JPS6336621B2 - - Google Patents
Info
- Publication number
- JPS6336621B2 JPS6336621B2 JP11727484A JP11727484A JPS6336621B2 JP S6336621 B2 JPS6336621 B2 JP S6336621B2 JP 11727484 A JP11727484 A JP 11727484A JP 11727484 A JP11727484 A JP 11727484A JP S6336621 B2 JPS6336621 B2 JP S6336621B2
- Authority
- JP
- Japan
- Prior art keywords
- weight
- bisphenol
- parts
- epoxy resin
- prepreg
- 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
Links
- 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 claims description 47
- 239000003822 epoxy resin Substances 0.000 claims description 38
- 229920000647 polyepoxide Polymers 0.000 claims description 38
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 29
- 239000011521 glass Substances 0.000 claims description 18
- 239000002966 varnish Substances 0.000 claims description 13
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 claims description 12
- 239000004744 fabric Substances 0.000 claims description 12
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 239000004745 nonwoven fabric Substances 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 4
- -1 imidazole compound Chemical class 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 2
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 claims description 2
- 230000001133 acceleration Effects 0.000 claims 1
- 229920003986 novolac Polymers 0.000 description 19
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 12
- 229920005989 resin Polymers 0.000 description 12
- 239000011347 resin Substances 0.000 description 12
- 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 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 239000004593 Epoxy Substances 0.000 description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- 238000005553 drilling Methods 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- 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 3
- 229920003319 Araldite® Polymers 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-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
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 229930003836 cresol Natural products 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000003063 flame retardant Substances 0.000 description 3
- 125000003055 glycidyl group Chemical group C(C1CO1)* 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
- UIDDPPKZYZTEGS-UHFFFAOYSA-N 3-(2-ethyl-4-methylimidazol-1-yl)propanenitrile Chemical compound CCC1=NC(C)=CN1CCC#N UIDDPPKZYZTEGS-UHFFFAOYSA-N 0.000 description 2
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 2
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 2
- 238000002845 discoloration Methods 0.000 description 2
- 150000002460 imidazoles Chemical class 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 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
- FBHPRUXJQNWTEW-UHFFFAOYSA-N 1-benzyl-2-methylimidazole Chemical compound CC1=NC=CN1CC1=CC=CC=C1 FBHPRUXJQNWTEW-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- PQAMFDRRWURCFQ-UHFFFAOYSA-N 2-ethyl-1h-imidazole Chemical compound CCC1=NC=CN1 PQAMFDRRWURCFQ-UHFFFAOYSA-N 0.000 description 1
- QUPKCFBHJFNUEW-UHFFFAOYSA-N 2-ethyl-4,5-dihydro-1h-imidazole Chemical compound CCC1=NCCN1 QUPKCFBHJFNUEW-UHFFFAOYSA-N 0.000 description 1
