JP4657073B2 - Paint composition - Google Patents
Paint composition Download PDFInfo
- Publication number
- JP4657073B2 JP4657073B2 JP2005293455A JP2005293455A JP4657073B2 JP 4657073 B2 JP4657073 B2 JP 4657073B2 JP 2005293455 A JP2005293455 A JP 2005293455A JP 2005293455 A JP2005293455 A JP 2005293455A JP 4657073 B2 JP4657073 B2 JP 4657073B2
- Authority
- JP
- Japan
- Prior art keywords
- polyester resin
- acid
- unsaturated polyester
- coating composition
- meth
- 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.)
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- 239000000203 mixture Substances 0.000 title description 45
- 239000003973 paint Substances 0.000 title description 14
- 229920006337 unsaturated polyester resin Polymers 0.000 claims description 57
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 23
- -1 hydroxyalkyl methacrylate Chemical compound 0.000 claims description 20
- ATVJXMYDOSMEPO-UHFFFAOYSA-N 3-prop-2-enoxyprop-1-ene Chemical group C=CCOCC=C ATVJXMYDOSMEPO-UHFFFAOYSA-N 0.000 claims description 18
- 238000000576 coating method Methods 0.000 claims description 18
- 239000008199 coating composition Substances 0.000 claims description 17
- 239000007787 solid Substances 0.000 claims description 16
- 150000005846 sugar alcohols Polymers 0.000 claims description 15
- 239000000049 pigment Substances 0.000 claims description 14
- 150000001875 compounds Chemical class 0.000 claims description 13
- 229910000831 Steel Inorganic materials 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 11
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 11
- 239000010959 steel Substances 0.000 claims description 11
- 239000003112 inhibitor Substances 0.000 claims description 8
- 150000004982 aromatic amines Chemical class 0.000 claims description 6
- ALVZNPYWJMLXKV-UHFFFAOYSA-N 1,9-Nonanediol Chemical compound OCCCCCCCCCO ALVZNPYWJMLXKV-UHFFFAOYSA-N 0.000 claims description 4
- VOAMNTKOJLSJCP-UHFFFAOYSA-N [Ca].[Zn].NC#N Chemical compound [Ca].[Zn].NC#N VOAMNTKOJLSJCP-UHFFFAOYSA-N 0.000 claims description 4
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 claims description 3
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims 1
- 229920000137 polyphosphoric acid Polymers 0.000 claims 1
- 150000003839 salts Chemical class 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 description 34
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 27
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 22
- 235000014113 dietary fatty acids Nutrition 0.000 description 21
- 239000000194 fatty acid Substances 0.000 description 21
- 229930195729 fatty acid Natural products 0.000 description 21
- 150000004665 fatty acids Chemical class 0.000 description 21
- 239000011248 coating agent Substances 0.000 description 16
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 15
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 15
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 12
- 239000003795 chemical substances by application Substances 0.000 description 12
- 238000001035 drying Methods 0.000 description 12
- YDIYEOMDOWUDTJ-UHFFFAOYSA-N 4-(dimethylamino)benzoic acid Chemical compound CN(C)C1=CC=C(C(O)=O)C=C1 YDIYEOMDOWUDTJ-UHFFFAOYSA-N 0.000 description 10
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 10
- 229920005989 resin Polymers 0.000 description 10
- 239000011347 resin Substances 0.000 description 10
- 238000006482 condensation reaction Methods 0.000 description 9
- 150000007519 polyprotic acids Polymers 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 7
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 7
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 230000003449 preventive effect Effects 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 6
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 5
- 239000001530 fumaric acid Substances 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- 235000019198 oils Nutrition 0.000 description 5
- 229920006395 saturated elastomer Polymers 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 4
- 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 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 4
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- QPKOBORKPHRBPS-UHFFFAOYSA-N bis(2-hydroxyethyl) terephthalate Chemical compound OCCOC(=O)C1=CC=C(C(=O)OCCO)C=C1 QPKOBORKPHRBPS-UHFFFAOYSA-N 0.000 description 4
- 229910001873 dinitrogen Inorganic materials 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 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
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 3
- 239000004640 Melamine resin Substances 0.000 description 3
- 229920000877 Melamine resin Polymers 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 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 3
- 239000003085 diluting agent Substances 0.000 description 3
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 3
- 238000001879 gelation Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 125000006606 n-butoxy group Chemical group 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 238000005498 polishing Methods 0.000 description 3
- 229920001225 polyester resin Polymers 0.000 description 3
- 239000004645 polyester resin Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000000454 talc Substances 0.000 description 3
- 229910052623 talc Inorganic materials 0.000 description 3
- 229920006305 unsaturated polyester Polymers 0.000 description 3
- 239000003981 vehicle Substances 0.000 description 3
- 238000004383 yellowing Methods 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- OJPDDQSCZGTACX-UHFFFAOYSA-N 2-[n-(2-hydroxyethyl)anilino]ethanol Chemical compound OCCN(CCO)C1=CC=CC=C1 OJPDDQSCZGTACX-UHFFFAOYSA-N 0.000 description 2
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 description 2
- NEGFNJRAUMCZMY-UHFFFAOYSA-N 3-(dimethylamino)benzoic acid Chemical compound CN(C)C1=CC=CC(C(O)=O)=C1 NEGFNJRAUMCZMY-UHFFFAOYSA-N 0.000 description 2
- JJYPMNFTHPTTDI-UHFFFAOYSA-N 3-methylaniline Chemical compound CC1=CC=CC(N)=C1 JJYPMNFTHPTTDI-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-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
- 239000004593 Epoxy Substances 0.000 description 2
- 239000004606 Fillers/Extenders Substances 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 229920000388 Polyphosphate Polymers 0.000 description 2
- 239000005819 Potassium phosphonate Substances 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 238000007259 addition reaction Methods 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 238000007605 air drying Methods 0.000 description 2
- 229920000180 alkyd Polymers 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- QBLDFAIABQKINO-UHFFFAOYSA-N barium borate Chemical compound [Ba+2].[O-]B=O.[O-]B=O QBLDFAIABQKINO-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
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- JQRRFDWXQOQICD-UHFFFAOYSA-N biphenylen-1-ylboronic acid Chemical compound C12=CC=CC=C2C2=C1C=CC=C2B(O)O JQRRFDWXQOQICD-UHFFFAOYSA-N 0.000 description 2
- 235000019437 butane-1,3-diol Nutrition 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
- 150000001768 cations Chemical class 0.000 description 2
- 239000007795 chemical reaction product 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
- 230000000052 comparative effect Effects 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- GGSUCNLOZRCGPQ-UHFFFAOYSA-N diethylaniline Chemical compound CCN(CC)C1=CC=CC=C1 GGSUCNLOZRCGPQ-UHFFFAOYSA-N 0.000 description 2
- YXXXKCDYKKSZHL-UHFFFAOYSA-M dipotassium;dioxido(oxo)phosphanium Chemical compound [K+].[K+].[O-][P+]([O-])=O YXXXKCDYKKSZHL-UHFFFAOYSA-M 0.000 description 2
- ORBFAMHUKZLWSD-UHFFFAOYSA-N ethyl 2-(dimethylamino)benzoate Chemical compound CCOC(=O)C1=CC=CC=C1N(C)C ORBFAMHUKZLWSD-UHFFFAOYSA-N 0.000 description 2
- CQNOGTUXPYIVDM-UHFFFAOYSA-N ethyl 3-(dimethylamino)benzoate Chemical compound CCOC(=O)C1=CC=CC(N(C)C)=C1 CQNOGTUXPYIVDM-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 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
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 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 2
- RZXMPPFPUUCRFN-UHFFFAOYSA-N p-toluidine Chemical compound CC1=CC=C(N)C=C1 RZXMPPFPUUCRFN-UHFFFAOYSA-N 0.000 description 2
- FZUGPQWGEGAKET-UHFFFAOYSA-N parbenate Chemical compound CCOC(=O)C1=CC=C(N(C)C)C=C1 FZUGPQWGEGAKET-UHFFFAOYSA-N 0.000 description 2
- 235000021317 phosphate Nutrition 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
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 239000001205 polyphosphate Substances 0.000 description 2
- 235000011176 polyphosphates Nutrition 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- XWKBMOUUGHARTI-UHFFFAOYSA-N tricalcium;diphosphite Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])[O-].[O-]P([O-])[O-] XWKBMOUUGHARTI-UHFFFAOYSA-N 0.000 description 2
- AUTOISGCBLBLBA-UHFFFAOYSA-N trizinc;diphosphite Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])[O-].[O-]P([O-])[O-] AUTOISGCBLBLBA-UHFFFAOYSA-N 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 2
- 229910000165 zinc phosphate Inorganic materials 0.000 description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- MUTGBJKUEZFXGO-OLQVQODUSA-N (3as,7ar)-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1CCC[C@@H]2C(=O)OC(=O)[C@@H]21 MUTGBJKUEZFXGO-OLQVQODUSA-N 0.000 description 1
- 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 1
- SORHAFXJCOXOIC-CCAGOZQPSA-N (z)-4-[2-[(z)-3-carboxyprop-2-enoyl]oxyethoxy]-4-oxobut-2-enoic acid Chemical compound OC(=O)\C=C/C(=O)OCCOC(=O)\C=C/C(O)=O SORHAFXJCOXOIC-CCAGOZQPSA-N 0.000 description 1
