JPS6368678A - Electrodeposition paint composition - Google Patents
Electrodeposition paint compositionInfo
- Publication number
- JPS6368678A JPS6368678A JP61214889A JP21488986A JPS6368678A JP S6368678 A JPS6368678 A JP S6368678A JP 61214889 A JP61214889 A JP 61214889A JP 21488986 A JP21488986 A JP 21488986A JP S6368678 A JPS6368678 A JP S6368678A
- Authority
- JP
- Japan
- Prior art keywords
- resin
- resin particles
- dispersion
- added
- aqueous
- 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.)
- Granted
Links
- 238000004070 electrodeposition Methods 0.000 title claims abstract description 37
- 239000003973 paint Substances 0.000 title abstract description 26
- 239000000203 mixture Substances 0.000 title description 16
- 229920005989 resin Polymers 0.000 claims abstract description 97
- 239000011347 resin Substances 0.000 claims abstract description 97
- 239000002245 particle Substances 0.000 claims abstract description 56
- 239000006185 dispersion Substances 0.000 claims abstract description 23
- 239000007787 solid Substances 0.000 claims abstract description 15
- 239000008199 coating composition Substances 0.000 claims description 9
- 125000002091 cationic group Chemical group 0.000 claims description 8
- 239000000839 emulsion Substances 0.000 claims description 8
- 125000000129 anionic group Chemical group 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 35
- 239000000178 monomer Substances 0.000 abstract description 20
- 238000000576 coating method Methods 0.000 abstract description 17
- 239000011248 coating agent Substances 0.000 abstract description 16
- 239000005062 Polybutadiene Substances 0.000 abstract description 14
- 229920002857 polybutadiene Polymers 0.000 abstract description 14
- 238000005260 corrosion Methods 0.000 abstract description 3
- 230000007797 corrosion Effects 0.000 abstract description 3
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 abstract 2
- 239000004615 ingredient Substances 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 description 38
- 238000000034 method Methods 0.000 description 19
- 239000008367 deionised water Substances 0.000 description 17
- 229910021641 deionized water Inorganic materials 0.000 description 17
- 238000003756 stirring Methods 0.000 description 16
- 239000002253 acid Substances 0.000 description 14
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 12
- 239000002966 varnish Substances 0.000 description 12
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- -1 2-ethylhexyl Chemical group 0.000 description 8
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 8
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 7
- 238000001723 curing Methods 0.000 description 7
- 239000000049 pigment Substances 0.000 description 7
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 239000003822 epoxy resin Substances 0.000 description 6
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 6
- 229920000647 polyepoxide Polymers 0.000 description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 5
- 150000001412 amines Chemical class 0.000 description 5
- 239000012736 aqueous medium Substances 0.000 description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 125000000524 functional group Chemical group 0.000 description 5
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
- 235000010582 Pisum sativum Nutrition 0.000 description 4
- 240000004713 Pisum sativum Species 0.000 description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 239000008096 xylene Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 3
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 235000011054 acetic acid Nutrition 0.000 description 3
- 239000000427 antigen Substances 0.000 description 3
- 102000036639 antigens Human genes 0.000 description 3
- 108091007433 antigens Proteins 0.000 description 3
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 3
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 229960002887 deanol Drugs 0.000 description 3
- 210000003298 dental enamel Anatomy 0.000 description 3
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 3
- 239000012972 dimethylethanolamine Substances 0.000 description 3
- 239000003995 emulsifying agent Substances 0.000 description 3
- 239000004310 lactic acid Substances 0.000 description 3
- 235000014655 lactic acid Nutrition 0.000 description 3
- 239000002609 medium Substances 0.000 description 3
- 229910052757 nitrogen 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
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 2
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 2
- KUDUQBURMYMBIJ-UHFFFAOYSA-N 2-prop-2-enoyloxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC(=O)C=C KUDUQBURMYMBIJ-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerol Natural products OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 2
- FQYUMYWMJTYZTK-UHFFFAOYSA-N Phenyl glycidyl ether Chemical compound C1OC1COC1=CC=CC=C1 FQYUMYWMJTYZTK-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 229910001870 ammonium persulfate Inorganic materials 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
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 2
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000013007 heat curing Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000003010 ionic group Chemical group 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 150000007974 melamines Chemical class 0.000 description 2
- 238000002156 mixing Methods 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
- 238000006386 neutralization reaction Methods 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- 238000005191 phase separation Methods 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- NVKTUNLPFJHLCG-UHFFFAOYSA-N strontium chromate Chemical compound [Sr+2].[O-][Cr]([O-])(=O)=O NVKTUNLPFJHLCG-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XOAAWQZATWQOTB-UHFFFAOYSA-N taurine Chemical compound NCCS(O)(=O)=O XOAAWQZATWQOTB-UHFFFAOYSA-N 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 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
- LGPAKRMZNPYPMG-UHFFFAOYSA-N (3-hydroxy-2-prop-2-enoyloxypropyl) prop-2-enoate Chemical compound C=CC(=O)OC(CO)COC(=O)C=C LGPAKRMZNPYPMG-UHFFFAOYSA-N 0.000 description 1
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 1
- MYWOJODOMFBVCB-UHFFFAOYSA-N 1,2,6-trimethylphenanthrene Chemical compound CC1=CC=C2C3=CC(C)=CC=C3C=CC2=C1C MYWOJODOMFBVCB-UHFFFAOYSA-N 0.000 description 1
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 description 1
- VDYWHVQKENANGY-UHFFFAOYSA-N 1,3-Butyleneglycol dimethacrylate Chemical compound CC(=C)C(=O)OC(C)CCOC(=O)C(C)=C VDYWHVQKENANGY-UHFFFAOYSA-N 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- BJELTSYBAHKXRW-UHFFFAOYSA-N 2,4,6-triallyloxy-1,3,5-triazine Chemical compound C=CCOC1=NC(OCC=C)=NC(OCC=C)=N1 BJELTSYBAHKXRW-UHFFFAOYSA-N 0.000 description 1
- SJIXRGNQPBQWMK-UHFFFAOYSA-N 2-(diethylamino)ethyl 2-methylprop-2-enoate Chemical compound CCN(CC)CCOC(=O)C(C)=C SJIXRGNQPBQWMK-UHFFFAOYSA-N 0.000 description 1
- HWSSEYVMGDIFMH-UHFFFAOYSA-N 2-[2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOCCOC(=O)C(C)=C HWSSEYVMGDIFMH-UHFFFAOYSA-N 0.000 description 1
- LTHJXDSHSVNJKG-UHFFFAOYSA-N 2-[2-[2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethoxy]ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOCCOCCOC(=O)C(C)=C LTHJXDSHSVNJKG-UHFFFAOYSA-N 0.000 description 1
- CVUYSVSDCCHRNV-UHFFFAOYSA-N 2-ethyl-2-(hydroxymethyl)propane-1,3-diol;2-methylprop-2-enoic acid Chemical compound CC(=C)C(O)=O.CC(=C)C(O)=O.CCC(CO)(CO)CO CVUYSVSDCCHRNV-UHFFFAOYSA-N 0.000 description 1
- XNFIEYMGNIUQIF-UHFFFAOYSA-N 2-ethyl-2-(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.CCC(CO)(CO)CO XNFIEYMGNIUQIF-UHFFFAOYSA-N 0.000 description 1
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical class C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 1
- DXIJHCSGLOHNES-UHFFFAOYSA-N 3,3-dimethylbut-1-enylbenzene Chemical compound CC(C)(C)C=CC1=CC=CC=C1 DXIJHCSGLOHNES-UHFFFAOYSA-N 0.000 description 1
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 1
- WTFUTSCZYYCBAY-SXBRIOAWSA-N 6-[(E)-C-[[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]methyl]-N-hydroxycarbonimidoyl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C/C(=N/O)/C1=CC2=C(NC(O2)=O)C=C1 WTFUTSCZYYCBAY-SXBRIOAWSA-N 0.000 description 1
