JPH0129816B2 - - Google Patents
Info
- Publication number
- JPH0129816B2 JPH0129816B2 JP15936988A JP15936988A JPH0129816B2 JP H0129816 B2 JPH0129816 B2 JP H0129816B2 JP 15936988 A JP15936988 A JP 15936988A JP 15936988 A JP15936988 A JP 15936988A JP H0129816 B2 JPH0129816 B2 JP H0129816B2
- Authority
- JP
- Japan
- Prior art keywords
- epoxy
- resin
- anhydride
- parts
- resin composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 239000003822 epoxy resin Substances 0.000 claims description 42
- 229920000647 polyepoxide Polymers 0.000 claims description 42
- 239000012778 molding material Substances 0.000 claims description 21
- 239000011342 resin composition Substances 0.000 claims description 21
- 239000004593 Epoxy Substances 0.000 claims description 18
- 229920005989 resin Polymers 0.000 claims description 17
- 239000011347 resin Substances 0.000 claims description 17
- 150000007519 polyprotic acids Polymers 0.000 claims description 14
- 239000012779 reinforcing material Substances 0.000 claims description 11
- 150000008065 acid anhydrides Chemical class 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 5
- 239000004850 liquid epoxy resins (LERs) Substances 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 229920001567 vinyl ester resin Polymers 0.000 claims description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 15
- 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 15
- -1 etc.) Chemical compound 0.000 description 11
- 230000000704 physical effect Effects 0.000 description 11
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 10
- 229920006241 epoxy vinyl ester resin Polymers 0.000 description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 9
- 239000002253 acid Substances 0.000 description 9
- 239000011521 glass Substances 0.000 description 9
- 239000011159 matrix material Substances 0.000 description 9
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 7
- 229920003986 novolac Polymers 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 239000003505 polymerization initiator Substances 0.000 description 6
- 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 4
- 229920000049 Carbon (fiber) Polymers 0.000 description 4
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 4
- 238000005452 bending Methods 0.000 description 4
- 239000004917 carbon fiber Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 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
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 4
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 4
- 239000004744 fabric Substances 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- 239000003365 glass fiber Substances 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 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 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- 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 3
- 229930185605 Bisphenol Natural products 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 3
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 3
- 235000011613 Pinus brutia Nutrition 0.000 description 3
- 241000018646 Pinus brutia Species 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 3
- 229910052794 bromium Inorganic materials 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000006835 compression Effects 0.000 description 3
- 238000007906 compression Methods 0.000 description 3
- 238000000748 compression moulding Methods 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
- 239000007788 liquid Substances 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- 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 2
- RHUYHJGZWVXEHW-UHFFFAOYSA-N 1,1-Dimethyhydrazine Chemical compound CN(C)N RHUYHJGZWVXEHW-UHFFFAOYSA-N 0.000 description 2
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-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
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- 239000004760 aramid Substances 0.000 description 2
- 229920003235 aromatic polyamide Polymers 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 150000005846 sugar alcohols Polymers 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
- LTVUCOSIZFEASK-MPXCPUAZSA-N (3ar,4s,7r,7as)-3a-methyl-3a,4,7,7a-tetrahydro-4,7-methano-2-benzofuran-1,3-dione Chemical compound C([C@H]1C=C2)[C@H]2[C@H]2[C@]1(C)C(=O)OC2=O LTVUCOSIZFEASK-MPXCPUAZSA-N 0.000 description 1
- KNDQHSIWLOJIGP-UMRXKNAASA-N (3ar,4s,7r,7as)-rel-3a,4,7,7a-tetrahydro-4,7-methanoisobenzofuran-1,3-dione Chemical compound O=C1OC(=O)[C@@H]2[C@H]1[C@]1([H])C=C[C@@]2([H])C1 KNDQHSIWLOJIGP-UMRXKNAASA-N 0.000 description 1
- 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
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- AYAUWVRAUCDBFR-ARJAWSKDSA-N (z)-4-oxo-4-propoxybut-2-enoic acid Chemical compound CCCOC(=O)\C=C/C(O)=O AYAUWVRAUCDBFR-ARJAWSKDSA-N 0.000 description 1
- WBYWAXJHAXSJNI-VOTSOKGWSA-M .beta-Phenylacrylic acid Natural products [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 description 1
- 150000005208 1,4-dihydroxybenzenes Chemical class 0.000 description 1
- XSZYESUNPWGWFQ-UHFFFAOYSA-N 1-(2-hydroperoxypropan-2-yl)-4-methylcyclohexane Chemical compound CC1CCC(C(C)(C)OO)CC1 XSZYESUNPWGWFQ-UHFFFAOYSA-N 0.000 description 1