- ROLAGNYPWIVYTG-UHFFFAOYSA-N 1,2-bis(4-methoxyphenyl)ethanamine;hydrochloride Chemical compound Cl.C1=CC(OC)=CC=C1CC(N)C1=CC=C(OC)C=C1 ROLAGNYPWIVYTG-UHFFFAOYSA-N 0.000 description 1
- 229940058015 1,3-butylene glycol Drugs 0.000 description 1
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-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
- JFZVSHAMRZPOPA-UHFFFAOYSA-N 1-[n-(2-hydroxypropyl)-4-methylanilino]propan-2-ol Chemical compound CC(O)CN(CC(C)O)C1=CC=C(C)C=C1 JFZVSHAMRZPOPA-UHFFFAOYSA-N 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- KRDSXENYLDIORL-UHFFFAOYSA-N 2-(1,3-benzothiazol-2-ylsulfanyl)butanedioic acid Chemical compound C1=CC=C2SC(SC(CC(=O)O)C(O)=O)=NC2=C1 KRDSXENYLDIORL-UHFFFAOYSA-N 0.000 description 1
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- URLKBWYHVLBVBO-UHFFFAOYSA-N p-dimethylbenzene Natural products CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 150000002976 peresters Chemical class 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing 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
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 239000003813 safflower oil Substances 0.000 description 1
- 235000005713 safflower oil Nutrition 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 239000008159 sesame oil Substances 0.000 description 1
- 235000011803 sesame oil Nutrition 0.000 description 1
- 235000019832 sodium triphosphate Nutrition 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
- 239000007921 spray Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 239000002600 sunflower oil Substances 0.000 description 1
- 239000003784 tall oil Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- XGFPOHQJFNFBKA-UHFFFAOYSA-B tetraaluminum;phosphonato phosphate Chemical compound [Al+3].[Al+3].[Al+3].[Al+3].[O-]P([O-])(=O)OP([O-])([O-])=O.[O-]P([O-])(=O)OP([O-])([O-])=O.[O-]P([O-])(=O)OP([O-])([O-])=O XGFPOHQJFNFBKA-UHFFFAOYSA-B 0.000 description 1
- AUHHYELHRWCWEZ-UHFFFAOYSA-N tetrachlorophthalic anhydride Chemical compound ClC1=C(Cl)C(Cl)=C2C(=O)OC(=O)C2=C1Cl AUHHYELHRWCWEZ-UHFFFAOYSA-N 0.000 description 1
- HQHCYKULIHKCEB-UHFFFAOYSA-N tetradecanedioic acid Natural products OC(=O)CCCCCCCCCCCCC(O)=O HQHCYKULIHKCEB-UHFFFAOYSA-N 0.000 description 1
- UFDHBDMSHIXOKF-UHFFFAOYSA-N tetrahydrophthalic acid Natural products OC(=O)C1=C(C(O)=O)CCCC1 UFDHBDMSHIXOKF-UHFFFAOYSA-N 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 239000013008 thixotropic agent Substances 0.000 description 1
- 230000009974 thixotropic effect Effects 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 239000000326 ultraviolet stabilizing agent Substances 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
- 239000008170 walnut oil Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- XAEWLETZEZXLHR-UHFFFAOYSA-N zinc;dioxido(dioxo)molybdenum Chemical compound [Zn+2].[O-][Mo]([O-])(=O)=O XAEWLETZEZXLHR-UHFFFAOYSA-N 0.000 description 1
- RVXKJRWBHPHVOV-UHFFFAOYSA-L zinc;oct-2-enoate Chemical compound [Zn+2].CCCCCC=CC([O-])=O.CCCCCC=CC([O-])=O RVXKJRWBHPHVOV-UHFFFAOYSA-L 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
- C09D167/06—Unsaturated polyesters having carbon-to-carbon unsaturation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/17—Amines; Quaternary ammonium compounds
- C08K5/18—Amines; Quaternary ammonium compounds with aromatically bound amino groups
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Paints Or Removers (AREA)
Description
本発明は、不飽和ポリエステル樹脂を含む塗料組成物であって、特に鋼板面に対する耐水付着性に優れた塗料組成物に関する。本発明の塗料組成物は、パテとして有用であり、特に自動車及び車両補修用パテとして非常に有用である。 The present invention relates to a coating composition containing an unsaturated polyester resin, and particularly to a coating composition having excellent water resistance adhesion to a steel sheet surface. The coating composition of the present invention is useful as a putty, and is particularly useful as a putty for repairing automobiles and vehicles.
一般的に不飽和ポリエステル樹脂は、他の樹脂に比べ比較的安価であり、また常温でも短時間で硬化するため作業性にすぐれ、さらに主原料の選択によって種々のすぐれた物理的及び化学的特性を有するため、例えば自動車及び車両補修用パテ、木工用塗料、成形物、シーリング材など各種用途に広く使用されている。これらの用途に使用されている不飽和ポリエステル樹脂組成物は、反応性希釈剤として、硬化性、物性等の面からスチレンが多用されてきたが、近年、その臭気や毒性による環境汚染が問題になっていた。 In general, unsaturated polyester resins are relatively inexpensive compared to other resins, and are cured in a short time even at room temperature, so that workability is excellent, and various physical and chemical properties can be improved by selecting main raw materials. Therefore, it is widely used in various applications such as automobile and vehicle repair putty, woodwork paints, molded products, and sealing materials. Unsaturated polyester resin compositions used in these applications have been frequently used as reactive diluents in terms of curability, physical properties, etc. In recent years, environmental pollution due to their odor and toxicity has become a problem. It was.
これに対し、スチレンの代替として臭気が低く安全性の高いモノマーを使用する方法等が提案されている。例えば特許文献１、特許文献２においては、分子量の高いアクリル誘導体を用いることが提案されているが、これらは乾燥性、硬化性、耐水性、耐薬品性などが不十分で用途の制限を受ける場合があった。そこで特許文献３では、空乾性不飽和ポリエステルを使用し、アルキル基の炭素数が１〜４であるヒドロキシアルキルメタクリレートを反応性希釈剤とする不飽和ポリエステル樹脂組成物が提案されている。
上記特許文献３の組成物は、低臭気で安全性が高く、乾燥性にも優れるが、やはり耐水性が不十分であり、特に基材が鋼板である場合に耐水付着性が不十分でハガレやブリスターが発生する不具合があった。
本発明の目的は、耐水性、乾燥性、付着性に優れた、不飽和ポリエステル樹脂を含む塗料組成物であって、さらに鋼板面に対する耐水付着性にも優れた、パテとして有用な塗料組成物を提供することにある。
The composition of Patent Document 3 has a low odor, high safety, and excellent drying properties, but still has insufficient water resistance. There was a problem that blisters occurred.
An object of the present invention is a coating composition containing an unsaturated polyester resin excellent in water resistance, drying property and adhesion, and further excellent in water resistance adhesion to a steel sheet surface, and useful as a putty. Is to provide.
本発明は、（Ａ）多価アルコールのアリルエーテル単位を有する不飽和ポリエステル樹脂、（Ｂ）重合性不飽和化合物、（Ｃ）顔料及び（Ｄ）防錆剤を含む塗料組成物であって、該防錆剤（Ｄ）を、不飽和ポリエステル樹脂（Ａ）及び重合性不飽和化合物（Ｂ）の合計固形分１００重量部に対して３〜５０重量部の範囲内で含有することを特徴とする塗料組成物、及びこれを基材面に塗布し硬化せしめた後、上塗り塗装することを特徴とする塗装方法に関する。 The present invention is a coating composition comprising (A) an unsaturated polyester resin having an allyl ether unit of a polyhydric alcohol, (B) a polymerizable unsaturated compound, (C) a pigment, and (D) a rust inhibitor. The rust inhibitor (D) is contained within a range of 3 to 50 parts by weight with respect to 100 parts by weight of the total solid content of the unsaturated polyester resin (A) and the polymerizable unsaturated compound (B). The present invention relates to a coating composition to be applied, and a coating method comprising applying a top coating to the substrate surface after curing the coating composition and curing the coating composition.
本発明によれば、耐水性、乾燥性、付着性に優れた、不飽和ポリエステル樹脂を含む塗料組成物が得られる。本発明の塗料組成物は、パテとして好適に使用でき、厚塗りにした際の内部乾燥性にも優れ、基材や上塗り塗料に対する付着性にも優れており、特に鋼板面に対する耐水付着性に非常に優れるものである。
従って本発明の塗料組成物は、特に自動車及び鉄道車両補修用パテとして非常に有用であり、さらに産業機器、木工類用パテなどにも有用である。またこれに限らず建築物や家
具類のひび割れの補修、目地止めやライニング材などにも使用できる。
According to the present invention, a coating composition containing an unsaturated polyester resin that is excellent in water resistance, drying property, and adhesion can be obtained. The coating composition of the present invention can be suitably used as a putty, has excellent internal drying properties when thickly coated, has excellent adhesion to a substrate and a top coating, and is particularly resistant to water adhesion to the steel plate surface. It is very good.
Therefore, the coating composition of the present invention is particularly useful as a putty for repairing automobiles and railway vehicles, and is also useful for putty for industrial equipment and woodwork. Moreover, it can be used not only for repairing cracks in buildings and furniture, but also for sealing joints and lining materials.
本発明において使用される不飽和ポリエステル樹脂（Ａ）としては、多価アルコールのアリルエーテル単位を有するものであれば、従来から塗料やパテに用いられているものが特に制限なく適用でき、通常、不飽和多塩基酸を含む多塩基酸と多価アルコールとの縮合反応によって得られるものが使用できる。
不飽和多塩基酸としては、例えばマレイン酸、無水マレイン酸、フマル酸、イタコン酸、無水イタコン酸、テトラヒドロフタル酸、無水テトラヒドロフタル酸、メチルテトラヒドロ無水フタル酸、テトラブロモ無水フタル酸、テトラクロロ無水フタル酸、無水ヘット酸、無水ハイミック酸等が挙げられ、これらは１種又は２種以上併用して使用できる。
As the unsaturated polyester resin (A) used in the present invention, those conventionally used in paints and putty can be applied without particular limitation as long as they have an allyl ether unit of a polyhydric alcohol. Those obtained by a condensation reaction between a polybasic acid containing an unsaturated polybasic acid and a polyhydric alcohol can be used.
Examples of unsaturated polybasic acids include maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, tetrahydrophthalic acid, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, tetrabromophthalic anhydride, tetrachlorophthalic anhydride Examples thereof include acid, het anhydride, and hymic anhydride, and these can be used alone or in combination of two or more.
上記不飽和多塩基酸には、飽和多塩基酸を併用してもよく、該飽和多塩基酸としては、例えば、フタル酸、無水フタル酸、ハロゲン化無水フタル酸、イソフタル酸、テレフタル酸、ヘキサヒドロフタル酸、ヘキサヒドロ無水フタル酸、ヘキサヒドロテレフタル酸、ヘキサヒドロイソフタル酸、コハク酸、マロン酸、グルタル酸、アジピン酸、セバシン酸、１，１２−ドデカン２酸，２，６−ナフタレンジカルボン酸、２，７−ナフタレンジカルボン酸、２，３−ナフタレンジカルボン酸、２，３−ナフタレンジカルボン酸無水物、４，４’−ビフェニルジカルボン酸、またこれらのジアルキルエステル等を挙げることができ、これらは１種又は２種以上併用して使用できる。 The unsaturated polybasic acid may be used in combination with a saturated polybasic acid. Examples of the saturated polybasic acid include phthalic acid, phthalic anhydride, halogenated phthalic anhydride, isophthalic acid, terephthalic acid, hexa Hydrophthalic acid, hexahydrophthalic anhydride, hexahydroterephthalic acid, hexahydroisophthalic acid, succinic acid, malonic acid, glutaric acid, adipic acid, sebacic acid, 1,12-dodecanedioic acid, 2,6-naphthalenedicarboxylic acid, Examples include 2,7-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid anhydride, 4,4′-biphenyldicarboxylic acid, and dialkyl esters thereof. It can be used in combination of two or more species.