- GZVHEAJQGPRDLQ-UHFFFAOYSA-N 6-phenyl-1,3,5-triazine-2,4-diamine Chemical compound NC1=NC(N)=NC(C=2C=CC=CC=2)=N1 GZVHEAJQGPRDLQ-UHFFFAOYSA-N 0.000 description 1
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- 241000255789 Bombyx mori Species 0.000 description 1
- WOSHQKYMJRBBMW-UHFFFAOYSA-N C(C=C)(=O)O.C(C(=C)C)(=O)O.C(C(=C)C)(=O)O.C(CCCO)O Chemical compound C(C=C)(=O)O.C(C(=C)C)(=O)O.C(C(=C)C)(=O)O.C(CCCO)O WOSHQKYMJRBBMW-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000004641 Diallyl-phthalate Substances 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- 239000004640 Melamine resin Substances 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
- 241001477965 Mycteroperca microlepis Species 0.000 description 1
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 1
- OPKOKAMJFNKNAS-UHFFFAOYSA-N N-methylethanolamine Chemical compound CNCCO OPKOKAMJFNKNAS-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 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
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 1
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 description 1
- ACIAHEMYLLBZOI-ZZXKWVIFSA-N Unsaturated alcohol Chemical class CC\C(CO)=C/C ACIAHEMYLLBZOI-ZZXKWVIFSA-N 0.000 description 1
- GQPVFBDWIUVLHG-UHFFFAOYSA-N [2,2-bis(hydroxymethyl)-3-(2-methylprop-2-enoyloxy)propyl] 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(CO)(CO)COC(=O)C(C)=C GQPVFBDWIUVLHG-UHFFFAOYSA-N 0.000 description 1
- CQHKDHVZYZUZMJ-UHFFFAOYSA-N [2,2-bis(hydroxymethyl)-3-prop-2-enoyloxypropyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(CO)COC(=O)C=C CQHKDHVZYZUZMJ-UHFFFAOYSA-N 0.000 description 1
- JUDXBRVLWDGRBC-UHFFFAOYSA-N [2-(hydroxymethyl)-3-(2-methylprop-2-enoyloxy)-2-(2-methylprop-2-enoyloxymethyl)propyl] 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(CO)(COC(=O)C(C)=C)COC(=O)C(C)=C JUDXBRVLWDGRBC-UHFFFAOYSA-N 0.000 description 1
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 description 1
- UKMBKKFLJMFCSA-UHFFFAOYSA-N [3-hydroxy-2-(2-methylprop-2-enoyloxy)propyl] 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(CO)OC(=O)C(C)=C UKMBKKFLJMFCSA-UHFFFAOYSA-N 0.000 description 1
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001253 acrylic acids Chemical class 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001491 aromatic compounds Chemical group 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
- ZDNFTNPFYCKVTB-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,4-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=C(C(=O)OCC=C)C=C1 ZDNFTNPFYCKVTB-UHFFFAOYSA-N 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 125000004386 diacrylate group Chemical group 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000001227 electron beam curing Methods 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000010556 emulsion polymerization method Methods 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 150000002118 epoxides Chemical class 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- FYZZJDABXBPMOG-UHFFFAOYSA-N ethanol;n-methylmethanamine Chemical compound CCO.CNC FYZZJDABXBPMOG-UHFFFAOYSA-N 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000011133 lead Substances 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
- CDOSHBSSFJOMGT-UHFFFAOYSA-N linalool Chemical compound CC(C)=CCCC(C)(O)C=C CDOSHBSSFJOMGT-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
- 239000011572 manganese Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- YDKNBNOOCSNPNS-UHFFFAOYSA-N methyl 1,3-benzoxazole-2-carboxylate Chemical compound C1=CC=C2OC(C(=O)OC)=NC2=C1 YDKNBNOOCSNPNS-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000011356 non-aqueous organic solvent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
- CABDEMAGSHRORS-UHFFFAOYSA-N oxirane;hydrate Chemical compound O.C1CO1 CABDEMAGSHRORS-UHFFFAOYSA-N 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 150000007519 polyprotic acids Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000011134 resol-type phenolic resin Substances 0.000 description 1
- 229920003987 resole Polymers 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 239000012086 standard solution Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 229960003080 taurine Drugs 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- GRPURDFRFHUDSP-UHFFFAOYSA-N tris(prop-2-enyl) benzene-1,2,4-tricarboxylate Chemical compound C=CCOC(=O)C1=CC=C(C(=O)OCC=C)C(C(=O)OCC=C)=C1 GRPURDFRFHUDSP-UHFFFAOYSA-N 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Landscapes
- Paints Or Removers (AREA)
Abstract
Description
【発明の詳細な説明】
■の −−
電着塗料は、形状を選ばない塗装作業性、その安全性の
ため、防食性機能を持つ下塗として広く使用されている
。電着塗料は、水を媒体として樹脂が分散あるいは溶解
した形態をとっているため、その安定性や通電によるつ
きまわり性の制御が塗装ライン安定化のためには必要と
なる。またその塗膜としての他部に関しても、特に自動
車の塗装系のように、高耐食性、耐チツピング性の必要
とされる分野においては、高膜厚や高性能の物性を有す
る塗膜が望まれる。また最近の消費者の高級品質への志
向から、塗膜外観においても高外観への志向が強くなっ
てきており、従来よりも高鮮映で高光沢な外観を有する
塗膜に対するニーズも高い。[Detailed Description of the Invention] (2) Electrodeposition paints are widely used as undercoats with anticorrosive properties because of their workability regardless of shape and their safety. Electrodeposition paints are in the form of resins dispersed or dissolved in water as a medium, so controlling their stability and throwing power through energization is necessary to stabilize the coating line. Regarding other parts of the coating, especially in fields where high corrosion resistance and chipping resistance are required, such as automobile coating systems, coatings with high film thickness and high performance physical properties are desired. . In addition, as consumers have recently become more conscious of high-quality products, there has been a strong desire for high-quality paint films, and there is a strong need for paint films that have higher definition and higher gloss than ever before.
従来、電着塗料、特にエマルジョン系電着塗料において
は、ベース樹脂自体の相分離がしばしば問題であった。Conventionally, in electrodeposition paints, especially emulsion-based electrodeposition paints, phase separation of the base resin itself has often been a problem.
相分離の傾向を減らすための方法としては、界面活性剤
の使用、ベース樹脂へ導入される親水性基の数をふやす
等の方法が考えられるが、これらの方法は塗膜性能、例
えば耐水性や耐食性に悪影響する。従って塗膜性能を犠
牲にすることなく、電着塗料の他の性能に悪影響するこ
となく、ベース樹脂の分散安定性を改善することを課題
とする。Possible methods to reduce the tendency for phase separation include the use of surfactants and increasing the number of hydrophilic groups introduced into the base resin, but these methods do not affect coating performance, such as water resistance. and has a negative effect on corrosion resistance. Therefore, it is an object of the present invention to improve the dispersion stability of the base resin without sacrificing the coating performance or adversely affecting other properties of the electrodeposition paint.
龍央方法
前記課題は、電着可能な水性樹脂(ベース樹脂)の水性
分散液へ、比較的小さい粒径を存し、かつベース樹脂の
sp値に比較的近いsp値を有する微小樹脂粒子を添加
することによって解決される。Ryuo method The above-mentioned problem is to add micro resin particles having a relatively small particle size and an SP value relatively close to the SP value of the base resin into an aqueous dispersion of an electrodepositable aqueous resin (base resin). Solved by adding
そのため本発明は、
(a) 電着可能な水性樹脂の水性分散液と、(b)
該水性樹脂の水性分散液中に均一に分散された、粒
径が0.01〜0.2μで、かつ前記水性樹脂とのSP
値の差が1以内である微小樹脂粒子とを必須成分として
含むことを特徴とする電着塗料組成物を提供する。Therefore, the present invention comprises: (a) an aqueous dispersion of an aqueous resin capable of electrodeposition; and (b)
SP particles having a particle size of 0.01 to 0.2μ, which are uniformly dispersed in the aqueous dispersion of the aqueous resin, and which are bonded to the aqueous resin.
Provided is an electrodeposition coating composition characterized in that it contains as an essential component fine resin particles whose values differ by 1 or less.
前記微小樹脂粒子が小さいため、塗料液中の水性樹脂の
エマルジョン粒子表面に付着してその電荷の状態を改質
し、エマルジョン粒子の分散安定性を向上させるほか、
微小樹脂粒子自体、水性ベース樹脂との相溶性が高いの
で塗料中に安定に分散され、塗料全体の安定性の向上に
寄与する。微小樹脂粒子は皮膜形成樹脂成分の一部とな
るので、塗料や塗膜の他の性能に悪影響することがない
。Since the micro resin particles are small, they adhere to the surface of the water-based resin emulsion particles in the coating liquid, modifying the state of charge, and improving the dispersion stability of the emulsion particles.
The fine resin particles themselves have high compatibility with the aqueous base resin, so they are stably dispersed in the paint, contributing to improving the stability of the paint as a whole. Since the fine resin particles become part of the film-forming resin component, they do not adversely affect other properties of the paint or coating film.
