JPH0216938B2 - - Google Patents
Info
- Publication number
- JPH0216938B2 JPH0216938B2 JP59164025A JP16402584A JPH0216938B2 JP H0216938 B2 JPH0216938 B2 JP H0216938B2 JP 59164025 A JP59164025 A JP 59164025A JP 16402584 A JP16402584 A JP 16402584A JP H0216938 B2 JPH0216938 B2 JP H0216938B2
- Authority
- JP
- Japan
- Prior art keywords
- acid
- resin
- unsaturated polyester
- polyester resin
- value
- 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 - Lifetime
Links
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 42
- 229920005989 resin Polymers 0.000 claims description 25
- 239000011347 resin Substances 0.000 claims description 25
- 239000002253 acid Substances 0.000 claims description 22
- 229920006337 unsaturated polyester resin Polymers 0.000 claims description 22
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 19
- 239000003973 paint Substances 0.000 claims description 19
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 150000005846 sugar alcohols Polymers 0.000 claims description 10
- 150000007519 polyprotic acids Polymers 0.000 claims description 9
- 239000005711 Benzoic acid Substances 0.000 claims description 8
- 235000010233 benzoic acid Nutrition 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 6
- 239000011248 coating agent Substances 0.000 claims description 5
- 238000000576 coating method Methods 0.000 claims description 5
- 230000000903 blocking effect Effects 0.000 claims description 4
- 238000007796 conventional method Methods 0.000 claims 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 11
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 10
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 10
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- 239000000654 additive Substances 0.000 description 5
- 238000007605 air drying Methods 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- ATVJXMYDOSMEPO-UHFFFAOYSA-N 3-prop-2-enoxyprop-1-ene Chemical compound C=CCOCC=C ATVJXMYDOSMEPO-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
- 239000000945 filler Substances 0.000 description 4
- 229920001225 polyester resin Polymers 0.000 description 4
- 239000004645 polyester resin Substances 0.000 description 4
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 4
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 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
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 235000011187 glycerol Nutrition 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000008439 repair process Effects 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- UICXTANXZJJIBC-UHFFFAOYSA-N 1-(1-hydroperoxycyclohexyl)peroxycyclohexan-1-ol Chemical compound C1CCCCC1(O)OOC1(OO)CCCCC1 UICXTANXZJJIBC-UHFFFAOYSA-N 0.000 description 2
- -1 2,3-butylene Chemical group 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
- 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
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-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
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 150000007513 acids Chemical class 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 229920000180 alkyd Polymers 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 238000004132 cross linking Methods 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
- 238000005886 esterification reaction Methods 0.000 description 2