- SHYARJUKNREDGB-UHFFFAOYSA-N 2-ethyl-5-methyl-4,5-dihydro-1h-imidazole Chemical compound CCC1=NCC(C)N1 SHYARJUKNREDGB-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
- NCVGSSQICKMAIA-UHFFFAOYSA-N 2-heptadecyl-4,5-dihydro-1h-imidazole Chemical compound CCCCCCCCCCCCCCCCCC1=NCCN1 NCVGSSQICKMAIA-UHFFFAOYSA-N 0.000 description 1
- VWSLLSXLURJCDF-UHFFFAOYSA-N 2-methyl-4,5-dihydro-1h-imidazole Chemical compound CC1=NCCN1 VWSLLSXLURJCDF-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
- BKCCAYLNRIRKDJ-UHFFFAOYSA-N 2-phenyl-4,5-dihydro-1h-imidazole Chemical compound N1CCN=C1C1=CC=CC=C1 BKCCAYLNRIRKDJ-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
- BTYIFQSAIPDZQW-UHFFFAOYSA-N 2-propan-2-yl-4,5-dihydro-1h-imidazole Chemical compound CC(C)C1=NCCN1 BTYIFQSAIPDZQW-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
- FQHUDZKKDCTQET-UHFFFAOYSA-N 2-undecyl-4,5-dihydro-1h-imidazole Chemical compound CCCCCCCCCCCC1=NCCN1 FQHUDZKKDCTQET-UHFFFAOYSA-N 0.000 description 1
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 description 1
- BVYPJEBKDLFIDL-UHFFFAOYSA-N 3-(2-phenylimidazol-1-yl)propanenitrile Chemical compound N#CCCN1C=CN=C1C1=CC=CC=C1 BVYPJEBKDLFIDL-UHFFFAOYSA-N 0.000 description 1
- 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 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- ZEKUBYLAUUDJJM-UHFFFAOYSA-N 4,5-diphenyl-4,5-dihydro-1h-imidazole Chemical compound N1C=NC(C=2C=CC=CC=2)C1C1=CC=CC=C1 ZEKUBYLAUUDJJM-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
- TYOXIFXYEIILLY-UHFFFAOYSA-N 5-methyl-2-phenyl-1h-imidazole Chemical compound N1C(C)=CN=C1C1=CC=CC=C1 TYOXIFXYEIILLY-UHFFFAOYSA-N 0.000 description 1
- JJUVAPMVTXLLFR-UHFFFAOYSA-N 5-methyl-2-phenyl-4,5-dihydro-1h-imidazole Chemical compound N1C(C)CN=C1C1=CC=CC=C1 JJUVAPMVTXLLFR-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- OWYWGLHRNBIFJP-UHFFFAOYSA-N Ipazine Chemical compound CCN(CC)C1=NC(Cl)=NC(NC(C)C)=N1 OWYWGLHRNBIFJP-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 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
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- WHHGLZMJPXIBIX-UHFFFAOYSA-N decabromodiphenyl ether Chemical compound BrC1=C(Br)C(Br)=C(Br)C(Br)=C1OC1=C(Br)C(Br)=C(Br)C(Br)=C1Br WHHGLZMJPXIBIX-UHFFFAOYSA-N 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- WJRBRSLFGCUECM-UHFFFAOYSA-N hydantoin Chemical compound O=C1CNC(=O)N1 WJRBRSLFGCUECM-UHFFFAOYSA-N 0.000 description 1
- 229940091173 hydantoin Drugs 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- 230000000873 masking effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 150000002903 organophosphorus compounds Chemical class 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical compound NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- QCTJRYGLPAFRMS-UHFFFAOYSA-N prop-2-enoic acid;1,3,5-triazine-2,4,6-triamine Chemical compound OC(=O)C=C.NC1=NC(N)=NC(N)=N1 QCTJRYGLPAFRMS-UHFFFAOYSA-N 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- USFPINLPPFWTJW-UHFFFAOYSA-N tetraphenylphosphonium Chemical compound C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 USFPINLPPFWTJW-UHFFFAOYSA-N 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
- DIHAURBCYGTGCV-UHFFFAOYSA-N xi-4,5-Dihydro-2,4(5)-dimethyl-1H-imidazole Chemical compound CC1CN=C(C)N1 DIHAURBCYGTGCV-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Reinforced Plastic Materials (AREA)
