′-biphenyltetracarboxylic dianhydride (BPDA) was added and stirred at room temperature for 1 hour in a nitrogen atmosphere. Thereafter, the reaction was completed by stirring at 60 ° C. for 20 hours. The solid content of the synthesized copolymer varnish was 16.2%. In this varnish, 1.2 equivalents of N, N-dimethylaminoethyl methacrylate (DAEM), which is a photopolymerizable monomer, with respect to the carboxylic acid of polyamic acid, and 2-benzyl 2- (dimethylaminodimethylamino) as a polymerization initiator. ) -1- [4- (4-morpholinyl) phenyl] -1-butanone and bis (η5-2,4-cyclopentadien-1-yl) -bis [2,6-difluoro-3- (1H-pyrrole) -1-yl) -phenyl] titanium was mixed with 4% and 2% of resin solids, respectively, and benzenesulfonanilide was mixed with 10% of resin solids to prepare a photosensitive resin composition.
得られた感光性樹脂組成物を用いて、実施例１と同様にプリベーク後の厚みが２０μｍであるポリイミド樹脂膜を作製した。硬化後、ポリイミド膜細部に剥がれが見られ、銅箔との接着力が充分に得られなかった。得られた硬化後ポリイミド膜の熱膨張係数は１８ｐｐｍ／℃、残膜率は９２％であった。
表面Ｎｉめっきの銅箔上に同様に塗工し、全面露光硬化のサンプルを作製してピール試験を実施したところ、密着力は、０．１ｋｇｆ／ｃｍと低かった。
Using the obtained photosensitive resin composition, a polyimide resin film having a thickness after pre-baking of 20 μm was prepared in the same manner as in Example 1. After curing, peeling was observed in the details of the polyimide film, and sufficient adhesive strength with the copper foil was not obtained. The obtained cured polyimide film had a thermal expansion coefficient of 18 ppm / ° C. and a residual film ratio of 92%.
When coating was similarly performed on a surface Ni-plated copper foil, a sample for whole surface exposure curing was prepared and a peel test was performed, the adhesion was as low as 0.1 kgf / cm.
（現像時間の評価）
実施例９と比較例３の感光性樹脂組成物を銅箔上に塗布し、実施例１と同様にポストベークまでの作業を行った後、有機溶剤系現像液を用いて現像する際の現像時間を測定した。なお現像液の主成分はＮ−メチルピロリドンである。フッ素化モノマーをジアミン合計量に対して４８％含有する実施例９の組成物では、１０分間の現像でパターンが作成可能であったが、フッ素化モノマーを含まない比較例３の組成物では、現像でパターンを作成するのに２２分間必要であった。
(Evaluation of development time)
The photosensitive resin composition of Example 9 and Comparative Example 3 was applied on a copper foil, and after the work up to post-baking was performed in the same manner as in Example 1, development was performed using an organic solvent developer. Time was measured. The main component of the developer is N-methylpyrrolidone. In the composition of Example 9 containing 48% of the fluorinated monomer with respect to the total amount of diamine, a pattern could be formed by development for 10 minutes, but in the composition of Comparative Example 3 that does not contain the fluorinated monomer, It took 22 minutes to create a pattern by development.
現像時間の違いは、ベースポリイミド前駆体のＮＭＰなどへの溶解性の違いに起因していると考えられる。すなわち、ベースポリイミド前駆体が、実施例９では、溶解性の高いフッ素化ジアミンを多く含んで且つジシロキサンジアミンを含んでいるのに対して、比較例３では、フッ素化ジアミンを含有せず、またジシロキサンジアミンも含んでいないためである。これより、フッ素化ジアミンを多く含有することでプロセス時間の短縮、設備の簡易化に有効であることがわかる。 The difference in development time is considered to be due to the difference in solubility of the base polyimide precursor in NMP or the like. That is, the base polyimide precursor contains a large amount of highly soluble fluorinated diamine and contains disiloxane diamine in Example 9, whereas Comparative Example 3 contains no fluorinated diamine, Moreover, it is because disiloxane diamine is not included. From this, it can be seen that containing a large amount of fluorinated diamine is effective in shortening the process time and simplifying the equipment.