本発明は、カチオン型およびアニオン型電着塗料のどち
らにも応用可能である。電着可能な水性樹脂(ベース樹
脂)は一般に電着に必要な電荷と親水性を与える官能基
を有するフィルム形成性樹脂である。主として水分散時
の形により、水溶液型、ディスパージョン型、エマルジ
ョン型、およびサスペンション型に分けられるが、ここ
ではそれらを総称して水性樹脂と呼ぶ。The present invention is applicable to both cationic and anionic electrodeposition paints. Electrodepositable aqueous resins (base resins) are generally film-forming resins that have functional groups that provide the charge and hydrophilicity necessary for electrodeposition. They are classified into aqueous solution type, dispersion type, emulsion type, and suspension type, mainly depending on their form when dispersed in water, and herein they are collectively referred to as aqueous resin.
電着塗料に使用する水性樹脂は種々のものが知られてお
り、本発明においては任意のこれら公知の水性樹脂を使
用することができる。Various types of water-based resins are known for use in electrodeposition paints, and any of these known water-based resins can be used in the present invention.
アニオン型電着塗料に使用する水性樹脂は、樹脂に電着
に必要な負の電荷と親水性を与えるため、カルボキシル
基のようなアニオン性官能基を持っている。典型的なそ
のような樹脂は、マレイン化天然もしくは合成乾性油、
マレイン化ポリブタジェン、それらのハーフェステル、
ハーフアミド等である。The water-based resin used in anionic electrodeposition paints has anionic functional groups such as carboxyl groups in order to give the resin the negative charge and hydrophilicity necessary for electrodeposition. Typical such resins include maleated natural or synthetic drying oils,
maleated polybutadiene, their halfesters,
Half amide etc.
カチオン型電着塗料に使用する水分散性樹脂は、正の電
荷と親水性を与えるためアミン基のようなカチオン性官
能基を持っている。このような樹脂の例には、エポキシ
系、ポリエーテル系、ポリエステル系、ポリウレタン系
、ポリアミド系、ポリブタジェン系など各種のものが知
られている。The water-dispersible resin used in cationic electrodeposition paints has a cationic functional group such as an amine group to impart positive charge and hydrophilicity. Various types of resins are known, such as epoxy resins, polyether resins, polyester resins, polyurethane resins, polyamide resins, and polybutadiene resins.
これらの樹脂は、その硬化反応のメカニズムに従って、
ラジカル重合や酸化重合によって樹脂自体で硬化する自
己架橋タイプと、硬化剤、例えばメラミン樹脂やプロフ
クボリイソシアネート化合物のような硬化剤との併用に
より硬化する硬化剤タイプ、両者を併用するタイプがあ
る。These resins, according to their curing reaction mechanism,
There are self-crosslinking types that are cured by the resin itself through radical polymerization or oxidative polymerization, hardening agent types that are hardened by using a hardening agent such as melamine resin or profukubolyisocyanate compounds, and types that use a combination of both. .
さらに硬化エネルギーのタイプに従って、常温硬化、熱
硬化、紫外線や電子線などの放射エネルギー硬化などの
タイプに分類することもできる。Furthermore, according to the type of curing energy, it can be classified into types such as room temperature curing, heat curing, and radiant energy curing such as ultraviolet rays and electron beams.
また、塗膜性能を向上させる目的で、電荷および親水性
を与える官能基を有しない樹脂、例えばエポキシアクリ
レート系樹脂を前記親水性樹脂とエマルジョンの形で併
用することも行われている。Furthermore, for the purpose of improving coating performance, resins that do not have functional groups that impart charge and hydrophilicity, such as epoxy acrylate resins, are also used in combination with the hydrophilic resins in the form of an emulsion.
本発明においてはこのような硬化剤および親水性官能基
を持たない樹脂との併用系をも含めて、水性樹脂と呼ぶ
。In the present invention, a system in which such a curing agent is used in combination with a resin having no hydrophilic functional group is also referred to as an aqueous resin.
このような電着可能な水性樹脂は当業者には良く知られ
ており、かつそれ自体本発明を構成するものではないか
らこれ以上の説明は必要としない。Such electrodepositable aqueous resins are well known to those skilled in the art and do not require further explanation as such do not form part of the present invention.
微全皿1政ヱ
従来微小樹脂粒子の製法としては各種の方法が提案され
ているが、その一つはエチレン性不飽和単量体および/
または架橋性の共重合ffi量体を水性媒体中でサスペ
ンション重合または乳化重合させて微小樹脂粒子分散液
を得るものであり、他の方法は脂肪族炭化水素等の低S
P有機溶媒あるいはエステル、ケトン、アルコール等の
内の高SP有機溶媒のようにモノマーは溶かすが重合体
は溶解しない非水性有機溶媒中でエチレン性不飽和単量
体および/または架橋性共重合体とを共重合させ、得ら
れる微小樹脂粒子共重合体を分散するNAD法あるいは
沈澱析出法と称せられる方法である。Various methods have been proposed to produce microscopic resin particles, one of which is the production of ethylenically unsaturated monomers and/or
Alternatively, a fine resin particle dispersion is obtained by suspension polymerization or emulsion polymerization of a crosslinkable copolymerized ffimer in an aqueous medium.
Ethylenically unsaturated monomers and/or crosslinkable copolymers in non-aqueous organic solvents that dissolve monomers but not polymers, such as P organic solvents or high SP organic solvents such as esters, ketones, alcohols, etc. This is a method called the NAD method or precipitation method, in which the resulting fine resin particle copolymer is copolymerized with the NAD method or precipitation method.
本発明の微小樹脂粒子は、上記いずれの方法で製造して
もよい。The fine resin particles of the present invention may be produced by any of the above methods.
エチレン性不飽和単量体としては、(メタ)アクリル酸
メチル、(メタ)アクリル酸エチル、(メタ)アクリル
酸イソブチル、(メタ)アクリル酸イソブチル、(メタ
)アクリル酸2−エチルヘキシル等のアクリル酸または
メタクリル酸のアルキルエステルや、これと共重合し得
るエチレン性不飽和結合を有する他の単量体、例えばス
チレン、α−メチルスチレン、ビニルトルエン、t−ブ
チルスチレン、エチレン、プロピレン、酢酸ビニル、プ
ロピオン酸ビニル、アクリロニトリル、メタクリレート
リル、(メタ)アクリル酸ジメチルアミノエチルなどが
ある。これら単量体は二種類以上用いてもよい。Examples of ethylenically unsaturated monomers include acrylic acids such as methyl (meth)acrylate, ethyl (meth)acrylate, isobutyl (meth)acrylate, isobutyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate. or alkyl esters of methacrylic acid or other monomers having ethylenically unsaturated bonds that can be copolymerized with them, such as styrene, α-methylstyrene, vinyltoluene, t-butylstyrene, ethylene, propylene, vinyl acetate, Examples include vinyl propionate, acrylonitrile, methacrylate trile, and dimethylaminoethyl (meth)acrylate. Two or more types of these monomers may be used.
架橋性共重合単量体は、分子内に2個以上のラジカル重
合可能なエチレン性不飽和結合を有する単量体および/
または相互に反応し得る基をそれぞれ担持する2種のエ
チレン性不飽和基含有単量体を含む。Crosslinkable comonomers are monomers and/or monomers having two or more radically polymerizable ethylenically unsaturated bonds in the molecule.
Alternatively, it contains two types of ethylenically unsaturated group-containing monomers each carrying groups that can react with each other.
分子内にH[Ii1以上のラジカル重合可能なエチレン
性不飽和基を有する単量体としては、多価アルコールの
重合性不飽和モノカルボン酸エステル、多塩基酸の重合
性不飽和アルコールエステル、および2個以上のビニル
基で置換された芳香族化合物などがあり、それらの例と
しては以下のような化合物がある。Monomers having a radically polymerizable ethylenically unsaturated group of H[Ii1 or more in the molecule include polymerizable unsaturated monocarboxylic acid esters of polyhydric alcohols, polymerizable unsaturated alcohol esters of polybasic acids, and There are aromatic compounds substituted with two or more vinyl groups, examples of which include the following compounds.
