JP7644439B2 - Adhesives, adhesive sheets and flexible copper-clad laminates - Google Patents
Adhesives, adhesive sheets and flexible copper-clad laminates Download PDFInfo
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- JP7644439B2 JP7644439B2 JP2020152144A JP2020152144A JP7644439B2 JP 7644439 B2 JP7644439 B2 JP 7644439B2 JP 2020152144 A JP2020152144 A JP 2020152144A JP 2020152144 A JP2020152144 A JP 2020152144A JP 7644439 B2 JP7644439 B2 JP 7644439B2
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- Prior art keywords
- adhesive
- mol
- polyimide
- dianhydride
- solvent
- Prior art date
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- 230000001070 adhesive effect Effects 0.000 title claims description 112
- 239000000853 adhesive Substances 0.000 title claims description 107
- 229920001721 polyimide Polymers 0.000 claims description 86
- 239000004642 Polyimide Substances 0.000 claims description 69
- 239000000539 dimer Substances 0.000 claims description 31
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 29
- 239000011889 copper foil Substances 0.000 claims description 26
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 21
- 239000012790 adhesive layer Substances 0.000 claims description 20
- QPJVMBTYPHYUOC-UHFFFAOYSA-N methyl benzoate Chemical group COC(=O)C1=CC=CC=C1 QPJVMBTYPHYUOC-UHFFFAOYSA-N 0.000 claims description 18
- 125000004427 diamine group Chemical group 0.000 claims description 17
- 239000000758 substrate Substances 0.000 claims description 16
- 229930185605 Bisphenol Natural products 0.000 claims description 10
- 150000004705 aldimines Chemical group 0.000 claims description 10
- 150000004658 ketimines Chemical group 0.000 claims description 10
- 229940095102 methyl benzoate Drugs 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 125000003277 amino group Chemical group 0.000 claims description 8
- 125000006159 dianhydride group Chemical group 0.000 claims description 8
- 230000018044 dehydration Effects 0.000 claims description 7
- 238000006297 dehydration reaction Methods 0.000 claims description 7
- 239000003799 water insoluble solvent Substances 0.000 claims description 6
- 238000010030 laminating Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 238000006798 ring closing metathesis reaction Methods 0.000 claims description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 39
- 239000000203 mixture Substances 0.000 description 29
- 150000004985 diamines Chemical class 0.000 description 28
- 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 26
- 229910052731 fluorine Inorganic materials 0.000 description 25
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 22
- 239000011737 fluorine Substances 0.000 description 22
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 21
- 238000006243 chemical reaction Methods 0.000 description 20
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 18
- 238000003786 synthesis reaction Methods 0.000 description 17
- 230000015572 biosynthetic process Effects 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- 238000010521 absorption reaction Methods 0.000 description 15
- -1 alkoxysilyl compound Chemical class 0.000 description 15
- 239000007787 solid Substances 0.000 description 15
- OZJPLYNZGCXSJM-UHFFFAOYSA-N 5-valerolactone Chemical compound O=C1CCCCO1 OZJPLYNZGCXSJM-UHFFFAOYSA-N 0.000 description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 238000010438 heat treatment Methods 0.000 description 14
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 13
- 229920001400 block copolymer Polymers 0.000 description 12
- 238000001816 cooling Methods 0.000 description 12
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 12
- 238000003860 storage Methods 0.000 description 12
- CMQCNTNASCDNGR-UHFFFAOYSA-N toluene;hydrate Chemical compound O.CC1=CC=CC=C1 CMQCNTNASCDNGR-UHFFFAOYSA-N 0.000 description 12
- 239000002904 solvent Substances 0.000 description 11
- MXPYJVUYLVNEBB-UHFFFAOYSA-N 2-[2-(2-carboxybenzoyl)oxycarbonylbenzoyl]oxycarbonylbenzoic acid Chemical compound OC(=O)C1=CC=CC=C1C(=O)OC(=O)C1=CC=CC=C1C(=O)OC(=O)C1=CC=CC=C1C(O)=O MXPYJVUYLVNEBB-UHFFFAOYSA-N 0.000 description 10
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 10
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 10
- 239000011347 resin Substances 0.000 description 10
- 229920005989 resin Polymers 0.000 description 10
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 9
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 description 9
- 125000004432 carbon atom Chemical group C* 0.000 description 9
- 239000003054 catalyst Substances 0.000 description 9
- 239000010410 layer Substances 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 125000001153 fluoro group Chemical group F* 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 150000004984 aromatic diamines Chemical group 0.000 description 7
- 239000011521 glass Substances 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 239000012299 nitrogen atmosphere Substances 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 230000000704 physical effect Effects 0.000 description 6
- 239000002798 polar solvent Substances 0.000 description 6
- 238000012545 processing Methods 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- 229910000679 solder Inorganic materials 0.000 description 6
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 5
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 5
- 239000002313 adhesive film Substances 0.000 description 5
- 239000003431 cross linking reagent Substances 0.000 description 5
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 5
- KIFDSGGWDIVQGN-UHFFFAOYSA-N 4-[9-(4-aminophenyl)fluoren-9-yl]aniline Chemical compound C1=CC(N)=CC=C1C1(C=2C=CC(N)=CC=2)C2=CC=CC=C2C2=CC=CC=C21 KIFDSGGWDIVQGN-UHFFFAOYSA-N 0.000 description 4
- QHHKLPCQTTWFSS-UHFFFAOYSA-N 5-[2-(1,3-dioxo-2-benzofuran-5-yl)-1,1,1,3,3,3-hexafluoropropan-2-yl]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)(C(F)(F)F)C(F)(F)F)=C1 QHHKLPCQTTWFSS-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 150000008064 anhydrides Chemical class 0.000 description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 4
- 238000004891 communication Methods 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 4
- GAEKPEKOJKCEMS-UHFFFAOYSA-N gamma-valerolactone Chemical compound CC1CCC(=O)O1 GAEKPEKOJKCEMS-UHFFFAOYSA-N 0.000 description 4
- 239000002966 varnish Substances 0.000 description 4
- NVKGJHAQGWCWDI-UHFFFAOYSA-N 4-[4-amino-2-(trifluoromethyl)phenyl]-3-(trifluoromethyl)aniline Chemical compound FC(F)(F)C1=CC(N)=CC=C1C1=CC=C(N)C=C1C(F)(F)F NVKGJHAQGWCWDI-UHFFFAOYSA-N 0.000 description 3
- IMYZQPCYWPFTAG-UHFFFAOYSA-N Mecamylamine Chemical compound C1CC2C(C)(C)C(NC)(C)C1C2 IMYZQPCYWPFTAG-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N dimethylmethane Natural products CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 3
- 230000005684 electric field Effects 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 230000009477 glass transition Effects 0.000 description 3
- 239000011810 insulating material Substances 0.000 description 3
- 238000003475 lamination Methods 0.000 description 3
- 235000006408 oxalic acid Nutrition 0.000 description 3
- 230000010287 polarization Effects 0.000 description 3
- 239000009719 polyimide resin Substances 0.000 description 3
- 239000001294 propane Substances 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 125000005370 alkoxysilyl group Chemical group 0.000 description 2
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical group C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 238000012661 block copolymerization Methods 0.000 description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000012024 dehydrating agents Substances 0.000 description 2
- 125000001028 difluoromethyl group Chemical group [H]C(F)(F)* 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 125000004216 fluoromethyl group Chemical group [H]C([H])(F)* 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 125000005462 imide group Chemical group 0.000 description 2
- 150000002596 lactones Chemical class 0.000 description 2
- 230000033001 locomotion Effects 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 2
- 239000003021 water soluble solvent Substances 0.000 description 2
- MAOBFOXLCJIFLV-UHFFFAOYSA-N (2-aminophenyl)-phenylmethanone Chemical compound NC1=CC=CC=C1C(=O)C1=CC=CC=C1 MAOBFOXLCJIFLV-UHFFFAOYSA-N 0.000 description 1
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- AVQQQNCBBIEMEU-UHFFFAOYSA-N 1,1,3,3-tetramethylurea Chemical compound CN(C)C(=O)N(C)C AVQQQNCBBIEMEU-UHFFFAOYSA-N 0.000 description 1
- FQYTUPYMTLWOOF-UHFFFAOYSA-N 1,3,4,6-tetramethylcyclohex-4-ene-1,3-diamine Chemical compound CC1C=C(C)C(C)(N)CC1(C)N FQYTUPYMTLWOOF-UHFFFAOYSA-N 0.000 description 1
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 1
- CGXGBCIINMEAQW-UHFFFAOYSA-N 1-phenyl-n-(3-triethoxysilylpropyl)ethanimine Chemical compound CCO[Si](OCC)(OCC)CCCN=C(C)C1=CC=CC=C1 CGXGBCIINMEAQW-UHFFFAOYSA-N 0.000 description 1
- CDRHUURBSOCCDK-UHFFFAOYSA-N 1-phenyl-n-(3-triethoxysilylpropyl)methanimine Chemical compound CCO[Si](OCC)(OCC)CCCN=CC1=CC=CC=C1 CDRHUURBSOCCDK-UHFFFAOYSA-N 0.000 description 1
- MDWZOAUWADLKNG-UHFFFAOYSA-N 1-phenyl-n-(3-trimethoxysilylpropyl)methanimine Chemical compound CO[Si](OC)(OC)CCCN=CC1=CC=CC=C1 MDWZOAUWADLKNG-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- FXGQUGCFZKMIJW-UHFFFAOYSA-N 2,4,5,6-tetrafluorobenzene-1,3-diamine Chemical compound NC1=C(F)C(N)=C(F)C(F)=C1F FXGQUGCFZKMIJW-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
- 229940075142 2,5-diaminotoluene Drugs 0.000 description 1
- ZGDMDBHLKNQPSD-UHFFFAOYSA-N 2-amino-5-(4-amino-3-hydroxyphenyl)phenol Chemical compound C1=C(O)C(N)=CC=C1C1=CC=C(N)C(O)=C1 ZGDMDBHLKNQPSD-UHFFFAOYSA-N 0.000 description 1
- OBCSAIDCZQSFQH-UHFFFAOYSA-N 2-methyl-1,4-phenylenediamine Chemical compound CC1=CC(N)=CC=C1N OBCSAIDCZQSFQH-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- JRBJSXQPQWSCCF-UHFFFAOYSA-N 3,3'-Dimethoxybenzidine Chemical compound C1=C(N)C(OC)=CC(C=2C=C(OC)C(N)=CC=2)=C1 JRBJSXQPQWSCCF-UHFFFAOYSA-N 0.000 description 1
- 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 1
- BDSPLIQKGRTNCG-UHFFFAOYSA-N 3,4-dimethylcyclohexa-1,5-diene-1,3-diamine Chemical group CC1C=CC(N)=CC1(C)N BDSPLIQKGRTNCG-UHFFFAOYSA-N 0.000 description 1
- GWHLJVMSZRKEAQ-UHFFFAOYSA-N 3-(2,3-dicarboxyphenyl)phthalic acid Chemical compound OC(=O)C1=CC=CC(C=2C(=C(C(O)=O)C=CC=2)C(O)=O)=C1C(O)=O GWHLJVMSZRKEAQ-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 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 1
- ZBMISJGHVWNWTE-UHFFFAOYSA-N 3-(4-aminophenoxy)aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=CC(N)=C1 ZBMISJGHVWNWTE-UHFFFAOYSA-N 0.000 description 1
- DFSUKONUQMHUKQ-UHFFFAOYSA-N 3-[2-(2,3-dicarboxyphenyl)-1,1,1,3,3,3-hexafluoropropan-2-yl]phthalic acid Chemical compound OC(=O)C1=CC=CC(C(C=2C(=C(C(O)=O)C=CC=2)C(O)=O)(C(F)(F)F)C(F)(F)F)=C1C(O)=O DFSUKONUQMHUKQ-UHFFFAOYSA-N 0.000 description 1
- PAHZZOIHRHCHTH-UHFFFAOYSA-N 3-[2-(2,3-dicarboxyphenyl)propan-2-yl]phthalic acid Chemical compound C=1C=CC(C(O)=O)=C(C(O)=O)C=1C(C)(C)C1=CC=CC(C(O)=O)=C1C(O)=O PAHZZOIHRHCHTH-UHFFFAOYSA-N 0.000 description 1
- DKKYOQYISDAQER-UHFFFAOYSA-N 3-[3-(3-aminophenoxy)phenoxy]aniline Chemical compound NC1=CC=CC(OC=2C=C(OC=3C=C(N)C=CC=3)C=CC=2)=C1 DKKYOQYISDAQER-UHFFFAOYSA-N 0.000 description 1
- WCXGOVYROJJXHA-UHFFFAOYSA-N 3-[4-[4-(3-aminophenoxy)phenyl]sulfonylphenoxy]aniline Chemical compound NC1=CC=CC(OC=2C=CC(=CC=2)S(=O)(=O)C=2C=CC(OC=3C=C(N)C=CC=3)=CC=2)=C1 WCXGOVYROJJXHA-UHFFFAOYSA-N 0.000 description 1
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
- WECDUOXQLAIPQW-UHFFFAOYSA-N 4,4'-Methylene bis(2-methylaniline) Chemical compound C1=C(N)C(C)=CC(CC=2C=C(C)C(N)=CC=2)=C1 WECDUOXQLAIPQW-UHFFFAOYSA-N 0.000 description 1
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 1
- QYIMZXITLDTULQ-UHFFFAOYSA-N 4-(4-amino-2-methylphenyl)-3-methylaniline Chemical compound CC1=CC(N)=CC=C1C1=CC=C(N)C=C1C QYIMZXITLDTULQ-UHFFFAOYSA-N 0.000 description 1
- NWIVYGKSHSJHEF-UHFFFAOYSA-N 4-[(4-amino-3,5-diethylphenyl)methyl]-2,6-diethylaniline Chemical compound CCC1=C(N)C(CC)=CC(CC=2C=C(CC)C(N)=C(CC)C=2)=C1 NWIVYGKSHSJHEF-UHFFFAOYSA-N 0.000 description 1
- OMHOXRVODFQGCA-UHFFFAOYSA-N 4-[(4-amino-3,5-dimethylphenyl)methyl]-2,6-dimethylaniline Chemical compound CC1=C(N)C(C)=CC(CC=2C=C(C)C(N)=C(C)C=2)=C1 OMHOXRVODFQGCA-UHFFFAOYSA-N 0.000 description 1
- CBEVWPCAHIAUOD-UHFFFAOYSA-N 4-[(4-amino-3-ethylphenyl)methyl]-2-ethylaniline Chemical compound C1=C(N)C(CC)=CC(CC=2C=C(CC)C(N)=CC=2)=C1 CBEVWPCAHIAUOD-UHFFFAOYSA-N 0.000 description 1
- GEYAGBVEAJGCFB-UHFFFAOYSA-N 4-[2-(3,4-dicarboxyphenyl)propan-2-yl]phthalic acid Chemical compound C=1C=C(C(O)=O)C(C(O)=O)=CC=1C(C)(C)C1=CC=C(C(O)=O)C(C(O)=O)=C1 GEYAGBVEAJGCFB-UHFFFAOYSA-N 0.000 description 1
- 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 1
- FOCQMELIWLXNGL-UHFFFAOYSA-N 4-[3-(3,4-dicarboxybenzoyl)benzoyl]phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1C(=O)C1=CC=CC(C(=O)C=2C=C(C(C(O)=O)=CC=2)C(O)=O)=C1 FOCQMELIWLXNGL-UHFFFAOYSA-N 0.000 description 1
- WUPRYUDHUFLKFL-UHFFFAOYSA-N 4-[3-(4-aminophenoxy)phenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=CC(OC=2C=CC(N)=CC=2)=C1 WUPRYUDHUFLKFL-UHFFFAOYSA-N 0.000 description 1
- FOMRNNDDNMWZFO-UHFFFAOYSA-N 4-[4-(3,4-dicarboxybenzoyl)benzoyl]phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1C(=O)C1=CC=C(C(=O)C=2C=C(C(C(O)=O)=CC=2)C(O)=O)C=C1 FOMRNNDDNMWZFO-UHFFFAOYSA-N 0.000 description 1
- JCRRFJIVUPSNTA-UHFFFAOYSA-N 4-[4-(4-aminophenoxy)phenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC(C=C1)=CC=C1OC1=CC=C(N)C=C1 JCRRFJIVUPSNTA-UHFFFAOYSA-N 0.000 description 1
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Description
本発明は、フレキシブルプリント配線板等に使用されるフレキシブル銅張積層板（ＦＣＣＬ：Flexible Cupper Clad Laminate）、それを製造するための接着剤及び接着シートに関する。 The present invention relates to flexible copper clad laminates (FCCLs) used in flexible printed wiring boards and the like, as well as adhesives and adhesive sheets for producing the same.
