JPH0912681A - Epoxy resin composition for use in printed wiring board - Google Patents
Epoxy resin composition for use in printed wiring boardInfo
- Publication number
- JPH0912681A JPH0912681A JP16067295A JP16067295A JPH0912681A JP H0912681 A JPH0912681 A JP H0912681A JP 16067295 A JP16067295 A JP 16067295A JP 16067295 A JP16067295 A JP 16067295A JP H0912681 A JPH0912681 A JP H0912681A
- Authority
- JP
- Japan
- Prior art keywords
- epoxy resin
- printed wiring
- wiring board
- bisphenol
- weight
- 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.)
- Pending
Links
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 44
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 44
- 239000000203 mixture Substances 0.000 title claims description 14
- 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 abstract description 35
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 16
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 238000005260 corrosion Methods 0.000 abstract description 10
- 230000007797 corrosion Effects 0.000 abstract description 10
- 238000002845 discoloration Methods 0.000 abstract description 10
- 238000010521 absorption reaction Methods 0.000 abstract description 5
- 229920003986 novolac Polymers 0.000 description 19
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 13
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 12
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 12
- 239000002966 varnish Substances 0.000 description 10
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 8
- 238000005452 bending Methods 0.000 description 7
- -1 glycidyl ester Chemical class 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 6
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 6
- UIDDPPKZYZTEGS-UHFFFAOYSA-N 3-(2-ethyl-4-methylimidazol-1-yl)propanenitrile Chemical compound CCC1=NC(C)=CN1CCC#N UIDDPPKZYZTEGS-UHFFFAOYSA-N 0.000 description 5
- 239000004593 Epoxy Substances 0.000 description 5
- 239000011889 copper foil Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 4
- 229910052794 bromium Inorganic materials 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 4
- 239000004744 fabric Substances 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 239000012948 isocyanate Substances 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 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 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 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
- 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
- 238000001035 drying Methods 0.000 description 3
- 150000004820 halides Chemical class 0.000 description 3
- 239000011810 insulating material Substances 0.000 description 3
- 238000009413 insulation Methods 0.000 description 3
- 150000002513 isocyanates Chemical class 0.000 description 3
- 229910000679 solder Inorganic materials 0.000 description 3
- 238000003860 storage Methods 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
- 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 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- LTPBRCUWZOMYOC-UHFFFAOYSA-N Beryllium oxide Chemical compound O=[Be] LTPBRCUWZOMYOC-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
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- 229910052581 Si3N4 Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-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
- 238000003491 array Methods 0.000 description 2
- 230000001588 bifunctional effect Effects 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 229930003836 cresol Natural products 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 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 2
- 238000007789 sealing Methods 0.000 description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 2
- 229910010271 silicon carbide Inorganic materials 0.000 description 2
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 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
- 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
- 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
- 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
- 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
- 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
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 1
- 229910052582 BN Inorganic materials 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-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
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229920001665 Poly-4-vinylphenol Polymers 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001339 alkali metal compounds Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 229910002026 crystalline silica Inorganic materials 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical group C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 1
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000006266 etherification reaction Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 229910052839 forsterite Inorganic materials 0.000 description 1
- 239000005350 fused silica glass Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 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 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
- 150000002460 imidazoles Chemical class 0.000 description 1
- 125000001841 imino group Chemical group [H]N=* 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 230000000873 masking effect Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910052863 mullite Inorganic materials 0.000 description 1
- 150000002903 organophosphorus compounds Chemical class 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
- 150000002989 phenols Chemical class 0.000 description 1
- 229920001291 polyvinyl halide Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229910052845 zircon Inorganic materials 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Resins (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、印刷配線板などの製造
に用いられる印刷配線板用エポキシ樹脂組成物に関す
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an epoxy resin composition for printed wiring boards used for manufacturing printed wiring boards and the like.
