JPS63101466A - Electrodeposition paint composition - Google Patents
Electrodeposition paint compositionInfo
- Publication number
- JPS63101466A JPS63101466A JP61246771A JP24677186A JPS63101466A JP S63101466 A JPS63101466 A JP S63101466A JP 61246771 A JP61246771 A JP 61246771A JP 24677186 A JP24677186 A JP 24677186A JP S63101466 A JPS63101466 A JP S63101466A
- Authority
- JP
- Japan
- Prior art keywords
- parts
- resin particles
- fine resin
- resin
- added
- 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 description 37
- 239000003973 paint Substances 0.000 title abstract description 23
- 239000000203 mixture Substances 0.000 title description 25
- 229920005989 resin Polymers 0.000 claims abstract description 106
- 239000011347 resin Substances 0.000 claims abstract description 106
- 239000002245 particle Substances 0.000 claims abstract description 74
- 239000006185 dispersion Substances 0.000 claims abstract description 22
- 239000007787 solid Substances 0.000 claims abstract description 12
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 6
- 229910052718 tin Inorganic materials 0.000 claims abstract description 5
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 4
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 4
- 229910052712 strontium Inorganic materials 0.000 claims abstract description 4
- 229910052742 iron Inorganic materials 0.000 claims abstract description 3
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 3
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 3
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 3
- 229910052802 copper Inorganic materials 0.000 claims abstract 2
- 229910052745 lead Inorganic materials 0.000 claims abstract 2
- 229910052744 lithium Inorganic materials 0.000 claims abstract 2
- 125000002091 cationic group Chemical group 0.000 claims description 10
- 239000008199 coating composition Substances 0.000 claims description 10
- 239000000839 emulsion Substances 0.000 claims description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 150000001450 anions Chemical group 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 50
- 239000000178 monomer Substances 0.000 abstract description 28
- 239000003054 catalyst Substances 0.000 abstract description 19
- 239000011248 coating agent Substances 0.000 abstract description 16
- 238000000576 coating method Methods 0.000 abstract description 16
- 230000001590 oxidative effect Effects 0.000 abstract description 12
- 239000000049 pigment Substances 0.000 abstract description 12
- 229910052782 aluminium Inorganic materials 0.000 abstract description 5
- 239000002904 solvent Substances 0.000 abstract description 5
- 229910052788 barium Inorganic materials 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- 230000002411 adverse Effects 0.000 abstract description 2
- 238000004132 cross linking Methods 0.000 abstract description 2
- 238000013508 migration Methods 0.000 abstract description 2
- 230000005012 migration Effects 0.000 abstract description 2
- 239000011541 reaction mixture Substances 0.000 abstract 1
- 239000008367 deionised water Substances 0.000 description 26
- 229910021641 deionized water Inorganic materials 0.000 description 26
- 238000004519 manufacturing process Methods 0.000 description 25
- 239000002253 acid Substances 0.000 description 23
- 238000000034 method Methods 0.000 description 23
- 239000007864 aqueous solution Substances 0.000 description 20
- 238000003756 stirring Methods 0.000 description 19
- 229910052751 metal Inorganic materials 0.000 description 16
- 239000002184 metal Substances 0.000 description 15
- 239000000243 solution Substances 0.000 description 15
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 14
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 14
- 239000005062 Polybutadiene Substances 0.000 description 14
- 229920002857 polybutadiene Polymers 0.000 description 14
- 229960002887 deanol Drugs 0.000 description 13
- 239000012972 dimethylethanolamine Substances 0.000 description 13
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 11
- -1 isocyanate compound Chemical class 0.000 description 11
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- 239000000843 powder Substances 0.000 description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 8
- 125000000129 anionic group Chemical group 0.000 description 8
- 238000006116 polymerization reaction Methods 0.000 description 8
- 239000008096 xylene Substances 0.000 description 8
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 7
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 7
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- 239000002966 varnish Substances 0.000 description 7
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 6
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 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
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 5
- 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
- 239000002585 base Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000003822 epoxy resin Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 229920000647 polyepoxide Polymers 0.000 description 5
- 229920001225 polyester resin Polymers 0.000 description 5
- 239000004645 polyester resin Substances 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 4
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 239000004593 Epoxy Substances 0.000 description 4
- 235000010582 Pisum sativum Nutrition 0.000 description 4
- 240000004713 Pisum sativum Species 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000001723 curing Methods 0.000 description 4
- 210000003298 dental enamel Anatomy 0.000 description 4
- 239000003995 emulsifying agent Substances 0.000 description 4
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 4
- 125000000524 functional group Chemical group 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
- 150000002736 metal compounds Chemical class 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- XOAAWQZATWQOTB-UHFFFAOYSA-N taurine Chemical compound NCCS(O)(=O)=O XOAAWQZATWQOTB-UHFFFAOYSA-N 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 239000004640 Melamine resin Substances 0.000 description 3
- 229920000877 Melamine resin Polymers 0.000 description 3
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 235000011054 acetic acid Nutrition 0.000 description 3
- 125000003277 amino group Chemical group 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
- 239000006229 carbon black Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 description 3
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 3
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 125000003010 ionic group Chemical group 0.000 description 3
- 239000004310 lactic acid Substances 0.000 description 3
- 235000014655 lactic acid Nutrition 0.000 description 3
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 238000001694 spray drying Methods 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 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
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-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
- 239000004925 Acrylic resin Substances 0.000 description 2
- 229920000178 Acrylic resin Polymers 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
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 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
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 239000000427 antigen Substances 0.000 description 2
- 102000036639 antigens Human genes 0.000 description 2
- 108091007433 antigens Proteins 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
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 2
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 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
- 239000012948 isocyanate Substances 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 238000013035 low temperature curing Methods 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- 239000002609 medium Substances 0.000 description 2
- 150000007974 melamines Chemical class 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 239000002685 polymerization catalyst Substances 0.000 description 2
- FBCQUCJYYPMKRO-UHFFFAOYSA-N prop-2-enyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC=C FBCQUCJYYPMKRO-UHFFFAOYSA-N 0.000 description 2
- 239000011134 resol-type phenolic resin Substances 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- 150000003335 secondary amines Chemical class 0.000 description 2
- 239000011734 sodium 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
- 230000002194 synthesizing effect Effects 0.000 description 2
- 229960003080 taurine Drugs 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- 238000005809 transesterification reaction Methods 0.000 description 2
- 229920002554 vinyl polymer Polymers 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
- NNNLYDWXTKOQQX-UHFFFAOYSA-N 1,1-di(prop-2-enoyloxy)propyl prop-2-enoate Chemical compound C=CC(=O)OC(CC)(OC(=O)C=C)OC(=O)C=C NNNLYDWXTKOQQX-UHFFFAOYSA-N 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
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- 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
- CLDPKFWKBZAVLP-UHFFFAOYSA-N 2-[methyl(1-phenylprop-2-enyl)amino]ethanesulfonic acid Chemical compound OS(=O)(=O)CCN(C)C(C=C)C1=CC=CC=C1 CLDPKFWKBZAVLP-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- KPCLERWFAKHLIJ-UHFFFAOYSA-N 2-methylprop-2-enoic acid;propane-1,1,1-triol Chemical compound CCC(O)(O)O.CC(=C)C(O)=O.CC(=C)C(O)=O KPCLERWFAKHLIJ-UHFFFAOYSA-N 0.000 description 1
- NRVFHZGBTDXOEY-UHFFFAOYSA-N 2-methylprop-2-enoic acid;zinc Chemical compound [Zn].CC(=C)C(O)=O NRVFHZGBTDXOEY-UHFFFAOYSA-N 0.000 description 1
- YEYKMVJDLWJFOA-UHFFFAOYSA-N 2-propoxyethanol Chemical compound CCCOCCO YEYKMVJDLWJFOA-UHFFFAOYSA-N 0.000 description 1