近年、エレクトロニクス製品の軽量化、小型化、高密度化に伴い、各種プリント配線板、中でもフレキシブルプリント配線板の需要が特に伸びている。フレキシブルプリント配線板は、絶縁性フィルム上に金属箔からなる回路が形成されている。フレキシブルプリント配線板用のフレキシブル銅張積層板は、一般にポリイミドフィルム等の絶縁性フィルムを基材とし、この基材の表面に各種の接着剤層を介して金属箔を加熱及び圧着して積層させた構造を有している。 In recent years, as electronic products have become lighter, smaller, and more dense, the demand for various printed wiring boards, especially flexible printed wiring boards, has been growing. Flexible printed wiring boards have a circuit made of metal foil formed on an insulating film. Flexible copper-clad laminates for flexible printed wiring boards generally have a structure in which an insulating film such as a polyimide film is used as a substrate, and metal foil is laminated on the surface of this substrate by heating and pressing it via various adhesive layers.
一方、第５世代の移動通信システム（５Ｇ）では、高速・大容量、信号の低遅延、端末の同時多接続という３つの機能が飛躍的に向上している。そこで、フレキシブル銅張積層板についても、５Ｇ通信や、自動運転などに用いられるミリ波レーダー向け電子部品に適した接着材料が要求されている。５Ｇ通信やミリ波レーダーには、従来から使用されている６ＧＨｚ以下の周波数バンドに加え、ミリ波領域といわれる２０ＧＨｚ以上の新たな周波数帯での通信が必要となる。そのため、フレキシブル銅張積層板についても、高い周波数帯域での通信に適した誘電特性と、半導体実装等に耐えられる耐熱性、導体配線との接着性などの物性値、及び良好な加工特性を満たす接着材料が求められている。 On the other hand, the fifth generation mobile communication system (5G) has dramatically improved three functions: high speed and large capacity, low signal latency, and simultaneous multiple connection of terminals. For this reason, there is a demand for adhesive materials for flexible copper-clad laminates that are suitable for electronic components for 5G communications and millimeter-wave radars used in autonomous driving. 5G communications and millimeter-wave radars require communications in a new frequency band of 20 GHz or higher, known as the millimeter-wave region, in addition to the conventionally used frequency band of 6 GHz or lower. For this reason, there is a demand for adhesive materials for flexible copper-clad laminates that have dielectric properties suitable for communications in high frequency bands, physical properties such as heat resistance to withstand semiconductor mounting, adhesion to conductor wiring, and good processing characteristics.
高周波回路では特に絶縁材料における誘電体損失が大きな問題となる。これらの損失は、信号伝達時に発熱やノイズ、高消費電力等の問題として現れる。誘電体損失は周波数、材料の誘電正接、及び誘電率のルートに比例するが、絶縁材料については、特に誘電正接の低減が大きな課題となる。このような誘電体損失の問題は、周波数帯として１ＧＨｚを超えたところから顕著になる。誘電正接は、主に材料構造中にある配向分極部位において、外部電界による振動に遅れが生じ、絶縁材料内の双極子が電場の振動に追従できなくなるため、運動エネルギーを消費する現象を反映している。 Dielectric loss is a major problem in high frequency circuits, especially in insulating materials. These losses manifest themselves as problems such as heat generation, noise, and high power consumption during signal transmission. Dielectric loss is proportional to the root of the frequency, the dielectric tangent of the material, and the dielectric constant, but for insulating materials, reducing the dielectric tangent is a major challenge. This type of dielectric loss problem becomes evident above 1 GHz in frequency bands. The dielectric tangent reflects the phenomenon in which a delay occurs in the vibration caused by an external electric field, mainly at oriented polarization sites in the material structure, causing the dipoles in the insulating material to be unable to follow the vibration of the electric field, resulting in the consumption of kinetic energy.
そこで、樹脂の分子構造を非極性化することによって外部電界に誘起される運動を抑制するという観点から分子設計を行なうことが、誘電体損失の低減に効果的である。即ち、高周波帯において誘電体損失を低下させるためには、高分子構造において分極の動きを抑えること（誘電正接）と分極を小さくすること（誘電率）が必要となる。 Therefore, molecular design from the viewpoint of suppressing the motion induced by an external electric field by making the molecular structure of the resin non-polarized is effective in reducing dielectric loss. In other words, to reduce dielectric loss in the high frequency band, it is necessary to suppress the movement of polarization in the polymer structure (dielectric tangent) and to reduce polarization (dielectric constant).
従来、フレキシブルプリント配線板に用いられる銅張積層板用の接着材料としては、ポリイミドを含有する種々の接着剤が報告されている（特許文献１～７）。中でも、低誘電特性を目指した接着剤として、ビスフェノール型酸二無水物残基及びダイマージアミン残基を有するポリイミドと架橋剤と反応性アルコキシシリル化合物を含有する接着剤が報告されている（特許文献２～７）。 Various adhesives containing polyimide have been reported as adhesive materials for copper-clad laminates used in flexible printed wiring boards (Patent Documents 1 to 7). Among them, adhesives containing polyimide having bisphenol-type dianhydride residues and dimer diamine residues, a crosslinking agent, and a reactive alkoxysilyl compound have been reported as adhesives aiming for low dielectric properties (Patent Documents 2 to 7).
上述したように、ポリイミド樹脂を含む銅張積層板用の接着剤として従来種々の接着剤が報告されているが、従来の接着剤はエポキシ等の架橋剤を必須成分として含んでいたため、そのような架橋剤を含まないポリイミド樹脂に比べ誘電正接が大きくなり、耐熱性が低下するという問題があった。また、従来の接着剤で具体的に使用されていた反応性アルコキシシリル化合物はアミノ系化合物であり、アミノ系化合物を用いると接着強度の向上に効果はあるが、接着剤としての基本特性である保存安定性が低下するという問題があった。さらに、ダイマージアミンのジアミン全体に占める量が多くなると、耐熱性、特にＴｇが低下するという問題もあった。 As mentioned above, various adhesives have been reported for use with copper-clad laminates containing polyimide resins. However, because the conventional adhesives contain a crosslinking agent such as epoxy as an essential component, there are problems with the dielectric tangent being larger and the heat resistance being reduced compared to polyimide resins that do not contain such crosslinking agents. In addition, the reactive alkoxysilyl compounds specifically used in conventional adhesives are amino-based compounds, and although the use of amino-based compounds is effective in improving adhesive strength, there is a problem with the storage stability, which is a basic property of an adhesive, being reduced. Furthermore, there is also a problem with the heat resistance, especially the Tg, being reduced when the amount of dimer diamine in the total diamine increases.
本発明者らは、接着剤の特性として必須である基材及び銅箔との間の接着強度、はんだ耐熱性と保存安定性を並立させるためには、アミノ系アルコキシシリル化合物と同等以上の接着強度の向上と吸湿後のはんだ耐熱性の向上が期待でき、アミノ系の欠点である保存安定性の低下を抑えることができるケチミン構造又はアルジミン構造を有する反応性アルコキシシリル化合物を添加剤として用いることが有効であることを見出した。また、本発明者らは、ＦＣＣＬに要求される低誘電特性に必須のダイマージアミンについては、Ｔｇ、接着特性、吸湿特性という基本特性と加工性、実装性などの加工特性のバランスを得るために、その添加量に制限を加えることが好ましいことを見出した。そして、従来必須であった架橋剤を添加しなくても、上記知見により、接着強度と保存安定性を両立させつつ、高Ｔｇ、優れた吸湿特性及び低誘電特性化を達成することができ、本発明を完成した。 The present inventors have found that in order to simultaneously achieve the adhesive strength between the substrate and the copper foil, solder heat resistance, and storage stability, which are essential characteristics of an adhesive, it is effective to use a reactive alkoxysilyl compound having a ketimine structure or an aldimine structure as an additive, which can be expected to improve adhesive strength equal to or greater than that of an amino-based alkoxysilyl compound and improve solder heat resistance after moisture absorption, and can suppress the decrease in storage stability, which is a drawback of amino-based compounds. In addition, the present inventors have found that it is preferable to limit the amount of dimer diamine, which is essential for the low dielectric properties required for FCCL, in order to achieve a balance between the basic properties of Tg, adhesive properties, and moisture absorption properties, and processing properties such as processability and mountability. And, based on the above findings, it has been possible to achieve high Tg, excellent moisture absorption properties, and low dielectric properties while simultaneously achieving both adhesive strength and storage stability, even without adding a crosslinking agent, which was previously essential, and thus the present invention has been completed.
本発明は以上の事情に鑑みなされたものであって、その目的は、架橋剤を用いなくても、誘電特性と、熱的特性、加工特性、接着特性、吸湿特性と、コストとをバランス良く並立できるフレキシブル銅張積層板用の接着剤、それを用いて製造する接着シート及びフレキシブル銅張積層板を提供することにある。
また、本発明の目的は、接着剤に閉環ポリイミドを用いることにより、ポリアミック酸タイプのポリイミドでは実現できない非脱水収縮や低温化を実現できるフレキシブル銅張積層板用の接着剤、それを用いて製造する接着シート及びフレキシブル銅張積層板を提供することにある。このような非脱水収縮と低温化により、大パネルサイズでの反りの減少や寸法安定性の向上を図ることができる。
The present invention has been made in consideration of the above circumstances, and its object is to provide an adhesive for flexible copper-clad laminates that can achieve a good balance of dielectric properties, thermal properties, processing properties, adhesive properties, moisture absorption properties, and cost without the need for a crosslinking agent, and an adhesive sheet and flexible copper-clad laminate produced using the same.
Another object of the present invention is to provide an adhesive for flexible copper-clad laminates that uses a ring-closed polyimide as an adhesive and can achieve non-dehydration shrinkage and low-temperature operation that cannot be achieved with polyamic acid-type polyimides, and an adhesive sheet and flexible copper-clad laminates manufactured using the adhesive. Such non-dehydration shrinkage and low-temperature operation can reduce warping and improve dimensional stability in large panel sizes.
本発明者らは、鋭意検討を重ねた結果、誘電特性（誘電率、誘電正接）は周波数に依存し、使用環境の温度、湿度に大きな影響を受け、接着剤に含まれる樹脂自体のＴｇを境に誘電特性の値が大きく変化する点に着目した。そして、誘電特性と、熱的特性（Ｔｇ）、加工特性、接着特性、吸湿特性と、コストとをバランス良く並立できるフレキシブル銅張積層板用の接着剤は、脱水閉環イミド化した溶剤可溶性ポリイミドとともに、特定の構造を有するシランカップリング剤を用いることにより実現できることを見出し、本発明を完成させた。 After extensive research, the inventors have noted that dielectric properties (dielectric constant, dielectric tangent) depend on frequency, are significantly affected by the temperature and humidity of the environment in which they are used, and that the values of the dielectric properties change significantly at the Tg of the resin itself contained in the adhesive. They have then discovered that an adhesive for flexible copper-clad laminates that can achieve a good balance between dielectric properties, thermal properties (Tg), processing properties, adhesive properties, moisture absorption properties, and cost can be achieved by using a silane coupling agent with a specific structure together with a solvent-soluble polyimide that has been subjected to dehydration ring-closing imidization, and have completed the present invention.