- 125000000524 functional group Chemical group 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
- 238000002156 mixing Methods 0.000 description 2
- 238000010422 painting Methods 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
- 230000000704 physical effect Effects 0.000 description 2
- 239000000049 pigment Substances 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
- 239000000454 talc Substances 0.000 description 2
- 229910052623 talc Inorganic materials 0.000 description 2
- 229920005992 thermoplastic resin Polymers 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
- 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
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 2
- 229920006305 unsaturated polyester Polymers 0.000 description 2
- 229940058015 1,3-butylene glycol Drugs 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N 1,4a-dimethyl-7-propan-2-yl-2,3,4,4b,5,6,10,10a-octahydrophenanthrene-1-carboxylic acid Chemical compound C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-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
- 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
- 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
- MMEDJBFVJUFIDD-UHFFFAOYSA-N 2-[2-(carboxymethyl)phenyl]acetic acid Chemical compound OC(=O)CC1=CC=CC=C1CC(O)=O MMEDJBFVJUFIDD-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
- IGDCJKDZZUALAO-UHFFFAOYSA-N 2-prop-2-enoxypropane-1,3-diol Chemical compound OCC(CO)OCC=C IGDCJKDZZUALAO-UHFFFAOYSA-N 0.000 description 1
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 description 1
- 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
- 229930185605 Bisphenol Natural products 0.000 description 1
- 229920000742 Cotton Polymers 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
- 229910001209 Low-carbon steel Inorganic materials 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- 229920000877 Melamine resin Polymers 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
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-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
- 229910000831 Steel Inorganic materials 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-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
- UGZICOVULPINFH-UHFFFAOYSA-N acetic acid;butanoic acid Chemical compound CC(O)=O.CCCC(O)=O UGZICOVULPINFH-UHFFFAOYSA-N 0.000 description 1
- 229920006243 acrylic copolymer Polymers 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- 238000005452 bending Methods 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
- 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 1
- 230000001680 brushing effect Effects 0.000 description 1
- 235000019437 butane-1,3-diol Nutrition 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920006217 cellulose acetate butyrate Polymers 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- MOUPNEIJQCETIW-UHFFFAOYSA-N lead chromate Chemical compound [Pb+2].[O-][Cr]([O-])(=O)=O MOUPNEIJQCETIW-UHFFFAOYSA-N 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
- 150000007974 melamines Chemical class 0.000 description 1
- 150000002739 metals Chemical class 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
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 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
