JP4894152B2 - Long-term storage method of radically polymerizable resin composition - Google Patents
Long-term storage method of radically polymerizable resin composition Download PDFInfo
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- JP4894152B2 JP4894152B2 JP2005083714A JP2005083714A JP4894152B2 JP 4894152 B2 JP4894152 B2 JP 4894152B2 JP 2005083714 A JP2005083714 A JP 2005083714A JP 2005083714 A JP2005083714 A JP 2005083714A JP 4894152 B2 JP4894152 B2 JP 4894152B2
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- Prior art keywords
- polymerizable resin
- radical polymerizable
- resin composition
- cobalt
- acid
- Prior art date
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- 238000000034 method Methods 0.000 title claims description 15
- 239000011342 resin composition Substances 0.000 title claims description 15
- 238000003860 storage Methods 0.000 title claims description 12
- 230000007774 longterm Effects 0.000 title claims description 10
- 229920005989 resin Polymers 0.000 claims description 30
- 239000011347 resin Substances 0.000 claims description 30
- -1 organic acid salt Chemical class 0.000 claims description 26
- 229910017052 cobalt Inorganic materials 0.000 claims description 21
- 239000010941 cobalt Substances 0.000 claims description 21
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 20
- 229910052757 nitrogen Inorganic materials 0.000 claims description 19
- 229920006337 unsaturated polyester resin Polymers 0.000 claims description 8
- 229920001567 vinyl ester resin Polymers 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- GEMHFKXPOCTAIP-UHFFFAOYSA-N n,n-dimethyl-n'-phenylcarbamimidoyl chloride Chemical group CN(C)C(Cl)=NC1=CC=CC=C1 GEMHFKXPOCTAIP-UHFFFAOYSA-N 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 17
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 12
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 10
- 239000002253 acid Substances 0.000 description 9
- 239000003822 epoxy resin Substances 0.000 description 9
- 229920000647 polyepoxide Polymers 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 7
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 7
- 239000000178 monomer Substances 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 6
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 5
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 4
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 4
- 229920003986 novolac Polymers 0.000 description 4
- 150000007934 α,β-unsaturated carboxylic acids Chemical class 0.000 description 4
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 3
- MOBNLCPBAMKACS-UHFFFAOYSA-N 2-(1-chloroethyl)oxirane Chemical compound CC(Cl)C1CO1 MOBNLCPBAMKACS-UHFFFAOYSA-N 0.000 description 3
- 229930185605 Bisphenol Natural products 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 3
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 3
- 239000001361 adipic acid Substances 0.000 description 3
- 235000011037 adipic acid Nutrition 0.000 description 3
- 238000001879 gelation Methods 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 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 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-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
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 2
- 230000001133 acceleration Effects 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 150000001869 cobalt compounds Chemical class 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000009849 deactivation Effects 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
- 239000007788 liquid Substances 0.000 description 2
- 229940049920 malate Drugs 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- 150000001451 organic peroxides Chemical class 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-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
- 239000000843 powder Substances 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical compound CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 2
- 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