- Laminated Bodies (AREA)
- Epoxy Resins (AREA)
Description
〔産業上の利用分野〕
本発明は印刷配線板の材料であるエポキシ―ガ
ラス布、エポキシ―ガラス不織布プリプレグの製
造方法に関するものである。
〔従来技術〕
印刷配線板の高密度化に伴ない多層化、スルー
ホール小径化などが進みドリル加工性の良好な印
刷配線板用プリプレグ、およびプリプレグを用い
て得られた金属張積層板が要求されている。ドリ
ル加工性のなかでもスミアの発生は内層回路銅と
スルーホールめつき銅との導通を防げることによ
つて著しくスルーホール信頼性を損なう。スミア
を除去するために印刷配線板メーカーではスミア
除去処理を行なうが、濃硫酸フツ化水素酸などを
用いるため安全上の問題がありまたスルーホール
内壁をあらし信頼性を低下させる原因ともなる。
スミアの発生原因はドリル加工時の摩擦熱により
軟化した樹脂がドリルによつて内層回路銅断面に
付着することにある。
従来エポキシ―ガラス布プリプレグ用硬化剤と
して用いられていたジシアンジアミドは樹脂との
相溶性が悪く未反応で残余することが多い。その
ため樹脂硬化物は250℃以上の温度では樹脂が分
解を伴ない軟化するこのような硬化物の軟化を防
ぐためにはエポキシ樹脂と十分に相溶し、しかも
反応性の良い硬化剤が必要とされる。またエポキ
シ樹脂も耐熱性がありしかも反応性の良いものが
要求される。
〔発明の目的〕
本発明は従来のエポキシ樹脂―ジシアンジアミ
ド系の欠点であるドリル加工性の改良およびエポ
キシ樹脂―ポリフエノール系の欠点である加熱変
色性、保存安定性の改良を目的とした印刷配線板
用エポキシ―ガラス布プリプレグならびにエポキ
シ―ガラス不織布プリプレグの製造方法に関する
ものである。
〔発明の構成〕
本発明は
(a) ビスフエノールAまたはビスフエノールFと
ホルムアルデヒドとの重縮合物のグリシジルエ
ーテル化物を1〜100重量%含むエポキシ樹脂
(b) ビスフエノールAとホルムアルデヒドの重縮
合物
(c) 硬化促進剤及び
(d) 溶剤
を必須成分として配合したワニスをガラス布また
はガラス不織布に含浸後、乾燥させることを特徴
とする印刷配線板用プリプレグの製造方法であ
る。
以下本発明を詳細に説明する。
(a)のエポキシ樹脂としては必須成分としてビス
フエノールAまたはビスフエノールFとホルムア
ルデヒドとの重縮合物のグリシジルエーテル化物
を1〜100重量%含有するが、このエポキシ樹脂
の分子量に制限はない。
上記以外の成分として用いられるエポキシ樹脂
の種類については制限はなく、本発明のエポキシ
樹脂はフエノールノボラツク型エポキシ樹脂、ク
レゾールノボラツク型エポキシ樹脂単独比べて硬
化速度も速く、架橋密度も上がる。従つてドリル
加工性は良好である。
これは、(a)のエポキシ樹脂が(b)の重縮物と同様
の骨格を有するエポキシ樹脂を含むため相溶性が
良好なためと思われる。
本発明のエポキシ樹脂中に含まれる他のエポキ
シ樹脂として例えばビスフエノールA型エポキシ
樹脂、ビスフエノールF型エポキシ樹脂、ビスフ
エノールS型エポキシ樹脂、フエノールノボラツ
ク型エポキシ樹脂、クレゾールノボラツク型エポ
キシ樹脂、脂環式エポキシ樹脂、グリシジルエス
テル型エポキシ樹脂、グリシジルアミン型エポキ
シ樹脂、ヒダントイン型エポキシ樹脂、イソシア
ヌレート型エポキシ樹脂、およびそれらのハロゲ
ン化物、水素添加物などがあり何種類かを併用す
ることもできる。またこれらのエポキシ樹脂を混
合する方法、温度にも制限はない。
製造されたプリプレグに難燃化が必要とされる
場合には、必須成分であるビスフエノールAまた
はビスフエノールFとホルムアルデヒドとの重縮
合物のグリシジルエーテル化物の他にハロゲン化
エポキシ樹脂が必要となる。
また製造されたプリプレグに難燃化が必要であ
り、しかも(a)のエポキシ樹脂として必須成分であ
るビスフエノールAまたはビスフエノールFとホ
ルムアルデヒドとの重縮合物のグリシジルエーテ
ル化物をエポキシ樹脂100重量部のうち80重量部
以上含むには、ハロゲン化エポキシ樹脂だけでは
十分な難燃性は得られずテトラブロモビスフエノ
ールA、デカブロモジフエニルエーテル、三酸化
アンチモン、テトラフエニルホスフインなど一般
に難燃剤と称される化合物を配合することが好ま
しい。印刷配線板用プリプレグとしての特性を保
たせるためにはハロゲン化エポキシ樹脂以外の難
燃剤の配合量は必要最少量にとどめるべきであ
り、多くともエポキシ樹脂100重量部に対して30
重量部以下であることが望ましい。
またエポキシ樹脂の硬化剤として通常のフエノ
ール樹脂を用いた場合硬化物の加熱変色性が問題
となるが、本発明では(b)ビスフエノールAとホル
ムアルデヒドの重縮合物を用いているため問題は
ない。
(b)のビスフエノールAとホルムアルデヒドの重
縮合物の分子量については制限がなく、ビスフエ
ノールAモノマーが含まれていてもよい。配合量
は制限はないが好ましくはエポキシ樹脂100重量
部に対して1〜100重量部である。
また本発明の効果を損ねない範囲でフエノール
ノボラツク樹脂を併用してもよい。
(c)の硬化促進剤としてはイミダゾール化合物、
有機リン化合物、第3級アミン、第4級アンモニ
ウム塩などが用いられるが、第2級アミノ基をア
クリロニトリル、イソシアネート、メラミン、ア
クリレートなどでマスク化されたイミダゾール化
合物を用いると従来の2倍以上の保存安定性プリ
プレグを得ることができる。ここで用いられるイ
ミダゾール化合物としてはイミダゾール、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―フエニルイミダゾール、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―ジフエニルイミダゾール、2―メチルイ
ミダゾリン、2―エチル―4―メチルイミダゾリ
ン、2―フエニルイミダゾリン、2―ウンデシル
イミダゾリン、2―ヘプタデシルイミダゾリン、
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、2―フエニル―4―メチルイミ
ダゾール、2―エチルイミダゾリン、2―イソプ
ロピルイミダゾリン、2,4―ジメチルイミダゾ
リン、2―フエニル―4―メチルイミダゾリンな
どがあり、マスク化剤としてはアクリロニトリ
ル、フエニレンジイソシアネート、トルエンジイ
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
エニルイソシアネート、メラミンアクリレートな
どがある。
これらの硬化促進剤は何種類かを併用してもよ
く配合量は好ましくはエポキシ樹脂100重量部に
対して0.01〜5重量部である。0.01重量部より少
ないと効果が小さく5重量部より多いと保存安定
性がない。
(d)の溶剤としてはアセトン、メチルエチルケト
ン、トルエン、キシレン、メチルイソブチルケト
ン、酢酸エチル、エチレングリコールモノメチル
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、メタノール、エタノ
ールなどがあり、これらは何種類かを混合して用
いてもよい。
また上記(a),(b),(c),(d)は必須成分であり他の
いかなる化合物を混合することも可能である。
上記(a),(b),(c),(d)を配合して得たワニスをガ
