JPH02269780A - Aqueous dispersion and matte electrodeposition coating composition - Google Patents
Aqueous dispersion and matte electrodeposition coating compositionInfo
- Publication number
- JPH02269780A JPH02269780A JP1091537A JP9153789A JPH02269780A JP H02269780 A JPH02269780 A JP H02269780A JP 1091537 A JP1091537 A JP 1091537A JP 9153789 A JP9153789 A JP 9153789A JP H02269780 A JPH02269780 A JP H02269780A
- Authority
- JP
- Japan
- Prior art keywords
- parts
- aqueous dispersion
- resin
- pref
- electrodeposition coating
- 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.)
- Pending
Links
- 238000004070 electrodeposition Methods 0.000 title claims abstract description 30
- 239000006185 dispersion Substances 0.000 title claims description 19
- 239000008199 coating composition Substances 0.000 title claims description 8
- 229920005989 resin Polymers 0.000 claims abstract description 25
- 239000011347 resin Substances 0.000 claims abstract description 25
- 239000002253 acid Substances 0.000 claims abstract description 20
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 6
- 150000001875 compounds Chemical class 0.000 claims description 21
- 239000006224 matting agent Substances 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 abstract description 25
- 238000000576 coating method Methods 0.000 abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 15
- 239000007787 solid Substances 0.000 abstract description 10
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 9
- 238000003860 storage Methods 0.000 abstract description 5
- 238000013329 compounding Methods 0.000 abstract 1
- OTARVPUIYXHRRB-UHFFFAOYSA-N diethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](C)(OCC)CCCOCC1CO1 OTARVPUIYXHRRB-UHFFFAOYSA-N 0.000 abstract 1
- 239000003973 paint Substances 0.000 description 23
- 239000000178 monomer Substances 0.000 description 15
- -1 silane compound Chemical class 0.000 description 15
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- 230000003472 neutralizing effect Effects 0.000 description 10
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 239000004593 Epoxy Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 125000005372 silanol group Chemical group 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 229920000877 Melamine resin Polymers 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 229920003180 amino resin Polymers 0.000 description 4
- 239000000839 emulsion Substances 0.000 description 4
- 125000003700 epoxy group Chemical group 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 4
- 238000009472 formulation Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- RSWGJHLUYNHPMX-UHFFFAOYSA-N 1,4a-dimethyl-7-propan-2-yl-2,3,4,4b,5,6,10,10a-octahydrophenanthrene-1-carboxylic acid Chemical compound C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N anhydrous diethylene glycol Natural products OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000003431 cross linking reagent Substances 0.000 description 3
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000005056 polyisocyanate Substances 0.000 description 3
- 229920001228 polyisocyanate Polymers 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000002966 varnish Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical group [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 229920006243 acrylic copolymer Polymers 0.000 description 2
- 125000004423 acyloxy group Chemical group 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 239000002537 cosmetic Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 125000005442 diisocyanate group Chemical group 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000011342 resin composition Substances 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 1
- VZXPHDGHQXLXJC-UHFFFAOYSA-N 1,6-diisocyanato-5,6-dimethylheptane Chemical compound O=C=NC(C)(C)C(C)CCCCN=C=O VZXPHDGHQXLXJC-UHFFFAOYSA-N 0.000 description 1
- HXKKHQJGJAFBHI-UHFFFAOYSA-N 1-aminopropan-2-ol Chemical compound CC(O)CN HXKKHQJGJAFBHI-UHFFFAOYSA-N 0.000 description 1
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-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
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 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
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-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
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 229920000298 Cellophane Polymers 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 241000207199 Citrus Species 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical class O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- OPKOKAMJFNKNAS-UHFFFAOYSA-N N-methylethanolamine Chemical compound CNCCO OPKOKAMJFNKNAS-UHFFFAOYSA-N 0.000 description 1
- DKYNGRASYPFOSE-UHFFFAOYSA-N N1=C(N)N=C(N)N=C1N.[F] Chemical compound N1=C(N)N=C(N)N=C1N.[F] DKYNGRASYPFOSE-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- RMKZLFMHXZAGTM-UHFFFAOYSA-N [dimethoxy(propyl)silyl]oxymethyl prop-2-enoate Chemical compound CCC[Si](OC)(OC)OCOC(=O)C=C RMKZLFMHXZAGTM-UHFFFAOYSA-N 0.000 description 1
- 230000005856 abnormality Effects 0.000 description 1
- NJYZCEFQAIUHSD-UHFFFAOYSA-N acetoguanamine Chemical compound CC1=NC(N)=NC(N)=N1 NJYZCEFQAIUHSD-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- LHIJANUOQQMGNT-UHFFFAOYSA-N aminoethylethanolamine Chemical compound NCCNCCO LHIJANUOQQMGNT-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000004104 aryloxy group Chemical group 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 150000007514 bases Chemical class 0.000 description 1
- 125000000051 benzyloxy group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])O* 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000002981 blocking agent Substances 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 235000020971 citrus fruits Nutrition 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper 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
- KQWGXHWJMSMDJJ-UHFFFAOYSA-N cyclohexyl isocyanate Chemical compound O=C=NC1CCCCC1 KQWGXHWJMSMDJJ-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- CPKTUMHHHOVSQC-UHFFFAOYSA-N diethyl-hydroxy-silylsilane Chemical compound CC[Si](O)([SiH3])CC CPKTUMHHHOVSQC-UHFFFAOYSA-N 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 229940043279 diisopropylamine Drugs 0.000 description 1
- JJQZDUKDJDQPMQ-UHFFFAOYSA-N dimethoxy(dimethyl)silane Chemical compound CO[Si](C)(C)OC JJQZDUKDJDQPMQ-UHFFFAOYSA-N 0.000 description 1
- JVUVKQDVTIIMOD-UHFFFAOYSA-N dimethoxy(dipropyl)silane Chemical compound CCC[Si](OC)(OC)CCC JVUVKQDVTIIMOD-UHFFFAOYSA-N 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- WOXXJEVNDJOOLV-UHFFFAOYSA-N ethenyl-tris(2-methoxyethoxy)silane Chemical compound COCCO[Si](OCCOC)(OCCOC)C=C WOXXJEVNDJOOLV-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- SBRXLTRZCJVAPH-UHFFFAOYSA-N ethyl(trimethoxy)silane Chemical group CC[Si](OC)(OC)OC SBRXLTRZCJVAPH-UHFFFAOYSA-N 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- CSTCGHZCMTZWEB-UHFFFAOYSA-N fluoroimino(oxo)methane Chemical compound FN=C=O CSTCGHZCMTZWEB-UHFFFAOYSA-N 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- AYLRODJJLADBOB-QMMMGPOBSA-N methyl (2s)-2,6-diisocyanatohexanoate Chemical compound COC(=O)[C@@H](N=C=O)CCCCN=C=O AYLRODJJLADBOB-QMMMGPOBSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-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
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920000548 poly(silane) polymer Chemical class 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- YOSXAXYCARLZTR-UHFFFAOYSA-N prop-2-enoyl isocyanate Chemical compound C=CC(=O)N=C=O YOSXAXYCARLZTR-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
- ZMYXZXUHYAGGKG-UHFFFAOYSA-N propoxysilane Chemical compound CCCO[SiH3] ZMYXZXUHYAGGKG-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 230000028327 secretion Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- ZQZCOBSUOFHDEE-UHFFFAOYSA-N tetrapropyl silicate Chemical compound CCCO[Si](OCCC)(OCCC)OCCC ZQZCOBSUOFHDEE-UHFFFAOYSA-N 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- DENFJSAFJTVPJR-UHFFFAOYSA-N triethoxy(ethyl)silane Chemical compound CCO[Si](CC)(OCC)OCC DENFJSAFJTVPJR-UHFFFAOYSA-N 0.000 description 1
- SOUMBTQFYKZXPN-UHFFFAOYSA-N trimethoxy(4-phenylbut-3-enyl)silane Chemical compound CO[Si](OC)(OC)CCC=CC1=CC=CC=C1 SOUMBTQFYKZXPN-UHFFFAOYSA-N 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical group CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 1
- VUWVDNLZJXLQPT-UHFFFAOYSA-N tripropoxy(propyl)silane Chemical compound CCCO[Si](CCC)(OCCC)OCCC VUWVDNLZJXLQPT-UHFFFAOYSA-N 0.000 description 1
- 229920006163 vinyl copolymer Polymers 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Resins (AREA)
- Paints Or Removers (AREA)
Abstract
Description
【発明の詳細な説明】
1鼠上凹■月分!
