JPH02206614A - Resin composition for impregnation and production of laminated board and intermediate material thereof - Google Patents
Resin composition for impregnation and production of laminated board and intermediate material thereofInfo
- Publication number
- JPH02206614A JPH02206614A JP2374089A JP2374089A JPH02206614A JP H02206614 A JPH02206614 A JP H02206614A JP 2374089 A JP2374089 A JP 2374089A JP 2374089 A JP2374089 A JP 2374089A JP H02206614 A JPH02206614 A JP H02206614A
- Authority
- JP
- Japan
- Prior art keywords
- resin composition
- laminate
- impregnated
- base material
- fibrous base
- 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
- 239000000463 material Substances 0.000 title claims abstract description 61
- 239000011342 resin composition Substances 0.000 title claims description 40
- 238000005470 impregnation Methods 0.000 title claims description 20
- 238000004519 manufacturing process Methods 0.000 title claims description 16
- 239000003822 epoxy resin Substances 0.000 claims abstract description 40
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 40
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 29
- 229920001567 vinyl ester resin Polymers 0.000 claims abstract description 23
- 150000008065 acid anhydrides Chemical class 0.000 claims abstract description 22
- 239000007788 liquid Substances 0.000 claims abstract description 20
- 150000007519 polyprotic acids Polymers 0.000 claims abstract description 20
- 239000003505 polymerization initiator Substances 0.000 claims abstract description 7
- 239000004593 Epoxy Substances 0.000 claims description 58
- 238000000034 method Methods 0.000 claims description 27
- 239000003431 cross linking reagent Substances 0.000 claims description 17
- 239000002904 solvent Substances 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 14
- 229910052751 metal Inorganic materials 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 11
- 239000011888 foil Substances 0.000 claims description 9
- 150000002148 esters Chemical class 0.000 claims description 6
- 125000004018 acid anhydride group Chemical group 0.000 claims description 4
- 238000003856 thermoforming Methods 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 238000004132 cross linking Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 abstract description 18
- UICXTANXZJJIBC-UHFFFAOYSA-N 1-(1-hydroperoxycyclohexyl)peroxycyclohexan-1-ol Chemical compound C1CCCCC1(O)OOC1(OO)CCCCC1 UICXTANXZJJIBC-UHFFFAOYSA-N 0.000 abstract description 2
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 abstract description 2
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 abstract description 2
- 239000000758 substrate Substances 0.000 abstract 2
- 230000001747 exhibiting effect Effects 0.000 abstract 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 39
- 238000006243 chemical reaction Methods 0.000 description 37
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 31
- 239000002585 base Substances 0.000 description 30
- 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 27
- 229920005989 resin Polymers 0.000 description 27
- 239000011347 resin Substances 0.000 description 27
- -1 phenol Chemical class 0.000 description 24
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 22
- 150000001875 compounds Chemical class 0.000 description 21
- 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 18
- 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 15
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 14
- 239000004850 liquid epoxy resins (LERs) Substances 0.000 description 13
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 12
- 239000002253 acid Substances 0.000 description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 10
- 239000011889 copper foil Substances 0.000 description 10
- 239000011521 glass Substances 0.000 description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 9
- 150000008064 anhydrides Chemical class 0.000 description 8
- 230000009477 glass transition Effects 0.000 description 8
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 8
- 238000000465 moulding Methods 0.000 description 8
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 8
- 239000004744 fabric Substances 0.000 description 7
- 150000002989 phenols Chemical class 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 229920002554 vinyl polymer Polymers 0.000 description 6
- 150000007513 acids Chemical class 0.000 description 5
- 239000000853 adhesive Substances 0.000 description 5
- 230000001070 adhesive effect Effects 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 5
- MEBONNVPKOBPEA-UHFFFAOYSA-N 1,1,2-trimethylcyclohexane Chemical compound CC1CCCCC1(C)C MEBONNVPKOBPEA-UHFFFAOYSA-N 0.000 description 4
- 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
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 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
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 4
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 4
- 238000005886 esterification reaction Methods 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 229940049920 malate Drugs 0.000 description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 4
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 4
- 239000008096 xylene Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 229930185605 Bisphenol Natural products 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000032050 esterification Effects 0.000 description 3
- 239000003365 glass fiber Substances 0.000 description 3
- 150000002460 imidazoles Chemical class 0.000 description 3
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 3
- 238000010030 laminating Methods 0.000 description 3
- BJEPYKJPYRNKOW-UHFFFAOYSA-N malic acid Chemical compound OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229920003986 novolac Chemical class 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000010298 pulverizing process Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 230000003068 static effect Effects 0.000 description 3
- 150000005846 sugar alcohols Polymers 0.000 description 3
- 238000004381 surface treatment Methods 0.000 description 3
- 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 2
- RHUYHJGZWVXEHW-UHFFFAOYSA-N 1,1-Dimethyhydrazine Chemical compound CN(C)N RHUYHJGZWVXEHW-UHFFFAOYSA-N 0.000 description 2
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 2
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- 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 2
- OBETXYAYXDNJHR-UHFFFAOYSA-N 2-Ethylhexanoic acid Chemical compound CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 2
- PQAMFDRRWURCFQ-UHFFFAOYSA-N 2-ethyl-1h-imidazole Chemical compound CCC1=NC=CN1 PQAMFDRRWURCFQ-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
- FUOZJYASZOSONT-UHFFFAOYSA-N 2-propan-2-yl-1h-imidazole Chemical compound CC(C)C1=NC=CN1 FUOZJYASZOSONT-UHFFFAOYSA-N 0.000 description 2
- LLEASVZEQBICSN-UHFFFAOYSA-N 2-undecyl-1h-imidazole Chemical compound CCCCCCCCCCCC1=NC=CN1 LLEASVZEQBICSN-UHFFFAOYSA-N 0.000 description 2
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-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
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 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
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 2
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 229920006241 epoxy vinyl ester resin Polymers 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- VYKXQOYUCMREIS-UHFFFAOYSA-N methylhexahydrophthalic anhydride Chemical compound C1CCCC2C(=O)OC(=O)C21C VYKXQOYUCMREIS-UHFFFAOYSA-N 0.000 description 2
- 239000004745 nonwoven fabric Substances 0.000 description 2
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 239000013034 phenoxy resin Substances 0.000 description 2
- 229920006287 phenoxy resin Polymers 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 239000005056 polyisocyanate Substances 0.000 description 2
- 229920001228 polyisocyanate Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000003860 storage Methods 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
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- 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
- 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 1
- 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 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
- NALFRYPTRXKZPN-UHFFFAOYSA-N 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane Chemical compound CC1CC(C)(C)CC(OOC(C)(C)C)(OOC(C)(C)C)C1 NALFRYPTRXKZPN-UHFFFAOYSA-N 0.000 description 1
- OUPZKGBUJRBPGC-UHFFFAOYSA-N 1,3,5-tris(oxiran-2-ylmethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound O=C1N(CC2OC2)C(=O)N(CC2OC2)C(=O)N1CC1CO1 OUPZKGBUJRBPGC-UHFFFAOYSA-N 0.000 description 1
- 150000005208 1,4-dihydroxybenzenes Chemical class 0.000 description 1
- OVBFMUAFNIIQAL-UHFFFAOYSA-N 1,4-diisocyanatobutane Chemical compound O=C=NCCCCN=C=O OVBFMUAFNIIQAL-UHFFFAOYSA-N 0.000 description 1
- FBHPRUXJQNWTEW-UHFFFAOYSA-N 1-benzyl-2-methylimidazole Chemical compound CC1=NC=CN1CC1=CC=CC=C1 FBHPRUXJQNWTEW-UHFFFAOYSA-N 0.000 description 1
- AYRQYSRFOWTRGV-UHFFFAOYSA-N 1-isocyanato-2-propan-2-ylidenecyclohexane Chemical compound C(C)(C)=C1C(CCCC1)N=C=O AYRQYSRFOWTRGV-UHFFFAOYSA-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
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- KUBDPQJOLOUJRM-UHFFFAOYSA-N 2-(chloromethyl)oxirane;4-[2-(4-hydroxyphenyl)propan-2-yl]phenol Chemical compound ClCC1CO1.C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 KUBDPQJOLOUJRM-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
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-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
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical compound NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 description 1
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-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
- KFGFVPMRLOQXNB-UHFFFAOYSA-N 3,5,5-trimethylhexanoyl 3,5,5-trimethylhexaneperoxoate Chemical compound CC(C)(C)CC(C)CC(=O)OOC(=O)CC(C)CC(C)(C)C KFGFVPMRLOQXNB-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
- AYKYXWQEBUNJCN-UHFFFAOYSA-N 3-methylfuran-2,5-dione Chemical compound CC1=CC(=O)OC1=O AYKYXWQEBUNJCN-UHFFFAOYSA-N 0.000 description 1
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 description 1
- UIKUBYKUYUSRSM-UHFFFAOYSA-N 3-morpholinopropylamine Chemical compound NCCCN1CCOCC1 UIKUBYKUYUSRSM-UHFFFAOYSA-N 0.000 description 1
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- PAHSHPLLVMLCCN-UHFFFAOYSA-N 5-butyl-5-ethenylcyclohexa-1,3-diene Chemical compound CCCCC1(C=C)CC=CC=C1 PAHSHPLLVMLCCN-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
- NHJIDZUQMHKGRE-UHFFFAOYSA-N 7-oxabicyclo[4.1.0]heptan-4-yl 2-(7-oxabicyclo[4.1.0]heptan-4-yl)acetate Chemical compound C1CC2OC2CC1OC(=O)CC1CC2OC2CC1 NHJIDZUQMHKGRE-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- ADAHGVUHKDNLEB-UHFFFAOYSA-N Bis(2,3-epoxycyclopentyl)ether Chemical compound C1CC2OC2C1OC1CCC2OC21 ADAHGVUHKDNLEB-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- AKTKYRNOAGAQDH-UHFFFAOYSA-N C1C2OC2CC(C)C1(C(O)=O)C1CC2OC2CC1C Chemical compound C1C2OC2CC(C)C1(C(O)=O)C1CC2OC2CC1C AKTKYRNOAGAQDH-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
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 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
- 239000004472 Lysine Substances 0.000 description 1
- KDXKERNSBIXSRK-UHFFFAOYSA-N Lysine Natural products NCCCCC(N)C(O)=O KDXKERNSBIXSRK-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- OPKOKAMJFNKNAS-UHFFFAOYSA-N N-methylethanolamine Chemical compound CNCCO OPKOKAMJFNKNAS-UHFFFAOYSA-N 0.000 description 1
- 229930192627 Naphthoquinone Natural products 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical class CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 235000014443 Pyrus communis Nutrition 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-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
- 229920006397 acrylic thermoplastic Polymers 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- QEZIKGQWAWNWIR-UHFFFAOYSA-N antimony(3+) antimony(5+) oxygen(2-) Chemical compound [O--].[O--].[O--].[O--].[Sb+3].[Sb+5] QEZIKGQWAWNWIR-UHFFFAOYSA-N 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
- 235000010233 benzoic acid Nutrition 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 210000001217 buttock Anatomy 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
- 239000004917 carbon fiber Substances 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 150000001734 carboxylic acid salts Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 229930016911 cinnamic acid Natural products 0.000 description 1
- 235000013985 cinnamic acid Nutrition 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 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
- 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 compound 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
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 229940043279 diisopropylamine Drugs 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- IUNMPGNGSSIWFP-UHFFFAOYSA-N dimethylaminopropylamine Chemical compound CN(C)CCCN IUNMPGNGSSIWFP-UHFFFAOYSA-N 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
- BXKDSDJJOVIHMX-UHFFFAOYSA-N edrophonium chloride Chemical compound [Cl-].CC[N+](C)(C)C1=CC=CC(O)=C1 BXKDSDJJOVIHMX-UHFFFAOYSA-N 0.000 description 1
- 235000013601 eggs Nutrition 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- BEFDCLMNVWHSGT-UHFFFAOYSA-N ethenylcyclopentane Chemical compound C=CC1CCCC1 BEFDCLMNVWHSGT-UHFFFAOYSA-N 0.000 description 1
- 210000004709 eyebrow Anatomy 0.000 description 1
- 238000001914 filtration Methods 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
- 238000001879 gelation Methods 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- FLBJFXNAEMSXGL-UHFFFAOYSA-N het anhydride Chemical compound O=C1OC(=O)C2C1C1(Cl)C(Cl)=C(Cl)C2(Cl)C1(Cl)Cl FLBJFXNAEMSXGL-UHFFFAOYSA-N 0.000 description 1
- 238000007602 hot air drying Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 150000002500 ions Chemical group 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
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000002655 kraft paper Substances 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 229960003505 mequinol Drugs 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 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
- 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
- QOHMWDJIBGVPIF-UHFFFAOYSA-N n',n'-diethylpropane-1,3-diamine Chemical compound CCN(CC)CCCN QOHMWDJIBGVPIF-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000002791 naphthoquinones Chemical class 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- FJDUDHYHRVPMJZ-UHFFFAOYSA-N nonan-1-amine Chemical compound CCCCCCCCCN FJDUDHYHRVPMJZ-UHFFFAOYSA-N 0.000 description 1
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-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
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- DGTNSSLYPYDJGL-UHFFFAOYSA-N phenyl isocyanate Chemical compound O=C=NC1=CC=CC=C1 DGTNSSLYPYDJGL-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920000921 polyethylene adipate Polymers 0.000 description 1
- 238000011417 postcuring Methods 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 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
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 238000005201 scrubbing Methods 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000004334 sorbic acid Substances 0.000 description 1
- 235000010199 sorbic acid Nutrition 0.000 description 1
- 229940075582 sorbic acid Drugs 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- CSKKAINPUYTTRW-UHFFFAOYSA-N tetradecoxycarbonyloxy tetradecyl carbonate Chemical compound CCCCCCCCCCCCCCOC(=O)OOC(=O)OCCCCCCCCCCCCCC CSKKAINPUYTTRW-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
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-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
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/032—Organic insulating material consisting of one material
- H05K1/0326—Organic insulating material consisting of one material containing O
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、プリント回路基板等に有用な積層板、その中
間材及びこれらに用いられる含浸用樹脂組成物に関する
つ
〔従来の技術〕
ガラスクロス等の繊維質基材に溶剤で希釈した硬化性樹
脂を含浸・乾燥させ、プリプレグを調製し、これを所定
枚数重ね合わせたものに銅箔を重ね合わせて加熱加圧す
る等して積層成形し、プリプレグの樹脂を硬化させるこ
とによってプリント回路基板用積層板を得ることは周知
である。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a laminate useful for printed circuit boards etc., an intermediate material therefor, and an impregnating resin composition used for these [Prior Art] Glass cloth A prepreg is prepared by impregnating and drying a curable resin diluted with a solvent into a fibrous base material such as, and then laminating a pre-preg by stacking a predetermined number of sheets on top of a copper foil and applying heat and pressure. It is well known to obtain printed circuit board laminates by curing prepreg resins.
