JPH02127415A - Epoxy resin composition and production of prepreg and laminated sheet - Google Patents
Epoxy resin composition and production of prepreg and laminated sheetInfo
- Publication number
- JPH02127415A JPH02127415A JP28093288A JP28093288A JPH02127415A JP H02127415 A JPH02127415 A JP H02127415A JP 28093288 A JP28093288 A JP 28093288A JP 28093288 A JP28093288 A JP 28093288A JP H02127415 A JPH02127415 A JP H02127415A
- Authority
- JP
- Japan
- Prior art keywords
- resin
- base material
- epoxy resin
- acid
- anhydride
- 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 43
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 43
- 239000000203 mixture Substances 0.000 title claims abstract description 38
- 238000004519 manufacturing process Methods 0.000 title claims description 13
- 229920006026 co-polymeric resin Polymers 0.000 claims abstract description 42
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 41
- 229920005989 resin Polymers 0.000 claims abstract description 40
- 239000011347 resin Substances 0.000 claims abstract description 40
- 239000000178 monomer Substances 0.000 claims abstract description 36
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 31
- -1 aromatic vinyl compound Chemical class 0.000 claims abstract description 28
- 150000008065 acid anhydrides Chemical class 0.000 claims abstract description 19
- 239000007788 liquid Substances 0.000 claims abstract description 12
- 239000002904 solvent Substances 0.000 claims abstract description 12
- PYSRRFNXTXNWCD-UHFFFAOYSA-N 3-(2-phenylethenyl)furan-2,5-dione Chemical compound O=C1OC(=O)C(C=CC=2C=CC=CC=2)=C1 PYSRRFNXTXNWCD-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229920000147 Styrene maleic anhydride Polymers 0.000 claims abstract description 10
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 9
- 239000003505 polymerization initiator Substances 0.000 claims abstract description 9
- 239000000463 material Substances 0.000 claims description 47
- 238000000034 method Methods 0.000 claims description 22
- 239000004593 Epoxy Substances 0.000 claims description 12
- 239000004850 liquid epoxy resins (LERs) Substances 0.000 claims description 11
- 239000011342 resin composition Substances 0.000 claims description 11
- 150000007519 polyprotic acids Polymers 0.000 claims description 9
- 238000003856 thermoforming Methods 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 abstract description 2
- 238000013329 compounding Methods 0.000 abstract 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 24
- 239000002253 acid Substances 0.000 description 19
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 17
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 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 description 11
- 229920006241 epoxy vinyl ester resin Polymers 0.000 description 11
- 239000000843 powder Substances 0.000 description 11
- 238000010438 heat treatment Methods 0.000 description 10
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 10
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 9
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 9
- 239000011521 glass Substances 0.000 description 9
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 8
- 150000007513 acids Chemical class 0.000 description 8
- 150000008064 anhydrides Chemical class 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 230000000704 physical effect Effects 0.000 description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000011889 copper foil Substances 0.000 description 6
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 6
- 239000011888 foil Substances 0.000 description 6
- 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 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 6
- 229920006337 unsaturated polyester resin Polymers 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- MWSKJDNQKGCKPA-UHFFFAOYSA-N 6-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1CC(C)=CC2C(=O)OC(=O)C12 MWSKJDNQKGCKPA-UHFFFAOYSA-N 0.000 description 5
- 229930185605 Bisphenol Natural products 0.000 description 5
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- 239000004744 fabric Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 150000002989 phenols Chemical class 0.000 description 5
- 150000005846 sugar alcohols Polymers 0.000 description 5
- CMQUQOHNANGDOR-UHFFFAOYSA-N 2,3-dibromo-4-(2,4-dibromo-5-hydroxyphenyl)phenol Chemical compound BrC1=C(Br)C(O)=CC=C1C1=CC(O)=C(Br)C=C1Br CMQUQOHNANGDOR-UHFFFAOYSA-N 0.000 description 4
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 description 4
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 4
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 4
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 4
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 150000002170 ethers Chemical class 0.000 description 4
- 239000003365 glass fiber Substances 0.000 description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 4
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 4
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 125000004018 acid anhydride group Chemical group 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 239000013040 bath agent Substances 0.000 description 3
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 235000011187 glycerol Nutrition 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 229940049920 malate Drugs 0.000 description 3
- 239000004745 nonwoven fabric Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- MUTGBJKUEZFXGO-OLQVQODUSA-N (3as,7ar)-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1CCC[C@@H]2C(=O)OC(=O)[C@@H]21 MUTGBJKUEZFXGO-OLQVQODUSA-N 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- OBETXYAYXDNJHR-UHFFFAOYSA-N 2-Ethylhexanoic acid Chemical compound CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 2
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 description 2
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 2
- JQXYBDVZAUEPDL-UHFFFAOYSA-N 2-methylidene-5-phenylpent-4-enoic acid Chemical compound OC(=O)C(=C)CC=CC1=CC=CC=C1 JQXYBDVZAUEPDL-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 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 2
- FJKROLUGYXJWQN-UHFFFAOYSA-M 4-hydroxybenzoate Chemical compound OC1=CC=C(C([O-])=O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-M 0.000 description 2
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- 239000004342 Benzoyl peroxide Substances 0.000 description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical group C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-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
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-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
- 235000019400 benzoyl peroxide Nutrition 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 2
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 2
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- HSOOVEKLGOIEFF-UHFFFAOYSA-N ethenyl nitrate Chemical compound [O-][N+](=O)OC=C HSOOVEKLGOIEFF-UHFFFAOYSA-N 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000001530 fumaric acid Substances 0.000 description 2
- NKHAVTQWNUWKEO-UHFFFAOYSA-N fumaric acid monomethyl ester Natural products COC(=O)C=CC(O)=O NKHAVTQWNUWKEO-UHFFFAOYSA-N 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 2
- 150000002460 imidazoles Chemical class 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- BJEPYKJPYRNKOW-UHFFFAOYSA-N malic acid Chemical compound OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229920003145 methacrylic acid copolymer Polymers 0.000 description 2
- 229940117841 methacrylic acid copolymer Drugs 0.000 description 2
- NKHAVTQWNUWKEO-IHWYPQMZSA-N methyl hydrogen fumarate Chemical compound COC(=O)\C=C/C(O)=O NKHAVTQWNUWKEO-IHWYPQMZSA-N 0.000 description 2
- VYKXQOYUCMREIS-UHFFFAOYSA-N methylhexahydrophthalic anhydride Chemical compound C1CCCC2C(=O)OC(=O)C21C VYKXQOYUCMREIS-UHFFFAOYSA-N 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 229920006287 phenoxy resin Polymers 0.000 description 2
- 239000013034 phenoxy resin Substances 0.000 description 2
- 229920002857 polybutadiene Polymers 0.000 description 2
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- LYDRKKWPKKEMNZ-UHFFFAOYSA-N tert-butyl benzoate Chemical compound CC(C)(C)OC(=O)C1=CC=CC=C1 LYDRKKWPKKEMNZ-UHFFFAOYSA-N 0.000 description 2
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- HGTUJZTUQFXBIH-UHFFFAOYSA-N (2,3-dimethyl-3-phenylbutan-2-yl)benzene Chemical group C=1C=CC=CC=1C(C)(C)C(C)(C)C1=CC=CC=C1 HGTUJZTUQFXBIH-UHFFFAOYSA-N 0.000 description 1
- QEQBMZQFDDDTPN-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy benzenecarboperoxoate Chemical compound CC(C)(C)OOOC(=O)C1=CC=CC=C1 QEQBMZQFDDDTPN-UHFFFAOYSA-N 0.000 description 1
- OBETXYAYXDNJHR-SSDOTTSWSA-M (2r)-2-ethylhexanoate Chemical compound CCCC[C@@H](CC)C([O-])=O OBETXYAYXDNJHR-SSDOTTSWSA-M 0.000 description 1
- LTVUCOSIZFEASK-MPXCPUAZSA-N (3ar,4s,7r,7as)-3a-methyl-3a,4,7,7a-tetrahydro-4,7-methano-2-benzofuran-1,3-dione Chemical compound C([C@H]1C=C2)[C@H]2[C@H]2[C@]1(C)C(=O)OC2=O LTVUCOSIZFEASK-MPXCPUAZSA-N 0.000 description 1
- KNDQHSIWLOJIGP-UMRXKNAASA-N (3ar,4s,7r,7as)-rel-3a,4,7,7a-tetrahydro-4,7-methanoisobenzofuran-1,3-dione Chemical compound O=C1OC(=O)[C@@H]2[C@H]1[C@]1([H])C=C[C@@]2([H])C1 KNDQHSIWLOJIGP-UMRXKNAASA-N 0.000 description 1
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- XLYMOEINVGRTEX-ONEGZZNKSA-N (e)-4-ethoxy-4-oxobut-2-enoic acid Chemical compound CCOC(=O)\C=C\C(O)=O XLYMOEINVGRTEX-ONEGZZNKSA-N 0.000 description 1
- ZMQWRASVUXJXGM-SREVYHEPSA-N (z)-4-cyclohexyloxy-4-oxobut-2-enoic acid Chemical compound OC(=O)\C=C/C(=O)OC1CCCCC1 ZMQWRASVUXJXGM-SREVYHEPSA-N 0.000 description 1
- WBYWAXJHAXSJNI-VOTSOKGWSA-M .beta-Phenylacrylic acid Natural products [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 description 1
- 150000005208 1,4-dihydroxybenzenes Chemical class 0.000 description 1
- UICXTANXZJJIBC-UHFFFAOYSA-N 1-(1-hydroperoxycyclohexyl)peroxycyclohexan-1-ol Chemical compound C1CCCCC1(O)OOC1(OO)CCCCC1 UICXTANXZJJIBC-UHFFFAOYSA-N 0.000 description 1
- HXKKHQJGJAFBHI-UHFFFAOYSA-N 1-aminopropan-2-ol Chemical compound CC(O)CN HXKKHQJGJAFBHI-UHFFFAOYSA-N 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 1
- FUIQBJHUESBZNU-UHFFFAOYSA-N 2-[(dimethylazaniumyl)methyl]phenolate Chemical compound CN(C)CC1=CC=CC=C1O FUIQBJHUESBZNU-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 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
- LLEASVZEQBICSN-UHFFFAOYSA-N 2-undecyl-1h-imidazole Chemical compound CCCCCCCCCCCC1=NC=CN1 LLEASVZEQBICSN-UHFFFAOYSA-N 0.000 description 1
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- DXIJHCSGLOHNES-UHFFFAOYSA-N 3,3-dimethylbut-1-enylbenzene Chemical compound CC(C)(C)C=CC1=CC=CC=C1 DXIJHCSGLOHNES-UHFFFAOYSA-N 0.000 description 1
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- WVRNUXJQQFPNMN-VAWYXSNFSA-N 3-[(e)-dodec-1-enyl]oxolane-2,5-dione Chemical compound CCCCCCCCCC\C=C\C1CC(=O)OC1=O WVRNUXJQQFPNMN-VAWYXSNFSA-N 0.000 description 1
- IZUVGRMMRWJVKU-UHFFFAOYSA-N 3-ethoxycarbonylbut-3-enoic acid Chemical compound CCOC(=O)C(=C)CC(O)=O IZUVGRMMRWJVKU-UHFFFAOYSA-N 0.000 description 1
- AYKYXWQEBUNJCN-UHFFFAOYSA-N 3-methylfuran-2,5-dione Chemical compound CC1=CC(=O)OC1=O AYKYXWQEBUNJCN-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-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
