JP4590982B2 - Metal foil with resin - Google Patents
Metal foil with resin Download PDFInfo
- Publication number
- JP4590982B2 JP4590982B2 JP2004246600A JP2004246600A JP4590982B2 JP 4590982 B2 JP4590982 B2 JP 4590982B2 JP 2004246600 A JP2004246600 A JP 2004246600A JP 2004246600 A JP2004246600 A JP 2004246600A JP 4590982 B2 JP4590982 B2 JP 4590982B2
- Authority
- JP
- Japan
- Prior art keywords
- resin
- metal foil
- resin composition
- examples
- base material
- 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.)
- Expired - Lifetime
Links
- 229920005989 resin Polymers 0.000 title claims description 167
- 239000011347 resin Substances 0.000 title claims description 167
- 239000011888 foil Substances 0.000 title claims description 111
- 229910052751 metal Inorganic materials 0.000 title claims description 106
- 239000002184 metal Substances 0.000 title claims description 106
- 239000011342 resin composition Substances 0.000 claims description 69
- 239000000835 fiber Substances 0.000 claims description 42
- 239000000463 material Substances 0.000 claims description 35
- 239000000758 substrate Substances 0.000 claims description 33
- 229920005575 poly(amic acid) Polymers 0.000 claims description 17
- 229920001187 thermosetting polymer Polymers 0.000 claims description 15
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 claims description 10
- 125000003368 amide group Chemical group 0.000 claims description 9
- 238000010030 laminating Methods 0.000 claims description 9
- 239000004925 Acrylic resin Substances 0.000 claims description 8
- 229920000178 Acrylic resin Polymers 0.000 claims description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 46
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 36
- 239000011889 copper foil Substances 0.000 description 35
- 230000000052 comparative effect Effects 0.000 description 33
- -1 siloxane structure Chemical group 0.000 description 29
- 239000002966 varnish Substances 0.000 description 28
- 239000004962 Polyamide-imide Substances 0.000 description 20
- 150000001412 amines Chemical class 0.000 description 20
- 239000003822 epoxy resin Substances 0.000 description 20
- 229920002312 polyamide-imide Polymers 0.000 description 20
- 229920000647 polyepoxide Polymers 0.000 description 20
- 239000010410 layer Substances 0.000 description 16
- 238000000034 method Methods 0.000 description 16
- 238000012360 testing method Methods 0.000 description 15
- 238000004519 manufacturing process Methods 0.000 description 14
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 238000001035 drying Methods 0.000 description 12
- 239000011521 glass Substances 0.000 description 12
- 229910052802 copper Inorganic materials 0.000 description 11
- 239000010949 copper Substances 0.000 description 11
- 238000010438 heat treatment Methods 0.000 description 11
- 239000004744 fabric Substances 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 125000003118 aryl group Chemical group 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 9
- 229910000679 solder Inorganic materials 0.000 description 9
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 238000005530 etching Methods 0.000 description 8
- 238000011156 evaluation Methods 0.000 description 8
- 229910052698 phosphorus Inorganic materials 0.000 description 8
- 239000011574 phosphorus Substances 0.000 description 8
- 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 7
- 230000015572 biosynthetic process Effects 0.000 description 7
- 238000005259 measurement Methods 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- 150000004985 diamines Chemical class 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000005011 phenolic resin Substances 0.000 description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 6
- XUSNPFGLKGCWGN-UHFFFAOYSA-N 3-[4-(3-aminopropyl)piperazin-1-yl]propan-1-amine Chemical compound NCCCN1CCN(CCCN)CC1 XUSNPFGLKGCWGN-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 150000004984 aromatic diamines Chemical class 0.000 description 5
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 229920001721 polyimide Polymers 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 125000006158 tetracarboxylic acid group Chemical group 0.000 description 5
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 4
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Natural products C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 4
- 238000005470 impregnation Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000009719 polyimide resin Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000003825 pressing Methods 0.000 description 4
- 229920002545 silicone oil Polymers 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 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 description 3
- VQVIHDPBMFABCQ-UHFFFAOYSA-N 5-(1,3-dioxo-2-benzofuran-5-carbonyl)-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)=O)=C1 VQVIHDPBMFABCQ-UHFFFAOYSA-N 0.000 description 3
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 150000008065 acid anhydrides Chemical class 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 239000000428 dust Substances 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 3
- 150000002460 imidazoles Chemical class 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 150000002989 phenols Chemical class 0.000 description 3
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 2
- BVYPJEBKDLFIDL-UHFFFAOYSA-N 3-(2-phenylimidazol-1-yl)propanenitrile Chemical compound N#CCCN1C=CN=C1C1=CC=CC=C1 BVYPJEBKDLFIDL-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229910001128 Sn alloy Inorganic materials 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 230000005856 abnormality Effects 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 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
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 238000005452 bending Methods 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
- 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 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000002131 composite material Substances 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
- 125000005442 diisocyanate group Chemical group 0.000 description 2
- 125000001033 ether group Chemical group 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 239000002798 polar solvent Substances 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 230000035939 shock Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002759 woven fabric Substances 0.000 description 2
- PMTMAFAPLCGXGK-JMTMCXQRSA-N (15Z)-12-oxophyto-10,15-dienoic acid Chemical compound CC\C=C/C[C@H]1[C@@H](CCCCCCCC(O)=O)C=CC1=O PMTMAFAPLCGXGK-JMTMCXQRSA-N 0.000 description 1
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- SBJCUZQNHOLYMD-UHFFFAOYSA-N 1,5-Naphthalene diisocyanate Chemical class C1=CC=C2C(N=C=O)=CC=CC2=C1N=C=O SBJCUZQNHOLYMD-UHFFFAOYSA-N 0.000 description 1
- ATOUXIOKEJWULN-UHFFFAOYSA-N 1,6-diisocyanato-2,2,4-trimethylhexane Chemical compound O=C=NCCC(C)CC(C)(C)CN=C=O ATOUXIOKEJWULN-UHFFFAOYSA-N 0.000 description 1
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 description 1
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 1
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical class C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 1
- ZGDMDBHLKNQPSD-UHFFFAOYSA-N 2-amino-5-(4-amino-3-hydroxyphenyl)phenol Chemical compound C1=C(O)C(N)=CC=C1C1=CC=C(N)C(O)=C1 ZGDMDBHLKNQPSD-UHFFFAOYSA-N 0.000 description 1
- NEAQRZUHTPSBBM-UHFFFAOYSA-N 2-hydroxy-3,3-dimethyl-7-nitro-4h-isoquinolin-1-one Chemical compound C1=C([N+]([O-])=O)C=C2C(=O)N(O)C(C)(C)CC2=C1 NEAQRZUHTPSBBM-UHFFFAOYSA-N 0.000 description 1
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- LJGHYPLBDBRCRZ-UHFFFAOYSA-N 3-(3-aminophenyl)sulfonylaniline Chemical compound NC1=CC=CC(S(=O)(=O)C=2C=C(N)C=CC=2)=C1 LJGHYPLBDBRCRZ-UHFFFAOYSA-N 0.000 description 1
- LGZNZXOHAFRWEN-UHFFFAOYSA-N 3-[4-(2,5-dioxopyrrol-3-yl)triazin-5-yl]pyrrole-2,5-dione Chemical compound O=C1NC(=O)C(C=2C(=NN=NC=2)C=2C(NC(=O)C=2)=O)=C1 LGZNZXOHAFRWEN-UHFFFAOYSA-N 0.000 description 1
- WCXGOVYROJJXHA-UHFFFAOYSA-N 3-[4-[4-(3-aminophenoxy)phenyl]sulfonylphenoxy]aniline Chemical compound NC1=CC=CC(OC=2C=CC(=CC=2)S(=O)(=O)C=2C=CC(OC=3C=C(N)C=CC=3)=CC=2)=C1 WCXGOVYROJJXHA-UHFFFAOYSA-N 0.000 description 1
- 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
- FYYYKXFEKMGYLZ-UHFFFAOYSA-N 4-(1,3-dioxo-2-benzofuran-5-yl)-2-benzofuran-1,3-dione Chemical compound C=1C=C2C(=O)OC(=O)C2=CC=1C1=CC=CC2=C1C(=O)OC2=O FYYYKXFEKMGYLZ-UHFFFAOYSA-N 0.000 description 1
- XUBKCXMWPKLPPK-UHFFFAOYSA-N 4-(4-amino-2,6-dimethylphenyl)-3,5-dimethylaniline Chemical compound CC1=CC(N)=CC(C)=C1C1=C(C)C=C(N)C=C1C XUBKCXMWPKLPPK-UHFFFAOYSA-N 0.000 description 1
- QYIMZXITLDTULQ-UHFFFAOYSA-N 4-(4-amino-2-methylphenyl)-3-methylaniline Chemical compound CC1=CC(N)=CC=C1C1=CC=C(N)C=C1C QYIMZXITLDTULQ-UHFFFAOYSA-N 0.000 description 1
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 1
- WUPRYUDHUFLKFL-UHFFFAOYSA-N 4-[3-(4-aminophenoxy)phenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=CC(OC=2C=CC(N)=CC=2)=C1 WUPRYUDHUFLKFL-UHFFFAOYSA-N 0.000 description 1
- JCRRFJIVUPSNTA-UHFFFAOYSA-N 4-[4-(4-aminophenoxy)phenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC(C=C1)=CC=C1OC1=CC=C(N)C=C1 JCRRFJIVUPSNTA-UHFFFAOYSA-N 0.000 description 1
- HHLMWQDRYZAENA-UHFFFAOYSA-N 4-[4-[2-[4-(4-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropan-2-yl]phenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=C(C(C=2C=CC(OC=3C=CC(N)=CC=3)=CC=2)(C(F)(F)F)C(F)(F)F)C=C1 HHLMWQDRYZAENA-UHFFFAOYSA-N 0.000 description 1
- 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 1
- HYDATEKARGDBKU-UHFFFAOYSA-N 4-[4-[4-(4-aminophenoxy)phenyl]phenoxy]aniline Chemical group C1=CC(N)=CC=C1OC1=CC=C(C=2C=CC(OC=3C=CC(N)=CC=3)=CC=2)C=C1 HYDATEKARGDBKU-UHFFFAOYSA-N 0.000 description 1
- UTDAGHZGKXPRQI-UHFFFAOYSA-N 4-[4-[4-(4-aminophenoxy)phenyl]sulfonylphenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=C(S(=O)(=O)C=2C=CC(OC=3C=CC(N)=CC=3)=CC=2)C=C1 UTDAGHZGKXPRQI-UHFFFAOYSA-N 0.000 description 1
- PJCCVNKHRXIAHZ-UHFFFAOYSA-N 4-[4-[[4-(4-aminophenoxy)phenyl]methyl]phenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC(C=C1)=CC=C1CC(C=C1)=CC=C1OC1=CC=C(N)C=C1 PJCCVNKHRXIAHZ-UHFFFAOYSA-N 0.000 description 1
- NVKGJHAQGWCWDI-UHFFFAOYSA-N 4-[4-amino-2-(trifluoromethyl)phenyl]-3-(trifluoromethyl)aniline Chemical compound FC(F)(F)C1=CC(N)=CC=C1C1=CC=C(N)C=C1C(F)(F)F NVKGJHAQGWCWDI-UHFFFAOYSA-N 0.000 description 1
- FVCSARBUZVPSQF-UHFFFAOYSA-N 5-(2,4-dioxooxolan-3-yl)-7-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C(C(OC2=O)=O)C2C(C)=CC1C1C(=O)COC1=O FVCSARBUZVPSQF-UHFFFAOYSA-N 0.000 description 1
- ZHBXLZQQVCDGPA-UHFFFAOYSA-N 5-[(1,3-dioxo-2-benzofuran-5-yl)sulfonyl]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(S(=O)(=O)C=2C=C3C(=O)OC(C3=CC=2)=O)=C1 ZHBXLZQQVCDGPA-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- QWDDUEWLXJRCDZ-UHFFFAOYSA-N C(#N)C(C)C=1N=C(N(C=1)C)CC Chemical compound C(#N)C(C)C=1N=C(N(C=1)C)CC QWDDUEWLXJRCDZ-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000009261 D 400 Substances 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- SQSPRWMERUQXNE-UHFFFAOYSA-N Guanylurea Chemical compound NC(=N)NC(N)=O SQSPRWMERUQXNE-UHFFFAOYSA-N 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- SRTZTZLIWQQIQY-UHFFFAOYSA-N NC1=CC=C(OC2=CC=C(C=C2)C(C)(C)C2=CC=C(C=C2)OC2=CC=C(C=C2)N)C=C1.NC1=CC=C(C=C1)C1=CCC(C=C1)(C1=CC=CC=C1)N Chemical compound NC1=CC=C(OC2=CC=C(C=C2)C(C)(C)C2=CC=C(C=C2)OC2=CC=C(C=C2)N)C=C1.NC1=CC=C(C=C1)C1=CCC(C=C1)(C1=CC=CC=C1)N SRTZTZLIWQQIQY-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- PMTMAFAPLCGXGK-UHFFFAOYSA-N OPDA Natural products CCC=CCC1C(CCCCCCCC(O)=O)C=CC1=O PMTMAFAPLCGXGK-UHFFFAOYSA-N 0.000 description 1
- 101100028078 Oryza sativa subsp. japonica OPR1 gene Proteins 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 239000004696 Poly ether ether ketone Substances 0.000 description 1
- 239000004697 Polyetherimide Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 229920000388 Polyphosphate Polymers 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- ZITLPXUUDFVIFO-UHFFFAOYSA-N bis(3-aminophenyl)methanone;bis(4-aminophenyl)methanone Chemical compound C1=CC(N)=CC=C1C(=O)C1=CC=C(N)C=C1.NC1=CC=CC(C(=O)C=2C=C(N)C=CC=2)=C1 ZITLPXUUDFVIFO-UHFFFAOYSA-N 0.000 description 1
- LSDYQEILXDCDTR-UHFFFAOYSA-N bis[4-(4-aminophenoxy)phenyl]methanone Chemical compound C1=CC(N)=CC=C1OC1=CC=C(C(=O)C=2C=CC(OC=3C=CC(N)=CC=3)=CC=2)C=C1 LSDYQEILXDCDTR-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- FNXLCIKXHOPCKH-UHFFFAOYSA-N bromamine Chemical compound BrN FNXLCIKXHOPCKH-UHFFFAOYSA-N 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- QSAWQNUELGIYBC-UHFFFAOYSA-N cyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCCCC1C(O)=O QSAWQNUELGIYBC-UHFFFAOYSA-N 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 238000007772 electroless plating Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 150000002366 halogen compounds Chemical class 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012784 inorganic fiber Substances 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 125000006838 isophorone group Chemical group 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- LQBJWKCYZGMFEV-UHFFFAOYSA-N lead tin Chemical compound [Sn].[Pb] LQBJWKCYZGMFEV-UHFFFAOYSA-N 0.000 description 1
- 229940018564 m-phenylenediamine Drugs 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- XLSZMDLNRCVEIJ-UHFFFAOYSA-N methylimidazole Natural products CC1=CNC=N1 XLSZMDLNRCVEIJ-UHFFFAOYSA-N 0.000 description 1
- YTVNOVQHSGMMOV-UHFFFAOYSA-N naphthalenetetracarboxylic dianhydride Chemical compound C1=CC(C(=O)OC2=O)=C3C2=CC=C2C(=O)OC(=O)C1=C32 YTVNOVQHSGMMOV-UHFFFAOYSA-N 0.000 description 1
- 125000004957 naphthylene group Chemical group 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- CLDVQCMGOSGNIW-UHFFFAOYSA-N nickel tin Chemical compound [Ni].[Sn] CLDVQCMGOSGNIW-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- OFNHPGDEEMZPFG-UHFFFAOYSA-N phosphanylidynenickel Chemical compound [P].[Ni] OFNHPGDEEMZPFG-UHFFFAOYSA-N 0.000 description 1
- 238000000206 photolithography Methods 0.000 description 1
- 150000003022 phthalic acids Chemical class 0.000 description 1
- CLYVDMAATCIVBF-UHFFFAOYSA-N pigment red 224 Chemical compound C=12C3=CC=C(C(OC4=O)=O)C2=C4C=CC=1C1=CC=C2C(=O)OC(=O)C4=CC=C3C1=C42 CLYVDMAATCIVBF-UHFFFAOYSA-N 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003192 poly(bis maleimide) Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920002530 polyetherether ketone Polymers 0.000 description 1
- 229920001601 polyetherimide Polymers 0.000 description 1
- 229920001955 polyphenylene ether Polymers 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 150000007519 polyprotic acids Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 229920003987 resole Polymers 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical class CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical class CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 1
- 125000005628 tolylene group Chemical group 0.000 description 1
- MBYLVOKEDDQJDY-UHFFFAOYSA-N tris(2-aminoethyl)amine Chemical compound NCCN(CCN)CCN MBYLVOKEDDQJDY-UHFFFAOYSA-N 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
Landscapes
- Laminated Bodies (AREA)
Description
本発明は樹脂付き金属箔に関する。 The present invention relates to a resin-coated metal foil.