本発明は水性分散液及び艶消し電着塗料組成物に関する
。[Detailed description of the invention] 1 mouse upper concave ■month! The present invention relates to aqueous dispersions and matte electrodeposition coating compositions.
′ の − びその・
従来、艶消し塗料用樹脂組成物として、α、β−エチレ
ン性不飽和カルボン酸樹脂及びエポキシ化合物を含有す
る水系エマルシぢンを加熱して得られる生成物を用いる
ことが、特開昭58−213058号公報に記載されて
いる。' - Biso・ Conventionally, a product obtained by heating an aqueous emulsion containing an α,β-ethylenically unsaturated carboxylic acid resin and an epoxy compound has been used as a resin composition for a matte paint. It is described in Japanese Patent Application Laid-Open No. 58-213058.
該樹脂組成物はカルボン酸樹脂とエポキシ化合物とを水
系エマルション粒子内で反応させ適度に高分子量化させ
ることによって平滑性に優れた艶消し塗膜を形成させる
ものであるが、該反応に際し、スルホン酸化合物等の強
酸性触媒及び水不溶性の中和剤を使用するため、長期ラ
ンニング中にエマルション粒子内で更に高分子量化され
、焼付けで流動性のないエマルション粒子となり塗膜の
平滑性が劣るという欠点があった。This resin composition forms a matte coating film with excellent smoothness by reacting a carboxylic acid resin and an epoxy compound within the water-based emulsion particles and increasing the molecular weight to an appropriate level. Because strong acidic catalysts such as acid compounds and water-insoluble neutralizers are used, the molecular weight of the emulsion particles increases during long-term running, resulting in emulsion particles with no fluidity when baked and resulting in poor coating film smoothness. There were drawbacks.
題占を するための
本発明者等は、上記した問題点を解決するために鋭意研
究を重ねた結果、アクリル系ポリカルボン酸樹脂とエポ
キシシラン化合物との反応物を必須成分として含有する
電着塗料組成物が貯蔵安定性に優れ、しかも美粧性に優
れた艶消し塗膜を形成することを見い出し、本発明を完
成するに至った。As a result of extensive research in order to solve the above-mentioned problems, the inventors of the present invention have developed an electrodeposited material containing a reaction product of an acrylic polycarboxylic acid resin and an epoxysilane compound as an essential component. The present inventors have discovered that the coating composition has excellent storage stability and forms a matte coating film with excellent cosmetic properties, and has completed the present invention.
即ち、本発明はアクリル系ポリカルボン酸樹脂とエポキ
シシラン化合物との反応物を樹脂成分として含有する艶
消し可能な水性分散液、並びに、該水性分散液を艶消し
剤成分として含有する艶消し電着塗料組成物に関する。That is, the present invention provides a matting aqueous dispersion containing a reaction product of an acrylic polycarboxylic acid resin and an epoxysilane compound as a resin component, and a matting electric dispersion containing the aqueous dispersion as a matting agent component. The present invention relates to a coating composition.
本発明で使用するアクリル系ポリカルボン酸樹脂として
は、従来から公知の例えばアニオン型アクリル系電着塗
料用樹脂等を使用することができる。具体的には、例え
ばカルボキシル基含有重合性不飽和単量体及び必要に応
じて水酸基含有重合性不飽和単量体、その他のラジカル
重合性不飽和単量体をラジカル重合反応させて得られる
重合体が好ましい。As the acrylic polycarboxylic acid resin used in the present invention, conventionally known anionic acrylic electrodeposition paint resins and the like can be used. Specifically, for example, a polymer obtained by radical polymerization of a carboxyl group-containing polymerizable unsaturated monomer, optionally a hydroxyl group-containing polymerizable unsaturated monomer, and other radically polymerizable unsaturated monomers. Combination is preferred.
上記のカルボキシル基含有重合性不飽和単量体としては
、例えば(メタ)アクリル酸、(無水)マレイン酸、フ
マル酸、クロトン酸、イタコン酸等を挙げることができ
る。該単量体成分によって重合体中にカルボキシル基が
導入され、該カルボキシル基はエポキシシラン化合物中
のエポキシ基との反応及び重合体の水性化に利用される
。該カルボキシル基含有重合性不飽和単量体の使用量は
、重合体の酸価が約20〜200、好ましくは約′30
〜100の範囲で使用するのがよい。酸価が約20未満
ではエポキシシラン化合物で消費された残りのカルボキ
シル基の含有量が少な(なり水性分散液の安定性が悪く
なる。他方、酸価が約200より大きいと塗膜の耐久性
が劣るため好ましくない。Examples of the carboxyl group-containing polymerizable unsaturated monomer include (meth)acrylic acid, (anhydrous) maleic acid, fumaric acid, crotonic acid, and itaconic acid. A carboxyl group is introduced into the polymer by the monomer component, and the carboxyl group is utilized for reaction with the epoxy group in the epoxysilane compound and for making the polymer water-soluble. The amount of the carboxyl group-containing polymerizable unsaturated monomer used is such that the acid value of the polymer is about 20 to 200, preferably about '30.