【０００２】[0002]
【従来の技術】電子機器の小型化、高性能化に伴い、そ
の中に搭載される印刷配線板は、高多層化、薄物化、ス
ルーホールの小径化及び穴間隔の減少などによる高密度
化が進行している。さらに近年では、半導体チップを印
刷配線板上に直接搭載し樹脂封止した、プラスチックピ
ングリッドアレイやプラスチックボールグリッドアレイ
等の半導体パッケージに、印刷配線板が用いられるよう
になっている。半導体パッケージに用いられる場合、印
刷配線板はその製造工程において１７５℃以上の高温で
ワイヤボンディングや樹脂封止といった工程を経ること
になる。その際に印刷配線板の強度や弾性率が不足する
とボンディングワイヤの接続不良や樹脂封止後のそり、
ねじれ等の問題が発生する。１７５℃以上の高温域での
強度や弾性率等の高温特性を向上させるためには、従来
以上の高いＴｇ（ガラス転移温度）が必要である。半導
体パッケージ用の印刷配線板はこれまで以上の高密度配
線が要求されており、絶縁信頼性も重要である。2. Description of the Related Art As electronic devices have become smaller and have higher performance, printed wiring boards mounted therein have higher densities due to higher multi-layers, thinner products, smaller through-hole diameters and smaller hole intervals. Is in progress. In recent years, printed wiring boards have come to be used in semiconductor packages such as plastic pin grid arrays and plastic ball grid arrays in which a semiconductor chip is directly mounted on a printed wiring board and sealed with a resin. When used for a semiconductor package, a printed wiring board undergoes processes such as wire bonding and resin sealing at a high temperature of 175 ° C. or higher in the manufacturing process. At that time, if the strength or elasticity of the printed wiring board is insufficient, poor connection of bonding wires and warpage after resin sealing,
Problems such as twisting occur. In order to improve high temperature characteristics such as strength and elastic modulus in a high temperature range of 175 ° C. or higher, a higher Tg (glass transition temperature) than ever before is required. Printed wiring boards for semiconductor packages require higher density wiring than ever before, and insulation reliability is also important.
【０００３】これらの要求に対して、印刷配線板の絶縁
材料としてはエポキシ樹脂の高Ｔｇ化が進んでいる。高
Ｔｇ化の手法としては、多官能エポキシ樹脂をジシアン
ジアミドで硬化させる系が広く検討されている。しかし
ながら、ジシアンジアミド硬化系では吸湿性が高くなる
欠点があり、今後の印刷配線板の更なる高密度化に伴う
高い絶縁信頼性を満足することは困難となっており、特
に絶縁特性の中でも、絶縁材料上または絶縁材料内の配
線や回路パターンあるいは電極などを構成する金属が、
高湿度環境下、電位差の作用によって絶縁材料上または
絶縁材料内を移行する金属マイグレーション（電食）の
発生は非常に大きな問題となってきた。In response to these requirements, epoxy resins having a higher Tg have been developed as insulating materials for printed wiring boards. As a method for increasing Tg, a system in which a polyfunctional epoxy resin is cured with dicyandiamide has been widely studied. However, the dicyandiamide curing system has a drawback that its hygroscopicity becomes high, and it is difficult to satisfy high insulation reliability due to higher density of printed wiring boards in the future. The metal that forms the wiring, circuit pattern, electrodes, etc. on the material or in the insulating material
In a high humidity environment, the occurrence of metal migration (electrolytic corrosion) that migrates on or in an insulating material due to the action of a potential difference has become a very serious problem.
【０００４】これに対して、多官能性フェノール樹脂を
硬化剤に用いた印刷配線板は、吸水率が低く耐電食性が
良好となる。ただし、このような多官能性フェノールを
用いた印刷配線板は、フェノール類の種類によっては加
熱処理時に変色する問題が生じる場合がある。特公昭６
２−２８１６８号公報では、この加熱変色性を向上させ
る目的で、フェノールまたはビスフェノールＡを主原料
とするハイオルソフェノール・ホルムアルデヒド樹脂を
配合した系を提案しているが、１７５℃以上の高温での
使用に耐えるＴｇは得られない。On the other hand, a printed wiring board using a polyfunctional phenol resin as a curing agent has a low water absorption rate and a good electrolytic corrosion resistance. However, a printed wiring board using such a polyfunctional phenol may cause a problem of discoloration during heat treatment depending on the type of phenol. Tokunosho 6
JP-A-2-28168 proposes a system in which a high orthophenol-formaldehyde resin containing phenol or bisphenol A as a main raw material is blended for the purpose of improving the heat discoloration property, but at a high temperature of 175 ° C. or higher. No Tg that can be used is obtained.
【０００５】[0005]
【発明が解決しようとする課題】本発明は、かかる状況
に鑑みなされたもので、印刷配線板とした場合に吸湿性
が低く、優れた耐熱性と高温特性、耐電食性、耐加熱変
色性を有し、かつ高いＴｇを与えるエポキシ樹脂組成物
を提供することを目的とする。SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances and has low hygroscopicity when used as a printed wiring board, and has excellent heat resistance and high temperature characteristics, electrolytic corrosion resistance, and thermal discoloration resistance. It is an object of the present invention to provide an epoxy resin composition having a high Tg.