多価アルコールとしては、例えば、エチレングリコール、ジエチレングリコール、トリエチレングリコール、ポリ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、ポリプロピレングリコール、２−メチル−１，３−プロパンジオール、１，３−ブタンジオール、ネオペンチルグリコール、水素化ビスフェノールＡ、１，４−ブタンジオール、１，６−ヘキサンジオール、１，９−ノナンジオール、ビスフェノールＡとプロピレンオキシドまたはエチレンオキシドの付加物、１，２，３，４−テトラヒドロキシブタン、グリセリン、トリメチロールプロパン、１，３−プロパンジオール、１，２−シクロヘキサングリコール、１，３−シクロヘキサングリコール、１，４−シクロヘキサングリコール、１，４−シクロヘキサンジメタノール、パラキシレングリコール、ビシクロヘキシル−４，４’−ジオール、２，６−デカリングリコール、２，７−デカリングリコール、ビスヒドロキシエチルテレフタレート等が挙げられ、これらは１種又は２種以上併用して使用できる。 Examples of the polyhydric alcohol include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, 2-methyl-1,3-propanediol, 1,3-butanediol, and neopentyl. Glycol, hydrogenated bisphenol A, 1,4-butanediol, 1,6-hexanediol, 1,9-nonanediol, adduct of bisphenol A and propylene oxide or ethylene oxide, 1,2,3,4-tetrahydroxybutane Glycerin, trimethylolpropane, 1,3-propanediol, 1,2-cyclohexane glycol, 1,3-cyclohexane glycol, 1,4-cyclohexane glycol, 1,4-cyclohexane Examples include sandimethanol, paraxylene glycol, bicyclohexyl-4,4′-diol, 2,6-decalin glycol, 2,7-decalin glycol, bishydroxyethyl terephthalate, and the like. These may be used alone or in combination of two or more. Can be used.
上記不飽和ポリエステル樹脂（Ａ）は、最終的に得られる塗膜の表面乾燥性を向上させるために、多価アルコールのアリルエーテル単位を有するものであり、その製造原料として多価アルコールのアリルエーテルなどの水酸基を有するアリル化合物を使用することが望ましい。該アリル化合物としては、エチレングリコールモノアリルエーテル、ジエチレングリコールモノアリルエーテル、トリエチレングリコールモノアリルエーテル、ポリエチレングリコールモノアリルエーテル、プロピレングリコールモノアリルエーテル、ジプロピレングリコールモノアリルエーテル、トリプロピレングリコールモノアリルエーテル、ポリプロピレングリコールモノアリルエーテル、１、２−ブチレングリコールモノアリルエーテル、１、３−ブチレングリコールモノアリルエーテル、ヘキシレングリコールモノアリルエーテル、オクチレングリコール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、グリセリンジアリルエーテル、ペンタエリスリトールトリアリルエーテル等を挙げることができる。 The unsaturated polyester resin (A) has an allyl ether unit of a polyhydric alcohol in order to improve the surface drying property of the finally obtained coating film, and the allyl ether of the polyhydric alcohol as a raw material for production thereof. It is desirable to use an allyl compound having a hydroxyl group such as Examples of the allyl compound include ethylene glycol monoallyl ether, diethylene glycol monoallyl ether, triethylene glycol monoallyl ether, polyethylene glycol monoallyl ether, propylene glycol monoallyl ether, dipropylene glycol monoallyl ether, tripropylene glycol monoallyl ether, Polypropylene glycol monoallyl ether, 1,2-butylene glycol monoallyl ether, 1,3-butylene glycol monoallyl ether, hexylene glycol monoallyl ether, octylene glycol monoallyl ether, trimethylolpropane diallyl ether, glyceryl diallyl ether, A pentaerythritol triallyl ether etc. can be mentioned.
また上記不飽和ポリエステル樹脂（Ａ）は、必要に応じて脂肪酸により変性されていてもよい。該脂肪酸としては、乾性油脂肪酸及び／又は半乾性油脂肪酸が好適であり、例えば、魚油脂肪酸、脱水ヒマシ油脂肪酸、サフラワー油脂肪酸、アマニ油脂肪酸、大豆油脂
肪酸、ゴマ油脂肪酸、ケシ油脂肪酸、エノ油脂肪酸、麻実油脂肪酸、ブドウ核油脂肪酸、トウモロコシ油脂肪酸、トール油脂肪酸、ヒマワリ油脂肪酸、綿実油脂肪酸、クルミ油脂肪酸、ゴム種油脂肪酸、ハイジエン脂肪酸等を挙げることができ、これらは１種又は２種以上併用して使用できる。
The unsaturated polyester resin (A) may be modified with a fatty acid as necessary. The fatty acid is preferably a dry oil fatty acid and / or a semi-dry oil fatty acid, such as fish oil fatty acid, dehydrated castor oil fatty acid, safflower oil fatty acid, linseed oil fatty acid, soybean oil fatty acid, sesame oil fatty acid, poppy oil fatty acid, Eno oil fatty acid, hemp seed fatty acid, grape kernel oil fatty acid, corn oil fatty acid, tall oil fatty acid, sunflower oil fatty acid, cottonseed oil fatty acid, walnut oil fatty acid, rubber seed oil fatty acid, Heidiene fatty acid, etc. Or it can be used in combination of two or more.
本発明では不飽和ポリエステル樹脂（Ａ）として、特に硬化性、表面乾燥性の点から、多価アルコールのアリルエーテル単位を全構造単位の合計モル数に基づいて５〜５０モル％、好ましくは１０〜３５モル％含有することが望ましい。
さらに不飽和ポリエステル樹脂（Ａ）として、特に硬化性及び耐水性、密着性などの点から、多価アルコールのアリルエーテル単位、テレフタル酸単位、及びエチレングリコール単位を樹脂骨格中に導入してなるものが好適に使用できる。その場合、硬化性、表面乾燥性の点からは、多価アルコールのアリルエーテル単位を全構造単位の合計モル数に基づいて５〜５０モル％、好ましくは１０〜３５モル％含有することが望ましく、耐水性や密着性の点からは、テレフタル酸単位を全構造単位の合計モル数に基づいて１〜３０モル％、好ましくは３〜２０モル％含有することが望ましく、不飽和ポリエステル樹脂の合成のし易さからは、エチレングリコール単位を全構造単位の合計モル数に基づいて３〜６０モル％、好ましくは５〜４０モル％含有することが望ましい。このような不飽和ポリエステル樹脂を用いた場合には、後述の（Ｂ）成分として２−ヒドロキシエチルメタクリレートなどの水酸基含有モノマーを用いたパテであっても、耐水性が低下することなく、硬化性、乾燥性、特に暴露後の鋼板面への密着性にも優れたパテ塗膜を形成することが可能である。
In the present invention, as the unsaturated polyester resin (A), from the viewpoint of curability and surface drying properties, the allyl ether unit of the polyhydric alcohol is preferably 5 to 50 mol%, preferably 10 based on the total number of moles of all structural units. It is desirable to contain -35 mol%.
Further, as the unsaturated polyester resin (A), in particular from the viewpoint of curability, water resistance, adhesion, etc., an allyl ether unit, a terephthalic acid unit, and an ethylene glycol unit of a polyhydric alcohol are introduced into the resin skeleton. Can be suitably used. In that case, from the viewpoint of curability and surface drying properties, it is desirable to contain 5 to 50 mol%, preferably 10 to 35 mol% of allyl ether units of polyhydric alcohol based on the total number of moles of all structural units. From the viewpoint of water resistance and adhesion, it is desirable to contain 1 to 30 mol%, preferably 3 to 20 mol% of terephthalic acid units based on the total number of moles of all structural units. From the viewpoint of ease of processing, it is desirable to contain 3 to 60 mol%, preferably 5 to 40 mol% of ethylene glycol units based on the total number of moles of all structural units. When such an unsaturated polyester resin is used, even if it is a putty using a hydroxyl group-containing monomer such as 2-hydroxyethyl methacrylate as the later-described component (B), the curability is not lowered. Moreover, it is possible to form a putty coating film having excellent drying properties, particularly adhesion to the steel plate surface after exposure.
これらの構造単位の不飽和ポリエステル樹脂（Ａ）への導入は、上述の多価アルコールのアリルエーテル、テレフタル酸、及びエチレングリコールを夫々製造原料として、さらに他の多塩基酸や多価アルコールと縮合反応を行うことができる。テレフタル酸単位及びエチレングリコール単位については、アリルエーテル基の反応を抑制する温度下での縮合反応とする点から、特にビスヒドロキシエチルテレフタレートを多価アルコール製造原料として用いることによって両方の構成単位を容易に１段階で導入することが可能である。ビスヒドロキシエチルテレフタレートとしては、ポリエチレンテレフタレート（ＰＥＴ）の分解再生物を用いることも可能である。 The introduction of these structural units into the unsaturated polyester resin (A) is achieved by condensation with other polybasic acids and polyhydric alcohols using the above-mentioned polyhydric alcohols, allyl ether, terephthalic acid, and ethylene glycol, as production raw materials, respectively. The reaction can be performed. For terephthalic acid units and ethylene glycol units, both structural units can be easily prepared by using bishydroxyethyl terephthalate as a raw material for producing polyhydric alcohols, because it is a condensation reaction at a temperature that suppresses the reaction of the allyl ether group. Can be introduced in one step. As bishydroxyethyl terephthalate, it is also possible to use a decomposition regenerated product of polyethylene terephthalate (PET).
上記不飽和ポリエステル樹脂（Ａ）は、定法によって製造することができ、例えば、前記不飽和多塩基酸と多価アルコールを含む成分を窒素雰囲気下で縮合反応させることにより得られる。縮合反応時の加熱温度は、１４０〜２５０℃、好ましくは１６０〜２００℃の範囲内であることがゲル化防止の点から望ましい。
得られた不飽和ポリエステル樹脂（Ａ）の酸価は、反応性、付着性の点から、１０〜５０ｍｇＫＯＨ／ｇ、好ましくは２０〜４０ｍｇＫＯＨ／ｇの範囲内が望ましい。
The unsaturated polyester resin (A) can be produced by a conventional method, and can be obtained, for example, by subjecting a component containing the unsaturated polybasic acid and a polyhydric alcohol to a condensation reaction in a nitrogen atmosphere. The heating temperature during the condensation reaction is desirably in the range of 140 to 250 ° C, preferably 160 to 200 ° C, from the viewpoint of preventing gelation.