また、この溶剤希釈型樹脂組成物を含浸させる方法にお
ける溶剤処理等に起こる問題点を解決する方法として、
エポキシ樹脂組成物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からなる実質的に無溶
剤の硬化性樹脂組成物を繊維基材に含浸させ、加熱によ
ってＢステージ化を行い、得られるプリプレグを加熱成
形してプリント基板用積層板を得る方法が知られている
（例えば特開昭５９−４９２４０号公報）。In addition, as a method to solve problems that occur in solvent treatment etc. in the method of impregnating this solvent diluted resin composition,
A substantially solvent-free curable resin composition consisting of an epoxy resin composition, an epoxy vinyl ester resin, and/or an unsaturated polyester resin is impregnated into a fiber base material, and the resulting prepreg is B-staged by heating. A method of obtaining a laminate for a printed circuit board by heat molding is known (for example, Japanese Patent Laid-Open No. 59-49240).
しかしながら、上記のエポキシ樹脂／酸無水物／エポキ
シビニルエステル樹脂の樹脂組成物を用いて得られる＠
層板の耐熱性、特にガラス転移温度が十分でないという
問題を有している。However, @ obtained using the above resin composition of epoxy resin/acid anhydride/epoxy vinyl ester resin
The problem is that the heat resistance of the laminate, especially the glass transition temperature, is insufficient.
本発明者らは、このような状況に鑑みて鋭意研究した結
果、エポキシ樹脂（Ａ）と、多塩基酸無水物（Ｂ）と、
エポキシビニルエステルと多塩基酸無水物との反応生成
物（Ｃ）と、重合開始剤（Ｄ）を少なくとも含有し、か
つ液状にした含浸用樹脂粗製物を用いると、従来問題で
あった積層板の耐熱性が向上するばかりでなく、積層板
に金属箔を接着させるときの接着強度、積層板の層間接
着強度も改良できることを見出し、本発明に至ったもの
である。As a result of intensive research in view of this situation, the present inventors found that epoxy resin (A), polybasic acid anhydride (B),
When using a liquefied impregnating resin crude product containing at least a reaction product (C) of an epoxy vinyl ester and a polybasic acid anhydride and a polymerization initiator (D), conventional problems have arisen in laminates. The inventors have discovered that not only the heat resistance of the laminate can be improved, but also the adhesive strength when bonding metal foil to the laminate and the interlayer adhesive strength of the laminate can be improved, leading to the present invention.
以下に本発明の詳細な説明する。The present invention will be explained in detail below.
本発明で用いるエポキシ樹脂（Ａ）としては、特に限定
されることなく、固型及び液状のものがいずれも使用で
きるが、常温で無溶剤液状のエポキシ樹脂の単独又は混
合物が望ましく、平均エポキシ当量が１００〜４００、
好ましくは１００〜２５０のものを使用する。その代表
例を挙げると、いずれも常温で無溶剤液状のエピクロル
ヒドリンとビスフェノールＡ、ビスフェノール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、プロピレングリコール、ポリエ
チレングリコール、ポリプロピレングリコール、ネオペ
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又は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
フタル酸又はダイマー酸の如きポリカルボン酸のポリグ
リシジルエステル類；シクロヘキセン又はその誘導体を
過酢酸などでエポキシ化させることにより得られるシク
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−シクロヘキシル−３，４−エポキシ−６−
メチル−シクロヘキサンカルボキシレート、３．４−エ
ポキシシクロヘキシルメチル−３，４−エポキシシクロ
ヘキサンカルボキシレート、！−エポキシエチルー３．
４−エポキシシクロヘキサンなど）；シクロペンタジェ
ンもしくはジシクロペンタジェン又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り得られるシク
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、ジシクロペンタジェンオキサイド、２
．３−エポキシシクロペ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があり、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Ａとからえられる無溶剤液状のエポキシ樹
脂が、また低粘度が得られる点で無溶剤液状のシクロヘ
キセン系エポキシ化合物類が好ましい。The epoxy resin (A) used in the present invention is not particularly limited, and both solid and liquid epoxy resins can be used. However, it is preferable to use epoxy resins that are solvent-free liquid at room temperature or in mixtures, and have an average epoxy equivalent. is 100-400,
Preferably, those having a number of 100 to 250 are used. Typical examples include epoxy resins obtained from epichlorohydrin, which is a solvent-free liquid at room temperature, and dihydric phenols such as bisphenol A, bisphenol F, and resorcinol; ethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol, and neopentyl glycol. , polyglycidyl ethers of polyhydric alcohols such as glycerin, trimethylolethane, trimethylolpropane or ethylene oxide or propylene oxide adducts of dihydric phenols; adipic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid or dimer acid. Polyglycidyl esters of polycarboxylic acids such as; cyclohexene-based epoxy compounds (3,4-epoxy-
6-methyl-cyclohexyl-3,4-epoxy-6-
Methyl-cyclohexanecarboxylate, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate,! -Epoxy ethyl 3.
4-epoxycyclohexane, etc.); cyclopentadiene-based epoxy compounds obtained by epoxidizing cyclopentadiene or dicyclopentadiene or their derivatives with peracetic acid etc. (cyclopentadiene oxide, dicyclopentadiene oxide, etc.); ,2
．． (3-epoxycyclopentyl ether, etc.); limonene dioxide; Preferably, the epoxy resin is a solvent-free liquid cyclohexene-based epoxy compound since low viscosity can be obtained.
さらに、本発明では、上記のような無溶剤液状エポキシ
樹脂１種以上と融点が５０℃以上のエポキシ樹脂の１種
以上を混合して使用することもでき、通常は平均粒径が
５０〜５００μｍ、好ましくは平均粒径
１００〜３００ｐｍの粉末状エポキシ樹脂を無溶剤液状
エポキシ樹脂中に溶解及び／又は分散させて用いる。そ
の代表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Ａ、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Ａ１
テトラブロモビスフエノールＦ１ビスフエノールＳなど
の２ｆｉｉフエノールとから得られるエポキシ樹脂又は
フェノキシ樹脂；フェノール、アルキルフェノール又は
ブロム化フェノール、ノボラン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価フェノールとノボ
ラック樹脂とからなる共縮エポキシ樹脂；アニリン、ｐ
−（又はｍ−）アミノフェノール、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
ボン酸のポリグリシジルエステル又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
単独又はこれと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Ａ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ＰＫＨＨ（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、さら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Ｈ
燃性に優れる点でそれぞれ好ましい。Furthermore, in the present invention, it is also possible to use a mixture of one or more solvent-free liquid epoxy resins as described above and one or more epoxy resins having a melting point of 50°C or higher, and usually have an average particle size of 50 to 500 μm. , preferably a powdered epoxy resin having an average particle size of 100 to 300 pm is used by dissolving and/or dispersing it in a solvent-free liquid epoxy resin. Typical examples include epichlorohydrin, bisphenol A, bisphenol F, resorcinol, and tetrabromobisphenol A1, all of which have melting points of 50°C or higher.
Epoxy resins or phenoxy resins obtained from 2fii phenols such as tetrabromobisphenol F1 and bisphenol S; polyglycidyl ethers of polyhydric phenols such as phenol, alkylphenols or brominated phenols, novolak resins; from dihydric phenols and novolak resins; Co-condensed epoxy resin; aniline, p
- (or m-) polyglycidylamine of a polyvalent amine such as aminophenol, diaminodiphenylmethane, polyglycidyl ether of the above-mentioned polyhydric alcohol, polyglycidyl ester of polycarboxylic acid or glycidyl ether ester of hydroxybenzoic acid; Collinear epoxy resins containing phenol alone or a mixture of phenol and monohydric phenol; triglycidyl isocyanurate, etc.
Among them, powdered epoxy resins obtained from epichlorohydrin and bisphenol A have a good balance of performance and are inexpensive, while ultra-high molecular weight phenoxy resins, such as PKHH (trade name) manufactured by UCC Corporation in the United States, are high when added in small amounts. In addition, powdered polyhydric phenol polyglycidyl ether has excellent heat resistance, and powdered epoxy resin obtained from epichlorohydrin and tetrabromobisphenol A and powdered bromine. Polyhydric phenol polyglycidyl ether is H
Each is preferable in terms of excellent flammability.
本発明で用いる多塩基酸無水物（Ｂ）として代表的なも
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
水フタル酸、メチルテトラヒドロ無水フタル酸、無水ナ
ジック酸、無水メチルナシ７り酸、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、無水クロレンディック酸、無水ベンゾフェノ
ンテトラカルポン酸、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−Ｌ ２−ジカルボン酸
、エチレングリコールビストリメリテート無水物又はグ
リセリントリメリテート無水物などがあり、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。な
かでも好ましいものとしては、液状のものが挙げられ、
例えばメチルへキサヒドロ無水フタル酸、無水ナジック
酸、無水メチルナジック酸等が挙げられる。Typical polybasic acid anhydrides (B) used in the present invention include phthalic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, and nadic anhydride. Acid, methyl pear heptalytic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, succinic anhydride, itaconic anhydride, citraconic anhydride, dodecenyl succinic anhydride, chlorendic anhydride, benzophenone tetracarpone anhydride Acid, cyclopentatetracarboxylic anhydride, 5(2,5-dioxotetrahydrofuryl)-3-
Examples include methyl-3-cyclohexene-L 2-dicarboxylic acid, ethylene glycol bistrimelitate anhydride, and glycerin trimellitate anhydride, and these are used alone or in the form of a mixture of two or more types. Among them, liquid ones are preferred,
Examples include methylhexahydrophthalic anhydride, nadic anhydride, methylnadic anhydride, and the like.
さらに本発明でエポキシビニルエステルと多塩基酸無水
物との反応生成物（Ｃ）を得るために用いられるエポキ
シビニルエステルとしては、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・タイプ又はノボラック・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るエ
ポキシビニルエステルが挙げられる。Furthermore, the epoxy vinyl ester used in the present invention to obtain the reaction product (C) of the epoxy vinyl ester and the polybasic acid anhydride is preferably a bisphenol type of the various epoxy resins described above as the epoxy resin. or novolak type epoxy resin,
Examples include epoxy vinyl esters obtained by reacting either alone or a mixture thereof with the following unsaturated basic acids in the presence of an esterification catalyst.
不飽和−塩基酸として代表的なものはアクリル酸、メタ
クリル酸、桂皮酸、クロトン酸、モノメチルマレート、
モノプロピルマレート、モツプナルマレート、ソルビン
酸又はモノ （２−エチル′へ、キシル）マレートなど
があるが、これら１．よ単独でも二榎以上の混合におい
ても用いることができる。Typical unsaturated basic acids are acrylic acid, methacrylic acid, cinnamic acid, crotonic acid, monomethyl malate,
These include monopropyl malate, motunal malate, sorbic acid, and mono (2-ethyl', xyl) malate. It can be used alone or in a mixture of two or more.