プリント配線板用積層板は、電気絶縁性樹脂組成物をマトリックスとするプリプレグと金属箔、または、プリプレグと樹脂付き金属箔を所定枚数重ね、加熱加圧して一体化したものである。プリント回路をサブトラクティブ法により形成する場合には、金属張積層板が用いられる。この金属張積層板は、プリプレグの表面（片面又は両面）に銅箔などの金属箔を重ねたり、プリプレグと樹脂付き金属箔を重ねて加熱加圧することにより製造される。また複数の回路層を備えた多層配線板では内層回路の上部にさらに第二の回路形成用の樹脂及び金属箔を積層し層間接続を施して回路加工することで製造する方法や絶縁性樹脂層を形成した後、無電解めっきと電気めっきにより上部回路層を形成することで製造する方法などがある。第二の回路形成用の樹脂及び金属箔を積層する方法としてはプリプレグと銅箔を同時に積層プレスする方法や銅箔の上にあらかじめ接着性を有する電気絶縁性樹脂層を設けた、いわゆる樹脂付き金属箔を積層する方法が行われている。電気絶縁性樹脂としては、フェノール樹脂、エポキシ樹脂、ポリイミド樹脂、ビスマレイミド−トリアジン樹脂などのような熱硬化性樹脂が汎用され、フッ素樹脂やポリフェニレンエーテル樹脂などのような熱可塑性樹脂が用いられることもある。 The laminate for a printed wiring board is obtained by stacking a predetermined number of prepregs and metal foils, or prepregs and metal foils with a resin, and integrating them by heating and pressing. When a printed circuit is formed by a subtractive method, a metal-clad laminate is used. This metal-clad laminate is manufactured by stacking a metal foil such as a copper foil on the surface (one side or both sides) of the prepreg, or by heating and pressing a prepreg and a metal foil with resin. In addition, in a multilayer wiring board having a plurality of circuit layers, an insulating resin layer or a method of manufacturing by laminating a resin and metal foil for forming a second circuit on the upper part of the inner layer circuit and performing circuit processing by providing interlayer connection And forming the upper circuit layer by electroless plating and electroplating. As a method of laminating the resin and metal foil for forming the second circuit, a method of laminating and pressing a prepreg and a copper foil at the same time, or providing an electrically insulating resin layer having adhesiveness on the copper foil in advance, so-called with resin A method of laminating metal foils has been performed. As the electrically insulating resin, a thermosetting resin such as a phenol resin, an epoxy resin, a polyimide resin, or a bismaleimide-triazine resin is widely used, and a thermoplastic resin such as a fluorine resin or a polyphenylene ether resin is used. There is also.
一方、パーソナルコンピュータや携帯電話等の情報端末機器の普及に伴ってこれらに搭載される印刷回路板は小型化、高密度化が進んでいる。その実装形態はピン挿入型から表面実装型へさらにはプラスチック基板を使用したＢＧＡ（ボールグリッドアレイ）に代表されるエリアアレイ型へと進んでいる。ＢＧＡのようなベアチップを直接実装する基板ではチップと基板の接続は、熱超音波圧着によるワイヤボンディングで行うのが一般的である。このため、ベアチップを実装する基板は１５０℃以上の高温にさらされることになり、電気絶縁性樹脂にはある程度の耐熱性が必要となる。 On the other hand, with the spread of information terminal devices such as personal computers and mobile phones, printed circuit boards mounted on them are becoming smaller and higher in density. The mounting form has progressed from a pin insertion type to a surface mounting type and further to an area array type represented by BGA (ball grid array) using a plastic substrate. In a substrate on which a bare chip such as a BGA is directly mounted, the connection between the chip and the substrate is generally performed by wire bonding by thermosonic bonding. For this reason, the substrate on which the bare chip is mounted is exposed to a high temperature of 150 ° C. or higher, and the electrically insulating resin needs a certain degree of heat resistance.
さらに一度実装したチップを外す、いわゆるリペア性も要求される場合があるが、これにはチップ実装時と同程度の熱がかけられるため、基板にはその後、再度チップ実装が施されることになりさらに熱処理が加わることになる。これに伴いリペア性の要求される基板では高温でのサイクル的な耐熱衝撃性も要求され、従来の絶縁性樹脂系では繊維基材と樹脂の間で剥離を起こす場合がある。 In addition, there is a case where so-called repairability is required to remove the chip once mounted, but since this is subject to the same level of heat as chip mounting, the substrate is then chip mounted again. In addition, heat treatment will be added. Along with this, a substrate requiring repairability is also required to have a cyclic thermal shock resistance at a high temperature, and in a conventional insulating resin system, peeling may occur between the fiber base material and the resin.
耐熱衝撃性、耐リフロー性、耐クラック性に優れ微細配線形成性を向上するために繊維基材にポリアミドイミドを必須成分とする樹脂組成物を含浸したプリプレグが提案されている（例えば特許文献１を参照）。またシリコーン変性ポリイミド樹脂と熱硬化性樹脂からなる樹脂組成物を繊維基材に含浸した耐熱性の基材が提案されている（例えば特許文献２を参照）。 A prepreg in which a fiber base material is impregnated with a resin composition containing polyamideimide as an essential component has been proposed in order to have excellent thermal shock resistance, reflow resistance, and crack resistance and to improve fine wiring formation (for example, Patent Document 1). See). In addition, a heat-resistant base material in which a fiber base material is impregnated with a resin composition composed of a silicone-modified polyimide resin and a thermosetting resin has been proposed (see, for example, Patent Document 2).
さらに電子機器の小型化、高性能化に伴い限られた空間に部品実装を施された印刷回路板を収納することが必要となってきている。これには複数の印刷回路板を多段に配し相互をワイヤーハーネスやフレキシブル配線板によって接続する方法がとられている。また、ポリイミドをベースとするフレキシブル基板と従来のリジッド基板を多層化したリジッド−フレックス基板が用いられている。 Furthermore, with the miniaturization and high performance of electronic devices, it has become necessary to accommodate printed circuit boards with component mounting in a limited space. In this method, a plurality of printed circuit boards are arranged in multiple stages and connected to each other by a wire harness or a flexible wiring board. In addition, a rigid-flex substrate in which a flexible substrate based on polyimide and a conventional rigid substrate are multilayered is used.
本発明は、上記従来技術の問題点を解消し、寸法安定性、耐熱性、耐発塵性、耐衝撃性に優れ、任意に折り曲げ可能な樹脂付き金属箔を提供するものである。 The present invention solves the above-mentioned problems of the prior art, and provides a resin-coated metal foil that is excellent in dimensional stability, heat resistance, dust generation resistance, and impact resistance and can be bent arbitrarily.
本発明は、次のものに関する。
１．樹脂組成物を含浸した繊維基材と、金属箔とを積層してなる樹脂付き金属箔であって、該樹脂組成物を硬化した樹脂硬化物の弾性率が、２５℃で０．１ＧＰａ以上、２．０ＧＰａ以下である樹脂付き金属箔。
２．繊維基材が、厚み５０μｍ以下の繊維基材である項１に記載の樹脂付き金属箔。
３．樹脂組成物が、熱硬化性樹脂を含む項１又は２に記載の樹脂付き金属箔。
４．熱硬化性樹脂が、グリシジル基を有する樹脂を含む熱硬化性樹脂である項３に記載の樹脂付き金属箔。
５．樹脂組成物が、アミド基を有する樹脂を含む樹脂組成物である項１乃至４いずれかに記載の樹脂付き金属箔。
６．樹脂組成物が、アクリル樹脂を含む樹脂組成物である項１乃至５いずれかに記載の樹脂付き金属箔。
７．樹脂組成物が、ポリアミック酸を含む樹脂組成物である項１乃至６いずれかに記載の樹脂付き金属箔。
８．項１乃至７いずれかに記載の樹脂付き金属箔であって、金属箔と繊維基材を重ねた状態で、繊維基材側から繊維基材に樹脂組成物を含浸させた後、乾燥して得られる樹脂付き金属箔。
９．項１乃至７いずれかに記載の樹脂付き金属箔であって、金属箔上に樹脂組成物を塗布した後、該樹脂組成物に繊維基材を重ね含浸させ、乾燥して得られる樹脂付き金属箔。
The present invention relates to the following.
1. A metal foil with a resin obtained by laminating a fiber base material impregnated with a resin composition and a metal foil, and an elastic modulus of a cured resin obtained by curing the resin composition is 0.1 GPa or more at 25 ° C., Metal foil with resin which is 2.0 GPa or less.
2. Item 2. The metal foil with resin according to Item 1, wherein the fiber substrate is a fiber substrate having a thickness of 50 μm or less.
3. Item 3. The metal foil with resin according to Item 1 or 2, wherein the resin composition contains a thermosetting resin.
4). Item 4. The resin-attached metal foil according to Item 3, wherein the thermosetting resin is a thermosetting resin containing a resin having a glycidyl group.
5). Item 5. The metal foil with resin according to any one of Items 1 to 4, wherein the resin composition is a resin composition containing a resin having an amide group.
6). Item 6. The resin-attached metal foil according to any one of Items 1 to 5, wherein the resin composition is a resin composition containing an acrylic resin.
7). Item 7. The metal foil with resin according to any one of Items 1 to 6, wherein the resin composition is a resin composition containing polyamic acid.
8). Item 8. The resin-attached metal foil according to any one of Items 1 to 7, wherein the fiber base material is impregnated with the resin composition from the fiber base side in a state where the metal foil and the fiber base material are stacked, and then dried. Obtained metal foil with resin.
9. Item 8. A metal foil with a resin according to any one of items 1 to 7, wherein the resin composition is obtained by applying a resin composition on the metal foil, then impregnating the resin composition with a fiber base material, and drying the resin base material. Foil.
本発明における樹脂付き金属箔は、繊維基材を含んでおり寸法安定性に優れる。繊維基材に含浸する樹脂組成物が該樹脂組成物の樹脂硬化物の室温（２５℃）での弾性率として０．１から２．０ＧＰａとなるようにすることで、樹脂付き金属箔を印刷回路板としたときに該印刷回路板に衝撃がかかった場合にも、その衝撃を吸収するため実装後の耐衝撃性が向上する。また繊維基材に含浸する樹脂組成物が該樹脂組成物の硬化物の弾性率として０．１から２．０ＧＰａとするために柔軟な樹脂を含浸するため、加工を行う際の発塵が少ない。また５０μｍ以下の繊維基材を使用することと相まって、印刷回路板は任意の部分で任意の状態に折り曲げ可能であり、該印刷回路板を搭載する筐体に高密度に収納することができる。また一般に乾燥収縮や硬化収縮の大きな樹脂では樹脂付き金属箔を製造する際に樹脂を内側に樹脂付き金属箔がカールする現象がみられるが、本発明では樹脂付き金属箔の製造時に金属箔と樹脂組成物を含ませた繊維基材を同時に積層し乾燥させて製造することによりカールがきわめて低減される。 The metal foil with resin in the present invention includes a fiber base material and is excellent in dimensional stability. The resin composition impregnated into the fiber base is printed with a resin-coated metal foil by setting the resin cured product of the resin composition to have an elastic modulus of 0.1 to 2.0 GPa at room temperature (25 ° C.). Even when an impact is applied to the printed circuit board when it is used as a circuit board, the impact resistance after mounting is improved because the impact is absorbed. In addition, since the resin composition impregnated in the fiber base is impregnated with a flexible resin so that the elastic modulus of the cured product of the resin composition is 0.1 to 2.0 GPa, dust generation during processing is small. . In addition, combined with the use of a fiber substrate of 50 μm or less, the printed circuit board can be bent into an arbitrary state at an arbitrary portion, and can be stored in a high density in a casing on which the printed circuit board is mounted. In general, when a resin-fitted metal foil is produced with a resin having a large drying shrinkage or curing shrinkage, a phenomenon that the resin-fitted metal foil curls inside the resin is seen. Curling is greatly reduced by simultaneously laminating and drying the fiber base material containing the resin composition.
