JPH0150329B2 - - Google Patents
Info
- Publication number
- JPH0150329B2 JPH0150329B2 JP17008883A JP17008883A JPH0150329B2 JP H0150329 B2 JPH0150329 B2 JP H0150329B2 JP 17008883 A JP17008883 A JP 17008883A JP 17008883 A JP17008883 A JP 17008883A JP H0150329 B2 JPH0150329 B2 JP H0150329B2
- Authority
- JP
- Japan
- Prior art keywords
- unsaturated polyester
- acid
- unsaturated
- epoxy resin
- producing
- 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
- 229920006305 unsaturated polyester Polymers 0.000 claims description 29
- ATVJXMYDOSMEPO-UHFFFAOYSA-N 3-prop-2-enoxyprop-1-ene Chemical compound C=CCOCC=C ATVJXMYDOSMEPO-UHFFFAOYSA-N 0.000 claims description 16
- 239000003822 epoxy resin Substances 0.000 claims description 14
- 229920000647 polyepoxide Polymers 0.000 claims description 14
- 150000007519 polyprotic acids Polymers 0.000 claims description 11
- 150000005846 sugar alcohols Polymers 0.000 claims description 11
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 10
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical group O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 9
- -1 hydroxyalkyl acrylate Chemical compound 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 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 claims description 6
- 150000008064 anhydrides Chemical class 0.000 claims description 5
- 125000003700 epoxy group Chemical group 0.000 claims description 5
- 239000004593 Epoxy Substances 0.000 claims description 3
- 230000001588 bifunctional effect Effects 0.000 claims description 3
- 230000032050 esterification Effects 0.000 claims description 2
- 238000005886 esterification reaction Methods 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 239000002253 acid Substances 0.000 description 11
- 238000000576 coating method Methods 0.000 description 8
- 239000003973 paint Substances 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000001035 drying Methods 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- 238000007605 air drying Methods 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 4
- JHSWSKVODYPNDV-UHFFFAOYSA-N 2,2-bis(prop-2-enoxymethyl)propane-1,3-diol Chemical compound C=CCOCC(CO)(CO)COCC=C JHSWSKVODYPNDV-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000001530 fumaric acid Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 3
- 229920006337 unsaturated polyester resin Polymers 0.000 description 3
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical compound OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-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
- SVHFBAAZRDCASE-UHFFFAOYSA-N 2-(2-methylphenyl)propan-2-amine Chemical compound CC1=CC=CC=C1C(C)(C)N SVHFBAAZRDCASE-UHFFFAOYSA-N 0.000 description 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-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
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- FYRWKWGEFZTOQI-UHFFFAOYSA-N 3-prop-2-enoxy-2,2-bis(prop-2-enoxymethyl)propan-1-ol Chemical compound C=CCOCC(CO)(COCC=C)COCC=C FYRWKWGEFZTOQI-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
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 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
- 239000000049 pigment Substances 0.000 description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 229920005992 thermoplastic resin Polymers 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 1
- ZWVMLYRJXORSEP-UHFFFAOYSA-N 1,2,6-Hexanetriol Chemical compound OCCCCC(O)CO ZWVMLYRJXORSEP-UHFFFAOYSA-N 0.000 description 1