The acid value of the obtained unsaturated polyester resin (A) is 10 to 50 mgKOH / g, preferably 20 to 40 mgKOH / g, from the viewpoints of reactivity and adhesion.
また不飽和ポリエステル樹脂（Ａ）の重量平均分子量は、１，０００〜１００，０００、好ましくは２，０００〜５０，０００の範囲内であることが望ましい。尚、本発明において重量平均分子量はゲルパーミエーションクロマトグラフィーで測定し、ポリスチレン換算した値である。ゲルパーミュエーションクロマトグラフ装置には「ＨＬＣ８１２０ＧＰＣ」（東ソー（株）社製、商品名）が使用でき、ゲルパーミュエーションクロマトグラフに用いるカラムとしては、「ＴＳＫｇｅｌ Ｇ−４０００Ｈ×Ｌ」、「ＴＳＫｇｅｌ Ｇ−３０００Ｈ×Ｌ」、「ＴＳＫｇｅｌ Ｇ−２５００Ｈ×Ｌ」、「ＴＳＫｇｅｌ Ｇ−２０００Ｈ×Ｌ」（いずれも東ソー（株）社製、商品名）の４本を使用することができる。 The weight average molecular weight of the unsaturated polyester resin (A) is 1,000 to 100,000, preferably 2,000 to 50,000. In the present invention, the weight average molecular weight is a value measured by gel permeation chromatography and converted to polystyrene. "HLC8120GPC" (trade name, manufactured by Tosoh Corporation) can be used for the gel permeation chromatograph apparatus, and "TSKgel G-4000HxL" and "TSKgel" are used as columns for the gel permeation chromatograph. Four of “G-3000H × L”, “TSKgel G-2500H × L”, and “TSKgel G-2000H × L” (both manufactured by Tosoh Corporation) can be used.
本発明において重合性不飽和化合物（Ｂ）は、反応性希釈剤として配合されるものであり、例えば、スチレン、α−メチルスチレン、クロロスチレン、ビニルトルエン、ｔ−ブ
チルスチレン、ジビニルベンゼン等の芳香族ビニル化合物；メチル（メタ）アクリレート、エチル（メタ）アクリレート、プロピル（メタ）アクリレート、ブチル（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレート、イソボルニル（メタ）アクリレート、ノルボルニル（メタ）アクリレート、アダマンチル（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、テトラメチロールメタンテトラ（メタ）アクリレート、テトラメチロールメタンテトラ（メタ）アクリレート、ジペンタエリスリトール（メタ）アクリレート、トリシクロデカンジメタノールジ（メタ）アクリレート、１，９−ノナンジオールジ（メタ）アクリレート、２−ブチル−２−エチル−１，３−プロパンジオールジ（メタ）アクリレート、ジシクロペンテニルオキシエチル（メタ）アクリレート、２，２−ビス（４−（３−メタクリロキシ−２−ヒドロキシプロポキシ）−フェニル）プロパン、ジ（メタクリロキシエチル）トリメチルヘキサメチレンジウレタン、２，２−ビス（４−メタクリロキシポリエトキシフェニル）プロパンなどの１価又は多価アルコールの（メタ）アクリル酸エステル；２−ヒドロキシエチル（メタ）アクリレート等のヒドロキシアルキル(メタ)アクリレート；エチレングリコールジマレート、プロピレングリコールジイタコネートなど；４−（メタ）アクリロイルオキシメトキシカルボニルフタル酸、４−（メタ）アクリロイルオキシエトキシカルボニルフタル酸などの４−（メタ）アクリロイルオキシル基含有芳香族ポリカルボン酸及びその酸無水物；ジアリルフタレート、ジアリルイソフタレ−ト、トリアリルフタレ−ト等のアリル化合物；エポキシ（メタ）アクリレート、ポリエステル（メタ）アクリレート、ポリジメチルシリコンジ（メタ）アクリレート、ウレタン（メタ）アクリレート等のオリゴマ−などが挙げられ、これらは１種又は２種以上併用して使用できる。
In the present invention, the polymerizable unsaturated compound (B) is blended as a reactive diluent. For example, a fragrance such as styrene, α-methylstyrene, chlorostyrene, vinyltoluene, t-butylstyrene, divinylbenzene and the like. Group vinyl compound; methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isobornyl (meth) acrylate, norbornyl (meth) acrylate, adamantyl ( (Meth) acrylate, trimethylolpropane tri (meth) acrylate, tetramethylolmethanetetra (meth) acrylate, tetramethylolmethanetetra (meth) acrylate, dipentaerythritol (meth) acrylate, trisyl Rhodecane dimethanol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 2-butyl-2-ethyl-1,3-propanediol di (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate 2,2-bis (4- (3-methacryloxy-2-hydroxypropoxy) -phenyl) propane, di (methacryloxyethyl) trimethylhexamethylenediurethane, 2,2-bis (4-methacryloxypolyethoxyphenyl) (Meth) acrylic acid esters of mono- or polyhydric alcohols such as propane; hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate; ethylene glycol dimaleate, propylene glycol diitaconate, etc .; 4- (meta ) Acryloyloxy Aromatic polycarboxylic acids containing 4- (meth) acryloyloxyl groups such as tooxycarbonylphthalic acid and 4- (meth) acryloyloxyethoxycarbonylphthalic acid and their anhydrides; diallyl phthalate, diallyl isophthalate, triallyl phthalate Allyl compounds such as epoxy (meth) acrylate, polyester (meth) acrylate, oligomers such as polydimethylsilicon di (meth) acrylate, urethane (meth) acrylate, and the like. These may be used alone or in combination of two or more. Can be used.
これらのうち、毒性や臭気の点から、重合性不飽和化合物（Ｂ）としては、その成分の少なくとも一部として、ヒドロキシアルキルメタクリレート、１，９−ノナンジオールジ（メタ）アクリレート、イソボルニル（メタ）アクリレートなどを含有することが望ましく、特に２−ヒドロキシエチルメタクリレートなどのヒドロキシアルキルメタクリレートを含有することが望ましい。 Among these, from the viewpoint of toxicity and odor, the polymerizable unsaturated compound (B) includes at least a part of its components, such as hydroxyalkyl methacrylate, 1,9-nonanediol di (meth) acrylate, isobornyl (meth). It is desirable to contain acrylate and the like, and it is particularly desirable to contain hydroxyalkyl methacrylate such as 2-hydroxyethyl methacrylate.
上記不飽和ポリエステル樹脂（Ａ）と該重合性不飽和化合物（Ｂ）との使用比は、固形分重量比で９０／１０〜１０／９０、好ましくは８０／２０〜２０／８０の範囲内が好適である。
本発明において使用される顔料（Ｃ）としては、体質顔料及び／又は着色顔料が使用でき、例えばタルク、マイカ、硫酸バリウム、カオリン、炭酸カルシウム、クレー、シリカ、石英、ガラスなどの体質顔料；チタン白、ベンガラ、カーボンブラック、鉄黒などの着色顔料が挙げられ、さらにガラスバルーン、プラスチックバルーンなども含むことができる。これらは１種又は２種以上併用して使用できる。該顔料（Ｃ）の使用量は、パテ用途での研磨作業性や仕上り性の面から、組成物中に含まれる樹脂固形分１００重量部に対し７０〜５００重量部、好ましくは８０〜２００重量部の範囲内が好適である。
The use ratio of the unsaturated polyester resin (A) to the polymerizable unsaturated compound (B) is 90/10 to 10/90, preferably 80/20 to 20/80 in terms of solid content by weight. Is preferred.
As the pigment (C) used in the present invention, extender pigments and / or colored pigments can be used. For example, extender pigments such as talc, mica, barium sulfate, kaolin, calcium carbonate, clay, silica, quartz, glass; titanium Color pigments such as white, bengara, carbon black, and iron black can be used, and glass balloons, plastic balloons, and the like can also be included. These can be used alone or in combination of two or more. The amount of the pigment (C) used is 70 to 500 parts by weight, preferably 80 to 200 parts by weight, based on 100 parts by weight of the resin solid content contained in the composition, in terms of polishing workability and finishability in putty applications. Within the range of part is preferred.
本発明では、形成膜の耐水付着性向上の点から、防錆剤（Ｄ）を配合する。該防錆剤（Ｄ）としては、例えばリン酸亜鉛、リン酸カルシウム、亜リン酸亜鉛、亜リン酸カリウム、亜リン酸カルシウム等のリン酸塩系；トリポリリン酸二水素アルミニウム等のポリリン酸系；モリブデン酸亜鉛、モリブデン酸カルシウム等のモリブデン酸塩系、リンモリブデン酸アルミニウム等のリンモリブデン酸塩系；ホウ酸塩系；メタホウ酸バリウム等のメタホウ酸塩系；シアナミド亜鉛カルシウム系；カルシウム、亜鉛、コバルト、鉛、ストロンチウム、バリウム等のカチオンを多孔質シリカ粒子に結合させた変性シリカ、カチオンをイオン交換によって結合させることによるイオン交換シリカ；ピロリン酸アルミニウム系；酸化亜鉛などの防錆顔料や、さらに、１−（ベンゾチアゾール−２−イルチオ）コハク酸、（２−ベンゾチアゾール−２−イルチオ）コハク酸ジ−（Ｃ１２−Ｃ１４アルキルアンモニウム塩などのベンゾチアゾール系化合物；４−メチル−γオキソ−ベンゼンブタン
酸とＮ−エチルモルフォリンとの付加反応物、４−メチル−γオキソ−ベンゼンブタン酸とジルコニウムとの付加反応物などのケトカルボン酸系などの有機防錆剤が挙げられ、これらは１種又は２種以上併用して使用できる。これらのうち、防錆剤（Ｄ）としては、特にリン酸塩系、ポリリン酸系、モリブデン酸塩系、リンモリブデン酸塩系、メタホウ酸塩系、シアナミド亜鉛カルシウム系から選ばれる少なくとも１種の防錆顔料であることが、特に鋼板面においての耐水付着性向上の点から好適である。
In this invention, a rust preventive agent (D) is mix | blended from the point of the water-resistant adhesion improvement of a formation film. Examples of the rust preventive (D) include phosphates such as zinc phosphate, calcium phosphate, zinc phosphite, potassium phosphite, and calcium phosphite; polyphosphates such as aluminum dihydrogen tripolyphosphate; zinc molybdate , Molybdates such as calcium molybdate, phosphomolybdates such as aluminum phosphomolybdate; borates; metaborates such as barium metaborate; cyanamide zinc calcium; calcium, zinc, cobalt, lead Modified silica in which cations such as strontium and barium are bound to porous silica particles, ion-exchanged silica by binding cations by ion exchange; aluminum pyrophosphate system; rust preventive pigments such as zinc oxide; (Benzothiazol-2-ylthio) succinic acid, (2-benzo 2-ylthio) succinic acid di - (C 12 -C 14 benzothiazole compounds such as alkyl ammonium salts; 4-methyl -γ-oxo - addition reaction product of benzene butanoic acid and N- ethylmorpholine, 4- Examples thereof include ketocarboxylic acid-based organic rust preventives such as an addition reaction product of methyl-γ oxo-benzenebutanoic acid and zirconium, and these can be used alone or in combination of two or more. The agent (D) is at least one rust preventive pigment selected from phosphate, polyphosphate, molybdate, phosphomolybdate, metaborate, and cyanamide zinc calcium. However, it is particularly preferable from the viewpoint of improving the water-resistant adhesion on the steel plate surface.