本発明の樹脂付き金属箔は、樹脂組成物を含浸した繊維基材と、金属箔とを積層してなる樹脂付き金属箔であって、該樹脂組成物を硬化した樹脂硬化物の弾性率が、２５℃で０．１ＧＰａ以上、２．０ＧＰａ以下である。本発明の樹脂付き金属箔は、繊維基材を含み吸湿や温度による寸法変化を抑え、基材の寸法安定性を高めている。なお、基材とは、樹脂付き金属箔を硬化したものである。また本発明の樹脂付き金属箔は、半硬化のＢステージ状態であることが好ましいが、硬化したＣステージ状態でもよい。樹脂硬化物の室温（２５℃）での弾性率が、０．１〜２．０ＧＰａの樹脂組成物を使用することで、基材の柔軟性を高め印刷回路板としたときの耐衝撃性を優れたものとしている。 The metal foil with resin of the present invention is a metal foil with resin obtained by laminating a fiber base material impregnated with a resin composition and a metal foil, and the elastic modulus of the cured resin product obtained by curing the resin composition is , At 25 ° C., 0.1 GPa or more and 2.0 GPa or less. The metal foil with resin of the present invention includes a fiber base material, suppresses dimensional changes due to moisture absorption and temperature, and improves the dimensional stability of the base material. In addition, a base material hardens | cures metal foil with resin. The metal foil with resin of the present invention is preferably in a semi-cured B stage state, but may be in a cured C stage state. By using a resin composition having an elastic modulus of 0.1 to 2.0 GPa at room temperature (25 ° C.) of the cured resin product, the impact resistance when a printed circuit board is obtained by increasing the flexibility of the substrate. It is excellent.
該樹脂組成物を硬化した樹脂硬化物の弾性率は、２５℃で、０．１ＧＰａ以上、２．０ＧＰａ以下であり、０．５〜２．０ＧＰａが好ましく、１〜１．５ＧＰａがより好ましい。弾性率が０．１ＧＰａ未満では、印刷回路板を製造する際の取り扱いが困難になるという問題があり、２．０ＧＰａ超では、耐衝撃性が低く、また任意の折り曲げが困難となる傾向がある。本発明での弾性率は、樹脂組成物を硬化した樹脂板（樹脂硬化物）の動的粘弾性曲線の２５℃における弾性率をいう。 The elastic modulus of the cured resin obtained by curing the resin composition is 0.1 GPa or more and 2.0 GPa or less at 25 ° C., preferably 0.5 to 2.0 GPa, more preferably 1 to 1.5 GPa. If the elastic modulus is less than 0.1 GPa, there is a problem that handling at the time of manufacturing a printed circuit board becomes difficult, and if it exceeds 2.0 GPa, impact resistance is low and arbitrary bending tends to be difficult. . The elastic modulus in the present invention refers to the elastic modulus at 25 ° C. of the dynamic viscoelastic curve of the resin plate (resin cured product) obtained by curing the resin composition.
本発明で使用する繊維基材としては、金属箔張り積層板や印刷回路板を製造する際に用いられるものであれば特に制限されないが、通常織布や不織布等の繊維基材が用いられる。繊維基材の材質としては、ガラス、アルミナ、アスベスト、ボロン、シリカアルミナガラス、シリカガラス、チラノ、炭化ケイ素、窒化ケイ素、ジルコニア等の無機繊維やアラミド、ポリエーテルエーテルケトン、ポリエーテルイミド、ポリエーテルサルフォン、カーボン、セルロース等の有機繊維等及びこれらの混抄系があり、特にガラス繊維の織布が好ましく用いられる。 Although it will not restrict | limit especially as a fiber base material used by this invention if it is used when manufacturing a metal foil clad laminated board and a printed circuit board, Usually fiber base materials, such as a woven fabric and a nonwoven fabric, are used. Examples of the fiber base material include glass, alumina, asbestos, boron, silica alumina glass, silica glass, tyrano, silicon carbide, silicon nitride, zirconia, and other inorganic fibers, aramid, polyetheretherketone, polyetherimide, polyether There are organic fibers such as sulfone, carbon, cellulose and the like and mixed papers thereof, and glass fiber woven fabrics are particularly preferably used.
繊維基材としては、５０μｍ以下の繊維基材が好ましいが、５〜５０μｍがより好ましく、１０〜４０μｍが特に好ましい。また、繊維基材としてガラスクロスが特に好適に用いられる。厚みが５０μｍ以下のガラスクロスを用いることで、本発明の樹脂付き金属箔は柔軟性を持ち、任意に折り曲げることも可能とし、印刷回路板としたときの耐衝撃性をさらに優れたものとできる。 The fiber base material is preferably a fiber base material of 50 μm or less, more preferably 5 to 50 μm, particularly preferably 10 to 40 μm. A glass cloth is particularly preferably used as the fiber base material. By using a glass cloth having a thickness of 50 μm or less, the resin-attached metal foil of the present invention has flexibility, can be arbitrarily bent, and can further improve impact resistance when used as a printed circuit board. .
本発明では、樹脂硬化物の室温（２５℃）での弾性率が、０．１〜２．０ＧＰａの樹脂組成物を構成する成分として熱硬化性樹脂を含むことが好ましい。熱硬化性樹脂としては、エポキシ樹脂、ポリイミド樹脂、不飽和ポリエステル樹脂、ポリウレタン樹脂、ビスマレイミド樹脂、トリアジン−ビスマレイミド樹脂、フェノール樹脂等が挙げられる。 In this invention, it is preferable that the thermosetting resin is included as a component which the elasticity modulus in room temperature (25 degreeC) of a resin cured material comprises 0.1-2.0 GPa. Examples of the thermosetting resin include epoxy resins, polyimide resins, unsaturated polyester resins, polyurethane resins, bismaleimide resins, triazine-bismaleimide resins, phenol resins, and the like.
本発明では熱硬化性樹脂として、グリシジル基を有する樹脂を含むことが好ましく、エポキシ樹脂を含むことがより好ましい。エポキシ樹脂としては、ビスフェノールＡ、ノボラック型フェノール樹脂、オルトクレゾールノボラック型フェノール樹脂等の多価フェノール又は１，４−ブタンジオール等の多価アルコールとエピクロルヒドリンを反応させて得られるポリグリシジルエーテル、フタル酸、ヘキサヒドロフタル酸等の多塩基酸とエピクロルヒドリンを反応させて得られるポリグリシジルエステル、アミン、アミド又は複素環式窒素塩基を有する化合物のＮ−グリシジル誘導体、脂環式エポキシ樹脂などが挙げられる。 In the present invention, the thermosetting resin preferably includes a resin having a glycidyl group, and more preferably includes an epoxy resin. Epoxy resins include polyglycidyl ethers and phthalic acids obtained by reacting polychlorophenols such as bisphenol A, novolak-type phenol resins, ortho-cresol novolac-type phenol resins or polyhydric alcohols such as 1,4-butanediol with epichlorohydrin. And polyglycidyl ester obtained by reacting a polybasic acid such as hexahydrophthalic acid with epichlorohydrin, an N-glycidyl derivative of a compound having an amine, an amide or a heterocyclic nitrogen base, an alicyclic epoxy resin, and the like.
本発明では、熱硬化性樹脂としてエポキシ樹脂を用いることが１８０℃以下の温度で硬化が可能で、熱的、機械的、電気的特性を向上させるため好ましく、２個以上のグリシジル基を持つエポキシ樹脂とその硬化剤、２個以上のグリシジル基を持つエポキシ樹脂とその硬化促進剤または２個以上のグリシジル基を持つエポキシ樹脂と硬化剤、硬化促進剤を用いることが好ましい。またグリシジル基は多いほどよく、３個以上であればさらに好ましい。グリシジル基の数により、配合量が異なり、グリシジル基が多いほど配合量が少なくてもよい。 In the present invention, it is preferable to use an epoxy resin as a thermosetting resin because it can be cured at a temperature of 180 ° C. or less, and is preferable in order to improve thermal, mechanical, and electrical characteristics, and an epoxy having two or more glycidyl groups. It is preferable to use a resin and its curing agent, an epoxy resin having two or more glycidyl groups and its curing accelerator, or an epoxy resin having two or more glycidyl groups, a curing agent, and a curing accelerator. Further, the more glycidyl groups, the better. The blending amount varies depending on the number of glycidyl groups, and the blending amount may be smaller as the glycidyl group is larger.
エポキシ樹脂の硬化剤、硬化促進剤は、エポキシ樹脂と反応するもの、または、硬化を促進させるものであれば制限なく、例えば、アミン類、イミダゾール類、多官能フェノール類、酸無水物類等が使用できる。アミン類として、ジシアンジアミド、ジアミノジフェニルメタン、グアニル尿素等が使用でき、多官能フェノール類としては、ヒドロキノン、レゾルシノール、ビスフェノールＡ及びこれらのハロゲン化合物、さらにホルムアルデヒドとの縮合物であるノボラック型フェノール樹脂、レゾール型フェノール樹脂などが使用でき、酸無水物類としては、無水フタル酸、ベンゾフェノンテトラカルボン酸二無水物、メチルハイミック酸等が使用できる。硬化促進剤としては、イミダゾール類としてアルキル基置換イミダゾール、ベンゾイミダゾール等が使用できる。 The curing agent and curing accelerator of the epoxy resin are not limited as long as they react with the epoxy resin or accelerate curing. For example, amines, imidazoles, polyfunctional phenols, acid anhydrides, etc. Can be used. As the amines, dicyandiamide, diaminodiphenylmethane, guanylurea and the like can be used. As the polyfunctional phenols, hydroquinone, resorcinol, bisphenol A and their halogen compounds, and a novolac type phenol resin which is a condensate with formaldehyde, a resol type A phenol resin or the like can be used. As the acid anhydrides, phthalic anhydride, benzophenone tetracarboxylic dianhydride, methyl hymic acid, or the like can be used. As the curing accelerator, alkyl group-substituted imidazole, benzimidazole and the like can be used as imidazoles.
これらの硬化剤または硬化促進剤の必要な量は、アミン類の場合は、アミンの活性水素の当量と、エポキシ樹脂のエポキシ当量がほぼ等しくなる量が好ましい。硬化促進剤である、イミダゾールの場合は、単純に活性水素との当量比とならず、経験的にエポキシ樹脂１００重量部に対して、０．００１〜１０重量部必要となる。多官能フェノール類や酸無水物類の場合、エポキシ樹脂１当量に対して、フェノール性水酸基やカルボキシル基０．６〜１．２当量必要である。これらの硬化剤または硬化促進剤の量は、少なければ未硬化のエポキシ樹脂が残り、Ｔｇ（ガラス転移温度）が低くなり、多すぎると、未反応の硬化剤及び硬化促進剤が残り、絶縁性が低下する。 In the case of amines, the necessary amounts of these curing agents or curing accelerators are preferably such that the equivalent of the active hydrogen of the amine is approximately equal to the epoxy equivalent of the epoxy resin. In the case of imidazole, which is a curing accelerator, it is not simply an equivalent ratio with active hydrogen, but is empirically required to be 0.001 to 10 parts by weight per 100 parts by weight of the epoxy resin. In the case of polyfunctional phenols and acid anhydrides, 0.6 to 1.2 equivalents of phenolic hydroxyl groups and carboxyl groups are required for 1 equivalent of epoxy resin. If the amount of these curing agents or accelerators is small, uncured epoxy resin remains, and Tg (glass transition temperature) is low. If too large, unreacted curing agent and curing accelerator remain, and insulating properties are maintained. Decreases.
また本発明に用いる樹脂組成物は、可とう性や耐熱性の向上を目的に高分子量の樹脂成分を含むことも可能である。この目的のための樹脂として、アミド基を有する樹脂やアクリル樹脂、ポリアミック酸を用いることが好ましい。 The resin composition used in the present invention can also contain a high molecular weight resin component for the purpose of improving flexibility and heat resistance. As the resin for this purpose, it is preferable to use a resin having an amide group, an acrylic resin, or a polyamic acid.
本発明で用いるアミド基を有する樹脂としては、ポリアミドイミド樹脂、ポリアミド樹脂、アミドエポキシ樹脂などが挙げられるが、ポリアミドイミド樹脂が好ましい。本発明で用いるポリアミドイミド樹脂としては、シロキサン構造を樹脂中に持ったシロキサン変性ポリアミドイミド樹脂がより好ましく、特に芳香族環を２個以上有するジアミン及びシロキサンジアミンの混合物と無水トリメリット酸を反応させて得られるジイミドジカルボン酸を含む混合物と芳香族ジイソシアネートを反応させて得ることが好ましい。また一分子中にアミド基を１０個以上含むポリアミドイミド分子を７０モル％以上含むポリアミドイミド樹脂であることが好ましい。その範囲はポリアミドイミド樹脂のＧＰＣから得られるクロマトグラムと別に求めた単位重量中のアミド基のｍｏｌ数（Ａ）から得ることができる。例えばポリアミドイミド（ａ）ｇ中に含まれるアミド基のモル数（Ａ）から１０×ａ／Ａを一分子中にアミド基を１０個含むポリアミドイミド樹脂の分子量（Ｃ）としＧＰＣで得られるクロマトグラムの数平均分子量がＣ以上となる領域が７０％以上となることと定義する。アミド基の定量方法はＮＭＲ、ＩＲ、ヒドロキサム酸−鉄呈色反応法、Ｎ−ブロモアミド法などを利用することができる。 Examples of the resin having an amide group used in the present invention include a polyamideimide resin, a polyamide resin, and an amide epoxy resin, and a polyamideimide resin is preferable. As the polyamide-imide resin used in the present invention, a siloxane-modified polyamide-imide resin having a siloxane structure in the resin is more preferable. In particular, a mixture of a diamine having two or more aromatic rings and a siloxane diamine is reacted with trimellitic anhydride. It is preferable to obtain by reacting a mixture containing diimidedicarboxylic acid obtained in this way with an aromatic diisocyanate. Moreover, it is preferable that it is a polyamideimide resin which contains 70 mol% or more of polyamideimide molecules containing 10 or more amide groups in one molecule. The range can be obtained from the number of moles (A) of amide groups in the unit weight obtained separately from the chromatogram obtained from GPC of the polyamideimide resin. For example, the chromatograph obtained by GPC using the number of moles of amide groups contained in the polyamideimide (a) (A) as the molecular weight (C) of 10 × a / A of the polyamideimide resin containing 10 amide groups in one molecule. The region where the number average molecular weight of gram is C or more is defined as 70% or more. NMR, IR, hydroxamic acid-iron coloring reaction method, N-bromoamide method, etc. can be used for the determination method of the amide group.
