WO1993009191A1 - Process for cathodic electrodeposition of a clear coating over a conductive paint layer - Google Patents
Process for cathodic electrodeposition of a clear coating over a conductive paint layer Download PDFInfo
- Publication number
- WO1993009191A1 WO1993009191A1 PCT/US1992/009207 US9209207W WO9309191A1 WO 1993009191 A1 WO1993009191 A1 WO 1993009191A1 US 9209207 W US9209207 W US 9209207W WO 9309191 A1 WO9309191 A1 WO 9309191A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- silica
- layer
- conductive
- pigment
- clear
- Prior art date
Links
- 238000004070 electrodeposition Methods 0.000 title claims abstract description 46
- 238000000034 method Methods 0.000 title claims abstract description 29
- 238000000576 coating method Methods 0.000 title claims description 30
- 239000011248 coating agent Substances 0.000 title claims description 27
- 239000003973 paint Substances 0.000 title description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 107
- 239000000049 pigment Substances 0.000 claims abstract description 61
- 239000000203 mixture Substances 0.000 claims abstract description 42
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 42
- 239000000758 substrate Substances 0.000 claims abstract description 30
- 239000011230 binding agent Substances 0.000 claims abstract description 26
- 239000000463 material Substances 0.000 claims abstract description 19
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 17
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910001887 tin oxide Inorganic materials 0.000 claims abstract description 14
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000004971 Cross linker Substances 0.000 claims description 12
- 239000011162 core material Substances 0.000 claims description 9
- 239000003431 cross linking reagent Substances 0.000 claims description 7
- 239000012948 isocyanate Substances 0.000 claims description 7
- 150000002513 isocyanates Chemical class 0.000 claims description 6
- 229920001225 polyester resin Polymers 0.000 claims description 6
- 239000004645 polyester resin Substances 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 5
- 239000011521 glass Substances 0.000 claims description 3
- 229910052914 metal silicate Inorganic materials 0.000 claims description 2
- QHGNHLZPVBIIPX-UHFFFAOYSA-N tin(ii) oxide Chemical class [Sn]=O QHGNHLZPVBIIPX-UHFFFAOYSA-N 0.000 claims description 2
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- 239000005056 polyisocyanate Substances 0.000 claims 3
- 229920003180 amino resin Polymers 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 abstract description 7
- 239000002184 metal Substances 0.000 abstract description 7
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- 239000011347 resin Substances 0.000 description 34
- 239000010410 layer Substances 0.000 description 26
- 239000000243 solution Substances 0.000 description 26
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 22
- 239000007787 solid Substances 0.000 description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 19
- 239000008367 deionised water Substances 0.000 description 12
- 229910021641 deionized water Inorganic materials 0.000 description 12
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 description 12
- 239000004310 lactic acid Substances 0.000 description 11
- 235000014655 lactic acid Nutrition 0.000 description 11
- 239000006185 dispersion Substances 0.000 description 10
- 238000002360 preparation method Methods 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000002245 particle Substances 0.000 description 9
- 239000002002 slurry Substances 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- 238000002156 mixing Methods 0.000 description 8
- 238000000227 grinding Methods 0.000 description 7
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 6
- 239000004593 Epoxy Substances 0.000 description 6
- 150000001412 amines Chemical class 0.000 description 6
- -1 aromatic isocyanates Chemical class 0.000 description 6
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- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
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- 239000006229 carbon black Substances 0.000 description 4
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- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical group COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
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- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 239000012736 aqueous medium Substances 0.000 description 3
- 239000002981 blocking agent Substances 0.000 description 3
- 229940072282 cardura Drugs 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- RUZYUOTYCVRMRZ-UHFFFAOYSA-N doxazosin Chemical compound C1OC2=CC=CC=C2OC1C(=O)N(CC1)CCN1C1=NC(N)=C(C=C(C(OC)=C2)OC)C2=N1 RUZYUOTYCVRMRZ-UHFFFAOYSA-N 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 3
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- 229920000877 Melamine resin Polymers 0.000 description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
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- 239000004111 Potassium silicate Substances 0.000 description 2
- 239000004115 Sodium Silicate Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 239000012975 dibutyltin dilaurate Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- HNRMPXKDFBEGFZ-UHFFFAOYSA-N ethyl trimethyl methane Natural products CCC(C)(C)C HNRMPXKDFBEGFZ-UHFFFAOYSA-N 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 235000013980 iron oxide Nutrition 0.000 description 2
- 239000001034 iron oxide pigment Substances 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229940043265 methyl isobutyl ketone Drugs 0.000 description 2
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- 230000000704 physical effect Effects 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 description 2
- 229910052913 potassium silicate Inorganic materials 0.000 description 2
- 235000019353 potassium silicate Nutrition 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- 229910052911 sodium silicate Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000000153 supplemental effect Effects 0.000 description 2