- RBHIUNHSNSQJNG-UHFFFAOYSA-N 6-methyl-3-(2-methyloxiran-2-yl)-7-oxabicyclo[4.1.0]heptane Chemical compound C1CC2(C)OC2CC1C1(C)CO1 RBHIUNHSNSQJNG-UHFFFAOYSA-N 0.000 description 1
- ASZFCDOTGITCJI-UHFFFAOYSA-N 6-oxabicyclo[3.1.0]hex-2-ene Chemical compound C1C=CC2OC12 ASZFCDOTGITCJI-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- WBYWAXJHAXSJNI-SREVYHEPSA-N Cinnamic acid Chemical compound OC(=O)\C=C/C1=CC=CC=C1 WBYWAXJHAXSJNI-SREVYHEPSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 101000958041 Homo sapiens Musculin Proteins 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- OPKOKAMJFNKNAS-UHFFFAOYSA-N N-methylethanolamine Chemical compound CNCCO OPKOKAMJFNKNAS-UHFFFAOYSA-N 0.000 description 1
- 229930192627 Naphthoquinone Natural products 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- BGNXCDMCOKJUMV-UHFFFAOYSA-N Tert-Butylhydroquinone Chemical compound CC(C)(C)C1=CC(O)=CC=C1O BGNXCDMCOKJUMV-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical class [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 238000012644 addition polymerization Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- 238000004380 ashing Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- NIDNOXCRFUCAKQ-UHFFFAOYSA-N bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1C2C=CC1C(C(=O)O)C2C(O)=O NIDNOXCRFUCAKQ-UHFFFAOYSA-N 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- SHZIWNPUGXLXDT-UHFFFAOYSA-N caproic acid ethyl ester Natural products CCCCCC(=O)OCC SHZIWNPUGXLXDT-UHFFFAOYSA-N 0.000 description 1
- 150000001722 carbon compounds Chemical class 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229930016911 cinnamic acid Natural products 0.000 description 1
- 235000013985 cinnamic acid Nutrition 0.000 description 1
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 1
- 229940018557 citraconic acid Drugs 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 229940120693 copper naphthenate Drugs 0.000 description 1
- SEVNKWFHTNVOLD-UHFFFAOYSA-L copper;3-(4-ethylcyclohexyl)propanoate;3-(3-ethylcyclopentyl)propanoate Chemical compound [Cu+2].CCC1CCC(CCC([O-])=O)C1.CCC1CCC(CCC([O-])=O)CC1 SEVNKWFHTNVOLD-UHFFFAOYSA-L 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- IFDVQVHZEKPUSC-UHFFFAOYSA-N cyclohex-3-ene-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCC=CC1C(O)=O IFDVQVHZEKPUSC-UHFFFAOYSA-N 0.000 description 1
- MIHINWMALJZIBX-UHFFFAOYSA-N cyclohexa-2,4-dien-1-ol Chemical class OC1CC=CC=C1 MIHINWMALJZIBX-UHFFFAOYSA-N 0.000 description 1
- QSAWQNUELGIYBC-UHFFFAOYSA-N cyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCCCC1C(O)=O QSAWQNUELGIYBC-UHFFFAOYSA-N 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical class C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 1
- JXBPSENIJJPTCI-UHFFFAOYSA-N ethyl cyanate Chemical compound CCOC#N JXBPSENIJJPTCI-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- XLYMOEINVGRTEX-UHFFFAOYSA-N fumaric acid monoethyl ester Natural products CCOC(=O)C=CC(O)=O XLYMOEINVGRTEX-UHFFFAOYSA-N 0.000 description 1
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 102000046949 human MSC Human genes 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 229940102253 isopropanolamine Drugs 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- BJHIKXHVCXFQLS-OTWZMJIISA-N keto-L-sorbose Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)C(=O)CO BJHIKXHVCXFQLS-OTWZMJIISA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000002655 kraft paper Substances 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- YBEFXFBAXWUBNQ-UHFFFAOYSA-N n-methylmethanamine;propan-1-amine Chemical compound CNC.CCCN YBEFXFBAXWUBNQ-UHFFFAOYSA-N 0.000 description 1
- 150000002791 naphthoquinones Chemical class 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- FJDUDHYHRVPMJZ-UHFFFAOYSA-N nonan-1-amine Chemical compound CCCCCCCCCN FJDUDHYHRVPMJZ-UHFFFAOYSA-N 0.000 description 1
- VIKNJXKGJWUCNN-XGXHKTLJSA-N norethisterone Chemical compound O=C1CC[C@@H]2[C@H]3CC[C@](C)([C@](CC4)(O)C#C)[C@@H]4[C@@H]3CCC2=C1 VIKNJXKGJWUCNN-XGXHKTLJSA-N 0.000 description 1
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 125000005461 organic phosphorous group Chemical group 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 238000011417 postcuring Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- POSICDHOUBKJKP-UHFFFAOYSA-N prop-2-enoxybenzene Chemical compound C=CCOC1=CC=CC=C1 POSICDHOUBKJKP-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 150000004053 quinones Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- WPZJSWWEEJJSIZ-UHFFFAOYSA-N tetrabromobisphenol-F Natural products C1=C(Br)C(O)=C(Br)C=C1CC1=CC(Br)=C(O)C(Br)=C1 WPZJSWWEEJJSIZ-UHFFFAOYSA-N 0.000 description 1
- UFDHBDMSHIXOKF-UHFFFAOYSA-N tetrahydrophthalic acid Natural products OC(=O)C1=C(C(O)=O)CCCC1 UFDHBDMSHIXOKF-UHFFFAOYSA-N 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- BEFUBHVQRFELBK-UHFFFAOYSA-N trihydroxy(diphenyl)-$l^{5}-phosphane Chemical compound C=1C=CC=CC=1P(O)(O)(O)C1=CC=CC=C1 BEFUBHVQRFELBK-UHFFFAOYSA-N 0.000 description 1
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
Landscapes
- Reinforced Plastic Materials (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Resins (AREA)
Abstract
Description
【発明の詳細な説明】
〈産業上の利用分野〉
本発明は耐熱性に優れ、しかも電気特性、特に誘電率が
低く、積層板用グリプレグ及び積層板の製造に好適なエ
ポキシ樹脂組成物、及びこの組成物を含浸させてなるグ
リプレグと積層板の製法に関する。Detailed Description of the Invention <Industrial Application Field> The present invention provides an epoxy resin composition that has excellent heat resistance and low electrical properties, particularly low dielectric constant, and is suitable for the production of gripregs for laminates and laminates; The present invention relates to a method for producing Gripregs and laminates impregnated with this composition.
〈従来の技術〉
ガラスクロス、ガラス繊維不織布、チ、ッグドストラン
ドグラス等の繊維質基材に溶剤で希釈した硬化性樹脂組
成物を含浸・乾燥させて成るプリプレグを調製し、この
プリプレグを１枚もしくは複数枚重ね合わせたものに銅
箔等の金属箔を重ね合わせて加熱加圧し、硬化させるこ
とによって積層板を得ることは周知である。<Prior art> A prepreg is prepared by impregnating and drying a curable resin composition diluted with a solvent into a fibrous base material such as glass cloth, glass fiber non-woven fabric, glass fiber, or hard strand glass. It is well known that a laminate can be obtained by laminating one or more metal foils such as copper foil on top of one another and heating and pressurizing and curing the foil.
この様な浴剤希釈型のエポキシ樹脂組成物を用いた場合
、乾燥の過程での浴剤の完全な除去は困難であり、グレ
プリグシート中の残留溶剤は加熱加圧時に気化してぎイ
ド発生の原因となシ、また得られた積層板の耐ハンダ性
、耐ミーズリング性。When using such a bath agent-diluted epoxy resin composition, it is difficult to completely remove the bath agent during the drying process, and the residual solvent in the Gleprig sheet evaporates during heating and pressurization. This is not the cause of the occurrence, and the solder resistance and measling resistance of the obtained laminate.
絶縁抵抗等の物性を大きく低下させてしまう欠点を有す
る。It has the disadvantage of greatly reducing physical properties such as insulation resistance.
この溶剤希釈樹脂含浸法の溶剤処理の欠点を克服する方
法として、常温液状エポキシ樹脂とエポキシ樹脂用硬化
剤とエポキシビニルエステル樹脂及び／又は不飽和ポリ
エステル樹脂と重合性ビニルモノマーとから成る、重合
性ビニルモノマー以外の溶剤を含まない、実質的に無溶
剤のエポキシ樹脂組成物を繊維質基材に含浸させ、加熱
によりてＢ−ステージ化を行ない得られるプリプレグを
加熱加圧成形して、積層板を得る方法が知られている（
特開昭５９−４９２４０号公報）。As a method to overcome the drawbacks of solvent treatment in this solvent diluted resin impregnation method, a polymerizable resin containing a room temperature liquid epoxy resin, a curing agent for epoxy resin, an epoxy vinyl ester resin and/or an unsaturated polyester resin, and a polymerizable vinyl monomer is used. A fibrous base material is impregnated with a substantially solvent-free epoxy resin composition that does not contain any solvent other than vinyl monomers, and B-staged by heating. The resulting prepreg is heated and pressure molded to form a laminate. It is known how to obtain (
(Japanese Unexamined Patent Publication No. 59-49240).
〈発明が解決しようとする課題〉
上記方法により得られる積層板の耐熱性及び電気特性は
、ジシアンジアミドを硬化剤とする従来の浴剤希釈温エ
ポキシ樹脂組成物を用いて得られる積層板に比べて良好
でおるが、必ずしも十分ではなく、更に耐熱性に優れ、
電気特性、特に誘電率も低い積層板が望まれている。<Problems to be Solved by the Invention> The heat resistance and electrical properties of the laminate obtained by the above method are superior to those obtained using a conventional bath agent diluted temperature epoxy resin composition containing dicyandiamide as a curing agent. Although it is good, it is not necessarily sufficient, and it has excellent heat resistance.
A laminate with low electrical properties, particularly low dielectric constant, is desired.
く課題を解決するだめの手段〉
本発明者等は、この様な状況に鑑みて鋭意研究した結果
、上記実質的に無溶剤のエポキシ樹脂組成物において、
芳香族ビニル化合物と不飽和カルボン識及び／又はその
酸無水物とを必須成分として得られる共重合樹脂をエポ
キシ樹脂用硬化剤として用いると、特に耐熱性に優れ、
しかも誘電率の低い積層板が得られること、また該共重
合樹脂が加熱に際して揮散しにくいためＢ−ステージ化
や予備硬化をよシ高温、短時間で容易に実施できること
を見い出し１本発明を完成するに至った。Means for Solving the Problem> As a result of intensive research in view of the above situation, the present inventors found that in the above-mentioned substantially solvent-free epoxy resin composition,
When a copolymer resin obtained as an essential component of an aromatic vinyl compound and an unsaturated carbon compound and/or its acid anhydride is used as a curing agent for epoxy resin, it has particularly excellent heat resistance,
Furthermore, they discovered that a laminate with a low dielectric constant can be obtained, and that the copolymer resin is difficult to volatilize when heated, so B-staging and pre-curing can be easily carried out at higher temperatures and in a shorter time. 1. Completed the present invention. I ended up doing it.
すなわち、本発明は、常温液状エポキシ樹脂（Ａ１）と
芳香族ビニル化合物と不飽和カルボン酸及び／又は七へ
水物とを必須成分として得られる共重合樹脂（Ａ２）と
重合性不飽和基を有する樹脂（Ｂｌ）と重合性ビニル七
ツマ−（Ｂ３ ）と重合開始剤（Ｂｉ）とを必須成分と
して含有し、カッｘ 会性ビニルモノマー（Ｂ２）以外
の溶剤を含有しないことを特徴とするエポキシ樹脂組成
物、を必須成分として得られる共重合樹脂（Ａｘ）と重
合性不飽和基を有する樹脂（Ｂｘ ）と重合性ビニル七
ツマ−（Ｂ３ ）と重合開始剤（Ｂ３ ）とを必須成分
として含有し、かつ重合性ビニルモノマ（Ｂｚ）以外の
浴剤を含有しないエポキシ樹脂組成物（Ｉ）を繊維質基
材（ｎ）に含浸させて含浸基材（ＩＩＩ）を得た後、Ｂ
−ステージ化することを特徴とするプリプレグの製法、
及び常温液状エポキシ得られる共重合樹脂（Ａ２）と重
合性不飽和基を有する樹１ｆｆｉ（Ｂ２）と重合性ビニ
ル七ツマ−（Ｂｘ）と重合開始剤（Ｂ３ ）とを必須成
分として含有し。That is, the present invention comprises a copolymer resin (A2) obtained as essential components of an epoxy resin (A1) that is liquid at room temperature, an aromatic vinyl compound, an unsaturated carboxylic acid and/or a heptahydride, and a polymerizable unsaturated group. It is characterized by containing a resin (Bl), a polymerizable vinyl monomer (B3), and a polymerization initiator (Bi) as essential components, and containing no solvent other than the polymerizable vinyl monomer (B2). An epoxy resin composition containing as essential components a copolymer resin (Ax), a resin having a polymerizable unsaturated group (Bx), a polymerizable vinyl nitrate (B3), and a polymerization initiator (B3) as essential components. After impregnating the fibrous base material (n) with the epoxy resin composition (I) containing as B and containing no bath agent other than the polymerizable vinyl monomer (Bz) to obtain the impregnated base material (III),
- A prepreg manufacturing method characterized by staging,
The copolymer resin (A2) obtained as a liquid epoxy at room temperature, a tree 1ffi (B2) having a polymerizable unsaturated group, a polymerizable vinyl nitrate (Bx), and a polymerization initiator (B3) are contained as essential components.
かつ重合性ビニルモノマー（Ｂ３）以外の溶剤を含有し
ないエポキシ樹脂組成物（Ｉ）を繊維質基材（ｎ）に含
浸式せて含浸基材（ＤＩ）を得た後、加熱成形すること
を特徴とする積層板の製法を提供するものである。The epoxy resin composition (I) containing no solvent other than the polymerizable vinyl monomer (B3) is impregnated onto the fibrous base material (n) to obtain an impregnated base material (DI), and then heated and molded. The present invention provides a manufacturing method for characteristic laminates.
