JPH03182514A - Laminating resin composition - Google Patents
Laminating resin compositionInfo
- Publication number
- JPH03182514A JPH03182514A JP32223889A JP32223889A JPH03182514A JP H03182514 A JPH03182514 A JP H03182514A JP 32223889 A JP32223889 A JP 32223889A JP 32223889 A JP32223889 A JP 32223889A JP H03182514 A JPH03182514 A JP H03182514A
- Authority
- JP
- Japan
- Prior art keywords
- resin
- resin composition
- allyl ester
- acid
- ester resin
- 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
- 239000011342 resin composition Substances 0.000 title claims abstract description 24
- 238000010030 laminating Methods 0.000 title abstract description 4
- 229920005989 resin Polymers 0.000 claims abstract description 52
- 239000011347 resin Substances 0.000 claims abstract description 52
- -1 halogenated allyl ester Chemical class 0.000 claims abstract description 40
- 229920006395 saturated elastomer Polymers 0.000 claims abstract description 27
- 150000005846 sugar alcohols Polymers 0.000 claims abstract description 14
- 150000007519 polyprotic acids Polymers 0.000 claims abstract description 12
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 20
- 229910052794 bromium Inorganic materials 0.000 claims description 20
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 18
- 239000000460 chlorine Substances 0.000 claims description 16
- 229910052801 chlorine Inorganic materials 0.000 claims description 16
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 15
- 229910052736 halogen Inorganic materials 0.000 claims description 9
- 150000002367 halogens Chemical class 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 abstract description 10
- 239000003063 flame retardant Substances 0.000 abstract description 7
- 229920006337 unsaturated polyester resin Polymers 0.000 abstract description 7
- 239000000203 mixture Substances 0.000 abstract description 6
- 238000002156 mixing Methods 0.000 abstract description 5
- 239000000178 monomer Substances 0.000 abstract description 5
- 238000004132 cross linking Methods 0.000 abstract description 4
- 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 abstract description 3
- XIRDTMSOGDWMOX-UHFFFAOYSA-N 3,4,5,6-tetrabromophthalic acid Chemical compound OC(=O)C1=C(Br)C(Br)=C(Br)C(Br)=C1C(O)=O XIRDTMSOGDWMOX-UHFFFAOYSA-N 0.000 abstract description 2
- 239000000945 filler Substances 0.000 abstract description 2
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 abstract description 2
- 229920001567 vinyl ester resin Polymers 0.000 abstract description 2
- CHUGKEQJSLOLHL-UHFFFAOYSA-N 2,2-Bis(bromomethyl)propane-1,3-diol Chemical compound OCC(CO)(CBr)CBr CHUGKEQJSLOLHL-UHFFFAOYSA-N 0.000 abstract 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 20
- 239000000463 material Substances 0.000 description 14
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 8
- 239000000123 paper Substances 0.000 description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 239000000853 adhesive Substances 0.000 description 6
- 230000001070 adhesive effect Effects 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 125000001931 aliphatic group Chemical group 0.000 description 5
- ZDNFTNPFYCKVTB-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,4-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=C(C(=O)OCC=C)C=C1 ZDNFTNPFYCKVTB-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- 239000011889 copper foil Substances 0.000 description 4
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 4
- 239000011888 foil Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000005011 phenolic resin Substances 0.000 description 4
- 229920000877 Melamine resin Polymers 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
- 150000008065 acid anhydrides Chemical class 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 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 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000002655 kraft paper Substances 0.000 description 3
- 150000001451 organic peroxides Chemical class 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- 239000003505 polymerization initiator Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 description 2
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- 239000004640 Melamine resin Substances 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- LJCFOYOSGPHIOO-UHFFFAOYSA-N antimony pentoxide Chemical compound O=[Sb](=O)O[Sb](=O)=O LJCFOYOSGPHIOO-UHFFFAOYSA-N 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 125000001246 bromo group Chemical group Br* 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 125000004185 ester group Chemical group 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- 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 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- 229920001568 phenolic resin Polymers 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 2
- 238000005809 transesterification reaction 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
- 229920002554 vinyl polymer Polymers 0.000 description 2
- NIDNOXCRFUCAKQ-UMRXKNAASA-N (1s,2r,3s,4r)-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1[C@H]2C=C[C@@H]1[C@H](C(=O)O)[C@@H]2C(O)=O NIDNOXCRFUCAKQ-UMRXKNAASA-N 0.000 description 1
- DJKGDNKYTKCJKD-BPOCMEKLSA-N (1s,4r,5s,6r)-1,2,3,4,7,7-hexachlorobicyclo[2.2.1]hept-2-ene-5,6-dicarboxylic acid Chemical compound ClC1=C(Cl)[C@]2(Cl)[C@H](C(=O)O)[C@H](C(O)=O)[C@@]1(Cl)C2(Cl)Cl DJKGDNKYTKCJKD-BPOCMEKLSA-N 0.000 description 1
- QEQBMZQFDDDTPN-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy benzenecarboperoxoate Chemical compound CC(C)(C)OOOC(=O)C1=CC=CC=C1 QEQBMZQFDDDTPN-UHFFFAOYSA-N 0.000 description 1