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 1
- BPIUIOXAFBGMNB-UHFFFAOYSA-N 1-hexoxyhexane Chemical class CCCCCCOCCCCCC BPIUIOXAFBGMNB-UHFFFAOYSA-N 0.000 description 1
- LXOFYPKXCSULTL-UHFFFAOYSA-N 2,4,7,9-tetramethyldec-5-yne-4,7-diol Chemical compound CC(C)CC(C)(O)C#CC(C)(O)CC(C)C LXOFYPKXCSULTL-UHFFFAOYSA-N 0.000 description 1
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 1
- BEWCNXNIQCLWHP-UHFFFAOYSA-N 2-(tert-butylamino)ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCNC(C)(C)C BEWCNXNIQCLWHP-UHFFFAOYSA-N 0.000 description 1
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical class CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
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- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 150000008055 alkyl aryl sulfonates Chemical class 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 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 1
- 238000009835 boiling Methods 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- ZQYNGPUHJGAACN-UHFFFAOYSA-L butan-1-ol 1-(2-butoxyethoxy)ethanol dibutyltin(2+) 2,4-diisocyanato-1-methylbenzene dodecanoate 2-ethyl-2-(hydroxymethyl)propane-1,3-diol 4-methylpentan-2-one Chemical compound CC(=O)CC(C)C.C(CCC)O.C(O)C(CC)(CO)CO.C(CCCCCCCCCCC)(=O)[O-].C(CCCCCCCCCCC)(=O)[O-].C(CCC)[Sn+2]CCCC.C(CCC)OCCOC(C)O.CC=1C(N=C=O)=CC(N=C=O)=CC1 ZQYNGPUHJGAACN-UHFFFAOYSA-L 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
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- 229940043237 diethanolamine Drugs 0.000 description 1
- LNGAGQAGYITKCW-UHFFFAOYSA-N dimethyl cyclohexane-1,4-dicarboxylate Chemical compound COC(=O)C1CCC(C(=O)OC)CC1 LNGAGQAGYITKCW-UHFFFAOYSA-N 0.000 description 1
- IUNMPGNGSSIWFP-UHFFFAOYSA-N dimethylaminopropylamine Chemical compound CN(C)CCCN IUNMPGNGSSIWFP-UHFFFAOYSA-N 0.000 description 1
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- 238000005227 gel permeation chromatography Methods 0.000 description 1
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- 239000002198 insoluble material Substances 0.000 description 1
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
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- REOJLIXKJWXUGB-UHFFFAOYSA-N mofebutazone Chemical group O=C1C(CCCC)C(=O)NN1C1=CC=CC=C1 REOJLIXKJWXUGB-UHFFFAOYSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
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- 150000003839 salts Chemical class 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- JMHCCAYJTTWMCX-QWPJCUCISA-M sodium;(2s)-2-amino-3-[4-(4-hydroxy-3,5-diiodophenoxy)-3,5-diiodophenyl]propanoate;pentahydrate Chemical compound O.O.O.O.O.[Na+].IC1=CC(C[C@H](N)C([O-])=O)=CC(I)=C1OC1=CC(I)=C(O)C(I)=C1 JMHCCAYJTTWMCX-QWPJCUCISA-M 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
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- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
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- BSVBQGMMJUBVOD-UHFFFAOYSA-N trisodium borate Chemical compound [Na+].[Na+].[Na+].[O-]B([O-])[O-] BSVBQGMMJUBVOD-UHFFFAOYSA-N 0.000 description 1
- 229940124543 ultraviolet light absorber Drugs 0.000 description 1
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/50—Multilayers
- B05D7/56—Three layers or more
- B05D7/57—Three layers or more the last layer being a clear coat
- B05D7/576—Three layers or more the last layer being a clear coat each layer being cured, at least partially, separately
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/44—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications
- C09D5/4488—Cathodic paints
- C09D5/4492—Cathodic paints containing special additives, e.g. grinding agents
-
- C—CHEMISTRY; METALLURGY
- 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
- C25D13/22—Servicing or operating apparatus or multistep processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/007—Processes for applying liquids or other fluent materials using an electrostatic field
Abstract
An electrocoating process in which a layer of an electrically conductive cathodic electrocoating composition containing film forming binder and pigment in a pigment to binder weight ratio of about 1:100 to 100:100, wherein the pigment comprises an electrically conductive pigment of silica which is either amorphous silica or a silica containing material, the silica is in association with a two-dimensional network of antimony-containing tin oxide crystallites in which the antimony content ranges from about 1-30 % by weight of the tin oxide is electrocoated onto a metal substrate and cured to form a coated substrate, wherein the resulting layer has a resistance of less than 10 X 1015 ohms, a layer of a clear cathodic electrocoating composition is electrocoated over the layer of the conductive composition and the layer clear composition is cured to form a clear layer on the substrate.
Description
TITLE PROCESS FOR CATHODIC ELECTRODEPOSITION OF A CLEAR COATING OVER A CONDUCTIVE PAINT LAYER
BACKGROUND OF THE INVENTION
This invention is directed to a process for cathodically electrodeposition a clear topcoat over one or more conductive paint layers which have been deposited by an electrodeposition process or by conventional spray application methods onto a conductive metal or another conductive surface.
The coating of electrically conductive substrates by an electrodeposition process (also called an electrocoating process) is a well known and important industrial process. The electrodeposition of primers to metal substrates used for auto and truck bodies is widely used in the automotive industry. In the electrodeposition of primers, a conductive article, such as an autobody or auto part, is immersed in a bath of a primer composition of an aqueous emulsion of film forming polymer and acts as one electrode in the electrodeposition process. An electric current is passed between the article and a counter-electrode in electrical contact with the aqueous emulsion, until a desired thickness of coating is deposited on the article. In a cathodic electrocoating process, the article to be coated is the cathode and counter-electrode is the anode.