- UICXTANXZJJIBC-UHFFFAOYSA-N 1-(1-hydroperoxycyclohexyl)peroxycyclohexan-1-ol Chemical compound C1CCCCC1(O)OOC1(OO)CCCCC1 UICXTANXZJJIBC-UHFFFAOYSA-N 0.000 description 1
- BJELTSYBAHKXRW-UHFFFAOYSA-N 2,4,6-triallyloxy-1,3,5-triazine Chemical compound C=CCOC1=NC(OCC=C)=NC(OCC=C)=N1 BJELTSYBAHKXRW-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
- FWLHAQYOFMQTHQ-UHFFFAOYSA-N 2-N-[8-[[8-(4-aminoanilino)-10-phenylphenazin-10-ium-2-yl]amino]-10-phenylphenazin-10-ium-2-yl]-8-N,10-diphenylphenazin-10-ium-2,8-diamine hydroxy-oxido-dioxochromium Chemical compound O[Cr]([O-])(=O)=O.O[Cr]([O-])(=O)=O.O[Cr]([O-])(=O)=O.Nc1ccc(Nc2ccc3nc4ccc(Nc5ccc6nc7ccc(Nc8ccc9nc%10ccc(Nc%11ccccc%11)cc%10[n+](-c%10ccccc%10)c9c8)cc7[n+](-c7ccccc7)c6c5)cc4[n+](-c4ccccc4)c3c2)cc1 FWLHAQYOFMQTHQ-UHFFFAOYSA-N 0.000 description 1
- WMYINDVYGQKYMI-UHFFFAOYSA-N 2-[2,2-bis(hydroxymethyl)butoxymethyl]-2-ethylpropane-1,3-diol Chemical compound CCC(CO)(CO)COCC(CC)(CO)CO WMYINDVYGQKYMI-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
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- LZDXRPVSAKWYDH-UHFFFAOYSA-N 2-ethyl-2-(prop-2-enoxymethyl)propane-1,3-diol Chemical compound CCC(CO)(CO)COCC=C LZDXRPVSAKWYDH-UHFFFAOYSA-N 0.000 description 1
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-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
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 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
- GHPWOVIAXFUGOY-UHFFFAOYSA-N CC=CC=C(O)O Chemical compound CC=CC=C(O)O GHPWOVIAXFUGOY-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- 239000004641 Diallyl-phthalate Substances 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- 239000000020 Nitrocellulose Substances 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
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 235000019485 Safflower oil Nutrition 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 1
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 description 1
- FJWGYAHXMCUOOM-QHOUIDNNSA-N [(2s,3r,4s,5r,6r)-2-[(2r,3r,4s,5r,6s)-4,5-dinitrooxy-2-(nitrooxymethyl)-6-[(2r,3r,4s,5r,6s)-4,5,6-trinitrooxy-2-(nitrooxymethyl)oxan-3-yl]oxyoxan-3-yl]oxy-3,5-dinitrooxy-6-(nitrooxymethyl)oxan-4-yl] nitrate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O)O[C@H]1[C@@H]([C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@@H](CO[N+]([O-])=O)O1)O[N+]([O-])=O)CO[N+](=O)[O-])[C@@H]1[C@@H](CO[N+]([O-])=O)O[C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O FJWGYAHXMCUOOM-QHOUIDNNSA-N 0.000 description 1
- NBICYCZLCAMSBG-UHFFFAOYSA-L [Co+2].CCCCCC=CC([O-])=O.CCCCCC=CC([O-])=O Chemical compound [Co+2].CCCCCC=CC([O-])=O.CCCCCC=CC([O-])=O NBICYCZLCAMSBG-UHFFFAOYSA-L 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- JQRRFDWXQOQICD-UHFFFAOYSA-N biphenylen-1-ylboronic acid Chemical compound C12=CC=CC=C2C2=C1C=CC=C2B(O)O JQRRFDWXQOQICD-UHFFFAOYSA-N 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
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 229920006217 cellulose acetate butyrate Polymers 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000003240 coconut oil Substances 0.000 description 1
- 235000019864 coconut oil Nutrition 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 235000012343 cottonseed oil Nutrition 0.000 description 1
- 239000002385 cottonseed oil Substances 0.000 description 1
- 239000006071 cream Substances 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 229940105990 diglycerin Drugs 0.000 description 1