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound 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
- 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
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 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
- 229930185605 Bisphenol Natural products 0.000 description 1
- NXHVXSLRWGQXHW-UHFFFAOYSA-M C(C(=C)C)(=O)O[Zr] Chemical compound C(C(=C)C)(=O)O[Zr] NXHVXSLRWGQXHW-UHFFFAOYSA-M 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
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 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
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- 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
- HDVDLQFPDLTOSI-UHFFFAOYSA-L O[AlH]O Chemical compound O[AlH]O HDVDLQFPDLTOSI-UHFFFAOYSA-L 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 235000002597 Solanum melongena Nutrition 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
- APQHKWPGGHMYKJ-UHFFFAOYSA-N Tributyltin oxide Chemical compound CCCC[Sn](CCCC)(CCCC)O[Sn](CCCC)(CCCC)CCCC APQHKWPGGHMYKJ-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
- 238000002441 X-ray diffraction Methods 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-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
- RKFMOTBTFHXWCM-UHFFFAOYSA-M [AlH2]O Chemical compound [AlH2]O RKFMOTBTFHXWCM-UHFFFAOYSA-M 0.000 description 1
- KZNMRPQBBZBTSW-UHFFFAOYSA-N [Au]=O Chemical compound [Au]=O KZNMRPQBBZBTSW-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
- 150000001242 acetic acid derivatives Chemical class 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
- 230000032683 aging Effects 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 125000000217 alkyl 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
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001491 aromatic compounds Chemical group 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-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
- 238000012662 bulk polymerization Methods 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- PIMYDFDXAUVLON-UHFFFAOYSA-M chloro(triethyl)stannane Chemical compound CC[Sn](Cl)(CC)CC PIMYDFDXAUVLON-UHFFFAOYSA-M 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 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
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- VITHRHRYZSQDDQ-UHFFFAOYSA-N diphenyllead Chemical compound C=1C=CC=CC=1[Pb]C1=CC=CC=C1 VITHRHRYZSQDDQ-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- POULHZVOKOAJMA-UHFFFAOYSA-M dodecanoate Chemical compound CCCCCCCCCCCC([O-])=O POULHZVOKOAJMA-UHFFFAOYSA-M 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000004945 emulsification 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
- 238000005886 esterification reaction Methods 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
- 238000001914 filtration Methods 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 229910001922 gold oxide Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- PYGSKMBEVAICCR-UHFFFAOYSA-N hexa-1,5-diene Chemical group C=CCCC=C PYGSKMBEVAICCR-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 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
- 229940070765 laurate Drugs 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
- YDTFRJLNMPSCFM-YDALLXLXSA-M levothyroxine sodium anhydrous Chemical group [Na+].IC1=CC(C[C@H](N)C([O-])=O)=CC(I)=C1OC1=CC(I)=C(O)C(I)=C1 YDTFRJLNMPSCFM-YDALLXLXSA-M 0.000 description 1
- 229940080162 levoxyl Drugs 0.000 description 1
- CDOSHBSSFJOMGT-UHFFFAOYSA-N linalool Chemical compound CC(C)=CCCC(C)(O)C=C CDOSHBSSFJOMGT-UHFFFAOYSA-N 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals 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
- KZKQGUVWZYKJBN-UHFFFAOYSA-N methyl 5-methylsulfonylpyridine-3-carboxylate Chemical compound COC(=O)C1=CN=CC(S(C)(=O)=O)=C1 KZKQGUVWZYKJBN-UHFFFAOYSA-N 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- GEMHFKXPOCTAIP-UHFFFAOYSA-N n,n-dimethyl-n'-phenylcarbamimidoyl chloride Chemical compound CN(C)C(Cl)=NC1=CC=CC=C1 GEMHFKXPOCTAIP-UHFFFAOYSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000011356 non-aqueous organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 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
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 235000011007 phosphoric acid Nutrition 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
- 239000011591 potassium Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012673 precipitation polymerization Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 150000003141 primary amines Chemical class 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
- 239000002994 raw material Substances 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 125000005504 styryl group Chemical group 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 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
- 239000000725 suspension Substances 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 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
- 238000004448 titration Methods 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- DBGVGMSCBYYSLD-UHFFFAOYSA-N tributylstannane Chemical compound CCCC[SnH](CCCC)CCCC DBGVGMSCBYYSLD-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
- 238000005406 washing Methods 0.000 description 1
- 150000003738 xylenes Chemical class 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Landscapes
- Paints Or Removers (AREA)
Abstract
Description
【発明の詳細な説明】
の ゛よび−
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
。電着塗料用の皮膜形成用樹脂としては多くのタイプの
ものが知られているが、その一つに天然および合成乾性
油や、液状ポリブタジェン等をベースとした酸化重合型
水性樹脂を使用したものがある。酸化重合型水性樹脂に
はアニオン型およびカチオン型の両方があるが、塗膜の
低温硬化を実現するためには硬化触媒が必要である。こ
の目的に使用される触媒は油性ペイントのドライヤーと
類似の役割を果たす金属化合物が使用される。電着塗料
に使用される金属ドライヤーは、これまで水溶性または
油溶性塩類の形や、酸化物などの金属化合物の形で使用
されていた。しかしながらこれらは樹脂を含む系内に均
一に分散しに＜＜、電着時車膜への移行が困難なため十
分な低温硬化機能を発揮し得ない場合があった。特にア
ニオン電着塗料では、金属イオンは被塗物と反対の極性
の電極へ向かって移動するから、安価に入手し得る酢酸
塩や他の水溶性塩を使用することができない、従って塗
料系内に均一に安定して分散することができ、電着塗膜
中に確実に取り込まれる酸化ｍ金触媒の開発が望まれる
。DETAILED DESCRIPTION OF THE INVENTION Electrodeposition paints are widely used as undercoats with anticorrosive properties because of their workability regardless of shape and their safety. Many types of film-forming resins for electrodeposition paints are known, one of which uses oxidative polymerization type water-based resins based on natural or synthetic drying oils or liquid polybutadiene. There is. There are both anionic and cationic types of oxidation-polymerizable aqueous resins, but a curing catalyst is required to achieve low-temperature curing of the coating film. The catalyst used for this purpose is a metal compound that plays a role similar to that of an oil-based paint dryer. Metal driers used in electrodeposition paints have so far been used in the form of water-soluble or oil-soluble salts, or metal compounds such as oxides. However, these materials cannot be uniformly dispersed in a resin-containing system and are difficult to transfer to a coating film during electrodeposition, so that they may not exhibit sufficient low-temperature curing functionality. Particularly in anionic electrocoating paints, the metal ions migrate toward the electrode of opposite polarity to the material being coated, making it impossible to use inexpensively available acetate or other water-soluble salts, and therefore preventing the use of acetates or other water-soluble salts within the paint system It is desired to develop a gold oxide catalyst that can be uniformly and stably dispersed in the electrodeposited coating and that can be reliably incorporated into the electrodeposited coating.
本発明は、このような問題を解決することを課題とする
。The present invention aims to solve such problems.
五夾左跋
前記課題は、酸化重合型水性樹脂を含む電着塗料に、触
媒機能を有する金属を表面に担持させた微小樹脂粒子を
添加することによって解決される。The above-mentioned problem can be solved by adding microscopic resin particles on the surface of which a metal having a catalytic function is supported to an electrodeposition coating material containing an oxidation-polymerizable aqueous resin.
そこで本発明は、 −
（ａ） 電着可能な酸化重合型水性樹脂の水性分散液
と、
（ｈｌ 該水性分散液中に均一に分散され、かつＭｎ
。Therefore, the present invention provides: - (a) an aqueous dispersion of an oxidation-polymerizable aqueous resin that can be electrodeposited;
.
Ｃｏｔ Ｃｕ、 Ｆｅ、 ｐｂ、 Ｚｎ＋ Ｚｒ、 ｔ
、ｔ、 Ｍｇ＋ ＡＩ＋ Ｂａ、 Ｓｒ＋Ｎｉ、 Ｃａ
ｔ Ｎａ、 ＫおよびＳｎから選ばれた金属の少なくと
も１種を表面に担持す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。Cot Cu, Fe, pb, Zn+ Zr, t
, t, Mg+ AI+ Ba, Sr+Ni, Ca
Provided is an electrodeposition coating composition comprising, as an essential component, fine resin particles carrying at least one metal selected from Na, K, and Sn on the surface.
本発明によれば、触媒を皮膜形成成分の一部である微小
樹脂粒子に担持させることにより、酸化重合型水性樹脂
と触媒とが均一に分散し易くなり、電着時車膜へ確実に
取り込まれるから塗膜の低温硬化が可能となる。しかも
担体である微小樹脂粒子自体皮膜形成成分の一部を構成
するので、触媒の移行や溶出による塗膜性能への悪影響
が避けられる。According to the present invention, by supporting the catalyst on the fine resin particles that are part of the film-forming component, the oxidation-polymerizable water-based resin and the catalyst can be easily dispersed uniformly, and the catalyst can be reliably incorporated into the car film during electrodeposition. This makes it possible to cure the coating film at low temperatures. Furthermore, since the fine resin particles serving as the carrier themselves constitute a part of the film-forming component, adverse effects on coating film performance due to migration or elution of the catalyst can be avoided.
群ｌ巳ｑ１論
本発明は、アニオン型およびカチオン型の酸化重合型水
性樹脂を含む電着塗料に応用可能である。Group Imiq1 Theory The present invention is applicable to electrodeposition paints containing anionic and cationic oxidation polymerizable water-based resins.
電着可能な水性樹脂（ベース樹脂）は、一般に電着に必
要な電荷と親木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。Electrodepositable aqueous resins (base resins) are generally film-forming resins that have functional groups that provide the charge and wood-philicity 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.