エチレングリコールジアクリレート、エチレングリコー
ルジメタクリレート、トリエチレングリコールジメタク
リレート、テトラエチレングリコールジメタクリレート
、1.3−ブチレングリコールジメタクリレート、トリ
メチロールプロパントリアクリレート、トリメチロール
プロパントリメタクリレート、1.4−ブタンジオール
ジアクリレート、ネオペンチルグリコールジアクリレー
ト、1.6−ヘキサンジオールジアクリレート、ペンタ
エリスリトールジアクリレート、ペンタエリスリトール
トリアクリレート、ペンタエリスリトールテトラアクリ
レート、ペンタエリスリトールジメタクリレート、ペン
タエリスリトールトリメタクリレート、ペンタエリスリ
トールテトラメタクリレート、グリセロールジメタクリ
レート、グリセロールジアクリレート、グリセロールア
リロキシジメタクリレート、1,1.1− )リスヒド
ロキシメチルエタンジアクリレート、1.Ll−)リス
ヒドロキシメチルエタントリアクリレート、1.1.1
〜トリスヒドロキシメチルエタンジメタクリレート、1
.11〜トリスヒドロキシメチルエタントリメタクリレ
ート、1,1.1− トリスヒドロキシメチルプロパン
ジアクリレート、1.1.1− トリスヒドロキシメチ
ルプロパントリアクリレート、1,1.1−トリスヒド
ロキシメチルプロパンジメタクリレート、1.1.1−
トリスヒドロキシメチルプロパントリメタクリレート
、トリアリルシアヌレート、トリアリルイソシアヌレー
ト、トリアリルトリメリテート、ジアリルテレフタレー
ト、ジアリルフタレートおよびジビニルベンゼン。Ethylene glycol diacrylate, ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, 1,4-butanediol dimethacrylate Acrylate, neopentyl glycol diacrylate, 1,6-hexanediol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, glycerol dimethacrylate , glycerol diacrylate, glycerol allyloxy dimethacrylate, 1,1.1-) lishydroxymethylethane diacrylate, 1. Ll-) Lishydroxymethylethane triacrylate, 1.1.1
~Trishydroxymethylethane dimethacrylate, 1
.. 11-trishydroxymethylethane trimethacrylate, 1,1.1-trishydroxymethylpropane diacrylate, 1.1.1-trishydroxymethylpropane triacrylate, 1,1.1-trishydroxymethylpropane dimethacrylate, 1. 1.1-
Trishydroxymethylpropane trimethacrylate, triallyl cyanurate, triallyl isocyanurate, triallyl trimellitate, diallyl terephthalate, diallyl phthalate and divinylbenzene.
また相互に反応し得る基をそれぞれ担持する2種のエチ
レン性不飽和基を有する単量体としては例えばグリシジ
ルアクリレート、グリシジルメタクリレートなどのエポ
キシ基含有エチレン性不飽和単量体と、アクリル酸、メ
タクリル酸、クロトン酸などカルボキシル基含有エチレ
ン性不飽和単量体が最も代表的なものであるが、相互に
反応性の基としてはこれらに限定されるものではなく、
例えばアミンとカルボニル、エポキシドとカルボン酸無
水物、アミンとカルボン酸塩化物、アルキレンイミンと
カルボニル、オルガノアルコキシシランとカルボキシル
、ヒドロキシルとイソシアナト等種々のものが提案され
ており、本発明はこれらを広く包含するものである。In addition, examples of monomers having two types of ethylenically unsaturated groups each carrying mutually reactive groups include epoxy group-containing ethylenically unsaturated monomers such as glycidyl acrylate and glycidyl methacrylate, and acrylic acid and methacrylic acid. Carboxyl group-containing ethylenically unsaturated monomers such as acid and crotonic acid are the most representative, but mutually reactive groups are not limited to these.
For example, various compounds have been proposed, such as amine and carbonyl, epoxide and carboxylic acid anhydride, amine and carboxylic acid chloride, alkyleneimine and carbonyl, organoalkoxysilane and carboxyl, hydroxyl and isocyanate, etc., and the present invention broadly encompasses these. It is something to do.
水性媒体または非水性有機媒体中で製造した微小樹脂粒
子は、口過、スプレー乾燥、凍結乾燥などの方法で微小
樹脂粒子を単離し、そのまましもくしはミルなどを用い
て適当な粒径に粉砕して用いることもできるし、さらに
合成した分散液をそのまま、または溶媒置換により媒体
を置換して用いることができる。Micro resin particles produced in an aqueous medium or a non-aqueous organic medium can be isolated by a method such as filtration, spray drying, or freeze drying, and then cut into appropriate particle sizes by using a mill or the like. It can be used after being pulverized, or the synthesized dispersion can be used as it is or by replacing the medium by solvent replacement.
一般的にいって得られる粒子の粒径はその重合法によっ
てコントロールするのが望ましい。0.01〜0.2μ
の粒子に対しては乳化重合法、NAD法が適している。Generally speaking, it is desirable to control the particle size of the particles obtained by the polymerization method. 0.01~0.2μ
Emulsion polymerization method and NAD method are suitable for the particles.
微小樹脂粒子のSP値は、七ツマー混合物の組成によっ
て制御することができる。特にエチレン性不飽和モノマ
ーの共重合体の場合は、モノマーの種類およびその割合
から計算によって決定することができる。The SP value of the fine resin particles can be controlled by the composition of the seven-mer mixture. In particular, in the case of copolymers of ethylenically unsaturated monomers, it can be determined by calculation from the types of monomers and their proportions.
微小樹脂粒子は、塗料中および電着浴中で安定な分散状
態を保つため、それ自体ベース樹脂である水性樹脂と同
じ極性のイオン化基を持っていることが好ましい、すな
わちアニオン電着にあってはカルボキシル基、スルホン
酸基等のアニオン性基を、カチオン電着にあってはアミ
ノ基や第4級アンモニウム基のカチオン性基をそれぞれ
担持することが好ましい、これを実現するには、エチレ
ン性不飽和結合とカルボキシル基とを有する単量体、例
えばアクリル酸、メタクリル酸や、エチレン性不飽和結
合と塩基性基とを有する単量体、例えばジメチルアミノ
エチル(メタ)アクリレート、ビニルピリジン類などを
微小樹脂粒子合成に際して単量体混合物へ添加するか、
または微小樹脂粒子の合成に対し、カチオン性末端を与
える開始剤を用いて単量体混合物を重合する方法がある
。In order to maintain a stable dispersion state in paints and electrodeposition baths, the microscopic resin particles preferably have ionizable groups with the same polarity as the aqueous resin that is the base resin. It is preferable to carry an anionic group such as a carboxyl group or a sulfonic acid group, and in the case of cationic electrodeposition, it is preferable to carry a cationic group such as an amino group or a quaternary ammonium group. Monomers having unsaturated bonds and carboxyl groups, such as acrylic acid and methacrylic acid; monomers having ethylenically unsaturated bonds and basic groups, such as dimethylaminoethyl (meth)acrylate, vinylpyridines, etc. is added to the monomer mixture during the synthesis of minute resin particles, or
Alternatively, for the synthesis of fine resin particles, there is a method of polymerizing a monomer mixture using an initiator that provides a cationic end.
微小樹脂粒子を構成するポリマー自体が無極性である場
合、微小樹脂粒子の合成時適当な乳化剤、特に両性イオ
ン基を有するオリゴソープ、ポリソープまたは反応性乳
化剤を使用し、微小樹脂粒子を安定に分散させることも
できる。これらの両性イオン基を持つ乳化剤は、本出願
人の特開昭56−24461、同57−21927.同
57−40522等に開示されている。If the polymer itself that makes up the micro resin particles is non-polar, use an appropriate emulsifier during synthesis of the micro resin particles, especially oligosoaps, polysoaps, or reactive emulsifiers that have amphoteric ionic groups to stably disperse the micro resin particles. You can also do it. These emulsifiers having amphoteric ionic groups are described in Japanese Patent Application Laid-open Nos. 56-24461 and 57-21927. 57-40522, etc.
蚕11料■炭腹
本発明の電着塗料組成物は、必須成分として前記電着可
能な水性樹脂と、前記微小樹脂粒子とを含んでいる。水
性樹脂と微小樹脂粒子との比率は、固形分として前者に
対し、後者1〜50重量%である。微小樹脂粒子の添加
量は、あまり少なければ効果がなく、あまり多いと塗料
の安定性や電着作業性を害する。Silkworm 11 Material ■ Charcoal Belly The electrodeposition coating composition of the present invention contains the above-mentioned electrodepositable aqueous resin and the above-mentioned fine resin particles as essential components. The ratio of the aqueous resin to the fine resin particles is 1 to 50% by weight of the latter based on the solid content of the former. If the amount of fine resin particles added is too small, there will be no effect, and if it is too large, the stability of the paint and the workability of electrodeposition will be impaired.
また使用する水分散性樹脂のタイプに応じ、メラミン樹
脂、ベンゾグアナミン樹脂、フェノール樹脂、ブロック
ポリイソシアネート化合物のような補助硬化剤や、マン
ガン、コバルト、銅、鉛、錫等の金属化合物を触媒とし
て含むことができるこれらの成分は、アニオン電着にあ
っては塩基、カチオン電着にあっては酸を含む水性媒体
中に分散される。これらの酸および塩基は電着可能な水
溶性樹脂を中和するために用いられる。Depending on the type of water-dispersible resin used, it may also contain auxiliary hardeners such as melamine resins, benzoguanamine resins, phenolic resins, blocked polyisocyanate compounds, and metal compounds such as manganese, cobalt, copper, lead, and tin as catalysts. These components that can be used are dispersed in an aqueous medium containing a base for anionic electrodeposition and an acid for cationic electrodeposition. These acids and bases are used to neutralize the electrodepositable water-soluble resin.