上記防錆剤（Ｄ）の配合量は、研磨作業性や仕上り性、硬化性や乾燥性、ヘラ付け性、耐熱黄変性等の面から、不飽和ポリエステル樹脂（Ａ）及び重合性不飽和化合物（Ｂ）の合計固形分１００重量部に対し３〜５０重量部、好ましくは５〜４５重量部の範囲内である。
本発明組成物は、上記（Ａ）〜（Ｄ）成分を必須として含有するものであり、さらに硬化性の向上を目的として、必要に応じて硬化促進剤を配合することができる。硬化促進剤としては、特に制限なく従来公知のものが使用できるが、特に硬化性、乾燥性の点から芳香族アミンが好ましく、さらにパテ組成物上に塗装した上塗り塗膜の黄変が少ないことから、かかる芳香族アミンの中でも、ジメチルアミノ基を有する化合物が好適である。具体的には、４−ジメチルアミノ安息香酸、４−ジメチルアミノ安息香酸エチル、４−ジメチルアミノ安息香酸（ｎ−ブトキシ）エチル、４−ジメチルアミノ安息香酸イソアミル、４−ジメチルアミノ安息香酸２−エチルヘキシル、３−ジメチルアミノ安息香酸、３−ジメチルアミノ安息香酸エチル、３−ジメチルアミノ安息香酸（ｎ−ブトキシ）エチル、３−ジメチルアミノ安息香酸イソアミル、３−ジメチルアミノ安息香酸２−エチルヘキシル、２−ジメチルアミノ安息香酸、２−ジメチルアミノ安息香酸エチル、２−ジメチルアミノ安息香酸（ｎ−ブトキシ）エチル、２−ジメチルアミノ安息香酸イソアミル、２−ジメチルアミノ安息香酸２−エチルヘキシル等が挙げられ、これらは１種又は２種以上併用して使用できる。これらの中でも４−ジメチルアミノ安息香酸、３−ジメチルアミノ安息香酸が適しており、特に４−ジメチルアミノ安息香酸がよい。
The blending amount of the rust preventive (D) is selected from the viewpoints of polishing workability, finish, curability, drying, spatability, heat-resistant yellowing, etc., unsaturated polyester resin (A) and polymerizable unsaturated compound. It is 3-50 weight part with respect to 100 weight part of total solid content of (B), Preferably it exists in the range of 5-45 weight part.
The composition of the present invention contains the components (A) to (D) as essential components, and a curing accelerator can be blended as necessary for the purpose of improving curability. As the curing accelerator, conventionally known ones can be used without any particular limitation, but aromatic amines are particularly preferable from the viewpoints of curability and drying properties, and the top coating film coated on the putty composition should have little yellowing. Therefore, among such aromatic amines, compounds having a dimethylamino group are preferred. Specifically, 4-dimethylaminobenzoic acid, ethyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate (n-butoxy), isoamyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate 3-dimethylaminobenzoic acid, ethyl 3-dimethylaminobenzoate, ethyl 3-dimethylaminobenzoate (n-butoxy), isoamyl 3-dimethylaminobenzoate, 2-dimethylhexyl 3-dimethylaminobenzoate, 2-dimethyl Examples include aminobenzoic acid, ethyl 2-dimethylaminobenzoate, ethyl 2-dimethylaminobenzoate (n-butoxy), isoamyl 2-dimethylaminobenzoate, 2-ethylhexyl 2-dimethylaminobenzoate, and the like. It can be used in combination of two or more species. Among these, 4-dimethylaminobenzoic acid and 3-dimethylaminobenzoic acid are suitable, and 4-dimethylaminobenzoic acid is particularly preferable.
上記芳香族アミンの使用量は、前記不飽和ポリエステル樹脂（Ａ）及び重合性不飽和化合物（Ｂ）の合計固形分１００重量部に対して０．０１〜２．０重量部、好ましくは０．０５〜１．５重量部の範囲内であることが、ポットライフ（ゲル化時間）、形成塗膜の空気乾燥性や研磨性、上塗り塗膜の耐熱黄変性などの点から望ましい。
上記芳香族アミン以外の他の硬化促進剤としては、例えばナフテン酸コバルト、ナフテン酸銅、ナフテン酸バリウム、オクテン酸コバルト、オクテン酸マンガン、オクテン酸亜鉛、オクテン酸バナジウム等の金属ドライヤー；上記例示の芳香族アミン以外の３級アミン類、４級アンモニウム塩が挙げられ、これらは１種又は２種以上併用して使用できる。上記金属ドライヤーを使用する場合、その量は不飽和ポリエステル樹脂（Ａ）及び重合性不飽和化合物（Ｂ）の合計固形分１００重量部に対して０．０１〜５重量部の範囲内が適している。
The aromatic amine is used in an amount of 0.01 to 2.0 parts by weight, preferably 0.000 parts by weight based on 100 parts by weight of the total solid content of the unsaturated polyester resin (A) and the polymerizable unsaturated compound (B). It is desirable that it is in the range of 0.5 to 1.5 parts by weight from the viewpoints of pot life (gelation time), air drying property and polishing property of the formed coating film, and heat yellowing of the top coating film.
Examples of curing accelerators other than the aromatic amine include metal dryers such as cobalt naphthenate, copper naphthenate, barium naphthenate, cobalt octenoate, manganese octenoate, zinc octenoate, and vanadium octenoate; Examples include tertiary amines and quaternary ammonium salts other than aromatic amines, and these can be used alone or in combination of two or more. When the metal dryer is used, the amount is suitably within the range of 0.01 to 5 parts by weight with respect to 100 parts by weight of the total solid content of the unsaturated polyester resin (A) and the polymerizable unsaturated compound (B). Yes.
本発明組成物には、さらに必要に応じて硬化助促進剤、重合禁止剤、有機溶剤、顔料、ラジカル硬化剤などを配合することができる。
硬化助促進剤としては、例えばアニリン、Ｎ，Ｎ−ジメチルアニリン、Ｎ，Ｎ−ジエチルアニリン、ｐ−トルイジン、Ｎ，Ｎ−ジメチル−ｐ−トルイジン、Ｎ，Ｎ−ビス（２−ヒドロキシエチル）−ｐ−トルイジン、４−（Ｎ，Ｎ−ジメチルアミノ）ベンズアルデヒド、４−［Ｎ，Ｎ−ビス（２-ヒドロキシエチル）アミノ］ベンズアルデヒド、４−（Ｎ
−メチル−Ｎ−ヒドロキシエチルアミノ）ベンズアルデヒド、Ｎ，Ｎ−ビス（２−ヒドロキシプロピル）−ｐ−トルイジン、Ｎ−エチル−ｍ−トルイジン、トリエタノールアミン、ｍ−トルイジン、ジエチレントリアミン、ピリジン、フェニリモルホリン、ピペリジン、Ｎ，Ｎ−ビス（ヒドロキシエチル）アニリン、ジエタノールアニリン等のＮ，Ｎ−置換アニリン、Ｎ，Ｎ−置換−ｐ−トルイジン、４−（Ｎ，Ｎ−置換アミノ）ベンズアルデヒ
ド等のアミン類が挙げられる。該硬化助促進剤は、単独で使用してもよいし２種以上の組み合わせで使用しても良い。
If necessary, the composition of the present invention may further contain a curing assistant accelerator, a polymerization inhibitor, an organic solvent, a pigment, a radical curing agent and the like.
Examples of the curing aid accelerator include aniline, N, N-dimethylaniline, N, N-diethylaniline, p-toluidine, N, N-dimethyl-p-toluidine, N, N-bis (2-hydroxyethyl)- p-toluidine, 4- (N, N-dimethylamino) benzaldehyde, 4- [N, N-bis (2-hydroxyethyl) amino] benzaldehyde, 4- (N
-Methyl-N-hydroxyethylamino) benzaldehyde, N, N-bis (2-hydroxypropyl) -p-toluidine, N-ethyl-m-toluidine, triethanolamine, m-toluidine, diethylenetriamine, pyridine, phenyl morpholine Amines such as N, N-substituted anilines such as piperidine, N, N-bis (hydroxyethyl) aniline, diethanolaniline, N, N-substituted-p-toluidine, 4- (N, N-substituted amino) benzaldehyde Is mentioned. These curing aid accelerators may be used alone or in combination of two or more.
重合禁止剤としては、例えばトリハイドロベンゼン、トリハイドロキノン、１４−ナフトキノン、パラベンゾキノン、ハイドロキノン、ベンゾキノン、ハイドロキノンモノメチルエーテル、ｐ−ｔｅｒｔ−ブチルカテコール、２，６−ジ−ｔｅｒｔ−ブチル−４−メチルフェノール等を挙げることができる。該重合禁止剤の添加量は、不飽和ポリエステル樹脂組成物に対して、１０〜１０００ｐｐｍ添加しうるものである。 Examples of the polymerization inhibitor include trihydrobenzene, trihydroquinone, 14-naphthoquinone, parabenzoquinone, hydroquinone, benzoquinone, hydroquinone monomethyl ether, p-tert-butylcatechol, 2,6-di-tert-butyl-4-methylphenol. Etc. The polymerization inhibitor may be added in an amount of 10 to 1000 ppm with respect to the unsaturated polyester resin composition.
