JPH04359052A - Polyaminobismalemide resin composition and production of copper-clad laminate sheet using the same - Google Patents
Polyaminobismalemide resin composition and production of copper-clad laminate sheet using the sameInfo
- Publication number
- JPH04359052A JPH04359052A JP13251091A JP13251091A JPH04359052A JP H04359052 A JPH04359052 A JP H04359052A JP 13251091 A JP13251091 A JP 13251091A JP 13251091 A JP13251091 A JP 13251091A JP H04359052 A JPH04359052 A JP H04359052A
- Authority
- JP
- Japan
- Prior art keywords
- bismaleimide resin
- polyamino bismaleimide
- copper
- masked
- resin composition
- 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.)
- Granted
Links
- 239000011342 resin composition Substances 0.000 title claims abstract description 18
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims abstract description 42
- 229920005989 resin Polymers 0.000 claims abstract description 41
- 239000011347 resin Substances 0.000 claims abstract description 41
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000011889 copper foil Substances 0.000 claims abstract description 23
- 125000001841 imino group Chemical group [H]N=* 0.000 claims abstract description 22
- -1 imidazole compound Chemical class 0.000 claims abstract description 18
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 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 claims description 58
- 229920003192 poly(bis maleimide) Polymers 0.000 claims description 56
- 125000001951 carbamoylamino group Chemical group C(N)(=O)N* 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 7
- 238000010030 laminating Methods 0.000 claims description 4
- 150000007945 N-acyl ureas Chemical class 0.000 abstract description 4
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 abstract description 3
- 239000000203 mixture Substances 0.000 abstract 1
- 239000002966 varnish Substances 0.000 description 11
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 10
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 8
- 239000003822 epoxy resin Substances 0.000 description 8
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 8
- 229920000647 polyepoxide Polymers 0.000 description 8
- 239000004744 fabric Substances 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 239000002904 solvent Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 150000002460 imidazoles Chemical class 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- LVNLBBGBASVLLI-UHFFFAOYSA-N 3-triethoxysilylpropylurea Chemical compound CCO[Si](OCC)(OCC)CCCNC(N)=O LVNLBBGBASVLLI-UHFFFAOYSA-N 0.000 description 3
- 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 3
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 3
- 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
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- LLPKQRMDOFYSGZ-UHFFFAOYSA-N 2,5-dimethyl-1h-imidazole Chemical compound CC1=CN=C(C)N1 LLPKQRMDOFYSGZ-UHFFFAOYSA-N 0.000 description 2
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 2
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 2
- XUSNPFGLKGCWGN-UHFFFAOYSA-N 3-[4-(3-aminopropyl)piperazin-1-yl]propan-1-amine Chemical compound NCCCN1CCN(CCCN)CC1 XUSNPFGLKGCWGN-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 238000006243 chemical reaction Methods 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- CATSNJVOTSVZJV-UHFFFAOYSA-N heptan-2-one Chemical compound CCCCCC(C)=O CATSNJVOTSVZJV-UHFFFAOYSA-N 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- YKNMIGJJXKBHJE-UHFFFAOYSA-N (3-aminophenyl)-(4-aminophenyl)methanone Chemical compound C1=CC(N)=CC=C1C(=O)C1=CC=CC(N)=C1 YKNMIGJJXKBHJE-UHFFFAOYSA-N 0.000 description 1
- MTZUIIAIAKMWLI-UHFFFAOYSA-N 1,2-diisocyanatobenzene Chemical compound O=C=NC1=CC=CC=C1N=C=O MTZUIIAIAKMWLI-UHFFFAOYSA-N 0.000 description 1
- ZXHZWRZAWJVPIC-UHFFFAOYSA-N 1,2-diisocyanatonaphthalene Chemical compound C1=CC=CC2=C(N=C=O)C(N=C=O)=CC=C21 ZXHZWRZAWJVPIC-UHFFFAOYSA-N 0.000 description 1
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-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
- PUKLCKVOVCZYKF-UHFFFAOYSA-N 1-[2-(2,5-dioxopyrrol-1-yl)ethyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1CCN1C(=O)C=CC1=O PUKLCKVOVCZYKF-UHFFFAOYSA-N 0.000 description 1
- IPJGAEWUPXWFPL-UHFFFAOYSA-N 1-[3-(2,5-dioxopyrrol-1-yl)phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC(N2C(C=CC2=O)=O)=C1 IPJGAEWUPXWFPL-UHFFFAOYSA-N 0.000 description 1
- AQGZJQNZNONGKY-UHFFFAOYSA-N 1-[4-(2,5-dioxopyrrol-1-yl)phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=C(N2C(C=CC2=O)=O)C=C1 AQGZJQNZNONGKY-UHFFFAOYSA-N 0.000 description 1
- PYTZZNUKESXWLN-UHFFFAOYSA-N 1-[4-[4-[2-[4-[4-(2,5-dioxopyrrol-1-yl)phenoxy]phenyl]-1,1,1,3,3,3-hexafluoropropan-2-yl]phenoxy]phenyl]pyrrole-2,5-dione Chemical compound C=1C=C(OC=2C=CC(=CC=2)N2C(C=CC2=O)=O)C=CC=1C(C(F)(F)F)(C(F)(F)F)C(C=C1)=CC=C1OC(C=C1)=CC=C1N1C(=O)C=CC1=O PYTZZNUKESXWLN-UHFFFAOYSA-N 0.000 description 1
- XAZPKEBWNIUCKF-UHFFFAOYSA-N 1-[4-[4-[2-[4-[4-(2,5-dioxopyrrol-1-yl)phenoxy]phenyl]propan-2-yl]phenoxy]phenyl]pyrrole-2,5-dione Chemical compound C=1C=C(OC=2C=CC(=CC=2)N2C(C=CC2=O)=O)C=CC=1C(C)(C)C(C=C1)=CC=C1OC(C=C1)=CC=C1N1C(=O)C=CC1=O XAZPKEBWNIUCKF-UHFFFAOYSA-N 0.000 description 1