中和に用いる塩基としては、例えばアンモニア、ジェタ
ノールアミン、トリエタノールアミン、メチルエタノー
ルアミン、ジエチルアミン、モルホリン、水酸化カリウ
ムなどがある。Examples of the base used for neutralization include ammonia, jetanolamine, triethanolamine, methylethanolamine, diethylamine, morpholine, and potassium hydroxide.
酸としては、リン酸、酢酸、プロピオン酸、乳酸等が用
いられる。As the acid, phosphoric acid, acetic acid, propionic acid, lactic acid, etc. are used.
水性媒体は水か、または水と水混和性有機溶剤との混合
物である。必要に応じ水性媒体は水不混和性有機溶剤を
含んでいてもよい。水混和性有機溶剤の例には、エチル
セロソルブ、プロビルセロソルフ、ブチルセロソルブ、
エチレングリコールジメチルエーテル、ジアセトンアル
コール、4−メトキシ−4−メチルペンタノン−2、メ
チルエチルケトンなどがある。また、水不混和性有機溶
剤の例には、キシレン、トルエン、メチルイソブチルケ
トン、2−エチルヘキサノールなどがある。The aqueous medium is water or a mixture of water and a water-miscible organic solvent. If necessary, the aqueous medium may contain a water-immiscible organic solvent. Examples of water-miscible organic solvents include ethyl cellosolve, probyl cellosolve, butyl cellosolve,
Examples include ethylene glycol dimethyl ether, diacetone alcohol, 4-methoxy-4-methylpentanone-2, and methyl ethyl ketone. Examples of water-immiscible organic solvents include xylene, toluene, methyl isobutyl ketone, and 2-ethylhexanol.
本発明の塗料組成物は顔料を含むことができる。The coating composition of the present invention can contain pigments.
その例としては、二酸化チタン、ベンガラ、カーボンブ
ラック等の着色顔料、ケイ酸アルミニウム、沈降性硫酸
バリウム等の体質顔料、およびリンモリブデン酸アルミ
ニウム、クロム酸ストロンチウム、塩基性ケイ酸鉛、ク
ロム酸鉛等の防錆顔料がある。Examples include coloring pigments such as titanium dioxide, red iron oxide, carbon black, extender pigments such as aluminum silicate, precipitated barium sulfate, and aluminum phosphomolybdate, strontium chromate, basic lead silicate, lead chromate, etc. There are anti-rust pigments.
本発明の塗料組成物は、塗料の不揮発分を10〜20%
程度に調節し、乾燥膜厚15〜30μに電着し、樹脂の
タイプに応じて常温硬化、熱硬化、紫外線硬化、電子線
硬化等により硬化させることができる。The coating composition of the present invention has a non-volatile content of the coating of 10 to 20%.
It can be electrodeposited to a dry film thickness of 15 to 30 μm and cured by room temperature curing, heat curing, ultraviolet curing, electron beam curing, etc. depending on the type of resin.
以下に本発明の製造例、実施例および比較例を示す。こ
れらの例において部および%は重量基準による。Production examples, examples and comparative examples of the present invention are shown below. Parts and percentages in these examples are by weight.
製造例1
カチオン ′ハ 1 の ゛
攪拌機、窒素導入管、温度制御装置、コンデンサー、デ
カンタ−を備えた21コルベンに、タウリンのナトリウ
ム塩73.5部、エチレングリコール100部、エチレ
ングリコールモノメチルエーテル200部を仕込み、か
きまぜながら加熱して温度を120℃に上げる。内容物
が均一な溶解伏態に達した後、エピコー)1001(シ
ェルケミカル社製、ビスフェノールAのジグリシジルエ
ーテル型エポキシ樹脂、エポキシ当量470)470部
とエチレングリコールモノメチルエーテル400部から
なる溶液を2時間で滴下する。滴下後20時間攪拌と加
熱を継続して変性エポキシ樹脂518部を得る。Production Example 1 73.5 parts of sodium salt of taurine, 100 parts of ethylene glycol, and 200 parts of ethylene glycol monomethyl ether were added to a 21-kolben equipped with a stirrer, a nitrogen inlet tube, a temperature control device, a condenser, and a decanter. Prepare and heat while stirring to raise the temperature to 120℃. After the contents reached a uniform state of dissolution, a solution consisting of 470 parts of Epicor 1001 (manufactured by Shell Chemical Co., diglycidyl ether type epoxy resin of bisphenol A, epoxy equivalent: 470) and 400 parts of ethylene glycol monomethyl ether was added to 2 Drip in time. After dropping, stirring and heating were continued for 20 hours to obtain 518 parts of a modified epoxy resin.
この樹脂のKOH滴定による酸価は49.4で、螢光X
線分析によるイオウの含量は2.8%であった。The acid value of this resin by KOH titration was 49.4, and the fluorescent
The sulfur content by line analysis was 2.8%.
攪拌機、冷却管、温度制御装置を備えた11の反応容器
に、脱イオン水306部、上で得た変性エポキシ樹脂7
.5部、ジメチルエタノールアミン1、0部を仕込み、
かきまぜながら80℃まで昇温させた。内容物が溶解し
た後、かきまぜながら温度を80℃に保持し、これにア
ゾビスシアノ吉草酸4.8部、ジメチルエタノールアミ
ン4.56部および塩イオン水48部からなる水溶液を
仕込み、ついでスチレン85.7部、メチルメタクリレ
ート114.3部、n−ブチルアクリレート28.6部
、n−ブチルメタクリレート57.1部、ジエチルアミ
ノエチルメタクリレート14.3部よりなる混合液を6
0分間を要して滴下した。滴下後さらに同温度でアゾビ
スシアノ吉草酸1.2部、ジメチルエタノールアミン1
.14部および脱イオン水12部からなる混合水溶液を
添加し、60分間攪拌を継続して粒子径123nm、S
P値10.1.不揮発分35%の微小樹脂分散液を得た
。Into 11 reaction vessels equipped with a stirrer, a cooling tube, and a temperature control device, 306 parts of deionized water and 7 parts of the modified epoxy resin obtained above were added.
.. 5 parts, dimethylethanolamine 1.0 parts,
The temperature was raised to 80°C while stirring. After the contents were dissolved, the temperature was maintained at 80°C while stirring, and an aqueous solution consisting of 4.8 parts of azobiscyanovaleric acid, 4.56 parts of dimethylethanolamine, and 48 parts of salt ion water was charged therein, and then 85% of styrene was added. 7 parts of methyl methacrylate, 114.3 parts of n-butyl acrylate, 57.1 parts of n-butyl methacrylate, and 14.3 parts of diethylaminoethyl methacrylate.
The dropwise addition took 0 minutes. After dropping, add 1.2 parts of azobiscyanovaleric acid and 1 part of dimethylethanolamine at the same temperature.
.. Add a mixed aqueous solution consisting of 14 parts of deionized water and 12 parts of deionized water and continue stirring for 60 minutes to obtain a particle size of 123 nm, S
P value 10.1. A fine resin dispersion with a nonvolatile content of 35% was obtained.
製造例2
日石ポリブタジェンB−2000(数平均分子量200
0゜1.2結合65%)を過酢酸を用いてエポキシ化し
、オキシラン酸素含有量6.4%のエポキシ化ポリブタ
ジェンを製造した。Production Example 2 Nisseki Polybutadiene B-2000 (number average molecular weight 200
0°1.2 bonds (65%) was epoxidized using peracetic acid to produce epoxidized polybutadiene with an oxirane oxygen content of 6.4%.
このエポキシ化ポリブタジェン1000gおよびエチル
セロソルブ354gを21オートクレーブに仕込んだ後
、ジメチルアミン62.1 gを加え、150℃で5時
間反応させた。未反応アミンを留去した後、120℃ま
で冷却しアクリル酸79.3g、ハイドロキノン7.6
gおよびエチルセロソルブ26.4 gの混合物を添加
し、さらに120℃で3時間45分反応させて樹脂溶液
(A)を製造した。このもののアミン価は85.2ミリ
モル/100g、酸価は10.0ミリモル/100gそ
して固形分濃度は75.0重量%であった。After charging 1000 g of this epoxidized polybutadiene and 354 g of ethyl cellosolve into a 21 autoclave, 62.1 g of dimethylamine was added and reacted at 150° C. for 5 hours. After distilling off unreacted amine, it was cooled to 120°C and 79.3 g of acrylic acid and 7.6 g of hydroquinone were added.