ラス布またはガラス不織布に含浸後、乾燥炉中で
80〜200℃の範囲で乾燥させ、印刷配線板用プリ
プレグを得る。プリプレグは加熱加圧して印刷配
線板または金属張積層板を製造することに用いら
れる。
以下本発明の実施例を記載する。
実施例 1
ビスフエノールA1000g、37%ホルマリン220
g、シユウ酸10gを冷却管および撹拌装置付四つ
口フラスコに入れて2時間環流して反応させた後
脱水濃縮しビスフエノールAノボラツク樹脂
〔A〕を得た。これを用い次のように配合してワ
ニスを得た。
エピクロンN―865(ビスフエノールノボラツク
型エポキシ樹脂) 100重量部
(商品名:大日本インキ(株)製)
ビスフエノールAノボラツク樹脂〔A〕
60重量部
2E4MZ―CN(1―シアノエチル―2エチル―
4―メチルイミダゾール) 0.5重量部
(商品名:四国化成(株)製)
メチルエチルケトン 100重量部
このワニスを0.1mm厚のガラス布に含浸させ、
130℃で5分間乾燥してプリプレグを得た。
実施例 2
実施例1におけるビスフエノールAノボラツク
樹脂〔A〕を用いて次のように配合してワニスを
得た。
アラルダイト8011(臭素化ビスフエノールAエ
ポキシ樹脂) 80重量部
(商品名:チバガイギー社製)
エピクロンN―865 20重量部
ビスフエノールAノボラツク樹脂〔A〕
30重量部
LX―1006(イソシアネートマスクイミダゾー
ル)
(商品名:第一工業製薬(株)製) 0.5重量部
アセトン 90重量部
このワニスを0.1mm厚のガラス布に含浸させ110
℃で5分間乾燥してプリプレグを得た。
実施例 3
実施例1におけるビスフエノールAノボラツク
樹脂〔A〕を用いて次のように配合してワニスを
得た。
エピクロンN―880(ビスフエノールAノボラツ
ク型エポキシ樹脂) 50重量部
(商品名:大日本インキ(株)製)
ESB―400(ブロム化ビスフエノールA型エポ
キシ樹脂) 50重量部
(商品名:住友化学(株)製)
ビスフエノールAノボラツク樹脂〔A〕
40重量部
C11Z―AZINE(2,4―ジアミノ―6{2′ウン
デシルイミダゾリル―(1′)}エチル―S―ト
リアジン) 1重量部
(商品名:四国化成(株)製)
メチルエチルケトン 90重量部
このワニスを0.1mm厚のガラス布に含浸させ130
℃で5分間乾燥してプリプレグを得た。
実施例 4
実施例1におけるビスフエノールAノボラツク
樹脂〔A〕を用いて次のように配合してワニスを
得た。
アラルダイト8011 80重量部
エピクロンN―880 20重量部
ビスフエノールAノボラツク樹脂〔A〕
10重量部
H―1(フエノールノボラツク樹脂) 20重量部
(商品名:明和化成(株)製)
2PZ―CN(1―シアノエチル―2―フエニルイ
ミダゾール) 0.5重量部
(商品名:四国化成(株)製)
アセトン 90重量部
このワニスを0.1mm厚のガラス布に含浸させ110
℃で5分間乾燥してプリプレグを得た。
比較例 1
アラルダイト8011 80重量部
EOCN102(クレゾールノボラツク型エポキシ樹
脂 20重量部
(商品名:日本化薬(株)製)
ジシアンジアミド 4重量部
BDMA(ベンジルジメチルアミン) 0.5重量部
メチルエチルケトン 30重量部
エチレングリコールモノメチルエーテル
40重量部
このワニスを0.1mm厚のガラス布に含浸させ160
℃で5分間乾燥してプリプレグを得た。
比較例 2
実施例1においてエピクロンN―865、100重量
部のかわりにEOCN102S100重量部を用いて実施
例1と同様にしてプリプレグを得た。
比較例 3
実施例2においてLX―1006、0.5重量部の代わ
りに2E4MZ(2―エチル―4―メチルイミダゾー
ル商品名:四国化成(株)製)0.3重量部を用いて実
施例2と同様にしてプリプレグを得た。
比較例 4
実施例2においてビスフエノールAノボラツク
樹脂〔A〕30重量部の代わりにフエノールノボラ
ツク樹脂H―1、30重量部を用いて実施例2と同
様にしてプリプレグを得た。
表1に実施例および比較例のワニス配合と乾燥
条件を示す。
[Industrial Application Field] The present invention relates to a method for manufacturing epoxy glass cloth and epoxy glass nonwoven fabric prepreg, which are materials for printed wiring boards. [Prior art] As the density of printed wiring boards increases, the number of layers increases, through holes become smaller in diameter, etc., and prepregs for printed wiring boards with good drillability and metal-clad laminates obtained using prepregs are in demand. has been done. In terms of drillability, the occurrence of smear significantly impairs through-hole reliability by preventing conduction between the inner layer circuit copper and the through-hole plated copper. In order to remove smear, printed wiring board manufacturers perform a smear removal process, but since it uses concentrated sulfuric acid, hydrofluoric acid, etc., there are safety issues and it also roughens the inner walls of the through holes, reducing reliability.
The cause of smear is that the resin softened by the frictional heat during drilling adheres to the cross section of the inner layer circuit copper due to the drilling. Dicyandiamide, which has been conventionally used as a curing agent for epoxy glass cloth prepregs, has poor compatibility with resins and often remains unreacted. Therefore, at temperatures above 250°C, the resin decomposes and softens.In order to prevent such softening of the cured product, a curing agent that is sufficiently compatible with the epoxy resin and has good reactivity is required. Ru. The epoxy resin