- HXKKHQJGJAFBHI-UHFFFAOYSA-N 1-aminopropan-2-ol Chemical compound CC(O)CN HXKKHQJGJAFBHI-UHFFFAOYSA-N 0.000 description 1
- FBHPRUXJQNWTEW-UHFFFAOYSA-N 1-benzyl-2-methylimidazole Chemical compound CC1=NC=CN1CC1=CC=CC=C1 FBHPRUXJQNWTEW-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- AHDSRXYHVZECER-UHFFFAOYSA-N 2,4,6-tris[(dimethylamino)methyl]phenol Chemical compound CN(C)CC1=CC(CN(C)C)=C(O)C(CN(C)C)=C1 AHDSRXYHVZECER-UHFFFAOYSA-N 0.000 description 1
- FOYHNROGBXVLLX-UHFFFAOYSA-N 2,6-diethylaniline Chemical compound CCC1=CC=CC(CC)=C1N FOYHNROGBXVLLX-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
- VVHFXJOCUKBZFS-UHFFFAOYSA-N 2-(chloromethyl)-2-methyloxirane Chemical compound ClCC1(C)CO1 VVHFXJOCUKBZFS-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
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-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
- 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
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 2-phenyl-1h-imidazole Chemical compound C1=CNC(C=2C=CC=CC=2)=N1 ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 0.000 description 1
- FUOZJYASZOSONT-UHFFFAOYSA-N 2-propan-2-yl-1h-imidazole Chemical compound CC(C)C1=NC=CN1 FUOZJYASZOSONT-UHFFFAOYSA-N 0.000 description 1
- LLEASVZEQBICSN-UHFFFAOYSA-N 2-undecyl-1h-imidazole Chemical compound CCCCCCCCCCCC1=NC=CN1 LLEASVZEQBICSN-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- DXIJHCSGLOHNES-UHFFFAOYSA-N 3,3-dimethylbut-1-enylbenzene Chemical compound CC(C)(C)C=CC1=CC=CC=C1 DXIJHCSGLOHNES-UHFFFAOYSA-N 0.000 description 1
- 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
- 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
- QIKYZXDTTPVVAC-UHFFFAOYSA-N 4-Aminobenzamide Chemical compound NC(=O)C1=CC=C(N)C=C1 QIKYZXDTTPVVAC-UHFFFAOYSA-N 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- OECTYKWYRCHAKR-UHFFFAOYSA-N 4-vinylcyclohexene dioxide Chemical compound C1OC1C1CC2OC2CC1 OECTYKWYRCHAKR-UHFFFAOYSA-N 0.000 description 1
- VQVIHDPBMFABCQ-UHFFFAOYSA-N 5-(1,3-dioxo-2-benzofuran-5-carbonyl)-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)=O)=C1 VQVIHDPBMFABCQ-UHFFFAOYSA-N 0.000 description 1
- HOOIIRHGHALACD-UHFFFAOYSA-N 5-(2,5-dioxooxolan-3-yl)-3-methylcyclohex-3-ene-1,2-dicarboxylic acid Chemical compound C1C(C(O)=O)C(C(O)=O)C(C)=CC1C1C(=O)OC(=O)C1 HOOIIRHGHALACD-UHFFFAOYSA-N 0.000 description 1
- ZYUVGYBAPZYKSA-UHFFFAOYSA-N 5-(3-hydroxybutan-2-yl)-4-methylbenzene-1,3-diol Chemical compound CC(O)C(C)C1=CC(O)=CC(O)=C1C ZYUVGYBAPZYKSA-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
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 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
- 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
- 229920003043 Cellulose 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
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-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
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- BGNXCDMCOKJUMV-UHFFFAOYSA-N Tert-Butylhydroquinone Chemical compound CC(C)(C)C1=CC(O)=CC=C1O BGNXCDMCOKJUMV-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical 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
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- UTOVMEACOLCUCK-PLNGDYQASA-N butyl maleate Chemical compound CCCCOC(=O)\C=C/C(O)=O UTOVMEACOLCUCK-PLNGDYQASA-N 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 229930016911 cinnamic acid Natural products 0.000 description 1
- 235000013985 cinnamic acid Nutrition 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 239000011889 copper foil 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
- 229930003836 cresol Natural products 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 238000007278 cyanoethylation reaction Methods 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
- NHADDZMCASKINP-HTRCEHHLSA-N decarboxydihydrocitrinin Natural products C1=C(O)C(C)=C2[C@H](C)[C@@H](C)OCC2=C1O NHADDZMCASKINP-HTRCEHHLSA-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
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-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
- 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
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- BEFDCLMNVWHSGT-UHFFFAOYSA-N ethenylcyclopentane Chemical compound C=CC1CCCC1 BEFDCLMNVWHSGT-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- NKHAVTQWNUWKEO-UHFFFAOYSA-N fumaric acid monomethyl ester Natural products COC(=O)C=CC(O)=O NKHAVTQWNUWKEO-UHFFFAOYSA-N 0.000 description 1
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 1
- 238000001879 gelation Methods 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
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 229940049920 malate Drugs 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N malic acid Chemical compound OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- NKHAVTQWNUWKEO-IHWYPQMZSA-N methyl hydrogen fumarate Chemical compound COC(=O)\C=C/C(O)=O NKHAVTQWNUWKEO-IHWYPQMZSA-N 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
