CA2306217C - Cationic electrodeposition coating composition - Google Patents
Cationic electrodeposition coating composition Download PDFInfo
- Publication number
- CA2306217C CA2306217C CA002306217A CA2306217A CA2306217C CA 2306217 C CA2306217 C CA 2306217C CA 002306217 A CA002306217 A CA 002306217A CA 2306217 A CA2306217 A CA 2306217A CA 2306217 C CA2306217 C CA 2306217C
- Authority
- CA
- Canada
- Prior art keywords
- electrodeposition coating
- parts
- coating composition
- cationic
- weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 238000004070 electrodeposition Methods 0.000 title claims abstract description 67
- 125000002091 cationic group Chemical group 0.000 title claims abstract description 66
- 239000008199 coating composition Substances 0.000 title claims abstract description 52
- 239000003960 organic solvent Substances 0.000 claims abstract description 35
- 229920005989 resin Polymers 0.000 claims abstract description 25
- 239000011347 resin Substances 0.000 claims abstract description 25
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 21
- 229920000570 polyether Polymers 0.000 claims abstract description 21
- 229920005862 polyol Polymers 0.000 claims abstract description 21
- 150000003077 polyols Chemical class 0.000 claims abstract description 21
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 13
- 125000000524 functional group Chemical group 0.000 claims abstract description 6
- 239000007787 solid Substances 0.000 claims description 31
- 238000009835 boiling Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 description 34
- 238000000576 coating method Methods 0.000 description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 32
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 24
- 239000008367 deionised water Substances 0.000 description 20
- 229910021641 deionized water Inorganic materials 0.000 description 20
- 239000000839 emulsion Substances 0.000 description 20
- 150000001875 compounds Chemical class 0.000 description 15
- -1 cellosolves Chemical class 0.000 description 14
- 238000004807 desolvation Methods 0.000 description 12
- 239000000049 pigment Substances 0.000 description 12
- 229910001868 water Inorganic materials 0.000 description 12
- 238000005260 corrosion Methods 0.000 description 11
- 230000007797 corrosion Effects 0.000 description 11
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- 239000002966 varnish Substances 0.000 description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 8
- 239000003822 epoxy resin Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 229920000647 polyepoxide Polymers 0.000 description 7
- 238000013019 agitation Methods 0.000 description 6
- 238000007865 diluting Methods 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 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 6
- 239000012855 volatile organic compound Substances 0.000 description 6
- 239000004593 Epoxy Substances 0.000 description 5
- 239000000956 alloy Substances 0.000 description 5
- 229910045601 alloy Inorganic materials 0.000 description 5
- 229910000831 Steel Inorganic materials 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- 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 4
- 238000010438 heat treatment Methods 0.000 description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 4
- 229920000768 polyamine Polymers 0.000 description 4
- 229920001228 polyisocyanate Polymers 0.000 description 4
- 239000005056 polyisocyanate Substances 0.000 description 4
- 239000010959 steel Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 201000006747 infectious mononucleosis Diseases 0.000 description 3
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 229930185605 Bisphenol Natural products 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 229940049676 bismuth hydroxide Drugs 0.000 description 2
- TZSXPYWRDWEXHG-UHFFFAOYSA-K bismuth;trihydroxide Chemical compound [OH-].[OH-].[OH-].[Bi+3] TZSXPYWRDWEXHG-UHFFFAOYSA-K 0.000 description 2
- 239000002981 blocking agent Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 229920003986 novolac Polymers 0.000 description 2
- 229920006122 polyamide resin Polymers 0.000 description 2
- 235000013824 polyphenols Nutrition 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 2
- FRASJONUBLZVQX-UHFFFAOYSA-N 1,4-dioxonaphthalene Natural products C1=CC=C2C(=O)C=CC(=O)C2=C1 FRASJONUBLZVQX-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
- 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 1
- PTTPXKJBFFKCEK-UHFFFAOYSA-N 2-Methyl-4-heptanone Chemical compound CC(C)CC(=O)CC(C)C PTTPXKJBFFKCEK-UHFFFAOYSA-N 0.000 description 1
- KKMOSYLWYLMHAL-UHFFFAOYSA-N 2-bromo-6-nitroaniline Chemical compound NC1=C(Br)C=CC=C1[N+]([O-])=O KKMOSYLWYLMHAL-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 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 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- YMVXZMOEVXBZTE-UHFFFAOYSA-N 4-(4,4-dihydroxycyclohexa-1,5-dien-1-yl)sulfonylcyclohexa-2,4-diene-1,1-diol Chemical compound C1=CC(O)(O)CC=C1S(=O)(=O)C1=CCC(O)(O)C=C1 YMVXZMOEVXBZTE-UHFFFAOYSA-N 0.000 description 1
- FNFYXIMJKWENNK-UHFFFAOYSA-N 4-[(2,4-dihydroxyphenyl)methyl]benzene-1,3-diol Chemical compound OC1=CC(O)=CC=C1CC1=CC=C(O)C=C1O FNFYXIMJKWENNK-UHFFFAOYSA-N 0.000 description 1
- 125000004203 4-hydroxyphenyl group Chemical group [H]OC1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229910000014 Bismuth subcarbonate Inorganic materials 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-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
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 229920000388 Polyphosphate Polymers 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229920003180 amino resin Polymers 0.000 description 1
- ZDHGGOUPMGSLBR-UHFFFAOYSA-K bis(2-hydroxypropanoyloxy)bismuthanyl 2-hydroxypropanoate Chemical compound [Bi+3].CC(O)C([O-])=O.CC(O)C([O-])=O.CC(O)C([O-])=O ZDHGGOUPMGSLBR-UHFFFAOYSA-K 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- JAONZGLTYYUPCT-UHFFFAOYSA-K bismuth subgallate Chemical compound OC(=O)C1=CC(O)=C2O[Bi](O)OC2=C1 JAONZGLTYYUPCT-UHFFFAOYSA-K 0.000 description 1
- 229960000199 bismuth subgallate Drugs 0.000 description 1
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(III) oxide Inorganic materials O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- IZRTVYMPRPTBAI-UHFFFAOYSA-K dibenzoyloxybismuthanyl benzoate Chemical compound [Bi+3].[O-]C(=O)C1=CC=CC=C1.[O-]C(=O)C1=CC=CC=C1.[O-]C(=O)C1=CC=CC=C1 IZRTVYMPRPTBAI-UHFFFAOYSA-K 0.000 description 1
- DQUIAMCJEJUUJC-UHFFFAOYSA-N dibismuth;dioxido(oxo)silane Chemical compound [Bi+3].[Bi+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O DQUIAMCJEJUUJC-UHFFFAOYSA-N 0.000 description 1
- FWIZHMQARNODNX-UHFFFAOYSA-L dibismuth;oxygen(2-);carbonate Chemical compound [O-2].[O-2].[Bi+3].[Bi+3].[O-]C([O-])=O FWIZHMQARNODNX-UHFFFAOYSA-L 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 238000006266 etherification reaction Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 235000013980 iron oxide Nutrition 0.000 description 1
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
- 239000012948 isocyanate Chemical group 0.000 description 1
- 150000002513 isocyanates Chemical group 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 150000003951 lactams Chemical class 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 150000002923 oximes Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000002987 primer (paints) Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 235000019832 sodium triphosphate Nutrition 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 229910000391 tricalcium phosphate Inorganic materials 0.000 description 1
- ZHXAZZQXWJJBHA-UHFFFAOYSA-N triphenylbismuthane Chemical compound C1=CC=CC=C1[Bi](C=1C=CC=CC=1)C1=CC=CC=C1 ZHXAZZQXWJJBHA-UHFFFAOYSA-N 0.000 description 1
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 description 1
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 description 1
- WQEVDHBJGNOKKO-UHFFFAOYSA-K vanadic acid Chemical compound O[V](O)(O)=O WQEVDHBJGNOKKO-UHFFFAOYSA-K 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
- SRWMQSFFRFWREA-UHFFFAOYSA-M zinc formate Chemical compound [Zn+2].[O-]C=O SRWMQSFFRFWREA-UHFFFAOYSA-M 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 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 1
- 229910000165 zinc phosphate Inorganic materials 0.000 description 1
- RVXKJRWBHPHVOV-UHFFFAOYSA-L zinc;oct-2-enoate Chemical compound [Zn+2].CCCCCC=CC([O-])=O.CCCCCC=CC([O-])=O RVXKJRWBHPHVOV-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- 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
- C09D5/4488—Cathodic paints
- C09D5/4492—Cathodic paints containing special additives, e.g. grinding agents
-
- 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
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3215—Polyhydroxy compounds containing aromatic groups or benzoquinone groups
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Molecular Biology (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Paints Or Removers (AREA)
Abstract
A cationic electrodeposition coating composition comprising (A) a cationic resin having a crosslinkable functional group and a cationic group in one molecule, (B) a crosslinking agent, and (C) polyether polyol, said cationic electrodeposition coating composition having a volatile organic solvent content in the range of 1 % by weight or less.