is also required to have heat resistance and good reactivity. [Object of the Invention] The present invention aims to improve the drill workability, which is a disadvantage of conventional epoxy resin-dicyandiamide systems, and the heat discoloration and storage stability, which are disadvantages of epoxy resin-polyphenol systems. The present invention relates to a method for producing an epoxy-glass cloth prepreg for plates and an epoxy-glass nonwoven prepreg. [Structure of the Invention] The present invention provides (a) an epoxy resin containing 1 to 100% by weight of a glycidyl etherified product of a polycondensate of bisphenol A or bisphenol F and formaldehyde; (b) a polycondensate of bisphenol A and formaldehyde; This is a method for producing a prepreg for a printed wiring board, which comprises impregnating a glass cloth or glass nonwoven fabric with a varnish containing (c) a curing accelerator and (d) a solvent as essential components, and then drying it. The present invention will be explained in detail below. The epoxy resin (a) contains 1 to 100% by weight of a glycidyl etherified polycondensate of bisphenol A or bisphenol F and formaldehyde as an essential component, but there is no restriction on the molecular weight of this epoxy resin. There are no restrictions on the type of epoxy resin used as a component other than the above, and the epoxy resin of the present invention has a faster curing speed and higher crosslinking density than a phenol novolak type epoxy resin or a cresol novolak type epoxy resin alone. Therefore, drill workability is good. This is thought to be because the epoxy resin (a) contains an epoxy resin having the same skeleton as the polycondensate (b), and therefore has good compatibility. Examples of other epoxy resins contained in the epoxy resin of the present invention include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, There are alicyclic epoxy resins, glycidyl ester type epoxy resins, glycidylamine type epoxy resins, hydantoin type epoxy resins, isocyanurate type epoxy resins, and their halogenated and hydrogenated products, and several types can be used together. . There are also no restrictions on the method or temperature for mixing these epoxy resins. When flame retardation is required for the manufactured prepreg, a halogenated epoxy resin is required in addition to the essential component glycidyl etherified polycondensate of bisphenol A or bisphenol F and formaldehyde. . In addition, the produced prepreg needs to be made flame retardant, and 100 parts by weight of the glycidyl ether of the polycondensate of bisphenol A or bisphenol F, which is an essential component of the epoxy resin (a), and formaldehyde is added to the epoxy resin. If 80 parts by weight or more of the halogenated epoxy resin is used, sufficient flame retardancy cannot be obtained with just the halogenated epoxy resin, and flame retardants such as tetrabromobisphenol A, decabromodiphenyl ether, antimony trioxide, and tetraphenylphosphine are generally used. It is preferable to blend a compound called . In order to maintain the properties of prepregs for printed wiring boards, the amount of flame retardants other than halogenated epoxy resins should be kept to the minimum necessary, and at most 30 parts by weight of epoxy resin.