【０００６】[0006]
【課題を解決するための手段】すなわち、本発明のエポ
キシ樹脂組成物は、（ａ）化１で表されるエポキシ樹脂
及び（ｂ）ビスフェノールＡとホルムアルデヒドの重縮
合物（ｃ）硬化促進剤を必須成分として配合してなるこ
とを特徴とする。That is, the epoxy resin composition of the present invention comprises (a) an epoxy resin represented by Chemical Formula 1 and (b) a polycondensate of bisphenol A and formaldehyde (c) a curing accelerator. It is characterized by being mixed as an essential component.
【０００７】[0007]
【化１】 Embedded image
【０００８】（式中、ＲはＨまたは、メチル、エチル、
プロピル、ｔｅｒｔ−ブチルなどのアルキル基であ
る。）(Wherein R is H or methyl, ethyl,
An alkyl group such as propyl and tert-butyl. )
【０００９】以下、本発明を詳細に説明する。（ａ）の
化１で表されるエポキシ樹脂としては、例えば、ＥＸＡ
−Ｔ６１０、ＥＸＡ−Ｔ７１０（大日本インキ化学工業
株式会社製商品名）などがある。また、本発明において
は、化１で表されるエポキシ樹脂以外のエポキシ樹脂を
併用してもよい。例えば、ビスフェノールＡ型エポキシ
樹脂、ビスフェノールＦ型エポキシ樹脂、ビスフェノー
ルＳ型エポキシ樹脂、フェノールノボラック型エポキシ
樹脂、クレゾールノボラック型エポキシ樹脂、ビスフェ
ノーＡノボラック型エポキシ樹脂、ビスフェノールＦノ
ボラック型エポキシ樹脂、脂環式エポキシ樹脂、脂肪族
鎖状エポキシ樹脂、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、その
他、二官能フェノール類のグリシジルエーテル化物、二
官能アルコールのグリシジルエーテル化物及びそれらの
ハロゲン化物、水素添加物などがある。これらの化合物
はどのようなものでもよく、また何種類かを併用するこ
とができる。Hereinafter, the present invention will be described in detail. Examples of the epoxy resin represented by Chemical Formula 1 in (a) include EXA.
-T610, EXA-T710 (trade name, manufactured by Dainippon Ink and Chemicals, Inc.) and the like. Further, in the present invention, an epoxy resin other than the epoxy resin represented by Chemical formula 1 may be used in combination. For example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, bispheno A novolac type epoxy resin, bisphenol F novolac type epoxy resin, alicyclic epoxy Resin, aliphatic chain epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, hydantoin type epoxy resin, isocyanurate type epoxy resin, other, glycidyl ether compound of bifunctional phenol, glycidyl ether compound of bifunctional alcohol And their halides and hydrogenated substances. Any of these compounds may be used, and several kinds thereof may be used in combination.
【００１０】（ｂ）のビスフェノール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
ェノールＡモノマーが含まれていても良い。また、ビス
フェノールＡとホルムアルデヒドの重縮合物以外の硬化
剤を併用してもよく、例えば、ビスフェノールＡ、ビス
フェノールＦ、ポリビニルフェノール及びこれらのハロ
ゲン化物、またはフェノール、クレゾール、アルキルフ
ェノール、カテコール、ビスフェノールＦなどのノボラ
ツク樹脂及びこれらのハロゲン化物などがある。これら
の化合物の分子量はどのようなものでも良く、また何種
類かを併用することができる。配合量は、エポキシ基に
対してフェノール性水酸基が０．５〜１．５当量の範囲
であることが好ましい。There is no limitation on the molecular weight of the polycondensate of bisphenol A and formaldehyde of (b), and a bisphenol A monomer may be contained. Further, a curing agent other than the polycondensate of bisphenol A and formaldehyde may be used in combination, and examples thereof include bisphenol A, bisphenol F, polyvinyl phenol and halides thereof, or phenol, cresol, alkylphenol, catechol and bisphenol F. Novolac resins and their halides. These compounds may have any molecular weight, and several kinds can be used in combination. The amount of the phenolic hydroxyl group is preferably in the range of 0.5 to 1.5 equivalents to the epoxy group.