Description
SPECIFICATION
Title of the Invention:
Cationic Electrodeposition Coating Composition Bac ground of the Invention:
(1) Field of the Invention:
The present invention relates to a cationic electrodeposition coating composition having a low volatile organic solvent content that is, having a low content of a volatile organic compound (hereinafter may be referred to as VOC).
Title of the Invention:
Cationic Electrodeposition Coating Composition Bac ground of the Invention:
(1) Field of the Invention:
The present invention relates to a cationic electrodeposition coating composition having a low volatile organic solvent content that is, having a low content of a volatile organic compound (hereinafter may be referred to as VOC).
(2) Description of Background Art:
The cationic electrodeposition coating composition has a high throwing power and is capable of forming a coating film showing good properties in durability, corrosion resistance and the like, and has widely been used as a primer coating composition coated on an electrically conductive metal such as an automobile body, electrical articles and the like, in which the above coating film properties are required.
The electrodeposition coating composition in the prior art needs to contain 2 % by weight or more of a volatile organic solvent such as monoalcohols, glycols, cellosolves, ketones and the like, so that a satisfactory film-forming properties may be maintained. On the other hand, demand on reducing a content of a volatile component in the electrodeposition coating composition, for example, an organic solvent from the standpoints of prevention of environmental disruption, saving of resources and the like has been increased.
In view of the above, it may be proposed to simply remove the volatile component in the electrodeposition coating composition so that a content of the volatile component may be 1 % by weight or less, resulting in that reduction in film-forming properties makes it di~cult to form a cured coating film having a film thickness of 15 ~m or more, and reduces smoothness and corrosion resistance. On the other hand, in the application of the electrodeposition coating composition to a galvanized alloy, for example, an automobile body as widely used as a substrate, a high energized voltage for the purpose of thickening the electrodeposition coating film develops pinholes due to generation of gas, resulting in undesirably reducing smoothness of the coating film.
It is an object of the present invention to provide a cationic electrodeposition coating composition having a volatile organic solvent content in the range of 1 % by weight or less without reducing throwing power, corrosion resistance, etc. and showing good film-forming properties, and is capable of forming a coating film showing good smoothness.
It is another object of the present invention to provide a cationic electrodeposition coating composition capable of applying to a galvanized alloy to form a thick coating film having a film thickness of 15 ~m or more without developing pinholes due to generation of gas.
That is, the present invention provides a cationic electrodeposition coating composition comprising (A) a cationic resin having a crosslinkable functional group and a cationic group in one molecule, (B) a crosslinking agent, and (C) polyether polyol, said cationic electrodeposition coating composition having a volatile organic solvent content in the range of 1 % by weight or less.
The cationic electrodeposition coating composition of the present invention may include a water-based coating composition which essentially contains a cationic resin (A) having a crosslinkable functional group such as hydroxyl group and a cationic group in one molecule, a crosslinking agent (B) and polyether polyol (C), and optionally contains color pigments, anti-corrosive pigments, extender pigments, organic solvents, acids for use in neutralization, anti-cissing agents, surface active agents, catalysts, inhibitors, rheology-controlling agents, pigment dispersants and the like.
The cationic resin (A) has a crosslinkable functional group such as hydroxyl group and a cationic group in one molecule, and may include, as a resin skelton, epoxy resin, acrylic resin, polybutadiene, alkyd resin, polyester resin and the like. Of these, a cationic resin prepared by addition of an amine to the epoxy resin is preferable from the standpoint of good corrosion resistance.
Examples of the cationic resin prepared by addition of the amine to the epoxy resin may include (1) adducts of an epoxy compound with primary mono or polyamine, secondary mono or polyamine, primary and secondary mixed polyamine or the like (see U.S. Patent No.
3984299 Specification); (2) adducts of an epoxy compound with a ketiminized, primary amino group-containing mono or polyamine (see U.S. Patent No. 4017438 Specification); (3) reaction products obtained by etherification between an epoxy compound and a ketiminized, primary amino group-containing hydroxyl compound (see Japanese Patent Application Laid-Open No. 43013/84), and the like. These may be modified with a modifier such as polyamide resin and the like.
The above epoxy compound has at least two epoxy groups in one molecule and a number average molecular weight in the range of 400 to 4000, and may be prepared by a reaction between a polyphenol compound and epichlorohydrin. Examples of the polyphenol compound may include bis (4-hydroxyphenyl)2,2-propane, 4,4-dihydroxybenzophenone, bis(4-hydroxyphenyl)-1,1-ethane, bis(4-hydroxyphenyl)-1,1-isobutane, bis(4-hydroxy-tert-butylphenyl)-2,2-propane, bis(2-hydroxynaphthyl)methane, 1,5-dihydroxynaphthalene, bis(2,4-dihydroxyphenyl)methane, tetra(4-hydroxyphenyl)-1,1,2,2-ethane, 4,4-dihydroxyphenylsulfone, phenol novolak, cresol novolak, and the like.
The crosslinking agent (B) may include known crosslinking agents such as blocked polyisocyanate compound, amino resin and the like. The blocked polyisocyanate compound may include a reaction product obtained by subjecting all of isocyanate groups to addition reaction of a blocking agent to the isocyanate groups. The polyisocyanate compound is a compound having at least two isocyanate groups in one molecule, and may include known aromatic, alicyclic and aliphatic polyisocyanate compounds, and isocyanate group-terminated prepolymers obtained by reacting a low molecular weight active hydrogen-containing compound such as glycol or triol with an excess amount of the above polyisocyante compounds. Examples of the blocking agent may include lactams, oximes, phenols, aliphatic alcohols, aromatic alkyl alcohols, ether alcohols, and the like.
A mixing ratio of the cationic resin (A) to the crosslinking agent (B) is such that the cationic resin (A) is in the range of 50 to 90 % by weight, preferably 65 to 80 % by weight, and the crosslinking agent (B) is in the range of 50 to 10 % by weight, preferably 35 to 20 % by weight based on a total weight of solid contents of both components (A) and (B) respectively.
The cationic resin (A) may be neutralized with a water-soluble organic acid such as formic acid, acetic acid, lactic acid and the like so as to be water-soluble or water-dispersible.
Examples of the anti-corrosive pigment may include zinc dust, zinc phosphate, calcium phosphate, aluminum phosphate, aluminum polyphosphate such as aluminum tripolyphosphate, aluminum orthophosphate, calcium orthophosphate, boric acid based anti-corrosive pigment, alkaline earth metal, zinc oxide and the like, compound oxides of iron oxides with at least one of the above compounds, tungstic acid based anti-corrosive pigments, phosphite based anti-corrosive pigments, hypophosphous acid based anti-corrosive pigments, nitrite based anti-corrosive pigments, vanadic acid based anti-corrosive pigments, zinc formate, zinc acetate, zinc octenate and the like, and further may include compounds represented by chemical formulas such as Zr(OI~4, Mg4A12(OI-~12C~3~3H2O, Mg6~2(0~16C~3~'~H2O and MgsAl7(OI~1sC03~4H20; and bismuth-containing compounds such as bismuth lactate, bismuth silicate, triphenylbismuth, bismuth gallate, bismuth hydroxide, bismuth trioxide, bismuth nitrate, bismuth benzoate, bismuth citrate, bismuth oxycarbonate, and the like.