It is desirable that the amount is less than parts by weight. In addition, when a normal phenol resin is used as a curing agent for an epoxy resin, there is a problem of heat discoloration of the cured product, but in the present invention, there is no problem because (b) a polycondensate of bisphenol A and formaldehyde is used. . There is no restriction on the molecular weight of the polycondensate of bisphenol A and formaldehyde (b), and bisphenol A monomer may be included. There is no limit to the amount of the compound, but it is preferably 1 to 100 parts by weight per 100 parts by weight of the epoxy resin. Furthermore, a phenol novolac resin may be used in combination within a range that does not impair the effects of the present invention. As the curing accelerator (c), an imidazole compound,
Organic phosphorus compounds, tertiary amines, quaternary ammonium salts, etc. are used, but when using imidazole compounds whose secondary amino groups are masked with acrylonitrile, isocyanate, melamine, acrylate, etc., the Storage stable prepregs can be obtained. The imidazole compounds used here include imidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 1-benzyl-2-methylimidazole, and 2-heptadecylimidazole. ,
4,5-diphenylimidazoline, 2-methylimidazoline, 2-ethyl-4-methylimidazoline, 2-phenylimidazoline, 2-undecylimidazoline, 2-heptadecylimidazoline,
2-isopropylimidazole, 2,4-dimethylimidazole, 2-phenyl-4-methylimidazole, 2-ethylimidazoline, 2-isopropylimidazoline, 2,4-dimethylimidazoline, 2-phenyl-4-methylimidazoline, etc. Examples of masking agents include acrylonitrile, phenylene diisocyanate, toluene diisocyanate, naphthalene diisocyanate, hexamethylene diisocyanate, methylene bisphenyl isocyanate, and melamine acrylate. Several types of these curing accelerators may be used in combination, and the blending amount is preferably 0.01 to 5 parts by weight per 100 parts by weight of the epoxy resin. If it is less than 0.01 parts by weight, the effect is small, and if it is more than 5 parts by weight, there is no storage stability. Solvents for (d) include acetone, methyl ethyl ketone, toluene, xylene, methyl isobutyl ketone, ethyl acetate, ethylene glycol monomethyl ether, N,N-dimethylformamide, N,
Examples include N-dimethylacetamide, methanol, and ethanol, and several types of these may be used in combination. Moreover, the above (a), (b), (c), and (d) are essential components, and any other compounds can be mixed. After impregnating glass cloth or glass nonwoven fabric with the varnish obtained by blending the above (a), (b), (c), and (d), it is placed in a drying oven.
Dry in the range of 80 to 200°C to obtain prepreg for printed wiring boards. Prepreg is used to manufacture printed wiring boards or metal-clad laminates by heating and pressing. Examples of the present invention will be described below. Example 1 Bisphenol A 1000g, 37% formalin 220
g and 10 g of oxalic acid were placed in a four-necked flask equipped with a condenser and a stirrer and refluxed for 2 hours to react, followed by dehydration and concentration to obtain a bisphenol A novolak resin [A]. Using this, a varnish was obtained by blending as follows. Epicron N-865 (bisphenol novolac type epoxy resin) 100 parts by weight (product name: Dainippon Ink Co., Ltd.) Bisphenol A novolac resin [A]
60 parts by weight 2E4MZ-CN (1-cyanoethyl-2ethyl-
4-Methylimidazole) 0.5 parts by weight (product name: Shikoku Kasei Co., Ltd.) Methyl ethyl ketone 100 parts by weight A 0.1 mm thick glass cloth was impregnated with this varnish.