アニオン型電着塗料に使用する酸化重合型水性樹脂は、
酸化重合し得る不飽和結合と、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、それらを水、アルコール、アンモニア、１級ま
たは２級アミンで開裂して得られるジカルボン酸、ハー
フェステル、ハーフアミド等である。The oxidative polymerization type water-based resin used in anionic electrodeposition paints is
It has unsaturated bonds that can undergo oxidative polymerization and anionic functional groups such as carboxyl groups to provide the negative charge and hydrophilicity necessary for electrodeposition. Typical such resins are maleated natural or synthetic drying oils, maleated polybutadiene, dicarboxylic acids obtained by cleavage thereof with water, alcohols, ammonia, primary or secondary amines, halfesters, halfamides, etc. be.
カチオン型電着塗料に使用する酸化重合型水性樹脂は、
酸化重合し得る不飽和基と、正の電荷と親水性を与える
ためのアミノ基のようなカチオン性官能基を持っている
。典型的なそのような樹脂は、エポキシ化液状ポリブタ
ジェンと２級アミンを反応させることにより、ポリブタ
ジェンヘアミノ基を導入することによって得られる。こ
のタイプのカチオン電着塗料は、本出願人が共同出願人
の一人である、特開昭６０−９０２７３．同６０−９０
２７４．同６０−２１９２７１．同６〇−２１９２７２
、同６０−２２９９６７、間６０−２２９９６８等に記
載されている。The oxidative polymerization type water-based resin used in cationic electrodeposition paints is
It has an unsaturated group that can undergo oxidative polymerization and a cationic functional group such as an amino group that gives it a positive charge and hydrophilicity. Typical such resins are obtained by introducing amino groups into polybutadiene by reacting epoxidized liquid polybutadiene with a secondary amine. This type of cationic electrodeposition paint is disclosed in Japanese Patent Application Laid-Open No. 60-90273, of which the present applicant is one of the co-applicants. 60-90
274. 60-219271. 60-219272
, No. 60-229967, No. 60-229968, etc.
これら電着塗料は、塗膜性能を向上させる目的で電荷お
よび親水性を与えない樹脂、例えばエポキシアクリレー
ト系樹脂を親水性樹脂とエマルジョンの形で併用するこ
とも行われており、また樹脂自体の自己架橋とあわせて
、ブロックイソシアネート化合物やメラミン樹脂、ポリ
エステル樹脂のような架橋剤を併用するものもある。本
発明においては、このような親水性官能基を持たない樹
脂および硬化剤との併用系をも含めて、酸化重合型水性
樹脂と呼ぶ。 以上述べた酸化重合型水性樹脂は当業者
には良（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。In order to improve the coating performance of these electrodeposition paints, resins that do not impart charge or hydrophilicity, such as epoxy acrylate resins, are used in combination with hydrophilic resins in the form of an emulsion. In addition to self-crosslinking, some use a crosslinking agent such as a blocked isocyanate compound, melamine resin, or polyester resin. In the present invention, a system in which a resin without such a hydrophilic functional group and a curing agent are used in combination is also referred to as an oxidative polymerization type aqueous resin. The oxidation-polymerizable aqueous resins described above are well known to those skilled in the art and do not themselves constitute the present invention, so no further explanation is necessary.
［ｌ
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単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
つくり、溶媒置換、共沸、遠心分離、乾燥などにより水
を除去して微小樹脂粒子を得るものであり、他の方法は
脂肪族炭化水素等の低ＳＰ有機溶媒あるいはエステル。[l Various methods have been proposed to produce fine resin particles, one of which involves suspension polymerization of ethylenically unsaturated monomers and/or crosslinkable comonomers in an aqueous medium. Alternatively, emulsion polymerization is performed to create a dispersion of fine resin particles, and water is removed by solvent substitution, azeotropy, centrifugation, drying, etc. to obtain fine resin particles. SP organic solvent or ester.
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。Ethylenically unsaturated monomers and/or crosslinkable copolymers are copolymerized in non-aqueous organic solvents that dissolve monomers but do not dissolve polymers, such as high SP organic solvents such as ketones and alcohols. This is a method called the NAD method or precipitation method, in which fine resin particle copolymers are dispersed.
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、これと共電合し得
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 coelectrified with methacrylic acid, such as styrene, α-methylstyrene, vinyltoluene, t-butylstyrene, ethylene, propylene, vinyl acetate. , vinyl propionate, acrylonitrile, methacrylaterile, dimethylaminoethyl (meth)acrylate, etc. Two or more types of these monomers may be used.
架橋性共重合単量体は、分子内にＨ［ｌｉ１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。The crosslinkable copolymerizable monomer is a monomer having H[li1 or more radically polymerizable ethylenically unsaturated bonds and/or a group capable of reacting with each other, respectively, in the molecule.
Contains certain ethylenically unsaturated group-containing monomers.
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（１１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 two or more radically polymerizable ethylenically unsaturated groups 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 11 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、１．１．１−１−リスヒド
ロキシメチルエタンジアクリレート、１，１．１−１−
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
、１．１．１− トリスヒドロキシメチルエタントリメ
タクリレート、１．１．１−１−リスヒドロキシメチル
プロパンジアクリレ−１−１１，１，１−）リスヒドロ
キシメチルプロパントリアクリレート、ｉ、ｉ、ｉ −
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− ）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、ジアリルテタレートオヨびジビニルベン
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, 1.1.1-1-lishydroxymethylethane diacrylate, 1,1.1-1-
Lishydroxymethylethane triacrylate, 1.1
．． 1-trishydroxymethylethane dimethacrylate, 1.1.1-trishydroxymethylethane trimethacrylate, 1.1.1-1-lishydroxymethylpropane diacrylate-1-11,1,1-)lishydroxymethyl Propane triacrylate, i, i, i −
Trishydroxymethylpropane dimethacrylate, 1
．． 1.1-) Lishydroxymethylpropane trimethacrylate, triallyl cyanurate, triallyl isocyanurate, triallyl trimellitate, diallyl terephthalate, diallyl tetalate 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力Ｊレボキシ
ル、ヒドロキシルとイソシアナト等積々のものが提案さ
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 combinations have been proposed, such as amine and carbonyl, epoxide and carboxylic anhydride, amine and carboxylic acid chloride, alkyleneimine and carbonyl, organoalkoxysilane and levoxyl, hydroxyl and isocyanate, etc. It broadly encompasses the following.
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、そのままもし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 are isolated by a method such as filtration, spray drying, or freeze drying, and then either left as is or ground to an appropriate particle size using a mill, etc. Furthermore, the synthesized dispersion liquid can be used as it is, or the medium can be replaced 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。０．０１〜０．６μ
の粒子に対しては乳化重合法、ＮＡＤ法が、０．２〜２
０μの粒子に対しては沈澱重合法が適している。Generally speaking, it is desirable to control the particle size of the particles obtained by the polymerization method. 0.01~0.6μ
For particles of 0.2 to 2, the emulsion polymerization method and NAD method
Precipitation polymerization is suitable for particles of 0μ.
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ろ水性樹脂と同
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際し、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 the paint and the electrodeposition bath, the fine resin particles preferably have an ionizable group of the same polarity as the base resin or aqueous resin. That is, in anionic electrodeposition, it is preferable to support an anionic group such as a carboxyl group or sulfonic acid group, and in cationic electrodeposition, it is preferable to support a cationic group such as an amino group or a quaternary ammonium group. To achieve this, a monomer having an ethylenically unsaturated bond and a basic group, such as dimethylaminoethyl (meth)acrylate or vinylpyridine, may be added to the monomer mixture during the synthesis of minute resin particles. Alternatively, there is a method in which a monomer mixture is polymerized using an initiator that provides a cationic end when synthesizing fine resin particles.
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ブ、ポリソーブまたは反応性乳
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
５７−５０５２２等に開示されている。If the polymer itself constituting the micro resin particles is non-polar, an appropriate emulsifier, especially an oligosorb, polysorb or reactive emulsifier having an amphoteric ionic group, is used during the synthesis of the micro resin particles to stably disperse the micro resin particles. You can also do that. These emulsifiers having amphoteric ionic groups are described in Japanese Patent Application Laid-open Nos. 56-24461 and 57-21927. 57-50522, etc.
微小樹脂粒子は、前記した単官能エチレン性不飽和単量
体および架橋性単量体を溶液重合または塊状重合等によ
って重合し、得られた重合体を粉砕した後所定粒度に分
級して得ることもできる。The fine resin particles can be obtained by polymerizing the monofunctional ethylenically unsaturated monomer and crosslinkable monomer described above by solution polymerization or bulk polymerization, crushing the resulting polymer, and then classifying it to a predetermined particle size. You can also do it.