ここで用いる常温液状エポキシ樹脂（人、）としては、
常温で無溶剤液状のエポキシ樹脂の単独又は混合物がい
ずれも使用できるが１通常は平均エポキシ当量がｌＯＯ
〜４００、好ましくは１ｏ。The room temperature liquid epoxy resin used here is:
Epoxy resins that are solvent-free liquid at room temperature can be used alone or as a mixture, but usually the average epoxy equivalent is 1OO.
~400, preferably 1o.
〜２５０のものを使用する。その代弐例を挙げると、い
ずれも常温で無溶剤液状のエピクロルヒドリントビスフ
エノール人、ビスフェノ−／Ｉ／Ｆ、レゾルシンなど２
価フェノールとから得られるエポキシ樹脂；エチレング
リコール、グロビレングリコール、ポリエチレングリコ
ール、ポリフロピレンゲリコール、ネオインチルグリコ
ール、グリセリン、トリメチロールエタン、トリメチロ
ールプロパンまたは２価フェノールのエチレンオキサイ
ドもしくはプロピレンオキサイド付加物の如き多価アル
コールのポリグリシジルエーテル類；アジピン酸、フタ
ル酸、テトラヒドロフタル酸、ヘキサヒドロフタル酸ま
たはダイマー酸の如きプリカル？ン酸のポリグリシジル
エステル類；シクロヘキセンまたはその誘導体を過酢酸
などでエポキシ化石せることによシ得られるシクロヘキ
セン系のエポキシ化合物類（３，４−エポキシ−６−メ
チル−シクロへキシル−３，４−エポキシ−６−メチル
シクロヘキサンカ／ｌ／ｒｆキシレー）、３．４−エポ
キシシクロヘキシルメチル−３，４−二ポキンシクロヘ
キサンカルデキシレート、１−エポキシエチル−３，４
−エポキシシクロヘキサンナト）；シクロペンタジェン
もしくはジシクロペンタジェンまたはそれらの誘導体を
過酢酸などでエポキシ化させることによね得られるシク
ロペンタジェン系のエポキシ化合物類（シクロペンタジ
ェンオキサイド、ジシクローンタジエンオキサイド、２
．３−エポキシシクロ４ンチルエーテルなど）；リモネ
ンジオキサイド；あるいはヒドロキシ安息香酸のグリシ
ジルエーテルエステルなどかあシ、なかでも性能上のバ
ランスが良好で価格が安い点でエピクロルヒドリンとビ
スフェノール人又はビスフェノールＦとから得られる常
温液状エポキシ樹脂が、また低粘度が得られる点で常温
液状のシクロヘキセン系エポキシ化合物類が好ましい。~250 are used. Examples include epichlorohydrintobisphenol, bisphenol/I/F, and resorcinol, all of which are solvent-free liquids at room temperature.
Epoxy resin obtained from ethylene glycol, globylene glycol, polyethylene glycol, polypropylene gellicol, neointyl glycol, glycerin, trimethylolethane, trimethylolpropane, or divalent phenol with ethylene oxide or propylene oxide addition Polyglycidyl ethers of polyhydric alcohols such as adipic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid or dimer acids; polyglycidyl esters of phosphoric acid; cyclohexene-based epoxy compounds obtained by epoxidizing cyclohexene or its derivatives with peracetic acid etc. (3,4-epoxy-6-methyl-cyclohexyl-3,4 -Epoxy-6-methylcyclohexanecal/l/rf xylene), 3,4-epoxycyclohexylmethyl-3,4-dipoquinecyclohexanecaldexylate, 1-epoxyethyl-3,4
-Epoxycyclohexannat); cyclopentadiene-based epoxy compounds (cyclopentadiene oxide, dicyclontadiene oxide) obtained by epoxidizing cyclopentadiene or dicyclopentadiene or their derivatives with peracetic acid etc. ,2
．． (3-epoxycycloquaternary ether, etc.); limonene dioxide; or glycidyl ether ester of hydroxybenzoic acid, among others, epichlorohydrin and bisphenol or bisphenol F have a good balance of performance and are inexpensive. Cyclohexene-based epoxy compounds, which are liquid at room temperature, are preferred because the resulting epoxy resin is liquid at room temperature and has a low viscosity.
更に１本発明では、上記の様な常温液状エポキシ樹脂１
種以上と常温固型のエポキシ樹脂の１種以上を混合して
常温液状エポキシ樹脂（Ａ１ ）として使用することも
でき、通常は平均粒径が５０〜５００胸、好ましくは平
均粒径１００〜３００μｍの粉末状エポキシ樹脂を常温
液状エポキシ樹脂中に溶解および／又は分散てせて用い
る。その代弐的なものを挙げると、いずれも融点が５０
℃以上のエピクロルヒドリンとビスフェノール人、ビス
フェノールＦ、レゾルシン、テトラブロモビスフェノー
ル人、テトラブロモビスフェノールＦ、ビスフェノール
Ｓなどの２価フェノールとから得られるエポキシ樹脂ま
たはフェノキシ樹脂；フェノール、アルキルフェノール
またはプロふ化フェノール・ノ？ラック樹脂の如き多価
フェノールのポリグリシジルエーテル；２価フェノール
とノぎラック樹脂とから成る共線エポキシ樹脂；アニリ
ン、ｐ−（またはｍ−）アミンフェノール、ジアミノジ
フェニルメタンの如き多価アミンのポリグリシジルアミ
ン、前述の多価アルコールのポリグリシジルエーテル、
ポリカルデン酸のボリグリシジルエステルまたはヒドロ
キシ安息香酸のグリシジルエーテルエステルと、２価フ
ェノールの単独またはこれと１価フェノールの混合物と
の共線エポキシ樹脂；トリグリシジルイソシアヌレート
などがあり、なかでもエピクロルヒドリンとビスフェノ
ール人とから得られる粉末状エポキシ樹脂が性能上のバ
ランスが良好で価格が安い点で、超高分子量フェノキシ
樹脂、例えば米国ＵＣＣ社製ＰＫＨＩＨ（商品名）が少
量の添加で高い圧縮成形性と高い性能が得られる点で、
また粉末状の多価フェノールポリグリシジルエーテルが
耐熱性に優れる点で。Furthermore, in the present invention, the above room temperature liquid epoxy resin 1
It can also be used as a room temperature liquid epoxy resin (A1) by mixing one or more types of epoxy resins that are solid at room temperature or above, and usually has an average particle size of 50 to 500 μm, preferably an average particle size of 100 to 300 μm. A powdered epoxy resin is dissolved and/or dispersed in a liquid epoxy resin at room temperature. To name a few, they all have a melting point of 50
Epoxy resin or phenoxy resin obtained from epichlorohydrin and dihydric phenols such as bisphenol, bisphenol F, resorcinol, tetrabromobisphenol, tetrabromobisphenol F, bisphenol S; phenol, alkylphenol or pro-proliferated phenol? Polyglycidyl ethers of polyhydric phenols such as lac resins; collinear epoxy resins consisting of dihydric phenols and nogilac resins; polyglycidyl ethers of polyhydric amines such as aniline, p- (or m-) amine phenol, and diaminodiphenylmethane. amines, polyglycidyl ethers of the aforementioned polyhydric alcohols;
Collinear epoxy resins of polyglycidyl esters of polycardic acid or glycidyl ether esters of hydroxybenzoic acid and dihydric phenols alone or in mixtures with monohydric phenols; triglycidyl isocyanurates, among others, epichlorohydrin and bisphenols. Powdered epoxy resin obtained from and has a good balance of performance and is inexpensive, and ultra-high molecular weight phenoxy resin, such as PKHIH (trade name) manufactured by UCC Corporation in the United States, has high compression moldability and high performance with the addition of a small amount. At the point where you can get
Also, powdered polyhydric phenol polyglycidyl ether has excellent heat resistance.
更にエピクロルヒドリンとテトラブロモビスフェノール
Ａとから得られる粉末状エポキシ樹脂と粉末状のブロム
化多価フェノールポリグリシジルエーテルが難燃性に優
れる点でそれぞれ好ましい。Furthermore, a powdered epoxy resin obtained from epichlorohydrin and tetrabromobisphenol A and a powdered brominated polyhydric phenol polyglycidyl ether are preferable because of their excellent flame retardancy.
次いで、芳香族ビニル化合物と不飽和カルデン酸及び／
又はその酸無水物とを必須成分として得られる共重合樹
脂（Ａ２）としては１例えば芳香族ビニル化合物と不飽
和カル？ン酸とを必須成分として乳化重合法、塊状重合
法、懸濁重合法、溶液重合法等により共重合させて得ら
れる共重合樹脂が挙げられる。Next, the aromatic vinyl compound and the unsaturated caldic acid and/or
The copolymer resin (A2) obtained as an essential component is an aromatic vinyl compound and an unsaturated carboxylic acid anhydride. Examples include copolymer resins obtained by copolymerizing with phosphoric acid as an essential component by emulsion polymerization, bulk polymerization, suspension polymerization, solution polymerization, etc.
ここで用いる芳香族ビニル化合物としては１例エバスチ
レン、ビニルトルエン、クロルスチレン。Examples of aromatic vinyl compounds used here include evastyrene, vinyltoluene, and chlorstyrene.
ブロムスチレン、メチルスチレン、ビニルピリジンなど
の芳香環に１個のビニル基を有する化合物が挙げられる
。Examples include compounds having one vinyl group in an aromatic ring such as bromustyrene, methylstyrene, and vinylpyridine.
不飽和カル？ン酸又はその無水物としては１例えばアク
リル酸、メタクリル酸、マレイン酸、無水マレイン酸、
フマル酸、イタコン酸、無水イタコン酸、シトラコン酸
、マレイン酸モノメチルエステル、マレイン酸モツプチ
ルエステル、マレイン酸モノシクロヘキシルエステル、
フマル酸モノエチルエステル、イタコン酸モノエチルエ
ステル等の少なくとも１個のカルブキシル基又は酸無水
物基を有する重合性不飽和化合物が挙げられ、なかでも
耐熱性の特に良好な積層板が得られる点で無水マレイン
酸、無水イタコン酸等の不飽和カルボン酸無水物が好ま
しく、特に無水マレイン酸が好ましい。Unsaturated Cal? Examples of acid or anhydride thereof include acrylic acid, methacrylic acid, maleic acid, maleic anhydride,
fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, maleic acid monomethyl ester, maleic acid monomethyl ester, maleic acid monocyclohexyl ester,
Examples include polymerizable unsaturated compounds having at least one carboxyl group or acid anhydride group, such as fumaric acid monoethyl ester and itaconic acid monoethyl ester, among which a laminate with particularly good heat resistance can be obtained. Unsaturated carboxylic acid anhydrides such as maleic anhydride and itaconic anhydride are preferred, and maleic anhydride is particularly preferred.
また、上記共重合樹脂（Ａりとしては、不飽和カル♂ン
酸酸無水物を用いて得られる共重合樹脂中の酸無水基を
アルコールによ多部分的にエステル化したものや、上記
２成分以外の他の重合性モノマー、例えば（メタ）アク
リル酸エステル類、酢酸ビニル、アリルアルコール、フ
ェニルアリルエーテル等を更に共重合成分として加えた
もの等も使用できる。In addition, the above-mentioned copolymer resin (A) may be a copolymer resin obtained by partially esterifying the acid anhydride groups in the copolymer resin obtained using unsaturated carboxyl acid anhydride with alcohol, or the above-mentioned 2 It is also possible to use polymerizable monomers other than the above components, such as (meth)acrylic esters, vinyl acetate, allyl alcohol, phenylallyl ether, etc., added as a copolymerization component.
上記共重合樹脂（Ａｍ）の酸価は、通常１０〜７００で
あるが、なかでも耐熱性に優れ、しかも誘電率の低い積
層板が得られる点で５０〜６００が好ましい。The acid value of the copolymer resin (Am) is usually 10 to 700, but preferably 50 to 600, since a laminate with excellent heat resistance and low dielectric constant can be obtained.
本発明では、上記共重合樹１ｍ（Ａ２）の一部を多塩基
酸無水物で置き換えても良く、エポキシ樹脂組成物（り
Ｏ粘度、硬化性、積層板の要求性能等から適宜多塩基酸
無水物が併用できる。In the present invention, a part of the above-mentioned copolymer resin 1m (A2) may be replaced with a polybasic acid anhydride, and the polybasic acid Anhydrous can be used together.