A prepreg was obtained by drying at 130°C for 5 minutes. Example 2 Using the bisphenol A novolak resin [A] in Example 1, a varnish was obtained by blending as follows. Araldite 8011 (brominated bisphenol A epoxy resin) 80 parts by weight (product name: manufactured by Ciba Geigy) Epicron N-865 20 parts by weight Bisphenol A novolak resin [A]
30 parts by weight LX-1006 (Isocyanate mask imidazole) (Product name: Daiichi Kogyo Seiyaku Co., Ltd.) 0.5 parts by weight Acetone 90 parts by weight A 0.1 mm thick glass cloth was impregnated with this varnish.
A prepreg was obtained by drying at °C for 5 minutes. Example 3 Using the bisphenol A novolak resin [A] in Example 1, a varnish was obtained by blending as follows. Epicron N-880 (bisphenol A novolac type epoxy resin) 50 parts by weight (product name: Dainippon Ink Co., Ltd.) ESB-400 (brominated bisphenol A type epoxy resin) 50 parts by weight (product name: Sumitomo Chemical) Co., Ltd.) Bisphenol A novolak resin [A]
40 parts by weight C 11 Z-AZINE (2,4-diamino-6{2'undecylimidazolyl-(1')}ethyl-S-triazine) 1 part by weight (product name: manufactured by Shikoku Kasei Co., Ltd.) Methyl ethyl ketone 90 Weight part Impregnated 0.1mm thick glass cloth with this varnish 130
A prepreg was obtained by drying at °C for 5 minutes. Example 4 Using the bisphenol A novolak resin [A] in Example 1, a varnish was obtained by blending as follows. Araldite 8011 80 parts by weight Epicron N-880 20 parts by weight Bisphenol A novolak resin [A]
10 parts by weight H-1 (phenol novolac resin) 20 parts by weight (product name: manufactured by Meiwa Kasei Co., Ltd.) 2PZ-CN (1-cyanoethyl-2-phenylimidazole) 0.5 parts by weight (product name: Shikoku Kasei Co., Ltd.) Co., Ltd.) Acetone 90 parts by weight A 0.1 mm thick glass cloth was impregnated with this varnish.
A prepreg was obtained by drying at °C for 5 minutes. Comparative Example 1 Araldite 8011 80 parts by weight EOCN102 (cresol novolak type epoxy resin 20 parts by weight (product name: manufactured by Nippon Kayaku Co., Ltd.) Dicyandiamide 4 parts by weight BDMA (benzyl dimethylamine) 0.5 parts by weight Methyl ethyl ketone 30 parts by weight ethylene glycol monomethyl ether
40 parts by weight Impregnate a 0.1 mm thick glass cloth with this varnish to 160 parts by weight.
A prepreg was obtained by drying at °C for 5 minutes. Comparative Example 2 A prepreg was obtained in the same manner as in Example 1 except that 100 parts by weight of EOCN102S was used instead of 100 parts by weight of Epiclon N-865. Comparative Example 3 In the same manner as in Example 2, except that 0.3 parts by weight of 2E4MZ (2-ethyl-4-methylimidazole trade name: manufactured by Shikoku Kasei Co., Ltd.) was used instead of 0.5 parts by weight of LX-1006. Got prepreg. Comparative Example 4 A prepreg was obtained in the same manner as in Example 2 except that 30 parts by weight of phenol novolak resin H-1 was used instead of 30 parts by weight of bisphenol A novolak resin [A]. Table 1 shows the varnish formulations and drying conditions of Examples and Comparative Examples.
【表】【table】
【表】
上記実施例1〜4、比較例1〜4で得たプリプ
レグ15枚と35μ銅箔6枚を用いて170℃、60分加
熱成形して6層印刷配線板を製しドリル加工を行
なつた。ドリル加工条件は回転数60000rpm、送
り速度3000mm/min、穴径1.0φmm、重ね枚数2枚
で12000hitsまで穴あけした。
6層印刷配線板のドリル加工性試験結果および
その他の特性試験結果を表2に示す。[Table] Using 15 sheets of prepreg obtained in Examples 1 to 4 and Comparative Examples 1 to 4 above and 6 sheets of 35μ copper foil, a 6-layer printed wiring board was produced by heat molding at 170℃ for 60 minutes, and drilled. I did it. Drilling conditions were rotation speed 60000 rpm, feed rate 3000 mm/min, hole diameter 1.0φmm, number of stacked sheets was 2, and holes were drilled up to 12000 hits. Table 2 shows the results of the drill workability test and other characteristic tests of the 6-layer printed wiring board.