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000014593 oils and fats Nutrition 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000007592 spray painting technique Methods 0.000 description 1
- 239000010959 steel Substances 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
- BSYVTEYKTMYBMK-UHFFFAOYSA-N tetrahydrofurfuryl alcohol Chemical compound OCC1CCCO1 BSYVTEYKTMYBMK-UHFFFAOYSA-N 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 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
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
Description
［産業上の利用分野］
本発明はポリエステル樹脂系の塗料に関し、特
に耐水性の改良された塗料を提供することを目的
とする。
［従来の技術］
従来多塩基酸、多価アルコール及び不飽和多塩
基酸を反応させて得られる不飽和ポリエステル樹
脂、あるいは更に多価アルコールアリルエーテル
などの空乾性付与成分を、導入した空乾性不飽和
ポリエステル樹脂が一般木工用の塗装に、更には
自動車補修用のパテあるいは建築物の目地部分、
サツシまわり、ガラスのはめ込み部等のシーリン
グ材として広く使用されている。
該塗料は優れた光沢、肉持ち感、美麗な仕上が
り等の長所を有しているが、戸外において使用さ
れることが多いため、常により高度な耐水性が要
求されている。
［発明が解決しようとする問題］
しかしながら従来の塗料は必ずしも充分な耐水
性を有してないため、近時耐水性向上への試みと
して不飽和ポリエステル樹脂の構成々分として更
に第三の成分を加えたり、耐水性付与添加剤を塗
料中に配合するなど種々提案されているが、樹脂
を製造する段階で高度な技術・操作を必要とした
り、コスト的に高価なものとなる。又、かかる樹
脂でも高湿時においてはハガレ、フクレ等の問題
が生じたり、あるいは塗膜に濁りを生じたりする
など種々の問題がある。
［問題点を解決するための手段］
しかるに本発明者等が製造法が比較的容易でか
つ耐水性はもとより、塗料としての総合的な物性
にも優れた不飽和ポリエステル樹脂系塗料を開発
すべく鋭意研究を重ねた結果、樹脂中の水酸基又
はカルボキシル基を安息香酸、又はメタノールに
よつて封鎖するという製造法によつて得られた不
飽和ポリエステル樹脂が、所期の目的を達成しう
ることを見出し、本発明を完成するに到つた。
上記安息香酸又はメタノールで不飽和ポリエス
テル樹脂中の水酸基又はカルボキシル基を封鎖す
る場合、基本的には温度150〜240℃で樹脂、安息
香酸又はメタノールを仕込んで反応させると良い
が、実用上は安息香酸とメタノールの反応による
無効消費を少くするため、あるいは操作を容易に
するために封鎖を行う前の不飽和ポリエステル樹
脂を製造する段階で予め原料となる多塩基酸又は
多価アルコールのいずれか一方を他の一方よりや
や過剰に仕込んで樹脂を製造し、樹脂中の残余官
能基、即ち水酸基又はカルボキシル基がいずれか
一方に偏るようにしておくことが好ましい。即
ち、例えば不飽和ポリエステル樹脂をメタノール
で封鎖しようとする場合、不飽和ポリエステル樹
脂の製造を多塩基酸過剰の条件下で行う。その仕
込み量は多価アルコール１当量に対して多塩基酸
1.1〜1.3当量の割合が適当である。重縮合反応に
際しては触媒と該原料を仕込んで必要に応じて減
圧下、温度150〜240℃でエステル化を行い、その
後温度150〜200℃で縮合を行つて目的物を得る。
かかる触媒としてはジブチルスズオキサイド、テ
トラノルマルブチルチタネート、三酸化アンチモ
ン等が任意に使用できる。但し、上記の条件は実
用上最適な方法を挙げたのであつて、必ずしもこ
れに限定されるものではない。しかる後、メタノ
ールを仕込んで樹脂中の官能基の大部分を占める
カルボキシル基と反応させ、封鎖する。該メタノ
ールを系中に仕込む時期としてはポリエステル樹
脂の酸価が30〜90KOHmg／ｇ、水酸基価が０〜
10KOHmg／ｇ、分子量1000〜4000程度となつた
時点で一括又は、分割して仕込む方法が最終的な
塗料物性の上から最も好ましい。該アルコールの
仕込み量は不飽和ポリエステル樹脂の理論酸価に
よつて適宜決定すれば良いが、普通多価アルコー
ル１当量に対して0.2〜0.6当量の割合である。上
記においては一例としてメタノールで封鎖する例
を示したが、安息香酸で行う場合には上記樹脂製
造過程において多価アルコール過剰とすること及
びポリエステル樹脂の水酸基価が30〜90KOH
mg／ｇ、酸価が０〜10KOHmg／ｇとなつた時点
で安息香酸を仕込むこと以外は上記に準じて行う
ことができる。
かかる方法によつて得られる封鎖された不飽和
ポリエステル樹脂の物性としては酸価が０〜
10KOHmg／ｇ、より好ましくは5KOHmg／ｇ以
下、水酸基価が０〜10KOHmg／ｇ、より好まし
くは5KOHmg／ｇ以下で、分子量1000〜4000の範
囲となるようにするのが塗料として最も好ましい
性能が発揮される。
上記不飽和ポリエステル樹脂製造に用いられる
多塩基酸としては通常、不飽和酸が用いられ、必
要に応じて飽和酸が併用される。
不飽和酸としては例えば無水マレイン酸、マレ
イン酸、フマール酸、無水イタコン酸、イタコン
酸等が挙げられ、飽和酸としては無水フタル酸、
フタル酸、テレフタル酸、イソフタル酸、ヘツト
酸、アジピン酸、テトラヒドロ無水フタル酸、ト
リメリツト酸、無水トリメリツト酸、ピロメリツ
ト酸、無水ピロメリツト酸、４―メチルシクロヘ
チレン―１，２，３トリカルボン酸無水物、トリ
メシン酸等が挙げられる。
又、該酸と縮重合させられ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、ジエチレングリコール、トリエチレングリ
コール、ジプロピレングリコール、ビスフエノー
ルジオキシプロピルエーテル、１，３―ブチレン
グリコール、２，３―ブチレングリコール、ネオ
ペンチルグリコール、トリメチロールプロパン、
トリメチロールエタン、ペンタエリスリトール、
グリセリンなどが挙げられる。
本発明の樹脂には、空乾性付与成分として通常
アリル基を含有する成分を上記多塩基酸、多価ア
ルコール成分と共に導入する。アリル基の含有量
は酸成分１モルに対しアリル基として0.05〜２モ
ル、より好ましくは0.1〜1.5モルが適当であり、
0.05モル以下では充分な空乾性を得られず、２モ
ル以上導入すると空乾性はある程度促進されても
塗料として他の性能、主に耐ブリスター性が低下
する傾向があり好ましくない。かかる成分として
具体的にはペンタエリスリトールトリアリルエー
テル、トリメチロールプロパンジアリルエーテ
ル、グリセリ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、グリセリンジアリ
ルエーテルなどがあげられる。特にアリル基を含
有し、かつ一官能のアルコールである化合物、例
えば上記グリセリンジアリルエーテル等は本発明
の特徴である樹脂封鎖用の一官能のアルコールと
しても有用である。
かくして得られる不飽和ポリエステル樹脂は架