- ZQHJVIHCDHJVII-OWOJBTEDSA-N (e)-2-chlorobut-2-enedioic acid Chemical compound OC(=O)\C=C(\Cl)C(O)=O ZQHJVIHCDHJVII-OWOJBTEDSA-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
- JCTXKRPTIMZBJT-UHFFFAOYSA-N 2,2,4-trimethylpentane-1,3-diol Chemical compound CC(C)C(O)C(C)(C)CO JCTXKRPTIMZBJT-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
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- 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
- IGDCJKDZZUALAO-UHFFFAOYSA-N 2-prop-2-enoxypropane-1,3-diol Chemical compound OCC(CO)OCC=C IGDCJKDZZUALAO-UHFFFAOYSA-N 0.000 description 1
- HNNQYHFROJDYHQ-UHFFFAOYSA-N 3-(4-ethylcyclohexyl)propanoic acid 3-(3-ethylcyclopentyl)propanoic acid Chemical compound CCC1CCC(CCC(O)=O)C1.CCC1CCC(CCC(O)=O)CC1 HNNQYHFROJDYHQ-UHFFFAOYSA-N 0.000 description 1
- CPHURRLSZSRQFS-UHFFFAOYSA-N 3-[4-[2-[4-(3-hydroxypropoxy)phenyl]propan-2-yl]phenoxy]propan-1-ol Chemical compound C=1C=C(OCCCO)C=CC=1C(C)(C)C1=CC=C(OCCCO)C=C1 CPHURRLSZSRQFS-UHFFFAOYSA-N 0.000 description 1
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical group CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- UUAGPGQUHZVJBQ-UHFFFAOYSA-N Bisphenol A bis(2-hydroxyethyl)ether Chemical compound C=1C=C(OCCO)C=CC=1C(C)(C)C1=CC=C(OCCO)C=C1 UUAGPGQUHZVJBQ-UHFFFAOYSA-N 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
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 229920002430 Fibre-reinforced plastic Polymers 0.000 description 1
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-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
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 229930016911 cinnamic acid Natural products 0.000 description 1
- 235000013985 cinnamic acid Nutrition 0.000 description 1
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 1
- 229940018557 citraconic acid Drugs 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000009918 complex formation Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229940120693 copper naphthenate Drugs 0.000 description 1
- SEVNKWFHTNVOLD-UHFFFAOYSA-L copper;3-(4-ethylcyclohexyl)propanoate;3-(3-ethylcyclopentyl)propanoate Chemical compound [Cu+2].CCC1CCC(CCC([O-])=O)C1.CCC1CCC(CCC([O-])=O)CC1 SEVNKWFHTNVOLD-UHFFFAOYSA-L 0.000 description 1
- 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
- PDXRQENMIVHKPI-UHFFFAOYSA-N cyclohexane-1,1-diol Chemical compound OC1(O)CCCCC1 PDXRQENMIVHKPI-UHFFFAOYSA-N 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- BEFDCLMNVWHSGT-UHFFFAOYSA-N ethenylcyclopentane Chemical compound C=CC1CCCC1 BEFDCLMNVWHSGT-UHFFFAOYSA-N 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000011151 fibre-reinforced plastic Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 150000002432 hydroperoxides Chemical class 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 150000002689 maleic acids Chemical class 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
- HNEGQIOMVPPMNR-NSCUHMNNSA-N mesaconic acid Chemical compound OC(=O)C(/C)=C/C(O)=O HNEGQIOMVPPMNR-NSCUHMNNSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- HNEGQIOMVPPMNR-UHFFFAOYSA-N methylfumaric acid Natural products OC(=O)C(C)=CC(O)=O HNEGQIOMVPPMNR-UHFFFAOYSA-N 0.000 description 1
- GUAWMXYQZKVRCW-UHFFFAOYSA-N n,2-dimethylaniline Chemical compound CNC1=CC=CC=C1C GUAWMXYQZKVRCW-UHFFFAOYSA-N 0.000 description 1
- YPEWWOUWRRQBAX-UHFFFAOYSA-N n,n-dimethyl-3-oxobutanamide Chemical compound CN(C)C(=O)CC(C)=O YPEWWOUWRRQBAX-UHFFFAOYSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- RUOPINZRYMFPBF-UHFFFAOYSA-N pentane-1,3-diol Chemical compound CCC(O)CCO RUOPINZRYMFPBF-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 239000004334 sorbic acid Substances 0.000 description 1
- 229940075582 sorbic acid Drugs 0.000 description 1
- 235000010199 sorbic acid Nutrition 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 150000004072 triols Chemical class 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Landscapes
- Macromonomer-Based Addition Polymer (AREA)
Description
本発明は、ラジカル重合性樹脂組成物の硬化性能を維持することが可能な長期保存方法に関する。 The present invention relates to a long-term storage method capable of maintaining the curing performance of a radical polymerizable resin composition.
