CA2461067C - Coating film-forming method - Google Patents
Coating film-forming method Download PDFInfo
- Publication number
- CA2461067C CA2461067C CA002461067A CA2461067A CA2461067C CA 2461067 C CA2461067 C CA 2461067C CA 002461067 A CA002461067 A CA 002461067A CA 2461067 A CA2461067 A CA 2461067A CA 2461067 C CA2461067 C CA 2461067C
- Authority
- CA
- Canada
- Prior art keywords
- compound
- electrodeposition coating
- coating film
- epoxy resin
- coating composition
- 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.)
- Expired - Lifetime
Links
- 239000011248 coating agent Substances 0.000 title claims abstract description 117
- 238000000576 coating method Methods 0.000 title claims abstract description 117
- 238000000034 method Methods 0.000 title claims abstract description 33
- 238000004070 electrodeposition Methods 0.000 claims abstract description 99
- -1 cyclic ester compound Chemical class 0.000 claims abstract description 66
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 54
- 239000008199 coating composition Substances 0.000 claims abstract description 49
- 125000002091 cationic group Chemical group 0.000 claims abstract description 48
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 48
- 239000003822 epoxy resin Substances 0.000 claims abstract description 46
- 150000001875 compounds Chemical class 0.000 claims abstract description 43
- 238000001723 curing Methods 0.000 claims abstract description 37
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 37
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 37
- 229920005989 resin Polymers 0.000 claims abstract description 30
- 239000011347 resin Substances 0.000 claims abstract description 30
- 150000003077 polyols Chemical class 0.000 claims abstract description 28
- 239000004593 Epoxy Substances 0.000 claims abstract description 19
- 229920005862 polyol Polymers 0.000 claims abstract description 19
- 239000002981 blocking agent Substances 0.000 claims abstract description 13
- 125000003277 amino group Chemical group 0.000 claims abstract description 11
- 238000013007 heat curing Methods 0.000 claims abstract description 10
- 235000013824 polyphenols Nutrition 0.000 claims abstract description 10
- 239000000758 substrate Substances 0.000 claims abstract description 10
- 125000002723 alicyclic group Chemical group 0.000 claims abstract description 6
- 125000003118 aryl group Chemical group 0.000 claims abstract description 5
- 230000009477 glass transition Effects 0.000 claims description 25
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims description 7
- 150000001622 bismuth compounds Chemical class 0.000 claims description 2
- 239000003518 caustics Substances 0.000 claims description 2
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 claims 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 abstract description 12
- 238000002360 preparation method Methods 0.000 description 29
- 239000007787 solid Substances 0.000 description 27
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 17
- 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 14
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 14
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 14
- 239000000203 mixture Substances 0.000 description 13
- 238000012360 testing method Methods 0.000 description 11
- 238000010521 absorption reaction Methods 0.000 description 10
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 9
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 9
- 239000000839 emulsion Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 150000001412 amines Chemical class 0.000 description 6
- 125000003700 epoxy group Chemical group 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 230000003595 spectral effect Effects 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 238000007865 diluting Methods 0.000 description 5
- 238000009472 formulation Methods 0.000 description 5
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 5
- 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 5
- 150000004658 ketimines Chemical class 0.000 description 5
- 150000007524 organic acids Chemical class 0.000 description 5
- 238000005070 sampling Methods 0.000 description 5
- KUBDPQJOLOUJRM-UHFFFAOYSA-N 2-(chloromethyl)oxirane;4-[2-(4-hydroxyphenyl)propan-2-yl]phenol Chemical compound ClCC1CO1.C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 KUBDPQJOLOUJRM-UHFFFAOYSA-N 0.000 description 4
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 4
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 4
- 239000005058 Isophorone diisocyanate Substances 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 4
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 4
- 239000010960 cold rolled steel Substances 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 229910001873 dinitrogen Inorganic materials 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 239000000049 pigment Substances 0.000 description 4
- 239000001294 propane Substances 0.000 description 4
- 239000010959 steel Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-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
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- WHIVNJATOVLWBW-UHFFFAOYSA-N n-butan-2-ylidenehydroxylamine Chemical compound CCC(C)=NO WHIVNJATOVLWBW-UHFFFAOYSA-N 0.000 description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- LFSYUSUFCBOHGU-UHFFFAOYSA-N 1-isocyanato-2-[(4-isocyanatophenyl)methyl]benzene Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=CC=C1N=C=O LFSYUSUFCBOHGU-UHFFFAOYSA-N 0.000 description 2
- JVYDLYGCSIHCMR-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)butanoic acid Chemical compound CCC(CO)(CO)C(O)=O JVYDLYGCSIHCMR-UHFFFAOYSA-N 0.000 description 2
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 2
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 2
- RXNYJUSEXLAVNQ-UHFFFAOYSA-N 4,4'-Dihydroxybenzophenone Chemical compound C1=CC(O)=CC=C1C(=O)C1=CC=C(O)C=C1 RXNYJUSEXLAVNQ-UHFFFAOYSA-N 0.000 description 2
- QHPQWRBYOIRBIT-UHFFFAOYSA-N 4-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C=C1 QHPQWRBYOIRBIT-UHFFFAOYSA-N 0.000 description 2
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-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
- 239000005977 Ethylene Substances 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-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
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- PMDCZENCAXMSOU-UHFFFAOYSA-N N-ethylacetamide Chemical compound CCNC(C)=O PMDCZENCAXMSOU-UHFFFAOYSA-N 0.000 description 2
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-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
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical class OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 229930003836 cresol Natural products 0.000 description 2
- VEZUQRBDRNJBJY-UHFFFAOYSA-N cyclohexanone oxime Chemical compound ON=C1CCCCC1 VEZUQRBDRNJBJY-UHFFFAOYSA-N 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 2
- KORSJDCBLAPZEQ-UHFFFAOYSA-N dicyclohexylmethane-4,4'-diisocyanate Chemical compound C1CC(N=C=O)CCC1CC1CCC(N=C=O)CC1 KORSJDCBLAPZEQ-UHFFFAOYSA-N 0.000 description 2
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 239000001282 iso-butane Substances 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- 229920003986 novolac Polymers 0.000 description 2
- 229920000768 polyamine Polymers 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 2
- 229910000165 zinc phosphate Inorganic materials 0.000 description 2
- 229940058015 1,3-butylene glycol Drugs 0.000 description 1
- ALQLPWJFHRMHIU-UHFFFAOYSA-N 1,4-diisocyanatobenzene Chemical compound O=C=NC1=CC=C(N=C=O)C=C1 ALQLPWJFHRMHIU-UHFFFAOYSA-N 0.000 description 1
- FRASJONUBLZVQX-UHFFFAOYSA-N 1,4-dioxonaphthalene Natural products C1=CC=C2C(=O)C=CC(=O)C2=C1 FRASJONUBLZVQX-UHFFFAOYSA-N 0.000 description 1
- SBJCUZQNHOLYMD-UHFFFAOYSA-N 1,5-Naphthalene diisocyanate Chemical compound C1=CC=C2C(N=C=O)=CC=CC2=C1N=C=O SBJCUZQNHOLYMD-UHFFFAOYSA-N 0.000 description 1
- BOKGTLAJQHTOKE-UHFFFAOYSA-N 1,5-dihydroxynaphthalene Chemical compound C1=CC=C2C(O)=CC=CC2=C1O BOKGTLAJQHTOKE-UHFFFAOYSA-N 0.000 description 1
- ZPANWZBSGMDWON-UHFFFAOYSA-N 1-[(2-hydroxynaphthalen-1-yl)methyl]naphthalen-2-ol Chemical compound C1=CC=C2C(CC3=C4C=CC=CC4=CC=C3O)=C(O)C=CC2=C1 ZPANWZBSGMDWON-UHFFFAOYSA-N 0.000 description 1
- RQBUVIFBALZGPC-UHFFFAOYSA-N 1-isocyanato-4-(4-isocyanatophenyl)benzene Chemical group C1=CC(N=C=O)=CC=C1C1=CC=C(N=C=O)C=C1 RQBUVIFBALZGPC-UHFFFAOYSA-N 0.000 description 1
- WAPNOHKVXSQRPX-UHFFFAOYSA-N 1-phenylethanol Chemical compound CC(O)C1=CC=CC=C1 WAPNOHKVXSQRPX-UHFFFAOYSA-N 0.000 description 1
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
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- IMSODMZESSGVBE-UHFFFAOYSA-N 2-Oxazoline Chemical compound C1CN=CO1 IMSODMZESSGVBE-UHFFFAOYSA-N 0.000 description 1
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- YEYKMVJDLWJFOA-UHFFFAOYSA-N 2-propoxyethanol Chemical compound CCCOCCO YEYKMVJDLWJFOA-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- CEZWFBJCEWZGHX-UHFFFAOYSA-N 4-isocyanato-n-(oxomethylidene)benzenesulfonamide Chemical compound O=C=NC1=CC=C(S(=O)(=O)N=C=O)C=C1 CEZWFBJCEWZGHX-UHFFFAOYSA-N 0.000 description 1
- NTDQQZYCCIDJRK-UHFFFAOYSA-N 4-octylphenol Chemical compound CCCCCCCCC1=CC=C(O)C=C1 NTDQQZYCCIDJRK-UHFFFAOYSA-N 0.000 description 1
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical compound C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 description 1
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
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- 239000002202 Polyethylene glycol Substances 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 1
- LHFURYICKMKJHJ-UHFFFAOYSA-L [benzoyloxy(dibutyl)stannyl] benzoate Chemical compound CCCC[Sn+2]CCCC.[O-]C(=O)C1=CC=CC=C1.[O-]C(=O)C1=CC=CC=C1 LHFURYICKMKJHJ-UHFFFAOYSA-L 0.000 description 1
- UFYYBMYIZKRDCG-UHFFFAOYSA-L [benzoyloxy(dioctyl)stannyl] benzoate Chemical compound [O-]C(=O)C1=CC=CC=C1.[O-]C(=O)C1=CC=CC=C1.CCCCCCCC[Sn+2]CCCCCCCC UFYYBMYIZKRDCG-UHFFFAOYSA-L 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- XQBCVRSTVUHIGH-UHFFFAOYSA-L [dodecanoyloxy(dioctyl)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCCCCCC)(CCCCCCCC)OC(=O)CCCCCCCCCCC XQBCVRSTVUHIGH-UHFFFAOYSA-L 0.000 description 1
- PXAJQJMDEXJWFB-UHFFFAOYSA-N acetone oxime Chemical compound CC(C)=NO PXAJQJMDEXJWFB-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000004705 aldimines Chemical class 0.000 description 1
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- XPNGNIFUDRPBFJ-UHFFFAOYSA-N alpha-methylbenzylalcohol Natural products CC1=CC=CC=C1CO XPNGNIFUDRPBFJ-UHFFFAOYSA-N 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- 229960004217 benzyl alcohol Drugs 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- YXVFYQXJAXKLAK-UHFFFAOYSA-N biphenyl-4-ol Chemical class C1=CC(O)=CC=C1C1=CC=CC=C1 YXVFYQXJAXKLAK-UHFFFAOYSA-N 0.000 description 1
- 229940049676 bismuth hydroxide Drugs 0.000 description 1
- TZSXPYWRDWEXHG-UHFFFAOYSA-K bismuth;trihydroxide Chemical compound [OH-].[OH-].[OH-].[Bi+3] TZSXPYWRDWEXHG-UHFFFAOYSA-K 0.000 description 1
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- 239000006229 carbon black Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
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- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 description 1
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- 229940028356 diethylene glycol monobutyl ether Drugs 0.000 description 1
- 125000005442 diisocyanate group Chemical group 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
- MCWXGJITAZMZEV-UHFFFAOYSA-N dimethoate Chemical compound CNC(=O)CSP(=S)(OC)OC MCWXGJITAZMZEV-UHFFFAOYSA-N 0.000 description 1
- 125000006182 dimethyl benzyl group Chemical group 0.000 description 1
- LQRUPWUPINJLMU-UHFFFAOYSA-N dioctyl(oxo)tin Chemical compound CCCCCCCC[Sn](=O)CCCCCCCC LQRUPWUPINJLMU-UHFFFAOYSA-N 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- SLAFUPJSGFVWPP-UHFFFAOYSA-M ethyl(triphenyl)phosphanium;iodide Chemical compound [I-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CC)C1=CC=CC=C1 SLAFUPJSGFVWPP-UHFFFAOYSA-M 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- JBFHTYHTHYHCDJ-UHFFFAOYSA-N gamma-caprolactone Chemical compound CCC1CCC(=O)O1 JBFHTYHTHYHCDJ-UHFFFAOYSA-N 0.000 description 1
- GAEKPEKOJKCEMS-UHFFFAOYSA-N gamma-valerolactone Chemical compound CC1CCC(=O)O1 GAEKPEKOJKCEMS-UHFFFAOYSA-N 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 150000004000 hexols Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- MTNDZQHUAFNZQY-UHFFFAOYSA-N imidazoline Chemical compound C1CN=CN1 MTNDZQHUAFNZQY-UHFFFAOYSA-N 0.000 description 1
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- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000013035 low temperature curing Methods 0.000 description 1
- QOHMWDJIBGVPIF-UHFFFAOYSA-N n',n'-diethylpropane-1,3-diamine Chemical compound CCN(CC)CCCN QOHMWDJIBGVPIF-UHFFFAOYSA-N 0.000 description 1
- LSHROXHEILXKHM-UHFFFAOYSA-N n'-[2-[2-[2-(2-aminoethylamino)ethylamino]ethylamino]ethyl]ethane-1,2-diamine Chemical compound NCCNCCNCCNCCNCCN LSHROXHEILXKHM-UHFFFAOYSA-N 0.000 description 1
- QJQAMHYHNCADNR-UHFFFAOYSA-N n-methylpropanamide Chemical compound CCC(=O)NC QJQAMHYHNCADNR-UHFFFAOYSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
- BTLSLHNLDQCWKS-UHFFFAOYSA-N oxocan-2-one Chemical compound O=C1CCCCCCO1 BTLSLHNLDQCWKS-UHFFFAOYSA-N 0.000 description 1
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920006389 polyphenyl polymer Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 239000002987 primer (paints) Substances 0.000 description 1
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 1
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 239000004071 soot Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 1
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 description 1
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 1
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 1
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 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
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- 150000004072 triols Chemical class 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/44—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/58—Epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/64—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63
- C08G18/6415—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63 having nitrogen
- C08G18/643—Reaction products of epoxy resins with at least equivalent amounts of amines
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/80—Masked polyisocyanates
- C08G18/8061—Masked polyisocyanates masked with compounds having only one group containing active hydrogen
- C08G18/8064—Masked polyisocyanates masked with compounds having only one group containing active hydrogen with monohydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/80—Masked polyisocyanates
- C08G18/8061—Masked polyisocyanates masked with compounds having only one group containing active hydrogen
- C08G18/807—Masked polyisocyanates masked with compounds having only one group containing active hydrogen with nitrogen containing compounds
- C08G18/8074—Lactams
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/80—Masked polyisocyanates
- C08G18/8061—Masked polyisocyanates masked with compounds having only one group containing active hydrogen
- C08G18/807—Masked polyisocyanates masked with compounds having only one group containing active hydrogen with nitrogen containing compounds
- C08G18/8077—Oximes
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/44—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications
- C09D5/4419—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications with polymers obtained otherwise than by polymerisation reactions only involving carbon-to-carbon unsaturated bonds
- C09D5/443—Polyepoxides
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/44—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications
- C09D5/4488—Cathodic paints
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/44—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications
- C09D5/4488—Cathodic paints
- C09D5/4492—Cathodic paints containing special additives, e.g. grinding agents
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- Chemical Kinetics & Catalysis (AREA)
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Abstract
A coating film-forming method, which method comprises coating a cationic electrodeposition coating composition onto a substrate, followed by heat curing to form a cured electrodeposition coating film, said cationic electrodeposition coating composition containing a base resin consisting of an amine-added epoxy resin (A) obtained by reacting an epoxy resin (a1) with at least one modifying agent selected from the group consisting of a polyhydric polyol (a2), an epoxy compound (a3) of the polyhydric polyol and a cyclic ester compound (a4), a polyphenol compound (a5) and an amino group-containing compound (a6), and a curing agent consisting of a blocked polyisocyanate curing agent (B) obtained by reacting at least one polyisocyanate compound (b1) selected from the group consisting of an aromatic polyisocyanate compound and an alicyclic polyisocyanate compound with at least one blocking agent (b2) selected from the group consisting of an oxime compound, aliphatic alcohols, aromatic alkyl alcohols and ether alcohols.
Description
SPECIFICATION
Title of the Invention:
Coating Film-Forming Method Background of the Invention:
Field of the Invention:
The present invention relates to a coating film-forming method, particularly to a coating film-forming method, which comprises coating a cationic electrodeposition coating composition containing a specified base resin and a specified curing agent consisting of a blocked polyisocyanate curing agent onto a substrate and which is capable of obtaining a coated product having good properties in throwing power, electrodeposition suitability for an anti-corrosive steel plate or coating properties for a galvanized sheet, and anti-corrosive properties.
Description of Background Art:
The cationic electrodeposition coating composition has good coating workability and is capable of forming a coating film showing high anti-corrosive properties, resulting in being widely used as a primer coating composition coated on an electrically conductive metal product such as an automobile body and the like, in which above properties are required. A many folds-structure of reinforcing materials for the purpose of increasing strength of the automobile body from the standpoint of improving collision safety in recent years makes difficult to flow through and may reduce a current density, resulting in making difficult a deposition of a coating film and in reducing anti-corrosive properties due to failure of coating. For the purpose of solving the above problem, forming a thick film on an inner plate area by raising a coating voltage is proposed.
The galvanized sheet is widely used as an anti-corrosive steel sheet from the standpoint of a low cost of the automobile body. On the other hand, an electrodeposition coating in a short period of time of 90 to 150 seconds is demanded from the standpoints of a saving of energy, saving of space and improvement in productivity in a coating line.
In view of the above problems, a high voltage electrodeposition coating was forced for the purpose of obtaining a high throwing power on the surface of a pouch area or inner plate, resulting in producing such problems that sparks generated during the electrodeposition coating of the galvanized sheet on the surface of an outer plate of the substrate may remain as pinholes after heat-curing of the coating film, resulting in reducing finished properties.
Japanese Patent Application Laid-Open No. 2001-19878 discloses a method of preparing a cationic electrodeposition coating composition capable of controlling development of pinholes due to gas generation on the galvanized sheet and obtaining a coating film showing high throwing power, and further discloses an electrodeposition coating film-forming method, which method comprises subjecting an electrodeposition coating conlposition controlled under such conditions that a minimum film-forming temperature of the cationic electrodeposition coating composition is in the range of 5 C of a predetermined electrodeposition coating temperature and an electrical conductivity on coating is in the range of 1000 to 1500 S/cm to an electrodeposition coating at the predetermined electrodeposition coating temperature.
Japanese Patent Application Laid-Open No. 2002-275690 discloses a coating film-forming method, which method comprises coating a cationic electrodeposition coating composition under an effective voltage (V) of 230 V or less, the cationic electrodeposition coating composition having a uniform coating properties capable of ensuring an inner film thickness ( m) without increasing an outer plate film thickness and showing good finished properties of the galvanized sheet, and having a polarization resistance (a) per unit film thickness in the range of 120 to 300 kS2=cm2/ m and a coating composition deposition amount (b) per unit electrical quantity in the range of 50 to 150 mg/C in the cationic electrodeposition coating.
Japanese Patent Application Laid-Open No. 2002-60680 discloses a cationic electrodeposition coating composition showing improved properties in throwing power and resistance to pinhole development due to gas generation and further discloses the cationic electrodeposition coating composition containing an amine-modified epoxy resin and a blocked polyisocyanate curing agent as a resin component and _ 3 _ containing an organic acid and a metal salt of the organic acid as the neutralizing agent under controlling a total amount of the organic acid and an equivalent ratio of the organic acid to the metal salt of the organic acid.
As above described, the cationic electrodeposition coating composition having both throwing power and electrodeposition coating suitability for the galvanized sheet is known in the art, but any cationic electrodeposition coating composition having throwing power, electrodeposition coating suitability for the galvanized sheet and good anti-corrosive properties in a short period of time of 90 to 150 seconds as an energizing time is not known in the art.
Summary of the Invention:
It is an object of the present invention to provide a coating film-forming method by use of a cationic electrodeposition coating composition having throwing power, electrodeposition coating suitability for the galvanized sheet and good anti-corrosive properties.
It is another object of the present invention is to provide a coated product obtained by the above method.
That is, the present invention relates to the following paragraphs 1 to 5:
1. A coating film-forming method, which method comprises coating a cationic electrodeposition coating composition onto a substrate, followed by heat curing to form a cured electrodeposition coating film, said cationic electrodeposition coating composition containing a base resin consisting of an amine-added epoxy resin (A) obtained by reacting an epoxy resin (al) with at least one modifying agent selected from the group consisting of a polyhydric polyol (a2), an epoxy compound (a3) of the polyhydric polyol and a cyclic ester compound (a4), a polyphenol compound (a5) and an amino group-containing compound (a6), and a curing agent consisting of a blocked polyisocyanate curing agent (B) obtained by reacting at least one polyisocyanate compound (bl) selected from the group consisting of an aromatic polyisocyanate compound and an alicyclic polyisocyanate compound with at least one blocking agent (b2) selected from the group consisting of an oxime compound, aliphatic alcohols, aromatic alkyl alcohols and ether alcohols, 2. A coating film-forming method as defined in paragraph 1, wherein the amine-added epoxy resin (A) has a glass transition temperature in the range of -10 to 60 C, and the blocked polyisocyanate curing agent (B) has a glass transition temperature in the range of -1.0 to 50 C, 3. A coating film-forming method as defined in paragraph 1 or 2, wherein the cationic electrodeposition coating composition further contains a bismuth compound as an anti-corrosive agent, 4. A coating film-forming method as defined in any one of paragraphs 1 to 3, wherein one minute after starting of energizing on the electrodeposition coating, a resulting coating film has an electrical resistance in the range of 400 kSL = cm2 to 850 kS2 = cm2 , and 5. A coated product obtained by the method as defined in any one of paragraphs 1 to 4.
Brief Description of the Drawings Fig. 1 is a schematic view of a jig used in a four sheets box throwing power coating test.
Fig. 2 is a wiring diagram for explaining the four sheets box throwing power coating test.
In Fig. 2, 10 represents surface (H), 11 represents surface (A), 12 represents surface (C), 13 represents surface (E) and 14 represents surface (G). In Figs. 1 and 2, 15 represents an opening of 8 mm in diameter. In Fig. 2, 20 represents a bath, 21 represents a cationic electrodeposition coating composition and 22 represents an anode.
Detailed Description of the Invention:
The coating film-forming method, which comprises coating a cationic electrodeposition coating composition containing a.specified base resin preferably having a specified glass transition temperature and a specified curing agent preferably having a specified glass transition temperature onto a substrate and heat-curing, in the present invention makes it possible to obtain a cured electrodeposition coating film having high throwing power, and good properties in electrodeposition coating suitability for the galvanized sheet and anti-corrosive properties with sufficient film thickness on a pouched area and inner plate area in a short period of time of 90 to 150 seconds on electrodeposition coating.
The use of such a cationic electrodeposition coating composition as the above cationic electrodeposition coating composition that a resulting coating film one minute after starting of energizing on the electrodeposition coating has an electrical resistance in the range of 400 kSZ=cm2 to 850 kS2 = cm2, preferably 480 k92 = cm2 to 650 kSZ cm2, makes it possible to easily obtain a cured electrodeposition coating film showing both high throwing power and electrodeposition coating suitability for the galvanized sheet.
The throwing power is evaluated by a four sheets box test method. As shown in Fig. 1, a box formed by placing four sheets of zinc phosphate-treated cold-rolled steel sheet at an interval of 20 mm in parallel is used. Three steel sheets other than the steel sheet with surfaces (G) and (H) have an opening of 8 mm in diameter at a lower center respectively. The electrodeposition coating may be carried out according to a wiring diagram as shown in Fig. 2, and throwing power evaluation may be made from a film thickness on the nearest surface (A) from the anode and a film thickness on the most distant surface (G) from the anode.
The film-forming method of the present invention makes it possible to obtain such a throwing power that film thickness ( m) on the surface (G)/film thickness ( m) on the surface (A) = 30 to 100%, preferably film thickness ( m) on the surface (G)/film thickness ( m) on the surface (A) = 50 to 100%.
Title of the Invention:
Coating Film-Forming Method Background of the Invention:
Field of the Invention:
The present invention relates to a coating film-forming method, particularly to a coating film-forming method, which comprises coating a cationic electrodeposition coating composition containing a specified base resin and a specified curing agent consisting of a blocked polyisocyanate curing agent onto a substrate and which is capable of obtaining a coated product having good properties in throwing power, electrodeposition suitability for an anti-corrosive steel plate or coating properties for a galvanized sheet, and anti-corrosive properties.
Description of Background Art:
The cationic electrodeposition coating composition has good coating workability and is capable of forming a coating film showing high anti-corrosive properties, resulting in being widely used as a primer coating composition coated on an electrically conductive metal product such as an automobile body and the like, in which above properties are required. A many folds-structure of reinforcing materials for the purpose of increasing strength of the automobile body from the standpoint of improving collision safety in recent years makes difficult to flow through and may reduce a current density, resulting in making difficult a deposition of a coating film and in reducing anti-corrosive properties due to failure of coating. For the purpose of solving the above problem, forming a thick film on an inner plate area by raising a coating voltage is proposed.
The galvanized sheet is widely used as an anti-corrosive steel sheet from the standpoint of a low cost of the automobile body. On the other hand, an electrodeposition coating in a short period of time of 90 to 150 seconds is demanded from the standpoints of a saving of energy, saving of space and improvement in productivity in a coating line.
In view of the above problems, a high voltage electrodeposition coating was forced for the purpose of obtaining a high throwing power on the surface of a pouch area or inner plate, resulting in producing such problems that sparks generated during the electrodeposition coating of the galvanized sheet on the surface of an outer plate of the substrate may remain as pinholes after heat-curing of the coating film, resulting in reducing finished properties.
Japanese Patent Application Laid-Open No. 2001-19878 discloses a method of preparing a cationic electrodeposition coating composition capable of controlling development of pinholes due to gas generation on the galvanized sheet and obtaining a coating film showing high throwing power, and further discloses an electrodeposition coating film-forming method, which method comprises subjecting an electrodeposition coating conlposition controlled under such conditions that a minimum film-forming temperature of the cationic electrodeposition coating composition is in the range of 5 C of a predetermined electrodeposition coating temperature and an electrical conductivity on coating is in the range of 1000 to 1500 S/cm to an electrodeposition coating at the predetermined electrodeposition coating temperature.
Japanese Patent Application Laid-Open No. 2002-275690 discloses a coating film-forming method, which method comprises coating a cationic electrodeposition coating composition under an effective voltage (V) of 230 V or less, the cationic electrodeposition coating composition having a uniform coating properties capable of ensuring an inner film thickness ( m) without increasing an outer plate film thickness and showing good finished properties of the galvanized sheet, and having a polarization resistance (a) per unit film thickness in the range of 120 to 300 kS2=cm2/ m and a coating composition deposition amount (b) per unit electrical quantity in the range of 50 to 150 mg/C in the cationic electrodeposition coating.
Japanese Patent Application Laid-Open No. 2002-60680 discloses a cationic electrodeposition coating composition showing improved properties in throwing power and resistance to pinhole development due to gas generation and further discloses the cationic electrodeposition coating composition containing an amine-modified epoxy resin and a blocked polyisocyanate curing agent as a resin component and _ 3 _ containing an organic acid and a metal salt of the organic acid as the neutralizing agent under controlling a total amount of the organic acid and an equivalent ratio of the organic acid to the metal salt of the organic acid.
As above described, the cationic electrodeposition coating composition having both throwing power and electrodeposition coating suitability for the galvanized sheet is known in the art, but any cationic electrodeposition coating composition having throwing power, electrodeposition coating suitability for the galvanized sheet and good anti-corrosive properties in a short period of time of 90 to 150 seconds as an energizing time is not known in the art.
Summary of the Invention:
It is an object of the present invention to provide a coating film-forming method by use of a cationic electrodeposition coating composition having throwing power, electrodeposition coating suitability for the galvanized sheet and good anti-corrosive properties.
It is another object of the present invention is to provide a coated product obtained by the above method.
That is, the present invention relates to the following paragraphs 1 to 5:
1. A coating film-forming method, which method comprises coating a cationic electrodeposition coating composition onto a substrate, followed by heat curing to form a cured electrodeposition coating film, said cationic electrodeposition coating composition containing a base resin consisting of an amine-added epoxy resin (A) obtained by reacting an epoxy resin (al) with at least one modifying agent selected from the group consisting of a polyhydric polyol (a2), an epoxy compound (a3) of the polyhydric polyol and a cyclic ester compound (a4), a polyphenol compound (a5) and an amino group-containing compound (a6), and a curing agent consisting of a blocked polyisocyanate curing agent (B) obtained by reacting at least one polyisocyanate compound (bl) selected from the group consisting of an aromatic polyisocyanate compound and an alicyclic polyisocyanate compound with at least one blocking agent (b2) selected from the group consisting of an oxime compound, aliphatic alcohols, aromatic alkyl alcohols and ether alcohols, 2. A coating film-forming method as defined in paragraph 1, wherein the amine-added epoxy resin (A) has a glass transition temperature in the range of -10 to 60 C, and the blocked polyisocyanate curing agent (B) has a glass transition temperature in the range of -1.0 to 50 C, 3. A coating film-forming method as defined in paragraph 1 or 2, wherein the cationic electrodeposition coating composition further contains a bismuth compound as an anti-corrosive agent, 4. A coating film-forming method as defined in any one of paragraphs 1 to 3, wherein one minute after starting of energizing on the electrodeposition coating, a resulting coating film has an electrical resistance in the range of 400 kSL = cm2 to 850 kS2 = cm2 , and 5. A coated product obtained by the method as defined in any one of paragraphs 1 to 4.
Brief Description of the Drawings Fig. 1 is a schematic view of a jig used in a four sheets box throwing power coating test.
Fig. 2 is a wiring diagram for explaining the four sheets box throwing power coating test.
In Fig. 2, 10 represents surface (H), 11 represents surface (A), 12 represents surface (C), 13 represents surface (E) and 14 represents surface (G). In Figs. 1 and 2, 15 represents an opening of 8 mm in diameter. In Fig. 2, 20 represents a bath, 21 represents a cationic electrodeposition coating composition and 22 represents an anode.
Detailed Description of the Invention:
The coating film-forming method, which comprises coating a cationic electrodeposition coating composition containing a.specified base resin preferably having a specified glass transition temperature and a specified curing agent preferably having a specified glass transition temperature onto a substrate and heat-curing, in the present invention makes it possible to obtain a cured electrodeposition coating film having high throwing power, and good properties in electrodeposition coating suitability for the galvanized sheet and anti-corrosive properties with sufficient film thickness on a pouched area and inner plate area in a short period of time of 90 to 150 seconds on electrodeposition coating.
The use of such a cationic electrodeposition coating composition as the above cationic electrodeposition coating composition that a resulting coating film one minute after starting of energizing on the electrodeposition coating has an electrical resistance in the range of 400 kSZ=cm2 to 850 kS2 = cm2, preferably 480 k92 = cm2 to 650 kSZ cm2, makes it possible to easily obtain a cured electrodeposition coating film showing both high throwing power and electrodeposition coating suitability for the galvanized sheet.
The throwing power is evaluated by a four sheets box test method. As shown in Fig. 1, a box formed by placing four sheets of zinc phosphate-treated cold-rolled steel sheet at an interval of 20 mm in parallel is used. Three steel sheets other than the steel sheet with surfaces (G) and (H) have an opening of 8 mm in diameter at a lower center respectively. The electrodeposition coating may be carried out according to a wiring diagram as shown in Fig. 2, and throwing power evaluation may be made from a film thickness on the nearest surface (A) from the anode and a film thickness on the most distant surface (G) from the anode.
The film-forming method of the present invention makes it possible to obtain such a throwing power that film thickness ( m) on the surface (G)/film thickness ( m) on the surface (A) = 30 to 100%, preferably film thickness ( m) on the surface (G)/film thickness ( m) on the surface (A) = 50 to 100%.
The coating film-forming method of the present invention also makes it possible to obtain such an electrodeposition coating suitability for the galvanized sheet that energizing a voltage, under which the above throwing power may be obtained, for example, 200 V or more, preferably 250 V or more, more preferably 300 V or more may develop no pinholes on the surface of the coating film.
As above described, the use of the cationic electrodeposition coating composition containing the specified base resin and the specified curing agent is essential for the purpose of obtaining both throwing power and electrodeposition coating suitability. The use of the cationic electrodeposition coating composition, which contains the specified resin preferably having a specified glass transition temperature and the specified curing agent preferably having a specified glass transition temperature, and which is more preferably such that the resulting coating film one minute after starting of energizing on the cationic electrodeposition coating has a specified electrical resistance, may further improve throwing power and electrodeposition coating suitability for the galvanized sheet.
The amine-added epoxy resin (A) used as the specified base resin and the blocked polyisocyanate curing agent (B) used as the specified curing agent in the cationic electrodeposition coating composition are explained hereinafter.
As above described, the use of the cationic electrodeposition coating composition containing the specified base resin and the specified curing agent is essential for the purpose of obtaining both throwing power and electrodeposition coating suitability. The use of the cationic electrodeposition coating composition, which contains the specified resin preferably having a specified glass transition temperature and the specified curing agent preferably having a specified glass transition temperature, and which is more preferably such that the resulting coating film one minute after starting of energizing on the cationic electrodeposition coating has a specified electrical resistance, may further improve throwing power and electrodeposition coating suitability for the galvanized sheet.
The amine-added epoxy resin (A) used as the specified base resin and the blocked polyisocyanate curing agent (B) used as the specified curing agent in the cationic electrodeposition coating composition are explained hereinafter.
The amine-added epoxy resin (A) is a base resin obtained by reacting an epoxy resin (al) with at least one modifying agent selected from the group consisting of a polyhydric polyol (a2), an epoxy compound (a3) of the polyhydric polyol on a cyclic ester compound (a4), a polyphenol compound (a5) and an amino group-containing compound (a6).
The epoxy resin (a1) may preferably include an epoxy resin obtained by reacting a polyphenol compound with epihalohydrin, such as epichlorohydrin from the standpoints such as anti-corrosive properties of the coating film.
The polyphenol compound used for obtaining the epoxy resin may include ones known in the art, for example, bis(4-hydroxyphenyl)-2,2-propane (bisphenol A), 4,4-dihydroxybenzophenone, bis (4-hydroxyphenyl) methane (bisphenol F), bis(4-hydroxyphenyl)-1,1-ethane, bis(4-hydroxyphenyl)-1,1-isobutane, bis(4-hydroxy-tert-butyl-phenyl)-2,2-propane, bis (2-hydroxynaphthyl) methane, tetra(4-hydroxyphenyl)-1,1,2,2-ethane, 4,4-dihydroxydiphenylsulfone (bisphenol S), phenol novolak, cresol novolak, and the like.
The epoxy resin obtained by the reaction of the polyphenol compound with epichlorohydrin may particularly include ones derived from bisphenol A and represented by the following formula:
p C3 ~ C~ O
H2C-HC-HZC-O C O-CHZ CHCHa O ~~ C O-CH2-CH-CH2 GHg OH CH3 n where n is 0 to 8.
The epoxy resin (a1) may preferably include an epoxy resin obtained by reacting a polyphenol compound with epihalohydrin, such as epichlorohydrin from the standpoints such as anti-corrosive properties of the coating film.
The polyphenol compound used for obtaining the epoxy resin may include ones known in the art, for example, bis(4-hydroxyphenyl)-2,2-propane (bisphenol A), 4,4-dihydroxybenzophenone, bis (4-hydroxyphenyl) methane (bisphenol F), bis(4-hydroxyphenyl)-1,1-ethane, bis(4-hydroxyphenyl)-1,1-isobutane, bis(4-hydroxy-tert-butyl-phenyl)-2,2-propane, bis (2-hydroxynaphthyl) methane, tetra(4-hydroxyphenyl)-1,1,2,2-ethane, 4,4-dihydroxydiphenylsulfone (bisphenol S), phenol novolak, cresol novolak, and the like.
The epoxy resin obtained by the reaction of the polyphenol compound with epichlorohydrin may particularly include ones derived from bisphenol A and represented by the following formula:
p C3 ~ C~ O
H2C-HC-HZC-O C O-CHZ CHCHa O ~~ C O-CH2-CH-CH2 GHg OH CH3 n where n is 0 to 8.
The epoxy resin (al) has an epoxy equivalent in the range of 180 to 2,.500, preferably 200 to 2,000, more preferably 400 to 1,500, and a number average molecular weight in the range of at least 200, particularly 400 to 4,000, more particularly 800 to 2,500.
Examples of commercially available trade names of the TM
epoxy resin may include Epikote 828 EL, Epikote 1002, Epikote 1004 and Epikote 1007 (trade names marketed by Japan Epoxy Resin Co. , Ltd. ) .
The polyhydric polyol (a2) used as the modifying agent is, for example, a compound having at least two alcoholic hydroxyl groups in one molecule, and may include, for example, diols such as ethylene glycol, propylene glycol, 1,3-butylene glycol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, dipropylene glycol, cyclohexane-l,4-dimethylol, neopentyl glycol, polypropylene glycol, polyethylene glycol, triethylene glycol, hydrogenated bisphenol A and the like;
triols such as glycerin, trimethylolethane, trimethylolpropane and the like; tetrols such as pentaerythritol, a-methylglucoside and the like; hexols such as sorbitol, dipentaerythritol and the like; and octols such as sucrose and the like.
The modifying agent may also include an epoxy compound (a3) of the polyhydric polyol as obtained by reacting the polyhydric polyol (a3) with epichlorohydrin.
The modifying agent may further include propylene oxide-modified bisphenol A diglycidyl, ethylene glycol oxide-modified bisphenol A diglycidyl and the like.
The cyclic ester compound (a4) used as the modifying agent may include a compound represented by the following formula (1) :
R-CH- (CH2)n-C=O (1) where R represents H or CH3 and n represents 3 to 6, and specifically may include, for example, S-vale.rolactone, s-caprolactone, ~-enolactone, rI-caprolactone, y-valerolactone, 6-caprolactone, s-enolactone, ~-caprolactone and the like.
Of these, s-caprolactone is particularly preferable.
In the addition reaction of the cyclic ester compound (a4) with the epoxy resin (al), ring opening of the cyclic ester compound (a4) represented by the formula (1) may be followed by reacting with a secondary hydroxyl group in the epoxy resin, imparting a primary hydroxyl group and.resulting in that a methylene chain moiety due to lactone may impart plasticity to the epoxy resin.
An amount of the modifying agent to be reacted with the epoxy resin (al), i.e. an amount of at least one modifying agent selected from the group consisting of the polyhydric polyol (a2), epoxy compound (a3) of the polyhydric polyol and cyclic ester compound (a4) may not be particularly limited, but may preferably be such that at least one modifying agent selected from the group consisting of the polyhydric polyol (a2), epoxy compound (a3) of the polyhydric polyol and cyclic ester compound (a4) may be in the range of 5 to 40% by weight, preferably 10 to 35% by weight.
The polyphenol compound (a5) may include, for example, phenol, cresols, p-octylphenol, nonylphenol, bisphenolpropane, bisphenolmethane, resorcinol, pyrocatechol, hydroquinone, P-tert-butylphenol, bisphenolsulfone, bisphenol ether, p-phenylphenols, bis(4-hydroxyphenyl)-2,2-propane, bis(4-hydroxyphenyl)-1,1-ethane, bis(4-hydroxyphenyl)-1,1-isobutane, 4,4'-dihydroxybenzophenone, bis(4-hydroxy-3-t-butylphenyl)-2,2-propane, bis(2-hydroxynaphthy.l)methane, 1,5-dihydroxy-naphthalene and the like. These may be used alone or in combination.
The amine-added epoxy resin (A) may be prepared as.
follows.
A reactor is charged with the epoxy resin (al), at least one modifying agent selected from the group consisting of the polyhydric polyol (a2), epoxy compound (a3) of the polyhydric polyol and cyclic ester compound (a4), and the polyphenol compound (a5), followed by adding an organic solvent, a basic amino compound catalyst such as dimethylbenzylamine, tributylamine, triethylamine and the like, and tetraethylammonium bromide, tetrabutylammonium bromide, tetraethylammonium hydroxide, triphenylethylphosphonium iodide and the like to obtain a modified epoxy resin.
The preparation of the modified epoxy resin may be carried out by adding the catalyst in an amount of 1 to 10,000 ppm based on a total solid content of the epoxy resin (al), at least one modifying agent selected from the group consisting of the polyhydric polyol (a2), epoxy compound (a3) of the polyhydric polyol and cyclic ester compound (a4) and polyphenol compound (a5), followed by heating at a temperature of about 50 C to about 200 C for about 30 minutes to about 10 hours.
Thereafter, the amino group-containing compound (a6) is added to the modified epoxy resin to obtain an amine-added epoxy resin (A).
The amino group-containing compound (a6) to react with the modified epoxy resin is a cationic properties-imparting component which introduces amino group into the epoxy resin and cationizes the epoxy resin, and may include one having at least one active hydrogen to react with the epoxy resin.
The amino group-containing compound (a6) may include, for example, mono- or di-alkylamine such as monomethylamine, dimethylamine, monoethylamine, diethylamine, monoisopropylamine, diisopropylamine, monobutylamine, dibutylamine and the like; alkanolamine such as monoethanolamine, diethanolamine, mono (2-hydroxypropyl) amine, di (2-hydroxypropyl) amine, tri (2-hydroxypropyl) amine, monomethylaminoethanol, monoethylaminoethanol and the like;
alkylene polyamine such as ethylenediamine, propylenediamine, butylenediamine, hexamethylenediamine, tetraethylenepentamine, pentaethylenehexamine, diethylaminopropylamine, diethylenetriamine, triethylenetetramine and the like, and a ketiminized product of these polyamines; an alkyleneimine such as ethyleneimine, propyleneimine and the like; a cyclic amine such as piperazine, morpholine, pyrazine and the like, and the like.
The amino group-containing compound (a6) may be reacted with the epoxy group of the modified epoxy resin under the conditions of a temperature in the range of about 30 C to about 150 C for 30 minutes to 150 minutes. Preferably, a compound containing a primary amine or N-hydroxyalkyl secondary amine of the above amines may be reacted with ketone, aldehyde, or carboxylic acid at 100 C to 230 C to be modified to aldimine, ketimine, oxazoline or imidazoline, followed by reacting with the epoxy group of the modified epoxy resin at about 80 C to about 200 C for about one hour to about 5 hours.
An amount of the amino group-containing compound (a6) may preferably be such that an amine value of the amine-added epoxy resin (A) may be in the range of 20 to.80 mg KOH/g, preferably 25 to 70 mg KOH/g. The amine-added epoxy resin (A) may preferably have a weight average molecular weight in the range of about 1,000 to about 10,000.
The amine-added epoxy resin (A) obtained as above has a glass transition temperature in the range of -10 C to 60 C.
The glass transition temperature in the present invention is a value measured by use of a Differential Thermal Analyzer, or measured by use of DSC-5200 (trade name, marketed by Seiko Instruments Inc., Differential Scanning Calorimeter) at a temperature-raising speed of 10 C/min.
Examples of commercially available trade names of the TM
epoxy resin may include Epikote 828 EL, Epikote 1002, Epikote 1004 and Epikote 1007 (trade names marketed by Japan Epoxy Resin Co. , Ltd. ) .
The polyhydric polyol (a2) used as the modifying agent is, for example, a compound having at least two alcoholic hydroxyl groups in one molecule, and may include, for example, diols such as ethylene glycol, propylene glycol, 1,3-butylene glycol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, dipropylene glycol, cyclohexane-l,4-dimethylol, neopentyl glycol, polypropylene glycol, polyethylene glycol, triethylene glycol, hydrogenated bisphenol A and the like;
triols such as glycerin, trimethylolethane, trimethylolpropane and the like; tetrols such as pentaerythritol, a-methylglucoside and the like; hexols such as sorbitol, dipentaerythritol and the like; and octols such as sucrose and the like.
The modifying agent may also include an epoxy compound (a3) of the polyhydric polyol as obtained by reacting the polyhydric polyol (a3) with epichlorohydrin.
The modifying agent may further include propylene oxide-modified bisphenol A diglycidyl, ethylene glycol oxide-modified bisphenol A diglycidyl and the like.
The cyclic ester compound (a4) used as the modifying agent may include a compound represented by the following formula (1) :
R-CH- (CH2)n-C=O (1) where R represents H or CH3 and n represents 3 to 6, and specifically may include, for example, S-vale.rolactone, s-caprolactone, ~-enolactone, rI-caprolactone, y-valerolactone, 6-caprolactone, s-enolactone, ~-caprolactone and the like.
Of these, s-caprolactone is particularly preferable.
In the addition reaction of the cyclic ester compound (a4) with the epoxy resin (al), ring opening of the cyclic ester compound (a4) represented by the formula (1) may be followed by reacting with a secondary hydroxyl group in the epoxy resin, imparting a primary hydroxyl group and.resulting in that a methylene chain moiety due to lactone may impart plasticity to the epoxy resin.
An amount of the modifying agent to be reacted with the epoxy resin (al), i.e. an amount of at least one modifying agent selected from the group consisting of the polyhydric polyol (a2), epoxy compound (a3) of the polyhydric polyol and cyclic ester compound (a4) may not be particularly limited, but may preferably be such that at least one modifying agent selected from the group consisting of the polyhydric polyol (a2), epoxy compound (a3) of the polyhydric polyol and cyclic ester compound (a4) may be in the range of 5 to 40% by weight, preferably 10 to 35% by weight.
The polyphenol compound (a5) may include, for example, phenol, cresols, p-octylphenol, nonylphenol, bisphenolpropane, bisphenolmethane, resorcinol, pyrocatechol, hydroquinone, P-tert-butylphenol, bisphenolsulfone, bisphenol ether, p-phenylphenols, bis(4-hydroxyphenyl)-2,2-propane, bis(4-hydroxyphenyl)-1,1-ethane, bis(4-hydroxyphenyl)-1,1-isobutane, 4,4'-dihydroxybenzophenone, bis(4-hydroxy-3-t-butylphenyl)-2,2-propane, bis(2-hydroxynaphthy.l)methane, 1,5-dihydroxy-naphthalene and the like. These may be used alone or in combination.
The amine-added epoxy resin (A) may be prepared as.
follows.
A reactor is charged with the epoxy resin (al), at least one modifying agent selected from the group consisting of the polyhydric polyol (a2), epoxy compound (a3) of the polyhydric polyol and cyclic ester compound (a4), and the polyphenol compound (a5), followed by adding an organic solvent, a basic amino compound catalyst such as dimethylbenzylamine, tributylamine, triethylamine and the like, and tetraethylammonium bromide, tetrabutylammonium bromide, tetraethylammonium hydroxide, triphenylethylphosphonium iodide and the like to obtain a modified epoxy resin.
The preparation of the modified epoxy resin may be carried out by adding the catalyst in an amount of 1 to 10,000 ppm based on a total solid content of the epoxy resin (al), at least one modifying agent selected from the group consisting of the polyhydric polyol (a2), epoxy compound (a3) of the polyhydric polyol and cyclic ester compound (a4) and polyphenol compound (a5), followed by heating at a temperature of about 50 C to about 200 C for about 30 minutes to about 10 hours.
Thereafter, the amino group-containing compound (a6) is added to the modified epoxy resin to obtain an amine-added epoxy resin (A).
The amino group-containing compound (a6) to react with the modified epoxy resin is a cationic properties-imparting component which introduces amino group into the epoxy resin and cationizes the epoxy resin, and may include one having at least one active hydrogen to react with the epoxy resin.
The amino group-containing compound (a6) may include, for example, mono- or di-alkylamine such as monomethylamine, dimethylamine, monoethylamine, diethylamine, monoisopropylamine, diisopropylamine, monobutylamine, dibutylamine and the like; alkanolamine such as monoethanolamine, diethanolamine, mono (2-hydroxypropyl) amine, di (2-hydroxypropyl) amine, tri (2-hydroxypropyl) amine, monomethylaminoethanol, monoethylaminoethanol and the like;
alkylene polyamine such as ethylenediamine, propylenediamine, butylenediamine, hexamethylenediamine, tetraethylenepentamine, pentaethylenehexamine, diethylaminopropylamine, diethylenetriamine, triethylenetetramine and the like, and a ketiminized product of these polyamines; an alkyleneimine such as ethyleneimine, propyleneimine and the like; a cyclic amine such as piperazine, morpholine, pyrazine and the like, and the like.
The amino group-containing compound (a6) may be reacted with the epoxy group of the modified epoxy resin under the conditions of a temperature in the range of about 30 C to about 150 C for 30 minutes to 150 minutes. Preferably, a compound containing a primary amine or N-hydroxyalkyl secondary amine of the above amines may be reacted with ketone, aldehyde, or carboxylic acid at 100 C to 230 C to be modified to aldimine, ketimine, oxazoline or imidazoline, followed by reacting with the epoxy group of the modified epoxy resin at about 80 C to about 200 C for about one hour to about 5 hours.
An amount of the amino group-containing compound (a6) may preferably be such that an amine value of the amine-added epoxy resin (A) may be in the range of 20 to.80 mg KOH/g, preferably 25 to 70 mg KOH/g. The amine-added epoxy resin (A) may preferably have a weight average molecular weight in the range of about 1,000 to about 10,000.
The amine-added epoxy resin (A) obtained as above has a glass transition temperature in the range of -10 C to 60 C.
The glass transition temperature in the present invention is a value measured by use of a Differential Thermal Analyzer, or measured by use of DSC-5200 (trade name, marketed by Seiko Instruments Inc., Differential Scanning Calorimeter) at a temperature-raising speed of 10 C/min.
Blocked Polyisocyanate Curing Agent (B) The blocked polyisocyanate curing agent (B) used as the curing agent in the present invention may be obtained by reacting at least one polyisocyanate compound (bl) selected from the group consisting of an aromatic polyisocyanate compound and an alicyclic polyisocyanate compound with at least one blocking agent (b2) selected from the group consisting of an oxime compound, aliphatic alcohols, aromatic alkyl alcohols and ether alcohols.
The aromatic diisocyanate may include, for example, 1,3- or 1,4-phenylene diisocyanate, 2,4- or 2,6-tolylene diisocyanate (TDI), crude TDI, 2,4'-and/or 4,4'-diphenylmethane diisocyanate (MDI), 4,4'-diisocyanatobiphenyl, 3,3'-dimethyl-4,4'-diisocyanatobisphenyl, 3,3'-dimethyl-4,4'-diisocyanatodiphenylmethane, crude MDI, 1,5-naphthylene diisocyanate, 4,4',4"-triphenylmethanetriisocyanate, m- or p-isocyanatophenylsulfonyl isocyanate and the like.
Of these, diphenylmethane-2,4'-diisocyanate, diphenylmethane-4,4'-diisocyanate (MDI) and crude MDI are preferable.
The crude MDI is a mixture mainly containing diphenylmethane-4,4'-diisocyanate, diphenylmethane-2,4'-diisocyanate and polymethylene polyphenyl polyisocyanate, and TM
may include trade names, for example, Cosmonate M-50, M-200, M-100, M-300 etc. (trade names, all marketed by Mitsui Chemicals, Inc.); SumidurM44V10, 44V20, 44V40, etc. (trade names, all marketed by Sumika Bayel Urethane Co., Ltd.);
The aromatic diisocyanate may include, for example, 1,3- or 1,4-phenylene diisocyanate, 2,4- or 2,6-tolylene diisocyanate (TDI), crude TDI, 2,4'-and/or 4,4'-diphenylmethane diisocyanate (MDI), 4,4'-diisocyanatobiphenyl, 3,3'-dimethyl-4,4'-diisocyanatobisphenyl, 3,3'-dimethyl-4,4'-diisocyanatodiphenylmethane, crude MDI, 1,5-naphthylene diisocyanate, 4,4',4"-triphenylmethanetriisocyanate, m- or p-isocyanatophenylsulfonyl isocyanate and the like.
Of these, diphenylmethane-2,4'-diisocyanate, diphenylmethane-4,4'-diisocyanate (MDI) and crude MDI are preferable.
The crude MDI is a mixture mainly containing diphenylmethane-4,4'-diisocyanate, diphenylmethane-2,4'-diisocyanate and polymethylene polyphenyl polyisocyanate, and TM
may include trade names, for example, Cosmonate M-50, M-200, M-100, M-300 etc. (trade names, all marketed by Mitsui Chemicals, Inc.); SumidurM44V10, 44V20, 44V40, etc. (trade names, all marketed by Sumika Bayel Urethane Co., Ltd.);
TM
Lupranate M-12, M-12S, M-20, M-20S, etc. (trade names, all TM
marketed by BASF AG. Germany); Mondur MR (LIGHT), etc. (trade name, marketed by Bayer Ltd.), and the like.
The alicyclic polyisocyanate compound may include, for example, isophorone diisocyanate (IPD), dicyclohexylmethane-4, 4 ' -diisocyanate (hydrogenated MDI), cyclohexylene diisocyanate, methylcyclohexylene diisocyanate (hydrogenated TDI), bi.s(2-isocyanatoethyl)-4-cyclohexene-1,2-dicarboxylate, 2,5- and/or 2,6-norbornene diisocyanate and the like.
In addition, the modified product of the above polyisocyanate compound may include a modified product of polyisocyanate, for example, a modified MDI such as urethane-modified MDI, carbodiimide-modified MDI and trihydrocarbicphosphate-modified MDI, urethane-modified TDI, biuret-modified HDI, isocyanurate-modified HDI, isocyanurate-modified IPDI and the like; mixtures thereof, for example, a mixture of modified MDI and urethane-modified TDI as isocyanate group-containing prepolymer.
The blocking agent is such that addition of the blocking agent to an isocyanate group in the polyisocyanate compound blocks the isocyanate group, and a resulting blocked polyisocyanate compound is stable at normal temperatures, but heating at a temperature in the range of about 100 C to 200 C, preferably 120 C to 150 C may dissociate the blocking agent to regenerate a free isocyanate group. The smaller the molecular weight of the dissociated blocking agent the less the resulting heating loss, resulting in reducing gum and soot in a drying oven.
The blocking agent may include, for example, an oxime compound such as methyl ethyl ketoxime, cyclohexanone oxime and the like; aliphatic alcohols such as n-butanol, 2-ethylhexanol and the like; aromatic alkyl alcohols such as phenylcarbinol, methylphenylcarbinol and the like; ether alcohols such as ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether and the like; a lactam compound such as c-caprolactam, y-butyrolactam and the like; a phenol compound such as phenol, p-t-butylphenol, cresol and the like; a low molecular weight amide compound such as n-methylacetamide, n-ethylacetamide, n-methylpropionamide, n-methylformamide and the like; and the like.
Of these, the oxime compound, aliphatic alcohols, aromatic alkyl alcohols and ether alcohols are preferable from the standpoints of throwing power and electrodeposition coating suitability for the galvanized sheet in the cationic electrodeposition coating composition of the present invention.
A mixing amount of the blocking agent is so as to be reacted at a ratio of 1:1 to 1:1.3 to NCO group of the polyisocyanate. A ratio more than 1.3 may reduce anti-corrosive properties of the coating film due to a remaining blocking agent. A ratio less than 1.0 may reduce stability of the coating composition due to a remaining NCO group.
The blocked polyisocyanate curing agent (B) of the _ 17 -cationic electrodeposition coating composition used in the film-forming method of the present invention may preferably be obtained by reacting at least one polyisocyanate compound (b1) selected from the group consisting of an aromatic polyisocyanate compound and an alicyclic polyisocyanate compound with at least one blocking agent (b2) selected from the group consisting of an oxime compound, aliphatic alcohols, aromatic alkyl alcohols and ether alcohols, so as to have a glass transition temperature in the range of 45 to 65 C.
The cationic electrodeposition coating composition contain the amine-added epoxy resin (A) and the blocked polyisocyanate curing agent as the essential components, and may optionally contain an organotin compound and a coating composition additive such as a color pigment, extender pigment, anti-corrosive pigment, organic solvent, water, neutralizing agent, pigment dispersant, coating film surface controlling agent and the like.
The organotin compound may promote dissociation of the blocking agent used in the blocked polyisocyanate curing agent (B) and functions as a curing catalyst, and may include, for example, an organotin oxide such as dibutyltin oxide, dioctyltin oxide and the like; aliphatic or aromatic carboxylic acid salt of dialkyltin, for example, dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin diacetate, dioctyltin dibenzoate, dibutyltin dibenzoate and the like.
Of these dialkyltin aromatic carboxylic acid salt is preferable from the standpoint of low temperature curing properties.
A mixing amount of the organotin compound in the .cationic coating composition of the present invention may not particularly be limited and may widely be varied depending on performances required for the coating composition, but is usually in the range of 0 (zero) to 8 parts by weight, preferably 0.05 to 5 parts by weight per 100 parts by weight of a resin solid content in the coating composition.
The cationic electrodeposition coating composition may be coated onto the surface of a predetermined substrate by an electrodeposition coating. The electrodeposition coating may be carried out by energizing under the conditions of a solid content concentration of about 5 to 40% by weight by diluting with deionized water, a pH in the range of 5.0 to 9.0, an electrodeposition coating bath temperature of 15 to 35 C, a loading voltage of 100 to 400 V, coating substrate as a cathode, energizing time of 30 seconds to 3 minutes, anode to cathode area ratio (A/C) 8/1 to 1/8, and distance between anode and cathode 10 cm to 300 cm.
An electrodeposition coating film thickness may not particularly be limited, but may generally be in the range of to 40 m, preferably 15 to 30 m. A heat curing temperature is generally in the range of about 100 to about 200 C, preferably about 120 C to about 170 C.
The coating film-forming method, which method comprises coating the cationic electrodeposition coating composition containing the specified base resin and the specified curing agent, makes it easily possible to form a coating film having an electrical resistance in the range of 400 kS2=cm2 to 850 kS2 = cm2, preferably 480 kS2 = cm2 to 650 kS2 cm2 one minute after starting of energizing on the electrodeposition coating, and makes it possible to obtain a cured electrodeposition coating film having high throwing power, and good properties in electrodeposition coating suitability for the galvanized sheet with sufficient film thickness on a pouched area and inner plate area in a short period of time of 90 to 150 seconds on electrodeposition coating.
The present invention can provide the following particular effects.
The coating film-forming method, which comprises coating a cationic electrodeposition coating composition containing a specified base resin preferably having a specified glass transition temperature and a specified curing agent preferably having a specified glass transition temperature onto a substrate and heat-curing, in the present invention makes it possible to obtain a coated product with a cured electrodeposition coating film having high throwing power, and good properties in electrodeposition coating suitability for the galvanized sheet and anti-corrosive properties with sufficient film thickness on a pouched area and inner plate area in a short period of time of 90 to 150 seconds on electrodeposition coating.
Further, the use of such a cationic electrodeposition coating composition as the above cationic electrodeposition coating composition that a resulting coating film one minute after starting of energizing on the electrodeposition coating has an electrical resistance in the range of 400 kSZ=cm2 to 850 kf2=cm2, makes it possible to easily obtain a cured electrodeposition coating film showing both high throwing power and electrodeposition coating suitability for the galvanized sheet.
Reasons why the above effects may be provided, may be guessed as follows.
An emulsion as a component constituting the cationic electrodeposition coating composition may be such that a core moiety of the emulsion is composed of the curing agent and a shell moiety is composed of the base resin, and the amino group of the base resin is neutralized to form an emulsion particle. Thus, it is guessed that a combination of the specified base resin and the specified curing agent, and preferably the glass transition temperature in the predetermined range may provide such effects that (1) formation of a coating film having a sufficient electrical resistance in a short period of time after starting energizing results in that a current consumed in the outer plate may also be consumed for forming a coating film onto the inner plate, and in that the throwing power may be improved, and that (2) hardness resisting to sparks on energizing due to the curing agent in the core moiety makes breakage of the coating film difficult, and on the other hand, even if gas holes should develop, softness of the shell moiety may repair pinholes, resulting in improving electrodeposition coating suitability for the galvanized sheet.
The film-forming method of the present invention makes possible an electrodeposition coating in a short period of time, resulting in improvement in productivity, saving of the coating line space and saving of energy. In addition thereto, the resulting high throwing power may result in that the pouch area and inner plate shows good anti-corrosive properties, that the galvanized sheet of the outer plate is free of pinholes, and that a coated product showing good finish appearance can be obtained.
Example The present invention is explained more in detail by reference to Examples, and should not be limited thereto only.
In Examples, "o" and "part" represent "% by weight" and "part by weight" respectively.
Preparation Example of Base Resin No. 1 Preparation Example 1 A reactor equipped with 'a thermometer, stirrer, refl_ux condenser and nitrogen gas inlet was charged with 525 parts of propylene oxide-modified bisphenol A diglycidyl ether (Note 1), 342 parts of bisphenol A, and 36 parts of a 80%
effective component methyl isobutyl ketone solution of a ketimine between monoethanolamine and methyl isobutyl ketone while introducing nitrogen gas, followed by reacting at 160 C
until the epoxy group disappear, adding 665 parts of bisphenol diglycidyl ether having an epoxy equivalent of about 190 and 232 parts of the 80% effective component methyl isobutyl ketone solut:ion of a ketimine between monoethanolamine and methyl isobutyl ketone, reacting at 140 C until an epoxy group content reaches 0.27 m mol/g to obtain an epoxy resin solution having a number average molecular weight of about 1,500, diluting and cooling down to 100 C with 365 parts of ethylene glycol monobutyl ether, adding 167 parts of an 80% effective component methyl isobutyl ketone solution of a diketimine between diethylenetriamine and methyl isobutyl ketone, reacting at 100 C until increase of viscosity stops to obtain a base resin No. 1 having a solid content of 80% and a glass transition temperature of 23 C.
(Note 1): propylene oxide-modified bisphenol A diglycidyl TM
ether (trade name, Glyciale BPP-350, marketed by Sanyo Chemical Industries, Ltd., epoxy equivalent about 340).
Preparation Example 2 (Preparation of Base Resin No. 2) The same reactor as in Preparation Example 1 was charged with 450 parts of ethylene oxide-modified bisphenol A
diglycidyl ether (Note 2) having an epoxy equivalent of about 300, 342 parts of bisphenol A, and 36 parts of a 80%
effective component methyl isobutyl ketone solution of a ketimine between monoethanolamine and methyl isobutyl ketone while introducing nitrogen gas, followed by reacting at 160 C
until the epoxy group disappears, adding 665 parts of bisphenol A diglycidyl ether having an epoxy equivalent of about 190 and 232 parts of a 80% effective component methyl isobutyl ketone soluti.on of a ketimine between monoethanolamine and methyl isobutyl ketone, reacting at 140 C until an epoxy group content reaches 0.29 m mol/g to obtain an epoxy resin solution having a number average molecular weight of about 1,500, diluting and cooling down to 100 C with 350 parts of ethylene glycol monobutyl ether, adding 167 parts of a 80% effective component methyl isobutyl ketone solution of a diketimine between diethylenetriamine and methyl isobutyl ketone, and reacting at 100 C until increase of viscosity stops to obtain a base resin No. 2 having a solid content of 80% and a glass transition temperature of 28 C.
(Note 2): ethylene oxide-modified bisphenol A glycidyl TM
ether (Glyciale BPE-300, trade name, marketed by Sanyo Chemical Industries, Ltd., epoxy equivalent about 300).
Preparation Example 3 (Preparation of Base Resin No. 3) A flask equipped with a stirrer, thermometer, nitrogen gas inlet and reflux condenser was charged with 518 parts of epoxy resin obtained by reaction of bisphenol A with epichiorohydrin and having a number average molecular weight of 370 and an epoxy equivalent of 185, followed by adding 57 parts of bisphenol A and 0.2 part of dimethylbenzylamine, reacting at 120 C until the epoxy equivalent reaches 250, adding 213 parts of s-caprolactone and 0.03 part of tetrabutoxytitanium, heating up to 170 C, sampling with time while keeping at that temperature, examiriing an amount of unreacted s-caprolactone by an infrared absorption spectral measurement, until a degree of conversiori reaches 98% or more, adding 148 parts of bisphenol A and 0.4 part of dimethylbenzylamine, reacting at 130 C uritil the epoxy equivalent reaches 936, adding 257.4 parts of methyl isobutyl ketone, 25.6 parts of diethylamine and 68.3 parts of diethanolamine, reacting at 80 C for 2 hours, and diluting with methyl ethyl ketone to obtain a base resin No. 3 having a solid content of 80% and a glass transition temperature of 38 C.
Preparation Example 4 (Preparation of Base Resin No. 4) A reactor was charged with 222 parts of isophorone diisocyanate, followed by slowly droppinq 113.1 parts of methyl ethyl ketoxime while keeping a reaction temperature at 30 to 40 C by an external cooling to obtain a partly blocked polyisocyanate.
Next, 83.7 parts of the above partly blocked polyisocyanate was mixed with 500 parts of the base resin No.
3 obtained in Preparation Example 3, followed by reacting at 100 C under a nitrogen stream until absorption of isocyanate group disappear by an infrared absorptiori spectral measurement, and diluting with diethylene glycol monobutyl ether to obtain a base resin No. 4 havinq a solid content of 80% and a glass transition temperature of: 44 C.
_ 25 -Preparation Example 5 (Preparation of Base Resin No. 5) A mixture of lOlOg of Epikote 828EL (trade name, marketed by Japan Epoxy Resin Co., Ltd., epoxy resin), 390g of bisphenol A and 0.2g of dimethylbenzyl.amine was reacted at 130 C so as to be an epoxy equivalent of 800, followed by adding 160g of diethanolamine and 65g of a ketiminized product of diethylenetriamine, reacting at 120 C for 4 hours, adding 355g of butylcellosolve to obtain a base resin No. 5 having an amine value of 67 mg KOH/g, a solid content of 80%
and a glass transition temperature of 90 'C.
Preparation Example 6 (Preparation of Curing Agent No. 1) A reactor was charged with 270 parts of Cosmonate M-200 (Note 3) and 25 parts of methyl isobutyl ketone, followed by heating up to 70 C, slowly adding 15 parts of 2,2-dimethylolbutyric acid, dropping 118 parts of ethylene glycol monobutyl ether, reacting at 70 C for one hour, cooling down to 60 C, adding 152 parts of propylene glycol, sampling with time while keeping at that temperature ar.Ld confirming that absorption of unreacted isocyanate group disappeared by an infrared absorption spectral measurement to obtain a curing agent No. 1 having a solid content of 80% and a glass transition temperature of 5 C.
(Note 3) Cosmonate M-200: trade name, marketed by Mitsui Chemicals, Inc., crude MDI.
Preparation Example 7 (Preparation of Curing Agent No. 2) A reactor was charged with 174 parts of tolylene diisocyanate, followed by heating up to 70 C, slowly adding 15 parts of 2,2- dimethylolbutyric acid, dropping 118 parts of ethylene glycol monobutyl ether, reacting at 70 C for one hour, cooling down to 60 C, adding 152 parts of propylene glycol, sampling with time while keeping at that temperature and confirming that absorption of unreacted isocyanate group disappeared by an infrared absorption spectral measurement to obtain a curing agent No. 2 having a solid content of 80% and a glass transition temperature of 10 C.
Preparation Example 8 (Preparation of Curing Agent No. 3) A reactor was charged with 222 parts of isophorone diisocyanate and 99 parts of methyl isobu.tyl ketone, followed by heating up to 50 C, slowly adding 174 parts of methyl ethyl ketoxime, heating up to 60 C, sampling with time while keeping at that temperature and confirming that absorption of unreacted isocyanate group disappeared by an infrared absorption spectral measurement, and controlling a solid content with an organic solvent to obtain a curing agent No.
3 having a solid content of 80% and a glass transition temperature of 8 C.
Preparation Example 9 (Preparation of Curing Agent No. 4) A reactor was charged with 50 parts of hexamethylene diisocyanate, followed by dropping 30 parts of methyl ketoxime and 10 parts of trimethylolpropane at 40 to 60 C, heating at 80 C for one hour, sampling wi_th time while keeping at that temperature and confirmirig that absorption of unreacted isocyanate group disappeared by an infrared absorption spectral measurement, and controlling a solid content with an organic solvent to obtain a curing agent No.
4 having a solid content of 80% and a glass transition temperature of -19 C.
Preparation Examples of Emulsion Nos. 1-9 (EM Nos. 1-9) for Use in Cationic Electrodeposition Coatinq Compositions Preparation Example 10 (Preparation of EM No. 1) A mixture of 87.5 parts (resin solid content 70 parts) of the base resin No. 1, 37.5 parts (resin solid content 30 parts) of the curing agent No. 1 and 13 parts of 10% acet:ic acid was uniformly stirred, followed by clropping deionized water while strongly stirring over about 15 minutes to obtain a EM No. 1 having a solid content of 34% as an emulsion for use in a cationic electrodeposition coating composition.
Preparation Examples 11-18 (Preparation of EM No. 2 to EM No. 9) Preparation Example 10 was duplicated except for respective formulations as shown in Table 1 to obtain EM No.
2 to No. 9 having a solid content of 34% as ari emulsion for use in a cationic electrodeposition coating composition respectively. In Table 1, the solid content is parenthesized.
Ln ^ LO
00 p m lP c' O
r r r M ~-I
Z ~
M
00 Ln LO
r . . p . p M lfl V' O
+"~ z ['~ r r m r-i LONCD
OO M
r Ln ^ ~ ^ ^
l0 . p . p m 0 ~N O ~ o rr rM ~ LO 'o p N
ul Q0 `n , `n ~o ~r o r-I td) = o = M m tn 61 0 Q.., s-4 Z .r r r ~ 00 m ~
n un ._ LO ^ ~o ~r o = O = p M LO Ol O
O 1-1 Z ~ Cv M M `- r-I N~-1 JP
~-I
(d w LO tn -, lO ~N O
C2~ CM = = m LO 61 O
y~..~ ~- Z ~ M M N r-I
a m Ln Ln N = O = O "o 'r z r r r m i ~
H
m m ~
N t,n .,,un ^ .-..
IH O o co ~O ~r o I
r-1 r r r m rl LO Ol O
pO M..~ r-f N 1-1 H Ln U) = O . p M V' O
~--1 = t~ r M ri tt) 61 O
pO ..~ m.~ ,-i Nr-1 olo o'P op olo dP ,-t da N oto M o'p ~ oP
p o 0 0 o 0 0 (D o ri Oo N ao C`') oo q< oJ LO oo = pJ = O7 . p7 = 00 . ..
~ +) = .0 ' 41 = -W z J-) z 1-) z -P Z 4J -ri U) O 0 O r. O $:~ O z O 9 s:: r~ 0 z U 13 z 41 z N z Q) '.~ N Z 0 -P N +J 4) 4J N -P 4) M tlf .43 l-) 13 1J +-) ~ 1.1 ~ +) 4J 1J $
-rl O -ri O -.-I O -i O -r-I O tT O m O lT 0 CT O -.I T3 ~n tn U 0 U ta U zn U rq U rZ4 0 d, 0 re 0 r:~ 0 d-J 4) ~
~ a a a a a~ 0 ~s rn zs ~ ~s a)ro ~~ 0 0 =r I - i -~ - 1 -r-I , -r-I r -r-I ~ -~-1 Z -=-I r r ~1 4J r i N-1 N-0 N r 1 N rl -r-I =-1 -.-1 '-i -r-I r-1 -r-I rA 0 r-1 rn O rn O m O u2 O m O s.~ O sa O N O $-a O aP -r1 0 ~ (t m rtf rn rtl v) ttt m rts u) ;:3 m 0 Q ;~ m :~ m o a) r:l PQ pqPQm U~- U= ~ A W
cP
m O
4-) r-1 r0 RS
~4 Ga Preparation of Pigment-Dispersed Paste Preparation Example 19 A mixture of 5.83 parts (solid content 3.5 parts) of 60% solid content quaternary ammonium salt type epoxy resin, 14.5 parts of titanium oxide, 7.0 parts of purified clay, 1.0 part of bismuth hydroxide, 1.0 part of organotin, 0.4 part of carbon black and 20.1 parts of deionized water was dispersed in a ball mill for 20 hours, followed by taking out to obtain a pigment-dispersed paste (solid content 27.4 parts) having a solid content of 55%.
Example 1 To 294 parts (solid content 100 parts) of the emulsion No. 1 were added 49.8 parts (solid conterit 27.4 parts) of the pigment-dispersed paste No. 1 and 293.2 parts of deionized water to prepare a 20% solid content cati_onic electrodeposition coating composition No. 1 (solid content 127.4 parts).
Examples 2-6 Example 1 was duplicated except that formulations shown in Table 2 were used respectively to obtain cationic electrodeposition coating compositions No. 2 to No. 6.
Comparative Examples 1-3 Example 1 was duplicated except that formulations shown in Table 3 were used respectively to obtain cationic electrodeposition coating compositions No. 7 to No. 9.
Coating Test Respective cationic electrodeposition coating compositions obtained in the above Examples and Comparative Examples were subjected to cationic electrodeposition coating onto a cold-rolled steel sheet or a galvanized sheet (0.8 x 150 x 70 mm, chemically treated with Palbond #3020, trade name, marketed by Nippon Parkerizing Co., Ltd., zinc phosphate treating agent, respectively), followed by heat curing to prepare coating test panels respectively.
Respective coating test panels were subjected to tests of throwing power, electrodeposition coating suitability for a galvanized sheet, and anti-corrosive properties as follows.
Coating composition formulations, coating film properties and test results for cationic electrodepositions No. 1 to No. 6 (Examples) are shown in Table 2, in which Tg represents a glass transition temperature.
~~ rn Q; o~ m o -~ r~r 0 O 0 O N d N ~ ~
z ~'1 ~ . 6~1 ~ 6Ml M ~ LO r- o O-I ~ o a N N O ~ l0 ~O
z m t` o to~= = cn m m ~ 0 O O
4) O N l0 l0 ~ z ~C M l O
M
w M = a, a, a, m d= ,a ' O i ~ O O
O N N l0 l9 z N
"'t' M C- (D N O N Ol N ~ 110 H ~ V' 0 c-1 CD to O 0 ~
~r ~ m r o ~= rn a; rn m O
N N ~ H ~ ~ ~ O uO O O
O ~, l0 z >~
o ~ I ~, ~4 v 0 v v 0 44 "' ~ ~ ~ ~ 0 ~ i-=~ v w ~ ~'t ~ >1 0 0 0 0 O 0 w tf) tf) t!~ tt) H dD =1~ (UG f~d ~ ~ ~
o .u ~ -u 0 ~ ~ d ~~I s~ G3 ~ ! ," ~ f~" U ri N ~ \ Q \ 4 ( ) -4 ts tn :T m m 0) ~3 ro U, ro rd ro rd (d b 0 O u =~ =~
~ ~ ~
o I i '-i H H tA ~ ^ ~ ^ N
U s-I t4 z4 Sa s-I S-I 0 44 4-I {'=., Lf7 U-) 4J
~J Q) 04 O O - = 1 - { O
U U U U U U N ~N ~ c ~~ ~~
~ ~ ~ ctl 0 U~ U) O 0 N 0 O
~ U U U U U U 0 , ~1 :=r-t =V 0 z .i.) U z u~
0 (Y) ao ao M r) 10 0 +-) S4 z 0 -z U N N m -W N N (1) U) vI Rf O 1=> 0 dj yJ
. ~+ C+ Cr t' ~"i f.' Ga ~1 (1) U) vl u) S.1 -!-) U) 1~i 1~ (1) ~
0 -i -I =i =~ -'-! -'-1 () 4-) d) N -=-I 4 0) =ri X! 04 -,1 m m U3 N m m tz, ~s U s4 ~I m m to ui o 4-, 4) a) (t) 0) 4) 4) 02 3 =r1 ~ N 0 0 0 0 ya -4 $4 1-4 ~4 s4 ~4 s~ .,1 0 0-I 4-) ~. 0410 P.
04v a, to rO -0 0=rl ro w a) u) v a) O r-1 N CV (L) M N v N U - ) Q) l 0 N I N=H J-> U (V bi T3 N tT 'LS tv uI v1 to u) tq u2 tJ N a! =rl rl f~' O=~-I ~G' 0-~-= rtS = Ri = ~S = r6 = rts = cC F-: =ri rtt va 14 N =11 14 q =ri ur~=~
a Q o si 0 s3 0 ~ o..Q o,.Q v0 0 0 -P +) 3 +-) rts 3 rts ul U z~ z a+ z is z tr Z tT z 0 on ~ m~~.'. s ~ a) ~~-1 s a aUi .1 U
U ~ W E H R. TS N U N~ 4-) 0) ~S 4-) N t7) ~ U
N Ul _ U
0 .~A > ~ 4J
~
= 4-) CD
O O
~p '- -N ul S-I O Ln 1) O
.,~ =rl ~ 4) O) N r-I N
~ O ~ O 0 04 ~ r:; l-4f p, 7 4=) +J .l-) 1) t.7) 0 O > 0 w N
~ 0 4.3 b~~ ~ Mo ~
(00 0 4) O z N O
[-4 U W u1 U W u) U
Coating composition formulations, coating film properties and test results for cationic electrodeposition No.
7 to No. 9 (Comparative Examples) are shown in Table 3, in which Tg represents a glass transition temperature.
(31 X a ,~ M N N lM 0 ~ rl co tn X l0 Z
co r O -10 N = ~ = (3) M ~ r ~ X r=i ~ l0 X O
O N N ~ r õ z ~
~4 (0 a r m ~ -+ = N ~ N ~ M ~ ,. '~ X 1-4 ~o X O
z ~
N
~ 0 W
>1 >1 0 0 ,-i =~ w u 0 , q w -i =.i ~ .u 11 o ~.. =~~-1 Uco ro p ro UM ap . .
~
O ~ ~'i ~ U =rl N 44 44 44 W
v y~.) m ~+ b~ b~ u ;-4 4i ~ a a~i { rtl ~ ~ 0 O s=a m c~r1 C~7 ~ u~1 ai (\~j i ul =rl U N
0 Cn I'F iT d-) tA V7 m tT
0 S-I ~4 ~4 0 4=1 4-I ~..r" f" tP) U ~ ~3 ::I a) fL O O - ~ =rl - =ri ~ M
U 0 U d.) a) ~N l) 4) v' -tJ 4) 0 m "0 (L) m rts v (o +.) z ~s 0 Uizi a) 0 o v 0 0--o 0 0 .u ~~ o U z o 0 z ~ o a o CS U ~ u z z ~
~ (7) rn rn U) 4) V1 ~ ~-- o=u - 0 J-) =~
0 7N 74 -I =H +3 =r-i (1) ,1 N
0 La 6) Q1 vl cn 64 4-1 (D S 4 1-) 4) s4 r=1 ri r4 N+-) N 41 =rl ..G (1) r-i .9~ N
0 Vl tA ul " Id U S-1 S-I 0 ul $ ul +/1 =,-.1 N 4) 4) m =rl C3 0) 0 0 0 0 p }) S-I s4 Sa =rl S: O r-I 4-J C14 04 T3 S]. Q ZS S i rl '0 tJ o-ri r6 vw N N N U) p., t/1 r N 00 N 61 a) ! N =.-1 -t-) U (d o1 0 (o uI v! 1) N 4-) =.=I =.4 N O= 1 0 O=rl N
= stS = r0 = R3 L"~ -.-I t~ U? S-I N~+' =ri S=1 C~' =r-1 S4 0 J
~ 0 Q 0=0 0=0 N 0 U O.u 4. U 4-) (3 -u rtS =,-f .a z.. z.. z.. ~ 0 a U~ 0 U> 0 () 5 tn 0 rn rs ~ -.-1 on ~ a~ a C s4 a) r-i s4 a) r-+ b 4 . ~ i J D -cV UU N~ x ~ N b+ ~ N~bl U O
U) > > -rt 0 l.s CD o (D 4-) U =11 ~a o LO u7 0 =~ 4-)ul N04 41 N c-1 N
0 U) a 0 , u a.' a v o +
~ 53 u ~ ~ ~
r~ ~u w ~^ 0 ~~ 0 w ~ ~ =~~ ~ ~~i~ ~
(u .~ M a -4 r. =14 0 .u P 04-) s4 0 4.3 fd U rt! N U rd tl) U af E- U W~n U W v~i U 0 (Note 4) Throwing power: A jig for a four sheets box throwing power test method was prepared by use of the above chemically treated cold-rolled steel sheet as shown in Fig. 1, followed by carrying out an electrodeposition coating under the conditions of a bath temperature of 28 C, coating voltage as shown in Tables, an energizing time of` 90 seconds or 150 seconds according to a wiring diagram as shown in Fig. 2, heat curing at 170 C for 20 minutes, and evaluating throwing power from a film thickness ( m) on the surface (A) as an outer plate, film thickness ( m) on the surface (G) as an inner plate and a ratio (%) of film thickness ( m) on the surface (G)/film thickness ( m.) on the surface (A).
(Note 5) Electrodeposition Coating Suitability for Galvanized Sheet: The chemically treated galvanized sheet was dipped in an electrodeposition coating bath as a cathode, followed by carrying out an electrodeposition coating under the conditions of a bath temperature of 28 C, a coating voltage as shown in Tables and energizing time of 90 seconds or 150 seconds, heat curing at 170 C for 20 minutes, and measuring a number of pinholes within 10 x 10 cm of the test panel.
0: No pinholes developed with good finished properties.
0: 3 to 5 pinholes developed.
X 10 or more pinholes developed.
(Note 6) Anti-corrosive properties: Cross cuts were formed by use of a knife on the surfaces of a test panel prepared by subjecting a chemically treated cold-rolled steel sheet to an electrodeposition coating so as to reach the coating substrate, followed by subjecting to a 840 hours salt water spray test in accordance with JIS Z-2371, and evaluating development of rust from the cross cut, and width of blisters as follows.
maximum width of rust and blisters less than 2 mm (one side).
0: maximum width of rust and blisters less than 3 mm (one side).
A: maximum width of rust and blisters 3 mm or more and less than 4 mm from cut (one side).
X: maximum width of rust and blisters 4 mm or more from cut (one side).
Lupranate M-12, M-12S, M-20, M-20S, etc. (trade names, all TM
marketed by BASF AG. Germany); Mondur MR (LIGHT), etc. (trade name, marketed by Bayer Ltd.), and the like.
The alicyclic polyisocyanate compound may include, for example, isophorone diisocyanate (IPD), dicyclohexylmethane-4, 4 ' -diisocyanate (hydrogenated MDI), cyclohexylene diisocyanate, methylcyclohexylene diisocyanate (hydrogenated TDI), bi.s(2-isocyanatoethyl)-4-cyclohexene-1,2-dicarboxylate, 2,5- and/or 2,6-norbornene diisocyanate and the like.
In addition, the modified product of the above polyisocyanate compound may include a modified product of polyisocyanate, for example, a modified MDI such as urethane-modified MDI, carbodiimide-modified MDI and trihydrocarbicphosphate-modified MDI, urethane-modified TDI, biuret-modified HDI, isocyanurate-modified HDI, isocyanurate-modified IPDI and the like; mixtures thereof, for example, a mixture of modified MDI and urethane-modified TDI as isocyanate group-containing prepolymer.
The blocking agent is such that addition of the blocking agent to an isocyanate group in the polyisocyanate compound blocks the isocyanate group, and a resulting blocked polyisocyanate compound is stable at normal temperatures, but heating at a temperature in the range of about 100 C to 200 C, preferably 120 C to 150 C may dissociate the blocking agent to regenerate a free isocyanate group. The smaller the molecular weight of the dissociated blocking agent the less the resulting heating loss, resulting in reducing gum and soot in a drying oven.
The blocking agent may include, for example, an oxime compound such as methyl ethyl ketoxime, cyclohexanone oxime and the like; aliphatic alcohols such as n-butanol, 2-ethylhexanol and the like; aromatic alkyl alcohols such as phenylcarbinol, methylphenylcarbinol and the like; ether alcohols such as ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether and the like; a lactam compound such as c-caprolactam, y-butyrolactam and the like; a phenol compound such as phenol, p-t-butylphenol, cresol and the like; a low molecular weight amide compound such as n-methylacetamide, n-ethylacetamide, n-methylpropionamide, n-methylformamide and the like; and the like.
Of these, the oxime compound, aliphatic alcohols, aromatic alkyl alcohols and ether alcohols are preferable from the standpoints of throwing power and electrodeposition coating suitability for the galvanized sheet in the cationic electrodeposition coating composition of the present invention.
A mixing amount of the blocking agent is so as to be reacted at a ratio of 1:1 to 1:1.3 to NCO group of the polyisocyanate. A ratio more than 1.3 may reduce anti-corrosive properties of the coating film due to a remaining blocking agent. A ratio less than 1.0 may reduce stability of the coating composition due to a remaining NCO group.
The blocked polyisocyanate curing agent (B) of the _ 17 -cationic electrodeposition coating composition used in the film-forming method of the present invention may preferably be obtained by reacting at least one polyisocyanate compound (b1) selected from the group consisting of an aromatic polyisocyanate compound and an alicyclic polyisocyanate compound with at least one blocking agent (b2) selected from the group consisting of an oxime compound, aliphatic alcohols, aromatic alkyl alcohols and ether alcohols, so as to have a glass transition temperature in the range of 45 to 65 C.
The cationic electrodeposition coating composition contain the amine-added epoxy resin (A) and the blocked polyisocyanate curing agent as the essential components, and may optionally contain an organotin compound and a coating composition additive such as a color pigment, extender pigment, anti-corrosive pigment, organic solvent, water, neutralizing agent, pigment dispersant, coating film surface controlling agent and the like.
The organotin compound may promote dissociation of the blocking agent used in the blocked polyisocyanate curing agent (B) and functions as a curing catalyst, and may include, for example, an organotin oxide such as dibutyltin oxide, dioctyltin oxide and the like; aliphatic or aromatic carboxylic acid salt of dialkyltin, for example, dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin diacetate, dioctyltin dibenzoate, dibutyltin dibenzoate and the like.
Of these dialkyltin aromatic carboxylic acid salt is preferable from the standpoint of low temperature curing properties.
A mixing amount of the organotin compound in the .cationic coating composition of the present invention may not particularly be limited and may widely be varied depending on performances required for the coating composition, but is usually in the range of 0 (zero) to 8 parts by weight, preferably 0.05 to 5 parts by weight per 100 parts by weight of a resin solid content in the coating composition.
The cationic electrodeposition coating composition may be coated onto the surface of a predetermined substrate by an electrodeposition coating. The electrodeposition coating may be carried out by energizing under the conditions of a solid content concentration of about 5 to 40% by weight by diluting with deionized water, a pH in the range of 5.0 to 9.0, an electrodeposition coating bath temperature of 15 to 35 C, a loading voltage of 100 to 400 V, coating substrate as a cathode, energizing time of 30 seconds to 3 minutes, anode to cathode area ratio (A/C) 8/1 to 1/8, and distance between anode and cathode 10 cm to 300 cm.
An electrodeposition coating film thickness may not particularly be limited, but may generally be in the range of to 40 m, preferably 15 to 30 m. A heat curing temperature is generally in the range of about 100 to about 200 C, preferably about 120 C to about 170 C.
The coating film-forming method, which method comprises coating the cationic electrodeposition coating composition containing the specified base resin and the specified curing agent, makes it easily possible to form a coating film having an electrical resistance in the range of 400 kS2=cm2 to 850 kS2 = cm2, preferably 480 kS2 = cm2 to 650 kS2 cm2 one minute after starting of energizing on the electrodeposition coating, and makes it possible to obtain a cured electrodeposition coating film having high throwing power, and good properties in electrodeposition coating suitability for the galvanized sheet with sufficient film thickness on a pouched area and inner plate area in a short period of time of 90 to 150 seconds on electrodeposition coating.
The present invention can provide the following particular effects.
The coating film-forming method, which comprises coating a cationic electrodeposition coating composition containing a specified base resin preferably having a specified glass transition temperature and a specified curing agent preferably having a specified glass transition temperature onto a substrate and heat-curing, in the present invention makes it possible to obtain a coated product with a cured electrodeposition coating film having high throwing power, and good properties in electrodeposition coating suitability for the galvanized sheet and anti-corrosive properties with sufficient film thickness on a pouched area and inner plate area in a short period of time of 90 to 150 seconds on electrodeposition coating.
Further, the use of such a cationic electrodeposition coating composition as the above cationic electrodeposition coating composition that a resulting coating film one minute after starting of energizing on the electrodeposition coating has an electrical resistance in the range of 400 kSZ=cm2 to 850 kf2=cm2, makes it possible to easily obtain a cured electrodeposition coating film showing both high throwing power and electrodeposition coating suitability for the galvanized sheet.
Reasons why the above effects may be provided, may be guessed as follows.
An emulsion as a component constituting the cationic electrodeposition coating composition may be such that a core moiety of the emulsion is composed of the curing agent and a shell moiety is composed of the base resin, and the amino group of the base resin is neutralized to form an emulsion particle. Thus, it is guessed that a combination of the specified base resin and the specified curing agent, and preferably the glass transition temperature in the predetermined range may provide such effects that (1) formation of a coating film having a sufficient electrical resistance in a short period of time after starting energizing results in that a current consumed in the outer plate may also be consumed for forming a coating film onto the inner plate, and in that the throwing power may be improved, and that (2) hardness resisting to sparks on energizing due to the curing agent in the core moiety makes breakage of the coating film difficult, and on the other hand, even if gas holes should develop, softness of the shell moiety may repair pinholes, resulting in improving electrodeposition coating suitability for the galvanized sheet.
The film-forming method of the present invention makes possible an electrodeposition coating in a short period of time, resulting in improvement in productivity, saving of the coating line space and saving of energy. In addition thereto, the resulting high throwing power may result in that the pouch area and inner plate shows good anti-corrosive properties, that the galvanized sheet of the outer plate is free of pinholes, and that a coated product showing good finish appearance can be obtained.
Example The present invention is explained more in detail by reference to Examples, and should not be limited thereto only.
In Examples, "o" and "part" represent "% by weight" and "part by weight" respectively.
Preparation Example of Base Resin No. 1 Preparation Example 1 A reactor equipped with 'a thermometer, stirrer, refl_ux condenser and nitrogen gas inlet was charged with 525 parts of propylene oxide-modified bisphenol A diglycidyl ether (Note 1), 342 parts of bisphenol A, and 36 parts of a 80%
effective component methyl isobutyl ketone solution of a ketimine between monoethanolamine and methyl isobutyl ketone while introducing nitrogen gas, followed by reacting at 160 C
until the epoxy group disappear, adding 665 parts of bisphenol diglycidyl ether having an epoxy equivalent of about 190 and 232 parts of the 80% effective component methyl isobutyl ketone solut:ion of a ketimine between monoethanolamine and methyl isobutyl ketone, reacting at 140 C until an epoxy group content reaches 0.27 m mol/g to obtain an epoxy resin solution having a number average molecular weight of about 1,500, diluting and cooling down to 100 C with 365 parts of ethylene glycol monobutyl ether, adding 167 parts of an 80% effective component methyl isobutyl ketone solution of a diketimine between diethylenetriamine and methyl isobutyl ketone, reacting at 100 C until increase of viscosity stops to obtain a base resin No. 1 having a solid content of 80% and a glass transition temperature of 23 C.
(Note 1): propylene oxide-modified bisphenol A diglycidyl TM
ether (trade name, Glyciale BPP-350, marketed by Sanyo Chemical Industries, Ltd., epoxy equivalent about 340).
Preparation Example 2 (Preparation of Base Resin No. 2) The same reactor as in Preparation Example 1 was charged with 450 parts of ethylene oxide-modified bisphenol A
diglycidyl ether (Note 2) having an epoxy equivalent of about 300, 342 parts of bisphenol A, and 36 parts of a 80%
effective component methyl isobutyl ketone solution of a ketimine between monoethanolamine and methyl isobutyl ketone while introducing nitrogen gas, followed by reacting at 160 C
until the epoxy group disappears, adding 665 parts of bisphenol A diglycidyl ether having an epoxy equivalent of about 190 and 232 parts of a 80% effective component methyl isobutyl ketone soluti.on of a ketimine between monoethanolamine and methyl isobutyl ketone, reacting at 140 C until an epoxy group content reaches 0.29 m mol/g to obtain an epoxy resin solution having a number average molecular weight of about 1,500, diluting and cooling down to 100 C with 350 parts of ethylene glycol monobutyl ether, adding 167 parts of a 80% effective component methyl isobutyl ketone solution of a diketimine between diethylenetriamine and methyl isobutyl ketone, and reacting at 100 C until increase of viscosity stops to obtain a base resin No. 2 having a solid content of 80% and a glass transition temperature of 28 C.
(Note 2): ethylene oxide-modified bisphenol A glycidyl TM
ether (Glyciale BPE-300, trade name, marketed by Sanyo Chemical Industries, Ltd., epoxy equivalent about 300).
Preparation Example 3 (Preparation of Base Resin No. 3) A flask equipped with a stirrer, thermometer, nitrogen gas inlet and reflux condenser was charged with 518 parts of epoxy resin obtained by reaction of bisphenol A with epichiorohydrin and having a number average molecular weight of 370 and an epoxy equivalent of 185, followed by adding 57 parts of bisphenol A and 0.2 part of dimethylbenzylamine, reacting at 120 C until the epoxy equivalent reaches 250, adding 213 parts of s-caprolactone and 0.03 part of tetrabutoxytitanium, heating up to 170 C, sampling with time while keeping at that temperature, examiriing an amount of unreacted s-caprolactone by an infrared absorption spectral measurement, until a degree of conversiori reaches 98% or more, adding 148 parts of bisphenol A and 0.4 part of dimethylbenzylamine, reacting at 130 C uritil the epoxy equivalent reaches 936, adding 257.4 parts of methyl isobutyl ketone, 25.6 parts of diethylamine and 68.3 parts of diethanolamine, reacting at 80 C for 2 hours, and diluting with methyl ethyl ketone to obtain a base resin No. 3 having a solid content of 80% and a glass transition temperature of 38 C.
Preparation Example 4 (Preparation of Base Resin No. 4) A reactor was charged with 222 parts of isophorone diisocyanate, followed by slowly droppinq 113.1 parts of methyl ethyl ketoxime while keeping a reaction temperature at 30 to 40 C by an external cooling to obtain a partly blocked polyisocyanate.
Next, 83.7 parts of the above partly blocked polyisocyanate was mixed with 500 parts of the base resin No.
3 obtained in Preparation Example 3, followed by reacting at 100 C under a nitrogen stream until absorption of isocyanate group disappear by an infrared absorptiori spectral measurement, and diluting with diethylene glycol monobutyl ether to obtain a base resin No. 4 havinq a solid content of 80% and a glass transition temperature of: 44 C.
_ 25 -Preparation Example 5 (Preparation of Base Resin No. 5) A mixture of lOlOg of Epikote 828EL (trade name, marketed by Japan Epoxy Resin Co., Ltd., epoxy resin), 390g of bisphenol A and 0.2g of dimethylbenzyl.amine was reacted at 130 C so as to be an epoxy equivalent of 800, followed by adding 160g of diethanolamine and 65g of a ketiminized product of diethylenetriamine, reacting at 120 C for 4 hours, adding 355g of butylcellosolve to obtain a base resin No. 5 having an amine value of 67 mg KOH/g, a solid content of 80%
and a glass transition temperature of 90 'C.
Preparation Example 6 (Preparation of Curing Agent No. 1) A reactor was charged with 270 parts of Cosmonate M-200 (Note 3) and 25 parts of methyl isobutyl ketone, followed by heating up to 70 C, slowly adding 15 parts of 2,2-dimethylolbutyric acid, dropping 118 parts of ethylene glycol monobutyl ether, reacting at 70 C for one hour, cooling down to 60 C, adding 152 parts of propylene glycol, sampling with time while keeping at that temperature ar.Ld confirming that absorption of unreacted isocyanate group disappeared by an infrared absorption spectral measurement to obtain a curing agent No. 1 having a solid content of 80% and a glass transition temperature of 5 C.
(Note 3) Cosmonate M-200: trade name, marketed by Mitsui Chemicals, Inc., crude MDI.
Preparation Example 7 (Preparation of Curing Agent No. 2) A reactor was charged with 174 parts of tolylene diisocyanate, followed by heating up to 70 C, slowly adding 15 parts of 2,2- dimethylolbutyric acid, dropping 118 parts of ethylene glycol monobutyl ether, reacting at 70 C for one hour, cooling down to 60 C, adding 152 parts of propylene glycol, sampling with time while keeping at that temperature and confirming that absorption of unreacted isocyanate group disappeared by an infrared absorption spectral measurement to obtain a curing agent No. 2 having a solid content of 80% and a glass transition temperature of 10 C.
Preparation Example 8 (Preparation of Curing Agent No. 3) A reactor was charged with 222 parts of isophorone diisocyanate and 99 parts of methyl isobu.tyl ketone, followed by heating up to 50 C, slowly adding 174 parts of methyl ethyl ketoxime, heating up to 60 C, sampling with time while keeping at that temperature and confirming that absorption of unreacted isocyanate group disappeared by an infrared absorption spectral measurement, and controlling a solid content with an organic solvent to obtain a curing agent No.
3 having a solid content of 80% and a glass transition temperature of 8 C.
Preparation Example 9 (Preparation of Curing Agent No. 4) A reactor was charged with 50 parts of hexamethylene diisocyanate, followed by dropping 30 parts of methyl ketoxime and 10 parts of trimethylolpropane at 40 to 60 C, heating at 80 C for one hour, sampling wi_th time while keeping at that temperature and confirmirig that absorption of unreacted isocyanate group disappeared by an infrared absorption spectral measurement, and controlling a solid content with an organic solvent to obtain a curing agent No.
4 having a solid content of 80% and a glass transition temperature of -19 C.
Preparation Examples of Emulsion Nos. 1-9 (EM Nos. 1-9) for Use in Cationic Electrodeposition Coatinq Compositions Preparation Example 10 (Preparation of EM No. 1) A mixture of 87.5 parts (resin solid content 70 parts) of the base resin No. 1, 37.5 parts (resin solid content 30 parts) of the curing agent No. 1 and 13 parts of 10% acet:ic acid was uniformly stirred, followed by clropping deionized water while strongly stirring over about 15 minutes to obtain a EM No. 1 having a solid content of 34% as an emulsion for use in a cationic electrodeposition coating composition.
Preparation Examples 11-18 (Preparation of EM No. 2 to EM No. 9) Preparation Example 10 was duplicated except for respective formulations as shown in Table 1 to obtain EM No.
2 to No. 9 having a solid content of 34% as ari emulsion for use in a cationic electrodeposition coating composition respectively. In Table 1, the solid content is parenthesized.
Ln ^ LO
00 p m lP c' O
r r r M ~-I
Z ~
M
00 Ln LO
r . . p . p M lfl V' O
+"~ z ['~ r r m r-i LONCD
OO M
r Ln ^ ~ ^ ^
l0 . p . p m 0 ~N O ~ o rr rM ~ LO 'o p N
ul Q0 `n , `n ~o ~r o r-I td) = o = M m tn 61 0 Q.., s-4 Z .r r r ~ 00 m ~
n un ._ LO ^ ~o ~r o = O = p M LO Ol O
O 1-1 Z ~ Cv M M `- r-I N~-1 JP
~-I
(d w LO tn -, lO ~N O
C2~ CM = = m LO 61 O
y~..~ ~- Z ~ M M N r-I
a m Ln Ln N = O = O "o 'r z r r r m i ~
H
m m ~
N t,n .,,un ^ .-..
IH O o co ~O ~r o I
r-1 r r r m rl LO Ol O
pO M..~ r-f N 1-1 H Ln U) = O . p M V' O
~--1 = t~ r M ri tt) 61 O
pO ..~ m.~ ,-i Nr-1 olo o'P op olo dP ,-t da N oto M o'p ~ oP
p o 0 0 o 0 0 (D o ri Oo N ao C`') oo q< oJ LO oo = pJ = O7 . p7 = 00 . ..