さらに別法として、エポキシ樹脂、メラミン樹脂、アル
キッド樹脂等の微小樹脂粒子の場合、液状の樹脂を水中
に乳化分散し、該乳化樹脂分散液を噴霧乾燥して所定粒
径の微小樹脂を得ることもできるし、樹脂が固体の場合
はそれを粉砕、分級し、所定粒径の微小樹脂とすること
もできる。As another method, in the case of fine resin particles such as epoxy resin, melamine resin, alkyd resin, etc., a liquid resin is emulsified and dispersed in water, and the emulsified resin dispersion is spray-dried to obtain a fine resin having a predetermined particle size. Alternatively, if the resin is solid, it can be pulverized and classified to form a fine resin with a predetermined particle size.
八 の ・。Eight...
酸化重合触媒を微小樹脂粒子の表面に担持させる方法の
一つは、触媒をあらかじめ合成した微小樹脂粒子へ物理
的に吸収または吸着させる方法である。この方法による
担持は、例えば触媒を触媒は溶かすが微小樹脂粒子は熔
かさない溶媒の溶液となし、該溶液で微小樹脂粒子を含
浸するか、または合成した微小樹脂の分散液へ触媒の溶
液を添加した後、先に記載した方法で微小樹脂粒子を単
離することによって達成することができる。One method for supporting an oxidative polymerization catalyst on the surface of fine resin particles is to physically absorb or adsorb the catalyst onto fine resin particles that have been synthesized in advance. Supporting by this method can be carried out, for example, by using a solution of the catalyst in a solvent that dissolves the catalyst but not the fine resin particles, and impregnating the fine resin particles with the solution, or by adding the catalyst solution to a dispersion of synthesized fine resin. After addition, this can be achieved by isolating the microscopic resin particles in the manner described above.
第２の方法としては、微小樹脂粒子の製造原料である単
量体中へ触媒を混合し、該混合物を重合することにより
合成時触媒を樹脂粒子中へ取り込むか、エポシ樹脂、メ
ラミン樹脂、アルキッド樹脂を後乳化し、噴霧乾燥させ
て微小樹脂粒子を製造する場合、乳化前の樹脂へ触媒を
添加し、後乳化、噴霧乾燥して微小樹脂粒子中へ触媒を
取り込む方法である。The second method is to mix a catalyst into monomers, which are the raw materials for manufacturing fine resin particles, and then polymerize the mixture to incorporate the catalyst into the resin particles during synthesis. When producing fine resin particles by post-emulsifying and spray-drying a resin, the method is to add a catalyst to the resin before emulsification, and then incorporate the catalyst into the fine resin particles by post-emulsifying and spray-drying.
第１および第２の方法は単独で酸化重合触媒として使用
されている公知の金属化合物を担持させることができる
。In the first and second methods, a known metal compound used alone as an oxidative polymerization catalyst can be supported.
第３の方法は、酸化重合触媒活性を有する重合性七ツマ
−を微小樹脂粒子を形成する他の単量体と共重合させる
ことである。A third method is to copolymerize a polymerizable heptamer having oxidative polymerization catalytic activity with other monomers to form fine resin particles.
この方法により、金属元素担持微小樹脂粒子は金属元素
含有重合性単量体を微小樹脂粒子合成用の単量体混合物
へ加え、共重合することによって得ることができる。According to this method, metal element-supporting fine resin particles can be obtained by adding a metal element-containing polymerizable monomer to a monomer mixture for synthesizing fine resin particles and copolymerizing the mixture.
金属元素含有重合性単量体としては、アクリル酸、メタ
クリル酸、イタコン酸、マレイン酸などの重合性有機酸
の金属エステル、金属塩やビニル金属、スチリル金属で
あればいずれも使用することができ、金属は水酸基、有
機酸残基、（置換）アルキル基などを持つこともある。As the metal element-containing polymerizable monomer, any metal ester or metal salt of a polymerizable organic acid such as acrylic acid, methacrylic acid, itaconic acid, or maleic acid, vinyl metal, or styryl metal can be used. , metals may have hydroxyl groups, organic acid residues, (substituted) alkyl groups, etc.
例えば、亜鉛では亜鉛モノ （メタ）アクリレート、亜
鉛ジ（メタ）アクリレートなど、錫ではトリブチル錫（
メタ）アクリレート、ジプチル錫ジ（メタ）アクリレー
トなど、アルミニウムとしてはジヒドロキシアルミニウ
ム（メタ）アクリレート、ヒドロキシアルミニウムジ（
メタ）アクリレートなど、ジルコニウムとしては（メタ
）アクリロキジジルコニウムオフテート、（メタ）アク
リロキシジルコニウムラウレートなど、チタニウムとし
てはイソプロピル（メタ）アクリロイルジイソステアロ
イルチタネート、イソプロピルジ（メタ）アクリロイル
イソステアロイルチタネートなど、
鉛としてはジフェニル鉛ジ（メタ）アクリレート、スチ
リルトリエチル鉛などがあり、一般式％式％
（式中門は金属元素、Ｒは（置換）アルキルまたは（置
換）フェニルまたはヒドロキシル、Ｒ゛はＨまたはメチ
ル、ｎは金属元素の原子価、Ｘはｎより小さい整数）な
どとして表される。For example, for zinc, zinc mono(meth)acrylate and zinc di(meth)acrylate, and for tin, tributyltin(
Aluminum includes dihydroxyaluminum (meth)acrylate, hydroxyaluminum di(meth)acrylate, diptyltin di(meth)acrylate, etc.
meth)acrylate, etc. Zirconium includes (meth)acrylokydizirconium oftate, (meth)acryloxyzirconium laurate, etc. Titanium includes isopropyl(meth)acryloyl diisostearoyl titanate, isopropyl di(meth)acryloyl isostearoyl titanate. Examples of lead include diphenyl lead di(meth)acrylate and styryl triethyl lead. H or methyl, n is the valence of the metal element, and X is an integer smaller than n).
また前記の如く金属元素含有重合性単量体を用いないで
ポリマーを形成した後、あと処理で化学反応により金属
元素を導入する方法としては公知の金属導入方法を用い
れば良いが、好ましくは金属化合物と酸とのエステル化
反応あるいはエステル交換反応である。この方法に用い
られる金属化合物としては、塩化マグネシウム、酸化カ
ルシウム、酸化亜鉛、トリブチル錫オキシド、ジブチル
錫オキシド、塩化トリエチル錫、塩化トリベンジル錫、
塩化ジエチルアルミニウム、水酸化アルミニウムなどの
金属酸化物、金属ハロゲン化物、金属水酸化物が好まし
い、これらの化合物は公知の方法によってポリマー中の
カルボキシル基または中和されたカルボキシル基と容易
にエステル化またはエステル交換し、ポリマーに金属元
素を導入できる。またナトリウム、カリウム、カルシウ
ム。Further, as described above, after forming a polymer without using a metal element-containing polymerizable monomer, a known metal introduction method may be used as a method for introducing a metal element through a chemical reaction in a post-treatment. This is an esterification reaction or transesterification reaction between a compound and an acid. Metal compounds used in this method include magnesium chloride, calcium oxide, zinc oxide, tributyltin oxide, dibutyltin oxide, triethyltin chloride, tribenzyltin chloride,
Metal oxides, metal halides, and metal hydroxides such as diethylaluminum chloride and aluminum hydroxide are preferred; these compounds are easily esterified or esterified with carboxyl groups or neutralized carboxyl groups in the polymer by known methods. Metal elements can be introduced into the polymer by transesterification. Also sodium, potassium, and calcium.
マグネシウム、バリウム、ストロンチウムなどのアルカ
リ金属元素やアルカリ土類金属元素は水酸゛化物を加え
るだけでポリマー中のカルボキシル基とイオン結合によ
って導入できる。Alkali metal elements and alkaline earth metal elements such as magnesium, barium, and strontium can be introduced by ionic bonding with carboxyl groups in the polymer simply by adding hydroxide.
１１１料■底惣
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。111 Material ■ Sokoso The electrodeposition coating composition of the present invention contains the electrodepositable aqueous material and the 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、ポリエステル
樹脂、ブロックポリイソシアネート化合物のような補助
硬化剤を含むことができる。Depending on the type of water-based resin used, melamine resin,
Auxiliary curing agents such as benzoguanamine resins, phenolic resins, polyester resins, blocked polyisocyanate compounds can be included.
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性樹脂を中和するた
めに用いられる。These components 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 aqueous 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、プロピルセロソルブ、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, propyl 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％
程度に関節し、乾燥膜厚１５〜３０μに電着し低温１例
えば１００〜１８０℃の温度において熱硬化させること
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 microns and thermally cured at a low temperature, for example, 100 to 180°C.