- NOBYOEQUFMGXBP-UHFFFAOYSA-N (4-tert-butylcyclohexyl) (4-tert-butylcyclohexyl)oxycarbonyloxy carbonate Chemical compound C1CC(C(C)(C)C)CCC1OC(=O)OOC(=O)OC1CCC(C(C)(C)C)CC1 NOBYOEQUFMGXBP-UHFFFAOYSA-N 0.000 description 1
- RVHSTXJKKZWWDQ-UHFFFAOYSA-N 1,1,1,2-tetrabromoethane Chemical compound BrCC(Br)(Br)Br RVHSTXJKKZWWDQ-UHFFFAOYSA-N 0.000 description 1
- QRFALSDGOMLVIR-UHFFFAOYSA-N 1,2,3,4-tetrabromobenzene Chemical compound BrC1=CC=C(Br)C(Br)=C1Br QRFALSDGOMLVIR-UHFFFAOYSA-N 0.000 description 1
- HGRZLIGHKHRTRE-UHFFFAOYSA-N 1,2,3,4-tetrabromobutane Chemical compound BrCC(Br)C(Br)CBr HGRZLIGHKHRTRE-UHFFFAOYSA-N 0.000 description 1
- ROLAGNYPWIVYTG-UHFFFAOYSA-N 1,2-bis(4-methoxyphenyl)ethanamine;hydrochloride Chemical compound Cl.C1=CC(OC)=CC=C1CC(N)C1=CC=C(OC)C=C1 ROLAGNYPWIVYTG-UHFFFAOYSA-N 0.000 description 1
- YAOMHRRYSRRRKP-UHFFFAOYSA-N 1,2-dichloropropyl 2,3-dichloropropyl 3,3-dichloropropyl phosphate Chemical compound ClC(Cl)CCOP(=O)(OC(Cl)C(Cl)C)OCC(Cl)CCl YAOMHRRYSRRRKP-UHFFFAOYSA-N 0.000 description 1
- VZXTWGWHSMCWGA-UHFFFAOYSA-N 1,3,5-triazine-2,4-diamine Chemical compound NC1=NC=NC(N)=N1 VZXTWGWHSMCWGA-UHFFFAOYSA-N 0.000 description 1
- PAOHAQSLJSMLAT-UHFFFAOYSA-N 1-butylperoxybutane Chemical compound CCCCOOCCCC PAOHAQSLJSMLAT-UHFFFAOYSA-N 0.000 description 1
- KTZVZZJJVJQZHV-UHFFFAOYSA-N 1-chloro-4-ethenylbenzene Chemical compound ClC1=CC=C(C=C)C=C1 KTZVZZJJVJQZHV-UHFFFAOYSA-N 0.000 description 1
- PMUPSYZVABJEKC-UHFFFAOYSA-N 1-methylcyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1(C)CCCCC1C(O)=O PMUPSYZVABJEKC-UHFFFAOYSA-N 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- NOSXUFXBUISMPR-UHFFFAOYSA-N 1-tert-butylperoxyhexane Chemical compound CCCCCCOOC(C)(C)C NOSXUFXBUISMPR-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
- YEVQZPWSVWZAOB-UHFFFAOYSA-N 2-(bromomethyl)-1-iodo-4-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=C(I)C(CBr)=C1 YEVQZPWSVWZAOB-UHFFFAOYSA-N 0.000 description 1
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- ODGCZQFTJDEYNI-UHFFFAOYSA-N 2-methylcyclohex-3-ene-1,2-dicarboxylic acid Chemical compound OC(=O)C1(C)C=CCCC1C(O)=O ODGCZQFTJDEYNI-UHFFFAOYSA-N 0.000 description 1
- WZHHYIOUKQNLQM-UHFFFAOYSA-N 3,4,5,6-tetrachlorophthalic acid Chemical compound OC(=O)C1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1C(O)=O WZHHYIOUKQNLQM-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
- 229920003043 Cellulose fiber Polymers 0.000 description 1
- 239000004709 Chlorinated polyethylene Substances 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- 241000238557 Decapoda Species 0.000 description 1
- 239000004641 Diallyl-phthalate Substances 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Natural products CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 229940058905 antimony compound for treatment of leishmaniasis and trypanosomiasis Drugs 0.000 description 1
- 150000001463 antimony compounds Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- BXIQXYOPGBXIEM-UHFFFAOYSA-N butyl 4,4-bis(tert-butylperoxy)pentanoate Chemical compound CCCCOC(=O)CCC(C)(OOC(C)(C)C)OOC(C)(C)C BXIQXYOPGBXIEM-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- DZCLVBQEPZQZNN-UHFFFAOYSA-N copper;phenol Chemical compound [Cu].OC1=CC=CC=C1 DZCLVBQEPZQZNN-UHFFFAOYSA-N 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 125000000853 cresyl group Chemical group C1(=CC=C(C=C1)C)* 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
- QSAWQNUELGIYBC-UHFFFAOYSA-N cyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCCCC1C(O)=O QSAWQNUELGIYBC-UHFFFAOYSA-N 0.000 description 1
- WHHGLZMJPXIBIX-UHFFFAOYSA-N decabromodiphenyl ether Chemical compound BrC1=C(Br)C(Br)=C(Br)C(Br)=C1OC1=C(Br)C(Br)=C(Br)C(Br)=C1Br WHHGLZMJPXIBIX-UHFFFAOYSA-N 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000012933 diacyl peroxide Substances 0.000 description 1
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 description 1
- ASMQGLCHMVWBQR-UHFFFAOYSA-M diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(=O)([O-])OC1=CC=CC=C1 ASMQGLCHMVWBQR-UHFFFAOYSA-M 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
- 238000010894 electron beam technology Methods 0.000 description 1
- 229920006332 epoxy adhesive Polymers 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- PYGSKMBEVAICCR-UHFFFAOYSA-N hexa-1,5-diene Chemical group C=CCCC=C PYGSKMBEVAICCR-UHFFFAOYSA-N 0.000 description 1
- 238000007602 hot air drying Methods 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000012784 inorganic fiber Substances 0.000 description 1
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
- 125000005395 methacrylic acid group Chemical class 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 125000005634 peroxydicarbonate group Chemical group 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 1
- 150000003022 phthalic acids Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000000758 substrate Substances 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
- 239000010409 thin film Substances 0.000 description 1
- HQUQLFOMPYWACS-UHFFFAOYSA-N tris(2-chloroethyl) phosphate Chemical compound ClCCOP(=O)(OCCCl)OCCCl HQUQLFOMPYWACS-UHFFFAOYSA-N 0.000 description 1
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
Abstract
Description
【発明の詳細な説明】
「産業上の利用分野」
本発明は、特に電気機蒸、電子機器、通信機藩等に使用
される電気用積層板を製造するに好適な積層板用樹脂組
成物に関するものである。Detailed Description of the Invention "Field of Industrial Application" The present invention relates to a resin composition for laminates suitable for producing electrical laminates particularly used in electric machinery, electronic equipment, communication equipment, etc. It is related to.