また、本発明に用いられるポリアミック酸は、シロキサン構造を含有するポリアミック酸であることが好ましく、更に前記ポリアミック酸を閉環させた際に、下記一般式（１）及び一般式（２）の構造を有する樹脂になるポリアミック酸であることがより好ましい。またシロキサン構造を含有するポリアミック酸としては、ジアミンとテトラカルボン酸二無水物の反応により得られるポリアミック酸であることが好ましい。 Further, the polyamic acid used in the present invention is preferably a polyamic acid containing a siloxane structure, and when the polyamic acid is further cyclized, the structures of the following general formulas (1) and (2) are used. It is more preferable that it is a polyamic acid that becomes a resin. The polyamic acid containing a siloxane structure is preferably a polyamic acid obtained by a reaction between a diamine and tetracarboxylic dianhydride.
（式中Ａｒ１は４価の芳香族基を示し、Ｒ１及びＲ２は２価の炭化水素基を示し、Ｒ３〜Ｒ６は炭素数１〜６の炭化水素基を示し、ｎは１〜５０の整数を示す）
(In the formula, Ar 1 represents a tetravalent aromatic group, R 1 and R 2 represent a divalent hydrocarbon group, R 3 to R 6 represent a hydrocarbon group having 1 to 6 carbon atoms, and n represents Represents an integer of 1 to 50)
（式中Ａｒ１は４価の芳香族基を示し、Ａｒ２は２価の芳香族基を示す）
(In the formula, Ar 1 represents a tetravalent aromatic group, and Ar 2 represents a divalent aromatic group)
本発明で使用するテトラカルボン酸二無水物としては、３，３’，４，４’−ジフェニルエーテルテトラカルボン酸二無水物、３，３’，４，４’−ジフェニルスルホンテトラカルボン酸二無水物、３，３’，４，４’−ベンゾフェノンテトラカルボン酸二無水物、２，２’，３，３’−ベンゾフェノンテトラカルボン酸二無水物、３，３’，４，４’−ビフェニルテトラカルボン酸二無水物、２，３，３’，４’−ビフェニルテトラカルボン酸二無水物、ピロメリット酸二無水物、１，４，５，８−ナフタレンテトラカルボン酸二無水物、１，４，５，６−ナフタレンテトラカルボン酸二無水物、３，４，９，１０−ペリレンテトラカルボン酸二無水物、３，３，６，７−アントラセンテトラカルボン酸二無水物、１，２，７，８−フェナントレンテトラカルボン酸二無水物、４，４’−（ヘキサフルオロイソプロピリデン）フタル酸二無水物などがあげられる。なおポリイミド樹脂の前駆体であるポリアミック酸にシロキサン構造を導入することにより、樹脂付き金属箔の折り曲げが、よりいっそう容易となる。 Examples of the tetracarboxylic dianhydride used in the present invention include 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride and 3,3 ′, 4,4′-diphenylsulfone tetracarboxylic dianhydride. 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 2,2 ′, 3,3′-benzophenone tetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic Acid dianhydride, 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride, pyromellitic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,4 5,6-naphthalenetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 3,3,6,7-anthracenetetracarboxylic dianhydride, 1,2,7, 8-Fena Tren tetracarboxylic dianhydride, 4,4 '- such as (hexafluoro isopropylidene) phthalic dianhydride and the like. By introducing a siloxane structure into the polyamic acid that is a precursor of the polyimide resin, the metal foil with resin can be bent more easily.
シロキサン構造を樹脂中に持ったシロキサン変性ポリアミドイミド樹脂、あるいはシロキサン構造を含有するポリアミック酸の合成は、芳香族環を有するジアミンａとシロキサンジアミンｂの混合比率が、ａ／ｂ＝９９．９／０．１〜０／１００（モル比）であると好ましく、ａ／ｂ＝９５／５〜３０／７０であると更に好ましく、ａ／ｂ＝９０／１０〜４０／６０であるとより一層好ましい。シロキサンジアミンｂの混合比率が多くなるとＴｇが低下する傾向にある。また、少なくなると樹脂付き金属箔を作製する場合に樹脂中に残存するワニス溶剤量が多くなる傾向がある。 In the synthesis of a siloxane-modified polyamideimide resin having a siloxane structure in the resin or a polyamic acid containing a siloxane structure, the mixing ratio of the diamine a having an aromatic ring and the siloxane diamine b is a / b = 99.9 / It is preferably 0.1 to 0/100 (molar ratio), more preferably a / b = 95/5 to 30/70, and even more preferably a / b = 90/10 to 40/60. . When the mixing ratio of siloxane diamine b increases, Tg tends to decrease. Moreover, when it decreases, when producing metal foil with resin, there exists a tendency for the amount of varnish solvent which remains in resin to increase.
芳香族ジアミン（芳香族環を有するジアミン）としては、例えば（３，３’―ジアミノ）ジフェニルエーテル、ｍ−フェニレンジアミン、ｐ−フェニレンジアミン、４，４’−ジアミノジフェニルメタン、４，４’−ジアミノジフェニルプロパン、ベンジジン、４，４’−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’−ジアミノジフェニルエーテル、４，４’−ジアミノ−ｐ−ターフェニル、２，２−ビス［４−（４−アミノフェノキシ）フェニル］プロパン（ＢＡＰＰ）、ビス［４−（３−アミノフェノキシ）フェニル］スルホン、ビス［４−（４−アミノフェノキシ）フェニル］スルホン、２，２−ビス［４−（４−アミノフェノキシ）フェニル］ヘキサフルオロプロパン、ビス［４−（４−アミノフェノキシ）フェニル］メタン、４，４’−ビス（４−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）フェニル］エーテル、ビス［４−（４−アミノフェノキシ）フェニル］ケトン、１，３−ビス（４−アミノフェノキシ）ベンゼン、１，４−ビス（４−アミノフェノキシ）ベンゼン、２，２’−ジメチルビフェニル−４，４’−ジアミン、２，２’−ビス（トリフルオロメチル）ビフェニル−４，４’−ジアミン、２，６，２’，６’−テトラメチルビフェニル−４，４’−ジアミン、５，５’−ジメチル−２，２’−スルフォニル−ビフェニル−４，４’−ジアミン、３，３’−ジヒドロキシビフェニル−４，４’−ジアミン、（４，４’−ジアミノ）ベンゾフェノン、（３，３’―ジアミノ）ベンゾフェノン等が例示できる。 Examples of the aromatic diamine (a diamine having an aromatic ring) include (3,3′-diamino) diphenyl ether, m-phenylenediamine, p-phenylenediamine, 4,4′-diaminodiphenylmethane, and 4,4′-diaminodiphenyl. Propane, benzidine, 4,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl ether, 4,4'-diamino-p-terphenyl 2,2-bis [4- (4-aminophenoxy) phenyl] propane (BAPP), bis [4- (3-aminophenoxy) phenyl] sulfone, bis [4- (4-aminophenoxy) phenyl] sulfone, 2,2-bis [4- (4-aminophenoxy) phenyl] hexa Fluoropropane, bis [4- (4-aminophenoxy) phenyl] methane, 4,4′-bis (4-aminophenoxy) biphenyl, bis [4- (4-aminophenoxy) phenyl] ether, bis [4- (4 -Aminophenoxy) phenyl] ketone, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 2,2'-dimethylbiphenyl-4,4'-diamine, 2 , 2′-bis (trifluoromethyl) biphenyl-4,4′-diamine, 2,6,2 ′, 6′-tetramethylbiphenyl-4,4′-diamine, 5,5′-dimethyl-2,2 '-Sulphonyl-biphenyl-4,4'-diamine, 3,3'-dihydroxybiphenyl-4,4'-diamine, (4,4'-diamino) benzophenone (3,3'-diamino) benzophenone and the like.
本発明で使用するシロキサンジアミンとしては、以下の一般式（３）〜（６）ものが挙げられる。なお下記一般式（３）〜（６）のｍ及びｎは、１以上の整数である。 Examples of the siloxane diamine used in the present invention include the following general formulas (3) to (6). In the following general formulas (3) to (6), m and n are integers of 1 or more.
なお、上記一般式（３）で表されるシロキサンジアミンとしては、Ｘ−２２−１６１ＡＳ（アミン当量４５０）、Ｘ−２２−１６１Ａ（アミン当量８４０）、Ｘ−２２−１６１Ｂ（アミン当量１５００）（以上、信越化学工業株式会社製商品名）、ＢＹ１６−８５３（アミン当量６５０）、ＢＹ１６−８５３Ｂ（アミン当量２２００）、（以上、東レダウコーニングシリコーン株式会社製商品名）等が例示できる。上記一般式（６）で表されるシロキサンジアミンとしては、Ｘ−２２−９４０９（アミン当量７００）、Ｘ−２２−１６６０Ｂ−３（アミン当量２２００）（以上、信越化学工業株式会社製商品名）等が例示できる。 In addition, as siloxane diamine represented by the said General formula (3), X-22-161AS (amine equivalent 450), X-22-161A (amine equivalent 840), X-22-161B (amine equivalent 1500) ( As mentioned above, Shin-Etsu Chemical Co., Ltd. product name), BY16-853 (amine equivalent 650), BY16-853B (amine equivalent 2200), (product name manufactured by Toray Dow Corning Silicone Co., Ltd.) and the like can be exemplified. As the siloxane diamine represented by the general formula (6), X-22-9409 (amine equivalent 700), X-22-1660B-3 (amine equivalent 2200) (above, trade name manufactured by Shin-Etsu Chemical Co., Ltd.) Etc. can be illustrated.
またシロキサン構造を樹脂中に持ったシロキサン変性ポリアミドイミド樹脂、あるいはシロキサン構造を含有するポリアミック酸の合成には、下記一般式（７）で表される脂肪族ジアミン類を、単独で用いても良く、芳香族ジアミンと併用しても良い。 In addition, an aliphatic diamine represented by the following general formula (7) may be used alone for the synthesis of a siloxane-modified polyamideimide resin having a siloxane structure in the resin or a polyamic acid containing a siloxane structure. It may be used in combination with an aromatic diamine.
但し、式中Ｘはメチレン基、スルホニル基、エーテル基、カルボニル基又は単結合、Ｒ１及びＲ２はそれぞれ水素原子、アルキル基、フェニル基または置換フェニル基を示し、ｐは１〜５０の整数を示す。Ｒ１及びＲ２の具体例としては、水素原子、炭素数が１〜３のアルキル基、フェニル基、置換フェニル基が好ましく、フェニル基に結合していてもよい置換基としては、炭素数１〜３のアルキル基、ハロゲン原子等が例示できる。脂肪族ジアミンは、低弾性率及び高Ｔｇの両立の観点から、上記一般式（７）におけるＸがエーテル基であることが好ましい。このような脂肪族ジアミンとしては、ジェファーミンD−４００（アミン当量４００）、ジェファーミンD−２０００（アミン当量１０００）以上サンテクノケミカル社製商品名等が例示できる。 Wherein X is a methylene group, sulfonyl group, ether group, carbonyl group or single bond, R 1 and R 2 are each a hydrogen atom, an alkyl group, a phenyl group or a substituted phenyl group, and p is an integer of 1 to 50 Indicates. Specific examples of R 1 and R 2 are preferably a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a phenyl group, and a substituted phenyl group. The substituent that may be bonded to the phenyl group is 1 carbon atom. -3 alkyl groups, halogen atoms and the like can be exemplified. In the aliphatic diamine, X in the general formula (7) is preferably an ether group from the viewpoint of achieving both low elastic modulus and high Tg. Examples of such aliphatic diamines include Jeffamine D-400 (amine equivalent 400), Jeffamine D-2000 (amine equivalent 1000) or more and trade names of Sun Techno Chemical Co., Ltd.
本発明のポリアミドイミド樹脂の製造方法に用いるジイソシアネートとしては、下記一般式（８）で表される化合物を用いることができる。 As the diisocyanate used in the method for producing the polyamideimide resin of the present invention, a compound represented by the following general formula (8) can be used.
式中、Dは少なくとも１つの芳香環を有する２価の有機基、又は、２価の脂肪族炭化水素基であり、−Ｃ6Ｈ4−ＣＨ2−Ｃ6Ｈ4−で表される基、トリレン基、ナフチレン基、ヘキサメチレン基、２，２，４−トリメチルヘキサメチレン基及びイソホロン基からなる群より選ばれる少なくとも１つの基であることが好ましい。 In the formula, D is a divalent organic group having at least one aromatic ring or a divalent aliphatic hydrocarbon group, and is a group represented by —C 6 H 4 —CH 2 —C 6 H 4 —. And at least one group selected from the group consisting of a tolylene group, a naphthylene group, a hexamethylene group, a 2,2,4-trimethylhexamethylene group and an isophorone group.
上記一般式（８）で表されるジイソシアネートとしては、脂肪族ジイソシアネート又は芳香族ジイソシアネートを用いることができるが、芳香族ジイソシアネートを用いることが好ましく、両者を併用することが特に好ましい。芳香族ジイソシアネートとしては、４，４’−ジフェニルメタンジイソシアネート（ＭＤＩ）、２，４−トリレンジイソシアネート、２，６−トリレンジイソシアネート、ナフタレン−１，５−ジイソシアネート、２，４−トリレンダイマー等が例示でき、ＭＤＩを用いることが特に好ましい。芳香族ジイソシアネートとしてＭＤＩを用いることにより、得られるポリアミドイミド樹脂の可撓性を向上させることができる。 As the diisocyanate represented by the general formula (8), an aliphatic diisocyanate or an aromatic diisocyanate can be used, but it is preferable to use an aromatic diisocyanate, and it is particularly preferable to use both in combination. Examples of aromatic diisocyanates include 4,4′-diphenylmethane diisocyanate (MDI), 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, naphthalene-1,5-diisocyanate, 2,4-tolylene dimer, and the like. As an example, it is particularly preferable to use MDI. By using MDI as the aromatic diisocyanate, the flexibility of the resulting polyamideimide resin can be improved.
脂肪族ジイソシアネートとしては、ヘキサメチレンジイソシアネート、２，２，４−トリメチルヘキサメチレンジイソシアネート、イソホロンジイソシアネート等が例示できる。 Examples of the aliphatic diisocyanate include hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, and isophorone diisocyanate.