【００１１】（ｃ）の硬化促進剤としては、エポキシ基
とフェノール性水酸基のエーテル化反応を促進させるよ
うな触媒機能を持つ化合物であればどのようなものでも
良く、例えば、アルカリ金属化合物、アルカリ土類金属
化合物、イミダゾール化合物、有機りん化合物、第二級
アミン、第三級アミン、第四級アンモニウム塩などがあ
る。イミノ基がアクリロニトリル、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
を用いると、従来の２倍以上の保存安定性を有するプリ
プレグを得ることができる。The curing accelerator (c) may be any compound as long as it has a catalytic function to accelerate the etherification reaction between the epoxy group and the phenolic hydroxyl group, and examples thereof include alkali metal compounds and alkalis. There are earth metal compounds, imidazole compounds, organic phosphorus compounds, secondary amines, tertiary amines, quaternary ammonium salts and the like. When imidazole whose imino group is masked with acrylonitrile, isocyanate, melamine acrylate or the like is used, a prepreg having a storage stability more than twice that of the conventional one can be obtained.
【００１２】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−フェニルイミダゾ
ール、２−ウンデシルイミダゾール、１−べンジル−２
−メチルイミダゾール、２−へ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−メチルイミ
ダゾリン、２−フェニルイミダゾリン、２−ウンデシル
イミダゾリン、２−へ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−フェニル−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−フェニル−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、フェニレンジイソシアネート、トルイジン
イソシアネート、ナフタ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、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、配合量はエポキシ樹脂１００重量部に対して
０．０１〜５重量部が好ましい。０．０１重量部より少
ないと促進効果が小さく、５重量部より多いと保存安定
性が悪くなる。Examples of the imidazole compound used here include imidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-undecylimidazole and 1-benzil-2.
-Methylimidazole, 2-heptadecylimidazole, 4,5-diphenylimidazole, 2-methylimidazoline, 2-phenylimidazoline, 2-undecylimidazoline, 2-heptadecylimidazoline, 2-isopropylimidazole, 2,4- Dimethyl imidazole, 2-phenyl-4-methyl imidazole, 2-ethyl imidazoline, 2-isopropyl imidazoline, 2,
There are 4-dimethylimidazoline, 2-phenyl-4-methylimidazoline and the like, and examples of the masking agent include acrylonitrile, phenylene diisocyanate, toluidine isocyanate, naphthalene diisocyanate, methylenebisphenyl isocyanate and melamine acrylate. Several kinds of these curing accelerators may be used in combination, and the compounding amount is preferably 0.01 to 5 parts by weight with respect to 100 parts by weight of the epoxy resin. If it is less than 0.01 part by weight, the promoting effect is small, and if it is more than 5 parts by weight, the storage stability becomes poor.
【００１３】本発明に係るエポキシ樹脂組成物は、各種
の形態で利用されるが基材に塗布、含浸する際にはしば
しば溶剤が用いられる。それらの溶剤としては、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
合しても良い。The epoxy resin composition according to the present invention is used in various forms, but a solvent is often used when coating and impregnating a substrate. As the solvent, there are acetone, methyl ethyl ketone, toluene, xylene, methyl isobutyl ketone, ethyl acetate, ethylene glycol monomethyl ether, N, N-dimethylacetamide, methanol, ethanol and the like, and these may be mixed in several kinds. .
【００１４】本発明に係るエポキシ樹脂組成物には、無
機充填剤として、結晶シリカ、溶融シリカ、アルミナ、
ジルコン、珪酸カルシウム、炭酸カルシウム、炭化珪
素、窒化珪素、窒化ホウ素、ベリリア、マグネシア、ジ
ルコニア、フォーステライト、ステアライト、スピネ
ル、ムライト、チタニアなどの粉体及びチタン酸カリウ
ム、炭化珪素、窒化珪素、アルミナなどの単結晶繊維、
ガラス繊維などを１種類以上配合することができる。The epoxy resin composition according to the present invention contains crystalline silica, fused silica, alumina,
Powders of zircon, calcium silicate, calcium carbonate, silicon carbide, silicon nitride, boron nitride, beryllia, magnesia, zirconia, forsterite, stearite, spinel, mullite, titania and potassium titanate, silicon carbide, silicon nitride, alumina. Single crystal fiber, such as
One or more kinds of glass fibers and the like can be blended.