（回路付きサスペンション基板の作成）
ＳＵＳフィルムの上に低ＣＴＥポリイミド約１０μｍのベース層を有し、その上に微細銅配線（回路）を形成した基材上に、実施例９と比較例３の樹脂組成物を塗布し、プリベーク後、微細パターンを有するマスクパターンを介して露光してポストベークを実施した後、有機系現像液で現像を行った。実施例９の組成物では、現像残渣なくパターンが形成されるのに６分間が必要であった。これに対して比較例３の組成物では、同様なパターンが形成されるのに１５分間の時間が必要であった。
(Creation of suspension board with circuit)
A resin composition of Example 9 and Comparative Example 3 was applied to a base material having a base layer of about 10 μm of low CTE polyimide on a SUS film and fine copper wiring (circuit) formed thereon, and prebaked. Thereafter, the film was exposed through a mask pattern having a fine pattern and post-baked, and then developed with an organic developer. The composition of Example 9 required 6 minutes to form a pattern without development residue. In contrast, the composition of Comparative Example 3 required 15 minutes to form a similar pattern.
現像後のサンプルは、窒素中３５０℃で硬化することにより、低ＣＴＥポリイミドのカバー（絶縁被覆膜）となり、ポリイミド樹脂膜を保護膜として有する回路付きサスペンション基板が得られる。 The developed sample is cured at 350 ° C. in nitrogen to become a low CTE polyimide cover (insulation coating film), and a suspension board with circuit having a polyimide resin film as a protective film is obtained.
得られた回路付きサスペンション基板に対して電解金めっき処理を行ったところ、実施例９の感光性樹脂組成物を用いたものでは、問題なく開口部（銅箔が露出している部分）に金メッキが可能であったが、比較例３の感光性樹脂組成物を用いたものでは、開口部周辺でメッキ液の染みこみ不良が発生した。これは、比較例３の組成物とＮｉめっき層とのの密着力が不足しているためと考えられる。 Electrolytic gold plating treatment was performed on the obtained suspension board with circuit. In the case where the photosensitive resin composition of Example 9 was used, the opening (the part where the copper foil was exposed) was gold-plated without any problem. However, in the case of using the photosensitive resin composition of Comparative Example 3, there was a poor penetration of the plating solution around the opening. This is presumably because the adhesion between the composition of Comparative Example 3 and the Ni plating layer is insufficient.
Claims (8)
前記ポリイミド前駆体樹脂は、芳香族テトラカルボン酸二無水物と２種類以上のジアミンとを縮合重合したものであり、
前記ジアミン又は前記芳香族テトラカルボン酸二無水物として、ビフェニル骨格を持つモノマーを２種類以上含有すると共に、該ビフェニル骨格を持つモノマーの含有量は、芳香族テトラカルボン酸二無水物とジアミンとの合計量に対して５０モル％以上であり、前記ジアミンとして、テトラメチルジシロキサン骨格を持つジアミンを、ジアミン合計量に対して０．５モル％以上５モル％以下含有し、
前記ジアミンとして、フッ素化モノマーをジアミン合計量に対して３０モル％以上７０モル％以下含有することを特徴とする、感光性樹脂組成物。 A negative photosensitive resin composition containing a polyimide precursor resin, a photopolymerizable monomer, and a photopolymerization initiator,
The polyimide precursor resin is a condensation polymerized aromatic tetracarboxylic dianhydride and two or more diamines,
As the diamine or the aromatic tetracarboxylic dianhydride, two or more types of monomers having a biphenyl skeleton are contained, and the content of the monomer having the biphenyl skeleton is the same as that of the aromatic tetracarboxylic dianhydride and the diamine. 50 mol% or more with respect to the total amount, and as the diamine, a diamine having a tetramethyldisiloxane skeleton is contained in an amount of 0.5 mol% or more and 5 mol% or less with respect to the total amount of diamine ,
A photosensitive resin composition comprising, as the diamine, a fluorinated monomer in an amount of 30 mol% to 70 mol% with respect to the total amount of diamine .
特徴とする、請求項７に記載のフレキシブルプリント配線板。 The flexible printed wiring board according to claim 7 , wherein the flexible printed wiring board is used as a substrate for a suspension used in a hard disk drive.
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