Resin compositions or polymers used in the bath of a typical cathodic electrodeposition process are also well known in the art. These resins are typically polyepoxides which have been chain extended and then an adduct is formed to include amine groups in the resin. Amine groups typically are introduced through a reaction of the resin with an amine
compound. These resins are blended with a crosslinking agent and then neutralized with an acid to form a water emulsion which is usually referred to as a principal emulsion. The principal emulsion is combined with a pigment paste, coalescent solvents, water and other additives to form the electrocoating bath. The electrocoating bath is placed in an insulated tank containing the anode. The article to be coated is the cathode and is passed through the tank containing the electrodeposition bath. The thickness of the coating deposited on the article is a function of the bath characteristics, the electrical operating characteristics, the immersion time and the like. The coated article is removed from the bath af er a given period of time and is rinsed with deionized water. The coating is cured typically in an oven at sufficient temperature to produce a crosslinked coating. Cathodic electrocoating compositions, resins, coating baths, and cathodic electrodeposition processes are disclosed in Jerabek et al U.S. Patent 3,922,253 issued November 25, 1975; ismer et al US 4,419,467 issued December 6 1983; Belanger US 4,137,140 issued January 30, 1979: Wismer et al US 4,468,307 issued August 28, 1984 which are incorporated herein by reference.
Cathodic electrodeposition is widely used in the automotive industry and other industries because it provides a finish that gives superior corrosion protection, covers recessed or hard to reach areas, deposits a uniform film thickness free of voids and defects such as sags or runs, is not labor intensive, has less emissions to the environment and provides for almost 100% material use.
It would be desirable to apply a clear topcoat by electrodeposition, over one or more previously applied paint layers because of the many advantages electrodeposition has over conventional spray applied clear topcoats, such as, improved edge coverage, uniform coatings (free of sags and runs) , fully automated operation, low volatile organic content, near 100% material use efficiency, no overspray, additional corrosion protection to recessed areas and interior cavities. However, for the electrodeposition process to be operative for the application of the clear coat, the previously applied paint layer must be electrically conductive. This has presented a particular problem since pigments that provide electrical conductivity are colored such as carbon black and iron oxide pigments making it difficult and often impossible to have very light colors such as white or beige of the previously applied paint layer.
SUMMARY OF THE INVENTION An electrocoating process in which a layer of an electrically conductive cathodic electrocoating composition containing film forming binder and pigment is electrocoated onto a metal substrate and cured to form a conductive layer on the substrate; wherein the resulting layer has a resistance of less than 10 X 1015 ohms and contains pigment in a pigment to binder weight ratio of about 1:100 to 100:100; wherein the pigment comprises an electrically conductive pigment of silica which is either amorphous silica or a silica containing material, the silica is in association with a two-dimensional network of antimony-containing tin oxide crystallites in which the antimony content ranges from about 1-30% by weight
of the tin oxide and a layer of a clear cathodic electrocoating composition is electrocoated over the layer of the conductive composition and the layer of clear composition is cured to form a clear layer on the substrate.
DETAILED DESCRIPTION OF THE INVENTION With the use of the electrically conductive silica based pigments in the the conductive layer, virtually any color from light to dark can be used and still have a coating that will be electrically conductive over which a clear coated can be electrocoated. This has not been possible with previously known electrically conductive pigments such a carbon black and iron oxides which limited the colors that could be used.
The electrocoating composition containing conductive pigment over which the clear coating composition is electrodeposited can be formed with a wide variety of different cathodic electrocoatable binder resins. Preferred are cathodic binder resins which are the typical epoxy resin-amine adducts and a blocked crosslinking agent which are described in the prior art. Preferred resins are primary hydroxy containing resins are disclosed in Kooymanus et al
U.S. Patent Number 4,397,990 issued August 9, 1983 and Ki≤.ιner et al US 4,419,467 issued December 6, 1983 which are incorporated herein by reference.
Likewise, the preferred blocked crosslinking agents also are well known in the prior art. Blocked aliphatic and aromatic isocyanates such as hexamethylene diisocyanate, toluene diisocyanate, methylene diphenyl diisocyanate and the like are used. These isocyanates are prereacted or blocked with a blocking agent such as oximes, alcohols, and
caprolactams which block the isocyanate functionality (i.e., the crosslinking functionality). Upon heating, the blocking agents separate and crosslinking occurs. These crosslinking agents and blocking agents are also disclosed in the aforementioned US 4,419,467.
A inoplast resins such as alkylated melamine resins also can be used as crosslinkers.
Curing catalysts such as tin catalysts are usually used in the composition and also are well known in the prior art. Examples are alkyl metal oxides such as dibutyltin oxide and alkyl metals esters such as dibutyltin dilaurate. When used, they are typically present in amounts of about 0.05 to 1 percent by weight based on weight of total binder of the composition.
The epoxy resin-amine adduct and the blocked isocyanate crosslinker are the principal film forming ingredients or binder in the electrocoating composition and are usually present in amount of about 30 to 50 percent by weight of solids. Generally, about 50-90% by weight, based on the weight of the binder, of the adduct is present and correspondingly, about 10-50% by weight, based on the weight of the binder, of crosslinker is present in the composition. Other components can be incorporated into the electrocoating composition such as antioxidants and ultraviolet light stabilizers.
There should be sufficient conductive pigment in the electrocoating composition to provide the resulting cured layer has a resistance of less than than lOxlO15 ohms and preferably about lOxlO6 - lOxlO15 ohms.
Resistance of a layer of coating is measured with an Advantest Digital Electrometer (model TR8652) with a TR-42 sample chamber.