多塩基酸無水物として代茨的なものを挙げれば、無水フ
タル酸、ヘキサヒドロ無水フタル酸、テトラヒドロ無水
フタル酸、メチルへキサヒドロ無水フタ／’Ｅｌ、メチ
ルテトラヒドロ無水フタル＠、無水ナノツク酸、無水メ
チルナジック酸、無水トリメリット酸、無水ピロメリッ
ト酸、無水マレイン酸、無水コハク酸、無水イタコン酸
、無水シトラコン酸、ドデセニル無水コハク酸、無水ｐ
ｏｖンディック酸、無水ペンゾフェノンテトラカルボン
酸、無水シクロペンタテトラカルボン酸、５−（２，５
−ジオキソテトラヒドロフリル）−３−メチル−３−シ
クロヘキセン−１，２−ノヵルゴン酸、エチレングリコ
ールビストリメリテート無水物またはグリセリントリメ
リテート無水物などかあシ、これらは単独で、あるいは
二種以上の混合物の形で用いられる。Typical examples of polybasic acid anhydrides include phthalic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methylhexahydrophthalic anhydride/'El, methyltetrahydrophthalic anhydride@, nanotsunic anhydride, and methyl anhydride. Nadic acid, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, succinic anhydride, itaconic anhydride, citraconic anhydride, dodecenyl succinic anhydride, p anhydride
ovundic acid, penzophenonetetracarboxylic anhydride, cyclopentatetracarboxylic anhydride, 5-(2,5
-dioxotetrahydrofuryl)-3-methyl-3-cyclohexene-1,2-nocargonic acid, ethylene glycol bistrimelitate anhydride or glycerin trimellitate anhydride, etc., either alone or in combination of two or more. used in the form of a mixture of
本発明で用いる重合性不飽和基を有する樹脂（以下、不
飽和樹脂と略記する。）（Ｂｒ）とは、重合可能な不飽
和基、好ましくは不飽和二重結合を含有し、該不飽和基
の東金反応によシ硬化する樹脂を言い、七の代弐例を挙
げるとエポキシビニルエステル樹脂、ウレタンアクリレ
ート樹脂、ポリエステルアクリレート樹脂、不飽和ポリ
エステル樹脂、ノアリルフタレートｗ脂、スピラン樹脂
。The resin having a polymerizable unsaturated group (hereinafter abbreviated as unsaturated resin) (Br) used in the present invention refers to a resin containing a polymerizable unsaturated group, preferably an unsaturated double bond, and the unsaturated It refers to resins that harden through the Togane reaction, and the following seven examples include epoxy vinyl ester resin, urethane acrylate resin, polyester acrylate resin, unsaturated polyester resin, noaryl phthalate resin, and spiran resin.
付加重合型ポリイミド等がおる。なかでもエポキシビニ
ルエステル樹脂及び／又は不飽和ポリエステル樹脂が好
ましく、特に耐熱性、金属箔との接着性に優れる点でエ
ポキシビニルエステル樹脂が好ましい。There are addition polymerization type polyimides, etc. Among these, epoxy vinyl ester resins and/or unsaturated polyester resins are preferred, and epoxy vinyl ester resins are particularly preferred since they are excellent in heat resistance and adhesiveness to metal foil.
ここで不飽和樹脂（Ｂ１ ）として用いるエポキシビニ
ルエステル樹脂としては、エポキシ樹脂として前記した
如き各種のエポキシ樹脂の、好ましくはビスフェノール
・タイプ又はノブラック・タイプのエポキシ樹脂の、そ
れぞれ単独又は混合物と、下記の如き不飽和−塩基酸と
を、エステル化触媒の存在下で反応させて得られた樹脂
が挙げられる。The epoxy vinyl ester resin used as the unsaturated resin (B1) here includes various epoxy resins as described above, preferably bisphenol type or noblack type epoxy resins, each singly or in a mixture; Examples include resins obtained by reacting unsaturated basic acids as shown below in the presence of an esterification catalyst.
ここにおいて、不飽和−塩基酸として代表的なものには
アクリ／Ｌ／＠、メタクリル醜、桂皮酸、クロトン酸、
モノメチルマレート、モツプチルマレート、モツプチル
マレート、ソルビンＷ１．またはモノ（２−エチルヘキ
シル）マレ−ドナとがアシ、これらは単独でも二種以上
の混合においても用いることができる。Here, typical unsaturated basic acids include acrylic/L/@, methacrylic acid, cinnamic acid, crotonic acid,
Monomethyl malate, motuptil malate, motuptil malate, sorbin W1. Alternatively, mono(2-ethylhexyl)maledona may be used, and these may be used alone or in a mixture of two or more.
また、上記エポキシビニルエステル樹脂と下記の如き二
塩基酸無水物とを反応させて得られるカルぎキシル基含
有エポキシビニルエステルＭｉｌｌｉ ４゜本発明でい
うエポキシビニルエステル樹脂として使用てれる。Furthermore, a carboxyl group-containing epoxy vinyl ester Milli 4° obtained by reacting the above epoxy vinyl ester resin with a dibasic acid anhydride as described below can be used as the epoxy vinyl ester resin in the present invention.
ここにおいて、二塩基酸無水物として代表的なものには
、無水フタル酸、ヘキサヒドロ無水フタ／Ｌ／Ｉ！、テ
トラヒドロ無水フタル酸、メチルへキサヒドロ無水フタ
ル酸、メチルテトラヒドロ無水フタｔｖ ｉ！ｌ 、無
水ナジック酸、無水メチルナジック酸。Here, typical dibasic acid anhydrides include phthalic anhydride, hexahydrophthalic anhydride/L/I! , tetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyltetrahydrophthalic anhydride tv i! l, nadic anhydride, methylnadic anhydride.
無水マレイン酸、無水プハク酸、無水イタコン酸等の前
記の多塩基酸無水物の代表例中の二塩基酸無水物がある
。Typical examples of the polybasic acid anhydrides include dibasic acid anhydrides such as maleic anhydride, phosphoric anhydride, and itaconic anhydride.
また、不飽和ポリエステル樹脂としては、不飽和二塩基
酸を含む二塩基酸類と多価アルコール類との反応で得ら
れたものが挙げられる。Further, examples of the unsaturated polyester resin include those obtained by reacting dibasic acids containing unsaturated dibasic acids with polyhydric alcohols.
ここで用いる不飽和二塩基酸として代表的なものには、
マレイン酸、無水マレイン酸、フマル欧、ハロダン化無
水マレイン敵などがあり、これら以外の飽和二塩基酸と
もいうべき酸類として代表的なものにはフタル酸、無水
フタル酸、ハロゲン化ｆＩＡ！フタル酸、イソフタル酸
、テレフタル酸、テトラヒドロ無水フタル酸、コノ・り
酸、アジピン酸。Typical unsaturated dibasic acids used here include:
Maleic acid, maleic anhydride, fumaric acid, halogenated maleic anhydride, etc. Other typical acids that can be called saturated dibasic acids include phthalic acid, phthalic anhydride, and halogenated fIA! Phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic anhydride, cono-phosphoric acid, adipic acid.
セ・々シン酸などがあシ、他方、多価アルコール類とし
て代表的なものにはエチレングリコール、ジエチレング
リコール、トリエチレングリコール、プロピレングリコ
ール、ジエチレングリコール、１．３−ブチレングリコ
ール、１．４−’；’チレングリコール、ネオインチル
グリコール、水添ビスフェノール入、１．６−ヘキサン
ジオール、ビスフェノールＡとエチレンオキサイドもし
くはプロピレンオキサイドとの付加物、グリセリン、ト
リメチロールプロパンなどがある。On the other hand, typical polyhydric alcohols include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, diethylene glycol, 1.3-butylene glycol, 1.4-'; Examples include tylene glycol, neointyl glycol, hydrogenated bisphenol containing, 1,6-hexanediol, adducts of bisphenol A and ethylene oxide or propylene oxide, glycerin, and trimethylolpropane.
これらの各原料を用いてエポキシビニルエステル樹脂又
は不飽和ポリエステル樹脂を得るには。To obtain epoxy vinyl ester resin or unsaturated polyester resin using each of these raw materials.
従来公知の方法に従えばよく、これら両樹脂を調製する
にていしては、樹脂ｍ製中のｒル化を防止する目的や、
生成樹脂の保存安定性あるいは硬化性の１ｌＩｎの目的
でそれぞれ重合禁止剤を使用することが推奨式れる。Conventionally known methods may be followed, and when preparing these two resins, the purpose of preventing rulation in the resin m,
It is recommended to use a polymerization inhibitor for the purpose of improving the storage stability and curing of the resulting resin.
かかる重合禁止剤として代表的なものを挙げればハイド
ロキノン、ｐ−ｔ−ブチルカテコール、モノ−ｔ−ブチ
ルハイドロキノンの如きハイドロキノン類；ハイドロキ
ノンモノメチルエーテル、ジーｔ−ｐ−りＶゾールの如
きフェノール類；ｐ−ベンゾキノン、ナフトキノン、ｐ
−）ルキノンの如きキノン類；またはナフテン酸銅の如
き銅塩などがある。Typical examples of such polymerization inhibitors include hydroquinones such as hydroquinone, pt-butylcatechol, and mono-t-butylhydroquinone; phenols such as hydroquinone monomethyl ether and di-tp-V sol; -benzoquinone, naphthoquinone, p
-) quinones such as luquinone; or copper salts such as copper naphthenate.
また、１合性ビニルモノマー（Ｂｘ）としては、何重は
スチレン、ビニルトルエン、ｔ−ブチルスチレン、クロ
ルスチレンもしくハシビニルベンゼンの如きスチレン及
びその誘導体；メチル（メタ）アクリレート、エチル（
メタ）アクリレート、クロビル（メタ）アクリレート、
イソプロピル（メタ）アクリレート、Ｕ−ブチル（メタ
）アクリレート、イソブチル（メタ）アクリレート、２
−エチルヘキシル（メタ）アクリレート、ラウリル（メ
タ）アクリレート％２−ヒドロキシエチル（メタ）アク
リレートもしくは２−ヒト党キシグロビル（メタ）アク
リレートの如ｉ！（メタ）アクリル酸の低沸点エステル
モノマー類；またはトリメチロールゾロ／臂ントリ（メ
タ）アクリレート。In addition, monomer vinyl monomers (Bx) include styrene and its derivatives such as styrene, vinyltoluene, t-butylstyrene, chlorostyrene, or hashivinylbenzene; methyl (meth)acrylate, ethyl (
meth)acrylate, clovir (meth)acrylate,
Isopropyl (meth)acrylate, U-butyl (meth)acrylate, isobutyl (meth)acrylate, 2
- Ethylhexyl (meth)acrylate, lauryl (meth)acrylate% 2-Hydroxyethyl (meth)acrylate or 2-hygrovir (meth)acrylate! Low-boiling ester monomers of (meth)acrylic acid; or trimethylolzolo/tri(meth)acrylate.
ジエチレングリコールジ（メタ）アクリレート。Diethylene glycol di(meth)acrylate.
１．４−ブタンジオールジ（メタ）アクリレートもしく
は１．６−ヘキサンシオールジ（メタ）アクリレートの
如き多価アルコールの（メタ）アクリレート類などが挙
げられ、なかでも揮発性に優れる点でスチレン、ビニル
トルエン、（メタ）アクリル酸の低沸点エステルモノマ
ー類が好ましく、スチレンが特に好ましい。Examples include (meth)acrylates of polyhydric alcohols such as 1.4-butanediol di(meth)acrylate and 1.6-hexanediol di(meth)acrylate, and among them, styrene and vinyl have excellent volatility. Toluene and low-boiling ester monomers of (meth)acrylic acid are preferred, and styrene is particularly preferred.
これらはそれぞれ単独で、あるいは二種以上を併用する
ことが可能であシ、通常エポキシビニルエステル樹脂、
不飽和ポリエステル樹脂等の不飽和樹脂（Ｂｌ ）４０
〜８０重量うに対して６０〜２０重量％（合計１００重
量％）の割合で使用てれる。These can be used alone or in combination of two or more, and usually include epoxy vinyl ester resin,
Unsaturated resin such as unsaturated polyester resin (Bl) 40
It is used in a proportion of 60 to 20% by weight (total 100% by weight) based on 80% by weight.
本発明で用いる重合開始剤（Ｂ２）としては、加熱加圧
成形温度よりも低い温度で分解するものが好ましく１例
えばシクロヘキサノンパーオキサイド、３，３．５−）
リメチルシクロヘキサノン／？−オキサイド、メチロネ
キサノン７臂−オキサイド、１．１−ビス（ｔ−プチル
ノ譬−オキシ）３，３．５−）リスチルシクロヘキサン
、クメンハイドロパーオキサイド、ジクミル／４−オキ
サイド、ラウロイルパーオキサイド、３，５．５−）リ
スチルヘキサノイルパーオキサイド、ベンゾイルパーオ
キサイド。The polymerization initiator (B2) used in the present invention is preferably one that decomposes at a temperature lower than the heating and pressing temperature (1, for example, cyclohexanone peroxide, 3,3.5-)
Limethylcyclohexanone/? -oxide, methylonexanone 7-oxide, 1.1-bis(t-butylno-oxy)3,3.5-)listylcyclohexane, cumene hydroperoxide, dicumyl/4-oxide, lauroyl peroxide, 3, 5.5-) Listylhexanoyl peroxide, benzoyl peroxide.
