US20100163423A1 - Electrocoat composition and process replacing phosphate pretreatment - Google Patents
Electrocoat composition and process replacing phosphate pretreatment Download PDFInfo
- Publication number
- US20100163423A1 US20100163423A1 US12/345,321 US34532108A US2010163423A1 US 20100163423 A1 US20100163423 A1 US 20100163423A1 US 34532108 A US34532108 A US 34532108A US 2010163423 A1 US2010163423 A1 US 2010163423A1
- Authority
- US
- United States
- Prior art keywords
- resin
- layer
- coating layer
- coating
- amine
- 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.)
- Abandoned
Links
- 238000000034 method Methods 0.000 title claims description 39
- 229910019142 PO4 Inorganic materials 0.000 title claims description 11
- 239000010452 phosphate Substances 0.000 title claims description 11
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 title claims description 9
- 239000000203 mixture Substances 0.000 title description 42
- 229920005989 resin Polymers 0.000 claims abstract description 147
- 239000011347 resin Substances 0.000 claims abstract description 147
- 239000011247 coating layer Substances 0.000 claims abstract description 56
- 239000010410 layer Substances 0.000 claims abstract description 51
- 239000011230 binding agent Substances 0.000 claims abstract description 46
- 239000008199 coating composition Substances 0.000 claims abstract description 28
- 229920000647 polyepoxide Polymers 0.000 claims description 56
- 238000000576 coating method Methods 0.000 claims description 37
- 239000002987 primer (paints) Substances 0.000 claims description 32
- 239000011248 coating agent Substances 0.000 claims description 31
- -1 phosphate ester Chemical class 0.000 claims description 28
- 229910052751 metal Inorganic materials 0.000 claims description 25
- 239000002184 metal Substances 0.000 claims description 25
- 239000003822 epoxy resin Substances 0.000 claims description 20
- 125000004437 phosphorous atom Chemical group 0.000 claims description 7
- 238000002203 pretreatment Methods 0.000 claims description 6
- 239000002131 composite material Substances 0.000 claims description 5
- 238000004140 cleaning Methods 0.000 claims description 4
- 239000001177 diphosphate Substances 0.000 claims description 2
- 235000011180 diphosphates Nutrition 0.000 claims description 2
- 150000003008 phosphonic acid esters Chemical class 0.000 claims description 2
- 239000000758 substrate Substances 0.000 abstract description 35
- 238000004070 electrodeposition Methods 0.000 abstract description 16
- 239000002253 acid Substances 0.000 description 48
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 43
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- 238000006243 chemical reaction Methods 0.000 description 22
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 21
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 20
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 19
- 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 18
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- 239000013065 commercial product Substances 0.000 description 17
- 239000000376 reactant Substances 0.000 description 16
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 15
- 150000001412 amines Chemical class 0.000 description 15
- 229920000642 polymer Polymers 0.000 description 15
- 239000000843 powder Substances 0.000 description 15
- 125000003277 amino group Chemical group 0.000 description 13
- 150000002118 epoxides Chemical class 0.000 description 13
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- 238000005260 corrosion Methods 0.000 description 12
- 239000000049 pigment Substances 0.000 description 12
- 238000002360 preparation method Methods 0.000 description 12
- 239000004971 Cross linker Substances 0.000 description 11
- 230000007797 corrosion Effects 0.000 description 11
- 238000012360 testing method Methods 0.000 description 11
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- 150000001875 compounds Chemical class 0.000 description 10
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical class C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 10
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- 125000000217 alkyl group Chemical group 0.000 description 9
- 150000002148 esters Chemical class 0.000 description 9
- 239000005056 polyisocyanate Substances 0.000 description 9
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- 239000002904 solvent Substances 0.000 description 8
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 6
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- 239000000047 product Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 6
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 5
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- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- 239000005062 Polybutadiene Substances 0.000 description 4
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- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 4
- 125000002877 alkyl aryl group Chemical group 0.000 description 4
- 150000008064 anhydrides Chemical class 0.000 description 4
- 125000003710 aryl alkyl group Chemical group 0.000 description 4
- 229930003836 cresol Natural products 0.000 description 4
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 4
- IUNMPGNGSSIWFP-UHFFFAOYSA-N dimethylaminopropylamine Chemical compound CN(C)CCCN IUNMPGNGSSIWFP-UHFFFAOYSA-N 0.000 description 4
- 239000000839 emulsion Substances 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 4
- TVZISJTYELEYPI-UHFFFAOYSA-N hypodiphosphoric acid Chemical compound OP(O)(=O)P(O)(O)=O TVZISJTYELEYPI-UHFFFAOYSA-N 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 239000004014 plasticizer Substances 0.000 description 4
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- 150000003077 polyols Chemical class 0.000 description 4
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 4
- 150000003512 tertiary amines Chemical class 0.000 description 4
- 238000011282 treatment Methods 0.000 description 4
- 229910052725 zinc Inorganic materials 0.000 description 4
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 3
- 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 3
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- 235000014113 dietary fatty acids Nutrition 0.000 description 3
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- HXFVOUUOTHJFPX-UHFFFAOYSA-N alumane;zinc Chemical compound [AlH3].[Zn] HXFVOUUOTHJFPX-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- LHIJANUOQQMGNT-UHFFFAOYSA-N aminoethylethanolamine Chemical compound NCCNCCO LHIJANUOQQMGNT-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 230000003254 anti-foaming effect Effects 0.000 description 1
- 229940053200 antiepileptics fatty acid derivative Drugs 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- 150000001622 bismuth compounds Chemical class 0.000 description 1
- OHJMTUPIZMNBFR-UHFFFAOYSA-N biuret Chemical compound NC(=O)NC(N)=O OHJMTUPIZMNBFR-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- BELZJFWUNQWBES-UHFFFAOYSA-N caldopentamine Chemical compound NCCCNCCCNCCCNCCCN BELZJFWUNQWBES-UHFFFAOYSA-N 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000006184 cosolvent Substances 0.000 description 1
- 238000007766 curtain coating Methods 0.000 description 1
- ZWAJLVLEBYIOTI-UHFFFAOYSA-N cyclohexene oxide Chemical class C1CCCC2OC21 ZWAJLVLEBYIOTI-UHFFFAOYSA-N 0.000 description 1
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 description 1
- XXKOQQBKBHUATC-UHFFFAOYSA-N cyclohexylmethylcyclohexane Chemical compound C1CCCCC1CC1CCCCC1 XXKOQQBKBHUATC-UHFFFAOYSA-N 0.000 description 1
- 229960002887 deanol Drugs 0.000 description 1
- GTBGXKPAKVYEKJ-UHFFFAOYSA-N decyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCOC(=O)C(C)=C GTBGXKPAKVYEKJ-UHFFFAOYSA-N 0.000 description 1
- FWLDHHJLVGRRHD-UHFFFAOYSA-N decyl prop-2-enoate Chemical compound CCCCCCCCCCOC(=O)C=C FWLDHHJLVGRRHD-UHFFFAOYSA-N 0.000 description 1
- 150000001983 dialkylethers Chemical class 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- KORSJDCBLAPZEQ-UHFFFAOYSA-N dicyclohexylmethane-4,4'-diisocyanate Chemical compound C1CC(N=C=O)CCC1CC1CCC(N=C=O)CC1 KORSJDCBLAPZEQ-UHFFFAOYSA-N 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
- 229940043276 diisopropanolamine Drugs 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- BEPAFCGSDWSTEL-UHFFFAOYSA-N dimethyl malonate Chemical compound COC(=O)CC(=O)OC BEPAFCGSDWSTEL-UHFFFAOYSA-N 0.000 description 1
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
- 239000012972 dimethylethanolamine Substances 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- XQRLCLUYWUNEEH-UHFFFAOYSA-N diphosphonic acid Chemical class OP(=O)OP(O)=O XQRLCLUYWUNEEH-UHFFFAOYSA-N 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
- 239000006185 dispersion Substances 0.000 description 1
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- RJUVPCYAOBNZAX-VOTSOKGWSA-N ethyl (e)-3-(dimethylamino)-2-methylprop-2-enoate Chemical compound CCOC(=O)C(\C)=C\N(C)C RJUVPCYAOBNZAX-VOTSOKGWSA-N 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 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
- 239000012362 glacial acetic acid Substances 0.000 description 1
- CATSNJVOTSVZJV-UHFFFAOYSA-N heptan-2-one Chemical compound CCCCCC(C)=O CATSNJVOTSVZJV-UHFFFAOYSA-N 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
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 1
- LNCPIMCVTKXXOY-UHFFFAOYSA-N hexyl 2-methylprop-2-enoate Chemical compound CCCCCCOC(=O)C(C)=C LNCPIMCVTKXXOY-UHFFFAOYSA-N 0.000 description 1
- LNMQRPPRQDGUDR-UHFFFAOYSA-N hexyl prop-2-enoate Chemical compound CCCCCCOC(=O)C=C LNMQRPPRQDGUDR-UHFFFAOYSA-N 0.000 description 1
- 239000008240 homogeneous mixture Substances 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- YAMHXTCMCPHKLN-UHFFFAOYSA-N imidazolidin-2-one Chemical compound O=C1NCCN1 YAMHXTCMCPHKLN-UHFFFAOYSA-N 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000006115 industrial coating Substances 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N itaconic acid Chemical class OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 238000009533 lab test Methods 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 1
- MOUPNEIJQCETIW-UHFFFAOYSA-N lead chromate Chemical compound [Pb+2].[O-][Cr]([O-])(=O)=O MOUPNEIJQCETIW-UHFFFAOYSA-N 0.000 description 1
- 125000005647 linker group Chemical group 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- REOJLIXKJWXUGB-UHFFFAOYSA-N mofebutazone Chemical group O=C1C(CCCC)C(=O)NN1C1=CC=CC=C1 REOJLIXKJWXUGB-UHFFFAOYSA-N 0.000 description 1
- DILRJUIACXKSQE-UHFFFAOYSA-N n',n'-dimethylethane-1,2-diamine Chemical compound CN(C)CCN DILRJUIACXKSQE-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
- SWVGZFQJXVPIKM-UHFFFAOYSA-N n,n-bis(methylamino)propan-1-amine Chemical compound CCCN(NC)NC SWVGZFQJXVPIKM-UHFFFAOYSA-N 0.000 description 1
- VGPBPWRBXBKGRE-UHFFFAOYSA-N n-(oxomethylidene)hydroxylamine Chemical compound ON=C=O VGPBPWRBXBKGRE-UHFFFAOYSA-N 0.000 description 1
- BXYVQNNEFZOBOZ-UHFFFAOYSA-N n-[3-(dimethylamino)propyl]-n',n'-dimethylpropane-1,3-diamine Chemical compound CN(C)CCCNCCCN(C)C BXYVQNNEFZOBOZ-UHFFFAOYSA-N 0.000 description 1
- WHIVNJATOVLWBW-UHFFFAOYSA-N n-butan-2-ylidenehydroxylamine Chemical compound CCC(C)=NO WHIVNJATOVLWBW-UHFFFAOYSA-N 0.000 description 1
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical class C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 239000004843 novolac epoxy resin Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 150000002923 oximes Chemical class 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- GYDSPAVLTMAXHT-UHFFFAOYSA-N pentyl 2-methylprop-2-enoate Chemical compound CCCCCOC(=O)C(C)=C GYDSPAVLTMAXHT-UHFFFAOYSA-N 0.000 description 1
- ULDDEWDFUNBUCM-UHFFFAOYSA-N pentyl prop-2-enoate Chemical compound CCCCCOC(=O)C=C ULDDEWDFUNBUCM-UHFFFAOYSA-N 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- 150000003007 phosphonic acid derivatives Chemical class 0.000 description 1
- 230000000865 phosphorylative effect Effects 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
- 239000004632 polycaprolactone Substances 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000151 polyglycol Polymers 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- 150000008442 polyphenolic compounds Chemical class 0.000 description 1
- 235000013824 polyphenols Nutrition 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920000909 polytetrahydrofuran Polymers 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 150000003141 primary amines Chemical group 0.000 description 1
- 239000013615 primer Substances 0.000 description 1
- BAVIDSCVXNQEBA-UHFFFAOYSA-N prop-2-enoyl prop-2-eneperoxoate Chemical class C=CC(=O)OOC(=O)C=C BAVIDSCVXNQEBA-UHFFFAOYSA-N 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- BOQSSGDQNWEFSX-UHFFFAOYSA-N propan-2-yl 2-methylprop-2-enoate Chemical compound CC(C)OC(=O)C(C)=C BOQSSGDQNWEFSX-UHFFFAOYSA-N 0.000 description 1
- LYBIZMNPXTXVMV-UHFFFAOYSA-N propan-2-yl prop-2-enoate Chemical compound CC(C)OC(=O)C=C LYBIZMNPXTXVMV-UHFFFAOYSA-N 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 1
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- NVKTUNLPFJHLCG-UHFFFAOYSA-N strontium chromate Chemical compound [Sr+2].[O-][Cr]([O-])(=O)=O NVKTUNLPFJHLCG-UHFFFAOYSA-N 0.000 description 1
- 229960002317 succinimide Drugs 0.000 description 1
- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-UHFFFAOYSA-N 0.000 description 1
- CCIYPTIBRAUPLQ-UHFFFAOYSA-M tetrabutylphosphanium;iodide Chemical compound [I-].CCCC[P+](CCCC)(CCCC)CCCC CCIYPTIBRAUPLQ-UHFFFAOYSA-M 0.000 description 1
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 1
- DDFYFBUWEBINLX-UHFFFAOYSA-M tetramethylammonium bromide Chemical compound [Br-].C[N+](C)(C)C DDFYFBUWEBINLX-UHFFFAOYSA-M 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 239000012974 tin catalyst Substances 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
- 150000003628 tricarboxylic acids Chemical class 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-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
- 239000001226 triphosphate Substances 0.000 description 1
- 235000011178 triphosphate Nutrition 0.000 description 1
- UNXRWKVEANCORM-UHFFFAOYSA-N triphosphoric acid Chemical class OP(O)(=O)OP(O)(=O)OP(O)(O)=O UNXRWKVEANCORM-UHFFFAOYSA-N 0.000 description 1
- AVWRKZWQTYIKIY-UHFFFAOYSA-N urea-1-carboxylic acid Chemical compound NC(=O)NC(O)=O AVWRKZWQTYIKIY-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 150000003739 xylenols Chemical class 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
- C09D5/4419—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
- C09D5/4434—Polyepoxides characterised by the nature of the epoxy binder
- C09D5/4442—Binder characterised by functional groups
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D13/00—Electrophoretic coating characterised by the process
- C25D13/04—Electrophoretic coating characterised by the process with organic material
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D13/00—Electrophoretic coating characterised by the process
- C25D13/12—Electrophoretic coating characterised by the process characterised by the article coated
Definitions
- the invention relates to coating methods, particularly coating methods including electrocoating a coating layer and applying an additional coating layer over the electrocoat coating layer.
- Industrial coating of metal articles that will be used in corrosive environments may include application of one or more inorganic and organic treatments and coatings.
- Painting systems (“paint shops”) in automotive assembly plants are large, complex, and expensive.
- Metal automotive vehicle bodies (the “body-in-white”) and parts, for instance, are given a many-step treatment of cleaning in one or more cleaning baths or spray tanks, application of an aqueous phosphate coating material as a metal pretreatment step in a phosphating bath, then various rinses and additional finishing treatments, such as described in Claffey, U.S. Pat. No. 5,868,820.
- the phosphating pre-treatment steps are undertaken to improve corrosion resistance of the metal and adhesion of subsequent coatings to the metal.
- the cleaning and phosphating steps may have 10 or 12 individual treatment stations of spray equipment or dip tanks.
- Electrocoat baths usually comprise an aqueous dispersion or emulsion of a principal film-forming epoxy resin (“polymer” and “resin” are used interchangeably in this disclosure), having ionic stabilization in water or a mixture of water and organic cosolvent.
- the electrocoat compositions are formulated to be curable (thermosetting) compositions. This is usually accomplished by emulsifying with the principal film-forming resin a crosslinking agent that can react with functional groups on the principal resin under appropriate conditions, such as with the application of heat, and so cure the coating.
- coating material containing the ionically-charged resin having a relatively low molecular weight is deposited onto a conductive substrate by submerging the substrate in the electrocoat bath and then applying an electrical potential between the substrate and a pole of opposite charge, for example, a stainless steel electrode.
- the charged coating material migrates to and deposits on the conductive substrate.
- the coated substrate is then heated to cure or crosslink the coating.
- the applied coating composition forms a uniform and contiguous layer over a variety of metallic substrates regardless of shape or configuration. This is especially advantageous when the coating is applied as an anticorrosive coating onto a substrate having an irregular surface, such as a motor vehicle body. The even, continuous coating layer over all portions of the metallic substrate provides maximum anticorrosion effectiveness.
- the phosphate pre-treatment has up to now been an indispensable step in protecting against corrosion for automotive vehicle bodies. McMurdie et al., U.S. Pat. No.
- hydrocarbyl phosphate and phosphonic acid esters which may include polyepoxide linking groups, can be incorporated into electrodeposition baths in amounts of up to 500 ppm on total bath weight for improved corrosion protection. Examples including phenylphosphonic acid were reported to have a modest increase in corrosion protection over untreated steel panels.