芳香族ジイソシアネート及び脂肪族ジイソシアネートを併用する場合は、脂肪族ジイソシアネートを芳香族ジイソシアネートに対して５〜１０モル％程度添加することが好ましく、かかる併用により、得られるポリアミドイミド樹脂の耐熱性を更に向上させることができる。 When using an aromatic diisocyanate and an aliphatic diisocyanate in combination, it is preferable to add the aliphatic diisocyanate to about 5 to 10 mol% with respect to the aromatic diisocyanate, and this combination further improves the heat resistance of the resulting polyamideimide resin. Can be made.
本発明の樹脂付き金属箔の樹脂組成物に含まれるアクリル樹脂としては、アクリル酸モノマ、メタクリル酸モノマ、アクリロニトリル、グリシジル基を有するアクリルモノマなどの単独もしくはこれらを複数共重合した共重合物を使用することが可能である。分子量は特に規定されるものではないが標準ポリスチレン換算の重量平均分子量で３０万〜１００万、好ましくは４０万〜８０万のものが用いられる。これらのアクリル樹脂にエポキシ樹脂、硬化剤、硬化促進剤を適宜加えて使用することが好ましい。なお、アクリル樹脂として、ＨＴＲ−８６０−Ｐ３（ナガセケムテックス株式会社製商品名、重量平均分子量８５万）、ＨＭ６−１Ｍ５０（ナガセケムテックス株式会社製商品名、重量平均分子量５０万）などが例示できる。 As the acrylic resin contained in the resin composition of the resin-coated metal foil of the present invention, an acrylic monomer, a methacrylic acid monomer, acrylonitrile, an acrylic monomer having a glycidyl group, or a copolymer obtained by copolymerizing a plurality thereof is used. Is possible. The molecular weight is not particularly specified, but a standard polystyrene equivalent weight average molecular weight of 300,000 to 1,000,000, preferably 400,000 to 800,000 is used. It is preferable to add an epoxy resin, a curing agent, and a curing accelerator as appropriate to these acrylic resins. Examples of acrylic resins include HTR-860-P3 (trade name, manufactured by Nagase ChemteX Corporation, weight average molecular weight 850,000), HM6-1M50 (trade name, manufactured by Nagase ChemteX Corporation, weight average molecular weight 500,000), and the like. it can.
また本発明では、難燃性の向上を目的に添加型の難燃剤を使用することもできる。本発明で使用する添加型の難燃剤としてはリンを含有するフィラーが好ましく、リン含有フィラーとしてはＯＰ９３０（クラリアント社製商品名、リン含有量２３．５重量％）、ＨＣＡ−ＨＱ（三光株式会社製商品名、リン含有量９．６重量％）、ポリリン酸メラミンＰＭＰ−１００（リン含有量１３．８重量％）ＰＭＰ−２００（リン含有量９．３重量％）ＰＭＰ−３００（リン含有量９．８重量％）以上日産化学株式会社製商品名等が挙げられる。 In the present invention, an additive-type flame retardant can also be used for the purpose of improving flame retardancy. As the additive-type flame retardant used in the present invention, a filler containing phosphorus is preferable. As the phosphorus-containing filler, OP930 (trade name manufactured by Clariant, phosphorus content 23.5% by weight), HCA-HQ (Sanko Co., Ltd.) Product name, phosphorus content 9.6 wt%), melamine polyphosphate PMP-100 (phosphorus content 13.8 wt%) PMP-200 (phosphorus content 9.3 wt%) PMP-300 (phosphorus content) 9.8% by weight) or more, trade names made by Nissan Chemical Co., Ltd. and the like.
本発明の樹脂付き金属箔の金属箔としては、銅箔やアルミニウム箔が一般的に用いられるが、通常積層板に用いられている厚み５〜２００μｍのものを使用でき、銅箔が好ましい。また、ニッケル、ニッケル−リン、ニッケル−スズ合金、ニッケル−鉄合金、鉛、鉛−スズ合金等を中間層とし、この両面に０．５〜１５μｍの銅層と１０〜３００μｍの銅層を設けた３層構造の複合箔あるいはアルミニウムと銅箔を複合した２層構造複合箔を用いることができる。 As the metal foil of the resin-attached metal foil of the present invention, a copper foil or an aluminum foil is generally used. However, a metal foil having a thickness of 5 to 200 μm which is usually used for a laminate can be used, and a copper foil is preferable. Also, nickel, nickel-phosphorus, nickel-tin alloy, nickel-iron alloy, lead, lead-tin alloy, etc. are used as intermediate layers, and a 0.5-15 μm copper layer and a 10-300 μm copper layer are provided on both sides. Alternatively, a three-layer composite foil or a two-layer composite foil in which aluminum and copper foil are combined can be used.
本発明では、樹脂組成物に、必要に応じて各種の樹脂や添加剤などを加え、有機溶媒中で混合、溶解、分散して、ワニス状にしても良い。このような有機溶媒としては、溶解性が得られるものであれば制限するものでなく、ジメチルアセトアミド、ジメチルホルムアミド、ジメチルスルホキシド、Ｎ−メチル−２−ピロリドン、γ−ブチロラクトン、スルホラン、シクロヘキサノン等が挙げられる。 In the present invention, various resins and additives may be added to the resin composition as necessary, and mixed, dissolved, and dispersed in an organic solvent to form a varnish. Such an organic solvent is not limited as long as solubility is obtained, and examples thereof include dimethylacetamide, dimethylformamide, dimethyl sulfoxide, N-methyl-2-pyrrolidone, γ-butyrolactone, sulfolane, and cyclohexanone. It is done.
本発明の樹脂付き金属箔の製造方法等は特に制限するものではないが，例えば以下の製造方法で、製造してもよい。金属箔の上に繊維基材を重ね、樹脂組成物のワニスを、繊維基材の側から供給して含浸させて塗工する、あるいは金属箔上に樹脂組成物のワニスを所定の厚みに塗布した後、繊維基材を重ねて樹脂組成物のワニスを含浸させた後、乾燥する。なお樹脂組成物のワニスを金属箔上に所定の厚みに塗布する方法としては、通常はギャップの間を被塗工物（金属箔）を通過させるコータが使用でき、そして樹脂組成物のワニス状態の塗膜厚みが、５０〜５００μｍの場合、コンマコータが好ましい。また、また、樹脂組成物のワニスを繊維基材のみに含浸させ、８０℃〜１８０℃の範囲で乾燥させて、プリプレグを製造し、更に金属箔と前記プリプレグを、プリプレグの硬化が進まない範囲、例えば８０℃〜１２０℃の範囲で、加熱加圧し、樹脂付き金属箔を製造してもよい。 Although the manufacturing method of the metal foil with resin of this invention is not restrict | limited in particular, For example, you may manufacture with the following manufacturing methods. The fiber base material is stacked on the metal foil, and the resin composition varnish is supplied from the fiber base material side and impregnated for coating, or the resin composition varnish is applied to the metal foil to a predetermined thickness. Then, the fiber base material is stacked and impregnated with the varnish of the resin composition, and then dried. In addition, as a method of applying the resin composition varnish to a predetermined thickness on the metal foil, a coater that normally allows the object to be coated (metal foil) to pass through the gap can be used, and the varnish state of the resin composition A comma coater is preferable when the thickness of the coating is 50 to 500 μm. In addition, the varnish of the resin composition is impregnated only in the fiber base material, dried in the range of 80 ° C. to 180 ° C. to produce a prepreg, and the metal foil and the prepreg are further cured with the prepreg. For example, you may heat-press in the range of 80 to 120 degreeC, and may manufacture metal foil with resin.
樹脂付き金属箔の製造条件等は特に制限するものではないが，ワニスに使用した有機溶媒が８０重量％以上揮発していることが好ましい。このため，製造方法や乾燥条件等も制限はなく，乾燥時の温度は８０℃〜１８０℃，時間はワニスのゲル化時間との兼ね合いで特に制限はない。ワニスの含浸量は、ワニス固形分と基材の総量に対して、ワニス固形分が３０〜８０重量％になるようにされることが好ましい。なお耐熱性の高いポリアミック酸やポリアミドイミド樹脂にシロキサン構造を持たせたことにより、残存有機溶媒分を少なくすることができ、熱処理の際のボイドの発生や積層工程において有機溶媒揮発によるフクレの発生を防止でき、はんだ耐熱性をより優れたものとすることができる。 The production conditions of the metal foil with resin are not particularly limited, but it is preferable that the organic solvent used for the varnish is volatilized by 80% by weight or more. For this reason, the production method and drying conditions are not limited, the drying temperature is 80 ° C. to 180 ° C., and the time is not particularly limited in view of the gelation time of the varnish. The amount of impregnation of the varnish is preferably 30 to 80% by weight with respect to the total amount of the varnish solid and the base material. In addition, by adding a siloxane structure to polyamic acid and polyamideimide resin with high heat resistance, the remaining organic solvent can be reduced, generating voids during heat treatment, and generating bulges due to organic solvent volatilization during the lamination process. Can be prevented, and the solder heat resistance can be further improved.
本発明の樹脂付き金属箔を用いた金属張積層板の製造方法は、例えば次の通りである。本発明における樹脂付き金属箔に銅箔を重ねるか又は２枚の樹脂付き金属箔を樹脂面が向かい合うようにして積層した積層体を通常１５０〜２８０℃、好ましくは１８０℃〜２５０℃の範囲の温度で、通常０．５〜２０ＭＰａ、好ましくは１〜８ＭＰａの範囲の圧力で、加熱加圧成形することにより金属張積層板を製造することができる。金属箔を使用して金属張積層板とすることにより、これに回路加工を施して印刷回路板とすることもできる。また前述したように、本発明の樹脂付き金属箔を加熱処理することでＣステージ状態の樹脂付き金属箔とすることができる。加熱処理条件は、例えば、通常１５０〜２８０℃、好ましくは１８０℃〜２５０℃の範囲の温度で、Ｃステージ状態の樹脂付き金属箔としてもよい。そしてＣステージ状態の樹脂付き金属箔を使用して、これに回路加工を施して印刷回路板とすることもできる。なお、回路加工は、一般的な方法であるサブトラクティブ法やアディティブ法を使用できる。 A method for producing a metal-clad laminate using the resin-coated metal foil of the present invention is, for example, as follows. In the present invention, a laminate in which a copper foil is laminated on a metal foil with resin or two resin foils are laminated so that the resin surfaces face each other is usually 150 to 280 ° C., preferably 180 ° C. to 250 ° C. A metal-clad laminate can be produced by heating and pressing at a temperature of usually 0.5 to 20 MPa, preferably 1 to 8 MPa. By using a metal foil to form a metal-clad laminate, circuit processing can be applied to this to obtain a printed circuit board. As described above, the resin-coated metal foil of the present invention can be heat-treated to form a C-staged resin-coated metal foil. The heat treatment condition may be, for example, a metal foil with a resin in a C-stage state at a temperature in the range of usually 150 to 280 ° C, preferably 180 ° C to 250 ° C. And it is also possible to use a metal foil with a resin in a C-stage state and perform circuit processing on this to obtain a printed circuit board. For circuit processing, a subtractive method and an additive method, which are general methods, can be used.
また樹脂付き金属箔を、別途作製した印刷回路板と積層することで、多層配線板とすることが可能である。このとき樹脂付き金属箔を介して各層の回路どうしを層間接続するには、樹脂付き金属箔に層間接続用の穴をレーザなどによりあらかじめ加工しておき導電ペーストやめっきにより接続する方法や、各回路板の内層回路上にあらかじめ設けた接続用バンプを用いる方法などがあるが、特に限定するものではない。 Moreover, it is possible to make a multilayer wiring board by laminating a resin-coated metal foil with a separately produced printed circuit board. At this time, in order to connect the circuits of each layer through the resin-coated metal foil, the method of connecting the holes for interlayer connection to the resin-coated metal foil with a laser in advance and connecting them with a conductive paste or plating, There is a method of using connection bumps provided in advance on the inner layer circuit of the circuit board, but there is no particular limitation.
以下に実施例を挙げて説明するが、本発明はこれらに限定されるものではない。
（合成例１）
環流冷却器を連結したコック付き２５ｍｌの水分定量受器、温度計、撹拌器を備えた１リットルのセパラブルフラスコに芳香族環を２個以上有するジアミンとしてＢＡＰＰ（２，２−ビス［４−（４−アミノフェノキシ）フェニル］プロパン）４１．０ｇ（０．５０ｍｏｌ）、シロキサンジアミンとして反応性シリコンオイルＸ−２２−９４０９（信越化学工業株式会社製商品名、アミン当量２２００）１３２．０ｇ（０．５０ｍｏｌ）、ＴＭＡ（無水トリメリット酸）８０．７ｇ（０．４２ｍｏｌ）を非プロトン性極性溶媒としてＮＭＰ（Ｎ−メチル−２−ピロリドン）５７３ｇを仕込み、８０℃で３０分間撹拌した。そして水と共沸可能な芳香族炭化水素としてトルエン１５０ｍｌを投入してから温度を上げ約１６０℃で２時間環流させた。水分定量受器に水が約７．２ｍｌ以上たまっていること、水の留出が見られなくなっていることを確認し、水分定量受器にたまっている留出液を除去しながら、約１９０℃まで温度を上げて、トルエンを除去した。その後、溶液を室温（２５℃）に戻し、芳香族ジイソシアネートとしてＭＤＩ（４，４’−ジフェニルメタンジイソシアネート）５５．０ｇ（０．２２ｍｏｌ）を投入し、１９０℃で２時間反応させた。反応終了後、ポリアミドイミド樹脂のＮＭＰ溶液（樹脂分３３重量％）を得た。
Examples are described below, but the present invention is not limited to these examples.
(Synthesis Example 1)
BAPP (2,2-bis [4-) is a diamine having two or more aromatic rings in a 1-liter separable flask equipped with a 25 ml water meter with a cock connected to a reflux condenser, a thermometer, and a stirrer. (4-aminophenoxy) phenyl] propane) 41.0 g (0.50 mol), reactive silicone oil X-22-9409 (trade name, amine equivalent 2200, manufactured by Shin-Etsu Chemical Co., Ltd.) as a siloxane diamine 132.0 g (0 .50 mol) and TMA (trimellitic anhydride) 80.7 g (0.42 mol) as an aprotic polar solvent were charged with 573 g of NMP (N-methyl-2-pyrrolidone) and stirred at 80 ° C. for 30 minutes. Then, 150 ml of toluene was added as an aromatic hydrocarbon azeotropic with water, and the temperature was raised and refluxed at about 160 ° C. for 2 hours. While confirming that about 7.2 ml or more of water has accumulated in the moisture determination receiver and that no water is being distilled, remove the distillate that has accumulated in the moisture determination receiver, The temperature was raised to 0 ° C. to remove toluene. Thereafter, the solution was returned to room temperature (25 ° C.), and 55.0 g (0.22 mol) of MDI (4,4′-diphenylmethane diisocyanate) was added as an aromatic diisocyanate, followed by reaction at 190 ° C. for 2 hours. After completion of the reaction, an NMP solution of polyamideimide resin (resin content 33% by weight) was obtained.