- GPLRAVKSCUXZTP-UHFFFAOYSA-N diglycerol Chemical compound OCC(O)COCC(O)CO GPLRAVKSCUXZTP-UHFFFAOYSA-N 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- QGEOKXWFGANCJL-UHFFFAOYSA-N ethenyl acetate;hydrochloride Chemical compound Cl.CC(=O)OC=C QGEOKXWFGANCJL-UHFFFAOYSA-N 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000000944 linseed oil Substances 0.000 description 1
- 235000021388 linseed oil Nutrition 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- SGGOJYZMTYGPCH-UHFFFAOYSA-L manganese(2+);naphthalene-2-carboxylate Chemical compound [Mn+2].C1=CC=CC2=CC(C(=O)[O-])=CC=C21.C1=CC=CC2=CC(C(=O)[O-])=CC=C21 SGGOJYZMTYGPCH-UHFFFAOYSA-L 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000007974 melamines Chemical class 0.000 description 1
- GEMHFKXPOCTAIP-UHFFFAOYSA-N n,n-dimethyl-n'-phenylcarbamimidoyl chloride Chemical compound CN(C)C(Cl)=NC1=CC=CC=C1 GEMHFKXPOCTAIP-UHFFFAOYSA-N 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 1
- 235000014593 oils and fats Nutrition 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 238000006116 polymerization reaction 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
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000005713 safflower oil Nutrition 0.000 description 1
- 239000003813 safflower oil Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 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
- ANRHNWWPFJCPAZ-UHFFFAOYSA-M thionine Chemical compound [Cl-].C1=CC(N)=CC2=[S+]C3=CC(N)=CC=C3N=C21 ANRHNWWPFJCPAZ-UHFFFAOYSA-M 0.000 description 1
- 235000010215 titanium dioxide Nutrition 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 239000002383 tung oil Substances 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
Landscapes
- Polyesters Or Polycarbonates (AREA)
- Epoxy Resins (AREA)
- Paints Or Removers (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Description
本発明は、従来よりも一段と諸性能の優れた不
飽和ポリエステルの製法に関する。
多塩基酸、多価アルコール及び多価アルコール
アリルエーテルを反応させて得られる不飽和ポリ
エステル樹脂は空乾性塗料として家具、内装材、
家庭用品等の塗装などに広く利用されている。該
塗料は硬化速度、乾燥速度、研磨性、塗膜硬度及
び耐水性等の面で優れた性質を有しており、実用
性の極めて高い塗料の一つとして益々その需要は
伸びつつある。
しかし、近年技術革新あるいは社会要請の高度
化に伴ない、かかる塗料の上記性質を更に一層向
上せしめることが要求されている。
しかるに本発明者らは、これまでの不飽和ポリ
エステル樹脂よりも更に一段と前記諸性能を向上
させるべく、空乾性塗料に関し鋭意研究を重ね
た。その結果、２官能ビスフエノールＡ型エポキ
シ樹脂中のエポキシ基に(a)アリルエーテル基及び
カルボキシル基を有する不飽和ポリエステル、及
び(b)アクリロキシ置換アルキル基及びカルボキシ
ル基を有する不飽和ポリエステルを結合させたエ
ポキシ樹脂変性不飽和ポリエステルは例えば厚膜
塗布をするような場合であつても硬化速度、乾燥
速度が極めて速く、その上に研磨性、塗膜硬度及
び耐水性の点で従来のアリルエーテル基含有ポリ
エステルをはるかに凌駕する優れた性質を有する
ことを見出し、本発明を完成するに至つた。
本発明中における２官能ビスフエノールＡ型エ
ポキシ樹脂（以下、単にエポキシ樹脂という）と
は、次のような構造式を持つ化合物で該式中ｎは
通常０〜３の範囲から適宜選ばれる。
又、該エポキシ樹脂のエポキシ当量は100〜
500、好ましくは180〜300の範囲がよく、100以下
ではガラス転移温度が低すぎて乾燥速度が落ちる
傾向があり、500以上では本発明の不飽和ポリエ
ステルを製造した時にアリルエーテル基、アクリ
ロキシ置換アルキル基の官能基当量が低くなりす
ぎて硬化速度が落ちるので好ましくない。
本発明に用いる不飽和ポリエステル(a)はアリル
エーテル基とカルボキシル基を含有する不飽和ポ
リエステルであり、要は該不飽和ポリエステル分
子中のカルボキシル基とエポキシ基を反応させる
のである。かかる不飽和ポリエステルは任意の方
法で製造できるが、普通多塩基酸、多価アルコー
ル、多価アルコールアリルエーテルを縮合させて
分子中の遊離のカルボキシル基が少なくとも１個
残存するアリル基含有不飽和ポリエステルを調製
する。多塩基酸としては、マレイン酸、フマル
酸、イタコン酸、シストラコン酸及びこれらの無
水物等の不飽和多塩基酸が用いられ、必要に応じ
てフタル酸、イソフタル酸、テレフタル酸、ヘツ
ト酸、アジピン酸、セバシン酸、コハク酸、アゼ
ライン酸及びこれらの無水物等の飽和多塩基酸も
併用することができる。多価アルコールとして
は、エチレングリコール、プロピレングリコー
ル、ブチレングリコール、ジエチレングリコー
ル、トリメチレングリコール、トリエチレングリ
コール、トリメチロ−ルエタン、トリメチロール
プロパン、ジヒドロキシペンタジエン、ペンタエ
リスリトール、ジグリセリン、ジトリメチロール
プロパン等が挙げられる。多価アルコールアリル
エーテルとしてはグリセリンモノアリルエーテ
ル、トリメチロールプロパンモノアリルエーテ
ル、トリメチロールプロパンジアリルエーテル、
トリメチロールエタンモノアリルエーテル、トリ
メチロールエタンジアリルエーテル、ペンタエリ
スリトールモノアリルエーテル、ペンタエリスリ
トールジアリルエーテル、ペンタエリスリトール
トリアリルエーテル１，２，６−ヘキサントリオ
ールモノアリルエーテル、１，２，６−ヘキサン
トリオールジアリルエーテル、ソルビタンモノア
リルエーテル、ソルビタンジアリルエーテルなど
が挙げられるが、本発明においてはこれらの化合