すなわち、本発明は、フレキシブル銅張積層板を構成するポリイミドフィルム基材と銅箔を接着させるためのフレキシブル銅張積層板用接着剤であって、下記一般式[Ｉ]で表される繰返し単位を有する脱水閉環イミド化した溶剤可溶性ポリイミドと、一般式[II]で表されるシランカップリング剤（但し、アミノ基を有するシランカップリング剤を除く）とを含有し、前記溶剤可溶性ポリイミドに含まれるダイマージアミン残基が全ジアミン残基の２０モル％以上３０モル％未満である、接着剤、を提供する。
(ＲＯ)３Ｓｉ－Ｘ [II]
（式中、Ｘはケチミン構造又はアルジミン構造を有する基であり、Ｒはアルキル基である)
That is, the present invention provides an adhesive for flexible copper-clad laminates for bonding a polyimide film substrate and copper foil that constitute a flexible copper-clad laminate, the adhesive comprising a solvent-soluble polyimide that has been subjected to dehydration ring-closure imidization and has a repeating unit represented by the following general formula [I], and a silane coupling agent represented by the general formula [II] (excluding silane coupling agents having an amino group) , wherein the dimer diamine residues contained in the solvent-soluble polyimide account for 20 mol % or more and less than 30 mol % of all diamine residues .
(RO) 3 Si-X [II]
(In the formula, X is a group having a ketimine structure or an aldimine structure, and R is an alkyl group.)
(ＲＯ)３Ｓｉ－Ｘ [II]
（式中、Ｘはケチミン構造又はアルジミン構造を有する基であり、Ｒはアルキル基である)
(RO) 3 Si-X [II]
(In the formula, X is a group having a ketimine structure or an aldimine structure, and R is an alkyl group.)
また、本発明は、フレキシブル銅張積層板を構成するポリイミドフィルム基材の片面又は両面に、銅箔を接着させるための接着剤層が積層されてなる、フレキシブル銅張積層板用の接着シートであって、前記接着剤層が前記本発明の接着剤を含有する接着シート、を提供する。 The present invention also provides an adhesive sheet for flexible copper-clad laminates, in which an adhesive layer for adhering copper foil is laminated on one or both sides of a polyimide film substrate constituting the flexible copper-clad laminate, the adhesive layer containing the adhesive of the present invention.
また、本発明は、ポリイミドフィルム基材の片面又は両面に接着剤層及び銅箔が順次積層されてなるフレキシブル銅張積層板であって、前記接着剤層が前記本発明の接着剤を含有するフレキシブル銅張積層板、を提供する。 The present invention also provides a flexible copper-clad laminate in which an adhesive layer and copper foil are laminated in sequence on one or both sides of a polyimide film substrate, the adhesive layer containing the adhesive of the present invention.
さらに、本発明は、前記本発明のフレキシブル銅張積層板の製造方法であって、前記本発明の接着シートに銅箔を２２０℃以下の温度で貼り合わせた後に、２２０℃以下の温度で接着剤層を熱処理することを含む製造方法、を提供する。 The present invention further provides a method for producing the flexible copper-clad laminate of the present invention, which includes laminating a copper foil to the adhesive sheet of the present invention at a temperature of 220°C or less, and then heat-treating the adhesive layer at a temperature of 220°C or less.
本発明の接着剤は、２００℃で９０分間加熱処理してフィルムを作成した場合に、誘電正接が０．００３（５ＧＨｚ）以下、誘電率が３．０（５ＧＨｚ）以下、及びＴｇが１１０℃以上となり、保存安定性が非常に良好で、吸水率の低いフィルムを作成することができる。Ｔｇが１１０℃以上であるため、常用使用温度１１０℃以下では誘電特性の急激な変化を起こさない材料を提供することができる。また、本発明の接着剤を用いてポリイミドフィルム基材と銅箔を接着させることにより、誘電率及び誘電正接が低く、耐熱性及び引きはがし強さが良好なフレキシブル銅張積層板を作成でき、誘電特性と、熱的特性（Ｔｇ）、加工特性、接着特性、吸湿特性及びコストとをバランス良く並立できるフレキシブル銅張積層板を提供できる。 When the adhesive of the present invention is heated at 200°C for 90 minutes to produce a film, it has a dielectric loss tangent of 0.003 (5 GHz) or less, a dielectric constant of 3.0 (5 GHz) or less, and a Tg of 110°C or more, and can produce a film with very good storage stability and low water absorption. Since the Tg is 110°C or more, it is possible to provide a material whose dielectric properties do not change suddenly at normal use temperatures of 110°C or less. In addition, by bonding a polyimide film substrate and copper foil using the adhesive of the present invention, it is possible to produce a flexible copper-clad laminate with a low dielectric constant and dielectric loss tangent, good heat resistance and peel strength, and a flexible copper-clad laminate that can balance dielectric properties with thermal properties (Tg), processing properties, adhesive properties, moisture absorption properties, and cost.
また、接着シートの接着剤層と銅箔とを２２０℃以下の温度で貼り合わせ、２２０℃以下の温度で接着剤層を熱処理することができる。そのため、寸法安定性悪化の主要因の一つである高温高圧でのラミネート工程を経る必要がなく、フレキシブル銅張積層板の寸法安定性を改善することができる。 In addition, the adhesive layer of the adhesive sheet and the copper foil can be bonded together at a temperature of 220°C or less, and the adhesive layer can be heat-treated at a temperature of 220°C or less. This eliminates the need for a lamination process at high temperature and pressure, which is one of the main causes of poor dimensional stability, and improves the dimensional stability of the flexible copper-clad laminate.
本発明の接着剤を用いて作製されるフレキシブル銅張積層板（ＦＣＣＬ：Ｆｌｅｘｉｂｌｅ Ｃｕｐｐｅｒ Ｃｌａｄ Ｌａｍｉｎａｔｅ ）は、フレキシブルプリント配線板等に使用され、特に従来の２層ＦＣＣＬより誘電特性（誘電率、誘電正接）に優れ、他特性は２層ＦＣＣＬと同等以上の物性及び加工性を有するため、以下、本発明のフレキシブル銅張積層板を低誘電２層ＦＣＣＬとも言う。 Flexible copper clad laminates (FCCLs) made using the adhesive of the present invention are used for flexible printed wiring boards and the like, and have superior dielectric properties (dielectric constant, dielectric dissipation factor) to conventional two-layer FCCLs, and other properties and processability that are equal to or better than those of two-layer FCCLs. Therefore, hereinafter, the flexible copper clad laminates of the present invention are also referred to as low dielectric two-layer FCCLs.
本発明のフレキシブル銅張積層板用接着剤は、フレキシブル銅張積層板を構成するポリイミドフィルム基材と銅箔を接着させるための接着剤であり、下記一般式[Ｉ]で表される繰返し単位を有する脱水閉環イミド化した溶剤可溶性ポリイミドと、一般式[II]で表されるシランカップリング剤とを含有する。 The adhesive for flexible copper-clad laminates of the present invention is an adhesive for bonding the polyimide film substrate and copper foil that constitute a flexible copper-clad laminate, and contains a solvent-soluble polyimide that has been dehydrated and ring-closed imidized and has a repeating unit represented by the following general formula [I], and a silane coupling agent represented by the general formula [II].
（式中、Ｚはビスフェノール型酸二無水物残基であり、Ａｒはダイマージアミン残基及び／又はフッ素含有ジアミン残基である）
(ＲＯ)３Ｓｉ－Ｘ [II]
（式中、Ｘはケチミン構造又はアルジミン構造を有する基であり、Ｒはアルキル基である)
(In the formula, Z is a bisphenol dianhydride residue, and Ar is a dimer diamine residue and/or a fluorine-containing diamine residue.)
(RO) 3 Si-X [II]
(In the formula, X is a group having a ketimine structure or an aldimine structure, and R is an alkyl group.)
（溶剤可溶性ポリイミド）
本発明の溶剤可溶性ポリイミドは、上記一般式[Ｉ]で表される繰返し単位をその一部に含むものであれば、その他の繰返し単位を有していてもよい。
上記一般式[Ｉ]で表される繰返し単位において、Ｚはビスフェノール型酸二無水物残基である。ビスフェノール型酸二無水物残基をポリイミドに導入するためのビスフェノール型酸二無水物としては、ビスフェノール型の構造を有するものであれば特に制限はないが、４，４’－（４，４’－イソプロピリデンジフェノキシ）ビス（無水フタル酸）（以下、ＢＰＡＤＡともいう）、４，４’－（４，４’－メチレンジフェノキシ）ビス（無水フタル酸）等が挙げられる。この中でもＢＰＡＤＡが好ましい。ＢＰＡＤＡの市販品としては、Ｓ Ａ Ｂ Ｉ Ｃ イノベーティブプラスチックスジャパン合同会社製の、ＢＩＳＤＡ－１０００、ＢＩＳＤＡ－３０００がある。
(Solvent-soluble polyimide)
The solvent-soluble polyimide of the present invention may contain other repeating units as long as it contains the repeating unit represented by the above general formula [I] as a part thereof.
In the repeating unit represented by the general formula [I], Z is a bisphenol dianhydride residue. The bisphenol dianhydride for introducing the bisphenol dianhydride residue into the polyimide is not particularly limited as long as it has a bisphenol structure, and examples thereof include 4,4'-(4,4'-isopropylidenediphenoxy)bis(phthalic anhydride) (hereinafter also referred to as BPADA) and 4,4'-(4,4'-methylenediphenoxy)bis(phthalic anhydride). Among these, BPADA is preferred. Commercially available BPADA products include BISDA-1000 and BISDA-3000 manufactured by S A B I C Innovative Plastics Japan LLC.
上記その他の繰返し単位は、ビスフェノール型酸二無水物残基（Ｚ）以外のジカルボン酸無水物残基を有する。ビスフェノール型酸二無水物残基（Ｚ）以外のジカルボン酸無水物残基としては、フッ素含有酸二無水物残基が挙げられる。フッ素含有酸二無水物残基をポリイミドに導入するためのフッ素含有酸二無水物としては、例えば２，２-ビス（３，４-ジカルボキシフェニル）-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（２，３-ジカルボキシフェニル）-１，１，１，３，３，３-ヘキサフルオロプロパン二無水物、４，４’-（ヘキサフルオロイソプロピリデン）ジフタル酸無水物、３，４’-（ヘキサフルオロイソプロピリデン）ジフタル酸無水物、３，３’-（ヘキサフルオロイソプロピリデン）ジフタル酸無水物等のフッ素含有芳香族テトラカルボン酸二無水物が挙げられる。 The other repeating units have a dicarboxylic acid anhydride residue other than the bisphenol-type dianhydride residue (Z). Examples of dicarboxylic acid anhydride residues other than the bisphenol-type dianhydride residue (Z) include fluorine-containing dianhydride residues. Examples of fluorine-containing dianhydrides for introducing fluorine-containing dianhydride residues into polyimides include fluorine-containing aromatic tetracarboxylic acid dianhydrides such as 2,2-bis(3,4-dicarboxyphenyl)-1,1,1,3,3,3-hexafluoropropane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)-1,1,1,3,3,3-hexafluoropropane dianhydride, 4,4'-(hexafluoroisopropylidene)diphthalic anhydride, 3,4'-(hexafluoroisopropylidene)diphthalic anhydride, and 3,3'-(hexafluoroisopropylidene)diphthalic anhydride.