- VYKXQOYUCMREIS-UHFFFAOYSA-N methylhexahydrophthalic anhydride Chemical compound C1CCCC2C(=O)OC(=O)C21C VYKXQOYUCMREIS-UHFFFAOYSA-N 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
- 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
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 125000005461 organic phosphorous group Chemical group 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001451 polypropylene glycol 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
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 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
- 230000002787 reinforcement Effects 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229940075582 sorbic acid Drugs 0.000 description 1
- 235000010199 sorbic acid Nutrition 0.000 description 1
- 239000004334 sorbic acid Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-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
- 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Reinforced Plastic Materials (AREA)
Description
本発明は必須の成分として特定の硬化性樹脂と
繊維質強化材とを含んで成る成形材料を用いる積
層板の製造方法に関する。
一般に、エポキシ樹脂とガラス繊維や炭素繊維
などの繊維質強化材とより成るエポキシ・プリプ
レグは、エポキシ樹脂の耐熱性、耐薬品性、耐水
性、密着性、電気特性および機械特性に優れ、し
かも硬化収縮が小さいこと、他方、プリプレグ自
体が成形材料として取り扱い易いことから、プリ
ント回路基板や航空、宇宙ないしは車輛関連の構
造材料として用いられている。
これらのうち、プリント回路基板用のエポキ
シ・プリプレグは、基材としてはガラス繊維が、
一方、樹脂としては溶剤を含んだエポキシ樹脂
が、主として用いられているが、経済性の改良と
低公害化とのために無溶剤化が望まれている。
ところで、無溶剤型エポキシ樹脂マトリツクス
としてはポリアミン硬化エポキシ樹脂系、ジシア
ンジアミド硬化エポキシ樹脂系、二塩基酸ヒドラ
ジツト硬化エポキシ樹脂系、多塩基酸無水物硬化
エポキシ樹脂系またはエポキシ基を開環させて硬
化せしめる、いわゆる開環重合硬化エポキシ樹脂
系などが挙げられるが、かかるマトリツクスとし
てのエポキシ樹脂系に望まれる要件は、均一であ
ること、繊維質強化材に含浸される樹脂が、まず
含浸用粘度に適合して充分に低粘度であること、
次にポツトライフの長いこと、しかも成形時にお
ける硬化速度が大であることである。
しかしながら、一般に、ポリアミン硬化エポキ
シ樹脂系の中で、脂肪族ポリアミン硬化剤とする
系では樹脂のポツトライフも短く、また芳香族ポ
リアミン硬化系ではポツトライフは長いものの、
樹脂系が不均一であつたり、均一であつても粘度
が高かつたりして好ましくない。
ジシアンジアミド硬化系や二塩基酸ヒドラジツ
ト硬化系では、硬化剤と樹脂とが不均一な系とな
り易く、加えて繊維質強化材の含浸にさいしての
低粘度化も困難であつて好ましくない。
また、エポキシ基の開環重合による硬化系で
は、繊維質強化材の含浸に必要な低粘度化が困難
であつて好ましくない。
さらに、多塩基酸無水物硬化系の中で、かかる
エポキシ樹脂用の硬化剤として広く用いられてい
る液状酸無水物を使用した場合には、比較的低粘
度物を与え、しかも樹脂とは均一に混ざり合い、
その上に長いポツトライフのものが得られるの
で、当該硬化系はマトリツクスとして好ましいも
のといえるが、それでも繊維質強化材の含浸に好
適なように充分に低い粘度のものとするには、特
に低粘度液状エポキシ樹脂のみに限られるし、諸
物性上からすれば好ましいものといえる高粘度ま
たは固形のエポキシ樹脂を使用するには、こうし
た低粘度化のために、いわゆる希釈剤を併用する
ことが絶対に必要になつてくる。
ところが、かかる希釈剤の使用によれば低粘度
化こそ可能とはなるけれども、その反面で、耐熱
性、耐湿性および機械特性などといつた物性が悪
化することになるし、他方、低粘度液状エポキシ
樹脂にしても、これと液状多塩基酸無水物との樹
脂組成物をマトリツクスとして用いた場合には、
一般に、反応速度が小さいために加熱圧縮成形時
の溶融粘度が低くなり過ぎてマトリツクスが流出
して歩留も悪く、しかも加熱圧縮成形時間も長く
なつて生産性が悪くなるといつた難点がある。
しかるに、本発明者らは上述した如き技術的背
景から、多塩基酸無水物硬化系、とくに無溶剤型
の多塩基酸無水物硬化エポキシ樹脂系をマトリツ
クスとして用いた積層板の製造方法について鋭意
研究した結果、多塩基酸無水物硬化エポキシ樹脂
系とエポキシビニルエステル樹脂とをマトリツク
スに用いると、従来の多塩基酸無水物硬化エポキ
シ樹脂をマトリツクスとする際の難点が悉く解消
され、作業性と成形性が良好で、優れた諸物性と
を有する積層板が容易に得られることを見出し
て、本発明を完成させるに到つた。
すなわち、本発明は平均エポキシ当量が100〜
400なる範囲にある無溶剤液状エポキシ樹脂に多
塩基酸無水物および硬化促進剤を配合させて成る
エポキシ樹脂組成物(A)と、エポキシビニルエステ
ル樹脂(B)とを、(A)対(B)の重量比が95/5〜30/70
となるように配合させて成る樹脂組成物()
と、繊維質強化材()とを必須の成分として含
んで成る、成形材料()を用いることを特徴と
する積層板の製造方法を提供するものであり、上
記樹脂(B)には、必須により重合開始剤を配合させ
て樹脂組成物の形で用いてもよい。
本発明でいう上記エポキシ樹脂組成物(A)を構成
するエポキシ樹脂としては代表的なものを挙げれ
ば、エピクロルヒドリンまたはβ―メチルエピク
ロルヒドリンとビスフエノールA、ビスフエノー
ルFまたはビスフエノールSとから得られるエポ
キシ樹脂;フエノールまたはアルキルフエノー
ル・ノボラツク樹脂のポリグリシジルエーテル
類;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
パンまたはビスフエノールA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、ヘキサヒドロフタル酸または
ダイマー酸の如きポルカルボン酸のポリグリシジ
ルエステル類;シクロヘキセンまたはその誘導体
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、1―エポキシエチル―3,4―エ
ポキシシクロヘキサンなど)、シクロペンタジエ
ンもしくはジシクロペンタジエンまたはそれらの
誘導体を過酢酸などでエポキシ化させることによ
り得られるシクロペンタジエン系のエポキシ化合
物類(シクロペンタジエンオキサイド、ジシクロ
ペンタジエンオキサイド、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
ドあるいはテトラブロモビスフエノールAのジグ
リシジルエーテルまたはヒドロキシ安息香酸のグ
リシジルエーテルエステルなどであるが、それら
のうち、当該エポキシ樹脂として用いられるもの
は、それ自体単独で平均エポキシ当量が100〜400
なる範囲内にあるもの、あるいは二種またはそれ
以上の混合物の形でこの範囲のエポキシ当量とな
るように適宜組み合わされたものであつて、かつ
常温で無溶剤液状のものである。
次いで、本発明でいう多塩基酸無水物として代
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、
メチルヘ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、無水ナジツク酸、無水メチ
ルナジツク酸、無水トリメリツト酸、無水ピロメ
リツト酸、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、無水クロレンデイツク酸、無水ベンゾ
フエノンテトラカルボン酸、無水シクロペンタテ
トラカルボン酸、5―(2,5―ジオキソテトラ
ヒドロフリル)―3―メチル―3―シクロヘキセ
ン―1,2―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またはグリセリントリ
メリテート無水物などであるが、これらは単独
で、あるいは二種以上の混合の形で用いられる。
また、本発明でいう硬化促進剤として代表的な
ものには、ジエチルアミン、トリエチルアミン、
ジイソプロピルアミン、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、メチルジエタノールアミ
ン、モノイソプロパノールアミン、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―ベンジルエタノールア
ミン、2,4,6―トリス―ジメチルアミノメチ
ルフエノールもしくはそのトリ―2―エチルヘキ
シル酸塩、2―ジメチルアミノメチルフエノー
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またはそれとフエノール、2
―エチルヘキサン酸、オレイン酸、ジフエニル亜
燐酸もしくは有機含燐酸類との塩類の如き各種ア
ミン類;2―メチルイミダゾール、2―イソプロ
ピルイミダゾール、2―ウンデシルイミダゾー
ル、2―フエニルイミダゾール、2―フエニル―
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Co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
アノエチレーシヨン・タイプのイミダゾールまた
はそれらとトリメツ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;
BF3―モノエタノールアミン、BF3―ベンジルア
ミン、BF3―ジメチルアニリン、BF3―トリエチ
ルアミン、BF3―n―ヘキシルアミン、BF3―
2,6―ジエチルアニリン、BF3―アニリンもし
くはBF3―ピペリジンの如きBF3―アミン錯体
類;1,1―ジメチルヒドラジンを出発原料とす
るアミンイミド化合物;トリフエニルホスフアイ
トの如き燐化合物またはオクチル酸錫の如き有機
酸金属塩類などがある。
さらに、本発明でいう前記エポキシビニルエス
テル樹脂とは、ビスフエノール・タイプのエポキ
シ樹脂またはノボラツク・タイプのエポキシ樹脂
などの如き前掲した如き各種エポキシ樹脂の単
独、とくにこれらビスフエノール・タイプまたは
ノボラツク・タイプの樹脂のそれぞれ単独と、あ
るいは各種タイプの混合物、とくにビスフエノー
ル・タイプとノボラツク・タイプとの両樹脂の混
合物と、下記する如き不飽和一塩基酸とを、エス
テル化触媒の存在下で反応させて得られるエポキ
シビニルエステルを、必要ならば重合性ビニルモ