The above anti-corrosive pigments may usually be used as a powder having a particle size of 10 pm or less, particularly 0.01 to 3 ~.m, and may suitably be used in the range of 0.5 to 100 parts by weight, particularly 1 to 50 parts by weight per 100 parts by weight of a total resin solid content of the cationic resin (A) and crosslinking agent (B) used in the cationic electrodeposition coating composition.
Examples of the polyether polyol (C) may include alkylene based polyether polyol such as polyoxymethylene glycol, polyoxyethylene glycol, polyoxypropylene glycol, polyoxybutylene glycol and the like;
aromatic ring-containing polyether polyol such as bisphenol alone and combination of bisphenol with glycol; and the like. The above polyether polyol suitably has a number average molecular weight of 200 to 3000, preferably 600 to 1500, and a boiling point of 200°C or higher. The above polyether polyol (C) does not include the volatile organic solvent.
The polyether polyol (C) may be contained in the range of 0.5 to 15 parts by weight, particularly 2 to 10 parts by weight per 100 parts by weight of a total resin solid content of the cationic resin (A) and the crosslinking agent (B).
The cationic electrodeposition coating composition of the present invention may be prepared, for example, by a process which comprises adding a cationic resin (A) having a crosslinkable functional group and a cationic group in one molecule and a crosslinking agent (B) into a volatile organic solvent, adding thereinto polyether polyol (C), followed by adding an acid to neutralize the cationic resin, dispersing into water to form an emulsion, uniformly mixing, and vacuuming and removing the volatile organic solvent contained in the emulsion.
The volatile organic solvent may preferably has a boiling point of about 130°C or Iower, preferably 120°C or lower, so that all or almost all of the organic solvent contained in the emulsion may be removed during the vacuuming step. Examples of the organic solvent having the above boiling points may include methyl ethyl ketone, mehyl isobutyl ketone, isopropanol and the like. Use of the above volatile organic solvent makes it possible to easily control a volatile organic solvent content in the electrodeposition coating bath on electrodeposition coating in the range of 1 % by weight or less. The vacuuming step may preferably be carried out under a vacuum of -700 mm Hg or lower.
The cationic electrodeposition coating composition prepared as above containing the component (C) has a volatile organic solvent content of 1 % by weight or less, preferably 0.5 % by weight or less and is coated under known electrodeposition coating conditions, resulting in showing good film-forming properties without reducing throwing power and corrosion resistance, and in making it possible to obtain a coating film showing good smoothness, particularly to coat so as to form a thick cured coating film of 15 ~m or more, preferably 20 ~,m or more even if coated onto a galvanized alloy without developing pinholes due to generation of gas. That is, use of the above cationic electrodeposition coating composition makes it possible to reduce a volatile organic solvent content to 1 % by weight or less without reducing corrosion resistance and smoothness, resulting in achieving an object of reducing the volatile organic compound (VOC).
The cationic electrodeposition coating composition of the present invention is diluted with deionized water or the like so as to be a solid content of about 5 to 40 % by weight and controlled so as to form an electrodeposition coating bath having a pH of 5.5 to 9Ø A coating object as a cathode is dipped into the electrodeposition coating bath to be energized under the conditions of a bath temperature of 15 to 35°C
and a loading voltage of 100 to 400V to carry out the electrodeposition coating. Even if coated onto a galvanized alloy, a cured coating film having a thickness of 15 ~m or more may easily be formed. After the completion of energizing, the coating object may be taken out of the electrodeposition coating bath, followed by washing with water, and heating at 100 to 200°C for 10 to 40 minutes to cure the coating film.
The cationic electrodeposition coating composition containing the polyether polyol has a volatile organic solvent content of 1 % by weight or less and is coated under known electrodeposition coating conditions, resulting in showing good film-forming properties without reducing throwing power and corrosion resistance, and in making it possible to obtain a coating film showing good smoothness, particularly to coat so as to form a thick cured coating film of 15 ~m or more, preferably 20 ~,m or more even if coated onto a galvanized sheet metal without developing pinholes due to generation of gas. That is, the present invention makes it possible to provide the cationic electrodeposition coating composition having a volatile organic solvent content of 1 % by weight or less without reducing corrosion resistance and smoothness, resulting in achieving an object of reducing the volatile organic compound (VOC).
The present invention will be explained more in detail by the following Examples and Comparative Examples, in which "part" and "%" mean "part by weight" and "% by weight" respectively. The pr esent invention should not be limited thereto. A film thickness of the coating film means a cured film thickness.
Preparation Example 1 (Preparation of a varnish (1) for use in cationic electrodeposition coating composition) TM
One thousand nine hundred parts of Epon 1004 (Trade name, marketed by Oil Shell Epoxy Co., Ltd., bisphenol A type epoxy resin, epoxy equivalent: about 950) was dissolved into 1012 parts of methyl isobutyl ketone, followed by heating at 80 to 100°C, dropping 124 parts of diethylamine, and reacting at 110°C for 2 hours to obtain an amine-TM
added epoxy resin. On the other hand, 1000 parts of Versamid (Trade name, marketed by Henkel Hakusui Corporation, dimer acid type polyamide resin, amine value 100) was dissolved into 429 parts of methyl isobutyl ketone, followed by heating and reffuxing at 130 to 150°C, distilling off a produced water and ketiminizing a terminal amino group of the amide resin, keeping at 150°C for about 3 hours, after the completion of distilling off the water cooling down to 60°C, adding to the amine-added epoxy resin, heating at 100°C and keeping for one hour, and cooling down to room temperature to obtain an amine-added, polyamide-modified epoxy resin varnish (1) having a solid content of 68 % and an amine value of 65.
F
A mixture of 103 parts (70 parts as the resin solid content) of the varnish (1) for use in a cationic electrodeposition coating composition, 30 parts of 2-ethylhexyl alcohol-blocked product of tolylene diisocyanate, 2 parts as the solid content of polyether polyol (a) (Note 1), and 15 parts of 10 % aqueous acetic acid solution was uniformly mixed, followed by dropping 150 parts of deionized water strongly stirring over about 15 minutes to obtain an emulsion for use in a cationic electrodeposition coating and having a solid content of 34 %, subjecting the emulsion to desolvation under vacuum at 30 to 40 °C so that a final cationic electrodeposition coating composition may have a volatile organic solvent content of 0.5 % or less, adding the same amount of deionized water as a total amount of the organic solvent, water, etc., which were removed during desolvation, adding with agitation 71 parts of a pigmented paste (Note 2) to 300 parts of the resulting emulsion, and diluting with deionized water to obtain a cationic electrodeposition coating composition having a solid content of 20 %.
(Note 1) Polyether polyol (a) represented by the formula:
HO ~ C2H40~Be-~ Be -f-O-C2H4~ OH
where "Be" means "benzene".
(Note 2) Pigmented paste:
A dispersion having a solid content of 43 % and consisting of 5 parts of the varnish (1) for use in the cationic electrodeposition coating composition, 2.6 parts of 10 % aqueous acetic acid solution, 17 parts of titanum oxide, 2 parts of bismuth hydroxide, 8 parts of purified clay, 0.3 part of carbon black and 36.5 parts of deionized water.
Ex~mpl.~
A mixture of 103 parts (70 parts as the solid content) of the varnish (1) for use in the cationic electrodeposition coating composition, 30 parts of 2-ethylhexyl alcohol-blocked product of tolylene diisocyanate, 5 parts as the solid content of polyether polyol (a) (Note 1) and 15 parts of 10 % aqueous acetic acid solution was uniformly mixed, dropping thereinto 156 parts of deionized water strongly stirring over about 15 minutes to obtain an emulsion for use in the cationic electrodeposition coating and having a solid content of 34 %, subjecting the emulsion to desolvation under vacuum at 30 to 40°C so that a final cationic electrodeposition coating composition may have a volatile organic solvent content of 0.5 % or less, adding the same amount of deionized water as a total amount of the organic solvent, water, etc., which were removed during desolvation, adding with agitation 71 parts of a pigmented paste (Note 2) to 300 parts of the resulting emulsion, and diluting with deionized water to obtain a cationic electrodeposition coating composition having a solid content of 20 %.
A mixture of 103 parts (70 parts as the resin solid content) of the varnish (1) for use in a cationic electrodeposition coating composition, 30 parts of 2-ethylhexyl alcohol-blocked product of tolylene diisocyanate, 2 parts as the solid content of polyether polyol (b) (Note 3) and 15 parts of 10 % aqueous acetic acid solution was uniformly mixed, followed by dropping 150 parts of deionized water strongly stirring over about 15 minutes to obtain an emulsion for use in a cationic electrodeposition coating composition and having a solid content of 34 %, subjecting the emulsion-to desolvation under vacuum at 30 to 40°C so that a final electrodeposition coating composition may have a volatile organic solvent content of 1 % by weight or less, adding the same amount of deionized water as a total amount of an organic solvent, water, etc., which were removed during desolvation, adding 71 parts of a pigmented paste (Note 2) with agitation to 300 parts of the resulting emulsion, and diluting with deionized water to obtain a cationic electrodeposition coating composition having a solid content of 20 %.
(Note 3): Polyether polyol (b) represented by the following formula:
HO--E CH2CH20~-Be-C(CH~Be~OCH2CH2~- OH
where "Be" means "benzene".
F_xamyle 4 A mixture of 103 parts (70 parts as the solid content) of the varnish (1) for use in a cationic electrodeposition coating composition, 30 parts of 2-ethylhexyl alcohol-blocked product of tolylene diisocyanate, 2 parts as the solid content of polyether polyol (c) (Note 4), and 15 parts of 10 % aqueous acetic acid solution was uniformly mixed, followed by dropping 150 parts of deionized water strongly stirring over about 15 minutes to obtain an emulsion for use in a cationic electrodeposition coating composition and having a solid content of 34 %, subjecting the emulsion to desolvation under vacuum at 30 to 40°C so that a final electrodeposition coating composition may have a volatile organic solvent content of 1 % or less, adding the same amount of deionized water as a total amount of an organic solvent, water, etc., which were removed during desolvation, adding with agitation 71 parts of the pigmented paste (Note 2) to 300 parts of the resulting emulsion, and diluting with deionized water to obtain a cationic electrodeposition coating composition having a solid content of 20 %.
(Note 4): Polyether polyol (c) represented by the following formula:
CH3 ~ ~H3 HO-f ~ CH2~Be-C(CH~Be-f-O-~-~~ OH
H H H
where "Be" means "benzene".
~omp~ra 'v . Example 1 A mixture of 103 parts (70 parts as the resin solid content) of the varnish (1) for use in a cationic electrodeposition coating composition, 30 parts of 2-ethylhexyl alcohol-blocked product of tolylene diisocyanate, and 15 parts of 10 % aqueous acetic acid solution was uniformly mixed, followed by dropping 146 parts of deionized water strongly stirring over about 15 minutes to obtain an emulsion for use in a cationic electrodeposition coating composition and having a solid content of 34 %, subjecting the emulsion to desolvation under vacuum at 30 to 40°C so that a final electrodeposition coating composition may have a volatile organic solvent content of about 2 %, adding the same amount of deionized water as a total amount of an organic solvent, water, etc., which were removed during desolvation, adding 71 parts of a pigmented paste (Note 2) with agitation to 294 parts of the resulting emulsion, and diluting with deionized water to obtain a cationic electrodeposition coating composition having a solid content of 20 %.
Con~narative Example 2 A mixture of 103 parts (70 parts as the resin solid content) of the varnish (1) for use in a cationic electrodeposition coating composition, 30 parts of 2-ethylhexyl alcohol-blocked product of tolylene diisocyanate, and 15 parts of 10 % aqueous acetic acid solution was uniformly mixed, followed by dropping 146 parts of deionized water strongly stirring over about 15 minutes to obtain an emulsion for use in a cationic electrodeposition coating composition and having a solid content of 34 %, subjecting the emulsion to desolvation under vacuum at 30 to 40°C so that a final electrodeposition coating composition may have a volatile organic solvent content of 0.5 % or less, adding the same amount of deionized water as a total amount of an organic solvent, water, etc., which were removed during desolvation, adding 71 parts of a pigmented paste (Note 2) with agitation to 300 parts of the resulting emulsion, and diluting with deionized water to obtain a cationic electrodeposition coating composition having a solid content of 20 %.
Cationic electrodeposition coating compositions obtained in the above Examples and Comparative Examples were subjected to tests of a volatile organic solvent content in a final electrodeposition coating composition, throwing power, corrosion resistance, film-forming properties, pinhole-developing properties due to gas generation, and smoothness. Test results are shown in Table 1.
Examples Comparative Exam les Volatile organic solvent0.5 0.5 1.0 1.0 2.2 0.5 content Throwin ower 3 3 3 3 3 3 Corrosion resistance 3 3 3 3 3 3 Film-formin ro erties3 3 3 3 3 1 Pinhole-developing Properties due to 3 3 3 3 3 1 gas Generation Smoothness 3 3 3 3 3 1 Volatile organic solvent content (%l:
A volatile organic solvent content (%) in respective cationic electrodeposition coating compositions having a solid content of 20 was measured by use of gas chromatography.
Throwing power:
Three of four 70 x 150 x 0.8 mm steel sheet have an opening having a diameter of 8 mm at the central portion, and the remaining steel sheet has no opening. The four sheets were successively placed at an interval of 20 mm to each other so that all sheets may face to an anode, that the sheet having no opening may be placed at the most distant place from the anode and that the sheet nearest to the anode may be at a distance of 110 mm from the anode. A surface facing to the anode of the sheet nearest to the anode and having the opening may be referred to as a surface (A), and a surface facing to the anode of the sheet at the most distant position from the anode and having no opening may be referred to as a surface (G). An electrodeposition coating film thickness as a cured film on the surface (G) was measured.
The thicker the film thickness, the better the throwing power. An electrodeposition coating was carried out under the conditions of a bath temperature of 28°C, a voltage of 250 V, and an energized time of 180 seconds. Evaluation was made as follows.
3: Film thickness on the surface (G) is 10 ~m or more; 2: film thickness on the surface (G) is 5 ~m or more but less than 10 ~,m; 1:
film thickness on the surface (G) is less than 5 Vim.
Corrosion resistance' A degreased steel sheet was subjected to electrodeposition coating so as to be a film thickness of 20 ~.m, followed by heat curing at 180°C for 30 minutes, cross-cutting the cured film so as to reach the base material, and subjecting the resulting cured film-coated steel sheet to a salt spray test for 480 hours. Appearance of the resulting film was examined and evaluated as follows.
3: No separation developed; 2: slight separation from the cut portion developed; l: considerable separation from the cut portion developed.
An electrodeposition coating was carried out under the conditions of a bath temperature of 28°C, a loading voltage of 250 V, and an energized time of 180 seconds, followed by forming a cured coating film, and measuring a thickness (N,m) of the cured coating film.
Evaluation was made as follows.
3: 20 ~,m or more; 2: 15 ~m or more but less than 20 Vim; 1: less than 15 Vim.
Pinhole-develo i~n~n~pPrtiP. due to g~generation:
A galvanized alloy was coated under the electrodeposition coating conditions of a bath temperature of 28°C and a loading voltage of 250 V, followed by measuring an amount of pinholes developed per 100 cm2 of the resulting coating film was measured. Evaluation was ' made as follows.
3: No pinholes developed; 2: pinholes developed in an amount of 5 to 10; 1: pinholes developed in an amount of more than 10.
smooth ness:
Smoothness was visually evaluated as follows.
3: Good; 2: slightly poor; 1: seriously poor.
The cationic electrodeposition coating composition has a high throwing power and is capable of forming a coating film showing good properties in durability, corrosion resistance and the like, and has widely been used as a primer coating composition coated on an electrically conductive metal such as an automobile body, electrical articles and the like, in which the above coating film properties are required.
The electrodeposition coating composition in the prior art needs to contain 2 % by weight or more of a volatile organic solvent such as monoalcohols, glycols, cellosolves, ketones and the like, so that a satisfactory film-forming properties may be maintained. On the other hand, demand on reducing a content of a volatile component in the electrodeposition coating composition, for example, an organic solvent from the standpoints of prevention of environmental disruption, saving of resources and the like has been increased.
In view of the above, it may be proposed to simply remove the volatile component in the electrodeposition coating composition so that a content of the volatile component may be 1 % by weight or less, resulting in that reduction in film-forming properties makes it di~cult to form a cured coating film having a film thickness of 15 ~m or more, and reduces smoothness and corrosion resistance. On the other hand, in the application of the electrodeposition coating composition to a galvanized alloy, for example, an automobile body as widely used as a substrate, a high energized voltage for the purpose of thickening the electrodeposition coating film develops pinholes due to generation of gas, resulting in undesirably reducing smoothness of the coating film.
It is an object of the present invention to provide a cationic electrodeposition coating composition having a volatile organic solvent content in the range of 1 % by weight or less without reducing throwing power, corrosion resistance, etc. and showing good film-forming properties, and is capable of forming a coating film showing good smoothness.
It is another object of the present invention to provide a cationic electrodeposition coating composition capable of applying to a galvanized alloy to form a thick coating film having a film thickness of 15 ~m or more without developing pinholes due to generation of gas.
That is, the present invention provides a cationic electrodeposition coating composition comprising (A) a cationic resin having a crosslinkable functional group and a cationic group in one molecule, (B) a crosslinking agent, and (C) polyether polyol, said cationic electrodeposition coating composition having a volatile organic solvent content in the range of 1 % by weight or less.
The cationic electrodeposition coating composition of the present invention may include a water-based coating composition which essentially contains a cationic resin (A) having a crosslinkable functional group such as hydroxyl group and a cationic group in one molecule, a crosslinking agent (B) and polyether polyol (C), and optionally contains color pigments, anti-corrosive pigments, extender pigments, organic solvents, acids for use in neutralization, anti-cissing agents, surface active agents, catalysts, inhibitors, rheology-controlling agents, pigment dispersants and the like.
The cationic resin (A) has a crosslinkable functional group such as hydroxyl group and a cationic group in one molecule, and may include, as a resin skelton, epoxy resin, acrylic resin, polybutadiene, alkyd resin, polyester resin and the like. Of these, a cationic resin prepared by addition of an amine to the epoxy resin is preferable from the standpoint of good corrosion resistance.
Examples of the cationic resin prepared by addition of the amine to the epoxy resin may include (1) adducts of an epoxy compound with primary mono or polyamine, secondary mono or polyamine, primary and secondary mixed polyamine or the like (see U.S. Patent No.
3984299 Specification); (2) adducts of an epoxy compound with a ketiminized, primary amino group-containing mono or polyamine (see U.S. Patent No. 4017438 Specification); (3) reaction products obtained by etherification between an epoxy compound and a ketiminized, primary amino group-containing hydroxyl compound (see Japanese Patent Application Laid-Open No. 43013/84), and the like. These may be modified with a modifier such as polyamide resin and the like.
The above epoxy compound has at least two epoxy groups in one molecule and a number average molecular weight in the range of 400 to 4000, and may be prepared by a reaction between a polyphenol compound and epichlorohydrin. Examples of the polyphenol compound may include bis (4-hydroxyphenyl)2,2-propane, 4,4-dihydroxybenzophenone, bis(4-hydroxyphenyl)-1,1-ethane, bis(4-hydroxyphenyl)-1,1-isobutane, bis(4-hydroxy-tert-butylphenyl)-2,2-propane, bis(2-hydroxynaphthyl)methane, 1,5-dihydroxynaphthalene, bis(2,4-dihydroxyphenyl)methane, tetra(4-hydroxyphenyl)-1,1,2,2-ethane, 4,4-dihydroxyphenylsulfone, phenol novolak, cresol novolak, and the like.
The crosslinking agent (B) may include known crosslinking agents such as blocked polyisocyanate compound, amino resin and the like. The blocked polyisocyanate compound may include a reaction product obtained by subjecting all of isocyanate groups to addition reaction of a blocking agent to the isocyanate groups. The polyisocyanate compound is a compound having at least two isocyanate groups in one molecule, and may include known aromatic, alicyclic and aliphatic polyisocyanate compounds, and isocyanate group-terminated prepolymers obtained by reacting a low molecular weight active hydrogen-containing compound such as glycol or triol with an excess amount of the above polyisocyante compounds. Examples of the blocking agent may include lactams, oximes, phenols, aliphatic alcohols, aromatic alkyl alcohols, ether alcohols, and the like.
A mixing ratio of the cationic resin (A) to the crosslinking agent (B) is such that the cationic resin (A) is in the range of 50 to 90 % by weight, preferably 65 to 80 % by weight, and the crosslinking agent (B) is in the range of 50 to 10 % by weight, preferably 35 to 20 % by weight based on a total weight of solid contents of both components (A) and (B) respectively.
The cationic resin (A) may be neutralized with a water-soluble organic acid such as formic acid, acetic acid, lactic acid and the like so as to be water-soluble or water-dispersible.
Examples of the anti-corrosive pigment may include zinc dust, zinc phosphate, calcium phosphate, aluminum phosphate, aluminum polyphosphate such as aluminum tripolyphosphate, aluminum orthophosphate, calcium orthophosphate, boric acid based anti-corrosive pigment, alkaline earth metal, zinc oxide and the like, compound oxides of iron oxides with at least one of the above compounds, tungstic acid based anti-corrosive pigments, phosphite based anti-corrosive pigments, hypophosphous acid based anti-corrosive pigments, nitrite based anti-corrosive pigments, vanadic acid based anti-corrosive pigments, zinc formate, zinc acetate, zinc octenate and the like, and further may include compounds represented by chemical formulas such as Zr(OI~4, Mg4A12(OI-~12C~3~3H2O, Mg6~2(0~16C~3~'~H2O and MgsAl7(OI~1sC03~4H20; and bismuth-containing compounds such as bismuth lactate, bismuth silicate, triphenylbismuth, bismuth gallate, bismuth hydroxide, bismuth trioxide, bismuth nitrate, bismuth benzoate, bismuth citrate, bismuth oxycarbonate, and the like.
The above anti-corrosive pigments may usually be used as a powder having a particle size of 10 pm or less, particularly 0.01 to 3 ~.m, and may suitably be used in the range of 0.5 to 100 parts by weight, particularly 1 to 50 parts by weight per 100 parts by weight of a total resin solid content of the cationic resin (A) and crosslinking agent (B) used in the cationic electrodeposition coating composition.
Examples of the polyether polyol (C) may include alkylene based polyether polyol such as polyoxymethylene glycol, polyoxyethylene glycol, polyoxypropylene glycol, polyoxybutylene glycol and the like;
aromatic ring-containing polyether polyol such as bisphenol alone and combination of bisphenol with glycol; and the like. The above polyether polyol suitably has a number average molecular weight of 200 to 3000, preferably 600 to 1500, and a boiling point of 200°C or higher. The above polyether polyol (C) does not include the volatile organic solvent.
The polyether polyol (C) may be contained in the range of 0.5 to 15 parts by weight, particularly 2 to 10 parts by weight per 100 parts by weight of a total resin solid content of the cationic resin (A) and the crosslinking agent (B).
The cationic electrodeposition coating composition of the present invention may be prepared, for example, by a process which comprises adding a cationic resin (A) having a crosslinkable functional group and a cationic group in one molecule and a crosslinking agent (B) into a volatile organic solvent, adding thereinto polyether polyol (C), followed by adding an acid to neutralize the cationic resin, dispersing into water to form an emulsion, uniformly mixing, and vacuuming and removing the volatile organic solvent contained in the emulsion.
The volatile organic solvent may preferably has a boiling point of about 130°C or Iower, preferably 120°C or lower, so that all or almost all of the organic solvent contained in the emulsion may be removed during the vacuuming step. Examples of the organic solvent having the above boiling points may include methyl ethyl ketone, mehyl isobutyl ketone, isopropanol and the like. Use of the above volatile organic solvent makes it possible to easily control a volatile organic solvent content in the electrodeposition coating bath on electrodeposition coating in the range of 1 % by weight or less. The vacuuming step may preferably be carried out under a vacuum of -700 mm Hg or lower.
The cationic electrodeposition coating composition prepared as above containing the component (C) has a volatile organic solvent content of 1 % by weight or less, preferably 0.5 % by weight or less and is coated under known electrodeposition coating conditions, resulting in showing good film-forming properties without reducing throwing power and corrosion resistance, and in making it possible to obtain a coating film showing good smoothness, particularly to coat so as to form a thick cured coating film of 15 ~m or more, preferably 20 ~,m or more even if coated onto a galvanized alloy without developing pinholes due to generation of gas. That is, use of the above cationic electrodeposition coating composition makes it possible to reduce a volatile organic solvent content to 1 % by weight or less without reducing corrosion resistance and smoothness, resulting in achieving an object of reducing the volatile organic compound (VOC).
The cationic electrodeposition coating composition of the present invention is diluted with deionized water or the like so as to be a solid content of about 5 to 40 % by weight and controlled so as to form an electrodeposition coating bath having a pH of 5.5 to 9Ø A coating object as a cathode is dipped into the electrodeposition coating bath to be energized under the conditions of a bath temperature of 15 to 35°C
and a loading voltage of 100 to 400V to carry out the electrodeposition coating. Even if coated onto a galvanized alloy, a cured coating film having a thickness of 15 ~m or more may easily be formed. After the completion of energizing, the coating object may be taken out of the electrodeposition coating bath, followed by washing with water, and heating at 100 to 200°C for 10 to 40 minutes to cure the coating film.
The cationic electrodeposition coating composition containing the polyether polyol has a volatile organic solvent content of 1 % by weight or less and is coated under known electrodeposition coating conditions, resulting in showing good film-forming properties without reducing throwing power and corrosion resistance, and in making it possible to obtain a coating film showing good smoothness, particularly to coat so as to form a thick cured coating film of 15 ~m or more, preferably 20 ~,m or more even if coated onto a galvanized sheet metal without developing pinholes due to generation of gas. That is, the present invention makes it possible to provide the cationic electrodeposition coating composition having a volatile organic solvent content of 1 % by weight or less without reducing corrosion resistance and smoothness, resulting in achieving an object of reducing the volatile organic compound (VOC).
The present invention will be explained more in detail by the following Examples and Comparative Examples, in which "part" and "%" mean "part by weight" and "% by weight" respectively. The pr esent invention should not be limited thereto. A film thickness of the coating film means a cured film thickness.
Preparation Example 1 (Preparation of a varnish (1) for use in cationic electrodeposition coating composition) TM
One thousand nine hundred parts of Epon 1004 (Trade name, marketed by Oil Shell Epoxy Co., Ltd., bisphenol A type epoxy resin, epoxy equivalent: about 950) was dissolved into 1012 parts of methyl isobutyl ketone, followed by heating at 80 to 100°C, dropping 124 parts of diethylamine, and reacting at 110°C for 2 hours to obtain an amine-TM
added epoxy resin. On the other hand, 1000 parts of Versamid (Trade name, marketed by Henkel Hakusui Corporation, dimer acid type polyamide resin, amine value 100) was dissolved into 429 parts of methyl isobutyl ketone, followed by heating and reffuxing at 130 to 150°C, distilling off a produced water and ketiminizing a terminal amino group of the amide resin, keeping at 150°C for about 3 hours, after the completion of distilling off the water cooling down to 60°C, adding to the amine-added epoxy resin, heating at 100°C and keeping for one hour, and cooling down to room temperature to obtain an amine-added, polyamide-modified epoxy resin varnish (1) having a solid content of 68 % and an amine value of 65.
F
A mixture of 103 parts (70 parts as the resin solid content) of the varnish (1) for use in a cationic electrodeposition coating composition, 30 parts of 2-ethylhexyl alcohol-blocked product of tolylene diisocyanate, 2 parts as the solid content of polyether polyol (a) (Note 1), and 15 parts of 10 % aqueous acetic acid solution was uniformly mixed, followed by dropping 150 parts of deionized water strongly stirring over about 15 minutes to obtain an emulsion for use in a cationic electrodeposition coating and having a solid content of 34 %, subjecting the emulsion to desolvation under vacuum at 30 to 40 °C so that a final cationic electrodeposition coating composition may have a volatile organic solvent content of 0.5 % or less, adding the same amount of deionized water as a total amount of the organic solvent, water, etc., which were removed during desolvation, adding with agitation 71 parts of a pigmented paste (Note 2) to 300 parts of the resulting emulsion, and diluting with deionized water to obtain a cationic electrodeposition coating composition having a solid content of 20 %.
(Note 1) Polyether polyol (a) represented by the formula:
HO ~ C2H40~Be-~ Be -f-O-C2H4~ OH
where "Be" means "benzene".
(Note 2) Pigmented paste:
A dispersion having a solid content of 43 % and consisting of 5 parts of the varnish (1) for use in the cationic electrodeposition coating composition, 2.6 parts of 10 % aqueous acetic acid solution, 17 parts of titanum oxide, 2 parts of bismuth hydroxide, 8 parts of purified clay, 0.3 part of carbon black and 36.5 parts of deionized water.
Ex~mpl.~
A mixture of 103 parts (70 parts as the solid content) of the varnish (1) for use in the cationic electrodeposition coating composition, 30 parts of 2-ethylhexyl alcohol-blocked product of tolylene diisocyanate, 5 parts as the solid content of polyether polyol (a) (Note 1) and 15 parts of 10 % aqueous acetic acid solution was uniformly mixed, dropping thereinto 156 parts of deionized water strongly stirring over about 15 minutes to obtain an emulsion for use in the cationic electrodeposition coating and having a solid content of 34 %, subjecting the emulsion to desolvation under vacuum at 30 to 40°C so that a final cationic electrodeposition coating composition may have a volatile organic solvent content of 0.5 % or less, adding the same amount of deionized water as a total amount of the organic solvent, water, etc., which were removed during desolvation, adding with agitation 71 parts of a pigmented paste (Note 2) to 300 parts of the resulting emulsion, and diluting with deionized water to obtain a cationic electrodeposition coating composition having a solid content of 20 %.
A mixture of 103 parts (70 parts as the resin solid content) of the varnish (1) for use in a cationic electrodeposition coating composition, 30 parts of 2-ethylhexyl alcohol-blocked product of tolylene diisocyanate, 2 parts as the solid content of polyether polyol (b) (Note 3) and 15 parts of 10 % aqueous acetic acid solution was uniformly mixed, followed by dropping 150 parts of deionized water strongly stirring over about 15 minutes to obtain an emulsion for use in a cationic electrodeposition coating composition and having a solid content of 34 %, subjecting the emulsion-to desolvation under vacuum at 30 to 40°C so that a final electrodeposition coating composition may have a volatile organic solvent content of 1 % by weight or less, adding the same amount of deionized water as a total amount of an organic solvent, water, etc., which were removed during desolvation, adding 71 parts of a pigmented paste (Note 2) with agitation to 300 parts of the resulting emulsion, and diluting with deionized water to obtain a cationic electrodeposition coating composition having a solid content of 20 %.
(Note 3): Polyether polyol (b) represented by the following formula:
HO--E CH2CH20~-Be-C(CH~Be~OCH2CH2~- OH
where "Be" means "benzene".
F_xamyle 4 A mixture of 103 parts (70 parts as the solid content) of the varnish (1) for use in a cationic electrodeposition coating composition, 30 parts of 2-ethylhexyl alcohol-blocked product of tolylene diisocyanate, 2 parts as the solid content of polyether polyol (c) (Note 4), and 15 parts of 10 % aqueous acetic acid solution was uniformly mixed, followed by dropping 150 parts of deionized water strongly stirring over about 15 minutes to obtain an emulsion for use in a cationic electrodeposition coating composition and having a solid content of 34 %, subjecting the emulsion to desolvation under vacuum at 30 to 40°C so that a final electrodeposition coating composition may have a volatile organic solvent content of 1 % or less, adding the same amount of deionized water as a total amount of an organic solvent, water, etc., which were removed during desolvation, adding with agitation 71 parts of the pigmented paste (Note 2) to 300 parts of the resulting emulsion, and diluting with deionized water to obtain a cationic electrodeposition coating composition having a solid content of 20 %.
(Note 4): Polyether polyol (c) represented by the following formula:
CH3 ~ ~H3 HO-f ~ CH2~Be-C(CH~Be-f-O-~-~~ OH
H H H
where "Be" means "benzene".
~omp~ra 'v . Example 1 A mixture of 103 parts (70 parts as the resin solid content) of the varnish (1) for use in a cationic electrodeposition coating composition, 30 parts of 2-ethylhexyl alcohol-blocked product of tolylene diisocyanate, and 15 parts of 10 % aqueous acetic acid solution was uniformly mixed, followed by dropping 146 parts of deionized water strongly stirring over about 15 minutes to obtain an emulsion for use in a cationic electrodeposition coating composition and having a solid content of 34 %, subjecting the emulsion to desolvation under vacuum at 30 to 40°C so that a final electrodeposition coating composition may have a volatile organic solvent content of about 2 %, adding the same amount of deionized water as a total amount of an organic solvent, water, etc., which were removed during desolvation, adding 71 parts of a pigmented paste (Note 2) with agitation to 294 parts of the resulting emulsion, and diluting with deionized water to obtain a cationic electrodeposition coating composition having a solid content of 20 %.
Con~narative Example 2 A mixture of 103 parts (70 parts as the resin solid content) of the varnish (1) for use in a cationic electrodeposition coating composition, 30 parts of 2-ethylhexyl alcohol-blocked product of tolylene diisocyanate, and 15 parts of 10 % aqueous acetic acid solution was uniformly mixed, followed by dropping 146 parts of deionized water strongly stirring over about 15 minutes to obtain an emulsion for use in a cationic electrodeposition coating composition and having a solid content of 34 %, subjecting the emulsion to desolvation under vacuum at 30 to 40°C so that a final electrodeposition coating composition may have a volatile organic solvent content of 0.5 % or less, adding the same amount of deionized water as a total amount of an organic solvent, water, etc., which were removed during desolvation, adding 71 parts of a pigmented paste (Note 2) with agitation to 300 parts of the resulting emulsion, and diluting with deionized water to obtain a cationic electrodeposition coating composition having a solid content of 20 %.
Cationic electrodeposition coating compositions obtained in the above Examples and Comparative Examples were subjected to tests of a volatile organic solvent content in a final electrodeposition coating composition, throwing power, corrosion resistance, film-forming properties, pinhole-developing properties due to gas generation, and smoothness. Test results are shown in Table 1.
Examples Comparative Exam les Volatile organic solvent0.5 0.5 1.0 1.0 2.2 0.5 content Throwin ower 3 3 3 3 3 3 Corrosion resistance 3 3 3 3 3 3 Film-formin ro erties3 3 3 3 3 1 Pinhole-developing Properties due to 3 3 3 3 3 1 gas Generation Smoothness 3 3 3 3 3 1 Volatile organic solvent content (%l:
A volatile organic solvent content (%) in respective cationic electrodeposition coating compositions having a solid content of 20 was measured by use of gas chromatography.
Throwing power:
Three of four 70 x 150 x 0.8 mm steel sheet have an opening having a diameter of 8 mm at the central portion, and the remaining steel sheet has no opening. The four sheets were successively placed at an interval of 20 mm to each other so that all sheets may face to an anode, that the sheet having no opening may be placed at the most distant place from the anode and that the sheet nearest to the anode may be at a distance of 110 mm from the anode. A surface facing to the anode of the sheet nearest to the anode and having the opening may be referred to as a surface (A), and a surface facing to the anode of the sheet at the most distant position from the anode and having no opening may be referred to as a surface (G). An electrodeposition coating film thickness as a cured film on the surface (G) was measured.
The thicker the film thickness, the better the throwing power. An electrodeposition coating was carried out under the conditions of a bath temperature of 28°C, a voltage of 250 V, and an energized time of 180 seconds. Evaluation was made as follows.
3: Film thickness on the surface (G) is 10 ~m or more; 2: film thickness on the surface (G) is 5 ~m or more but less than 10 ~,m; 1:
film thickness on the surface (G) is less than 5 Vim.
Corrosion resistance' A degreased steel sheet was subjected to electrodeposition coating so as to be a film thickness of 20 ~.m, followed by heat curing at 180°C for 30 minutes, cross-cutting the cured film so as to reach the base material, and subjecting the resulting cured film-coated steel sheet to a salt spray test for 480 hours. Appearance of the resulting film was examined and evaluated as follows.
3: No separation developed; 2: slight separation from the cut portion developed; l: considerable separation from the cut portion developed.
An electrodeposition coating was carried out under the conditions of a bath temperature of 28°C, a loading voltage of 250 V, and an energized time of 180 seconds, followed by forming a cured coating film, and measuring a thickness (N,m) of the cured coating film.
Evaluation was made as follows.
3: 20 ~,m or more; 2: 15 ~m or more but less than 20 Vim; 1: less than 15 Vim.
Pinhole-develo i~n~n~pPrtiP. due to g~generation:
A galvanized alloy was coated under the electrodeposition coating conditions of a bath temperature of 28°C and a loading voltage of 250 V, followed by measuring an amount of pinholes developed per 100 cm2 of the resulting coating film was measured. Evaluation was ' made as follows.
3: No pinholes developed; 2: pinholes developed in an amount of 5 to 10; 1: pinholes developed in an amount of more than 10.
smooth ness:
Smoothness was visually evaluated as follows.
3: Good; 2: slightly poor; 1: seriously poor.
Claims
1. A cationic electrodeposition coating composition comprising (A) a cationic resin having a crosslinkable functional group and a cationic group in one molecule, (B) a crosslinking agent, and (C) polyether polyol, said cationic electrodeposition coating composition having a volatile organic solvent content in the range of 0-1% by weight in use, a mixing ratio of the cationic resin (A) to the crosslinking agent (B) being such that the former is in the range of 50 to 90%
by weight and the latter is in the range of 50 to 10% by weight based on a total solid contents of the both components (A) and (B), said polyether polyol (C) being contained in the range of 0.5 to 15 parts by weight per 100 parts by weight of a total resin solid content of the cationic resin (A) and the crosslinking agent (B), said polyether polyol (C) having a number average molecular weight in the range of 200 to 3000 and a boiling point in the range of 200° C or higher.
by weight and the latter is in the range of 50 to 10% by weight based on a total solid contents of the both components (A) and (B), said polyether polyol (C) being contained in the range of 0.5 to 15 parts by weight per 100 parts by weight of a total resin solid content of the cationic resin (A) and the crosslinking agent (B), said polyether polyol (C) having a number average molecular weight in the range of 200 to 3000 and a boiling point in the range of 200° C or higher.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP112991/99 | 1999-04-21 | ||
| JP11299199 | 1999-04-21 | ||
| JP113043/00 | 2000-04-14 | ||
| JP2000113043A JP4662213B2 (en) | 1999-04-21 | 2000-04-14 | Cationic electrodeposition paint |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2306217A1 CA2306217A1 (en) | 2000-10-21 |
| CA2306217C true CA2306217C (en) | 2004-02-10 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002306217A Expired - Fee Related CA2306217C (en) | 1999-04-21 | 2000-04-19 | Cationic electrodeposition coating composition |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US6342546B1 (en) |
| JP (1) | JP4662213B2 (en) |
| CA (1) | CA2306217C (en) |
| GB (1) | GB2349643B (en) |
Families Citing this family (22)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JP4663870B2 (en) * | 1999-11-30 | 2011-04-06 | 日本ペイント株式会社 | Method for producing pigment dispersed resin for cationic electrodeposition coating |
| TW574328B (en) * | 1999-11-30 | 2004-02-01 | Nippon Paint Co Ltd | Method for producing pigment dispersing resin for cationic electrodeposition paint |
| WO2003010245A1 (en) * | 2001-07-24 | 2003-02-06 | Kaneka Corporation | Process for producing surface-treated inorganic particle and surface-treated inorganic particle |
| WO2004090055A1 (en) * | 2003-04-10 | 2004-10-21 | Kansai Paint Co., Ltd. | Polyaddition product and cationic electrodeposition coating comprising said polyaddition product |
| US7928152B2 (en) * | 2004-05-17 | 2011-04-19 | Kansai Paint Co., Ltd. | Electrodeposition paint |
| CN100451081C (en) * | 2004-05-17 | 2009-01-14 | 关西涂料株式会社 | Electrodeposition paint |
| US20060009593A1 (en) * | 2004-07-08 | 2006-01-12 | Hideki Iijima | Polyaddition compound and cationic electrodeposition paint which contains polyaddition compound |
| US7763359B2 (en) * | 2004-08-30 | 2010-07-27 | Bunge Fertilizantes S.A. | Aluminum phosphate, polyphosphate and metaphosphate particles and their use as pigments in paints and method of making same |
| BRPI0403713B1 (en) * | 2004-08-30 | 2021-01-12 | Universidade Estadual De Campinas - Unicamp | manufacturing process of a white pigment based on the synthesis of hollow particles of aluminum orthophosphate or polyphosphate |
| JP4839033B2 (en) * | 2005-07-13 | 2011-12-14 | 関西ペイント株式会社 | Cationic electrodeposition paint |
| WO2008017135A1 (en) * | 2006-08-11 | 2008-02-14 | Bunge Fertilizantes S.A. | Preparation of aluminum phosphate or polyphosphate particles |
| JP5567767B2 (en) | 2007-05-18 | 2014-08-06 | 関西ペイント株式会社 | Cationic electrodeposition coating composition |
| US8729196B2 (en) | 2007-09-11 | 2014-05-20 | Kansai Paint Co., Ltd. | Cationic electrodeposition paint compositions |
| US9023145B2 (en) * | 2008-02-12 | 2015-05-05 | Bunge Amorphic Solutions Llc | Aluminum phosphate or polyphosphate compositions |
| AR075381A1 (en) * | 2009-02-10 | 2011-03-30 | Unicamp | USE OF PARTICLES OF PHOSPHATE, POLYPHOSPHATE AND METAPHOSPHATE, OF ALUMINUM IN PAPER COATING APPLICATIONS. |
| US9005355B2 (en) | 2010-10-15 | 2015-04-14 | Bunge Amorphic Solutions Llc | Coating compositions with anticorrosion properties |
| US9371454B2 (en) | 2010-10-15 | 2016-06-21 | Bunge Amorphic Solutions Llc | Coating compositions with anticorrosion properties |
| US9078445B2 (en) | 2012-04-16 | 2015-07-14 | Bunge Amorphic Solutions Llc | Antimicrobial chemical compositions |
| US9611147B2 (en) | 2012-04-16 | 2017-04-04 | Bunge Amorphic Solutions Llc | Aluminum phosphates, compositions comprising aluminum phosphate, and methods for making the same |
| US9155311B2 (en) | 2013-03-15 | 2015-10-13 | Bunge Amorphic Solutions Llc | Antimicrobial chemical compositions |
| HUE053711T2 (en) * | 2015-05-21 | 2021-07-28 | Swimc Llc | Antimicrobial agent for coating composition |
| WO2023183770A1 (en) * | 2022-03-21 | 2023-09-28 | Ppg Industries Ohio, Inc. | Electrodepositable coating compositions |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3984299A (en) | 1970-06-19 | 1976-10-05 | Ppg Industries, Inc. | Process for electrodepositing cationic compositions |
| US4017438A (en) | 1974-12-16 | 1977-04-12 | Ppg Industries, Inc. | Ketimine-blocked primary amine group-containing cationic electrodepositable resins |
| JPS5943013A (en) | 1982-09-03 | 1984-03-09 | Kansai Paint Co Ltd | Epoxy resin derivative and its production |
| US4810738A (en) * | 1985-04-29 | 1989-03-07 | Dresser Industries, Inc. | Coating composition and method to increase electrophoretic film thickness |
| US4867854A (en) | 1986-09-24 | 1989-09-19 | The Dow Chemical Company | Controlled film build epoxy coatings applied by cathodic electrodeposition |
| AU600836B2 (en) | 1987-08-13 | 1990-08-23 | Dow Chemical Company, The | Cross-linking agent for controlled film build epoxy coatings applied by cathoid electrodeposition |
| JP2577749B2 (en) * | 1987-09-10 | 1997-02-05 | 関西ペイント株式会社 | Method for improving smoothness of electrodeposition coating film |
| CA2010820A1 (en) | 1990-02-23 | 1991-08-23 | Peter D. Clark | Cathodic electrocoat primer containing water insoluble organo-lead compounds as corrosion inhibitors |
| JP2975061B2 (en) | 1990-07-17 | 1999-11-10 | 関西ペイント株式会社 | Coating method |
| JPH04306271A (en) * | 1991-04-03 | 1992-10-29 | Kansai Paint Co Ltd | Dispersing process |
| JPH0892509A (en) * | 1994-09-21 | 1996-04-09 | Shinto Paint Co Ltd | Production of resin composition for cationic electrodeposition paint |
| US6130274A (en) * | 1998-07-15 | 2000-10-10 | Daihan Paint & Ink Co., Ltd. | Aqueous dispersion of low-temperature curable cationic electrodeposition resin composition and process for preparing the same |
-
2000
- 2000-04-14 JP JP2000113043A patent/JP4662213B2/en not_active Expired - Lifetime
- 2000-04-19 CA CA002306217A patent/CA2306217C/en not_active Expired - Fee Related
- 2000-04-19 US US09/552,515 patent/US6342546B1/en not_active Expired - Fee Related
- 2000-04-20 GB GB0009953A patent/GB2349643B/en not_active Expired - Fee Related
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| Publication number | Publication date |
|---|---|
| JP4662213B2 (en) | 2011-03-30 |
| US6342546B1 (en) | 2002-01-29 |
| GB2349643A (en) | 2000-11-08 |
| CA2306217A1 (en) | 2000-10-21 |
| GB0009953D0 (en) | 2000-06-07 |
| JP2001003005A (en) | 2001-01-09 |
| GB2349643B (en) | 2001-09-05 |
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