有機溶剤は、粘度調整用として添加することができ、特に代表的なもののみを例示すれば、トルエン、キシレン、メタノール、エタノール、プロパノール、ブタノール、酢酸エチル、酢酸ブチル、アセトン、メチルエチルケトン等が挙げられる。
ラジカル硬化剤は、例えば使用直前に混合配合されることが望ましい。該ラジカル硬化剤としては、有機過酸化物が挙げられ、具体的にはジアシ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従来公知のものが使用され、これらは単独で使用してもよいし２種以上を併用してもよい。ラジカル硬化剤の配合量は、不飽和ポリエステル樹脂（Ａ）及び重合性不飽和化合物（Ｂ）の合計固形分１００重量部に対して、０．１〜６重量部の範囲内が好ましい。
The organic solvent can be added for viscosity adjustment, and if only typical ones are exemplified, toluene, xylene, methanol, ethanol, propanol, butanol, ethyl acetate, butyl acetate, acetone, methyl ethyl ketone and the like can be mentioned. .
The radical curing agent is desirably mixed and blended immediately before use, for example. Examples of the radical curing agent include organic peroxides. Specifically, diacyl peroxides, peroxyesters, hydroperoxides, dialkyl peroxides, ketone peroxides, peroxyketals, alkyls. Conventionally known ones such as peresters and percarbonates may be used, and these may be used alone or in combination of two or more. The amount of the radical curing agent is preferably in the range of 0.1 to 6 parts by weight with respect to 100 parts by weight of the total solid content of the unsaturated polyester resin (A) and the polymerizable unsaturated compound (B).
本発明組成物には、さらに必要に応じて、例えば紫外線安定剤、紫外線吸収剤、低収縮剤、酸化防止剤、皮張り防止剤、可塑剤、骨材、難燃剤、安定剤、強化材、減粘剤等の粘度調節剤、顔料分散剤、改質用樹脂、溶剤、チキソ剤、チキソ助剤、消泡剤、レベリング剤、シランカップリング剤、パラフィン等の空気遮断剤、アルデヒド捕捉剤等を配合することが可能である。 The composition of the present invention further contains, for example, an ultraviolet stabilizer, an ultraviolet absorber, a low shrinkage agent, an antioxidant, an anti-skinning agent, a plasticizer, an aggregate, a flame retardant, a stabilizer, a reinforcing material, if necessary. Viscosity modifiers such as viscosity reducers, pigment dispersants, modifying resins, solvents, thixotropic agents, thixotropic aids, antifoaming agents, leveling agents, silane coupling agents, paraffin and other air blocking agents, aldehyde scavengers, etc. Can be blended.
本発明組成物の塗装は従来公知の方法で行うことができ、塗装された塗膜は、常温又は強制乾燥をすることにより塗膜内部まで硬化することができる。基材面としては、鉄、亜鉛、アルミなどの金属面やその化学処理面、プラスチック、木など、さらにこれらに塗装された旧塗膜面などが挙げられ、被塗面が損傷部の場合には、該損傷部を中心に必要によりその周囲までサンディングを行っておくのが適当である。 The composition of the present invention can be applied by a conventionally known method, and the coated film can be cured to the inside of the film by normal temperature or forced drying. Examples of substrate surfaces include metal surfaces such as iron, zinc, and aluminum, chemically treated surfaces, plastics, wood, etc., and old paint surfaces painted on them. It is appropriate to perform sanding around the damaged part as necessary.
本発明では、上記組成物による塗膜に対して上塗り塗装を行ってもよく、該上塗り塗料としてはアクリルラッカー、アクリルメラミン樹脂系塗料、ウレタン硬化型塗料、アクリルウレタン樹脂系塗料、酸−エポキシ硬化型塗料、フッ素樹脂系塗料、アルキド樹脂系塗料、アルキド樹脂メラミン樹脂系塗料、ポリエステルメラミン樹脂系塗料などの通常使用されている有機溶剤系、水系、粉体等の塗料が特に制限なく使用できる。 In the present invention, a top coat may be applied to the coating film of the above composition, and as the top coat, acrylic lacquer, acrylic melamine resin-based paint, urethane curable paint, acrylic urethane resin-based paint, acid-epoxy cured Commonly used organic solvent-based, water-based, powder and other paints such as mold paints, fluororesin paints, alkyd resin paints, alkyd resin melamine resin paints, and polyester melamine resin paints can be used without particular limitation.
以下、本発明を実施例により説明するが、本発明はこれらの実施例に限定されるものではない。なお、下記例中の「部」及び「％」はそれぞれ「重量部」及び「重量％」を意味する。 EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to these Examples. In the examples below, “parts” and “%” mean “parts by weight” and “% by weight”, respectively.
不飽和ポリエステル樹脂組成物の製造
製造例１
攪拌機、ガス導入管、精留塔、温度計、減圧装置及び還流冷却器を備えた２リットルの四つ口フラスコに、ジエチレングリコール３９７．５ｇ、ジプロピレングリコール１３４ｇ、フマル酸５８０ｇ、ペンタエリスリトールトリアリルエーテル２５６ｇ、及びハイドロキノン０．５ｇを入れ、窒素ガスを吹き込みながら１５０℃に加熱後、１８０℃まで昇温した。つづいて同温度で精留塔を水分離器に換え、トルエンを還流させて縮合反応を行
ない、反応終了時にはトルエンを減圧下で除いて、酸価３５ｍｇＫＯＨ／ｇ、重量平均分子量３，０００の不飽和ポリエステル樹脂（Ａ−１）を得た。該樹脂（Ａ−１）を２−ヒドロキシエチルメタクリレートに溶解し、固形分濃度６５％になるように調整し、不飽和ポリエステル樹脂溶液を得た。該不飽和ポリエステル樹脂溶液１００部に対して４−ジメチルアミノ安息香酸を０．２５部添加した後、６０℃のウォーターバス中で一時間保温して均一に分散、溶解し、不飽和ポリエステル樹脂組成物（Ｔ−１）を得た。
Manufacture example 1 of unsaturated polyester resin composition
Diethylene glycol 397.5 g, dipropylene glycol 134 g, fumaric acid 580 g, pentaerythritol triallyl ether were added to a 2 liter four-necked flask equipped with a stirrer, gas inlet tube, rectifying column, thermometer, pressure reducing device and reflux condenser. 256 g and hydroquinone 0.5 g were added, heated to 150 ° C. while blowing nitrogen gas, and then heated to 180 ° C. Subsequently, the rectification column is changed to a water separator at the same temperature, and the condensation reaction is performed by refluxing toluene. At the end of the reaction, the toluene is removed under reduced pressure, and an acid value of 35 mgKOH / g and a weight average molecular weight of 3,000 is obtained. A saturated polyester resin (A-1) was obtained. The resin (A-1) was dissolved in 2-hydroxyethyl methacrylate and adjusted to a solid content concentration of 65% to obtain an unsaturated polyester resin solution. After adding 0.25 part of 4-dimethylaminobenzoic acid to 100 parts of the unsaturated polyester resin solution, the mixture is kept dispersed in a water bath at 60 ° C. for 1 hour to uniformly disperse and dissolve, and the unsaturated polyester resin composition A product (T-1) was obtained.
製造例２
製造例１において、２−ヒドロキシエチルメタクリレートの代わりにイソボルニルアクリレートを同量使用する以外は、製造例１と同様にして不飽和ポリエステル樹脂組成物（Ｔ−２）を得た。
製造例３
製造例１において、２−ヒドロキシエチルメタクリレートの代わりにイソボルニルアクリレート及び２−ヒドロキシエチルメタクリレートを重量比で１７／１８の割合で同量使用する以外は、製造例１と同様にして不飽和ポリエステル樹脂組成物（Ｔ−３）を得た。
Production Example 2
In Production Example 1, an unsaturated polyester resin composition (T-2) was obtained in the same manner as in Production Example 1 except that the same amount of isobornyl acrylate was used instead of 2-hydroxyethyl methacrylate.
Production Example 3
In Production Example 1, unsaturated polyester was used in the same manner as in Production Example 1 except that isobornyl acrylate and 2-hydroxyethyl methacrylate were used in the same amount at a ratio of 17/18 instead of 2-hydroxyethyl methacrylate. A resin composition (T-3) was obtained.
製造例４
製造例１と同じ装置を用いて、ジエチレングリコール１７４．８ｇ、ペンタエリスリトールトリアリルエーテル５４１．２ｇ、トリメチロールプロパン１８４．２ｇ、フマル酸４３４．８ｇ及びハイドロキノン０．６ｇを仕込み、窒素ガス雰囲気下で１５０℃に加熱後、１８０℃まで昇温した。つづいて同温度で精留塔を水分離器に換え、トルエンを還流させて縮合反応を行い、反応終了時にはトルエンを減圧下で除いて酸価が３１ｍｇＫＯＨ／ｇ、重量平均分子量２９００の不飽和ポリエステル樹脂（Ａ−２）を得た。該樹脂（Ａ−２）を２−ヒドロキシエチルメタクリレートに溶解し、固形分濃度６５％になるように調整し不飽和ポリエステル樹脂溶液を得た。該不飽和ポリエステル樹脂（Ａ−２）溶液１００部に対して４−ジメチルアミノ安息香酸を０．２５部添加した後、６０℃のウォーターバス中で一時間保温して均一に分散、溶解し、不飽和ポリエステル樹脂組成物（Ｔ−４）を得た。
Production Example 4
Using the same apparatus as in Production Example 1, 174.8 g of diethylene glycol, 541.2 g of pentaerythritol triallyl ether, 184.2 g of trimethylolpropane, 434.8 g of fumaric acid, and 0.6 g of hydroquinone were charged under a nitrogen gas atmosphere. After heating to ° C, the temperature was raised to 180 ° C. Subsequently, the rectification column is changed to a water separator at the same temperature, and the condensation reaction is performed by refluxing toluene. At the end of the reaction, the toluene is removed under reduced pressure, and the unsaturated polyester having an acid value of 31 mgKOH / g and a weight average molecular weight of 2900 is obtained. Resin (A-2) was obtained. The resin (A-2) was dissolved in 2-hydroxyethyl methacrylate and adjusted to a solid content concentration of 65% to obtain an unsaturated polyester resin solution. After adding 0.25 part of 4-dimethylaminobenzoic acid to 100 parts of the unsaturated polyester resin (A-2) solution, it is kept dispersed in a water bath at 60 ° C. for 1 hour to uniformly disperse and dissolve, An unsaturated polyester resin composition (T-4) was obtained.