（合成例２）
環流冷却器を連結したコック付き２５ｍｌの水分定量受器、温度計、撹拌器を備えた１リットルのセパラブルフラスコに芳香族環を２個以上有するジアミンとしてＤＤＳ（ジアミノジフェニルスルホン）１４．９ｇ（０．０６ｍｏｌ）、シロキサンジアミンとして反応性シリコンオイルＫＦ−８０１０（信越化学工業株式会社製商品名、アミン当量４３０）４３．０ｇ（０．０５ｍｏｌ）、脂肪族ジアミンとしてジェファーミンＤ２０００（サンテクノケミカル社製商品名、アミン当量１０００）９０．０ｇ（０．０４５ｍｏｌ）、ジアミンとしてワンダミン（新日本理化株式会社製商品名）１１．５ｇ（０．０５５ｍｏｌ）、ＴＭＡ（無水トリメリット酸）８０．７ｇ（０．４２ｍｏｌ）を非プロトン性極性溶媒としてＮＭＰ（Ｎ−メチル−２−ピロリドン）６９０ｇを仕込み、８０℃で３０分間撹拌した。そして水と共沸可能な芳香族炭化水素としてトルエン１５０ｍｌを投入してから温度を上げ約１６０℃で２時間環流させた。水分定量受器に水が約７．２ｍｌ以上たまっていること、水の留出が見られなくなっていることを確認し、水分定量受器にたまっている留出液を除去しながら、約１９０℃まで温度を上げて、トルエンを除去した。その後、溶液を室温（２５℃）に戻し、芳香族ジイソシアネートとしてＭＤＩ（４，４’−ジフェニルメタンジイソシアネート）５５．１ｇ（０．２２ｍｏｌ）を投入し、１９０℃で２時間反応させた。反応終了後、ポリアミドイミド樹脂のＮＭＰ溶液（樹脂分２８重量％）を得た。
(Synthesis Example 2)
14.9 g of DDS (diaminodiphenylsulfone) as a diamine having two or more aromatic rings in a 1-liter separable flask equipped with a 25 ml moisture meter with a cock connected to a reflux condenser, a thermometer, and a stirrer ( 0.06 mol), reactive silicone oil KF-8010 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd., amine equivalent 430) 43.0 g (0.05 mol) as siloxane diamine, and Jeffamine D2000 (manufactured by Sun Techno Chemical Co., Ltd.) as aliphatic diamine Product name, amine equivalent 1000) 90.0 g (0.045 mol), Wandamine (trade name, manufactured by Shin Nippon Chemical Co., Ltd.) 11.5 g (0.055 mol), TMA (trimellitic anhydride) 80.7 g (0 .42 mol) as an aprotic polar solvent, NMP (N-methyl) Were charged 2-pyrrolidone) 690 g, it was stirred at 80 ° C. 30 min. Then, 150 ml of toluene was added as an aromatic hydrocarbon azeotropic with water, and the temperature was raised and refluxed at about 160 ° C. for 2 hours. While confirming that approximately 7.2 ml or more of water has accumulated in the moisture determination receiver and that no distillation of water has been observed, while removing the distillate accumulated in the moisture determination receiver, The temperature was raised to 0 ° C. to remove toluene. Then, the solution was returned to room temperature (25 ° C.), 55.1 g (0.22 mol) of MDI (4,4′-diphenylmethane diisocyanate) was added as an aromatic diisocyanate, and reacted at 190 ° C. for 2 hours. After completion of the reaction, an NMP solution of polyamideimide resin (resin content 28% by weight) was obtained.
（実施例１）
合成例１のシロキサン変性ポリアミドイミド樹脂のＮＭＰ溶液全量８５８ｇ（樹脂固形分３３重量％）とエポキシ樹脂としてＺＸ１５４８−３（東都化成株式会社製商品名）１８８．０ｇ（樹脂固形分５０重量％のジメチルアセトアミド溶液）、１−シアノエチル−２−エチル−１−メチルイミダゾール０．７ｇを配合し、均一になるまで約１時間撹拌した後、脱泡のため２４時間、室温（２５℃）で静置して樹脂組成物ワニスとした。
Example 1
858 g of the total amount of NMP solution of the siloxane-modified polyamideimide resin of Synthesis Example 1 (resin solid content 33 wt%) and ZX1548-3 (trade name, manufactured by Tohto Kasei Co., Ltd.) as an epoxy resin 188.0 g (dimethyl resin having a resin solid content of 50 wt%) Acetamide solution) and 0.7 g of 1-cyanoethyl-2-ethyl-1-methylimidazole were mixed and stirred for about 1 hour until uniform, then allowed to stand at room temperature (25 ° C.) for 24 hours for defoaming. To obtain a resin composition varnish.
（実施例２）
合成例２のシロキサン変性ポリアミドイミド樹脂のＮＭＰ溶液全量９５９ｇ（樹脂固形分２８重量％）とエポキシ樹脂としてＮＣ３０００（日本化薬株式会社製商品名）１７９．０ｇ（樹脂固形分５０重量％のジメチルアセトアミド溶液）、１−シアノエチル−２−フェニルイミダゾール０．２ｇを配合し、均一になるまで約１時間撹拌した後、リン含有フィラーとしてＯＰ９３０（クラリアント社製商品名）５６ｇを加えさらに１時間撹拌したのち２００メッシュのナイロン布を通し、室温（２５℃）で静置して樹脂組成物ワニスとした。
(Example 2)
NMP solution total amount 959g (resin solid content 28 wt%) of siloxane-modified polyamideimide resin of Synthesis Example 2 and NC resin (trade name made by Nippon Kayaku Co., Ltd.) 179.0g as epoxy resin (dimethylacetamide with resin solid content 50 wt%) Solution), 0.2 g of 1-cyanoethyl-2-phenylimidazole was mixed and stirred for about 1 hour until uniform, and then 56 g of OP930 (trade name, manufactured by Clariant) was added as a phosphorus-containing filler, and the mixture was further stirred for 1 hour. A 200-mesh nylon cloth was passed through and allowed to stand at room temperature (25 ° C.) to obtain a resin composition varnish.
（実施例３）
エポキシ樹脂としてＥＰＩＣＬＯＮ１５３（大日本インキ株式会社製商品名）３４０．０ｇ、硬化剤としてＦＧ−２０００（帝人化成株式会社製商品名）１８１ｇ、硬化促進剤として１−シアノエチル−２−フェニルイミダゾール、１．０ｇをメチルイソブチルケトン６００．０ｇに溶解した後、アクリル樹脂としてＨＴＲ−８６０−Ｐ３（ナガセケムテックス株式会社製商品名：１５重量％メチルエチルケトン溶液）２８７．０ｇを加えてさらに１時間、撹拌して樹脂組成物ワニスとした。
(Example 3)
340.0 g of EPICLON 153 (trade name, manufactured by Dainippon Ink Co., Ltd.) as an epoxy resin, 181 g of FG-2000 (trade name, manufactured by Teijin Chemicals Ltd.) as a curing agent, 1-cyanoethyl-2-phenylimidazole as a curing accelerator, After dissolving 0 g in 600.0 g of methyl isobutyl ketone, 287.0 g of HTR-860-P3 (trade name: 15 wt% methyl ethyl ketone solution manufactured by Nagase ChemteX Corporation) was added as an acrylic resin, and the mixture was further stirred for 1 hour. A resin composition varnish was obtained.
（実施例４）
エポキシ樹脂としてＢＲＥＮ−Ｓ（日本化薬株式会社製商品名）３００ｇ、硬化剤としてＦＧ−２０００（帝人化成株式会社製商品名）１８１．０ｇ、硬化促進剤として１−シアノエチル−２−エチル−１−メチルイミダゾール、１．０ｇをメチルイソブチルケトン６００．０ｇに溶解した後、アクリル樹脂としてＨＴＲ−８６０−Ｐ３（ナガセケムテックス株式会社製商品名：１５重量％メチルエチルケトン溶液）２８７．０ｇを加えてさらに１時間、撹拌して樹脂組成物ワニスとした。
Example 4
300 g of BREN-S (trade name, manufactured by Nippon Kayaku Co., Ltd.) as an epoxy resin, 181.0 g of FG-2000 (trade name, manufactured by Teijin Chemicals Ltd.) as a curing agent, and 1-cyanoethyl-2-ethyl-1 as a curing accelerator -After dissolving 1.0 g of methylimidazole in 600.0 g of methyl isobutyl ketone, 287.0 g of HTR-860-P3 (trade name: 15 wt% methyl ethyl ketone solution manufactured by Nagase ChemteX Corporation) was added as an acrylic resin. The resin composition varnish was stirred for 1 hour.
（実施例５）
１リットルのセパラブルフラスコに３，３’，４，４’−ジフェニルエーテルテトラカルボン酸二無水物（ＯＰＤＡ）３１．０ｇ（０．１０ｍｏｌ）、ＮＭＰ（Ｎ−メチル−２−ピロリドン）２５０ｇ、を入れ室温で撹拌した。シロキサンジアミンとして反応性シリコンオイルＫＦ−８０１０（信越化学工業株式会社製商品名、アミン当量４３０）３４．４ｇ（０．０４ｍｏｌ）を滴下ロートを用いて滴下し、この反応溶液を撹拌下で氷冷し、芳香族ジアミンとしてＢＡＰＰ（２，２−ビス［４−（４−アミノフェノキシ）フェニル］プロパン）２４．６ｇ（０．０６ｍｏｌ）添加して室温（２５℃）で２時間撹拌してポリアミック酸を得た。これを樹脂組成物ワニスとした。
(Example 5)
In a 1 liter separable flask, 31.0 g (0.10 mol) of 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride (OPDA) and 250 g of NMP (N-methyl-2-pyrrolidone) were placed. Stir at room temperature. 34.4 g (0.04 mol) of reactive silicone oil KF-8010 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd., amine equivalent 430) was added dropwise as a siloxane diamine using a dropping funnel, and the reaction solution was ice-cooled with stirring. Then, 24.6 g (0.06 mol) of BAPP (2,2-bis [4- (4-aminophenoxy) phenyl] propane) as an aromatic diamine was added and stirred at room temperature (25 ° C.) for 2 hours to obtain a polyamic acid. Got. This was made into the resin composition varnish.
（実施例６）
１リットルのセパラブルフラスコに３，３’，４，４’−ベンゾフェノンテトラカルボン酸二無水物（ＢＴＤＡ）３２．２ｇ（０．１０ｍｏｌ）、ＮＭＰ（Ｎ−メチル−２−ピロリドン）３００ｇ、を入れ室温で撹拌した。シロキサンジアミンとして反応性シリコンオイルＸ−２２−１６１Ｂ（信越化学工業株式会社製商品名、アミン当量１５６０）１２４．８ｇ（０．０４ｍｏｌ）を滴下ロートを用いて滴下し、この反応溶液を撹拌下で氷冷し、芳香族ジアミンとしてＢＡＰＰ（２，２−ビス［４−（４−アミノフェノキシ）フェニル］プロパン）２４．６ｇ（０．０６ｍｏｌ）添加して室温（２５℃）で２時間撹拌してポリアミック酸を得た。これを樹脂組成物ワニスとした。
(Example 6)
Into a 1 liter separable flask was placed 32.2 g (0.10 mol) of 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride (BTDA) and 300 g of NMP (N-methyl-2-pyrrolidone). Stir at room temperature. Reactive silicon oil X-22-161B (trade name, manufactured by Shin-Etsu Chemical Co., Ltd., amine equivalent 1560) 124.8 g (0.04 mol) as siloxane diamine was dropped using a dropping funnel, and the reaction solution was stirred. Ice-cooled, 24.6 g (0.06 mol) of BAPP (2,2-bis [4- (4-aminophenoxy) phenyl] propane) as an aromatic diamine was added, and the mixture was stirred at room temperature (25 ° C.) for 2 hours. A polyamic acid was obtained. This was made into the resin composition varnish.
（実施例７）
１リットルのセパラブルフラスコに３，３’，４，４’−ビフェニルテトラカルボン酸二無水物（ＢＰＤＡ）２９．４ｇ（０．１０ｍｏｌ）、ＮＭＰ（Ｎ−メチル−２−ピロリドン）３００ｇ、を入れ室温で撹拌した。シロキサンジアミンとして反応性シリコンオイルＸ−２２−１６１Ａ（信越化学工業株式会社製商品名、アミン当量９００）７２．０ｇ（０．０４ｍｏｌ）を滴下ロートを用いて滴下し、この反応溶液を撹拌下で氷冷し、芳香族ジアミンとしてＢＡＰＰ（２，２−ビス［４−（４−アミノフェノキシ）フェニル］プロパン）２４．６ｇ（０．０６ｍｏｌ）添加して室温（２５℃）で２時間撹拌してポリアミック酸を得た。これを樹脂組成物ワニスとした。
(Example 7)
Into a 1 liter separable flask, 29.4 g (0.10 mol) of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride (BPDA) and 300 g of NMP (N-methyl-2-pyrrolidone) were placed. Stir at room temperature. 72.0 g (0.04 mol) of reactive silicone oil X-22-161A (trade name, amine equivalent 900, manufactured by Shin-Etsu Chemical Co., Ltd.) was added dropwise as a siloxane diamine using a dropping funnel, and this reaction solution was stirred. Ice-cooled, 24.6 g (0.06 mol) of BAPP (2,2-bis [4- (4-aminophenoxy) phenyl] propane) as an aromatic diamine was added, and the mixture was stirred at room temperature (25 ° C.) for 2 hours. A polyamic acid was obtained. This was made into the resin composition varnish.