上記フッ素含有酸二無水物としては、フッ素原子を有しないテトラカルボン酸二無水物の水素原子の一部又は全てを、フッ素原子を有する置換基で置換したものを用いることもできる。フッ素原子を有する置換基としては、具体的には、フルオロ基、フルオロメチル基、ジフルオロメチル基、トリフルオロメチル基、トリフルオロメトキシ基、ＨＣＦ２ＣＦ２-、ＣＦ３ＣＦ２-、ＣＦ３ＣＨ２-、ＣＦ３ＣＦ２ＣＦ２ＣＦ２-、ＣＦ３ＣＦ２ＣＦ２ＣＨ２-が好ましく、フルオロ基、フルオロメチル基、ジフルオロメチル基、トリフルオロメチル基、ＣＦ３ＣＦ２-、ＨＣＦ２ＣＦ２-がより好ましい。フッ素原子を有しないテトラカルボン酸二無水物としては、例えばシクロヘキサ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、ジシクロヘキサン-３，４，３’，４’-テトラカルボン酸二無水物、ピロメリット酸二無水物、３，３’，４，４’-ベンゾフェノンテトラカルボン酸二無水物、２，２’，３，３’-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、２，２’，３，３’-ビフェニルテトラカルボン酸二無水物、４，４’-（メチリデン）ジフタル酸無水物、２，２-ビス（３，４-ジカルボキシフェニル）プロパン二無水物、２，２-ビス（２，３-ジカルボキシフェニル）プロパン二無水物、ビス（３，４-ジカルボキシフェニル）エーテル二無水物、ビス（３，４-ジカルボキシフェニル）スルホン二無水物、１，１-ビス（２，３-ジカルボキシフェニル）エタン二無水物、ビス（２，３-ジカルボキシフェニル）メタン二無水物、ビス（３，４-ジカルボキシフェニル）メタン二無水物、１，３-ビス〔（３，４-ジカルボキシ）ベンゾイル〕ベンゼン二無水物、１，４-ビス〔（３，４-ジカルボキシ）ベンゾイル〕ベンゼン二無水物、２，２-ビス｛４-〔４-（１，２-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-（１，２-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｛４-〔４-（１，２-ジカルボキシ）フェノキシ〕フェニル｝ケトン二無水物、ビス｛４-〔３-（１，２-ジカルボキシ）フェノキシ〕フェニル｝ケトン二無水物、４，４’-ビス〔４-（１，２-ジカルボキシ）フェノキシ〕ビフェニル二無水物、４，４’-ビス〔３-（１，２-ジカルボキシ）フェノキシ〕ビフェニル二無水物、ビス｛４-〔４-（１，２-ジカルボキシ）フェノキシ〕フェニル｝ケトン二無水物、ビス｛４-〔３-（１，２-ジカルボキシ）フェノキシ〕フェニル｝ケトン二無水物、ビス｛４-〔４-（１，２-ジカルボキシ）フェノキシ〕フェニル｝スルホン二無水物、ビス｛４-〔３-（１，２-ジカルボキシ）フェノキシ〕フェニル｝スルホン二無水物、ビス｛４-〔４-（１，２-ジカルボキシ）フェノキシ〕フェニル｝スルフィド二無水物、ビス｛４-〔３-（１，２-ジカルボキシ）フェノキシ〕フェニル｝スルフィド二無水物、２，３，６，７-ナフタレンテトラカルボン酸二無水物、１，４，５，８-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、１，２，３，４-ベンゼンテトラカルボン酸二無水物、３，４，９，１０-ぺ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等が挙げられる。 As the above-mentioned fluorine-containing acid dianhydride, it is also possible to use a tetracarboxylic acid dianhydride that does not have a fluorine atom, in which a part or all of the hydrogen atoms are replaced with a substituent having a fluorine atom.Specifically, as the substituent having a fluorine atom, fluoro group, fluoromethyl group, difluoromethyl group, trifluoromethyl group , trifluoromethoxy group, HCF2CF2- , CF3CF2- , CF3CH2- , CF3CF2CF2CF2- , CF3CF2CF2CH2- are preferred, and fluoro group, fluoromethyl group, difluoromethyl group, trifluoromethyl group , CF3CF2- , HCF2CF2- are more preferred. Examples of tetracarboxylic dianhydrides not having fluorine atoms include cyclohexane tetracarboxylic dianhydride, cyclopentane tetracarboxylic dianhydride, dicyclohexane-3,4,3',4'-tetracarboxylic dianhydride, pyromellitic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 2,2',3,3'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-biphenyl tetracarboxylic dianhydride, 2,2',3,3'-biphenyl tetracarboxylic dianhydride, 4,4'-(methylidene)diphthalic anhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, and the like. 1,3-bis[(3,4-dicarboxy)benzoyl]benzene dianhydride, 1,4-bis[(3,4-dicarboxy)benzoyl]benzene dianhydride, 2,2-bis{4-[4-(1,2-dicarboxy)phenoxy]phenyl}propane dianhydride, 2,2-bis{4-[3-(1,2-dicarboxy)phenoxy]phenyl}propane dianhydride, }propane dianhydride, bis{4-[4-(1,2-dicarboxy)phenoxy]phenyl}ketone dianhydride, bis{4-[3-(1,2-dicarboxy)phenoxy]phenyl}ketone dianhydride, 4,4'-bis[4-(1,2-dicarboxy)phenoxy]biphenyl dianhydride, 4,4'-bis[3-(1,2-dicarboxy)phenoxy]biphenyl dianhydride, bis{4-[4-(1,2-dicarboxy)phenoxy]phenyl}ketone dianhydride, bis{4-[3-(1,2-dicarboxy)phenoxy]phenyl}ketone dianhydride, bis{4-[4-(1,2-dicarboxy)phenoxy]phenyl}sulfone dianhydride, bis{4-[3-(1,2-dicarboxy)phenoxy]phenyl}sulfone dianhydride, bis{4-[4-(1,2-dicarboxy)phenoxy]phenyl}sulfone dianhydride, bis{4-[4-(1,2-dicarboxy)phenoxy]phenyl}sulfide dianhydride, bis{4-[3-(1,2-dicarboxy)phenoxy]phenyl}sulfide dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 2,3,6,7-anthracenetetracarboxylic dianhydride, 1,2,7,8-phenanthrenetetracarboxylic dianhydride, and the like.
溶剤可溶性ポリイミドを構成するビスフェノール型酸二無水物成分（Ｚ成分）の含有量は、低い誘電特性と高いＴｇを達成する観点から、全ジカルボン酸無水物成分の７０ｍｏｌ％以上、更には７５ｍｏｌ％以上、特には８０ｍｏｌ％以上とするのが好ましい。 From the viewpoint of achieving low dielectric properties and high Tg, the content of the bisphenol dianhydride component (Z component) constituting the solvent-soluble polyimide is preferably 70 mol % or more, more preferably 75 mol % or more, and particularly preferably 80 mol % or more of the total dicarboxylic acid anhydride components.
一方、フッ素含有酸二無水物残基を有するポリイミドにおいては、誘電率や吸水率などの物性は、ポリイミドに占めるフッ素原子とイミド基の含有率でほぼ決定され、化学構造(一次構造)や電子構造にはあまり関係がない。そのためこれらの物性を制御するためには、反応性と得られるポリイミドの耐熱性を損なわない範囲でフッ素含有酸二無水物を適宜選択すればよい。 On the other hand, in polyimides having fluorine-containing dianhydride residues, physical properties such as dielectric constant and water absorption are largely determined by the content of fluorine atoms and imide groups in the polyimide, and are not closely related to the chemical structure (primary structure) or electronic structure. Therefore, in order to control these physical properties, it is sufficient to appropriately select a fluorine-containing dianhydride within a range that does not impair the reactivity and heat resistance of the resulting polyimide.
上記一般式[Ｉ]で表される繰返し単位において、Ａｒはダイマージアミン残基及び／又はフッ素含有ジアミン残基である。
ダイマージアミン残基をポリイミドに導入するためのダイマージアミンとは、オレイン酸等の不飽和脂肪酸の二量体であるダイマー酸の全てのカルボキシル基を一級アミノ基に置換したものであり、更に水素添加して得られる水添ダイマージアミンも含み（特開平９－１２ ７１２号公報等参照）、各種公知のものを特に制限なく使用できる。以下、ダイマージアミンの非限定的な一般式を示す（各式において、ｍ＋ｎ＝６～１７が好ましく、ｐ＋ｑ＝８～１９が好ましく、破線部は炭素－炭素単結合又は炭素－炭素二重結合を意味する）。ダイマージアミンは脂環構造を有するものがより好ましい。
In the repeating unit represented by the above general formula [I], Ar is a dimer diamine residue and/or a fluorine-containing diamine residue.
The dimer diamine for introducing a dimer diamine residue into a polyimide is a dimer acid, which is a dimer of an unsaturated fatty acid such as oleic acid, in which all carboxyl groups have been replaced with primary amino groups, and also includes hydrogenated dimer diamine obtained by further hydrogenation (see JP-A-9-12712, etc.), and various known dimer diamines can be used without particular restriction. Non-limiting general formulas of dimer diamines are shown below (in each formula, m+n is preferably 6 to 17, p+q is preferably 8 to 19, and the dashed line represents a carbon-carbon single bond or a carbon-carbon double bond). Dimer diamines having an alicyclic structure are more preferred.
ダイマージアミンは、分子量約５３０～６２０の巨大分子の脂肪族又は脂環式の構造を有するため、分子のモル体積を大きくし、ポリイミドの極性基を相対的に減らすことができる。また、２つの自由に動く炭素数７～９の疎水鎖と、炭素数１８に近い長さを持つ２つの鎖状の脂肪族アミノ基とを有するので、ポリイミドに柔軟性を与えるのみならず、ポリイミドを非対象的な化学構造や非平面的な化学構造とすることができ、その結果ポリイミドの低誘電率化及び低誘電正接化を図ることができる。ダイマージアミン残基は、高分子鎖間のπ－πスタッキング等の相互作用を減少させ、溶剤に対する溶解性を向上させることができ、また芳香族ジアミン残基と芳香族ジテトラカルボン酸無水物残基との間の電荷移動（ＣＴ）を起こりにくくすることができる。 Dimer diamine has a macromolecular aliphatic or alicyclic structure with a molecular weight of approximately 530 to 620, which increases the molecular molar volume and relatively reduces the polar groups of the polyimide. In addition, it has two freely movable hydrophobic chains with 7 to 9 carbon atoms and two chain-like aliphatic amino groups with a length close to 18 carbon atoms, which not only gives flexibility to the polyimide but also allows the polyimide to have an asymmetrical or non-planar chemical structure, resulting in a low dielectric constant and low dielectric tangent of the polyimide. The dimer diamine residue reduces interactions such as π-π stacking between polymer chains, improving solubility in solvents and making it less likely for charge transfer (CT) to occur between the aromatic diamine residue and the aromatic ditetracarboxylic anhydride residue.
ダイマージアミンの市販品としては、バーサミン５５１（コグニクスジャパン（株）製）、バーサミン５５２（コグニクスジャパン（株）製；バーサミン５５１の水添物）、ＰＲＩＡＭＩＮＥ１０７５、ＰＲＩＡＭＩＮＥ１０７４（いずれもクローダジャパン（株）製）等が挙げられる。 Commercially available dimer diamine products include VERSAMINE 551 (manufactured by Cognics Japan Co., Ltd.), VERSAMINE 552 (manufactured by Cognics Japan Co., Ltd.; hydrogenated VERSAMINE 551), PRIAMINE 1075, and PRIAMINE 1074 (all manufactured by Croda Japan Co., Ltd.).
フッ素含有ジアミン残基をポリイミドに導入するためのフッ素含有芳香族ジアミンとしては、２，２’-ビス(トリフルオロメチル)ベンジジン、２，２-ビス（４-（４-アミノフェノキシ）フェニル）ヘキサフルオロプロパン、２，２-ビス（４-アミノフェニル）ヘキサフルオロプロパン、２，２’―ビス（４―アミノフェニル）ヘキサフルオロプロパン、１，３-ジアミノ-２，４，５，６-テトラフルオロベンゼン等のフッ素含有芳香族ジアミンが挙げられる。 Fluorine-containing aromatic diamines for introducing fluorine-containing diamine residues into polyimides include fluorine-containing aromatic diamines such as 2,2'-bis(trifluoromethyl)benzidine, 2,2-bis(4-(4-aminophenoxy)phenyl)hexafluoropropane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2'-bis(4-aminophenyl)hexafluoropropane, and 1,3-diamino-2,4,5,6-tetrafluorobenzene.
溶剤可溶性ポリイミドを構成する、ダイマージアミン成分（Ａｒ成分）の含有量は、低い誘電特性と高いＴｇを得る観点から、下限値は、全ジアミン成分の２０ｍｏｌ％以上、２１ｍｏｌ％以上、２２ｍｏｌ％以上、２３ｍｏｌ％以上、２４ｍｏｌ％以上、２５ｍｏｌ％以上、２６ｍｏｌ％以上、２７ｍｏｌ％以上とするのがよく、上限値は、全ジアミン成分の３０ｍｏｌ％未満、更には２９ｍｏｌ％以下とするのが好ましい。 From the viewpoint of obtaining low dielectric properties and high Tg, the content of the dimer diamine component (Ar component) constituting the solvent-soluble polyimide is preferably set at a lower limit of 20 mol% or more, 21 mol% or more, 22 mol% or more, 23 mol% or more, 24 mol% or more, 25 mol% or more, 26 mol% or more, or 27 mol% or more of the total diamine components, and the upper limit is preferably set at less than 30 mol%, and even more preferably at 29 mol% or less of the total diamine components.
Ａｒ成分としてダイマージアミンを用いる場合には、Ｔｇを更に改善することが好ましく、フッ素含有芳香族ジアミンを用いる場合には、Ｔｇ及び接着性能を更に改善することが好ましい。したがって、Ａｒ成分としてダイマージアミン及び／又はフッ素含有芳香族ジアミンを用いる場合でも、Ｔｇ及び接着性能を含む特性バランスを持たせるために、その他のジアミン成分を併用することが好ましい。 When a dimer diamine is used as the Ar component, it is preferable to further improve the Tg, and when a fluorine-containing aromatic diamine is used, it is preferable to further improve the Tg and adhesive performance. Therefore, even when a dimer diamine and/or a fluorine-containing aromatic diamine is used as the Ar component, it is preferable to use other diamine components in combination in order to achieve a balance of properties including Tg and adhesive performance.
一方、フッ素含有ジアミン残基を有するポリイミドにおいては、誘電率や吸水率などの物性は、ポリイミドに占めるフッ素原子とイミド基の含有率でほぼ決定され、化学構造(一次構造)や電子構造にはあまり関係がない。そのためこれらの物性を制御するためには、反応性と得られるポリイミドの耐熱性を損なわない範囲でフッ素含有ジアミンを適宜選択すればよい。 On the other hand, in polyimides having fluorine-containing diamine residues, physical properties such as dielectric constant and water absorption are determined almost entirely by the content of fluorine atoms and imide groups in the polyimide, and are not related to the chemical structure (primary structure) or electronic structure. Therefore, in order to control these physical properties, it is sufficient to appropriately select a fluorine-containing diamine within a range that does not impair the reactivity and heat resistance of the resulting polyimide.
溶剤可溶性ポリイミドは、上記一般式［Ｉ］で表される繰返し単位以外の別の繰返し単位を有するブロックロック共重合体であってもよく、ダイマージアミンやフッ素含有芳香族ジアミンの上記欠点を補填するためにも有効である。 The solvent-soluble polyimide may be a block-lock copolymer having a repeating unit other than the repeating unit represented by the general formula [I] above, and is also effective in compensating for the above-mentioned shortcomings of dimer diamines and fluorine-containing aromatic diamines.