ノマーに溶解せしめた樹脂を指称するものであ
る。
ここにおいて、不飽和一塩基酸として代表的な
ものにはアクリル酸、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、モノブチルマレート、ソルビン酸または
モノ(2―エチルヘキシル)マレートなどがある
が、これらは単独でも二種以上の混合においても
用いることができる。
そして、これらエポキシ樹脂と不飽和一塩基酸
との反応は従来公知の方法により行なわれ、かく
して得られるエポキシビニルエステル樹脂は、必
要ならば、慣用の重合性ビニルモノマーに溶解さ
せて安定な樹脂溶液とされるが、重合性ビニルモ
ノマーのうちでも代表的なものとしてはスチレ
ン、ビニルトルエン、t―ブチルスチレン、クロ
ルスチレンもしくはジビニルベンゼンの如きスチ
レンおよびその誘導体;2―エチルヘキシル(メ
タ)アクリレート、ラウリル(メタ)アクリレー
ト、2―ヒドロキシエチル(メタ)アクリレート
もしくは2―ヒドロキシプロピル(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;また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
サンジオールジ(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物
として使用される。
本発明における前記樹脂(B)を構成するエポキシ
ビニルエステル樹脂を調製するにさいしては、樹
脂調製中のゲル化を防止する目的や、生成樹脂の
保存安定性あるいは硬化性の調整の目的で重合禁
止剤を使用することが推奨されるが、かかる重合
禁止剤として代表的なものを挙げればハイドロキ
ノン、p―t―ブチルカテコール、モノ―t―ブ
チルハイドロキノンの如きハイドロキノン類;ハ
イドロキノンモノメチルエーテル、ジ―t―p―
クレゾールの如きフエノール類;p―ベンゾキノ
ン、ナフトキノン、p―トルキノンの如きキノン
類;またはナフテン酸銅の如き銅塩などである。
ところで、このようにして得られる(B)成分樹脂
は触媒を使用することなく、単に加熱するだけで
充分硬化させることもできるが、必要ならば、ベ
ンゾイルパーオキサイド、p―メンタンハイドロ
パーオキサイド、t―ブチルパーベンゾエート、
1,1―ジ―t―ブチルパーオキシ―3,3,5
―トリメチルシクロヘキサノンなどの有機過酸化
物を重合開始剤として用いることができ、こうし
た場合には、本発明における当該(B)成分は樹脂と
重合開始剤とから成る樹脂組成物として観念でき
る。
そして、特定の平均エポキシ当量の範囲内にあ
る無溶剤液状エポキシ樹脂に多塩基酸無水物およ
び硬化促進剤を配合させて成る前記のエポキシ樹
脂組成物(A)と、エポキシビニルエステル樹脂(B)と
の、さらに必要ならば、重合開始剤をも加えた形
の樹脂組成物(B)との重量比率は、要求される特性
や作業上の条件などによつて適宜選定すればよい
が、(B)成分の割合が大きくなりすぎるときは、エ
ポキシビニルエステル樹脂自体の物性に近いもの
となり、(A)成分たる多塩基酸無水物硬化エポキシ
樹脂の特性である、たとえば硬化収縮が小さいと
いう良さが損われる結果となる。
したがつて、両成分(A)対(B)の重量比は95/5〜
30/70、好ましくは95/5〜70/30なる範囲が適
当である。
成分(A)と成分(B)とは、それぞれ別々に調製され
たのち混合してもよいし、あるいは成分(A)中のエ
ポキシ樹脂または多塩基酸無水物に、まず成分(B)
たるエポキシビニルエステル樹脂、必要ならば重
合開止剤を混合したのち、次いで残余の(A)成分化
合物を加えるという方法も採れるので、各成分化
合物の配合順序は限定されるものではない。
また、樹脂組成物()中には、内部離型剤ま
たは顔料などの慣用の添加剤を添加することも可
能である。
他方、前記()成分たる繊維状強化材として
代表的なものを挙げれば、ガラス繊維、炭素繊維
または芳香族ポリアミド系繊維などであるが、こ
れらのうちまずガラス繊維としては、その原料面
から、E―グラス、C―グラス、A―グラスおよ
びS―グラスなどが存在しているが、本発明にお
いてはいずれの種類のものも適用できる。
次に、炭素繊維としてはポリアクリロニトリル
系繊維、セルローズ系繊維、ピツチ、芳香族炭化
水素またはカーボンブラツクなどを原料として製
造されるものが挙げられるし、また芳香族ポリア
ミド系繊維とは多官能の芳香族アミンと芳香族多
塩基酸との反応によりアミド結合を有する重合体
から作られるものであり、代表的な重合体として
は、ポリ―p―フエニレンテトラフタルアミドま
たはポリ―p―アミノベンズアミドなどが挙げら
れる。
これらの繊維質強化材()は、その形状によ
りロービング、チヨツプドストランドマツト、コ
ンテイニアスマツト、クロス、ロービングクロ
ス、サーフエシングマツトおよびチヨツプドスト
ランドがあるが、上掲した如き種類や形状は、目
的とする形成物の用途および性能により適宜選択
されるものであつて、必要によつては二以上の種
類または形状からの混合使用であつてもよい。
本発明で用いる成形材料()を得るにさいし
て、繊維質強化材()の容積比率は成形材料
()の30〜70%なる範囲内が適当である。
そして、本発明で用いる成形材料()を得る
には、室温またはそれよりも高い温度で前記強化
材()に前記樹脂組成物()を含浸させてシ
ート状にすればよく、更に必要ならば離型用シー
トでサンドイツチ物となし、同様に室温またはそ
れよりも高い温度で熟成させてB―ステージ状態
まで増粘せしめるという方法がある。
かかる手法で得られた本発明で用いる成形材料
()は、次いで加熱圧縮成形させることにより
所望の成形物を与えるが、このさい、必要によつ
ては、成形用金型から離型したのち、さらに後硬
化を施すこともできる。
次に、本発明を実施例および比較例により具体
的に説明する。以下において、部および%は特に
断りのない限りは、すべて重量基準であるものと
する。
実施例 1
ビスフエノール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190なるエポキ
シ樹脂16.9部、テトラブロモビスフエノール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26.5部、メチル
テトラヒドロ無水フタル酸26.6部、ベンジルジメ
チルアミン0.7部、テトラブロモビスフエノール
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なるエポキシ樹脂のメタクリ
レート(60%)とスチレンモノマー(40%)とよ
り成るエポキシビニルエステル樹脂30部および
「パーヘキサ3M」(日本油脂(株)製の重合開始剤)
0.6部を混合せしめて樹脂組成物を調製した。こ
のものの粘度は650cpsであり、臭素含有率は20%
であつた。
次いで、この樹脂組成物の40部をガラスクロス
の60部に含浸させたのち40℃で約30時間熟成せし
めて、タツク・フリーなる成形材料(−1)を
得た。
しかるのち、この成形材料(−1)の9枚と
銅箔とを重ねて40Kg/cm2なる圧力下に160℃で30
分間加熱圧縮を行なつた。
かくして得られた銅張積層板についての諸物性
を第1表に示す。
比較例 1
ビスフエノール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190なるエポキ
シ樹脂の20.8部、テトラブロモビスフエノール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なるエポキシ樹脂の42.2部、メ
チルテトラヒドロ無水フタル酸の37.0部およびベ
ンジルジメチルアミンの0.6部を混合して樹脂組
成物を調製した。
ここに得られた粘度が2100cpsで、臭素含有率
が20%なる樹脂組成物の40部を60部のガラスクロ
スに含浸させたのち、40℃で約40時間熟成せしめ
て、タツクフリーなる成形材料(−1′)を得
た。
以後、この成形材料(−1′)を用いるように
変更した他は、実施例1と同様にして、比較対照
用の銅張積層板を得た。
この積層板についての諸物性の結果は第1表に
示す。
比較例 2
この例は、難燃性プリント回路基板用として慣
用されている、溶剤型ジシアンジアミド硬化エポ
キシ樹脂系を用いた、比較対照用の銅張積層板の
作製についてのものである。
まず、ビスフエノールAとテトラブロモビスフ
エノールAとエピクロルヒドリンとを反応させて
得られる、臭素含有率が21%でエポキシ当量が
485なるエポキシ樹脂のメチルエチルケトン溶液
(不揮発分=80%)の125部と、アセトンの34部
と、別に4部のジシアンジアミドおよび0.2部の
ジメチルベンジルアミンを30部のメチルセロソル
ブに溶解させて得られた硬化剤溶液とを混合して
樹脂組成物を得た。
次いで、この樹脂組成物をガラスクロスに含浸
させたのち、160℃で5分間熟成させて、タツク
フリーなる成形材料(−2′)を得た。
以後、加熱圧縮時間を1時間に変更して本例の
成形材料(−2′)を用いた他は、実施例1と同
様にして銅張積層板を得た。
この積層板についての諸物性を第1表に示す。
The present invention relates to a method for producing a laminate using a molding material containing a specific curable resin and a fibrous reinforcing material as essential components. In general, epoxy prepregs made of epoxy resin and fibrous reinforcing materials such as glass fibers and carbon fibers have excellent heat resistance, chemical resistance, water resistance, adhesion, electrical properties, and mechanical properties of epoxy resins, and also harden. Because of its low shrinkage and the fact that prepreg itself is easy to handle as a molding material, it is used as a structural material for printed circuit boards, aviation, space, and vehicles. Among these, epoxy prepreg for printed circuit boards uses glass fiber as the base material.
On the other hand, epoxy resins containing solvents are mainly used as resins, but solvent-free resins are desired in order to improve economic efficiency and reduce pollution. By the way, as a solvent-free epoxy resin matrix, polyamine-cured epoxy resins, dicyandiamide-cured epoxy resins, dibasic acid hydrazide-cured epoxy resins, polybasic acid anhydride-cured epoxy resins, or cured by ring-opening of epoxy groups are used. , so-called ring-opening polymerization cured epoxy resin systems, etc., but the requirements for the epoxy resin system as such a matrix are that it be uniform, and that the resin impregnated into the fibrous reinforcing material must first meet the viscosity for impregnation. and have a sufficiently low viscosity;