橋性単量体と混合して塗料用に用いられる。
架橋性単量体としては、スチレン、ビニルトル
エン、モノクロロスチレン、ジアリルフタレー
ト、メタクリル酸メチル、酢酸ビニル、メタクリ
ル酸グリシジルをはじめ公知の不飽和ポリエステ
ル樹脂用の架橋単量体がいずれも用いられてい
る。
その他の塗料用添加剤としては顔料、充填剤、
光重合開始剤、硬化剤、硬化促進剤、希釈剤、熱
可塑性樹脂などがある。
顔料としてはチタン白、シアニンブルー、クロ
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あげ
られる。
充填剤としては炭酸カルシウム、クレー、タル
ク、マイカ、アスベスト粉末、微粉シリカ、硫酸
バリウム、ステアリン酸亜鉛、リトポンなどがあ
げられる。硬化剤としてはメチルエチルケトンパ
ーオキシド、シクロヘキサノンパーオキシド、ベ
ンゾイルパーオキシド、ジクミルパーオキシド、
ターシヤリーブチルパーベンゾエートなどがあげ
られる。
硬化促進剤としてはオクテン酸コバルト、ナフ
テン酸コバルト、ナフテン酸マンガンなどがあげ
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、メタノール、エタノール、ブタ
ノール、アセトン、メチルイソブチルケトン、メ
チルエチルケトン、セロソルプ、ジアセトンアル
コールなどがあげられる。
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、塩化ビニル、酢酸
ビニル系樹脂、酢酸ビニル樹脂、アクリル樹脂及
びこの共重合体、ブチル化メラミン、ブチル化尿
素などがあげられる。
その他添加剤としてはリン酸、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あげられる。
［発明の効果］
本発明の方法によつて得られる不飽和ポリエス
テル樹脂は上記各種添加剤を適宜配合することに
より、金属・木材・モルタル等あらゆる基材の塗
料用として非常に有用であるが、かかる中でも金
属に対する密着が良好であり、前記架橋性単量
体、充填剤との組合せによつて自動車等の補修用
パテ、スチール家具用プライマー、建築物の目地
部分、サツシまわり、ガラスのはめこみ部等のシ
ーリング材として、特に優れた性能を示すもので
ある。かかる用途は塗料用途の中でも特に高度の
耐水性、それに伴うフクレ、ハガレなどの耐ブリ
スター性が要求されるものである。実用的な配合
量としては本発明の不飽和ポリエステル樹脂10〜
45重量部（樹脂固形分換算）、架橋性単量体５〜
20重量部、充填剤50〜70重量部の範囲から選ばれ
る。塗装方法としてはスプレー塗装、ヘラ塗り、
刷毛塗り等任意の手段が採用される。
自動車の補修用パテ等として使用した時は更に
上塗り塗料を塗布することが出来る。該上塗り塗
料は従来より用いられている着色塗料及びメタリ
ツク塗料等で、例えばアクリルウレタン樹脂、ア
クリルアルキツド硝化綿樹脂、アクリルセルロー
ス、アセテートブチレート樹脂、アルキドメラミ
ン樹脂等が挙げられる。
［実施例］
次に実施例を挙げて本発明の塗料を更に具体的
に説明する。尚、例中「％」とあるのは特にこと
わりのない限り、重量基準である。
実施例 １
撹拌器、還流冷却器付きの２フラスコに無水
マレイン酸0.65モル、テトラヒドロ無水フタル酸
0.35モル、エチレングリコール0.20モル、ジエチ
レングリコール0.40モル、トリエチレングリコー
ル0.50モル、トリアリルエーテルペンタエリスリ
トール0.10モル、溶媒としてキシレン3.0％、重
合禁止剤0.03％を仕込み、150℃から200℃まで３
時間かけて昇温し、200℃で４時間エステル化反
応を行い、酸価7KOHmg／ｇ、水酸基価40KOH
mg／ｇ、分子量約2500とした。
反応系中に更に安息香酸0.25モルを仕込み、
200℃で２時間反応させ、樹脂中の水酸基の9/10
（理論上）を封鎖し、150℃で減圧下にて30分間か
けてキシレンを除去した。
得られた封鎖後の不飽和ポリエステル樹脂の酸
価は5KOHmg／ｇ、水酸基価は4KOHmg／ｇ、分
子量2500であつた。これをスチレンにて希釈し、
固形分65％、粘度1500cps（20℃にて測定、以下同
様）の樹脂液を得た。
又対照例１として安息香酸による封鎖を行わず
に不飽和ポリエステル樹脂（酸価7KOHmg／ｇ、
水酸基価は45KOHmg／ｇ、分子量2300）をその
まま使用してスチレンにて希釈し、固形分65％、
粘度1200cpsの樹脂液を得た。
この樹脂液を更にスチレンで希釈し、オクテン
酸コバルト（８％コバルト含有）を0.5％メチル
エチルケトンパーオキサイド（パーメツク―Ｎ、
日本油脂製）を1.0％混合した後、刷毛を用いて、
ボンデ板上に塗布し、クリヤーの塗膜の耐水性、
金属密着性を調べた。
また、更に実施例―１及び対照例―１の樹脂液
320ｇに対してスチレン65ｇ、タルク546ｇ、酸化
チタン55ｇ、オクテン酸コバルト（８％コバルト
含有）10ｇを加えて、ニーダーにて混練りして、
自動車補修用のパテを製造し、これにシクロヘキ
サノンパーオキサイド（サイボツクスPL川口薬
品製）を、2.0％加えて、磨き軟鋼板にヘラ塗り
し、耐水性及び金属密着性を調べた。
評価方法は、ソルトスプレーにて、24時間，48
時間，96時間後のブリスターの有無及び、折り曲
げによる金属密着性の良否を比較した。パテにお
いては更に乾燥性についても評価した。
結果を第１表に示す。
実施例 ２
第２表に示す如き不飽和ポリエステルを実施例
１に準じて製造した。但し、原料の不飽和ポリエ
ステルの酸価は52KOHmg／ｇ、水酸基価5KOH
mg／ｇ、分子量は3200であつた。その結果を第２
表に示す。
対照例―２として第２表に示す如き一官能のカ
ルボン酸と他の成分を一括仕込みして樹脂を得
て、同様に塗料として評価した。
結果を第２表に示す。
尚、表中の略号は次の意味である。
MAn：無水マレイン酸
THFA：テトラヒドロ無水フタル酸
EG：エチレングリコール
DEG：ジエチレングリコール
TEG：トリエチレングリコール
TAPE：トリアリルペンタエリスリトール
MeOH：メチルアルコール
[Industrial Field of Application] The present invention relates to a polyester resin paint, and in particular, an object of the present invention is to provide a paint with improved water resistance. [Prior art] Conventionally, unsaturated polyester resins obtained by reacting polybasic acids, polyhydric alcohols, and unsaturated polybasic acids, or air-drying unsaturated resins in which an air-drying property imparting component such as polyhydric alcohol allyl ether is further introduced. Saturated polyester resin can be used as a paint for general woodworking, as well as putty for automobile repairs, joints in buildings, etc.