- OBPBQKFGLIVSKR-UHFFFAOYSA-N 1-[4-[4-[[4-[4-(2,5-dioxopyrrol-1-yl)phenoxy]phenyl]methyl]phenoxy]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1OC(C=C1)=CC=C1CC(C=C1)=CC=C1OC1=CC=C(N2C(C=CC2=O)=O)C=C1 OBPBQKFGLIVSKR-UHFFFAOYSA-N 0.000 description 1
- PYVHLZLQVWXBDZ-UHFFFAOYSA-N 1-[6-(2,5-dioxopyrrol-1-yl)hexyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1CCCCCCN1C(=O)C=CC1=O PYVHLZLQVWXBDZ-UHFFFAOYSA-N 0.000 description 1
- FBHPRUXJQNWTEW-UHFFFAOYSA-N 1-benzyl-2-methylimidazole Chemical compound CC1=NC=CN1CC1=CC=CC=C1 FBHPRUXJQNWTEW-UHFFFAOYSA-N 0.000 description 1
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 1
- PQAMFDRRWURCFQ-UHFFFAOYSA-N 2-ethyl-1h-imidazole Chemical compound CCC1=NC=CN1 PQAMFDRRWURCFQ-UHFFFAOYSA-N 0.000 description 1
- YTWBFUCJVWKCCK-UHFFFAOYSA-N 2-heptadecyl-1h-imidazole Chemical compound CCCCCCCCCCCCCCCCCC1=NC=CN1 YTWBFUCJVWKCCK-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
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 2-phenyl-1h-imidazole Chemical compound C1=CNC(C=2C=CC=CC=2)=N1 ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 0.000 description 1
- FUOZJYASZOSONT-UHFFFAOYSA-N 2-propan-2-yl-1h-imidazole Chemical compound CC(C)C1=NC=CN1 FUOZJYASZOSONT-UHFFFAOYSA-N 0.000 description 1
- LLEASVZEQBICSN-UHFFFAOYSA-N 2-undecyl-1h-imidazole Chemical compound CCCCCCCCCCCC1=NC=CN1 LLEASVZEQBICSN-UHFFFAOYSA-N 0.000 description 1
- JRBJSXQPQWSCCF-UHFFFAOYSA-N 3,3'-Dimethoxybenzidine Chemical compound C1=C(N)C(OC)=CC(C=2C=C(OC)C(N)=CC=2)=C1 JRBJSXQPQWSCCF-UHFFFAOYSA-N 0.000 description 1
- NUIURNJTPRWVAP-UHFFFAOYSA-N 3,3'-Dimethylbenzidine Chemical group C1=C(N)C(C)=CC(C=2C=C(C)C(N)=CC=2)=C1 NUIURNJTPRWVAP-UHFFFAOYSA-N 0.000 description 1
- 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
- NYRFBMFAUFUULG-UHFFFAOYSA-N 3-[4-[2-[4-(3-aminophenoxy)phenyl]propan-2-yl]phenoxy]aniline Chemical compound C=1C=C(OC=2C=C(N)C=CC=2)C=CC=1C(C)(C)C(C=C1)=CC=C1OC1=CC=CC(N)=C1 NYRFBMFAUFUULG-UHFFFAOYSA-N 0.000 description 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
- LDMRLRNXHLPZJN-UHFFFAOYSA-N 3-propoxypropan-1-ol Chemical compound CCCOCCCO LDMRLRNXHLPZJN-UHFFFAOYSA-N 0.000 description 1
- LVACOMKKELLCHJ-UHFFFAOYSA-N 3-trimethoxysilylpropylurea Chemical compound CO[Si](OC)(OC)CCCNC(N)=O LVACOMKKELLCHJ-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
- CPHGOBGXZQKCKI-UHFFFAOYSA-N 4,5-diphenyl-1h-imidazole Chemical compound N1C=NC(C=2C=CC=CC=2)=C1C1=CC=CC=C1 CPHGOBGXZQKCKI-UHFFFAOYSA-N 0.000 description 1
- MITHMOYLTXMLRB-UHFFFAOYSA-N 4-(4-aminophenyl)sulfinylaniline Chemical compound C1=CC(N)=CC=C1S(=O)C1=CC=C(N)C=C1 MITHMOYLTXMLRB-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
- BEKFRNOZJSYWKZ-UHFFFAOYSA-N 4-[2-(4-aminophenyl)-1,1,1,3,3,3-hexafluoropropan-2-yl]aniline Chemical compound C1=CC(N)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(N)C=C1 BEKFRNOZJSYWKZ-UHFFFAOYSA-N 0.000 description 1
- ZYEDGEXYGKWJPB-UHFFFAOYSA-N 4-[2-(4-aminophenyl)propan-2-yl]aniline Chemical compound C=1C=C(N)C=CC=1C(C)(C)C1=CC=C(N)C=C1 ZYEDGEXYGKWJPB-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
- 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
- 229940126062 Compound A Drugs 0.000 description 1
- 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 1
- 239000004641 Diallyl-phthalate Substances 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000008430 aromatic amides Chemical class 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- TUQQUUXMCKXGDI-UHFFFAOYSA-N bis(3-aminophenyl)methanone Chemical compound NC1=CC=CC(C(=O)C=2C=C(N)C=CC=2)=C1 TUQQUUXMCKXGDI-UHFFFAOYSA-N 0.000 description 1
- ZLSMCQSGRWNEGX-UHFFFAOYSA-N bis(4-aminophenyl)methanone Chemical compound C1=CC(N)=CC=C1C(=O)C1=CC=C(N)C=C1 ZLSMCQSGRWNEGX-UHFFFAOYSA-N 0.000 description 1
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 239000004643 cyanate ester Substances 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000005350 fused silica glass Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 229940018564 m-phenylenediamine Drugs 0.000 description 1
- 230000000873 masking effect Effects 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- IYMSIPPWHNIMGE-UHFFFAOYSA-N silylurea Chemical compound NC(=O)N[SiH3] IYMSIPPWHNIMGE-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/032—Organic insulating material consisting of one material
- H05K1/0346—Organic insulating material consisting of one material containing N
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
- H05K1/0373—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement containing additives, e.g. fillers
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Resins (AREA)
- Laminated Bodies (AREA)
Abstract
Description
【０００１】0001
【産業上の利用分野】本発明はポリアミノビスマレイミ
ド樹脂組成物及びそれを用いた銅張積層板の製造方法に
関し、更に詳しくは耐熱性が高く、銅箔との接着性に優
れた樹脂組成物及びそれを用いた銅張積層板の製造方法
に関する。[Industrial Application Field] The present invention relates to a polyamino bismaleimide resin composition and a method for producing copper-clad laminates using the same, and more specifically, a resin composition that has high heat resistance and excellent adhesion to copper foil. and a method for manufacturing a copper-clad laminate using the same.