（樹脂付き金属箔の作製）
電解銅箔Ｆ２−ＷＳ−１８（古河電工株式会社製商品名）の上に厚さ２０μｍのガラスクロス（旭シュエーベル株式会社製商品名１０２７）を重ね、実施例１〜４で作製した樹脂組成物ワニスを乾燥後の厚みが５０μｍになるように塗布し、１５０℃で１５分加熱、乾燥して樹脂分７０重量％の樹脂付き金属箔（Ｂステージ状態）を得た。
(Production of metal foil with resin)
A resin composition produced in Examples 1 to 4 by superposing a glass cloth (trade name 1027 manufactured by Asahi Schavel Co., Ltd.) having a thickness of 20 μm on electrolytic copper foil F2-WS-18 (trade name manufactured by Furukawa Electric Co., Ltd.). The varnish was applied so that the thickness after drying was 50 μm, heated at 150 ° C. for 15 minutes, and dried to obtain a metal foil with a resin having a resin content of 70% by weight (B stage state).
また厚さ１２μｍの電解銅箔（古河電工株式会社製、商品名Ｆ２−ＷＳ−１２）と厚さ２８μｍのガラスクロス（旭シュエーベル株式会社製、商品名１０３７）を重ねて、実施例５のポリアミック酸のＮＭＰ溶液（樹脂組成物ワニス）を含浸乾燥後の樹脂組成物の厚みが５０μｍになるように、ガラスクロスに含浸し１５０℃で１５分乾燥し、樹脂付き金属箔（Ｂステージ状態）を作製した。更にその後２５０℃の加熱条件で６０分処理し、Ｃステージ状態の樹脂付き金属箔とした。 Further, a 12 μm thick electrolytic copper foil (Furukawa Electric Co., Ltd., trade name F2-WS-12) and a 28 μm thick glass cloth (Asahi Schavel Co., Ltd., trade name 1037) are layered to form a polyamic of Example 5. A glass cloth is impregnated with an acid NMP solution (resin composition varnish) so that the thickness of the resin composition after impregnation and drying is 50 μm, and dried at 150 ° C. for 15 minutes. Produced. Furthermore, it processed for 60 minutes on 250 degreeC heating conditions after that, and was set as the metal foil with a resin of a C stage state.
また厚さ１２μｍの電解銅箔（古河電工株式会社製、商品名Ｆ２−ＷＳ−１２）と厚さ２８μｍのガラスクロス（旭シュエーベル株式会社製、商品名１０３７）を重ねて、実施例６のポリアミック酸のＮＭＰ溶液（樹脂組成物ワニス）を含浸乾燥後の樹脂組成物の厚みが４０μｍになるように、ガラスクロスに含浸し１５０℃で１５分乾燥し、樹脂付き金属箔（Ｂステージ状態）を作製した。更にその後２５０℃の加熱条件で６０分処理し、Ｃステージ状態の樹脂付き金属箔とした。 Also, a 12 μm thick electrolytic copper foil (Furukawa Electric Co., Ltd., trade name F2-WS-12) and a 28 μm thick glass cloth (Asahi Schavel Co., Ltd., trade name 1037) are layered to form the polyamic of Example 6. A glass cloth is impregnated with an acid NMP solution (resin composition varnish) so that the thickness of the resin composition after impregnation and drying is 40 μm, and dried at 150 ° C. for 15 minutes. Produced. Furthermore, it processed for 60 minutes on 250 degreeC heating conditions after that, and was set as the metal foil with a resin of a C stage state.
また厚さ１２μｍの電解銅箔（古河電工株式会社製、商品名Ｆ２−ＷＳ−１２）と厚さ２８μｍのガラスクロス（旭シュエーベル株式会社製、商品名１０３７）を重ねて、実施例７のポリアミック酸のＮＭＰ溶液（樹脂組成物ワニス）を含浸乾燥後の樹脂組成物の厚みが４０μｍになるように、ガラスクロスに含浸し１５０℃で１５分乾燥し、樹脂付き金属箔（Ｂステージ状態）を作製した。更にその後２５０℃の加熱条件で６０分処理し、Ｃステージ状態の樹脂付き金属箔とした。 Also, a 12 μm thick electrolytic copper foil (Furukawa Electric Co., Ltd., trade name F2-WS-12) and a 28 μm thick glass cloth (Asahi Schavel Co., trade name 1037) are stacked to form the polyamic of Example 7. A glass cloth is impregnated with an acid NMP solution (resin composition varnish) so that the thickness of the resin composition after impregnation and drying is 40 μm, and dried at 150 ° C. for 15 minutes. Produced. Furthermore, it processed for 60 minutes on 250 degreeC heating conditions after that, and was set as the metal foil with a resin of a C stage state.
（両面銅張積層板の作製）
実施例１〜４の樹脂付き金属箔をそれぞれ樹脂面が合わさるようにして重ね、下記表１に示した条件でプレス積層し両面銅張積層板を作製した。
(Production of double-sided copper-clad laminate)
The resin-coated metal foils of Examples 1 to 4 were stacked so that the resin surfaces were aligned, and press-laminated under the conditions shown in Table 1 below to prepare a double-sided copper-clad laminate.
（比較例１）
電解銅箔Ｆ２−ＷＳ−１８の上に実施例１で作製した樹脂組成物ワニスを乾燥後の厚みが５０μｍになるように塗布し、１５０℃で１５分加熱、乾燥して繊維基材を含まない樹脂分７０重量％の樹脂付き金属箔（Ｂステージ状態）を得た。更に樹脂付き金属箔をそれぞれ樹脂面が合わさるようにして重ね、下記表１に示した条件でプレス積層し両面銅張積層板を作製した。
(Comparative Example 1)
The resin composition varnish produced in Example 1 was applied onto electrolytic copper foil F2-WS-18 so that the thickness after drying was 50 μm, heated at 150 ° C. for 15 minutes, and dried to include a fiber substrate. A resin-added metal foil (B stage state) having a resin content of 70% by weight was obtained. Further, the metal foils with resin were stacked so that the resin surfaces were combined, and press laminated under the conditions shown in Table 1 below to prepare a double-sided copper-clad laminate.
（比較例２）
電解銅箔Ｆ２−ＷＳ−１８の上に実施例１で作製した樹脂組成物ワニスを乾燥後の厚みが５０μｍになるように塗布し、１５０℃で１５分加熱、乾燥して繊維基材を含まない樹脂分７０重量％の樹脂付き金属箔（Ｂステージ状態）を得た。更に樹脂付き金属箔をそれぞれ樹脂面が合わさるようにして重ね、下記表１に示した条件でプレス積層し両面銅張積層板を作製した。
(Comparative Example 2)
The resin composition varnish produced in Example 1 was applied onto electrolytic copper foil F2-WS-18 so that the thickness after drying was 50 μm, heated at 150 ° C. for 15 minutes, and dried to include a fiber substrate. A resin-added metal foil (B stage state) having a resin content of 70% by weight was obtained. Further, the metal foils with resin were stacked so that the resin surfaces were combined, and press laminated under the conditions shown in Table 1 below to prepare a double-sided copper-clad laminate.
（比較例３）
厚さ１２μｍの電解銅箔（古河電工株式会社製、商品名Ｆ２−ＷＳ−１２）上に、実施例６のポリアミック酸のＮＭＰ溶液（樹脂組成物ワニス）を、乾燥後の厚みが４０μｍとなるように塗布し、１５０℃で１５分乾燥し、繊維基材を含まない樹脂付き金属箔（Ｂステージ状態）を作製した。さらに２００℃で６０分熱硬化処理を行って、繊維基材を含まないＣステージ状態の樹脂付き金属箔とした。
(Comparative Example 3)
On the electrolytic copper foil (product name F2-WS-12, manufactured by Furukawa Electric Co., Ltd.) having a thickness of 12 μm, the polyamic acid NMP solution (resin composition varnish) of Example 6 has a thickness after drying of 40 μm. And dried at 150 ° C. for 15 minutes to prepare a metal foil with a resin (B stage state) that does not contain a fiber base material. Furthermore, the thermosetting process was performed at 200 degreeC for 60 minutes, and it was set as the metal foil with resin of the C stage state which does not contain a fiber base material.
（弾性率の測定）
実施例１〜７、比較例１〜３の樹脂組成物を厚さ１２μｍの電解銅箔（古河電工株式会社製、商品名Ｆ２−ＷＳ−１２）に試料厚みが約５０〜１００μｍになるように塗工し、以下の条件で硬化した。実施例１〜２は、１５０℃で１５分加熱後、２３０℃で６０分加熱、実施例３〜４は、１５０℃で１５分加熱後、１８０℃で６０分加熱、実施例５〜７は、１５０℃で１５分加熱後、２５０℃で６０分加熱、比較例１は、１５０℃で１５分加熱後
２３０℃で６０分加熱、比較例２は、１５０℃で１５分加熱後、１８０℃で６０分加熱、比較例３は、１５０℃で１５分加熱後、２５０℃で６０分加熱した。その後、銅箔をエッチングにより除去して得られた樹脂硬化物を試験用基板とした。この試験用基板を約３０ｍｍ×５ｍｍに切り出し、ＵＢＭ社製動的粘弾性測定装置Ｒｅｏｇｅｌ−Ｅ−４０００を用い、測定長２０ｍｍ、測定周波数１０Ｈｚの条件で測定を行った。得られた動的粘弾性曲線の２５℃の弾性率を測定値とした。結果を表２に示した。
(Measurement of elastic modulus)
The resin compositions of Examples 1 to 7 and Comparative Examples 1 to 3 are placed on an electrolytic copper foil (Furukawa Electric Co., Ltd., trade name F2-WS-12) having a thickness of 12 μm so that the sample thickness is about 50 to 100 μm. It was coated and cured under the following conditions. Examples 1-2 were heated at 150 ° C. for 15 minutes, then heated at 230 ° C. for 60 minutes, Examples 3-4 were heated at 150 ° C. for 15 minutes, then heated at 180 ° C. for 60 minutes, and Examples 5-7 were After heating at 150 ° C. for 15 minutes, heating at 250 ° C. for 60 minutes, Comparative Example 1 is heated at 150 ° C. for 15 minutes and then heated at 230 ° C. for 60 minutes, Comparative Example 2 is heated at 150 ° C. for 15 minutes and then 180 ° C. And Comparative Example 3 was heated at 150 ° C. for 15 minutes and then heated at 250 ° C. for 60 minutes. Thereafter, the cured resin obtained by removing the copper foil by etching was used as a test substrate. This test substrate was cut out to about 30 mm × 5 mm and measured using a dynamic viscoelasticity measuring device Regel-E-4000 manufactured by UBM under the conditions of a measurement length of 20 mm and a measurement frequency of 10 Hz. The elastic modulus at 25 ° C. of the obtained dynamic viscoelastic curve was taken as a measured value. The results are shown in Table 2.
（線熱膨張係数の測定）
実施例１〜４及び比較例１〜２の両面銅張積層板の銅をエッチングにより除去し、試験用基板とした。また実施例５〜７及び比較例３のＣステージ状態の樹脂付き金属箔（銅箔）の銅をエッチングにより除去し、試験用基板とした。この試験用基板を５ｍｍ×２０ｍｍに切り出し、熱機械分析装置（ＴＭＡ）により引張りモード、昇温速度１０℃／分の条件で線熱膨張係数を測定した。結果を表２に示した。
(Measurement of linear thermal expansion coefficient)
The copper of the double-sided copper clad laminates of Examples 1 to 4 and Comparative Examples 1 to 2 was removed by etching to obtain a test substrate. Moreover, the copper of the metal foil with a resin (copper foil) of the C-stage state of Examples 5-7 and Comparative Example 3 was removed by etching to obtain a test substrate. This test substrate was cut out to 5 mm × 20 mm, and the linear thermal expansion coefficient was measured by a thermomechanical analyzer (TMA) under conditions of a tensile mode and a temperature rising rate of 10 ° C./min. The results are shown in Table 2.
（吸湿時の寸法変化率の測定）
実施例１〜４及び比較例１〜２の両面銅張積層板の銅をエッチングにより除去し、試験用基板とした。この試験用基板を１０５℃で１時間乾燥後２５０ｍｍ×２５０ｍｍに切り出し、１００ｍｍ間隔に２ｍｍφのドリルで穴を明け三次元測定装置でドリル穴の中心間距離を測定した。その後プレッシャークッカーを用いて１２１℃飽和の条件で２時間吸湿させ表面の水分を拭き取ってから再度、三次元測定装置でドリル穴の中心間距離を測定した。吸湿前後のドリル穴の中心間距離から吸湿時の寸法変化率を求めた。結果を表２に示した。
(Measurement of dimensional change during moisture absorption)
The copper of the double-sided copper clad laminates of Examples 1 to 4 and Comparative Examples 1 to 2 was removed by etching to obtain a test substrate. This test substrate was dried at 105 ° C. for 1 hour, cut into 250 mm × 250 mm, drilled with a 2 mmφ drill at 100 mm intervals, and the distance between centers of the drill holes was measured with a three-dimensional measuring device. Then, using a pressure cooker, moisture was absorbed for 2 hours under conditions of 121 ° C. saturation, and the surface moisture was wiped off. Then, the distance between the centers of the drill holes was measured again with a three-dimensional measuring device. The dimensional change rate during moisture absorption was determined from the distance between the centers of the drill holes before and after moisture absorption. The results are shown in Table 2.
（耐衝撃性の評価）
実施例１〜４及び比較例１〜２の両面銅張積層板と、実施例５〜７及び比較例３のＣステージ状態の樹脂付き金属箔（銅箔）に通常のドリル加工、めっき、フォトリソ工程により直径０．２５ｍｍの接続穴２５０穴を有するデイジーチェーンパターン４列の印刷回路板を作製し、それぞれの始点と終点をはんだによりリード線で接続し、一列１０００穴の導通パターンとして初期の抵抗を測定した。その後、各印刷回路板を所定の筐体に搭載し高さ１．５ｍから所定の回数落下させ断線の有無、抵抗値を測定した。１０００回落下させた後、抵抗値の変化率が、１０％以内を○、１０％超を×とした。結果を表２に示した。
(Evaluation of impact resistance)
Conventional drilling, plating, photolithography on double-sided copper-clad laminates of Examples 1-4 and Comparative Examples 1-2, and metal foils (copper foils) with resin in the C-stage state of Examples 5-7 and Comparative Example 3 A printed circuit board with four rows of daisy chain patterns having 250 connection holes with a diameter of 0.25 mm is manufactured by the process, and the start point and the end point of each are connected by lead wires with solder, and the initial resistance as a conduction pattern of one row with 1000 holes Was measured. Thereafter, each printed circuit board was mounted in a predetermined housing and dropped a predetermined number of times from a height of 1.5 m, and the presence or absence of disconnection and the resistance value were measured. After dropping 1000 times, the change rate of the resistance value is within 10%, and over 10% is made x. The results are shown in Table 2.