製造例５
製造例４において、２−ヒドロキシエチルメタクリレートの代わりにイソボルニルアクリレートを同量使用する以外は、製造例４と同様にして不飽和ポリエステル樹脂組成物（Ｔ−５）を得た。
製造例６
上記製造例１で製造した不飽和ポリエステル樹脂（Ａ−１）をスチレンに溶解し、固形分濃度６５％になるように調整し不飽和ポリエステル樹脂溶液を得た。該不飽和ポリエステル樹脂溶液１００部に対して４−ジメチルアミノ安息香酸を０．２５部添加した後、６０℃のウォーターバス中で一時間保温して均一に分散、溶解し、不飽和ポリエステル樹脂組成物（Ｔ−６）を得た。
Production Example 5
In Production Example 4, an unsaturated polyester resin composition (T-5) was obtained in the same manner as in Production Example 4 except that the same amount of isobornyl acrylate was used instead of 2-hydroxyethyl methacrylate.
Production Example 6
The unsaturated polyester resin (A-1) produced in Production Example 1 was dissolved in styrene and adjusted to a solid content concentration of 65% to obtain an unsaturated polyester resin solution. After adding 0.25 part of 4-dimethylaminobenzoic acid to 100 parts of the unsaturated polyester resin solution, the mixture is kept dispersed in a water bath at 60 ° C. for 1 hour to uniformly disperse and dissolve, and the unsaturated polyester resin composition A product (T-6) was obtained.
製造例７
温度コントローラー、還流冷却器、攪拌装置を備えた２リットルのガラスフラスコに、フマル酸２３２ｇ、ビスヒドロキシエチルテレフタレート２２８．６ｇ、トリメチロールプロパン９３．８ｇ、ペンタエリスリトールトリアリルエーテル２８１．６ｇ、パラベンゾキノン０．４ｇを仕込み、１８０℃に昇温して脱水縮合反応を行い、酸価が３５ｍｇＫＯＨ／ｇになったところで加熱を停止し、１００℃まで冷却した。２−ヒドロキシエチルメタクリレート４２１ｇを加え、均一溶液になるまで攪拌し、固形分濃度６５％の不飽和ポリエステル樹脂（Ａ−３）溶液を得た。該不飽和ポリエステル樹脂（Ａ−３）の重量平均分子量は３，０００であった。該不飽和ポリエステル樹脂（Ａ−３）溶液１００部に対して４−ジメチルアミノ安息香酸を０．２５部添加した後、６０℃のウォーターバス中で
一時間保温して均一に分散、溶解し、不飽和ポリエステル樹脂組成物（Ｔ−７）を得た。
Production Example 7
In a 2 liter glass flask equipped with a temperature controller, reflux condenser, and stirrer, 232 g of fumaric acid, 228.6 g of bishydroxyethyl terephthalate, 93.8 g of trimethylolpropane, 281.6 g of pentaerythritol triallyl ether, parabenzoquinone 0 .4 g was charged, the temperature was raised to 180 ° C., a dehydration condensation reaction was carried out, and when the acid value reached 35 mgKOH / g, the heating was stopped and the mixture was cooled to 100 ° C. 421 g of 2-hydroxyethyl methacrylate was added and stirred until a uniform solution was obtained to obtain an unsaturated polyester resin (A-3) solution having a solid concentration of 65%. The unsaturated polyester resin (A-3) had a weight average molecular weight of 3,000. After adding 0.25 part of 4-dimethylaminobenzoic acid to 100 parts of the unsaturated polyester resin (A-3) solution, the mixture is kept dispersed in a water bath at 60 ° C. for 1 hour to uniformly disperse and dissolve, An unsaturated polyester resin composition (T-7) was obtained.
製造例８
製造例７において、２−ヒドロキシエチルメタクリレート４２１ｇの代わりにイソボルニルアクリレート２２９ｇ及び２−ヒドロキシエチルメタクリレート１９２ｇを使用する以外は、製造例７と同様にして不飽和ポリエステル樹脂組成物（Ｔ−８）を得た。
製造例９
製造例７において、２−ヒドロキシエチルメタクリレートの代わりにイソボルニルアクリレートを同量使用する以外は、製造例７と同様にして不飽和ポリエステル樹脂組成物（Ｔ−９）を得た。
Production Example 8
In Production Example 7, unsaturated polyester resin composition (T-8) was prepared in the same manner as in Production Example 7, except that 229 g of isobornyl acrylate and 192 g of 2-hydroxyethyl methacrylate were used instead of 421 g of 2-hydroxyethyl methacrylate. Got.
Production Example 9
In Production Example 7, an unsaturated polyester resin composition (T-9) was obtained in the same manner as in Production Example 7, except that the same amount of isobornyl acrylate was used instead of 2-hydroxyethyl methacrylate.
製造例１０
製造例１と同じ装置を用いて、ジエチレングリコール５３０ｇ、トリメチロールプロパンジアリルエーテル１０７ｇ、フマル酸５８０ｇ、及びハイドロキノン０．３３ｇを仕込み、窒素ガス雰囲気下で１５０℃に加熱後、１９０℃まで昇温した。つづいて同温度で精留塔を水分離器に換え、トルエンを還流させて縮合反応を行ない、反応終了時にはトルエンを減圧下で除いて酸価が３５ｍｇＫＯＨ／ｇ、重量平均分子量３，０００の不飽和ポリエステル樹脂（Ａ−４）を得た。該樹脂（Ａ−４）を２−ヒドロキシエチルメタクリレートに溶解し、固形分濃度６５％になるように調整し不飽和ポリエステル樹脂溶液を得た。該不飽和ポリエステル樹脂（Ａ−４）溶液１００部に対して４−ジメチルアミノ安息香酸を０．２５部添加した後、６０℃のウォーターバス中で一時間保温して均一に分散、溶解し、不飽和ポリエステル樹脂組成物（Ｔ−１０）を得た。
Production Example 10
Using the same apparatus as in Production Example 1, 530 g of diethylene glycol, 107 g of trimethylolpropane diallyl ether, 580 g of fumaric acid, and 0.33 g of hydroquinone were charged, heated to 150 ° C. in a nitrogen gas atmosphere, and then heated to 190 ° C. Subsequently, the rectification column is changed to a water separator at the same temperature, and the condensation reaction is performed by refluxing toluene. At the end of the reaction, toluene is removed under reduced pressure, and the acid value is 35 mgKOH / g and the weight average molecular weight is 3,000. A saturated polyester resin (A-4) was obtained. The resin (A-4) was dissolved in 2-hydroxyethyl methacrylate and adjusted to a solid content concentration of 65% to obtain an unsaturated polyester resin solution. After adding 0.25 part of 4-dimethylaminobenzoic acid to 100 parts of the unsaturated polyester resin (A-4) solution, the mixture is kept dispersed in a water bath at 60 ° C. for 1 hour to uniformly disperse and dissolve, An unsaturated polyester resin composition (T-10) was obtained.
製造例１１
製造例１０において、２−ヒドロキシエチルメタクリレートの代わりにイソボルニルアクリレートを同量使用する以外は、製造例１０と同様にして不飽和ポリエステル樹脂組成物（Ｔ−１１）を得た。
製造例１２
製造例１において、４−ジメチルアミノ安息香酸を配合しない以外は、製造例１と同様にして不飽和ポリエステル樹脂組成物（Ｔ−１２）を得た。
Production Example 11
In Production Example 10, an unsaturated polyester resin composition (T-11) was obtained in the same manner as in Production Example 10 except that the same amount of isobornyl acrylate was used instead of 2-hydroxyethyl methacrylate.
Production Example 12
In Production Example 1, an unsaturated polyester resin composition (T-12) was obtained in the same manner as in Production Example 1 except that 4-dimethylaminobenzoic acid was not blended.
製造例１３（比較例用）
製造例１と同じ装置を用いて、プロピレングリコール２５１ｇ、ジエチレングリコール２８６ｇ、無水マレイン酸３２３ｇ、無水フタル酸３２６ｇ、及びハイドロキノン０．３６ｇを仕込み、窒素ガス雰囲気下で１５０℃に加熱後、１９０℃まで昇温した。つづいて同温度で精留塔を水分離器に換え、トルエンを還流させて縮合反応を行ない、反応終了時にはトルエンを減圧下で除いて酸価が３５ｍｇＫＯＨ／ｇ、重量平均分子量２，９００の不飽和ポリエステル樹脂（Ａ−５）を得た。該樹脂（Ａ−５）を２−ヒドロキシエチルメタクリレートに溶解し、固形分濃度６５％になるように調整し不飽和ポリエステル樹脂溶液を得た。該不飽和ポリエステル樹脂（Ａ−５）溶液１００部に対して４−ジメチルアミノ安息香酸を０．２５部添加した後、６０℃のウォーターバス中で一時間保温して均一に分散、溶解し、不飽和ポリエステル樹脂組成物（Ｔ−１３）を得た。
Production Example 13 (for comparative example)
Using the same apparatus as in Production Example 1, 251 g of propylene glycol, 286 g of diethylene glycol, 323 g of maleic anhydride, 326 g of phthalic anhydride, and 0.36 g of hydroquinone were charged, heated to 150 ° C. in a nitrogen gas atmosphere, and then raised to 190 ° C. Warm up. Subsequently, the rectification column is replaced with a water separator at the same temperature, and the condensation reaction is performed by refluxing toluene. At the end of the reaction, the toluene is removed under reduced pressure, and the acid value is 35 mgKOH / g and the weight average molecular weight is 2,900. A saturated polyester resin (A-5) was obtained. The resin (A-5) was dissolved in 2-hydroxyethyl methacrylate and adjusted to a solid content concentration of 65% to obtain an unsaturated polyester resin solution. After adding 0.25 part of 4-dimethylaminobenzoic acid to 100 parts of the unsaturated polyester resin (A-5) solution, the mixture is kept dispersed in a water bath at 60 ° C. for 1 hour to uniformly disperse and dissolve. An unsaturated polyester resin composition (T-13) was obtained.
下記表１に各不飽和ポリエステル樹脂組成物（Ｔ−１）〜（Ｔ−１３）の配合組成を示す。尚、表中の各不飽和ポリエステル樹脂の量は固形分表示である。 Table 1 below shows the composition of each unsaturated polyester resin composition (T-1) to (T-13). In addition, the quantity of each unsaturated polyester resin in a table | surface is a solid content display.