【００１５】前記（ａ）〜（ｃ）を必須成分として配合
して得たワニスは、ガラス布、ガラス不織布または紙、
ガラス以外を成分とする布などの基材に含浸させ、乾燥
炉内で８０〜２００℃の範囲で乾燥させることにより、
印刷配線板用プリプレグを得る。プリプレグは１５０〜
１９０℃、２０〜８０ｋｇｆ／ｃｍ2の範囲で加熱加圧
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。ここでの乾燥とは、溶剤を使用した場合には
溶剤を除去すること、溶剤を使用しない場合には室温で
流動性がなくなるようにすることをいう。The varnish obtained by blending the above (a) to (c) as an essential component is a glass cloth, a glass non-woven cloth or paper,
By impregnating a base material such as cloth having a component other than glass as a component, and drying in a range of 80 to 200 ° C. in a drying furnace,
Obtain a prepreg for a printed wiring board. 150 ~ for prepreg
It is used for producing a printed wiring board or a metal-clad laminate by heating and pressing at 190 ° C. in the range of 20 to 80 kgf / cm 2 . The drying here means removing the solvent when the solvent is used, and making the fluidity disappear at room temperature when the solvent is not used.
【００１６】[0016]
【作用】本発明では、化１で表されるエポキシ樹脂及び
ビスフェノールＡとホルムアルデヒドの重縮合物、硬化
促進剤を必須成分として用いることにより、従来のエポ
キシ樹脂組成物に比べグリシジルエーテル基とフェノー
ル性水酸基の反応率が高く、硬化物の架橋密度が高くな
るため、印刷配線板とした場合に吸湿性が低く、優れた
耐熱性と高温特性、耐電食性を有し、かつ高いＴｇを与
えるエポキシ樹脂組成物を得ることができる。In the present invention, by using the epoxy resin represented by Chemical formula 1, the polycondensate of bisphenol A and formaldehyde, and the curing accelerator as essential components, the glycidyl ether group and the phenolic property are improved as compared with the conventional epoxy resin composition. Epoxy resin that has a high reaction rate of hydroxyl groups and a high crosslink density of the cured product, has low hygroscopicity when used as a printed wiring board, has excellent heat resistance, high temperature characteristics, and electrolytic corrosion resistance, and also provides a high Tg. A composition can be obtained.
【００１７】[0017]
【実施例】以下、本発明を実施例に基づいて詳細に説明
するが、本発明はこれに限定されるものではない。The present invention will be described below in detail with reference to examples, but the present invention is not limited to these examples.
【００１８】［実施例１］ＥＸＡ−Ｔ７１０（大日本イ
ンキ化学工業株式会社商品名、エポキシ当量２２１）１
００重量部とビスフェノールＡノボラック樹脂（水酸基
当量１１４）３２重量部及びテトラブロモビスフェノー
ルＡ（臭素含有率５８％、水酸基当量２７２）４６重量
部をメチルエチルケトンで溶解した。硬化促進剤とし
て、１−シアノエチルー２−エチル−４−メチルイミダ
ゾール０．３重量部を配合し、不揮発分６５％のワニス
を作製した。[Example 1] EXA-T710 (trade name of Dainippon Ink and Chemicals, Inc., epoxy equivalent 221) 1
00 parts by weight, 32 parts by weight of bisphenol A novolac resin (hydroxyl group equivalent 114) and 46 parts by weight of tetrabromobisphenol A (bromine content 58%, hydroxyl equivalent 272) were dissolved with methyl ethyl ketone. 0.3 part by weight of 1-cyanoethyl-2-ethyl-4-methylimidazole was added as a curing accelerator to prepare a varnish having a nonvolatile content of 65%.
【００１９】［実施例２］ＥＸＡ−Ｔ７１０ ５６重量
部と臭素化ビスフェノールＡ型エポキシ樹脂（臭素含有
率４９％、エポキシ当量４００）４４重量部及びビスフ
ェノールＡノボラック樹脂４１重量部をメチルエチルケ
トンで溶解した。硬化促進剤として、１−シアノエチル
−２−エチル−４−メチルイミダゾール０．３重量部を
配合し、不揮発分６５％のワニスを作製した。Example 2 56 parts by weight of EXA-T710, 44 parts by weight of brominated bisphenol A type epoxy resin (bromine content 49%, epoxy equivalent 400) and 41 parts by weight of bisphenol A novolac resin were dissolved in methyl ethyl ketone. 0.3 part by weight of 1-cyanoethyl-2-ethyl-4-methylimidazole was added as a curing accelerator to prepare a varnish having a nonvolatile content of 65%.