【０００２】0002
【従来の技術】従来、高度な耐熱性、寸法安定性、電気
特性等を要求される耐熱性接着剤、耐熱性積層板、耐熱
性封止材等の分野には、特公昭４６−２３２５０号公報
に示されているようなＮ，Ｎ′−４，４′−ジフェニル
メタンビスマレイミドと４，４′−ジアミノジフェニル
メタンよりなるポリアミノビスマレイミド樹脂が使用さ
れてきた。[Prior Art] Conventionally, in the fields of heat-resistant adhesives, heat-resistant laminates, heat-resistant sealants, etc. that require high heat resistance, dimensional stability, electrical properties, etc., there has been published Japanese Patent Publication No. 46-23250. A polyamino bismaleimide resin consisting of N,N'-4,4'-diphenylmethane bismaleimide and 4,4'-diaminodiphenylmethane as disclosed in the publication has been used.
【０００３】0003
【発明が解決しようとする課題】しかし、このポリアミ
ノビスマレイミド樹脂は耐熱性は高いが、銅箔との接着
性に劣るという問題点があった。本発明は耐熱性、銅箔
との接着性ともに優れるポリアミノビスマレイミド樹脂
組成物及びそれを用いた銅張積層板の製造方法を提供す
るものである。[Problems to be Solved by the Invention] However, although this polyamino bismaleimide resin has high heat resistance, it has a problem in that it has poor adhesion to copper foil. The present invention provides a polyamino bismaleimide resin composition that has excellent heat resistance and adhesion to copper foil, and a method for producing a copper-clad laminate using the same.
【０００４】0004
【課題を解決するための手段】本発明者らは、特定のイ
ミダゾール化合物をポリアミノビスマレイミド樹脂に配
合することにより、前記目的を達成しうることを見出し
、本発明に至った。すなわち、本発明のポリアミノビス
マレイミド樹脂組成物は、ポリアミノビスマレイミド樹
脂、好ましくはエポキシ変性ポリアミノビスマレイミド
樹脂に、イミノ基をマスクしたイミダゾール化合物を配
合してなることを特徴とするものである。[Means for Solving the Problems] The present inventors have discovered that the above object can be achieved by blending a specific imidazole compound into a polyamino bismaleimide resin, leading to the present invention. That is, the polyamino bismaleimide resin composition of the present invention is characterized by blending a polyamino bismaleimide resin, preferably an epoxy-modified polyamino bismaleimide resin, with an imidazole compound whose imino groups are masked.
【０００５】更に、本発明では、イミノ基をマスクした
イミダゾール化合物とウレイド系シランカップリング剤
とを配合することにより、銅箔との接着性を更に向上さ
せることができる。Furthermore, in the present invention, adhesion to copper foil can be further improved by blending an imidazole compound with masked imino groups and a ureide-based silane coupling agent.
【０００６】また、本発明のポリアミノビスマレイミド
樹脂銅張積層板の製造方法は、ポリアミノビスマレイミ
ド樹脂、好ましくはエポキシ変性ポリアミノビスマレイ
ミド樹脂に、イミノ基をマスクしたイミダゾール化合物
を配合してなるポリアミノビスマレイミド樹脂組成物を
基材に含浸させてプリプレグとし、このプリプレグを所
定枚数積層して、片側あるいは両側に銅箔を重ね、加熱
加圧硬化することを特徴とするものである。[0006] Furthermore, the method for producing a polyamino bismaleimide resin copper-clad laminate of the present invention includes a polyamino bismaleimide resin, preferably an epoxy-modified polyamino bismaleimide resin, mixed with an imidazole compound whose imino groups are masked. It is characterized by impregnating a base material with a maleimide resin composition to form a prepreg, laminating a predetermined number of sheets of the prepreg, overlapping copper foil on one or both sides, and curing under heat and pressure.
【０００７】更に、本発明では、ポリアミノビスマレイ
ミド樹脂にイミノ基をマスクしたイミダゾール化合物と
ウレイド系シランカップリング剤とを配合してなるポリ
アミノビスマレイミド樹脂組成物を基材に含浸させてプ
リプレグとし、このプリプレグを所定枚数積層して片側
あるいは両側に銅箔を重ね、加熱加圧硬化することによ
り銅箔との接着性を更に向上させたポリアミノビスマレ
イミド樹脂積層板を製造することができる。Furthermore, in the present invention, a prepreg is obtained by impregnating a base material with a polyamino bismaleimide resin composition obtained by blending a polyamino bismaleimide resin with an imidazole compound having masked imino groups and a ureide silane coupling agent. By laminating a predetermined number of prepregs, overlapping copper foil on one or both sides, and curing under heat and pressure, a polyamino bismaleimide resin laminate with further improved adhesion to the copper foil can be produced.