Widely used as a sealant around sash and glass insets. This paint has advantages such as excellent gloss, texture, and beautiful finish, but since it is often used outdoors, a higher level of water resistance is always required. [Problem to be solved by the invention] However, conventional paints do not necessarily have sufficient water resistance, so in recent attempts to improve water resistance, a third component has been added as a constituent of unsaturated polyester resin. Various proposals have been made, such as adding water-resistant additives or adding water-resistant additives to the paint, but these require advanced technology and operations at the stage of manufacturing the resin, and are expensive. In addition, even such resins have various problems such as peeling and blistering under high humidity conditions, or clouding of the coating film. [Means for Solving the Problems] However, the present inventors set out to develop an unsaturated polyester resin paint that is relatively easy to manufacture and has excellent overall physical properties as well as water resistance. As a result of extensive research, we have found that unsaturated polyester resin obtained by a manufacturing method in which the hydroxyl or carboxyl groups in the resin are blocked with benzoic acid or methanol can achieve the desired purpose. This led to the completion of the present invention. When blocking the hydroxyl groups or carboxyl groups in an unsaturated polyester resin with the above benzoic acid or methanol, it is basically best to charge the resin and benzoic acid or methanol and react at a temperature of 150 to 240°C. In order to reduce ineffective consumption due to the reaction between acid and methanol, or to facilitate operation, either polybasic acid or polyhydric alcohol is used as a raw material in advance at the stage of producing unsaturated polyester resin before sealing. It is preferable to produce a resin by charging one in excess of the other so that the remaining functional groups in the resin, ie, hydroxyl groups or carboxyl groups, are biased toward one side. That is, for example, when an unsaturated polyester resin is intended to be capped with methanol, the unsaturated polyester resin is produced under conditions where the polybasic acid is in excess. The amount to be charged is polybasic acid per equivalent of polyhydric alcohol.
A proportion of 1.1 to 1.3 equivalents is suitable. In the polycondensation reaction, a catalyst and the raw materials are charged, and if necessary, esterification is carried out at a temperature of 150 to 240°C under reduced pressure, and then condensation is carried out at a temperature of 150 to 200°C to obtain the desired product.
As such a catalyst, dibutyltin oxide, tetra-n-butyl titanate, antimony trioxide, etc. can be used as desired. However, the above conditions are a practical optimum method, and are not necessarily limited to these. Thereafter, methanol is charged to react with carboxyl groups, which account for most of the functional groups in the resin, to seal them. The timing of charging the methanol into the system is when the acid value of the polyester resin is 30 to 90 KOHmg/g and the hydroxyl value is 0 to 0.
From the viewpoint of the final paint properties, it is most preferable to charge the mixture all at once or in portions when it reaches 10 KOH mg/g and a molecular weight of about 1000 to 4000. The amount of the alcohol to be added may be appropriately determined depending on the theoretical acid value of the unsaturated polyester resin, but is usually in a proportion of 0.2 to 0.6 equivalents per equivalent of the polyhydric alcohol. In the above, an example of blocking with methanol was shown, but when using benzoic acid, it is necessary to use an excess of polyhydric alcohol in the resin manufacturing process and the hydroxyl value of the polyester resin is 30 to 90 KOH.
mg/g, and the same procedure as above can be carried out except that benzoic acid is added when the acid value reaches 0 to 10 KOH mg/g. The physical properties of the blocked unsaturated polyester resin obtained by this method include an acid value of 0 to 0.