前記その他の芳香族ジアミンとしては、ｐ-フェニレンジアミン、ｍ-フェニレンジアミン、２，４-ジアミノトルエン、２，５-ジアミノトルエン、２，４-ジアミノキシレン、２，４-ジアミノデュレン、４，４’-ジアミノジフェニルメタン、４，４’-メチレンビス（２-メチルアニリン）、４，４’-メチレンビス（２-エチルアニリン）、４，４’-メチレンビス（２，６-ジメチルアニリン）、４，４’-メチレンビス（２，６-ジエチルアニリン）、４，４’-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、３，３’-ジアミノジフェニルエーテル、２，４’-ジアミノジフェニルエーテル、４，４’-ジアミノジフェニルスルホン、３，３’-ジアミノジフェニルスルホン、４，４’-ジアミノベンゾフェノン、３，３’-ジアミノベンゾフェノン、４，４’-ジアミノベンズアニリド、４-アミノフェニル-４’-アミノベンゾエート、ベンジジン、３，３’-ジヒドロキシベンジジン、３，３’-ジメトキシベンジジン、ｏ-トリジン、ｍ-トリジン、１，４-ビス（４-アミノフェノキシ）ベンゼン、１，３-ビス（４-アミノフェノキシ）ベンゼン、１，３-ビス（３-アミノフェノキシ）ベンゼン、４，４’-ビス（４－アミノフェノキシ）ビフェニル、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、２，２-ビス（４-（４-アミノフェノキシ）フェニル）プロパン、９，９－ビス（４－アミノフェニル）フルオレン等が挙げられる。 The other aromatic diamines include p-phenylenediamine, m-phenylenediamine, 2,4-diaminotoluene, 2,5-diaminotoluene, 2,4-diaminoxylene, 2,4-diaminodurene, 4,4'-diaminodiphenylmethane, 4,4'-methylenebis(2-methylaniline), 4,4'-methylenebis(2-ethylaniline), 4,4'-methylenebis(2,6-dimethylaniline), 4,4'-methylenebis(2,6-diethylaniline), 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 2,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl Examples of such compounds include aminobenzophenone, 3,3'-diaminobenzophenone, 4,4'-diaminobenzanilide, 4-aminophenyl-4'-aminobenzoate, benzidine, 3,3'-dihydroxybenzidine, 3,3'-dimethoxybenzidine, o-tolidine, m-tolidine, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, bis(4-(3-aminophenoxy)phenyl)sulfone, bis(4-(4-aminophenoxy)phenyl)sulfone, 2,2-bis(4-(4-aminophenoxy)phenyl)propane, and 9,9-bis(4-aminophenyl)fluorene.
上記一般式［Ｉ］で表される繰返し単位を有する溶剤可溶性ポリイミドは、ビスフェノール型酸二無水物とダイマージアミン及び／又はフッ素含有ジアミンを脱水縮合反応させることにより得られる。 The solvent-soluble polyimide having the repeating unit represented by the above general formula [I] can be obtained by a dehydration condensation reaction between a bisphenol dianhydride and a dimer diamine and/or a fluorine-containing diamine.
溶剤可溶性ポリイミドの合成方法は公知の方法を用いればよく、特に制限されないが、上述したビスフェノール型酸二無水物とダイマージアミン及び／又はフッ素含有ジアミンをほぼ等量用いて、有機極性溶媒中、触媒及び脱水剤の存在下、１６０～２００℃で数時間反応させることにより、溶剤可溶性のポリイミドを合成できる。有機極性溶媒としては、Ｎ－メチルピロリドン（ＮＭＰ）、γ－ブチロラクトン、Ｎ，Ｎ－ジメチルアセトアミド、Ｎ，Ｎ－ジメチルホルムアミド、ジメチルスルホキシド、テトラメチル尿素、テトラヒドロチオフェン－１，１－オキシド等が用いられる。 The synthesis method of the solvent-soluble polyimide may be a known method and is not particularly limited, but the above-mentioned bisphenol-type acid dianhydride and dimer diamine and/or fluorine-containing diamine are reacted in approximately equal amounts in an organic polar solvent in the presence of a catalyst and a dehydrating agent at 160 to 200°C for several hours to synthesize the solvent-soluble polyimide. Examples of the organic polar solvent that can be used include N-methylpyrrolidone (NMP), γ-butyrolactone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethylsulfoxide, tetramethylurea, and tetrahydrothiophene-1,1-oxide.
溶剤可溶性ポリイミドはブロック共重合体であるのが好ましく、ブロック共重合体はブロック共重合反応を行うことにより合成することができる。例えば、二段階の逐次添加反応によって製造することができ、第一段階でビスフェノール型酸二無水物とダイマージアミン及び／又はフッ素含有ジアミンからポリイミドオリゴマーを合成し、次いで第二段階で、更にフッ素含有ジアミン及び／又はダイマージアミンを添加して、重縮合させてブロック共重合ポリイミドとすることができる。 The solvent-soluble polyimide is preferably a block copolymer, and the block copolymer can be synthesized by carrying out a block copolymerization reaction. For example, it can be produced by a two-stage sequential addition reaction, in which in the first stage, a polyimide oligomer is synthesized from a bisphenol-type acid dianhydride and a dimer diamine and/or a fluorine-containing diamine, and then in the second stage, a fluorine-containing diamine and/or a dimer diamine is further added and polycondensed to produce a block copolymer polyimide.
ブロック共重合反応の触媒としては、ラクトンの平衡反応を利用した二成分系の酸－塩基触媒を用いることにより、脱水イミド化反応を促進することができる。具体的には、γ－バレロラクトンとピリジン又はＮ－メチルモルホリンの二成分系触媒を用いる。下記式に示すように、イミド化が進むにつれて水が生成し、生成した水がラクトンの平衡に関与して、酸－塩基触媒となり触媒作用を示す。 The dehydration imidization reaction can be accelerated by using a two-component acid-base catalyst that utilizes the lactone equilibrium reaction as a catalyst for the block copolymerization reaction. Specifically, a two-component catalyst of γ-valerolactone and pyridine or N-methylmorpholine is used. As shown in the formula below, water is generated as the imidization proceeds, and the generated water participates in the lactone equilibrium, becoming an acid-base catalyst and exhibiting catalytic action.
イミド化反応によって生成する水は、極性溶媒中に共存するトルエン又はキシレン等の脱水剤と共沸によって系外に除かれる。反応が完結すると溶液中の水が除去され、酸－塩基触媒はγ－バレロラクトンとピリジン又はＮ－メチルモルホリンとなり系外に除去される。このようにして高純度のポリイミド溶液を得ることができる。 The water produced by the imidization reaction is removed from the system by azeotropy with a dehydrating agent, such as toluene or xylene, that coexists in the polar solvent. When the reaction is completed, the water in the solution is removed, and the acid-base catalyst becomes γ-valerolactone and pyridine or N-methylmorpholine, which are removed from the system. In this way, a high-purity polyimide solution can be obtained.
他の二成分系触媒としては、シュウ酸又はマロン酸とピリジン又はＮ－メチルモルホリンを用いることができる。１６０～２００℃の反応溶液中で、シュウ酸塩又はマロン酸塩は酸触媒としてイミド化反応を促進する。生成したポリイミド溶媒中には触媒量のシュウ酸又はマロン酸が残留する。このポリイミド溶液を基材に塗布した後に２００℃以上に加熱し、脱溶媒を行って製膜をする時に、ポリイミド中に残存するシュウ酸又はマロン酸は、下記式に示すように熱分解し、ガスとして系外に除かれる。 Other two-component catalysts that can be used are oxalic acid or malonic acid and pyridine or N-methylmorpholine. In a reaction solution at 160 to 200°C, the oxalate or malonate acts as an acid catalyst to promote the imidization reaction. A catalytic amount of oxalic acid or malonic acid remains in the resulting polyimide solvent. When this polyimide solution is applied to a substrate and then heated to 200°C or higher to remove the solvent and form a film, the oxalic acid or malonic acid remaining in the polyimide is thermally decomposed as shown in the following formula and removed from the system as a gas.
以上の方法により、高純度の溶剤可溶性ポリイミドを得ることができる。シュウ酸－ピリジン系触媒は、バレロラクトン－ピリジン系触媒に比べて活性が強く、短時間で高分子量のポリイミドを生成することができる。 By using the above method, it is possible to obtain high-purity, solvent-soluble polyimide. The oxalic acid-pyridine catalyst is more active than the valerolactone-pyridine catalyst, and can produce high-molecular-weight polyimide in a short period of time.
合成された溶剤可溶性ポリイミドの分子量は、ポリスチレン換算の重量平均分子量（Ｍｗ）として１万～４０万が好ましい。溶剤可溶性ポリイミドの分子量がこの範囲内であると良好な溶剤可溶性、膜物性及び絶縁性を達成できるため好ましい。
本発明における「溶剤可溶性」なる用語は、ポリイミドの合成において使用する有機極性溶剤と、後述する接着剤組成物に使用する溶剤に対して使用する用語であり、これらの溶剤を用いてポリイミドが２０重量％固形分の溶液を作製可能であることを意味する。溶剤としては、ＮＭＰ、γ-ブチロラクトン、ＤＭＦ、ＤＭＡＣなどが挙げられる。合成されたポリイミドは、上記有機極性溶剤又は後述する接着剤組成物に使用する溶剤に、例えば、固形分が１０～３０重量％となるよう溶解させた溶液の状態で用いることができる。
The molecular weight of the synthesized solvent-soluble polyimide is preferably 10,000 to 400,000 in terms of polystyrene equivalent weight average molecular weight (Mw). When the molecular weight of the solvent-soluble polyimide is within this range, it is preferable because good solvent solubility, film properties, and insulating properties can be achieved.
The term "solvent-soluble" in the present invention is used for the organic polar solvent used in the synthesis of polyimide and the solvent used in the adhesive composition described later, and means that a solution of polyimide with a solid content of 20% by weight can be prepared using these solvents. Examples of the solvent include NMP, γ-butyrolactone, DMF, and DMAC. The synthesized polyimide can be used in the form of a solution dissolved in the organic polar solvent or the solvent used in the adhesive composition described later so that the solid content is, for example, 10 to 30% by weight.
また、本発明の溶剤可溶性ポリイミドは完全に脱水閉環イミド化したポリイミドであるため、接着剤をポリイミドフィルム基材に塗布した後にイミド化のための高温での熱処理を必要としない。従って、接着剤をポリイミドフィルム基材に塗布した後にイミド化のための高温での熱処理（３００℃以上）を要するポリアミック酸（ポリイミド前駆体）に比べ、寸法安定性の高いフレキシブル銅張積層板を提供できるという利点がある。 In addition, since the solvent-soluble polyimide of the present invention is a polyimide that has been completely dehydrated and ring-closed and imidized, it does not require high-temperature heat treatment for imidization after the adhesive is applied to the polyimide film substrate. Therefore, compared to polyamic acid (polyimide precursor), which requires high-temperature heat treatment (300°C or higher) for imidization after the adhesive is applied to the polyimide film substrate, there is an advantage in that it is possible to provide a flexible copper-clad laminate with high dimensional stability.
（シランカップリング剤）
本発明のシランカップリング剤は、下記一般式[II]で表される構造を有する。
(ＲＯ)３Ｓｉ－Ｘ [II]
（式中、Ｘはケチミン構造又はアルジミン構造を有する基であり、Ｒはアルキル基である)
(Silane coupling agent)
The silane coupling agent of the present invention has a structure represented by the following general formula [II].
(RO) 3 Si-X [II]
(In the formula, X is a group having a ketimine structure or an aldimine structure, and R is an alkyl group.)
Ｘが表すケチミン構造を有する基とは、一般式(1)：－Ｒ１－Ｎ＝ＣＲ２Ｒ３で表される基であり、Ｘが表すアルジミン構造を有する基とは、一般式(2)：－Ｒ１－Ｎ＝ＣＨＲ２で表される基である。 The group having a ketimine structure represented by X is a group represented by general formula (1): -R 1 -N=CR 2 R 3 , and the group having an aldimine structure represented by X is a group represented by general formula (2): -R 1 -N=CHR 2 .
一般式(1)及び(2)中、Ｒ１は炭素数１～１０、好ましくは２～７のアルキレン基であり、Ｒ２、Ｒ３は炭素数１～１０、好ましくは１～７の直鎖状又は分岐状のアルキル基或いは置換されていてもよいフェニル基である。Ｒはアルキル基であり、炭素数１～７、更には炭素数１～５、特には炭素数１～３の直鎖状又は分岐状のアルキル基が好ましい。 In general formulas (1) and (2), R1 is an alkylene group having 1 to 10 carbon atoms, preferably 2 to 7 carbon atoms, and R2 and R3 are linear or branched alkyl groups having 1 to 10 carbon atoms, preferably 1 to 7 carbon atoms, or phenyl groups which may be substituted. R is an alkyl group, and is preferably a linear or branched alkyl group having 1 to 7 carbon atoms, more preferably 1 to 5 carbon atoms, and particularly preferably 1 to 3 carbon atoms.
本発明のシランカップリング剤としては、ケチミン構造を有するものとして３－トリエトキシシリル－Ｎ－（１，３－ジメチル－ブチリデン）プロピルアミン(下記化合物III)、３－トリメトキシシリル－Ｎ－（１，３－ジメチル－ブチリデン）プロピルアミン、Ｎ－（１－フェニルエチリデン）－３－（トリエトキシシリル）－１－プロピルアミン、Ｎ－（１－フェニルエチリデン）－３－（トリメトキシシリル）－１－プロピルアミンが挙げられる。 Examples of the silane coupling agent of the present invention that have a ketimine structure include 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine (compound III below), 3-trimethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, N-(1-phenylethylidene)-3-(triethoxysilyl)-1-propylamine, and N-(1-phenylethylidene)-3-(trimethoxysilyl)-1-propylamine.
また、アルジミン構造を有するものとしてＮ－（フェニルメチレン）－３－（トリエトキシシリル）－１－プロピルアミン（化合物IV）、Ｎ－（フェニルメチレン）－３－（トリメトキシシリル）－１－プロピルアミンが挙げられる。 Other examples having an aldimine structure include N-(phenylmethylene)-3-(triethoxysilyl)-1-propylamine (compound IV) and N-(phenylmethylene)-3-(trimethoxysilyl)-1-propylamine.
本発明のシランカップリング剤に相当する市販品としては、信越化学工業製ＫＢＥ－９１０３Ｐ（ケチミン構造）やＸ－１２－１１７２ＥＳ（アルジミン構造）等がある。 Commercially available products equivalent to the silane coupling agent of the present invention include KBE-9103P (ketimine structure) and X-12-1172ES (aldimine structure) manufactured by Shin-Etsu Chemical Co., Ltd.