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
′ハ 、の＋１
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、ビスヒドロキシエチ
ルタウリン１３４部、ネオペンチルグリコール１３０部
、アゼライン酸２３６部、無水フタル酸１８６部および
キシレン２７部を仕込み昇温する。反応により生成する
水をキシレンと共沸還流させ除去する。還流開始より約
２時間かけて温度を１９０℃にし、カルボン酸相当の酸
価が１４５になるまで攪拌と脱水を継続し、１４−０℃
まで冷却する。Production Example 1 'C, +1 In a 21 Kolben equipped with a stirrer, nitrogen inlet tube, temperature control device, condenser, and decanter, 134 parts of bishydroxyethyl taurine, 130 parts of neopentyl glycol, 236 parts of azelaic acid, and phthalic anhydride were added. 186 parts and 27 parts of xylene were charged and the temperature was raised. Water produced by the reaction is removed by azeotropic reflux with xylene. The temperature was raised to 190°C over about 2 hours from the start of reflux, stirring and dehydration were continued until the acid value equivalent to carboxylic acid reached 145, and the temperature was raised to 14-0°C.
Cool until cool.
上と同じ装置を用い、コルベン中に塩イオン水３３０部
を入れ８０℃に昇温した。次いで上で得た両性イオン基
含有ポリエステル樹脂を１６部とジメチルエタノールア
ミン１．６部、脱イオン水１０４部よりなる分散安定剤
の水溶液を作りこれをディスパーで攪拌しながらメタク
リル酸メチル１４部、アクリル酸ｎ−ブチル２８部、メ
タクリル酸アリル１８部、１．６−ヘキサフシオールジ
メタクリレート６０部の混合上ツマー液を徐々に加えて
プレ乳化液を作った。これと別にアゾビスシアノ吉草酸
１．６部とジメチルエタノールアミン１．１部、脱イオ
ン水４０部よりなる水溶液を調整した。Using the same apparatus as above, 330 parts of salt ionized water was placed in a Kolben and the temperature was raised to 80°C. Next, an aqueous solution of a dispersion stabilizer was made of 16 parts of the above-obtained zwitterionic group-containing polyester resin, 1.6 parts of dimethylethanolamine, and 104 parts of deionized water, and while stirring this with a disper, 14 parts of methyl methacrylate, A pre-emulsion was prepared by mixing 28 parts of n-butyl acrylate, 18 parts of allyl methacrylate, and 60 parts of 1,6-hexafthiol dimethacrylate, and gradually adding Zummer's solution. Separately, an aqueous solution consisting of 1.6 parts of azobiscyanovaleric acid, 1.1 parts of dimethylethanolamine, and 40 parts of deionized water was prepared.
このようにしてｍｍした水溶液を５０分間で滴下した。The aqueous solution thus made into mm was added dropwise over 50 minutes.
この水溶液の滴下開始５分後にさきに調製したプレ乳化
液を３５分間かけて滴下した。前者の水溶液の滴下終了
後、同温度にて３０分間熟成した。その後、アゾビスシ
アノ吉草酸１部、ジメチルエタノールアミン０．７部、
脱イオン水３０部よりなる混合水溶液を４５分間かけて
滴下したが、該水溶液の滴下開始５分後、スチレン２８
部、メタクリル酸メチル１６部、メタクリル酸ｎ−ブチ
ル３３部、メタクリル酸３部、ジメチルエタノールアミ
ン３．２部のモノマー混合液を３０分かけて滴下した。Five minutes after the start of dropping this aqueous solution, the previously prepared pre-emulsion was added dropwise over a period of 35 minutes. After dropping the former aqueous solution, the mixture was aged at the same temperature for 30 minutes. Then, 1 part of azobiscyanovaleric acid, 0.7 part of dimethylethanolamine,
A mixed aqueous solution consisting of 30 parts of deionized water was dropped over a period of 45 minutes, but 5 minutes after the start of dropping of the aqueous solution, 28 parts of styrene
A monomer mixture containing 16 parts of methyl methacrylate, 33 parts of n-butyl methacrylate, 3 parts of methacrylic acid, and 3.2 parts of dimethylethanolamine was added dropwise over 30 minutes.
前者の水溶液滴下後、同温度で６０分間熟成して反応を
終了した。After dropping the former aqueous solution, the mixture was aged at the same temperature for 60 minutes to complete the reaction.
これをフリーズドライヤーを用いて水分を除去した後、
得られた粒子粉末６０部を５００成のナスフラスコに入
れ、キシレン１８０部を追加した。After removing the water using a freeze dryer,
60 parts of the obtained powder particles were placed in a 500-size eggplant flask, and 180 parts of xylene was added thereto.
７０℃に保ちながらエバポレーター中で粒子粉末をキシ
レンに分散させた後、ジブチル錫オキシド４．３部を加
えてさらにエバポレーター攪拌を続けた。約２０分後、
脱水がなくなったところで反応を終了した。After dispersing the particles in xylene in an evaporator while maintaining the temperature at 70°C, 4.3 parts of dibutyltin oxide was added and stirring in the evaporator was continued. After about 20 minutes,
The reaction was terminated when dehydration ceased.
このキシレン分散液を減圧下で乾燥した後、粉砕機で粉
砕し、平均１０μの粉体を得た。螢光Ｘ線分析による錫
濃度は粉体中８５００ｐｐｍであった。This xylene dispersion was dried under reduced pressure and then pulverized using a pulverizer to obtain a powder having an average size of 10 μm. The tin concentration in the powder was found to be 8500 ppm by fluorescent X-ray analysis.
製造例２
′ 昌 ｔ の ゛
製造例１において変性ポリエステル樹脂の製造に用いた
装置を用い、エチレングリコールモノメチルエーテル１
００部を仕込み、１００℃に昇温保持する。滴下ロート
を二本用意し、一方に１００部のエチレングリコールモ
ノメチルエーテルを入れその中にＮ−メチル−Ｎ−（ビ
ニルベンジル）タウリンを７５部溶かす。この際、熔解
補助剤として少量のジメチルエタノールアミンを加える
。Production Example 2 ′ Chang's ゛Using the equipment used to produce modified polyester resin in Production Example 1, ethylene glycol monomethyl ether 1
00 parts was charged, and the temperature was raised and maintained at 100°C. Prepare two dropping funnels, put 100 parts of ethylene glycol monomethyl ether into one, and dissolve 75 parts of N-methyl-N-(vinylbenzyl)taurine in the funnel. At this time, a small amount of dimethylethanolamine is added as a melting aid.
さらに一方の滴下ロートに２−ヒドロキシエチルアクリ
レート５０部、アクリル酸１０部、メチルメタクリレー
ト１１０部、スチレン１１０部、ｎ−ブチルアクリレー
ト１４５部およびラウリルメルカプタン１０部を混合し
、アゾビスイソブチロニトリル１０部を溶解する。Furthermore, 50 parts of 2-hydroxyethyl acrylate, 10 parts of acrylic acid, 110 parts of methyl methacrylate, 110 parts of styrene, 145 parts of n-butyl acrylate, and 10 parts of lauryl mercaptan were mixed in one dropping funnel, and 10 parts of azobisisobutyronitrile was added. Dissolve the parts.
二本の滴下ロート内容物を１２０分間で滴下しその後温
度を１００℃に保持して６０分間攪拌を継続する。次い
で、この樹脂溶液の溶媒をロータリーエバポレーターで
除去し、樹脂固型分９６％でＭｎが４５００のアクリル
樹脂を得た。The contents of the two dropping funnels are added dropwise over a period of 120 minutes, after which the temperature is maintained at 100°C and stirring is continued for 60 minutes. Next, the solvent of this resin solution was removed using a rotary evaporator to obtain an acrylic resin with a resin solid content of 96% and Mn of 4500.
製造例１と同じ装置を用い、コルベン中に脱イオン水３
３０部を入れ８０℃に昇温した。次いで上で得た両性イ
オン基含有アクリル樹脂を４０部とジメチルエタノール
アミン４部、脱イオン水１６０部よりなる分散安定剤の
水溶液を作り、これをディスパーで攪拌しながらメタク
リル酸メチル３０部、アクリル酸ｎ−ブチル４０部、マ
レイン酸モツプチルとグリシジルメタクリレート付加物
１４部、エチレングリコールジメタクリレート５６部の
混合モノマー液を徐々に加えてプレ乳化液を作った。こ
れと別にアブビスシアノ吉草酸２部とジメチルエタノー
ルアミン１．３部、脱イオン水４０部よりなる水溶液を
開裂した。Using the same equipment as in Preparation Example 1, add 3 parts of deionized water to the Kolben.
30 parts were added and the temperature was raised to 80°C. Next, an aqueous solution of a dispersion stabilizer was made of 40 parts of the zwitterionic group-containing acrylic resin obtained above, 4 parts of dimethylethanolamine, and 160 parts of deionized water, and while stirring with a disper, 30 parts of methyl methacrylate and acrylic were added. A mixed monomer solution of 40 parts of n-butyl acid, 14 parts of an adduct of motuptil maleate and glycidyl methacrylate, and 56 parts of ethylene glycol dimethacrylate was gradually added to prepare a pre-emulsion. Separately, an aqueous solution consisting of 2 parts of abbiscyanovaleric acid, 1.3 parts of dimethylethanolamine, and 40 parts of deionized water was cleaved.