「従来の技術」
電気用積層板に用いられる樹脂としては従来フェノール
樹脂、エポキシ樹脂、不飽和ポリエステル樹脂が代表的
なものであり、各種の基材と複合化して用いられている
。"Prior Art" Typical resins used in electrical laminates are phenol resins, epoxy resins, and unsaturated polyester resins, which are used in combination with various base materials.
しかし、フェノール樹脂は硬化時の反応副生物の発生や
溶剤の除去の問題があり、エポキシ樹脂は上記同様、溶
剤の除去の問題がある。不飽和ポリエステル樹脂はこれ
らの問題がなく、ラジカル硬化型で使用しやすい反面、
耐熱性及び難燃性が共に優れた両性能のバランスのとれ
た積層板を得ることは困難であり、現在大きな課題とな
っている。However, phenolic resins have problems with the generation of reaction by-products during curing and removal of solvents, and epoxy resins have the same problems with solvent removal as described above. Unsaturated polyester resin does not have these problems and is a radical curing type that is easy to use, but on the other hand,
It is difficult to obtain a well-balanced laminate that has both excellent heat resistance and flame retardancy, and is currently a major challenge.
例えば特公平１−１３４１８号公報に示されるように不
飽和ポリエステル樹脂中に脂肪族臭素及び／または脂環
族臭素を含有し、かつ芳香族臭素を含有する不飽和ポリ
エステル樹脂系積層板が提案されているが、なお問題は
十分に解決されているとは言えない。For example, as shown in Japanese Patent Publication No. 1-13418, an unsaturated polyester resin laminate containing aliphatic bromine and/or alicyclic bromine and aromatic bromine in an unsaturated polyester resin has been proposed. However, it cannot be said that the problem has been fully resolved.
「発明が解決しようとする課題」
本発明の課題は、高い難燃性を有し、かつ優れた耐熱性
を合わせ持つ電気用積層板を製造するに好適なラジカル
硬化性の積層用樹脂組成物を提供することにある。``Problems to be Solved by the Invention'' The problem of the present invention is to provide a radical-curable laminating resin composition suitable for producing electrical laminates that have both high flame retardancy and excellent heat resistance. Our goal is to provide the following.
「課題を解決するための手段」
本発明者はこれらの目的達成に努力した結果、ラジカル
硬化性樹脂に特定のハロゲン含有化合物を配合した樹脂
組成物を用いることにより、耐熱性及び難燃性が共に優
れた電気用積層板を作り得ることを見出し、本発明を完
成した。"Means for Solving the Problems" As a result of efforts to achieve these objectives, the inventors of the present invention have achieved heat resistance and flame retardancy by using a resin composition in which a specific halogen-containing compound is blended with a radical curable resin. They discovered that it is possible to make an excellent electrical laminate using both methods, and completed the present invention.
即ち、本発明の要旨は、ラジカル硬化性樹脂９０ｗｔ％
以下に対して、臭素または塩素を含む飽和多塩基酸及び
／または臭素または塩素を含む飽和多価アルコールを構
成成分として含むハロゲン含有アリルエステル樹脂１０
ｖｔ％以上を配合してなる電気用積層板用樹脂組成物に
ある。That is, the gist of the present invention is that 90 wt% of radical curable resin
For the following, halogen-containing allyl ester resin 10 containing a saturated polybasic acid containing bromine or chlorine and/or a saturated polyhydric alcohol containing bromine or chlorine as a constituent component
There is a resin composition for electrical laminates which contains vt% or more.
以下、本発明の詳細な説明する。The present invention will be explained in detail below.
本発明にいうラジカル硬化性樹脂とは、不飽和結合を有
する化合物が熱、光または触媒などにより生ずるフリー
ラジカルによって連鎖的に重合することにより硬化する
樹脂をさし、例えば、不飽和ポリエステル樹脂、ビニル
エステル樹脂、ジアリルフタレート樹脂、アリルエステ
ル樹脂をいう。The term "radically curable resin" as used in the present invention refers to a resin that is cured by chain polymerization of a compound having an unsaturated bond by free radicals generated by heat, light, or a catalyst, such as unsaturated polyester resin, Refers to vinyl ester resin, diallyl phthalate resin, and allyl ester resin.
上記アリルエステル樹脂とは飽和多塩基酸と飽和多価ア
ルコールより構成されてなる飽和ポリエステルの末端に
アリルエステル基を有する樹脂をいう。The above-mentioned allyl ester resin refers to a resin having an allyl ester group at the end of a saturated polyester composed of a saturated polybasic acid and a saturated polyhydric alcohol.
飽和多塩基酸としては、例えば二塩基酸としてオルソフ
タル酸、オルソフタル酸無水物、イソフタル酸、テレフ
タル酸等のフタル酸類、テトラヒドロフタル酸、メチル
テトラヒドロフタル酸、エンドメチレンテトラヒドロフ
タル酸、メチルエンドメチレンテトラヒドロフタル酸、
ヘキサヒドロフタル酸、メチルへキサヒドロフタル酸、
及びそれらの酸無水物等のヒドロフタル酸類、マロン酸
、コハク酸、グルタル酸、アジピン酸等の脂肪族二塩基
酸があげられる。三官能以上の多塩基酸としてはトリメ
リット酸、ピロメリット酸及びそれらの酸無水物があげ
られる。これらは、単独でもまたは混合しても用いるこ
とができる。Saturated polybasic acids include, for example, dibasic acids such as orthophthalic acid, orthophthalic anhydride, isophthalic acid, phthalic acids such as terephthalic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, endomethylenetetrahydrophthalic acid, methylendomethylenetetrahydrophthalate. acid,
Hexahydrophthalic acid, methyl hexahydrophthalic acid,
and hydrophthalic acids such as acid anhydrides thereof, aliphatic dibasic acids such as malonic acid, succinic acid, glutaric acid, and adipic acid. Examples of trifunctional or higher-functional polybasic acids include trimellitic acid, pyromellitic acid, and acid anhydrides thereof. These can be used alone or in combination.