物に限定されるわけでない。
又、不飽和ポリエステル(a)としては必ずしも上
記組成に限る必要はなく、多塩基酸、好ましくは
無水マレイン酸、フマル酸、イタコン酸等の不飽
和多価カルボン酸と分子中に少なくとも１個の水
酸基を持つ多価アルコールアリルエーテルとの部
分エステル化物の如き低分子化合物であつても差
支えない。
更に(b)はアクリロキシ置換アルキル基及びカル
ボキシル基を有する不飽和ポリエステルであり、
(a)と同様分子中のカルボキシル基とエポキシ樹脂
中のエポキシ基を反応させる。かかる不飽和ポリ
エステル類は多塩基酸と多価アルコールとの縮合
反応時にヒドロキシアルキルアクリレート類を共
存させることによつて製造されうる。勿論、その
分子中に少なくとも１個のカルボキシル基が残存
する様に製造条件をコントロールする必要があ
る。最も実用的には無水マレイン酸、フマル酸等
の不飽和多価カルボン酸を２−ヒドロキシエチル
アクリレート、２−ヒドロキシエチルメタクリレ
ート等のヒドロキシアルキルアクリレート類で部
分エステル化することにによつて得られるものが
使用される。
上記(a)，(b)をエポキシ樹脂と結合させるには任
意の方法が可能である。例えば(a)，(b)を予め別々
に調整しておき、これらを逐次エポキシ樹脂と反
応させる方法、(a)，(b)の原料である多塩基酸、多
価アルコール、多価アルコールアリルエーテル及
びヒドロキシアルキルアクリレートを一括混合し
て反応させ(a)，(b)を系内に生成せしめ、この混合
物にエポキシ樹脂を混合して反応を続けてもよ
い。反応時の温度は60〜90℃程度で充分である。
又、反応触媒として少量のトリメチルベンジルア
ミン、ジエチルアミン、２−メチルイミダゾール
等が添加される。この場合特に溶媒の使用は必ず
しも必要でないが、必要に応じてキシレン、トル
エン等が用いられる。
以上の如く(a)，(b)をエポキシ樹脂中のエポキシ
基に結合せしめることによつて本発明の不飽和ポ
リエステル中にはアリルエーテル基、及びエポキ
シ樹脂成分、無水マレイン酸に基く不飽和酸二重
結合、アクリル酸残基に基く二重結合等の種々の
成分が存在する。かかる成分の存在により前記し
た如き硬化速度、乾燥速度、研磨性、塗膜硬度及
び耐水性等が従来の空乾性ポリエステル樹脂に対
して一段と向上するのである。
本発明の不飽和ポリエステルにおけるエポキシ
樹脂、(a)及び(b)の構成比は、エポキシ樹脂に対し
(a)が0.5〜1.5モル比、(b)が0.5〜1.5モル比の範囲
であることが望ましい。特にアリルエーテル基及
びアクリロキシ置換アルキル基のエポキシ樹脂に
対する含有量は各々0.1〜0.6モル比、0.9〜1.8モ
ル比の範囲から選ばれるべきであり、この範囲以
外では充分な空気乾燥性が得られなくなつたり、
内部硬化と表面硬化のバランスがくずれて表面ち
ぢみ現象（硬化の過程で内部硬化より表面硬化が
先行する現象）が起つたりするので好ましくな
い。該不飽ポリエステルの分子量は1000〜3000、
より好ましくは1500〜2500の範囲が好適である。
分子量が1000以下になると塗装粘度が低すぎて硬
化速度が低下するし、3000以上の場合は該粘度が
高すぎて、スチレン等を大量に使用せねば塗装粘
度に致らず結果として硬化速度の低下を招くので
避けるべきである。
更に該不飽和ポリエステルを塗料用に用いる時
は、一般に重合性単量体と混合する。重合性単量
体としてはスチレン、ビニルトルエン、クロロス
チレン、α−メチルスチレン、ジビニルベンゼ
ン、（メタ）アクリル酸エステル、グリシジルメ
タアクリレート、酢酸ビニル、ジアリルフタレー
ト、トリアリルシアヌレート、トリメチロールプ
ロパントリアクリレート、トリメチロールプロパ
ントリメタアクリレート、桐油、アマニ油、大豆
油、綿実油、サフラワ油、やし油などが挙げられ
る。
塗料用として用いる場合には更に添加剤として
顔料、充填剤、硬化剤、硬化促進剤、希釈剤、熱
可塑性樹脂などを添加して使用することも多い。
顔料としてはチタン白、シアニンブルー、クリ
ームイエロー、ウオツチングレツド、ベンガラ、
カーボンブラツク、アニリンブラツクなどが挙げ
られる。
硬化剤としてはメチルエチルケトンパーオキサ
イド、シクロヘキサノンパーオキサイド、ベンゾ
イルパーオキサイド、ジクミルパーオキサイド、
ターシヤリーブチルパーベンゾエートなどが挙げ
られる。
硬化促進剤としてはオクチル酸コバルト、ナフ
テン酸コバルト、ナフテン酸マンガンなどが挙げ
られる。
希釈剤としては酢酸エチル、トルエン、キシレ
ン、メタノール、エタノール、ブタノール、アセ
トン、メチルエチルケトン、メチルイソブチルケ
トン、セロソルブ、ジアセトンアルコールなどが
挙げられる。
熱可塑性樹脂としてはセルロースアセテートブ
チレート、ニトロセルロース、塩化酢酸ビニル樹
脂、酢酸ビニル樹脂、アクリル樹脂及びこれらの
共重合体、ブチル化メラミン、ブチル化尿素など
が挙げられる。
その他の添加剤としてはりん酸、酒石酸、亜り
ん酸、油脂類、シリコーンオイル、界面活性剤
類、パラフインワツクスなどが挙げられる。
以下実施例を挙げて本発明を具体的に説明す
る。尚例中「部」及び「％」とあるのはいずれも
重量基準である。
実施例 １
(a)成分としてジアリルペンタエリスリトール
1.1モル、無水マレイン酸１モル、無水フタル酸
１モルを温度60℃で５時間反応させて得られた不
飽和ポリエステル30部、(b)成分として２−ヒドロ
キシエチルアクリレート１モル、無水マレイン酸
１モルを温度60℃で時間反応させた不飽和ポリエ
ステル20部をエポキシ樹脂（東都化成製造、エポ
トートYD−128）50部、及び全系に対して0.5％
量のトリメチルベンジルアミンを一括仕込みし
て、80℃で12時間反応させ、樹脂分60％、酸価が
11.5KOHmg／ｇの不飽和ポリエステルを得、こ
れに重合抑制剤としてハイドロキノンを該不飽和
ポリエステルに対し、0.03％加えた。かくして塗
料用に用いた時の性能を以下に示す方法で評価し
た。
１ 硬化速度： 得られた樹脂分60％の塗料をス
チレン溶液で更に50％に希釈した後、オク
テン酸コバルト（コバルト含有量８％）を
0.5％及びパーメツクＮ（日本油脂製メチル
エチルケトンパーオキサイド55％溶液）を
１％添加した。以下、JISK−6901に準じ
て測定した。
２ 乾燥速度： 20℃、65％RH雰囲気中でガラ
ス板に0.5mlアプリケータで塗布し、指触
によつて判定した。
３ 研磨性： 20℃、65％RH雰囲気中でガラス
板に0.5mlアプリケータで塗布して、５時
間後、24時間後におけるペーパー＃320の
研磨性を測定した。
４ 塗膜硬度： JISK5401にもとづき鉛筆の跡
を消しゴムで消してみて、キズがついてい
ない時の鉛筆の硬度値で示した。
５ 耐水性： 90℃の純水中で72時間浸漬後の塗
膜状態を調べた。
実施例 ２〜６
(a)成分のジアリルペンタエリスリトール及び(b)
成分の２−ヒドロキシエチルアクリレート以外の
成分を第１表に示す如く変更した以外は実施例１
と同様にして製造・評価を行つた。但し、(a)成分
においては各酸又はアルコールを仕込んで220℃
で８時間脱水エステル化を行つて、不飽和ポリエ
ステル樹脂を得た。
The present invention relates to a method for producing unsaturated polyester that has various properties that are even better than conventional methods. Unsaturated polyester resin obtained by reacting polybasic acid, polyhydric alcohol, and polyhydric alcohol allyl ether can be used as an air-drying paint for furniture, interior materials,
