JP7453434B2 - Metal-clad laminates and circuit boards - Google Patents
Metal-clad laminates and circuit boards Download PDFInfo
- Publication number
- JP7453434B2 JP7453434B2 JP2023001881A JP2023001881A JP7453434B2 JP 7453434 B2 JP7453434 B2 JP 7453434B2 JP 2023001881 A JP2023001881 A JP 2023001881A JP 2023001881 A JP2023001881 A JP 2023001881A JP 7453434 B2 JP7453434 B2 JP 7453434B2
- Authority
- JP
- Japan
- Prior art keywords
- thermoplastic polyimide
- diamine
- layer
- metal
- parts
- 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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- 229920006259 thermoplastic polyimide Polymers 0.000 claims description 113
- 125000004427 diamine group Chemical group 0.000 claims description 79
- 239000011347 resin Substances 0.000 claims description 64
- 229920005989 resin Polymers 0.000 claims description 64
- -1 diamine compound Chemical class 0.000 claims description 27
- 150000000000 tetracarboxylic acids Chemical group 0.000 claims description 25
- 229910052751 metal Inorganic materials 0.000 claims description 23
- 239000002184 metal Substances 0.000 claims description 23
- 125000004432 carbon atom Chemical group C* 0.000 claims description 17
- 238000012545 processing Methods 0.000 claims description 13
- 125000005843 halogen group Chemical group 0.000 claims description 9
- 125000003342 alkenyl group Chemical group 0.000 claims description 8
- 125000003545 alkoxy group Chemical group 0.000 claims description 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 8
- 125000005647 linker group Chemical group 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 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 claims description 5
- 239000004215 Carbon black (E152) Substances 0.000 claims description 5
- 229930195733 hydrocarbon Natural products 0.000 claims description 5
- 150000002430 hydrocarbons Chemical class 0.000 claims description 5
- KMKWGXGSGPYISJ-UHFFFAOYSA-N 4-[4-[2-[4-(4-aminophenoxy)phenyl]propan-2-yl]phenoxy]aniline Chemical compound C=1C=C(OC=2C=CC(N)=CC=2)C=CC=1C(C)(C)C(C=C1)=CC=C1OC1=CC=C(N)C=C1 KMKWGXGSGPYISJ-UHFFFAOYSA-N 0.000 claims description 4
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 125000006157 aromatic diamine group Chemical group 0.000 claims 1
- 239000010410 layer Substances 0.000 description 179
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 84
- 229920001721 polyimide Polymers 0.000 description 54
- 239000011889 copper foil Substances 0.000 description 47
- 239000004642 Polyimide Substances 0.000 description 44
- 229920005575 poly(amic acid) Polymers 0.000 description 42
- 229910052802 copper Inorganic materials 0.000 description 37
- 239000010949 copper Substances 0.000 description 37
- 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 23
- 238000006116 polymerization reaction Methods 0.000 description 23
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 20
- 238000003756 stirring Methods 0.000 description 20
- 238000000034 method Methods 0.000 description 19
- 230000007423 decrease Effects 0.000 description 18
- 230000009477 glass transition Effects 0.000 description 18
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 17
- 230000015572 biosynthetic process Effects 0.000 description 16
- 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 description 16
- 238000003786 synthesis reaction Methods 0.000 description 16
- 125000005462 imide group Chemical group 0.000 description 15
- 238000005259 measurement Methods 0.000 description 15
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 14
- 238000010438 heat treatment Methods 0.000 description 14
- XUSNPFGLKGCWGN-UHFFFAOYSA-N 3-[4-(3-aminopropyl)piperazin-1-yl]propan-1-amine Chemical compound NCCCN1CCN(CCCN)CC1 XUSNPFGLKGCWGN-UHFFFAOYSA-N 0.000 description 13
- 238000005452 bending Methods 0.000 description 13
- 239000010408 film Substances 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 12
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 11
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- 239000007787 solid Substances 0.000 description 10
- 238000003860 storage Methods 0.000 description 9
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 8
- 229920001169 thermoplastic Polymers 0.000 description 8
- 239000004416 thermosoftening plastic Substances 0.000 description 8
- 239000002904 solvent Substances 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 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 5
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 125000006158 tetracarboxylic acid group Chemical group 0.000 description 5
- 239000010409 thin film Substances 0.000 description 5
- 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 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 239000004305 biphenyl Substances 0.000 description 4
- 235000010290 biphenyl Nutrition 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 238000005530 etching Methods 0.000 description 4
- 239000011888 foil Substances 0.000 description 4
- 238000003475 lamination Methods 0.000 description 4
- 125000006160 pyromellitic dianhydride group Chemical group 0.000 description 4
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 3
- LDFYRFKAYFZVNH-UHFFFAOYSA-N 4-[4-[4-(4-aminophenoxy)phenoxy]phenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC(C=C1)=CC=C1OC(C=C1)=CC=C1OC1=CC=C(N)C=C1 LDFYRFKAYFZVNH-UHFFFAOYSA-N 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 229940018564 m-phenylenediamine Drugs 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 239000001294 propane Substances 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- LJGHYPLBDBRCRZ-UHFFFAOYSA-N 3-(3-aminophenyl)sulfonylaniline Chemical compound NC1=CC=CC(S(=O)(=O)C=2C=C(N)C=CC=2)=C1 LJGHYPLBDBRCRZ-UHFFFAOYSA-N 0.000 description 2
- ZBMISJGHVWNWTE-UHFFFAOYSA-N 3-(4-aminophenoxy)aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=CC(N)=C1 ZBMISJGHVWNWTE-UHFFFAOYSA-N 0.000 description 2
- CKOFBUUFHALZGK-UHFFFAOYSA-N 3-[(3-aminophenyl)methyl]aniline Chemical compound NC1=CC=CC(CC=2C=C(N)C=CC=2)=C1 CKOFBUUFHALZGK-UHFFFAOYSA-N 0.000 description 2
- FGWQCROGAHMWSU-UHFFFAOYSA-N 3-[(4-aminophenyl)methyl]aniline Chemical compound C1=CC(N)=CC=C1CC1=CC=CC(N)=C1 FGWQCROGAHMWSU-UHFFFAOYSA-N 0.000 description 2
- NYRFBMFAUFUULG-UHFFFAOYSA-N 3-[4-[2-[4-(3-aminophenoxy)phenyl]propan-2-yl]phenoxy]aniline Chemical compound C=1C=C(OC=2C=C(N)C=CC=2)C=CC=1C(C)(C)C(C=C1)=CC=C1OC1=CC=CC(N)=C1 NYRFBMFAUFUULG-UHFFFAOYSA-N 0.000 description 2
- NQZOFDAHZVLQJO-UHFFFAOYSA-N 3-[4-[4-(3-aminophenoxy)phenoxy]phenoxy]aniline Chemical compound NC1=CC=CC(OC=2C=CC(OC=3C=CC(OC=4C=C(N)C=CC=4)=CC=3)=CC=2)=C1 NQZOFDAHZVLQJO-UHFFFAOYSA-N 0.000 description 2
- 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 2
- YSMXOEWEUZTWAK-UHFFFAOYSA-N 3-[4-[[4-(3-aminophenoxy)phenyl]methyl]phenoxy]aniline Chemical compound NC1=CC=CC(OC=2C=CC(CC=3C=CC(OC=4C=C(N)C=CC=4)=CC=3)=CC=2)=C1 YSMXOEWEUZTWAK-UHFFFAOYSA-N 0.000 description 2
- QGYPADVOHRLQJM-UHFFFAOYSA-N 4-(4-amino-2-ethenylphenyl)-3-ethenylaniline Chemical group C=CC1=CC(N)=CC=C1C1=CC=C(N)C=C1C=C QGYPADVOHRLQJM-UHFFFAOYSA-N 0.000 description 2
- JPHCYDSESBJECU-UHFFFAOYSA-N 4-(4-amino-2-ethoxyphenyl)-3-ethoxyaniline Chemical group CCOC1=CC(N)=CC=C1C1=CC=C(N)C=C1OCC JPHCYDSESBJECU-UHFFFAOYSA-N 0.000 description 2
- GPQSJXRIHLUAKX-UHFFFAOYSA-N 4-(4-amino-2-ethylphenyl)-3-ethylaniline Chemical group CCC1=CC(N)=CC=C1C1=CC=C(N)C=C1CC GPQSJXRIHLUAKX-UHFFFAOYSA-N 0.000 description 2
- NFQBTSSEKRSELB-UHFFFAOYSA-N 4-(4-amino-2-propoxyphenyl)-3-propoxyaniline Chemical group CCCOC1=CC(N)=CC=C1C1=CC=C(N)C=C1OCCC NFQBTSSEKRSELB-UHFFFAOYSA-N 0.000 description 2
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 2
- HESXPOICBNWMPI-UHFFFAOYSA-N 4-[2-[4-[2-(4-aminophenyl)propan-2-yl]phenyl]propan-2-yl]aniline Chemical compound C=1C=C(C(C)(C)C=2C=CC(N)=CC=2)C=CC=1C(C)(C)C1=CC=C(N)C=C1 HESXPOICBNWMPI-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- JTERLNYVBOZRHI-RIIGGKATSA-N [(2r)-3-[2-aminoethoxy(hydroxy)phosphoryl]oxy-2-[(5e,8e,11e,14e)-icosa-5,8,11,14-tetraenoyl]oxypropyl] (5e,8e,11e,14e)-icosa-5,8,11,14-tetraenoate Chemical compound CCCCC\C=C\C\C=C\C\C=C\C\C=C\CCCC(=O)OC[C@H](COP(O)(=O)OCCN)OC(=O)CCC\C=C\C\C=C\C\C=C\C\C=C\CCCCC JTERLNYVBOZRHI-RIIGGKATSA-N 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 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
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 2
- 239000012965 benzophenone Substances 0.000 description 2
- TUQQUUXMCKXGDI-UHFFFAOYSA-N bis(3-aminophenyl)methanone Chemical compound NC1=CC=CC(C(=O)C=2C=C(N)C=CC=2)=C1 TUQQUUXMCKXGDI-UHFFFAOYSA-N 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 150000004985 diamines Chemical class 0.000 description 2
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000011342 resin composition Substances 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- YKNMIGJJXKBHJE-UHFFFAOYSA-N (3-aminophenyl)-(4-aminophenyl)methanone Chemical compound C1=CC(N)=CC=C1C(=O)C1=CC=CC(N)=C1 YKNMIGJJXKBHJE-UHFFFAOYSA-N 0.000 description 1
- YTCGLFCOUJIOQH-UHFFFAOYSA-N 1,3,4-oxadiazole-2,5-diamine Chemical compound NC1=NN=C(N)O1 YTCGLFCOUJIOQH-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-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
- BWAPJIHJXDYDPW-UHFFFAOYSA-N 2,5-dimethyl-p-phenylenediamine Chemical compound CC1=CC(N)=C(C)C=C1N BWAPJIHJXDYDPW-UHFFFAOYSA-N 0.000 description 1
- MJAVQHPPPBDYAN-UHFFFAOYSA-N 2,6-dimethylbenzene-1,4-diamine Chemical compound CC1=CC(N)=CC(C)=C1N MJAVQHPPPBDYAN-UHFFFAOYSA-N 0.000 description 1
- JZWGLBCZWLGCDT-UHFFFAOYSA-N 2,7-dichloronaphthalene-1,4,5,8-tetracarboxylic acid Chemical compound ClC1=CC(C(O)=O)=C2C(C(=O)O)=CC(Cl)=C(C(O)=O)C2=C1C(O)=O JZWGLBCZWLGCDT-UHFFFAOYSA-N 0.000 description 1
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- 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 group C1=C(N)C(C)=CC(C=2C=C(C)C(N)=CC=2)=C1 NUIURNJTPRWVAP-UHFFFAOYSA-N 0.000 description 1
- GWHLJVMSZRKEAQ-UHFFFAOYSA-N 3-(2,3-dicarboxyphenyl)phthalic acid Chemical group 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
- NBAUUNCGSMAPFM-UHFFFAOYSA-N 3-(3,4-dicarboxyphenyl)phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1C1=CC=CC(C(O)=O)=C1C(O)=O NBAUUNCGSMAPFM-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
- 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
- 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
- INQGLILZDPLSJY-UHFFFAOYSA-N 3-[3-(4-aminophenoxy)phenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=CC(OC=2C=C(N)C=CC=2)=C1 INQGLILZDPLSJY-UHFFFAOYSA-N 0.000 description 1
- LBPVOEHZEWAJKQ-UHFFFAOYSA-N 3-[4-(3-aminophenoxy)phenoxy]aniline Chemical compound NC1=CC=CC(OC=2C=CC(OC=3C=C(N)C=CC=3)=CC=2)=C1 LBPVOEHZEWAJKQ-UHFFFAOYSA-N 0.000 description 1
- POXPSTWTPRGRDO-UHFFFAOYSA-N 3-[4-(3-aminophenyl)phenyl]aniline Chemical group NC1=CC=CC(C=2C=CC(=CC=2)C=2C=C(N)C=CC=2)=C1 POXPSTWTPRGRDO-UHFFFAOYSA-N 0.000 description 1
- JUEHTVCFYYHXRP-UHFFFAOYSA-N 3-[4-(4-aminophenoxy)phenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC(C=C1)=CC=C1OC1=CC=CC(N)=C1 JUEHTVCFYYHXRP-UHFFFAOYSA-N 0.000 description 1
- MFTFTIALAXXIMU-UHFFFAOYSA-N 3-[4-[2-[4-(3-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropan-2-yl]phenoxy]aniline Chemical compound NC1=CC=CC(OC=2C=CC(=CC=2)C(C=2C=CC(OC=3C=C(N)C=CC=3)=CC=2)(C(F)(F)F)C(F)(F)F)=C1 MFTFTIALAXXIMU-UHFFFAOYSA-N 0.000 description 1
- FYLGFBUSMXTESP-UHFFFAOYSA-N 3-[4-[9-[4-(3-aminophenoxy)phenyl]fluoren-9-yl]phenoxy]aniline Chemical compound NC1=CC=CC(OC=2C=CC(=CC=2)C2(C3=CC=CC=C3C3=CC=CC=C32)C=2C=CC(OC=3C=C(N)C=CC=3)=CC=2)=C1 FYLGFBUSMXTESP-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
- ICNFHJVPAJKPHW-UHFFFAOYSA-N 4,4'-Thiodianiline Chemical compound C1=CC(N)=CC=C1SC1=CC=C(N)C=C1 ICNFHJVPAJKPHW-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
- QGRZMPCVIHBQOE-UHFFFAOYSA-N 4,8-dimethyl-1,2,3,5,6,7-hexahydronaphthalene-1,2,5,6-tetracarboxylic acid Chemical compound OC(=O)C1C(C(O)=O)CC(C)=C2C(C(O)=O)C(C(O)=O)CC(C)=C21 QGRZMPCVIHBQOE-UHFFFAOYSA-N 0.000 description 1
- OMHOXRVODFQGCA-UHFFFAOYSA-N 4-[(4-amino-3,5-dimethylphenyl)methyl]-2,6-dimethylaniline Chemical group CC1=C(N)C(C)=CC(CC=2C=C(C)C(N)=C(C)C=2)=C1 OMHOXRVODFQGCA-UHFFFAOYSA-N 0.000 description 1
- DZIHTWJGPDVSGE-UHFFFAOYSA-N 4-[(4-aminocyclohexyl)methyl]cyclohexan-1-amine Chemical compound C1CC(N)CCC1CC1CCC(N)CC1 DZIHTWJGPDVSGE-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Laminated Bodies (AREA)
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Description
本発明は、金属張積層板及び回路基板に関する。 The present invention relates to a metal-clad laminate and a circuit board.
近年、電子機器の小型化、軽量化、省スペース化の進展に伴い、薄く軽量で、可撓性を有し、屈曲を繰り返しても優れた耐久性を持つフレキシブルプリント配線板（ＦＰＣ；Ｆｌｅｘｉｂｌｅ Ｐｒｉｎｔｅｄ Ｃｉｒｃｕｉｔｓ）の需要が増大している。ＦＰＣは、限られたスペースでも立体的かつ高密度の実装が可能であるため、例えば、ＨＤＤ、ＤＶＤ、携帯電話等の電子機器の可動部分の配線や、ケーブル、コネクター等の部品にその用途が拡大しつつある。 In recent years, as electronic devices have become smaller, lighter, and space-saving, flexible printed circuit boards (FPCs) have become thinner, lighter, more flexible, and have excellent durability even after repeated bending. Demand for circuits is increasing. FPC can be mounted three-dimensionally and with high density even in a limited space, so it can be used, for example, in the wiring of moving parts of electronic devices such as HDDs, DVDs, and mobile phones, as well as parts such as cables and connectors. It is expanding.
ＦＰＣは、銅張積層板（ＣＣＬ）の銅層をエッチングして配線加工することによって製造される。携帯電話やスマートフォンにおいて、連続屈曲や１８０°折り曲げされるＦＰＣには、銅層の材料として、圧延銅箔が多く用いられている。例えば、特許文献１では、圧延銅箔を用いて作製された銅張積層板の耐屈曲性を耐はぜ折り回数で規定する提案がなされている。また、特許文献２では、光沢度と折り曲げ回数で規定された圧延銅箔を用いた銅張積層板が提案されている。 FPC is manufactured by etching the copper layer of a copper clad laminate (CCL) and processing the wiring. In mobile phones and smartphones, rolled copper foil is often used as a material for the copper layer in FPCs that are continuously bent or bent by 180 degrees. For example, Patent Document 1 proposes that the bending resistance of a copper-clad laminate made using rolled copper foil is defined by the number of seams it can withstand. Further, Patent Document 2 proposes a copper-clad laminate using rolled copper foil that is defined by glossiness and number of times of bending.
銅張積層板に対するフォトリソグラフィ工程や、ＦＰＣ実装の過程では、銅張積層板に設けられたアライメントマークを基準に接合、切断、露光、エッチング等のさまざまな加工が行われる。これらの工程での加工精度は、ＦＰＣを搭載した電子機器の信頼性を維持する上で重要となる。しかし、銅張積層板は、熱膨張係数が異なる銅層と樹脂層とを積層した構造を有するため、銅層と樹脂層との熱膨張係数の差によって、層間に応力が発生する。この応力は、その一部分又は全部が、銅層をエッチングして配線加工した場合に解放されることによって伸縮を生じさせ、配線パターンの寸法を変化させる要因となる。そのため、最終的にＦＰＣの段階で寸法変化が生じてしまい、配線間もしくは配線と端子との接続不良を引き起こす原因となり、回路基板の信頼性や歩留まりを低下させる。従って、回路基板材料としての銅張積層板において、寸法安定性は非常に重要な特性である。しかし、上記特許文献１、２では、銅張積層板の寸法安定性については何ら考慮されていない。 In the photolithography process and FPC mounting process for copper-clad laminates, various processes such as bonding, cutting, exposure, and etching are performed based on alignment marks provided on the copper-clad laminates. Machining accuracy in these steps is important in maintaining the reliability of electronic devices equipped with FPCs. However, since a copper-clad laminate has a structure in which a copper layer and a resin layer are laminated with different coefficients of thermal expansion, stress is generated between the layers due to the difference in coefficient of thermal expansion between the copper layer and the resin layer. Part or all of this stress is released when the copper layer is etched to process wiring, causing expansion and contraction, which causes a change in the dimensions of the wiring pattern. As a result, dimensional changes ultimately occur at the FPC stage, causing poor connections between wirings or between wirings and terminals, reducing the reliability and yield of the circuit board. Therefore, dimensional stability is a very important property in copper-clad laminates as circuit board materials. However, in Patent Documents 1 and 2, no consideration is given to the dimensional stability of the copper-clad laminate.