ジ−ミリスチルパーオキシシカ−？ネート、を−ブチル
ノーオキシ（２−エチルヘキサノエート）。Di-myristyl peroxysica? ate, -butyloxy(2-ethylhexanoate).
ｔ−ブチルノ、４−オキシ−３，５，５−）リメチルヘ
キサノエート、ｔ−ブチルパーオキシベンゾエート。t-Butylno,4-oxy-3,5,5-)limethylhexanoate, t-butylperoxybenzoate.
クミルパーオキシオクトエートなどの有機過酸化物が挙
げられる。Examples include organic peroxides such as cumyl peroxyoctoate.
本発明では、上記常温液状エポキシ樹脂（ＡＩ）とに＊
余村Ｋ（、Ａ 重）の硬化を促進するために必要によシ
硬化促進剤を加えることができる。In the present invention, the above room temperature liquid epoxy resin (AI) and *
If necessary, a hardening accelerator can be added to accelerate the hardening of Yomura K (, A Heavy).
ここで必要に応じて用いる硬化促進剤として代表的なも
のには、ジエチルアミン、トリエチルアミン、ジイソグ
ロビルアミン、モノエタノールアミン、ジェタノールア
ミン、トリエタノールアミン、メチルエタノールアミン
、メチルジェタノールアミン、モノイソプロパツールア
ミン、ノニルアミン、ジメチルアミンプロピルアミン、
ジエチルアミノゾロビルアミン、α−ベンジルエタノー
ルアミン：２，４．６−）リス−ジメチルアミノメチル
フェノールもしくはそのトリー２−エチルヘキシル酸塩
；２−ジメチルアミノメチルフェノール。Typical curing accelerators used here if necessary include diethylamine, triethylamine, diisoglobilamine, monoethanolamine, jetanolamine, triethanolamine, methylethanolamine, methyljetanolamine, and monoethanolamine. Isopropanolamine, nonylamine, dimethylaminepropylamine,
Diethylaminozolobylamine, α-benzylethanolamine: 2,4.6-)lis-dimethylaminomethylphenol or its tri-2-ethylhexylate; 2-dimethylaminomethylphenol.
ピリジン、ビイリジン、Ｎ−アミノゾロピルモルホリン
、１．８−ジアゾビシクロ（５，４，０）ウンデセン−
７まタハそれとフェノール、２−エチルヘキサン酸、オ
レイン酸、ジフェニル亜燐酸もしくは有機含燐酸類との
塩類の如き各種アミン類；２−メチルイミダゾール、２
−インゾロビルイミダゾール、２−ウンデシルイミダゾ
ール、２−フェニルイミダゾール、２−エチル−４−メ
チルイミダゾール、２−フェニル−４−メチルイミダゾ
ール、１−ベンジＡ／−２−メチルイミタソール、イミ
ダゾールとＣｕ、 ＮｌもしくはＧｏなどの金属塩錯体
；２−メチルイミダゾールをアクリロニトリルと灰石さ
せて得られるシアノエチレーシ、／・タイプのイミダゾ
ールまたはそれらとトリメリット酸との付加物もしくは
ジシアンジアミドとの反応物の如きイミダゾール類：Ｂ
Ｆ、−モノエタノールアミン、 ＢＦ −ベンジルア
ミン、ＢＦ３−ジメチルアニリン、ＢＦ、 −）ジエチ
ルアミン、ＢＦｓ −ｎ −ヘキシルアミン、ＢＦ３−
２．６−ジエチルアミン、ＢＦ −アニリンもしくは
ＢＦ、−ピペリジンの如きＢＦ、−アミン錯体類；１．
１−ジメチルヒドラジンを出発原料とするアミンイミド
化合物；トリフェニルホスファイトの如き燐化合物また
はオクチル酸錫の知性有機酸金属塩類などがある。Pyridine, Biiridine, N-aminozolopylmorpholine, 1,8-diazobicyclo(5,4,0)undecene-
7. Various amines such as salts of it and phenol, 2-ethylhexanoic acid, oleic acid, diphenylphosphorous acid or organic phosphorous acids; 2-methylimidazole, 2
- inzolobyl imidazole, 2-undecylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, 2-phenyl-4-methylimidazole, 1-bendiA/-2-methylimitasole, imidazole and Metal salt complexes such as Cu, Nl or Go; imidazoles such as cyanoethylate obtained by ashing 2-methylimidazole with acrylonitrile, / type imidazoles or their adducts with trimellitic acid or reactants with dicyandiamide; Class: B
F, -monoethanolamine, BF -benzylamine, BF3-dimethylaniline, BF, -)diethylamine, BFs -n-hexylamine, BF3-
2. BF,-amine complexes such as 6-diethylamine, BF-aniline or BF,-piperidine;1.
Examples include amine imide compounds using 1-dimethylhydrazine as a starting material; phosphorus compounds such as triphenyl phosphite, and intelligent organic acid metal salts of tin octylate.
本発明の常温液状エポキシ樹脂組成物（Ｉ）とは、前記
（ＡＩ）、（Ａｍ）、（Ｂｌ ）、（Ｂ２）及び（Ｂｓ
）成分を必須成分として用い、更に必要に厄じて多塩
基酸無水物、硬化促進剤、内部離型剤。The room temperature liquid epoxy resin composition (I) of the present invention includes the above-mentioned (AI), (Am), (Bl), (B2) and (Bs
) are used as essential ingredients, and if necessary, polybasic acid anhydride, curing accelerator, and internal mold release agent are used.
顔料、充填剤、改質剤等の添加剤を加えてなシ、かつ前
記（Ｂ２）Ｘ分以外の溶剤を実質的に含有しない組成物
であって、しかも繊維質基材（Ｉｆ）に含浸可能なもの
を言う。尚、固温の成分は、含浸に際して、必ずしも液
状成分中に溶解又は浴融嘔せて用いる必要はなく、液状
成分中に粉末状で分散させて用いてもよい。A composition that does not contain additives such as pigments, fillers, modifiers, etc., and does not substantially contain any solvent other than the component (B2) X, and is impregnated into the fibrous base material (If). say what is possible. Note that the solid component does not necessarily need to be dissolved in the liquid component or melted in a bath during impregnation, but may be used in the form of a powder dispersed in the liquid component.
上記共重合樹脂（Ｂ）の使用量としては、エポキシ樹脂
組成物（Ｉ）中に含まれるエポキシ基１個に対して該共
重合樹脂（Ｂ）中のカル？キシル基の数（但し、酸無水
物基はカルブキシル基２個と見なす。）が通常０．２〜
２．６個となる範囲であるが、耐熱性に優れ、ｎ電車が
低く、更に吸湿性の低い積層板が得られる点で０．６〜
１．８個の範囲が好ましい。The amount of the copolymer resin (B) to be used is as follows: Calcium in the copolymer resin (B) per one epoxy group contained in the epoxy resin composition (I). The number of xyl groups (however, an acid anhydride group is considered to be two carboxyl groups) is usually 0.2 to
The range is 0.6 to 2.6, but it is possible to obtain a laminate with excellent heat resistance, low n-electrode, and low hygroscopicity.
A range of 1.8 is preferred.
上記エポキシ樹脂組成物（Ｉ）中に含浸させる前記常温
液状エポキシ樹脂（Ａｌ）及び共重合樹脂（Ａ２）と不
飽和樹脂（Ｂ１ ）の重量比Ｃ（ＡＩ）＋ （Ａり：ｌ
／ （Ｂ１）は通常９８／２〜３０／７０であるが、硬
化時の収縮が少なく、金属、特に銅箔との接着性に優れ
る点で９５１５〜５０１５０が好ましい。Weight ratio C(AI)+ (A ratio: l
/ (B1) is usually 98/2 to 30/70, but 9515 to 50150 is preferable in terms of less shrinkage during curing and excellent adhesion to metals, especially copper foil.
エポキシ樹脂組成物（Ｉ）に必要に応じて加えられる充
填剤は、要求性能、作業条件などにょシ適宜選択でれる
が１例を挙げると水酸化アルミニウム、ケイ酸アルミニ
ウム、コロイダルシリカ、炭酸カルシウム、硫酸カルシ
ウム、マイカ、タルク、二酸化チタン、石英粉末、ケイ
Ｉｌｌジル；ニウム、ガラス粉末、アスベスト粉末、ケ
イ藻土、三酸化アンチモンなどがある。The filler to be added to the epoxy resin composition (I) as needed can be selected depending on the required performance and working conditions, but examples include aluminum hydroxide, aluminum silicate, colloidal silica, calcium carbonate, Examples include calcium sulfate, mica, talc, titanium dioxide, quartz powder, silica, glass powder, asbestos powder, diatomaceous earth, and antimony trioxide.
また、改質剤としては、例えばブタジェンゴム誘導体、
ニトリルゴム誘導体、ポリ酸無水物、低分子量ポリスル
フィド、フェノール樹脂、キシレン樹脂、ケトン樹脂等
があυ、なかでも銅箔との接着性と層間剥離強度の向上
に効果がある点でブタジェンゴム誘導体およびニトリル
ゴム誘導体が好ましい。In addition, examples of the modifier include butadiene rubber derivatives,
Nitrile rubber derivatives, polyacid anhydrides, low molecular weight polysulfides, phenolic resins, xylene resins, ketone resins, etc. are used, but among them, butadiene rubber derivatives and nitrile are effective in improving adhesion with copper foil and interlayer peel strength. Rubber derivatives are preferred.
エポキシ樹脂組成物（Ｉ）を得るに際しての各成分の配
合方法および配合順序は特に限定されるものでなく、（
ＡＩ ）と（Ａ２）、更に必要に応じて多塩基酸無水物
からなる樹脂組成物と（Ｂｔ ）と（Ｂ雪 ）と（Ｂ３
）からなる樹脂組成物とを別々に調製した後、混合し
てもよいが、液状成分を混合した後、固型の成分を粉末
状で添加して１分散又は溶解させる方法が好ましい。The blending method and blending order of each component in obtaining the epoxy resin composition (I) are not particularly limited, and (
AI) and (A2), and if necessary, a resin composition comprising a polybasic acid anhydride, (Bt), (Byuki), and (B3).
) may be prepared separately and then mixed, but it is preferable to mix the liquid components and then add the solid components in powder form to disperse or dissolve them.
他方、本発明で用いる繊維質基材（Ｉｆ）として代表的
なものを挙げれば、ガラス繊維、炭素繊維または芳香族
ポリアミド系繊維などであり、なかでもガラス繊維が好
ましい。これらのうちまずがラス繊維としては、その原
料面から、Ｅ−グラス、Ｃ−グラス、Ａ−グラスおよび
Ｓ−グラスなどが存在しているが、本発明においてはい
ずれの種類のものも適用できる。On the other hand, typical examples of the fibrous base material (If) used in the present invention include glass fibers, carbon fibers, and aromatic polyamide fibers, and among them, glass fibers are preferred. Among these, the lath fibers include E-glass, C-glass, A-glass, and S-glass in terms of their raw materials, but any of these types can be applied in the present invention. .
これらの繊維質基材（ｎ）は、その形状によジローピン
グ、チョツプドストランドマツト、コンティニアスマッ
ト、クロス、不織布、ロービングクロス、サーフェシン
グマットおよびチョツプドストランドがあるが、上掲し
た如き種類や形状は、目的とする成形物の用途および性
能によシ適宜選択嘔れるものであって、必要によっては
二以上の種類または形状からの混合使用であってもよい
。These fibrous base materials (n) are classified into jiroping, chopped strand mat, continuous mat, cloth, non-woven fabric, roving cloth, surfacing mat, and chopped strand depending on their shape, but the above-mentioned types can be used. The shape and shape can be selected as appropriate depending on the intended use and performance of the molded product, and two or more types or shapes may be used in combination, if necessary.
なかでもクロス、不織布が好ましい。Among them, cloth and nonwoven fabric are preferred.