一般的なシランカップリング剤は、ビニル基、エポキシ基、スチリル基、メタクリル基、アクリル基、アミノ基、ウレイド基、メルカプト基、イソシアネート基などの有機官能基を有する。本発明の溶剤可溶性ポリイミドに関してはアミノ基を有するシランカップリング剤が適するが、アミノ基は反応性が大きいために接着剤の保存安定性が低下する。アミノ基を保護したケチミン構造又はアルジミン構造を有するシランカップリング剤を用いることで、アミノ基含有アルコキシシリル化合物と同等以上の接着強度の向上が期待でき、接着剤の保存安定性の低下を抑えることができる。 General silane coupling agents have organic functional groups such as vinyl groups, epoxy groups, styryl groups, methacryl groups, acrylic groups, amino groups, ureido groups, mercapto groups, and isocyanate groups. Silane coupling agents having amino groups are suitable for the solvent-soluble polyimides of the present invention, but the high reactivity of amino groups reduces the storage stability of the adhesive. By using a silane coupling agent having a ketimine structure or aldimine structure in which the amino group is protected, it is possible to expect an improvement in adhesive strength equal to or greater than that of amino group-containing alkoxysilyl compounds, and to suppress a decrease in the storage stability of the adhesive.
本発明においては、低誘電率、低誘電正接及び吸水率を下げるために、溶剤可溶性ポリイミドへの極性基の導入を出来得る限り抑え、ダイマージアミンの量も制限を加えている。これらの極性基とダイマージアミンは接着強度に関係するため、接着剤の接着強度は低下する傾向にあるが、本発明のシランカップリング剤を用いることにより適正な接着強度を確保することができ、同時に吸湿後のはんだ耐熱性も向上することができる。 In the present invention, in order to reduce the dielectric constant, dielectric tangent, and water absorption, the introduction of polar groups into the solvent-soluble polyimide is suppressed as much as possible, and the amount of dimer diamine is also limited. Since these polar groups and dimer diamine are related to the adhesive strength, the adhesive strength of the adhesive tends to decrease, but by using the silane coupling agent of the present invention, it is possible to ensure appropriate adhesive strength and at the same time improve the solder heat resistance after moisture absorption.
本発明のシランカップリング剤の接着剤に対する添加量は、ポリイミド溶液の固形分１００重量部に対し、下限値は０．０１重量部以上、更には０．１重量部以上、特には０．５重量部以上とするのが好ましく、上限値は１０重量部以下、更には７重量部以下、特には５重量部以下とするのが好ましい。シランカップリング剤の添加量の下限値を０．０１重量部未満とすると、接着剤の引きはがし強度が低下する傾向にある。また、シランカップリング剤の添加量の上限値が１０重量部を超えると、接着剤の保存安定性や引きはがし強度が低下する傾向にある。 The amount of the silane coupling agent of the present invention added to the adhesive is preferably 0.01 parts by weight or more, more preferably 0.1 parts by weight or more, and especially 0.5 parts by weight or more, and the upper limit is preferably 10 parts by weight or less, more preferably 7 parts by weight or less, and especially 5 parts by weight or less, per 100 parts by weight of the solid content of the polyimide solution. If the lower limit of the amount of the silane coupling agent added is less than 0.01 parts by weight, the peel strength of the adhesive tends to decrease. Also, if the upper limit of the amount of the silane coupling agent added exceeds 10 parts by weight, the storage stability and peel strength of the adhesive tend to decrease.
（非水溶性溶剤）
本発明の接着剤は、接着剤としての保存安定性等の吸湿性能を緩和するために非水溶性溶剤で希釈してもよい。ポリイミドの有機合成で使用する有機極性溶媒としてはＮＭＰやγ－ブチロラクトンが最適であるが、これらは水溶性溶剤であるため、非水溶性溶剤で希釈することが好ましい。非水溶性溶剤としては、安息香酸メチル等が最適である。
(Non-water-soluble solvent)
The adhesive of the present invention may be diluted with a water-insoluble solvent to reduce the moisture absorption performance of the adhesive, such as storage stability. NMP and γ-butyrolactone are optimal organic polar solvents used in the organic synthesis of polyimide, but since these are water-soluble solvents, it is preferable to dilute the adhesive with a water-insoluble solvent. Methyl benzoate and the like are optimal as the water-insoluble solvent.
（接着剤）
本発明のフレキシブル銅張積層板用接着剤は、上述した溶剤可溶性ポリイミド、シランカップリング剤、非水溶性溶剤以外にも、難燃剤、イミド化剤、フィラー等を含む接着剤組成物であってもよい。
フィラーとしては低誘電特性を有するものが好ましい。接着剤としての沈降性やＦＣＣＬとしての加工性の観点から、シリカのサブミクロンフィラー又はナノフィラーが特に好ましい。
(glue)
The adhesive for flexible copper-clad laminates of the present invention may be an adhesive composition that contains, in addition to the above-mentioned solvent-soluble polyimide, silane coupling agent, and water-insoluble solvent, a flame retardant, an imidizing agent, a filler, and the like.
The filler is preferably one having low dielectric properties, and from the viewpoint of settling properties as an adhesive and processability as an FCCL, a submicron or nano-filler of silica is particularly preferred.
溶剤可溶性ポリイミドと共に、必要に応じ他の樹脂成分等の成分を混合して得られた混合物に溶剤を加え、樹脂固形分２０～６０重量％の樹脂ワニスを調製することにより接着剤（組成物）を作製することができる。 The adhesive (composition) can be produced by mixing the solvent-soluble polyimide with other resin components and other ingredients as necessary, adding a solvent to the resulting mixture, and preparing a resin varnish with a resin solids content of 20 to 60% by weight.
（接着剤フィルムの物性）
本発明の接着剤（組成物）は、接着剤（組成物）から作製した低揮発分状態の接着剤フィルムを２００℃で９０分間加熱処理して得られたフィルムの誘電正接が０．００３（５ＧＨｚ）以下、誘電率が３．０（５ＧＨｚ）以下となり、Ｔｇ（ガラス転移温度）が１１０℃以上となる。樹脂の誘電特性はＴｇを境として急激に変化する。この観点から、接着剤から作製したフィルムのＴｇ（ガラス転移温度）は、この接着剤を使用してできるＦＣＣＬが使用される電子機器等の常用使用温度よりも高いことが望まれる。そのため、本発明において、接着剤から作製したフィルムのＴｇ（ガラス転移温度）は、下限値が１１０℃以上、更には１２０℃以上、特には１３０℃以上が好ましく、上限値は１９０℃以下、更には１８０℃以下、特には１７０℃以下が好ましい。
(Physical properties of adhesive film)
The adhesive (composition) of the present invention is a film obtained by heating an adhesive film in a low volatile state made from the adhesive (composition) at 200°C for 90 minutes, and the dielectric tangent of the film obtained is 0.003 (5 GHz) or less, the dielectric constant is 3.0 (5 GHz) or less, and the Tg (glass transition temperature) is 110°C or more. The dielectric properties of a resin change rapidly at the Tg. From this viewpoint, it is desired that the Tg (glass transition temperature) of the film made from the adhesive is higher than the normal use temperature of electronic devices and the like in which the FCCL made using this adhesive is used. Therefore, in the present invention, the lower limit of the Tg (glass transition temperature) of the film made from the adhesive is preferably 110°C or more, more preferably 120°C or more, and particularly preferably 130°C or more, and the upper limit is preferably 190°C or less, more preferably 180°C or less, and particularly preferably 170°C or less.
（接着シート）
本発明の接着剤（組成物）をポリイミドフィルム基材の片面又は両面に塗工し、加熱して低揮発分化することにより、ラミネート法低誘電２層ＦＣＣＬ用の接着シートを得ることができる。具体的には、前述のように本発明の接着剤（組成物）をＮＭＰ、γ－ブチロラクトン等の好適な有機溶剤で希釈して調製した樹脂ワニスを、コア材料であるポリイミドフィルム基材の片面又は両面にダイコーター、グラビアコーター等を用いて塗工する。
(Adhesive sheet)
An adhesive sheet for a laminate method low dielectric two-layer FCCL can be obtained by applying the adhesive (composition) of the present invention to one or both sides of a polyimide film substrate and heating it to reduce volatility. Specifically, as described above, a resin varnish prepared by diluting the adhesive (composition) of the present invention with a suitable organic solvent such as NMP or γ-butyrolactone is applied to one or both sides of a polyimide film substrate, which is the core material, using a die coater, gravure coater, or the like.
接着剤層の塗工厚さは、積層する銅箔の粗化面を埋め込める最低厚さ以上であることが必要であり、具体的には銅箔のＲｚ（ＪＩＳ Ｂ ０６０１－２００１に準拠して測定）以上の厚さが好ましい。ただし、この塗工厚さはＦＣＣＬとしての誘電特性に影響するため、目標とする誘電特性に応じて変化させる。 The coating thickness of the adhesive layer must be at least the minimum thickness that can embed the roughened surface of the copper foil to be laminated, and specifically, a thickness equal to or greater than the Rz of the copper foil (measured in accordance with JIS B 0601-2001) is preferable. However, this coating thickness affects the dielectric properties of the FCCL, so it should be changed according to the target dielectric properties.
接着剤層の塗工温度（塗工後の乾燥温度を含む）は、含有溶剤を低揮発分化させることができる最低温度が好ましい。この観点から接着剤層の塗工温度は１５０℃以上が好ましく、更には１６０℃～１８０℃が好ましい。また、接着剤層を塗工後の乾燥温度は２２０℃以下が好ましく、更には１９０℃～２１０℃、特には１８０℃～２００℃が好ましい。 The coating temperature of the adhesive layer (including the drying temperature after coating) is preferably the lowest temperature at which the contained solvent can be made to have low volatility. From this perspective, the coating temperature of the adhesive layer is preferably 150°C or higher, and more preferably 160°C to 180°C. In addition, the drying temperature after coating the adhesive layer is preferably 220°C or lower, and more preferably 190°C to 210°C, and particularly preferably 180°C to 200°C.
（ラミネート法低誘電２層フレキシブル銅張積層板）
上記のようにして作製した接着シートの接着剤層の表面に銅箔を貼り合わせた（ラミネートした）後に、接着剤層を加熱処理することにより、ラミネート法低誘電２層フレキシブル銅張積層板を作製することができる。ラミネート温度の上限値は２２０℃以下、更には２１０℃以下、特には２００以下が好ましく、下限値は１７０℃以上、更には１７５℃以上、特には１８０℃以上が好ましい。接着剤層の加熱処理温度は熱歪みの最大の要因であるため、上限値は２２０℃以下、更には２１０℃以下、特には２００以下が好ましく、下限値は１８０℃以上、更には１８５℃以上、特には１９０℃以上が好ましい。
(Laminated low dielectric two-layer flexible copper-clad laminate)
After bonding (laminating) copper foil to the surface of the adhesive layer of the adhesive sheet prepared as described above, the adhesive layer is heat-treated to prepare a laminated low dielectric two-layer flexible copper-clad laminate. The upper limit of the lamination temperature is preferably 220°C or less, more preferably 210°C or less, and particularly preferably 200°C or less, and the lower limit is preferably 170°C or more, more preferably 175°C or more, and particularly preferably 180°C or more. Since the heat treatment temperature of the adhesive layer is the largest factor of thermal distortion, the upper limit is preferably 220°C or less, more preferably 210°C or less, and particularly preferably 200°C or less, and the lower limit is preferably 180°C or more, more preferably 185°C or more, and particularly preferably 190°C or more.
以下、本発明を実施例に基づき詳細に説明するが、本発明は様々な他の実施形態に変形できるものであり、下記実施例に限定されることはない。 The present invention will be described in detail below with reference to examples, but the present invention can be modified into various other embodiments and is not limited to the following examples.
１． 溶剤可溶性ポリイミド樹脂の合成
（合成例１）
ガラス製のセパラブル三つ口フラスコに、撹拌機、チッ素導入管、及び水分受容器を備えた冷却管を取り付けた。４，４’－［プロパン－２，２－ジイルビス（１，４－フェニレンオキシ）］ジフタル酸二無水物６７．６ｇ（０．１３モル）、ＰＲＩＡＭＩＮＥ１０７５（クローダジャパン（株）製）３５．６９ｇ（０．０６５モル）、バレロラクトン１．５ｇ（０．０１５モル）、ピリジン２．４ｇ（０．０３モル）、ＮＭＰ３６０ｇ、トルエン９０ｇを仕込み、室温で、窒素雰囲気下、２００ｒｐｍで３０分撹拌した後、１８０℃に昇温して３時間加熱撹拌した。反応中、トルエン－水の共沸分を除いた。
室温に冷却して、４，４’－［プロパン－２，２－ジイルビス（１，４－フェニレンオキシ）］ジフタル酸二無水物４９．９２ｇ（０．０９６モル）、９，９－ビス（４－アミノフェニル）フルオレン５０．５３ｇ（０．１４５モル）、４，４’－ジアミノジフェニルエーテル３．２２ｇ（０．０１６モル）、ＮＭＰ１３０ｇ、トルエン３０ｇを加え、室温で３０分撹拌した後、１８０℃に昇温して、１時間加熱撹拌した。水－トルエンの共沸の還流物を系外に除きながら、１８０℃で３時間３０分加熱撹拌して反応を終了した。得られた生成物に安息香酸メチルを加えて希釈し、固形分２０重量％のブロック共重合ポリイミド溶液を得た。
1. Synthesis of Solvent-Soluble Polyimide Resin (Synthesis Example 1)
A separable three-necked glass flask was fitted with a stirrer, a nitrogen inlet tube, and a cooling tube equipped with a water receiver. 67.6 g (0.13 mol) of 4,4'-[propane-2,2-diylbis(1,4-phenyleneoxy)]diphthalic dianhydride, 35.69 g (0.065 mol) of PRIAMINE 1075 (manufactured by Croda Japan Co., Ltd.), 1.5 g (0.015 mol) of valerolactone, 2.4 g (0.03 mol) of pyridine, 360 g of NMP, and 90 g of toluene were charged and stirred at room temperature under a nitrogen atmosphere at 200 rpm for 30 minutes, and then heated to 180°C and stirred for 3 hours. During the reaction, the toluene-water azeotrope was removed.