１ポキシビニルエステルを得るには、従来公知の方法に
従えばよく、反応中のゲル化を防止する目的や生成物の
保存安定性あるいは硬化性の調整の目的てそれぞれ重合
禁止剤を使用することが推奨される。To obtain 1-poxyvinyl ester, conventionally known methods may be followed, and polymerization inhibitors may be used to prevent gelation during the reaction and to adjust the storage stability or curability of the product. is recommended.
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−フ゛チルカテコール、モノーｔ−
ブチル八イドロキノンの卵＾ハイドロキノン類；ハイド
ロキノン七ツメチルエーテル、ジ−ｔ−ｐ−クレゾール
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；又はナフテン酸銅の
如き銅塩などがある。Typical examples of such polymerization inhibitors include hydroquinone, p-t-phytylcatechol, and mono-t-
Eggs of butyl octahydroquinone Hydroquinones; phenols such as hydroquinone methyl ether and di-t-p-cresol; quinones such as p-benzoquinone, naphthoquinone, and p-)luquinone; or copper salts such as copper naphthenate, etc. There is.
また、反応生成物（Ｃ）を得るためにもう１つの成分で
ある多塩基酸無水物としては前記の多塩基＠濠・に物（
Ｂ）と同一のものが使用可能である。、エポキシビニル
エステルと多塩基酸無水物との反応生成物（Ｃ）は、例
えばエポキシビニルエステルと多塩基酸無水物を無触媒
下で７０＝１２Ｑ℃程度の温度範囲で１〜１０時間反応
させることによって得られるが、原材料の種類によって
は反応しにくい場合には第３級アミンやトリフェニルフ
ォスフインのようなエステル化触媒などを適宜用いても
良い、このエポキシビニルエステルと多塩基酸無水物と
の反応は、主としてエポキシビニルエステル中の水酸基
と多塩基酸無水物中の酸無水物基とのエステル化反応で
あり、その結果酸無水物基開環により生成するカルボン
酸はそのまま残存するハーフエステルの構造となってい
る。In addition, as the polybasic acid anhydride, which is another component to obtain the reaction product (C), the polybasic @Hori・Nimono (
The same one as B) can be used. The reaction product (C) of epoxy vinyl ester and polybasic acid anhydride can be obtained by, for example, reacting epoxy vinyl ester and polybasic acid anhydride in a temperature range of about 70=12Q°C for 1 to 10 hours in the absence of a catalyst. However, if it is difficult to react depending on the type of raw materials, an esterification catalyst such as a tertiary amine or triphenylphosphine may be used as appropriate. The reaction with is mainly an esterification reaction between the hydroxyl group in the epoxy vinyl ester and the acid anhydride group in the polybasic acid anhydride, and as a result, the carboxylic acid generated by ring opening of the acid anhydride group remains as a half. It has an ester structure.
エポキシビニルエステルに対する多塩基酸無水物の使用
量はエポキシビニルエステル中の水酸基の６０％以上が
エステル化される量であり、好ましくは８０％以上であ
る。エステル化が６０％より少なくなるように多塩基酸
無水物を用いた場合、得られた反応生成ｖｊ（Ｃ）を用
いた含浸用樹脂組成物を用いて得られる積層板のガラス
転移温度が低下して好ましくない。The amount of polybasic acid anhydride used relative to the epoxy vinyl ester is such that 60% or more of the hydroxyl groups in the epoxy vinyl ester are esterified, preferably 80% or more. When a polybasic acid anhydride is used so that esterification is less than 60%, the glass transition temperature of a laminate obtained using an impregnation resin composition using the obtained reaction product vj (C) is lowered. I don't like it.
本発明で用いられる重合開始剤（Ｄ）としては、加熱加
圧成形温度よりも低い温度で分解して上記エポキシビニ
ルエステルと多塩基酸無水物との反応生成物を硬化させ
るものが挙げられ、例えばシクロヘキザノンバーオキサ
イド、３，３．５−１−リメチルシクロヘキサノンバー
オキサイド、メチロネキサノンパーオキサイド、１，１
−ビス（ｔ−ブチルパーオキシ）３，３．５− ）リ
メチルシクロヘキサン、クメンハイドロパーオキサイド
、ジクミルパーオキサイド、ラウロイルパーオキサイド
、３，５．５− トリメ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、ジ−ミリスチルパーオ
キシジカーボネート、ｔ−ブチルパーオキシ（２−エチ
ルヘキサノエート）、ｔ−ブチルパーオキシ−３，５，
５−ト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、クミルパーオキシオクトエートなどの有
機過酸化物がある。Examples of the polymerization initiator (D) used in the present invention include those that decompose at a temperature lower than the heating and pressing temperature to cure the reaction product of the epoxy vinyl ester and polybasic acid anhydride, For example, cyclohexanone peroxide, 3,3,5-1-limethylcyclohexanone peroxide, methylonexanone peroxide, 1,1
-bis(t-butylperoxy)3,3.5-)limethylcyclohexane, cumene hydroperoxide, dicumyl peroxide, lauroyl peroxide, 3,5.5-trimethylhexanoyl peroxide, benzoyl peroxide, Di-myristyl peroxydicarbonate, t-butyl peroxy (2-ethylhexanoate), t-butyl peroxy-3,5,
Organic peroxides include 5-trimethylhexanoate, t-butylperoxybenzoate, and cumylperoxyoctoate.
本発明では硬化促進剤（Ｅ）を使用しても良く、ジエチ
ルアミン、トリエチルアミン、ジイソプロピルアミン、
モノエタノールアミン、ジエタノー・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７フイソブロバノールアミン、ノニ
ルアミン、ジメチルアミノプロピルアミン、ジエチルア
ミノプロピルアミン、α−ベンジルジェタノールアミン
ｉ２．４゜６−ドリスージメチルアミノメチルフエノー
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、ピリジン、ピペリジン
、Ｎ−アミノプロピルモルホリン、１．８−ジアザビシ
クロ（５，４，０）ウンデセン−７又はそれとフェノー
ル、２−エチルへキサン酸、オレイゾ酸、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−エチルイミダゾール、２−イソプロピルイミダゾ
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−フェニル−４−メチルイミダゾール、１
−ベンジル−２−メチルイミダゾール、イミダゾールと
Ｃｕ、 Ｎｉ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反応させて得られ
るシアノエチレーシッン・タイプのイミダゾール又はそ
れらとトリメリフ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； ＢＦｌ−モノ
エタノールアミン５ＢＦ３−ベンジルアミン、ＢＦｌ−
ジメチルアニリン、ａｐ３−トリエチルアミン、、 Ｂ
Ｆ３−ｎ−ヘキシルアミン、ＢＦ３−２，６−ジメチル
アニリン、ＢＦ、−アニリンもしくはＢＦ、−ピペリジ
ンの如きＢＦ３−アミン錯体；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又はオクチル酸錫の如
き有機酸金属塩類などがある。In the present invention, curing accelerators (E) may be used, such as diethylamine, triethylamine, diisopropylamine,
Monoethanolamine, diethanolamine, triethanolamine, methylethanolamine, methyljetanolamine, mo7 physobrobanolamine, nonylamine, dimethylaminopropylamine, diethylaminopropylamine, α-benzyljetanolamine i2.4゜6 - Dolys-dimethylaminomethylphenol or its tri-2-ethylhexylate; 2-dimethylaminomethylphenol, pyridine, piperidine, N-aminopropylmorpholine, 1,8-diazabicyclo(5,4,0)undecene-7 or Various amines such as phenol, 2-ethylhexanoic acid, oleizoic acid, diphenylphosphorous acid or salts with organic phosphorous acids; 2-ethylimidazole, 2-isopropylimidazole, 2-undecylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1
-benzyl-2-methylimidazole, complexes of imidazole with metal salts such as Cu, Ni or Go; cyanoethylene-type imidazoles obtained by reacting 2-methylimidazole with acrylonitrile, or their addition with trimeliftic acid; Imidazoles such as compounds or reactants with dicyandiamide; BFl-monoethanolamine 5BF3-benzylamine, BFL-
Dimethylaniline, ap3-triethylamine, B
F3-Amine complexes such as F3-n-hexylamine, BF3-2,6-dimethylaniline, BF,-aniline or BF,-piperidine; Amineimide compounds starting from 1,1-dimethylhydrazine; Triphenylphosphite and organic acid metal salts such as tin octylate.
また、エポキシ化合物とイミダゾール化合物あるいはイ
ミダゾール化合物のカルボン酸との付加物をイソシアネ
ート基を有する化合物で処理した化合物などがあり、こ
れは上記促進剤の中でも含浸用樹脂組成物の貯蔵安定形
成という点から特に好ましい。In addition, there are compounds in which an adduct of an epoxy compound and an imidazole compound or an imidazole compound with a carboxylic acid is treated with a compound having an isocyanate group. Particularly preferred.
この促進剤を得るために用いられるエポキシ化合物とし
ては前記した如き各種のエポキシ樹脂と同種のもの及び
脂肪族グリシジルエーテル、芳香族グリシジルエーテル
、グリシジルアルキレート等のモノエポキシ化合物が用
いられる。また、イミダゾール化合物としては、イミダ
ゾール、２−メチルイミダゾール、２−エチルイミダゾ
ール、２−エチル−４−メチルイミダゾール、２−イソ
プロピルイミダゾール、２−ウンデシルイミダゾール、
２−７エニルイミダゾール等が用いられ、イミダゾール
化合物とカルボン酸塩との付加物を得るためのカルボン
酸としては、酢酸、乳酸、サリチル酸、安息香酸、アジ
ピン酸、フタル酸、クエン酸、酒石酸、マレイン酸、ト
リメリット酸等が挙げられる。The epoxy compounds used to obtain this promoter include those of the same type as the various epoxy resins mentioned above, and monoepoxy compounds such as aliphatic glycidyl ether, aromatic glycidyl ether, and glycidyl alkylate. Further, as imidazole compounds, imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-isopropylimidazole, 2-undecylimidazole,
2-7 enylimidazole etc. are used, and the carboxylic acids to obtain the adduct of imidazole compound and carboxylate include acetic acid, lactic acid, salicylic acid, benzoic acid, adipic acid, phthalic acid, citric acid, tartaric acid, maleic acid. Examples include acids, trimellitic acid, and the like.
イミダゾール化合物とエポキシ化合物の付加物の反応は
従来公知の一般的方法で行うことができる。エポキシ化
合物とイミダゾール化合物あるいはイミダゾール化合物
のカルボン酸塩との反応はイミダゾール化合物の活性水
素１個当たりエポキシ基が１．０〜１．５になるように
し、好ましくは１．２〜１．４である。付加反応は無溶
剤で行っても良いが、適当な溶剤にイミダゾール化合物
を熔解し、エポキシ化合物を滴下又は分割添加する方法
等が用いられる。溶剤は芳香族系、ケトン系が好ましい
０例えばトルエン、キシレン、メチルエチルケトン、メ
チルイソブチルケトン等が挙げられる。無溶剤で反応さ
せた場合には、得られた反応物を所要の粒子サイズに粉
砕して用いる。溶剤を用いる場合には、反応終了後スプ
レーライ方式で噴霧乾燥する方法、溶剤を除去して粉砕
する方法等が採用される。粒子径としては３０μｍ以下
であり、好ましくは１０μ薄以下、特に好ましくは５．
０μ信以下である。３０μｍ以上では硬化促進剤として
使用される場合に母材中での均一分散性に問題が生じて
好ましくない。The reaction of the adduct of the imidazole compound and the epoxy compound can be carried out by a conventionally known general method. The reaction between the epoxy compound and the imidazole compound or the carboxylic acid salt of the imidazole compound is carried out so that the number of epoxy groups per active hydrogen of the imidazole compound is 1.0 to 1.5, preferably 1.2 to 1.4. . Although the addition reaction may be carried out without a solvent, a method is used in which the imidazole compound is dissolved in a suitable solvent and the epoxy compound is added dropwise or in portions. The solvent is preferably aromatic or ketone, such as toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, and the like. When the reaction is carried out without a solvent, the obtained reaction product is ground to the required particle size and used. When a solvent is used, a method of spray drying after completion of the reaction, a method of removing the solvent and pulverization, etc. are employed. The particle size is 30 μm or less, preferably 10 μm or less, particularly preferably 5.0 μm or less.
It is less than 0μ faith. If it is 30 μm or more, it is not preferable because when it is used as a curing accelerator, a problem arises in uniform dispersibility in the base material.