A mixture of 26.4 g of ethyl cellosolve and 26.4 g of ethyl cellosolve was added thereto, and the mixture was further reacted at 120° C. for 3 hours and 45 minutes to produce a resin solution (A). The amine value of this product was 85.2 mmol/100g, the acid value was 10.0 mmol/100g, and the solid content concentration was 75.0% by weight.
製造例3
エポキシ当量950を持つビスフェノールタイプエポキ
シ樹脂(商品名エピコート1004油化シエルエポキシ
@!Iり1000gをエチルセロソルブ343gに熔解
し、アクリル酸76.3g、ハイドロキノン10gおよ
びN、N−ジメチルアミンエタノールを5g添加し、1
00℃に加熱して5時間反応させ、樹脂溶液(B>を合
成した。固形分濃度75重量%
製造例4
日石ポリブタジェンB−1000(数平均分子量100
0、1.2結合60%)1000g、無水マレイン酸2
65.8g、キシレン10g、アンチゲン6C(住友化
学商品名)Igを還流冷却器を設置した2Eセパラブル
フラスコに仕込み窒素気流下にて190℃で5時間反応
させた次に未反応無水マレイン酸、キシレンを減圧下に
留去し、酸価214ミリモル/100gのマレイン化ポ
リブタジェンを合成した。Production Example 3 1000 g of a bisphenol type epoxy resin having an epoxy equivalent weight of 950 (trade name Epicote 1004 oil-based Ciel Epoxy @!I) was dissolved in 343 g of ethyl cellosolve, and 76.3 g of acrylic acid, 10 g of hydroquinone and N,N-dimethylamine ethanol were dissolved. Add 5g of
The resin solution (B> was synthesized by heating to 00°C and reacting for 5 hours. Solid content concentration 75% by weight. Production example 4 Nisseki Polybutadiene B-1000 (number average molecular weight 100
0, 1.2 bonds 60%) 1000g, maleic anhydride 2
65.8 g of xylene, 10 g of xylene, and Antigen 6C (trade name of Sumitomo Chemical) Ig were placed in a 2E separable flask equipped with a reflux condenser and reacted at 190°C for 5 hours under a nitrogen stream. Next, unreacted maleic anhydride, Xylene was distilled off under reduced pressure to synthesize maleated polybutadiene with an acid value of 214 mmol/100 g.
次にマレイン化ポリブタジェンtooog、エチルセロ
ソルブ212.4gを還流冷却器を備えた21セパラブ
ルフラスコに仕込み攪住下に120℃で2時間反応させ
、マレイン化ポリブタジェンの半エステル化物(C)を
製造した。固形分濃度98重量%
実施例1
製造例2で製造した(A)400g、製造例3で製造し
た(B)240gおよび製造例4で製造した(C)19
.2gを均一になるまで混合した。Next, maleated polybutadiene tooog and 212.4 g of ethyl cellosolve were charged into a 21 separable flask equipped with a reflux condenser and reacted at 120°C for 2 hours with stirring to produce a half-esterified product (C) of maleated polybutadiene. . Solid content concentration 98% by weight Example 1 400 g of (A) produced in Production Example 2, 240 g of (B) produced in Production Example 3, and (C) 19 produced in Production Example 4
.. 2g were mixed until homogeneous.
ワニスのSp(+iHo、s、その後酢酸8.1gを加
え十分にかきまぜ中和した。Varnish Sp(+iHo,s) was added, and then 8.1 g of acetic acid was added and thoroughly stirred to neutralize.
このワニスへ幾イオン水1835gを徐々に加えて固形
分濃度約20%のエマルジョンを得た。1,835 g of ionized water was gradually added to this varnish to obtain an emulsion with a solid content concentration of about 20%.
その後製造例1の微小樹脂分散液200gを添加し、固
形分濃度が約20%(塗料浴中の微小樹脂粒子固形公約
3%)の水溶液を調製した。Thereafter, 200 g of the fine resin dispersion of Production Example 1 was added to prepare an aqueous solution having a solid content concentration of about 20% (about 3% solids of the fine resin particles in the paint bath).
上記電着塗料液を用いてカーボン電極を陽極とし、リン
酸亜鉛処理板を陰極とじ100vで3分間陰極析出型筒
着塗装を行った。焼付175℃×30分。テスト結果を
表−1に示した。Using the above electrodeposition coating solution, a carbon electrode was used as an anode, and a zinc phosphate treated plate was closed as a cathode, and cathode deposition type tube coating was performed at 100V for 3 minutes. Baking at 175℃ x 30 minutes. The test results are shown in Table-1.
製造例5 4 アンモニウム E 1800−6.5 (日本石油■製。Manufacturing example 5 4 Ammonium E 1800-6.5 (made by Nippon Oil ■).
エポキシ化ポリブタジェン) 1000gブ
チルセロソルブ 349gジメチル
アミン 46g50%乳酸
138g脱イオン水
473gフェニルグリシジルエーテ
ル 117gエポキシ化ポリブタジェンE 1
800−6.5およびブチルセロソルブをオートクレー
ブに仕込んだ後、ジメチルアミンを加え150℃で5時
間反応させた。未反応アミンを留去した後、60℃まで
冷却し、50%乳酸と脱イオン水の混合液を添加した、
後80℃で30分間攪拌保温する。その後フェニルグリ
シジルエーテルを加え、110℃まで昇温し、攪拌保温
しながら内容物の酸価をフェノールフタレンを指示薬と
してアルコール性KoHを規定液とする通常の方法で測
定し、酸fil!io、1以下を確認するまで反応させ
た後製造を終了する。不揮発分55%
製造例6
皿且さ二久上
製造例5ワニス 231g
脱イオン水 315g
カーボンブランク 16g
酸化チタン 92g
カオリン 220g
塩基性珪酸鉛 58g
製造例5のワニスに脱イオン水を加えて熔解した後、顔
料を加えディスパーで約1時間攪拌混合する。この混合
物にガラスピーズを加えた後サンドミルで粒度20μ以
下に分散し、ガラスピーズを日別した後製造を終了する
。不揮発分55%実施例2
製造例2で製造した(A)400g、製造例3で製造し
た(B)240g、製造例4で製造した(c)19.2
gを均一になるまで混合した後、酢酸8.1gを加え十
分にかきまぜ中和した。このワニスヘ税イオン水183
5gを徐々に加えて固形分濃度約20%のエマルジョン
を得た。その後、前記製造例6の顔料ペースト360
g、脱イオン水550 g、製造例1の微小樹脂粒子分
散液260gを均一に攪拌し、エナメル電着浴(塗料中
の微小樹脂粒子固形公約2%)を調製した。(epoxidized polybutadiene) 1000g butyl cellosolve 349g dimethylamine 46g 50% lactic acid
138g deionized water
473g phenyl glycidyl ether 117g epoxidized polybutadiene E 1
After charging 800-6.5 and butyl cellosolve into an autoclave, dimethylamine was added and reacted at 150°C for 5 hours. After distilling off the unreacted amine, it was cooled to 60°C, and a mixture of 50% lactic acid and deionized water was added.
After that, stir and keep warm at 80°C for 30 minutes. After that, phenylglycidyl ether was added, the temperature was raised to 110°C, and while stirring and keeping warm, the acid value of the contents was measured by the usual method using phenolphthalene as an indicator and alcoholic KoH as a standard solution, and acid fil! After reacting until confirmation of io, 1 or less, production is terminated. Non-volatile content 55% Production Example 6 Dish Katsuji Production Example 5 Varnish 231g Deionized water 315g Carbon blank 16g Titanium oxide 92g Kaolin 220g Basic lead silicate 58g After adding deionized water to the varnish of Production Example 5 and melting it. Add the pigment and mix with a disperser for about 1 hour. Glass peas are added to this mixture, and then dispersed in a sand mill to a particle size of 20 μm or less, and after the glass peas are divided into days, the production is completed. Non-volatile content 55% Example 2 400 g of (A) produced in Production Example 2, 240 g of (B) produced in Production Example 3, (c) 19.2 produced in Production Example 4
After mixing until homogeneous, 8.1 g of acetic acid was added and thoroughly stirred for neutralization. The tax on this varnish is 183 yen of ionized water.
5 g was gradually added to obtain an emulsion with a solid content concentration of about 20%. After that, the pigment paste 360 of Production Example 6
g, 550 g of deionized water, and 260 g of the fine resin particle dispersion of Production Example 1 were uniformly stirred to prepare an enamel electrodeposition bath (approximately 2% solid fine resin particles in the paint).
かかる電着浴を使用して、実施例1と同じ条件で電着、
硬化させた塗膜の性能を表−1に示す。Using this electrodeposition bath, electrodeposition was carried out under the same conditions as in Example 1.