飽和多価アルコールとしては、エチレングリコール、ｌ
、２−プロピレングリコール、１，４−ブタンジオール
、１，６−ヘキサンジオール、ネオペンチルグリコール
、１．４−シフａへ牛すンジメタ／−ル、パラキシレン
グリコール等の脂肪族、脂環族または芳香族を含む二価
のアルコールの他、一般式夏（０（ＣＨＲＣＨ，Ｏ）、
ｌＨ（ＲはＨまたはＣ，Ｈｔ−、＋ 、ｍは１〜５の整
数、ｎは２〜ｌＯの整数）で表わされるエチレンオキサ
イド、プロピレンオキサイド等のアルキレンオキサイド
の付加反応によって得られる二価のアルコールがあげら
れる。三価以上の多価アルコールとしては、例えばグリ
セリン、トリメチロールプロパン等の脂肪族の三価のア
ルコールやペンタエリスリトール、ソルビトール等の四
価以上のアルコールがあげられる。これらは、単独でも
または混合しても用いることができる。Saturated polyhydric alcohols include ethylene glycol, l
aliphatic, alicyclic or In addition to dihydric alcohols containing aromatics, general formulas (0 (CHRCH, O),
A divalent compound obtained by the addition reaction of alkylene oxides such as ethylene oxide and propylene oxide, represented by lH (R is H or C, Ht-, +, m is an integer of 1 to 5, and n is an integer of 2 to lO). Alcohol can be given. Examples of trihydric or higher polyhydric alcohols include aliphatic trihydric alcohols such as glycerin and trimethylolpropane, and tetrahydric or higher alcohols such as pentaerythritol and sorbitol. These can be used alone or in combination.
一方、本発明にいうハロゲン含有アリルエステル樹脂と
は、臭素または塩素を含む飽和多塩基酸及び／または臭
素または塩素を含む飽和多価アルコールを構成成分とし
て含むアリルエステル樹脂をさす。臭素または塩素を含
む飽和多塩基酸とは、上記飽和多塩基酸が１個または複
数個の臭素または塩素により置換された化合物をさし、
例えば、テトラブロムフタル酸、テトラクロロフタル酸
、クロレンド酸、及びそれらの酸無水物等があげられる
が、これらに限定されるものではない。臭素または塩素
を含む飽和多価アルコールとは、上記飽和多価アルコー
ルが１個または複数個の臭素または塩素により置換され
た化合物をさし、例えば、ジブロムネオペンチルグリコ
ール、テトラブロムビスフェノールＡのエチレンオキサ
イドやプロピレンオキサイド付加物等があげられるが、
これらに限定されるものではない。本発明にいうハロゲ
ン含有アリルエステル樹脂は臭素または塩素を含む一種
類または二種類以上の飽和多塩基酸及び／または臭素ま
たは塩素を含む一種類または二種類以上の飽和多価アル
コールを構成成分として含まれるように製造され、臭素
または塩素を含まない飽和多塩基酸及び／または臭素ま
たは塩素を含まない飽和多価アルコールを併用して製造
することも可能である。On the other hand, the halogen-containing allyl ester resin according to the present invention refers to an allyl ester resin containing as a constituent a saturated polybasic acid containing bromine or chlorine and/or a saturated polyhydric alcohol containing bromine or chlorine. A saturated polybasic acid containing bromine or chlorine refers to a compound in which the above saturated polybasic acid is substituted with one or more bromine or chlorine,
Examples include, but are not limited to, tetrabromophthalic acid, tetrachlorophthalic acid, chlorendic acid, and acid anhydrides thereof. A saturated polyhydric alcohol containing bromine or chlorine refers to a compound in which the above saturated polyhydric alcohol is substituted with one or more bromine or chlorine, such as dibrome neopentyl glycol, tetrabromo bisphenol A, ethylene, etc. Examples include oxide and propylene oxide adducts,
It is not limited to these. The halogen-containing allyl ester resin according to the present invention contains as a constituent component one or more saturated polybasic acids containing bromine or chlorine and/or one or more saturated polyhydric alcohols containing bromine or chlorine. It is also possible to produce it in combination with a bromine- or chlorine-free saturated polybasic acid and/or a bromine- or chlorine-free saturated polyhydric alcohol.
アリルエステル樹脂の製造法は既に公知であり、例えば
特願昭８３−２６２２１７号に述べられている。例えば
、アリルエステル樹脂はジアリルテレフタレートのよう
な飽和二塩基酸のジアリルエステルと飽和多価アルコー
ルとをエステル交換触媒と共に反応器に仕込みアリルア
ルコールを留去させながら反応させ製造される。工業的
に更に有効な方法としては、ジアリルテレフタレートの
代わりにジメチルテレフタレートのような飽和二塩基酸
のジアルキルエステルをアリルアルコール、多価アルコ
ール及びエステル交換触媒と共に反応器に仕込み、メタ
ノール等の副生するアルコールを留去させながら反応さ
せて得ることができる。The method for producing allyl ester resins is already known and is described, for example, in Japanese Patent Application No. 83-262217. For example, an allyl ester resin is produced by charging a diallyl ester of a saturated dibasic acid such as diallyl terephthalate and a saturated polyhydric alcohol together with a transesterification catalyst into a reactor and reacting the allyl alcohol while distilling off the allyl alcohol. As an industrially more effective method, instead of diallyl terephthalate, a dialkyl ester of a saturated dibasic acid such as dimethyl terephthalate is charged into a reactor together with allyl alcohol, a polyhydric alcohol, and a transesterification catalyst to produce by-products such as methanol. It can be obtained by reacting while distilling off the alcohol.
また、反応温度によってはハイドロキノンのような重合
禁止剤を反応液中に共存させてもよい。このようにして
飽和ポリエステルの末端にアリルエステル基を有するア
リルエステル樹脂を製造することができる。Further, depending on the reaction temperature, a polymerization inhibitor such as hydroquinone may be allowed to coexist in the reaction solution. In this way, an allyl ester resin having an allyl ester group at the end of a saturated polyester can be produced.