Secondly, it has a long pot life and also has a high curing speed during molding. However, among polyamine-cured epoxy resin systems, those that use an aliphatic polyamine curing agent generally have a short pot life, while aromatic polyamine-cured systems have a long pot life.
This is not preferable because the resin system is non-uniform, or even if it is uniform, the viscosity is high. In dicyandiamide curing systems and dibasic acid hydrazide curing systems, the curing agent and resin tend to be non-uniform systems, and in addition, it is difficult to reduce the viscosity when impregnating the fibrous reinforcing material, which is undesirable. In addition, a curing system based on ring-opening polymerization of an epoxy group is not preferred because it is difficult to reduce the viscosity necessary for impregnating the fibrous reinforcing material. Furthermore, among polybasic acid anhydride curing systems, when a liquid acid anhydride, which is widely used as a curing agent for such epoxy resins, is used, it gives a relatively low viscosity product and is uniform in composition with the resin. mixed with,
The curing system is preferred as a matrix because of its long pot life, but it still requires a particularly low viscosity to be suitable for impregnating fibrous reinforcements. In order to use high viscosity or solid epoxy resins, which are limited to liquid epoxy resins and are preferred from the viewpoint of various physical properties, it is absolutely necessary to use a so-called diluent in order to lower the viscosity. It becomes necessary. However, although the use of such diluents makes it possible to lower the viscosity, on the other hand, physical properties such as heat resistance, moisture resistance, and mechanical properties deteriorate; Even when using epoxy resin, when a resin composition of this and liquid polybasic acid anhydride is used as a matrix,
In general, because the reaction rate is low, the melt viscosity during hot compression molding becomes too low, causing the matrix to flow out, resulting in a poor yield, and furthermore, the hot compression molding time becomes longer, resulting in poor productivity. However, based on the technical background as described above, the present inventors have conducted extensive research into a method for producing a laminate using a polybasic acid anhydride curing system, particularly a solvent-free polybasic acid anhydride curing epoxy resin system, as a matrix. As a result, when a polybasic acid anhydride-cured epoxy resin system and an epoxy vinyl ester resin are used as a matrix, all the difficulties associated with using a conventional polybasic acid anhydride-cured epoxy resin as a matrix are solved, and workability and moldability are improved. The present inventors have discovered that a laminate having good properties and excellent physical properties can be easily obtained, and have completed the present invention. That is, in the present invention, the average epoxy equivalent is 100 to
An epoxy resin composition (A) prepared by blending a polybasic acid anhydride and a curing accelerator with a solvent-free liquid epoxy resin in the range of 400 and an epoxy vinyl ester resin (B), ) weight ratio is 95/5 to 30/70
A resin composition () that is blended so that
and a fibrous reinforcing material () as essential components. It may be used in the form of a resin composition by incorporating a polymerization initiator therein. Typical epoxy resins constituting the epoxy resin composition (A) in the present invention include epoxy resins obtained from epichlorohydrin or β-methylepichlorohydrin and bisphenol A, bisphenol F, or bisphenol S. Resin; polyglycidyl ethers of phenol or alkylphenol novolac resin; ethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol, neopentyl glycol, glycerin, trimethylolethane, trimethylolpropane or bisphenol A, ethylene oxide or propylene oxide Polyglycidyl ethers of polyhydric alcohols such as adducts; polyglycidyl esters of polycarboxylic acids such as adipic acid, phthalic acid, hexahydrophthalic acid or dimer acid; by epoxidizing cyclohexene or its derivatives with peracetic acid etc. The resulting cyclohexene-based epoxy compounds (3,
4-epoxy-6-methyl-cyclohexyl-
3,4-epoxy-6-methylcyclohexanecarboxylate, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 1-epoxyethyl-3,4-epoxycyclohexane, etc.), cyclopentadiene or dicyclopentadiene or cyclopentadiene-based epoxy compounds (cyclopentadiene oxide, dicyclopentadiene oxide, 2,3-epoxycyclopentyl ether, etc.) obtained by epoxidizing their derivatives with peracetic acid, limonene dioxide, or tetrabromobis These include diglycidyl ether of phenol A or glycidyl ether ester of hydroxybenzoic acid, among which the ones used as the epoxy resin have an average epoxy equivalent of 100 to 400.