【０００８】本発明について更に具体的に説明する。本
発明で使用するポリアミノビスマレイミド樹脂は、Ｎ，
Ｎ′−エチレンビスマレイミド、Ｎ，Ｎ′−ｍ−フェニ
レンビスマレイミド、Ｎ，Ｎ′−ｐ−フェニレンビスマ
レイミド、Ｎ，Ｎ′−ヘキサメチレンビスマレイミド、
Ｎ，Ｎ′−４，４′−ジフェニルメタンビスマレイミド
、２，２−ビス［４−（４−マレイミドフェノキシ）フ
ェニル］プロパン、ビス［４−（４−マレイミドフェノ
キシ）フェニル］メタン、１，１，１，３，３，３−ヘ
キサフルオロ−２，２−ビス［４−（４−マレイミドフ
ェノキシ）フェニル］プロパン、Ｎ，Ｎ′−ｐ，ｐ′−
ジフェニルジメチルシリルビスマレイミド、Ｎ，Ｎ′−
ｐ，ｐ′−ジフェニルエーテルビスマレイミド、Ｎ，Ｎ
′−ｐ，ｐ′−ジフェニルスルホンビスマレイミド、Ｎ
，Ｎ′−ジシクロヘキシルメタンビスマレイミド、Ｎ，
Ｎ′−ｍ−キシレンビスマレイミド、Ｎ，Ｎ′−（３，
３′−ジクロロ−ｐ，ｐ′−ビスフェニレン）ビスマレ
イミド、Ｎ，Ｎ′−（３，３′−ジフェニルオキシ）ビ
スマレイミド等のビスマレイミドと、ｍ−フェニレンジ
アミン、ｐ−フェニレンジアミン、３，３′−ジメチル
−４，４′−ジアミノビフェニル、３，３′−ジメトキ
シベンジジン、４，４′−ジアミノジフェニルメタン、
１，１−ビス（４−アミノフェニル）エタン、ビス［４
−（４−アミノフェノキシ）フェニル］スルホン、ビス
［４−（３−アミノフェノキシ）フェニル］スルホン、
ビス［４−（４−アミノフェノキシ）フェニル］エーテ
ル、ビス［４−（３−アミノフェノキシ）フェニル］エ
ーテル、ビス［４−（４−アミノフェノキシ）フェニル
］メタン、ビス［４−（３−アミノフェノキシ）フェニ
ル］メタン、２，２−ビス［４−（４−アミノフェノキ
シ）フェニル］プロパン、１，１，１，３，３，３−ヘ
キサフルオロ−２，２−ビス［４−（４−アミノフェノ
キシ）フェニル］プロパン、２，２−ビス［４−（３−
アミノフェノキシ）フェニル］プロパン、２，２−ビス
（４−アミノフェニル）プロパン、２，２−ビス（４−
アミノフェニル）ヘキサフルオロプロパン、２，２−ビ
ス（４−アミノフェニル）１，３−ジクロロ−１，１−
３，３−テトラフルオロプロパン、４，４′−ジアミノ
ジフェニルエーテル、４，４′−ジアミノジフェニルス
ルファイド、４，４′−ジアミノジフェニルスルホキシ
ド、４，４′−ジアミノジフェニルスルホン、３，３′
−ジアミノジフェニルスルホン、３，３′−ジアミノベ
ンゾフェノン、４，４′−ジアミノベンゾフェノン、３
，４′−ジアミノベンゾフェノン等のジアミンとを単独
あるいは併用して加熱反応させることにより得られる。The present invention will be explained in more detail. The polyamino bismaleimide resin used in the present invention includes N,
N'-ethylene bismaleimide, N,N'-m-phenylene bismaleimide, N,N'-p-phenylene bismaleimide, N,N'-hexamethylene bismaleimide,
N,N'-4,4'-diphenylmethanebismaleimide, 2,2-bis[4-(4-maleimidophenoxy)phenyl]propane, bis[4-(4-maleimidophenoxy)phenyl]methane, 1,1, 1,3,3,3-hexafluoro-2,2-bis[4-(4-maleimidophenoxy)phenyl]propane, N,N'-p,p'-
diphenyldimethylsilyl bismaleimide, N,N'-
p,p'-diphenyl ether bismaleimide, N,N
'-p,p'-diphenylsulfone bismaleimide, N
, N'-dicyclohexylmethane bismaleimide, N,
N'-m-xylene bismaleimide, N,N'-(3,
Bismaleimides such as 3'-dichloro-p,p'-bisphenylene)bismaleimide, N,N'-(3,3'-diphenyloxy)bismaleimide, m-phenylenediamine, p-phenylenediamine, 3, 3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxybenzidine, 4,4'-diaminodiphenylmethane,
1,1-bis(4-aminophenyl)ethane, bis[4
-(4-aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)phenyl]sulfone,
Bis[4-(4-aminophenoxy)phenyl]ether, bis[4-(3-aminophenoxy)phenyl]ether, bis[4-(4-aminophenoxy)phenyl]methane, bis[4-(3-amino) phenoxy)phenyl]methane, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 1,1,1,3,3,3-hexafluoro-2,2-bis[4-(4- aminophenoxy)phenyl]propane, 2,2-bis[4-(3-
aminophenoxy)phenyl]propane, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-
aminophenyl)hexafluoropropane, 2,2-bis(4-aminophenyl)1,3-dichloro-1,1-
3,3-tetrafluoropropane, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylsulfide, 4,4'-diaminodiphenylsulfoxide, 4,4'-diaminodiphenylsulfone, 3,3'
-diaminodiphenylsulfone, 3,3'-diaminobenzophenone, 4,4'-diaminobenzophenone, 3
, 4'-diaminobenzophenone and other diamines alone or in combination.
【０００９】このようなポリアミノビスマレイミド樹脂
としては、Ｎ，Ｎ′−４，４′−ジフェニルメタンビス
マレイミドと、４，４′−ジアミノジフェニルメタン（
ＤＤＭ）、あるいは２，２−ビス［４−（４−アミノフ
ェノキシ）フェニル］プロパン（ＢＡＰＰ）とを反応さ
せたポリアミノビスマレイミド樹脂が好ましく用いられ
る。Such polyamino bismaleimide resins include N,N'-4,4'-diphenylmethane bismaleimide and 4,4'-diaminodiphenylmethane (
A polyamino bismaleimide resin reacted with DDM) or 2,2-bis[4-(4-aminophenoxy)phenyl]propane (BAPP) is preferably used.
【００１０】本発明に使用する変性用のエポキシ樹脂は
二官能タイプのビスフェノールＡ型エポキシ樹脂や、多
官能タイプのエポキシ樹脂である。エポキシ樹脂の変性
量はポリアミノビスマレイミド樹脂１００重量部に対し
、エポキシ樹脂２００重量部以下の範囲が好ましい。
エポキシ樹脂をこれ以上配合すると耐熱性が低下してし
まう。好ましくは４０〜１００重量部である。The epoxy resin for modification used in the present invention is a bifunctional type bisphenol A type epoxy resin or a polyfunctional type epoxy resin. The amount of modification of the epoxy resin is preferably in the range of 200 parts by weight or less of the epoxy resin per 100 parts by weight of the polyamino bismaleimide resin. If more epoxy resin is added, the heat resistance will decrease. Preferably it is 40 to 100 parts by weight.