【００２０】［実施例３］ＥＸＡ−Ｔ７１０ ３９重量
部と臭素化フェノールノボラック型エポキシ樹脂（臭素
含有率３５．３％、エポキシ当量２８４）６１重量部及
びビスフェノールＡノボラソク樹脂４５重量部をメチル
エチルケトンで溶解した。硬化促進剤として、１−シア
ノエチル−２−エチル−４−メチルイミダゾール０．３
重量部を配合し、不揮発分６５％のワニスを作製した。Example 3 39 parts by weight of EXA-T710, 61 parts by weight of brominated phenol novolac type epoxy resin (bromine content 35.3%, epoxy equivalent 284) and 45 parts by weight of bisphenol A novolak resin were dissolved in methyl ethyl ketone. did. As a curing accelerator, 1-cyanoethyl-2-ethyl-4-methylimidazole 0.3
A varnish having a nonvolatile content of 65% was prepared by blending parts by weight.
【００２１】［実施例４］１−シアノエチル−２−エチ
ル−４−メチルイミダゾールに代えて、イソシアネート
マスクイミダゾールを０．５重量部配合した以外は実施
例１と同様の配合でワニスを作製した。Example 4 A varnish was prepared in the same manner as in Example 1 except that 0.5 part by weight of isocyanate mask imidazole was added instead of 1-cyanoethyl-2-ethyl-4-methylimidazole.
【００２２】［比較例１］実施例１において、ＥＸＡ−
Ｔ７１０に代えて、ｏ−クレゾールノボラック型エポキ
シ樹脂（エポキシ当量１９５）１００重量部とビスフェ
ノールＡノボラック樹脂３８重量部及びテトラブロモビ
スフェノールＡ４８重量部とした以外は実施例１と同様
の配合でワニスを作製した。COMPARATIVE EXAMPLE 1 In Example 1, EXA-
A varnish was prepared in the same manner as in Example 1 except that 100 parts by weight of o-cresol novolac type epoxy resin (epoxy equivalent 195), 38 parts by weight of bisphenol A novolac resin and 48 parts by weight of tetrabromobisphenol A were used in place of T710. did.
【００２３】［比較例２］実施例１において、ビスフェ
ノールＡノボラック樹脂に代えてフェノールノボラツク
樹脂（水酸基当量１０６）３０重量部及びテトラブロモ
ビスフェノールＡ４６重量部とした以外は実施例１と同
様の配合でワニスを作製した。[Comparative Example 2] The same composition as in Example 1 except that in Example 1, 30 parts by weight of a phenol novolac resin (hydroxyl equivalent 106) and 46 parts by weight of tetrabromobisphenol A were used in place of the bisphenol A novolac resin. A varnish was prepared with.
【００２４】［比較例３］低臭素化エポキシ樹脂（臭素
含有率２１％、エポキシ当量４８５）８０重量部とＥＸ
Ａ−Ｔ７１０ ２０重量部に、あらかじめエチレングリ
コールモノメチルエーテルに溶解したジシアンジアミド
１重量部を配合した。硬化促進剤として１−シアノエチ
ル−２−エチル−４−メチルイミダゾール０．２重量部
を配合し、不揮発分６５％のワニスを作製した。Comparative Example 3 80 parts by weight of low brominated epoxy resin (bromine content 21%, epoxy equivalent 485) and EX
20 parts by weight of A-T710 was mixed with 1 part by weight of dicyandiamide previously dissolved in ethylene glycol monomethyl ether. 0.2 parts by weight of 1-cyanoethyl-2-ethyl-4-methylimidazole was added as a curing accelerator to prepare a varnish having a nonvolatile content of 65%.
【００２５】［比較例４］比較例３において、ＥＸＡ−
Ｔ７１０に代えてｏ−クレゾールノボラック型エポキシ
樹脂とした以外は、比較例３と同様の配合でワニスを作
製した。[Comparative Example 4] In Comparative Example 3, EXA-
A varnish was prepared in the same composition as in Comparative Example 3 except that o-cresol novolac type epoxy resin was used instead of T710.