or in the form of a mixture of two or more of them, appropriately combined so as to have an epoxy equivalent within this range, and which is a solvent-free liquid at room temperature. Typical polybasic acid anhydrides in the present invention include phthalic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride,
Methylhexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, nadic anhydride, methyl nadic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, succinic anhydride, itaconic anhydride, citraconic anhydride, dodecenyl succinic anhydride, Chlorendic acid anhydride, benzophenonetetracarboxylic anhydride, cyclopentatetracarboxylic anhydride, 5-(2,5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexene-1,2-dicarboxylic acid, ethylene glycol bistri These include mellitate anhydride and glycerin trimellitate anhydride, and these may be used alone or in the form of a mixture of two or more. In addition, typical curing accelerators used in the present invention include diethylamine, triethylamine,
diisopropylamine, monoethanolamine,
Diethanolamine, triethanolamine, methylethanolamine, methyldiethanolamine, monoisopropanolamine, nonylamine, dimethylaminopropylamine, diethylaminopropylamine, α-benzylethanolamine, 2,4,6-tris-dimethylaminomethylphenol or its tri- 2-ethylhexylate, 2-dimethylaminomethylphenol, pyridine, piperidine, N-aminopropylmorpholine, 1,8-diazabicyclo(5,4,
0) Undecene-7 or it and phenol, 2
- Various amines such as ethylhexanoic acid, oleic acid, diphenylphosphous acid or salts with organic phosphorous acids; 2-methylimidazole, 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 Co, cyanoethylation type imidazole obtained by reacting 2-methylimidazole with acrylonitrile, or with them. imidazoles such as adducts with trimethic acid or reactants with dicyandiamide;
BF 3 -monoethanolamine, BF 3 -benzylamine, BF 3 -dimethylaniline, BF 3 -triethylamine, BF3 -n -hexylamine, BF 3 -
BF 3 -amine complexes such as 2,6-diethylaniline, BF 3 -aniline or BF 3 -piperidine; amine imide compounds starting from 1,1-dimethylhydrazine; phosphorus compounds such as triphenylphosphite or octylic acid Examples include organic acid metal salts such as tin. Furthermore, the epoxy vinyl ester resin as used in the present invention refers to the above-mentioned various epoxy resins alone, such as bisphenol type epoxy resins or novolac type epoxy resins, and particularly to these bisphenol type or novolac type epoxy resins. Each of these resins alone or a mixture of various types, in particular a mixture of both bisphenol type and novolak type resins, is reacted with an unsaturated monobasic acid as described below in the presence of an esterification catalyst. This refers to a resin obtained by dissolving the epoxy vinyl ester obtained by dissolving in a polymerizable vinyl monomer, if necessary. Here, typical unsaturated monobasic acids include acrylic acid, methacrylic acid, cinnamic acid, crotonic acid, monomethyl maleate, monopropyl maleate, monobutyl maleate, sorbic acid, and mono(2-ethylhexyl). These include malate, which can be used alone or in combination of two or more. The reaction between these epoxy resins and unsaturated monobasic acids is carried out by a conventionally known method, and if necessary, the epoxy vinyl ester resin obtained in this way can be dissolved in a conventional polymerizable vinyl monomer to form a stable resin solution. However, typical examples of polymerizable vinyl monomers include styrene and its derivatives such as styrene, vinyltoluene, t-butylstyrene, chlorostyrene, or divinylbenzene; 2-ethylhexyl (meth)acrylate, lauryl ( Low boiling ester monomers of (meth)acrylic acid such as meth)acrylate, 2-hydroxyethyl (meth)acrylate or 2-hydroxypropyl (meth)acrylate; or trimethylolpropane tri(meth)acrylate, diethylene glycol di(meth)acrylate acrylate, (meth)acrylates of polyhydric alcohols such as 1,4-butanediol di(meth)acrylate or 1,6-hexanediol di(meth)acrylate, etc., which may be used alone or in combination of two or more kinds. Used as a mixture. When preparing the epoxy vinyl ester resin constituting the resin (B) in the present invention, polymerization is carried out for the purpose of preventing gelation during resin preparation and for adjusting the storage stability or curability of the resulting resin. It is recommended to use an inhibitor, and typical examples of such polymerization inhibitors include hydroquinones such as hydroquinone, pt-butylcatechol, and mono-t-butylhydroquinone; hydroquinone monomethyl ether, di- t-p-
Phenols such as cresol; quinones such as p-benzoquinone, naphthoquinone, p-torquinone; or copper salts such as copper naphthenate. By the way, the component (B) resin obtained in this way can be sufficiently cured by simply heating without using a catalyst, but if necessary, benzoyl peroxide, p-menthane hydroperoxide, t- -Butyl perbenzoate,
1,1-di-t-butylperoxy-3,3,5
An organic peroxide such as -trimethylcyclohexanone can be used as a polymerization initiator, and in such a case, the component (B) in the present invention can be considered as a resin composition consisting of a resin and a polymerization initiator. The above-mentioned epoxy resin composition (A) is prepared by blending a polybasic acid anhydride and a curing accelerator with a solvent-free liquid epoxy resin having a specific average epoxy equivalent weight, and an epoxy vinyl ester resin (B). The weight ratio of the resin composition (B) to the resin composition (B) containing a polymerization initiator, if necessary, may be selected as appropriate depending on the required properties and working conditions. If the ratio of component B) becomes too large, the physical properties will be close to those of the epoxy vinyl ester resin itself, and the characteristics of the polybasic acid anhydride-cured epoxy resin, which is component (A), such as low curing shrinkage, will be lost. This will result in damage. Therefore, the weight ratio of both components (A) to (B) is 95/5 ~
A range of 30/70, preferably 95/5 to 70/30 is suitable. Component (A) and component (B) may be prepared separately and then mixed together, or component (B) may be added to the epoxy resin or polybasic acid anhydride in component (A) first.