従来、不飽和ポリエステル樹脂、ビニルエステル樹脂は常温またはこれに近い温度で硬
化させるためにはコバルトの有機酸塩からなる硬化促進剤の使用が不可欠である。
しかしこのコバルトの有機酸塩をベース樹脂に内添し、長期保存した場合、ゲル化時間
および硬化時間が遅延する現象が見られ、一般にゲルタイムドリフトと呼ばれる。このゲ
ルタイムドリフトはベース樹脂の酸価が高い場合や、シリカ微粉末を配合した場合に顕著
にみられる。この現象が発生する原因としては、樹脂中に残存するフリー酸とコバルトと
の錯体形成によるコバルトの失活、あるいは樹脂中のシリカ微粉末にコバルトの有機酸塩が吸着されること等が推定されている。
この現象に対して、例えばＮ，Ｎ’−ジメチルアニリン等のアミン系化合物を硬化促進
助剤として用いる場合があるがその効果は十分ではない。
また硬化促進助剤としてＮ，Ｎ’−ジメチルアセトアセトアミドを不飽和ポリエステル
樹脂、ビニルエステル樹脂に使用し、常温ないしそれに近い温度で、短時間の硬化時間で
、黄変の少ない硬化物が得られることが記載されている（例えば特許文献１及び特許文献
２参照）。しかし、これらの技術では、使用に際しゲルタイムは短くなるが、保存中にゲ
ル化が生じるという問題があった。
Conventionally, in order to cure unsaturated polyester resin and vinyl ester resin at room temperature or a temperature close to this, it is indispensable to use a curing accelerator made of an organic acid salt of cobalt.
However, when this organic acid salt of cobalt is internally added to the base resin and stored for a long period of time, a phenomenon in which the gelation time and the curing time are delayed is observed, and this is generally called gel time drift. This gel time drift is noticeable when the acid value of the base resin is high or when silica fine powder is blended. Possible causes of this phenomenon are the deactivation of cobalt due to the complex formation of free acid and cobalt remaining in the resin, or the adsorption of organic acid salts of cobalt to the fine silica powder in the resin. ing.
For this phenomenon, for example, an amine compound such as N, N′-dimethylaniline may be used as a curing accelerator, but the effect is not sufficient.
In addition, N, N'-dimethylacetoacetamide is used as an accelerator for curing in unsaturated polyester resins and vinyl ester resins, and a cured product with little yellowing can be obtained at room temperature or a temperature close to it at a short curing time. (For example, see Patent Document 1 and Patent Document 2). However, these techniques have a problem that gelation occurs during storage, although the gel time is shortened during use.
コバルトの有機酸塩及びアミン系化合物をラジカル重合性樹脂に添加し、ゲルタイムドリフト現象の発生を防止し、硬化性能を維持することができる長期保存方法を提供するものである。 An organic acid salt of cobalt and an amine compound are added to a radical polymerizable resin to provide a long-term storage method capable of preventing the occurrence of a gel time drift phenomenon and maintaining curing performance.
本発明者らは、前記課題について鋭意検討した結果、特定量のコバルトの有機酸塩及びアセトアミド構造を持ったアミン系化合物を添加すると、長期保存中のゲルタイムドリフトを防止することができることを見いだし、本発明を完成するに至った。
すなわち本発明は、ラジカル重合性樹脂と硬化剤とを含むラジカル重合性樹脂組成物に、コバルトの有機酸塩及びＮ，Ｎ’−ジメチルアセトアセトアミドを添加することによりラジカル重合性樹脂組成物を長期保存する方法であって、前記Ｎ，Ｎ’−ジメチルアセトアセトアミドが、ラジカル重合性樹脂１００重量部に対し、０．０１〜０．１８重量部であり、前記コバルトの有機酸塩が、ラジカル重合性樹脂１００重量部に対し、０．１〜２．０重量部であることを特徴とするラジカル重合性樹脂組成物の長期保存方法を提供するものである。
As a result of intensive studies on the above problems, the present inventors have found that, when a specific amount of an organic acid salt of cobalt and an amine compound having an acetamide structure are added, gel time drift during long-term storage can be prevented, The present invention has been completed.