~ +) = .0 ' 41 = -W z J-) z 1-) z -P Z 4J -ri U) O 0 O r. O $:~ O z O 9 s:: r~ 0 z U 13 z 41 z N z Q) '.~ N Z 0 -P N +J 4) 4J N -P 4) M tlf .43 l-) 13 1J +-) ~ 1.1 ~ +) 4J 1J $
-rl O -ri O -.-I O -i O -r-I O tT O m O lT 0 CT O -.I T3 ~n tn U 0 U ta U zn U rq U rZ4 0 d, 0 re 0 r:~ 0 d-J 4) ~
~ a a a a a~ 0 ~s rn zs ~ ~s a)ro ~~ 0 0 =r I - i -~ - 1 -r-I , -r-I r -r-I ~ -~-1 Z -=-I r r ~1 4J r i N-1 N-0 N r 1 N rl -r-I =-1 -.-1 '-i -r-I r-1 -r-I rA 0 r-1 rn O rn O m O u2 O m O s.~ O sa O N O $-a O aP -r1 0 ~ (t m rtf rn rtl v) ttt m rts u) ;:3 m 0 Q ;~ m :~ m o a) r:l PQ pqPQm U~- U= ~ A W
cP
m O
4-) r-1 r0 RS
~4 Ga Preparation of Pigment-Dispersed Paste Preparation Example 19 A mixture of 5.83 parts (solid content 3.5 parts) of 60% solid content quaternary ammonium salt type epoxy resin, 14.5 parts of titanium oxide, 7.0 parts of purified clay, 1.0 part of bismuth hydroxide, 1.0 part of organotin, 0.4 part of carbon black and 20.1 parts of deionized water was dispersed in a ball mill for 20 hours, followed by taking out to obtain a pigment-dispersed paste (solid content 27.4 parts) having a solid content of 55%.
Example 1 To 294 parts (solid content 100 parts) of the emulsion No. 1 were added 49.8 parts (solid conterit 27.4 parts) of the pigment-dispersed paste No. 1 and 293.2 parts of deionized water to prepare a 20% solid content cati_onic electrodeposition coating composition No. 1 (solid content 127.4 parts).
Examples 2-6 Example 1 was duplicated except that formulations shown in Table 2 were used respectively to obtain cationic electrodeposition coating compositions No. 2 to No. 6.
Comparative Examples 1-3 Example 1 was duplicated except that formulations shown in Table 3 were used respectively to obtain cationic electrodeposition coating compositions No. 7 to No. 9.
Coating Test Respective cationic electrodeposition coating compositions obtained in the above Examples and Comparative Examples were subjected to cationic electrodeposition coating onto a cold-rolled steel sheet or a galvanized sheet (0.8 x 150 x 70 mm, chemically treated with Palbond #3020, trade name, marketed by Nippon Parkerizing Co., Ltd., zinc phosphate treating agent, respectively), followed by heat curing to prepare coating test panels respectively.
Respective coating test panels were subjected to tests of throwing power, electrodeposition coating suitability for a galvanized sheet, and anti-corrosive properties as follows.
Coating composition formulations, coating film properties and test results for cationic electrodepositions No. 1 to No. 6 (Examples) are shown in Table 2, in which Tg represents a glass transition temperature.
~~ rn Q; o~ m o -~ r~r 0 O 0 O N d N ~ ~
z ~'1 ~ . 6~1 ~ 6Ml M ~ LO r- o O-I ~ o a N N O ~ l0 ~O
z m t` o to~= = cn m m ~ 0 O O
4) O N l0 l0 ~ z ~C M l O
M
w M = a, a, a, m d= ,a ' O i ~ O O
O N N l0 l9 z N
"'t' M C- (D N O N Ol N ~ 110 H ~ V' 0 c-1 CD to O 0 ~
~r ~ m r o ~= rn a; rn m O
N N ~ H ~ ~ ~ O uO O O
O ~, l0 z >~
o ~ I ~, ~4 v 0 v v 0 44 "' ~ ~ ~ ~ 0 ~ i-=~ v w ~ ~'t ~ >1 0 0 0 0 O 0 w tf) tf) t!~ tt) H dD =1~ (UG f~d ~ ~ ~
o .u ~ -u 0 ~ ~ d ~~I s~ G3 ~ ! ," ~ f~" U ri N ~ \ Q \ 4 ( ) -4 ts tn :T m m 0) ~3 ro U, ro rd ro rd (d b 0 O u =~ =~
~ ~ ~
o I i '-i H H tA ~ ^ ~ ^ N
U s-I t4 z4 Sa s-I S-I 0 44 4-I {'=., Lf7 U-) 4J
~J Q) 04 O O - = 1 - { O
U U U U U U N ~N ~ c ~~ ~~
~ ~ ~ ctl 0 U~ U) O 0 N 0 O
~ U U U U U U 0 , ~1 :=r-t =V 0 z .i.) U z u~
0 (Y) ao ao M r) 10 0 +-) S4 z 0 -z U N N m -W N N (1) U) vI Rf O 1=> 0 dj yJ
. ~+ C+ Cr t' ~"i f.' Ga ~1 (1) U) vl u) S.1 -!-) U) 1~i 1~ (1) ~
0 -i -I =i =~ -'-! -'-1 () 4-) d) N -=-I 4 0) =ri X! 04 -,1 m m U3 N m m tz, ~s U s4 ~I m m to ui o 4-, 4) a) (t) 0) 4) 4) 02 3 =r1 ~ N 0 0 0 0 ya -4 $4 1-4 ~4 s4 ~4 s~ .,1 0 0-I 4-) ~. 0410 P.
04v a, to rO -0 0=rl ro w a) u) v a) O r-1 N CV (L) M N v N U - ) Q) l 0 N I N=H J-> U (V bi T3 N tT 'LS tv uI v1 to u) tq u2 tJ N a! =rl rl f~' O=~-I ~G' 0-~-= rtS = Ri = ~S = r6 = rts = cC F-: =ri rtt va 14 N =11 14 q =ri ur~=~
a Q o si 0 s3 0 ~ o..Q o,.Q v0 0 0 -P +) 3 +-) rts 3 rts ul U z~ z a+ z is z tr Z tT z 0 on ~ m~~.'. s ~ a) ~~-1 s a aUi .1 U
U ~ W E H R. TS N U N~ 4-) 0) ~S 4-) N t7) ~ U
N Ul _ U
0 .~A > ~ 4J
~
= 4-) CD
O O
~p '- -N ul S-I O Ln 1) O
.,~ =rl ~ 4) O) N r-I N
~ O ~ O 0 04 ~ r:; l-4f p, 7 4=) +J .l-) 1) t.7) 0 O > 0 w N
~ 0 4.3 b~~ ~ Mo ~
(00 0 4) O z N O
[-4 U W u1 U W u) U
Coating composition formulations, coating film properties and test results for cationic electrodeposition No.
7 to No. 9 (Comparative Examples) are shown in Table 3, in which Tg represents a glass transition temperature.
(31 X a ,~ M N N lM 0 ~ rl co tn X l0 Z
co r O -10 N = ~ = (3) M ~ r ~ X r=i ~ l0 X O
O N N ~ r õ z ~
~4 (0 a r m ~ -+ = N ~ N ~ M ~ ,. '~ X 1-4 ~o X O
z ~
N
~ 0 W
>1 >1 0 0 ,-i =~ w u 0 , q w -i =.i ~ .u 11 o ~.. =~~-1 Uco ro p ro UM ap . .
~
O ~ ~'i ~ U =rl N 44 44 44 W
v y~.) m ~+ b~ b~ u ;-4 4i ~ a a~i { rtl ~ ~ 0 O s=a m c~r1 C~7 ~ u~1 ai (\~j i ul =rl U N
0 Cn I'F iT d-) tA V7 m tT
0 S-I ~4 ~4 0 4=1 4-I ~..r" f" tP) U ~ ~3 ::I a) fL O O - ~ =rl - =ri ~ M
U 0 U d.) a) ~N l) 4) v' -tJ 4) 0 m "0 (L) m rts v (o +.) z ~s 0 Uizi a) 0 o v 0 0--o 0 0 .u ~~ o U z o 0 z ~ o a o CS U ~ u z z ~
~ (7) rn rn U) 4) V1 ~ ~-- o=u - 0 J-) =~
0 7N 74 -I =H +3 =r-i (1) ,1 N
0 La 6) Q1 vl cn 64 4-1 (D S 4 1-) 4) s4 r=1 ri r4 N+-) N 41 =rl ..G (1) r-i .9~ N
0 Vl tA ul " Id U S-1 S-I 0 ul $ ul +/1 =,-.1 N 4) 4) m =rl C3 0) 0 0 0 0 p }) S-I s4 Sa =rl S: O r-I 4-J C14 04 T3 S]. Q ZS S i rl '0 tJ o-ri r6 vw N N N U) p., t/1 r N 00 N 61 a) ! N =.-1 -t-) U (d o1 0 (o uI v! 1) N 4-) =.=I =.4 N O= 1 0 O=rl N
= stS = r0 = R3 L"~ -.-I t~ U? S-I N~+' =ri S=1 C~' =r-1 S4 0 J
~ 0 Q 0=0 0=0 N 0 U O.u 4. U 4-) (3 -u rtS =,-f .a z.. z.. z.. ~ 0 a U~ 0 U> 0 () 5 tn 0 rn rs ~ -.-1 on ~ a~ a C s4 a) r-i s4 a) r-+ b 4 . ~ i J D -cV UU N~ x ~ N b+ ~ N~bl U O
U) > > -rt 0 l.s CD o (D 4-) U =11 ~a o LO u7 0 =~ 4-)ul N04 41 N c-1 N
0 U) a 0 , u a.' a v o +
~ 53 u ~ ~ ~
r~ ~u w ~^ 0 ~~ 0 w ~ ~ =~~ ~ ~~i~ ~
(u .~ M a -4 r. =14 0 .u P 04-) s4 0 4.3 fd U rt! N U rd tl) U af E- U W~n U W v~i U 0 (Note 4) Throwing power: A jig for a four sheets box throwing power test method was prepared by use of the above chemically treated cold-rolled steel sheet as shown in Fig. 1, followed by carrying out an electrodeposition coating under the conditions of a bath temperature of 28 C, coating voltage as shown in Tables, an energizing time of` 90 seconds or 150 seconds according to a wiring diagram as shown in Fig. 2, heat curing at 170 C for 20 minutes, and evaluating throwing power from a film thickness ( m) on the surface (A) as an outer plate, film thickness ( m) on the surface (G) as an inner plate and a ratio (%) of film thickness ( m) on the surface (G)/film thickness ( m.) on the surface (A).
(Note 5) Electrodeposition Coating Suitability for Galvanized Sheet: The chemically treated galvanized sheet was dipped in an electrodeposition coating bath as a cathode, followed by carrying out an electrodeposition coating under the conditions of a bath temperature of 28 C, a coating voltage as shown in Tables and energizing time of 90 seconds or 150 seconds, heat curing at 170 C for 20 minutes, and measuring a number of pinholes within 10 x 10 cm of the test panel.
0: No pinholes developed with good finished properties.
0: 3 to 5 pinholes developed.
X 10 or more pinholes developed.
(Note 6) Anti-corrosive properties: Cross cuts were formed by use of a knife on the surfaces of a test panel prepared by subjecting a chemically treated cold-rolled steel sheet to an electrodeposition coating so as to reach the coating substrate, followed by subjecting to a 840 hours salt water spray test in accordance with JIS Z-2371, and evaluating development of rust from the cross cut, and width of blisters as follows.
maximum width of rust and blisters less than 2 mm (one side).
0: maximum width of rust and blisters less than 3 mm (one side).
A: maximum width of rust and blisters 3 mm or more and less than 4 mm from cut (one side).
X: maximum width of rust and blisters 4 mm or more from cut (one side).
Claims (5)
1. A coating film-forming method, which method comprises coating a cationic electrodeposition coating composition onto a substrate by an electrodeposition coating, followed by heat curing to form a cured electrodeposition coating film, said cationic electrodeposition coating composition containing a base resin consisting of an amine-added epoxy resin (A) obtained by reacting an epoxy resin (a1) with at least one modifying agent consisting of a polyhydric polyol (a2), an epoxy compound (a3) of the polyhydric polyol or a cyclic ester compound (a4), or any combination thereof, and with a polyphenol compound (a5) to form a modified epoxy resin, followed by adding an amino group-containing compound (a6) to the modified epoxy resin for reacting, and a curing agent consisting of a blocked polyisocyanate curing agent (B) obtained by reacting at least one polyisocyanate compound (b1) consisting of an aromatic polyisocyanate compound or an alicyclic polyisocyanate compound, or both, with at least one blocking agent (b2) consisting of an oxime compound, an aliphatic alcohol, an aromatic alkyl alcohol or an ether alcohol, or any combination thereof, the amine-added epoxy resin (A) having a glass transition temperature in the range of -10 to 60°C, and the blocked polyisocyanate curing agent (B) having a glass transition temperature in the range of -10 to 50°C.
2. A coating film-forming method as claimed in claim 1, wherein the cationic electrodeposition coating composition further contains a bismuth compound as an anti-corrosive agent.
3. A coating film-forming method as claimed in claim 1 or 2, wherein one minute after starting of energizing on the electrodeposition coating, a resulting coating film has an electrical resistance in the range of 400 k.OMEGA..cndot.cm2 to 850 k.OMEGA..cndot.cm2.
4. A coating film-forming method as claimed in any one of claims 1 to 3, wherein an electrodeposition coating time is in the range of 90 to 150 seconds.
5. A coated product obtained by the method as defined in any one of claims 1 to 4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA002461067A CA2461067C (en) | 2004-03-09 | 2004-03-09 | Coating film-forming method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA002461067A CA2461067C (en) | 2004-03-09 | 2004-03-09 | Coating film-forming method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2461067A1 CA2461067A1 (en) | 2005-09-09 |
| CA2461067C true CA2461067C (en) | 2009-08-18 |
Family
ID=34976971
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002461067A Expired - Lifetime CA2461067C (en) | 2004-03-09 | 2004-03-09 | Coating film-forming method |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA2461067C (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6406842B2 (en) * | 2014-03-25 | 2018-10-17 | 日本ペイント・オートモーティブコーティングス株式会社 | Electrodeposition coating composition and electrodeposition coating method |
| EP3397402B1 (en) | 2015-12-31 | 2023-05-24 | Henkel AG & Co. KGaA | Low bake autodeposition coatings |
-
2004
- 2004-03-09 CA CA002461067A patent/CA2461067C/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| CA2461067A1 (en) | 2005-09-09 |
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