The most desirable performance as a paint is achieved when the hydroxyl value is 10KOHmg/g, more preferably 5KOHmg/g or less, the hydroxyl value is 0 to 10KOHmg/g, more preferably 5KOHmg/g or less, and the molecular weight is in the range of 1000 to 4000. be done. As the polybasic acid used for producing the above-mentioned unsaturated polyester resin, an unsaturated acid is usually used, and a saturated acid is used in combination as necessary. Examples of unsaturated acids include maleic anhydride, maleic acid, fumaric acid, itaconic anhydride, itaconic acid, etc., and saturated acids include phthalic anhydride,
Phthalic acid, terephthalic acid, isophthalic acid, hettic acid, adipic acid, tetrahydrophthalic anhydride, trimellitic acid, trimellitic anhydride, pyromellitic acid, pyromellitic anhydride, 4-methylcyclohethylene-1,2,3 tricarboxylic anhydride , trimesic acid and the like. In addition, examples of the polyhydric alcohol to be polycondensed with the acid include ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, bisphenol dioxypropyl ether, 1,3-butylene glycol, and 2,3-butylene. glycol, neopentyl glycol, trimethylolpropane,
Trimethylolethane, pentaerythritol,
Examples include glycerin. In the resin of the present invention, a component containing an allyl group is generally introduced as an air-drying component together with the polybasic acid and polyhydric alcohol component. The content of the allyl group is suitably 0.05 to 2 mol, more preferably 0.1 to 1.5 mol, per 1 mol of the acid component.
If less than 0.05 mol is introduced, sufficient air-drying properties cannot be obtained, and if 2 mol or more is introduced, even though air-drying properties are promoted to some extent, other properties as a coating material, mainly blister resistance, tend to deteriorate, which is not preferable. Specific examples of such components include pentaerythritol triallyl ether, trimethylolpropane diallyl ether, glycerin monoallyl ether, trimethylolethane diallyl ether, and glycerin diallyl ether. In particular, compounds containing an allyl group and which are monofunctional alcohols, such as the above-mentioned glycerin diallyl ether, are also useful as monofunctional alcohols for resin capping, which is a feature of the present invention. The unsaturated polyester resin thus obtained is mixed with a crosslinkable monomer and used for paints. As the crosslinking monomer, all known crosslinking monomers for unsaturated polyester resins are used, including styrene, vinyltoluene, monochlorostyrene, diallyl phthalate, methyl methacrylate, vinyl acetate, and glycidyl methacrylate. . Other paint additives include pigments, fillers,
These include photopolymerization initiators, curing agents, curing accelerators, diluents, thermoplastic resins, etc. Pigments include titanium white, cyanine blue, chrome yellow, watching red, red iron,
Examples include carbon black and aniline black. Examples of fillers include calcium carbonate, clay, talc, mica, asbestos powder, finely divided silica, barium sulfate, zinc stearate, and lithopone. 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 octenoate, cobalt naphthenate, and manganese naphthenate. Examples of the diluent include ethyl acetate, toluene, xylene, methanol, methanol, ethanol, butanol, acetone, methyl isobutyl ketone, methyl ethyl ketone, cellosolve, and diacetone alcohol. Examples of the thermoplastic resin include cellulose acetate butyrate, nitrocellulose, vinyl chloride, vinyl acetate resin, vinyl acetate resin, acrylic resin and copolymers thereof, butylated melamine, butylated urea, and the like. Other additives include phosphoric acid, tartaric acid, phosphorous acid, oils and fats, silicone oil, surfactants,
Examples include paraffin wax. [Effects of the Invention] The unsaturated polyester resin obtained by the method of the present invention is very useful as a paint for all kinds of base materials such as metal, wood, mortar, etc. by appropriately blending the various additives mentioned above. Among these, it has good adhesion to metals, and when combined with the crosslinkable monomer and filler, it can be used as repair putty for automobiles, primer for steel furniture, joints in buildings, around sash, and inset parts of glass. It shows particularly excellent performance as a sealing material. Among other paint applications, such applications require particularly high water resistance and accompanying blistering resistance such as blistering and peeling. The practical amount of the unsaturated polyester resin of the present invention is 10~
45 parts by weight (resin solid content equivalent), crosslinkable monomer 5~
20 parts by weight, filler from 50 to 70 parts by weight. Painting methods include spray painting, spatula painting,
Any means such as brushing may be used. When used as a putty for repairing automobiles, a top coat can be further applied. The top coat is a conventionally used colored paint or metallic paint, and includes, for example, acrylic urethane resin, acrylic alkyd nitrified cotton resin, acrylic cellulose, acetate butyrate resin, alkyd melamine resin, and the like. [Example] Next, the coating material of the present invention will be described in more detail with reference to Examples. In addition, "%" in the examples is based on weight unless otherwise specified. Example 1 0.65 mol of maleic anhydride and tetrahydrophthalic anhydride in two flasks equipped with a stirrer and a reflux condenser.
0.35 mol, ethylene glycol 0.20 mol, diethylene glycol 0.40 mol, triethylene glycol 0.50 mol, triallyl ether pentaerythritol 0.10 mol, xylene 3.0% as a solvent, and polymerization inhibitor 0.03%, and heated from 150℃ to 200℃ 3
The temperature was raised over time and the esterification reaction was carried out at 200℃ for 4 hours, resulting in an acid value of 7KOHmg/g and a hydroxyl value of 40KOH.
mg/g, molecular weight approximately 2500. Furthermore, 0.25 mol of benzoic acid was added to the reaction system.