本発明の樹脂組成物に使用できるアリルエステル樹脂の
種類は、一種類でも二種類以上混合してもよい。飽和多
塩基酸と飽和多価アルコールの種類を種々選択すること
によって、耐熱性を維持しながら電気特性、難燃性等の
良好な電気用積層板を得ることができる。The types of allyl ester resins that can be used in the resin composition of the present invention may be one type or a mixture of two or more types. By selecting various types of saturated polybasic acids and saturated polyhydric alcohols, it is possible to obtain electrical laminates with good electrical properties, flame retardance, etc. while maintaining heat resistance.
本発明者の検討によれば、ハロゲン含有アリルエステル
樹脂を配合することにより、臭素または塩素による自己
消火性を発現できる一方、耐熱性の高いアリルエステル
樹脂骨格中に臭素または塩素を結合させているために添
加型の難燃剤でしばしば問題となる機械的強度、耐電圧
特性等の耐熱劣化の程度が小さく、非常にすぐれた電気
用積層板を製造することができる。さらに、本発明にお
ける積層板用樹脂に配合する樹脂は樹脂組成物であって
も何ら差し支えなく、目的の積層板性能に合わせて適宜
配合を選択できる。According to the inventor's studies, by blending a halogen-containing allyl ester resin, self-extinguishing properties due to bromine or chlorine can be expressed, while bromine or chlorine is bonded to the highly heat-resistant allyl ester resin skeleton. Therefore, the degree of heat resistance deterioration in mechanical strength, withstand voltage characteristics, etc., which is often a problem with additive-type flame retardants, is small, and it is possible to manufacture extremely excellent electrical laminates. Furthermore, the resin blended into the resin for a laminate in the present invention may be a resin composition, and the blend can be appropriately selected depending on the desired performance of the laminate.
本発明の樹脂組成物中に配合するラジカル硬化性樹脂と
ハロゲン含有アリルエステル樹脂との混合比率は積層板
性能の必要によって適宜選択できるが、ラジカル硬化性
樹脂０〜９０ｗｔ％に対して、ハロゲン含有アリルエス
テル樹脂１００〜１０ｗｔ％が好ましい。例えば紙糸積
層板の場合、銅箔エツチング後の積層板中の樹脂含有量
が４０〜６０ｗｔ％のときは、樹脂中に脂肪族臭素とし
て最低４〜５ｗｔ％含まれるように設定することにより
、高度な難燃効果を発揮することができ、機械特性、電
気特性等もすぐれた電気用積層板を得ることが可能であ
る。The mixing ratio of the radical curable resin and the halogen-containing allyl ester resin to be blended into the resin composition of the present invention can be appropriately selected depending on the needs of the laminate performance. The allyl ester resin is preferably 100 to 10 wt%. For example, in the case of a paper yarn laminate, when the resin content in the laminate after copper foil etching is 40 to 60 wt%, by setting the resin to contain at least 4 to 5 wt% as aliphatic bromine, It is possible to obtain an electrical laminate that can exhibit a high flame retardant effect and has excellent mechanical properties, electrical properties, etc.
また、本発明の樹脂組成物には、上記ラジカル硬化性樹
脂及びノ＼ロゲン含有アリルエステル樹脂以外に添加型
の難燃剤を併用することも可能である。添加型の難燃剤
としては、トルメチルホスフェート、トルメチルホスフ
ェート、）ルブチルホスフェート、トリオクチルホスフ
ェート、トリフェニルホスフェート、トリクレジルホス
フェート、トリス（クロルエチル）ホスフェート、トリ
ス（ジクロルプロピル）ホスフェート、クレジルジフェ
ニルホスフェート、トリフェニルホスファイト等のリン
系難燃剤、塩素化パラフィン、塩素化ポリエチレン、デ
カブロムジフェニルエーテル、テトラブロムジフェニル
エーテル、テトラブロムエタン、テトラブロムブタン、
１，２．３−１−リブロムプロパン、テトラブロムベン
ゼン、テトラブロムビスフェノールＡ等のノ＼ロゲン系
難燃剤、三酸化アンチモン、五酸化アンチモン等のアン
チモン化合物、ホウ酸亜鉛、水酸化アルミニウム等があ
げられる。Further, in addition to the above-mentioned radical curable resin and allyl ester resin containing norogen, an additive type flame retardant can also be used in the resin composition of the present invention. Additive flame retardants include tolumethyl phosphate, tolumethyl phosphate, )rubutyl phosphate, trioctyl phosphate, triphenyl phosphate, tricresyl phosphate, tris (chloroethyl) phosphate, tris (dichloropropyl) phosphate, and cresyl. Phosphorous flame retardants such as diphenyl phosphate and triphenyl phosphite, chlorinated paraffin, chlorinated polyethylene, decabrom diphenyl ether, tetrabrom diphenyl ether, tetrabromo ethane, tetrabromo butane,
1,2.3-1-ribromopropane, tetrabromobenzene, tetrabromobisphenol A, and other nitrogen-based flame retardants, antimony compounds such as antimony trioxide and antimony pentoxide, zinc borate, aluminum hydroxide, etc. can give.