Generally, the composition contains conductive pigment in a P/B (pigment to binder weight ratio) of about 1:100 to 100:100 and preferably in a P/B of about 15:100 to 50:100. The electroconductive pigment used in the electrocoating composition is incorporated in the form of a pigment paste. The paste is prepared by grinding or dispersing the conductive pigment into a grinding vehicle with optional ingredients such as wetting agents, surfactants, and defoamers. Pigment grinding vehicles are well known in the art. After grinding, the particle size of the pigment should be a Hegman grinding gauge of about 8 to 7. Overgrinding should be avoided since it will adversely effect the stability of the electrocoating bath, degrade film appearance and adversely affect the conductivity of the resulting cured film.
Supplemental pigments also can be used in conjunction with the electroconductive pigment to impart color to the coating and enhance corrosion protection. The supplemental pigments which can be employed include titanium dioxide, basic lead silicate, strontium chrornate, carbon black, iron oxide, clay and the like. Pigments with high surface areas and oil absorbencies (such as carbon blacks) should be used judiciously because they can have an undesirable effect on coalescence and flow.
The electrically conductive pigment used in the electrocoating composition is a two dimensional network of crystallites of antimony-containing tin oxide which exists in a unique association with amorphous silica or a silica-containing material. The antimony-containing tin oxide forms a two-dimensional network of densely packed crystallites on the surface of the silica or silica-containing material. The
silica or silica-containing material is a substrate, and the network comprises a generally uniform layer of crystallites in which the crystallites form an electrically conducting pathway to adjacent crystallites. The layer of tin oxide crystallites is typically about 5 to 20 nm in thickness, but covers the surface of a particle with major dimensions that are typically ten to ten thousand times as large as the thickness of the tin oxide layer. The crystallites are, thus, part of a continuous conducting layer in two dimensions.
The silica substrate can be practically any shape. In the form of flakes or hollow shells, satisfactory results may be achieved when the two-dimensional network is formed on only one side of the silica substrate. In general, however, best results are obtained when practically all of the exposed surface of the silica substrate is coated with the crystallite layer. The silica containing material of the silica substrate can be a metal silicate, silica containing glass or a material having an extensive covalent network of Siθ4 units.
The pigment is a powder comprising shaped particles of amorphous silica which are coated with a two-dimensional network of antimony-containing tin oxide [Snθ2(Sb)] crystallites. The finished particles, typically, are tens of microns to sub-micron in size, and they, in turn, are capable of forming an electroconductive network within the matrix of a thin paint film. The shaped particles of amorphous silica may be in the form of needles, platelets, spheres, dendritic structures or irregular particles. These provide an extended surface for the deposition of the antimony-containing tin oxide.
In one preferred pigment, the amorphous silica powder comprises thin shells or platelets less than or about 20 nm in thickness. The pigment, when dispersed in a vehicle, is generally transparent, and its presence as a component of pigment in paint has little impact on color and related properties.
A process for preparing the electrically conductive pigment comprises:
(A) providing a substrate of amorphous hydroxylated silica or active silica-containing material,
(B) applying a coating layer to the substrate surface consisting essentially of hydrous oxides of antimony and tin, and
(C) calcining the coated substrate at a temperature in the range of 400° to 900°C in an oxygen-containing atmosphere. The coating layer of hydrous oxides of antimony and tin is applied to the hydroxylated substrate surface by adding aqueous solutions of hydrolyzable Sn and Sb salts to a slurry containing the silica at a pH in the range of about 1.5 to about 3.5, preferably at a pH of 2.0. Calcining the coated silica substrate perfects the crystalline phase of the Snθ2(Sb) coating layer which imparts the desired electroconductive properties to the individual particles of the composition. According to one aspect of the process for making the pigment, the substrate of amorphous hydroxylated silica or active silica-containing material is prepared by coating a finely divided solid core material with active silica and then removing the core material without unduly disturbing the silica
coating. The substrate thus produced comprises hollow silica particles which are substantially translucent and which have the general shape of the core material. This silica coating should be sufficiently thin, for this purpose, so as not to reflect light. This will normally mean a thickness of less than about 250 nm. For most applications, thickness in the range of about 5 to 20 nm are preferred.
Active silica is conveniently prepared by gradually neutralizing an aqueous solution of sodium silicate or potassium silicate with a mineral acid, such as, for example, sulfuric acid or hydrochloric acid.
Active silica-containing materials may conveniently be applied as coatings for a selected core material by including other components along with the active silica in the reacting solution. For example, by adding sodium borate along with the sodium or potassium silicate, a silica-boria coating may be obtained. Such coatings are effective as a substrate so long as the surface of the coating contains hydroxylated silica functionality. If the other component or components present in the silica-containing substrate inhibit the retention of hydroxyl groups on the substrates surface, then the subsequent Snθ2(Sb) coating may not adhere completely and may, thus be less effective.
The electroconductive pigment may also be in a form where the core material remains encapsulated with the shell of amorphous silica or silica-containing material, i.e., it is not removed. Examples of suitable core materials for this embodiment include Tiθ2, mica, Kaolin, talc, and BaSθ4. In either case, the silica coating is coherent and is bound upon the core material forming a coating
layer which is substantially uniform in thickness from about 5 to 20nm. The preferred core materials are Tiθ2 and mica.
The electroconductive pigments are described in more detail in co-pending application Serial No. 07/386,765 filed August 2, 1989.
The coating compositions of the invention can contain optional ingredients such as wetting agents, surfactants, defoamers and the like. Examples of surfactants and wetting agents include alkyl imidazolines such as those available from Ciba-Geigy Industrial Chemicals as "Amine C", acetylenic alcohols available from Air Products and Chemicals as "Surfynol 104". These optional ingredients, when present, constitute from about 0 to 20 percent by weight of resin solids. Plasticizers are optional ingredients because they promote flow. Examples are high boiling water insoluble materials such as ethylene or propylene oxide adducts of nonyl phenols or bisphenol A. Plasticizers are usually used at levels of about 0 to 15 percent by weight resin solids.