After cooling to room temperature, 49.92 g (0.096 mol) of 4,4'-[propane-2,2-diylbis(1,4-phenyleneoxy)]diphthalic dianhydride, 50.53 g (0.145 mol) of 9,9-bis(4-aminophenyl)fluorene, 3.22 g (0.016 mol) of 4,4'-diaminodiphenyl ether, 130 g of NMP, and 30 g of toluene were added and stirred at room temperature for 30 minutes, and then the temperature was raised to 180°C and heated and stirred for 1 hour. The reaction was terminated by heating and stirring at 180°C for 3 hours and 30 minutes while removing the refluxed product of the water-toluene azeotrope from the system. The obtained product was diluted with methyl benzoate to obtain a block copolymer polyimide solution with a solid content of 20% by weight.
（合成例２）
ガラス製のセパラブル三つ口フラスコに、撹拌機、チッ素導入管、及び水分受容器を備えた冷却管を取り付けた。４，４’－［プロパン－２，２－ジイルビス（１，４－フェニレンオキシ）］ジフタル酸二無水物５５．１２ｇ（０．１０６モル）、ＰＲＩＡＭＩＮＥ１０７５（クローダジャパン（株）製）２９．６５ｇ（０．０５４モル）、バレロラクトン１．５ｇ（０．０１５モル）、ピリジン２．４ｇ（０．０３モル）、ＮＭＰ３９０ｇ、トルエン９０ｇを仕込み、室温で、窒素雰囲気下、２００ｒｐｍで３０分撹拌した後、１８０℃に昇温して３時間加熱撹拌した。反応中、トルエン－水の共沸分を除いた。
室温に冷却して、４，４’－［プロパン－２，２－ジイルビス（１，４－フェニレンオキシ）］ジフタル酸二無水物８３．７２ｇ（０．１６１モル）、４，４’-ジアミノジフェニルエーテル３４．０４ｇ（０．１７０モル）、９，９－ビス（４－アミノフェニル）フルオレン１４．９８ｇ（０．０４３モル）、ＮＭＰ１１０ｇ、トルエン３０ｇを加え、室温で３０分撹拌した後、１８０℃に昇温して、１時間加熱撹拌した。水－トルエンの共沸の還流物を系外に除きながら、１８０℃で２時間３０分加熱撹拌して反応を終了した。得られた生成物に安息香酸メチルを加えて希釈し、固形分２０重量％のブロック共重合ポリイミド溶液を得た。
(Synthesis Example 2)
A separable three-necked glass flask was fitted with a stirrer, a nitrogen inlet tube, and a cooling tube equipped with a water receiver. 55.12 g (0.106 mol) of 4,4'-[propane-2,2-diylbis(1,4-phenyleneoxy)]diphthalic dianhydride, 29.65 g (0.054 mol) of PRIAMINE 1075 (manufactured by Croda Japan Co., Ltd.), 1.5 g (0.015 mol) of valerolactone, 2.4 g (0.03 mol) of pyridine, 390 g of NMP, and 90 g of toluene were charged and stirred at room temperature under a nitrogen atmosphere at 200 rpm for 30 minutes, and then heated to 180°C and stirred for 3 hours. During the reaction, the toluene-water azeotrope was removed.
After cooling to room temperature, 83.72 g (0.161 mol) of 4,4'-[propane-2,2-diylbis(1,4-phenyleneoxy)]diphthalic dianhydride, 34.04 g (0.170 mol) of 4,4'-diaminodiphenyl ether, 14.98 g (0.043 mol) of 9,9-bis(4-aminophenyl)fluorene, 110 g of NMP, and 30 g of toluene were added and stirred at room temperature for 30 minutes, and then the temperature was raised to 180°C and heated and stirred for 1 hour. The reaction was terminated by heating and stirring at 180°C for 2 hours and 30 minutes while removing the water-toluene azeotropic reflux from the system. The obtained product was diluted with methyl benzoate to obtain a block copolymer polyimide solution with a solid content of 20% by weight.
（合成例３）
ガラス製のセパラブル三つ口フラスコに、撹拌機、チッ素導入管、及び水分受容器を備えた冷却管を取り付けた。４，４’－［プロパン－２，２－ジイルビス（１，４－フェニレンオキシ）］ジフタル酸二無水物８０．０８ｇ（０．１５４モル）、ＰＲＩＡ ＭＩＮＥ１０７５（クローダジャパン（株）製）４２．２７ｇ（０．０７７モル）、バレロラクトン１．５ｇ（０．０１５モル）、ピリジン２．４ｇ（０．０３モル）、ＮＭＰ３９０ｇ、トルエン９０ｇを仕込み、室温で、窒素雰囲気下、２００ｒｐｍで３０分撹拌した後、１８０℃に昇温して３時間加熱撹拌した。反応中、トルエン－水の共沸分を除いた。
室温に冷却して、４，４’－［プロパン－２，２－ジイルビス（１，４－フェニレンオキシ）］ジフタル酸二無水物５８．７６ｇ（０．１１３モル）、２，２’－ビス（トリフルオロメチル）ベンジジン６０．８５ｇ（０．１９０モル）、ＮＭＰ１６０ｇ、トルエン３０ｇを加え、室温で３０分撹拌した後、１８０℃に昇温して、１時間加熱撹拌した。水－トルエンの共沸の還流物を系外に除きながら、１８０℃で３時間３０分加熱撹拌して反応を終了した。得られた生成物に安息香酸メチルを加えて希釈し、固形分２０重量％のブロック共重合ポリイミド溶液を得た。
(Synthesis Example 3)
A separable three-necked glass flask was fitted with a stirrer, a nitrogen inlet tube, and a cooling tube equipped with a water receiver. 80.08 g (0.154 mol) of 4,4'-[propane-2,2-diylbis(1,4-phenyleneoxy)]diphthalic dianhydride, 42.27 g (0.077 mol) of PRIA MINE 1075 (manufactured by Croda Japan Co., Ltd.), 1.5 g (0.015 mol) of valerolactone, 2.4 g (0.03 mol) of pyridine, 390 g of NMP, and 90 g of toluene were charged and stirred at room temperature under a nitrogen atmosphere at 200 rpm for 30 minutes, and then heated to 180°C and stirred for 3 hours. During the reaction, the toluene-water azeotrope was removed.
After cooling to room temperature, 58.76 g (0.113 mol) of 4,4'-[propane-2,2-diylbis(1,4-phenyleneoxy)]diphthalic dianhydride, 60.85 g (0.190 mol) of 2,2'-bis(trifluoromethyl)benzidine, 160 g of NMP, and 30 g of toluene were added and stirred at room temperature for 30 minutes, and then the temperature was raised to 180°C and heated and stirred for 1 hour. While removing the water-toluene azeotropic reflux product from the system, the reaction was terminated by heating and stirring at 180°C for 3 hours and 30 minutes. The obtained product was diluted with methyl benzoate to obtain a block copolymer polyimide solution with a solid content of 20% by weight.
（合成例４）
ガラス製のセパラブル三つ口フラスコに、撹拌機、チッ素導入管、及び水分受容器を備えた冷却管を取り付けた。４，４’－［プロパン－２，２－ジイルビス（１，４－フェニレンオキシ）］ジフタル酸二無水物８０．０８ｇ（０．１５４モル）、ＰＲＩＡＭＩＮＥ１０７５（クローダジャパン（株）製）４２．２７ｇ（０．０７７モル）、バレロラクトン１．５ｇ（０．０１５モル）、ピリジン２．４ｇ（０．０３モル）、ＮＭＰ４３０ｇ、トルエン９０ｇを仕込み、室温で、窒素雰囲気下、２００ｒｐｍで３０分撹拌した後、１８０℃に昇温して３時間加熱撹拌した。反応中、トルエン－水の共沸分を除いた。
室温に冷却して、４，４’－［プロパン－２，２－ジイルビス（１，４－フェニレンオキシ）］ジフタル酸二無水物５８．７６ｇ（０．１１３モル）、４，４’-ジアミノジフェニルエーテル３０．４４ｇ（０．１５２モル）、９，９－ビス（４－アミノフェニル）フルオレン１３．２４ｇ（０．０３８モル）、ＮＭＰ８５ｇ、トルエン３０ｇを加え、室温で３０分撹拌した後、１８０℃に昇温して、１時間加熱撹拌した。水－トルエンの共沸の還流物を系外に除きながら、１８０℃で２時間３０分加熱撹拌して反応を終了した。得られた生成物に安息香酸メチルを加えて希釈し、固形分２０重量％のブロック共重合ポリイミド溶液を得た。
(Synthesis Example 4)
A separable three-necked glass flask was fitted with a stirrer, a nitrogen inlet tube, and a cooling tube equipped with a water receiver. 80.08 g (0.154 mol) of 4,4'-[propane-2,2-diylbis(1,4-phenyleneoxy)]diphthalic dianhydride, 42.27 g (0.077 mol) of PRIAMINE 1075 (manufactured by Croda Japan Co., Ltd.), 1.5 g (0.015 mol) of valerolactone, 2.4 g (0.03 mol) of pyridine, 430 g of NMP, and 90 g of toluene were charged and stirred at room temperature under a nitrogen atmosphere at 200 rpm for 30 minutes, and then heated to 180°C and stirred for 3 hours. During the reaction, the toluene-water azeotrope was removed.
After cooling to room temperature, 58.76 g (0.113 mol) of 4,4'-[propane-2,2-diylbis(1,4-phenyleneoxy)]diphthalic dianhydride, 30.44 g (0.152 mol) of 4,4'-diaminodiphenyl ether, 13.24 g (0.038 mol) of 9,9-bis(4-aminophenyl)fluorene, 85 g of NMP, and 30 g of toluene were added and stirred at room temperature for 30 minutes, and then the temperature was raised to 180°C and heated and stirred for 1 hour. The reaction was terminated by heating and stirring at 180°C for 2 hours and 30 minutes while removing the water-toluene azeotropic reflux product from the system. The obtained product was diluted with methyl benzoate to obtain a block copolymer polyimide solution with a solid content of 20% by weight.
（合成例５）
実施例１で製造した固形分２０重量％のブロック共重合ポリイミド溶液１００ｇにアドマナノ１０ｎｍ(（株）アドマテックス社製)を１２ｇ、ＮＭＰを４８ｇ仕込み、自転・公転ミキサー「あわとり練太郎」（株式会社シンキー製）で２時間混錬し、固形分２０重量％のブロック共重合ポリイミド溶液を得た。
(Synthesis Example 5)
12 g of Admanano 10 nm (manufactured by Admatechs Co., Ltd.) and 48 g of NMP were added to 100 g of the block copolymer polyimide solution having a solid content of 20% by weight produced in Example 1, and the mixture was kneaded for 2 hours using a centrifugal mixer “Awatori Rentaro” (manufactured by Thinky Corporation) to obtain a block copolymer polyimide solution having a solid content of 20% by weight.
（合成比較例１）
ガラス製のセパラブル三つ口フラスコに、撹拌機、チッ素導入管、及び水分受容器を備えた冷却管を取り付けた。４，４’－［プロパン－２，２－ジイルビス（１，４－フェニレンオキシ）］ジフタル酸二無水物１３８．９７ｇ（０．２６７モル）、３，４’-ジアミノジフェニルエーテル５３．４６ｇ（０．２６７モル）、バレロラクトン１．５ｇ（０．０１５モル）、ピリジン２．４ｇ（０．０３モル）、ＮＭＰ４５０ｇ、トルエン９０ｇを仕込み、室温で、窒素雰囲気下、２００ｒｐｍで３０分撹拌した後、１８０℃に昇温して１時間加熱撹拌した。水－トルエンの共沸の還流物を系外に除きながら、１８０℃で３時間３０分加熱撹拌して反応を終了した。得られた生成物に安息香酸メチルを加えて希釈し、固形分２０重量％のブロック共重合ポリイミド溶液を得た。
(Comparative Synthesis Example 1)
A three-necked separable glass flask was fitted with a stirrer, a nitrogen inlet tube, and a cooling tube equipped with a water receiver. 138.97 g (0.267 mol) of 4,4'-[propane-2,2-diylbis(1,4-phenyleneoxy)]diphthalic dianhydride, 53.46 g (0.267 mol), 1.5 g (0.015 mol) of valerolactone, 2.4 g (0.03 mol) of pyridine, 450 g of NMP, and 90 g of toluene were charged, and the mixture was stirred at room temperature under a nitrogen atmosphere at 200 rpm for 30 minutes, and then heated to 180°C and stirred for 1 hour. The reaction was terminated by heating and stirring at 180°C for 3 hours and 30 minutes while removing the reflux product of the water-toluene azeotrope from the system. The product obtained was diluted with methyl benzoate to obtain a block copolymer polyimide solution with a solid content of 20% by weight.
（合成比較例２）
ガラス製のセパラブル三つ口フラスコに、撹拌機、チッ素導入管、及び水分受容器を備えた冷却管を取り付けた。４，４’－［プロパン－２，２－ジイルビス（１，４－フェニレンオキシ）］ジフタル酸二無水物１３８．９７ｇ（０．２６７モル）、ＰＲＩＡＭＩＮＥ１０７５（クローダジャパン（株）製）１１７．４９ｇ（０．２１４モル）、４，４’-ジアミノジフェニルエーテル１０．６１ｇ（０．０５３モル）、バレロラクトン１．５ｇ（０．０１５モル）、ピリジン２．４ｇ（０．０３モル）、ＮＭＰ６７０ｇ、トルエン９０ｇを仕込み、室温で、窒素雰囲気下、２００ｒｐｍで３０分撹拌した後、１８０℃に昇温して１時間加熱撹拌した。水－トルエンの共沸の還流物を系外に除きながら、１８０℃で４時間３０分加熱撹拌して反応を終了した。得られた生成物に安息香酸メチルを加えて希釈し、固形分２０重量％のブロック共重合ポリイミド溶液を得た。
(Comparative Synthesis Example 2)
A separable three-necked glass flask was equipped with a stirrer, a nitrogen inlet tube, and a cooling tube equipped with a water receiver. 138.97 g (0.267 mol) of 4,4'-[propane-2,2-diylbis(1,4-phenyleneoxy)]diphthalic dianhydride, 117.49 g (0.214 mol) of PRIAMINE 1075 (manufactured by Croda Japan Co., Ltd.), 10.61 g (0.053 mol) of 4,4'-diaminodiphenyl ether, 1.5 g (0.015 mol) of valerolactone, 2.4 g (0.03 mol) of pyridine, 670 g of NMP, and 90 g of toluene were charged and stirred at room temperature under a nitrogen atmosphere at 200 rpm for 30 minutes, and then heated to 180°C and stirred for 1 hour. The reaction was terminated by heating and stirring at 180° C. for 4 hours and 30 minutes while removing the water-toluene azeotropic reflux product from the system. The resulting product was diluted with methyl benzoate to obtain a block copolymer polyimide solution with a solid content of 20% by weight.