That is, the present invention provides a radical polymerizable resin composition for a long time by adding an organic acid salt of cobalt and N, N′-dimethylacetoacetamide to a radical polymerizable resin composition containing a radical polymerizable resin and a curing agent. a method of storing, the N, N'-dimethyl acetoacetamide is, relative to 100 parts by weight of the radical polymerizable resin, Ri 0.01 to 0.18 parts by weight der, an organic acid salt of the cobalt, the radical the polymerizable resin 100 parts by weight, there is provided a long-term storage methods of the radical polymerizable resin composition comprising 0.1 to 2.0 parts by weight der Rukoto.
本発明は、コバルトの失活等によるゲルタイムドリフト現象の発生を防止することにより、ラジカル重合性樹脂組成物の保存期間を延長することができる。 The present invention can extend the storage period of the radical polymerizable resin composition by preventing the occurrence of a gel time drift phenomenon due to cobalt deactivation or the like.
次に本発明の詳細について説明する。
本発明のラジカル重合性樹脂組成物の長期保存方法は、コバルトの有機酸塩を硬化促進剤として用い、かつＮ，Ｎ’−ジメチルアセトアセトアミドを硬化促進助剤として用いることが特徴である。
かかるコバルトの有機酸塩としては、ナフテン酸コバルト（６％コバルト）、オクチル酸コバルト（８％コバルト）などの有機コバルト化合物が挙げられる。これらのコバルト化合物を単独又は組み合わせて用いることができる。
またＮ，Ｎ’−ジメチルアセトアセトアミドは下記の化学構造式にて表される。
Next, details of the present invention will be described.
The long-term storage method of the radical polymerizable resin composition of the present invention is characterized in that an organic acid salt of cobalt is used as a curing accelerator and N, N′-dimethylacetoacetamide is used as a curing accelerator.
Examples of the organic acid salt of cobalt include organic cobalt compounds such as cobalt naphthenate (6% cobalt) and cobalt octylate (8% cobalt). These cobalt compounds can be used alone or in combination.
N, N′-dimethylacetoacetamide is represented by the following chemical structural formula.
本発明は、ラジカル重合性樹脂１００重量部に対し、Ｎ，Ｎ’−ジメチルアセトアセト
アミドを、０．０１〜０．１８重量部、好ましくは０．０３重量部〜０．１５重量部用い
るものである。またコバルトの有機酸塩を、ラジカル重合性樹脂１００重量部に対し、０．１〜２．０重量部であり、好ましくは０．３〜１．０重量部用いるものである。
コバルトの有機酸塩及びＮ，Ｎ’−ジメチルアセトアセトアミドをかかる範囲量用いることにより、ラジカル重合性樹脂組成物のゲルタイムドリフト現象の発生を効果的に防止し、長期間保存することが可能となる。
In the present invention, 0.01 to 0.18 parts by weight, preferably 0.03 to 0.15 parts by weight of N, N′-dimethylacetoacetamide is used with respect to 100 parts by weight of the radical polymerizable resin. is there. The cobalt organic acid salt is used in an amount of 0.1 to 2.0 parts by weight, preferably 0.3 to 1.0 parts by weight, based on 100 parts by weight of the radical polymerizable resin.
By using such a range amount of the organic acid salt of cobalt and N, N′-dimethylacetoacetamide, the occurrence of the gel time drift phenomenon of the radical polymerizable resin composition can be effectively prevented, and it can be stored for a long time. .
本発明に使用するラジカル重合性樹脂としては、不飽和ポリエステル樹脂、ビニルエステル樹脂、ウレタン（メタ）アクリレート樹脂、ポリエステル（メタ）アクリレート樹脂等が挙げられる。これらのうち、不飽和ポリエステル樹脂、ビニルエステル樹脂が好ましい。
かかる不飽和ポリエステル樹脂は、α，β−不飽和カルボン酸又は場合により飽和カルボン酸を含むα，β−不飽和カルボン酸とアルコール類とから得られるオリゴマーである。
Examples of the radical polymerizable resin used in the present invention include unsaturated polyester resins, vinyl ester resins, urethane (meth) acrylate resins, and polyester (meth) acrylate resins. Of these, unsaturated polyester resins and vinyl ester resins are preferred.