こうして得られる粉末状の付加物を溶解しない溶剤、例
えばトルエン、キシレン、アセトン、メチルエチルケト
ン等にまず所定量のイソシアネート基を育する化合物を
溶解させ、ついで上記粉末状付加物をこの中に分散させ
、表面処理して溶剤を飛散、乾燥して目的とする硬化促
進剤が得られる。インシアネート基を有する化合物の使
用量は上記付加物１００重量部に対し０．５〜２０重量
部であり、好ましくは１．０〜１０重量部である。多過
ぎると表面処理硬化は良好であるが、樹脂の硬化性を低
下させるし、少な過ぎると表面処理効果が少なく、樹脂
の貯蔵安定性が低下する。First, a predetermined amount of the compound that grows isocyanate groups is dissolved in a solvent that does not dissolve the powdered adduct thus obtained, such as toluene, xylene, acetone, methyl ethyl ketone, etc., and then the powdered adduct is dispersed therein, The target curing accelerator is obtained by surface treatment, scattering of the solvent, and drying. The amount of the incyanate group-containing compound used is 0.5 to 20 parts by weight, preferably 1.0 to 10 parts by weight, per 100 parts by weight of the above adduct. If the amount is too large, the surface treatment and curing will be good, but the curability of the resin will be reduced, and if it is too small, the surface treatment effect will be small and the storage stability of the resin will be reduced.
イソシアネート基を有する化合物としては、例えばフェ
ニルイソシアネート、トリルイソシアネート等のモノイ
ソシアネート化合物、テトラメチレンジイソシアネート
、ヘキサメチレンジイソシアネート、トリレンジイソシ
アネート、キシリレンジイソシアネート、ジフェニルメ
タンジイソジアネート、イソプロピリデンシクロヘキシ
ルイソシアネート、リジンイソシアネート、トリレンジ
イソシアネートとトリメチロールプロパンの付加物、ト
リレンジイソシアネートとペンタエリスリトールの付加
物、トリレンジイソシアネートとポリエチレングリコー
ルの付加物、トリレンジイソシアネートとポリプロピレ
ングリコールの付加物、ヘキサメチレンジイソシアネー
トとポリエチレンアジペートのプレポリマー等のポリイ
ソシアネート化合物等が挙げられる。モノイソシアネー
ト化合物よりもポリイソシアネート化合物の方が好まし
い。Examples of compounds having an isocyanate group include monoisocyanate compounds such as phenyl isocyanate and tolyl isocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, isopropylidene cyclohexyl isocyanate, lysine isocyanate, Adducts of tolylene diisocyanate and trimethylolpropane, adducts of tolylene diisocyanate and pentaerythritol, adducts of tolylene diisocyanate and polyethylene glycol, adducts of tolylene diisocyanate and polypropylene glycol, prepolymers of hexamethylene diisocyanate and polyethylene adipate Examples include polyisocyanate compounds such as. Polyisocyanate compounds are preferred over monoisocyanate compounds.
また、本発明では上記反応生成物（Ｃ）の架橋用に重合
性架橋剤（Ｆ）を用いても良く、これには重合性ビニル
七ツマ−が挙げられ、単独で無溶剤型含浸用樹脂組成物
の成分として添加使用されても良いし、反応生成物（Ｃ
）に必要量予め添加されていても良く、その際に使用さ
れる前記の重合性ビニルモノマー等は単独又は２種以上
併用でき・【・含浸用樹脂組成物中のビニルモ、′マー
成分は含浸用樹脂組成物を所望の粘度に合わせるという
観点から適宜決定されれば良いが、通常２〜４０ｆｆ量
％、好ましくは５〜３０重量％である。In addition, in the present invention, a polymerizable crosslinking agent (F) may be used for crosslinking the reaction product (C), and examples thereof include polymerizable vinyl heptamer, which alone can be used as a solvent-free impregnating resin. It may be added and used as a component of the composition, or it may be used as a reaction product (C
) may be added in advance in the necessary amount, and the above-mentioned polymerizable vinyl monomers used in this case can be used alone or in combination of two or more. It may be determined appropriately from the viewpoint of adjusting the viscosity of the resin composition for use, but it is usually 2 to 40 ff% by weight, preferably 5 to 30% by weight.
上記重合性ビニルモノマーのうちで代表的なものとして
は、スチレン、ビニルトルエン、１−ブチルスチレン、
クロルスチレンもしくはジビニルペゼンの如きスチレン
及びその誘導体；エチル（メタ）アクリレート、プロピ
ル（メタ）アクリレート、イソプロピル（メタ）アクリ
レート、 ｎ −ブチル（メタ）アクリレート、ｎ−
ブチル（メタ）アクリレート、イソブチル（メタ）アク
リレート１．２−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）クリレートもしくは２−ヒドロキシプロピル
（メタ）アクリレートの如き（メタ）アクリル酸の低沸
点エステルモノマー類；又はトリメチロールプロパント
リ （メタ）アクリレート、ジエチレングリコールジ（
メタ）アクリレート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、これらは単独であるいは二
種以上の混合として、通常エポキシビニルエステル４０
〜８０重量％に対して６０〜２０重量％（合計１００重
量％）の割合で使用される。Typical examples of the above polymerizable vinyl monomers include styrene, vinyltoluene, 1-butylstyrene,
Styrene and its derivatives such as chlorstyrene or divinylpezene; ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, n-
(meth)acrylics such as butyl (meth)acrylate, isobutyl (meth)acrylate 1.2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, 2-hydroxyethyl (meth)acrylate or 2-hydroxypropyl (meth)acrylate low-boiling ester monomers of acids; or trimethylolpropane tri(meth)acrylate, diethylene glycol di(
meth)acrylate 1,4-butanediol di(meth)
Examples include (meth)acrylates of polyhydric alcohols such as acrylate or 1,6-hexanethiol di(meth)acrylate, and these are usually used alone or as a mixture of two or more of epoxy vinyl esters 40
It is used in a proportion of 60 to 20% by weight (total 100% by weight) to 80% by weight.
これらの重合性架橋剤は液状のものが好ましく、常温又
は加熱により揮発性のものも好ましく用いられる。These polymerizable crosslinking agents are preferably liquid ones, and those that are volatile at room temperature or by heating are also preferably used.
本発明の含浸用樹脂組成物を用いてプリプレグ積層板を
得るに当たり適正な成形性、ＩＩ層板の性能を得るため
にには、樹脂成分（（Ａ） ＋（Ｂ） ＝（（Ｃ）
を得るために用いた多塩基酸無水物（Ｃ゛）′Ｊ〕の成
分の、（（Ｃ）を得るために用いたエポキシビニルエス
テルの重量（Ｃ”））に対する重量比、〔（八） ＋
（Ｂ） ＋（Ｃ’）） ／（Ｃ”）は通常９５１５〜
３０／ワＯであるが、硬化収縮が小さく、金属、特に銅
箔との接着性に優れる点で９０／１０〜５０１５０が好
ましう゛Ｑ成分（Ａ）の成分（Ｂ） 、（Ｃ’）に対す
る使用量は、通常（Ａ）中のエポキシ基１ヶに対し、成
分（Ｂ）、（Ｃ゛）中の酸無水物中の酸無水物基、すな
わちエポキシ当量（Ａ−ｅｑ ）の成分（８） 、（Ｃ
’）の酸当量（Ｂ−ｅｑ）と（Ｃ’−ｅｑ）に対する当
量比（Ａｅｑ ） ／ ［８ｅｑ＋Ｃ’−ｅｑ ）が
０．８〜１．２５の範囲であり、好ましくは０．９〜１
．１である。When obtaining a prepreg laminate using the resin composition for impregnation of the present invention, in order to obtain appropriate moldability and II laminate performance, the resin component ((A) + (B) = ((C)
The weight ratio of the component of the polybasic acid anhydride (C')'J] used to obtain (the weight (C'') of the epoxy vinyl ester used to obtain (C)), [(8) +
(B) + (C')) / (C") is usually 9515 ~
30/W O, but 90/10 to 50150 is preferable in terms of small curing shrinkage and excellent adhesion to metals, especially copper foil.Q component (A) components (B), (C') The amount used is usually one epoxy group in (A), the acid anhydride group in the acid anhydride in components (B) and (C゛), that is, the epoxy equivalent (A-eq) of the component ( 8) , (C
') to the acid equivalent (B-eq) and the equivalent ratio (Aeq)/[8eq+C'-eq) to (C'-eq) is in the range of 0.8 to 1.25, preferably 0.9 to 1
．． It is 1.
この当量比が０．８より小さいと、硬化物の耐アルカリ
性が低下するし、１．２５より大きいと耐熱性が低下し
て好ましくない。If this equivalent ratio is less than 0.8, the alkali resistance of the cured product will decrease, and if it is greater than 1.25, the heat resistance will decrease, which is not preferable.
本発明の含浸用樹脂組成物は、前記（Ａ）〜（Ｄ）成分
を少な（とも含有するが、さらに必要に応じて内部離型
剤、顔料、充填剤等の添加剤を加えてなる組成物であっ
て、かつ繊維質基材に含浸可能なものであっても良い。The impregnating resin composition of the present invention contains a small amount of the components (A) to (D), and further contains additives such as an internal mold release agent, a pigment, and a filler as necessary. It may also be a material that can be impregnated into a fibrous base material.
なお固形の成分は含浸に際してかならずしも液状成分中
に溶解又は溶融さ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も良い。Note that the solid component does not necessarily need to be dissolved or melted in the liquid component during impregnation, and may be dispersed in powder form in the liquid component.
充填剤は、要求性能、作業条件などにより適宜選択され
るが、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
イ酸ジルコニウム、ガラス粉末７、アスベスト粉末、ケ
イ藻土、二酸化アンチモンなどがある。The filler is selected as appropriate depending on the required performance, working conditions, etc., but examples include aluminum hydroxide, aluminum silicate, colloidal silica, calcium carbonate, calcium sulfate, mica, talc, titanium dioxide, quartz powder, and silicic acid. Examples include zirconium, glass powder7, asbestos powder, diatomaceous earth, and antimony dioxide.
また、本発明の含浸用樹脂組成物は液状にするが、それ
には前記（Ａ）〜（Ｄ）成分等に液状物を選択使用して
も良いし、重合性架橋剤に液状物を使用し、他の液状物
、固形物を熔解又は分散させても良く、これが好ましい
が、溶剤を使用又は併用して他の液状物、固形物を溶解
又は分散させても良い。Further, the resin composition for impregnation of the present invention is made into a liquid, and for this purpose, a liquid may be selectively used for the components (A) to (D), etc., or a liquid may be used as the polymerizable crosslinking agent. , other liquids or solids may be dissolved or dispersed, which is preferred, but other liquids or solids may be dissolved or dispersed using or in combination with a solvent.
含浸用ｔｈ脂組成物を得るに際しての各成分の配合方法
及び配合順序は特に限定されるものではないが、固形成
分を使用する場合には、液状成分を混合した後、固形の
成分を粉末状で添加して、分散又は溶解させる方法が好
ましい。There are no particular limitations on the method and order of blending each component when obtaining a th fat composition for impregnation, but when solid components are used, after mixing the liquid components, the solid components are mixed into powder form. A preferred method is to add the compound and disperse or dissolve it.
本発明は上記含浸用樹脂組成物を繊維質基材に含浸させ
た含浸繊維質基材を用いた一枚毎のプリプレグ、その重
合性架橋剤の含有量を４重量％以下にしたプリプレグ、
これらプリプレグを積層して得られる、積層プリプレグ
等の積層板用中間Ｌオ、含浸繊維質基材を未乾燥状態で
重ね合わせ、さらにこの重ね合わせ体の両側にフィルム
を道ねて部分硬化させた積層板用中間材、さらには含浸
繊維質基材を未乾燥状態で重ね合わせその重合性架橋剤
をその含有量が８重量％以下になるようにしてから銅箔
等の金属箔、フィルムを重ね合わせ体の両面に少なくと
もいずれか一方が金属箔になるように重ね、部分硬化さ
せた積層板用中間材も提供するものである。これらの部
分硬化には、Ｂステージ化も含まれ、これより硬化程度
が低く、タックフリーにならないものも含まれる。The present invention provides prepregs each using an impregnated fibrous base material in which a fibrous base material is impregnated with the above impregnating resin composition, a prepreg in which the content of a polymerizable crosslinking agent is 4% by weight or less,
Intermediate L for laminates such as laminated prepregs obtained by laminating these prepregs and impregnated fibrous base materials were laminated in an undried state, and furthermore, films were placed on both sides of this laminated body and partially cured. Intermediate materials for laminates and impregnated fibrous base materials are layered in an undried state, and the polymerizable crosslinking agent content is 8% by weight or less, and then metal foil such as copper foil or film is layered. The present invention also provides an intermediate material for a laminate in which at least one of the surfaces of the combined body is made of metal foil and partially cured. These partial cures include B-stage, and also include those whose degree of cure is lower than this and which does not become tack-free.
また、本発明は上記積層板用中間材を加熱成形して得ら
れる積層板、さらには上記含浸用樹脂組成物を繊維質基
材に含浸させ、その含浸繊維質基材を未乾燥又はプリプ
レグ状態で重ね合わせ、連続ラインで加熱成形すること
により得られる積層板も提供するものである。The present invention also provides a laminate obtained by thermoforming the intermediate material for a laminate, and furthermore, a fibrous base material is impregnated with the above impregnating resin composition, and the impregnated fibrous base material is in an undried or prepreg state. The present invention also provides a laminate obtained by laminating the sheets in a continuous line and heat forming them in a continuous line.