It is also possible to mix the epoxy vinyl ester resin and, if necessary, a polymerization initiator, and then add the remaining component (A), so the order in which each component compound is blended is not limited. It is also possible to add customary additives such as internal mold release agents or pigments to the resin composition (). On the other hand, typical examples of the fibrous reinforcing material as the component () include glass fiber, carbon fiber, and aromatic polyamide fiber. Although there are E-glass, C-glass, A-glass, S-glass, etc., any type can be applied in the present invention. Next, carbon fibers include those manufactured using polyacrylonitrile fibers, cellulose fibers, pitch, aromatic hydrocarbons, or carbon black as raw materials, and aromatic polyamide fibers are polyfunctional aromatic fibers. It is made from a polymer having an amide bond through the reaction of a group amine and an aromatic polybasic acid. Typical polymers include poly-p-phenylenetetraphthalamide and poly-p-aminobenzamide. can be mentioned. These fibrous reinforcing materials () are classified into roving, chopped strand pine, continuous pine, cross, roving cloth, surficing pine, and chopped strand depending on their shape. The type and shape are appropriately selected depending on the intended use and performance of the formed product, and if necessary, two or more types or shapes may be used in combination. When obtaining the molding material (2) used in the present invention, the volume ratio of the fibrous reinforcing material (2) is suitably within the range of 30 to 70% of the molding material (2). To obtain the molding material () used in the present invention, the reinforcing material () may be impregnated with the resin composition () at room temperature or higher temperature to form a sheet. There is a method in which a release sheet is used to make a sandwich, and the product is similarly aged at room temperature or a higher temperature to thicken it to a B-stage state. The molding material used in the present invention obtained by such a method is then heated and compression molded to give a desired molded product. At this time, if necessary, after being released from the molding die, Furthermore, post-curing can also be performed. Next, the present invention will be specifically explained using Examples and Comparative Examples. In the following, all parts and percentages are based on weight unless otherwise specified. Example 1 16.9 parts of an epoxy resin with an epoxy equivalent of 190 obtained by the reaction of bisphenol A and epichlorohydrin, 26.5 parts of an epoxy resin with an epoxy equivalent of 370 obtained by the reaction of tetrabromobisphenol A with epichlorohydrin, methyl Consists of 26.6 parts of tetrahydrophthalic anhydride, 0.7 parts of benzyldimethylamine, methacrylate (60%) of an epoxy resin with an epoxy equivalent of 370 obtained by the reaction of tetrabromobisphenol A and epichlorohydrin, and styrene monomer (40%). 30 parts of epoxy vinyl ester resin and "Perhexa 3M" (polymerization initiator manufactured by NOF Corporation)
A resin composition was prepared by mixing 0.6 parts. The viscosity of this stuff is 650cps and the bromine content is 20%
It was hot. Next, 60 parts of glass cloth was impregnated with 40 parts of this resin composition and then aged at 40°C for about 30 hours to obtain a tack-free molding material (-1). After that, nine sheets of this molding material (-1) were stacked with copper foil and heated at 160℃ for 30 minutes under a pressure of 40Kg/ cm2 .
Heat compression was performed for minutes. Table 1 shows the physical properties of the copper-clad laminate thus obtained. Comparative Example 1 20.8 parts of an epoxy resin with an epoxy equivalent of 190 obtained by the reaction of bisphenol A and epichlorohydrin, tetrabromobisphenol A
A resin composition was prepared by mixing 42.2 parts of an epoxy resin having an epoxy equivalent of 370 obtained by the reaction between the epoxy resin and epichlorohydrin, 37.0 parts of methyltetrahydrophthalic anhydride, and 0.6 parts of benzyldimethylamine. After impregnating 60 parts of glass cloth with 40 parts of the resulting resin composition with a viscosity of 2100 cps and a bromine content of 20%, it was aged at 40°C for about 40 hours to obtain a tack-free molding material ( −1′) was obtained. Thereafter, a copper-clad laminate for comparison was obtained in the same manner as in Example 1, except that this molding material (-1') was used. The results of various physical properties of this laminate are shown in Table 1. Comparative Example 2 This example concerns the preparation of a comparative copper clad laminate using a solvent-based dicyandiamide cured epoxy resin system commonly used for flame retardant printed circuit boards. First, the bromine content is 21% and the epoxy equivalent is obtained by reacting bisphenol A, tetrabromobisphenol A, and epichlorohydrin.
485 epoxy resin in methyl ethyl ketone solution (non-volatile content = 80%), 34 parts of acetone, 4 parts of dicyandiamide and 0.2 parts of dimethylbenzylamine were dissolved in 30 parts of methyl cellosolve. A resin composition was obtained by mixing with a curing agent solution. Next, a glass cloth was impregnated with this resin composition and then aged at 160°C for 5 minutes to obtain a tack-free molding material (-2'). Thereafter, a copper-clad laminate was obtained in the same manner as in Example 1, except that the heating compression time was changed to 1 hour and the molding material (-2') of this example was used. Table 1 shows the physical properties of this laminate.
【表】
実施例 2
ビスフエノールAとエピクロルヒドリンとの反
応によつて得られたエポキシ当量が190なるエポ
キシ樹脂の100部、メチルテトラヒドロ無水フタ
ル酸の87部およびベンジルジメチルアミンの1部
と、別にフエノール・ノボラツク樹脂とエピクロ
ルヒドリンとの反応により得られたエポキシ当量
が182なるエポキシ樹脂のメタクリレート(70%)
とスチレンモノマー(30%)とより成るエポキシ
ビニルエステル樹脂の46部と、「パーヘキサ3M」
の0.9部とを混合せしめて樹脂組成物を調製した。
次いで、この樹脂組成物の30部を炭素繊維ロー
ビングの70部に含浸させ、一方向のシート状物と
なしたのち、40℃で約40時間熟成せしめて成形材
料(−2)を得た。
しかるのち、この成形材料(−2)の3枚を
加熱圧縮(50Kg/cm2、160゜/6分間)成形を行な
つたのち、電熱乾燥機で170℃に1時間なる後硬
化を行なつた。
次いで、かくして得られた積層板についての諸
物性は下記の通りであつた。
曲げ強度 192Kg/mm2
曲げ弾性率 13600 〃
層間剪断強度 9.2 〃
引張強度 188 〃
引張弾性率 14000 〃
実施例 3
実施例2で得られた樹脂組成物の40部をカツト
長が1インチなるチヨツプドストランド・グラス
に含浸させたのち、40℃で約30時間熟成せしめ