It is widely used for painting household items, etc. This paint has excellent properties in terms of curing speed, drying speed, abrasiveness, coating hardness, water resistance, etc., and as one of the most practical paints, the demand for it is increasing. However, in recent years, as technological innovations and social demands have become more sophisticated, it has become necessary to further improve the above-mentioned properties of such paints. However, the present inventors have conducted intensive research on air-drying paints in order to further improve the above-mentioned properties compared to conventional unsaturated polyester resins. As a result, (a) an unsaturated polyester having an allyl ether group and a carboxyl group, and (b) an unsaturated polyester having an acryloxy-substituted alkyl group and a carboxyl group were bonded to the epoxy group in the bifunctional bisphenol A type epoxy resin. Epoxy resin-modified unsaturated polyesters have extremely fast curing and drying speeds, even when applying thick films, and are superior to conventional allyl ether bases in terms of polishability, coating hardness, and water resistance. It was discovered that the polyester has superior properties that far exceed those of polyester containing polyester, and the present invention was completed. The bifunctional bisphenol A type epoxy resin (hereinafter simply referred to as epoxy resin) in the present invention is a compound having the following structural formula, in which n is usually appropriately selected from the range of 0 to 3. In addition, the epoxy equivalent of the epoxy resin is 100~
500, preferably in the range of 180 to 300. If it is less than 100, the glass transition temperature will be too low and the drying rate will tend to decrease; if it is more than 500, allyl ether groups, acryloxy-substituted alkyl This is not preferred because the functional group equivalent of the group becomes too low and the curing rate decreases. The unsaturated polyester (a) used in the present invention is an unsaturated polyester containing an allyl ether group and a carboxyl group, and the key is to react the carboxyl group and epoxy group in the unsaturated polyester molecule. Such unsaturated polyesters can be produced by any method, but are usually allyl group-containing unsaturated polyesters in which at least one free carboxyl group remains in the molecule by condensing polybasic acids, polyhydric alcohols, and polyhydric alcohol allyl ethers. Prepare. As the polybasic acid, unsaturated polybasic acids such as maleic acid, fumaric acid, itaconic acid, cistraconic acid and anhydrides thereof are used, and if necessary, phthalic acid, isophthalic acid, terephthalic acid, hettic acid, and adipine acid are used. Saturated polybasic acids such as sebacic acid, succinic acid, azelaic acid, and anhydrides thereof can also be used in combination. Examples of the polyhydric alcohol include ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, trimethylene glycol, triethylene glycol, trimethylol ethane, trimethylolpropane, dihydroxypentadiene, pentaerythritol, diglycerin, ditrimethylolpropane, and the like. Examples of polyhydric alcohol allyl ethers include glycerin monoallyl ether, trimethylolpropane monoallyl ether, trimethylolpropane diallyl ether,