このようにして調製した水溶液を６５分間で滴下したが
、この水溶液の滴下開始１０分後にプレ乳化液を４５分
間かけて滴下した。アゾビスシアノ吉草酸の滴下終了後
、同温度にて２０分間熟成した。この後、アゾビスシア
ノ吉草酸０．８部、ジメチルエタノールアミン０．６部
、脱イオン水２０部の混合水溶液を４０分間かけて滴下
したがこの水溶液の滴下開始１０分後に、スチレン１８
部、メタクリル酸メチル８部、メタクリル酸ｎ−ブチル
２３部、メタクリル酸２−ヒドロキシエチル１０部、メ
タクリロキシジルコニウムオフテート１部の七ツマー混
合液を、２０分かけて滴下した。The aqueous solution prepared in this way was dropped over a period of 65 minutes, and 10 minutes after the start of dropping of this aqueous solution, the pre-emulsion liquid was dropped over a period of 45 minutes. After completing the dropwise addition of azobiscyanovaleric acid, the mixture was aged at the same temperature for 20 minutes. After this, a mixed aqueous solution of 0.8 parts of azobiscyanovaleric acid, 0.6 parts of dimethylethanolamine, and 20 parts of deionized water was added dropwise over a period of 40 minutes.
A seven-mer mixture of 1 part, 8 parts of methyl methacrylate, 23 parts of n-butyl methacrylate, 10 parts of 2-hydroxyethyl methacrylate, and 1 part of methacryloxyzirconium oftate was added dropwise over 20 minutes.
同温度で９０分間熟成して反応を終了した。粒子径１２
０ｎｍ
製造例３
′ハ １ の１゛
攪拌機、温度制御計、滴下ロート、窒素導入管、冷却用
コンデンサーを備えた１１コルベンに脱イオン水３３０
部を入れ８０℃に昇温した。次いで製造例１で得た両性
イオン基含有ポリエステル樹脂１２部とジメチルエタノ
ールアミン１．２部、脱イオン水１０４部よりなる分散
安定剤の水溶液をつくり、これをディスパーで攪拌しな
がらメタクリル酸メチル６６部、アクリル酸ｎ−ブチル
６０部、メタクリル酸アリル１４部、エチレングリコー
ルジメタクリレート４０部の混合モノマー液を徐々に加
えてプレ乳化液を作った。これと別にアゾビスシアノ吉
草酸２部とジメチルエタノールアミン１．３部、脱イオ
ン水４０部よりなる水溶液を調製した。The reaction was completed by aging at the same temperature for 90 minutes. Particle size 12
0 nm Production Example 3 'C 1-1' 330 liters of deionized water was placed in a 11-kolben equipped with a stirrer, temperature controller, dropping funnel, nitrogen introduction pipe, and cooling condenser.
The temperature was raised to 80°C. Next, an aqueous solution of a dispersion stabilizer was prepared from 12 parts of the amphoteric ionic group-containing polyester resin obtained in Production Example 1, 1.2 parts of dimethylethanolamine, and 104 parts of deionized water, and while stirring this with a disper, 66 parts of methyl methacrylate was added. A pre-emulsion was prepared by gradually adding a mixed monomer solution of 60 parts of n-butyl acrylate, 14 parts of allyl methacrylate, and 40 parts of ethylene glycol dimethacrylate. Separately, an aqueous solution consisting of 2 parts of azobiscyanovaleric acid, 1.3 parts of dimethylethanolamine, and 40 parts of deionized water was prepared.
このようにしてｍｌした水溶液を８０分間で滴下し、プ
レ乳化液は水溶液の滴下開始１０分後から６０分間かけ
て滴下した。同温度にて３０分間放置後、スチレン１２
部、メタクリル酸メチル２部、メタクリル酸ｎ−ブチル
４部、亜鉛モノメタクリレート２部の混合液とアゾビス
シアノ吉草酸０．８部、ジメチルエタノールアミン０．
６部、塩イオン水２０部の混合水溶液を２０分間かけて
滴下した後、１時間熟成して反応を終了した。粒子径５
０ｎｍ
製造例４
′ ハ 製 の ゛
製造例１で用いたジブチル錫オキサイド４．３部の代わ
りに塩化ジエチルアルミニウム４．２部を用いる以外は
全く同じ方法でアルミニウム含有樹脂粉末を得た。螢光
Ｘ線分析装置によるアルミニウム濃度は粉末中、３８０
０ｐｐｍであった。The aqueous solution thus prepared in ml was added dropwise over a period of 80 minutes, and the pre-emulsion was added dropwise over a period of 60 minutes starting 10 minutes after the start of dropping the aqueous solution. After leaving at the same temperature for 30 minutes, Styrene 12
2 parts of methyl methacrylate, 4 parts of n-butyl methacrylate, 2 parts of zinc monomethacrylate, 0.8 part of azobiscyanovaleric acid, and 0.8 parts of dimethylethanolamine.
A mixed aqueous solution of 6 parts of salt ion water and 20 parts of salt ion water was added dropwise over 20 minutes, and then aged for 1 hour to complete the reaction. Particle size 5
0 nm Production Example 4' Made by C. Aluminum-containing resin powder was obtained in exactly the same manner except that 4.2 parts of diethylaluminum chloride was used in place of 4.3 parts of dibutyltin oxide used in Production Example 1. The aluminum concentration in the powder was determined by a fluorescent X-ray analyzer to be 380.
It was 0 ppm.
製造例５
′ ハ １ の ゛
攪拌機、窒素導入管、温度制御装置、コンテンサー、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
が均一な溶解状態に達した後、エピコート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）４
７０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反応を終了する。反応物を乾燥して
、変性エポキシ樹脂５１８部を得る。Production Example 5 ``C 1'' In a 21-kolben equipped with a stirrer, nitrogen inlet tube, temperature control device, condenser, and decanter, 73.5 parts of sodium salt of taurine, 100 parts of ethylene glycol, and 200 parts of ethylene glycol monomethyl ether were added. Prepare and heat while stirring to raise the temperature to 120℃. After the contents reach a uniform state of dissolution, Epicoat 1001.
(Manufactured by Shell Chemical Co., diglycidyl ether type epoxy resin of bisphenol A, epoxy equivalent 470) 4
70 parts and 400 parts of ethylene glycol monomethyl ether
of the solution was added dropwise over a period of 2 hours. After dropping, stirring and heating were continued for 20 hours to complete the reaction. The reaction product is dried to obtain 518 parts of 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、冷却器、温度制御装置を備えた１１の反応容器
に脱イオン水３８０部、上で得た両性イオン基を有する
乳化剤５０部およびジメチルエタノールアミン７部を仕
込み、攪拌下温度を８０℃にしながら溶解し、これにア
ゾビスシアノ吉草酸２．５部を説イオン水５０部とジメ
チルエタノールアミン１．６部に溶解した液およびスチ
レン２００部、エチレングリコールジメタクリレート５
０部およびナフテン酸コバルト（不揮発分２０％、キシ
レン溶液）１２．５部よりなる混合液とを９０分を要し
て滴下し、その後さらに９０分間攪拌を続けた後、不揮
発分４０．８％、ｐＨ９，８の微小樹脂粒子水分散液が
得られた。この微小樹脂粒子水分散液を噴霧乾燥して微
小樹脂粉末を得た。その平均粒子径は３μであった。380 parts of deionized water, 50 parts of the emulsifier having a zwitterionic group obtained above, and 7 parts of dimethylethanolamine were placed in 11 reaction vessels equipped with a stirrer, a cooler, and a temperature control device, and the temperature was brought to 80°C while stirring. A solution prepared by dissolving 2.5 parts of azobiscyanovaleric acid in 50 parts of ionized water and 1.6 parts of dimethylethanolamine, 200 parts of styrene, and 5 parts of ethylene glycol dimethacrylate was added to this solution.
A mixture of 0 parts and 12.5 parts of cobalt naphthenate (20% non-volatile content, xylene solution) was added dropwise over 90 minutes, and stirring was continued for an additional 90 minutes, resulting in a solution with a non-volatile content of 40.8%. , an aqueous dispersion of fine resin particles with a pH of 9.8 was obtained. This fine resin particle aqueous dispersion was spray-dried to obtain a fine resin powder. The average particle size was 3μ.