（埋め込み性の評価）
ライン／スペースがそれぞれ５０μｍ／５０μｍ、７５μｍ／７５μｍ、１００μｍ／１００μｍの櫛形パターンを形成した内層回路板（導体厚み１２μｍ）の上に実施例１〜４及び比較例１〜２の樹脂付き金属箔（銅箔）を、内層回路板の回路面と、樹脂付き金属箔（銅箔）の樹脂面が合わさるようにして重ね、表１に示した条件で積層プレスした。得られた積層板の銅箔をエッチングにより除去し、内層回路板の内層回路への樹脂の埋め込み性を目視により評価した。○：ボイドやかすれなし、×：ボイドやかすれありとした。結果を表２に示した。
(Evaluation of embeddability)
Resin-coated metal foils of Examples 1 to 4 and Comparative Examples 1 to 2 on an inner layer circuit board (conductor thickness: 12 μm) on which comb-shaped patterns having lines / spaces of 50 μm / 50 μm, 75 μm / 75 μm, and 100 μm / 100 μm were formed ( The copper foil was stacked so that the circuit surface of the inner circuit board and the resin surface of the resin-attached metal foil (copper foil) were put together and laminated and pressed under the conditions shown in Table 1. The copper foil of the obtained laminated board was removed by etching, and the embedding property of the resin in the inner layer circuit of the inner layer circuit board was visually evaluated. ○: No voids or blurs, ×: Voids or blurs. The results are shown in Table 2.
（銅箔引き剥がし強さの測定）
実施例１〜４及び比較例１〜２の両面銅張積層板と、実施例５〜７及び比較例３のＣステージ状態の樹脂付き金属箔（銅箔）の金属箔接着強度（銅箔引き剥がし強さ）を測定した。結果を表２に示した。
(Measurement of peel strength of copper foil)
Metal foil adhesion strength (copper foil drawing) of double-sided copper-clad laminates of Examples 1 to 4 and Comparative Examples 1 to 2 and metal foils with resin (copper foil) in the C-stage state of Examples 5 to 7 and Comparative Example 3 Peel strength) was measured. The results are shown in Table 2.
（はんだ耐熱性の評価）
実施例１〜４及び比較例１〜２の両面銅張積層板と、実施例５〜７及び比較例３のＣステージ状態の樹脂付き金属箔（銅箔）を、２６０℃、２８８℃及び３００℃のはんだ浴に浸漬し、はんだ耐熱性を評価した。表２には、３００℃のはんだ浴に浸漬した際の、ふくれ、剥がれ等の異常が認められるまでの時間を示した。
(Evaluation of solder heat resistance)
The double-sided copper-clad laminates of Examples 1 to 4 and Comparative Examples 1 to 2, and the metal foils with a C-stage resin (copper foil) of Examples 5 to 7 and Comparative Example 3 were 260 ° C., 288 ° C. and 300 ° C. It was immersed in a solder bath at 0 ° C. and the solder heat resistance was evaluated. Table 2 shows the time until abnormalities such as blistering and peeling were observed when immersed in a 300 ° C. solder bath.
（１８０度折り曲げ性の評価）
実施例１〜４及び比較例１〜２の両面銅張積層板の銅をエッチングにより除去し、試験用基板とした。また実施例５〜７及び比較例３のＣステージ状態の樹脂付き金属箔（銅箔）の銅をエッチングにより除去し、試験用基板とした。この試験用基板を直径２ｍｍのガラス棒と、試験用基板の折り曲げ箇所の内側を隙間なく接触させるように１８０度折り曲げ、試験用基板のクラックや破断の有無を調べた。○：クラックや破断なし、×：クラックや破断ありとした。結果を表２に示した。
(Evaluation of 180 degree bendability)
The copper of the double-sided copper clad laminates of Examples 1 to 4 and Comparative Examples 1 to 2 was removed by etching to obtain a test substrate. Moreover, the copper of the metal foil with a resin (copper foil) of the C-stage state of Examples 5-7 and Comparative Example 3 was removed by etching to obtain a test substrate. This test substrate was bent 180 degrees so that the glass rod having a diameter of 2 mm and the inside of the bent portion of the test substrate were brought into contact with no gap, and the presence or absence of cracks or breakage of the test substrate was examined. ○: No cracks or breakage, ×: Cracks or breakage. The results are shown in Table 2.
（発塵性の評価）
実施例１〜７及び比較例１〜３の樹脂付き金属箔（Ｂステージ状態）をカッターで所定の大きさに切り出し、樹脂粉の発生の有無を調べた。○：樹脂粉の発生なし、×：樹脂粉の発生ありとした。結果を表２に示した。
(Dust generation evaluation)
The resin-coated metal foils of Examples 1 to 7 and Comparative Examples 1 to 3 (B stage state) were cut into a predetermined size with a cutter, and the presence or absence of generation of resin powder was examined. ○: Resin powder was not generated, and X: Resin powder was generated. The results are shown in Table 2.
（吸水率の測定）
実施例５〜７及び比較例３のＣステージ状態の樹脂付き金属箔（銅箔）の銅をエッチングにより除去し、試験用基板とした。この試験用基板をプレッシャークッカーを用いて１２１℃飽和の条件で２時間吸湿させ、吸水率を求めた。結果を表２に示した。
(Measurement of water absorption)
The copper of the resin-attached metal foil (copper foil) in the C stage state of Examples 5 to 7 and Comparative Example 3 was removed by etching to obtain a test substrate. The test substrate was absorbed for 2 hours under a condition of 121 ° C. saturation using a pressure cooker, and the water absorption was determined. The results are shown in Table 2.
（樹脂付き金属箔のカールの評価）
実施例１〜７及び比較例１〜３の樹脂付き金属箔（Ｂステージ状態）のカールの状態を評価した。結果を表２に示した。
(Evaluation of curling of metal foil with resin)
The curl state of the metal foil with resin (B stage state) of Examples 1 to 7 and Comparative Examples 1 to 3 was evaluated. The results are shown in Table 2.
実施例１〜７の樹脂組成物ワニスを用いて作製した繊維基材を含む樹脂付き金属箔（Ｂステージ状態）は、カールなどはみられず外観上の問題もないことがわかった。それに対し比較例１〜３に示したように銅箔に直接、樹脂組成物ワニスを塗工したものは、樹脂面を内側にしてカールがみられ、そのカールも大きかった。 It turned out that the metal foil with a resin (B stage state) containing the fiber base material produced using the resin composition varnish of Examples 1-7 does not have curls or the like and has no problem in appearance. On the other hand, as shown in Comparative Examples 1 to 3, when the resin composition varnish was directly applied to the copper foil, the curl was seen with the resin surface inside, and the curl was also large.
作製した両面銅張積層板及びＣステージ状態の樹脂付き金属箔（銅箔）の金属箔接着強度（銅箔引き剥がし強さ）は、いずれも０．９〜１．２ｋＮ／ｍであった。また２６０℃、２８８℃及び３００℃のはんだ浴に浸漬し、はんだ耐熱性を測定した結果、いずれの温度でも５分以上、ふくれ、剥がれ等の異常が見られなかった。なお、比較例３のＣステージ状態の樹脂付き金属箔（銅箔）では、熱硬化処理の際、銅箔を外側にしてカールが生じ、平坦な樹脂付き金属箔（銅箔）は、得られず、はんだ耐熱性の評価は不可であった。なお実施例５〜７の吸水率は、０．８８〜０．９６重量％であった。そして繊維基材を含まない比較例３では、１．８１重量％であった。 Metal foil adhesion strength (copper foil peeling strength) of the prepared double-sided copper-clad laminate and metal foil with a resin in the C-stage state (copper foil) was 0.9 to 1.2 kN / m. Moreover, as a result of immersing in a solder bath of 260 ° C., 288 ° C. and 300 ° C. and measuring solder heat resistance, no abnormality such as blistering or peeling was observed at any temperature for 5 minutes or more. In addition, in the C-staged resin-attached metal foil (copper foil) of Comparative Example 3, curling occurs with the copper foil facing outside during the thermosetting treatment, and a flat resin-attached metal foil (copper foil) is obtained. Therefore, evaluation of solder heat resistance was not possible. In addition, the water absorption of Examples 5-7 was 0.88-0.96 weight%. And in the comparative example 3 which does not contain a fiber base material, it was 1.81 weight%.
実施例１〜７の樹脂組成物を硬化した樹脂硬化物の弾性率は、０．８〜１．５ＧＰａであった。弾性率が、０．８〜１．５ＧＰａの樹脂硬化物（樹脂組成物）を用いた試験用基板の線熱膨張係数は、実施例１〜７では９〜１６ｐｐｍと小さな値であったが、繊維基材を含まない比較例１及び２では、それぞれ１５０ｐｐｍ、３００ｐｐｍと大きかった。また比較例３では、３０ｐｐｍであった。また吸湿時の寸法変化率は、実施例１〜４では０．０１％〜０．０２％と小さな値であったが、比較例１及び２では０．５％、０．２％と大きかった。 The elastic modulus of the cured resin obtained by curing the resin compositions of Examples 1 to 7 was 0.8 to 1.5 GPa. The linear thermal expansion coefficient of the test substrate using a cured resin (resin composition) having an elastic modulus of 0.8 to 1.5 GPa was a small value of 9 to 16 ppm in Examples 1 to 7, In Comparative Examples 1 and 2 that did not include a fiber substrate, they were as large as 150 ppm and 300 ppm, respectively. In Comparative Example 3, it was 30 ppm. Further, the dimensional change rate during moisture absorption was as small as 0.01% to 0.02% in Examples 1 to 4, but was large as 0.5% and 0.2% in Comparative Examples 1 and 2. .
１８０度の折り曲げを行ったところ、実施例１〜７及び比較例１〜３のいずれもクラックなどを生じずに折り曲げることが可能であった。また樹脂付き金属箔をカッターで所定の大きさに切り出したところ、実施例１〜７及び比較例１〜３のいずれも樹脂粉などの発生はみられなかった。また内層回路の埋め込み性は、実施例１〜４及び比較例１〜２のいずれも良好であった。また耐衝撃性に関しても、実施例１〜７及び比較例１〜２のいずれも、良好であった。なお、比較例３のＣステージ状態の樹脂付き金属箔（銅箔）では、熱硬化処理の際、銅箔を外側にしてカールが生じ、平坦な印刷回路板は、得られず、耐衝撃性の評価は不可であった。
When bending was performed at 180 degrees, it was possible to fold all of Examples 1 to 7 and Comparative Examples 1 to 3 without causing cracks or the like. Moreover, when metal foil with resin was cut out to the predetermined | prescribed magnitude | size with the cutter, generation | occurrence | production of resin powder etc. was not seen in any of Examples 1-7 and Comparative Examples 1-3. Further, the embedding property of the inner layer circuit was good in each of Examples 1 to 4 and Comparative Examples 1 and 2. Moreover, also about impact resistance, all of Examples 1-7 and Comparative Examples 1-2 were favorable. In addition, in the C-staged resin-coated metal foil (copper foil) of Comparative Example 3, during the thermosetting treatment, curling occurs with the copper foil facing outside, and a flat printed circuit board cannot be obtained, resulting in impact resistance. Evaluation of was impossible.
Claims (9)
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| JP4962001B2 (en) * | 2006-04-28 | 2012-06-27 | 日立化成工業株式会社 | Insulating substrate, substrate with metal foil, and printed wiring board |
| JP5470725B2 (en) * | 2007-04-10 | 2014-04-16 | 日立化成株式会社 | Metal foil-clad laminate and printed wiring board |
| WO2008126817A1 (en) * | 2007-04-11 | 2008-10-23 | Hitachi Chemical Company, Ltd. | Metallic foil-clad laminate plate and printed wiring board |
| US12064927B2 (en) * | 2018-11-08 | 2024-08-20 | The Boeing Company | Establishing electronics in composite parts by locating electronics on lay-up mandrels |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS544374A (en) * | 1977-06-10 | 1979-01-13 | Sumitomo Bakelite Co | Method of making base plate for flexible print wiring |
| JPH08193139A (en) * | 1995-01-17 | 1996-07-30 | Nippon Steel Chem Co Ltd | Prepreg for printed wiring board and metal-clad laminate using the same |
| JPH09302313A (en) * | 1996-05-09 | 1997-11-25 | Hitachi Chem Co Ltd | Metallic foil with adhesive, bonding sheet and multilayered wiring board |
| JPH11505184A (en) * | 1995-05-09 | 1999-05-18 | ザ ダウ ケミカル カンパニー | Printed wiring board having polyimide benzoxazole dielectric layer and its manufacture |
| JPH11177195A (en) * | 1997-12-05 | 1999-07-02 | Ube Ind Ltd | Flexible printed circuit board and its manufacture |
| JP2000198969A (en) * | 1999-01-07 | 2000-07-18 | Ube Ind Ltd | Adhesive-coated aromatic polyimide film, metal-clad laminate, and circuit board |
| JP2002353583A (en) * | 2001-05-23 | 2002-12-06 | Matsushita Electric Works Ltd | Resin-attached metal foil and multilayered printed wiring board |
-
2004
- 2004-08-26 JP JP2004246600A patent/JP4590982B2/en not_active Expired - Lifetime
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS544374A (en) * | 1977-06-10 | 1979-01-13 | Sumitomo Bakelite Co | Method of making base plate for flexible print wiring |
| JPH08193139A (en) * | 1995-01-17 | 1996-07-30 | Nippon Steel Chem Co Ltd | Prepreg for printed wiring board and metal-clad laminate using the same |
| JPH11505184A (en) * | 1995-05-09 | 1999-05-18 | ザ ダウ ケミカル カンパニー | Printed wiring board having polyimide benzoxazole dielectric layer and its manufacture |
| JPH09302313A (en) * | 1996-05-09 | 1997-11-25 | Hitachi Chem Co Ltd | Metallic foil with adhesive, bonding sheet and multilayered wiring board |
| JPH11177195A (en) * | 1997-12-05 | 1999-07-02 | Ube Ind Ltd | Flexible printed circuit board and its manufacture |
| JP2000198969A (en) * | 1999-01-07 | 2000-07-18 | Ube Ind Ltd | Adhesive-coated aromatic polyimide film, metal-clad laminate, and circuit board |
| JP2002353583A (en) * | 2001-05-23 | 2002-12-06 | Matsushita Electric Works Ltd | Resin-attached metal foil and multilayered printed wiring board |
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