（合成比較例３）
ガラス製のセパラブル三つ口フラスコに、撹拌機、チッ素導入管、及び水分受容器を備えた冷却管を取り付けた。４，４’-（ヘキサフルオロイソプロピリデン）ジフタル酸無水物６８．４１ｇ（０．１５４モル）、ＰＲＩＡＭＩＮＥ１０７５（クローダジャパン（株）製）４２．２７ｇ（０．０７７モル）、バレロラクトン１．５ｇ（０．０１５モル）、ピリジン２．４ｇ（０．０３モル）、ＮＭＰ３４０ｇ、トルエン９０ｇを仕込み、室温で、窒素雰囲気下、２００ｒｐｍで３０分撹拌した後、１８０℃に昇温して３時間加熱撹拌した。反応中、トルエン－水の共沸分を除いた。
室温に冷却して、４，４’-（ヘキサフルオロイソプロピリデン）ジフタル酸無水物５０．２０ｇ（０．１１３モル）、２，２’－ビス（トリフルオロメチル）ベンジジン６０．８５ｇ（０．１９０モル）、ＮＭＰ１６０ｇ、トルエン３０ｇを加え、室温で３０分撹拌した後、１８０℃に昇温して、１時間加熱撹拌した。水－トルエンの共沸の還流物を系外に除きながら、１８０℃で２時間３０分加熱撹拌して反応を終了した。得られた生成物に安息香酸メチルを加えて希釈し、固形分２０重量％のブロック共重合ポリイミド溶液を得た。
(Comparative Synthesis Example 3)
A glass separable three-neck flask was equipped with a stirrer, a nitrogen inlet tube, and a cooling tube equipped with a water receiver. 68.41 g (0.154 mol) of 4,4'-(hexafluoroisopropylidene)diphthalic anhydride, 42.27 g (0.077 mol) of PRIAMINE 1075 (manufactured by Croda Japan Co., Ltd.), 1.5 g (0.015 mol) of valerolactone, 2.4 g (0.03 mol) of pyridine, 340 g of NMP, and 90 g of toluene were charged and stirred at room temperature under a nitrogen atmosphere at 200 rpm for 30 minutes, and then heated to 180°C and stirred for 3 hours. During the reaction, the toluene-water azeotrope was removed.
After cooling to room temperature, 50.20 g (0.113 mol) of 4,4'-(hexafluoroisopropylidene)diphthalic anhydride, 60.85 g (0.190 mol) of 2,2'-bis(trifluoromethyl)benzidine, 160 g of NMP, and 30 g of toluene were added and stirred at room temperature for 30 minutes, and then the temperature was raised to 180°C and heated and stirred for 1 hour. While removing the water-toluene azeotropic reflux from the system, the reaction was terminated by heating and stirring at 180°C for 2 hours and 30 minutes. The obtained product was diluted with methyl benzoate to obtain a block copolymer polyimide solution with a solid content of 20% by weight.
２． 接着剤組成物の製造
合成例１～５で合成したポリイミド溶液１００重量部にシランカップリング剤ＫＢＥ－９１０３Ｐ（信越化学工業社製）をその固形分１００部に対し１部を添加して撹拌を行い、接着剤組成物１～５を製造した。
合成例１で合成したポリイミド溶液１００部にシランカップリング剤ＫＢＥ－９０３（信越化学工業社製）をその固形分１００部に対し１部を添加して撹拌を行い、接着剤組成物６を製造した。
合成比較例１～２で合成したポリイミド溶液はシランカップリング剤を添加することなく、そのまま接着剤組成物とした。
2. Preparation of Adhesive Compositions Adhesive Compositions 1 to 5 were prepared by adding 1 part of a silane coupling agent KBE-9103P (manufactured by Shin-Etsu Chemical Co., Ltd.) per 100 parts of solid content to 100 parts by weight of the polyimide solutions synthesized in Synthesis Examples 1 to 5 and stirring the mixture.
To 100 parts of the polyimide solution synthesized in Synthesis Example 1, 1 part of a silane coupling agent KBE-903 (manufactured by Shin-Etsu Chemical Co., Ltd.) was added per 100 parts of the solid content, and the mixture was stirred to prepare an adhesive composition 6.
The polyimide solutions synthesized in Comparative Synthesis Examples 1 and 2 were directly used as adhesive compositions without adding a silane coupling agent.
（接着剤フィルムの誘電率、誘電正接及びＴｇ）
接着剤組成物1～６、及び合成比較例１～２で合成したポリイミド溶液（樹脂ワニス）から作製したフィルムの誘電特性とＴｇを以下の方法で測定した。
接着剤組成物又は樹脂ワニスを１８μｍ電解銅箔のシャイニー面にバーコーターで塗布し、１６０℃の温度で乾燥して接着剤付き銅箔（接着剤厚さ：約２１μｍ）を製造した。溶剤の揮発分は０．６ｗｔ％に調整した。この接着剤付き銅箔の接着シート面に１８μｍ電解銅箔シャイニー面を重ねあわせ、真空プレスに仕込み２００℃×９０分、１ＭＰａで加熱・加圧（真空度５ｔｏｒｒ）成形した。次いで銅箔を全面エッチングして得られた約２０μｍの接着フィルムについて誘電率、誘電正接及びＴｇを測定した。誘電率及び誘電正接はＪＩＳ Ｃ２５６５準拠の円筒空洞共振器法で測定し、ＴｇはＩＰＣ－ＴＭ－６５０－２．４．２４．３に準拠して測定した。保存安定性は、接着剤組成物を密閉容器に移し、２５℃の恒温槽に放置して経時毎に粘度をレオメーターで測定し、経時粘度／初期粘度の比で表した。
(Dielectric constant, dielectric tangent and Tg of adhesive film)
The dielectric properties and Tg of films prepared from the adhesive compositions 1 to 6 and the polyimide solutions (resin varnishes) synthesized in Comparative Synthesis Examples 1 and 2 were measured by the following methods.
The adhesive composition or resin varnish was applied to the shiny side of 18 μm electrolytic copper foil with a bar coater and dried at a temperature of 160° C. to produce an adhesive-attached copper foil (adhesive thickness: about 21 μm). The volatile content of the solvent was adjusted to 0.6 wt%. The shiny side of the 18 μm electrolytic copper foil was placed on the adhesive sheet side of this adhesive-attached copper foil, and the resulting product was placed in a vacuum press and heated and pressed at 200° C. for 90 minutes at 1 MPa (vacuum degree 5 torr) for molding. The copper foil was then etched over its entire surface, and the dielectric constant, dielectric loss tangent, and Tg were measured for the adhesive film of about 20 μm obtained. The dielectric constant and dielectric loss tangent were measured by a cylindrical cavity resonator method in accordance with JIS C2565, and Tg was measured in accordance with IPC-TM-650-2.4.24.3. The storage stability was evaluated by transferring the adhesive composition into a sealed container and leaving it in a thermostatic chamber at 25° C., measuring the viscosity over time with a rheometer, and expressing it as the ratio of viscosity over time to the initial viscosity.
合成例１～５から製造した接着剤組成物1～６、及び合成比較例１～３から製造した接着剤組成物７～９から作製した接着剤フィルムの特性評価結果を下記表１に示す。表１中、保存安定性の「－」は未測定を意味する。 The results of evaluating the properties of the adhesive films made from adhesive compositions 1 to 6 produced from Synthesis Examples 1 to 5, and adhesive compositions 7 to 9 produced from Synthesis Comparative Examples 1 to 3, are shown in Table 1 below. In Table 1, "-" for storage stability means not measured.
（ＦＣＣＬ各種特性の評価）
接着剤組成物１～６、接着剤組成物７～９を、２５μｍポリイミドフィルム（ＫＡＰＴＯＮ（登録商標）（東レデュポン社製）１００ＥＮ、ＦＳ－１００（ＳＫＣ社製））上にダイコーターで塗布し、１６０℃の温度で乾燥して両面塗工のＢ状態の接着シート（片側膜厚さ：１２μｍ）を製造した。揮発分は０．６ｗｔ％に調整した。この接着シートに１２μｍのＲｚ＝１．８μｍの銅箔を両面に１９０℃でラミネートし、その後乾燥機で２００℃×９０分加熱処理し、両面銅箔ＦＣＣＬを作製した。
接着剤組成物８は、樹脂フローが大きく、膜厚を制御できなかったため、銅箔ラミネート及び加熱処理により正常なＦＣＣＬを製造できなかった。
(Evaluation of various FCCL characteristics)
Adhesive compositions 1 to 6 and adhesive compositions 7 to 9 were applied onto a 25 μm polyimide film (KAPTON (registered trademark) (manufactured by Toray DuPont) 100EN, FS-100 (manufactured by SKC Corporation)) using a die coater and dried at a temperature of 160°C to produce a double-sided coated B-state adhesive sheet (film thickness on one side: 12 μm). The volatile content was adjusted to 0.6 wt%. 12 μm copper foil with Rz = 1.8 μm was laminated on both sides of this adhesive sheet at 190°C, and then heat-treated in a dryer at 200°C for 90 minutes to produce a double-sided copper foil FCCL.
Adhesive composition 8 had a large resin flow and the film thickness could not be controlled, so that a normal FCCL could not be produced by copper foil lamination and heat treatment.
上記のように作製した両面銅箔ＦＣＣＬを用いて、引きはがし強さ、はんだ耐熱性の評価を行った結果を下記表２－１及び表２－２に示す。試験方法はＪＩＳ Ｃ ６４７１、ＪＩＳ Ｃ ６４８１に準拠した。
また、作製した両面銅箔ＦＣＣＬの銅箔を全面エッチングしたフィルムを使用して、誘電特性（誘電率及び誘電正接）を円筒空洞共振器法により測定した。
また、比較例５として、市販のラミネート法２層ＦＣＣＬの特性を評価した。
The peel strength and solder heat resistance of the double-sided copper foil FCCL prepared as above were evaluated, and the results are shown in the following Tables 2-1 and 2-2. The test method was in accordance with JIS C 6471 and JIS C 6481.
In addition, the copper foil of the double-sided copper foil FCCL thus produced was entirely etched to obtain a film, and the dielectric properties (dielectric constant and dielectric loss tangent) were measured by a cylindrical cavity resonator method.
As Comparative Example 5, the characteristics of a commercially available two-layer FCCL produced by a laminate method were evaluated.
表１の結果から、本発明の接着剤組成物１～６から作製したフィルムは、接着剤組成物誘電率及び誘電正接が低く、Ｔｇも１１０℃以上を達成し、保存安定性に非常に優れ、吸水率も低く、吸湿後のはんだ耐熱性にも優れるバランスの優れた特性を有することが分かる。
また、表２－１及び表２－２の結果から、本発明の接着剤組成物１～５を用いたＦＣＣＬ（実施例１～５）は、接着剤組成物６～９を用いたＦＣＣＬ（比較例１～３）及びラミネート法2層FCCLに比べ、誘電特性、はんだ耐熱性、引きはがし強さのバランスに優れていることが分かる。
From the results in Table 1, it can be seen that the films produced from the adhesive compositions 1 to 6 of the present invention have a low adhesive composition dielectric constant and dielectric tangent, achieve a Tg of 110°C or higher, have very excellent storage stability, have a low water absorption rate, and have excellent solder heat resistance after moisture absorption, resulting in an excellent balance of properties.
Furthermore, the results in Tables 2-1 and 2-2 show that the FCCLs using adhesive compositions 1 to 5 of the present invention (Examples 1 to 5) have a superior balance of dielectric properties, solder heat resistance, and peel strength compared to the FCCLs using adhesive compositions 6 to 9 (Comparative Examples 1 to 3) and the two-layer FCCL by the laminate method.
本発明の接着剤及び接着シートを用いることにより、誘電特性と、熱的特性、加工特性、接着特性、吸湿特性と、コストとをバランス良く並立できるラミネート法低誘電２層ＦＣＣＬを提供することができる。 By using the adhesive and adhesive sheet of the present invention, it is possible to provide a laminated low dielectric two-layer FCCL that has a good balance of dielectric properties, thermal properties, processing properties, adhesive properties, moisture absorption properties, and cost.
Claims (8)
(ＲＯ)３Ｓｉ－Ｘ [II]
（式［II］中、Ｘはケチミン構造又はアルジミン構造を有する基であり、Ｒはアルキル基である) The adhesive for flexible copper-clad laminates is used to bond a polyimide film substrate and copper foil that constitute a flexible copper-clad laminate, the adhesive comprising a solvent-soluble polyimide that has been subjected to dehydration ring-closure imidization and has a repeating unit represented by the following general formula [I], and a silane coupling agent represented by the following general formula [II] (excluding silane coupling agents having an amino group) , wherein the dimer diamine residues contained in the solvent-soluble polyimide account for 20 mol % or more and less than 30 mol % of all diamine residues .
(RO) 3 Si-X [II]
(In formula [II], X is a group having a ketimine structure or an aldimine structure, and R is an alkyl group.)
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