【００１１】また、本発明に使用するイミノ基をマスク
したイミダゾール化合物はイミダゾール、２−メチルイ
ミダゾール、２−エチルイミダゾール、２−エチル−４
−メチルイミダゾール、２−フェニルイミダゾール、２
−ウンデシルイミダゾール、１−ベンジル−２−メチル
イミダゾール、２−ヘプタデシルイミダゾール、４，５
−ジフェニルイミダゾール、２−イソプロピルイミダゾ
ール、２，４−ジメチルイミダゾール等のイミダゾール
類のイミノ基をフェニレンジイソシアネート、トリレン
ジイソシアネート、ナフタレンジイソシアネート、ヘキ
サメチレンジイソシアネート、メチレンビスフェニルイ
ソシアネート等のマスク剤でマスクしたイミダゾール化
合物である。これらのマスクしたイミダゾール化合物の
配合量はポリアミノビスマレイミド樹脂１００重量部に
対し０．０１〜５．０重量部が好ましい。マスクしたイ
ミダゾール化合物の配合量が０．０１重量部より少ない
と樹脂と銅箔との接着性が十分ではなく、また５．０重
量部より多いと耐熱性が低下してしまう。[0011] Further, imidazole compounds with masked imino groups used in the present invention include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4
-Methylimidazole, 2-phenylimidazole, 2
-undecylimidazole, 1-benzyl-2-methylimidazole, 2-heptadecyl imidazole, 4,5
- Imidazole compounds in which the imino groups of imidazoles such as diphenylimidazole, 2-isopropylimidazole, and 2,4-dimethylimidazole are masked with masking agents such as phenylene diisocyanate, tolylene diisocyanate, naphthalene diisocyanate, hexamethylene diisocyanate, and methylene bisphenyl isocyanate. It is. The blending amount of these masked imidazole compounds is preferably 0.01 to 5.0 parts by weight per 100 parts by weight of the polyamino bismaleimide resin. If the amount of the masked imidazole compound is less than 0.01 part by weight, the adhesion between the resin and the copper foil will not be sufficient, and if it is more than 5.0 parts by weight, the heat resistance will decrease.
【００１２】更に、これらのイミダゾール化合物と併用
するウレイド系シランカップリング剤としてはγ−ウレ
イドプロピルトリエトキシシラン、γ−ウレイドプロピ
ルトリメトキシシラン等がある。ウレイド系シランカッ
プリング剤の配合量はポリアミノビスマレイミド樹脂１
００重量部に対し０．１〜５．０重量部が好ましい。ウ
レイド系シランカップリング剤の配合量が０．１重量部
より少ないと樹脂と銅箔との接着性が十分ではなく、ま
た５．０重量部より多いと耐熱性が低下してしまう。Furthermore, examples of ureido-based silane coupling agents used in combination with these imidazole compounds include γ-ureidopropyltriethoxysilane and γ-ureidopropyltrimethoxysilane. The amount of ureide silane coupling agent is 1 part of polyamino bismaleimide resin.
It is preferably 0.1 to 5.0 parts by weight per 00 parts by weight. If the amount of the ureido-based silane coupling agent is less than 0.1 parts by weight, the adhesion between the resin and the copper foil will not be sufficient, and if it is more than 5.0 parts by weight, the heat resistance will decrease.
【００１３】更に、本発明では上記ポリアミノビスマレ
イミド樹脂、エポキシ樹脂、マスクしたイミダゾール化
合物、ウレイド系シランカップリング剤のほかに、必要
に応じてジアリルフタレート樹脂、イソシアネート樹脂
、シアネートエステル樹脂、多価マレイミド樹脂、ポリ
ブタジエン等の変性樹脂又はガラスパウダー、溶融シリ
カ、炭酸カルシウム、クレー、タルク等の充填剤及びハ
ロゲン系、リン系、アンチモン系の難燃剤等を併用する
ことも可能である。Furthermore, in the present invention, in addition to the above-mentioned polyamino bismaleimide resin, epoxy resin, masked imidazole compound, and ureido-based silane coupling agent, diallylphthalate resin, isocyanate resin, cyanate ester resin, and polyvalent maleimide are optionally added. It is also possible to use resins, modified resins such as polybutadiene, or glass powders, fillers such as fused silica, calcium carbonate, clay, and talc, and halogen-based, phosphorus-based, and antimony-based flame retardants.
【００１４】本発明のポリアミドビスマレイミド樹脂組
成物はこれに更に溶媒を加えてワニス状態で使用される
。ワニス濃度は４０〜７０ｗｔ％、好ましくは５０〜６
０ｗｔ％である。The polyamide bismaleimide resin composition of the present invention is used in the form of a varnish by adding a solvent to it. Varnish concentration is 40-70 wt%, preferably 50-6
It is 0wt%.
【００１５】ポリアミノビスマレイミド樹脂のプレポリ
マー化反応及びマスクしたイミダゾール化合物とウレイ
ド系シランカップリング剤の添加を溶媒中で行うとポリ
アミドビスマレイミド樹脂組成物ワニスが得られる。溶
媒としては、例えばエチレングリコールモノエチルエー
テル、エチレングリコールモノエチルエーテル、プロピ
レングリコールモノメチルエーテル、プロピレングリコ
ールモノプロピルエーテル、Ｎ，Ｎ−ジメチルホルムア
ミド、Ｎ，Ｎ−ジメチルアセトアミド、ジオキサン、Ｎ
−メチル−２−ピロリドン、メチルエチルケトン、メチ
ルイソブチルケトン、シクロヘキサノン、２−ヘプタノ
ン等が好ましく用いられる。A polyamide bismaleimide resin composition varnish is obtained by performing a prepolymerization reaction of a polyamino bismaleimide resin and adding a masked imidazole compound and a ureido silane coupling agent in a solvent. Examples of the solvent include ethylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monopropyl ether, N,N-dimethylformamide, N,N-dimethylacetamide, dioxane, N
-Methyl-2-pyrrolidone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, 2-heptanone, etc. are preferably used.
【００１６】本発明の銅張積層板は、従来行われている
溶媒を用いる乾式塗工方式で作製される。すなわち、前
記のポリアミノビスマレイミド樹脂組成物ワニスを基材
に含浸させてプリプレグとし、このプリプレグを所定枚
数積層して片側あるいは両側に銅箔を重ね、加熱加圧硬
化する方法で作製される。The copper-clad laminate of the present invention is produced by a conventional dry coating method using a solvent. That is, it is produced by impregnating a base material with the polyamino bismaleimide resin composition varnish to form a prepreg, laminating a predetermined number of sheets of this prepreg, overlapping copper foil on one or both sides, and curing under heat and pressure.
【００１７】基材としてはガラスクロス、石英ガラスク
ロス、芳香族アミド繊維布、ガラス不織布、紙、有機繊
維布等、従来知られている基材はいずれも使用可能であ
る。As the base material, any conventionally known base material such as glass cloth, quartz glass cloth, aromatic amide fiber cloth, glass nonwoven cloth, paper, organic fiber cloth, etc. can be used.