上記積層板用中間材、積層板を製造する場合、重合性架
橋剤を含有する又は含有せず、かつ溶剤を含有しない含
浸用樹脂組成物を使用することも好ましく、さらに重合
性架橋剤は揮発性のものを用いプリプレグにあってはそ
の含有量を４Ｍ量％以下、好ましくは後に成形した積層
板の眉間接着力の点から２．０ 重量％以下であり、未
乾燥状態の含浸繊維質基材を重ね合わせて得られる中間
材については８重量％以下になるように揮発除去するこ
とも好ましい。なお、残存重合性架橋剤は試料をアセト
ン等の溶剤Ｓこｌ昼夜浸漬し、溶出する重合性架橋剤を
ガスクロマトグラフィー等により定量できる。When producing the above intermediate material for laminates and laminates, it is also preferable to use a resin composition for impregnation that contains or does not contain a polymerizable crosslinking agent and does not contain a solvent, and furthermore, the polymerizable crosslinking agent is volatile. In the case of a prepreg using a non-dried prepreg, the content is 4M% or less, preferably 2.0% by weight or less from the viewpoint of glabella adhesive strength of the laminated plate formed afterwards, and the impregnated fibrous base in an undried state is used. It is also preferable to volatilize and remove the intermediate material obtained by stacking the materials so that the content is 8% by weight or less. The residual polymerizable crosslinking agent can be determined by soaking the sample in a solvent such as acetone day and night, and then quantifying the eluted polymerizable crosslinking agent by gas chromatography or the like.
上記繊維質基材として代表的なものを挙げれば、ガラス
繊維、炭素繊維又は芳香族ポリアミ下系繊維などであり
、なかでもガラス繊維が好ましい。これらのうちまずガ
ラス繊維としては、その原料面かち、Ｅ−グラス、Ｃ−
グラス、八−グラス及び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
。Typical examples of the above-mentioned fibrous base material include glass fiber, carbon fiber, and aromatic polyamide-based fiber, with glass fiber being particularly preferred. Among these, first of all, glass fibers include E-glass, C-glass, and
Glass, 8-glass, S-glass, etc. exist, but any of these types can be applied in the present invention.
これらの繊維質基材は、その形状によりロービング、チ
ョツプドストランドマット、コンティニアスマット、ク
ロス、不織布、ロービングクロス、サーフェシングマソ
ト及びチョツプドストランドがあるが、上記した如き種
類や形状は、目的とする成形物の用途及び性能により適
宜選択されるものであって、必要によっては二基上の種
類又は形状からの混合使用であっても良いが、クロス、
不織布が好ましい。These fibrous base materials are classified into roving, chopped strand mat, continuous mat, cloth, nonwoven fabric, roving cloth, surfacing material, and chopped strand depending on their shape. It is selected as appropriate depending on the intended use and performance of the molded product, and if necessary, a mixture of two or more types or shapes may be used, but cloth,
Non-woven fabrics are preferred.
本発明で用いる繊維質基材に含浸用樹脂組成物を含浸さ
せた含浸繊維質基材を得るに際し、繊維質基材の容積比
率は含浸繊維質基材の３０〜７０％なる範囲が適当であ
る。When obtaining the impregnated fibrous base material used in the present invention by impregnating the fibrous base material with the resin composition for impregnation, the volume ratio of the fibrous base material is suitably in the range of 30 to 70% of the impregnated fibrous base material. be.
プリプレグを得るに当たっては上記含浸繊維質基材から
重合性架橋剤を除去し、Ｂステージ化すればよいが、除
去と８ステージ化は同時であっても良いし、逐次的であ
っても良い０例えば熱風を上記含浸繊維質基材に吹きつ
ける方法、加熱と吸引又は減圧を併用する方法、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
が重合性架橋剤としての例えば重合性ビニル七ツマ−の
効率的な除去方法であるが、これらに限定されるもので
はない、プリプレグを短時間で得るためには通常７０〜
１５０℃で加熱処理され、９０〜１４０℃が好ましい温
度範囲である。In order to obtain a prepreg, the polymerizable crosslinking agent may be removed from the impregnated fibrous base material and B-staged, but the removal and 8-staging may be done simultaneously or sequentially. For example, a method of blowing hot air onto the impregnated fibrous base material, a method of using a combination of heating and suction or reduced pressure, a method of using infrared rays or far infrared rays, a method of using high frequency heating, etc. This is an efficient method for removing dirt, but is not limited to these methods. Usually 70~
Heat treatment is performed at 150°C, with a preferred temperature range of 90-140°C.
積層板を得るに当っては、プリプレグを所定枚数重ね合
わせ、ついで必要であれば金属箔をさらに重ねたものを
加熱成形する方法、含浸用樹脂組成物を繊維質基材に所
定量含浸させて所定枚数を重ね合わせ、ついで必要があ
れば金属箔をさらに張り合わせたものを従来公知のスタ
テックプレスあるいは連続ベルトプレスで圧力を調整し
つつ、Ｂステージ化し、ついで加熱成形する方法、含浸
後、加熱炉で部分硬化（予備反応）を進めておき、つい
で上記のプレス内で加熱成形する方法等が挙げられる。To obtain a laminate, a predetermined number of prepreg sheets are stacked, and then, if necessary, metal foil is further stacked and then heated and formed, and a fibrous base material is impregnated with a predetermined amount of an impregnating resin composition. A method in which a predetermined number of sheets are stacked together, and then, if necessary, metal foil is further laminated, and the pressure is adjusted using a conventionally known static press or continuous belt press to form a B stage, and then heat molding is performed.After impregnation, heating is performed. Examples include a method of proceeding with partial curing (preliminary reaction) in a furnace and then heating and forming it in the above-mentioned press.
前者のプレス内でＢステージ化する方法では、加熱成形
温度よりも低い温度でかつ通常接触圧〜２０Ｋｇ／ ａ
Ａ、好ましくは接触圧〜１０Ｋｇ／−の圧力下で樹脂の
過剰流出を住じないように調整し、重合開始剤（Ｄ）を
分解させて反応生成物（Ｃ）の硬化を進め、ついで成形
温度（’ｒ＋）まで加温して加熱成形する方法などが好
ましい。In the former method of B-staging in a press, the temperature is lower than the heat forming temperature and the contact pressure is usually ~20 kg/a.
A. Preferably under a contact pressure of ~10 kg/-, the pressure is adjusted so as not to cause excessive outflow of the resin, the polymerization initiator (D) is decomposed and the reaction product (C) is cured, and then molded. A method of heating to a temperature ('r+) and heat-forming is preferred.
また、後者の加熱炉中で予備反応を進めておく方法では
含浸繊維質基材を一枚づつ離型フィルムでサンドイッチ
し予備加熱し、離型フィルムをはがした後、所定枚数重
ねる方法、所定枚数の含浸繊維質基材を重ね合わせ、金
属箔あるいは離型フィルムでサントイ７チし、予備加熱
する方法などが挙げられる。この際の予備加熱温度は重
合開始剤（１））の分解する温度が好ましく、８０〜１
５０℃である。予備加熱方法としては熱風乾燥法、遠赤
外線、赤外線法、マイクロ波加熱法、高周波電熱加熱法
などが挙げられるが、これに限定されない。In addition, in the latter method of proceeding with the preliminary reaction in a heating furnace, the impregnated fibrous base material is sandwiched with a release film one by one, preheated, and after the release film is peeled off, a predetermined number of sheets are stacked. Examples include a method in which several sheets of impregnated fibrous base materials are stacked one on top of the other, covered with metal foil or release film, and preheated. The preheating temperature at this time is preferably the temperature at which the polymerization initiator (1)) decomposes, and is 80 to 1
The temperature is 50°C. Preheating methods include, but are not limited to, hot air drying, far infrared rays, infrared rays, microwave heating, and high frequency electrothermal heating.
ついで、従来公知のスタテックプレスあるいは連続ダブ
ルベルトプレスで成形温度（ＴＪで加熱成形される。Then, it is heated and formed at a forming temperature (TJ) using a conventionally known static press or continuous double belt press.
上記の成形温度ＴＩ％Ｔ２は９通常１３０〜２２０℃、
好ましくは１４０〜１８０℃である。また、成形圧力は
通常接触圧〜５０Ｋｇ／ ｄ、好ましくは５〜４０Ｋｇ
／−である。The above molding temperature TI%T2 is 9 usually 130-220℃,
Preferably it is 140-180°C. In addition, the molding pressure is usually contact pressure ~50Kg/d, preferably 5~40Kg
/-.
スタテックプレスでの成形では含浸繊維質基材を所定サ
イズに切断後、重ね合わせるが連続ベルトプレスでの成
形では含浸繊維質基材は長尺のまま所定枚数連続的に重
ね合わせ積層され、加熱、加圧成形される。In forming with a static press, the impregnated fibrous base material is cut to a predetermined size and then stacked, but in forming with a continuous belt press, a predetermined number of long impregnated fibrous base materials are continuously stacked and laminated, and heated. , pressure molded.
この際、必要ならば加熱成形機から取り出した後、さら
に後硬化を施すこともできる。At this time, if necessary, post-curing can be further performed after taking out from the heat molding machine.
なお、含浸用樹脂組成物中の成分Ｃ（Ａ） ＋（８）
）と（Ｃ）の配合比率を変えた異種の含浸用樹脂組成
物を含浸させて得られる異種の含浸繊維質基材を目的に
応じて組み合わせて用いることも可能であるし、本発明
に係わる含浸繊維質基材を他の樹脂を含浸させて得られ
るプリプレグと組み合わせて使用することも可能である
。In addition, component C (A) + (8) in the resin composition for impregnation
It is also possible to use different types of impregnated fibrous base materials obtained by impregnating different types of impregnating resin compositions with different blending ratios of ) and (C) depending on the purpose, and according to the present invention. It is also possible to use the impregnated fibrous base material in combination with prepregs obtained by impregnating other resins.
Ｌ実施例１ 次に本発明の詳細な説明する。L Example 1 Next, the present invention will be explained in detail.
なお、部は重量部、％は重量％を示す。In addition, parts indicate parts by weight, and % indicates weight %.
実施例を説明する前に、使用成分の製造法を説明する。Before explaining the Examples, the manufacturing method of the components used will be explained.
（反応生成物Ｃ−１の製造）
テトラブロモビスフェノールＡとエピクロルヒドリンと
の反応により得られたエポキシ当量が３７５であるエポ
キシ樹脂のメタクリレート（７３％）とスチレン（２３
％）とよりなるエポキシビニルエステルのスチレン溶液
ｉｏｏ ｓにメチルテトラヒドロ無水フタル酸２９．６
部を加え、８５℃で３時間反応させ、未反応のメチルテ
トラヒドロ無水フタル＃１０゜９％を含む反応生成！？
Ｊ（Ｃ−１）を１２９．６部得た。(Production of reaction product C-1) Methacrylate (73%) of an epoxy resin with an epoxy equivalent of 375 obtained by the reaction of tetrabromobisphenol A and epichlorohydrin and styrene (23%)
29.6%) of methyltetrahydrophthalic anhydride in a styrene solution of epoxy vinyl ester consisting of ioo s
10% of unreacted methyltetrahydrophthalanhydride #10. ?
129.6 parts of J(C-1) were obtained.
（反応生成物Ｃ−２の製造）
テトラブロモビスフェノールＡとエピクロルヒドリンと
の反応により得られたエポキシ当量が３７５であるエポ
キシ樹脂のメタクリレート（７３％）とスチレン（２３
％）とよりなるエポキシビニルエステルのスチレン溶液
１００部にメチルテトラヒドロ無水フタル酸２３．７部
を加え、９０℃で２．５時間反応させ、未反応のメチル
テトラヒドロ無水フタル酸０．７％を含む反応生成物（
Ｃ−２）を１２３．７部得た。(Production of reaction product C-2) Methacrylate (73%) of an epoxy resin with an epoxy equivalent of 375 obtained by the reaction of tetrabromobisphenol A and epichlorohydrin and styrene (23%)
23.7 parts of methyltetrahydrophthalic anhydride was added to 100 parts of a styrene solution of epoxy vinyl ester consisting of Reaction product (
123.7 parts of C-2) were obtained.
（反応生成物Ｃ−３の製造）
テトラブロモビスフェノールＡとエピクロルヒドリンと
の反応により得られたエポキシ当量が３７５であるエポ
キシ樹脂のメタクリレート（７３％）とスチレン（２３
％）とよりなるエポキシビニルエステルのスチレン溶液
１００部にメチルテトラヒドロ無水フタル酸１９．２部
を加え、８５℃で３時間反応させ、未反応のメチルテト
ラヒドロ無水フタル酸０．３％を含む反応生成物（Ｃ−
３）を１１９．２部得た。(Production of reaction product C-3) Methacrylate (73%) of an epoxy resin with an epoxy equivalent of 375 obtained by the reaction of tetrabromobisphenol A and epichlorohydrin and styrene (23%)
19.2 parts of methyltetrahydrophthalic anhydride was added to 100 parts of a styrene solution of epoxy vinyl ester consisting of thing (C-
119.2 parts of 3) were obtained.