実施例１
ヱ玉土之１置塗料
その１
日石ボリフ゛タジエンＢ−１５００＊ １） １０
００ｇアンチゲン６Ｃ＊２） １
０ｇ無水マレイン酸 ２５０ｇ
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＊１）日本石油化学■製
： Ｍｎ １５００、ビニル６５％、トランス１４％
、シス１６％
＊２）住人化学＠％：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２１
コルベンに、日石ポリブタジェンＢ−１５００１０００
ｇを仕込み、アンチゲン６Ｃ１０ｇと無水マレイン酸２
５０ｇを添加する。攪拌しながら、内温を１９０〜２０
０℃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。Example 1 Etama Dono 1-piece paint No. 1 Nisseki Bolibutadiene B-1500* 1) 10
00g Antigen 6C*2) 1
0g maleic anhydride 250g
Deionized water 20g Diethylamine 0.5g Propylene glycol 100g Ethyl cellosolve
340g*1) Made by Nippon Petrochemical ■: Mn 1500, vinyl 65%, trans 14%
, cis 16% *2) Resident chemistry @%: N-methyl-N'-(1,3 dimethylbutyl), p-phenylenediamine with cooling tube 21
Nisseki Polybutadiene B-15001000 for Kolben
g, 10 g of Antigen 6C and 2 maleic anhydride.
Add 50g. While stirring, lower the internal temperature to 190-20
The addition reaction of maleic acid to polybutadiene is carried out while maintaining the temperature at 0°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、説イオン水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％。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 ionized 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. 80% non-volatile content.
その２
エポトート ＹＤ−０１４＊ ３）
９５０ ｇエチルセロソルブ ２
４０ｇハイドロキノン １０
ｇ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ｆｆ１９５０
冷却管付２ＥコルベンにエボトートＶＤ−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を均一に溶解スる。そ
の後ハイドロキノン１０ｇを加え、さらにアクリル酸６
５ｇ、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
。不揮発分８゜その１のフェス１２５ｇ、その２のフェ
ス７５ｇ、ブチル化メラミン（不揮発分５０％）４０ｇ
。Part 2 Epotote YD-014* 3)
950 g ethyl cellosolve 2
40g hydroquinone 10
g Acrylic acid 65g Dimethylbenzylamine 5g *3) Manufactured by Tobu Kasei ■, epoxy resin, epoxy ff1950 Evotote VD-014950 in 2E Kolben with cooling tube
Add 240 g of ethyl cellosolve and 240 g of ethyl cellosolve and gradually reduce to 120 g.
Uniformly dissolve YD-014 while stirring until the temperature reaches ℃. Then add 10 g of hydroquinone and add 6 acrylic acid.
Add 5g of dimethylbenzylamine and 5g of dimethylbenzylamine. 120℃
After reacting for 4 hours, it was confirmed that the acid value was 1 or less. Nonvolatile content 8° Part 1 Fes 125g, Part 2 Fes 75g, Butylated melamine (50% nonvolatile content) 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を加え均一に攪
拌した後、トリエチルアミン１３ｇ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熔解
し、製造例２の微小樹脂粒子分散液６０ｇを添加し、固
形分濃度的２０％（塗料中の微小樹脂粒子固形公約２％
）の塗料浴を調製した。40 g of resol type phenolic resin (nonvolatile content 50%) was collected, 2 g of nonionic surfactant was added thereto, and the mixture was stirred uniformly. 13 g of triethylamine was then added, and then 707 g of deionized water was gradually added while stirring uniformly. Melt and add 60g of the fine resin particle dispersion of Production Example 2 to 20% solid content (approximately 2% fine resin particle solids in the paint).
) paint bath 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
塗物を陽極として電着塗装した。その後被塗物表面を水
洗し、焼付炉で１４０℃×３０分間焼付け、膜厚約２０
μ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 was immersed in a paint bath, and electrodeposition was applied using the object to be coated as an anode. After that, the surface of the object to be coated was washed with water and baked in a baking oven at 140℃ for 30 minutes, resulting in a film thickness of approximately 20℃.
A coated plate of μ was obtained. Table 1 shows the results of testing the performance of the obtained coating film.
実施例２
実施例１において製造例２の微小樹脂粒子分散液６０ｇ
を製造例３の微小樹脂粒子分散液６０ｇに代える以外は
全く同様にして実施した。Example 2 60 g of the fine resin particle dispersion of Production Example 2 in Example 1
The same procedure was repeated except that 60 g of the fine resin particle dispersion of Production Example 3 was used instead.
実施例３
面辛り達ニス」一
実施例１そのｌ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溶解し、不揮発分２６％のワニスと
する。次に二酸化チタン１５０ｇ、ケイ酸鉛５０ｇ、ス
トロンチウムクロメート２５ｇ、カーボンブラック２５
ｇ、製造例１の微小樹脂粒子粉末１２５ ｇ、脱イオン
水１００ｇ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１＆製造を終了する。不揮発分５５％呈豊盃±Ｌ土
実施例１そのｌのワニス１２５ｇ、その２のワニス７５
ｇ、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を加え均一に攪拌し
た後、トリエチルアミン１３ｇを加え、次いで脱イオン
水７０７ｇを加える。次に上で得た顔料ペースト１６９
ｇ、脱イオン水２９６ｇ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分約２％）を調整した。Example 3 Take 125 g of varnish from Example 1, add 13 g of triethylamine, and then add 250 g of deionized water.
Gradually add and dissolve uniformly to make a varnish with a non-volatile content of 26%. Next, 150 g of titanium dioxide, 50 g of lead silicate, 25 g of strontium chromate, and 25 g of carbon black.
g, 125 g of the fine resin particle powder of Production Example 1, and 100 g of deionized water were added, and mixed and stirred 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 separated into 1&manufacturing by day. Non-volatile content 55% Shihogaku ± L soil Example 1 125g of varnish, Part 2 varnish 75
g, butylated melamine (50% non-volatile content), 40 g of resol type phenolic resin (50% non-volatile content) were collected, 2 g of nonionic surfactant was added thereto, and after stirring uniformly, 13 g of triethylamine was added, and then desorbed. Add 707g of ionized water. Next, the pigment paste 169 obtained above
g, and 296 g of deionized water were uniformly stirred to prepare an enamel electrodeposition bath (the solid content of fine resin particles in the paint was about 2%).
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.
実施例４
その１
日石ポリブタジェンＢ−２０００（数平均分子量２゜０
００．１．２結合６５％）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。Example 4 Part 1 Nisseki Polybutadiene B-2000 (number average molecular weight 2°0
00.1.2 bonding 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／１００
ｇ、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 is 85.2
mmol/100g, acid value is 10.0 mmol/100
g, and the solid content concentration was 75.0% by weight.
その２
エポキシ当ｆｆ１９５０を持つビスフェノールタイプエ
ボキシ樹脂（商品名エピコート１００４油化シエルエポ
キシ■製）１０００ｇをエチルセロソルブ３４３ｇに溶
解し、アクリル酸７６．３ｇ、ハイドロキノン１０ｇお
よびＮ、Ｎ−ジメチルアミノエタノールを５ｇ添加し、
１００℃に加熱して５時間反応させ、樹脂溶液（Ｂ）を
合成した。Part 2 Dissolve 1000 g of bisphenol type epoxy resin (product name: Epicote 1004 manufactured by Yuka Ciel Epoxy ■) with an epoxy weight of 1950 in 343 g of ethyl cellosolve, and add 76.3 g of acrylic acid, 10 g of hydroquinone, and 5 g of N,N-dimethylaminoethanol. Add,
The mixture was heated to 100°C and reacted for 5 hours to synthesize a resin solution (B).
その３
日石ポリブタジェンＢ−１０００（数平均分子量１゜０
００．１．２−結合６０％）１０００ｇ、無水マレイン
酸２６５．８ｇ、キジ１フ１０
（住人化学商品名）Ｉｇを還流冷却器を設置した２１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。Part 3 Nisseki Polybutadiene B-1000 (number average molecular weight 1°0
00.1.2 - 1000 g of 60% bond), 265.8 g of maleic anhydride, and 10 Kiji 1 Fu 10 (Jumin Chemical product name) Ig were placed in a 21 separable flask equipped with a reflux condenser and heated to 190°C under a nitrogen stream. So 5
Allowed time to react. Next, unreacted maleic anhydride and xylene were distilled off under reduced pressure to synthesize maleated polybutadiene having an acid value of 214 mmol/100 g.
次にマレイン化ポリブタジェン１ ０ ０ ０ ｇ，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拌下に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。Next, 1000 g of maleated polybutadiene and 212.4 g of ethyl cellosolve were added to a 21-liter tube equipped with a reflux condenser.
The mixture was charged into a separable flask and reacted with stirring at 120° C. for 2 hours to produce a half-esterified product (C) of maleated polybutadiene.
、立１ｒ二乙重ｊＪＬ社
その１で製造した（Ａ）４００ｇ、その２で製造した（
Ｂ）２４０ｇおよびその３で製造した（Ｃ）１９．２ｇ
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。, 400g of (A) manufactured by JL Company Part 1, manufactured by Part 2 (
B) 240g and (C) 19.2g produced in Part 3
After mixing until homogeneous, 8.1 g of acetic acid was added and thoroughly stirred to neutralize.