【００１８】加熱加圧硬化させる条件は、温度が１５０
〜２５０℃、圧力が５×１０５〜８×１０６Ｐａの範囲
が好ましく、反応時間は３０〜４８０分の範囲が好まし
い。反応温度、反応時間が上記範囲をはずれると、得ら
れる積層板の耐熱性が低下してしまう。[0018] The conditions for curing under heat and pressure are that the temperature is 150℃.
-250°C, the pressure is preferably in the range of 5 x 105 - 8 x 106 Pa, and the reaction time is preferably in the range of 30 to 480 minutes. If the reaction temperature and reaction time are out of the above range, the heat resistance of the resulting laminate will be reduced.
【００１９】[0019]
【作用】本発明によるポリアミノビスマレイミド樹脂組
成物及びそれを用いた銅張積層板は、耐熱性が高く、銅
箔との接着性に優れている。この理由としては、イミノ
基をマスクしたイミダゾール化合物、あるいはこのイミ
ダゾール化合物とウレイド系シランカップリング剤が、
樹脂と接着する銅箔の表面を改質するためと考えられる
が、詳細については不明である。[Function] The polyamino bismaleimide resin composition of the present invention and the copper-clad laminate using the same have high heat resistance and excellent adhesion to copper foil. The reason for this is that an imidazole compound with an imino group masked, or this imidazole compound and a ureido-based silane coupling agent,
It is thought that this is to modify the surface of the copper foil that will be bonded to the resin, but the details are unknown.
【００２０】[0020]
【実施例】以下、本発明について実施例をもって詳細に
説明する。ただし、本発明は以下の実施例に限定される
ものではない。
実施例１
冷却管、攪拌機、温度計を具備した４つ口フラスコを用
いて以下の合成を行った。Ｎ，Ｎ′−４，４′−ジフェ
ニルメタンビスマレイミド（ＢＭＩ）８１重量部と、４
，４′−ジアミノジフェニルメタン（ＤＤＭ）１９重量
部とを１２３重量部のエチレングリコールモノメチルエ
ーテル中にてオイルバス温度１３０℃で３０分間攪拌し
、加熱反応させてポリアミノビスマレイミド樹脂のワニ
スを得た。その後室温まで冷却し、このワニスにヘキサ
メチレンジイソシアネートでイミノ基をマスクした２−
エチル−４−メチルイミダゾール０．１重量部を添加し
、均一になるまでよく攪拌した。このワニスを０．１８
ｍｍ厚のガラスクロス、日東紡績社製Ｇ−９０２０−Ｂ
Ｘに含浸させた後、塗工温度１７０℃、塗工速度３ｍ／
ｍｉｎで溶剤除去するための乾燥塗工を行い、プリプレ
グを得た。このプリプレグを切断後９枚重ね、その両側
に古河サーキットフォイール社製３５μｍ電解銅箔ＴＳ
ＴＯを重ね、これらを２枚の鏡板にはさみ、圧力４ＭＰ
ａ、温度１８０℃で２時間加熱加圧し、その後冷却して
取り出し、更に２００℃で２時間アフターキュアを行い
、１．６ｍｍ厚の銅張積層板を得た。この銅張積層板の
耐熱性、銅箔引きはがし強さ、電気特性、難燃性の試験
結果を表１に示す。EXAMPLES The present invention will be explained in detail below using examples. However, the present invention is not limited to the following examples. Example 1 The following synthesis was carried out using a four-necked flask equipped with a condenser, a stirrer, and a thermometer. 81 parts by weight of N,N'-4,4'-diphenylmethane bismaleimide (BMI), and 4
, 19 parts by weight of 4'-diaminodiphenylmethane (DDM) were stirred in 123 parts by weight of ethylene glycol monomethyl ether at an oil bath temperature of 130°C for 30 minutes, and reacted with heat to obtain a polyamino bismaleimide resin varnish. The varnish was then cooled to room temperature, and the varnish was coated with 2-
0.1 part by weight of ethyl-4-methylimidazole was added and stirred well until uniform. This varnish is 0.18
mm thick glass cloth, G-9020-B manufactured by Nittobo Co., Ltd.
After impregnation with X, the coating temperature was 170°C and the coating speed was 3 m/
A prepreg was obtained by dry coating to remove the solvent at min. After cutting this prepreg, nine sheets were stacked, and 35 μm electrolytic copper foil TS manufactured by Furukawa Circuit Foil Co., Ltd. was used on both sides.
Stack the TOs, sandwich them between two mirror plates, and apply 4MP pressure.
a. The product was heated and pressurized at a temperature of 180°C for 2 hours, then cooled and taken out, and further after-cured at 200°C for 2 hours to obtain a copper-clad laminate with a thickness of 1.6 mm. Table 1 shows the test results of the heat resistance, copper foil peel strength, electrical properties, and flame retardance of this copper-clad laminate.
【００２１】実施例２
Ｎ，Ｎ′−４，４′−ジフェニルメタンビスマレイミド
（ＢＭＩ）７５重量部と、２，２−ビス［４−（４−ア
ミノフェノキシ）フェニル］プロパン（ＢＡＰＰ）２５
重量部とを１２３重量部のエチレングリコールモノメチ
ルエーテル中にてオイルバス温度１３０℃で６０分間攪
拌し、加熱反応させてポリアミノビスマレイミド樹脂の
ワニスを得た。その後室温まで冷却し、このワニスにク
レゾールノボラック型エポキシ樹脂、住友化学社製ＥＳ
ＣＮ２２０を３０重量部と、ヘキサメチレンジイソシア
ネートでイミノ基をマスクした２−エチル−４−メチル
イミダゾール０．１重量部を添加し、均一になるまでよ
く攪拌した。このワニスを用いて実施例１と同様にして
銅張積層板を得た。この銅張積層板の耐熱性、銅箔引き
はがし強さ、電気特性、難燃性の試験結果を表１に示す
。Example 2 75 parts by weight of N,N'-4,4'-diphenylmethane bismaleimide (BMI) and 25 parts by weight of 2,2-bis[4-(4-aminophenoxy)phenyl]propane (BAPP)
parts by weight were stirred in 123 parts by weight of ethylene glycol monomethyl ether at an oil bath temperature of 130° C. for 60 minutes, and reacted with heat to obtain a polyamino bismaleimide resin varnish. After that, it was cooled to room temperature, and this varnish was coated with cresol novolak type epoxy resin and Sumitomo Chemical's ES.