（反応生成物Ｃ−４の製造ン
テトラブロモビスフェノールＡとエピクロルヒドリンと
の反応により得られたエポキシ当量が３７５であるエポ
キシ樹脂のメタクリレート（７３％）とスチレン（２３
％）とよりなるエポキシビニルエステルのスチレン溶液
１００部に無水メチルハイミック酸３１．３部を加え、
９０℃で３時間反応させ、未反応の無水メチルハイミッ
ク酸１．０％を含む反応生成物（Ｃ−４）を１３１．３
部得た。(Production of reaction product C-4) Methacrylate (73%) of an epoxy resin with an epoxy equivalent weight of 375 obtained by the reaction of tetrabromobisphenol A and epichlorohydrin and styrene (23%)
%) to 100 parts of a styrene solution of epoxy vinyl ester, add 31.3 parts of methylhimic anhydride,
After reacting at 90°C for 3 hours, the reaction product (C-4) containing 1.0% of unreacted methylhimic anhydride was reduced to 131.3
I got it.
（硬化促進剤Ｄ−１の製造）
ビスフェノールＡとエピクロルヒドリンとの反応により
得られたエポキシ当量が１８８であるエポキシ樹脂と２
−メチルイミダシルとをキシレン中で１２０℃、１．５
時間反応させ付加物（反応モル比１；２）を得、溶剤で
あるキシレンを分離し、さらに乾燥した。ついで粗粉砕
、微粉砕をおこない平均粒子径３．０μｍの粉末を得た
。(Production of curing accelerator D-1) An epoxy resin having an epoxy equivalent of 188 obtained by the reaction of bisphenol A and epichlorohydrin and 2
- methylimidacyl in xylene at 120°C, 1.5
The mixture was reacted for a period of time to obtain an adduct (reaction molar ratio 1:2), the solvent xylene was separated, and the mixture was further dried. Then, coarse pulverization and fine pulverization were performed to obtain powder with an average particle size of 3.0 μm.
このもの１００部をヘキサン２５０部に分散させ、６０
℃に加熱して攪拌しながらキシリレンジイソシアネート
を３部添加し、１時間攪拌を続け、その後濾過し、減圧
乾燥して硬化促進剤（Ｄ−１）を得た。Disperse 100 parts of this in 250 parts of hexane, and
3 parts of xylylene diisocyanate were added while stirring and heating to .degree. C., and stirring was continued for 1 hour, followed by filtration and drying under reduced pressure to obtain a curing accelerator (D-1).
実施例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り
得られたエポキシ当量１８８なる無溶剤液状エポキシ樹
脂１５．７部と、テトラブロモビスフェノールＡとエピ
クロルヒドリンとの反応により得られたエポキシ当量が
３７５なるエポキシ樹脂２４．５部と、メチルテトラヒ
ドロ無水フタル酸２０．９部と、前記反応生成物（Ｃ−
１）４４．２部と、２−エチル−４−メチルイミダゾー
ル０．２４部と、１．１−ビス（ｔ−ブチルパーオキシ
）３，３．５− ）リメチルシクロヘキサン０．８１
ｉと、スチレンモノマー４．０部を混合せしめ、含浸用
樹脂組成物Ｃｌ−１）を調製した。Example 1 15.7 parts of a solvent-free liquid epoxy resin with an epoxy equivalent of 188 obtained by the reaction of bisphenol A and epichlorohydrin and an epoxy resin 24 with an epoxy equivalent of 375 obtained by the reaction of tetrabromobisphenol A and epichlorohydrin .5 parts of methyltetrahydrophthalic anhydride, 20.9 parts of methyltetrahydrophthalic anhydride, and the reaction product (C-
1) 44.2 parts, 0.24 parts of 2-ethyl-4-methylimidazole, and 0.81 parts of 1,1-bis(t-butylperoxy)3,3.5-)limethylcyclohexane.
i and 4.0 parts of styrene monomer were mixed to prepare a resin composition for impregnation Cl-1).
この含浸用樹脂組成物（１−１）の４８部を縦３００鶴
、横３００ｆｉ、厚さｏ、ｉｓｗのガラスクロス５８部
に含浸させ、１２０℃の熱風循環乾燥機内で６分間加熱
乾燥し、樹脂分（ガラスクロスを除いたもの）中のスチ
レンモノマー合有量０．８％（アセトンに溶出してガス
クロマトグラフィーで定量）、樹脂含有率４２％のプリ
プレグを得た。このプリプレグはタックフリーで柔軟性
があった。これを８枚重ねた両面に３５μｌ厚さの銅箔
を貼り合わせ、ついでその両面に２枚の鏡面仕上げをし
たステンレス板、更にクツション材としてのクラフト紙
で挟み込み、１７０℃の加熱成形機（スタティックプレ
ス）に仕込み、１０Ｋｇ／ ｃ！Ａの圧力で５分間圧縮
した後、４０Ｋｇ／−の圧力で６０分間加熱成形し、そ
の後圧力を維持したまま３０℃まで冷却し、厚み１６
Ｍの積層板を得た。かくして得られた積層板について樹
脂流出量、厚み精度、銅箔接着強度（剥離強度）、層間
接着強度（剥離強度）、ガラス転移温度の測定を以下の
ように行い、その結果を表に示す。48 parts of this resin composition for impregnation (1-1) was impregnated into 58 parts of glass cloth with a length of 300 mm, a width of 300 fi, and a thickness of o and isw, and heated and dried for 6 minutes in a hot air circulation dryer at 120 ° C. A prepreg was obtained in which the total amount of styrene monomer in the resin component (excluding glass cloth) was 0.8% (determined by gas chromatography after elution with acetone), and the resin content was 42%. This prepreg was tack-free and flexible. Copper foil with a thickness of 35 μl is pasted on both sides of 8 sheets of this, then two mirror-finished stainless steel plates are sandwiched between both sides, and kraft paper is used as a cushioning material. press), 10Kg/c! After compressing at pressure A for 5 minutes, heat molding at a pressure of 40 kg/- for 60 minutes, then cooling to 30 ° C while maintaining the pressure, and a thickness of 16
A laminate of M was obtained. The resin flow rate, thickness accuracy, copper foil adhesive strength (peel strength), interlayer adhesive strength (peel strength), and glass transition temperature of the thus obtained laminate were measured as follows, and the results are shown in the table.
樹脂流出量（％）・嶋バーＸ１００にて算出した。Resin outflow amount (%) was calculated using Shima Bar X100.
（ただし、臀・は所定面積３００ｍＸ ３００ｍの積層
板の重量、Ｗ、は上記所定面積からはみ出した部分の重
量である。）
厚み精度：３００鶴Ｘ３００ｍの積層板の３００ｎ長の
辺のうち左側の１辺の中心から内側に１０ｆｌの部分■
と、中央部■と、３００鶴長の辺のうちの右側の１辺の
中心から１０鶴の部分■の位置の厚みをそれぞれ測定し
た。(However, Buttocks is the weight of the laminate with a predetermined area of 300m x 300m, and W is the weight of the part that protrudes from the above predetermined area.) Thickness accuracy: The left side of the 300n long side of the 300m x 300m laminate. 10fl part inward from the center of one side■
The thicknesses were measured at the central part (■), and at the position (■) of the 10 cranes from the center of the right side of the 300 cranes long side.
銅箔剥離強度：ＪＩＳＣ−６４８１に準じて測定した。Copper foil peel strength: Measured according to JISC-6481.
眉間剥離強度二層外層の繊維質基材をｆＪ箔の付いた状
態で最外層に隣接する繊維質基材から剥がし、テンシロ
ン（引張り強度試験機）にて最外層基材除去面に対する
引き剥がし方向の角度を９０度に保ちつつ、剥離強度を
測定した。Peel strength between the eyebrows: Peel off the two-layer outer layer fibrous base material with the fJ foil attached from the fibrous base material adjacent to the outermost layer, and use a Tensilon (tensile strength tester) to measure the peeling direction relative to the surface from which the outermost layer base material was removed. The peel strength was measured while keeping the angle at 90 degrees.
ガラス転移温度（Ｔｇ）： Ｒｈｏｍｅｔｒｉｃｓ社製
Ｒ５Ａ−ＩＩ社製的５Ａ粘弾性測定器にて測定した。Glass transition temperature (Tg): Measured using a 5A viscoelasticity meter manufactured by R5A-II manufactured by Rhometrics.
実施例２
ビスフェノールＡとエピクロルヒドリンとの反応により
得られたエポキシ当量１８８なる無溶剤液状エポキシ樹
脂１５．７部と、テトラブロモビスフェノールＡとエピ
クロルヒドリンとの反応により得られたエポキシ当量が
３７５なるエポキシ樹脂２４．５部と、メチルテトラヒ
ドロ無水フタル酸２０．９部と、前記反応生成物（Ｃ−
１）３８．９部と、前記の硬化促進剤（Ｄ−１）０．４
０部と、１．１−ビス（ｔ−ブチルパーオキシ）３．３
．５− １−リメチルシクロヘキサン０．６１部と、ス
チレンモノマー４．０部を混合せしめ、含浸用樹脂組成
物（Ｉ−２）を鋼製した。Example 2 15.7 parts of a solvent-free liquid epoxy resin with an epoxy equivalent of 188 obtained by the reaction of bisphenol A and epichlorohydrin and an epoxy resin 24 with an epoxy equivalent of 375 obtained by the reaction of tetrabromobisphenol A and epichlorohydrin .5 parts of methyltetrahydrophthalic anhydride, 20.9 parts of methyltetrahydrophthalic anhydride, and the reaction product (C-
1) 38.9 parts and 0.4 parts of the above curing accelerator (D-1)
0 parts and 1.1-bis(t-butylperoxy) 3.3
．． 0.61 part of 5-1-limethylcyclohexane and 4.0 parts of styrene monomer were mixed to prepare a resin composition for impregnation (I-2) into steel.
以下実施例１と同様にして樹脂分中のスチレンモノマー
含有量０．６％、樹脂含有率４２％のタックフリーで柔
軟なプリプレグを得た。このプリプレグを用いた以外は
同様にして厚み１．６ｆｌの積層板を得た。これについ
ても実施例１と同様に測定した結果を表に示す。Thereafter, in the same manner as in Example 1, a tack-free and flexible prepreg with a styrene monomer content of 0.6% and a resin content of 42% was obtained. A laminate with a thickness of 1.6 fl was obtained in the same manner except that this prepreg was used. This was also measured in the same manner as in Example 1, and the results are shown in the table.
実施例３
ビスフェノールｊとエピクロルヒドリンとの反応により
得られたエポキシ当量１８８なる無溶剤液状エポキシ樹
脂１５．７部と、テトラブロモビスフェノールＡとエピ
クロルヒドリンとの反応により得られたエポキシ当量が
３７５なるエポキシ樹脂２４．５部と、メチルテトラヒ
ドロ無水フタル酸２０．９部と、前記反応生成物（Ｃ−
２）３７．１部と、ジメチルベンジルアミン０．２４部
と、１．１−ビス（ｔ−ブチルパーオキシ）３，３．５
− １−リメチルシクロヘキサン０．６１部と、スチレ
ンモノマー４．０部を混合せしめ、含浸樹脂組成物（１
−３）を調製した。Example 3 15.7 parts of a solvent-free liquid epoxy resin with an epoxy equivalent of 188 obtained by the reaction of bisphenol j and epichlorohydrin and an epoxy resin 24 with an epoxy equivalent of 375 obtained by the reaction of tetrabromobisphenol A and epichlorohydrin .5 parts of methyltetrahydrophthalic anhydride, 20.9 parts of methyltetrahydrophthalic anhydride, and the reaction product (C-
2) 37.1 parts, 0.24 parts of dimethylbenzylamine, and 3,3.5 parts of 1,1-bis(t-butylperoxy)
- 0.61 parts of 1-limethylcyclohexane and 4.0 parts of styrene monomer were mixed to form an impregnated resin composition (1
-3) was prepared.
以下実施例１と同様にして樹脂分中のスチレンモノマー
含有量０．６％、樹脂含有率４１％のタックフリーで柔
軟なプリプレグを得た。このプリプレグを用いた以外は
同様にして厚み１．６ｎの積層板を得た。これについて
も実施例１と同様に測定した結果を表に示す。Thereafter, in the same manner as in Example 1, a tack-free and flexible prepreg with a styrene monomer content of 0.6% and a resin content of 41% was obtained. A laminate with a thickness of 1.6 nm was obtained in the same manner except that this prepreg was used. This was also measured in the same manner as in Example 1, and the results are shown in the table.