It is preferable to use the range of 100 to 100. If the acid value is less than about 20, the content of remaining carboxyl groups consumed by the epoxy silane compound will be small (and the stability of the aqueous dispersion will be poor).On the other hand, if the acid value is greater than about 200, the durability of the coating film will be poor. It is not preferable because it is inferior in quality.
上記の水酸基含有重合性不飽和単量体としては、例えば
(メタ)アクリル酸2−ヒドロキシエチル、(メタ)ア
クリル酸2−ヒト゛′ロキシブロビル等を挙げることが
できる。該単量体成分によって重合体中に水酸基が導入
され、該水酸基はアミノ樹脂及びブロックイソシアネー
ト化合物等の架橋剤と反応させ硬化塗膜を得るために利
用できる。水酸基の含有量は、樹脂水酸基価200以下
、好ましくは20−100の範囲がよい。Examples of the above-mentioned hydroxyl group-containing polymerizable unsaturated monomers include 2-hydroxyethyl (meth)acrylate and 2-hydroxybrobyl (meth)acrylate. A hydroxyl group is introduced into the polymer by the monomer component, and the hydroxyl group can be used to react with a crosslinking agent such as an amino resin and a blocked isocyanate compound to obtain a cured coating film. The content of hydroxyl groups is preferably in the range of 200 to 100, preferably 200 to 100.
上記アミノ樹脂としては、メラミン、尿素、ベンゾグア
ナミン、アセトグアナミンあるいはそれらの混合物のホ
ルムアルデヒド付加物及びそのアルコールエーテル化物
が使用され、アミノ樹脂が水溶性である必要はない。ブ
ロックポリイソシアネートは、ポリイソシアネート化合
物にブロッキング剤(例えばアルコール、フェノールな
ど)を反応させたものであり、イソシアネート化合物と
してはトリレンジイソシアネート、4,4′−ジフェニ
ルメタンジイソシアネート、キシリレンジイソシアネー
ト、メタキシ1ルンジイソシアネート、ヘキサメチレン
ジイソシアネート、リジンジイソシアネート、4.4′
−メチレンビス(シクロヘキシルイソシアネート)、メ
チルシクロヘキサン2.4 (2,6)ジイソシアネー
ト、1.3−(インシアネートメチル)シクロヘキサン
、イソホロンジイソシアネート、トリメチルへキサメチ
レンジイソシアネートなどがあげられる。As the above-mentioned amino resin, formaldehyde adducts of melamine, urea, benzoguanamine, acetoguanamine, or mixtures thereof and alcohol etherified products thereof are used, and the amino resin does not need to be water-soluble. Blocked polyisocyanate is a polyisocyanate compound reacted with a blocking agent (e.g. alcohol, phenol, etc.), and examples of the isocyanate compound include tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate, and metaxyl diisocyanate. , hexamethylene diisocyanate, lysine diisocyanate, 4.4'
-methylenebis(cyclohexyl isocyanate), methylcyclohexane 2.4 (2,6) diisocyanate, 1,3-(incyanatomethyl)cyclohexane, isophorone diisocyanate, trimethylhexamethylene diisocyanate, and the like.
前記したアミノ樹脂及びブロックポリイソシアネートは
それぞれ単独で使用しても、両者を混合して使用しても
よい。その使用量は樹脂固形分換算で50重量%以下で
ある。The above-mentioned amino resin and block polyisocyanate may be used alone or in combination. The amount used is 50% by weight or less in terms of resin solid content.
上記のその他のラジカル重合性不飽和単量体としては5
例えば(メタ)アクリル酸メチル、(メタ)アクリル酸
エチル、(メタ)アクリル酸プロピル、(メタ)アクリ
ル酸ブチル、(メタ)アクリル酸ヘキシル、(メタ)ア
クリル酸オクチル、(メタ)アクリル酸ラウリル等の(
メタ)アクリル酸のアルキルC1〜24エステル;スチ
レン、α−メチルスチレン、ビニルトルエンなどのビニ
ル芳香族単量体;アクリル酸又はメタクリル酸のアミド
化合物;アクリロニトリル、メタクリロニトリルなど通
常アクリル樹脂の合成に用いられる公知の単量体を使用
することができる。これらの単量体は要求される性能に
応じて適宜選択して使用することができる。Other radically polymerizable unsaturated monomers mentioned above include 5
For example, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, hexyl (meth)acrylate, octyl (meth)acrylate, lauryl (meth)acrylate, etc. of(
Alkyl C1-24 esters of meth)acrylic acid; Vinyl aromatic monomers such as styrene, α-methylstyrene, and vinyltoluene; Amide compounds of acrylic acid or methacrylic acid; Usually used in the synthesis of acrylic resins such as acrylonitrile and methacrylonitrile Any known monomer can be used. These monomers can be appropriately selected and used depending on the required performance.
上記したアクリル系ポリカルボン酸樹脂は、約1000
〜i ooooo、好ましくは約2000〜5oooo
の範囲の数平均分子量を有することができる。分子量が
約1000より小さいと十分な艶消し効果が得られず、
他方、分子量が約1oooooより大きいと樹脂が高粘
度化して水分散化時に均一な微粒子を形成しにくくなり
、貯蔵安定性が劣る傾向にあるので好ましくない。The above-mentioned acrylic polycarboxylic acid resin has approximately 1,000
~ioooooo, preferably about 2000-5oooo
can have a number average molecular weight in the range of . If the molecular weight is less than about 1000, a sufficient matting effect cannot be obtained,
On the other hand, if the molecular weight is greater than about 1 ooooo, the resin becomes highly viscous, making it difficult to form uniform fine particles during water dispersion, and storage stability tends to be poor, which is not preferable.
本発明で使用するエポキシシラン化合物は、1分子中に
それぞれ平均1個以上のエポキシ基とヒドロキシシラン
基及び/又は珪素原子に直接結合した加水分解性基とを
有する数平均分子量約130〜9000、好ましくは約
130〜1000範囲を有するものがよい。The epoxysilane compound used in the present invention has a number average molecular weight of about 130 to 9000, each having an average of one or more epoxy groups and a hydroxysilane group and/or a hydrolyzable group directly bonded to a silicon atom in one molecule; Preferably, it has a range of about 130 to 1000.
上記珪素原子に直接結合した加水分解性基は、水又は湿
気によって加水分解しヒドロキシシラン基を生成する残
基であって、例えば水素原子:C1〜Sアルコキシ基;
フェノキシ基、トリルオキシ基、バラメトキシフェノキ
シ基、バラニトロフェノキシ基、ベンジルオキシ基等の
アリールオキシ基;アセトキシ基、プロピオニルオキシ
基、ブタノイルオキシ基、ベンゾイルオキシ基、フェニ
ルアセトキシ基、ホルミルオキシ基等のアシロキシ基;
次式
%式%
(Rは同一もしくは異なってC+”sアルキル基を示す
。)
で表わされる残基等を挙げることができる。中でも好ま
しくは容易に加水分解してポリシロキサン結合を生じる
ことからアルコキシ基、アシロキシ基等が好適である。The hydrolyzable group directly bonded to the silicon atom is a residue that is hydrolyzed by water or moisture to produce a hydroxysilane group, such as a hydrogen atom: a C1-S alkoxy group;
Aryloxy groups such as phenoxy, tolyloxy, varamethoxyphenoxy, varanitrophenoxy, benzyloxy; acetoxy, propionyloxy, butanoyloxy, benzoyloxy, phenylacetoxy, formyloxy, etc. Acyloxy group;
Examples include residues represented by the following formula % formula % (R is the same or different and represents a C+"s alkyl group). Among them, alkoxy and acyloxy groups are suitable.
1分子中に1個以上のエポキシ基とヒドロキシ基及び/
又は珪素原子に直接結合した加水分解性基とを有するエ
ポキシシラン化合物としては、例えば
OCR。One or more epoxy groups and hydroxy groups and/or
Or as an epoxysilane compound having a hydrolyzable group directly bonded to a silicon atom, for example, OCR.
(:、H2−CH−CHz−0−CsHa−5L−OC
Hs\ / 1
0 0CH。(:, H2-CH-CHz-0-CsHa-5L-OC
Hs\ / 1 0 0CH.
CH。CH.
CR3 CH。CR3 CH.
OC,H。O.C., H.
CCHs
CH2−CH−CH,−0−C,、Hs−SL−OCC
I3QC)I。CCHs CH2-CH-CH, -0-C,, Hs-SL-OCC
I3QC)I.
Hs 0CCI。Hs 0CCI.
等のエポキシシラン化合物;該エポキシシラン化合物と
ポリシラン化合物(例えばテトラメトキシシラン、テト
ラプロポキシシラン、メチルトリメトキシシラン、エチ
ルトリエトキシシラン、プロピルトリプロポキシシラン
、ジメチルジメトキシシラン、ジエチルジェトキシシラ
ン、ジプロピルジプロポキシシラン、ジエチルジシラノ
ール、ジフェニルジェトキシシラン等)とを反応させて
得られるエポキシポリシラン化合物:エポキシ基含有重
合性不飽和単量体(例えばグリシジル(メタ)アクリレ
ート、アリルグリシジルエーテル、3.4−エポキシシ
クロヘキシルメチル(メタ)アクリレート等)ヒドロキ
シシラン基および/又は珪素原子に直接結合した加水分
解性基を有する重合性不飽和単量体(例えばビニルトリ
ス(βメトキシエトキシ)シラン、ビニルトリエトキシ
シラン、ビニルトリメトキシシラン、γ−(メタ)アク
リロキシプロピルトリメトキシシラン、2−スチリルエ
チルトリメトキシシラン、γ−(メタ)アクリロキシブ
口ビルトリメトキシシラノール等)を必須単量体成分と
する共重合体等を挙げることができる。これらの中でも
使用量が少な(て美粧性に優れた艶消し塗膜を形成する
エポキシシラン化合物を用いることが好適である。Epoxysilane compounds such as; such epoxysilane compounds and polysilane compounds (e.g. tetramethoxysilane, tetrapropoxysilane, methyltrimethoxysilane, ethyltriethoxysilane, propyltripropoxysilane, dimethyldimethoxysilane, diethyljethoxysilane, dipropyl dimethoxysilane); Epoxypolysilane compounds obtained by reacting propoxysilane, diethyldisilanol, diphenyljethoxysilane, etc. with epoxy group-containing polymerizable unsaturated monomers (e.g. glycidyl (meth)acrylate, allyl glycidyl ether, 3.4- Polymerizable unsaturated monomers having a hydroxysilane group and/or a hydrolyzable group directly bonded to a silicon atom (e.g. vinyltris(β-methoxyethoxy)silane, vinyltriethoxysilane, vinyl Copolymers containing trimethoxysilane, γ-(meth)acryloxypropyltrimethoxysilane, 2-styrylethyltrimethoxysilane, γ-(meth)acryloxib-vinyltrimethoxysilanol, etc. as essential monomer components. can be mentioned. Among these, it is preferable to use an epoxysilane compound which is used in a small amount (and forms a matte coating film with excellent cosmetic properties).
上記したエポキシシラン化合物は1種もしくは2種以上
混合して使用することができる。The above-mentioned epoxysilane compounds can be used alone or in combination of two or more.
上記エポキシシラン化合物の使用量はアクリル系ポリカ
ルボン酸樹脂ioo重量部に対して約0.1〜20重量
部、好ましくは約0.5〜10重量部の範囲である。使
用量が約0.1重量部未満では充分な艶消し塗膜を得る
ことができず、他方、使用量が約20重量部より多いと
水性分散液の安定性が悪くなるので好ましくない。The amount of the epoxy silane compound used is about 0.1 to 20 parts by weight, preferably about 0.5 to 10 parts by weight, based on ioo parts by weight of the acrylic polycarboxylic acid resin. If the amount used is less than about 0.1 parts by weight, a sufficient matte coating film cannot be obtained, while if the amount used is more than about 20 parts by weight, the stability of the aqueous dispersion will deteriorate, which is not preferred.
本発明水性分散液は、例えばアクリル系ポリカルボン酸
樹脂を有機溶剤に溶解した溶液を中和剤で中和後もしく
は中和前に前記架橋剤、前記エポキシシラン化合物を添
加し、中和前に添加した場合には中和後、水中に分散化
したのち、加熱して反応を行なうことにより調整できる
。The aqueous dispersion of the present invention can be prepared, for example, by adding the crosslinking agent and the epoxysilane compound after or before neutralizing a solution of an acrylic polycarboxylic acid resin dissolved in an organic solvent with a neutralizing agent. When added, it can be adjusted by neutralizing, dispersing in water, and then heating to carry out the reaction.
有機溶剤としては、アクリル系ポリカルボン酸樹脂を溶
解もしくは分散が可能で、前記エポキシシラン化合物と
反応に乏しく、かつ親水性の有機溶剤を用いることが好
ましい。具体的には、例えば、メチルアルコール、エチ
ルアルコール、イソプロピルアルコール、ブチルアルコ
ールなどのアルコール類、エチレングリコールモノメチ
ルニー、チル、エチレングリコールモノエチルエーテル
、エチレングリコールモノブチルエーテルなどのセロソ
ルブ系溶剤、プロピレングリコールエーテル類、ジエチ
レングリコールエーテル類などが使用できる。As the organic solvent, it is preferable to use an organic solvent that is capable of dissolving or dispersing the acrylic polycarboxylic acid resin, does not easily react with the epoxysilane compound, and is hydrophilic. Specifically, for example, alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol, and butyl alcohol, cellosolve solvents such as ethylene glycol monomethyl, ethylene glycol monoethyl ether, and ethylene glycol monobutyl ether, and propylene glycol ethers. , diethylene glycol ethers, etc. can be used.
また、中和剤としては、従来から公知の塩基性化合物を
使用することができ、例えばアンモニア、ジメチルアミ
ン、トリメチルアミン、ジエチルアミン、トリエチルア
ミン、ジイソプロピルアミン、ブチルアミン、モノエタ
ノールアミン、ジェタノールアミン、トリエタノールア
ミン、モノイソプロパツールアミン、ジイソプロパツー
ルアミン、トリイソプロパツールアミン、N−メチルエ
タノールアミン、N−アミノエチルエタノールアミン、
N−メチルジェタノールアミン、ポリグツコールアミン
などが挙げられる。これら中和剤はアクリル系ポリカル
ボン酸樹脂のカルボキシル基に対して約0.3〜1.2
当量の範囲で使用できる。Further, as the neutralizing agent, conventionally known basic compounds can be used, such as ammonia, dimethylamine, trimethylamine, diethylamine, triethylamine, diisopropylamine, butylamine, monoethanolamine, jetanolamine, triethanolamine. , monoisopropanolamine, diisopropanazine, triisopropanazine, N-methylethanolamine, N-aminoethylethanolamine,
Examples include N-methyljetanolamine and polygutucolamine. These neutralizing agents have a ratio of about 0.3 to 1.2 to the carboxyl group of the acrylic polycarboxylic acid resin.
It can be used within the equivalent range.
上記水性分散液の固形分は通常、約3〜60重量%、好
ましくは約7〜45重量%°に調整される。The solids content of the aqueous dispersion is usually adjusted to about 3 to 60% by weight, preferably about 7 to 45% by weight.
水性分散液の反応は、上記水性分散液を約り0℃〜還流
温度に昇温し、かくはんを行なって反応を終了する。The reaction of the aqueous dispersion is completed by raising the temperature of the aqueous dispersion to about 0° C. to reflux temperature and stirring.
また、本発明水性分散液は、上記した以外にもアクリル
系ポリカルボン酸樹脂の有機溶剤溶液を中和剤で中和後
もしくは中和剤にエポキシシラン化合物を添加し、反応
を行なった後、更に、中和剤を添加していない場合には
中和剤を添加した後、必要に応じて架橋剤を配合し、こ
のものを水中に分散化することにより調整できる。In addition to the above, the aqueous dispersion of the present invention can be prepared by neutralizing an organic solvent solution of acrylic polycarboxylic acid resin with a neutralizing agent or by adding an epoxysilane compound to the neutralizing agent and performing a reaction. Furthermore, when a neutralizing agent is not added, after the neutralizing agent is added, a crosslinking agent is blended as needed, and this can be adjusted by dispersing this in water.
上記反応は、通常、約り0℃〜還流温度に昇温すること
により行なうことができる。The above reaction can usually be carried out by raising the temperature from about 0°C to reflux temperature.
本発明においてアクリル系ポリカルボン酸樹脂とエポキ
シシラン化合物との反応は樹脂酸価もしくはエポキシ当
量を測定することにより管理することができる。該樹脂
酸価は初期樹脂酸価より約1以上減少すれば十分と思わ
れる。In the present invention, the reaction between the acrylic polycarboxylic acid resin and the epoxysilane compound can be controlled by measuring the resin acid value or epoxy equivalent. It is believed that it is sufficient that the resin acid value is reduced by about 1 or more from the initial resin acid value.
か(して得られる水性分散液は、それ自体電着塗料とし
て使用するか、もしくは該水性分散液を艶消し剤とし艶
有り電着塗料と混合して使用することができる。The aqueous dispersion obtained in this manner can be used as an electrodeposition paint by itself, or it can be used as a matting agent and mixed with a glossy electrodeposition paint.
該艶有り電着塗料としては、従来から公知のアニオン型
電着塗料、例えばアクリル−メラミン系、アクリル−イ
ソシアネート系、フッ素−メラミン系、フッ素−イソシ
アネート系等の電着塗料を使用することができる。As the glossy electrodeposition paint, conventionally known anionic electrodeposition paints, such as acrylic-melamine type, acrylic-isocyanate type, fluorine-melamine type, fluorine-isocyanate type, etc., can be used. .
艷有り電着塗料と水性分散液との混合割合は要求される
光沢に応じて適宜配合することができるが、通常、塗料
樹脂固形分100重量部に対して水性分散液の樹脂固形
分で10重量部以上、好ましくは20重量部以上の範囲
で使用できる。The mixing ratio of the coated electrodeposition paint and the aqueous dispersion can be adjusted as appropriate depending on the required gloss, but usually the resin solid content of the aqueous dispersion is 10 parts by weight based on 100 parts by weight of the resin solid content of the paint. It can be used in an amount of at least 20 parts by weight, preferably at least 20 parts by weight.
本発明艶消し電着塗料組成物には、必要に応じて着色顔
料、体質顔料、塗面調整剤等を含有すイことができる。The matte electrodeposition coating composition of the present invention may contain coloring pigments, extender pigments, coating surface conditioners, etc., if necessary.
本発明艶消し電着塗料組成物は、通常、樹脂C形分約3
〜20重量%、好ましくは約5〜15M舒%の範囲に調
製して電着塗装に供される。The matte electrodeposition coating composition of the present invention usually has a resin type C content of about 3
It is prepared in a range of 20% by weight, preferably about 5% to 15% by weight, and subjected to electrodeposition coating.
本発明艶消し電着塗料組成物を用いて電看塗さする方法
及び装置としては、従来から陽極電着な装において使用
されているそれ自体既知の方法刃び装置を使用すること
ができる。用いつる密着泌装条件は一般的には浴温20
〜30℃、電B100〜400V (好ましくは100
〜30Cv)、通電時間30秒〜lO分で電着すること
力好ましい。塗装乾燥膜厚は、通常、約2〜5Cμ、好
ましくは約5〜30μの範囲で十分と思とれる。As the method and apparatus for coating with the matte electrodeposition coating composition of the present invention, any known method and apparatus conventionally used in anodic electrodeposition can be used. The conditions for close contact secretion used are generally a bath temperature of 20°C.
~30℃, electric B100~400V (preferably 100
~30 Cv) and a current application time of 30 seconds to 10 minutes. A dry coating thickness of approximately 2 to 5 Cμ, preferably approximately 5 to 30 μ, is considered sufficient.
また、電着塗装する被塗物としては、導電性も有する、
素材、例えば鉄、鉄鋼、銅、アルミニウム、鉄鋼表面に
亜鉛、スズ、クロム、アルミニウム等をメツキしたメツ
キw4根、鉄鋼の表面をクロム酸、リン酸等で化学処理
或いは電解処理した金属素材等が挙げられる。中でも好
ましくは陽極酸化処理を施したアルミニウムの種々の形
状(例えば板状、棒状、ホーロー状等)の物品である。In addition, as a coating material to be electrodeposited, it also has electrical conductivity.
Materials, such as iron, steel, copper, aluminum, plating W4 base where the surface of steel is plated with zinc, tin, chromium, aluminum, etc., metal materials whose surface is chemically or electrolytically treated with chromic acid, phosphoric acid, etc. Can be mentioned. Among these, articles of various shapes (for example, plate-like, rod-like, enamel-like, etc.) made of anodic oxidized aluminum are preferred.
被塗物上に形成された電着塗膜は、電着浴中から引上げ
られた後、該電着塗膜上に付着した余分の塗料を、水又
は逆浸透法で透過した水で洗浄を行なって、通常、約1
50〜220’C1好ましくは約160〜200℃で約
10〜60分間、好ましくは約20〜40分間焼付けが
行なわれる。After the electrodeposition coating film formed on the object to be coated is pulled up from the electrodeposition bath, excess paint adhering to the electrodeposition coating film is washed with water or water passed through by reverse osmosis. Usually about 1
Baking is carried out at 50-220' C1, preferably at about 160-200 DEG C. for about 10-60 minutes, preferably for about 20-40 minutes.
(作用及び発明の効果)
本発明において、エポキシシラン化合物はアクリル系ポ
リカルボン酸樹脂と反応し該樹脂中にシラン基が導入さ
れ該シラン基が水分散化の過程で加水分解してヒドロキ
シシラン基を生成し、次にこれらの基同志もしくはこれ
らの基と加水分解性基との縮合反応によって粒子内ゲル
構造となり、しかもその粒子表面は親水性ヒドロキシシ
ラン基が多く存在するので微細で安定な水分散粒子を形
成する。このものを電着塗装して得られる塗膜は親水性
が強いので余分に付着した電着塗料を水等で取り除(水
洗処理適性がよく、水洗あと等による仕上り欠陥のない
艶消し塗膜を得ることができる。また、電着塗膜を焼付
ける際に、粒子表面におけるヒドロキシ基同志の反応に
よりポリシロキサン結合を生成するので耐候性、耐薬品
性等に優れた艶消し塗膜を得ることができる。(Action and Effect of the Invention) In the present invention, an epoxysilane compound reacts with an acrylic polycarboxylic acid resin to introduce a silane group into the resin, and the silane group is hydrolyzed in the process of water dispersion to form a hydroxysilane group. is formed, and then a condensation reaction between these groups or between these groups and a hydrolyzable group results in an intraparticle gel structure, and since there are many hydrophilic hydroxysilane groups on the particle surface, fine and stable water is formed. Forming dispersed particles. The coating film obtained by electrocoating this product is highly hydrophilic, so remove excess electrocoating paint with water, etc. (It is a matte coating film that has good suitability for washing with water and has no finishing defects after washing.) In addition, when baking the electrodeposition coating, polysiloxane bonds are generated by the reaction between hydroxyl groups on the particle surface, resulting in a matte coating with excellent weather resistance, chemical resistance, etc. be able to.
罠施旦
本発明をさらに詳しく説明する。実施例中の「部」及び
「%」は重量基準である。The present invention will now be described in more detail. "Parts" and "%" in the examples are based on weight.
実施例1
反応容器中にイソプロピルアルコール100部を仕込み
80℃に保持した中へ、スチレン18部、メチルメタク
リレート31部、n−ブチルアクリレート19部、エチ
ルアクリレ−810部、ヒドロキシエチルアクリレート
15部、アクリル酸7部及びアゾビスジメチルバレロニ
トリル1.0部の混合物を3時間かけて滴下し反応を行
なった。数平均分子量30000、酸価53、水酸基価
72のアクリル系共重合体ワニスを得た。Example 1 100 parts of isopropyl alcohol was charged into a reaction vessel and maintained at 80°C, and 18 parts of styrene, 31 parts of methyl methacrylate, 19 parts of n-butyl acrylate, 810 parts of ethyl acrylate, 15 parts of hydroxyethyl acrylate, and acrylic acid were added. A mixture of 7 parts of azobisdimethylvaleronitrile and 1.0 parts of azobisdimethylvaleronitrile was added dropwise over 3 hours to carry out a reaction. An acrylic copolymer varnish having a number average molecular weight of 30,000, an acid value of 53, and a hydroxyl value of 72 was obtained.
次に、上記ワニス140部にメチルメチロール化メラミ
ン樹脂(日立化成工業株式会社製、メラン620、固形
分含有量70%)42部及びγ−グリシドキシプロビル
メチルジェトキシシランを5部を加え、均一になるよう
によく混合した。混合物に脱イオン水857部を加え、
固形分の濃度を10%にしたのち、撹拌しながら70’
Cで4時間反応を行なって実施例1の電着塗料を得た。Next, 42 parts of methylmethylolated melamine resin (manufactured by Hitachi Chemical Co., Ltd., Melan 620, solid content 70%) and 5 parts of γ-glycidoxypropyl methyljethoxysilane were added to 140 parts of the above varnish. , mixed well to make it homogeneous. Add 857 parts of deionized water to the mixture;
After adjusting the solid content to 10%, it was heated for 70' while stirring.
The reaction was carried out at C for 4 hours to obtain the electrodeposition paint of Example 1.
実施例2
実施例1で用いたγ−グリシドキシプロビルメチルジェ
トキシシランをγ−グリシドキシプロビルトリメトキシ
シランに置き換えた以外は実施例1と同様の配合及び製
造方法で実施例2の電着塗料を得た。Example 2 Example 2 was carried out using the same formulation and manufacturing method as in Example 1, except that γ-glycidoxypropylmethyljethoxysilane used in Example 1 was replaced with γ-glycidoxypropyltrimethoxysilane. An electrodeposited paint was obtained.
実施例3
実施例1で用いたγ−グリシドキシプロビルメチルジェ
トキシシランをβ−(3,4エポキシシクロヘキシル)
エチルトリメトキシシランに置き換えた以外は実施例1
と同様の配合及び製造方法で実施例3の電着塗料を得た
。Example 3 The γ-glycidoxypropylmethyljethoxysilane used in Example 1 was converted into β-(3,4 epoxycyclohexyl)
Example 1 except that it was replaced with ethyltrimethoxysilane
The electrodeposition paint of Example 3 was obtained using the same formulation and manufacturing method.
実施例4
前記アクリル系共重合体ワニス140部とγ−グリシド
キシプロビルメチルジェトキシシラン5部との混合物を
80℃で4時間反応を行なって反応物を得た。次に該反
応物を室温まで冷却しメラン620を42部加え、均一
になるようによく混合した。更に混合物に脱イオン水8
57部を加え固形分10%の実施例4の電着塗料を得た
。Example 4 A mixture of 140 parts of the acrylic copolymer varnish and 5 parts of γ-glycidoxypropylmethyljethoxysilane was reacted at 80° C. for 4 hours to obtain a reaction product. Next, the reaction mixture was cooled to room temperature, 42 parts of Melan 620 was added, and the mixture was thoroughly mixed to become uniform. Add 8 ounces of deionized water to the mixture.
57 parts were added to obtain the electrodeposition paint of Example 4 having a solid content of 10%.
実施例5
アニオン型艶有り電着塗料(関西ペイント社製、AG−
200,アクリル−メラミン系電@塗料、固形分10%
)700部に実施例1の電着塗料(固形分lO%)30
0部を加え、均一になるようによく混合して実施例5の
電着塗料を得た。Example 5 Anionic glossy electrodeposition paint (manufactured by Kansai Paint Co., Ltd., AG-
200, acrylic-melamine paint, solid content 10%
) 700 parts of the electrodeposition paint of Example 1 (solid content 1O%) 30
0 parts was added thereto and mixed thoroughly to obtain a uniform electrodeposited paint of Example 5.
比較例1
実施例1で用いたγ−グリシドキシプロビルメチルジェ
トキシシランを用いなかった以外は実施例1と同様の配
合及び製造方法で比較例1の電着塗料を得た。Comparative Example 1 An electrodeposition paint of Comparative Example 1 was obtained using the same formulation and manufacturing method as in Example 1, except that the γ-glycidoxypropylmethyljethoxysilane used in Example 1 was not used.
比較例2
実施例1で用いたγ−グリシドキシプロビルメチルジェ
トキシシラン5部をエポキシ樹脂(シェル化学社製、エ
ピコート834)10部に置き換えた以外は実施例1と
同様の配合及び製造方法で比較例2の電蓄塗料を得た。Comparative Example 2 The same formulation and production as in Example 1 except that 5 parts of γ-glycidoxypropyl methyljethoxysilane used in Example 1 was replaced with 10 parts of epoxy resin (Epicoat 834, manufactured by Shell Chemical Co., Ltd.). An electrical storage paint of Comparative Example 2 was obtained by the method.
アルマイト処理を施した6063Sアルミニウム合金板
(アルマイト 膜厚10μ)を被塗装物(陽極)とし、
前記実施例及び比較例の電着塗料浴中で、浴温22℃、
乾燥膜厚約lOμになる様に付加電圧を設定し3分間通
電を行なって、被塗装物上に電析膜を形成させ、次いで
水洗を行なった後、180℃−30分間焼付は試験用の
塗板を得た。An anodized 6063S aluminum alloy plate (anodized film thickness 10μ) is used as the object to be coated (anode),
In the electrodeposition paint baths of the above Examples and Comparative Examples, the bath temperature was 22°C;
The applied voltage was set so that the dry film thickness was about 10μ, and electricity was applied for 3 minutes to form an electrodeposited film on the object to be coated.After washing with water, baking was carried out at 180℃ for 30 minutes. I got a painted plate.
塗料貯蔵安定性:密閉状態で30℃、2ケ月間放置した
のち、電着塗装を行なって試験前の塗膜外観と比較し、
塗膜外観の変化を観察した。Paint storage stability: After being left in a sealed state at 30℃ for 2 months, electrodeposition coating was performed and the appearance of the coating film was compared with that before the test.
Changes in the appearance of the paint film were observed.
塗面平滑性:塗装後の塗膜の外観を肉眼で観察し、ユズ
膚、ピンホール、凹凸、外観の具合を調べた。Painted surface smoothness: The appearance of the painted film after painting was observed with the naked eye to check for citrus skin, pinholes, unevenness, and appearance.
光沢:光沢計(E!′本電色工業株式会社製VG2PD
)を使用し60部鏡面反射率(単位二%)を測定した。Gloss: Gloss meter (E!' VG2PD manufactured by Hondenshoku Kogyo Co., Ltd.
) was used to measure the specular reflectance (unit: 2%) at 60 parts.
ゴバン目付着性:塗膜にカッターナイフで1mm角の折
目100個の切り目を入れ、セロハン粘着テープで10
回剥離試験を行い、残存した折目数を求めた。Goban adhesion: Make 100 1 mm square creases in the coating film with a cutter knife, and cut 100 creases with cellophane adhesive tape.
A peel test was conducted to determine the number of remaining folds.
耐アルカリ性=1重量%の水酸化ナトリウムの水溶液に
72時間浸漬した後の塗膜の外観を肉眼で観察し、ブリ
スター発生の有無を調べた。After being immersed in an aqueous solution of sodium hydroxide having alkali resistance of 1% by weight for 72 hours, the appearance of the coating film was observed with the naked eye to determine the presence or absence of blistering.
(○:異常なし、@:若干ブリスター発生、Δニブリス
ター発生、×:著しくブリスター発生)
耐候性:ウェザ−メーター(スガ試験機株式会社製、デ
ユーサイクル、照射60分/暗黒60分、ブラックパネ
ル温度63℃)で100時間の促進耐候性試験を行い、
光沢保持率(単位二%)及び外観を調べた。(○: No abnormality, @: Slight blistering, Δ niblistering, ×: Significant blistering) Weather resistance: Weather meter (manufactured by Suga Test Instruments Co., Ltd., Ducycle, 60 minutes of irradiation/60 minutes of darkness, black An accelerated weathering test was conducted for 100 hours at a panel temperature of 63°C.
The gloss retention rate (unit: 2%) and appearance were examined.
Claims (2)
化合物との反応物を樹脂成分として含有する艶消し可能
な水性分散液。(1) A mattable aqueous dispersion containing a reaction product of an acrylic polycarboxylic acid resin and an epoxysilane compound as a resin component.
含有する艶消し電着塗料組成物。(2) A matte electrodeposition coating composition containing the aqueous dispersion according to claim 1 as a matting agent component.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP1091537A JPH02269780A (en) | 1989-04-11 | 1989-04-11 | Aqueous dispersion and matte electrodeposition coating composition |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP1091537A JPH02269780A (en) | 1989-04-11 | 1989-04-11 | Aqueous dispersion and matte electrodeposition coating composition |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH02269780A true JPH02269780A (en) | 1990-11-05 |
Family
ID=14029216
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP1091537A Pending JPH02269780A (en) | 1989-04-11 | 1989-04-11 | Aqueous dispersion and matte electrodeposition coating composition |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH02269780A (en) |
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1995031512A1 (en) * | 1994-05-12 | 1995-11-23 | Zeneca Limited | Aqueous coating compositions |
US5476692A (en) * | 1991-05-24 | 1995-12-19 | British Technology Group Ltd | Method of strengthening glass |
EP0687716A1 (en) | 1994-06-16 | 1995-12-20 | Shinto Paint Company, Limited | Microgel-containing anionic water-dispersible resin composition and electrodeposition coating composition containing the same |
EP0743901A4 (en) * | 1994-02-08 | 1998-06-24 | Potters Industries Inc | Durable polymeric deposits on inorganic material substrate |
JP2001139890A (en) * | 1999-11-15 | 2001-05-22 | Fuji Xerox Co Ltd | Electrodeposition liquid, cured electrodeposition film and its production method, and electronic device |
JP2004204215A (en) * | 2002-10-30 | 2004-07-22 | Honny Chem Ind Co Ltd | Anionic flat electrodeposition coating resin composition |
JP2005002217A (en) * | 2003-06-12 | 2005-01-06 | Honny Chem Ind Co Ltd | Resin composition for anionic-type delustering electrodeposition liquid |
JP2006169334A (en) * | 2004-12-15 | 2006-06-29 | Nissan Motor Co Ltd | Flat coating composition and flat coating film |
US20110086980A1 (en) * | 2009-10-09 | 2011-04-14 | Nan Ya Plastics Corporation | Adhesive composition for use in bonding of polarizing plate |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS58138762A (en) * | 1982-02-15 | 1983-08-17 | Dainichi Seika Kogyo Kk | Polishing agent composition for inorganic film |
JPS6414281A (en) * | 1987-07-08 | 1989-01-18 | Kansai Paint Co Ltd | Matte electrodeposition coating composition |
JPS6420203A (en) * | 1987-05-08 | 1989-01-24 | Unilever Nv | Production of copolymer emulsion, copolymer emulsion, tile adhesive and emulsion paint |
-
1989
- 1989-04-11 JP JP1091537A patent/JPH02269780A/en active Pending
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS58138762A (en) * | 1982-02-15 | 1983-08-17 | Dainichi Seika Kogyo Kk | Polishing agent composition for inorganic film |
JPS6420203A (en) * | 1987-05-08 | 1989-01-24 | Unilever Nv | Production of copolymer emulsion, copolymer emulsion, tile adhesive and emulsion paint |
JPS6414281A (en) * | 1987-07-08 | 1989-01-18 | Kansai Paint Co Ltd | Matte electrodeposition coating composition |
Cited By (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5476692A (en) * | 1991-05-24 | 1995-12-19 | British Technology Group Ltd | Method of strengthening glass |
AU665350B2 (en) * | 1991-05-24 | 1996-01-04 | British Technology Group Limited | A method of strengthening glass |
EP0743901A4 (en) * | 1994-02-08 | 1998-06-24 | Potters Industries Inc | Durable polymeric deposits on inorganic material substrate |
WO1995031512A1 (en) * | 1994-05-12 | 1995-11-23 | Zeneca Limited | Aqueous coating compositions |
US5691400A (en) * | 1994-05-12 | 1997-11-25 | Zeneca Limited | Compositions |
EP0687716A1 (en) | 1994-06-16 | 1995-12-20 | Shinto Paint Company, Limited | Microgel-containing anionic water-dispersible resin composition and electrodeposition coating composition containing the same |
JP2001139890A (en) * | 1999-11-15 | 2001-05-22 | Fuji Xerox Co Ltd | Electrodeposition liquid, cured electrodeposition film and its production method, and electronic device |
JP2004204215A (en) * | 2002-10-30 | 2004-07-22 | Honny Chem Ind Co Ltd | Anionic flat electrodeposition coating resin composition |
JP2005002217A (en) * | 2003-06-12 | 2005-01-06 | Honny Chem Ind Co Ltd | Resin composition for anionic-type delustering electrodeposition liquid |
JP2006169334A (en) * | 2004-12-15 | 2006-06-29 | Nissan Motor Co Ltd | Flat coating composition and flat coating film |
JP4674795B2 (en) * | 2004-12-15 | 2011-04-20 | 日産自動車株式会社 | Matte paint composition and matte paint film |
US20110086980A1 (en) * | 2009-10-09 | 2011-04-14 | Nan Ya Plastics Corporation | Adhesive composition for use in bonding of polarizing plate |
US8314186B2 (en) * | 2009-10-09 | 2012-11-20 | Nan Ya Plastics Corporation | Adhesive composition for use in bonding of polarizing plate |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP2625480B2 (en) | Cationic electrodeposition gelled fine particle polymer and cationic electrodeposition coating composition containing the same | |
WO1997020004A1 (en) | Curable resin composition for water-based paints | |
JP2777190B2 (en) | Composite coating | |
JPH02269780A (en) | Aqueous dispersion and matte electrodeposition coating composition | |
US5242972A (en) | Fluorine based aqueous dispersion, process for preparing the same, and fluorine based matte anionic electrodeposition coating composition containing the same | |
JP3593772B2 (en) | Crosslinked polymer dispersion | |
JPS5967396A (en) | Dull finish coating method by electrodeposition | |
JP3443455B2 (en) | Microgel-containing anionic water-dispersible resin composition and electrodeposition coating composition containing the same | |
JP4743683B2 (en) | Water-based paint and coated article formed by coating the water-based paint | |
JP3272969B2 (en) | Electrodeposition coating composition having electrodeposition potential and electrodeposition coating method | |
JP2749132B2 (en) | Anionic matte electrodeposition coating composition | |
KR20000035474A (en) | Adhesion promoters for paint films | |
JPS5934743B2 (en) | Matte coating method for aluminum and aluminum alloys | |
WO1995033795A1 (en) | Flat electrodeposition coating composition and flat electrodeposition coating method | |
JPH0328278A (en) | Cationic electrodeposition coating composition for transparent finish | |
JP3378665B2 (en) | Low temperature curing matte anion electrodeposition coating composition and coating film forming method | |
JP3468583B2 (en) | Anionic water-dispersed resin composition and method for producing the same | |
JPH02255871A (en) | Water-based matte coating composition | |
JPH05171100A (en) | Coating composition, its production, and formation of coating film | |
JPH10183031A (en) | Electrodeposition coating composition and coating film made by using the same | |
JP3378652B2 (en) | Low temperature curable matte electrodeposition coating composition and method for forming coating film | |
JPH06116519A (en) | Coating of surface of metallic building material | |
JPH0347853A (en) | Fluorinated aqueous dispersion, production of fluorinated aqueous dispersion and fluorinated electrodeposition coating composition of anionic matte type | |
JP4737791B2 (en) | Matte electrodeposition paint and its electrodeposition coating method | |
JPH0466172A (en) | Method for forming film excellent in edge coating properties |