30 parts by weight of CN220 and 0.1 part by weight of 2-ethyl-4-methylimidazole whose imino groups were masked with hexamethylene diisocyanate were added and stirred well until uniform. A copper-clad laminate was obtained in the same manner as in Example 1 using this varnish. Table 1 shows the test results of the heat resistance, copper foil peel strength, electrical properties, and flame retardance of this copper-clad laminate.
【００２２】実施例３
実施例２において、ヘキサメチレンジイソシアネートで
イミノ基をマスクした２−エチル−４−メチルイミダゾ
ール０．１重量部添加し、更にγ−ウレイドプロピルト
リエトキシシラン０．５重量部を添加する以外は実施例
２と同様にして銅張積層板を作製し、特性評価を行った
。結果を表１に示す。Example 3 In Example 2, 0.1 part by weight of 2-ethyl-4-methylimidazole whose imino groups were masked with hexamethylene diisocyanate was added, and further 0.5 part by weight of γ-ureidopropyltriethoxysilane was added. A copper-clad laminate was produced in the same manner as in Example 2 except for the addition of the compound, and its characteristics were evaluated. The results are shown in Table 1.
【００２３】実施例４
実施例３において、ヘキサメチレンジイソシアネートで
イミノ基をマスクした２−エチル−４−メチルイミダゾ
ールのかわりにメチレンビスフェニルイソシアネートで
イミノ基をマスクした２−エチル−４−メチルイミダゾ
ール０．１重量部添加する以外は実施例３と同様にして
銅張積層板を作製し、特性評価を行った。結果を表１に
示す。Example 4 In Example 3, 2-ethyl-4-methylimidazole 0 whose imino groups were masked with methylene bisphenyl isocyanate was used instead of 2-ethyl-4-methylimidazole whose imino groups were masked with hexamethylene diisocyanate. A copper-clad laminate was produced in the same manner as in Example 3 except that .1 part by weight was added, and its characteristics were evaluated. The results are shown in Table 1.
【００２４】比較例１
実施例２において、ヘキサメチレンジイソシアネートで
イミノ基をマスクした２−エチル−４−メチルイミダゾ
ールを添加しないこと以外は実施例２と同様にして銅張
積層板を作製し、特性評価を行った。結果を表１に示す
。Comparative Example 1 A copper-clad laminate was prepared in the same manner as in Example 2, except that 2-ethyl-4-methylimidazole whose imino groups were masked with hexamethylene diisocyanate was not added, and the characteristics were determined. We conducted an evaluation. The results are shown in Table 1.
【００２５】比較例２
実施例２において、ヘキサメチレンジイソシアネートで
イミノ基をマスクした２−エチル−４−メチルイミダゾ
ールのかわりに、２−エチル−４−メチルイミダゾール
（２Ｅ４ＭＺ）を０．１重量部添加すること以外は実施
例２と同様にして銅張積層板を作製し、特性評価を行っ
た。結果を表１に示す。Comparative Example 2 In Example 2, 0.1 part by weight of 2-ethyl-4-methylimidazole (2E4MZ) was added instead of 2-ethyl-4-methylimidazole whose imino groups were masked with hexamethylene diisocyanate. A copper-clad laminate was produced in the same manner as in Example 2 except that the characteristics were evaluated. The results are shown in Table 1.
【００２６】比較例３
実施例３において、ヘキサメチレンジイソシアネートで
イミノ基をマスクした２−エチル−４−メチルイミダゾ
ールを添加しないで、γ−ウレイドプロピルトリエトキ
シシラン０．５重量部のみを添加すること以外は実施例
３と同様にして銅張積層板を作製し、特性評価を行った
。結果を表１及び表２に示す。Comparative Example 3 In Example 3, only 0.5 parts by weight of γ-ureidopropyltriethoxysilane was added without adding 2-ethyl-4-methylimidazole whose imino groups were masked with hexamethylene diisocyanate. A copper-clad laminate was produced in the same manner as in Example 3 except for this, and its characteristics were evaluated. The results are shown in Tables 1 and 2.
【００２７】[0027]
【表１】[Table 1]
【００２８】イミダゾール化合物Ａ：イミノ基をヘキサ
メチレンジイソシアネートでマスクした２Ｅ４ＭＺイミ
ダゾール化合物Ｂ：イミノ基をメチレンビスフェニルイ
ソシアネートでマスクした２Ｅ４ＭＺイミダゾール化合
物Ｃ：２Ｅ４ＭＺImidazole compound A: 2E4MZ imidazole compound whose imino group was masked with hexamethylene diisocyanate B: 2E4MZ imidazole compound whose imino group was masked with methylene bisphenyl isocyanate C: 2E4MZ
【００２９】１） 理学電機製熱機械試験機ＴＭＡ−
８１４１を使用した。
昇温速度５℃／分、荷重５ｇｒ。
２） ＪＩＳ−Ｃ−６４８１に準拠して測定した。
３） ＵＬ規格Ｓｕｂｊｅｃｔ９４垂直法に従って測
定した。1) Thermomechanical testing machine TMA- manufactured by Rigaku Denki
8141 was used. Temperature increase rate: 5°C/min, load: 5gr. 2) Measured in accordance with JIS-C-6481. 3) Measured according to UL standard Subject 94 vertical method.
【００３０】[0030]
【表２】[Table 2]
【００３１】表１及び表２の結果からわかるように、実
施例１〜４の銅張積層板は耐熱性、銅箔引きはがし強さ
ともに優れており、その他の特性も良好な値である。イ
ミノ基をマスクしたイミダゾール化合物や、ウレイド系
シランカップリング剤を添加しない比較例１〜３では、
常態での銅箔引きはがし強さ及び塩酸処理後（１８％の
塩酸水溶液に試験片を室温で１時間浸漬処理する）の銅
箔引きはがし強さの値が非常に低くなってしまっている
。As can be seen from the results in Tables 1 and 2, the copper-clad laminates of Examples 1 to 4 were excellent in both heat resistance and copper foil peeling strength, and other properties were also good. In Comparative Examples 1 to 3 in which no imidazole compound with an imino group masked or a ureido-based silane coupling agent was added,
The peel strength of the copper foil under normal conditions and the peel strength of the copper foil after hydrochloric acid treatment (the test piece is immersed in an 18% hydrochloric acid aqueous solution at room temperature for 1 hour) are very low.
【００３２】[0032]
【発明の効果】以上説明してきたように、本発明による
と、耐熱性、銅箔との接着性ともに優れたポリアミノビ
スマレイミド樹脂組成物及びそれを用いた銅張積層板を
得ることができ、その工業的価値は極めて大である。As explained above, according to the present invention, it is possible to obtain a polyamino bismaleimide resin composition having excellent heat resistance and adhesion to copper foil, and a copper-clad laminate using the same. Its industrial value is extremely large.