React at 200℃ for 2 hours to reduce 9/10 of the hydroxyl groups in the resin.
(theoretical) and xylene was removed under reduced pressure at 150° C. for 30 minutes. The obtained unsaturated polyester resin after blocking had an acid value of 5KOHmg/g, a hydroxyl value of 4KOHmg/g, and a molecular weight of 2500. Dilute this with styrene,
A resin liquid with a solid content of 65% and a viscosity of 1500 cps (measured at 20°C, hereinafter the same) was obtained. In addition, as a control example 1, unsaturated polyester resin (acid value 7KOHmg/g, acid value 7KOHmg/g,
Hydroxyl value is 45KOHmg/g, molecular weight is 2300), diluted with styrene, solids content is 65%,
A resin liquid with a viscosity of 1200 cps was obtained. This resin solution was further diluted with styrene, and cobalt octenoate (containing 8% cobalt) was added to 0.5% methyl ethyl ketone peroxide (Permeku-N,
After mixing 1.0% of Nippon Oil & Fats Co., Ltd.), using a brush,
The water resistance of the clear coating is applied on the bond board,
Metal adhesion was investigated. Furthermore, the resin liquid of Example-1 and Control Example-1
Add 65 g of styrene, 546 g of talc, 55 g of titanium oxide, and 10 g of cobalt octoate (containing 8% cobalt) to 320 g and knead with a kneader.
Putty for automobile repair was manufactured, 2.0% cyclohexanone peroxide (manufactured by Cybox PL Kawaguchi Pharmaceutical Co., Ltd.) was added to it, and the putty was applied to a polished mild steel plate to examine its water resistance and metal adhesion. The evaluation method was to use salt spray for 24 hours and 48 hours.
The presence or absence of blisters after 96 hours and the quality of metal adhesion by bending were compared. The drying properties of the putty were also evaluated. The results are shown in Table 1. Example 2 Unsaturated polyesters as shown in Table 2 were produced according to Example 1. However, the acid value of the unsaturated polyester raw material is 52KOHmg/g, and the hydroxyl value is 5KOH.
mg/g, and the molecular weight was 3200. The second result is
Shown in the table. As Control Example 2, a monofunctional carboxylic acid and other components as shown in Table 2 were charged at once to obtain a resin, which was similarly evaluated as a paint. The results are shown in Table 2. The abbreviations in the table have the following meanings. MAn: Maleic anhydride THFA: Tetrahydrophthalic anhydride EG: Ethylene glycol DEG: Diethylene glycol TEG: Triethylene glycol TAPE: Triallylpentaerythritol MeOH: Methyl alcohol
【表】【table】
Claims (1)
酸又はメタノールによつて封鎖することを特徴と
する耐水性の向上した不飽和ポリエステル樹脂塗
料の製造方法。 ２ 多価アルコール１当量に対し、多塩基酸を
1.1〜1.3当量の割合で仕込んで酸価30〜90KOHｍ
ｇ／ｇ、水酸基価０〜10KOHmg／ｇ、分子量
1000〜4000の不飽和ポリエステル樹脂を常法を用
いて製造し、しかる後、メタノールを仕込んで該
樹脂中のカルボキシル基を封鎖して酸価０〜
10KOHmg／ｇ、水酸基価０〜10KOHmg／ｇ、分
子量1000〜4000とすることを特徴とする特許請求
の範囲第１項記載の不飽和ポリエステル樹脂塗料
の製造方法。 ３ 多塩基酸１当量に対し、多価アルコールを
1.1〜1.3当量の割合で仕込んで水酸基価30〜
90KOHmg／ｇ、酸価０〜10KOHmg／ｇ、分子量
1000〜4000の不飽和ポリエステル樹脂を常法を用
いて製造し、しかる後、安息香酸を仕込んで該樹
脂中の水酸基を封鎖して水酸基価０〜10KOH
mg／ｇ、酸価０〜10KOHmg／ｇ、分子量1000〜
4000とすることを特徴とする特許請求の範囲第１
項記載の不飽和ポリエステル樹脂塗料の製造方
法。[Claims] 1. A method for producing an unsaturated polyester resin paint with improved water resistance, which comprises blocking hydroxyl groups or carboxyl groups in the resin with benzoic acid or methanol. 2 Polybasic acid for 1 equivalent of polyhydric alcohol
Charge at a ratio of 1.1 to 1.3 equivalents to obtain an acid value of 30 to 90 KOHm
g/g, hydroxyl value 0-10KOHmg/g, molecular weight
An unsaturated polyester resin having an acid value of 0 to 4000 is produced using a conventional method, and then methanol is added to block the carboxyl groups in the resin to give an acid value of 0 to 4000.