実施例４
ビスフェノールＡとエビクロル−ヒドリ二／との反応に
より得られたエポキシ当量１８８なる無溶剤液状エポキ
シ樹脂１５．７部と、テトラブロモビスフェノールＡと
エピクロルヒドリンとの反応により得られたエポキシ当
量が３７５なるエポキシ樹脂２４．５部と、メチルテト
ラヒドロ無水フタル酸２０．９部と、前記反応生成物（
Ｃ−３）３５．８部と、前記の硬化促進剤（Ｄ−１）０
．４部と、１．１−ビス（ｔ−ブチルパーオキシ）３，
３．５− トリメチルシクロヘキサン０．６１部と、
スチレンモノマー４．０部を混合せしめ、含浸用樹脂組
成物（Ｉ−４）を調製した。Example 4 15.7 parts of a solvent-free liquid epoxy resin with an epoxy equivalent of 188 was obtained by the reaction of bisphenol A and epichlorohydrin, and an epoxy equivalent of 375 was obtained by the reaction of tetrabromobisphenol A with epichlorohydrin. 24.5 parts of epoxy resin, 20.9 parts of methyltetrahydrophthalic anhydride, and the reaction product (
C-3) 35.8 parts and the curing accelerator (D-1) 0
．． 4 parts and 1,1-bis(t-butylperoxy)3,
3.5-0.61 parts of trimethylcyclohexane,
A resin composition for impregnation (I-4) was prepared by mixing 4.0 parts of styrene monomer.
以下実施例１と同様にして樹脂分中のスチレンモノマー
含有量０．５％、樹脂含有率４１％のタックフリーで柔
軟なプリプレグを得た。このプリプレグを用いた以外は
同様にして厚み１．６ｆｉの積層板を得た。これについ
ても実施例１と同様に測定した結果を表に示す。Thereafter, in the same manner as in Example 1, a tack-free and flexible prepreg with a styrene monomer content of 0.5% and a resin content of 41% was obtained. A laminate with a thickness of 1.6 fi was obtained in the same manner except that this prepreg was used. This was also measured in the same manner as in Example 1, and the results are shown in the table.
実施例５
ビスフェノール八とエピクロルヒドリンとの反応により
得られたエポキシ当量１８８なる無溶剤液状エポキシ樹
脂１５．７部と、テトラブロモビスフェノールＡとエピ
クロルヒドリンとの反応により得られたエポキシ当量が
３７５なるエポキシ樹脂２４．５部と、無水メチルハイ
ミック酸２２．１部と、前記反応生成物（Ｃ−４）３９
．５部と、前記の硬化促進剤（Ｄ−１）０．４０部と、
１．１−ビス（ｔ−ブチルパーオキシ）３．３．５−ト
リメチルシクロヘキサン０．６１部と、スチレンモノマ
ー４．０部を混合せしめ、樹脂組成物（■−５）を調製
した。Example 5 15.7 parts of a solvent-free liquid epoxy resin with an epoxy equivalent of 188 obtained by the reaction of bisphenol 8 and epichlorohydrin and an epoxy resin 24 with an epoxy equivalent of 375 obtained by the reaction of tetrabromobisphenol A and epichlorohydrin .5 parts, 22.1 parts of methylhimic anhydride, and 39 parts of the reaction product (C-4).
．． 5 parts, and 0.40 parts of the curing accelerator (D-1),
A resin composition (■-5) was prepared by mixing 0.61 parts of 1.1-bis(t-butylperoxy)3.3.5-trimethylcyclohexane and 4.0 parts of styrene monomer.
以下実施例１と同様にして樹脂分中のスチレンモノマー
含有量０．９％、樹脂含有率４１％のタックフリーで柔
軟なプリプレグを得た。このプリプレグを用いた以外は
同様にして厚み１．６ｆｉの積層板を得た。これについ
ても実施例１と同様に測定した結果を表に示す。Thereafter, in the same manner as in Example 1, a tack-free and flexible prepreg with a styrene monomer content of 0.9% and a resin content of 41% was obtained. A laminate with a thickness of 1.6 fi was obtained in the same manner except that this prepreg was used. This was also measured in the same manner as in Example 1, and the results are shown in the table.
実施例６
ビスフェノールＡとエピクロルヒドリンとの反応により
得られたエポキシ当量１８８なる無溶剤液状エポキシ樹
脂１５．７部と、テトラブロモビスフェノールＡとエピ
クロルヒドリンとの反応により得られたエポキシ当量が
３７５なるエポキシ樹脂２４．５部と、メチルテトラヒ
ドロ無水フタル酸２０．９部と、前記反応生成物（Ｃ−
１）３８．９部と、２−エチル−４−メチルイミダゾー
ル０．２４部と、１．１−ビス（ｔ−ブチルパーオキシ
）３，３．５− トリメチルシクロヘキサン０．６１Ｎ
と、スチレンモノマー８．０部を混合せしめ、樹脂組成
物（１−６）を調製した。Example 6 15.7 parts of a solvent-free liquid epoxy resin with an epoxy equivalent of 188 obtained by the reaction of bisphenol A and epichlorohydrin and an epoxy resin 24 with an epoxy equivalent of 375 obtained by the reaction of tetrabromobisphenol A and epichlorohydrin .5 parts of methyltetrahydrophthalic anhydride, 20.9 parts of methyltetrahydrophthalic anhydride, and the reaction product (C-
1) 38.9 parts, 0.24 parts of 2-ethyl-4-methylimidazole, and 0.61N of 1,1-bis(t-butylperoxy)3,3.5-trimethylcyclohexane
and 8.0 parts of styrene monomer were mixed to prepare a resin composition (1-6).
この樹脂粗製物（１−６）を幅１０２００の連続な厚み
０．１８ｎの８枚のガラスクロスに連続的に分離した状
態で含浸させ、樹脂含有率４２％の含浸繊維質基材を得
、これを８枚重ね合わせ、さらに３５ｆｉ厚さの銅箔を
両面に貼り合わせた。This resin crude product (1-6) was impregnated into 8 continuous sheets of glass cloth with a width of 10200 mm and a thickness of 0.18 nm in a separated state to obtain an impregnated fibrous base material with a resin content of 42%. Eight sheets of this were stacked together, and copper foil with a thickness of 35 fi was laminated on both sides.
次いで１１０℃、２Ｋｇ／ａｊの条件で２．５分間、ラ
イで１７０℃、１５Ｋｇ／ ｃｊの条件で１０分間連続
的にダブルベルトプレス内で加熱成形し、さらに加圧状
態で１００℃まで冷却し、ギロチンカッターで１０００
ｍ長さに切断し、両端を１０１０２Ｏ幅に切断した。得
られた１、６０■Ｘ １０００ｍ ｘ １０２０ｍを１
６０℃で１時間後硬化させ、積層板を得た。Next, it was heated and molded continuously in a double belt press for 2.5 minutes at 110℃ and 2Kg/aj, then in a dry state for 10 minutes at 170℃ and 15Kg/cj, and then cooled to 100℃ under pressure. , 1000 with a guillotine cutter
It was cut into a length of m, and both ends were cut into a width of 10102O. The obtained 1,60■ x 1000m x 1020m is 1
It was post-cured at 60° C. for 1 hour to obtain a laminate.
このようにして得られた積層板について、実施例１と同
様に測定した結果を表に示す。The results of measurements performed on the thus obtained laminate in the same manner as in Example 1 are shown in the table.
なお、樹脂流出量（％）は、Ｗ。を所定面積１１０００
１１１１Ｘ１０２０の積層板の重量、１をこの所定面積
からはみ出した部分の重量とし、厚み精度は、１１００
ＯＩｎＸ１０２Ｑの積層板の１０２０ｗｍ長の辺のうち
の左側の１辺の中心から内側にＩｏｎの部分■と、中央
部分■と、１１０２０ｔ長の辺のうちの右側の１辺の中
心からｌ０Ｃ１１の部分■の位置の厚みをそれぞれ測定
した。Note that the resin flow rate (%) is W. The specified area is 11000
The weight of the 1111 x 1020 laminate is 1, which is the weight of the part that protrudes from this predetermined area, and the thickness accuracy is 1100.
Of the 1020wm long sides of the OInX102Q laminate, there is an Ion part (■) inward from the center of the left side, a center part (■), and a l0C11 part (■) from the center of the right side of the 11020t long sides. The thickness at each position was measured.
実施例７
ビスフェノールＡとエピクロルヒドリンとの反応により
得られたエポキシ当量１８８なる無溶剤液状エポキシ樹
脂１５．７部と、テトラブロモビスフェノールＡとエピ
クロルヒドリンとの反応により得られたエポキシ当量が
３７５なるエポキシ樹脂２４．５部と、メチルテトラヒ
ドロ無水フタル酸２０．９部と、前記反応生成物（Ｃ−
２）３７．１部と、ジメチルベンジルアミン０．２４部
と、１，１−ビス（ｔ−ブチルパーオキシ）３．３．５
− ）リメチルシクロヘキサン０．６１部と、スチレ
ンモノマー８．０部を混合せしめ、樹脂組成物（Ｉ−７
）を調製した。Example 7 15.7 parts of a solvent-free liquid epoxy resin with an epoxy equivalent of 188 obtained by the reaction of bisphenol A and epichlorohydrin, and an epoxy resin 24 with an epoxy equivalent of 375 obtained by the reaction of tetrabromobisphenol A and epichlorohydrin. .5 parts of methyltetrahydrophthalic anhydride, 20.9 parts of methyltetrahydrophthalic anhydride, and the reaction product (C-
2) 37.1 parts, 0.24 parts of dimethylbenzylamine, and 3.3.5 parts of 1,1-bis(t-butylperoxy)
-) 0.61 parts of remethylcyclohexane and 8.0 parts of styrene monomer were mixed to form a resin composition (I-7
) was prepared.
以下、実施例６と同様にして積層板を得、実施例６と同
様にして測定した結果を表に示す。Hereinafter, a laminate was obtained in the same manner as in Example 6, and the results were measured in the same manner as in Example 6 and are shown in the table.
実施例８
ビスフェノールＡとエピクロルヒドリンとの反応により
得られたエポキシ当量１８８なる無溶剤液状エポキシ樹
脂１５．７部と、テトラブロモビスフェノールＡとエピ
クロルヒドリンとの反応により得られたエポキシ当量が
３７５なるエポキシ樹脂２４．５部と、無水メチルハイ
ミンク酸２２．１部と、前記反応生成物（Ｃ−４）３９
．５部と、前記の硬化促進剤（Ｄ−１）０．４０部と、
１．１−ビス（ｔ−ブチルパーオキシ）３．３．５トリ
メチルシクロヘキサン０．６１部と、スチレンモノマー
８．０部を混合せしめ、樹脂組成物（Ｉ −８）を１！
製した。Example 8 15.7 parts of a solvent-free liquid epoxy resin with an epoxy equivalent of 188 obtained by the reaction of bisphenol A and epichlorohydrin and an epoxy resin 24 with an epoxy equivalent of 375 obtained by the reaction of tetrabromobisphenol A and epichlorohydrin .5 parts, 22.1 parts of methylheiminic anhydride, and 39 parts of the reaction product (C-4).
．． 5 parts, and 0.40 parts of the curing accelerator (D-1),
1.1-bis(t-butylperoxy) 3.3.5 0.61 parts of trimethylcyclohexane and 8.0 parts of styrene monomer were mixed to form a resin composition (I-8) of 1.5 parts.
Manufactured.
以下、実施例６と同様にして積層板を得、実施例６と同
様にして測定した結果を表に示す。Hereinafter, a laminate was obtained in the same manner as in Example 6, and the results were measured in the same manner as in Example 6 and are shown in the table.
比較例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り
得られたエポキシ当量１８８なる無溶剤液状エポキシ樹
脂１５．７部と、テトラブロモビスフェノールＡとエピ
クロルヒドリンとの反応により得られたエポキシ当量が
３７０なるエポキシ樹脂２４．５部を溶解せしめたエポ
キシ樹脂混合物４０．２部と、メチルテトラヒドロ無水
フタル酸２４．７部と、２−エチル−４−メチルイミダ
ゾール０．２４部と、テトラブロモビスフェノール＾と
エピクロルヒドリンとの反応により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ート（６０％
）とスチレンモノルー（４０％）とよりなるエポキシビ
ニルエステルのスチレン溶液２７．９部と、１．１−ビ
ス（Ｌ−ブチルパーオキシ）３．３．５− ）リメチ
ルシクロヘキサン０．６１部を混合せしめ、含浸用樹脂
組成物（１−９）を調製した。Comparative Example 1 15.7 parts of a solvent-free liquid epoxy resin with an epoxy equivalent of 188 obtained by the reaction of bisphenol A and epichlorohydrin, and an epoxy resin 24 with an epoxy equivalent of 370 obtained by the reaction of tetrabromobisphenol A and epichlorohydrin. Reaction of 40.2 parts of an epoxy resin mixture in which .5 parts were dissolved, 24.7 parts of methyltetrahydrophthalic anhydride, 0.24 parts of 2-ethyl-4-methylimidazole, tetrabromobisphenol and epichlorohydrin. Methacrylate (60%) of an epoxy resin with an epoxy equivalent of 370 obtained by
) and styrene monomer (40%), and 27.9 parts of a styrene solution of epoxy vinyl ester, and 0.61 parts of 1,1-bis(L-butylperoxy)3.3.5-)limethylcyclohexane. were mixed to prepare a resin composition for impregnation (1-9).