上記の各種原材料を用いてプリグレグ全得るには、前記
エポキシ樹脂組成物（Ｉ）を繊維質基材（Ｉ）に含浸さ
せて含浸基材（ＩＩＩ）を得た後、Ｂ−ステージ化すれ
ばよい、Ｂ−ステージ化の方法は特に限定されないが、
Ｂ−ステージ化の前又はＢ−ステージ化と同時、好まし
くはＢ−ステージ化と同時に１枚づつ該含浸基材（Ｉｌ
ｌ）中の重合性ビニルモノマー（Ｂ２）（Ｄ除去を行い
、樹脂成分中に残存する重合性ビニルモノマー（Ｂりの
量を８．０重量％以下、好ましくは６．０重量％以下に
コントロールすると、金属箔との剥離強度及び眉間剥離
強度に優れるプリプレグが得られるので好ましく、タッ
クフリーなプリプレグを得るためには４． ＯＸ量に以
下が特に好ましい。In order to obtain all of the pregregs using the above-mentioned various raw materials, the epoxy resin composition (I) is impregnated into the fibrous base material (I) to obtain the impregnated base material (III), and then B-staged. A good B-staging method is not particularly limited, but
The impregnated substrate (Il
The polymerizable vinyl monomer (B2) in l) (D is removed and the amount of polymerizable vinyl monomer (B) remaining in the resin component is controlled to 8.0% by weight or less, preferably 6.0% by weight or less) This is preferable because a prepreg having excellent peel strength with metal foil and glabellar peel strength can be obtained, and in order to obtain a tack-free prepreg, the following 4.OX amount is particularly preferable.
また、積層板を得るには、上記と同様にして含浸基材（
Ｉ［［）を得た後、必要に応じて予備硬化（Ｂ−ステー
ジ化も含む）を行い、加熱成形すればよい。この時、含
浸基材は通常２〜１５枚、好ましくは３〜１０枚重ね合
せて成形される。必要に応じて行なわれる予備硬化の方
法は特に限定されないが、予備硬化の前又は予備硬化と
同時、好ましくは予備硬化と同時に該含浸基材（Ｉｌｌ
）中の重合性ビニルモノマー（Ｂ３）の除去を行い、樹
脂成分中に残存する１合性ビニルモノマー（Ｂｚ ）の
量を８．０重量５以下、好ましくは６．０重量５以下に
コントロールすると、金属箔との剥離強度及び眉間剥離
強度に優れる積層板が得られるので好ましい。尚、予備
硬化と１合性ビニルモノマー（Ｂａ ）の除去は、含浸
基材（ＩＩＩ）を１枚づつ分離した状態で行ってもよい
し、２枚以上重ね合せた状態で行ってもよい。In addition, to obtain a laminate, an impregnated base material (
After obtaining I[[), preliminary curing (including B-staging) may be performed as needed, followed by thermoforming. At this time, the impregnated base material is usually formed by stacking 2 to 15 sheets, preferably 3 to 10 sheets. The method of preliminary curing, which is carried out as necessary, is not particularly limited, but the impregnated base material (Ill.
) by removing the polymerizable vinyl monomer (B3) and controlling the amount of the monomerizable vinyl monomer (Bz ) remaining in the resin component to 8.0% by weight or less, preferably 6.0% by weight or less. This is preferable because a laminate having excellent peel strength with metal foil and glabella peel strength can be obtained. The preliminary curing and the removal of the monomerizable vinyl monomer (Ba 2 ) may be carried out with the impregnated substrates (III) separated one by one, or with two or more impregnated substrates stacked one on top of the other.
１合性ビニルモノマー（Ｂａ）の除去と含浸基材（Ｉ［
ｌ）のＢ−ステージ化又は予備硬化を同時に行う方法と
しては、７０〜１５０℃、好ましくは９０℃〜１４０℃
に加熱する方法が通常採用される。７０℃以下では重合
性ビニルモノマーは揮散しにくいし、１５０℃以上では
含浸基材（ＩＩＩ）中の成分（Ａ２）と（人Ｓ）の反応
及び成分（Ｂ１ ）と（Ｂ、）と（Ｂ３）の反応が同時
に進行し、加熱成形時の適正な樹脂の流動性を得ること
が難しくなって好ましくない。Removal of monomer vinyl monomer (Ba) and impregnation base material (I[
The method of simultaneously performing B-staging or preliminary curing of l) is 70 to 150°C, preferably 90 to 140°C.
A method of heating is usually adopted. At temperatures below 70°C, the polymerizable vinyl monomer is difficult to volatilize, and at temperatures above 150°C, reactions between component (A2) and (S) in the impregnated base material (III) and components (B1), (B, ) and (B3) occur. ) reactions proceed at the same time, making it difficult to obtain appropriate fluidity of the resin during heat molding, which is undesirable.
また重合性ビニルモノマーを効率良く揮散嘔せる方法と
しては１例えば熱風を含浸基材（ＩＩＩ）に吹きつける
方法、加熱と吸引又は減圧を同時又は別に行う方法、赤
外線や遠赤外線を用いる方法、高周波加熱を用いる方法
など挙げられる。なかでも、これらの方法は不活性ガス
、好ましくは窒素ガス雰囲気下で行ってもよく、その場
合不活性ガス雰囲気中の酸素濃度が３モル％以下である
と特に好ましい。In addition, methods for efficiently volatilizing the polymerizable vinyl monomer include 1, for example, a method of blowing hot air onto the impregnated base material (III), a method of performing heating and suction or depressurization simultaneously or separately, a method of using infrared rays or far infrared rays, and a method of using high frequency Examples include a method using heating. Among these, these methods may be carried out under an inert gas atmosphere, preferably a nitrogen gas atmosphere, and in this case, it is particularly preferable that the oxygen concentration in the inert gas atmosphere is 3 mol % or less.
尚、上記残存重合性ビニルモノマーは上記重合性ビニル
モノマー除去後の含浸乾燥材料（Ｆ／）をアセトン等の
溶剤に１昼夜浸漬し、溶出するモノマーをガスクロマト
グラフィーで定量することができる。The remaining polymerizable vinyl monomer can be determined by immersing the impregnated dry material (F/) from which the polymerizable vinyl monomer has been removed in a solvent such as acetone for one day and then quantifying the eluted monomer by gas chromatography.
また、本発明において含浸基材（■）の予備硬化とＢ−
ステージ化は、樹脂成分の反応が進み、常温無圧下では
実質的に流動性を失う程、該樹脂成分の粘度が高くなっ
ているが、１４０℃以上に加熱されると再度流動性を示
した後、硬化する状態にまで反応を進めるととｔ−言い
、なかでもＢ−ステージ化は、この範囲内で更に含浸基
材（Ｉｌｌ）の弐面がべとつきのないタックフリーの状
態、あるいはこれに近い状態にまで反応を進めることを
言う。In addition, in the present invention, preliminary curing of the impregnated base material (■) and B-
In staging, the reaction of the resin component progresses, and the viscosity of the resin component becomes so high that it essentially loses its fluidity at room temperature and under no pressure, but it shows fluidity again when heated to 140°C or higher. After that, the reaction is progressed to a state where it hardens, which is called t-stage, and in particular, B-stage is when the second side of the impregnated base material (Ill) is in a tack-free state without stickiness, or something close to this. It means to advance the reaction to the state.
いずれの場合も、平板上で１５０℃Ｘ １５ ｋｌ？／
ｃｍ”の条件で加熱加圧した時、含浸基材＜ｍ＞中に含
浸されていた樹脂成分の中から基材外にＫｌｔｌた樹脂
成分の割合（流出率）が４〜３５重量％となる範囲まで
予備硬化又はＢ−ステージ化すると好ましい。In either case, on a flat plate at 150℃ x 15 kl? /
When heated and pressurized under the conditions of "cm", the proportion of the resin component (flow rate) out of the resin component impregnated in the impregnated base material <m> to the outside of the base material is 4 to 35% by weight. Pre-curing or B-staging to a certain extent is preferred.
本発明のグリプレグ及び積層板を得るに際して、繊維質
基材（ｎ）の容積比率は重合性ビニルモノマー除去後の
含浸基材の３０〜７０％なる範囲内が適当である。When obtaining the gripregs and laminates of the present invention, the volume ratio of the fibrous base material (n) is suitably within the range of 30 to 70% of the impregnated base material after removal of the polymerizable vinyl monomer.
加熱成形方法としては、例えば上記の様にして得た含浸
基材を必要であれば重ね合せ、更に両面に離型フィルム
及び／又は金属箔を重ね合せ、従来公知のスタテックプ
レス、連続ベルトプレス等で加熱成形する方法等が挙げ
られる。成形温度は通常１３０〜２２０℃、好ましくは
１４０〜１８０℃である。底形圧力は１通常接触圧〜５
０ ｋｇ７ｃｍ”でおシ、好ましくは５〜４０時／α２
である。例えば、スタテックプレスでの成形では含浸基
材を所定サイズに切断後１重ね會せるが、連続ベルトプ
レスでの成形では含浸基材は長尺のまま、必要であれば
連続的に重ね合せ積層した後、連続ベルトプレスで成形
される。この際必要・であれば、加熱成形機から取シ出
した後、更に後硬化を施すこともできる。As a heat forming method, for example, the impregnated base materials obtained as described above are superimposed if necessary, and a release film and/or metal foil is further superimposed on both sides, and conventionally known static press or continuous belt press is used. For example, a method of heating and forming the material by heating or the like can be mentioned. The molding temperature is usually 130-220°C, preferably 140-180°C. Bottom pressure is 1 normal contact pressure ~ 5
0 kg7cm", preferably 5-40 hours/α2
It is. For example, when forming with a static press, the impregnated base material is cut to a predetermined size and then stacked together, but when forming with a continuous belt press, the impregnated base material remains long and is continuously layered and laminated if necessary. After that, it is molded using a continuous belt press. At this time, if necessary, post-curing may be further performed after taking it out from the heat forming machine.
尚、樹脂成分の配合比率を変えた異種の樹脂組成物を含
浸させて得られる異種の含浸基材を目的に応じ組合せて
用いることも可能であるし、本発明で用いる含浸基材と
他の樹脂を含浸させて得られる含浸基材とを組合せるこ
とも可能である。In addition, it is also possible to use different types of impregnated base materials obtained by impregnating different types of resin compositions with different blending ratios of resin components depending on the purpose, and it is also possible to use the impregnated base materials used in the present invention and other types of impregnated base materials in combination depending on the purpose. It is also possible to combine it with an impregnated base material obtained by impregnating it with a resin.
〈実施例〉
次に本発明を実施例及び比較例を挙げて更に具体的に説
明する。<Examples> Next, the present invention will be described in more detail by giving examples and comparative examples.
尚、例中の部及び５は特に断υのない限シはすべて重量
基準である。In addition, all parts and 5 in the examples are based on weight unless otherwise specified.
参考例１（スチレン−無水マレイン酸共重合樹脂の合成
）
攪拌機を備えた内容積５１の満液製反応器をスチレン５
０部とメチルイソブチルケトン５０部の割合で混合した
混合物で満たし、攪拌しながら１０５℃まで昇温し、以
後この温度を保持しながらメチルイソブチルケトン５０
部、スチレン２５部、無水マレイン酸２５部およびター
シャリブチルベンゾエート０．５部の割合で混合してな
るモノマー混合液を毎時２００Ｃｅの割合で供給すると
共に、この供給量に見合う分のポリマー溶液を抜き員し
つつ１００時間重合を行っに０反応液を反応器から取シ
出した後、真空下５０℃から２００℃まで徐々に昇温し
ながら揮発物を除き、酸価４５０のスチレン−無水マレ
イン酸共重合樹脂（Ｂ１−１ ）を得た。このものを粗
砕、精粉枠し、平均粒径５．０μｍの粉末とした。Reference Example 1 (Synthesis of styrene-maleic anhydride copolymer resin) A full-liquid reactor with an internal volume of 51 and equipped with a stirrer was heated with styrene 5
The mixture was filled with a mixture of 0 parts of methyl isobutyl ketone and 50 parts of methyl isobutyl ketone, and the temperature was raised to 105°C while stirring.
A monomer mixture of 25 parts of styrene, 25 parts of maleic anhydride, and 0.5 parts of tert-butyl benzoate was supplied at a rate of 200 Ce per hour, and an amount of polymer solution corresponding to this supply amount was supplied. Polymerization was carried out for 100 hours while emptying, and after taking out the reaction solution from the reactor, volatile substances were removed while gradually heating from 50°C to 200°C under vacuum, and styrene-maleic anhydride with an acid value of 450 was prepared. An acid copolymer resin (B1-1) was obtained. This material was coarsely crushed and refined into powder with an average particle size of 5.0 μm.
参考例２（同上）
メチルイソブチルケトンＳＯ部、スチレン３７．５部、
無水マレインｗＬ１２．５部およびターシャリブチルベ
ンゾエート０．５部の割合で混合してなる七ツマー混合
液を用いた以外は参考例１と同様にして酸価２５０のス
チレン−無水マレイン酸共重合樹脂（Ｂ１−２ ）を得
、平均粒径５μｍの粉末とした。Reference Example 2 (same as above) Methyl isobutyl ketone SO part, styrene 37.5 parts,
A styrene-maleic anhydride copolymer resin with an acid value of 250 was prepared in the same manner as in Reference Example 1, except that a 7-mer mixture prepared by mixing 12.5 parts of maleic anhydride wL and 0.5 parts of tert-butyl benzoate was used. (B1-2) was obtained and made into a powder with an average particle size of 5 μm.