【００２６】各実施例及び比較例１〜４の主な配合を表
１に示す。各実施例及び比較例１〜４で得られたワニス
を、厚みが０．２ｍｍのガラス布に含浸し、１６０℃で
２〜５分加熱してプリプレグを得た。得られたプリプレ
グ４枚を重ね、その両側に１８μｍの銅箔を重ねて、１
７５℃、９０分、２．５ＭＰａのプレス条件で両面銅張
積層板を作製した。得られた両面銅張積層板について、
Ｔｇ、はんだ耐熱性、吸水率、加熱変色性、耐電食性な
らびに常温及び２００℃での曲げ強さ、曲げ弾性率を調
べた。その結果を表２及び表３に示す。Table 1 shows the main composition of each Example and Comparative Examples 1 to 4. A glass cloth having a thickness of 0.2 mm was impregnated with the varnish obtained in each of Examples and Comparative Examples 1 to 4 and heated at 160 ° C. for 2 to 5 minutes to obtain a prepreg. 4 pieces of the obtained prepreg are piled up, 18 μm copper foil is piled up on both sides of the prepreg, and 1
A double-sided copper-clad laminate was produced under a press condition of 75 ° C., 90 minutes and 2.5 MPa. About the obtained double-sided copper clad laminate,
Tg, solder heat resistance, water absorption, heat discoloration, electrolytic corrosion resistance, bending strength at room temperature and 200 ° C., and bending elastic modulus were examined. The results are shown in Tables 2 and 3.
【００２７】試験方法は以下の通りである。 Ｔｇ：銅箔をエッチングし、ＴＭＡ（熱機械分析）によ
り測定。単位：℃ はんだ耐熱性：銅箔をエッチングし、プレッシャークッ
カーテスター中に２時間保持した後、２６０℃のはんだ
に２０秒間浸漬して、外観を目視で調べた。表中ＮＧと
は、ミーズリング、ふくれ発生を意味する。 吸水率：銅箔をエッチングし、プレッシャークッカーテ
スター中に４時間保持した前後の重量の差から算出し
た。単位：％ 加熱変色性：銅箔をエッチングし、気中において１６０
℃で５時間処理した後、目視により評価した。変色のな
いものを〇、若干変色したものを△、変色したものを×
とした。 耐電食性試験：スルーホール穴壁間隔を３５０μｍとし
たテストパターンを用いて、各試料について４００穴の
絶縁抵抗を経時的に測定した。試験条件は、８５℃、９
０％ＲＨ雰囲気中１００Ｖ印加して行い、導通破壊が発
生するまでの時間を測定した。 曲げ試験：ＪＩＳ Ｃ６４８１に従い、常温及び２００
℃で測定した。単位：曲げ強さ（ＭＰａ）、曲げ弾性率
（ＧＰａ）The test method is as follows. Tg: Copper foil is etched and measured by TMA (thermomechanical analysis). Unit: ° C Solder heat resistance: The copper foil was etched, held in a pressure cooker tester for 2 hours, immersed in solder at 260 ° C for 20 seconds, and the appearance was visually inspected. NG in the table means occurrence of measling and blistering. Water absorption rate: Calculated from the difference in weight before and after the copper foil was etched and held in a pressure cooker tester for 4 hours. Unit:% Thermal discoloration: 160 in air after etching copper foil
After treating at 5 ° C. for 5 hours, it was visually evaluated. No discoloration ○, slightly discolored △, discolored ×
And Electrolytic corrosion resistance test: The insulation resistance of 400 holes was measured with time for each sample using a test pattern in which the wall spacing between through holes was 350 μm. The test conditions were 85 ° C, 9
The measurement was performed by applying a voltage of 100 V in a 0% RH atmosphere, and the time until the breakdown occurred was measured. Bending test: Room temperature and 200 according to JIS C6481
Measured in ° C. Unit: Flexural strength (MPa), Flexural modulus (GPa)
【００２８】[0028]
【表１】 [Table 1]
【００２９】[0029]
【表２】 [Table 2]
【００３０】[0030]
【表３】 [Table 3]
【００３１】以上の結果から、次のことが分る。エポキ
シ樹脂に、ＥＸＡ−Ｔ７１０を用いた実施例１〜４は、
１９０℃以上の高いＴｇを有し、はんだ耐熱性、耐電食
性も良好である。また、常温における曲げ強さ、曲げ弾
性率に対する２００℃における曲げ強さ、曲げ弾性率の
低下が小さい。また、硬化促進剤にイソシアネートマス
クイミダゾールを用いた実施例４は、プリプレグの保存
安定性が良好である。さらに、ビスフェノールＡノボラ
ック樹脂を用いた実施例１〜４及び比較例１は加熱変色
性が良好である。これに対して、エポキシ樹脂にｏ−ク
レゾールノボラック型エポキシ樹脂を用いた比較例１及
び、ビスフェノールＡノボラック樹脂に代えてフェノー
ルノボラック樹脂を用いた比較例２は、Ｔｇが低く、２
００℃における曲げ強さ、曲げ弾性率とも低い。さら
に、硬化剤にフェノールノボラックを用いた比較例２
は、加熱変色性が悪く、またジシアンジアミドを用いた
比較例３及び４は吸水率が大きく、耐電食性に劣る。From the above results, the following can be understood. Examples 1 to 4 using EXA-T710 as the epoxy resin,