Claims (6)
ミノ基をマスクしたイミダゾール化合物を配合してなる
ことを特徴とするポリアミノビスマレイミド樹脂組成物
。1. A polyamino bismaleimide resin composition comprising a polyamino bismaleimide resin and an imidazole compound whose imino groups are masked.
キシ変性ポリアミノビスマレイミド樹脂である請求項１
記載のポリアミノビスマレイミド樹脂組成物。[Claim 2] Claim 1, wherein the polyamino bismaleimide resin is an epoxy-modified polyamino bismaleimide resin.
The polyamino bismaleimide resin composition described.
ミノ基をマスクしたイミダゾール化合物とウレイド系シ
ランカップリング剤とを配合してなることを特徴とする
ポリアミノビスマレイミド樹脂組成物。3. A polyamino bismaleimide resin composition comprising a polyamino bismaleimide resin, an imidazole compound whose imino groups are masked, and a ureido-based silane coupling agent.
ミノ基をマスクしたイミダゾール化合物を配合してなる
ポリアミノビスマレイミド樹脂組成物を基材に含浸させ
てプリプレグとし、このプリプレグを所定枚数積層して
、片側あるいは両側に銅箔を重ね、加熱加圧硬化するこ
とを特徴とするポリアミノビスマレイミド樹脂銅張積層
板の製造方法。4. A prepreg is obtained by impregnating a base material with a polyamino bismaleimide resin composition prepared by blending a polyamino bismaleimide resin with an imidazole compound whose imino groups are masked. A method for producing a polyamino bismaleimide resin copper-clad laminate, which comprises stacking copper foil on both sides and curing under heat and pressure.
キシ変性ポリアミノビスマレイミド樹脂である請求項４
記載のポリアミノビスマレイミド樹脂銅張積層板の製造
方法。[Claim 5]Claim 4, wherein the polyamino bismaleimide resin is an epoxy-modified polyamino bismaleimide resin.
The method for producing the polyamino bismaleimide resin copper-clad laminate described above.
ミノ基をマスクしたイミダゾール化合物とウレイド系シ
ランカップリング剤とを配合してなるポリアミノビスマ
レイミド樹脂組成物を、基材に含浸させてプリプレグと
し、このプリプレグを所定枚数積層して、片側あるいは
両側に銅箔を重ね、加熱加圧硬化することを特徴とする
ポリアミノビスマレイミド樹脂銅張積層板の製造方法。6. A prepreg is obtained by impregnating a base material with a polyamino bismaleimide resin composition obtained by blending a polyamino bismaleimide resin with an imidazole compound whose imino groups are masked and a ureido-based silane coupling agent. A method for producing a polyamino bismaleimide resin copper-clad laminate, which comprises laminating a predetermined number of polyamino bismaleimide resin copper foil laminates, overlapping copper foil on one or both sides, and curing under heat and pressure.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3132510A JP2776056B2 (en) | 1991-06-04 | 1991-06-04 | Polyaminobismaleimide resin composition and method for producing copper-clad laminate using same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3132510A JP2776056B2 (en) | 1991-06-04 | 1991-06-04 | Polyaminobismaleimide resin composition and method for producing copper-clad laminate using same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04359052A true JPH04359052A (en) | 1992-12-11 |
| JP2776056B2 JP2776056B2 (en) | 1998-07-16 |
Family
ID=15083035
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3132510A Expired - Lifetime JP2776056B2 (en) | 1991-06-04 | 1991-06-04 | Polyaminobismaleimide resin composition and method for producing copper-clad laminate using same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2776056B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009099918A1 (en) * | 2008-02-05 | 2009-08-13 | E. I. Du Pont De Nemours And Company | Highly adhesive polyimide copper clad laminate and method of making the same |
| JP2010260971A (en) * | 2009-05-08 | 2010-11-18 | Hitachi Chem Co Ltd | Adhesive film for interlayer insulating layer and multilayer printed wiring board |
| JP2013064136A (en) * | 2009-03-27 | 2013-04-11 | Hitachi Chemical Co Ltd | Thermosetting resin composition, and prepreg, laminate plate and multilayer printed wiring board each obtained using the same |
| US10119047B2 (en) | 2009-03-27 | 2018-11-06 | Hitachi Chemical Company, Ltd. | Thermosetting resin composition, and prepreg, insulating film with support, laminate plate, and printed wiring board, each obtained using same |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6445463A (en) * | 1987-08-13 | 1989-02-17 | Shinetsu Chemical Co | Addition type polyimide polymer composition |
| JPH02218722A (en) * | 1989-02-20 | 1990-08-31 | Hitachi Chem Co Ltd | Heat-resistant resin composition |
| JPH02294361A (en) * | 1989-04-10 | 1990-12-05 | Rhone Poulenc Chim | Imido-containing polymer prepared from hindered diamine |
-
1991
- 1991-06-04 JP JP3132510A patent/JP2776056B2/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6445463A (en) * | 1987-08-13 | 1989-02-17 | Shinetsu Chemical Co | Addition type polyimide polymer composition |
| JPH02218722A (en) * | 1989-02-20 | 1990-08-31 | Hitachi Chem Co Ltd | Heat-resistant resin composition |
| JPH02294361A (en) * | 1989-04-10 | 1990-12-05 | Rhone Poulenc Chim | Imido-containing polymer prepared from hindered diamine |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009099918A1 (en) * | 2008-02-05 | 2009-08-13 | E. I. Du Pont De Nemours And Company | Highly adhesive polyimide copper clad laminate and method of making the same |
| JP2013064136A (en) * | 2009-03-27 | 2013-04-11 | Hitachi Chemical Co Ltd | Thermosetting resin composition, and prepreg, laminate plate and multilayer printed wiring board each obtained using the same |
| US10119047B2 (en) | 2009-03-27 | 2018-11-06 | Hitachi Chemical Company, Ltd. | Thermosetting resin composition, and prepreg, insulating film with support, laminate plate, and printed wiring board, each obtained using same |
| JP2010260971A (en) * | 2009-05-08 | 2010-11-18 | Hitachi Chem Co Ltd | Adhesive film for interlayer insulating layer and multilayer printed wiring board |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2776056B2 (en) | 1998-07-16 |
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