Such an unsaturated polyester resin is an oligomer obtained from an α, β-unsaturated carboxylic acid or an α, β-unsaturated carboxylic acid containing an optionally saturated carboxylic acid and an alcohol.
α，β−不飽和カルボン酸としては、例えばフマ−ル酸、マレイン酸、無水マレイン酸、イタコン酸、シトラコン酸、メサコン酸、クロロマレイン酸、あるいはこれらのジメチルエステル類などが挙げられる。これらのα，β−不飽和カルボン酸はそれぞれ単独で用いても良いし、２種以上を組み合わせて用いても良い。また、飽和カルボン酸としては、例えば、フタル酸、無水フタル酸、イソフタル酸、テレフタル酸、ヘット酸、ヘキサヒドロ無水フタル酸、アジピン酸、セバチン酸、アゼライン酸などが挙げられる。これらの飽和カルボン酸はそれぞれ単独で用いても良いし、２種以上を組み合わせて用いても良い。 Examples of the α, β-unsaturated carboxylic acid include fumaric acid, maleic acid, maleic anhydride, itaconic acid, citraconic acid, mesaconic acid, chloromaleic acid, and dimethyl esters thereof. These α, β-unsaturated carboxylic acids may be used alone or in combination of two or more. Examples of the saturated carboxylic acid include phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, hetic acid, hexahydrophthalic anhydride, adipic acid, sebacic acid, and azelaic acid. These saturated carboxylic acids may be used alone or in combination of two or more.
一方、アルコール類としては、例えば、エチレングリコール、ジエチレングリコール、プロピレングリコール、ジプロピレングリコール、トリエチレングリコール、１，３−ブタンジオール、１，４−ブタンジオール、１，３−ペンタンジオール、１，６−ヘキサンジオール、シクロヘキサンジオール、ネオペンチルグリコール、２，２，４−トリメチル−１，３−ペンタンジオール、グリセリンモノアリルエーテル、水素化ビスフェノールＡ、２，２−ビス（４−ヒドロキシプロボキシフェニル）プロパン、２，２−ビス（４−ヒドロキシエトキシフェニル）プロパンなどのジオール類、トリメチロールプロパンなどのトリオール類、ペンタエリスリトールなどのテトラオール類などが挙げられる。これらのアルコールはそれぞれ単独で用いても、２種類以上を組み合わせて用いても良い。 On the other hand, examples of alcohols include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, triethylene glycol, 1,3-butanediol, 1,4-butanediol, 1,3-pentanediol, 1,6- Hexanediol, cyclohexanediol, neopentyl glycol, 2,2,4-trimethyl-1,3-pentanediol, glycerol monoallyl ether, hydrogenated bisphenol A, 2,2-bis (4-hydroxypropoxyphenyl) propane, Examples thereof include diols such as 2,2-bis (4-hydroxyethoxyphenyl) propane, triols such as trimethylolpropane, and tetraols such as pentaerythritol. These alcohols may be used alone or in combination of two or more.
前記ビニルエステル樹脂としては、従来一般に慣用されている公知のエポキシ（メタ）アクリレート樹脂が使用できる。例えばビスフェノールタイプのエポキシ樹脂単独またはビスフェノールタイプのエポキシ樹脂とノボラックタイプのエポキシ樹脂とを混合したものと不飽和一塩基酸とを付加反応せしめたものが挙げられる。
ビスフェノールタイプのエポキシ樹脂としては、エピクロルヒドリンとビスフェノールＡまたはビスフェノ―ルＦとの反応により得られるグリシジルエーテル型のエポキシ樹脂、メチルエピクロルヒドリンとビスフェノールＡまたはビスフェノールＦとの反応により得られるジメチルグリシジルエーテル型のエポキシ樹脂あるいはビスフェノールＡのアルキレンオキサイド付加物とエピクロルヒドリンまたはメチルエピクロルヒドリンとから得られるエポキシ樹脂などが挙げられる。
ノボラックタイプのエポキシ樹脂としては、フェノールノボラックまたはクレゾールノボラックと、エピクロルヒドリンまたはメチルエピクロルヒドリンとの反応により得られるエポキシ樹脂などが挙げられる。
As the vinyl ester resin, a known epoxy (meth) acrylate resin that is generally used conventionally can be used. For example, a bisphenol type epoxy resin alone or a mixture of a bisphenol type epoxy resin and a novolac type epoxy resin and an unsaturated monobasic acid may be added.
Examples of bisphenol type epoxy resins include glycidyl ether type epoxy resins obtained by reaction of epichlorohydrin with bisphenol A or bisphenol F, and dimethyl glycidyl ether type epoxy obtained by reaction of methyl epichlorohydrin with bisphenol A or bisphenol F. Examples thereof include an epoxy resin obtained from a resin or an alkylene oxide adduct of bisphenol A and epichlorohydrin or methyl epichlorohydrin.
Examples of the novolak type epoxy resin include an epoxy resin obtained by a reaction of a phenol novolak or cresol novolak with epichlorohydrin or methyl epichlorohydrin.
不飽和一塩基酸としては、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、ソルビン酸あるいはモノ（２−エチルヘキシル）マレート等が挙げられる。これらの不飽和一塩基酸は単独又は２種以上組み合わせて用いられる。 Examples of the unsaturated monobasic acid include acrylic acid, methacrylic acid, cinnamic acid, crotonic acid, monomethyl malate, sorbic acid or mono (2-ethylhexyl) malate. These unsaturated monobasic acids are used alone or in combination of two or more.
本発明に使用するラジカル重合性樹脂組成物は、エチレン性不飽和単量体を含むものである。エチレン性不飽和単量体としては、例えば（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸プロピル、（メタ）アクリル酸イソプロピル、（メタ）アクリル酸ブチル、（メタ）アクリル酸イソブチル、（メタ）アクリル酸シクロヘキシル等の（メタ）アクリル酸エステル類が挙げられる。さらに、これらのほかに、例えば炭素数が１〜１２のアルキル基を有する（メタ）アクリル酸エステル、スチレン、α−メチルスチレン、（メタ）アクリル酸アミド、炭素数１〜４のアルキル基を有するマレイン酸エステル及びフマ−ル酸エステル等が挙げられる。これらのうち、スチレンが好ましい。 The radical polymerizable resin composition used in the present invention contains an ethylenically unsaturated monomer. Examples of the ethylenically unsaturated monomer include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, and (meth) acrylic. Examples include (meth) acrylic acid esters such as isobutyl acid and cyclohexyl (meth) acrylate. In addition to these, for example, a (meth) acrylic acid ester having 1 to 12 carbon atoms, styrene, α-methylstyrene, (meth) acrylic acid amide, or an alkyl group having 1 to 4 carbon atoms. Examples thereof include maleic acid esters and fumaric acid esters. Of these, styrene is preferred.
また、前記エチレン性不飽和単量体に多官能性重合性単量体を併用することができる。かかる多官能性重合性単量体としては、例えばエチレングリコールジ（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、トリエチレングリコールジ（メタ）アクリレート、ブチレングリコールジ（メタ）アクリレート、トリメチロールプロパンジ（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、ペンタエリスリトールジ（メタ）アクリレート、ヘキサンジオールジ（メタ）アクリレート、オリゴエチレンジ（メタ）アクリレートなどが挙げられる。 Moreover, a polyfunctional polymerizable monomer can be used in combination with the ethylenically unsaturated monomer. Examples of such polyfunctional polymerizable monomers include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, trimethylolpropane di ( Examples include meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol di (meth) acrylate, hexanediol di (meth) acrylate, and oligoethylene di (meth) acrylate.
ラジカル重合性樹脂とエチレン性不飽和単量体との割合は、重量比でラジカル重合性樹脂：エチレン性不飽和単量体＝４０〜８０：６０〜２０であることが好ましい。 The ratio of the radical polymerizable resin to the ethylenically unsaturated monomer is preferably radical polymerizable resin: ethylenically unsaturated monomer = 40 to 80:60 to 20 by weight ratio.
本発明のラジカル重合性樹脂組成物には、有機過酸化物等の硬化剤を用いることができ
る。
有機過酸化物としては、例えばジアリルパーオキサイド系、パーオキシエステル系、ハ
イドロパーオキサイド系、ジアルキルパーオキサイド系、ケトンパーオキサイド系、パー
オキシケタール系、アルキルパーエステル系、パーカーボネート系等の公知のものが使用
され硬化温度により適時選択される。また、必要に応じて、有機系、無機系の着色剤、充
填剤を用いることができる。例えば樹脂にチキソ性を付与するための乾式シリカや着色用
トナーが挙げられる。
本発明の長期保存方法は、ラジカル重合性樹脂の常温硬化の分野、例えば繊維強化プラスチック、塗料、ライニング、注型等の分野で用いられる。
In the radical polymerizable resin composition of the present invention, a curing agent such as an organic peroxide can be used.
Examples of the organic peroxide include known diallyl peroxides, peroxyesters, hydroperoxides, dialkyl peroxides, ketone peroxides, peroxyketals, alkyl peroxides, and carbonates. The one used is selected as appropriate according to the curing temperature. Moreover, an organic type and an inorganic type coloring agent and a filler can be used as needed. Examples thereof include dry silica and color toner for imparting thixotropy to the resin.
The long-term storage method of the present invention is used in the field of room temperature curing of radically polymerizable resins, for example, in the fields of fiber reinforced plastics, paints, linings, casting and the like.
以下本発明を実施例によって更に詳細に説明するが、本発明はこれらの実施例に限定されるものではない。また、文中「部」「％」とあるのは、重量部、重量％を示すものである。 EXAMPLES Hereinafter, although an Example demonstrates this invention still in detail, this invention is not limited to these Examples. In the text, “parts” and “%” indicate parts by weight and% by weight.
合成例１
温度計、アンカー型攪拌翼及び冷却器を具備した５Ｌ三口フラスコで、エピクロン１０５０[ビスフェノールＡとエピクロルヒドリンとの反応により得られたエポキシ当量が４７０のエポキシ樹脂、大日本インキ化学工業(株)製]４６００ｇ、メタクリル酸８６０ｇ（エポキシ基／カルボキシル基＝１／１モル比）とハイドロキノンの１．３６ｇ及びトリエチルアミンの１０．８ｇを仕込んで、１２０℃まで昇温させ、同温度で１０時間反応を続けた。サンプリングして、酸価が３．５、色数が２で冷却した。トルハイドロキノン２５ｐｐｍ、ナフテン酸銅１０ｐｐｍを添加し、スチレンで希釈し、不揮発分６０％の液状のビニルエステル樹脂を得た。このビニルエステル樹脂を以下ＶＥ−１という。
Synthesis example 1
Epicron 1050 [Epoxy resin having an epoxy equivalent of 470 obtained by reaction of bisphenol A and epichlorohydrin, manufactured by Dainippon Ink & Chemicals, Inc.] in a 5 L three-necked flask equipped with a thermometer, an anchor type stirring blade and a cooler 4600 g, 860 g of methacrylic acid (epoxy group / carboxyl group = 1/1 molar ratio), 1.36 g of hydroquinone and 10.8 g of triethylamine were charged, the temperature was raised to 120 ° C., and the reaction was continued at the same temperature for 10 hours. . Sampling and cooling with an acid value of 3.5 and a color number of 2. Toluhydroquinone 25 ppm and naphthenic acid copper 10 ppm were added and diluted with styrene to obtain a liquid vinyl ester resin having a nonvolatile content of 60%. This vinyl ester resin is hereinafter referred to as VE-1.