It has a high Tg of 190 ° C or higher, and has good solder heat resistance and electrolytic corrosion resistance. Further, the decrease in bending strength and bending elastic modulus at 200 ° C. relative to the bending strength and bending elastic modulus at room temperature is small. Further, in Example 4 in which isocyanate mask imidazole was used as the curing accelerator, the storage stability of the prepreg was good. Furthermore, Examples 1 to 4 and Comparative Example 1 using the bisphenol A novolac resin have good heat discoloration. On the other hand, Comparative Example 1 in which an o-cresol novolac type epoxy resin was used as the epoxy resin and Comparative Example 2 in which the phenol novolac resin was used instead of the bisphenol A novolac resin had a low Tg.
Both flexural strength and flexural modulus at 00 ° C are low. Furthermore, Comparative Example 2 using phenol novolac as the curing agent
Shows a poor heat discoloration property, and Comparative Examples 3 and 4 using dicyandiamide have a large water absorption rate and are inferior in electrolytic corrosion resistance.
【００３２】[0032]
【発明の効果】本発明の印刷配線板用エポキシ樹脂組成
物は、印刷配線板とした場合に吸湿性が低く、優れた耐
熱性と高温特性、耐電食性、耐加熱変色性を有し、かつ
高いＴｇを与えるエポキシ樹脂組成物を得ることができ
る。The epoxy resin composition for a printed wiring board of the present invention has low hygroscopicity when used as a printed wiring board, has excellent heat resistance and high temperature characteristics, electrolytic corrosion resistance, and heat discoloration resistance, and An epoxy resin composition giving a high Tg can be obtained.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 佐瀬 茂雄 茨城県下館市大字小川1500番地 日立化成 工業株式会社下館研究所内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Shigeo Sase 1500 Ogawa, Ogawa, Shimodate-shi, Ibaraki Hitachi Chemical Co., Ltd. Shimodate Research Laboratory
Claims (1)
（ｂ）ビスフェノールＡとホルムアルデヒドの重縮合
物、（ｃ）硬化促進剤を必須成分として配合してなる印
刷配線板用エポキシ樹脂組成物。 【化１】 （式中、ＲはＨまたは、メチル、エチル、プロピル、ｔ
ｅｒｔ−ブチルなどのアルキル基である。）1. An epoxy resin represented by formula (a) 1, and
An epoxy resin composition for printed wiring boards, which comprises (b) a polycondensate of bisphenol A and formaldehyde and (c) a curing accelerator as essential components. Embedded image (In the formula, R is H or methyl, ethyl, propyl, t
It is an alkyl group such as ert-butyl. )
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16067295A JPH0912681A (en) | 1995-06-27 | 1995-06-27 | Epoxy resin composition for use in printed wiring board |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16067295A JPH0912681A (en) | 1995-06-27 | 1995-06-27 | Epoxy resin composition for use in printed wiring board |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0912681A true JPH0912681A (en) | 1997-01-14 |
Family
ID=15719992
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP16067295A Pending JPH0912681A (en) | 1995-06-27 | 1995-06-27 | Epoxy resin composition for use in printed wiring board |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0912681A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007314748A (en) * | 2006-04-27 | 2007-12-06 | Hitachi Chem Co Ltd | Epoxy resin composition, epoxy resin prepreg, metal-clad laminate and printed wiring board |
-
1995
- 1995-06-27 JP JP16067295A patent/JPH0912681A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007314748A (en) * | 2006-04-27 | 2007-12-06 | Hitachi Chem Co Ltd | Epoxy resin composition, epoxy resin prepreg, metal-clad laminate and printed wiring board |
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