The electrodepositable coating compositions used herein are dispersed in aqueous medium. The term "dispersion" as used within the context of the present invention is believed to be a two-phase translucent or opaque aqueous resinous system in which the resin is in the dispersed- phase and water the continuous phase. The average particle size diameter of the resinous phase is about 0.1 to 10 microns, preferably less than 5 microns. The concentration of the resinous products in the aqueous medium is, in general, not critical, but ordinarily the major portion of the aqueous dispersion is water. The aqueous dispersion usually contains from about 3 to 40 percent by weight resin solids. Aqueous resin concentrates which are to be
further diluted with water, generally range from 10 to 30 percent by total weight solids.
Besides water, the aqueous medium may also contain a coalescing solvent. Useful coalescing solvents include hydrocarbons, alcohols, esters, ethers and ketones. The preferred coalescing solvents include alcohols, polyols and ketones. Specific coalescing solvents include monobutyl and monohexyl ethers of ethylene glycol, and phenyl ether of propylene glycol. The amount of coalescing solvent is not unduly 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. The conductive electrocoating composition is applied to a metal substrate such as a phosphatized steel substrate by conventional cathodic electrocoating techniques in which the bath is at a temperature of about 15-35°C and a DC current of about 75-200 volts is used and the composition is electrodeposited for about 0.5-5 minutes. The resulting coated substrate is baked at about 125-200°C for about 5-30 minutes to form a cured conductive layer or finish on the metal substrate. It may be necessary or desirable to apply a layer of another conductive electrocoating composition or a conductive primer or primer/surfacer over the electrodeposited layer to provide color or improved physical properties to the resulting finish. The aforementioned conductive pigment is used to provide the necessary level of conductivity which needs to be in the same range as the electrodeposited layer so that a clear layer of coating can be electrodeposited. Primers or pri er/surfacers can be applied by conventional spray techniques and are cured to provide
a conductive finish. Typical alkyd resin, polyesters, acrylic resin with conventional crosslinking agents such as melamine resins can be used as the film forming binders of such compositions. One useful primer/surfacer is described in US Patent Application Serial No. 07/461,471 filed December 28, 1989 which has been allowed and which is hereby incorporated by reference.
The clear coating is electrodeposited over the conductive coating on the substrate using the same electrocoating process described above to apply the conductive layer and baked under the same conditions to form a cured finish having an excellent appearance and good physical properties. The clear coating composition can be the same as the conductive composition but without the pigments. The clear and the conductive composition need not be identical but roust be compatible to have acceptable intercoat adhesion. Any of the aforementioned binders used for the conductive coat can be used for the clear coat. The clear coating composition also may contain about 0.1-5% by weight, based on the weight of the binder, of ultraviolet light absorbers and antioxidants that are well known in the coating art. Small amounts of pigment that has the same refractive index as the clear coating can be added such as finely divided silica and still allow the coating to remain clear.
The following examples illustrate the invention. All parts and percentages are on a weight basis unless otherwise indicated.
EXAMPLE 1 Preparation of Electrocoat Backbone Resin
A primary hydroxy containing backbone resin was prepared as follows:
To a solution of epoxy resin Epon® 1001 (289.2 parts; 0.6 epoxy equivalent) in ethylene glycol monobutyl ether (161 parts) were added diethanol amine (21.0 parts; 0.2 mole), 3-(N,N-dimethyl amino) propylamine (10.2 parts; 0.1 mole) and an adduct of 1,6-diamino hexane and Cardura E-10® (61.6 parts; 0.1 mole of adduct) . (Cardura E-10® is a glycidyl ester of Cio carboxylic acid available from Shell Chemical Company.) The adduct was prepared by reacting 1,6 diamino hexane (116 parts; 1 mole) with Cardura E-10® (500 parts; 2 moles) at 80°C for 3 hours. The mixture of the epoxy resin Epon® 1001 and the amines was reacted by heating first at 85 - 90βC for 4 hours with stirring, and then at 120°C for 1 hour. The epoxy content was then zero. The theoretical amine milliequivalent per gm solid 1.57; hydroxy content of 0.47 equivalent/100 gms. and theoretical solids of 70.0%.
Preparation of Conductive TiO?/Silica Dispersion A dispersion was prepared as follows:
Parts by W t Backbone resin (prepared above) Aqueous lactic acid solution
Total 100.00
Conductive pigment particles of hollow shells of silica with fine crystallites of antimony-doped tine oxide forming a uniform, two-dimensional network on the surface of the silica containing 46% Sn (as Snθ2) , 22% Si (as Siθ2) , 18% Ba (as BaO) , and 4% Sb as (Sb2θ3). The conductive pigment is prepared as described in co-pending application Serial Number 07/386,765 filed August 2, 1989.
The aqueous lactic acid solution was added to the above resin and mixed thoroughly, for about five minutes. Deionized water was the added slowly with mixing to emulsify the neutralized resin. The conductive pigment was then added slowly with stirring to produce a slurry with a premix viscosity of 59 Krebs Units when measured on a Brookfield viscometer. This slurry was then ground in a sand mill until fineness on a Hegman grinding gauge of 8 to 7 was obtained. The resulting dispersion had 50.0% solids contents, (37.50% pigment, 12.50 resin non-volatiles) and a 3/1 pigment to binder weight ratio.