【表】【table】
このように本発明印刷配線板用プリプレグは従
来技術に比べ多層配線板のドリル加工性およびプ
リプレグの保存安定性が格段に向上していること
がわかる。
As described above, it can be seen that the prepreg for printed wiring boards of the present invention has significantly improved drilling workability for multilayer wiring boards and storage stability of the prepreg compared to the prior art.
Claims (1)
Fとホルムアルデヒドとの重縮合物のグリシジ
ルエーテル化物を含有するエポキシ樹脂 (b) ビスフエノールAとホルムアルデヒドの重縮
合物 (c) 硬化促進剤および (d) 溶剤 を必須成分として配合したワニスをガラス布また
はガラス不織布に含浸後、乾燥させることを特徴
とする印刷配線板用プリプレグの製造方法。 2 硬化促進剤が第2級のアミノ基がマスクされ
たイミダゾール化合物である特許請求の範囲第1
項記載の印刷配線板用プリプレグの製造方法。[Scope of Claims] 1 (a) An epoxy resin containing a glycidyl ether of a polycondensate of bisphenol A or bisphenol F and formaldehyde (b) A polycondensate of bisphenol A and formaldehyde (c) Curing acceleration 1. A method for producing a prepreg for a printed wiring board, which comprises impregnating a glass cloth or glass nonwoven fabric with a varnish containing an agent and (d) a solvent as essential components, and then drying the impregnated glass cloth or glass nonwoven fabric. 2. Claim 1, wherein the curing accelerator is an imidazole compound with a masked secondary amino group.
A method for manufacturing a prepreg for a printed wiring board as described in .
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP11727484A JPS60260627A (en) | 1984-06-07 | 1984-06-07 | Production of prepreg for printed wiring board |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP11727484A JPS60260627A (en) | 1984-06-07 | 1984-06-07 | Production of prepreg for printed wiring board |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS60260627A JPS60260627A (en) | 1985-12-23 |
JPS6336621B2 true JPS6336621B2 (en) | 1988-07-21 |
Family
ID=14707697
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP11727484A Granted JPS60260627A (en) | 1984-06-07 | 1984-06-07 | Production of prepreg for printed wiring board |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS60260627A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH11209456A (en) * | 1998-01-29 | 1999-08-03 | Hitachi Chem Co Ltd | Flame-retardant epoxy resin composition for printed circuit board, and prepreg and metal-clad laminate prepared therefrom |
Families Citing this family (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS61246228A (en) * | 1985-04-24 | 1986-11-01 | Shin Kobe Electric Mach Co Ltd | Resin composition for laminate |
JPH075768B2 (en) * | 1986-05-07 | 1995-01-25 | 東芝ケミカル株式会社 | Epoxy resin laminate |
US4816531A (en) * | 1987-02-05 | 1989-03-28 | Shell Oil Company | Bismaleimide resin composition containing epoxy resin and a phenolic curing agent therefor |
JPS63235345A (en) * | 1987-03-25 | 1988-09-30 | Shin Kobe Electric Mach Co Ltd | Production of laminate |
JPS641753A (en) * | 1987-06-24 | 1989-01-06 | Matsushita Electric Works Ltd | Epoxy resin composition for glass-epoxy laminate |
JPH02283753A (en) * | 1989-04-25 | 1990-11-21 | Mitsubishi Electric Corp | Laminate resin composition |
JPH0776282B2 (en) * | 1989-10-06 | 1995-08-16 | 日立化成工業株式会社 | Method for manufacturing prepreg for printed wiring board |
JPH03237120A (en) * | 1990-02-15 | 1991-10-23 | Mitsubishi Electric Corp | Resin composition for laminate |
JP2868984B2 (en) * | 1992-11-13 | 1999-03-10 | インターナショナル・ビジネス・マシーンズ・コーポレイション | Circuit board |
JPH06345883A (en) * | 1993-06-08 | 1994-12-20 | Hitachi Chem Co Ltd | Production of prepreg for printed wiring board |
-
1984
- 1984-06-07 JP JP11727484A patent/JPS60260627A/en active Granted
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH11209456A (en) * | 1998-01-29 | 1999-08-03 | Hitachi Chem Co Ltd | Flame-retardant epoxy resin composition for printed circuit board, and prepreg and metal-clad laminate prepared therefrom |
US6214468B1 (en) | 1998-01-29 | 2001-04-10 | Hitachi Chemical Company, Ltd. | Flame retardant epoxy resin composition for printed board, and prepreg and metal foil clad laminate using the same |
Also Published As
Publication number | Publication date |
---|---|
JPS60260627A (en) | 1985-12-23 |
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