Trimethylolethane monoallyl ether, trimethylolethane diallyl ether, pentaerythritol monoallyl ether, pentaerythritol diallyl ether, pentaerythritol triallyl ether 1,2,6-hexanetriol monoallyl ether, 1,2,6-hexanetriol diallyl Examples include ether, sorbitan monoallyl ether, sorbitan diallyl ether, but the present invention is not limited to these compounds. In addition, the unsaturated polyester (a) is not necessarily limited to the above composition, but contains a polybasic acid, preferably an unsaturated polycarboxylic acid such as maleic anhydride, fumaric acid, and itaconic acid, and at least one polycarboxylic acid in the molecule. It may be a low-molecular compound such as a partially esterified product with a polyhydric alcohol allyl ether having a hydroxyl group. Furthermore, (b) is an unsaturated polyester having an acryloxy-substituted alkyl group and a carboxyl group,
As in (a), the carboxyl group in the molecule and the epoxy group in the epoxy resin are reacted. Such unsaturated polyesters can be produced by coexisting hydroxyalkyl acrylates during the condensation reaction of a polybasic acid and a polyhydric alcohol. Of course, it is necessary to control the manufacturing conditions so that at least one carboxyl group remains in the molecule. Most practically, it is obtained by partially esterifying unsaturated polycarboxylic acids such as maleic anhydride and fumaric acid with hydroxyalkyl acrylates such as 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate. is used. Any method can be used to bond the above (a) and (b) with the epoxy resin. For example, methods for preparing (a) and (b) separately in advance and reacting them sequentially with an epoxy resin, polybasic acids, polyhydric alcohols, and polyhydric alcohol allyls that are the raw materials for (a) and (b). The ether and hydroxyalkyl acrylate may be mixed together and reacted to produce (a) and (b) in the system, and the epoxy resin may be mixed into this mixture to continue the reaction. A temperature of about 60 to 90°C during the reaction is sufficient.
Further, a small amount of trimethylbenzylamine, diethylamine, 2-methylimidazole, etc. is added as a reaction catalyst. In this case, although the use of a solvent is not necessarily required, xylene, toluene, etc. may be used as necessary. As described above, by bonding (a) and (b) to the epoxy group in the epoxy resin, the unsaturated polyester of the present invention contains an allyl ether group, an epoxy resin component, and an unsaturated acid based on maleic anhydride. There are various components such as double bonds, double bonds based on acrylic acid residues, etc. Due to the presence of such components, the curing rate, drying rate, polishability, coating hardness, water resistance, etc. described above are further improved compared to conventional air-drying polyester resins. The composition ratio of the epoxy resin (a) and (b) in the unsaturated polyester of the present invention is
It is desirable that (a) be in a 0.5-1.5 molar ratio and (b) be in a 0.5-1.5 molar ratio. In particular, the content of allyl ether groups and acryloxy-substituted alkyl groups in the epoxy resin should be selected from the ranges of 0.1 to 0.6 molar ratio and 0.9 to 1.8 molar ratio, respectively; outside this range, sufficient air drying properties cannot be obtained. Summer,
This is undesirable because the balance between internal hardening and surface hardening is lost, resulting in a surface shrinkage phenomenon (a phenomenon in which surface hardening precedes internal hardening during the curing process). The molecular weight of the unsaturated polyester is 1000 to 3000,
More preferably, the range is from 1500 to 2500.