以下実施例１と同様にしてタックフリーで樹脂分中のス
チレンモノツー含有量０．８％、樹脂含有率４２％のタ
ックフリーで柔軟なプリプレグを得た。Thereafter, in the same manner as in Example 1, a tack-free and flexible prepreg having a styrene mono-two content of 0.8% in the resin and a resin content of 42% was obtained.
さらに実施例１と同様にして測定した結果を表に示す。Furthermore, the results of measurements conducted in the same manner as in Example 1 are shown in the table.
比較例２
ビスフェノールＡとエピクロルヒドリンとの反応により
得られたエポキシ当量１８Ｂなる無溶剤液状エポキシ樹
脂１５．７部と、テトラブロモビスフェノールＡとエピ
クロルヒドリンとの反応により得られたエポキシ当量が
３７５なるエポキシ樹脂２４．５部と、メチルテトラヒ
ドロ無水フタル酸２５．０部と、テトラブロモビスフェ
ノール八とエピクロルヒドリンとの反応により得られた
エポキシ当量が３７５なるエポキシ樹脂のメタクリレー
ト（７３％）とス瀉剤（ＣＩ−１）Ｏ１４ｏ９Ｐ
と、１．１−ビス（ｔ−ブチ
ルバーオキシ）３．３．５− トリメチルシクロヘキサ
ン０．６１部と、スチレンモノマー４．０部を混合せし
め、含浸用樹脂組成物（ｌ−１０）を調製した。Comparative Example 2 15.7 parts of a solvent-free liquid epoxy resin with an epoxy equivalent of 18B obtained by the reaction of bisphenol A and epichlorohydrin and an epoxy resin 24 with an epoxy equivalent of 375 obtained by the reaction of tetrabromobisphenol A and epichlorohydrin methacrylate (73%) of an epoxy resin with an epoxy equivalent of 375 obtained by the reaction of 25.0 parts of methyltetrahydrophthalic anhydride, 25.0 parts of methyltetrahydrophthalic anhydride, and 8 tetrabromobisphenol and epichlorohydrin (73%) and a scrubbing agent (CI-1) O14o9P, 0.61 part of 1.1-bis(t-butylbaroxy)3.3.5-trimethylcyclohexane, and 4.0 parts of styrene monomer were mixed to form a resin composition for impregnation (l-10). Prepared.
以下、プレス条件を１１０℃、接触圧で２．５分間、つ
いで１７０℃、１５Ｋｇ／−で１０分間とした以外は実
施例６と同様にして積層板を得、実施例６と同様に測定
した結果を表に示す。Hereinafter, a laminate was obtained in the same manner as in Example 6, except that the pressing conditions were 110°C and contact pressure for 2.5 minutes, then 170°C and 15 kg/- for 10 minutes, and measurements were made in the same manner as in Example 6. The results are shown in the table.
上記結果より、比較例１は本発明で使用した反応生成物
（Ｃ）の代わりに通常のビニルエステルポリマーの重合
性モノマー溶液を用い、重合性ビニル七ツマ−を除去し
てＢ−ステージ化する方法であり、ガラス転移温度が低
過ぎることがわかる。これに対し、実施例１〜５で得ら
れる本発明の積層板はガラス転移温度が高く、銅箔剥離
強度や眉間剥離強度も改良されていることがわかる。又
は、比較例２は本発明の反応性成物（Ｃ）の代わりに通
常のビニルエステルポリマーの重合性ビニルモノマー溶
液を用い、重合性ビニル七ツマー除去することなく、実
施例６と同様に短時間（２，５分）で部分硬化させた例
であるが、成形時の樹脂流出量が多く、厚み精度に劣り
、遅硬化性であり、かつガラス転移温度も十分でないこ
とがわかる。これに対し、実施例６〜８では、成形時の
樹脂流出量が少なく、厚み精度に優れ、速硬化性であり
、かつガラス転移温度が高く、銅箔剥離強度、眉間剥離
強度も改良されていることがわかる。From the above results, Comparative Example 1 uses a normal polymerizable monomer solution of vinyl ester polymer instead of the reaction product (C) used in the present invention, removes the polymerizable vinyl heptamer, and B-stages it. method, and it can be seen that the glass transition temperature is too low. On the other hand, it can be seen that the laminates of the present invention obtained in Examples 1 to 5 have high glass transition temperatures and improved copper foil peel strength and glabellar peel strength. Alternatively, in Comparative Example 2, a polymerizable vinyl monomer solution of a normal vinyl ester polymer was used instead of the reactive composition (C) of the present invention, and a short reaction was carried out in the same manner as in Example 6 without removing the polymerizable vinyl monomer. This is an example in which the resin was partially cured for a few minutes (2.5 minutes), but it can be seen that the amount of resin flowing out during molding was large, the thickness accuracy was poor, the curing was slow, and the glass transition temperature was not sufficient. On the other hand, in Examples 6 to 8, the amount of resin flowing out during molding was small, the thickness accuracy was excellent, the curing was fast, the glass transition temperature was high, and the copper foil peel strength and glabella peel strength were also improved. I know that there is.
［発明の効果Ｊ
本発明によれば、エポキシビニルエステルに多塩基酸無
水物を反応させた反応生成物（Ｃ）を用いたエポキシ樹
脂、多塩基酸無水物系の含浸用樹脂組成物を提供するこ
とができ、得られるプリプレグもタックフリーで柔軟性
を有し、作業性に優れるものであり、また、このプリプ
レグ等の中間材から得られる積層板は耐熱性に優れ、し
かも銅箔剥離強度、眉間剥離強度も改良できる。[Effect of the Invention J According to the present invention, an epoxy resin and a polybasic acid anhydride-based impregnating resin composition using a reaction product (C) obtained by reacting an epoxy vinyl ester with a polybasic acid anhydride are provided. The prepreg obtained is also tack-free, flexible, and has excellent workability.The laminate obtained from intermediate materials such as this prepreg has excellent heat resistance and copper foil peel strength. , the glabella peel strength can also be improved.
平成１年２月３日February 3, 1999
Claims (12)
、エポキシビニルエステルと多塩基酸無水物との反応生
成物（Ｃ）と、重合開始剤（Ｄ）を少なくとも含有し、
かつ液状にしたことを特徴とする含浸用樹脂組成物。(1) Contains at least an epoxy resin (A), a polybasic acid anhydride (B), a reaction product of an epoxy vinyl ester and a polybasic acid anhydride (C), and a polymerization initiator (D),
A resin composition for impregnation, characterized in that the resin composition is in a liquid state.
ないことを特徴とする請求項１記載の含浸用樹脂組成物
。(2) The resin composition for impregnation according to claim 1, which contains a liquid polymerizable crosslinking agent and no other solvent.
の６０％以上と多塩基酸無水物中の酸無水物基とを反応
して得られるハーフエステルであることを特徴とする請
求項１又は２記載の含浸用樹脂組成物。(3) Component (C) is a half ester obtained by reacting 60% or more of the hydroxyl groups in the epoxy vinyl ester with the acid anhydride groups in the polybasic acid anhydride, or 2. The impregnating resin composition according to 2.
を繊維質基材に含浸させた含浸繊維質基材を用いてプリ
プレグを製造することを特徴とする積層板用中間材の製
造方法。(4) Production of an intermediate material for a laminate, characterized in that a prepreg is produced using an impregnated fibrous base material obtained by impregnating a fibrous base material with the impregnating resin composition according to any one of claims 1 to 3. Method.
用した請求項２記載の含浸用樹脂組成物を繊維質基材に
含浸させてＢステージ化させかつ揮発性の重合性架橋剤
を揮発させてプリプレグを製造することを特徴とする積
層板用中間材の製造方法。(5) A fibrous base material is impregnated with the impregnating resin composition according to claim 2, in which a volatile polymerizable crosslinking agent is used as the liquid polymerizable crosslinking agent, and B-staged and volatile polymerizable crosslinking is performed. A method for producing an intermediate material for a laminate, the method comprising producing a prepreg by volatilizing an agent.
ることを特徴とする請求項５記載の積層板の中間材の製
造方法。(6) The method for producing an intermediate material for a laminate according to claim 5, wherein the remaining amount of the liquid polymerizable crosslinking agent is 4% by weight or less.
含浸させた複数の未乾燥含浸シートを形成し、これら未
乾燥含浸シートを重ね合わせ、かつこの重ね合わせ体の
両側にフィルムを重ね、加熱処理をして部分硬化させる
ことを特徴とする積層板用中間材の製造方法。(7) A plurality of undried impregnated sheets are formed by impregnating a fibrous base material with the resin composition for impregnation according to claim 2, and these undried impregnated sheets are stacked, and a film is placed on both sides of the stacked body. 1. A method for producing an intermediate material for a laminate, which comprises stacking and partially curing the intermediate materials by heat treatment.
用した請求項２記載の含浸用樹脂組成物を繊維質基材に
含浸させた複数の未乾燥含浸シートを形成し、これら未
乾燥含浸シートを重ね合わせ、上記重合性架橋剤を揮発
させてその含有量を８重量％以下にした重ね合わせ体の
両面に金属箔及びフィルムを少なくとも何れか一方を金
属箔にして重ね、加熱処理をして部分硬化させることを
特徴とする積層板用中間材の製造方法。(8) forming a plurality of undried impregnated sheets in which a fibrous base material is impregnated with the resin composition for impregnation according to claim 2, in which a volatile polymerizable crosslinking agent is used as the liquid polymerizable crosslinking agent; The undried impregnated sheets are stacked together, and the polymerizable crosslinking agent is volatilized to reduce the content to 8% by weight or less. Metal foil and film are stacked on both sides of the stack, with at least one of them being metal foil, and heated. A method for producing an intermediate material for a laminate, the method comprising processing and partially curing the intermediate material.
基材に含浸させかつタックフリーにした複数のタックフ
リー含浸シートを形成し、このタックフリー含浸シート
を積層したことを特徴とする積層板用中間材の製造方法
。(9) A fibrous base material is impregnated with the impregnating resin composition according to claim 1 or 2 to form a plurality of tack-free impregnated sheets, and the tack-free impregnated sheets are laminated. A method for manufacturing an intermediate material for laminates.
に含浸させ、この含浸繊維質基材を複数枚重ね合わせ、
加熱成形して得られることを特徴とする積層板の製造方
法。(10) Impregnating a fibrous base material with the impregnating resin composition according to claim 1, and stacking a plurality of sheets of the impregnated fibrous base material,
A method for producing a laminate, characterized in that it is obtained by thermoforming.
に含浸させ、この含浸繊維質基材を複数枚重ね合わせ、
加熱成形して得られることを特徴とする積層板の製造方
法。(11) Impregnating a fibrous base material with the impregnating resin composition according to claim 2, and stacking a plurality of sheets of the impregnated fibrous base material,
A method for producing a laminate, characterized in that it is obtained by thermoforming.
て加熱成形して得られることを特徴とする積層板の製造
方法。(12) A method for producing a laminate, which is obtained by thermoforming the intermediate material for a laminate according to any one of claims 4 to 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2374089A JPH02206614A (en) | 1989-02-03 | 1989-02-03 | Resin composition for impregnation and production of laminated board and intermediate material thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2374089A JPH02206614A (en) | 1989-02-03 | 1989-02-03 | Resin composition for impregnation and production of laminated board and intermediate material thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02206614A true JPH02206614A (en) | 1990-08-16 |
Family
ID=12118705
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2374089A Pending JPH02206614A (en) | 1989-02-03 | 1989-02-03 | Resin composition for impregnation and production of laminated board and intermediate material thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02206614A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH073122A (en) * | 1993-06-17 | 1995-01-06 | Nippon Steel Chem Co Ltd | Thermoplastic resin composition, cured material thereof and color filter material |
| JP2005247879A (en) * | 2004-03-01 | 2005-09-15 | Showa Highpolymer Co Ltd | Composition for fiber-reinforced composite material and its molding material |
-
1989
- 1989-02-03 JP JP2374089A patent/JPH02206614A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH073122A (en) * | 1993-06-17 | 1995-01-06 | Nippon Steel Chem Co Ltd | Thermoplastic resin composition, cured material thereof and color filter material |
| JP2005247879A (en) * | 2004-03-01 | 2005-09-15 | Showa Highpolymer Co Ltd | Composition for fiber-reinforced composite material and its molding material |
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