Preparation of the Electrocoat Crosslinker A blocked toluene diisocyanate crosslinker was prepared as follows:
30% aqueous phosphoric acid solution 80,20 toluene diisocyanate Butoxyethoxy ethanol Dibutyl tin dilaurate Trimethylol propane Butanol Methylisobutyl ketone
The phosphoric acid solution and 80,20 toluene diisocyanate were charged into a reactor, which was fitted with a stirrer, condenser and has capability for heating and/or cooling, and mixing. Butoxyethoxy ethanol was added slowly over a three hour period, with stirring while holding the exotherm temperature to a maximum of 70°C. When the addition was completed, the reaction mixture was held at 65-70°C and samples, were taken every 30 minutes until the percent isocyanate was 11.9 to 12.9.
Dibutyl tin dilaurate was added and mixed into the reaction mixture. Then trimethyl propane was added slowly over a three hour period. The batch temperature was allowed to rise to a temperature of 120°C at the end of this addition. The temperature was held at 120°C until the percent isocyanate was zero. Butanol was slowly added, followed by methyl isobutyl ketone. The reaction mixture was cooled to 70°C and filtered while holding the temperature at about 70°C. The resulting composition had 74-76% solids content, zero percent isocyanate and a 40-60 second viscosity at 25°C.
Preparation of Dibutyl Tin Oxide Paste
A dibutyl tin oxide paste was prepared as ronows:
Parts by Weight Backbone resin (prepared above) 14.22
Aqueous lactic acid solution (described 1.58 above) Deionized water 54.20 Dibutyl tin oxide powder 30.00 Total 100.00
Lactic acid solution was added to the backbone resin while mixing; then the deionized water was added slowly while the resulting mixture was emulsified. Dibutyl tin oxide was then added slowly while stirring to produce a slurry. This slurry was then processed in a stainless steel attritor for 13 hours to provide a 40% solids paste, of 30% dibutyl tin oxide and 10% resin solids for a 3/1 pigment to binder ratio.
Preparation of a Conductive Silica Dispersion
A conductive silica dispersion was prepared as follows: Parts by eight
Flexible polyester resin solution1 40.7
Butyl Acetate 15.3
Xylene 11.4 Conductive Pigment (described above) 32.6
Total 100.0
180% solids solution in toluene of a polyester polyol of dimethyl 1,4 cyclohexane dicarboxylate, isophthalic acid, adipic acid, neopentyl glycol and trimethylol propane having a l- dioxyl value of about 150, a number average molecular weight of about 1000-2200 determined by gel permeation chromatography using polystryene as the standard.
The solvents were added to the polyester resin solution with stirring. The conductive pigment was then added slowly with stirring to produce a slurry. This slurry was ground one pass in a Dynomill high speed mixer, using 0.8 mil glass bead media. The
resulting dispersion had a 65.2% solids content and a fineness of 71/2 on a Hegman gauge and contained 32.6% pigment and 32.6% resin non-volatiles and had a 1.0/1.0 pigment to binder ratio.
Preparation of Red Dispersion
A red dispersion was prepared as follows:
Parts by Weight
Flexible polyester resin solution1 30.0
(described above)
Methanol 10.0
Red iron oxide pigment 60.0 Total 100.0
Methanol was added to the polyester resin solution with stirring. The pigment was then added slowly with stirring to produce a slurry. This slurry was then ground in a sand mill until a fineness on a Hegman grinding gauge of 6 maximum was obtained. This dispersion had a 84.0% solids content (60.0% pigment, 24.0% resin non-volatiles) and a 1.0/0.4 pigment to binder ratio.
Preparation of an Acrylic Backbone Resin
An acrylic resin was prepared as follows: 1483.0 parts ethylene glycol mono-butyl ether solvent was changed into a reactor, which was fitted with a stirrer, condenser, and capability for heating and/or cooling and mixing. The solvent was heated to 120°C. A mixture of 183.6 parts styrene monomers, 275.4 parts methyl methacrylate monomer (MMA), 550.8 parts butyl acrylate monomer (BA) , 550.8
parts hydroxyethyl methacrylate monomer (HEMA) , 275.4 parts t-butylaminoethyl methacrylate monomer (TBAEMA) and 150.0 parts ethylene glycol mono-butyl ether to provide a polymer having a weight ratio of 10/15/30/30/15 of S/MMA/BA/HEMA/TBAEMA) was fed to the reactor over 210 minutes and held at 120°C. A solution of 37.0 parts t-butyl peroctoate and 203.0 parts ethylene glycol mono-butyl ether was fed concurrently into the reactor over 210 minutes and the reduction mixture was held at 120°C . The reaction mixture was then held at 120°C for 30 minutes with stirring, then cooled and filtered. The theoretical amine milliequivalent per gram solids of the composition was 0.81 and the theoretical solids was 50.0%.
The composition was vacuum stripped at room temperature to remove the ethylene glycol mono-butyl ether and was replaced with methyl isobutyl ketone to provide a composition having a solids content of 55.9%.
Preparation of Conductive Electrocoat Paint Bath
A cathodic electrocoat paint bath was prepared as follows:
Parts by Weight Electrocoat backbone resin solution 8.21
(prepared above) Aqueous lactic acid solution 0.68
(described above) Electrocoat crosslinker (prepared above) 6.22 Conductive Tiθ2/silica dispersion 17.78
(prepared above) Dibutyl tin oxide paste (prepared above) 0.44
Deionized water 66.67
Total 100.00
The lactic acid solution was mixed with the acrylic backbone resin solution. To this mixture the conductive Tiθ2/ silica dispersion, dibutyltin oxide paste and deionized water were added in order with mixing. An 80% neutralized paint bath with 20% solids and a 50/100 pigment to binder ratio was formed. This bath was stirred in an open vessel for about 24 hours to allow for solvent evaporation prior to electrocoating. The bath had a pH of 5.3, and a conductivity of 1900 micro mhol,s/cm.