If the molecular weight is less than 1000, the viscosity of the coating will be too low and the curing rate will be low, and if it is more than 3000, the viscosity will be too high and the viscosity of the coating will not be achieved unless a large amount of styrene is used, resulting in a decrease in the curing rate. This should be avoided as it may lead to deterioration. Furthermore, when the unsaturated polyester is used for coatings, it is generally mixed with a polymerizable monomer. Polymerizable monomers include styrene, vinyltoluene, chlorostyrene, α-methylstyrene, divinylbenzene, (meth)acrylic acid ester, glycidyl methacrylate, vinyl acetate, diallyl phthalate, triallyl cyanurate, trimethylolpropane triacrylate. , trimethylolpropane trimethacrylate, tung oil, linseed oil, soybean oil, cottonseed oil, safflower oil, coconut oil, and the like. When used as a coating material, additives such as pigments, fillers, curing agents, curing accelerators, diluents, and thermoplastic resins are often added. Pigments include titanium white, cyanine blue, cream yellow, watching red, red red,
Examples include carbon black and aniline black. As a curing agent, methyl ethyl ketone peroxide, cyclohexanone peroxide, benzoyl peroxide, dicumyl peroxide,
Examples include tertiary butyl perbenzoate. Examples of the curing accelerator include cobalt octylate, cobalt naphthenate, and manganese naphthenate. Examples of the diluent include ethyl acetate, toluene, xylene, methanol, ethanol, butanol, acetone, methyl ethyl ketone, methyl isobutyl ketone, cellosolve, and diacetone alcohol. Examples of the thermoplastic resin include cellulose acetate butyrate, nitrocellulose, vinyl acetate chloride resin, vinyl acetate resin, acrylic resin, copolymers thereof, butylated melamine, butylated urea, and the like. Other additives include phosphoric acid, tartaric acid, phosphorous acid, oils and fats, silicone oil, surfactants, paraffin wax, and the like. The present invention will be specifically explained below with reference to Examples. In the examples, "parts" and "%" are all based on weight. Example 1 Diallylpentaerythritol as component (a)
1.1 mol, 30 parts of unsaturated polyester obtained by reacting 1 mol of maleic anhydride and 1 mol of phthalic anhydride at a temperature of 60°C for 5 hours, 1 mol of 2-hydroxyethyl acrylate as component (b), 1 mol of maleic anhydride. 20 parts of unsaturated polyester obtained by reacting moles at 60°C for a period of time, 50 parts of epoxy resin (Toto Kasei Manufacturing Co., Ltd., Epototh YD-128), and 0.5% of the total system.
Amount of trimethylbenzylamine was charged at once and reacted at 80℃ for 12 hours until the resin content was 60% and the acid value was
An unsaturated polyester containing 11.5 KOH mg/g was obtained, and 0.03% of hydroquinone was added as a polymerization inhibitor based on the unsaturated polyester. Thus, the performance when used for paint was evaluated by the method shown below. 1 Curing speed: After diluting the resulting paint with a resin content of 60% to 50% with a styrene solution, cobalt octenoate (cobalt content 8%) was added.
0.5% and 1% of Permec N (methyl ethyl ketone peroxide 55% solution manufactured by NOF Corporation) were added. The following measurements were made in accordance with JISK-6901. 2. Drying speed: It was applied to a glass plate with a 0.5 ml applicator in an atmosphere of 20°C and 65% RH, and judged by touch with a finger. 3 Abrasiveness: The abrasiveness of paper #320 was measured after 5 hours and 24 hours after it was applied to a glass plate with a 0.5 ml applicator in an atmosphere of 20°C and 65% RH. 4. Paint film hardness: Based on JISK5401, pencil marks were erased with an eraser, and the hardness value of the pencil was shown when there were no scratches. 5 Water resistance: The state of the coating film was examined after immersion in pure water at 90°C for 72 hours. Examples 2 to 6 (a) component diallylpentaerythritol and (b)
Example 1 except that the components other than 2-hydroxyethyl acrylate were changed as shown in Table 1.