本発明の樹脂組成物には、上記ラジカル硬化性樹脂及び
ハロゲン含有アリルエステル樹脂以外にラジカル重合可
能な架橋性モノマーを使用することができ、公知のもの
はいずれも使用可能であるが、例えば、ジアリルオルソ
フタレート、ジアリルイソフタレート、ジアリルテレフ
タレートのようなジアリルフタレート類；スチレン、α
−メチルスチレン、ｐ−メチルスチレン、ｐ−クロルス
チレン、ブロムスチレン、ジビニルベンゼンのような置
換スチレン類； （メタ）アクリル酸メチル、（メタ）
アクリル酸エチル、（メタ）アクリル酸ブチル、（メタ
）アクリル酸２−エチルヘキシル、（メタ）アクリル酸
ラウリル、（メタ）アクリル酸ベンジル、ブロム化フェ
ニル（メタ）アクリル酸エステルのようなアクリル酸ま
たはメタアクリル酸エステル類；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、トリメチロールプロパントリ （メ
タ）アクリレート、ジアクリル化インシアヌレート、ペ
ンタエリスリトールトリ（メタ）アクリレート、ペンタ
エリスリトールテトラ（メタ）アクリレート、グリセリ
ンジ（メタ）アクリレート、ネオペンチルグリコールジ
（メタ）アクリレート、ビスフェノールＡジ（メタ）ア
クリレート等のビニル多官能アクリル酸またはメタアク
リル酸エステル類：ポリウレタン（メタ）アクリレート
、ポリエーテル（メタ〉アクリレート、エビクロルヒド
リノ変性ビスフェノールＡジ（メタ）アクリレート、エ
チレンオキシド変性ビスフェノールＡジ（メタ）アクリ
レート、ポリエチレングリコールシ（メタ）アクリレー
ト、ボリブロピレングリコールジ（メタ）アクリレート
等のビニル多官能オＪゴエステル類等が含まれる。In the resin composition of the present invention, radically polymerizable crosslinking monomers can be used in addition to the above-mentioned radical curable resins and halogen-containing allyl ester resins, and any known monomers can be used, but for example, Diallyl phthalates such as diallyl orthophthalate, diallyl isophthalate, diallyl terephthalate; styrene, alpha
- substituted styrenes such as methylstyrene, p-methylstyrene, p-chlorostyrene, bromstyrene, divinylbenzene; (meth)acrylate, (meth)
Acrylic or methacrylic acids such as ethyl acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, benzyl (meth)acrylate, brominated phenyl (meth)acrylate Acrylic acid esters: ethylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, diacrylated incyanurate, pentaerythritol tri(meth)acrylate, pentaerythritol Vinyl polyfunctional acrylic acid or methacrylic acid esters such as tetra(meth)acrylate, glycerin di(meth)acrylate, neopentyl glycol di(meth)acrylate, bisphenol A di(meth)acrylate: polyurethane(meth)acrylate, poly Vinyl polyfunctional materials such as ether (meth)acrylate, shrimp chlorohydrino-modified bisphenol A di(meth)acrylate, ethylene oxide-modified bisphenol A di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, etc. Contains OJ goesters, etc.
この架橋性モノマーは目的に応じて二種類またはそれ以
上を組み合わせて用いても何ら差しつかえない。本発明
において架橋性モノマーを配合すると、本来、固形もし
くは粘稠な液体であるアリルエステル樹脂の粘度を下げ
ることができ、かつ、溶剤等を使用したプリプレグ状態
を経ることなく、積層板の製造工程を簡略化することが
可能である。There is no problem in using two or more types of crosslinking monomers in combination depending on the purpose. In the present invention, by blending the crosslinking monomer, the viscosity of the allyl ester resin, which is originally a solid or viscous liquid, can be lowered, and the manufacturing process of the laminate can be reduced without going through the prepreg state using a solvent or the like. It is possible to simplify.
本発明の樹脂組成物は汎用の有機過酸化物を用いて硬化
させることができ、有機過酸化物とともにまたは単独で
、光に感応する重合開始剤や放射線、電子線に感応する
重合開始剤等の公知の重合開始剤も利用できる。The resin composition of the present invention can be cured using a general-purpose organic peroxide, and may be used together with the organic peroxide or alone, such as a polymerization initiator that is sensitive to light, a polymerization initiator that is sensitive to radiation, or an electron beam. Known polymerization initiators can also be used.
有機過酸化物としては、例えば、メチルエチルケトンパ
ーオキサイド、アセチルアセトンパーオキサイド等のケ
トンバーオサイド類、ｌ、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、ｎ−ブ
チル−４，４−ビス（ｔ−ブチルパーオキシ）バレレー
ト等のパーオキシケタール類、ｔ−ブチルノ１イドロバ
ーオキサイド、クメンハイドロパーオキサイド、ｐ−メ
ンタンハイドロパーオキサイド等のノ＼イドロバーオキ
サイド類、ジ−ｔ−ブチルパーオキサイド、ジクミルパ
ーオキサイド、２，５−ジメチル−２゜５−ジ（ｔ−ブ
チルパーオキシ）ヘキサン等のジアルキルパーオキサイ
ド類、ラウロイルパーオキサイド、ベンゾイルパーオキ
サイド等のジアシルパーオキサイド類、ジー１ｓｏ−プ
ロピルパーオキ７ジカーボネート、ジミリスチルバーオ
キシジカーホネート、ビス（４−ｔ−ブチルシクロヘキ
シル）パーオキシジカーボネート等のパーオキシジカー
ボネート類、ｔ−ブチルパーオキシビバレート、（−ウ
ヒルパーオキシー２−エチルヘキサノエート、ｔ−ブチ
ルパーオキシベンゾエート等のパーオキシエステル類が
あげられる。これらは−種類または二種類以上混合して
、樹脂の種類、硬化条件に応じて用いることができる。Examples of organic peroxides include ketone peroxides such as methyl ethyl ketone peroxide and acetylacetone peroxide, l,1-bis(t-butylperoxy)3,3.5-trimethylcyclohexane, n-butyl-4 , 4-bis(t-butylperoxy)valerate, and other peroxyketals; - dialkyl peroxides such as butyl peroxide, dicumyl peroxide, 2,5-dimethyl-2゜5-di(t-butylperoxy)hexane, diacyl peroxides such as lauroyl peroxide, benzoyl peroxide, Peroxydicarbonates such as di-1so-propylperoxydicarbonate, dimyristylbaroxydicarbonate, bis(4-t-butylcyclohexyl)peroxydicarbonate, t-butylperoxybivalate, (- Examples include peroxyesters such as peroxy-2-ethylhexanoate and t-butylperoxybenzoate.These can be used in one type or in a mixture of two or more types depending on the type of resin and curing conditions. can.
本発明の樹脂組成物には必要に応じて充填材、補強材、
離型材、着色剤、硬化剤、促進剤、安定剤等を併用して
積層板の性能を一層高めることも可能である。The resin composition of the present invention may include fillers, reinforcing materials,
It is also possible to further enhance the performance of the laminate by using a release agent, a coloring agent, a curing agent, an accelerator, a stabilizer, etc. in combination.