Table 1 shows the performance of the cured coating film.
製造例7
日石ポリフ゛タジエンB−1500* 1) 10
00gアンチゲン6C* 2)
10 g無水マレイン酸 25
0g脱イオン水 20gジエ
チルアミン 0.5gプロピレ
ングリコール 100gエチルセロソル
ブ 340g*l)日本石油化学■
製; Mn 1500、ビニル65%、トランス14
%、シス16%
*2)住友化学■製; N−メチル−N’−(1,3−
ジメチルブチル)、p−フェニレンジアミン冷却管付2
1コルベンに、6石ポリブタジェンB−1500100
0gを仕込み、アンチゲン6C10gと無水マレイン酸
250gを添加する。攪拌しながら、内湯を190〜2
00℃に保ちながらマレイン酸のポリブタジェンへの付
加反応を行う。Production Example 7 Nisseki Polyphytadiene B-1500* 1) 10
00g Antigen 6C* 2)
10 g maleic anhydride 25
0g deionized water 20g diethylamine 0.5g propylene glycol 100g ethyl cellosolve 340g*l) Nippon Petrochemical ■
Made: Mn 1500, vinyl 65%, trans 14
%, cis 16% *2) Manufactured by Sumitomo Chemical ■; N-methyl-N'-(1,3-
dimethylbutyl), p-phenylenediamine with cooling tube 2
6 stones polybutadiene B-1500100 in 1 Kolben
0 g, and add 10 g of Antigen 6C and 250 g of maleic anhydride. While stirring, heat the indoor bath to 190~2
The addition reaction of maleic acid to polybutadiene is carried out while maintaining the temperature at 00°C.
昇温後約5時間でジメチルアニリン呈色反応で反応が終
了したことを確認した。その後内温を100℃まで冷却
し、脱イオン水20gとジエチルアミン0.5gの混合
物を約30分間で滴下する。さらに滴下終了後約1時間
攪拌を続け、酸価が140であることを確認した。その
後プロピレングリコール100gを添加し110℃で3
時間反応させ全酸価が125であることを確認した。そ
の後エチルセロソルブ340gを加え、80℃で約1時
間攪拌した後、合成を終了した。不揮発分80%
製造例8
エボトート YD−01413) 9
50 gエチルセロソルブ 240
gハイドロキノン 10gア
クリル酸 65gジメチ
ルベンジルアミン 5g*3)東部化
成@製、エポキシ樹脂、エポキシ当量950
冷却管付21コルベンにエポトートYD−014950
gとエチルセロソルブ240gを仕込み、徐々に120
℃まで攪拌しながらYD−014を均一に熔解する。そ
の後ハイドロキノン10gを加え、更にアクリル酸65
g、ジメチルベンジルアミン5gを加える。120℃で
4時間反応して後酸価が1以下であることを確認した。Approximately 5 hours after the temperature was raised, it was confirmed that the reaction was completed by a dimethylaniline color reaction. Thereafter, the internal temperature was cooled to 100° C., and a mixture of 20 g of deionized water and 0.5 g of diethylamine was added dropwise over about 30 minutes. Further, stirring was continued for about 1 hour after the completion of the dropwise addition, and the acid value was confirmed to be 140. After that, 100g of propylene glycol was added and heated to 110℃ for 3 hours.
It was confirmed that the total acid value was 125 after reacting for a period of time. Thereafter, 340 g of ethyl cellosolve was added, and after stirring at 80° C. for about 1 hour, the synthesis was completed. Non-volatile content 80% Production example 8 Evototo YD-01413) 9
50 g ethyl cellosolve 240
g Hydroquinone 10 g Acrylic acid 65 g Dimethylbenzylamine 5 g *3) Manufactured by Tobu Kasei@, epoxy resin, epoxy equivalent 950 Epotote YD-014950 in 21 Kolben with cooling tube
Add 240 g of ethyl cellosolve and 240 g of ethyl cellosolve and gradually reduce to 120 g.
Uniformly melt YD-014 while stirring at ℃. Then add 10g of hydroquinone and add 65g of acrylic acid.
g, and add 5 g of dimethylbenzylamine. After reacting at 120° C. for 4 hours, it was confirmed that the post-acid value was 1 or less.
不揮発分80%製造例9
アニオン ′ハ 1 の ゛
攪拌機、温度計を備えたフラスコに、脱イオン水426
部を入れ、温度を80℃に加熱した。窒素気流下過硫酸
アンモニウム1部と脱イオン水20部からなる水溶液を
滴下した。さらにスチレン5部、n−ブチルアクリレー
ト5部よりなる七ツマー混合液を加え、10分間反応さ
せた後、過硫酸アンモニウム1部と脱イオン水20部か
らなる水溶液と、メチルメタクリレート40部、n−ブ
チルメタクリレート20部、スチレン30部および2−
ヒドロキシエチルメタクリレート10部からなる七ツマ
ー混合液とを60分間をかけて滴下した。さらに温度8
0℃で2時間保温し、反応を終了した。Non-volatile content 80% Production Example 9 Add 426 ml of deionized water to a flask equipped with a stirrer and a thermometer.
and heated to 80°C. An aqueous solution consisting of 1 part of ammonium persulfate and 20 parts of deionized water was added dropwise under a nitrogen stream. Furthermore, a 7-mer mixture consisting of 5 parts of styrene and 5 parts of n-butyl acrylate was added, and after reacting for 10 minutes, an aqueous solution consisting of 1 part of ammonium persulfate and 20 parts of deionized water, 40 parts of methyl methacrylate, and n-butyl acrylate was added. 20 parts of methacrylate, 30 parts of styrene and 2-
A 7-mer mixture consisting of 10 parts of hydroxyethyl methacrylate was added dropwise over 60 minutes. Further temperature 8
The reaction was completed by keeping the temperature at 0°C for 2 hours.
粒径320nm、軟化温度70℃、不揮発分35%の微
小樹脂粒子分散液を得た。A fine resin particle dispersion having a particle size of 320 nm, a softening temperature of 70° C., and a non-volatile content of 35% was obtained.
製造例10
皿料ベニ人玉
製造例7のワニス125gを採取し、これにトリエチル
アミン13gを加え、次いで脱イオン水250gを徐々
に加え、均一に熔解し、不揮発分26%のワニスとする
。Production Example 10 125 g of the varnish from Production Example 7 was collected, 13 g of triethylamine was added thereto, and then 250 g of deionized water was gradually added to dissolve uniformly to obtain a varnish with a non-volatile content of 26%.
次に二酸化チタン150 g、ケイ酸鉛50g。Next, 150 g of titanium dioxide and 50 g of lead silicate.
ストロンチウムクロメ−)25g、カーボンブラック2
5gを加え、ディスパーザ−で約1時間混合かきまぜる
。この混合物にガラスピーズを加えた後、サンドミルで
粒度20μ以下に分散し、ガラスピーズを日別した後製
造を終了する。不揮発分55%
実施例3
製造例7のワニス125 g、製造例8のワニス75g
、ブチル化メラミン(不揮発分50%)40g、 レ
ゾール型フェノール樹脂(不揮発分50%)40gを採
取し、これにノニオン界面活性剤2gとナフテン酸コバ
ルト3gを加え均一に攪拌した後、トリエチルアミン1
3gを加え、次いで塩イオン水707gを徐々に加えな
がら均一に攪拌して溶解し、製造例9の微小樹脂粒子分
散液47gを添加し、固形分濃度約20%(塗料中の微
小樹脂粒子分散液約2%)の塗料浴を調製した。Strontium chromate) 25g, carbon black 2
Add 5g and stir with a disperser for about 1 hour. After glass peas are added to this mixture, they are dispersed in a sand mill to a particle size of 20 μm or less, and the glass peas are divided into days to complete the production. Non-volatile content 55% Example 3 125 g of varnish from Production Example 7, 75 g of varnish from Production Example 8
, butylated melamine (50% non-volatile content), 40 g of resol type phenolic resin (50% non-volatile content) were collected, 2 g of nonionic surfactant and 3 g of cobalt naphthenate were added thereto, stirred uniformly, and triethylamine 1.
Then, 707 g of salt ion water was gradually added and dissolved by stirring uniformly. 47 g of the fine resin particle dispersion of Production Example 9 was added, and the solid content concentration was approximately 20% (fine resin particle dispersion in the paint). A paint bath of approximately 2% liquid was prepared.