実施例１、２及び比較例１、２
ＶＥ−１を用い、硬化促進剤及び硬化促進助剤を表−１のとおり配合した。
ゲルタイムの測定方法は、ＪＩＳ Ｋ６９０１ ５．１０．１[常温ゲル化時間（Ａ法）]によるものである。またゲルタイム測定は、配合直後から３ヶ月後まで実施した。
Examples 1 and 2 and Comparative Examples 1 and 2
Using VE-1, a curing accelerator and a curing acceleration assistant were blended as shown in Table 1.
The measuring method of gel time is based on JIS K6901 5.10.1 [normal temperature gelation time (Method A)]. The gel time was measured from immediately after compounding to 3 months later.
６％コバルト ：６％ナフテン酸コバルト
ＤＭＡ ：ジメチルアニリン
ＤＭＡＡＭ ：ジメチルアセトアセトアミド
ＱＳ−２０Ｌ ：レオロシール ＱＳ−２０Ｌ[(株)トクヤマ製]
５５％ＭＥＫＰＯ：５５％メチルエチルケトンパーオキサイド
55% MEKPO: 55% methyl ethyl ketone peroxide
合成例２
温度計、アンカー型攪拌翼及び冷却器を具備した５Ｌ三口フラスコに、ジエチレングリコール（ＤＥＧ）３．５モル、テレフタル酸（ＴＰＡ）１．２モル、アジピン酸（ＡＡ）０．５モル、ジブチル錫オキサイド１０００ｐｐｍを仕込んで窒素気流下２１５℃で１２時間反応を続け、ソリッド酸価が３以下になったところで、１５０℃まで冷却し、無水フタル酸０．８モル、無水マレイン酸１．０モルを仕込み、２０５℃まで昇温した。同温度で１６時間反応を続けた。サンプリングは６０％スチレン溶液で行い、酸価１０〜２０、ガードナー粘度Ｋ〜Ｌで冷却した。トルハイドロキノン３０ｐｐｍ、ナフテン酸銅１０ｐｐｍを添加し、スチレンで希釈し、不揮発分６０％の液状の不飽和ポリエステル樹脂を得た。この不飽和ポリエステル樹脂をＵＰ−１という。
Synthesis example 2
In a 5 L three-necked flask equipped with a thermometer, an anchor-type stirring blade and a condenser, diethylene glycol (DEG) 3.5 mol, terephthalic acid (TPA) 1.2 mol, adipic acid (AA) 0.5 mol, dibutyltin oxide The reaction was continued for 12 hours at 215 ° C. under a nitrogen stream when 1000 ppm was added. When the solid acid value became 3 or less, the mixture was cooled to 150 ° C., and 0.8 mol of phthalic anhydride and 1.0 mol of maleic anhydride were added. The temperature was raised to 205 ° C. The reaction was continued for 16 hours at the same temperature. Sampling was performed with a 60% styrene solution and cooled with an acid value of 10 to 20 and a Gardner viscosity of K to L. 30 ppm of toluhydroquinone and 10 ppm of copper naphthenate were added and diluted with styrene to obtain a liquid unsaturated polyester resin having a nonvolatile content of 60%. This unsaturated polyester resin is referred to as UP-1.
実施例３及び比較例３
ＵＰ−１を用い、硬化促進剤及び硬化促進助剤を表−２のとおり配合した。ゲルタイムの測定方法は、前記と同様である。
Example 3 and Comparative Example 3
Using UP-1, a curing accelerator and a curing acceleration assistant were blended as shown in Table 2. The method for measuring the gel time is the same as described above.
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| JPH01254723A (en) * | 1988-04-01 | 1989-10-11 | Showa Highpolymer Co Ltd | Cure promotion of radically curable resin |
| JP2005036176A (en) * | 2003-06-25 | 2005-02-10 | Japan Composite Co Ltd | Method for curing resin composition |
| JP2006176715A (en) * | 2004-12-24 | 2006-07-06 | Hitachi Chem Co Ltd | Composition for decorative laminate and decorative laminate using the same resin composition for decorative laminate |
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