また、特許文献３では、絶縁樹脂層の熱膨張係数を下げ、寸法安定性を高めるため、敢えて熱可塑性ポリイミド層を設けず、銅箔と非熱可塑性ポリイミド層からなるフレキシブル金属張積層板において、非熱可塑性ポリイミド層のジアミン成分として、ｐ－フェニレンジアミン（ｐ－ＰＤＡ）又は２，２’－ジメチル－４，４’－ジアミノビフェニル（ｍ－ＴＢ）からなるジアミン化合物と、１，３－ビス（４－アミノフェノキシ）ベンゼン（ＴＰＥ－Ｒ）等のジアミン化合物とを用いることが提案されている。ｐ－ＰＤＡは、熱膨張係数を下げ、寸法安定性に寄与するモノマーであるが、分子量が小さいため、イミド基濃度が増加してポリイミドの吸湿性が高くなってしまうという問題があった。ポリイミドの吸湿性が高くなると、回路加工時の加熱などの環境変化によって寸法変化や反りが発生しやすくなる、という問題がある。 In addition, in Patent Document 3, in order to lower the thermal expansion coefficient of the insulating resin layer and increase the dimensional stability, a thermoplastic polyimide layer is intentionally not provided, and in a flexible metal-clad laminate made of copper foil and a non-thermoplastic polyimide layer, As the diamine component of the non-thermoplastic polyimide layer, a diamine compound consisting of p-phenylenediamine (p-PDA) or 2,2'-dimethyl-4,4'-diaminobiphenyl (m-TB) and 1,3-bis It has been proposed to use diamine compounds such as (4-aminophenoxy)benzene (TPE-R). p-PDA is a monomer that lowers the coefficient of thermal expansion and contributes to dimensional stability, but due to its small molecular weight, there is a problem in that the concentration of imide groups increases and the hygroscopicity of polyimide increases. When the hygroscopicity of polyimide increases, there is a problem in that dimensional changes and warping are more likely to occur due to environmental changes such as heating during circuit processing.
一方、特許文献４では、回路加工時のクラックの発生が抑制された多層ポリイミドフィルムにおいて、非熱可塑性ポリイミドの原料のジアミン化合物として、ｍ－ＴＢとｐ－ＰＤＡを組み合わせて使用することが開示されている。しかしながら、特許文献４のモノマー組成では、ジアミン化合物中のｐ－ＰＤＡのモル比が大きすぎるため、上記と同様に、ポリイミドの吸湿性が高くなって、回路加工時の環境変化によって寸法変化や反りが発生しやすくなる、という問題がある。なお、特許文献４には、ジアミン化合物として、ｍ－ＴＢとｐ－ＰＤＡと２，２－ビス［４－（４－アミノフェノキシ）フェニル］プロパン（ＢＡＰＰ）を組み合わせて使用した場合、クラック耐性が悪化することが記載されている。この場合も、ジアミン化合物中のｐ－ＰＤＡのモル比が大きすぎるため、上記と同様に、ポリイミドの吸湿性が高くなるという問題があると考えられる。 On the other hand, Patent Document 4 discloses the use of a combination of m-TB and p-PDA as a diamine compound as a raw material for non-thermoplastic polyimide in a multilayer polyimide film that suppresses the occurrence of cracks during circuit processing. ing. However, in the monomer composition of Patent Document 4, the molar ratio of p-PDA in the diamine compound is too large, and as mentioned above, the hygroscopicity of the polyimide becomes high, causing dimensional changes and warping due to environmental changes during circuit processing. The problem is that it becomes more likely to occur. In addition, Patent Document 4 states that when m-TB, p-PDA, and 2,2-bis[4-(4-aminophenoxy)phenyl]propane (BAPP) are used in combination as diamine compounds, crack resistance increases. It is reported that it gets worse. In this case as well, since the molar ratio of p-PDA in the diamine compound is too large, it is thought that there is a problem in that the hygroscopicity of the polyimide becomes high, similar to the above.
本発明は、回路加工工程、基板積層工程及び部品実装工程などの工程中の温度、湿度及び圧力の変化並びに工程間の温度・湿度環境変化に対する寸法変化を低減させることができる金属張積層板を提供することを目的とする。 The present invention provides a metal-clad laminate that can reduce dimensional changes due to changes in temperature, humidity, and pressure during processes such as circuit processing, board lamination, and component mounting, as well as changes in temperature and humidity environments between processes. The purpose is to provide.
本発明者らは、鋭意検討した結果、絶縁樹脂層の面内複屈折率（Δｎ）及び厚さ方向の複屈折率を制御することによって上記課題を解決し得ることを見出し、本発明を完成するに至った。 As a result of intensive studies, the present inventors discovered that the above problems could be solved by controlling the in-plane birefringence (Δn) and the birefringence in the thickness direction of the insulating resin layer, and completed the present invention. I ended up doing it.
すなわち、本発明の金属張積層板は、絶縁樹脂層と、この絶縁樹脂層の少なくとも片面に積層された金属層とを備えた金属張積層板であって、前記絶縁樹脂層が、非熱可塑性ポリイミドを含む非熱可塑性ポリイミド層の少なくとも一方の面に熱可塑性ポリイミドを含む熱可塑性ポリイミド層を有している。そして、本発明の金属張積層板は、前記絶縁樹脂層が下記の条件(i)～(iv)を満たすことを特徴とする。
(i)面内複屈折率（Δｎ）の値が２×１０－３以下であること。
(ii)幅方向（ＴＤ方向）の面内複屈折率（Δｎ）のばらつき［Δ（Δｎ）］が４×１０－４以下であること。
(iii) 前記非熱可塑性ポリイミド層の厚さ方向において、一方の面を基点とする中央部方向に１．５μｍの点における複屈折率（Δｎａ）と、他方の面を基点とする中央部方向に１．５μｍの点における複屈折率（Δｎｂ）との差（Δｎａ－Δｎｂ）が±０．０１以下であること。
(iv) 前記Δｎａ及び前記Δｎｂ並びに厚さ方向の中央部における複屈折率（Δｎｃ）の合計（Δｎａ＋Δｎｂ＋Δｎｃ）の平均値（Δｎｖ）との差が、前記Δｎａ及びΔｎｂのいずれにおいても±０．０１以下であること。
That is, the metal-clad laminate of the present invention is a metal-clad laminate comprising an insulating resin layer and a metal layer laminated on at least one side of the insulating resin layer, wherein the insulating resin layer is a non-thermoplastic A thermoplastic polyimide layer containing thermoplastic polyimide is provided on at least one surface of the non-thermoplastic polyimide layer containing polyimide. The metal-clad laminate of the present invention is characterized in that the insulating resin layer satisfies the following conditions (i) to (iv).
(i) The value of in-plane birefringence (Δn) is 2×10 −3 or less.
(ii) The variation in in-plane birefringence (Δn) in the width direction (TD direction) [Δ(Δn)] is 4×10 −4 or less.
(iii) In the thickness direction of the non-thermoplastic polyimide layer, the birefringence (Δna) at a point of 1.5 μm in the direction of the center from one surface and the direction of the center from the other surface. The difference (Δna−Δnb) from the birefringence index (Δnb) at a point of 1.5 μm is ±0.01 or less.
(iv) The difference from the average value (Δnv) of the sum (Δna+Δnb+Δnc) of the birefringence (Δnc) at the central portion in the thickness direction of the Δna and Δnb is ±0.01 for both the Δna and Δnb. Must be below.
本発明の金属張積層板において、前記非熱可塑性ポリイミドはテトラカルボン酸残基及びジアミン残基を含み、全ジアミン残基の１００モル部に対して、下記一般式（１）で表されるジアミン化合物から誘導されるジアミン残基が２０モル部以上であってもよい。 In the metal-clad laminate of the present invention, the non-thermoplastic polyimide contains a tetracarboxylic acid residue and a diamine residue, and the diamine represented by the following general formula (1) is The diamine residue derived from the compound may be 20 mole parts or more.
一般式（１）において、連結基Ｚは単結合若しくは－ＣＯＯ－を示し、Ｙは独立にハロゲン若しくはフェニル基で置換されてもよい炭素数１～３の１価の炭化水素又は炭素数１～３のアルコキシ基、又は炭素数１～３のパーフルオロアルキル基、又はアルケニル基を示し、ｎは０～２の整数を示し、ｐ及びｑは独立に０～４の整数を示す。 In the general formula (1), the linking group Z represents a single bond or -COO-, and Y is a monovalent hydrocarbon having 1 to 3 carbon atoms or a monovalent hydrocarbon having 1 to 3 carbon atoms, which may be independently substituted with a halogen or phenyl group. represents an alkoxy group of 3, a perfluoroalkyl group having 1 to 3 carbon atoms, or an alkenyl group, n represents an integer of 0 to 2, and p and q independently represent an integer of 0 to 4.
本発明の金属張積層板は、前記非熱可塑性ポリイミドに含まれる全ジアミン残基の１００モル部に対して、前記一般式（１）で表されるジアミン化合物から誘導されるジアミン残基が７０モル部～９５モル部の範囲内であってもよく、下記の一般式（２）及び（３）から選ばれるジアミン残基の合計量が５～３０モル部の範囲内であってもよい。 In the metal-clad laminate of the present invention, the diamine residue derived from the diamine compound represented by the general formula (1) is 70 moles per 100 mole parts of the total diamine residues contained in the non-thermoplastic polyimide. The total amount of diamine residues selected from the following general formulas (2) and (3) may be within the range of 5 to 30 mole parts.
一般式（２）及び一般式（３）において、Ｒ５、Ｒ６、Ｒ７及びＲ８はそれぞれ独立にハロゲン原子、又は炭素数１～４のハロゲン原子で置換されてもよいアルキル基もしくはアルコキシ基、又はアルケニル基を示し、Ｘは独立に－Ｏ－、－Ｓ－、－ＣＨ２－、－ＣＨ(ＣＨ３)－、－Ｃ(ＣＨ３)２－、－ＣＯ－、－ＣＯＯ－、－ＳＯ２－、－ＮＨ－又は－ＮＨＣＯ－から選ばれる２価の基を示し、Ｘ１及びＸ２はそれぞれ独立に単結合、－Ｏ－、－Ｓ－、－ＣＨ２－、－ＣＨ(ＣＨ３)－、－Ｃ(ＣＨ３)２－、－ＣＯ－、－ＣＯＯ－、－ＳＯ２－、－ＮＨ－又は－ＮＨＣＯ－から選ばれる２価の基を示すが、Ｘ１及びＸ２の両方が単結合である場合を除くものとし、ｍ、ｎ、ｏ及びｐは独立に０～４の整数を示す。 In general formula (2) and general formula (3), R 5 , R 6 , R 7 and R 8 are each independently a halogen atom, or an alkyl group or alkoxy group which may be substituted with a halogen atom having 1 to 4 carbon atoms. group or alkenyl group, and X independently represents -O-, -S-, -CH 2 -, -CH(CH 3 )-, -C(CH 3 ) 2 -, -CO-, -COO-, It represents a divalent group selected from -SO 2 -, -NH- or -NHCO-, and X 1 and X 2 each independently represent a single bond, -O-, -S-, -CH 2 -, -CH( It represents a divalent group selected from CH 3 )-, -C(CH 3 ) 2 -, -CO-, -COO-, -SO 2 -, -NH- or -NHCO-, but X 1 and X 2 m, n, o and p each independently represent an integer of 0 to 4.
本発明の金属張積層板において、前記熱可塑性ポリイミドはテトラカルボン酸残基及びジアミン残基を含み、全ジアミン残基の１００モル部に対して、上記の一般式（２）及び（３）から選ばれるジアミン残基の合計量が５０モル部以上であってもよい。 In the metal-clad laminate of the present invention, the thermoplastic polyimide contains a tetracarboxylic acid residue and a diamine residue, and based on 100 mole parts of the total diamine residue, The total amount of selected diamine residues may be 50 mole parts or more.
本発明の金属張積層板において、前記一般式（２）で表されるジアミン残基が、１,３－ビス（４‐アミノフェノキシ）ベンゼンから誘導されるジアミン残基であってもよく、
前記一般式（３）で表されるジアミン残基が、２，２－ビス［４－（４－アミノフェノキシ）フェニル］プロパンから誘導されるジアミン残基であってもよい。
In the metal-clad laminate of the present invention, the diamine residue represented by the general formula (2) may be a diamine residue derived from 1,3-bis(4-aminophenoxy)benzene,
The diamine residue represented by the general formula (3) may be a diamine residue derived from 2,2-bis[4-(4-aminophenoxy)phenyl]propane.
本発明の金属張積層板において、前記非熱可塑性ポリイミド層の厚み（Ａ）と前記熱可塑性ポリイミド層の厚み（Ｂ）の厚み比（Ａ）／（Ｂ）が１～２０の範囲内であってもよい。 In the metal-clad laminate of the present invention, the thickness ratio (A)/(B) of the thickness (A) of the non-thermoplastic polyimide layer and the thickness (B) of the thermoplastic polyimide layer is within the range of 1 to 20. You can.
本発明の金属張積層板において、幅方向（ＴＤ方向）の長さが４９０ｍｍ以上であってもよい。 In the metal-clad laminate of the present invention, the length in the width direction (TD direction) may be 490 mm or more.
本発明の回路基板は、上記いずれかに記載の金属張積層板の前記金属層を配線に加工してなるものである。 The circuit board of the present invention is obtained by processing the metal layer of any of the metal clad laminates described above into wiring.
本発明の金属張積層板は、条件(i)～(iv)を具備することによって、高温・高圧の環境下や湿度変化の環境下においても絶縁樹脂層の寸法安定性に優れているため、回路加工工程、基板積層工程、及び部品実装工程の際の環境変化（例えば、高温や高圧、湿度変化など）によって、反りなどの不具合が発生しにくい。特に、幅広の金属張積層板においても、絶縁樹脂層の全幅において寸法変化率が低く、寸法が安定しているので、該金属張積層板から得られるＦＰＣを高密度実装が可能なものにすることができる。従って、本発明の金属張積層板をＦＰＣ材料として利用することによって、回路基板の信頼性と歩留まりの向上を図ることができる。 By satisfying conditions (i) to (iv), the metal-clad laminate of the present invention has excellent dimensional stability of the insulating resin layer even under high temperature and high pressure environments and environments with humidity changes. Problems such as warping are less likely to occur due to environmental changes (for example, high temperature, high pressure, humidity changes, etc.) during the circuit processing process, board lamination process, and component mounting process. In particular, even in wide metal-clad laminates, the dimensional change rate is low and the dimensions are stable over the entire width of the insulating resin layer, making FPCs obtained from the metal-clad laminates capable of high-density mounting. be able to. Therefore, by using the metal-clad laminate of the present invention as an FPC material, it is possible to improve the reliability and yield of circuit boards.
次に、本発明の実施の形態について説明する。 Next, embodiments of the present invention will be described.
＜金属張積層板＞
本実施の形態の金属張積層板は、絶縁樹脂層と、この絶縁樹脂層の少なくとも片面に積層された金属層とを備えている。
<Metal-clad laminate>
The metal-clad laminate of this embodiment includes an insulating resin layer and a metal layer laminated on at least one side of the insulating resin layer.
＜絶縁樹脂層＞
本実施の形態の金属張積層板において、絶縁樹脂層は、非熱可塑性ポリイミド層の少なくとも一方に熱可塑性ポリイミド層を有する。すなわち、熱可塑性ポリイミド層は非熱可塑性ポリイミド層の片面又は両面に設けられている。例えば本実施の形態の金属張積層板において、金属層は熱可塑性ポリイミド層の面に積層する。
ここで、非熱可塑性ポリイミドとは、一般に加熱しても軟化、接着性を示さないポリイミドのことであるが、本発明では、動的粘弾性測定装置（ＤＭＡ）を用いて測定した、３０℃における貯蔵弾性率が１．０×１０９Ｐａ以上であり、３６０℃における貯蔵弾性率が１．０×１０８Ｐａ以上であるポリイミドをいう。また、熱可塑性ポリイミドとは、一般にガラス転移温度（Ｔｇ）が明確に確認できるポリイミドのことであるが、本発明では、ＤＭＡを用いて測定した、３０℃における貯蔵弾性率が１．０×１０９Ｐａ以上であり、３６０℃における貯蔵弾性率が１．０×１０８Ｐａ未満であるポリイミドをいう。
<Insulating resin layer>
In the metal-clad laminate of this embodiment, the insulating resin layer has a thermoplastic polyimide layer on at least one of the non-thermoplastic polyimide layers. That is, the thermoplastic polyimide layer is provided on one or both sides of the non-thermoplastic polyimide layer. For example, in the metal-clad laminate of this embodiment, the metal layer is laminated on the surface of the thermoplastic polyimide layer.
Here, non-thermoplastic polyimide generally refers to polyimide that does not soften or exhibit adhesive properties even when heated. A polyimide having a storage modulus of 1.0×10 9 Pa or more at 360° C. and a storage modulus of 1.0×10 8 Pa or more at 360° C. In addition, thermoplastic polyimide generally refers to polyimide whose glass transition temperature (Tg) can be clearly confirmed, but in the present invention, the storage modulus at 30°C measured using DMA is 1.0 × 10 9 Pa or more, and a storage modulus at 360° C. of less than 1.0×10 8 Pa.
本実施の形態の金属張積層板は、絶縁樹脂層が下記の条件(i)～(iv)を満たすものである。
(i)面内複屈折率（Δｎ）の値が２×１０－３以下であること。
(ii)幅方向（ＴＤ方向）の面内複屈折率（Δｎ）のばらつき［Δ（Δｎ）］が４×１０－４以下であること。
(iii) 前記非熱可塑性ポリイミド層の厚さ方向において、一方の面を基点とする中央部方向に１．５μｍの点における複屈折率（Δｎａ）と、他方の面を基点とする中央部方向に１．５μｍの点における複屈折率（Δｎｂ）との差（Δｎａ－Δｎｂ）が±０．０１以下であること。
(iv) 前記Δｎａ及び前記Δｎｂ並びに厚さ方向の中央部における複屈折率（Δｎｃ）の合計（Δｎａ＋Δｎｂ＋Δｎｃ）の平均値（Δｎｖ）との差が、前記Δｎａ及びΔｎｂのいずれにおいても±０．０１以下であること。
In the metal-clad laminate of this embodiment, the insulating resin layer satisfies the following conditions (i) to (iv).
(i) The value of in-plane birefringence (Δn) is 2×10 −3 or less.
(ii) The variation in in-plane birefringence (Δn) in the width direction (TD direction) [Δ(Δn)] is 4×10 −4 or less.
(iii) In the thickness direction of the non-thermoplastic polyimide layer, the birefringence (Δna) at a point of 1.5 μm in the direction of the center from one surface and the direction of the center from the other surface. The difference (Δna−Δnb) from the birefringence index (Δnb) at a point of 1.5 μm is ±0.01 or less.
(iv) The difference from the average value (Δnv) of the sum (Δna+Δnb+Δnc) of the birefringence (Δnc) at the central portion in the thickness direction of the Δna and Δnb is ±0.01 for both the Δna and Δnb. Must be below.
上記の条件(i)～(iv)を満たすことによって、絶縁樹脂層を構成するポリイミドの配向性が高まり、寸法安定性が向上するとともに反りの発生が抑制される。 By satisfying the above conditions (i) to (iv), the orientation of the polyimide constituting the insulating resin layer is enhanced, the dimensional stability is improved, and the occurrence of warpage is suppressed.
面内複屈折率（Δｎ）の値が２×１０－３を超えると面内配向の異方性が大きくなり寸法安定性悪化の原因となる。Δｎの値の下限値は特に限定されないが、面内配向が等方的で寸法安定性が向上する一方で熱膨張係数が過度に低下し、金属箔の熱膨張係数との不整合による反りを抑制する観点から、２×１０－４以上とすることが好ましい。以上の観点から、絶縁樹脂層の面内複屈折率（Δｎ）の値は、好ましくは２×１０－４以上８×１０－４以下の範囲内、より好ましくは２×１０－４以上６×１０－４以下の範囲内である。 When the value of the in-plane birefringence (Δn) exceeds 2×10 −3 , the anisotropy of the in-plane orientation becomes large, causing deterioration of dimensional stability. The lower limit of the value of Δn is not particularly limited, but while the in-plane orientation is isotropic and dimensional stability is improved, the coefficient of thermal expansion is excessively reduced, and warping due to mismatch with the coefficient of thermal expansion of the metal foil may occur. From the viewpoint of suppression, it is preferable to set it to 2×10 −4 or more. From the above viewpoint, the value of the in-plane birefringence (Δn) of the insulating resin layer is preferably in the range of 2×10 −4 or more and 8×10 −4 or less, more preferably 2×10 −4 or more and 6× It is within the range of 10-4 or less.
また、ＴＤ方向のΔｎのばらつき［Δ（Δｎ）］が４×１０－４を超えると、面内配向のばらつきが大きくなり寸法変化率の面内ばらつきの原因となる。ＴＤ方向のΔｎのばらつき［Δ（Δｎ）］は、好ましくは２×１０－４以下、より好ましくは１．２×１０－４以下である。このような範囲内であれば、例えばスケールアップした場合であっても、高い寸法精度を維持できる。 Furthermore, if the variation in Δn [Δ(Δn)] in the TD direction exceeds 4×10 −4 , the variation in in-plane orientation becomes large, causing in-plane variation in dimensional change rate. The variation in Δn in the TD direction [Δ(Δn)] is preferably 2×10 −4 or less, more preferably 1.2×10 −4 or less. Within this range, high dimensional accuracy can be maintained even when scaled up, for example.
また、非熱可塑性ポリイミド層の厚さ方向における複屈折率の差（Δｎａ－Δｎｂ）が±０．０１以下であり、かつ、前記Δｎａ及びΔｎｂと平均値（Δｎｖ）との差（Δｎｖ－Δｎａ）及び差（Δｎｖ－Δｎｂ）が、いずれも±０．０１以下であることによって、厚さ方向におけるポリイミド配向の均質性が高まり、反りの発生を抑制できる。差（Δｎｖ－Δｎａ）及び差（Δｎｖ－Δｎｂ）は、±０．００８以下が好ましく、±０．００６以下がより好ましい。 Further, the difference in birefringence (Δna-Δnb) in the thickness direction of the non-thermoplastic polyimide layer is ±0.01 or less, and the difference (Δnv-Δnv) between the above-mentioned Δna and Δnb and the average value (Δnv) is ±0.01 or less. ) and the difference (Δnv−Δnb) are both ±0.01 or less, thereby increasing the homogeneity of the polyimide orientation in the thickness direction and suppressing the occurrence of warpage. The difference (Δnv−Δna) and the difference (Δnv−Δnb) are preferably ±0.008 or less, more preferably ±0.006 or less.
上記の条件(i)～(iv)を満たすことによって、回路加工工程、基板積層工程及び部品実装工程の際の環境変化（例えば高温・高圧環境、湿度変化など）による寸法変化や反りを効果的に抑制できる。上記の条件(i)～(iv)のいずれか１つでも具備しない場合には、回路加工工程、基板積層工程及び部品実装工程時の高温や高圧、湿度変化などによって、寸法変化量が大きくなって寸法精度が低下したり、反りが発生したりする。 By satisfying the above conditions (i) to (iv), it is possible to effectively prevent dimensional changes and warping caused by environmental changes (e.g. high temperature/high pressure environment, humidity changes, etc.) during the circuit processing process, board lamination process, and component mounting process. can be suppressed to If any of the above conditions (i) to (iv) are not met, the amount of dimensional change will increase due to high temperature, high pressure, humidity changes, etc. during the circuit processing process, board lamination process, and component mounting process. The dimensional accuracy may decrease or warping may occur.
本実施の形態の金属張積層板は、例えば回路基板材料として適用する場合において、反りの発生や寸法安定性の低下を防止するために、絶縁樹脂層の熱膨張係数（ＣＴＥ）が１０ｐｐｍ／Ｋ以上３０ｐｐｍ／Ｋ以下の範囲内であることが重要であり、好ましくは１０ｐｐｍ／Ｋ以上２５ｐｐｍ／Ｋ以下の範囲内がよい。ＣＴＥが１０ｐｐｍ／Ｋ未満であるか、又は３０ｐｐｍ／Ｋを超えると、反りが発生したり、寸法安定性が低下したりする。また、本実施の形態の金属張積層板において、銅箔などからなる金属層のＣＴＥに対して絶縁樹脂層のＣＴＥが、±５ｐｐｍ／Ｋ以下の範囲内がより好ましく、±２ｐｐｍ／Ｋ以下の範囲内が最も好ましい。 When the metal-clad laminate of this embodiment is applied, for example, as a circuit board material, the coefficient of thermal expansion (CTE) of the insulating resin layer is 10 ppm/K in order to prevent the occurrence of warpage and a decrease in dimensional stability. It is important that the content be within the range of 30 ppm/K or less, preferably 10 ppm/K or more and 25 ppm/K or less. If the CTE is less than 10 ppm/K or more than 30 ppm/K, warping may occur or dimensional stability may decrease. Further, in the metal-clad laminate of the present embodiment, the CTE of the insulating resin layer is more preferably within the range of ±5 ppm/K or less, and is preferably within the range of ±2 ppm/K or less relative to the CTE of the metal layer made of copper foil or the like. Most preferably within this range.
絶縁樹脂層において、非熱可塑性ポリイミド層は低熱膨張性のポリイミド層を構成し、熱可塑性ポリイミド層は高熱膨張性のポリイミド層を構成する。ここで、低熱膨張性のポリイミド層は、熱膨張係数（ＣＴＥ）が好ましくは１ｐｐｍ／Ｋ以上２５ｐｐｍ／Ｋ以下の範囲内、より好ましくは３ｐｐｍ／Ｋ以上２５ｐｐｍ／Ｋ以下の範囲内のポリイミド層をいう。また、高熱膨張性のポリイミド層は、ＣＴＥが好ましくは３５ｐｐｍ／Ｋ以上、より好ましくは３５ｐｐｍ／Ｋ以上８０ｐｐｍ／Ｋ以下の範囲内、更に好ましくは３５ｐｐｍ／Ｋ以上７０ｐｐｍ／Ｋ以下の範囲内のポリイミド層をいう。ポリイミド層は、使用する原料の組合せ、厚み、乾燥・硬化条件を適宜変更することで所望のＣＴＥを有するポリイミド層とすることができる。 In the insulating resin layer, the non-thermoplastic polyimide layer constitutes a low thermal expansion polyimide layer, and the thermoplastic polyimide layer constitutes a high thermal expansion polyimide layer. Here, the low thermal expansion polyimide layer is a polyimide layer having a coefficient of thermal expansion (CTE) preferably in the range of 1 ppm/K or more and 25 ppm/K or less, more preferably in the range of 3 ppm/K or more and 25 ppm/K or less. say. The high thermal expansion polyimide layer is made of polyimide having a CTE of preferably 35 ppm/K or more, more preferably 35 ppm/K or more and 80 ppm/K or less, and even more preferably 35 ppm/K or more and 70 ppm/K or less. refers to a layer. The polyimide layer can be made into a polyimide layer having a desired CTE by appropriately changing the combination of raw materials used, the thickness, and drying/curing conditions.
絶縁樹脂層の厚みは、使用する目的に応じて、所定の範囲内の厚みに設定することができるが、例えば４～５０μｍの範囲内にあることが好ましく、１１～２６μｍの範囲内にあることがより好ましい。絶縁樹脂層の厚みが上記下限値に満たないと、電気絶縁性が担保出来ないことや、ハンドリング性の低下により製造工程にて取扱いが困難になるなどの問題が生じることがある。一方、絶縁樹脂層の厚みが上記上限値を超えると、面内複屈折率（Δｎ）及び厚さ方向の複屈折率（Δｎ）を制御するために、製造条件を高精度に制御する必要があり、生産性低下などの不具合が生じる。 The thickness of the insulating resin layer can be set within a predetermined range depending on the purpose of use, but for example, it is preferably within the range of 4 to 50 μm, and preferably within the range of 11 to 26 μm. is more preferable. If the thickness of the insulating resin layer is less than the above lower limit, problems may occur, such as failure to ensure electrical insulation and reduced handling properties, making handling difficult during the manufacturing process. On the other hand, if the thickness of the insulating resin layer exceeds the above upper limit, it is necessary to control the manufacturing conditions with high precision in order to control the in-plane birefringence (Δn) and the birefringence in the thickness direction (Δn). This causes problems such as decreased productivity.
また、絶縁樹脂層において、非熱可塑性ポリイミド層の厚み（Ａ）と熱可塑性ポリイミド層の厚み（Ｂ）との厚み比（（Ａ）／（Ｂ））が１～２０の範囲内であることが好ましく、２～１２の範囲内がより好ましい。なお、非熱可塑性ポリイミド層及び／又は熱可塑性ポリイミド層の層数が複数である場合は、厚み（Ａ）や厚み（Ｂ）は、合計の厚みを意味する。この比の値が、１に満たないと絶縁樹脂層全体に対する非熱可塑性ポリイミド層が薄くなるため、面内複屈折率（Δｎ）のばらつきが大きくなりやすく、２０を超えると熱可塑性ポリイミド層が薄くなるため、絶縁樹脂層と金属層との接着信頼性が低下しやすくなる。ここで、面内複屈折率（Δｎ）の制御は、絶縁樹脂層を構成する各ポリイミド層の樹脂構成とその厚みに相関がある。接着性すなわち高熱膨張性又は軟化を付与した樹脂構成である熱可塑性ポリイミド層は、その厚みが大きくなる程、絶縁樹脂層のΔｎの値に大きく影響する。そこで、非熱可塑性ポリイミド層の厚みの比率を大きくし、熱可塑性ポリイミド層の厚みの比率を小さくして、絶縁樹脂層のΔｎの値とそのばらつきを小さくすることが好ましい。後述するように、本実施の形態では、熱可塑性ポリイミド層の厚みの比率を小さくする場合でも、熱可塑性ポリイミド層が一般式（２）及び（３）から選ばれるジアミン残基を所定量含有するように設計することによって、金属層と絶縁樹脂層との接着性を確保できる。 In addition, in the insulating resin layer, the thickness ratio ((A)/(B)) between the thickness (A) of the non-thermoplastic polyimide layer and the thickness (B) of the thermoplastic polyimide layer is within the range of 1 to 20. is preferable, and a range of 2 to 12 is more preferable. In addition, when the number of non-thermoplastic polyimide layers and/or thermoplastic polyimide layers is plural, thickness (A) and thickness (B) mean the total thickness. If the value of this ratio is less than 1, the non-thermoplastic polyimide layer becomes thinner with respect to the entire insulating resin layer, which tends to increase the variation in in-plane birefringence (Δn), and if it exceeds 20, the thermoplastic polyimide layer becomes thinner than the entire insulating resin layer. Since the thickness becomes thinner, the reliability of adhesion between the insulating resin layer and the metal layer tends to decrease. Here, control of the in-plane birefringence (Δn) has a correlation with the resin composition of each polyimide layer constituting the insulating resin layer and its thickness. The greater the thickness of the thermoplastic polyimide layer, which is a resin composition imparted with adhesiveness, ie, high thermal expansion or softening properties, the greater the influence on the value of Δn of the insulating resin layer. Therefore, it is preferable to increase the thickness ratio of the non-thermoplastic polyimide layer and decrease the thickness ratio of the thermoplastic polyimide layer to reduce the value of Δn of the insulating resin layer and its variation. As described later, in this embodiment, even when the thickness ratio of the thermoplastic polyimide layer is reduced, the thermoplastic polyimide layer contains a predetermined amount of diamine residues selected from general formulas (2) and (3). By designing in this manner, adhesiveness between the metal layer and the insulating resin layer can be ensured.
絶縁樹脂層の寸法精度の改善効果をより大きく発現させる観点から、本実施の形態の金属張積層板は、幅方向（ＴＤ方向）の長さ（フィルム幅）が好ましくは４９０ｍｍ以上１２００ｍｍ以下の範囲内、より好ましくは５２０ｍｍ以上１１００ｍｍ以下の範囲内がよく、長尺状の長さが２０ｍ以上のものが好ましい。本実施の形態の金属張積層板が連続的に製造される場合、幅方向（ＴＤ方向）が広いほど発明の効果が特に顕著となる。なお、本実施の形態の金属張積層板が連続的に製造された後、長尺な金属張積層板の長手方向（ＭＤ方向）及びＴＤ方向にある一定の値でスリットされた金属張積層板も含まれる。 From the viewpoint of achieving a greater effect of improving the dimensional accuracy of the insulating resin layer, the length (film width) in the width direction (TD direction) of the metal-clad laminate of this embodiment is preferably in the range of 490 mm or more and 1200 mm or less. More preferably, the length is in the range of 520 mm or more and 1100 mm or less, and the elongated length is preferably 20 m or more. When the metal-clad laminate of this embodiment is manufactured continuously, the effect of the invention becomes particularly remarkable as the width direction (TD direction) becomes wider. Note that after the metal-clad laminate of this embodiment is continuously manufactured, the metal-clad laminate is slit at a certain value in the longitudinal direction (MD direction) and TD direction of the long metal-clad laminate. Also included.
また、絶縁樹脂層は、ポリイミドフィルムとしたときの引張弾性率が３．０～１０．０ＧＰａの範囲内であることが好ましく、４．５～８．０ＧＰａの範囲内であるのがより好ましい。ポリイミドフィルムとしたときの引張弾性率が３．０ＧＰａに満たないとポリイミド自体の強度が低下することによって、金属張積層板を回路基板へ加工する際に絶縁樹脂層の裂けなどのハンドリング上の問題が生じることがある。反対に、ポリイミドフィルムとしたときの引張弾性率が１０．０ＧＰａを超えると、金属張積層板の折り曲げに対する剛性が上昇する結果、金属張積層板を折り曲げた際に金属配線に加わる曲げ応力が上昇し、折り曲げ耐性が低下してしまう。ポリイミドフィルムとしたときの引張弾性率を上記範囲内とすることで、絶縁樹脂層の強度と柔軟性を担保することができる。 Further, the insulating resin layer preferably has a tensile modulus of elasticity in the range of 3.0 to 10.0 GPa, more preferably in the range of 4.5 to 8.0 GPa when formed into a polyimide film. If the tensile modulus when made into a polyimide film is less than 3.0 GPa, the strength of the polyimide itself will decrease, resulting in handling problems such as tearing of the insulating resin layer when processing the metal-clad laminate into a circuit board. may occur. On the other hand, if the tensile modulus of the polyimide film exceeds 10.0 GPa, the bending rigidity of the metal-clad laminate increases, resulting in an increase in the bending stress applied to the metal wiring when the metal-clad laminate is bent. However, the bending resistance decreases. By controlling the tensile modulus of the polyimide film within the above range, the strength and flexibility of the insulating resin layer can be ensured.
（非熱可塑性ポリイミド）
本実施の形態において、非熱可塑性ポリイミド層を構成する非熱可塑性ポリイミドは、テトラカルボン酸残基及びジアミン残基を含み、これらはいずれも芳香族基を含むことが好ましい。非熱可塑性ポリイミドに含まれるテトラカルボン酸残基及びジアミン残基が、いずれも芳香族基を含むことで、非熱可塑性ポリイミドの秩序構造を形成しやすくし、絶縁樹脂層の高温環境下での面内複屈折率（Δｎ）の変化量を小さくして面内複屈折率（Δｎ）のばらつきを抑制するとともに、厚さ方向の複屈折率変化を抑制することができる。
(Non-thermoplastic polyimide)
In this embodiment, the non-thermoplastic polyimide constituting the non-thermoplastic polyimide layer contains a tetracarboxylic acid residue and a diamine residue, both of which preferably contain an aromatic group. The tetracarboxylic acid residues and diamine residues contained in the non-thermoplastic polyimide both contain aromatic groups, making it easier to form an ordered structure in the non-thermoplastic polyimide and making it easier for the insulating resin layer to withstand high-temperature environments. By reducing the amount of change in the in-plane birefringence (Δn), variations in the in-plane birefringence (Δn) can be suppressed, and changes in the birefringence in the thickness direction can be suppressed.
なお、本発明において、テトラカルボン酸残基とは、テトラカルボン酸二無水物から誘導された４価の基のことを表し、ジアミン残基とは、ジアミン化合物から誘導された２価の基のことを表す。また、「ジアミン化合物」は、末端の二つのアミノ基における水素原子が置換されていてもよく、例えば－ＮＲ３Ｒ４（ここで、Ｒ３，Ｒ４は、独立にアルキル基などの任意の置換基を意味する）であってもよい。 In the present invention, a tetracarboxylic acid residue refers to a tetravalent group derived from a tetracarboxylic dianhydride, and a diamine residue refers to a divalent group derived from a diamine compound. represents something. Further, in the "diamine compound", the hydrogen atoms in the two terminal amino groups may be substituted, for example, -NR 3 R 4 (here, R 3 and R 4 are independently any arbitrary group such as an alkyl group). ) may also mean a substituent.
非熱可塑性ポリイミドに含まれるテトラカルボン酸残基としては、特に制限はないが、例えば、ピロメリット酸二無水物（ＰＭＤＡ）から誘導されるテトラカルボン酸残基（以下、ＰＭＤＡ残基ともいう。）、３,３',４,４'-ビフェニルテトラカルボン酸二無水物（ＢＰＤＡ）から誘導されるテトラカルボン酸残基（以下、ＢＰＤＡ残基ともいう。）が好ましく挙げられる。これらのテトラカルボン酸残基は、秩序構造を形成しやすく、高温環境下での面内複屈折率（Δｎ）の変化量を小さくするとともに、厚さ方向の複屈折率変化を抑制することができる。また、ＰＭＤＡ残基は、熱膨張係数の制御とガラス転移温度の制御の役割を担う残基である。更に、ＢＰＤＡ残基は、テトラカルボン酸残基の中でも極性基がなく比較的分子量が大きいため、非熱可塑性ポリイミドのイミド基濃度を下げ、絶縁樹脂層の吸湿を抑制する効果も期待できる。このような観点から、ＰＭＤＡ残基及び／又はＢＰＤＡ残基の合計量が、非熱可塑性ポリイミドに含まれる全テトラカルボン酸残基の１００モル部に対して、好ましくは５０モル部以上、より好ましくは５０～１００モル部の範囲内、最も好ましくは７０～１００モル部の範囲内であることがよい。 The tetracarboxylic acid residue contained in the non-thermoplastic polyimide is not particularly limited, but for example, a tetracarboxylic acid residue derived from pyromellitic dianhydride (PMDA) (hereinafter also referred to as PMDA residue). ), 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA)-derived tetracarboxylic acid residues (hereinafter also referred to as BPDA residues) are preferred. These tetracarboxylic acid residues easily form an ordered structure, and can reduce the amount of change in in-plane birefringence (Δn) in a high-temperature environment and suppress the change in birefringence in the thickness direction. can. Furthermore, the PMDA residue is a residue that plays a role in controlling the coefficient of thermal expansion and the glass transition temperature. Furthermore, since the BPDA residue has no polar group and has a relatively large molecular weight among tetracarboxylic acid residues, it can be expected to have the effect of lowering the imide group concentration of the non-thermoplastic polyimide and suppressing moisture absorption in the insulating resin layer. From this point of view, the total amount of PMDA residues and/or BPDA residues is preferably 50 parts by mole or more, more preferably is preferably within the range of 50 to 100 mole parts, most preferably within the range of 70 to 100 mole parts.
非熱可塑性ポリイミドに含まれる他のテトラカルボン酸残基としては、例えば、２,３',３,４’-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、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、４,４’-オキシジフタル酸無水物、２,２',３,３'-、２,３,３',４'-又は３,３',４,４'-ベンゾフェノンテトラカルボン酸二無水物、２,３',３,４'-ジフェニルエーテルテトラカルボン酸二無水物、ビス(２,３-ジカルボキシフェニル)エーテル二無水物、３,３'',４,４''-、２,３,３'',４''-又は２,２'',３,３''-p-テルフェニルテトラカルボン酸二無水物、２,２-ビス(２,３-又は３,４-ジカルボキシフェニル)-プロパン二無水物、ビス(２,３-又は３.４-ジカルボキシフェニル)メタン二無水物、ビス(２,３-又は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-又は３,４-ジカルボキシフェニル)エタン二無水物、１,２,７,８-、１,２,６,７-又は１,２,９,１０-フェナンスレン-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、２,２-ビス（３,４-ジカルボキシフェニル）テトラフルオロプロパン二無水物、２,３,５,６-シクロヘキサン二無水物、１,２,５,６-ナフタレンテトラカルボン酸二無水物、１,４,５,８-ナフタレンテトラカルボン酸二無水物、２,３,６,７－ナフタレンテトラカルボン酸二無水物、４,８-ジメチル-１,２,３,５,６,７-ヘキサヒドロナフタレン-１,２,５,６-テトラカルボン酸二無水物、２,６-又は２,７-ジクロロナフタレン-１,４,５,８-テトラカルボン酸二無水物、２,３,６,７-（又は１,４,５,８-）テトラクロロナフタレン-１,４,５,８-（又は２,３,６,７-）テトラカルボン酸二無水物、２,３,８,９-、３,４,９,１０-、４,５,１０,１１-又は５,６,１１,１２-ペリレン-テトラカルボン酸二無水物、シクロペンタン-１,２,３,４-テトラカルボン酸二無水物、ピラジン-２,３,５,６-テトラカルボン酸二無水物、ピロリジン-２,３,４,５-テトラカルボン酸二無水物、チオフェン-２,３,４,５-テトラカルボン酸二無水物、４,４’-ビス（２,３-ジカルボキシフェノキシ）ジフェニルメタン二無水物等の芳香族テトラカルボン酸二無水物から誘導されるテトラカルボン酸残基が挙げられる。 Examples of other tetracarboxylic acid residues contained in the non-thermoplastic polyimide include 2,3',3,4'-biphenyltetracarboxylic dianhydride and 2,2',3,3'-biphenyltetracarboxylic acid residue. Acid dianhydride, 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride, 4,4'-oxydiphthalic anhydride, 2,2',3,3'-,2,3,3 ',4'- or 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 2,3',3,4'-diphenyl ether tetracarboxylic dianhydride, bis(2,3-dicarboxylic dianhydride) phenyl)ether dianhydride, 3,3'',4,4''-, 2,3,3'',4''- or 2,2'',3,3''-p-terphenyltetra Carboxylic dianhydride, 2,2-bis(2,3- or 3,4-dicarboxyphenyl)-propane dianhydride, bis(2,3- or 3,4-dicarboxyphenyl)methane dianhydride , bis(2,3- or 3,4-dicarboxyphenyl)sulfone dianhydride, 1,1-bis(2,3- or 3,4-dicarboxyphenyl)ethane dianhydride, 1,2,7 , 8-, 1,2,6,7- or 1,2,9,10-phenanthrene-tetracarboxylic dianhydride, 2,3,6,7-anthracenetetracarboxylic dianhydride, 2,2- Bis(3,4-dicarboxyphenyl)tetrafluoropropane dianhydride, 2,3,5,6-cyclohexane dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 1,4, 5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 4,8-dimethyl-1,2,3,5,6,7-hexahydronaphthalene- 1,2,5,6-tetracarboxylic dianhydride, 2,6- or 2,7-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,3,6,7- (or 1,4,5,8-)tetrachloronaphthalene-1,4,5,8-(or 2,3,6,7-)tetracarboxylic dianhydride, 2,3,8,9-, 3,4,9,10-, 4,5,10,11- or 5,6,11,12-perylene-tetracarboxylic dianhydride, cyclopentane-1,2,3,4-tetracarboxylic dianhydride Anhydride, pyrazine-2,3,5,6-tetracarboxylic dianhydride, pyrrolidine-2,3,4,5-tetracarboxylic dianhydride, thiophene-2,3,4,5-tetracarboxylic acid Examples include tetracarboxylic acid residues derived from aromatic tetracarboxylic dianhydrides such as dianhydride and 4,4'-bis(2,3-dicarboxyphenoxy)diphenylmethane dianhydride.
非熱可塑性ポリイミドに含まれるジアミン残基としては、一般式（１）で表されるジアミン化合物から誘導されるジアミン残基が好ましく挙げられる。 As the diamine residue contained in the non-thermoplastic polyimide, a diamine residue derived from a diamine compound represented by general formula (1) is preferably mentioned.
一般式（１）において、連結基Ｚは単結合若しくは－ＣＯＯ－を示し、Ｙは独立にハロゲン若しくはフェニル基で置換されてもよい炭素数１～３の１価の炭化水素又は炭素数１～３のアルコキシ基、又は炭素数１～３のパーフルオロアルキル基、又はアルケニル基を示し、ｎは０～２の整数を示し、ｐ及びｑは独立に０～４の整数を示す。ここで、「独立に」とは、上記式（１）において、複数の置換基Ｙ、整数ｐ、ｑが同一でもよいし、異なっていてもよいことを意味する。 In the general formula (1), the linking group Z represents a single bond or -COO-, and Y is a monovalent hydrocarbon having 1 to 3 carbon atoms or a monovalent hydrocarbon having 1 to 3 carbon atoms, which may be independently substituted with a halogen or phenyl group. represents an alkoxy group of 3, a perfluoroalkyl group having 1 to 3 carbon atoms, or an alkenyl group, n represents an integer of 0 to 2, and p and q independently represent an integer of 0 to 4. Here, "independently" means that in the above formula (1), the plurality of substituents Y and the integers p and q may be the same or different.
一般式（１）で表されるジアミン化合物から誘導されるジアミン残基（以下、「ジアミン残基（１）」と記すことがある）は、秩序構造を形成しやすく、寸法安定性を高め、特に高温環境下での面内複屈折率（Δｎ）の変化量とともに、厚さ方向の複屈折率変化を効果的に抑制するができる。このような観点から、ジアミン残基（１）は、非熱可塑性ポリイミドに含まれる全ジアミン残基の１００モル部に対して、２０モル部以上、好ましくは７０～９５モル部の範囲内、より好ましくは８０～９０モル部の範囲内で含有することがよい。 The diamine residue derived from the diamine compound represented by general formula (1) (hereinafter sometimes referred to as "diamine residue (1)") easily forms an ordered structure, increases dimensional stability, In particular, it is possible to effectively suppress the change in birefringence in the thickness direction as well as the amount of change in the in-plane birefringence (Δn) in a high-temperature environment. From this point of view, the diamine residue (1) should be present in an amount of at least 20 mole parts, preferably within a range of 70 to 95 mole parts, based on 100 mole parts of all diamine residues contained in the non-thermoplastic polyimide. The content is preferably in the range of 80 to 90 parts by mole.
ジアミン残基（１）の好ましい具体例としては、ｐ－フェニレンジアミン（ｐ－ＰＤＡ）、２，２’－ジメチル－４，４’－ジアミノビフェニル（ｍ－ＴＢ）、２,２’－ジエチル－４,４’－ジアミノビフェニル（ｍ－ＥＢ）、２,２’－ジエトキシ－４,４’－ジアミノビフェニル（ｍ－ＥＯＢ）、２,２’－ジプロポキシ－４,４’－ジアミノビフェニル（ｍ－ＰＯＢ）、２,２’－ｎ－プロピル－４,４’－ジアミノビフェニル（ｍ－ＮＰＢ）、２,２’－ジビニル－４,４’－ジアミノビフェニル（ＶＡＢ）、４，４’－ジアミノビフェニル、４,４’-ジアミノ-２,２’-ビス(トリフルオロメチル)ビフェニル（ＴＦＭＢ）等のジアミン化合物から誘導されるジアミン残基が挙げられる。これらの中でも特に、２，２’－ジメチル－４，４’－ジアミノビフェニル（ｍ－ＴＢ）は、秩序構造を形成しやすく、高温環境下での面内複屈折率（Δｎ）の変化量を小さくするとともに、厚さ方向の複屈折率変化を抑制することができるので特に好ましい。 Preferred specific examples of the diamine residue (1) include p-phenylenediamine (p-PDA), 2,2'-dimethyl-4,4'-diaminobiphenyl (m-TB), and 2,2'-diethyl- 4,4'-diaminobiphenyl (m-EB), 2,2'-diethoxy-4,4'-diaminobiphenyl (m-EOB), 2,2'-dipropoxy-4,4'-diaminobiphenyl (m- POB), 2,2'-n-propyl-4,4'-diaminobiphenyl (m-NPB), 2,2'-divinyl-4,4'-diaminobiphenyl (VAB), 4,4'-diaminobiphenyl , 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl (TFMB) and other diamine residues derived from diamine compounds. Among these, 2,2'-dimethyl-4,4'-diaminobiphenyl (m-TB) is particularly likely to form an ordered structure, and the amount of change in in-plane birefringence (Δn) in a high-temperature environment is This is particularly preferable since it is possible to reduce the thickness and suppress changes in birefringence in the thickness direction.
また、絶縁樹脂層の弾性率を下げ、伸度及び折り曲げ耐性等を向上させるため、非熱可塑性ポリイミドが、下記の一般式（２）及び（３）で表されるジアミン残基からなる群より選ばれる少なくとも１種のジアミン残基を含むことが好ましい。 In addition, in order to lower the elastic modulus of the insulating resin layer and improve elongation and bending resistance, non-thermoplastic polyimide is selected from the group consisting of diamine residues represented by the following general formulas (2) and (3). Preferably, it contains at least one selected diamine residue.
上記式（２）及び式（３）において、Ｒ５、Ｒ６、Ｒ７及びＲ８はそれぞれ独立にハロゲン原子、又は炭素数１～４の、ハロゲン原子で置換されてもよいアルキル基もしくはアルコキシ基、又はアルケニル基を示し、Ｘは独立に－Ｏ－、－Ｓ－、－ＣＨ２－、－ＣＨ(ＣＨ３)－、－Ｃ(ＣＨ３)２－、－ＣＯ－、－ＣＯＯ－、－ＳＯ２－、－ＮＨ－又は－ＮＨＣＯ－から選ばれる２価の基を示し、Ｘ１及びＸ２はそれぞれ独立に単結合、－Ｏ－、－Ｓ－、－ＣＨ２－、－ＣＨ(ＣＨ３)－、－Ｃ(ＣＨ３)２－、－ＣＯ－、－ＣＯＯ－、－ＳＯ２－、－ＮＨ－又は－ＮＨＣＯ－から選ばれる２価の基を示すが、Ｘ１及びＸ２の両方が単結合である場合を除くものとし、ｍ、ｎ、ｏ及びｐは独立に０～４の整数を示す。
なお、「独立に」とは、上記式（２）、（３）の内の一つにおいて、または両方において、複数の連結基Ｘ、連結基Ｘ１とＸ２、複数の置換基Ｒ５、Ｒ６、Ｒ７、Ｒ８、さらに、整数ｍ、ｎ、ｏ、ｐが、同一でもよいし、異なっていてもよいことを意味する。
In the above formulas (2) and (3), R 5 , R 6 , R 7 and R 8 are each independently a halogen atom, or an alkyl group or alkoxy group having 1 to 4 carbon atoms which may be substituted with a halogen atom. group or alkenyl group, and X independently represents -O-, -S-, -CH 2 -, -CH(CH 3 )-, -C(CH 3 ) 2 -, -CO-, -COO-, It represents a divalent group selected from -SO 2 -, -NH- or -NHCO-, and X 1 and X 2 each independently represent a single bond, -O-, -S-, -CH 2 -, -CH( It represents a divalent group selected from CH 3 )-, -C(CH 3 ) 2 -, -CO-, -COO-, -SO 2 -, -NH- or -NHCO-, but X 1 and X 2 m, n, o and p each independently represent an integer of 0 to 4.
Note that "independently" refers to a plurality of linking groups X, linking groups X 1 and X 2 , a plurality of substituents R 5 , in one or both of the above formulas (2) and (3), This means that R 6 , R 7 , R 8 , and the integers m, n, o, and p may be the same or different.
一般式（２）及び（３）で表されるジアミン残基は、屈曲性の部位を有するので、絶縁樹脂層に柔軟性を付与することができる。ここで、一般式（３）で表されるジアミン残基は、ベンゼン環が４個であるので、熱膨張係数（ＣＴＥ）の増加を抑制するために、ベンゼン環に結合する末端基はパラ位とすることが好ましい。また、絶縁樹脂層に柔軟性を付与しながら熱膨張係数（ＣＴＥ）の増加を抑制する観点から、一般式（２）及び（３）で表されるジアミン残基は、非熱可塑性ポリイミドに含まれる全ジアミン残基の１００モル部に対して、好ましくは５～３０モル部の範囲内、より好ましくは１０～２０モル部の範囲内で含有することがよい。一般式（２）及び（３）で表されるジアミン残基が５モル部未満であると、絶縁樹脂層の弾性率が増加して伸度が低下し、折り曲げ耐性等の低下が生じることがあり、３０モル部を超えると、分子の配向性が低下し、低ＣＴＥ化が困難となることがある。 Since the diamine residues represented by general formulas (2) and (3) have flexible sites, they can impart flexibility to the insulating resin layer. Here, since the diamine residue represented by general formula (3) has four benzene rings, in order to suppress an increase in the coefficient of thermal expansion (CTE), the terminal group bonded to the benzene ring is placed at the para position. It is preferable that In addition, from the viewpoint of suppressing an increase in the coefficient of thermal expansion (CTE) while imparting flexibility to the insulating resin layer, diamine residues represented by general formulas (2) and (3) are included in the non-thermoplastic polyimide. The content is preferably in the range of 5 to 30 moles, more preferably in the range of 10 to 20 moles, based on 100 moles of all diamine residues. If the diamine residue represented by general formulas (2) and (3) is less than 5 mole parts, the elastic modulus of the insulating resin layer will increase, the elongation will decrease, and the bending resistance will decrease. If the amount exceeds 30 mole parts, the molecular orientation may deteriorate, making it difficult to lower the CTE.
一般式（２）で表されるジアミン残基は、ｍ、ｎ及びｏの一つ以上が０であるものが好ましく、また、基Ｒ５、Ｒ６及びＲ７の好ましい例としては、炭素数１～４のハロゲン原子で置換されてもよいアルキル基、あるいは炭素数１～３のアルコキシ基、又は炭素数２～３のアルケニル基を挙げることができる。また、一般式（２）において、連結基Ｘの好ましい例としては、－Ｏ－、－Ｓ－、－ＣＨ２－、－ＣＨ（ＣＨ３）－、－ＳＯ２－又は－ＣＯ－を挙げることができる。一般式（２）で表されるジアミン残基の好ましい具体例としては、１,３－ビス（４－アミノフェノキシ）ベンゼン（ＴＰＥ－Ｒ）、１,４－ビス（４-アミノフェノキシ）ベンゼン（ＴＰＥ－Ｑ）、ビス（４‐アミノフェノキシ）－２,５－ジ－ｔｅｒｔ－ブチルベンゼン（ＤＴＢＡＢ）、４,４－ビス（４-アミノフェノキシ）ベンゾフェノン（ＢＡＰＫ）、１,３-ビス[２-(４-アミノフェニル)-２-プロピル]ベンゼン、１,４-ビス[２-(４-アミノフェニル)-２-プロピル]ベンゼン等のジアミン化合物から誘導されるジアミン残基が挙げられる。 The diamine residue represented by the general formula (2) preferably has one or more of m, n and o of 0, and preferable examples of the groups R 5 , R 6 and R 7 include the carbon number Examples include an alkyl group optionally substituted with 1 to 4 halogen atoms, an alkoxy group having 1 to 3 carbon atoms, or an alkenyl group having 2 to 3 carbon atoms. In general formula (2), preferred examples of the linking group X include -O-, -S-, -CH 2 -, -CH(CH 3 )-, -SO 2 - or -CO-. Can be done. Preferred specific examples of the diamine residue represented by general formula (2) include 1,3-bis(4-aminophenoxy)benzene (TPE-R), 1,4-bis(4-aminophenoxy)benzene ( TPE-Q), bis(4-aminophenoxy)-2,5-di-tert-butylbenzene (DTBAB), 4,4-bis(4-aminophenoxy)benzophenone (BAPK), 1,3-bis[2 Examples include diamine residues derived from diamine compounds such as -(4-aminophenyl)-2-propyl]benzene and 1,4-bis[2-(4-aminophenyl)-2-propyl]benzene.
一般式（３）で表されるジアミン残基は、ｍ、ｎ、ｏ及びｐの一つ以上が０であるものが好ましく、また、基Ｒ５、Ｒ６、Ｒ７及びＲ８の好ましい例としては、炭素数１～４のハロゲン原子で置換されてもよいアルキル基、あるいは炭素数１～３のアルコキシ基、又は炭素数２～３のアルケニル基を挙げることができる。また、一般式（３）において、連結基Ｘ１及びＸ２の好ましい例としては、単結合、－Ｏ－、－Ｓ－、－ＣＨ２－、－ＣＨ（ＣＨ３）－、－ＳＯ２－又は－ＣＯ－を挙げることができる。但し、屈曲部位を付与する観点から、連結基Ｘ１及びＸ２の両方が単結合である場合を除くものとする。一般式（３）で表されるジアミン残基の好ましい具体例としては、４，４’－ビス(４－アミノフェノキシ)ビフェニル（ＢＡＰＢ）、２,２’－ビス[４－(４－アミノフェノキシ)フェニル]プロパン（ＢＡＰＰ）、２,２’－ビス[４－(４－アミノフェノキシ)フェニル]エーテル（ＢＡＰＥ）、ビス［４－（４－アミノフェノキシ）フェニル］スルホン等のジアミン化合物から誘導されるジアミン残基が挙げられる。 The diamine residue represented by general formula (3) is preferably one in which one or more of m, n, o and p is 0, and preferable examples of groups R 5 , R 6 , R 7 and R 8 Examples include an alkyl group having 1 to 4 carbon atoms which may be substituted with a halogen atom, an alkoxy group having 1 to 3 carbon atoms, or an alkenyl group having 2 to 3 carbon atoms. In general formula (3), preferable examples of the linking groups X 1 and X 2 include a single bond, -O-, -S-, -CH 2 -, -CH(CH 3 )-, -SO 2 - or -CO-. However, from the viewpoint of providing a bending site, the case where both the connecting groups X 1 and X 2 are single bonds is excluded. Preferred specific examples of the diamine residue represented by the general formula (3) include 4,4'-bis(4-aminophenoxy)biphenyl (BAPB), 2,2'-bis[4-(4-aminophenoxy) ) phenyl]propane (BAPP), 2,2'-bis[4-(4-aminophenoxy)phenyl]ether (BAPE), bis[4-(4-aminophenoxy)phenyl]sulfone, etc. Examples include diamine residues.
一般式（２）で表されるジアミン残基の中でも、１,３－ビス（４－アミノフェノキシ）ベンゼン（ＴＰＥ－Ｒ）から誘導されるジアミン残基（「ＴＰＥ－Ｒ残基」と記すことがある）が特に好ましく、一般式（３）で表されるジアミン残基の中でも、２,２’－ビス[４－(４－アミノフェノキシ)フェニル]プロパン（ＢＡＰＰ）から誘導されるジアミン残基（「ＢＡＰＰ残基」と記すことがある）が特に好ましい。ＴＰＥ－Ｒ残基及びＢＡＰＰ残基は、屈曲性の部位を有するので、絶縁樹脂層の弾性率を低下させ、柔軟性を付与することができる。また、ＢＡＰＰ残基は分子量が大きいため、非熱可塑性ポリイミドのイミド基濃度を下げ、絶縁樹脂層の吸湿を抑制する効果も期待できる。 Among the diamine residues represented by general formula (2), diamine residues derived from 1,3-bis(4-aminophenoxy)benzene (TPE-R) (hereinafter referred to as "TPE-R residues") Among the diamine residues represented by general formula (3), diamine residues derived from 2,2'-bis[4-(4-aminophenoxy)phenyl]propane (BAPP) are particularly preferred. (sometimes referred to as "BAPP residue") is particularly preferred. Since the TPE-R residue and the BAPP residue have flexible sites, they can lower the elastic modulus of the insulating resin layer and impart flexibility. Furthermore, since the BAPP residue has a large molecular weight, it can be expected to have the effect of lowering the imide group concentration of the non-thermoplastic polyimide and suppressing moisture absorption in the insulating resin layer.
非熱可塑性ポリイミドに含まれる他のジアミン残基としては、例えば、ｍ‐フェニレンジアミン（ｍ－ＰＤＡ）、４,４'-ジアミノジフェニルエーテル（４,４'-ＤＡＰＥ）、３,３'－ジアミノジフェニルエーテル、３,４'－ジアミノジフェニルエーテル、４,４'－ジアミノジフェニルメタン、３,３'－ジアミノジフェニルメタン、３,４'－ジアミノジフェニルメタン、４,４'－ジアミノジフェニルプロパン、３,３'－ジアミノジフェニルプロパン、３,４'－ジアミノジフェニルプロパン、４,４'－ジアミノジフェニルスルフィド、３,３'－ジアミノジフェニルスルフィド、３,４'－ジアミノジフェニルスルフィド、４,４'－ジアミノジフェニルスルホン、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、３,４'－ジアミノベンゾフェノン、３,３'－ジアミノベンゾフェノン、2,2-ビス-［4-（3-アミノフェノキシ）フェニル］プロパン、ビス［4-（３－アミノフェノキシ）フェニル］スルホン、ビス［4-（3-アミノフェノキシ）ビフェニル、ビス［1-（3-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］メタン、ビス［4-（3-アミノフェノキシ）フェニル］エーテル、ビス［4-（3-アミノフェノキシ）］ベンゾフェノン、9,9-ビス［4-（3-アミノフェノキシ）フェニル］フルオレン、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-（3-アミノフェノキシ）フェニル］ヘキサフルオロプロパン、3，3’-ジメチル-4,4’-ジアミノビフェニル、4,4’-メチレンジ-o-トルイジン、4,4’-メチレンジ-2,6-キシリジン、4,4’-メチレン-2,6-ジエチルアニリン、3,3’-ジアミノジフェニルエタン、3,3’-ジアミノビフェニル、3,3’-ジメトキシベンジジン、3,3''-ジアミノ-p-テルフェニル、4,4'-［1,4-フェニレンビス（1-メチルエチリデン）］ビスアニリン、4,4'-［1,3-フェニレンビス（1-メチルエチリデン）］ビスアニリン、ビス(p-アミノシクロヘキシル)メタン、ビス(p-β-アミノ-t-ブチルフェニル)エーテル、ビス(p-β-メチル-δ-アミノペンチル)ベンゼン、p-ビス(2-メチル-4-アミノペンチル)ベンゼン、p-ビス(1,1-ジメチル-5-アミノペンチル)ベンゼン、1,5-ジアミノナフタレン、2,6-ジアミノナフタレン、2,4-ビス(β-アミノ-t-ブチル)トルエン、2,4-ジアミノトルエン、m-キシレン-2,5-ジアミン、p-キシレン-2,5-ジアミン、m-キシリレンジアミン、p-キシリレンジアミン、2,6-ジアミノピリジン、2,5-ジアミノピリジン、2,5-ジアミノ-1,3,4-オキサジアゾール、ピペラジン等の芳香族ジアミン化合物から誘導されるジアミン残基が挙げられる。 Other diamine residues contained in the non-thermoplastic polyimide include, for example, m-phenylenediamine (m-PDA), 4,4'-diaminodiphenyl ether (4,4'-DAPE), and 3,3'-diaminodiphenyl ether. , 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylpropane, 3,3'-diaminodiphenylpropane , 3,4'-diaminodiphenylpropane, 4,4'-diaminodiphenylsulfide, 3,3'-diaminodiphenylsulfide, 3,4'-diaminodiphenylsulfide, 4,4'-diaminodiphenylsulfone, 3,3' -diaminodiphenylsulfone, 4,4'-diaminobenzophenone, 3,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 2,2-bis-[4-(3-aminophenoxy)phenyl]propane, bis[ 4-(3-aminophenoxy)phenyl] sulfone, bis[4-(3-aminophenoxy)biphenyl, bis[1-(3-aminophenoxy)]biphenyl, bis[4-(3-aminophenoxy)phenyl]methane , bis[4-(3-aminophenoxy)phenyl]ether, bis[4-(3-aminophenoxy)]benzophenone, 9,9-bis[4-(3-aminophenoxy)phenyl]fluorene, 2,2- Bis-[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis-[4-(3-aminophenoxy)phenyl]hexafluoropropane, 3,3'-dimethyl-4,4'- Diaminobiphenyl, 4,4'-methylenedi-o-toluidine, 4,4'-methylenedi-2,6-xylidine, 4,4'-methylene-2,6-diethylaniline, 3,3'-diaminodiphenylethane, 3,3'-diaminobiphenyl, 3,3'-dimethoxybenzidine, 3,3''-diamino-p-terphenyl, 4,4'-[1,4-phenylenebis(1-methylethylidene)]bisaniline, 4,4'-[1,3-phenylenebis(1-methylethylidene)]bisaniline, bis(p-aminocyclohexyl)methane, bis(p-β-amino-t-butylphenyl)ether, bis(p-β) -Methyl-δ-aminopentyl)benzene, p-bis(2-methyl-4-aminopentyl)benzene, p-bis(1,1-dimethyl-5-aminopentyl)benzene, 1,5-diaminonaphthalene, 2 ,6-diaminonaphthalene, 2,4-bis(β-amino-t-butyl)toluene, 2,4-diaminotoluene, m-xylene-2,5-diamine, p-xylene-2,5-diamine, m -Derived from aromatic diamine compounds such as xylylene diamine, p-xylylene diamine, 2,6-diaminopyridine, 2,5-diaminopyridine, 2,5-diamino-1,3,4-oxadiazole, piperazine, etc. Examples include diamine residues.
非熱可塑性ポリイミドにおいて、上記テトラカルボン酸残基及びジアミン残基の種類や、２種以上のテトラカルボン酸残基又はジアミン残基を適用する場合のそれぞれのモル比を選定することにより、熱膨張係数、貯蔵弾性率、引張弾性率等を制御することができる。また、非熱可塑性ポリイミドにおいて、ポリイミドの構造単位を複数有する場合は、ブロックとして存在しても、ランダムに存在していてもよいが、面内複屈折率（Δｎ）のばらつきを抑制する観点から、ランダムに存在することが好ましい。 In non-thermoplastic polyimide, thermal expansion can be controlled by selecting the types of the above-mentioned tetracarboxylic acid residues and diamine residues, and the molar ratio of two or more types of tetracarboxylic acid residues or diamine residues. Modulus, storage modulus, tensile modulus, etc. can be controlled. In addition, when non-thermoplastic polyimide has multiple polyimide structural units, they may exist as blocks or randomly, but from the viewpoint of suppressing variations in in-plane birefringence (Δn), , preferably exist randomly.
非熱可塑性ポリイミドのイミド基濃度は、３５重量％以下であることが好ましい。ここで、「イミド基濃度」は、ポリイミド中のイミド基部（－（ＣＯ）２－Ｎ－）の分子量を、ポリイミドの構造全体の分子量で除した値を意味する。イミド基濃度が３５重量％を超えると、樹脂自体の分子量が小さくなるとともに、極性基の増加によって低吸湿性も悪化する。上記酸無水物とジアミン化合物の組み合わせを選択することによって、非熱可塑性ポリイミド中の分子の配向性を制御することで、イミド基濃度低下に伴うＣＴＥの増加を抑制し、低吸湿性を担保している。 The imide group concentration of the non-thermoplastic polyimide is preferably 35% by weight or less. Here, "imide group concentration" means the value obtained by dividing the molecular weight of the imide group (-(CO) 2 -N-) in polyimide by the molecular weight of the entire polyimide structure. When the imide group concentration exceeds 35% by weight, the molecular weight of the resin itself decreases, and the low hygroscopicity also deteriorates due to the increase in polar groups. By selecting the combination of the above acid anhydride and diamine compound, the orientation of the molecules in the non-thermoplastic polyimide can be controlled, thereby suppressing the increase in CTE due to a decrease in the imide group concentration and ensuring low hygroscopicity. ing.
非熱可塑性ポリイミドの重量平均分子量は、例えば１０,０００～４００,０００の範囲内が好ましく、５０,０００～３５０,０００の範囲内がより好ましい。重量平均分子量が１０,０００未満であると、絶縁樹脂層の強度が低下して脆化しやすい傾向となる。一方、重量平均分子量が４００,０００を超えると、過度に粘度が増加して塗工作業の際に厚みムラ、スジ等の不良が発生しやすい傾向になる。 The weight average molecular weight of the non-thermoplastic polyimide is, for example, preferably within the range of 10,000 to 400,000, more preferably within the range of 50,000 to 350,000. When the weight average molecular weight is less than 10,000, the strength of the insulating resin layer decreases and tends to become brittle. On the other hand, if the weight average molecular weight exceeds 400,000, the viscosity increases excessively and defects such as uneven thickness and streaks tend to occur during coating operations.
（熱可塑性ポリイミド）
本実施の形態において、熱可塑性ポリイミド層を構成する熱可塑性ポリイミドは、テトラカルボン酸残基及びジアミン残基を含み、これらがいずれも芳香族基を含むことが好ましい。熱可塑性ポリイミドに含まれるテトラカルボン酸残基及びジアミン残基が、いずれも芳香族基を含むことによって、絶縁樹脂層の高温環境下での面内複屈折率（Δｎ）の変化量を抑制するとともに、厚さ方向の複屈折率変化を抑制することができる。
(Thermoplastic polyimide)
In this embodiment, the thermoplastic polyimide constituting the thermoplastic polyimide layer contains a tetracarboxylic acid residue and a diamine residue, and it is preferable that both of these contain an aromatic group. Both the tetracarboxylic acid residue and the diamine residue contained in the thermoplastic polyimide contain an aromatic group, thereby suppressing the amount of change in the in-plane birefringence (Δn) of the insulating resin layer in a high-temperature environment. At the same time, changes in birefringence in the thickness direction can be suppressed.
熱可塑性ポリイミドに含まれるテトラカルボン酸残基としては、特に制限はないが、例えば、ピロメリット酸二無水物（ＰＭＤＡ）から誘導されるテトラカルボン酸残基（以下、ＰＭＤＡ残基ともいう。）、３,３',４,４'-ビフェニルテトラカルボン酸二無水物（ＢＰＤＡ）から誘導されるテトラカルボン酸残基（以下、ＢＰＤＡ残基ともいう。）が好ましく挙げられる。これらのテトラカルボン酸残基は、秩序構造を形成しやすく、高温環境下での面内複屈折率（Δｎ）の変化量を小さくするとともに、厚さ方向の複屈折率変化を抑制することができる。また、ＰＭＤＡ残基は、熱膨張係数の制御とガラス転移温度の制御の役割を担う残基である。更に、ＢＰＤＡ残基は、テトラカルボン酸残基の中でも極性基がなく比較的分子量が大きいため、熱可塑性ポリイミドのイミド基濃度を下げ、絶縁樹脂層の吸湿を抑制する効果も期待できる。このような観点から、ＰＭＤＡ残基及び／又はＢＰＤＡ残基の合計量が、熱可塑性ポリイミドに含まれる全テトラカルボン酸残基の１００モル部に対して、好ましくは５０モル部以上、より好ましくは５０～１００モル部の範囲内、最も好ましくは７０～１００モル部の範囲内であることがよい。 The tetracarboxylic acid residue contained in the thermoplastic polyimide is not particularly limited, but for example, a tetracarboxylic acid residue derived from pyromellitic dianhydride (PMDA) (hereinafter also referred to as PMDA residue). , 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA) (hereinafter also referred to as BPDA residue). These tetracarboxylic acid residues easily form an ordered structure, and can reduce the amount of change in in-plane birefringence (Δn) in a high-temperature environment and suppress the change in birefringence in the thickness direction. can. Furthermore, the PMDA residue is a residue that plays a role in controlling the coefficient of thermal expansion and the glass transition temperature. Furthermore, since the BPDA residue has no polar group and has a relatively large molecular weight among tetracarboxylic acid residues, it can be expected to have the effect of lowering the imide group concentration of the thermoplastic polyimide and suppressing moisture absorption in the insulating resin layer. From this point of view, the total amount of PMDA residues and/or BPDA residues is preferably 50 parts by mole or more, more preferably It is preferably within the range of 50 to 100 mole parts, most preferably within the range of 70 to 100 mole parts.
熱可塑性ポリイミドに含まれる他のテトラカルボン酸残基としては、上記非熱可塑性ポリイミドで例示したものと同様の芳香族テトラカルボン酸二無水物から誘導されるテトラカルボン酸残基が挙げられる。 Other tetracarboxylic acid residues contained in the thermoplastic polyimide include tetracarboxylic acid residues derived from aromatic tetracarboxylic dianhydrides similar to those exemplified in the non-thermoplastic polyimide.
本実施の形態において、熱可塑性ポリイミドに含まれるジアミン残基としては、上記一般式（２）及び（３）から選ばれる少なくとも一種のジアミン残基が好ましい。一般式（２）及び（３）から選ばれるジアミン残基は、全ジアミン残基の１００モル部に対して、合計で５０モル部以上であることが好ましく、５０～１００モル部であることがより好ましく、７０～１００モル部の範囲内が最も好ましい。一般式（２）及び（３）から選ばれるジアミン残基を、全ジアミン残基の１００モル部に対して、合計で５０モル部以上含むことによって、熱可塑性ポリイミド層に柔軟性と接着性を付与し、金属層に対する接着層として機能させることができる。また、一般式（２）で表されるジアミン残基の中でも、ＴＰＥ－Ｒ残基が特に好ましく、一般式（３）で表されるジアミン残基の中でもＢＡＰＰ残基が特に好ましい。ＴＰＥ－Ｒ残基及びＢＡＰＰ残基は、屈曲性の部位を有するので、絶縁樹脂層の弾性率を低下させ、柔軟性を付与することができる。また、ＢＡＰＰ残基は分子量が大きいため、熱可塑性ポリイミドのイミド基濃度を下げ、絶縁樹脂層の吸湿を抑制する効果も期待できる。 In this embodiment, the diamine residue contained in the thermoplastic polyimide is preferably at least one type of diamine residue selected from the above general formulas (2) and (3). The total amount of diamine residues selected from general formulas (2) and (3) is preferably 50 parts by mole or more, and preferably 50 to 100 parts by mole, based on 100 parts by mole of all diamine residues. More preferably, it is within the range of 70 to 100 parts by mole. By containing a total of 50 mole parts or more of diamine residues selected from general formulas (2) and (3) based on 100 mole parts of all diamine residues, flexibility and adhesion are imparted to the thermoplastic polyimide layer. It can be applied as an adhesive layer to the metal layer. Further, among the diamine residues represented by general formula (2), TPE-R residues are particularly preferred, and among diamine residues represented by general formula (3), BAPP residues are particularly preferred. Since TPE-R residues and BAPP residues have flexible sites, they can lower the elastic modulus of the insulating resin layer and impart flexibility. Furthermore, since the BAPP residue has a large molecular weight, it can be expected to have the effect of lowering the imide group concentration of the thermoplastic polyimide and suppressing moisture absorption in the insulating resin layer.
また、上述のように、非熱可塑性ポリイミド層を構成する非熱可塑性ポリイミドが、一般式（２）及び（３）から選ばれるジアミン残基を含有する場合には、熱可塑性ポリイミド層を構成する熱可塑性ポリイミドも、ジアミン残基として、類似した構造、好ましくは一般式（２）及び（３）から選ばれる同種のジアミン残基を含有することがよい。この場合、熱可塑性ポリイミドと非熱可塑性ポリイミドでは、ジアミン残基の含有比率は異なるものとなるが、類似若しくは同種のジアミン残基を含有することで、特にキャスト法によってポリイミドフィルムを形成する際に、熱可塑性ポリイミド層と非熱可塑性ポリイミド層の配向制御が容易になり、寸法精度を管理しやすくなる。このような観点から、本実施の形態では、非熱可塑性ポリイミド層を構成する非熱可塑性ポリイミドと、熱可塑性ポリイミド層を構成する熱可塑性ポリイミドがいずれも上記一般式（２）及び（３）から選ばれる少なくとも一種のジアミン残基を含有することが好ましく、該ジアミン残基が、ＴＰＥ－Ｒ残基及び／又はＢＡＰＰ残基を含有することが最も好ましい。 Moreover, as mentioned above, when the non-thermoplastic polyimide constituting the non-thermoplastic polyimide layer contains a diamine residue selected from general formulas (2) and (3), the non-thermoplastic polyimide layer constituting the thermoplastic polyimide layer The thermoplastic polyimide may also contain diamine residues having similar structures, preferably the same type of diamine residues selected from general formulas (2) and (3). In this case, the content ratio of diamine residues will be different between thermoplastic polyimide and non-thermoplastic polyimide, but by containing similar or the same type of diamine residues, it is especially useful when forming a polyimide film by a casting method. , it becomes easier to control the orientation of the thermoplastic polyimide layer and the non-thermoplastic polyimide layer, and it becomes easier to manage dimensional accuracy. From this point of view, in this embodiment, the non-thermoplastic polyimide constituting the non-thermoplastic polyimide layer and the thermoplastic polyimide constituting the thermoplastic polyimide layer are both expressed by the above general formulas (2) and (3). It is preferable to contain at least one selected diamine residue, and it is most preferable that the diamine residue contains a TPE-R residue and/or a BAPP residue.
本実施の形態において、熱可塑性ポリイミドに含まれる、上記一般式（２）及び（３）以外のジアミン残基としては、例えば、２，２’－ジメチル－４，４’－ジアミノビフェニル（ｍ－ＴＢ）、２,２’－ジエチル－４,４’－ジアミノビフェニル（ｍ－ＥＢ）、２,２’－ジエトキシ－４,４’－ジアミノビフェニル（ｍ－ＥＯＢ）、２,２’－ジプロポキシ－４,４’－ジアミノビフェニル（ｍ－ＰＯＢ）、２,２’－ｎ－プロピル－４,４’－ジアミノビフェニル（ｍ－ＮＰＢ）、２,２’－ジビニル－４,４’－ジアミノビフェニル（ＶＡＢ）、４，４’－ジアミノビフェニル、４,４’-ジアミノ-２,２’-ビス(トリフルオロメチル)ビフェニル（ＴＦＭＢ）、ｐ‐フェニレンジアミン（ｐ－ＰＤＡ）、ｍ‐フェニレンジアミン（ｍ－ＰＤＡ）、3,3’-ジアミノジフェニルメタン、3,3’-ジアミノジフェニルプロパン、3,3’-ジアミノジフェニルスルフィド、3,3’-ジアミノジフェニルスルホン、3,3-ジアミノジフェニルエーテル、3,4'-ジアミノジフェニルエーテル、3,4’-ジアミノジフェニルメタン、3,4’-ジアミノジフェニルプロパン、3,4’-ジアミノジフェニルスルフィド、3,3’-ジアミノベンゾフェノン、(3,3’-ビスアミノ)ジフェニルアミン、1,4-ビス（3-アミノフェノキシ）ベンゼン、3-[4-（4-アミノフェノキシ）フェノキシ]ベンゼンアミン、3-[3-（4-アミノフェノキシ）フェノキシ]ベンゼンアミン、1,3-ビス（3-アミノフェノキシ）ベンゼン（ＡＰＢ）、4,4'-[2-メチル-(1,3-フェニレン)ビスオキシ]ビスアニリン、4,4'-[4-メチル-(1,3-フェニレン)ビスオキシ]ビスアニリン、4,4'-[5-メチル-(1,3-フェニレン)ビスオキシ]ビスアニリン、ビス［4-（3-アミノフェノキシ）フェニル］メタン、ビス［4-（3-アミノフェノキシ）フェニル］プロパン、ビス［4-（3-アミノフェノキシ）フェニル］エーテル、ビス［4-（3-アミノフェノキシ）フェニル］スルホン、ビス［4-（3-アミノフェノキシ）］ベンゾフェノン、ビス［4,4'-（3-アミノフェノキシ）］ベンズアニリド、4-[3-[4-(4-アミノフェノキシ)フェノキシ]フェノキシ]アニリン、4,4’-[オキシビス（3,1-フェニレンオキシ）]ビスアニリン、ビス［4-（4-アミノフェノキシ）フェニル］エーテル（ＢＡＰＥ）、ビス［4-（4-アミノフェノキシ）フェニル］ケトン（ＢＡＰＫ）、ビス［4-（3-アミノフェノキシ）］ビフェニル、ビス［4-（4-アミノフェノキシ）］ビフェニル等のジアミン化合物から誘導されるジアミン残基を挙げることができる。 In the present embodiment, diamine residues other than the above general formulas (2) and (3) contained in the thermoplastic polyimide include, for example, 2,2'-dimethyl-4,4'-diaminobiphenyl (m- TB), 2,2'-diethyl-4,4'-diaminobiphenyl (m-EB), 2,2'-diethoxy-4,4'-diaminobiphenyl (m-EOB), 2,2'-dipropoxy- 4,4'-diaminobiphenyl (m-POB), 2,2'-n-propyl-4,4'-diaminobiphenyl (m-NPB), 2,2'-divinyl-4,4'-diaminobiphenyl ( VAB), 4,4'-diaminobiphenyl, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl (TFMB), p-phenylenediamine (p-PDA), m-phenylenediamine (m -PDA), 3,3'-diaminodiphenylmethane, 3,3'-diaminodiphenylpropane, 3,3'-diaminodiphenyl sulfide, 3,3'-diaminodiphenylsulfone, 3,3-diaminodiphenyl ether, 3,4' -diaminodiphenyl ether, 3,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylpropane, 3,4'-diaminodiphenyl sulfide, 3,3'-diaminobenzophenone, (3,3'-bisamino)diphenylamine, 1, 4-Bis(3-aminophenoxy)benzene, 3-[4-(4-aminophenoxy)phenoxy]benzenamine, 3-[3-(4-aminophenoxy)phenoxy]benzenamine, 1,3-bis(3 -aminophenoxy)benzene (APB), 4,4'-[2-methyl-(1,3-phenylene)bisoxy]bisaniline, 4,4'-[4-methyl-(1,3-phenylene)bisoxy]bisaniline , 4,4'-[5-methyl-(1,3-phenylene)bisoxy]bisaniline, bis[4-(3-aminophenoxy)phenyl]methane, bis[4-(3-aminophenoxy)phenyl]propane, Bis[4-(3-aminophenoxy)phenyl]ether, bis[4-(3-aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)]benzophenone, bis[4,4'-(3 -aminophenoxy)]benzanilide, 4-[3-[4-(4-aminophenoxy)phenoxy]phenoxy]aniline, 4,4'-[oxybis(3,1-phenyleneoxy)]bisaniline, bis[4-( 4-aminophenoxy)phenyl]ether (BAPE), bis[4-(4-aminophenoxy)phenyl]ketone (BAPK), bis[4-(3-aminophenoxy)]biphenyl, bis[4-(4-amino Examples include diamine residues derived from diamine compounds such as phenoxy)]biphenyl.
熱可塑性ポリイミドにおいて、上記テトラカルボン酸残基及びジアミン残基の種類や、２種以上のテトラカルボン酸残基又はジアミン残基を適用する場合のそれぞれのモル比を選定することにより、熱膨張係数、引張弾性率、ガラス転移温度等を制御することができる。また、熱可塑性ポリイミドにおいて、ポリイミドの構造単位を複数有する場合は、ブロックとして存在しても、ランダムに存在していてもよいが、ランダムに存在することが好ましい。 In thermoplastic polyimide, the coefficient of thermal expansion can be adjusted by selecting the types of the above-mentioned tetracarboxylic acid residues and diamine residues, and the molar ratio of two or more types of tetracarboxylic acid residues or diamine residues. , tensile modulus, glass transition temperature, etc. can be controlled. Furthermore, when the thermoplastic polyimide has a plurality of polyimide structural units, they may exist as blocks or randomly, but it is preferable that they exist randomly.
熱可塑性ポリイミド層を構成する熱可塑性ポリイミドは、金属層との密着性を向上させることができる。このような熱可塑性ポリイミドは、ガラス転移温度が２００℃以上３５０℃以下の範囲内、好ましくは２００℃以上３２０℃以下の範囲内である。 The thermoplastic polyimide constituting the thermoplastic polyimide layer can improve adhesion to the metal layer. Such a thermoplastic polyimide has a glass transition temperature of 200°C or more and 350°C or less, preferably 200°C or more and 320°C or less.
熱可塑性ポリイミドのイミド基濃度は、３５重量％以下であることが好ましい。ここで、「イミド基濃度」は、ポリイミド中のイミド基部（－（ＣＯ）２－Ｎ－）の分子量を、ポリイミドの構造全体の分子量で除した値を意味する。イミド基濃度が３５重量％を超えると、樹脂自体の分子量が小さくなるとともに、極性基の増加によって低吸湿性も悪化する。上記酸無水物とジアミン化合物の組み合わせを選択することによって、熱可塑性ポリイミド中の分子の配向性を制御することで、イミド基濃度低下に伴うＣＴＥの増加を抑制し、低吸湿性を担保している。 The imide group concentration of the thermoplastic polyimide is preferably 35% by weight or less. Here, "imide group concentration" means the value obtained by dividing the molecular weight of the imide group (-(CO) 2 -N-) in polyimide by the molecular weight of the entire polyimide structure. When the imide group concentration exceeds 35% by weight, the molecular weight of the resin itself decreases, and the low hygroscopicity also deteriorates due to the increase in polar groups. By selecting a combination of the above acid anhydride and diamine compound, the orientation of molecules in the thermoplastic polyimide can be controlled, suppressing the increase in CTE due to a decrease in imide group concentration and ensuring low hygroscopicity. There is.
熱可塑性ポリイミドの重量平均分子量は、例えば１０,０００～４００,０００の範囲内が好ましく、５０,０００～３５０,０００の範囲内がより好ましい。重量平均分子量が１０,０００未満であると、絶縁樹脂層の強度が低下して脆化しやすい傾向となる。一方、重量平均分子量が４００,０００を超えると、過度に粘度が増加して塗工作業の際に厚みムラ、スジ等の不良が発生しやすい傾向になる。 The weight average molecular weight of the thermoplastic polyimide is, for example, preferably within the range of 10,000 to 400,000, more preferably within the range of 50,000 to 350,000. When the weight average molecular weight is less than 10,000, the strength of the insulating resin layer decreases and tends to become brittle. On the other hand, if the weight average molecular weight exceeds 400,000, the viscosity increases excessively and defects such as uneven thickness and streaks tend to occur during coating operations.
（非熱可塑性ポリイミド及び熱可塑性ポリイミドの合成）
一般にポリイミドは、テトラカルボン酸二無水物と、ジアミン化合物を溶媒中で反応させ、ポリアミド酸を生成したのち加熱閉環させることにより製造できる。例えば、テトラカルボン酸二無水物とジアミン化合物をほぼ等モルで有機溶媒中に溶解させて、０～１００℃の範囲内の温度で３０分～２４時間撹拌し重合反応させることでポリイミドの前駆体であるポリアミド酸が得られる。反応にあたっては、生成する前駆体が有機溶媒中に５～３０重量％の範囲内、好ましくは１０～２０重量％の範囲内となるように反応成分を溶解する。重合反応に用いる有機溶媒としては、例えば、Ｎ,Ｎ－ジメチルホルムアミド（ＤＭＦ）、Ｎ,Ｎ－ジメチルアセトアミド（ＤＭＡｃ）、Ｎ,Ｎ－ジエチルアセトアミド、Ｎ－メチル－２－ピロリドン（ＮＭＰ）、２－ブタノン、ジメチルスホキシド（ＤＭＳＯ）、ヘキサメチルホスホルアミド、Ｎ－メチルカプロラクタム、硫酸ジメチル、シクロヘキサノン、ジオキサン、テトラヒドロフラン、ジグライム、トリグライム、クレゾール等が挙げられる。これらの溶媒を２種以上併用して使用することもでき、更にはキシレン、トルエンのような芳香族炭化水素の併用も可能である。また、このような有機溶媒の使用量としては特に制限されるものではないが、重合反応によって得られるポリアミド酸溶液の濃度が５～３０重量％程度になるような使用量に調整して用いることが好ましい。
(Synthesis of non-thermoplastic polyimide and thermoplastic polyimide)
Generally, polyimide can be produced by reacting a tetracarboxylic dianhydride and a diamine compound in a solvent to produce a polyamic acid, which is then ring-closed by heating. For example, a polyimide precursor can be obtained by dissolving approximately equimolar amounts of tetracarboxylic dianhydride and a diamine compound in an organic solvent, stirring at a temperature within the range of 0 to 100°C for 30 minutes to 24 hours, and causing a polymerization reaction. A polyamic acid is obtained. In the reaction, the reaction components are dissolved in the organic solvent so that the amount of the precursor to be produced is within the range of 5 to 30% by weight, preferably within the range of 10 to 20% by weight. Examples of organic solvents used in the polymerization reaction include N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAc), N,N-diethylacetamide, N-methyl-2-pyrrolidone (NMP), 2 -butanone, dimethyl sulfoxide (DMSO), hexamethylphosphoramide, N-methylcaprolactam, dimethyl sulfate, cyclohexanone, dioxane, tetrahydrofuran, diglyme, triglyme, cresol and the like. Two or more of these solvents can be used in combination, and aromatic hydrocarbons such as xylene and toluene can also be used in combination. Further, the amount of such an organic solvent to be used is not particularly limited, but it should be adjusted to an amount such that the concentration of the polyamic acid solution obtained by the polymerization reaction is about 5 to 30% by weight. is preferred.
合成されたポリアミド酸は、通常、反応溶媒溶液として使用することが有利であるが、必要により濃縮、希釈又は他の有機溶媒に置換することができる。また、ポリアミド酸は一般に溶媒可溶性に優れるので、有利に使用される。ポリアミド酸の溶液の粘度は、５００ｃｐｓ～１００,０００ｃｐｓの範囲内であることが好ましい。この範囲を外れると、コーター等による塗工作業の際にフィルムに厚みムラ、スジ等の不良が発生し易くなる。ポリアミド酸をイミド化させる方法は、特に制限されず、例えば前記溶媒中で、８０～４００℃の範囲内の温度条件で１～２４時間かけて加熱するといった熱処理が好適に採用される。 It is usually advantageous to use the synthesized polyamic acid as a reaction solvent solution, but it can be concentrated, diluted, or replaced with another organic solvent if necessary. In addition, polyamic acids generally have excellent solvent solubility, so they are advantageously used. Preferably, the viscosity of the polyamic acid solution is within the range of 500 cps to 100,000 cps. Outside this range, defects such as uneven thickness and streaks are likely to occur in the film during coating operations using a coater or the like. The method of imidizing polyamic acid is not particularly limited, and for example, heat treatment such as heating in the above-mentioned solvent at a temperature within the range of 80 to 400° C. for 1 to 24 hours is preferably employed.
＜金属層＞
金属層を構成する金属としては、例えば、銅、アルミニウム、ステンレス、鉄、銀、パラジウム、ニッケル、クロム、モリブデン、タングステン、ジルコニウム、金、コバルト、チタン、タンタル、亜鉛、鉛、錫、シリコン、ビスマス、インジウム又はこれらの合金などから選択される金属を挙げることができる。金属層は、スパッタ、蒸着、めっき等の方法で形成することもできるが、接着性の観点から金属箔を用いることが好ましい。導電性の点で特に好ましいものは銅箔である。銅箔は、電解銅箔、圧延銅箔のいずれでもよい。なお、本実施の形態の金属張積層板を連続的に生産する場合には、金属箔として、所定の厚さのものがロール状に巻き取られた長尺状の金属箔が用いられる。
<Metal layer>
Examples of metals constituting the metal layer include copper, aluminum, stainless steel, iron, silver, palladium, nickel, chromium, molybdenum, tungsten, zirconium, gold, cobalt, titanium, tantalum, zinc, lead, tin, silicon, and bismuth. , indium, or an alloy thereof. Although the metal layer can be formed by sputtering, vapor deposition, plating, or other methods, it is preferable to use metal foil from the viewpoint of adhesiveness. Copper foil is particularly preferred in terms of conductivity. The copper foil may be either an electrolytic copper foil or a rolled copper foil. In addition, when the metal-clad laminate of this embodiment is continuously produced, a long metal foil having a predetermined thickness is wound into a roll as the metal foil.
以下、金属張積層板の好ましい実施の形態として、銅層を有する銅張積層板を挙げて、説明する。 Hereinafter, a copper-clad laminate having a copper layer will be cited and described as a preferred embodiment of the metal-clad laminate.
＜銅張積層板＞
本実施の形態の銅張積層板は、絶縁層と、該絶縁層の少なくとも一方の面に銅箔等の銅層を備えていればよい。また、絶縁層と銅層の接着性を高めるために、絶縁層における銅層に接する層が、熱可塑性ポリイミド層である。銅層は、絶縁層の片面又は両面に設けられている。つまり、本実施の形態の銅張積層板は、片面銅張積層板（片面ＣＣＬ）でもよいし、両面銅張積層板（両面ＣＣＬ）でもよい。片面ＣＣＬの場合、絶縁層の片面に積層された銅層を、本発明における「第１の銅層」とする。両面ＣＣＬの場合、絶縁層の片面に積層された銅層を、本発明における「第１の銅層」とし、絶縁層において、第１の銅層が積層された面とは反対側の面に積層された銅層を、本発明における「第２の銅層」とする。本実施の形態の銅張積層板は、銅層をエッチングするなどして配線回路加工して銅配線を形成し、ＦＰＣとして使用される。
<Copper-clad laminate>
The copper-clad laminate of this embodiment may include an insulating layer and a copper layer such as copper foil on at least one surface of the insulating layer. Furthermore, in order to improve the adhesion between the insulating layer and the copper layer, the layer in the insulating layer that is in contact with the copper layer is a thermoplastic polyimide layer. The copper layer is provided on one or both sides of the insulating layer. That is, the copper-clad laminate of this embodiment may be a single-sided copper-clad laminate (single-sided CCL) or a double-sided copper-clad laminate (double-sided CCL). In the case of a single-sided CCL, the copper layer laminated on one side of the insulating layer is referred to as the "first copper layer" in the present invention. In the case of a double-sided CCL, the copper layer laminated on one side of the insulating layer is referred to as the "first copper layer" in the present invention, and the insulating layer has a copper layer laminated on the side opposite to the side on which the first copper layer is laminated. The laminated copper layer is referred to as a "second copper layer" in the present invention. The copper-clad laminate of this embodiment is used as an FPC by processing a wiring circuit by etching the copper layer to form copper wiring.
銅張積層板は、例えば樹脂フィルムを用意し、これに金属をスパッタリングしてシード層を形成した後、例えば銅メッキによって銅層を形成することによって調製してもよい。 A copper-clad laminate may be prepared, for example, by preparing a resin film, sputtering metal onto it to form a seed layer, and then forming a copper layer by, for example, copper plating.
また、銅張積層板は、樹脂フィルムを用意し、これに銅箔を熱圧着などの方法でラミネートすることによって調製してもよい。 Further, the copper-clad laminate may be prepared by preparing a resin film and laminating copper foil thereon by a method such as thermocompression bonding.
さらに、銅張積層板は、銅箔の上にポリイミドの前駆体であるポリアミド酸を含有する塗布液をキャストし、乾燥して塗布膜とした後、熱処理してイミド化し、ポリイミド層を形成することによって調製してもよい。 Furthermore, copper-clad laminates are produced by casting a coating solution containing polyamic acid, which is a precursor of polyimide, onto copper foil, drying it to form a coating film, and then heat-treating it to imidize it to form a polyimide layer. It may be prepared by
（第１の銅層）
本実施の形態の銅張積層板において、第１の銅層に使用される銅箔（以下、「第１の銅箔」と記すことがある）は、特に限定されるものではなく、例えば、圧延銅箔でも電解銅箔でもよい。
(first copper layer)
In the copper-clad laminate of this embodiment, the copper foil used for the first copper layer (hereinafter sometimes referred to as "first copper foil") is not particularly limited, and for example, It may be rolled copper foil or electrolytic copper foil.
第１の銅箔の厚みは、好ましくは１３μｍ以下であり、より好ましくは６～１２μｍの範囲内がよい。第１の銅箔の厚みが１３μｍを超えると、銅張積層板（又はＦＰＣ）を折り曲げた際の銅層（又は銅配線）に加わる曲げ応力が大きくなることにより耐折り曲げ性が低下することとなる。また、生産安定性及びハンドリング性の観点から、第１の銅箔の厚みの下限値は６μｍとすることが好ましい。 The thickness of the first copper foil is preferably 13 μm or less, more preferably within the range of 6 to 12 μm. If the thickness of the first copper foil exceeds 13 μm, the bending stress applied to the copper layer (or copper wiring) when the copper-clad laminate (or FPC) is bent increases, resulting in a decrease in bending resistance. Become. Moreover, from the viewpoint of production stability and handling property, it is preferable that the lower limit of the thickness of the first copper foil is 6 μm.
また、第１の銅箔の引張弾性率は、例えば、１０～３５ＧＰａの範囲内であることが好ましく、１５～２５ＧＰａの範囲内がより好ましい。本実施の形態で第１の銅箔として圧延銅箔を使用する場合は、熱処理によってアニールされると、柔軟性が高くなりやすい。従って、銅箔の引張弾性率が上記下限値に満たないと、長尺な第１の銅箔上に絶縁層を形成する工程において、加熱によって第１の銅箔自体の剛性が低下してしまう。一方、引張弾性率が上記上限値を超えるとＦＰＣを折り曲げた際に銅配線により大きな曲げ応力が加わることとなり、その耐折り曲げ性が低下する。なお、圧延銅箔は、銅箔上に絶縁層を形成する際の熱処理条件や、絶縁層を形成した後の銅箔のアニール処理などにより、その引張弾性率が変化する傾向がある。従って、本実施の形態では、最終的に得られた銅張積層板において、第１の銅箔の引張弾性率が上記範囲内にあればよい。 Further, the tensile modulus of the first copper foil is preferably within the range of 10 to 35 GPa, and more preferably within the range of 15 to 25 GPa, for example. When a rolled copper foil is used as the first copper foil in this embodiment, flexibility tends to increase when it is annealed by heat treatment. Therefore, if the tensile modulus of the copper foil is less than the above lower limit, the rigidity of the first copper foil itself will decrease due to heating in the step of forming an insulating layer on the long first copper foil. . On the other hand, if the tensile modulus exceeds the above upper limit, a greater bending stress will be applied to the copper wiring when the FPC is bent, resulting in a decrease in its bending resistance. Note that the tensile modulus of rolled copper foil tends to change depending on heat treatment conditions when forming an insulating layer on the copper foil, annealing treatment of the copper foil after forming the insulating layer, and the like. Therefore, in this embodiment, it is sufficient that the tensile modulus of the first copper foil is within the above range in the copper-clad laminate finally obtained.
第１の銅箔は、特に限定されるものではなく、市販されている圧延銅箔を用いることができる。 The first copper foil is not particularly limited, and commercially available rolled copper foil can be used.
（第２の銅層）
第２の銅層は、絶縁層における第１の銅層とは反対側の面に積層されている。第２の銅層に使用される銅箔（第２の銅箔）としては、特に限定されるものではなく、例えば、圧延銅箔でも電解銅箔でもよい。また、第２の銅箔として、市販されている銅箔を用いることもできる。なお、第２の銅箔として、第１の銅箔と同じものを使用してもよい。
(Second copper layer)
The second copper layer is laminated on the surface of the insulating layer opposite to the first copper layer. The copper foil (second copper foil) used for the second copper layer is not particularly limited, and may be, for example, rolled copper foil or electrolytic copper foil. Moreover, a commercially available copper foil can also be used as the second copper foil. Note that the second copper foil may be the same as the first copper foil.