このワニスへ製造例４の微小樹脂粉末３０ｇを添加し、
ディスパーによる攪拌により十分に分散し、次に脱イオ
ン水１９５０ｇを徐々に加え固形分濃度が約２０％（塗
料浴中の微小樹脂粒子固形分約２％）の水溶液をｒｊＩ
ｉ製した。30 g of fine resin powder of Production Example 4 was added to this varnish,
Thoroughly disperse by stirring with a disper, then gradually add 1950g of deionized water to create an aqueous solution with a solid content of about 20% (solid content of minute resin particles in the paint bath is about 2%).
Made by i.
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（日本テストパネル社、Ｂｔ３００４、０
．８Ｘ７０Ｘ１５０ｍｍ）を陰極とし陰極析出型電着塗
装を行い、水洗後１６０℃×３０分で硬化を行い、膜厚
２０μの塗膜を形成した。テスト結果を表−１に示した
。Using the above electrodeposition coating liquid, a carbon electrode was used as an anode, and a zinc phosphate treated plate (Japan Test Panel Co., Ltd., Bt3004, 0
．． 8 x 70 x 150 mm) was used as a cathode, cathodic deposition type electrodeposition coating was performed, and after washing with water, curing was performed at 160° C. for 30 minutes to form a coating film with a thickness of 20 μm. The test results are shown in Table-1.
実施例５
その１
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Ｋ ＯＨを規定液とする通常の方法で測
定し、酸価０．１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％。Example 5 Part 1 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, the mixture was cooled to 60°C, a mixture of 50% lactic acid and deionized water was added, and the mixture was stirred and kept 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 normal solution, and the acid value was 0. After reacting until confirmation of 1 or less, production is terminated. Non-volatile content 55%.
その２
厘↑ヒサ≦と１
製造例５その１のワニス ２３１ｇ脱イオン水
４７６ｇ製造例５の微小樹脂粒子
１９６ｇカーボンブラック １６ｇ
酸化チタン ９２ｇカオリン
２２０ｇ塩基性珪酸鉛
５８ｇその１のワニスに説イオン水を加えて
溶解した後、製造例５の微小樹脂粒子粉末および顔料を
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０別した後製造を終了する。Part 2 厘↑HISA≦ and 1 Varnish of Production Example 5 Part 1 231g deionized water
476g Fine resin particles of Production Example 5
196g carbon black 16g
Titanium oxide 92g kaolin
220g basic lead silicate
After adding and dissolving ionized water to 58 g of the varnish in Part 1, the fine resin particle powder and pigment of Production Example 5 were added, and the mixture was stirred and mixed with a disper 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 sieved to zero, the production is completed.
不揮発分５５％
カチオン１ エ メル
実施例４その１の（Ａ）４００ｇ、その２の（Ｂ）２４
０ｇ、その３の（Ｃ）１９．２ｇ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。Non-volatile content 55% Cation 1 Emel Example 4 Part 1 (A) 400g, Part 2 (B) 24
After mixing 19.2 g of Part 3 (C) until homogeneous, 8.1 g of acetic acid was added and thoroughly stirred to neutralize.
次に上で得た顔料ペースト５１２ｇ、脱イオン水８９６
ｇを加え均一に攪拌し、エナメル電着浴（塗料中の微小
樹脂粒子固形公約２％）を調整した。Next, 512 g of the pigment paste obtained above, 896 g of deionized water
g was added and stirred uniformly 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、実施例４と同じ条件で電着、硬
化させた塗膜の性能を表−１に示す。Table 1 shows the performance of the coating film electrodeposited and cured using this electrodeposition bath under the same conditions as in Example 4.
比較例１
実施例１で製造例２の微小樹脂粒子分散液６０ｇを添加
しない以外は実施例１と同じ。Comparative Example 1 Same as Example 1 except that 60 g of the fine resin particle dispersion liquid of Production Example 2 was not added.
比較例２
実施例３で製造例１の微小樹脂粒子１２５ｇ、脱イオン
水１００ｇを添加せずに顔料ペーストを作成し、エナメ
ルへの顔料ペースト添加量１６９ｇを１２５ｇに、脱イ
オン水２９６ｇを２２０ｇに変更する以外は実施例３と
同じ。Comparative Example 2 In Example 3, a pigment paste was created without adding 125 g of the fine resin particles of Production Example 1 and 100 g of deionized water, and the amount of pigment paste added to the enamel was changed from 169 g to 125 g, and from 296 g of deionized water to 220 g. Same as Example 3 except for the changes.
比較例３
実施例４で製造例４の微小樹脂粒子３０ｇを添加せず脱
イオン水１９５０ｇを１７７０ｇに変更する以外は実施
例４と同じ。Comparative Example 3 Same as Example 4 except that 30 g of fine resin particles of Production Example 4 were not added and 1950 g of deionized water was changed to 1770 g.
比較例４
実施例５で製造例５の微小樹脂粒子１９６ｇを添加せず
脱イオン水４７６ｇを３８３ｇに変更した顔料ペースト
を作成し、エナメルへの顔料ペースト添加量５１２ｇを
３６０ｇに、脱イオン水８９６ｇを６３０ｇに変更する
以外は実施例５と同じ。Comparative Example 4 In Example 5, a pigment paste was created in which 196 g of the fine resin particles of Production Example 5 were not added and 476 g of deionized water was changed to 383 g, and the amount of pigment paste added to the enamel was changed from 512 g to 360 g, and 896 g of deionized water was added. Same as Example 5 except that the weight was changed to 630g.
（以下余白）(Margin below)
Claims (7)
液と、 （ｂ）該水性分散液中に均一に分散され、かつＭｎ、Ｃ
ｏ、Ｃｕ、Ｆｅ、Ｐｂ、Ｚｎ、Ｚｒ、Ｌｉ、Ｍｇ、Ａｌ
、Ｂａ、Ｓｒ、Ｎｉ、Ｃａ、Ｎａ、ＫおよびＳｎから選
ばれた金属の少なくとも１種を表面に担持する微小樹脂
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 oxidation-polymerizable aqueous resin that can be electrodeposited; (b) an aqueous dispersion of Mn, C and
o, Cu, Fe, Pb, Zn, Zr, Li, Mg, Al
, Ba, Sr, Ni, Ca, Na, K, and Sn, as an essential component.
電着塗料組成物。(2) The electrodeposition coating composition according to item 1, wherein the fine resin particles are internally crosslinked.
１項または第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 fine resin particles have a particle size of 0.01 to 20 μm.
である第１項、第２項または第３項記載の電着塗料組成
物。(4) The electrodeposition coating composition according to item 1, 2, or 3, wherein the aqueous dispersion of the oxidatively polymerizable aqueous resin is an emulsion.
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 oxidatively polymerizable aqueous resin has an anion group.
１項ないし第４項のいずれかに記載の電着塗料組成物。(6) The electrodeposition coating composition according to any one of items 1 to 4, wherein the oxidatively polymerizable aqueous resin has a cationic group.
固形分の１〜５０重量％である第１項ないし第６項のい
ずれかに記載の電着塗料組成物。(7) The electrodeposition coating composition according to any one of items 1 to 6, wherein the amount of the fine resin particles is 1 to 50% by weight of the solid content of the oxidation-polymerizable aqueous resin.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61246771A JPH089699B2 (en) | 1986-10-16 | 1986-10-16 | Electrodeposition coating composition |
| AU79718/87A AU595938B2 (en) | 1986-10-16 | 1987-10-13 | Electrodeposition coating composition |
| EP87115100A EP0264834B1 (en) | 1986-10-16 | 1987-10-15 | Electrodeposition coating composition |
| DE8787115100T DE3767645D1 (en) | 1986-10-16 | 1987-10-15 | ELECTRO-DEPOSIBLE COATING MIXTURE. |
| KR1019870011510A KR940004197B1 (en) | 1986-10-16 | 1987-10-16 | Electrodeposition coating composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61246771A JPH089699B2 (en) | 1986-10-16 | 1986-10-16 | Electrodeposition coating composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63101466A true JPS63101466A (en) | 1988-05-06 |
| JPH089699B2 JPH089699B2 (en) | 1996-01-31 |
Family
ID=17153421
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61246771A Expired - Lifetime JPH089699B2 (en) | 1986-10-16 | 1986-10-16 | Electrodeposition coating composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH089699B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008001788A (en) * | 2006-06-22 | 2008-01-10 | Kansai Paint Co Ltd | Anionic electrodeposition coating composition |
-
1986
- 1986-10-16 JP JP61246771A patent/JPH089699B2/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008001788A (en) * | 2006-06-22 | 2008-01-10 | Kansai Paint Co Ltd | Anionic electrodeposition coating composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH089699B2 (en) | 1996-01-31 |
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