て、シヨアーA型硬度計で75〜85なる硬度を有す
る、タツクフリーで屈曲可能な成形材料(−
3)を得た。
以後も、この成形材料(−3)を用いるよう
に変更した以外は、実施例2と同様にして積層板
を得た。
次いで、この積層板についてJIS規格に従つて
物性の評価を行なつた処、下記の通りであつた。
曲げ強度 47Kg/m2
曲げ弾性率 1580 〃
引張強度 26 〃
引張弾性率 1640 〃
伸び率 2.0 %
比較例 3
フエノール・ノボラツク樹脂とエピクロルヒド
リンとから得られるノボラツク・タイプのエポキ
シ樹脂のメタクリレート、スチレンモノマーおよ
び「パーヘキサ3M」の使用を一切欠如した以外
は、実施例2と同様にして樹脂組成物を調製し
た。
次いで、この樹脂組成物の40部をカツト長が1
インチなるチヨツプドストランド・グラスの60部
に含浸させたのち、40℃で約40時間熟成せしめ
て、シヨアーA型硬度計で75〜85なる硬度を有し
た、タツクフリーで屈曲可能な成形材料(−
3′)を得た。
以後は、この比較対照用の成形材料(−3′)
を用いるように変更した以外は、実施例3と同様
にして成形を行なつた処、マトリツクスの流出が
多く、また積層板には泡が多く残つていたし、し
かも離型後において室温まで冷却する途中で積層
板が変形してしまつて、物性の評価ができるよう
な代物ではなかつた。
実施例 4
実施例3で得られた樹脂組成物の40部をガラス
繊維のコンテイニアス・マツトの60部に含浸させ
たのち、40℃で約40時間熟成せしめて成形材料
(−4)を得た。
次いで、この成形材料(−4)の3枚を用い
るように変更した以外は、実施例2と同様にして
積層板を得た。
この積層板についての諸物性を示せば、下記の
通りであつた。
体積抵抗率 6×1015Ω・cm
煮沸2時間後の体積抵抗率 2×1014 〃
曲げ強度 52Kg/mm2 [Table] Example 2 100 parts of an epoxy resin with an epoxy equivalent of 190 obtained by the reaction of bisphenol A and epichlorohydrin, 87 parts of methyltetrahydrophthalic anhydride and 1 part of benzyldimethylamine, and separately phenol・Epoxy resin methacrylate with an epoxy equivalent of 182 obtained by the reaction of novolac resin and epichlorohydrin (70%)
and 46 parts of epoxy vinyl ester resin consisting of styrene monomer (30%) and "Perhexa 3M"
A resin composition was prepared by mixing 0.9 parts of Next, 30 parts of this resin composition was impregnated into 70 parts of carbon fiber roving to form a unidirectional sheet-like product, which was then aged at 40°C for about 40 hours to obtain a molding material (-2). Thereafter, three sheets of this molding material (-2) were subjected to heat compression molding (50 kg/cm 2 , 160°/6 minutes), and then post-cured at 170°C for 1 hour in an electric dryer. Ta. Next, the physical properties of the thus obtained laminate were as follows. Bending strength 192Kg/ mm2 Bending modulus 13600 Interlaminar shear strength 9.2 Tensile strength 188 Tensile modulus 14000 Example 3 40 parts of the resin composition obtained in Example 2 was cut into pieces with a cut length of 1 inch. After impregnating Pudstrand glass and aging at 40°C for about 30 hours, a tack-free and bendable molding material (-
3) was obtained. Thereafter, a laminate was obtained in the same manner as in Example 2, except that this molding material (-3) was used. Next, the physical properties of this laminate were evaluated according to JIS standards, and the properties were as follows. Bending strength 47Kg/ m2 Flexural modulus 1580 Tensile strength 26 Tensile modulus 1640 Elongation 2.0% Comparative example 3 Novolac type epoxy resin obtained from phenolic novolac resin and epichlorohydrin, methacrylate, styrene monomer and A resin composition was prepared in the same manner as in Example 2, except that "Perhexa 3M" was not used at all. Next, 40 parts of this resin composition was added to a cut length of 1.
A tack-free and bendable molding material obtained by impregnating 60 parts of inch chopped strand glass and aging it at 40°C for about 40 hours to have a hardness of 75 to 85 on the Shore A hardness tester. (−
3′) was obtained. From now on, this comparative molding material (-3′)
Molding was carried out in the same manner as in Example 3, except that the mold was changed to use a mold. However, there was a lot of matrix flowing out, and a lot of bubbles remained in the laminate. The laminate was deformed during the process and was not suitable for evaluation of physical properties. Example 4 40 parts of the resin composition obtained in Example 3 was impregnated into 60 parts of a continuous mat of glass fiber, and then aged at 40°C for about 40 hours to obtain a molding material (-4). . Next, a laminate was obtained in the same manner as in Example 2, except that three sheets of this molding material (-4) were used. The physical properties of this laminate were as follows. Volume resistivity 6×10 15 Ω・cm Volume resistivity after 2 hours of boiling 2×10 14 〃 Bending strength 52Kg/mm 2
Claims (1)
囲にある無溶剤液状エポキシ樹脂に多塩基酸無
水物および硬化促進剤を配合させて成るエポキ
シ樹脂組成物(A)と、 エポキシビニルエステル樹脂(B)とを、 (A)対(B)の重量比が95/5〜30/70となるよう
に配合させて成る樹脂組成物と、 () 繊維質強化材 とを必須の成分として含んで成る成形材料()
を用いることを特徴とする積層板の製造方法。[Claims] 1 () An epoxy resin composition (A) comprising a solvent-free liquid epoxy resin having an average epoxy equivalent weight of 100 to 400 mixed with a polybasic acid anhydride and a curing accelerator; A resin composition comprising a vinyl ester resin (B) in a weight ratio of (A) to (B) of 95/5 to 30/70, and () a fibrous reinforcing material as an essential component. Molding material () comprising as a component
A method for manufacturing a laminate, characterized by using.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP15936988A JPS6426654A (en) | 1988-06-29 | 1988-06-29 | Production of laminated board |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP15936988A JPS6426654A (en) | 1988-06-29 | 1988-06-29 | Production of laminated board |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS6426654A JPS6426654A (en) | 1989-01-27 |
JPH0129816B2 true JPH0129816B2 (en) | 1989-06-14 |
Family
ID=15692329
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP15936988A Granted JPS6426654A (en) | 1988-06-29 | 1988-06-29 | Production of laminated board |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS6426654A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2012051130A (en) * | 2010-08-31 | 2012-03-15 | Mitsubishi Electric Corp | Method for producing fiber-reinforced composite material and method for manufacturing elevator car |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP4833174B2 (en) * | 2007-09-21 | 2011-12-07 | シャープ株式会社 | Sheet member conveying apparatus, automatic document conveying apparatus and document reading apparatus using the same |
-
1988
- 1988-06-29 JP JP15936988A patent/JPS6426654A/en active Granted
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2012051130A (en) * | 2010-08-31 | 2012-03-15 | Mitsubishi Electric Corp | Method for producing fiber-reinforced composite material and method for manufacturing elevator car |
Also Published As
Publication number | Publication date |
---|---|
JPS6426654A (en) | 1989-01-27 |
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