参考例３（同上）
メチルイソブチルケトン５０部、スチレン４１部、無水
マレイン酸９部およびターシャリッチルペンゾエート０
．５部の割合で混合してなる七ツマー混合液を用いた以
外は参考ｆ１１と同様にして酸価８５のスチレン−無水
マレイン酸共重合樹脂（Ｂｘ−３）を得、平均粒径５μ
ｍの粉末とした。Reference Example 3 (same as above) 50 parts of methyl isobutyl ketone, 41 parts of styrene, 9 parts of maleic anhydride, and 0 parts of tert-rich penzoate
．． A styrene-maleic anhydride copolymer resin (Bx-3) with an acid value of 85 was obtained in the same manner as Reference f11 except that a 7-mer mixture of 5 parts was used, and the average particle size was 5μ.
m powder.
参考ｆ１１４（スチレン−メタクリル酸共重合樹脂の合
成）
フラスコにスチレン７５部、メタクリル酸２５部、トル
エン１００ｉ１Ｓ及びベンゾイルパーオキシド０．５部
を投入し、９０℃の水浴中で窒素雰囲気下で５時間攪拌
しながら反応させた。次いで反応液を４０００部のメタ
ノール中に加えて生じた沈澱智をＰ別、水洗、乾燥して
、酸価１４５のスチレン−メタクリル酸共重合樹脂（Ｂ
ｔ−４）を得、平均粒径５μＳＯ粉末とした。Reference f114 (synthesis of styrene-methacrylic acid copolymer resin) 75 parts of styrene, 25 parts of methacrylic acid, 100i1S of toluene, and 0.5 part of benzoyl peroxide were placed in a flask, and the mixture was heated in a water bath at 90°C under a nitrogen atmosphere for 5 hours. The reaction was carried out with stirring. Next, the reaction solution was added to 4000 parts of methanol, and the resulting precipitate was separated from P, washed with water, and dried to obtain a styrene-methacrylic acid copolymer resin (B) having an acid value of 145.
t-4) was obtained as SO powder with an average particle size of 5 μm.
笑施例１
ビスフェノールＡとエピクロルヒドリンとの反応によシ
得られたエポキシ当量が１９０なる液状エポキシ樹脂１
５．９部にテトラブロモビスフェノ−ルＡ トエビクロ
ルヒドリンとの反応によシ得られた工４キシ当量が３７
０なるエポキシ樹脂粉末２４．９部を溶解せしめたエポ
キシ樹脂混合初切、８部に、スチレン−無水マレイン酸
共重合樹脂（Ｂｌ−１）１８．９部を分散混合し、更に
テトラブロモビスフェノール人とエピクロルヒドリンと
の反応によシ得られたエポキシ当量が３７０なるエポキ
シ樹脂のメタクリレ−）（６２，５％）とスチレンモノ
マー（３７，５％）とよシ成るエポキシビニルエステル
樹脂組成物３３．０部、２−エチル−４−メチルイミダ
ゾール０．３３部、１．１−ビス（ｉ−プチルノ々−オ
キシ）−３，３，５−）リメチルシクロヘキサン０．５
６部を加え、エポキシ樹脂組成物（Ｉ−１）を調製した
。Example 1 Liquid epoxy resin 1 with an epoxy equivalent of 190 obtained by the reaction of bisphenol A and epichlorohydrin
5.9 parts of tetrabromobisphenol A.
18.9 parts of styrene-maleic anhydride copolymer resin (Bl-1) was dispersed into 8 parts of the epoxy resin mixture in which 24.9 parts of epoxy resin powder 0 was dissolved, and then tetrabromobisphenol was added. An epoxy vinyl ester resin composition consisting of an epoxy resin (methacrylate) (62.5%) and a styrene monomer (37.5%) having an epoxy equivalent of 370 obtained by reaction with epichlorohydrin (33.0%) parts, 0.33 parts of 2-ethyl-4-methylimidazole, 0.5 parts of 1,1-bis(i-butylnot-oxy)-3,3,5-)limethylcyclohexane
6 parts were added to prepare an epoxy resin composition (I-1).
この樹脂組成物（Ｉ−１）を＠１０２０■の連続なガラ
スクロス８枚に連続的にそれぞれ別個の含浸槽で含浸さ
せ、含浸基材（ｍ−ｉ）ｔ−得た。この含浸基材（ＩＩ
Ｉ） Ｏ樹脂付着率は４２％であった。この含浸基材（
ＩＩＩ−１）８枚を重ね合せ、更に上下両面に厚さ３５
μｍの銅箔を重ね合せ、連続ダブルベルトプレスに搬送
し、１２０℃×３分間Ｘ ５ ｋｌｉｌ／ｃｒ１１スの
条件下で予備頂化させ、次いで１８０℃×３分間Ｘ １
５ ｋｌ？／ｃｐｓ”の条件下で加熱加圧成形し、同圧
力下で１００℃まで冷却し、ギロチンカッターで１００
０−長に切断したのち、両端を切断し、更に１７０℃で
１時間後硬化１せて、１．６０ｗＸ １０００ｇｘ１０
０Ｏ四の積層板を得た。かくして得られた積層板につい
て物性（ガラス転移温度ブレラシャークツカ−テストに
よる吸水率及び誘電率）の測定を以下の様に行なった。This resin composition (I-1) was impregnated into eight continuous glass cloths of @1020 mm in separate impregnating baths to obtain an impregnated base material (m-i). This impregnated base material (II
I) O resin adhesion rate was 42%. This impregnated base material (
III-1) Stack 8 sheets and add 35mm thickness on both top and bottom sides.
Copper foils with a thickness of 1.0 μm are overlapped, conveyed to a continuous double belt press, pre-topped under conditions of 120°C x 3 minutes x 5 kli/cr11, and then heated at 180°C x 3 minutes x 1
5 kl? /cps”, cooled to 100°C under the same pressure, and cut to 100°C with a guillotine cutter.
After cutting to 0-length, cut both ends, and then cure at 170℃ for 1 hour to 1.60wX 1000gx10
A 0O4 laminate was obtained. The physical properties (water absorption and dielectric constant by glass transition temperature Brella-Schatzker test) of the thus obtained laminate were measured as follows.
結果を第１表に示す。The results are shown in Table 1.
Ｏガラス転移温度（Ｔｇ） ：レオメトリック社製Ｒ８
人−１動的固体粘弾性測定器にて１℃／ｗｉｍで昇温し
て測定した。O glass transition temperature (Tg): R8 manufactured by Rheometric
Measurement was performed using a human-1 dynamic solid viscoelasticity measuring device at a rate of 1° C./wim.
拳吸水率：成形板の片面の銅箔をエツチングで除去した
後、１２０℃、２気圧の条件で６時間プレックヤークッ
カーテストを行い１次式に基いて吸水率を算出した。Fist water absorption rate: After removing the copper foil on one side of the molded plate by etching, a 6-hour pre-kettle cooker test was conducted at 120°C and 2 atm, and the water absorption rate was calculated based on the linear equation.
ｗ’ −ｗ
吸水率（％） −−Ｘ １０α
（ただしＷは試験前の積層板重量、Ｗ′は試験板の積層
板重量である。）
・誘電率（−） Ｓ ＪＩＳ Ｃ−６４８１に基いてＩ
ＭＨｚ、 ２５℃の条件でＱメーターにて測定した。w' -w Water absorption rate (%) - - I
Measured using a Q meter at MHz and 25°C.
実施例２
共重合樹脂（Ｂｌ−１）１８．９部の代わυに共重合樹
１ｆｆｌ（Ｂｌ−２）３３．９部を溶解させて用いた以
外は、実施例１と全く同様にして積層板を得、次いで同
様に物性の測定を行った。結果を第１表に示す。Example 2 Lamination was carried out in exactly the same manner as in Example 1, except that 33.9 parts of copolymer resin (Bl-2) was dissolved in υ instead of 18.9 parts of copolymer resin (Bl-1). A plate was obtained, and then its physical properties were measured in the same manner. The results are shown in Table 1.
実施例３
共Ｘ合樹脂（Ｂ１−１）１８．９部の代わシに共重合樹
脂（Ｂｌ−３）３３．４部を分散させて用い、更にメチ
ルテトラヒドロ無水フタル酸１６．９部を加えた以外は
、実施例１と全く同様にして積層板を得１次いで同様に
物性の測定を行った。結果を第１表に示す。Example 3 33.4 parts of copolymer resin (Bl-3) was dispersed in place of 18.9 parts of co-X polymer resin (B1-1), and 16.9 parts of methyltetrahydrophthalic anhydride was added. A laminate was obtained in exactly the same manner as in Example 1, except for the above, and its physical properties were measured in the same manner. The results are shown in Table 1.
実施例４
共重合樹脂（Ｂじ１）１８．９部の代わシに共重合樹脂
（Ｂビ４）１１．０部を分教場せて用い、更にメチルテ
トラヒドロ無水フタル酸１２．７部を加えた以外は、実
施例１と全く同様にして積層板を得１次いで同様に物性
の測定を行った。結果を第１表に示す。Example 4 11.0 parts of copolymer resin (B-4) was used instead of 18.9 parts of copolymer resin (B-1), and 12.7 parts of methyltetrahydrophthalic anhydride was added. Except for this, a laminate was obtained in exactly the same manner as in Example 1, and its physical properties were then measured in the same manner. The results are shown in Table 1.
比較例１
共重合樹脂（Ｂｌ−１） １８．９部の代わシにメチル
テトラヒドロ無水フタル酸１ｒ２５．４部用いた以外は
、実施例１と全く同様にして積層板を得、次いで同様に
物性の測定を行った。結果を第１表に示す。Comparative Example 1 A laminate was obtained in the same manner as in Example 1, except that 25.4 parts of methyltetrahydrophthalic anhydride 1r was used in place of 18.9 parts of copolymer resin (Bl-1), and then the physical properties were determined in the same manner. Measurements were made. The results are shown in Table 1.
実施例５
ビスフェノールＡとエピクロルヒドリンとの反応によシ
得られたエポキシ当量が１９０なる液状エポキシ樹脂１
６．９部にテトラブロモビスフェノール人とエピクロル
ヒドリンとの反応によシ得られたエポキシ当量が３７０
なるエポキシ樹脂粉末２４．９部を溶解せしめたエポキ
シ樹脂混合物２６．５部に、スチレン−無水マレイン酸
共重合樹脂（Ｂｌ−２）３５．５部を溶解させ、更にテ
トラブロモビスフェノ−／Ｌ／Ａとエピクロルヒドリン
との反応によυ得られたエポキシ当量が３７０なる工Ｉ
キシ樹脂のメタクリレ−）（６０％）とスチレンモノ−
ｒ−（４０％）トよシ成るエポキシビニルエステル樹脂
組成物３０．０部、ジメチルベンジルアミン０．７０部
、１．１−ビス（ｔ−プチルノぐ一オキシ）−３，３，
５−トリメチルシクロヘキサン０．５６部を加え、エイ
キシ樹脂組成物（Ｉ−５）を調製した。Example 5 Liquid epoxy resin 1 with an epoxy equivalent of 190 obtained by the reaction of bisphenol A and epichlorohydrin
The epoxy equivalent obtained by the reaction of tetrabromobisphenol and epichlorohydrin is 370 parts in 6.9 parts.
35.5 parts of styrene-maleic anhydride copolymer resin (Bl-2) was dissolved in 26.5 parts of an epoxy resin mixture in which 24.9 parts of epoxy resin powder was dissolved, and further tetrabromobisphenol/L A process I with an epoxy equivalent of 370 obtained by the reaction of /A with epichlorohydrin
methacrylate (60%) and styrene mono-
30.0 parts of an epoxy vinyl ester resin composition consisting of r-(40%) resin, 0.70 parts of dimethylbenzylamine, 1.1-bis(t-butyloxy)-3,3,
0.56 part of 5-trimethylcyclohexane was added to prepare an Eixy resin composition (I-5).
この樹脂組成物（Ｉ−５）を厚さ０．１８■、縦３００
ｍ、横３００冒のガラスクロスに含浸させ。This resin composition (I-5) was coated with a thickness of 0.18 cm and a length of 300 cm.
Impregnate a glass cloth with a width of 300 mm.