＜回路基板＞
本実施の形態の金属張積層板は、主にＦＰＣ等の回路基板の材料として有用である。例えば、上記に例示の銅張積層板の銅層を常法によってパターン状に加工して配線層を形成することによって、本発明の一実施の形態であるＦＰＣ等の回路基板を製造できる。
<Circuit board>
The metal-clad laminate of this embodiment is mainly useful as a material for circuit boards such as FPCs. For example, a circuit board such as an FPC, which is an embodiment of the present invention, can be manufactured by processing the copper layer of the above-exemplified copper-clad laminate into a pattern by a conventional method to form a wiring layer.
以下に実施例を示し、本発明の特徴をより具体的に説明する。ただし、本発明の範囲は、実施例に限定されない。なお、以下の実施例において、特にことわりのない限り各種測定、評価は下記によるものである。 Examples are shown below to explain the features of the present invention more specifically. However, the scope of the present invention is not limited to the examples. In addition, in the following examples, various measurements and evaluations are as follows unless otherwise specified.
［粘度の測定］
粘度の測定は、Ｅ型粘度計（ブルックフィールド社製、商品名；ＤＶ－ＩＩ＋Ｐｒｏ）を用いて、２５℃における粘度を測定した。トルクが１０％～９０％になるよう回転数を設定し、測定を開始してから２分経過後、粘度が安定した時の値を読み取った。
[Measurement of viscosity]
The viscosity was measured at 25° C. using an E-type viscometer (manufactured by Brookfield, trade name: DV-II+Pro). The rotational speed was set so that the torque was 10% to 90%, and the value was read when the viscosity stabilized 2 minutes after starting the measurement.
［ガラス転移温度（Ｔｇ）の測定］
ガラス転移温度は、５ｍｍ×２０ｍｍのサイズのポリイミドフィルムを、動的粘弾性測定装置（ＤＭＡ：ユー・ビー・エム社製、商品名；Ｅ４０００Ｆ）を用いて、３０℃から４００℃まで昇温速度４℃／分、周波数１１Ｈｚで測定を行い、弾性率変化（ｔａｎδ）が最大となる温度をガラス転移温度とした。なお、ＤＭＡを用いて測定された３０℃における貯蔵弾性率が１．０×１０９Ｐａ以上であり、３６０℃における貯蔵弾性率が１．０×１０８Ｐａ未満を示すものを「熱可塑性」とし、３０℃における貯蔵弾性率が１．０×１０９Ｐａ以上であり、３６０℃における貯蔵弾性率が１．０×１０８Ｐａ以上を示すものを「非熱可塑性」とした。
[Measurement of glass transition temperature (Tg)]
The glass transition temperature was determined by heating a polyimide film with a size of 5 mm x 20 mm from 30°C to 400°C using a dynamic viscoelasticity analyzer (DMA: manufactured by UBM, trade name: E4000F). Measurement was performed at 4° C./min and a frequency of 11 Hz, and the temperature at which the change in elastic modulus (tan δ) was maximum was defined as the glass transition temperature. In addition, "thermoplastic" means that the storage elastic modulus at 30° C. measured using DMA is 1.0×10 9 Pa or more, and the storage elastic modulus at 360° C. is less than 1.0×10 8 Pa. Those exhibiting a storage modulus of 1.0×10 9 Pa or more at 30° C. and a storage modulus of 1.0×10 8 Pa or more at 360° C. were defined as “non-thermoplastic.”
［熱膨張係数（ＣＴＥ）の測定］
３ｍｍ×２０ｍｍのサイズのポリイミドフィルムを、サーモメカニカルアナライザー（Ｂｒｕｋｅｒ社製、商品名；４０００ＳＡ）を用い、５．０ｇの荷重を加えながら一定の昇温速度で３０℃から２６５℃まで昇温させ、更にその温度で１０分保持した後、５℃／分の速度で冷却し、２５０℃から１００℃までの平均熱膨張係数（熱膨張係数）を求めた。
[Measurement of coefficient of thermal expansion (CTE)]
A polyimide film with a size of 3 mm x 20 mm was heated from 30° C. to 265° C. at a constant heating rate while applying a load of 5.0 g using a thermomechanical analyzer (manufactured by Bruker, trade name: 4000SA). After further holding at that temperature for 10 minutes, it was cooled at a rate of 5°C/min, and the average coefficient of thermal expansion (coefficient of thermal expansion) from 250°C to 100°C was determined.
［面内リタデーション（ＲＯ）の測定］
複屈折率計（フォトニックラティス社製、商品名；ワイドレンジ複屈折評価システムＷＰＡ－１００、測定エリア；ＭＤ：１４０ｍｍ×ＴＤ：１００ｍｍ）を用いて、所定のサンプルの面内方向のリタデーションを求めた。なお、入射角は、０°、測定波長は、５４３ｎｍである。
[Measurement of in-plane retardation (RO)]
Using a birefringence meter (manufactured by Photonic Lattice, trade name: Wide Range Birefringence Evaluation System WPA-100, measurement area: MD: 140 mm x TD: 100 mm), determine the in-plane retardation of a given sample. Ta. Note that the incident angle is 0° and the measurement wavelength is 543 nm.
［面内リタデーション（ＲＯ）の評価用サンプルの調製］
長尺状の金属張積層板の金属層をエッチングして得られたポリイミドフィルムにおけるＴＤ方向の左右２つの端部（Ｌｅｆｔ及びＲｉｇｈｔ）並びに中央部（Ｃｅｎｔｅｒ）のそれぞれにおいて、Ａ４サイズ（ＴＤ：２１０ｍｍ×ＭＤ：２９７ｍｍ）に切断し、サンプルＬ（Ｌｅｆｔ）、サンプルＲ（Ｒｉｇｈｔ）及びサンプルＣ（Ｃｅｎｔｅｒ）を調製した。
[Preparation of sample for evaluation of in-plane retardation (RO)]
In each of the two left and right ends (Left and Right) and the center (Center) in the TD direction of a polyimide film obtained by etching the metal layer of a long metal-clad laminate, A4 size (TD: 210 mm) x MD: 297 mm) to prepare sample L (Left), sample R (Right), and sample C (Center).
［面内複屈折率（Δｎ）の評価］
サンプルＬ、サンプルＲ及びサンプルＣのそれぞれについて面内リタデーション（ＲＯ）をそれぞれ測定した。各サンプルの測定値の最大値を評価用サンプルの厚さで除した値を「面内複屈折率（Δｎ）」とし、面内リタデーション（ＲＯ）の測定値における最大値と最小値の差を「幅方向（ＴＤ方向）の面内リタデーション（ＲＯ）のばらつき（ΔＲＯ）」とし、このΔＲＯを評価用サンプルの厚さで除した値を「幅方向（ＴＤ方向）の面内複屈折率（Δｎ）のばらつき［Δ（Δｎ）］」とした。
[Evaluation of in-plane birefringence (Δn)]
In-plane retardation (RO) was measured for each of Sample L, Sample R, and Sample C. The value obtained by dividing the maximum measured value of each sample by the thickness of the evaluation sample is defined as the "in-plane birefringence (Δn)", and the difference between the maximum and minimum values of the measured in-plane retardation (RO) is defined as the "in-plane birefringence (Δn)". The variation in in-plane retardation (RO) in the width direction (TD direction) (ΔRO) is defined as the value obtained by dividing this ΔRO by the thickness of the evaluation sample. Δn) variation [Δ(Δn)]”.
［厚さ方向のリタデーション及び複屈折率の測定］
絶縁樹脂層としてのポリイミド層について、ウルトラミクロトームによる厚さ０．５μｍの薄膜切片作製を実施し、厚さ方向のリタデーション測定を実施した。この際、複屈折率計（フォトニックラティス社製、商品名；顕微鏡取付用複屈折分布観察カメラＰＩ－ｍｉｃｒｏ）を用いた。なお、測定波長は５２０ｎｍ、入射角は ０ °である。
ＲＯａとは、ポリイミド層（フィルム）における非熱可塑性ポリイミド層の一方の面を基点とする中央部方向に１．５μｍの点におけるリタデーションの値である。
ＲＯｂとは、ポリイミド層（フィルム）における非熱可塑性ポリイミド層の他方の面を基点とする中央部方向に１．５μｍの点におけるリタデーションの値である。
ＲＯｖとは、ＲＯａ、ＲＯｂ、及び、ポリイミド層（フィルム）における非熱可塑性ポリイミド層の厚さ方向の中央部におけるリタデーションの値（ＲＯｃ）の合計（ＲＯａ＋ＲＯｂ＋ＲＯｃ）の平均値である。
また、ＲＯａの値を薄膜切片の厚さ（０．５μｍ）で除した値を「非熱可塑性ポリイミド層の厚さ方向において、一方の面を基点とする中央部方向に１．５μｍの点における複屈折率（Δｎａ）」とし、ＲＯｂの値を薄膜切片の厚さ（０．５μｍ）で除した値を「非熱可塑性ポリイミド層の厚さ方向において、他方の面を基点とする中央部方向に１．５μｍの点における複屈折率（Δｎｂ）」とし、ＲＯｃの値を薄膜切片の厚さ（０．５μｍ）で除した値を「非熱可塑性ポリイミド層の厚さ方向の中央部における複屈折率（Δｎｃ）」とした。
Δｎｖは、Δｎａ、Δｎｂ及びΔｎｃの合計（Δｎａ＋Δｎｂ＋Δｎｃ）の平均値である。
[Measurement of retardation and birefringence in the thickness direction]
Regarding the polyimide layer as an insulating resin layer, a thin film section with a thickness of 0.5 μm was prepared using an ultramicrotome, and retardation in the thickness direction was measured. At this time, a birefringence meter (manufactured by Photonic Lattice, trade name: PI-micro, a birefringence distribution observation camera for attaching to a microscope) was used. Note that the measurement wavelength was 520 nm and the incident angle was 0°.
ROa is the value of retardation at a point of 1.5 μm in the direction of the center of the polyimide layer (film) from one surface of the non-thermoplastic polyimide layer.
ROb is the value of retardation at a point of 1.5 μm in the direction of the center of the polyimide layer (film) from the other surface of the non-thermoplastic polyimide layer.
ROv is the average value of ROa, ROb, and the sum (ROa+ROb+ROc) of the retardation value (ROc) at the center in the thickness direction of the non-thermoplastic polyimide layer in the polyimide layer (film).
In addition, the value obtained by dividing the value of ROa by the thickness of the thin film section (0.5 μm) is calculated as follows: Birefringence (Δna)", and the value obtained by dividing the value of ROb by the thickness of the thin film section (0.5 μm) is defined as "birefringence index (Δna)", and the value obtained by dividing the value of ROb by the thickness of the thin film section (0.5 μm) is "in the thickness direction of the non-thermoplastic polyimide layer, in the direction of the center part from the other surface as the base point. The birefringence (Δnb) at a point of 1.5 μm in the thickness direction of the non-thermoplastic polyimide layer is calculated by dividing the ROc value by the thickness of the thin film section (0.5 μm). refractive index (Δnc).
Δnv is the average value of the sum of Δna, Δnb, and Δnc (Δna+Δnb+Δnc).
［反りの測定］
５０ｍｍ×５０ｍｍのサイズのポリイミドフィルムを、２３℃、５０％ＲＨ下で２４時間調湿後、カールしている方向を上面とし、平滑な台上に設置した。その際のカール量についてノギスを用いて測定を行った。この際、フィルムが基材エッチング面側にカールした場合をプラス表記、反対面にカールした場合をマイナス表記とし、フィルムの４角の測定値の平均をカール量とした。
[Measurement of warpage]
A polyimide film with a size of 50 mm x 50 mm was conditioned for 24 hours at 23° C. and 50% RH, and then placed on a smooth table with the curled direction facing up. The amount of curl at that time was measured using calipers. At this time, the case where the film curled toward the etched surface of the base material was indicated as a plus, the case where the film curled on the opposite side was indicated as a minus, and the average of the measured values of the four corners of the film was defined as the amount of curl.
［ピール強度の測定］
片面銅張積層板（銅箔／樹脂層）の銅箔を幅１．０ｍｍに回路加工した後、幅；８ｃｍ×長さ；４ｃｍに切断し、測定サンプルを調製した。テンシロンテスター（東洋精機製作所製、商品名；ストログラフＶＥ－１Ｄ）を用いて、測定サンプルの樹脂層側を両面テープによりアルミ板に固定し、銅箔を９０°方向に５０ｍｍ／分の速度で、銅箔を樹脂層から１０ｍｍ剥離したときの中央強度を求めた。
[Measurement of peel strength]
A copper foil of a single-sided copper-clad laminate (copper foil/resin layer) was circuit-processed to a width of 1.0 mm, and then cut to a width of 8 cm x length of 4 cm to prepare a measurement sample. Using a Tensilon tester (manufactured by Toyo Seiki Seisakusho, product name: Strograph VE-1D), the resin layer side of the measurement sample was fixed to an aluminum plate with double-sided tape, and the copper foil was fixed in a 90° direction at a speed of 50 mm/min. , the central strength was determined when the copper foil was peeled off by 10 mm from the resin layer.
実施例及び比較例に用いた略号は、以下の化合物を示す。
ＰＭＤＡ：ピロメリット酸二無水物
ＢＰＤＡ：３,３',４,４'‐ビフェニルテトラカルボン酸二無水物
ｍ‐ＴＢ：２,２'‐ジメチル‐４,４'‐ジアミノビフェニル
ＴＰＥ－Ｒ：１,３-ビス（４‐アミノフェノキシ）ベンゼン
ＤＡＰＥ：４,４'-ジアミノジフェニルエーテル
ＢＡＰＰ：２，２－ビス［４－（４－アミノフェノキシ）フェニル］プロパン
ｐ‐ＰＤＡ：ｐ－フェニレンジアミン
ＤＭＡｃ：Ｎ,Ｎ‐ジメチルアセトアミド
Abbreviations used in Examples and Comparative Examples indicate the following compounds.
PMDA: Pyromellitic dianhydride BPDA: 3,3',4,4'-biphenyltetracarboxylic dianhydride m-TB: 2,2'-dimethyl-4,4'-diaminobiphenyl TPE-R: 1 ,3-bis(4-aminophenoxy)benzene DAPE: 4,4'-diaminodiphenyl ether BAPP: 2,2-bis[4-(4-aminophenoxy)phenyl]propane p-PDA: p-phenylenediamine DMAc: N ,N-dimethylacetamide
（合成例１）
窒素気流下で、反応槽に、２３．０重量部のｍ－ＴＢ（０．１０８モル部）及び３．５重量部のＴＰＥ－Ｒ（０．０１２モル部）並びに重合後の固形分濃度が１５重量％となる量のＤＭＡｃを投入し、室温で撹拌して溶解させた。次に、２６．０重量部のＰＭＤＡ（０．１１９モル部）を添加した後、室温で３時間撹拌を続けて重合反応を行い、ポリアミド酸溶液ａを得た。ポリアミド酸溶液ａの溶液粘度は４１，１００ｃｐｓであった。このポリアミド酸溶液ａから得られたポリイミドのガラス転移温度は４２１℃で、非熱可塑性、熱膨張係数は１０（ｐｐｍ／Ｋ）であった。
(Synthesis example 1)
Under a nitrogen stream, 23.0 parts by weight of m-TB (0.108 mol parts) and 3.5 parts by weight of TPE-R (0.012 mol parts) and the solid content concentration after polymerization were added to the reaction tank. DMAc in an amount of 15% by weight was added and dissolved by stirring at room temperature. Next, after adding 26.0 parts by weight of PMDA (0.119 parts by mole), stirring was continued for 3 hours at room temperature to carry out a polymerization reaction to obtain polyamic acid solution a. The solution viscosity of polyamic acid solution a was 41,100 cps. The polyimide obtained from this polyamic acid solution a had a glass transition temperature of 421° C., was non-thermoplastic, and had a coefficient of thermal expansion of 10 (ppm/K).
（合成例２）
窒素気流下で、反応槽に、１７．３重量部のｍ－ＴＢ（０．０８１モル部）及び１０．２重量部のＴＰＥ－Ｒ（０．０３５モル部）並びに重合後の固形分濃度が１５重量％となる量のＤＭＡｃを投入し、室温で撹拌して溶解させた。次に、２５．１重量部のＰＭＤＡ（０．１１５モル部）を添加した後、室温で３時間撹拌を続けて重合反応を行い、ポリアミド酸溶液ｂを得た。ポリアミド酸溶液ｂの溶液粘度は３８，２００ｃｐｓであった。このポリアミド酸溶液ｂから得られたポリイミドのガラス転移温度は４２７℃で、非熱可塑性、熱膨張係数は２２（ｐｐｍ／Ｋ）であった。
(Synthesis example 2)
Under a nitrogen stream, 17.3 parts by weight of m-TB (0.081 mol part) and 10.2 parts by weight of TPE-R (0.035 mol part) and the solid content concentration after polymerization were added to the reaction tank. DMAc in an amount of 15% by weight was added and dissolved by stirring at room temperature. Next, after adding 25.1 parts by weight of PMDA (0.115 parts by mole), stirring was continued for 3 hours at room temperature to carry out a polymerization reaction to obtain polyamic acid solution b. The solution viscosity of polyamic acid solution b was 38,200 cps. The polyimide obtained from this polyamic acid solution b had a glass transition temperature of 427° C., was non-thermoplastic, and had a coefficient of thermal expansion of 22 (ppm/K).
（合成例３）
窒素気流下で、反応槽に、１６．４重量部のｍ－ＴＢ（０．０７７モル部）及び９．７重量部のＴＰＥ－Ｒ（０．０３３モル部）並びに重合後の固形分濃度が１５重量％となる量のＤＭＡｃを投入し、室温で撹拌して溶解させた。次に、１６．７重量部のＰＭＤＡ（０．０７７モル部）及び９．７重量部のＢＰＤＡ（０．０３３モル部）を添加した後、室温で３時間撹拌を続けて重合反応を行い、ポリアミド酸溶液ｃを得た。ポリアミド酸溶液ｃの溶液粘度は４６，７００ｃｐｓであった。このポリアミド酸溶液ｃから得られたポリイミドのガラス転移温度は３６６℃で、非熱可塑性、熱膨張係数は２３（ｐｐｍ／Ｋ）であった。
(Synthesis example 3)
Under a nitrogen stream, 16.4 parts by weight of m-TB (0.077 mol parts) and 9.7 parts by weight of TPE-R (0.033 mol parts) and the solid content concentration after polymerization were added to the reaction tank. DMAc in an amount of 15% by weight was added and dissolved by stirring at room temperature. Next, after adding 16.7 parts by weight of PMDA (0.077 mol parts) and 9.7 parts by weight of BPDA (0.033 mol parts), stirring was continued for 3 hours at room temperature to carry out a polymerization reaction. A polyamic acid solution c was obtained. The solution viscosity of polyamic acid solution c was 46,700 cps. The polyimide obtained from this polyamic acid solution c had a glass transition temperature of 366°C, was non-thermoplastic, and had a coefficient of thermal expansion of 23 (ppm/K).
（合成例４）
窒素気流下で、反応槽に、２２．４重量部のｍ－ＴＢ（０．１０５モル部）及び４．８重量部のＢＡＰＰ（０．０１２モル部）並びに重合後の固形分濃度が１５重量％となる量のＤＭＡｃを投入し、室温で撹拌して溶解させた。次に、２５．３重量部のＰＭＤＡ（０．１１６モル部）を添加した後、室温で３時間撹拌を続けて重合反応を行い、ポリアミド酸溶液ｄを得た。ポリアミド酸溶液ｄの溶液粘度は３６，８００ｃｐｓであった。このポリアミド酸溶液ｄから得られたポリイミドのガラス転移温度は４０８℃で、非熱可塑性、熱膨張係数は９（ｐｐｍ／Ｋ）であった。
(Synthesis example 4)
Under a nitrogen stream, 22.4 parts by weight of m-TB (0.105 mol parts) and 4.8 parts by weight of BAPP (0.012 mol parts) and a solid content concentration of 15 parts by weight after polymerization were added to the reaction tank. % of DMAc was added and dissolved by stirring at room temperature. Next, after adding 25.3 parts by weight of PMDA (0.116 parts by mole), stirring was continued for 3 hours at room temperature to carry out a polymerization reaction to obtain a polyamic acid solution d. The solution viscosity of polyamic acid solution d was 36,800 cps. The polyimide obtained from this polyamic acid solution d had a glass transition temperature of 408° C., was non-thermoplastic, and had a coefficient of thermal expansion of 9 (ppm/K).