- the process uses an aqueous electrocoat coating composition, also called an electrocoat bath, with a binder comprising a cathodically electrodepositable resin having at least one phosphorous-containing group
- X is a hydrogen, a monovalent hydrocarbon group (i.e., hydrocarbyl group), an alkyl group such as an aminoalkyl group, an aryl group, an alkylaryl group, an arylalkyl group, or an oxygen atom having a single covalent bond to the phosphorous atom, and each oxygen atom has a covalent bond to a hydrogen atom, an alkyl group, an aryl group, an alkylaryl group, an arylalkyl group, or the cathodically electrodepositable resin, with the caveat that at least one oxygen atom has a covalent bond to the cathodically electrodepositable resin.
- the alkyl groups may be cycloalkyl groups.
- resin is used in this disclosure to encompass resin, oligomer, and polymer, and the cathodically electodepositable resin having the phosphorous-containing group will be referred to as an amine-functional phosphorylated resin.
- Binder refers to the film-forming components of the coating composition. Typically the binder is thermosetting or curable.
- the amine-functional phosphorylated resin comprises an amine-functional monophosphate ester or monophosphonic acid ester of a polyepoxide resin. In another embodiment, the amine-functional phosphorylated resin comprises an amine-functional diphosphate ester, triphosphate ester, or diphosphonic acid ester of a polyepoxide resin. In other embodiments, the amine-functional phosphorylated resin includes a combination of these esters. The remaining oxygens on the phosphorous atom that are not covalently bound between the resin and the phosphorous atom may also be esterified. In certain embodiments, at least one P—OH group remains unesterified; that is, the phosphorous containing group has at least one P—OH group.
- the amine-functional phosphorylated resin has one phosphorous atom or a plurality of phosphorous atoms.
- the amine-functional phosphorylated resin may be prepared using a polyepoxide extended by reaction with one or more extenders, an extender being a material having at least two active hydrogen-containing groups.
- the amine-functional phosphorylated resin may be from about 0.01 to about 99% by weight of the total binder in the electrodeposition coating composition. Among these embodiments are those in which the amine-functional phosphorylated resin is from about 1 to about 90% by weight of total binder in the electrodeposition coating composition and those in which the amine-functional phosphorylated resin is from about 5 to about 80% by weight of total binder in the electrodeposition coating composition.
- the binder comprises a crosslinker for the amine-functional phosphorylated resin.
- the binder comprises a second amine-functional resin other than the amine-functional phosphorylated resin.
- the binder may also comprises a crosslinker which reacts during cure of the electrodeposited coating layer with the amine-functional phosphorylated resin, the second amine-functional resin, or both.
- a method of coating an electrically conductive substrate such as a metal automotive vehicle body or part, which comprises placing the electrically conductive substrate into the aqueous electrodeposition coating composition having a binder comprising an amine-functional phosphorylated resin salted with an acid and, using the electrically conductive substrate as the cathode, passing a current through the aqueous electrodeposition coating composition to deposit a coating layer comprising the binder onto the electrically conductive substrate. At least one additional coating layer is applied over the electrodeposited coating layer.
- the electrodeposited coating layer may be cured to a cured coating layer either before or after the additional coating layer is applied over it. Subsequent coating layers may be applied on the additional coating layer before or after the additional coating layer is cured.
- a topcoat layer or topcoat layers may be applied over the electrodeposited coating layer.
- the electrodeposited layer may be cured before application of any of these additional layers or co-cured with one or more additional layer applied.
- the electrically conductive substrate is unphosphated before it is coated with an electrodeposited coating comprising the phosphorylated resin; that is, the substrate is free of a phosphate pre-treatment.
- a metal automotive vehicle body is cleaned, and the cleaned metal automotive vehicle body is electrodeposited with an aqueous coating composition comprising amine-functional phosphorylated resin salted with an acid and at least one further coating layer.
- the binder of the electrocoat coating composition may include a second amine-functional resin that does not have phosphate groups, and generally a crosslinker reactive with one or both amine-functional resins is included in the coating composition so that the electrodeposited coating layer may be cured.
- a coated, electrically conductive substrate comprises an electrically deposited coating layer on the substrate, the electrically deposited coating layer comprising a cured coating formed from a binder comprising an amine-functional phosphorylated resin; and at least one further coating layer applied over the electrically deposited coating layer.
- the binder of the electrically deposited coating layer further comprises a crosslinker reactive with the phosphorylated epoxy resin, a second resin, or both which reacts during cure to form the cured coating.
- the at least one further coating layer may be a topcoat layer; in certain embodiments, at least a basecoat/clearcoat composite coating is applied over the electrically deposited coating layer.
- the phosphorylated resin electrodepositable By making the phosphorylated resin electrodepositable, a greater amount of the phosphorous-containing groups can be incorporated into the coating composition, resulting in significant improvement in corrosion protection over untreated, particularly unphosphated, metallic substrates such as cold rolled steel.
- a metal substrate which may be unphosphated, is electrocoated with an aqueous electrocoat coating composition having a binder comprising an amine-functional phosphorylated resin, then at least one additional coating layer is applied over the electrocoat coating layer.
- the amine-functional phosphorylated resin is salted with an acid.
- the electrodeposited coating layer may be cured before being overcoated with the at least one additional coating layer.
- the amine-functional phosphorylated resin has at least one covalently bonded, phosphorous-containing group having a structure
- X is a hydrogen, a monovalent hydrocarbon group, an alkyl group such as an aminoalkyl group, an aryl group, an alkylaryl group, an arylalkyl group, or an oxygen atom singly bonded to the phosphorous atom, and each oxygen atom has a covalent bond to a hydrogen atom, an alkyl group, an aryl group, an alkylaryl group, an arylalkyl group, or the cathodically electrodepositable resin, with the caveat that at least one oxygen atom has a covalent bond to the cathodically electrodepositable resin.
- an alkyl group may be a cycloalkyl group.
- the amine-functional phosphorylated resin may be prepared using any resin or polymerizable monomer that may be esterified with the phosphorous-containing group. Electrocoat coating binders often include epoxy resins, and the amine-functional phosphorylated resin may, for example, be an epoxy resin.
- An amine-functional phosphorylated epoxy resin may be prepared in various ways. n a first way, an amine-functional phosphorylated epoxy resin may be prepared by reaction of an epoxide-functional or hydroxyl-functional epoxy resin with a —P(OR) 2 ⁇ O group-containing acid or acid derivative, with at least one R being a hydrogen atom or a low alkyl group (by which we mean an alkyl group having one to four carbon atoms), particularly methyl, ethyl, propyl, isopropyl, isobutyl, butyl, or tert-butyl, that can be transesterified, such as phosphoric acid, a mono- or diester of phosphoric acid, hypophosphoric acid, a monoester of hypophosphoric acid, alkyl- or arylphosphonic acid, a monoester of alkyl- or arylphosphonic acid, and combinations of these.
- R being a hydrogen atom or a low alkyl group (by
- the epoxide-functional resin has at least one epoxide or hydroxyl group for reaction with the phosphorous-containing acid or acid derivative and has either an amine group or a further group (which may also be an epoxide group) for reaction with a compound containing an amine group.
- R is H, methyl, or ethyl
- n is an integer from 0 to 10. In certain embodiments, n is an integer from 1 to 5.
- diglycidyl ethers of aliphatic diols including the diglycidyl ethers of 1,4-butanediol, cyclohexanedimethanols, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, polypropylene glycol, polyethylene glycol, poly(tetrahydrofuran), 1,3-propanediol, 2,2,4-trimethyl-1,3-pentanediol, 1,6-hexanediol, 2,2-bis(4-hydroxycyclohexyl)propane, and the like.
- Diglycidyl esters of dicarboxylic acids can also be used as polyepoxides.
- Specific examples of compounds include the diglycidyl esters of oxalic acid, cyclohexanediacetic acids, cylcohexanedicarboxylic acids, succinic acid, glutaric acid, phthalic acid, terephthalic acid, isophthalic acid, naphthalene dicarboxylic acids, and the like.
- a polyglycidyl reactant may be used, preferably in a minor amount in combination with diepoxide reactant.
- Novolac epoxies may be used as a polyepoxide-functional reactant.
- the novolac epoxy resin may be selected from epoxy phenol novolac resins or epoxy cresol novolac resins.
- suitable higher-functionality polyepoxides are glycidyl ethers and esters of triols and higher polyols such as the triglycidyl ethers of trimethylolpropane, trimethylolethane, 2,6-bis(hydroxymethyl)-p-cresol, and glycerol; tricarboxylic acids or polycarboxylic acids.
- Also useful as polyepoxides are epoxidized alkenes such as cyclohexene oxides and epoxidized fatty acids and fatty acid derivatives such as epoxidized soybean oil.
- polyepoxides include, without limitation, polyepoxide polymers such as acrylic, polyester, polyether, and epoxy resins and polymers, and epoxy-modified polybutadiene, polyisoprene, acrylobutadiene nitrile copolymer, or other epoxy-modified rubber-based polymers that have a plurality of epoxide groups.
- the polyepoxide resin may be reacted with an extender to prepare a polyepoxide resin having a higher molecular weight having beta-hydroxy ester linkages.
- extenders include polycarboxylic acids, polyols, polyphenols, and amines having two or more amino hydrogens, especially dicarboxylic acids, diols, diphenols, and diamines.
- suitable extenders include diphenols, diols, and diacids such as those mentioned above in connection with forming the polyepoxide; polycaprolactone diols, and ethoxylated bisphenol A resins such as those available from BASF Corporation under the trademark MACOL®.
- Suitable extenders include, without limitation, carboxy- or amine-functional acrylic, polyester, polyether, and epoxy resins and polymers. Still other suitable extenders include, without limitation, polyamines, including diamines such as ethylenediamine, diethylenetriamine, triethylenetetramine, dimethylaminopropylamine, dimethylaminobutylamine, diethylaminopropylamine, diethylaminobutylamine, dipropylamine, and piperizines such as 1-(2-aminoethyl)piperazine, polyalkylenepolyamines such as triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, tripropylenetetramine, tetrapropylenepentamine, pentapropylenehexamine, N,N′-bis(3-aminopropyl)ethylenediamine, N-(2-hydroxyethyl)propane-1,3-diamine, and polyoxyalkylene amines
- a monofunctional reactant may optionally be reacted with the polyepoxide resin and the extender or after reaction of the polyepoxide with the extender to prepare an epoxide-functional resin.
- monofunctional reactants include phenol, alkylphenols such as nonylphenol and dodecylphenol, other monofunctional, epoxide-reactive compounds such as dimethylethanolamine and monoepoxides such as the glycidyl ether of phenol, the glycidyl ether of nonylphenol, or the glycidyl ether of cresol, and dimer fatty acid.
- Useful catalysts for the reaction of the polyepoxide resin with the extender and optional monofunctional reactant include any that activate an oxirane ring, such as tertiary amines or quaternary ammonium salts (e.g., benzyldimethylamine, dimethylaminocyclohexane, triethylamine, N-methylimidazole, tetramethyl ammonium bromide, and tetrabutyl ammonium hydroxide.), tin and/or phosphorous complex salts (e.g., (CH 3 ) 3 SNI, (CH 3 ) 4 PI, triphenylphosphine, ethyltriphenyl phosphonium iodide, tetrabutyl phosphonium iodide) and so on.
- tertiary amines or quaternary ammonium salts e.g., benzyldimethylamine, dimethylaminocyclo
- tertiary amine catalysts may be preferred with some reactants.
- the reaction may be carried out at a temperature of from about 100° C. to about 350° C. (in other embodiments 160° C. to 250° C.) in solvent or neat.
- Suitable solvents include, without limitation, inert organic solvent such as a ketone, including methyl isobutyl ketone and methyl amyl ketone, aromatic solvents such as toluene, xylene, Aromatic 100, and Aromatic 150, and esters, such as butyl acetate, n-propyl acetate, hexyl acetate.
- the polyepoxide resin may be reacted with the phosphorous-containing acid or acid derivative before, during, or after reaction of the polyepoxide resin with the extender and optional monofunctional reactant.
- the reaction with the acid or acid derivative if carried out before or after the reaction with the extender, may be carried out at a temperature of from about 50° C. to about 150° C. in solvent, including any of those already mentioned, or neat.
- the polyepoxide resin may also be reacted with the phosphorous-containing acid or acid derivative and optionally a monofunctional reactant such as those already described and not be reacted with an extender.
- the amine-functional phosphorylated resin has at least one amine group, and this amine functionality may introduced before or after the phosphorylating reaction. If before, the amine functionality may be introduced by reaction of the polyepoxide resin with an extender having a tertiary amine group or with a monofunctional reactant having a tertiary amine group.
- Suitable, nonlimiting examples of extenders and monofunctional reactants having an amine group include diethanolamine, dipropanolamine, diisopropanolamine, dibutanolamine, diisobutanolamine, diglycolamine, methylethanolamine, dimethylaminopropylamine, and compounds having a primary amine group that has been protected by forming a ketimine, such as the ketimine of diethylenetriamine.
- the polyepoxide resin, extended polyepoxide resin, or epoxide-functional resin is then reacted with the phosphorous-containing acid or acid derivative to make a phosphorylated resin.
- Suitable phosphorous containing acid derivatives include esterifiable esters and anhydrides of phosphorous-containing acids.
- —P(OR) 2 ⁇ O group-containing acids or acid derivatives having at least one R that is a hydrogen atom or a low alkyl group (up to four carbon atoms, particularly methyl, ethyl, propyl, isopropyl, and tert-butyl) than can be transesterified, such as phosphoric acid, an mono- or diester of phosphoric acid, hypophosphoric acid, a monoester of hypophosphoric acid, alkyl- or arylphosphonic acid, a monoester of alkyl- or arylphosphonic acid, and combinations of these.
- Phosphoric acid or a source of phosphoric acid that may be used in the reaction may be nonaqueous phosphoric acid, 85% in water, a more dilute aqueous phosphoric acid, pyrophosphoric acid, or polyphosphoric acid.
- Other suitable phosphoric acid sources are described in Campbell et al., U.S. Pat. No. 4,397,970, incorporated herein by reference.
- the polyepoxide resin, extended polyepoxide resin, or epoxide-functional resin is reacted with phosphoric acid or a source of phosphoric acid to make a phosphorylated resin.
- the phosphoric acid or source of phosphoric acid used in the reaction may be nonaqueous phosphoric acid, 85% in water, a more dilute aqueous phosphoric acid, pyrophosphoric acid, or polyphosphoric acid.
- Other suitable phosphoric acid sources are described in Campbell et al., U.S. Pat. No. 4,397,970, incorporated herein by reference.
- the polyepoxide resin, extended polyepoxide resin, or epoxide-functional resin is reacted with another phosphorous-containing acid or acid derivative such as one of those mentioned above.
- the phosphorylated resin may include monophosphonic acid esters, diphosphonic acid esters, monophosphate ester, diphosphate esters, and triphosphate esters, as well as combinations of these.
- the phosphorylated resin may have one or a plurality of the phosphorous-containing ester groups.
- the extent of esterification of phosphorous-containing acid or acid derivative and the number of phosphorous-containing ester groups incorporated into the resin is controlled, inter alia, by the relative equivalents of the reactants. In one example, from about 1 to about 3 equivalents of resin (based on epoxide and hydroxyl groups) is reacted with each equivalent of phosphoric acid or phosphoric acid derivative.
- reactants that may be used in addition to the resin and phosphorous-containing acid or acid derivative may include alcohols such as n-butanol, isopropanol, and n-propanol; glycol ethers such as ethylene glycol monobutyl ether, propylene glycol monobutyl ether, and propylene glycol monopropyl ether; amines such as any of those mentioned above; water; and combinations of these. These reactants can also be used to react with excess oxirane groups after the reaction of the resin with the acid or acid derivative.
- the amine functionality may be imparted to the phosphorylated resin in one of two ways.
- an amine having at least one active hydrogen reactive with an epoxide group is included as a reactant in the reaction of the epoxide-functional resin and phosphoric acid or source of phosphoric acid.
- the reaction product of the epoxide-functional epoxy resin and phosphoric acid (and any further reactants) is an epoxide-functional product that is then further reacted with an amine having at least one active hydrogen reactive with an epoxide group.
- Suitable amine compounds include, without limitation, dimethylaminopropylamine, N,N-diethylaminopropylamine, dimethylaminoethylamine, N-aminoethylpiperazine, aminopropylmorpholine, tetramethyldipropylenetriamine, methylamine, ethylamine, dimethylamine, dibutylamine, ethylenediamine, diethylenetriamine, triethylenetetramine, dimethylaminobutylamine, diethylaminopropylamine, diethylaminobutylamine, dipropylamine, methylbutylamine, alkanolamines such as methylethanolamine, aminoethylethanolamine, aminopropylmonomethylethanolamine, and diethanolamine, diketimine (a reaction product of 1 mole diethylenetriamine and 2 moles methyl isobutyl ketone), and polyoxyalkylene amines.
- dimethylaminopropylamine N,
- the phosphorylated resin is an epoxide-functional resin that is reacted with an extender, such any of those already mentioned.
- the amine-functional phosphorylated resin is used to prepare an electrocoat coating composition (also known as an electrocoat bath).
- an electrocoat coating composition also known as an electrocoat bath.
- a binder is prepared comprising the amine-functional phosphorylated resin, then the binder is dispersed in an aqueous medium by salting amine groups present in the binder with an acid.