実施例１〜２１及び比較例１〜５
上記製造例で得られた各不飽和ポリエステル樹脂組成物１００部（固形分）に、「５％ナフテックスコバルト」（商品名、日本化学産業社製、ナフテン酸コバルト）、ハイドロキノン、「ＣＲ−９５」（商品名、石原産業社製、酸化チタン）、「クラウンタルクＤＲ」（商品名、松村産業社製、タルク）、および「ＬＦボウセイ Ｍ−ＰＳＮ」（商品名、キクチカラー社製、モリブデン酸亜鉛）あるいは「ＢＵＳＡＮ １１−Ｍ１」（商品名、堺化学社製、メタホウ酸バリウム）、「ＬＦボウセイ ＺＫ−Ｓ２」（商品名、キクチカラー社製、シアナミド亜鉛カルシウム）、「Ｋ−ＷＨＩＴＥ１０５」（商品名、テイカ社製、トリポリリン酸二水素アルミニウム・酸化亜鉛の混合物）、「ＥＸＰＥＲＴ ＮＰ−
１００７」（商品名、東邦顔料工業社製、リン酸亜鉛・亜リン酸カルシウムの混合物）、「ＥＸＰＥＲＴ ＮＰ−１５３０」（商品名、東邦顔料工業社製、亜リン酸亜鉛・亜リン
酸カリウムの混合物）を、表２に示す配合組成で夫々配合攪拌し、これを３００ｍｌ採取し、高速混練機で２０分間混合分散して、各組成物を得た。
Examples 1-21 and Comparative Examples 1-5
To 100 parts (solid content) of each unsaturated polyester resin composition obtained in the above production example, “5% naphthex cobalt” (trade name, manufactured by Nippon Chemical Industry Co., Ltd., cobalt naphthenate), hydroquinone, “CR-95” (Trade name, manufactured by Ishihara Sangyo Co., Ltd., titanium oxide), “Crown Talc DR” (trade name, manufactured by Matsumura Sangyo Co., Ltd., talc), and “LF Bowsei M-PSN” (trade name, manufactured by Kikuchi Color, Molybdic acid Zinc) or “BUSAN 11-M1” (trade name, manufactured by Sakai Chemical Co., Ltd., barium metaborate), “LF Bowsei ZK-S2” (trade name, manufactured by Kikuchi Color Co., Ltd., cyanamide zinc calcium), “K-WHITE 105” ( Trade name, manufactured by Teika, a mixture of aluminum dihydrogen triphosphate and zinc oxide), “EXPERT NP-
1007 "(trade name, manufactured by Toho Pigment Industries Co., Ltd., a mixture of zinc phosphate and calcium phosphite)," EXPERT NP-1530 "(trade name, manufactured by Toho Pigment Industries Co., Ltd., a mixture of zinc phosphite and potassium phosphite) Were mixed and stirred in the composition shown in Table 2, 300 ml of this was sampled, and mixed and dispersed for 20 minutes with a high-speed kneader to obtain each composition.
「ＳＰＣＣ−ＳＢ」（日本テストパネル（株）製、商品名、軟鋼板）の表面を耐水ペーパー＃２４０で軽く研磨し、これを基材面とした。上記で得られた各組成物に、「ＬＵＣ共通硬化剤」（商品名、主成分：シクロヘキサノンパーオキサイド、関西ペイント社製）を２％各々添加し、均一に混合したものをパテとして基材面上にヘラで塗布し、ならして２ｍｍ厚に塗布した。 The surface of “SPCC-SB” (manufactured by Nippon Test Panel Co., Ltd., trade name, mild steel plate) was lightly polished with water-resistant paper # 240, and this was used as the substrate surface. 2% each of “LUC common curing agent” (trade name, main component: cyclohexanone peroxide, manufactured by Kansai Paint Co., Ltd.) was added to each composition obtained above, and the mixture was uniformly mixed with the putty as a base. It was applied to the top with a spatula and then applied to a thickness of 2 mm.
評価試験
上記で得た各組成物について下記評価方法、基準にて試験を行った。その結果を表２に示す。
（＊１）乾燥性：各試験塗板を常温（２０℃）で２０分放置後、各試験塗板の表面のタック及び内部の硬化を指触にて調べた。（○：良好、△：表面に若干タックあるが内部は硬化良好、×：表面にタックあり、内部も硬化不良）。
The following evaluation methods for each composition obtained in the evaluation tests described above, the test by the reference was carried out. The results are shown in Table 2.
(* 1) Drying: Each test coating plate was allowed to stand at room temperature (20 ° C.) for 20 minutes, and then the surface tack and internal curing of each test coating plate were examined by finger touch. (◯: good, Δ: slightly tacky on the surface, but hardened inside, x: tacky on the surface, poorly cured inside).
（＊２）ヘラ付け性：各組成物に硬化剤を均一に混合したものをパテとして基材面上にヘラで塗布する際のノビやヘラ切れ、ヘラさばきなどを調べた（○：良好、△：若干不良、×：不良）。
（＊３）ポットライフ：硬化剤を配合してからの常温（２０℃）放置でのゲル化時間。値が大きい程良好である。
(* 2) Spatability: Nobbling, cutting off of the spatula, cutting off of the spatula, etc. were investigated when applying a mixture of each composition with a curing agent uniformly on the substrate surface with a spatula (○: good, (Triangle | delta): Somewhat bad, x: Defect).
(* 3) Pot life: Gelation time at room temperature (20 ° C.) after blending the curing agent. The higher the value, the better.
塗装板の作成
上記試験塗板を室温（２０℃）で６時間放置乾燥させた後、該塗面を＃４００耐水ペ−パ−で軽く研磨し、「レタンＰＧ８０ホワイトベース」（商品名、アクリルウレタン樹脂系上塗り塗料、関西ペイント（株）社製）を乾燥膜厚５０μｍになるようスプレ−塗装し、６０℃で３０分間乾燥させて各塗装板を得た。
Preparation of painted plate The test coated plate was left to dry at room temperature (20 ° C.) for 6 hours, and then the coated surface was lightly polished with a # 400 water-resistant paper to obtain “Letane PG80 White Base” (trade name, acrylic urethane). Resin-based top coat paint (manufactured by Kansai Paint Co., Ltd.) was spray-coated to a dry film thickness of 50 μm and dried at 60 ° C. for 30 minutes to obtain each coated plate.
上記で得られた各塗装板について付着性を下記の通り評価した。
（＊４）付着性１：各塗装板を４０℃の水に１０日間浸漬した後、水中より取り出した各塗装板を中央部より折り曲げて、折り曲げ部の塗膜状態を観察した（○：良好、△：塗膜が鋼板−パテ間から僅かに剥離している、×：塗膜が鋼板−パテ間から完全に剥離している）。
The adhesion was evaluated as follows for each of the coated plates obtained above.
(* 4) Adhesion 1: After each coated plate was immersed in water at 40 ° C. for 10 days, each coated plate taken out from the water was folded from the center, and the coating state of the folded portion was observed (◯: good) (Triangle | delta): The coating film has peeled slightly from between steel plates and putty, x: The coating film has peeled completely from between steel plates and putty).
（＊５）付着性２：各塗装板を８０℃の温水に１日間没水後、中央部より９０°角に折り曲げて、該折り曲げ部の塗膜の状態を観察した（○：良好、△：塗膜が鋼板−パテ間から僅かに剥離している、×：塗膜が鋼板−パテ間から完全に剥離している）。 (* 5) Adhesion 2: Each coated plate was immersed in warm water at 80 ° C. for 1 day, then bent at a 90 ° angle from the center, and the state of the coating film at the bent portion was observed (◯: Good, Δ : The coating film is slightly peeled from the steel plate to the putty. ×: The coating film is completely peeled from the steel plate to the putty).
Claims (4)
A coating method comprising applying a coating composition according to any one of claims 1 to 3 to a steel plate surface and curing the coating composition, followed by overcoating.
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| JP2005293455A JP4657073B2 (en) | 2004-12-28 | 2005-10-06 | Paint composition |
| KR1020050106415A KR100649074B1 (en) | 2004-12-28 | 2005-11-08 | Coating composition |
| CNB2005101191967A CN100393828C (en) | 2004-12-28 | 2005-11-09 | Paint composition |
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| JP5732851B2 (en) * | 2010-04-06 | 2015-06-10 | 三菱レイヨン株式会社 | Antifouling paint composition, method for producing antifouling coating film, and antifouling coating film |
| TWI553068B (en) * | 2010-04-07 | 2016-10-11 | 三菱麗陽股份有限公司 | Antifouling coating composition, manufacturing method of antifouling coating film and antifouling coating film |
| JP5548112B2 (en) * | 2010-12-15 | 2014-07-16 | モメンティブ・パフォーマンス・マテリアルズ・ジャパン合同会社 | Room temperature curable organopolysiloxane composition |
| JP2015110486A (en) * | 2012-03-23 | 2015-06-18 | 日産化学工業株式会社 | Method for producing zinc cyanamide |
| CN102702941A (en) * | 2012-06-12 | 2012-10-03 | 天长市巨龙车船涂料有限公司 | Coating composition |
| JP6178679B2 (en) * | 2013-09-17 | 2017-08-09 | 大日本塗料株式会社 | Railcar exterior with laminated coating |
| CN103525271A (en) * | 2013-09-28 | 2014-01-22 | 芜湖中集瑞江汽车有限公司 | Metal rust-removing anti-rust paint and preparation method thereof |
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| US10308804B2 (en) * | 2016-07-13 | 2019-06-04 | Illinois Tool Works Inc. | Unsaturated polyester composition for autobody repair with improved adhesion to metal substrates |
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| KR102035319B1 (en) * | 2019-01-14 | 2019-10-22 | 김유진 | Method of manufacturing putty composition and putty composition manufactured thereby |
| CN112160014A (en) * | 2020-09-17 | 2021-01-01 | 扬州市金杨电镀设备有限公司 | Three-cylinder barrel plating machine |
| JP7284136B2 (en) * | 2020-10-28 | 2023-05-30 | 矢崎総業株式会社 | Anti-corrosion, electric wires with terminals and wire harnesses |
| JP7050882B1 (en) * | 2020-11-16 | 2022-04-08 | 日本ペイント・インダストリアルコ－ティングス株式会社 | Putty paint composition |
| CN113549364B (en) * | 2021-09-02 | 2022-04-12 | 株洲华联高科有限责任公司 | Water-based environment-friendly unsaturated polyester putty for rail transit vehicles and preparation method thereof |
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| KR20060076179A (en) | 2006-07-04 |
| CN100393828C (en) | 2008-06-11 |
| CN1807531A (en) | 2006-07-26 |
| KR100649074B1 (en) | 2006-11-27 |
| JP2006206873A (en) | 2006-08-10 |
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