10. The method for producing an unsaturated polyester resin paint according to claim 1, characterized in that the coating has a hydroxyl value of 10 KOH mg/g, a hydroxyl value of 0 to 10 KOH mg/g, and a molecular weight of 1000 to 4000. 3 Polyhydric alcohol for 1 equivalent of polybasic acid
Prepared at a ratio of 1.1 to 1.3 equivalents to achieve a hydroxyl value of 30~
90KOHmg/g, acid value 0-10KOHmg/g, molecular weight
An unsaturated polyester resin having a molecular weight of 1,000 to 4,000 is produced using a conventional method, and then benzoic acid is added to block the hydroxyl groups in the resin to obtain a hydroxyl value of 0 to 10 KOH.
mg/g, acid value 0~10KOHmg/g, molecular weight 1000~
4000. Claim 1 characterized in that
A method for producing an unsaturated polyester resin paint as described in Section 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16402584A JPS6142575A (en) | 1984-08-03 | 1984-08-03 | Preparation of unsaturated polyester resin coating |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16402584A JPS6142575A (en) | 1984-08-03 | 1984-08-03 | Preparation of unsaturated polyester resin coating |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6142575A JPS6142575A (en) | 1986-03-01 |
| JPH0216938B2 true JPH0216938B2 (en) | 1990-04-18 |
Family
ID=15785362
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP16402584A Granted JPS6142575A (en) | 1984-08-03 | 1984-08-03 | Preparation of unsaturated polyester resin coating |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6142575A (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5118783A (en) * | 1990-09-12 | 1992-06-02 | Reichhold Chemicals, Inc. | Chain-stopped unsaturated polyester resins |
| JPH05214600A (en) * | 1992-02-04 | 1993-08-24 | Tsutsumi Seisakusho:Kk | Electrolytic grinding method and device therefor |
| EP0928820A3 (en) * | 1998-01-06 | 2001-11-07 | Cytec Technology Corp. | Wet adhesion promoter |
| JP4623357B2 (en) * | 2003-12-24 | 2011-02-02 | 日立化成工業株式会社 | Unsaturated polyester resin composition and putty paint |
| US20060160986A1 (en) * | 2005-01-18 | 2006-07-20 | Hazen Benjamin R | Low viscosity unsaturated polyester resin with reduced VOC emission levels |
| JP6178679B2 (en) * | 2013-09-17 | 2017-08-09 | 大日本塗料株式会社 | Railcar exterior with laminated coating |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5728126A (en) * | 1980-07-28 | 1982-02-15 | Mitsubishi Rayon Co Ltd | Intermediate of carbon fiber composite |
-
1984
- 1984-08-03 JP JP16402584A patent/JPS6142575A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5728126A (en) * | 1980-07-28 | 1982-02-15 | Mitsubishi Rayon Co Ltd | Intermediate of carbon fiber composite |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6142575A (en) | 1986-03-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JPH0216937B2 (en) | ||
| JP3498971B2 (en) | Powder thermosetting composition for producing matte coating | |
| US20030153640A1 (en) | Powdered thermosetting composition for coatings | |
| MXPA02008053A (en) | Powdered thermosetting composition for coatings. | |
| JPS6019941B2 (en) | Compositions useful for in-mold coatings | |
| JPH0216938B2 (en) | ||
| JPS6324023B2 (en) | ||
| US6461742B1 (en) | Polyester containing tertiary carboxyl groups, preparation method and thermosetting powder compositions containing same | |
| US5902646A (en) | Coating medium, a method of producing multi-layer coatings and the use of the coating medium | |
| US4529757A (en) | Thermosetting resin patching compound | |
| US4075261A (en) | Powder coating composition | |
| JPS6039283B2 (en) | Method for producing polybutadiene-modified unsaturated polyester | |
| JPH0216327B2 (en) | ||
| SU1037845A3 (en) | Process for producing thermohardening polymeric coatings | |
| JPS58215421A (en) | Production of air-drying unsaturated polyester resin | |
| JP3225982B2 (en) | Copolyester resin for steel plate paint | |
| JPH06102753B2 (en) | Unsaturated polyester resin composition for paint | |
| AU551772B2 (en) | Patching compound | |
| JPH04227713A (en) | Polyester resin composition for powder coating compound | |
| JPH0129387B2 (en) | ||
| JP2951369B2 (en) | Putty composition | |
| KR102310666B1 (en) | Primer coating composition | |
| JPS61101513A (en) | Curing of unsaturated polyester | |
| JPS59179669A (en) | Air-drying unsaturated polyester resin paint | |
| JPS63227657A (en) | Alkyd resin composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |