JPH0339370A - Dull electrodeposition coating composition - Google Patents
Dull electrodeposition coating compositionInfo
- Publication number
- JPH0339370A JPH0339370A JP17483989A JP17483989A JPH0339370A JP H0339370 A JPH0339370 A JP H0339370A JP 17483989 A JP17483989 A JP 17483989A JP 17483989 A JP17483989 A JP 17483989A JP H0339370 A JPH0339370 A JP H0339370A
- Authority
- JP
- Japan
- Prior art keywords
- acid
- ethylenically unsaturated
- parts
- electrodeposition coating
- weight
- 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
- 239000008199 coating composition Substances 0.000 title claims abstract description 12
- 238000000576 coating method Methods 0.000 claims abstract description 34
- 239000011248 coating agent Substances 0.000 claims abstract description 33
- 239000002253 acid Substances 0.000 claims abstract description 29
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 14
- 239000011342 resin composition Substances 0.000 claims abstract description 14
- 229920005989 resin Polymers 0.000 claims abstract description 13
- 239000011347 resin Substances 0.000 claims abstract description 13
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- MBHRHUJRKGNOKX-UHFFFAOYSA-N [(4,6-diamino-1,3,5-triazin-2-yl)amino]methanol Chemical compound NC1=NC(N)=NC(NCO)=N1 MBHRHUJRKGNOKX-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000010992 reflux Methods 0.000 claims abstract description 8
- 150000007514 bases Chemical class 0.000 claims abstract description 3
- 239000000839 emulsion Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000004480 active ingredient Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 abstract description 7
- 150000001408 amides Chemical class 0.000 abstract description 6
- 150000001732 carboxylic acid derivatives Chemical class 0.000 abstract description 6
- 150000002148 esters Chemical class 0.000 abstract description 5
- 125000005907 alkyl ester group Chemical group 0.000 abstract description 3
- 125000002768 hydroxyalkyl group Chemical group 0.000 abstract description 3
- 239000003973 paint Substances 0.000 description 15
- 239000002585 base Substances 0.000 description 10
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 10
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 9
- -1 α -Alkylstyrene Chemical compound 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 7
- 229910052782 aluminium Inorganic materials 0.000 description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 7
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 5
- 235000019441 ethanol Nutrition 0.000 description 5
- 230000002209 hydrophobic effect Effects 0.000 description 5
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 150000001735 carboxylic acids Chemical class 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 150000007522 mineralic acids Chemical class 0.000 description 4
- 150000007524 organic acids Chemical class 0.000 description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000011550 stock solution Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 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
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 2
- UCDCOJNNUVYFKJ-UHFFFAOYSA-N 4-undecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCC1=CC=C(S(O)(=O)=O)C=C1 UCDCOJNNUVYFKJ-UHFFFAOYSA-N 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-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
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 150000003973 alkyl amines Chemical class 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 229960002887 deanol Drugs 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- CJMZLCRLBNZJQR-UHFFFAOYSA-N ethyl 2-amino-4-(4-fluorophenyl)thiophene-3-carboxylate Chemical compound CCOC(=O)C1=C(N)SC=C1C1=CC=C(F)C=C1 CJMZLCRLBNZJQR-UHFFFAOYSA-N 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 235000005985 organic acids Nutrition 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 150000003460 sulfonic acids Chemical class 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- HXKKHQJGJAFBHI-UHFFFAOYSA-N 1-aminopropan-2-ol Chemical compound CC(O)CN HXKKHQJGJAFBHI-UHFFFAOYSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- XHAFIUUYXQFJEW-UHFFFAOYSA-N 1-chloroethenylbenzene Chemical compound ClC(=C)C1=CC=CC=C1 XHAFIUUYXQFJEW-UHFFFAOYSA-N 0.000 description 1
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- JIAGYOWSALSPII-UHFFFAOYSA-N 2,3-dioctylnaphthalene-1-sulfonic acid Chemical compound C1=CC=C2C(S(O)(=O)=O)=C(CCCCCCCC)C(CCCCCCCC)=CC2=C1 JIAGYOWSALSPII-UHFFFAOYSA-N 0.000 description 1
- OLQFXOWPTQTLDP-UHFFFAOYSA-N 2-(2-hydroxyethoxy)ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCO OLQFXOWPTQTLDP-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
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- OZDGMOYKSFPLSE-UHFFFAOYSA-N 2-Methylaziridine Chemical compound CC1CN1 OZDGMOYKSFPLSE-UHFFFAOYSA-N 0.000 description 1
- RSTAYRVGFDRAMI-UHFFFAOYSA-N 2-amino-1-(diethylamino)ethanol Chemical class CCN(CC)C(O)CN RSTAYRVGFDRAMI-UHFFFAOYSA-N 0.000 description 1
- SZTBMYHIYNGYIA-UHFFFAOYSA-N 2-chloroacrylic acid Chemical compound OC(=O)C(Cl)=C SZTBMYHIYNGYIA-UHFFFAOYSA-N 0.000 description 1
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 description 1
- VHSHLMUCYSAUQU-UHFFFAOYSA-N 2-hydroxypropyl methacrylate Chemical compound CC(O)COC(=O)C(C)=C VHSHLMUCYSAUQU-UHFFFAOYSA-N 0.000 description 1
- GWZMWHWAWHPNHN-UHFFFAOYSA-N 2-hydroxypropyl prop-2-enoate Chemical compound CC(O)COC(=O)C=C GWZMWHWAWHPNHN-UHFFFAOYSA-N 0.000 description 1
- JMADMUIDBVATJT-UHFFFAOYSA-N 2-methylprop-2-enamide;propan-2-one Chemical compound CC(C)=O.CC(C)=O.CC(=C)C(N)=O JMADMUIDBVATJT-UHFFFAOYSA-N 0.000 description 1
- OPALPISTWJJCNH-UHFFFAOYSA-N 2-nitrooxyethyl prop-2-enoate Chemical compound C(C=C)(=O)OCCO[N+](=O)[O-] OPALPISTWJJCNH-UHFFFAOYSA-N 0.000 description 1
- HCGFUIQPSOCUHI-UHFFFAOYSA-N 2-propan-2-yloxyethanol Chemical compound CC(C)OCCO HCGFUIQPSOCUHI-UHFFFAOYSA-N 0.000 description 1
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 description 1
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 description 1
- KIARZJWXAPZVQI-UHFFFAOYSA-N 3-nonylbenzenesulfonic acid Chemical compound CCCCCCCCCC1=CC=CC(S(O)(=O)=O)=C1 KIARZJWXAPZVQI-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- UASQKKHYUPBQJR-UHFFFAOYSA-N 4-decylbenzenesulfonic acid Chemical compound CCCCCCCCCCC1=CC=C(S(O)(=O)=O)C=C1 UASQKKHYUPBQJR-UHFFFAOYSA-N 0.000 description 1
- YKXAYLPDMSGWEV-UHFFFAOYSA-N 4-hydroxybutyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCCO YKXAYLPDMSGWEV-UHFFFAOYSA-N 0.000 description 1
- JTHZUSWLNCPZLX-UHFFFAOYSA-N 6-fluoro-3-methyl-2h-indazole Chemical compound FC1=CC=C2C(C)=NNC2=C1 JTHZUSWLNCPZLX-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical compound C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Natural products C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- SLINHMUFWFWBMU-UHFFFAOYSA-N Triisopropanolamine Chemical compound CC(O)CN(CC(C)O)CC(C)O SLINHMUFWFWBMU-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 1
- 229940018557 citraconic acid Drugs 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- LVTYICIALWPMFW-UHFFFAOYSA-N diisopropanolamine Chemical compound CC(O)CNCC(C)O LVTYICIALWPMFW-UHFFFAOYSA-N 0.000 description 1
- 229940043279 diisopropylamine Drugs 0.000 description 1
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 description 1
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 description 1
- CCIVGXIOQKPBKL-UHFFFAOYSA-M ethanesulfonate Chemical compound CCS([O-])(=O)=O CCIVGXIOQKPBKL-UHFFFAOYSA-M 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- MDNFYIAABKQDML-UHFFFAOYSA-N heptyl 2-methylprop-2-enoate Chemical compound CCCCCCCOC(=O)C(C)=C MDNFYIAABKQDML-UHFFFAOYSA-N 0.000 description 1
- SCFQUKBBGYTJNC-UHFFFAOYSA-N heptyl prop-2-enoate Chemical compound CCCCCCCOC(=O)C=C SCFQUKBBGYTJNC-UHFFFAOYSA-N 0.000 description 1
- LNMQRPPRQDGUDR-UHFFFAOYSA-N hexyl prop-2-enoate Chemical compound CCCCCCOC(=O)C=C LNMQRPPRQDGUDR-UHFFFAOYSA-N 0.000 description 1
- 238000007602 hot air drying Methods 0.000 description 1
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 description 1
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000006224 matting agent Substances 0.000 description 1
- HNEGQIOMVPPMNR-NSCUHMNNSA-N mesaconic acid Chemical compound OC(=O)C(/C)=C/C(O)=O HNEGQIOMVPPMNR-NSCUHMNNSA-N 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 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
- HNEGQIOMVPPMNR-UHFFFAOYSA-N methylfumaric acid Natural products OC(=O)C(C)=CC(O)=O HNEGQIOMVPPMNR-UHFFFAOYSA-N 0.000 description 1
- OMNKZBIFPJNNIO-UHFFFAOYSA-N n-(2-methyl-4-oxopentan-2-yl)prop-2-enamide Chemical compound CC(=O)CC(C)(C)NC(=O)C=C OMNKZBIFPJNNIO-UHFFFAOYSA-N 0.000 description 1
- DNTMQTKDNSEIFO-UHFFFAOYSA-N n-(hydroxymethyl)-2-methylprop-2-enamide Chemical compound CC(=C)C(=O)NCO DNTMQTKDNSEIFO-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- HMZGPNHSPWNGEP-UHFFFAOYSA-N octadecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C(C)=C HMZGPNHSPWNGEP-UHFFFAOYSA-N 0.000 description 1
- 229940065472 octyl acrylate Drugs 0.000 description 1
- ANISOHQJBAQUQP-UHFFFAOYSA-N octyl prop-2-enoate Chemical compound CCCCCCCCOC(=O)C=C ANISOHQJBAQUQP-UHFFFAOYSA-N 0.000 description 1
- 235000006408 oxalic acid Nutrition 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
- 230000000704 physical effect Effects 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- BOQSSGDQNWEFSX-UHFFFAOYSA-N propan-2-yl 2-methylprop-2-enoate Chemical compound CC(C)OC(=O)C(C)=C BOQSSGDQNWEFSX-UHFFFAOYSA-N 0.000 description 1
- LYBIZMNPXTXVMV-UHFFFAOYSA-N propan-2-yl prop-2-enoate Chemical compound CC(C)OC(=O)C=C LYBIZMNPXTXVMV-UHFFFAOYSA-N 0.000 description 1
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 1
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- RKBCYCFRFCNLTO-UHFFFAOYSA-N triisopropylamine Chemical compound CC(C)N(C(C)C)C(C)C RKBCYCFRFCNLTO-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Paints Or Removers (AREA)
Abstract
Description
【発明の詳細な説明】
（発明の技術分野）
本発明は艶消電着塗料組成物に関し、−回の電着塗装で
厚膜でかつ外観に優れる艶消電着塗膜ができる塗料組成
物に関する。DETAILED DESCRIPTION OF THE INVENTION (Technical Field of the Invention) The present invention relates to a matte electrodeposition coating composition, which enables a matte electrodeposition coating film with a thick film and an excellent appearance to be produced in -times of electrodeposition coating. Regarding.
（従来技術）
近年、電着塗装においては艶消外観を形成しうる艶消型
＠塗装が広〈実施されるようになっている。この方法は
、系外から艶消剤を添加することなく、電着塗料組成物
を特殊な条件で反応させて得られる特定の塗料組成物を
使用するものである。(Prior Art) In recent years, matte type @ coating that can form a matte appearance has become widely practiced in electrodeposition coating. This method uses a specific coating composition obtained by reacting an electrodeposition coating composition under special conditions without adding a matting agent from outside the system.
（特開昭５８−８４８６９号公報参照）しかしながら、
この塗料組成物を電着塗装に用いた場合、低光沢の美麗
な艶消電着塗膜外観が形成されるが、厚膜の塗膜が形成
出来ないという欠点があった。(Refer to Japanese Patent Application Laid-open No. 58-84869) However,
When this coating composition is used for electrodeposition coating, a beautiful matte electrodeposition coating with low gloss is formed, but it has the disadvantage that a thick coating cannot be formed.
〈発明の目的〉
本発明は、前記特定の電着塗料組成物が有する欠点を解
消することを目的とし、−回の電着塗装で厚膜の表面外
観に優れる艶消型＠塗膜を形成しうる艶消電着塗料組成
物を提供するものである。<Purpose of the Invention> The present invention aims to eliminate the drawbacks of the above-mentioned specific electrodeposition coating composition, and forms a matte type @ coating film with an excellent thick film surface appearance in - times of electrodeposition coating. The object of the present invention is to provide a matte electrodeposition coating composition that can be coated.
（発明の構成〉
本発明者等の研究によると、本発明が対象とする特定の
艶消型＠塗料に、ポリビニルアルコールを特定量配合す
ることにより、厚膜でかつ美麗な外観を有する艶消電着
塗膜が形成できるという知見を得て、本発明を完成した
のである。(Structure of the Invention) According to research by the present inventors, it has been found that by blending a specific amount of polyvinyl alcohol into a specific matte type @ paint targeted by the present invention, a matte coating with a thick film and beautiful appearance can be obtained. The present invention was completed based on the knowledge that an electrodeposited coating film could be formed.
本発明の艶消電着塗料組成物について解説すると（ａ）
α、β−エチレン性不飽和ポリカルボン酸樹脂及び（ｂ
）アルコキシル化メチロールメラミンを塗膜形成成分と
し、この（ａ）成分及び（ｂ）成分を混合し塩基性化合
物で中和し、これを水に分散してなるエマルジョンを４
０℃〜環流温度で加熱して得られる生成物を有効成分と
して含有する樹脂組成物に、（ｃ）ポリビニルアルコー
ルを樹脂組成物の不揮発成分１００重量部に対し１．５
〜４．５重量部の割合で配合してなるものである。To explain the matte electrodeposition coating composition of the present invention (a)
α, β-ethylenically unsaturated polycarboxylic acid resin and (b
) Alkoxylated methylolmelamine is used as a coating film-forming component, components (a) and (b) are mixed, neutralized with a basic compound, and dispersed in water to form an emulsion.
A resin composition containing a product obtained by heating at 0°C to reflux temperature as an active ingredient is added with (c) polyvinyl alcohol at 1.5 parts by weight per 100 parts by weight of non-volatile components of the resin composition.
-4.5 parts by weight.
本発明をより詳細に説明すると、本発明で使用する（ａ
）成分のα、β−エチレン性不飽和ポリカルボン酸樹脂
は、（イ〉α、β−エチレン性不飽和カルボン酸３〜３
０重量％、（口〉α、β−エチレン性不飽和カルボン酸
のヒドロキシアルキル含有エステル又はアミド若しくは
アミド誘導体５〜３０重量％、（ハ）α、β−エチレン
性不飽和カルボン酸のアルチルエステル
％、（二〉その他の共重性単量体Ｏ〜２ＯＩ量％よりな
り、総量が１００重量％となるように配合した単量体組
成を反応させて得られるものであって、酸価１０〜２０
０のものが好ましい。To explain the present invention in more detail, (a) used in the present invention
The α,β-ethylenically unsaturated polycarboxylic acid resin of component ) is composed of (a) α,β-ethylenic unsaturated carboxylic acid 3 to
0% by weight, (g) 5 to 30% by weight of hydroxyalkyl-containing ester or amide or amide derivative of α,β-ethylenically unsaturated carboxylic acid, (c) % of alkyl ester of α,β-ethylenically unsaturated carboxylic acid , (2) It is obtained by reacting a monomer composition consisting of O to 2 OI amount% of other copolymerizable monomers and blended so that the total amount is 100% by weight, and has an acid value of 10 to 20% by weight. 20
0 is preferred.
適当な（イ）α、β−エチレン性不飽和カルボン酸とし
ては、アクリル酸、α−クロロアクリル酸、メタクリル
酸、イタコン酸、無水マレイン酸、フマル酸、クロトン
酸、シトラコン酸、メサコン酸等の単独又は混合物、あ
るいは少なくとも１個のカルボキシル基を有するそれら
の官能性誘導体、例えば不飽和のジー又はポリ−カルボ
ン酸の部分的エステル又はアミドである。Suitable (a) α, β-ethylenically unsaturated carboxylic acids include acrylic acid, α-chloroacrylic acid, methacrylic acid, itaconic acid, maleic anhydride, fumaric acid, crotonic acid, citraconic acid, mesaconic acid, etc. Alone or in mixtures, or their functional derivatives having at least one carboxyl group, such as partial esters or amides of unsaturated di- or poly-carboxylic acids.
次に（口〉α、β−エチレン性不飽和カルボン酸のヒド
ロキシアルキル含有エステル又はアミド若しくはアミド
誘導体としては、２−ｔｌニトロキシエチルアクリレー
ト、２−ヒドロキシエチルメタクリレート、２−ヒドロ
キシプロピルアクリレート、２−ヒドロキシプロピルメ
タクリレート、３−ヒドロキシプロピルアクリレート、
３−ヒドロキシプロピルメタクリレート、４−ヒドロキ
シブチルメタクリレート、ジエチレングリコールモノ７
クリレート、ジエチレングリコールモノメタクリレート
、アクリルアミド、メタクリルアミド、メチロールアク
リルアミド、メチロールメタクリルアミド、アルコキシ
メチロールアクリルアミド、アルコキシメチロールメタ
クリルアミド、ジアセトンアクリルアミド、ジアセトン
メタクリルアミド等がある。（ハ）α、β−エチレン性
不飽和カルボン酸のアルキルエステルの例としては、メ
チルアクリレート、メチルメタクリレート、エチルアク
リレート、エチルメタクリレート、ｎ−プロピルアクリ
レート、ｎ−プロピルメタクリレート、イソプロピルア
クリレート、イソプロピルメタクリレート、ブチルアク
リレート、ブチルメタクリレート、ラウリルアクリレー
ト、ラウリルメタクリレート、ステアリルアクリレート
、ステアリルメタクリレート、ヘキシルアクリレート、
２−エチルへキシルメタクリレート、ヘプチルアクリレ
ート、ヘプチルメタクリレート等があり、アルキル基内
に炭素原子約２０までを有する同様なエステルが使用で
きる。Next, examples of hydroxyalkyl-containing esters or amides or amide derivatives of α,β-ethylenically unsaturated carboxylic acids include 2-tl nitroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2- Hydroxypropyl methacrylate, 3-hydroxypropyl acrylate,
3-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, diethylene glycol mono 7
Examples include acrylate, diethylene glycol monomethacrylate, acrylamide, methacrylamide, methylol acrylamide, methylol methacrylamide, alkoxymethylol acrylamide, alkoxymethylol methacrylamide, diacetone acrylamide, diacetone methacrylamide, and the like. (c) Examples of alkyl esters of α,β-ethylenically unsaturated carboxylic acids include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, butyl Acrylate, butyl methacrylate, lauryl acrylate, lauryl methacrylate, stearyl acrylate, stearyl methacrylate, hexyl acrylate,
Similar esters having up to about 20 carbon atoms in the alkyl group can be used, such as 2-ethylhexyl methacrylate, heptyl acrylate, heptyl methacrylate, and the like.
（二）その他の共重合性単量体としては、スチレン、α
−アルキルスチレン、α−クロロスチレン、ビニルトル
エン、アクリロニトリル、酢酸ビニル等がある。(2) Other copolymerizable monomers include styrene, α
-Alkylstyrene, α-chlorostyrene, vinyltoluene, acrylonitrile, vinyl acetate, etc.
一方（ｂ）成分として使用するアルコキシル化メチロー
ルメラミンは、メチロール基の少なくとも一部を低級ア
ルコールでアルコキシル化したものであればよい。低級
アルコールとしてはメチルアルコール、エチルアルコー
ル、プロピルアルコール、イソプロピルアルコール、ブ
チルアルコール等の一種又は二種以上を使用する。On the other hand, the alkoxylated methylol melamine used as component (b) may be one in which at least a portion of the methylol group is alkoxylated with a lower alcohol. As the lower alcohol, one or more of methyl alcohol, ethyl alcohol, propyl alcohol, isopropyl alcohol, butyl alcohol, etc. is used.
本発明における前記α、β−不飽和ポリカルボン酸樹脂
とアルコキシル化メチロールメラミンとの組成割合は、
α、β−エチレン性不飽和ポリカルボン酸樹脂５〜９５
重量部、アルコキシル化メチロールメラミン５〜９５重
量部の範囲で使用できる。The composition ratio of the α,β-unsaturated polycarboxylic acid resin and alkoxylated methylolmelamine in the present invention is as follows:
α, β-ethylenically unsaturated polycarboxylic acid resin 5-95
It can be used in a range of 5 to 95 parts by weight of the alkoxylated methylolmelamine.
本発明では前記（ａ）成分と（ｂ）成分を混合して得ら
れる生成分を有効成分として含有する樹脂組成物にポリ
ビニルアルコールを添加配合することによって艶消電着
塗膜の増膜をはかるものである。ポリビニルアルコール
は、ポリ酢酸ビニルをアルカリ、酸、アンモニア水など
でケン化する事により得られるが、多少の酢酸基を残存
する部分ケン化型であってもよい。In the present invention, the thickness of the matte electrodeposition coating film is increased by adding polyvinyl alcohol to a resin composition containing as an active ingredient the product obtained by mixing the components (a) and (b). It is something. Polyvinyl alcohol can be obtained by saponifying polyvinyl acetate with an alkali, acid, aqueous ammonia, etc., but it may be of a partially saponified type in which some acetic acid groups remain.
これらのポリビニルアルコールは、前記艶消電着塗料樹
脂組成物の不揮発成分１００重量部に対し、１．５〜４
．５重量部の範囲の割合で添加配合する。配合量が１．
５重量部未満の場合は、艶消電着塗膜の増膜効果が認め
られず、一方４．５重量部よりも多くなると、異常電着
による外観不良が生じる為好ましくない。These polyvinyl alcohols are used in an amount of 1.5 to 4 parts by weight based on 100 parts by weight of the nonvolatile components of the matte electrodeposition coating resin composition.
．． It is added and blended in a proportion within the range of 5 parts by weight. The blending amount is 1.
If the amount is less than 5 parts by weight, no effect of increasing the thickness of the matte electrodeposited coating film will be observed, while if it is more than 4.5 parts by weight, poor appearance will occur due to abnormal electrodeposition, which is not preferable.
本発明の艶消Ｎ＠塗料組成物は、例えば次のような方法
で製造することができる。The matte N@ coating composition of the present invention can be produced, for example, by the following method.
撹拌装置、温度計及び環流冷却器を備えた反応容器に、
（ａ）α、β−エチレン性不飽和ポリカルボン酸樹脂、
（ｂ）アルコキシル化メチロールメラミンを有機溶剤の
存在下で混合する。この混合時、又は混合後に撹拌を続
けながら親水性塩基を添加し、更に水を加えエマルジョ
ン化を行う。In a reaction vessel equipped with a stirrer, a thermometer and a reflux condenser,
(a) α, β-ethylenically unsaturated polycarboxylic acid resin,
(b) Mixing the alkoxylated methylol melamine in the presence of an organic solvent. During or after this mixing, a hydrophilic base is added while stirring, and water is further added to form an emulsion.
次いで４０℃〜環流温環流界温し、更に撹拌を続けて反
応を終了する。この加熱温度が低いほど反応時間又は常
温放置時間が長くなる。ポリビニルアルコールは、反応
終了後の水系エマルジョンに添加するか、又は該水系エ
マルジョンを希釈した後に添加し、十分撹拌を行い混合
する。Next, the mixture is heated to 40° C. to reflux temperature, and stirring is continued to complete the reaction. The lower the heating temperature, the longer the reaction time or room temperature standing time. Polyvinyl alcohol is added to the aqueous emulsion after completion of the reaction, or added after diluting the aqueous emulsion, and thoroughly stirred and mixed.
有機溶剤としては、例えばメタノール、エタノール、ｎ
−プロピルアルコール、イソプロピルアルコール、ｎ−
ブタノール、イソブタノール、５ｅｃ−ブタノール、ｔ
−ブタノール、ペンタノールなどのようなアルコール類
、メチルセロソルブ、エチルセロソルブ、イソプロピル
セロソルブ、ブチルセロソルブ、５ｅＣ−ブチルセロソ
ルブなどのようなセロソルブを使用する。Examples of organic solvents include methanol, ethanol, n
-propyl alcohol, isopropyl alcohol, n-
Butanol, isobutanol, 5ec-butanol, t
- Using alcohols such as butanol, pentanol, etc., cellosolves such as methyl cellosolve, ethyl cellosolve, isopropyl cellosolve, butyl cellosolve, 5eC-butyl cellosolve, etc.
親水性塩基としては、アンモニア、モノメチルアミン、
ジメチルアミン、トリメチルアミン、モノエチルアミン
、ジエチルアミン、トリエチルアミン、モノイソプロピ
ルアミン、ジイソプロピルアミン、トリイソプロピルア
ミン、モノブチルアミン、ジブチルアミン、トリブチル
アミン等のようなアルキルアミン類、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（２−ヒドロキシプロピル〉アミン、ジ（２−ヒドロ
キシプロピル）アミン、トリ（２−ヒドロキシプロピル
）アミン、ジメチルアミノエタノール、ジエチルアミノ
エタノール
アミン類、エチレンジアミン、プロピレンジアミン、ジ
エチレントリアミン、トリエチレンテトラミン等のアル
キレンポリアミン類、エチレンイミン、プロピレンイミ
ン等のアルキレンイミン類、ピペラジン、モルホリン、
ピラジン、ピリジンの他、水酸化ナトリウム、水酸化カ
リウム、水酸化リチウム等の金属水酸化物が挙げられる
。親水性塩基は、α、β−エチレン性不飽和ポリカルボ
ン酸樹脂のカルボキシル基に対し、モル比が０． １〜
０．８となるように添加すればよい。Hydrophilic bases include ammonia, monomethylamine,
Alkylamines such as dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, triisopropylamine, monobutylamine, dibutylamine, tributylamine etc., monoethanolamine, jetanolamine, triethanolamine , mono(2-hydroxypropyl)amine, di(2-hydroxypropyl)amine, tri(2-hydroxypropyl)amine, dimethylaminoethanol, diethylaminoethanolamines, ethylenediamine, propylenediamine, diethylenetriamine, triethylenetetramine, and other alkylenes. Polyamines, alkylene imines such as ethyleneimine and propylene imine, piperazine, morpholine,
Examples include pyrazine, pyridine, and metal hydroxides such as sodium hydroxide, potassium hydroxide, and lithium hydroxide. The molar ratio of the hydrophilic base to the carboxyl group of the α,β-ethylenically unsaturated polycarboxylic acid resin is 0. 1~
What is necessary is just to add so that it may become 0.8.
本発明の艶消電着塗料の樹脂組成物においては、酸を配
合すると、反応時間の短縮及び塗膜焼付時間の短縮がな
され好ましい結果が得られる。これは、酸がα、β−エ
チレン性不飽和ポリカルボン酸樹脂とアルコキシル化メ
チロールメラミンとの反応生成物の生成反応を促進し、
また塗膜の加熱焼付時に架橋触媒として働くためである
と推定される。In the resin composition of the matte electrodeposition paint of the present invention, when an acid is blended, the reaction time and the coating film baking time are shortened, and favorable results can be obtained. This is because the acid promotes the reaction of α, β-ethylenically unsaturated polycarboxylic acid resin and alkoxylated methylol melamine to form a reaction product,
It is also presumed that this is because it acts as a crosslinking catalyst during heating and baking of the coating film.
本発明で、樹脂組成物に配合可能な酸としては、有機酸
及び無機酸がある。有機酸としては、ギ酸、酢酸、シュ
ウ酸、スルホン酸化合物などがあり、一方無機酸として
は、硫酸、塩酸、硝酸、リン酸などが挙げられる。本発
明では有機酸又は無機酸の少なくとも一種以上、あるい
は有機酸と無機酸との混合いずれも使用できる。本発明
では、スルホン酸化合物の使用が特に優れた効果を発揮
するため好ましい。スルホン酸化合物としては、脂肪族
スルホン酸あるいは芳香族スルホン酸がある。In the present invention, acids that can be blended into the resin composition include organic acids and inorganic acids. Examples of organic acids include formic acid, acetic acid, oxalic acid, and sulfonic acid compounds, while examples of inorganic acids include sulfuric acid, hydrochloric acid, nitric acid, and phosphoric acid. In the present invention, at least one type of organic acid or inorganic acid, or a mixture of an organic acid and an inorganic acid can be used. In the present invention, it is preferable to use a sulfonic acid compound because it exhibits particularly excellent effects. Sulfonic acid compounds include aliphatic sulfonic acids and aromatic sulfonic acids.
脂肪族スルホン酸としては、メタンスルホン酸、エタン
スルホン酸等のフルカンスルホン酸、芳香族スルホン酸
としては、ｍ−ノニルベンゼンスルホン酸、ｐ−デシル
ベンゼンスルホン酸、ｐ−ウンデシルベンゼンスルホン
酸、ｐ−ドデシルベンゼンスルホン酸、ｐ−トルエンス
ルホン酸等のアルキルベンゼンスルホン酸、ジノニルナ
フタレンスルホン酸、ジノニルナフタレンジスルホン酸
、ジアキルナフタレンスルホン酸、ジアルキルナフタレ
ンスルホン酸、ジオクチルナフタレンジスルホン酸、ジ
デシルナフタレンジスルホン酸等のジアルキルナフタレ
ンスルホン酸又はジスルホン酸等を使用する。Examples of aliphatic sulfonic acids include flucansulfonic acids such as methanesulfonic acid and ethanesulfonic acid; examples of aromatic sulfonic acids include m-nonylbenzenesulfonic acid, p-decylbenzenesulfonic acid, p-undecylbenzenesulfonic acid, and p-undecylbenzenesulfonic acid. -Alkylbenzenesulfonic acids such as dodecylbenzenesulfonic acid and p-toluenesulfonic acid, dinonylnaphthalenesulfonic acid, dinonylnaphthalenesulfonic acid, diakylnaphthalenesulfonic acid, dialkylnaphthalenesulfonic acid, dioctylnaphthalenesulfonic acid, didecylnaphthalenesulfonic acid A dialkylnaphthalene sulfonic acid or a disulfonic acid such as the like is used.
酸の配合は任意になされ、その添加は塗膜形成成分の混
合時又は混合後、例えば親水性塩基の添加前に行えばよ
い。又、酸を添加するにあたり、疎水性塩基と同時にあ
るいは別々に添加してもよく、場合により、該塩基との
反応生成物を含む塩含有物を配合してもよく、これらの
場合は、酸単独添加と同じ効果が得られる。The acid may be added as desired, and may be added during or after mixing the coating film-forming components, for example, before adding the hydrophilic base. In addition, when adding an acid, it may be added simultaneously or separately with a hydrophobic base, and in some cases, a salt-containing substance containing a reaction product with the base may be added. The same effect as adding it alone can be obtained.
本発明において、酸の中和に疎水性塩基を使用する理由
は、酸は通常塩基により中和され水溶化するが、疎水性
塩基を用いると中和されても疎水化しており、このよう
な疎水化した中和物は、塗膜形成成分の樹脂中に包含さ
れる形となるため、塗料をイオン交換処理しても除去さ
れず、したがって連続稼働によっても塗料中の酸の量の
変動を小さく保持するためである。In the present invention, the reason why a hydrophobic base is used to neutralize an acid is that an acid is normally neutralized by a base and becomes water-soluble, but when a hydrophobic base is used, it becomes hydrophobic even after being neutralized. Since the hydrophobized neutralized product is included in the resin that forms the paint film, it is not removed even if the paint is ion-exchanged, and therefore, even with continuous operation, fluctuations in the amount of acid in the paint can be prevented. This is to keep it small.
前記の酸又は塩含有物は、樹脂組成物の塗膜形成成分に
対して１０重量％以内、好ましくは、５重量％以内、特
に好ましくは１．０重量％以内の量を添加することが適
当である。これは、得られる艶消塗膜の優れた物理的性
質を保持する為に必要なことである。It is appropriate that the acid or salt-containing substance is added in an amount of 10% by weight or less, preferably 5% by weight or less, particularly preferably 1.0% by weight or less based on the coating film forming components of the resin composition. It is. This is necessary in order to maintain the excellent physical properties of the resulting matte coating.
前記の疎水性塩基としては、水難溶性又は水不溶性のも
のが特に好ましい。その例としては、長鎖アルキルアミ
ン又はアラルキル基含有アミン等がある。As the hydrophobic base, those that are sparingly soluble or insoluble in water are particularly preferred. Examples include long chain alkyl amines or amines containing aralkyl groups.
本発明の艶消塗装用樹脂組成物は、樹脂固形分濃度が３
〜５０重量％の範囲で使用でき、各種塗装手段より適当
な濃度に水で希釈して使用すればよい。その際常用の着
色剤、その他塗料用添加剤を混合して使用することもで
きる。The resin composition for matte coating of the present invention has a resin solid content concentration of 3
It can be used in a range of up to 50% by weight, and may be used by diluting it with water to an appropriate concentration using various coating methods. At that time, commonly used colorants and other paint additives may be mixed and used.
また、本発明の艶消塗装用樹脂組成物は、光沢に優れる
塗膜を形成する塗料組成物と混合して塗膜の光沢を任意
に調製する事もできる。Furthermore, the resin composition for matte coating of the present invention can be mixed with a coating composition that forms a coating film with excellent gloss to adjust the gloss of the coating film as desired.
このように調製した艶消電着塗料で被塗物を塗装すると
被塗物の材質、形状、大きざにかかわらず均一かつ厚膜
の美麗な艶消塗膜が形成できる。When an object is coated with the matte electrodeposition paint prepared in this manner, a uniform, thick, and beautiful matte coating can be formed regardless of the material, shape, and size of the object.
（発明の実施例）
以下、本発明をより具体的に説明するため実施例を示す
。(Examples of the Invention) Examples are shown below to more specifically explain the present invention.
（艶消電着塗料原液の調整）
撹拌装置、温度計及び環流冷却器を備えた容器にアクリ
ル酸 １０部、２−とドロキシエチルメタクリレート
１５部、スチレン １５部、オクチルアクリレート １
５部、ブチルアクリレート１０部、メチルメタクリレー
ト ３５部、アゾビスイソブチロニトリル １．５部、
エチレングリコールモノブチルエーテル １２部、イソ
プロピルアルコール ３５部を仕込み、環流下で６時間
撹拌を行いα、β−エチレン性不飽和ポリカルボン酸樹
脂溶液（酸価７８）を調製した。(Preparation of matte electrodeposition paint stock solution) In a container equipped with a stirrer, thermometer and reflux condenser, add 10 parts of acrylic acid, 2- and droxyethyl methacrylate.
15 parts, styrene 15 parts, octyl acrylate 1
5 parts, butyl acrylate 10 parts, methyl methacrylate 35 parts, azobisisobutyronitrile 1.5 parts,
12 parts of ethylene glycol monobutyl ether and 35 parts of isopropyl alcohol were charged and stirred for 6 hours under reflux to prepare an α,β-ethylenically unsaturated polycarboxylic acid resin solution (acid value 78).
別に用意した撹拌装置、温度計及び環流冷却器を備えた
反応容器に前記のα、β−エチレン性不飽和ポリカルボ
ン酸樹脂溶液 １００部、メトキシブトキシ混合メチロ
ールメラミン（商品名 ＭＸ−４０三相ケミカル社製＞
３０部を仕込み撹拌を行ない混合した。次いで、撹拌を
続けながらトリエチルアミン ４．２部を添加した後、
更に脱イオン水を１５０部加え、エマルジョン化した。In a reaction vessel equipped with a separately prepared stirrer, thermometer, and reflux condenser, 100 parts of the above α,β-ethylenically unsaturated polycarboxylic acid resin solution, methoxybutoxy mixed methylolmelamine (trade name MX-40 three-phase chemical) Made by company＞
30 parts were charged and mixed by stirring. Then, after adding 4.2 parts of triethylamine while continuing to stir,
Furthermore, 150 parts of deionized water was added to form an emulsion.
このエマルジョン化した内容を約９０℃に昇温し１２時
間撹拌を続けて反応を終了し艶消電着塗料原液を調製し
た。The emulsified contents were heated to about 90° C. and stirred for 12 hours to complete the reaction and prepare a matte electrodeposition paint stock solution.
実施例１
艶消電＠塗料原液２７０重量部を脱イオン水７２０１量
部と混合し、更にエチレングリフールモノブチルエーテ
ル １２重量部、ジメチルアミノエタノール １重量部
を添加し、更にポリビニルアルコール（商品名 ゴーセ
ノールにロー１７日本合成化学工業株式会社製）を樹脂
組成分の不揮発成分１００重量部に対し３．５重量部添
加し十分に混合して艶消電着塗料を調製した。Example 1 270 parts by weight of matt electrostatic @ paint stock solution was mixed with 7201 parts by weight of deionized water, 12 parts by weight of ethylene glyfur monobutyl ether and 1 part by weight of dimethylaminoethanol were added, and polyvinyl alcohol (trade name: Gohsenol) was added. 3.5 parts by weight of Rho 17 (manufactured by Nippon Gosei Kagaku Kogyo Co., Ltd.) was added to 100 parts by weight of the nonvolatile components of the resin composition and thoroughly mixed to prepare a matte electrodeposition paint.
実施例２〜７及び比較例１〜３
実施例１の方法においてポリビニルアルコールの添加量
を第１表に示すように変量させる以外は、すべて同じ方
法を実施し、艶消電着塗料をそれぞれ調製した。Examples 2 to 7 and Comparative Examples 1 to 3 Matte electrodeposition paints were prepared by carrying out the same method as in Example 1 except that the amount of polyvinyl alcohol added was varied as shown in Table 1. did.
以下余白
実施例８〜１０
実施例１の方法において、ポリビニルアルコールを次に
示す種類のものを用いる以外はすべて同じ方法を実施し
艶消電着塗料をそれぞれ調製した。Examples 8 to 10 Matte electrodeposition paints were prepared in the same manner as in Example 1, except that the following types of polyvinyl alcohol were used.
第２表
応用例１
実施例１〜１０、比較例１〜３で調製した各塗料中に陽
極酸化処理を施し、更に無機電解着色したアルミニウム
板を陽極に、陰極にステンレス板を結線して浸漬し、両
極間に電圧１８０ボルトを印加し、初期電流密度１．〇
へ／ｄ＋ｎで２分間直流通電を行った。この時の塗料液
温は、すべて２３℃で行った。電着塗装終了後、各アル
ミニウム板を取出し、十分に水洗処理をした後、１８０
℃で３０分間熱風乾燥を行った。Table 2 Application Example 1 Each paint prepared in Examples 1 to 10 and Comparative Examples 1 to 3 was anodized, and an inorganic electrolytically colored aluminum plate was connected to the anode and a stainless steel plate was connected to the cathode and immersed. Then, a voltage of 180 volts was applied between the two electrodes, and an initial current density of 1. DC current was applied to 〇/d+n for 2 minutes. The temperature of the paint liquid at this time was 23°C. After finishing the electrodeposition coating, each aluminum plate was removed and thoroughly washed with water.
Hot air drying was performed at ℃ for 30 minutes.
この結果、各アルミニウム板上に形成された電着塗膜は
、第３表に示すとおりであった。As a result, the electrodeposition coating films formed on each aluminum plate were as shown in Table 3.
以 下 余 白
応用例２
実施例１、比較例１で調製した各塗料中に陽極酸化処理
を施し、更に無機電解着色したアルミニウム板を陽極に
、陰極にステンレス板を結線して浸漬し電圧、通電時間
、液温を第４表の条件にて、通電を行った。電着塗装終
了後、各アルミニウム板を取出し十分に水洗処理をした
後、１８０℃で３０分間熱風乾燥を行った。この結果台
アルミニウム板上に形成された電着塗膜は、第４表に示
すとおりであった。Application Example 2 The paints prepared in Example 1 and Comparative Example 1 were anodized, and an inorganic electrolytically colored aluminum plate was connected to the anode and a stainless steel plate was connected to the cathode. Electricity was applied under the conditions of the electricity application time and liquid temperature shown in Table 4. After the electrodeposition coating was completed, each aluminum plate was taken out, thoroughly washed with water, and then dried with hot air at 180° C. for 30 minutes. As a result, the electrodeposited coating film formed on the base aluminum plate was as shown in Table 4.
以 下 余 白
第
表
比較例１・・・ポリビニルアルコール
添加なし
応用例３
実施例１で調製した塗料中に応用例１の方法にて処理し
たアルミニウム板上に形成された電着塗膜を性能試験実
施した結果は、第５表に示すとおりであった。Table 1 Comparative Example 1 Application example 3 without addition of polyvinyl alcohol An electrodeposition coating film formed on an aluminum plate treated by the method of Application example 1 in the paint prepared in Example 1 was evaluated for performance. The results of the test were as shown in Table 5.
以
下
余
白
第
表
（１）、（２）、〈３〉は接触試験
（発明の効果）
以上、結果より明らかなように本発明の艶消電着塗料組
成物は１回の電着塗装で厚膜でかつ外観に優れる艶消電
着塗膜を形成できるものである。Tables (1), (2), and <3> below are contact tests (effects of the invention). It is possible to form a matte electrodeposition coating film that is thick and has an excellent appearance.
Claims (1)
び（ｂ）アルコキシル化メチロールメラミンを塗膜形成
成分とし、この（ａ）成分及び（ｂ）成分を混合し塩基
性化合物で中和し、これを水に分散してなるエマルジョ
ンを４０℃〜環流温度で加熱して得られる生成分を有効
成分として含有する樹脂組成物に（ｃ）ポリビニルアル
コールを樹脂組成物の不揮発成分１００重量部に対し１
．５〜４．５重量部配合してなる艶消電着塗料組成物。(a) α, β-ethylenically unsaturated polycarboxylic acid resin and (b) alkoxylated methylolmelamine are used as coating film forming components, and the (a) and (b) components are mixed and neutralized with a basic compound. , into a resin composition containing as an active ingredient the product obtained by heating an emulsion obtained by dispersing this in water at 40°C to reflux temperature, and (c) polyvinyl alcohol to 100 parts by weight of the non-volatile components of the resin composition. Against 1
．． A matte electrodeposition coating composition containing 5 to 4.5 parts by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17483989A JPH0339370A (en) | 1989-07-05 | 1989-07-05 | Dull electrodeposition coating composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17483989A JPH0339370A (en) | 1989-07-05 | 1989-07-05 | Dull electrodeposition coating composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0339370A true JPH0339370A (en) | 1991-02-20 |
Family
ID=15985557
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP17483989A Pending JPH0339370A (en) | 1989-07-05 | 1989-07-05 | Dull electrodeposition coating composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0339370A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001181566A (en) * | 1999-12-24 | 2001-07-03 | Kansai Paint Co Ltd | Thermosetting coating composition |
| JP2003504448A (en) * | 1999-06-30 | 2003-02-04 | ビーエーエスエフ コーティングス アクチェンゲゼルシャフト | Electrodeposition coating bath having water-soluble polyvinyl alcohol (co) polymer |
| EP3845612A1 (en) * | 2019-12-30 | 2021-07-07 | Axalta Coating Systems GmbH | Low density electrocoat composition with improved throwing power |
-
1989
- 1989-07-05 JP JP17483989A patent/JPH0339370A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003504448A (en) * | 1999-06-30 | 2003-02-04 | ビーエーエスエフ コーティングス アクチェンゲゼルシャフト | Electrodeposition coating bath having water-soluble polyvinyl alcohol (co) polymer |
| JP2001181566A (en) * | 1999-12-24 | 2001-07-03 | Kansai Paint Co Ltd | Thermosetting coating composition |
| EP3845612A1 (en) * | 2019-12-30 | 2021-07-07 | Axalta Coating Systems GmbH | Low density electrocoat composition with improved throwing power |
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