（合成例５）
窒素気流下で、反応槽に、１２．３重量部のｍ－ＴＢ（０．０５８モル部）、１０．１重量部のＴＰＥ－Ｒ（０．０３５モル部）及び２．５重量部のｐ－ＰＤＡ（０．０２３モル部）並びに重合後の固形分濃度が１５重量％となる量のＤＭＡｃを投入し、室温で撹拌して溶解させた。次に、１７．５重量部のＰＭＤＡ（０．０８０モル部）及び１０．１重量部のＢＰＤＡ（０．０３４モル部）を添加した後、室温で３時間撹拌を続けて重合反応を行い、ポリアミド酸溶液ｅを得た。ポリアミド酸溶液ｅの溶液粘度は４２，７００ｃｐｓであった。このポリアミド酸溶液ｅから得られたポリイミドのガラス転移温度は３６０℃で、非熱可塑性、熱膨張係数は１８（ｐｐｍ／Ｋ）であった。
(Synthesis example 5)
Under a nitrogen stream, 12.3 parts by weight of m-TB (0.058 mol parts), 10.1 parts by weight of TPE-R (0.035 mol parts) and 2.5 parts by weight of p were added to the reaction tank. -PDA (0.023 mol part) and DMAc in an amount such that the solid content concentration after polymerization was 15% by weight were added, and dissolved by stirring at room temperature. Next, after adding 17.5 parts by weight of PMDA (0.080 mol parts) and 10.1 parts by weight of BPDA (0.034 mol parts), stirring was continued for 3 hours at room temperature to carry out a polymerization reaction. A polyamic acid solution e was obtained. The solution viscosity of polyamic acid solution e was 42,700 cps. The polyimide obtained from this polyamic acid solution e had a glass transition temperature of 360° C., was non-thermoplastic, and had a coefficient of thermal expansion of 18 (ppm/K).
（合成例６）
窒素気流下で、反応槽に、２．２重量部のｍ－ＴＢ（０．０１０モル部）及び２７．６重量部のＴＰＥ－Ｒ（０．０９４モル部）並びに重合後の固形分濃度が１５重量％となる量のＤＭＡｃを投入し、室温で撹拌して溶解させた。次に、２２．７重量部のＰＭＤＡ（０．１０４モル部）を添加した後、室温で３時間撹拌を続けて重合反応を行い、ポリアミド酸溶液ｆを得た。ポリアミド酸溶液ｆの溶液粘度は３３，９００ｃｐｓであった。このポリアミド酸溶液ｆから得られたポリイミドのガラス転移温度は４４６℃で、熱可塑性、熱膨張係数は５５（ｐｐｍ／Ｋ）であった。
(Synthesis example 6)
Under a nitrogen stream, 2.2 parts by weight of m-TB (0.010 mol parts) and 27.6 parts by weight of TPE-R (0.094 mol parts) and the solid content concentration after polymerization were added to the reaction tank. DMAc in an amount of 15% by weight was added and dissolved by stirring at room temperature. Next, after adding 22.7 parts by weight of PMDA (0.104 parts by mole), stirring was continued for 3 hours at room temperature to carry out a polymerization reaction to obtain a polyamic acid solution f. The solution viscosity of polyamic acid solution f was 33,900 cps. The glass transition temperature of the polyimide obtained from this polyamic acid solution f was 446° C., and the thermoplasticity and thermal expansion coefficient were 55 (ppm/K).
（合成例７）
窒素気流下で、反応槽に、３０．２重量部のＢＡＰＰ（０．０７４モル部）及び重合後の固形分濃度が１５重量％となる量のＤＭＡｃを投入し、室温で撹拌して溶解させた。次に、２２．３重量部のＢＰＤＡ（０．０７６モル部）を添加した後、室温で３時間撹拌を続けて重合反応を行い、ポリアミド酸溶液ｇを得た。ポリアミド酸溶液ｇの溶液粘度は９，８００ｃｐｓであった。このポリアミド酸溶液ｇから得られたポリイミドのガラス転移温度は２５２℃で、熱可塑性、熱膨張係数は４６（ｐｐｍ／Ｋ）であった。
(Synthesis example 7)
Under a nitrogen stream, 30.2 parts by weight of BAPP (0.074 mol parts) and DMAc in an amount such that the solid content concentration after polymerization is 15% by weight were charged into a reaction tank, and dissolved by stirring at room temperature. Ta. Next, after adding 22.3 parts by weight of BPDA (0.076 parts by mole), stirring was continued for 3 hours at room temperature to carry out a polymerization reaction to obtain a polyamic acid solution g. The solution viscosity of polyamic acid solution g was 9,800 cps. The glass transition temperature of the polyimide obtained from this polyamic acid solution g was 252° C., and the thermoplasticity and thermal expansion coefficient were 46 (ppm/K).
（合成例８）
窒素気流下で、反応槽に、２５．８重量部のＴＰＥ－Ｒ（０．０８８モル部）及び重合後の固形分濃度が１５重量％となる量のＤＭＡｃを投入し、室温で撹拌して溶解させた。次に、２６．７重量部のＢＰＤＡ（０．０９１モル部）を添加した後、室温で３時間撹拌を続けて重合反応を行い、ポリアミド酸溶液ｈを得た。ポリアミド酸溶液ｈの溶液粘度は８，８００ｃｐｓであった。このポリアミド酸溶液ｈから得られたポリイミドのガラス転移温度は２４３℃で、熱可塑性、熱膨張係数は６５（ｐｐｍ／Ｋ）であった。
(Synthesis example 8)
Under a nitrogen stream, 25.8 parts by weight of TPE-R (0.088 mol part) and DMAc in an amount such that the solid content concentration after polymerization is 15% by weight were placed in a reaction tank, and the mixture was stirred at room temperature. Dissolved. Next, after adding 26.7 parts by weight of BPDA (0.091 parts by mole), stirring was continued for 3 hours at room temperature to carry out a polymerization reaction to obtain a polyamic acid solution h. The solution viscosity of polyamic acid solution h was 8,800 cps. The glass transition temperature of the polyimide obtained from this polyamic acid solution h was 243° C., and the thermoplasticity and thermal expansion coefficient were 65 (ppm/K).
（合成例９）
窒素気流下で、反応槽に、１７．６重量部のＴＰＥ－Ｒ（０．０６０モル部）及び１．６重量部のｐ－ＰＤＡ（０．０１５モル部）並びに重合後の固形分濃度が１５重量％となる量のＤＭＡｃを投入し、室温で撹拌して溶解させた。次に、２２．８重量部のＢＰＤＡ（０．０７７モル部）を添加した後、室温で３時間撹拌を続けて重合反応を行い、ポリアミド酸溶液ｉを得た。ポリアミド酸溶液ｉの溶液粘度は７，８００ｃｐｓであった。このポリアミド酸溶液ｉから得られたポリイミドのガラス転移温度は２３９℃で、熱可塑性、熱膨張係数は６５（ｐｐｍ／Ｋ）であった。
(Synthesis example 9)
Under a nitrogen stream, 17.6 parts by weight of TPE-R (0.060 mol parts) and 1.6 parts by weight of p-PDA (0.015 mol parts) and the solid content concentration after polymerization were added to the reaction tank. DMAc in an amount of 15% by weight was added and dissolved by stirring at room temperature. Next, after adding 22.8 parts by weight of BPDA (0.077 parts by mole), stirring was continued for 3 hours at room temperature to carry out a polymerization reaction to obtain polyamic acid solution i. The solution viscosity of polyamic acid solution i was 7,800 cps. The glass transition temperature of the polyimide obtained from this polyamic acid solution i was 239° C., and the thermoplasticity and thermal expansion coefficient were 65 (ppm/K).
（合成例１０）
窒素気流下で、反応槽に、１１．７重量部のＤＡＰＥ（０．０５８モル部）及び１１．４重量部のＴＰＥ－Ｒ（０．０３９モル部）並びに重合後の固形分濃度が１５重量％となる量のＤＭＡｃを投入し、室温で撹拌して溶解させた。次に、２９．５重量部のＢＰＤＡ（０．１００モル部）を添加した後、室温で３時間撹拌を続けて重合反応を行い、ポリアミド酸溶液ｊを得た。ポリアミド酸溶液ｊの溶液粘度は１１，２００ｃｐｓであった。このポリアミド酸溶液ｊから得られたポリイミドのガラス転移温度は２６５℃で、熱可塑性、熱膨張係数は５８（ｐｐｍ／Ｋ）であった。
(Synthesis example 10)
Under a nitrogen stream, 11.7 parts by weight of DAPE (0.058 mol parts), 11.4 parts by weight of TPE-R (0.039 mol parts) and a solid content concentration of 15 parts by weight after polymerization were added to the reaction tank. % of DMAc was added and dissolved by stirring at room temperature. Next, after adding 29.5 parts by weight of BPDA (0.100 parts by mole), stirring was continued for 3 hours at room temperature to carry out a polymerization reaction to obtain polyamic acid solution j. The solution viscosity of polyamic acid solution j was 11,200 cps. The polyimide obtained from this polyamic acid solution j had a glass transition temperature of 265°C, thermoplasticity, and a coefficient of thermal expansion of 58 (ppm/K).
［実施例１］
厚さ１２μｍで幅１，０８０ｍｍの長尺状の電解銅箔の片面に合成例７で調製したポリアミド酸溶液ｇを硬化後の厚みが２．５μｍとなるように均一に塗布した後（第１層目）、１２０℃で加熱乾燥し溶媒を除去した。その上に合成例１で調製したポリアミド酸溶液ａを硬化後の厚みが２０μｍとなるように均一に塗布した後（第２層目）、１２０℃で加熱乾燥し溶媒を除去した。更に、その上に合成例７で調製したポリアミド酸溶液ｇを硬化後の厚みが２．５μｍとなるように均一に塗布した後（第３層目）、１２０℃で加熱乾燥し溶媒を除去した。その後、１３０℃から３６０℃まで段階的な熱処理を行い、イミド化を完結して、片面銅張積層板を調製した。
[Example 1]
After uniformly applying the polyamic acid solution g prepared in Synthesis Example 7 on one side of a long electrolytic copper foil with a thickness of 12 μm and a width of 1,080 mm so that the thickness after curing would be 2.5 μm (first layer), and the solvent was removed by heating and drying at 120°C. The polyamic acid solution a prepared in Synthesis Example 1 was uniformly applied thereon so that the thickness after curing was 20 μm (second layer), and the solvent was removed by heating and drying at 120° C. Furthermore, the polyamic acid solution g prepared in Synthesis Example 7 was uniformly applied thereon so that the thickness after curing was 2.5 μm (third layer), and then the solvent was removed by heating and drying at 120°C. . Thereafter, stepwise heat treatment was performed from 130° C. to 360° C. to complete imidization, and a single-sided copper-clad laminate was prepared.
［実施例２～８および比較例１～３］
電解銅箔の片面にポリアミド酸の樹脂溶液を塗布後、加熱乾燥および段階的な熱処理を行い片面銅張積層板を調製するにあたり、第１層～第３層目に使用した樹脂ならびに厚みを、下記表１に記載した構成に変更したこと以外は、実施例１と同様にして片面銅張積層板を得た。
[Examples 2 to 8 and Comparative Examples 1 to 3]
After coating a resin solution of polyamic acid on one side of electrolytic copper foil, heat drying and stepwise heat treatment are performed to prepare a single-sided copper-clad laminate.The resin used for the first to third layers and the thickness are as follows: A single-sided copper-clad laminate was obtained in the same manner as in Example 1, except that the configuration was changed to the one shown in Table 1 below.
表１に、実施例１～８及び比較例1～３で得た片面銅張積層板の絶縁樹脂層における非熱可塑性ポリイミド層（Ａ）と熱可塑性ポリイミド層（Ｂ）との厚み比（非熱可塑性ポリイミド層（Ａ）／熱可塑性ポリイミド層（Ｂ））、面内リタデーション（ＲＯ）、幅方向（ＴＤ方向）の面内リタデーション（ＲＯ）のばらつき（ΔＲＯ）及び非熱可塑性ポリイミド層の厚さ方向におけるリタデーションの差（｜ＲＯａ－ＲＯｂ｜，｜ＲＯｖ－ＲＯａ｜，｜ＲＯｖ－ＲＯｂ｜）、反り量およびピール強度を示す。また、表２に、実施例１～８及び比較例1～３で得た片面銅張積層板の絶縁樹脂層における面内複屈折率（Δｎ）、幅方向（ＴＤ方向）の面内複屈折率（Δｎ）のばらつき［Δ（Δｎ）］及び非熱可塑性ポリイミド層の厚さ方向における複屈折率の差（｜Δｎａ－Δｎｂ｜，｜Δｎｖ－Δｎａ｜，｜Δｎｖ－Δｎｂ｜）を示す。 Table 1 shows the thickness ratio (non-thermoplastic polyimide layer Thermoplastic polyimide layer (A)/thermoplastic polyimide layer (B)), in-plane retardation (RO), variation in in-plane retardation (RO) in the width direction (TD direction) (ΔRO), and thickness of non-thermoplastic polyimide layer The difference in retardation in the horizontal direction (|ROa-ROb|, |ROv-ROa|, |ROv-ROb|), the amount of warpage, and the peel strength are shown. Table 2 also shows the in-plane birefringence (Δn) of the insulating resin layer of the single-sided copper-clad laminates obtained in Examples 1 to 8 and Comparative Examples 1 to 3, and the in-plane birefringence in the width direction (TD direction). The variation in index (Δn) [Δ(Δn)] and the difference in birefringence in the thickness direction of the non-thermoplastic polyimide layer (|Δna−Δnb|, |Δnv−Δna|, |Δnv−Δnb|) are shown.
＜ＩＣチップ実装性＞
実施例１～８および比較例１～３にて作製した片面銅張積層板の銅箔表面にドライフィルムをラミネートし、ドライフィルムレジストをパターニング後、そのパターンに沿って銅箔をエッチングして回路を形成し、回路基板を調製した。得られた回路基板の銅配線側に４００℃、０．５秒間のボンディング処理にてＩＣチップを実装したところ、実施例１～８については、銅配線とＩＣチップとの位置ずれはなく、不具合は発生しなかった。一方で、比較例１については、銅配線とＩＣチップとの位置ずれが発生し、比較例２および３については、銅配線とＩＣチップの位置ずれと回路基板の反りが発生し、実装に不具合が生じた。
<IC chip mountability>
A dry film was laminated on the copper foil surface of the single-sided copper-clad laminates prepared in Examples 1 to 8 and Comparative Examples 1 to 3. After patterning the dry film resist, the copper foil was etched along the pattern to form a circuit. A circuit board was prepared. When an IC chip was mounted on the copper wiring side of the obtained circuit board by bonding at 400°C for 0.5 seconds, in Examples 1 to 8, there was no misalignment between the copper wiring and the IC chip, and there was no problem. did not occur. On the other hand, in Comparative Example 1, misalignment occurred between the copper wiring and the IC chip, and in Comparative Examples 2 and 3, misalignment between the copper wiring and the IC chip and warping of the circuit board occurred, resulting in mounting problems. occurred.
以上、本発明の実施の形態を例示の目的で詳細に説明したが、本発明は上記実施の形態に制約されることはなく、種々の変形が可能である。
Although the embodiments of the present invention have been described above in detail for the purpose of illustration, the present invention is not limited to the above embodiments and can be modified in various ways.
Claims (7)
前記絶縁樹脂層が、非熱可塑性ポリイミドを含む非熱可塑性ポリイミド層の少なくとも一方の面に熱可塑性ポリイミドを含む熱可塑性ポリイミド層を有し、
前記非熱可塑性ポリイミド及び前記熱可塑性ポリイミドに含まれるテトラカルボン酸残基及びジアミン残基は、いずれも、芳香族テトラカルボン酸残基及び芳香族ジアミン残基であり、
前記非熱可塑性ポリイミドに含まれる全ジアミン残基の１００モル部に対して、下記の一般式（２）及び（３）から選ばれるジアミン残基の合計量が５～３０モル部の範囲内であり、
前記熱可塑性ポリイミドに含まれる全ジアミン残基の１００モル部に対して、下記の一般式（２）及び（３）から選ばれるジアミン残基の合計量が５０モル部以上であり、
前記絶縁樹脂層が下記の条件(i)～(iv);
(i)面内複屈折率（Δｎ）の値が２×１０－３以下であること；
(ii)幅方向（ＴＤ方向）の面内複屈折率（Δｎ）のばらつき［Δ（Δｎ）］が４×１０－４以下であること；
(iii) 前記非熱可塑性ポリイミド層の厚さ方向において、一方の面を基点とする中央部方向に１．５μｍの点における複屈折率（Δｎａ）と、他方の面を基点とする中央部方向に１．５μｍの点における複屈折率（Δｎｂ）との差（Δｎａ－Δｎｂ）が±０．０１以下であること；
(iv)前記Δｎａ及び前記Δｎｂ並びに厚さ方向の中央部における複屈折率（Δｎｃ）の合計（Δｎａ＋Δｎｂ＋Δｎｃ）の平均値（Δｎｖ）との差が、前記Δｎａ及びΔｎｂのいずれにおいても±０．０１以下であること；
を満たすことを特徴とする金属張積層板。 A metal-clad laminate comprising an insulating resin layer and a metal layer laminated on at least one side of the insulating resin layer,
The insulating resin layer has a thermoplastic polyimide layer containing thermoplastic polyimide on at least one surface of the non-thermoplastic polyimide layer containing non-thermoplastic polyimide,
The tetracarboxylic acid residue and diamine residue contained in the non-thermoplastic polyimide and the thermoplastic polyimide are both an aromatic tetracarboxylic acid residue and an aromatic diamine residue,
The total amount of diamine residues selected from the following general formulas (2) and (3) is within the range of 5 to 30 parts by mole relative to 100 parts by mole of all diamine residues contained in the non-thermoplastic polyimide. can be,
The total amount of diamine residues selected from the following general formulas (2) and (3) is 50 parts by mole or more with respect to 100 parts by mole of all diamine residues contained in the thermoplastic polyimide,
The insulating resin layer meets the following conditions (i) to (iv);
(i) The value of in-plane birefringence (Δn) is 2×10 −3 or less;
(ii) The variation in in-plane birefringence (Δn) in the width direction (TD direction) [Δ(Δn)] is 4×10 −4 or less;
(iii) In the thickness direction of the non-thermoplastic polyimide layer, the birefringence (Δna) at a point of 1.5 μm in the direction of the center from one surface and the direction of the center from the other surface. The difference (Δna−Δnb) from the birefringence index (Δnb) at a point of 1.5 μm is ±0.01 or less;
(iv) The difference from the average value (Δnv) of the sum (Δna+Δnb+Δnc) of the birefringence (Δnc) at the central portion in the thickness direction and the Δna and Δnb is ±0.01 for both Δna and Δnb. Must be less than or equal to;
A metal-clad laminate that satisfies the following requirements.
前記一般式（３）で表されるジアミン残基が、２，２－ビス［４－（４－アミノフェノキシ）フェニル］プロパンから誘導されるジアミン残基であることを特徴とする請求項１に記載の金属張積層板。 The diamine residue represented by the general formula (2) is a diamine residue derived from 1,3-bis(4-aminophenoxy)benzene,
Claim 1, wherein the diamine residue represented by the general formula (3) is a diamine residue derived from 2,2-bis[4-(4-aminophenoxy)phenyl]propane. The metal-clad laminate described.
A circuit board formed by processing the metal layer of the metal-clad laminate according to any one of claims 1 to 6 into wiring.
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