含浸基材（ＩＩＩ−５）を得、次いでこれを１３０℃の
熱風循環式乾燥機内で３分間加熱乾燥してスチレンモノ
マーの除去とＢ−ステージ化を行ない、樹脂付着率４２
％、樹脂底分中の残存スチレンモノマー含有率０．８％
、のグリシレグを得た。このグリシレグはタックフリー
で巻き取シが可能な程の柔軟性がおり、取扱作業性に優
れるものであった。An impregnated base material (III-5) was obtained, which was then heated and dried for 3 minutes in a hot air circulation dryer at 130°C to remove styrene monomer and B-stage, resulting in a resin adhesion rate of 42.
%, residual styrene monomer content in resin bottom 0.8%
, obtained Grisileg. This Grishireg was flexible enough to be rolled up without tack, and was excellent in handling workability.
次いでこのグリプレグ１ｃ８枚重ね、その両面に厚１３
５μｍの銅箔を貼り合せ、次いでその両面に２枚の鏡面
仕上げしたステンレス板、更にクツション材としてのク
ラフト紙に挾み込み、１７０℃の加熱成形機に仕込み、
２０ ｋ！ｌ／ａｎ２の圧力で５分間圧縮したのち、４
０ｋｇ／♂の圧力下で６０分間加熱加圧成形し、その後
圧力を維持したまま３０℃まで冷却し、厚み１．６ ｍ
の積層板を得、次いで実施例１と同様にして物性の測定
を行った。結果を第１弐に示す。Next, stack 8 sheets of Gripreg 1c and coat both sides with a thickness of 13mm.
A 5μm copper foil was pasted on, then two mirror-finished stainless steel plates were placed on both sides, and then sandwiched between kraft paper as a cushioning material, and placed in a heat forming machine at 170°C.
20k! After compressing for 5 minutes at a pressure of l/an2,
Heat and pressure mold for 60 minutes under a pressure of 0 kg/♂, then cool to 30°C while maintaining the pressure to a thickness of 1.6 m.
A laminate was obtained, and the physical properties were then measured in the same manner as in Example 1. The results are shown in Part 2.
比較例２
共重合樹脂（Ｂｌ−２）３５．５部の代わシにメチルテ
トラヒドロ無水フタル酸２６．６部を用い、１２０℃の
熱風乾燥機内で６分間加熱乾燥してスチレンモノマーの
除去とＢ−ステージ化を行った以外は、実施例５と全く
同様にして厚み１．６四の積層板を得、次いで実施例１
と同様にして物性の測定を行った。結果を第１表に示す
。Comparative Example 2 26.6 parts of methyltetrahydrophthalic anhydride was used in place of 35.5 parts of the copolymer resin (Bl-2), and heat-dried for 6 minutes in a hot air dryer at 120°C to remove the styrene monomer and B. - A 1.64-thick laminate was obtained in exactly the same manner as in Example 5, except for staging, and then Example 1
The physical properties were measured in the same manner as above. The results are shown in Table 1.
７／
〈発明の効果〉
実施例及び比較例から明らかなように、芳香族ビニ〃化
合物と不飽和カル？ン酸及び／又はそのＩｌ無水物とを
必須成分として得られる共重合樹脂を用いた本発明のエ
ポキシ樹脂組成物又はこれを含浸させてなるプリプレグ
を使用すると、ｆラス転移温度の高い誘電特性に優れる
積層板が得られる。また、実施例５のように本発明のエ
ポキシ樹脂組成物を用いると１重合性ビニルモノマー會
揮散させてＢ−ステージ化し、プリプレグを得るに際し
て、該共重合樹脂が揮散しにくいため高温短時間でのグ
リプレグ化が容易である。7/ <Effects of the Invention> As is clear from the Examples and Comparative Examples, aromatic vinyl compounds and unsaturated Cal? When using the epoxy resin composition of the present invention using a copolymer resin obtained as an essential component with phosphoric acid and/or its Il anhydride, or a prepreg impregnated with the same, dielectric properties with a high f-las transition temperature can be obtained. An excellent laminate can be obtained. In addition, when the epoxy resin composition of the present invention is used as in Example 5, when the monopolymerizable vinyl monomer is volatilized to form a B-stage and a prepreg is obtained, the copolymer resin is difficult to volatilize, so the copolymer resin is difficult to volatilize, so it can be used at high temperatures and in a short time. It is easy to convert into Gripreg.
代理人 弁理士 高 橋 勝 利Agent Patent Attorney Katsutoshi Takahashi
Claims (1)
合物と不飽和カルボン酸及び／又はその酸無水物とを必
須成分として得られる共重合樹脂（Ａ＿２）と重合性不
飽和基を有する樹脂（Ｂ＿１）と重合性ビニルモノマー
（Ｂ＿２）と重合開始剤（Ｂ＿３）とを必須成分として
含有し、かつ重合性ビニルモノマー（Ｂ＿２）以外の溶
剤を含有しないことを特徴とするエポキシ樹脂組成物。 ２、芳香族ビニル化合物と不飽和カルボン酸及び／又は
その酸無水物とを必須成分として得られる共重合樹脂（
Ａ＿２）が、スチレン−無水マレイン酸共重合樹脂であ
る請求項１記載の樹脂組成物。 ３、更に多塩基酸無水物も必須成分として含有する請求
項１記載の樹脂組成物。 ４、常温液状エポキシ樹脂（Ａ＿１）と芳香族ビニル化
合物と不飽和カルボン酸及び／又はその酸無水物とを必
須成分として得られる共重合樹脂（Ａ＿２）と重合性不
飽和基を有する樹脂（Ｂ＿１）と重合性ビニルモノマー
（Ｂ＿２）と重合開始剤（Ｂ＿３）とを必須成分として
含有し、かつ重合性ビニルモノマー（Ｂ＿２）以外の溶
剤を含有しないエポキシ樹脂組成物（ I ）を繊維質基
材（II）に含浸させて含浸基材（III）を得た後、Ｂ−
ステージ化することを特徴とするプリプレグの製法。 ５、芳香族ビニル化合物と不飽和カルボン酸及び／又は
その酸無水物とを必須成分として得られる共重合樹脂（
Ａ＿２）が、スチレン−無水マレイン酸共重合樹脂であ
る請求項４記載のプリプレグの製法。 ６、エポキシ樹脂組成物（ I ）が、多塩基酸無水物を
含有するものである請求項４記載のプリプレグの製法。 ７、含浸基材（III）を得た後、該含浸基材（III）中の
重合性ビニルモノマーの除去とＢ−ステージ化を行う請
求項４記載のプリプレグの製法。 ８、常温液状エポキシ樹脂（Ａ＿１）と芳香族ビニル化
合物と不飽和カルボン酸及び／又はその酸無水物とを必
須成分として得られる共重合樹脂（Ａ＿１）と重合性不
飽和基を有する樹脂（Ｂ＿１）と重合性ビニルモノマー
（Ｂ＿２）と重合開始剤（Ｂ＿３）とを必須成分として
含有し、かつ重合性ビニルモノマー（Ｂ＿２）以外の溶
剤を含有しないエポキシ樹脂組成物（ I ）を繊維質基
材（II）に含浸させて含浸基材（III）を得た後、加熱
成形することを特徴とする積層板の製法。 ９、芳香族ビニル化合物と不飽和カルボン酸及び／又は
その酸無水物とを必須成分として得られる共重合樹脂（
Ａ＿２）が、スチレン−無水マレイン酸共重合樹脂であ
る請求項８記載の積層板の製法。 １０、エポキシ樹脂組成物（ I ）が、多塩基酸無水物
を含有するものである請求項８記載の積層板の製法。 １１、含浸基材（III）を得た後、該含浸基材（III）中
の重合性ビニルモノマーの除去と予備硬化を行い、次い
で加熱加圧成形する請求項８記載の積層板の製法。[Claims] 1. A copolymer resin (A_2) obtained as essential components of an epoxy resin that is liquid at room temperature (A_1), an aromatic vinyl compound, an unsaturated carboxylic acid and/or its acid anhydride, and a polymerizable unsaturated An epoxy characterized by containing a resin having a group (B_1), a polymerizable vinyl monomer (B_2), and a polymerization initiator (B_3) as essential components, and containing no solvent other than the polymerizable vinyl monomer (B_2). Resin composition. 2. Copolymer resin obtained as essential components of an aromatic vinyl compound and an unsaturated carboxylic acid and/or its acid anhydride (
The resin composition according to claim 1, wherein A_2) is a styrene-maleic anhydride copolymer resin. 3. The resin composition according to claim 1, further comprising a polybasic acid anhydride as an essential component. 4. Room temperature liquid epoxy resin (A_1), aromatic vinyl compound, unsaturated carboxylic acid and/or its acid anhydride as essential components, copolymer resin (A_2), and resin having a polymerizable unsaturated group (B_1) ), a polymerizable vinyl monomer (B_2), and a polymerization initiator (B_3) as essential components, and an epoxy resin composition (I) containing no solvent other than the polymerizable vinyl monomer (B_2) is used as a fibrous base material. After impregnating with (II) to obtain an impregnated base material (III),
A prepreg manufacturing method characterized by staging. 5. Copolymer resin obtained as essential components of an aromatic vinyl compound and an unsaturated carboxylic acid and/or its acid anhydride (
The method for producing a prepreg according to claim 4, wherein A_2) is a styrene-maleic anhydride copolymer resin. 6. The method for producing a prepreg according to claim 4, wherein the epoxy resin composition (I) contains a polybasic acid anhydride. 7. The prepreg manufacturing method according to claim 4, wherein after obtaining the impregnated base material (III), the polymerizable vinyl monomer in the impregnated base material (III) is removed and B-staged. 8. Room-temperature liquid epoxy resin (A_1), an aromatic vinyl compound, an unsaturated carboxylic acid and/or its acid anhydride, and a copolymer resin (A_1) obtained as essential components, and a resin having a polymerizable unsaturated group (B_1) ), a polymerizable vinyl monomer (B_2), and a polymerization initiator (B_3) as essential components, and an epoxy resin composition (I) containing no solvent other than the polymerizable vinyl monomer (B_2) is used as a fibrous base material. A method for manufacturing a laminate, which comprises impregnating the base material (II) to obtain the impregnated base material (III), followed by thermoforming. 9. Copolymer resin obtained as essential components of an aromatic vinyl compound and an unsaturated carboxylic acid and/or its acid anhydride (
The method for manufacturing a laminate according to claim 8, wherein A_2) is a styrene-maleic anhydride copolymer resin. 10. The method for producing a laminate according to claim 8, wherein the epoxy resin composition (I) contains a polybasic acid anhydride. 11. The method for manufacturing a laminate according to claim 8, wherein after obtaining the impregnated base material (III), the polymerizable vinyl monomer in the impregnated base material (III) is removed and precured, and then heated and press-molded.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28093288A JPH02127415A (en) | 1988-11-07 | 1988-11-07 | Epoxy resin composition and production of prepreg and laminated sheet |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28093288A JPH02127415A (en) | 1988-11-07 | 1988-11-07 | Epoxy resin composition and production of prepreg and laminated sheet |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02127415A true JPH02127415A (en) | 1990-05-16 |
Family
ID=17631936
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP28093288A Pending JPH02127415A (en) | 1988-11-07 | 1988-11-07 | Epoxy resin composition and production of prepreg and laminated sheet |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02127415A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016063506A1 (en) * | 2014-10-22 | 2016-04-28 | パナソニックＩｐマネジメント株式会社 | Resin composition, prepreg, metal foil with resin, metal-clad laminated plate, and printed wiring board |
| CN112912423A (en) * | 2018-10-16 | 2021-06-04 | 三菱化学株式会社 | Sheet molding compound and molded article |
-
1988
- 1988-11-07 JP JP28093288A patent/JPH02127415A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016063506A1 (en) * | 2014-10-22 | 2016-04-28 | パナソニックＩｐマネジメント株式会社 | Resin composition, prepreg, metal foil with resin, metal-clad laminated plate, and printed wiring board |
| US9681541B2 (en) | 2014-10-22 | 2017-06-13 | Panasonic Intellectual Property Management Co., Ltd. | Resin composition, prepreg, metal foil with resin, metal-clad laminated plate, and printed wiring board |
| JPWO2016063506A1 (en) * | 2014-10-22 | 2017-08-10 | パナソニックＩｐマネジメント株式会社 | Resin composition, prepreg, metal foil with resin, metal-clad laminate and printed wiring board |
| TWI706002B (en) * | 2014-10-22 | 2020-10-01 | 日商松下知識產權經營股份有限公司 | Resin composition, pre-stained body, metal foil with resin, metal-laminated laminate and printed circuit board |
| CN112912423A (en) * | 2018-10-16 | 2021-06-04 | 三菱化学株式会社 | Sheet molding compound and molded article |
| EP3868815A4 (en) * | 2018-10-16 | 2021-12-15 | Mitsubishi Chemical Corporation | Sheet molding compound and molded article |
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