The bath was heated to 30βC and zinc phosphated cold rolled steel panels were cathodically electrocoated using 225 volts D.C. for 2 minutes and rinsed with deionized water. The panels were cured for 30 minutes at 162°C, giving a cured film thickness of 0.8 to 1.1 mils thickness. These films had a resistance of 3.5 x 108 ohms.
Preparation of Conductive Red Primer Surfacer
A conductive red primer surfacer was prepared as follows:
Parts by
Weight
Conductive Silica dispersion(prepared above) 55.67 Red pigment dispersion (prepared above) 7.14 Flexible polyester resin solution 9.24
(described above) Melamine/formaldehyde resin 14.70 Hindered amine UV light absorber 0.52 Leveling additive (surface tension reducer) 0.21 Methanol 1.81
Butanol
The above constituents were added in the above order with mixing to form a primer surfacer for spray application having a pigment to binder ratio of 0.52/1.0 and a viscosity of 30-38 seconds in a #2
Fisher cup. The primer surfacer was spray applied to the above prepared electrocoated steel panels and baked for 30 minutes at 120°C. The panels had a total dry film build of 1.8 mils, 1.0 mil conductive electrocoat and 0.8 mil conductive red primer surfacer.
Preparation of Clear Epoxy Cathodic Electrodeposition Bath
A clear epoxy cathodic electrodeposition bath was prepared as follows:
Parts by
Weight Electrocoat backbone resin (prepared above) 16.67
Aqueous lactic acid solution (described above) 1.51
Electrocoat crosslinker (prepared above) 9.33
Dibutyl tin oxide paste (prepared above) 0.67
Deionized water 71.82 Total 100.00
The lactic acid solution was mixed with the electrocoat backbone resin solution and the electrocoat crosslinker, dibutyl tin oxide paste and deionized water were added in order with mixing. 100%
neutralized clear electrocoat bath with 20% solids was formed. The bath was stirred in an open vessel for about 24 hours to allow for solvent evaporation prior to electrocoating. The bath had a pH of 5.1 and a conductivity of 2700 micro mhol,s/cm.
The bath was heated to 30°C and the above prepared zinc phosphated steel panels, electrocoated with conductive paint and coated with primer surfacer were cathodically electrocoated using 125 volts D.C. for 2 minutes and rinsed. The panels were baked for 30 minutes at 162°C to give a total film thickness of 2.6 mils which comprises 1.0 mil conductive electrocoat, 0.8 mil conductive primer surfacer and 0.8 mil of clear topcoat. The panels had a good appearance and were smooth and glossy.
EXAMPLE 2
A clear acrylic cathodic electrodeposition bath was prepared as follows:
Parts by Weight Aqueous acrylic backbone resin solution 25.04 (prepared in Example 1) Aqueous lactic acid solution 0.99
(described in Example 1)
Electrocoat crosslinker 8.00
(prepared in Example 1)
Dibutyl tin oxide paste 10.67 (prepared in example 1)
Deionized water 65.30
Total 100.00
The lactic acid solution was mixed with the backbone resin solution and the electrocoat
crosslinker, dibutyl tin oxide paste and deionized water were added in order with mixing. An 80% neutralized clear electrocoat bath having 20% solids was formed. The bath was stirred in an open vessel for about 24 hours to allow for solvent evaporation prior to electrocoating. The bath had a pH of 5.2 and a conductivity of 1450 micro mhol's/cm.
The bath was heated to 30°C and zinc phosphated steel panels, electrocoated with the Example I conductive electrocoat and primer surfacer were cathodically electrocoated using 100 volts D.C. for 2 minutes and rinsed. The panels were baked for 30 minutes at 162βC giving a total film thickness of 2.5 mils comprising 1.0 mil conductive electrocoat, 0.8 mil conductive primer surfacer and 0.7 mil of clear topcoat. The panels had a good appearance and were smooth and glossy.
Claims
1. An improved electrocoating process in which a layer of an electrically conductive cathodic electrocoating composition containing film forming binder and pigment in a pigment to binder weight ratio of about 1:100 to 100:100 is cathodically electrocoated onto a conductive substrate and cured to form a conductive layer and subsequently a layer of a clear cathodic electrocoating composition is electrocoated over the layer of the conductive composition and the layer of clear composition is cured to form a clear layer on the substrate; the improvement used therewith comprises an electrically conductive pigment of silica which is either amorphous silica or a silica containing material, the silica is in association with a two-dimensional network of antimony-containing tin oxide crystallites in which the antimony content ranges from about 1-30% by weight of the tin oxides and provides the cured conductive layer with a resistance of less than 10 X 1015 ohms.
2. The process of claim 1 in which the conductive pigment comprises an inert core material having a coating selected from the group consisting of an amorphous silica coating or a silica-containing coating which is surface coated with a two-dimensional conducting network of antimony-containing tin oxide crystallites.
3. The process of claim 2 in which the conductive pigment comprises a hollow shell of amorphous silica or silica containing material surface coated with a two-dimensional conducting network of antimony-containing tin oxide crystallites.