- the amine-functional phosphorylated resin comprises from about 0.01 to about 99% by weight of binder in the electrodeposition coating composition.
- the amine-functional phosphorylated resin may comprise from about 0.01 to about 99% by weight of binder, 1 to about 90% by weight of binder, or from about 5 to about 80% by weight of binder in the electrodeposition coating composition.
- the binder may also comprise a crosslinker that reacts with the amine-functional phosphorylated resin during curing of a coating layer formed on a substrate. Suitable examples of crosslinking agents, include, without limitation, blocked polyisocyanates.
- aromatic, aliphatic or cycloaliphatic polyisocyanates include diphenylmethane-4,4′-diisocyanate (MDI), 2,4- or 2,6-toluene diisocyanate (TDI), p-phenylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane-4,4′-diisocyanate, isophorone diisocyanate, mixtures of phenylmethane-4,4′-diisocyanate, polymethylene polyphenylisocyanate, 2-isocyanatopropylcyclohexyl isocyanate, dicyclohexylmethane 2,4′-diisocyanate, 1,3-bis(iso-cyanatomethyl)cyclohexane, diisocyanates derived from dimer fatty acids, as sold under the commercial designation DDI 1410 by Henkel
- Suitable polyisocyantes also include polyisocyanates derived from these that containing isocyanurate, biuret, allophanate, iminooxadiazinedione, urethane, urea, or uretdione groups.
- Polyisocyanates containing urethane groups are obtained by reacting some of the isocyanate groups with polyols, such as trimethylolpropane, neopentyl glycol, and glycerol, for example. The isocyanate groups are reacted with a blocking agent.
- blocking agents examples include phenol, cresol, xylenol, epsilon-caprolactam, delta-valerolactam, gamma-butyrolactam, diethyl malonate, dimethyl malonate, ethyl acetoacetate, methyl acetoacetate, alcohols such as methanol, ethanol, isopropanol, propanol, isobutanol, tert-butanol, butanol, glycol monoethers such as ethylene or propylene glycol monoethers, acid amides (e.g. acetoanilide), imides (e.g. succinimide), amines (e.g. diphenylamine), imidazole, urea, ethylene urea, 2-oxazolidone, ethylene imine, oximes (e.g. methylethyl ketoxime), and the like.
- alcohols such as methanol, ethanol, isopropano
- the binder may include one or more additional resins.
- suitable additional resins include epoxy resins, polyesters, polyurethanes, vinyl resins such as polyacrylate resins, and polybutadiene resins.
- the additional resin may be, for example, any of the polyepoxide resins, extended polyepoxide resins, or epoxide-functional resins already mentioned, optionally reacted with a compound having at least one epoxide-reactive group.
- the binder comprises another amine-functional resin.
- suitable amine-functional resins include amine-functional epoxy resins, polyesters, polyurethanes, vinyl resins such as polyacrylate resins, and polybutadiene resins.
- Amine-functional epoxy resins may be prepared by reacting any of the polyepoxide resins, extended polyepoxide resins, or epoxide-functional resins already mentioned with an amine, including any of those mentioned above as suitable for preparing the amine-functional phosphorylated resin.
- Cationic polyurethanes and polyesters may also be used. Such materials may be prepared by endcapping with, for example, an aminoalcohol or, in the case of the polyurethane, the same compound comprising a saltable amine group previously described may also be useful.
- Polybutadiene, polyisoprene, or other epoxy-modified rubber-based polymers can be used as the resin in the present invention.
- the epoxy-rubber can be capped with a compound comprising a saltable amine group.
- Cationic acrylic resins may be made cathodic by incorporation of amino-containing monomers, such as acrylamide, methacrylamide, N,N′-dimethylaminoethyl methacrylate tert-butylaminoethyl methacrylate. 2-vinylpyridine, 4-vinylpyridine, vinylpyrrolidine or other such amino monomers.
- epoxy groups may be incorporated by including an epoxy-functional monomer in the polymerization reaction.
- Such epoxy-functional acrylic polymers may be made cathodic by reaction of the epoxy groups with amines according to the methods previously described for the epoxy resins.
- the polymerization may also include a hydroxyl-functional monomer.
- Useful hydroxyl-functional ethylenically unsaturated monomers include, without limitation, hydroxyethyl methacrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, hydroxybutyl methacrylate, the reaction product of methacrylic acid with styrene oxide, and so on.
- Preferred hydroxyl monomers are methacrylic or acrylic acid esters in which the hydroxyl-bearing alcohol portion of the compound is a linear or branched hydroxy alkyl moiety having from 1 to about 8 carbon atoms.
- the monomer bearing the hydroxyl group and the monomer bearing the group for salting may be polymerized with one or more other ethylenically unsaturated monomers.
- Such monomers for copolymerization are known in the art.
- Illustrative examples include, without limitation, alkyl esters of acrylic or methacrylic acid, e.g., methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, butyl acrylate, butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, t-butyl acrylate, t-butyl methacrylate, amyl acrylate, amyl methacrylate, isoamyl acrylate, isoamyl methacrylate, hexyl acrylate, hexyl methacrylate, 2-ethylhexyl acrylate, decyl acrylate, decyl methacrylate, isodecyl acrylate, isodecyl methacrylate, dodecyl
- polymerizable co-monomers include, for example, alkoxyethyl acrylates and methacrylates, acryloxy acrylates and methacrylates, and compounds such as acrylonitrile, methacrylonitrile, acrolein, and methacrolein. Combinations of these are usually employed.
- the binder may also comprise a crosslinker that reacts with the amine-functional resin other than the phosphorylated resin during curing of a coating layer formed on a substrate, or the binder may also comprise a crosslinker that reacts with both the amine-functional resin other than the phosphorylated resin and the phosphorylated resin during curing of a coating layer formed on a substrate.
- plasticizer or solvents or both can be added to the binder mixture.
- coalescing solvents include alcohols, glycol ethers, polyols, and ketones.
- coalescing solvents include monobutyl and monohexyl ethers of ethylene glycol, phenyl ether of propylene glycol, monoalkyl ethers of ethylene glycol such as the monomethyl, monoethyl, monopropyl, and monobutyl ethers of ethylene glycol or propylene glycol; dialkyl ethers of ethylene glycol or propylene glycol such as ethylene glycol dimethyl ether and propylene glycol dimethyl ether; butyl carbitol; diacetone alcohol.
- Nonlimiting examples of plasticizers include ethylene or propylene oxide adducts of nonyl phenols, bisphenol A, cresol, or other such materials, or polyglycols based on ethylene oxide and/or propylene oxide.
- the amount of coalescing solvent is not critical and is generally between about 0 to 15 percent by weight, preferably about 0.5 to 5 percent by weight based on total weight of the resin solids.
- Plasticizers can be used at levels of up to 15 percent by weight resin solids.
- the binder is emulsified in water in the presence of an acid.
- suitable acids include phosphoric acid, phosphonic acid, propionic acid, formic acid, acetic acid, lactic acid, or citric acid.
- the salting acid may be blended with the binder, mixed with the water, or both, before the binder is added to the water.
- the acid is used in an amount sufficient to neutralize enough of the amine groups to impart water-dispersibility to the binder.
- the amine groups may be fully neutralized; however, partial neutralization is usually sufficient to impart the required water-dispersibility.
- the degree of neutralization that is required to afford the requisite water-dispersibility for a particular binder will depend upon its composition, molecular weight of the resins, weight percent of amine-functional resin, and other such factors and can readily be determined by one of ordinary skill in the art through straightforward experimentation.
- the binder emulsion is then used in preparing an electrocoat coating composition (or bath).
- the electrocoat bath may contain no pigment so as to produce a colorless or clear electrodeposited coating layer, but the electrocoat bath usually includes one or more pigments, separately added as part of a pigment paste, and may contain any further desired materials such as coalescing aids, antifoaming aids, and other additives that may be added before or after emulsifying the resin.
- Conventional pigments for electrocoat primers include titanium dioxide, ferric oxide, carbon black, aluminum silicate, precipitated barium sulfate, aluminum phosphomolybdate, strontium chromate, basic lead silicate or lead chromate.
- the pigments may be dispersed using a grind resin or a pigment dispersant.
- the pigment-to-resin weight ratio in the electrocoat bath can be important and should be preferably less than 50:100, more preferably less than 40:100, and usually about 10 to 30:100. Higher pigment-to-resin solids weight ratios have been found to adversely affect coalescence and flow.
- the pigment is 10-40 percent by weight of the nonvolatile material in the bath.
- the pigment is 15 to 30 percent by weight of the nonvolatile material in the bath.
- Any of the pigments and fillers generally used in electrocoat primers may be included. Inorganic extenders such as clay and anti-corrosion pigments are commonly included.
- the electrodeposition coating compositions can contain optional ingredients such as dyes, flow control agents, plasticizers, catalysts, wetting agents, surfactants, UV absorbers, HALS compounds, antioxidants, defoamers and so forth.
- surfactants and wetting agents include alkyl imidazolines such as those available from Ciba-Geigy Industrial Chemicals as AMINE C® acetylenic alcohols such as those available from Air Products and Chemicals under the tradename SURFYNOL®.
- Surfactants and wetting agents when present, typically amount to up to 2 percent by weight resin solids.
- Curing catalysts such as tin catalysts can be used in the coating composition.
- tin catalysts can be used in the coating composition.
- Typical examples are without limitation, tin and bismuth compounds including dibutyltin dilaurate, dibutyltin oxide, and bismuth octoate.
- catalysts are typically present in amounts of about 0.05 to 2 percent by weight tin based on weight of total resin solids.
- the electrocoat coating composition is electrodeposited onto a metallic substrate.
- the substrate may be, as some nonlimiting examples, cold-rolled steel, galvanized (zinc coated) steel, electrogalvanized steel, stainless steel, pickled steel, GALVANNEAL® GALVALUME®, and GALVAN® zinc-aluminum alloys coated upon steel, and combinations of these.
- Nonlimiting examples of useful non-ferrous metals include aluminum, zinc, magnesium and alloys of these.
- the electrodeposition of the coating preparations according to the invention may be carried out by known processes.
- the electrodeposition coating composition may be applied preferably to a dry film thickness of 10 to 35 ⁇ m.
- the electrically conductive substrate is unphosphated; that is, it is free of a phosphate pre-treatment
- the article coated with the composition of the invention may be a metallic automotive part or body.
- a method of coating an electrically conductive substrate such as a metal automotive vehicle body or part, comprises placing an electrically conductive substrate, cleaned but preferably not given a phosphate pre-treatment, into the electrocoat coating composition and, using the electrically conductive substrate as the cathode, passing a current through the electrocoat coating composition causing a coating layer to deposit onto the electrically conductive substrate.
- the coated article is removed from the bath and rinsed with deionized water.
- the coating may be cured under appropriate conditions, for example by baking at from about 275° F. to about 375° F. for between about 15 and about 60 minutes, before applying an additional coating layer over the electrodeposited coating layer.
- An automotive vehicle body may be electrocoated.
- the automotive vehicle body is cleaned, and the cleaned metal automotive vehicle body is electrocoated with an aqueous electrodeposition coating composition comprising the phosphorylated resin.
- One or more additional coating layers may be applied over the electrocoat layer.
- a single layer topcoat is also referred to as a topcoat enamel.
- the topcoat is typically a basecoat that is overcoated with a clearcoat layer.
- a primer surfacer and the topcoat enamel or basecoat and clearcoat composite topcoat may be waterborne, solventborne, or a powder coating, which may be a dry powder or an aqueous powder slurry.
- the composite coating of the invention may have, as one layer, a primer coating layer, which may also be termed a primer-surfacer or filler coating layer.
- the primer coating layer can be formed from a solventborne composition, waterborne composition, or powder composition, including powder slurry composition.
- the primer composition preferably has a binder that is thermosetting, although thermoplastic binders are also known. Suitable thermosetting binders may have self-crosslinking polymers or resins, or may include a crosslinker reactive with a polymer or resin in the binder.
- suitable binder polymers or resins include acrylics, polyesters, and polyurethanes.
- Such polymers or resins may include as functional groups hydroxyl groups, carboxyl groups, anhydride groups, epoxide groups, carbamate groups, amine groups, and so on.
- suitable crosslinkers reactive with such groups are aminoplast resins (which are reactive with hydroxyl, carboxyl, carbamate, and amine groups), polyisocyanates, including blocked polyisocyanates (which are reactive with hydroxyl groups and amine groups), polyepoxides (which are reactive with carboxyl, anhydride, hydroxyl, and amine groups), and polyacids and polyamines (which are reactive with epoxide groups).
- suitable primer compositions are disclosed, for example, in U.S. Pat. Nos.
- the primer coating composition applied over the electrocoat primer may then be cured to form a primer coating layer.
- the electrocoat primer may be cured at the same time as the primer coating layer in a process known as “wet-on-wet” coating.
- a topcoat composition may be applied over the electrocoat layer or primer coating layer and, preferably, cured to form a topcoat layer.
- the electrocoat layer or primer layer is coated with a topcoat applied as a color-plus-clear (basecoat-clearcoat) topcoat.
- basecoat-clearcoat topcoat an underlayer of a pigmented coating, the basecoat, is covered with an outer layer of a transparent coating, the clearcoat.
- Basecoat-clearcoat topcoats provide an attractive smooth and glossy finish and generally improved performance.
- Crosslinking compositions are preferred as the topcoat layer or layers. Coatings of this type are well-known in the art and include waterborne compositions, solventborne compositions, and powder and powder slurry compositions. Polymers known in the art to be useful in basecoat and clearcoat compositions include, without limitation, acrylics, vinyls, polyurethanes, polycarbonates, polyesters, alkyds, and polysiloxanes. Acrylics and polyurethanes are among preferred polymers for topcoat binders.
- Thermoset basecoat and clearcoat compositions are also preferred, and, to that end, preferred polymers comprise one or more kinds of crosslinkable functional groups, such as carbamate, hydroxy, isocyanate, amine, epoxy, acrylate, vinyl, silane, acetoacetate, and so on.
- the polymer may be self-crosslinking, or, preferably, the composition may include a crosslinking agent such as a polyisocyanate or an aminoplast resin.
- suitable topcoat compositions are disclosed, for example, in U.S. Pat. Nos.
- the further coating layers can be applied to the electrocoat coating layer according to any of a number of techniques well-known in the art. These include, for example, spray coating, dip coating, roll coating, curtain coating, and the like.
- the further coating layer or layers are preferably applied by spray coating, particularly electrostatic spray methods. Coating layers of one mil or more are usually applied in two or more coats, separated by a time sufficient to allow some of the solvent or aqueous medium to evaporate, or “flash,” from the applied layer.
- the flash may be at ambient or elevated temperatures, for example, the flash may use radiant heat.
- the coats as applied can be from 0.5 mil up to 3 mils dry, and a sufficient number of coats are applied to yield the desired final coating thickness.
- a primer layer may be cured before the topcoat is applied.
- the cured primer layer may be from about 0.5 mil to about 2 mils thick, preferably from about 0.8 mils to about 1.2 mils thick.
- Color-plus-clear topcoats are usually applied wet-on-wet.
- the compositions are applied in coats separated by a flash, as described above, with a flash also between the last coat of the color composition and the first coat the clear.
- the two coating layers are then cured simultaneously.
- the cured basecoat layer is 0.5 to 1.5 mils thick
- the cured clear coat layer is 1 to 3 mils, more preferably 1.6 to 2.2 mils, thick.
- the primer layer and the topcoat can be applied “wet-on-wet.”
- the primer composition can be applied, then the applied layer flashed; then the topcoat can be applied and flashed; then the primer and the topcoat can be cured at the same time.
- the topcoat can include a basecoat layer and a clearcoat layer applied wet-on-wet.
- the primer layer can also be applied to an uncured electrocoat coating layer, and all layers cured together.
- the coating compositions described are preferably cured with heat.
- Curing temperatures are preferably from about 70° C. to about 180° C., and particularly preferably from about 170° F. to about 200° F. for a topcoat or primer composition including an unblocked acid catalyst, or from about 240° F. to about 275° F. for a topcoat or primer composition including a blocked acid catalyst.
- Typical curing times at these temperatures range from 15 to 60 minutes, and preferably the temperature is chosen to allow a cure time of from about 15 to about 30 minutes.
- the coated article is an automotive body or part.
- a reactor equipped with an agitator and reflux condenser is charged with 25.85 parts by weight of normal butanol, 10.20 parts by weight of ethylene glycol monobutyl ether, and 55.62 parts by weight of the diglycidyl ether of Bisphenol A.
- the reactor contents are stirred for about5 minutes followed by addition of a 3.11 parts of diethanolamine.
- the resulting mixture is heated to 77° F. (25° C.); heat is then discontinued, and the reaction mixture is allowed to exotherm.
- the temperature of the reaction continues to increase to 120.2-122° F. (49-50° C.).
- the reaction mixture is maintained at 140-149° F. (60-65° C.) for 30 minutes.
- reaction mixture is maintained at 220-250° F. (104.4-121.1° C.) for one hour.
- a final portion of deionized water, 0.70 parts by weight, is then added to the reaction mixture. Again the reaction mixture is maintained at 220-250° F. (104.4-121.1° C.) for one hour.
- the product is then diluted with normal butanol to 72% nonvolatile by weight.
- reaction mixture is allowed to stir for an additional 30 minutes at 221° F. (105° C.) after reaching exotherm. After stirring for 30 minutes, 3-dimethylaminopropylamine is added at 221° F. (105° C.) (0.84 parts by weight), and the exotherm is recorded as 280.4° F. (138° C.). The mixture is stirred for an additional hour.
- a crosslinker (a blocked isocyanate based on polymeric MDI and monofunctional alcohols) (13.6 parts by weight) is added. The mixture is stirred for 30 minutes at 221-230° F. (105-110° C.).
- Preparation A the amine-functional phosphorylated epoxy resin, (6.47 parts by weight) is added and the mixture is stirred for an additional 15 minutes at 221-230° F. (105-110° C.).
- the resins and crosslinker blend are added to an acid/water mixture, under constant stirring, of deionized water (34.95 parts by weight) and formic acid (88%) (0.62 parts by weight). After thoroughly mixing all components using a metal spatula, the solids are further reduced by addition of water (18.55 parts by weight). A flow-additive package (2.51 parts by weight) is added to the acid mixture.
- an aqueous-organic grinding resin solution is prepared by reacting, in the first stage, 2598 parts of bisphenol A diglycidyl ether (epoxy equivalent weight (EEW) 188 g/eq), 787 parts of bisphenol A, 603 parts of dodecylphenol, and 206 parts of butyl glycol in a stainless steel reaction vessel in the presence of 4 parts of triphenylphosphine at 130° C. until an EEW of 865 g/eq is reached.
- EW epoxy equivalent weight
- the batch is diluted with 849 parts of butyl glycol and 1534 parts of D.E.R® 732 (polypropylene glycol diglycidyl ether, DOW Chemical, USA) and is reacted further at 90° C. with 266 parts of 2,2′-aminoethoxyethanol and 212 parts of N,N-dimethylaminopropylamine.
- the viscosity of the resin solution is constant (5.3 dPas; 40% in SOLVENON® PM (methoxypropanol, BASF/Germany); cone and plate viscometer at 23° C.).
- a premix is first formed from 1897 parts of water and 1750 parts of the grinding resin solution of Preparation C. Then 21 parts of DISPERBYK® 110 (Byk-Chemie GmbH/Germany), 14 parts of Lanco Wax®. PE W 1555 (Langer & Co./Germany), 42 parts of carbon black, 420 parts of aluminum hydrosilicate ASP 200 (Langer & Co./Germany), 2667 parts of titanium dioxide TI-PURE® R 900 (DuPont, USA) and 189 parts of di-n-butyl tin oxide are added. The mixture is predispersed for 30 minutes under a high-speed dissolver stirrer.
- the mixture is subsequently dispersed in a small laboratory mill (Motor Mini Mill, Eiger Engineering Ltd, Great Britain) until it measures a Hegmann fineness of less than or equal to 12 ⁇ m and is adjusted to solids content with additional water.
- a separation-stable pigment paste is obtained. Solids content: 60.0% by weight (1 ⁇ 2 h at 180° C.).
- a bath was prepared by combining 964.4 parts Preparation B, 144.8 parts Preparation D, and 1290.8 parts deionized water.
- the water and Preparation B resin emulsion are combined in a container with constant stirring, and Preparation D is added with stirring.
- the bath solids content is 19% by weight.
- Example 1 is tested by coating both phosphated and bare cold rolled steel 4-inch-by-6-inch test panels at 225 volts (0.5 ampere) in the Example 1 bath at bath temperatures from 88-98° F. (31-36.7° C.) for 2.2 minutes, dehydrating and/or baking the coated panels for 28 minutes at 350° F. (177° C.).
- the deposited, baked coating has a film build of about 0.8 mil (20 ⁇ m). Three panels were coated for each temperature and substrate.
- Control panels were prepared as described for Example 1 but using U32AD500 (commercial product sold by BASF Corporation).
- panels are tested as follows or further coated with a top coat and then tested.
- GMW15288 Each panel is scribed directly down the middle and tested by corrosion test (GMW15288) The description of GMW15288 is as follows: On a Monday, each panel is held at 60° C. for one hour in an air-circulating oven and is then subjected to a cold cabinet at -25° C. for 30 minutes. Following, the panels are immersed for 15 minutes in a 5 wt. % NaCl solution in water (saline solution). After removal, the panels are allowed to air dry for 75 minutes at room temperature. The panels are then transferred to a humidity cabinet (60° C., 85% humidity) with an air flow not exceeding 15 m/ft across the panel and held for 21 hours.
- a humidity cabinet 60° C., 85% humidity
- the panels are immersed again in the saline solution for 15 minutes, allowed to air dry to 75 minutes at room temperature, and then returned to the humidity cabinet (22 hours). On Saturday and Sunday the panels remain in the humidity cabinet. The entire exposure sequence from Monday to the following Monday constitutes 5 cycles. The test is then repeated for a total of 20 cycles. After completion, each panel is rinsed with water and scraped with a metal spatula. The corrosion is measured as the average of scribe width of selected points along the scribe length.
- SAE J2334 DEC2003 After baking, each panel is scribed directly down the middle and tested in accordance with SAE J2334 DEC2003.
- the test description is as follows: For 6 hours the test panels are subjected to 100% relative humidity (RH) at 50° C., 15 minute salt solution dip at ambient conditions, where the salt solution consists of 0.5% NaCl, 0.1% CaCl 2 and 0.075% NaHCO 3 . For the remaining 17 hours and 45 minutes the test panels are placed in a cabinet at 60° C. and 50% RH. The cycle is repeated 20 times. After completion, each panel is rinsed with water and scraped with a metal spatula. The corrosion is measured as the average of scribe width of selected points along the scribe length.
- Humidity testing was performed in accordance with ASTM D3359 and chip testing was performed in accordance with GMW 14700.
Abstract
An electrically conductive substrate is electrocoated with an aqueous electrodeposition coating composition comprising a cathodically electrodepositable binder, the binder comprising an amine-functional phosphorylated resin and at least one additional coating layer, such as a second primer layer, a topcoat layer, or both.
Description
- The invention relates to coating methods, particularly coating methods including electrocoating a coating layer and applying an additional coating layer over the electrocoat coating layer.
- The statements in this section merely provide background information related to this disclosure and may not constitute prior art.
- Industrial coating of metal articles that will be used in corrosive environments may include application of one or more inorganic and organic treatments and coatings. Painting systems (“paint shops”) in automotive assembly plants are large, complex, and expensive. Metal automotive vehicle bodies (the “body-in-white”) and parts, for instance, are given a many-step treatment of cleaning in one or more cleaning baths or spray tanks, application of an aqueous phosphate coating material as a metal pretreatment step in a phosphating bath, then various rinses and additional finishing treatments, such as described in Claffey, U.S. Pat. No. 5,868,820. The phosphating pre-treatment steps are undertaken to improve corrosion resistance of the metal and adhesion of subsequent coatings to the metal. The cleaning and phosphating steps may have 10 or 12 individual treatment stations of spray equipment or dip tanks.
- An electrodeposition coating (“electrocoat”) is applied after the pretreatment steps to the metal vehicle body. Electrocoat baths usually comprise an aqueous dispersion or emulsion of a principal film-forming epoxy resin (“polymer” and “resin” are used interchangeably in this disclosure), having ionic stabilization in water or a mixture of water and organic cosolvent. In automotive or industrial applications for which durable electrocoat films are desired, the electrocoat compositions are formulated to be curable (thermosetting) compositions. This is usually accomplished by emulsifying with the principal film-forming resin a crosslinking agent that can react with functional groups on the principal resin under appropriate conditions, such as with the application of heat, and so cure the coating. During electrodeposition, coating material containing the ionically-charged resin having a relatively low molecular weight is deposited onto a conductive substrate by submerging the substrate in the electrocoat bath and then applying an electrical potential between the substrate and a pole of opposite charge, for example, a stainless steel electrode. The charged coating material migrates to and deposits on the conductive substrate. The coated substrate is then heated to cure or crosslink the coating.
- One of the advantages of electrocoat compositions and processes is that the applied coating composition forms a uniform and contiguous layer over a variety of metallic substrates regardless of shape or configuration. This is especially advantageous when the coating is applied as an anticorrosive coating onto a substrate having an irregular surface, such as a motor vehicle body. The even, continuous coating layer over all portions of the metallic substrate provides maximum anticorrosion effectiveness. The phosphate pre-treatment, however, has up to now been an indispensable step in protecting against corrosion for automotive vehicle bodies. McMurdie et al., U.S. Pat. No. 6,110,341 teaches that hydrocarbyl phosphate and phosphonic acid esters, which may include polyepoxide linking groups, can be incorporated into electrodeposition baths in amounts of up to 500 ppm on total bath weight for improved corrosion protection. Examples including phenylphosphonic acid were reported to have a modest increase in corrosion protection over untreated steel panels.
- We disclose a process for finishing a metallic substrate including electrodepositing an electrocoat coating having phosphorous-containing groups on a metal substrate, particularly on an unphosphated metal substrate, (that is, a metal substrate that has not undergone a phosphate pretreatment) and applying at least one further coating layer over the electrocoat coating
- The process uses an aqueous electrocoat coating composition, also called an electrocoat bath, with a binder comprising a cathodically electrodepositable resin having at least one phosphorous-containing group
- in which X is a hydrogen, a monovalent hydrocarbon group (i.e., hydrocarbyl group), an alkyl group such as an aminoalkyl group, an aryl group, an alkylaryl group, an arylalkyl group, or an oxygen atom having a single covalent bond to the phosphorous atom, and each oxygen atom has a covalent bond to a hydrogen atom, an alkyl group, an aryl group, an alkylaryl group, an arylalkyl group, or the cathodically electrodepositable resin, with the caveat that at least one oxygen atom has a covalent bond to the cathodically electrodepositable resin. The alkyl groups may be cycloalkyl groups. For convenience, “resin” is used in this disclosure to encompass resin, oligomer, and polymer, and the cathodically electodepositable resin having the phosphorous-containing group will be referred to as an amine-functional phosphorylated resin. “Binder” refers to the film-forming components of the coating composition. Typically the binder is thermosetting or curable.
- In one embodiment, the amine-functional phosphorylated resin comprises an amine-functional monophosphate ester or monophosphonic acid ester of a polyepoxide resin. In another embodiment, the amine-functional phosphorylated resin comprises an amine-functional diphosphate ester, triphosphate ester, or diphosphonic acid ester of a polyepoxide resin. In other embodiments, the amine-functional phosphorylated resin includes a combination of these esters. The remaining oxygens on the phosphorous atom that are not covalently bound between the resin and the phosphorous atom may also be esterified. In certain embodiments, at least one P—OH group remains unesterified; that is, the phosphorous containing group has at least one P—OH group.
- In various embodiments, the amine-functional phosphorylated resin has one phosphorous atom or a plurality of phosphorous atoms. The amine-functional phosphorylated resin may be prepared using a polyepoxide extended by reaction with one or more extenders, an extender being a material having at least two active hydrogen-containing groups.
- In certain embodiments, the amine-functional phosphorylated resin may be from about 0.01 to about 99% by weight of the total binder in the electrodeposition coating composition. Among these embodiments are those in which the amine-functional phosphorylated resin is from about 1 to about 90% by weight of total binder in the electrodeposition coating composition and those in which the amine-functional phosphorylated resin is from about 5 to about 80% by weight of total binder in the electrodeposition coating composition. In certain embodiments, the binder comprises a crosslinker for the amine-functional phosphorylated resin. In certain embodiments, the binder comprises a second amine-functional resin other than the amine-functional phosphorylated resin. In any of these embodiments, the binder may also comprises a crosslinker which reacts during cure of the electrodeposited coating layer with the amine-functional phosphorylated resin, the second amine-functional resin, or both.
- We disclose a method of coating an electrically conductive substrate, such as a metal automotive vehicle body or part, which comprises placing the electrically conductive substrate into the aqueous electrodeposition coating composition having a binder comprising an amine-functional phosphorylated resin salted with an acid and, using the electrically conductive substrate as the cathode, passing a current through the aqueous electrodeposition coating composition to deposit a coating layer comprising the binder onto the electrically conductive substrate. At least one additional coating layer is applied over the electrodeposited coating layer. The electrodeposited coating layer may be cured to a cured coating layer either before or after the additional coating layer is applied over it. Subsequent coating layers may be applied on the additional coating layer before or after the additional coating layer is cured. For example, other layers such as an optional spray-applied primer surfacer and a topcoat layer or topcoat layers (e.g., a colored basecoat layer and a clearcoat layer) may be applied over the electrodeposited coating layer. The electrodeposited layer may be cured before application of any of these additional layers or co-cured with one or more additional layer applied.
- In one embodiment of the method, the electrically conductive substrate is unphosphated before it is coated with an electrodeposited coating comprising the phosphorylated resin; that is, the substrate is free of a phosphate pre-treatment.
- In one embodiment of the method, a metal automotive vehicle body is cleaned, and the cleaned metal automotive vehicle body is electrodeposited with an aqueous coating composition comprising amine-functional phosphorylated resin salted with an acid and at least one further coating layer. Thus, no phosphate pretreatment is used. The binder of the electrocoat coating composition may include a second amine-functional resin that does not have phosphate groups, and generally a crosslinker reactive with one or both amine-functional resins is included in the coating composition so that the electrodeposited coating layer may be cured.
- A coated, electrically conductive substrate comprises an electrically deposited coating layer on the substrate, the electrically deposited coating layer comprising a cured coating formed from a binder comprising an amine-functional phosphorylated resin; and at least one further coating layer applied over the electrically deposited coating layer. In various embodiments, the binder of the electrically deposited coating layer further comprises a crosslinker reactive with the phosphorylated epoxy resin, a second resin, or both which reacts during cure to form the cured coating. The at least one further coating layer may be a topcoat layer; in certain embodiments, at least a basecoat/clearcoat composite coating is applied over the electrically deposited coating layer.
- By making the phosphorylated resin electrodepositable, a greater amount of the phosphorous-containing groups can be incorporated into the coating composition, resulting in significant improvement in corrosion protection over untreated, particularly unphosphated, metallic substrates such as cold rolled steel.
- “A,” “an,” “the,” “at least one,” and “one or more” are used interchangeably to indicate that at least one of the item is present; a plurality of such items may be present. Other than in the working examples provides at the end of the detailed description, all numerical values of parameters (e.g., of quantities or conditions) in this specification, including the appended claims, are to be understood as being modified in all instances by the term “about” whether or not “about” actually appears before the numerical value. “About” indicates that the stated numerical value allows some slight imprecision (with some approach to exactness in the value; approximately or reasonably close to the value; nearly). If the imprecision provided by “about” is not otherwise understood in the art with this ordinary meaning, then “about” as used herein indicates at least variations that may arise from ordinary methods of measuring and using such parameters. In addition, disclosure of ranges includes disclosure of all values and further divided ranges within the entire range.
- Further areas of applicability will become apparent from the description provided herein. It should be understood that the description and specific examples are intended for purposes of illustration only and are not intended to limit the scope of the present disclosure.
- The following description is merely exemplary in nature and is not intended to limit the present disclosure, application, or uses.
- A metal substrate, which may be unphosphated, is electrocoated with an aqueous electrocoat coating composition having a binder comprising an amine-functional phosphorylated resin, then at least one additional coating layer is applied over the electrocoat coating layer. The amine-functional phosphorylated resin is salted with an acid. The electrodeposited coating layer may be cured before being overcoated with the at least one additional coating layer. The amine-functional phosphorylated resin has at least one covalently bonded, phosphorous-containing group having a structure
- in which X is a hydrogen, a monovalent hydrocarbon group, an alkyl group such as an aminoalkyl group, an aryl group, an alkylaryl group, an arylalkyl group, or an oxygen atom singly bonded to the phosphorous atom, and each oxygen atom has a covalent bond to a hydrogen atom, an alkyl group, an aryl group, an alkylaryl group, an arylalkyl group, or the cathodically electrodepositable resin, with the caveat that at least one oxygen atom has a covalent bond to the cathodically electrodepositable resin. In each case, an alkyl group may be a cycloalkyl group.
- The amine-functional phosphorylated resin may be prepared using any resin or polymerizable monomer that may be esterified with the phosphorous-containing group. Electrocoat coating binders often include epoxy resins, and the amine-functional phosphorylated resin may, for example, be an epoxy resin.
- An amine-functional phosphorylated epoxy resin may be prepared in various ways. n a first way, an amine-functional phosphorylated epoxy resin may be prepared by reaction of an epoxide-functional or hydroxyl-functional epoxy resin with a —P(OR)2═O group-containing acid or acid derivative, with at least one R being a hydrogen atom or a low alkyl group (by which we mean an alkyl group having one to four carbon atoms), particularly methyl, ethyl, propyl, isopropyl, isobutyl, butyl, or tert-butyl, that can be transesterified, such as phosphoric acid, a mono- or diester of phosphoric acid, hypophosphoric acid, a monoester of hypophosphoric acid, alkyl- or arylphosphonic acid, a monoester of alkyl- or arylphosphonic acid, and combinations of these. The epoxide-functional resin has at least one epoxide or hydroxyl group for reaction with the phosphorous-containing acid or acid derivative and has either an amine group or a further group (which may also be an epoxide group) for reaction with a compound containing an amine group.
- Suitable, nonlimiting examples of polyepoxide resins that may be reacted with the —P(OR)2═O group-containing acid include epoxy resins with a plurality of epoxide groups, such as diglycidyl aromatic compounds such as the diglycidyl ethers of polyhydric phenols such as 2,2-bis(4-hydroxyphenyl)propane (bisphenol A), 2,2-bis(4-hydroxy-3-methylphenyl)propane, 4,4′-dihydroxybenzophenone, dihydroxyacetophenones, 1,1-bis(4hydroxyphenylene)ethane, bis(4-hydroxyphenyl)methane, 1,1-bis(4hydroxyphenyl)isobutane, 2,2-bis(4-hydroxy-tert-butylphenyl)propane, 1,4-bis(2-hydroxyethyl)piperazine, 2-methyl-1,1-bis(4-hydroxyphenyl)propane, bis-(2-hydroxynaphthyl)methane, 1,5-dihydroxy-3-naphthalene, and other dihydroxynaphthylenes, catechol, resorcinol, and the like, including diglycidyl ethers of bisphenol A and bisphenol A-based resins having a structure
- wherein Q is
- R is H, methyl, or ethyl, and n is an integer from 0 to 10. In certain embodiments, n is an integer from 1 to 5. Also suitable are the diglycidyl ethers of aliphatic diols, including the diglycidyl ethers of 1,4-butanediol, cyclohexanedimethanols, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, polypropylene glycol, polyethylene glycol, poly(tetrahydrofuran), 1,3-propanediol, 2,2,4-trimethyl-1,3-pentanediol, 1,6-hexanediol, 2,2-bis(4-hydroxycyclohexyl)propane, and the like. Diglycidyl esters of dicarboxylic acids can also be used as polyepoxides. Specific examples of compounds include the diglycidyl esters of oxalic acid, cyclohexanediacetic acids, cylcohexanedicarboxylic acids, succinic acid, glutaric acid, phthalic acid, terephthalic acid, isophthalic acid, naphthalene dicarboxylic acids, and the like. A polyglycidyl reactant may be used, preferably in a minor amount in combination with diepoxide reactant. Novolac epoxies may be used as a polyepoxide-functional reactant. The novolac epoxy resin may be selected from epoxy phenol novolac resins or epoxy cresol novolac resins. Other suitable higher-functionality polyepoxides are glycidyl ethers and esters of triols and higher polyols such as the triglycidyl ethers of trimethylolpropane, trimethylolethane, 2,6-bis(hydroxymethyl)-p-cresol, and glycerol; tricarboxylic acids or polycarboxylic acids. Also useful as polyepoxides are epoxidized alkenes such as cyclohexene oxides and epoxidized fatty acids and fatty acid derivatives such as epoxidized soybean oil. Other useful polyepoxides include, without limitation, polyepoxide polymers such as acrylic, polyester, polyether, and epoxy resins and polymers, and epoxy-modified polybutadiene, polyisoprene, acrylobutadiene nitrile copolymer, or other epoxy-modified rubber-based polymers that have a plurality of epoxide groups.
- The polyepoxide resin may be reacted with an extender to prepare a polyepoxide resin having a higher molecular weight having beta-hydroxy ester linkages. Suitable, nonlimiting examples of extenders include polycarboxylic acids, polyols, polyphenols, and amines having two or more amino hydrogens, especially dicarboxylic acids, diols, diphenols, and diamines. Particular, nonlimiting examples of suitable extenders include diphenols, diols, and diacids such as those mentioned above in connection with forming the polyepoxide; polycaprolactone diols, and ethoxylated bisphenol A resins such as those available from BASF Corporation under the trademark MACOL®. Other suitable extenders include, without limitation, carboxy- or amine-functional acrylic, polyester, polyether, and epoxy resins and polymers. Still other suitable extenders include, without limitation, polyamines, including diamines such as ethylenediamine, diethylenetriamine, triethylenetetramine, dimethylaminopropylamine, dimethylaminobutylamine, diethylaminopropylamine, diethylaminobutylamine, dipropylamine, and piperizines such as 1-(2-aminoethyl)piperazine, polyalkylenepolyamines such as triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, tripropylenetetramine, tetrapropylenepentamine, pentapropylenehexamine, N,N′-bis(3-aminopropyl)ethylenediamine, N-(2-hydroxyethyl)propane-1,3-diamine, and polyoxyalkylene amines such as those available from BASF AG under the trademark POLYAMIN® or from Huntsman under the trademark JEFFAMINE®.
- A monofunctional reactant may optionally be reacted with the polyepoxide resin and the extender or after reaction of the polyepoxide with the extender to prepare an epoxide-functional resin. Suitable, nonlimiting examples of monofunctional reactants include phenol, alkylphenols such as nonylphenol and dodecylphenol, other monofunctional, epoxide-reactive compounds such as dimethylethanolamine and monoepoxides such as the glycidyl ether of phenol, the glycidyl ether of nonylphenol, or the glycidyl ether of cresol, and dimer fatty acid.
- Useful catalysts for the reaction of the polyepoxide resin with the extender and optional monofunctional reactant include any that activate an oxirane ring, such as tertiary amines or quaternary ammonium salts (e.g., benzyldimethylamine, dimethylaminocyclohexane, triethylamine, N-methylimidazole, tetramethyl ammonium bromide, and tetrabutyl ammonium hydroxide.), tin and/or phosphorous complex salts (e.g., (CH3)3 SNI, (CH3)4 PI, triphenylphosphine, ethyltriphenyl phosphonium iodide, tetrabutyl phosphonium iodide) and so on. It is known in the art that tertiary amine catalysts may be preferred with some reactants. The reaction may be carried out at a temperature of from about 100° C. to about 350° C. (in other embodiments 160° C. to 250° C.) in solvent or neat. Suitable solvents include, without limitation, inert organic solvent such as a ketone, including methyl isobutyl ketone and methyl amyl ketone, aromatic solvents such as toluene, xylene, Aromatic 100, and Aromatic 150, and esters, such as butyl acetate, n-propyl acetate, hexyl acetate.
- The polyepoxide resin may be reacted with the phosphorous-containing acid or acid derivative before, during, or after reaction of the polyepoxide resin with the extender and optional monofunctional reactant. The reaction with the acid or acid derivative, if carried out before or after the reaction with the extender, may be carried out at a temperature of from about 50° C. to about 150° C. in solvent, including any of those already mentioned, or neat. The polyepoxide resin may also be reacted with the phosphorous-containing acid or acid derivative and optionally a monofunctional reactant such as those already described and not be reacted with an extender.
- The amine-functional phosphorylated resin has at least one amine group, and this amine functionality may introduced before or after the phosphorylating reaction. If before, the amine functionality may be introduced by reaction of the polyepoxide resin with an extender having a tertiary amine group or with a monofunctional reactant having a tertiary amine group. Suitable, nonlimiting examples of extenders and monofunctional reactants having an amine group include diethanolamine, dipropanolamine, diisopropanolamine, dibutanolamine, diisobutanolamine, diglycolamine, methylethanolamine, dimethylaminopropylamine, and compounds having a primary amine group that has been protected by forming a ketimine, such as the ketimine of diethylenetriamine.
- The polyepoxide resin, extended polyepoxide resin, or epoxide-functional resin is then reacted with the phosphorous-containing acid or acid derivative to make a phosphorylated resin. Suitable phosphorous containing acid derivatives include esterifiable esters and anhydrides of phosphorous-containing acids. Among suitable examples are those —P(OR)2═O group-containing acids or acid derivatives having at least one R that is a hydrogen atom or a low alkyl group (up to four carbon atoms, particularly methyl, ethyl, propyl, isopropyl, and tert-butyl) than can be transesterified, such as phosphoric acid, an mono- or diester of phosphoric acid, hypophosphoric acid, a monoester of hypophosphoric acid, alkyl- or arylphosphonic acid, a monoester of alkyl- or arylphosphonic acid, and combinations of these. Phosphoric acid or a source of phosphoric acid that may be used in the reaction may be nonaqueous phosphoric acid, 85% in water, a more dilute aqueous phosphoric acid, pyrophosphoric acid, or polyphosphoric acid. Other suitable phosphoric acid sources are described in Campbell et al., U.S. Pat. No. 4,397,970, incorporated herein by reference. In certain particular embodiments, the polyepoxide resin, extended polyepoxide resin, or epoxide-functional resin is reacted with phosphoric acid or a source of phosphoric acid to make a phosphorylated resin. The phosphoric acid or source of phosphoric acid used in the reaction may be nonaqueous phosphoric acid, 85% in water, a more dilute aqueous phosphoric acid, pyrophosphoric acid, or polyphosphoric acid. Other suitable phosphoric acid sources are described in Campbell et al., U.S. Pat. No. 4,397,970, incorporated herein by reference. In other embodiments, the polyepoxide resin, extended polyepoxide resin, or epoxide-functional resin is reacted with another phosphorous-containing acid or acid derivative such as one of those mentioned above.
- The phosphorylated resin may include monophosphonic acid esters, diphosphonic acid esters, monophosphate ester, diphosphate esters, and triphosphate esters, as well as combinations of these. In addition, the phosphorylated resin may have one or a plurality of the phosphorous-containing ester groups. The extent of esterification of phosphorous-containing acid or acid derivative and the number of phosphorous-containing ester groups incorporated into the resin is controlled, inter alia, by the relative equivalents of the reactants. In one example, from about 1 to about 3 equivalents of resin (based on epoxide and hydroxyl groups) is reacted with each equivalent of phosphoric acid or phosphoric acid derivative. In another example, from about 1 to about 2 equivalents of resin (based on epoxide and hydroxyl groups) is reacted with each equivalent of phosphonic acid or phosphonic acid derivative. The equivalents of the resin reactive groups may also be in excess of the equivalents of acid or acid derivative. The resin and phosphoric or phosphonic acid or acid derivative may be mixed together and allowed to react until a desired extent of reaction is obtained. In certain embodiments, the weight per epoxide after reaction of an epoxide-functional resin is from about 180 to about 1200.
- Other reactants that may be used in addition to the resin and phosphorous-containing acid or acid derivative may include alcohols such as n-butanol, isopropanol, and n-propanol; glycol ethers such as ethylene glycol monobutyl ether, propylene glycol monobutyl ether, and propylene glycol monopropyl ether; amines such as any of those mentioned above; water; and combinations of these. These reactants can also be used to react with excess oxirane groups after the reaction of the resin with the acid or acid derivative.
- The amine functionality may be imparted to the phosphorylated resin in one of two ways. In a first way, an amine having at least one active hydrogen reactive with an epoxide group is included as a reactant in the reaction of the epoxide-functional resin and phosphoric acid or source of phosphoric acid. In a second way, the reaction product of the epoxide-functional epoxy resin and phosphoric acid (and any further reactants) is an epoxide-functional product that is then further reacted with an amine having at least one active hydrogen reactive with an epoxide group. Examples of suitable amine compounds include, without limitation, dimethylaminopropylamine, N,N-diethylaminopropylamine, dimethylaminoethylamine, N-aminoethylpiperazine, aminopropylmorpholine, tetramethyldipropylenetriamine, methylamine, ethylamine, dimethylamine, dibutylamine, ethylenediamine, diethylenetriamine, triethylenetetramine, dimethylaminobutylamine, diethylaminopropylamine, diethylaminobutylamine, dipropylamine, methylbutylamine, alkanolamines such as methylethanolamine, aminoethylethanolamine, aminopropylmonomethylethanolamine, and diethanolamine, diketimine (a reaction product of 1 mole diethylenetriamine and 2 moles methyl isobutyl ketone), and polyoxyalkylene amines.
- In certain embodiments, the phosphorylated resin is an epoxide-functional resin that is reacted with an extender, such any of those already mentioned.
- The amine-functional phosphorylated resin is used to prepare an electrocoat coating composition (also known as an electrocoat bath). In general, a binder is prepared comprising the amine-functional phosphorylated resin, then the binder is dispersed in an aqueous medium by salting amine groups present in the binder with an acid.
- In certain embodiments, the amine-functional phosphorylated resin comprises from about 0.01 to about 99% by weight of binder in the electrodeposition coating composition. The amine-functional phosphorylated resin may comprise from about 0.01 to about 99% by weight of binder, 1 to about 90% by weight of binder, or from about 5 to about 80% by weight of binder in the electrodeposition coating composition. The binder may also comprise a crosslinker that reacts with the amine-functional phosphorylated resin during curing of a coating layer formed on a substrate. Suitable examples of crosslinking agents, include, without limitation, blocked polyisocyanates. Examples of aromatic, aliphatic or cycloaliphatic polyisocyanates include diphenylmethane-4,4′-diisocyanate (MDI), 2,4- or 2,6-toluene diisocyanate (TDI), p-phenylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane-4,4′-diisocyanate, isophorone diisocyanate, mixtures of phenylmethane-4,4′-diisocyanate, polymethylene polyphenylisocyanate, 2-isocyanatopropylcyclohexyl isocyanate, dicyclohexylmethane 2,4′-diisocyanate, 1,3-bis(iso-cyanatomethyl)cyclohexane, diisocyanates derived from dimer fatty acids, as sold under the commercial designation DDI 1410 by Henkel, 1,8-diisocyanato-4-isocyanatomethyloctane, 1,7-diisocyanato-4-isocyanato-methylheptane or 1-isocyanato-2-(3-isocyanatopropyl)-cyclohexane, and higher polyisocyanates such as triphenylmethane-4,4′,4″-triisocyanate, or mixtures of these polyisocyanates. Suitable polyisocyantes also include polyisocyanates derived from these that containing isocyanurate, biuret, allophanate, iminooxadiazinedione, urethane, urea, or uretdione groups. Polyisocyanates containing urethane groups, for example, are obtained by reacting some of the isocyanate groups with polyols, such as trimethylolpropane, neopentyl glycol, and glycerol, for example. The isocyanate groups are reacted with a blocking agent. Examples of suitable blocking agents include phenol, cresol, xylenol, epsilon-caprolactam, delta-valerolactam, gamma-butyrolactam, diethyl malonate, dimethyl malonate, ethyl acetoacetate, methyl acetoacetate, alcohols such as methanol, ethanol, isopropanol, propanol, isobutanol, tert-butanol, butanol, glycol monoethers such as ethylene or propylene glycol monoethers, acid amides (e.g. acetoanilide), imides (e.g. succinimide), amines (e.g. diphenylamine), imidazole, urea, ethylene urea, 2-oxazolidone, ethylene imine, oximes (e.g. methylethyl ketoxime), and the like.
- The binder may include one or more additional resins. Nonlimiting examples of suitable additional resins include epoxy resins, polyesters, polyurethanes, vinyl resins such as polyacrylate resins, and polybutadiene resins. The additional resin may be, for example, any of the polyepoxide resins, extended polyepoxide resins, or epoxide-functional resins already mentioned, optionally reacted with a compound having at least one epoxide-reactive group.
- In certain embodiments the binder comprises another amine-functional resin. Nonlimiting examples of suitable amine-functional resins include amine-functional epoxy resins, polyesters, polyurethanes, vinyl resins such as polyacrylate resins, and polybutadiene resins. Amine-functional epoxy resins may be prepared by reacting any of the polyepoxide resins, extended polyepoxide resins, or epoxide-functional resins already mentioned with an amine, including any of those mentioned above as suitable for preparing the amine-functional phosphorylated resin.
- Cationic polyurethanes and polyesters may also be used. Such materials may be prepared by endcapping with, for example, an aminoalcohol or, in the case of the polyurethane, the same compound comprising a saltable amine group previously described may also be useful.
- Polybutadiene, polyisoprene, or other epoxy-modified rubber-based polymers can be used as the resin in the present invention. The epoxy-rubber can be capped with a compound comprising a saltable amine group.
- Cationic acrylic resins may be made cathodic by incorporation of amino-containing monomers, such as acrylamide, methacrylamide, N,N′-dimethylaminoethyl methacrylate tert-butylaminoethyl methacrylate. 2-vinylpyridine, 4-vinylpyridine, vinylpyrrolidine or other such amino monomers. Alternatively, epoxy groups may be incorporated by including an epoxy-functional monomer in the polymerization reaction. Such epoxy-functional acrylic polymers may be made cathodic by reaction of the epoxy groups with amines according to the methods previously described for the epoxy resins. The polymerization may also include a hydroxyl-functional monomer. Useful hydroxyl-functional ethylenically unsaturated monomers include, without limitation, hydroxyethyl methacrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, hydroxybutyl methacrylate, the reaction product of methacrylic acid with styrene oxide, and so on. Preferred hydroxyl monomers are methacrylic or acrylic acid esters in which the hydroxyl-bearing alcohol portion of the compound is a linear or branched hydroxy alkyl moiety having from 1 to about 8 carbon atoms.
- The monomer bearing the hydroxyl group and the monomer bearing the group for salting (amine for a cationic group or acid or anhydride for anionic group) may be polymerized with one or more other ethylenically unsaturated monomers. Such monomers for copolymerization are known in the art. Illustrative examples include, without limitation, alkyl esters of acrylic or methacrylic acid, e.g., methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, butyl acrylate, butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, t-butyl acrylate, t-butyl methacrylate, amyl acrylate, amyl methacrylate, isoamyl acrylate, isoamyl methacrylate, hexyl acrylate, hexyl methacrylate, 2-ethylhexyl acrylate, decyl acrylate, decyl methacrylate, isodecyl acrylate, isodecyl methacrylate, dodecyl acrylate, dodecyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, substituted cyclohexyl acrylates and methacrylates, 3,5,5-trimethylhexyl acrylate, 3,5,5-trimethylhexyl methacrylate, the corresponding esters of maleic, fumaric, crotonic, isocrotonic, vinylacetic, and itaconic acids, and the like; and vinyl monomers such as styrene, t-butyl styrene, alpha-methyl styrene, vinyl toluene and the like. Other useful polymerizable co-monomers include, for example, alkoxyethyl acrylates and methacrylates, acryloxy acrylates and methacrylates, and compounds such as acrylonitrile, methacrylonitrile, acrolein, and methacrolein. Combinations of these are usually employed.
- The binder may also comprise a crosslinker that reacts with the amine-functional resin other than the phosphorylated resin during curing of a coating layer formed on a substrate, or the binder may also comprise a crosslinker that reacts with both the amine-functional resin other than the phosphorylated resin and the phosphorylated resin during curing of a coating layer formed on a substrate. Optionally, plasticizer or solvents or both can be added to the binder mixture. Nonlimiting examples of coalescing solvents include alcohols, glycol ethers, polyols, and ketones. Specific coalescing solvents include monobutyl and monohexyl ethers of ethylene glycol, phenyl ether of propylene glycol, monoalkyl ethers of ethylene glycol such as the monomethyl, monoethyl, monopropyl, and monobutyl ethers of ethylene glycol or propylene glycol; dialkyl ethers of ethylene glycol or propylene glycol such as ethylene glycol dimethyl ether and propylene glycol dimethyl ether; butyl carbitol; diacetone alcohol. Nonlimiting examples of plasticizers include ethylene or propylene oxide adducts of nonyl phenols, bisphenol A, cresol, or other such materials, or polyglycols based on ethylene oxide and/or propylene oxide. The amount of coalescing solvent is not critical and is generally between about 0 to 15 percent by weight, preferably about 0.5 to 5 percent by weight based on total weight of the resin solids. Plasticizers can be used at levels of up to 15 percent by weight resin solids.
- The binder is emulsified in water in the presence of an acid. Nonlimiting examples of suitable acids include phosphoric acid, phosphonic acid, propionic acid, formic acid, acetic acid, lactic acid, or citric acid. The salting acid may be blended with the binder, mixed with the water, or both, before the binder is added to the water. The acid is used in an amount sufficient to neutralize enough of the amine groups to impart water-dispersibility to the binder. The amine groups may be fully neutralized; however, partial neutralization is usually sufficient to impart the required water-dispersibility. By saying that the resin is at least partially neutralized, we mean that at least one of the saltable groups of the binder is neutralized, and up to all of such groups may be neutralized. The degree of neutralization that is required to afford the requisite water-dispersibility for a particular binder will depend upon its composition, molecular weight of the resins, weight percent of amine-functional resin, and other such factors and can readily be determined by one of ordinary skill in the art through straightforward experimentation.
- The binder emulsion is then used in preparing an electrocoat coating composition (or bath). The electrocoat bath may contain no pigment so as to produce a colorless or clear electrodeposited coating layer, but the electrocoat bath usually includes one or more pigments, separately added as part of a pigment paste, and may contain any further desired materials such as coalescing aids, antifoaming aids, and other additives that may be added before or after emulsifying the resin. Conventional pigments for electrocoat primers include titanium dioxide, ferric oxide, carbon black, aluminum silicate, precipitated barium sulfate, aluminum phosphomolybdate, strontium chromate, basic lead silicate or lead chromate. The pigments may be dispersed using a grind resin or a pigment dispersant. The pigment-to-resin weight ratio in the electrocoat bath can be important and should be preferably less than 50:100, more preferably less than 40:100, and usually about 10 to 30:100. Higher pigment-to-resin solids weight ratios have been found to adversely affect coalescence and flow. Usually, the pigment is 10-40 percent by weight of the nonvolatile material in the bath. Preferably, the pigment is 15 to 30 percent by weight of the nonvolatile material in the bath. Any of the pigments and fillers generally used in electrocoat primers may be included. Inorganic extenders such as clay and anti-corrosion pigments are commonly included.
- The electrodeposition coating compositions can contain optional ingredients such as dyes, flow control agents, plasticizers, catalysts, wetting agents, surfactants, UV absorbers, HALS compounds, antioxidants, defoamers and so forth. Examples of surfactants and wetting agents include alkyl imidazolines such as those available from Ciba-Geigy Industrial Chemicals as AMINE C® acetylenic alcohols such as those available from Air Products and Chemicals under the tradename SURFYNOL®. Surfactants and wetting agents, when present, typically amount to up to 2 percent by weight resin solids.
- Curing catalysts such as tin catalysts can be used in the coating composition. Typical examples are without limitation, tin and bismuth compounds including dibutyltin dilaurate, dibutyltin oxide, and bismuth octoate. When used, catalysts are typically present in amounts of about 0.05 to 2 percent by weight tin based on weight of total resin solids.
- The electrocoat coating composition is electrodeposited onto a metallic substrate. The substrate may be, as some nonlimiting examples, cold-rolled steel, galvanized (zinc coated) steel, electrogalvanized steel, stainless steel, pickled steel, GALVANNEAL® GALVALUME®, and GALVAN® zinc-aluminum alloys coated upon steel, and combinations of these. Nonlimiting examples of useful non-ferrous metals include aluminum, zinc, magnesium and alloys of these. The electrodeposition of the coating preparations according to the invention may be carried out by known processes. The electrodeposition coating composition may be applied preferably to a dry film thickness of 10 to 35 μm. In one embodiment of the method, the electrically conductive substrate is unphosphated; that is, it is free of a phosphate pre-treatment The article coated with the composition of the invention may be a metallic automotive part or body. A method of coating an electrically conductive substrate, such as a metal automotive vehicle body or part, comprises placing an electrically conductive substrate, cleaned but preferably not given a phosphate pre-treatment, into the electrocoat coating composition and, using the electrically conductive substrate as the cathode, passing a current through the electrocoat coating composition causing a coating layer to deposit onto the electrically conductive substrate. After application, the coated article is removed from the bath and rinsed with deionized water. The coating may be cured under appropriate conditions, for example by baking at from about 275° F. to about 375° F. for between about 15 and about 60 minutes, before applying an additional coating layer over the electrodeposited coating layer.
- An automotive vehicle body may be electrocoated. The automotive vehicle body is cleaned, and the cleaned metal automotive vehicle body is electrocoated with an aqueous electrodeposition coating composition comprising the phosphorylated resin.
- One or more additional coating layers, such as a spray-applied primer-surfacer, single topcoat layer, or composite color coat (basecoat) and clearcoat layer, may be applied over the electrocoat layer. A single layer topcoat is also referred to as a topcoat enamel. In the automotive industry, the topcoat is typically a basecoat that is overcoated with a clearcoat layer. A primer surfacer and the topcoat enamel or basecoat and clearcoat composite topcoat may be waterborne, solventborne, or a powder coating, which may be a dry powder or an aqueous powder slurry.
- The composite coating of the invention may have, as one layer, a primer coating layer, which may also be termed a primer-surfacer or filler coating layer. The primer coating layer can be formed from a solventborne composition, waterborne composition, or powder composition, including powder slurry composition. The primer composition preferably has a binder that is thermosetting, although thermoplastic binders are also known. Suitable thermosetting binders may have self-crosslinking polymers or resins, or may include a crosslinker reactive with a polymer or resin in the binder. Nonlimiting examples of suitable binder polymers or resins include acrylics, polyesters, and polyurethanes. Such polymers or resins may include as functional groups hydroxyl groups, carboxyl groups, anhydride groups, epoxide groups, carbamate groups, amine groups, and so on. Among suitable crosslinkers reactive with such groups are aminoplast resins (which are reactive with hydroxyl, carboxyl, carbamate, and amine groups), polyisocyanates, including blocked polyisocyanates (which are reactive with hydroxyl groups and amine groups), polyepoxides (which are reactive with carboxyl, anhydride, hydroxyl, and amine groups), and polyacids and polyamines (which are reactive with epoxide groups). Examples of suitable primer compositions are disclosed, for example, in U.S. Pat. Nos. 7,338,989; 7,297,742; 6,916,877; 6,887,526; 6,727,316; 6,437,036; 6,413,642; 6,210,758; 6,099,899; 5,888,655; 5,866,259; 5,552,487; 5,536,785; 4,882,003; and 4,190,569, each assigned to BASF and each incorporated herein by reference.
- The primer coating composition applied over the electrocoat primer may then be cured to form a primer coating layer. The electrocoat primer may be cured at the same time as the primer coating layer in a process known as “wet-on-wet” coating.
- A topcoat composition may be applied over the electrocoat layer or primer coating layer and, preferably, cured to form a topcoat layer. In a preferred embodiment, the electrocoat layer or primer layer is coated with a topcoat applied as a color-plus-clear (basecoat-clearcoat) topcoat. In a basecoat-clearcoat topcoat, an underlayer of a pigmented coating, the basecoat, is covered with an outer layer of a transparent coating, the clearcoat. Basecoat-clearcoat topcoats provide an attractive smooth and glossy finish and generally improved performance.
- Crosslinking compositions are preferred as the topcoat layer or layers. Coatings of this type are well-known in the art and include waterborne compositions, solventborne compositions, and powder and powder slurry compositions. Polymers known in the art to be useful in basecoat and clearcoat compositions include, without limitation, acrylics, vinyls, polyurethanes, polycarbonates, polyesters, alkyds, and polysiloxanes. Acrylics and polyurethanes are among preferred polymers for topcoat binders. Thermoset basecoat and clearcoat compositions are also preferred, and, to that end, preferred polymers comprise one or more kinds of crosslinkable functional groups, such as carbamate, hydroxy, isocyanate, amine, epoxy, acrylate, vinyl, silane, acetoacetate, and so on. The polymer may be self-crosslinking, or, preferably, the composition may include a crosslinking agent such as a polyisocyanate or an aminoplast resin. Examples of suitable topcoat compositions are disclosed, for example, in U.S. Pat. Nos. 7,375,174; 7,342,071; 7,297,749; 7,261,926; 7,226,971; 7,160,973; 7,151,133; 7,060,357; 7,045,588; 7,041,729; 6,995,208; 6,927,271; 6,914,096; 6,900,270; 6,818,303; 6,812,300; 6,780,909; 6,737,468; 6,652,919; 6,583,212; 6,462,144; 6,337,139; 6,165,618; 6,129,989; 6,001,424; 5,981,080; 5,855,964; 5,629,374; 5,601,879; 5,508,349; 5,502,101; 5,494,970; 5,281,443; and, each assigned to BASF and each incorporated herein by reference.
- The further coating layers can be applied to the electrocoat coating layer according to any of a number of techniques well-known in the art. These include, for example, spray coating, dip coating, roll coating, curtain coating, and the like. For automotive applications, the further coating layer or layers are preferably applied by spray coating, particularly electrostatic spray methods. Coating layers of one mil or more are usually applied in two or more coats, separated by a time sufficient to allow some of the solvent or aqueous medium to evaporate, or “flash,” from the applied layer. The flash may be at ambient or elevated temperatures, for example, the flash may use radiant heat. The coats as applied can be from 0.5 mil up to 3 mils dry, and a sufficient number of coats are applied to yield the desired final coating thickness.
- A primer layer may be cured before the topcoat is applied. The cured primer layer may be from about 0.5 mil to about 2 mils thick, preferably from about 0.8 mils to about 1.2 mils thick.
- Color-plus-clear topcoats are usually applied wet-on-wet. The compositions are applied in coats separated by a flash, as described above, with a flash also between the last coat of the color composition and the first coat the clear. The two coating layers are then cured simultaneously. Preferably, the cured basecoat layer is 0.5 to 1.5 mils thick, and the cured clear coat layer is 1 to 3 mils, more preferably 1.6 to 2.2 mils, thick.
- Alternatively the primer layer and the topcoat can be applied “wet-on-wet.” For example, the primer composition can be applied, then the applied layer flashed; then the topcoat can be applied and flashed; then the primer and the topcoat can be cured at the same time. Again, the topcoat can include a basecoat layer and a clearcoat layer applied wet-on-wet. The primer layer can also be applied to an uncured electrocoat coating layer, and all layers cured together.
- The coating compositions described are preferably cured with heat. Curing temperatures are preferably from about 70° C. to about 180° C., and particularly preferably from about 170° F. to about 200° F. for a topcoat or primer composition including an unblocked acid catalyst, or from about 240° F. to about 275° F. for a topcoat or primer composition including a blocked acid catalyst. Typical curing times at these temperatures range from 15 to 60 minutes, and preferably the temperature is chosen to allow a cure time of from about 15 to about 30 minutes. In a preferred embodiment, the coated article is an automotive body or part.
- The invention is further described in the following example. The example is merely illustrative and does not in any way limit the scope of the invention as described and claimed. All parts are parts by weight unless otherwise noted.
- Preparation A: Preparation of Amine-Functional Phosphorylated Epoxy Resin
- A reactor equipped with an agitator and reflux condenser is charged with 25.85 parts by weight of normal butanol, 10.20 parts by weight of ethylene glycol monobutyl ether, and 55.62 parts by weight of the diglycidyl ether of Bisphenol A. The reactor contents are stirred for about5 minutes followed by addition of a 3.11 parts of diethanolamine. The resulting mixture is heated to 77° F. (25° C.); heat is then discontinued, and the reaction mixture is allowed to exotherm. The temperature of the reaction continues to increase to 120.2-122° F. (49-50° C.). The reaction mixture is maintained at 140-149° F. (60-65° C.) for 30 minutes. To the reactor is added a mixture of 4.261 parts by weight phosphoric acid (75% aqueous) and 1.77 parts by weight normal butanol. During the addition the temperature is held to below 102.2° F. (49° C.). The reaction mixture is stirred for about 15 minutes, then the reactor is heated to 220-250° F. (104.4-121.1° C.). Reaction is continued until the weight per epoxide of the product is 800 or greater. Then, deionized water is added in a first portion of 0.899 parts by weight, and the reaction mixture is maintained at 220-250° F. (104.4-121.1° C.) for one hour. A second portion of deionized water, 0.70 parts by weight, is then added to the reaction mixture. Again the reaction mixture is maintained at 220-250° F. (104.4-121.1° C.) for one hour. A final portion of deionized water, 0.70 parts by weight, is then added to the reaction mixture. Again the reaction mixture is maintained at 220-250° F. (104.4-121.1° C.) for one hour. The product is then diluted with normal butanol to 72% nonvolatile by weight.
- Preparation B: Preparation of Binder Emulsion with Amine-Functional Phosphorylated Epoxy Resin
- The following materials are combined in a 5-L flask with an associated heating mantle: diglycidyl ether of bisphenol A, (18.03 parts by weight), bisphenol A, (4.1 parts by weight), phenol (1.41 parts by weight), and propylene glycol n-butyl ether (0.36 parts by weight).
- While stirring, the temperature is raised to 257° F. (125° C.). Subsequently, triphenylphosphine (0.04 parts by weight) is added and the exotherm is recorded as 392° F. (200° C.). The mixture is then allowed to cool to 275° F. (135° C.), and a weight per epoxide (WPE) determination (target=525±25) is conducted and is 526. After cooling to 194° F. (90° C.) and turning off the heating mantle, 2.36 parts by weight of PLURACOL® 710R (sold by BASF Corporation) is added, then 1.73 parts by weight of diethanolamine is introduced and the exotherm is recorded 239° F. (115° C.). The reaction mixture is allowed to stir for an additional 30 minutes at 221° F. (105° C.) after reaching exotherm. After stirring for 30 minutes, 3-dimethylaminopropylamine is added at 221° F. (105° C.) (0.84 parts by weight), and the exotherm is recorded as 280.4° F. (138° C.). The mixture is stirred for an additional hour. A crosslinker (a blocked isocyanate based on polymeric MDI and monofunctional alcohols) (13.6 parts by weight) is added. The mixture is stirred for 30 minutes at 221-230° F. (105-110° C.). Preparation A, the amine-functional phosphorylated epoxy resin, (6.47 parts by weight) is added and the mixture is stirred for an additional 15 minutes at 221-230° F. (105-110° C.).
- After achieving a homogeneous mixture, the resins and crosslinker blend are added to an acid/water mixture, under constant stirring, of deionized water (34.95 parts by weight) and formic acid (88%) (0.62 parts by weight). After thoroughly mixing all components using a metal spatula, the solids are further reduced by addition of water (18.55 parts by weight). A flow-additive package (2.51 parts by weight) is added to the acid mixture.
- Preparation C: Grinding Resin Solution having Tertiary Ammonium Groups
- In accordance with EP 0 505 445 B1, an aqueous-organic grinding resin solution is prepared by reacting, in the first stage, 2598 parts of bisphenol A diglycidyl ether (epoxy equivalent weight (EEW) 188 g/eq), 787 parts of bisphenol A, 603 parts of dodecylphenol, and 206 parts of butyl glycol in a stainless steel reaction vessel in the presence of 4 parts of triphenylphosphine at 130° C. until an EEW of 865 g/eq is reached. In the course of cooling, the batch is diluted with 849 parts of butyl glycol and 1534 parts of D.E.R® 732 (polypropylene glycol diglycidyl ether, DOW Chemical, USA) and is reacted further at 90° C. with 266 parts of 2,2′-aminoethoxyethanol and 212 parts of N,N-dimethylaminopropylamine. After 2 hours, the viscosity of the resin solution is constant (5.3 dPas; 40% in SOLVENON® PM (methoxypropanol, BASF/Germany); cone and plate viscometer at 23° C.). It is diluted with 1512 parts of butyl glycol and the base groups are partly neutralized with 201 parts of glacial acetic acid, and the product is diluted further with 1228 parts of deionized water and discharged. This gives a 60% strength by weight aqueous-organic resin solution whose 10% dilution has a pH of 6.0. The resin solution is used in direct form for paste preparation.
- Preparation D: Pigment Paste
- For this purpose, a premix is first formed from 1897 parts of water and 1750 parts of the grinding resin solution of Preparation C. Then 21 parts of DISPERBYK® 110 (Byk-Chemie GmbH/Germany), 14 parts of Lanco Wax®. PE W 1555 (Langer & Co./Germany), 42 parts of carbon black, 420 parts of aluminum hydrosilicate ASP 200 (Langer & Co./Germany), 2667 parts of titanium dioxide TI-PURE® R 900 (DuPont, USA) and 189 parts of di-n-butyl tin oxide are added. The mixture is predispersed for 30 minutes under a high-speed dissolver stirrer. The mixture is subsequently dispersed in a small laboratory mill (Motor Mini Mill, Eiger Engineering Ltd, Great Britain) until it measures a Hegmann fineness of less than or equal to 12 μm and is adjusted to solids content with additional water. A separation-stable pigment paste is obtained. Solids content: 60.0% by weight (½ h at 180° C.).
- A bath was prepared by combining 964.4 parts Preparation B, 144.8 parts Preparation D, and 1290.8 parts deionized water. The water and Preparation B resin emulsion are combined in a container with constant stirring, and Preparation D is added with stirring. The bath solids content is 19% by weight.
- Example 1 is tested by coating both phosphated and bare cold rolled steel 4-inch-by-6-inch test panels at 225 volts (0.5 ampere) in the Example 1 bath at bath temperatures from 88-98° F. (31-36.7° C.) for 2.2 minutes, dehydrating and/or baking the coated panels for 28 minutes at 350° F. (177° C.). The deposited, baked coating has a film build of about 0.8 mil (20 μm). Three panels were coated for each temperature and substrate.
- Control
- Control panels were prepared as described for Example 1 but using U32AD500 (commercial product sold by BASF Corporation).
- After dehydrating and/or baking, panels are tested as follows or further coated with a top coat and then tested.
- Description of Corrosion test GMW15288: Each panel is scribed directly down the middle and tested by corrosion test (GMW15288) The description of GMW15288 is as follows: On a Monday, each panel is held at 60° C. for one hour in an air-circulating oven and is then subjected to a cold cabinet at -25° C. for 30 minutes. Following, the panels are immersed for 15 minutes in a 5 wt. % NaCl solution in water (saline solution). After removal, the panels are allowed to air dry for 75 minutes at room temperature. The panels are then transferred to a humidity cabinet (60° C., 85% humidity) with an air flow not exceeding 15 m/ft across the panel and held for 21 hours. From Tuesday to Friday, the panels are immersed again in the saline solution for 15 minutes, allowed to air dry to 75 minutes at room temperature, and then returned to the humidity cabinet (22 hours). On Saturday and Sunday the panels remain in the humidity cabinet. The entire exposure sequence from Monday to the following Monday constitutes 5 cycles. The test is then repeated for a total of 20 cycles. After completion, each panel is rinsed with water and scraped with a metal spatula. The corrosion is measured as the average of scribe width of selected points along the scribe length.
- Description SAE J2334 DEC2003: After baking, each panel is scribed directly down the middle and tested in accordance with SAE J2334 DEC2003. The test description is as follows: For 6 hours the test panels are subjected to 100% relative humidity (RH) at 50° C., 15 minute salt solution dip at ambient conditions, where the salt solution consists of 0.5% NaCl, 0.1% CaCl2 and 0.075% NaHCO3. For the remaining 17 hours and 45 minutes the test panels are placed in a cabinet at 60° C. and 50% RH. The cycle is repeated 20 times. After completion, each panel is rinsed with water and scraped with a metal spatula. The corrosion is measured as the average of scribe width of selected points along the scribe length.
- The top coating process for each of the following systems were preformed by hand application using the following products/procedure:
- Integrated Process Solventborne:
-
- U28AU227 (commercial product sold by BASF Corporation) applied to 0.9 mils followed by 5 minute, room-temperature flash
- E38WU466L (commercial product sold by BASF Corporation) applied to 0.9 mils followed by 8 minute, room-temperature flash
- R10CG392 (commercial product sold by BASF Corporation) applied to 1.8 mils followed by 8 minutes, room-temperature flash, followed by 5 minutes at 200° F., followed by 17 minutes at 285° F.
- Waterborne Basecoat/2K Clearcoat Process:
- U28WW554 (commercial product sold by BASF Corporation) applied to 1.0 mils, flash 5 minutes room temperature (“RT”) followed by 30 minutes at 265F
-
- E54WW301 (commercial product sold by BASF Corporation) applied to 0.5 mils flash 5 minutes at 150° F.
- E21WW328 (commercial product sold by BASF Corporation) applied to 0.4 mils flash 5 minutes at 150° F.
- E10CG081 (commercial product sold by BASF Corporation) applied to 1.8 mils, flashed 10 minutes at room temperature followed by 10 minutes at 180° F. followed by 25 minutes at 255° F.
- Urethane Powder Topcoat Process:
-
- 960KM0002 (commercial product sold by BASF Corporation) applied to 2.0 mils and cured 20 minutes at 340° F.
- Co-Cure with Urethane Powder Topcoat
-
- 960KM0002 (commercial product sold by BASF Corporation) applied to the dehydrated but uncured electrocoat at 2.0 mils and the two films are cured together for 20 minutes at 340° F.
- Co-Cure with Powder Primer/Solventborne Topcoat
-
- G27AM258 (commercial product sold by BASF Corporation) applied to the dehydrated but uncured electrocoat at 2.0 mils and the two films are cured together for 20 minutes at 340° F.
- E38WU466L (commercial product sold by BASF Corporation) applied to 0.9 mils followed by 8 minute, room-temperature flash
- R10CG392 (commercial product sold by BASF Corporation) applied to 1.8 mils followed by 8 minutes, room-temperature flash, followed by 5 minutes at 200° F., followed by 17 minutes at 285° F.
- Co-Cure with Powder Primer/Waterborne Topcoat
-
- G27AM258 (commercial product sold by BASF Corporation) applied to the dehydrated but uncured electrocoat at 2.0 mils and the two films are cured together for 20 minutes at 340° F.
- E54WW301 (commercial product sold by BASF Corporation) applied to 0.5 mils flash 5 minutes at 150° F.
- E21WW328 (commercial product sold by BASF Corporation) applied to 0.4 mils flash 5 minutes at 150° F.
- E10CG081 (commercial product sold by BASF Corporation) applied to 1.8 mils, flashed 10 minutes at RT followed by 10 minutes at 180 F followed by 25 minutes at 255° F.
- Humidity testing was performed in accordance with ASTM D3359 and chip testing was performed in accordance with GMW 14700.
- Results of testing are shown in the following Tables 1-3.
-
TABLE 1 Corrosion test GMW15288 Ave mm Scribe width after 20 Cycles GMW15288 Substrate Control Example 1 Cold Roll Steel B958 P90 0.9 1.6 Cold Roll Steel Clean Bare Unpolished 16.9 3.5 Electrogalvanized Zn Bare 0.3 0.7 Electrogalvanized B958 P90 2.9 2.2 Zinc/Iron Bare 0.3 0.3 Zinc/Iron B958 P90 0.3 0.3 -
TABLE 2 SAE J2334 Corrosion on topcoated panels mm Scribe creep after 20 Cycles J2334 Control with Integrated Process SB 19 Example 1 with Integrated Process SB 13 Control with WBBC/2K 13 Example A with WBBC/2K 6 -
TABLE 3 Chip and Humidity on topcoated panels Example A Control Humidity Humidity Chip* Adhesion** Chip* Adhesion** Integrated Process SB 8 5A 8 5A Waterborne/2K 9 5A 9 5A Urethane Powder 9 5A 9 5A Topcoat Co-cure with Urethane 9 5A 9 5A Powder Topcoat Co-cure with powder 9 5A 9 5A primer/SB Topcoat Co-cure with powder 9 5A 9 5A primer/WB Topcoat *ASTM D3359 **GMW14700 - Throw power was performed in accordance with FORD Laboratory Test method B1 120-02 Results are shown in Table 4.
-
TABLE 4 Throwpower cm from Filmbuild (microns) @ bottom specified cm throw of panel Control Example A 1 19.81 18.54 2 19.3 16.76 4 17.78 14.73 6 16 12.7 8 12.95 11.18 10 10.92 8.64 12 7.87 6.35 14 4.83 4.83 16 2.54 3.56 18 0.76 1.52 20 0 0 - The description is merely exemplary in nature and, thus, variations that do not depart from the gist of the disclosure are a part of the invention. Variations are not to be regarded as a departure from the spirit and scope of the disclosure.
Claims (16)
1. A method of coating a metal automotive vehicle body, comprising:
(a) cleaning the metal automotive vehicle body;
(b) placing the cleaned metal automotive vehicle body into an aqueous electrocoat coating composition comprising an amine-functional phosphorylated resin.;
(c) connecting the metal automotive vehicle body as a cathode in an electric circuit and passing a current through the aqueous electrocoat coating composition to deposit an electrocoat coating layer onto the metal automotive vehicle body; and
(d) applying a further coating layer over the electrocoat coating layer.
2. A method according to claim 1 , wherein the further coating layer is a primer coating layer.
3. A method according to claim 1 , wherein the further coating layer is a topcoat coating layer.
4. A method according to claim 1 , wherein the electrocoat coating layer is cured before step (d).
5. A method according to claim 1 , wherein the electrocoat coating layer and the further coating layer are cured together after step (d).
6. A method according to claim 2 , further comprising
(e) applying a topcoat layer over the primer coating layer layer.
7. A method according to claim 6 , wherein the topcoat layer comprises a basecoat/clearcoat composite coating.
8. A method according to claim 6 , wherein the primer layer is cured before applying the topcoat layer.
9. A method according to claim 6 , wherein the primer layer and the topcoat layer are cured together.
10. A method according to claim 6 , wherein the electrocoat coating layer, the primer layer, and the topcoat layer are cured together.
11. A method according to claim 1 , wherein the metal automotive vehicle body is free of a phosphate pre-treatment.
12. A method according to claim 1 , wherein the phosphorylated resin comprises a phosphate ester of a polyepoxide resin, a phosphonic acid ester of a polyepoxide resin, or a combination thereof.
13. A method according to claim 1 , wherein the phosphorylated resin comprises a diphosphate ester of a polyepoxide resin, a diphosphonic acid ester of a polyepoxide resin, or a combination thereof.
14. A method according to claim 1 , wherein the phosphorylated resin comprises, on average, more than one phosphorous atom per molecule.
15. A method according to claim 1 , wherein the phosphorylated resin is an epoxy resin.
16. A method according to claim 1 , wherein the phosphorylated epoxy resin is at least about 5 weight percent of electrocoat coating binder.
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US12/345,321 US20100163423A1 (en) | 2008-12-29 | 2008-12-29 | Electrocoat composition and process replacing phosphate pretreatment |
CN2009801527917A CN102264953A (en) | 2008-12-29 | 2009-12-16 | Electrocoat composition and process replacing phosphate pretreatment |
EP09774800A EP2382338A2 (en) | 2008-12-29 | 2009-12-16 | Electrocoat composition and process replacing phosphate pretreatment |
PCT/US2009/068156 WO2010077896A2 (en) | 2008-12-29 | 2009-12-16 | Electrocoat composition and process replacing phosphate pretreatment |
JP2011544461A JP2012513897A (en) | 2008-12-29 | 2009-12-16 | Electrodeposition compositions and alternative methods for phosphate pretreatment |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US12/345,321 US20100163423A1 (en) | 2008-12-29 | 2008-12-29 | Electrocoat composition and process replacing phosphate pretreatment |
Publications (1)
Publication Number | Publication Date |
---|---|
US20100163423A1 true US20100163423A1 (en) | 2010-07-01 |
Family
ID=42227392
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US12/345,321 Abandoned US20100163423A1 (en) | 2008-12-29 | 2008-12-29 | Electrocoat composition and process replacing phosphate pretreatment |
Country Status (5)
Country | Link |
---|---|
US (1) | US20100163423A1 (en) |
EP (1) | EP2382338A2 (en) |
JP (1) | JP2012513897A (en) |
CN (1) | CN102264953A (en) |
WO (1) | WO2010077896A2 (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2016167928A1 (en) * | 2015-04-15 | 2016-10-20 | Henkel Ag & Co. Kgaa | Thin corrosion protective coatings incorporating polyamidoamine polymers |
WO2019060183A1 (en) * | 2017-09-19 | 2019-03-28 | Ppg Industries Ohio, Inc. | Low voc anionic electrodepositable coating composition |
US10421880B2 (en) | 2013-08-28 | 2019-09-24 | Basf Coatings Gmbh | Dimer fatty acid/polyesterdiol reaction product and use thereof in coating materials |
Citations (38)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4164487A (en) * | 1976-12-23 | 1979-08-14 | The Dow Chemical Company | Water-thinnable mixtures of base-neutralized products of reaction of H3 PO4 with polyether epoxides and with other type epoxides |
US4321335A (en) * | 1979-06-19 | 1982-03-23 | Dainippon Ink & Chemicals, Inc. | Powder coating resin composition |
US4397970A (en) * | 1981-06-24 | 1983-08-09 | The Dow Chemical Company | Process for epoxy phosphate coating resins |
US4425451A (en) * | 1982-09-29 | 1984-01-10 | Desoto, Inc. | Epoxy-phosphate aqueous dispersions |
US4461857A (en) * | 1982-09-29 | 1984-07-24 | Desoto, Inc. | Thermosetting aqueous coating compositions containing epoxy-phosphate dispersions |
US4487859A (en) * | 1983-11-21 | 1984-12-11 | Scm Corporation | Self-curing water dispersed polymers |
US4508765A (en) * | 1981-10-20 | 1985-04-02 | International Paint Public Limited Company | Synthetic resins and coating compositions containing them |
US4692484A (en) * | 1985-09-25 | 1987-09-08 | Desoto, Inc. | Epoxy-phosphate/phenolic electrocoating compositions |
US4992525A (en) * | 1987-04-28 | 1991-02-12 | Vianova Kunstharz, A.G. | Diester of phosphoric acid and monoepoxide reacted with epoxide to form product reacted with monoisocyanate |
US5095050A (en) * | 1990-11-21 | 1992-03-10 | The Dow Chemical Company | Advanced epoxy compositions, curable compositions and cured products |
US5141815A (en) * | 1987-05-22 | 1992-08-25 | The Dow Chemical Company | Coating containing epoxy resin-phospho(r or n)ic acid product |
US5264469A (en) * | 1991-10-01 | 1993-11-23 | The Valspar Corporation | Aqueous epoxy resin-based coating compositions useful for coating metal containers |
US5389704A (en) * | 1991-12-16 | 1995-02-14 | The Dow Chemical Company | Epoxy phosphate ester resin, its production and coating composition containing the resin |
US5635049A (en) * | 1991-07-01 | 1997-06-03 | The Valspar Corporation | Epoxy resin based coating composition and method |
US5859095A (en) * | 1987-05-11 | 1999-01-12 | Morton International, Inc. | Epoxy corrosion-inhibiting coating composition |
US5866259A (en) * | 1997-06-30 | 1999-02-02 | Basf Corporation | Primer coating compositions containing carbamate-functional acrylic polymers |
US6110341A (en) * | 1998-10-22 | 2000-08-29 | Ppg Industries Ohio, Inc. | Electrodeposition baths containing organic phosphorous-based compounds |
US6319988B1 (en) * | 1998-08-31 | 2001-11-20 | Ppg Industries Ohio, Inc. | Thermosetting compositions containing hydroxy functional polymers prepared by atom transfer radical polymerization |
US20030004231A1 (en) * | 1999-12-16 | 2003-01-02 | Eduard Ehmann | Method for the anodic electrophoretic enamelling and electrophoretic paints |
US6750274B2 (en) * | 2001-02-08 | 2004-06-15 | Ppg Industries Ohio. Inc. | Weldable coating of phosphated epoxy polymer, curing agent and electroconductive pigment |
US6777034B2 (en) * | 1998-12-01 | 2004-08-17 | Ppg Industries Ohio, Inc. | Weldable, coated metal substrates and methods for preparing and inhibiting corrosion of the same |
US6887526B1 (en) * | 1999-09-16 | 2005-05-03 | Basf Coatings Ag | Integrated coating method for auto body parts containing plastic parts or for cabins of passenger cars and utility vehicles as well as for their replacement parts and add-on parts |
US6942902B2 (en) * | 2001-05-28 | 2005-09-13 | Basf Coatings Ag | Aqueous functional coating material and integrated method for production of coloured or effect-generating multi-layer coatings |
US20050256260A1 (en) * | 2004-05-11 | 2005-11-17 | Ohrbom Walter H | Low VOC waterborne primer with high film smoothness |
US7008998B2 (en) * | 2001-11-16 | 2006-03-07 | Basf Corporation | Method for making an aqueous dispersion |
US7030185B2 (en) * | 2002-07-17 | 2006-04-18 | Kansai Paint Co., Ltd. | Electrodeposition coating compositions and articles coated therewith |
US20060127678A1 (en) * | 2002-11-06 | 2006-06-15 | Pawlik Michael J | Corrosion and alkali-resistant compositions and methods for using the same |
US7163979B2 (en) * | 2002-03-29 | 2007-01-16 | Kansai Paint Co. Ltd. | Water based intercoat coating composition and multi-layer coating film-forming method by use of the same |
US7268171B2 (en) * | 2000-04-27 | 2007-09-11 | Dainippon Ink And Chemicals, Inc. | Water-based coating composition curable with actinic energy ray, coated metallic material with cured film of the composition, production process, and method of bonding coated metallic material |
US20070244270A1 (en) * | 2006-03-30 | 2007-10-18 | Basf Corporation | A method of catalyzing a reaction to form a urethane coating and a complex for use in the method |
US20070275256A1 (en) * | 2005-08-26 | 2007-11-29 | Ppg Industries Ohio, Inc. | Coating compositions exhibiting corrosion resistance properties, related coated substrates, and methods |
US20080103268A1 (en) * | 2006-10-26 | 2008-05-01 | Basf Corporation | Metal coordinating and film-forming materials |
US20080102214A1 (en) * | 2006-10-26 | 2008-05-01 | Basf Corporation | Method of producing a coating having metal coordinating and film-forming materials |
US20080103269A1 (en) * | 2006-10-26 | 2008-05-01 | Basf Corporation | Metal coordinating and film-forming materials |
US20080194843A1 (en) * | 2007-02-08 | 2008-08-14 | Basf Corporation | Crosslinkers containing phosphorous |
US20080193664A1 (en) * | 2007-02-08 | 2008-08-14 | Basf Corporation | Methods of producing coating compositions containing phosphorous |
US20080194783A1 (en) * | 2007-02-08 | 2008-08-14 | Basf Corporation | Film-forming material containing phosphorous |
US7531074B2 (en) * | 2002-02-13 | 2009-05-12 | Ppg Industries Ohio, Inc. | Coating line and process for forming a multilayer composite coating on a substrate |
Family Cites Families (47)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4190569A (en) | 1977-06-24 | 1980-02-26 | Basf Aktiengesellschaft | Baking finishes of low solvent content |
US4882003A (en) | 1988-07-19 | 1989-11-21 | Basf Corporation | Sealant primer composition and method |
DE3942766A1 (en) | 1989-12-23 | 1991-06-27 | Basf Lacke & Farben | PROCESS FOR COATING ELECTRICALLY CONDUCTIVE SUBSTRATES, WAESSRIGER PAINT, EPOXY AMINADDUCT AND THE USE OF THE EPOXY AMINO ADDUCT AS A REIN RESIN FOR THE MANUFACTURE OF PIGMENT PASTES |
DE4009857A1 (en) | 1990-03-28 | 1991-10-02 | Basf Lacke & Farben | METHOD FOR PRODUCING A MULTILAYER LACQUERING AND AQUEOUS BASE PAINTS SUITABLE FOR THIS METHOD |
CA2083952C (en) | 1991-03-27 | 2004-08-03 | Anna M. Budde | Post-extended anionic acrylic dispersion |
US5494970A (en) | 1991-08-06 | 1996-02-27 | Basf Corporation | Coating composition for a clearcoat with improved solvent and acid resistance |
US5281443A (en) | 1991-12-20 | 1994-01-25 | Basf Corporation | Coating method for one-component blocked isocyanate-crosslinked clearcoat |
DE4237032A1 (en) | 1992-11-03 | 1994-05-05 | Basf Lacke & Farben | Process for the production of a multi-layer coating |
US6165618A (en) | 1994-11-03 | 2000-12-26 | Basf Corporation | Curable coating compositions containing carbamate resin and additives |
DE4339870A1 (en) | 1993-11-23 | 1995-05-24 | Basf Lacke & Farben | Process for producing a two-layer paint and aqueous paints |
US5508349A (en) | 1994-05-09 | 1996-04-16 | Basf Corporation | Reactive flow agent for powder coatings |
US5498783A (en) | 1994-08-22 | 1996-03-12 | Basf Corporation | Powder coating composition resistant to overspray incompatibility defects |
US5605949A (en) | 1994-10-11 | 1997-02-25 | Basf Corporation | Latex composition employing specifically defined alcohol ethoxylate surfactant and hydrophobic defoaming agent |
US5711996A (en) | 1995-09-28 | 1998-01-27 | Man-Gill Chemical Company | Aqueous coating compositions and coated metal surfaces |
BR9612224A (en) | 1995-12-21 | 1999-09-21 | Basf Coatings Ag | Process for the preparation of multilayer coatings. |
DE19622878A1 (en) | 1996-06-07 | 1997-12-11 | Basf Lacke & Farben | Multi-layer painting, process for its production and suitable non-aqueous top coat |
DE19650157A1 (en) | 1996-12-04 | 1998-06-10 | Basf Coatings Ag | Process for coating substrates, preferably of metal |
US6099899A (en) | 1997-05-21 | 2000-08-08 | Basf Corporation | Method for a multilayer coating |
US5888655A (en) | 1997-06-30 | 1999-03-30 | Basf Corporation | Primer coating compositions containing carbamate-functional novolac resins |
DE19730890C2 (en) | 1997-07-18 | 2001-07-05 | Basf Coatings Ag | Process for the production of multilayer coatings and substrates coated therewith |
DE19908001A1 (en) | 1999-02-25 | 2000-08-31 | Basf Coatings Ag | Highly scratch-resistant multi-layer coating, process for their production and their use |
DE19930067A1 (en) | 1999-06-30 | 2001-01-11 | Basf Coatings Ag | Coating material and its use for the production of filler layers and stone chip protection primers |
DE19930665A1 (en) | 1999-07-02 | 2001-01-11 | Basf Coatings Ag | Basecoat and its use for the production of color and / or effect basecoats and multi-layer coating |
US6210758B1 (en) | 1999-11-17 | 2001-04-03 | Basf Corporation | Composite coating with improved chip resistance |
US6437036B1 (en) | 1999-11-17 | 2002-08-20 | Basf Corporation | Waterborne primer with improved chip resistance |
US6362285B1 (en) | 1999-12-15 | 2002-03-26 | Basf Corporation | Curable coating compositions containing carbamate functional reactive additives |
DE10027290C2 (en) | 2000-06-02 | 2002-07-11 | Basf Coatings Ag | Powder clearcoat dispersions (powder slurry clearcoats) and their use |
US6916877B2 (en) | 2000-06-16 | 2005-07-12 | Basf Corporation | Coating composition including a water-based copolymer cross-linking with a water-dispersible cross-linking agent, method of preparing the same, and a cured film thereof |
DE10055464B4 (en) | 2000-11-09 | 2006-06-14 | Basf Coatings Ag | Structural viscous, clear of organic solvents and external emulsifiers powder clearcoat slurry and their use |
DE10058870A1 (en) | 2000-11-27 | 2002-06-06 | Basf Coatings Ag | Aqueous coating material, process for its preparation and its use |
DE10060765A1 (en) | 2000-12-07 | 2002-06-20 | Basf Coatings Ag | Color and / or effect powder slurry, process for their preparation and their use |
US6462144B1 (en) | 2000-12-22 | 2002-10-08 | Basf Corporation | Carbamate-functional resins and their use in high solids coating compositions |
US7226971B2 (en) | 2000-12-22 | 2007-06-05 | Basf Corporation | Polyester resin with carbamate functionality, a method of preparing the resin, and a coating composition utilizing the resin |
US6583212B2 (en) | 2000-12-31 | 2003-06-24 | Basf Corporation | Aqueous dispersions for coating compositions |
US6780909B2 (en) | 2001-04-10 | 2004-08-24 | Basf Corporation | Coating composition having low volatile organic content |
DE10129899A1 (en) | 2001-06-21 | 2003-01-09 | Basf Coatings Ag | Aqueous coating material curable physically, thermally or thermally and with actinic radiation and its use |
US6900270B2 (en) | 2002-10-31 | 2005-05-31 | Basf Corporation | Curable coating compositions with carbamate compounds |
US6812300B2 (en) | 2001-11-29 | 2004-11-02 | Basf Corporation | Method for making multifunctional materials |
US6995208B2 (en) | 2001-12-11 | 2006-02-07 | Basf Corporation | Clearcoat composition for primerless MVSS adhesion |
AU2002364601A1 (en) | 2001-12-17 | 2003-06-30 | Basf Corporation | Urethane polymers that reduce the effect of polylactone linkages |
DE60225328T2 (en) | 2001-12-17 | 2009-02-26 | Basf Corp., Southfield | ASYMMETRIC DIISOCYANATE MONOMERS IN URETANOLPOLYMERS AND OLIGOMERS FOR CRYSTALLINE INITIALIZATION LIGHTING |
US6927271B2 (en) | 2002-01-10 | 2005-08-09 | Basf Corporation | Hydroxyl and carbamate functional resins |
US7060357B2 (en) | 2002-10-04 | 2006-06-13 | Basf Corporation | Powder coatings containing symmetrical additives |
US7342071B2 (en) | 2002-10-31 | 2008-03-11 | Basf Corporation | Clearcoat paint composition |
US7045588B2 (en) | 2004-02-12 | 2006-05-16 | Basf Corporation | Polyester resin composition for use in a coating composition and method of preparing the same |
US7375174B2 (en) | 2004-03-04 | 2008-05-20 | Basf Corporation | Acrylic composition and a curable coating composition including the same |
CA2635857A1 (en) * | 2007-02-08 | 2008-08-08 | Basf Corporation | Film-forming material containing phosphorous and methods of producing coating compositions containing phosphorous |
-
2008
- 2008-12-29 US US12/345,321 patent/US20100163423A1/en not_active Abandoned
-
2009
- 2009-12-16 WO PCT/US2009/068156 patent/WO2010077896A2/en active Application Filing
- 2009-12-16 EP EP09774800A patent/EP2382338A2/en not_active Withdrawn
- 2009-12-16 CN CN2009801527917A patent/CN102264953A/en active Pending
- 2009-12-16 JP JP2011544461A patent/JP2012513897A/en not_active Withdrawn
Patent Citations (40)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4164487A (en) * | 1976-12-23 | 1979-08-14 | The Dow Chemical Company | Water-thinnable mixtures of base-neutralized products of reaction of H3 PO4 with polyether epoxides and with other type epoxides |
US4321335A (en) * | 1979-06-19 | 1982-03-23 | Dainippon Ink & Chemicals, Inc. | Powder coating resin composition |
US4397970A (en) * | 1981-06-24 | 1983-08-09 | The Dow Chemical Company | Process for epoxy phosphate coating resins |
US4508765A (en) * | 1981-10-20 | 1985-04-02 | International Paint Public Limited Company | Synthetic resins and coating compositions containing them |
US4425451A (en) * | 1982-09-29 | 1984-01-10 | Desoto, Inc. | Epoxy-phosphate aqueous dispersions |
US4461857A (en) * | 1982-09-29 | 1984-07-24 | Desoto, Inc. | Thermosetting aqueous coating compositions containing epoxy-phosphate dispersions |
US4487859A (en) * | 1983-11-21 | 1984-12-11 | Scm Corporation | Self-curing water dispersed polymers |
US4692484A (en) * | 1985-09-25 | 1987-09-08 | Desoto, Inc. | Epoxy-phosphate/phenolic electrocoating compositions |
US4992525A (en) * | 1987-04-28 | 1991-02-12 | Vianova Kunstharz, A.G. | Diester of phosphoric acid and monoepoxide reacted with epoxide to form product reacted with monoisocyanate |
US5859095A (en) * | 1987-05-11 | 1999-01-12 | Morton International, Inc. | Epoxy corrosion-inhibiting coating composition |
US5141815A (en) * | 1987-05-22 | 1992-08-25 | The Dow Chemical Company | Coating containing epoxy resin-phospho(r or n)ic acid product |
US5095050A (en) * | 1990-11-21 | 1992-03-10 | The Dow Chemical Company | Advanced epoxy compositions, curable compositions and cured products |
US5635049A (en) * | 1991-07-01 | 1997-06-03 | The Valspar Corporation | Epoxy resin based coating composition and method |
US5264469A (en) * | 1991-10-01 | 1993-11-23 | The Valspar Corporation | Aqueous epoxy resin-based coating compositions useful for coating metal containers |
US5389704A (en) * | 1991-12-16 | 1995-02-14 | The Dow Chemical Company | Epoxy phosphate ester resin, its production and coating composition containing the resin |
US5866259A (en) * | 1997-06-30 | 1999-02-02 | Basf Corporation | Primer coating compositions containing carbamate-functional acrylic polymers |
US6319988B1 (en) * | 1998-08-31 | 2001-11-20 | Ppg Industries Ohio, Inc. | Thermosetting compositions containing hydroxy functional polymers prepared by atom transfer radical polymerization |
US6110341A (en) * | 1998-10-22 | 2000-08-29 | Ppg Industries Ohio, Inc. | Electrodeposition baths containing organic phosphorous-based compounds |
US6777034B2 (en) * | 1998-12-01 | 2004-08-17 | Ppg Industries Ohio, Inc. | Weldable, coated metal substrates and methods for preparing and inhibiting corrosion of the same |
US6887526B1 (en) * | 1999-09-16 | 2005-05-03 | Basf Coatings Ag | Integrated coating method for auto body parts containing plastic parts or for cabins of passenger cars and utility vehicles as well as for their replacement parts and add-on parts |
US20030004231A1 (en) * | 1999-12-16 | 2003-01-02 | Eduard Ehmann | Method for the anodic electrophoretic enamelling and electrophoretic paints |
US7268171B2 (en) * | 2000-04-27 | 2007-09-11 | Dainippon Ink And Chemicals, Inc. | Water-based coating composition curable with actinic energy ray, coated metallic material with cured film of the composition, production process, and method of bonding coated metallic material |
US6750274B2 (en) * | 2001-02-08 | 2004-06-15 | Ppg Industries Ohio. Inc. | Weldable coating of phosphated epoxy polymer, curing agent and electroconductive pigment |
US6942902B2 (en) * | 2001-05-28 | 2005-09-13 | Basf Coatings Ag | Aqueous functional coating material and integrated method for production of coloured or effect-generating multi-layer coatings |
US7008998B2 (en) * | 2001-11-16 | 2006-03-07 | Basf Corporation | Method for making an aqueous dispersion |
US7531074B2 (en) * | 2002-02-13 | 2009-05-12 | Ppg Industries Ohio, Inc. | Coating line and process for forming a multilayer composite coating on a substrate |
US7163979B2 (en) * | 2002-03-29 | 2007-01-16 | Kansai Paint Co. Ltd. | Water based intercoat coating composition and multi-layer coating film-forming method by use of the same |
US7030185B2 (en) * | 2002-07-17 | 2006-04-18 | Kansai Paint Co., Ltd. | Electrodeposition coating compositions and articles coated therewith |
US20060127678A1 (en) * | 2002-11-06 | 2006-06-15 | Pawlik Michael J | Corrosion and alkali-resistant compositions and methods for using the same |
US7345101B2 (en) * | 2002-11-06 | 2008-03-18 | Ppg Industries Ohio, Inc. | Aqueous composition of reaction product of epoxy and phosphorus materials with curing agent |
US20050256260A1 (en) * | 2004-05-11 | 2005-11-17 | Ohrbom Walter H | Low VOC waterborne primer with high film smoothness |
US20070275256A1 (en) * | 2005-08-26 | 2007-11-29 | Ppg Industries Ohio, Inc. | Coating compositions exhibiting corrosion resistance properties, related coated substrates, and methods |
US20070244270A1 (en) * | 2006-03-30 | 2007-10-18 | Basf Corporation | A method of catalyzing a reaction to form a urethane coating and a complex for use in the method |
US20080102214A1 (en) * | 2006-10-26 | 2008-05-01 | Basf Corporation | Method of producing a coating having metal coordinating and film-forming materials |
US20080103269A1 (en) * | 2006-10-26 | 2008-05-01 | Basf Corporation | Metal coordinating and film-forming materials |
US20080103268A1 (en) * | 2006-10-26 | 2008-05-01 | Basf Corporation | Metal coordinating and film-forming materials |
US20080194843A1 (en) * | 2007-02-08 | 2008-08-14 | Basf Corporation | Crosslinkers containing phosphorous |
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US20080194783A1 (en) * | 2007-02-08 | 2008-08-14 | Basf Corporation | Film-forming material containing phosphorous |
US7674874B2 (en) * | 2007-02-08 | 2010-03-09 | Basf Coatings Ag | Methods of producing coating compositions containing phosphorous |
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US10421880B2 (en) | 2013-08-28 | 2019-09-24 | Basf Coatings Gmbh | Dimer fatty acid/polyesterdiol reaction product and use thereof in coating materials |
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Also Published As
Publication number | Publication date |
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WO2010077896A2 (en) | 2010-07-08 |
JP2012513897A (en) | 2012-06-21 |
CN102264953A (en) | 2011-11-30 |
EP2382338A2 (en) | 2011-11-02 |
WO2010077896A3 (en) | 2010-08-26 |
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