リン酸亜鉛処理を施したダル鋼板を塗料浴に浸漬し、被
塗物を陽極として、膜J!220μに電着塗装した。そ
の後、被塗物表面を水洗し、焼付炉で140℃X30分
間焼付け、膜厚的20μの塗装板を得た。得られた塗膜
の性能を試験した結果を表−1に示す。A dull steel plate treated with zinc phosphate is immersed in a paint bath, and the object to be coated is used as an anode.Membrane J! Electrodeposition coating was applied to 220μ. Thereafter, the surface of the object to be coated was washed with water and baked in a baking oven at 140° C. for 30 minutes to obtain a coated plate with a film thickness of 20 μm. Table 1 shows the results of testing the performance of the obtained coating film.
実施例4
製造例7のワニス125g、製造例8のワニス75g、
ブチル化メラミン(不揮発分50%)4Og、 レゾ
ール型フェノール樹脂(不揮発分50%)40gを採取
し、これにノニオン界面活性剤2gとナフテン酸コバル
ト3gを加え均一に攪拌した後、トリエチルアミン13
gを加え、次いで脱イオン水707gを徐々に加えなが
ら均一に攪拌して溶解し、次いで製造例10の顔料ペー
スト125g、塩イオン水220 g、製造例9の微小
樹脂粒子分散液80gを均一に攪拌し、エナメル電着浴
(塗料中の微小樹脂粒子固形公約10%)をmML、た
。Example 4 125 g of the varnish of Production Example 7, 75 g of the varnish of Production Example 8,
40 g of butylated melamine (50% non-volatile content) and 40 g of resol type phenol resin (50% non-volatile content) were collected, and 2 g of nonionic surfactant and 3 g of cobalt naphthenate were added thereto and stirred uniformly, followed by 13 g of triethylamine.
Then, 707 g of deionized water was gradually added and dissolved by stirring uniformly, and then 125 g of the pigment paste of Production Example 10, 220 g of salt ionized water, and 80 g of the fine resin particle dispersion of Production Example 9 were uniformly added. With stirring, the enamel electrodeposition bath (approximately 10% solids of microscopic resin particles in the paint) was added to the milliliter of the enamel electrodeposition bath.
かかる電着浴を使用して、実施例3と同じ条件で電着、
硬化させた塗膜の性能を表−1に示す。Using this electrodeposition bath, electrodeposition was carried out under the same conditions as in Example 3.
Table 1 shows the performance of the cured coating film.
比較例1
実施例1で製造例1の微小樹脂粒子200gを添加せず
、説イオン水1835gを1800gに変更する以外は
実施例工と同様に実施した。Comparative Example 1 The same procedure as in Example 1 was carried out except that 200 g of the fine resin particles of Production Example 1 were not added and 1,835 g of the ionized water was changed to 1,800 g.
比較例2
実施例2で製造例1の微小樹脂粒子260gを添加せず
、塩イオン水1835gを1800gに変更する以外は
実施例2と同様に実施した。Comparative Example 2 The same procedure as in Example 2 was carried out except that 260 g of the fine resin particles of Production Example 1 were not added and 1835 g of salt ionized water was changed to 1800 g.
比較例3
実施例3で製造例10の微小樹脂粒子60gを添加せず
、脱イオン水707gを662gに変更する以外は実施
例3と同様に実施した。Comparative Example 3 The same procedure as in Example 3 was carried out except that 60 g of the fine resin particles of Production Example 10 were not added and 707 g of deionized water was changed to 662 g.
比較例4
実施例4で製造例10の微小樹脂粒子80gを添加せず
、脱イオン水707gを662gに変更する以外は実施
例4と同様に実施した。Comparative Example 4 The same procedure as in Example 4 was carried out except that 80 g of the fine resin particles of Production Example 10 were not added and 707 g of deionized water was changed to 662 g.
(以下余白)
手続補正書
昭和61年10月 9日
昭和61年特許願第214889号
2、 発明の名称
電着塗料組成物
3、補正をする者
事件との関係 特許出願人
名 称 日本ペイント株式会社
4、代理人
自 発
6、補正により増加する発明の数 なし補正の内容
1、 明細書第19頁下から2行目の「日本石油■」を
「日本石油化学■」に訂正する。(Leaving space below) Procedural amendment October 9, 1988 Patent Application No. 214889 2 Name of the invention Electrodeposition paint composition 3 Relationship with the person making the amendment Name of patent applicant Title Nippon Paint Co., Ltd. 4. Spontaneous request by the agent 6. No increase in the number of inventions due to the amendment Contents of the amendment 1. Correct "Nippon Oil ■" in the second line from the bottom of page 19 of the specification to "Nippon Petrochemical ■".
2、同第21頁第14行の「・・・・・・混合した後」
の次に「(ワニスのSPPtO26)Jを挿入する。2. "... after mixing" on page 21, line 14
Next to ``(varnish SPPtO26) insert J.
3、同第24頁第8行の「アニオン性」を削除する。3. Delete "anionicity" on page 24, line 8.
4、同第25頁第2行のr320nm、軟化温度70℃
、」をr196nm、SPPtO21,Jに訂正する。4. r320nm, softening temperature 70℃ on page 25, line 2
," is corrected to r196nm, SPPtO21,J.
5、同第26頁第1行および第18行の「これに」の次
に「(ワニスのSPPtO25)Jを挿入する。5. Insert ``(varnish SPPtO25)J'' after ``to this'' in the 1st and 18th lines of page 26.
6、同第27頁第5行の「固形分約10%」を「固形分
約2%」に訂正する。6. On page 27, line 5, "solid content approximately 10%" is corrected to "solid content approximately 2%."
Claims (5)
)該水性樹脂の水性分散液中に均一に分散された、粒径
が0.01〜0.2μで、かつ前記水性樹脂とのSP値
の差が1以内である微小樹脂粒子とを必須成分として含
むことを特徴とする電着塗料組成物。(1) (a) an aqueous dispersion of an electrodepositable aqueous resin; and (b)
) Fine resin particles uniformly dispersed in the aqueous dispersion of the aqueous resin and having a particle size of 0.01 to 0.2 μ and a difference in SP value from the aqueous resin of 1 or less are essential components. An electrodeposition coating composition comprising:
ョンである第1項記載の電着塗料組成物。(2) The electrodeposition coating composition according to item 1, wherein the aqueous dispersion of the electrodepositable aqueous resin is an emulsion.
たは第2項記載の電着塗料組成物。(3) The electrodeposition coating composition according to item 1 or 2, wherein the aqueous resin has a cationic group.
たは第2項記載の電着塗料組成物。(4) The electrodeposition coating composition according to item 1 or 2, wherein the aqueous resin has an anionic group.
形分の1〜50重量%である第1項ないし第4項のいず
れかに記載の電着塗料組成物。(5) The electrodeposition coating composition according to any one of items 1 to 4, wherein the amount of the fine resin particles is 1 to 50% by weight of the solid content of the aqueous resin.
Priority Applications (7)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP61214889A JPS6368678A (en) | 1986-09-10 | 1986-09-10 | Electrodeposition paint composition |
AU77684/87A AU590960B2 (en) | 1986-09-04 | 1987-08-28 | Electrodeposition coating composition |
CA000545993A CA1285671C (en) | 1986-09-04 | 1987-09-02 | Electrodeposition coating composition |
KR1019870009795A KR940011829B1 (en) | 1986-09-04 | 1987-09-04 | Electrodeposition coating composition |
DE8787307840T DE3785711T2 (en) | 1986-09-04 | 1987-09-04 | ELECTRO-DIP PAINT COATING. |
EP87307840A EP0259181B1 (en) | 1986-09-04 | 1987-09-04 | Electrodeposition coating composition |
US07/301,096 US4975475A (en) | 1986-09-04 | 1989-01-25 | Electrodeposition coating composition |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP61214889A JPS6368678A (en) | 1986-09-10 | 1986-09-10 | Electrodeposition paint composition |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS6368678A true JPS6368678A (en) | 1988-03-28 |
JPH0347667B2 JPH0347667B2 (en) | 1991-07-22 |
Family
ID=16663242
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP61214889A Granted JPS6368678A (en) | 1986-09-04 | 1986-09-10 | Electrodeposition paint composition |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS6368678A (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0249077A (en) * | 1988-08-11 | 1990-02-19 | Shinto Paint Co Ltd | Bath for electrodeposition coating |
CN112424298A (en) * | 2018-07-27 | 2021-02-26 | 关西涂料株式会社 | Aqueous coating composition |
-
1986
- 1986-09-10 JP JP61214889A patent/JPS6368678A/en active Granted
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0249077A (en) * | 1988-08-11 | 1990-02-19 | Shinto Paint Co Ltd | Bath for electrodeposition coating |
CN112424298A (en) * | 2018-07-27 | 2021-02-26 | 关西涂料株式会社 | Aqueous coating composition |
Also Published As
Publication number | Publication date |
---|---|
JPH0347667B2 (en) | 1991-07-22 |
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