本発明の樹脂組成物は公知方法に従って電気用積層板の
製造に使用することもできる。即ち、基材に１一記樹脂
組成物を含浸し、含浸した基材を複数枚積層し、金属箔
張り積層板にあっては片面もしくは両面にあらかじめ接
着剤を塗布した、あるいは塗布しない金属箔を重ね、無
圧または加圧下で加熱、硬化、成形することによって、
電気用積層板を製造することができる。この時、金属箔
は含浸積層基材の硬化成形後、貼りつけてもよい。The resin composition of the present invention can also be used for manufacturing electrical laminates according to known methods. In other words, a base material is impregnated with the resin composition described in 1. By layering, heating, curing, and forming under no pressure or pressure,
Electrical laminates can be manufactured. At this time, the metal foil may be attached after the impregnated laminated base material is cured and molded.
上記基材としては、従来の電気用積層板に用いられてい
る基材と同じものが使用でき、例えば、ガラス繊維布、
ガラス不織布等のガラス系基材、クラフト紙、リンター
紙、コツトン紙等のセルロース系紙基材、無機質繊維系
のシート状または帯状基材等をさす。基材として紙を用
いる場合、含浸性や品質の観点から風乾時の密度が０．
３〜０．７ｇ／ｃ＋ｍ３であるようなセルロース繊維を
主体とした紙、例えばクラフト紙が好ましい。As the base material, the same base materials used for conventional electrical laminates can be used, such as glass fiber cloth,
Refers to glass base materials such as glass nonwoven fabric, cellulose paper base materials such as kraft paper, linter paper, cotton paper, and inorganic fiber sheet or band base materials. When using paper as a base material, from the viewpoint of impregnability and quality, the density when air-dried should be 0.
Paper mainly composed of cellulose fibers having a weight of 3 to 0.7 g/c+m3, such as kraft paper, is preferred.
これら基材は、本発明の樹脂組成物で含浸する前にあら
かじめ、尿素樹脂、メラミン樹脂、グアナミン樹脂等の
Ｎ−メチロール化合物、フェノール樹脂、シランカップ
リング剤等によって含浸乾燥処理を施すことにより、電
気特性の向上を図ることも可能である。Before impregnating these base materials with the resin composition of the present invention, they are pre-impregnated and dried with N-methylol compounds such as urea resins, melamine resins, and guanamine resins, phenol resins, silane coupling agents, etc. It is also possible to improve electrical characteristics.
金属箔としては、電気回路用銅箔張り積層板への用途を
目的とした電解銅箔が市販されており、これを用いるこ
とが、耐食性、エツチング性、接着性の観点から好まし
い。金属箔の厚さは１０〜１００μｍ程度か好ましい。As the metal foil, electrolytic copper foil is commercially available for use in copper foil-clad laminates for electric circuits, and it is preferable to use this from the viewpoints of corrosion resistance, etching property, and adhesiveness. The thickness of the metal foil is preferably about 10 to 100 μm.
金属箔と樹脂含浸基材との接着を効果的に達成するため
には、接着剤を用いることが好ましく、接着剤としては
硬化過程で不必要な副反応生成物の発生しない液状もし
くは半流動状のものが好ましい。かかる観点から、アク
リレート系接着剤、エポキシ系接着剤、エポキシアクリ
レート系接着剤、インシアネート系接着剤、もしくはこ
れらの各種変住接着剤が用いられる。このようにして得
られる電気用積層板の厚みは、基材の種類、硬化配合樹
脂液の組成、積層板の用途によって異なるか、通常、０
５〜５１である。また、電気用積層板中の樹脂組成物の
割合は３０〜８０ｗｔ％である。In order to effectively achieve adhesion between the metal foil and the resin-impregnated substrate, it is preferable to use an adhesive, which is a liquid or semi-liquid adhesive that does not generate unnecessary side reaction products during the curing process. Preferably. From this point of view, acrylate adhesives, epoxy adhesives, epoxy acrylate adhesives, incyanate adhesives, or various modified adhesives thereof are used. The thickness of the electrical laminate obtained in this way varies depending on the type of base material, the composition of the cured compound resin liquid, and the use of the laminate, or is usually 0.
5-51. Further, the proportion of the resin composition in the electrical laminate is 30 to 80 wt%.
以下、
本発明を実施例によって詳しく述べるが、本発明の要旨
を逸脱しない限り、これらの実施例のみに限定されるも
のではない。なお、この明細書を通じて、温度はすべて
°Ｃであり、部及び％は特記しない限り重量基準である
。Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples unless it departs from the gist of the present invention. Throughout this specification, all temperatures are in degrees Celsius, and parts and percentages are by weight unless otherwise specified.
「実施例」
製造例１ アリルエステル樹脂（１）の製、Ｍ蒸留装置
を具備した１１の反応器に、ジアリルテレフタレート６
００ ｇ （２，４４ｍｏ（り 、プロピレングリコー
ル９５．９ ｇ （１，２６ｍｏ１２） 、ジブチル錫
オキサイド０．１ｇ を仕込んで窒素気流下で１８０
’Ｃに加熱し、生成してくるアリルアルコールヲ留去
シタ。アリルアルコール力１４０ ｇ（２，４１ｍｏ１
２）留出したところで、反応器内を５０ ｆｆｌＩｎ）
Ｉｇまで減圧にし留去速度を速めた。プロピレングリコ
ールと当量のアリルアルコールカ留出シた後、反応液を
薄膜蒸留器を用いて２００℃に維持しながら１ ＋ｎ＋
＋Ｈｇにおいて未反応のジアリルテレフタレートを留出
した。反応液をバットにあけ、冷却、粉砕して粉状のア
リルエステル樹脂（１）を得た。"Example" Production Example 1 Diallyl terephthalate 6 was added to 11 reactors equipped with an M distillation apparatus made of allyl ester resin (1).
00 g (2,44 mo), 95.9 g (1,26 mo12) of propylene glycol, and 0.1 g of dibutyltin oxide were charged and heated to 180 g under a nitrogen stream.