4. The process of claims 1, 2 or 3 in which the silica-containing material is a composition selected from the group consisting of metal silicates, silica-containing glass and material having an extensive co-valent network of Siθ4 units.
5. The process of claims 1,2 or 3 in which the silica-containing material is a silica-boria material.
6. The process of claim 1 in which the conductive pigment consists of hollow shells of amorphous silica with a two-dimensional conducting network of antimony-containing tin oxide crystallites.
7. The process of claim 1 in which an intermediate conductive layer is applied over the conductive' layer and cured before the clear composition is electrocoated.
8. The process of claim 7 in which the intermediate conductive layer contains a conductive pigment and a binder of a hydroxy containing polyester resin and aminoplast crosslinking agent or an isocyanate crosslinking agent.
9. The process of claim 1 in which the binder of the conductive layer comprises an epoxy-amine adduct and a blocked polyisocyanate crosslinker.
10. The process of claim 9 in which the binder of the clear layer comprises an epoxy-amine adduct and a blocked polyisocyanate crosslinker.
11. The process of claim 1 in which the binder of the clear layer comprises an epoxy-amine adduct and a blocked polyisocyanate.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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US784,241 | 1977-04-04 | ||
US07/784,241 US5203975A (en) | 1991-10-29 | 1991-10-29 | Process for cathodic electrodeposition of a clear coating over a conductive paint layer |
Publications (1)
Publication Number | Publication Date |
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WO1993009191A1 true WO1993009191A1 (en) | 1993-05-13 |
Family
ID=25131801
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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PCT/US1992/009207 WO1993009191A1 (en) | 1991-10-29 | 1992-10-29 | Process for cathodic electrodeposition of a clear coating over a conductive paint layer |
Country Status (3)
Country | Link |
---|---|
US (1) | US5203975A (en) |
MX (1) | MX9206206A (en) |
WO (1) | WO1993009191A1 (en) |
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US5626948A (en) * | 1996-01-03 | 1997-05-06 | Ferber Technologies L.L.C. | Electrical system having a multilayer conductive composition |
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DE19643082C2 (en) * | 1995-10-18 | 2003-10-30 | Volkswagen Ag | Process for the interior and exterior coating of a body with cavities |
DE19643082A1 (en) * | 1995-10-18 | 1997-04-24 | Volkswagen Ag | Method for inner and outer coating of car body structure with hollow spaces |
EP2298900A1 (en) | 1996-09-17 | 2011-03-23 | Novartis Vaccines and Diagnostics, Inc. | Compositions and methods for treating intracellular diseases |
EP2386629A1 (en) | 1997-10-14 | 2011-11-16 | Darwin Molecular Corporation | Thymidine kinase mutants and fusion proteins having thymidine kinase and guanylate kinase activities |
EP2386630A1 (en) | 1997-10-14 | 2011-11-16 | Darwin Molecular Corporation | Thymidine kinase mutants and fusion proteins having thymidine kinase and guanylate kinase activities |
WO2000009693A2 (en) | 1998-08-11 | 2000-02-24 | Darwin Discovery Ltd. | Identification of the gene causing the mouse scurfy phenotype and its human ortholog |
WO2000032773A1 (en) | 1998-11-27 | 2000-06-08 | Darwin Discovery Ltd. | Compositions and methods for increasing bone mineralization |
EP1950297A2 (en) | 2000-05-31 | 2008-07-30 | Novartis Vaccines and Diagnostics, Inc. | Compositions and methods for treating neoplastic disease using chemotherapy and radiation sensitizers |
EP1967525A2 (en) | 2001-05-08 | 2008-09-10 | Darwin Molecular Corporation | A method for regulating immune function in primates using the foxp3 protein |
EP2341071A1 (en) | 2003-06-16 | 2011-07-06 | UCB Manufacturing, Inc. | Compostion and methods for increasing bone mineralization |
EP2338906A1 (en) | 2003-06-16 | 2011-06-29 | UCB Manufacturing, Inc. | Compostion and methods for increasing bone mineralization |
US9532994B2 (en) | 2003-08-29 | 2017-01-03 | The Regents Of The University Of California | Agents and methods for enhancing bone formation by oxysterols in combination with bone morphogenic proteins |
US9670244B2 (en) | 2006-02-27 | 2017-06-06 | The Regents Of The University Of California | Oxysterol compounds and the hedgehog pathway |
US9526737B2 (en) | 2007-12-03 | 2016-12-27 | The Regents Of The University Of California | Oxysterols for activation of hedgehog signaling, osteoinduction, antiadipogenesis, and Wnt signaling |
US9717742B2 (en) | 2012-05-07 | 2017-08-01 | The Regents Of The University Of California | Oxysterol analogue OXY133 induces osteogenesis and hedgehog signaling and inhibits adipogenesis |
US9683009B2 (en) | 2013-05-02 | 2017-06-20 | The Regents Of The University Of California | Bone-selective osteogenic oxysterol-bone targeting agents |
EP3695841A2 (en) | 2013-07-01 | 2020-08-19 | The Research Foundation for the State University of New York | Ship inhibition to combat obesity |
WO2015195812A1 (en) | 2014-06-17 | 2015-12-23 | The Research Foundation For The State University Of New York | Ship inhibition to induce activation of natural killer cells |
EP3845612A1 (en) * | 2019-12-30 | 2021-07-07 | Axalta Coating Systems GmbH | Low density electrocoat composition with improved throwing power |
Also Published As
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US5203975A (en) | 1993-04-20 |
MX9206206A (en) | 1993-04-01 |
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