Manufactured and evaluated in the same manner as above. However, for component (a), add each acid or alcohol and heat at 220℃.
Dehydration and esterification was carried out for 8 hours to obtain an unsaturated polyester resin.
【表】
実施例 ７
(a)成分として無水マレイン酸とトリアリルペン
タエリスリトールとの部分エステル化物、(b)成分
として無水マレイン酸と２−ヒドロキシエチルア
クリレートとの部分エステル化物を用いた以外は
実施例１と同様にして不飽和ポリエステル（酸価
12.5KOHmg／ｇ）を得て、評価を行つた。
対照例
(a)成分及び(b)成分に、無水マレイン酸１モル、
テレフタル酸１モル及びエチレングリコール1.1
モルを反応させた普通の不飽和ポリエステルを用
いた以外は、実施例１と同様にして製造・評価を
行つた。尚、得られた不飽和ポリエステルの酸価
は13KOHmg／ｇであつた。
実施例１〜７及び対照例の評価の結果を第２表
にまとめて記す。[Table] Example 7 Implemented except that (a) a partial ester of maleic anhydride and triallylpentaerythritol was used as the component, and a partial ester of maleic anhydride and 2-hydroxyethyl acrylate was used as the component (b). Unsaturated polyester (acid value
12.5KOHmg/g) was obtained and evaluated. Control example 1 mol of maleic anhydride was added to component (a) and component (b).
1 mole of terephthalic acid and 1.1 mole of ethylene glycol
Production and evaluation were carried out in the same manner as in Example 1, except that an ordinary unsaturated polyester prepared by reacting moles was used. The acid value of the unsaturated polyester obtained was 13 KOHmg/g. The evaluation results of Examples 1 to 7 and the control example are summarized in Table 2.
【表】【table】
【表】
不良 ×〓
[Table] Defective ×〓
Claims (1)
エポキシ基に (a) アリルエーテル及びカルボキシル基を有する
不飽和ポリエステル及び (b) アクリロキシ置換アルキル基及びカルボキシ
ル基を有する不飽和ポリエステルを結合せしめ
ることを特徴とするエポキシ樹脂変性不飽和ポ
リエステルの製法。 ２ (a)が不飽和多塩基酸又はその無水物と１個の
水酸基を持つ多価アルコールアリルエーテルとの
部分エステル化物である特許請求の範囲第１項記
載の不飽和ポリエステルの製法。 ３ (b)が不飽和多塩基酸又はその無水物とヒドロ
キシアルキルアクリレートとの部分エステル化物
である特許請求の範囲第１項記載の不飽和ポリエ
ステルの製法。 ４ 不飽和多塩基酸又はその無水物が無水マレイ
ン酸である特許請求の範囲第２項又は第３項記載
の不飽和ポリエステルの製法。[Claims] 1. The epoxy groups in the bifunctional bisphenol A type epoxy resin include (a) an unsaturated polyester having an allyl ether and a carboxyl group, and (b) an unsaturated polyester having an acryloxy-substituted alkyl group and a carboxyl group. A method for producing an epoxy resin-modified unsaturated polyester characterized by bonding. 2. The method for producing an unsaturated polyester according to claim 1, wherein (a) is a partial esterification product of an unsaturated polybasic acid or its anhydride and a polyhydric alcohol allyl ether having one hydroxyl group. 3. The method for producing an unsaturated polyester according to claim 1, wherein (b) is a partially esterified product of an unsaturated polybasic acid or its anhydride and a hydroxyalkyl acrylate. 4. The method for producing an unsaturated polyester according to claim 2 or 3, wherein the unsaturated polybasic acid or its anhydride is maleic anhydride.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17008883A JPS6060129A (en) | 1983-09-14 | 1983-09-14 | Production of epoxy resin-modified unsaturated polyester |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17008883A JPS6060129A (en) | 1983-09-14 | 1983-09-14 | Production of epoxy resin-modified unsaturated polyester |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6060129A JPS6060129A (en) | 1985-04-06 |
| JPH0150329B2 true JPH0150329B2 (en) | 1989-10-30 |
Family
ID=15898419
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP17008883A Granted JPS6060129A (en) | 1983-09-14 | 1983-09-14 | Production of epoxy resin-modified unsaturated polyester |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6060129A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB9609703D0 (en) * | 1996-05-09 | 1996-07-10 | Scott Bader Co | Crosslinkable allyl vinyl ester resin compositions |
-
1983
- 1983-09-14 JP JP17008883A patent/JPS6060129A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6060129A (en) | 1985-04-06 |
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