Heat to 'C and distill off the allyl alcohol that forms. Allyl alcohol power 140 g (2,41 mo1
2) After distillation, the inside of the reactor was heated to 50 fflIn)
The pressure was reduced to Ig and the distillation rate was increased. After distilling off an amount of allyl alcohol equivalent to propylene glycol, the reaction solution was heated to 1+n+ while maintaining it at 200°C using a thin film distiller.
Unreacted diallyl terephthalate was distilled off at +Hg. The reaction solution was poured into a vat, cooled and pulverized to obtain powdered allyl ester resin (1).
製造例２ 臭素を含有するアリルエステル樹脂（２）の
製造
第１表に示した条件を除いてはアリルエステル樹脂（１
）と同様に操作し、臭素を含有するアリルエステル樹脂
（２）を得た。Production Example 2 Production of allyl ester resin (2) containing bromine Except for the conditions shown in Table 1, allyl ester resin (1
) to obtain a bromine-containing allyl ester resin (2).
製造例３ 塩素を含有するアリルエステル樹脂（３）の
製造
第１表に示した条件を除いてはアリルエステル樹脂（１
）と同様に操作し、塩素を含有するアリルエステル樹脂
（３）を得た。Production Example 3 Production of allyl ester resin (3) containing chlorine Except for the conditions shown in Table 1, allyl ester resin (1
) to obtain a chlorine-containing allyl ester resin (3).
実施例１〜４
坪ｆｉ！ １５５ ｇ／ｍ” 、厚さ３００μｍのクラ
フト紙をメラミン樹脂（日本カーバイド社製Ｓ−３０５
）水溶岐に浸してローラで絞り、１２０°Ｃ１３０分乾
燥させた。得られた紙基材中にメラミン樹脂が１５％付
着した。この紙基材を第２表に示した樹脂組成物の配合
岐に浮かべ片面より樹脂液を含浸させ、７枚を重ね合わ
せ、更に片面に接着剤付き銅箔（三井金属鉱業製ＭＫ−
６１）を重ね合わせ、両面に５０μｍのポリエステルフ
ィルムをラミネートした後、プレス機で加熱、加圧成形
した。加熱加圧条件は１４０℃、３０分、３０ｋｇ／ｃ
ｍ”であった。プレス後、熱風乾燥炉中で１５０℃、１
２０分加熱を行ない、厚さ１．６１の銅箔張り積層板を
得た。該銅箔張りの積層板の試験結果を第３表に示す。Examples 1 to 4 Tsubo fi! 155 g/m", 300 μm thick kraft paper with melamine resin (S-305 manufactured by Nippon Carbide Co., Ltd.)
) It was soaked in water, squeezed with a roller, and dried at 120°C for 130 minutes. 15% of the melamine resin was adhered to the obtained paper base material. This paper base material was floated on the composition of the resin composition shown in Table 2, impregnated with resin liquid from one side, and seven sheets were stacked on top of each other.
61) and laminated with a 50 μm polyester film on both sides, and then heated and pressure-molded using a press machine. Heating and pressing conditions: 140℃, 30 minutes, 30kg/c
m”. After pressing, it was heated at 150°C in a hot air drying oven for 1
Heating was performed for 20 minutes to obtain a copper foil-clad laminate having a thickness of 1.61 mm. The test results of the copper foil-clad laminate are shown in Table 3.
比較例１〜３
第２表に示した比較例の樹脂組成物の配合液を使用した
他は実施例１〜４と同様にして銅箔張り積層板を製造し
た。該銅箔張り積層板の試験結果を第３表に示す。Comparative Examples 1 to 3 Copper foil-clad laminates were produced in the same manner as Examples 1 to 4, except that the blended resin compositions of the comparative examples shown in Table 2 were used. The test results of the copper foil clad laminate are shown in Table 3.
比較例４
市販の紙フエノール銅箔張り積層板（厚さ１．６ｎｕ＋
、ＸＰＣグレード）について実施例と同様にして物性を
試験した。試験結果を第３表に示す。Comparative Example 4 Commercially available paper phenol copper foil laminate (thickness 1.6nu+
, XPC grade) were tested for physical properties in the same manner as in the examples. The test results are shown in Table 3.
第３表から明らかなように、ハロゲン含有アリルエステ
ル樹脂を含む樹脂組成物からなる電気用積層板は、比較
例１．２の不飽和ポリエステル樹脂系積層板より耐熱性
が高く、比較例４のフエノ−ル樹脂系積層板より電気特
性に優れている。As is clear from Table 3, the electrical laminate made of a resin composition containing a halogen-containing allyl ester resin has higher heat resistance than the unsaturated polyester resin laminate of Comparative Example 1.2, and that of Comparative Example 4. It has better electrical properties than phenolic resin laminates.
「発明の効果」
本発明の積層板用樹脂組成物によれば、耐熱性、難燃性
に優れ、しかも他の特性を充分に満足した銅箔張り積層
板等の電気用積層板を得ることができる。"Effects of the Invention" According to the resin composition for laminates of the present invention, it is possible to obtain electrical laminates such as copper foil-clad laminates that have excellent heat resistance and flame retardancy, and also fully satisfy other properties. I can do it.
Claims (1)
は塩素を含む飽和多塩基酸及び／または臭素または塩素
を含む飽和多価アルコールを構成成分として含むハロゲ
ン含有アリルエステル樹脂１０ｗｔ％以上を配合したこ
とを特徴とする積層板用樹脂組成物。10 wt % or more of a halogen-containing allyl ester resin containing a saturated polybasic acid containing bromine or chlorine and/or a saturated polyhydric alcohol containing bromine or chlorine as a component is blended with 90 wt % or less of a radical curable resin. Characteristic resin composition for laminates.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32223889A JPH03182514A (en) | 1989-12-12 | 1989-12-12 | Laminating resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32223889A JPH03182514A (en) | 1989-12-12 | 1989-12-12 | Laminating resin composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03182514A true JPH03182514A (en) | 1991-08-08 |
Family
ID=18141464
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP32223889A Pending JPH03182514A (en) | 1989-12-12 | 1989-12-12 | Laminating resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03182514A (en) |
-
1989
- 1989-12-12 JP JP32223889A patent/JPH03182514A/en active Pending
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