WO1995023038A1 - Water-borne autodepositing coating compositions - Google Patents
Water-borne autodepositing coating compositions Download PDFInfo
- Publication number
- WO1995023038A1 WO1995023038A1 PCT/US1995/001935 US9501935W WO9523038A1 WO 1995023038 A1 WO1995023038 A1 WO 1995023038A1 US 9501935 W US9501935 W US 9501935W WO 9523038 A1 WO9523038 A1 WO 9523038A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- water
- borne
- autodepositing
- carbon black
- dispersant
- Prior art date
Links
- 239000008199 coating composition Substances 0.000 title claims abstract description 42
- 238000000576 coating method Methods 0.000 claims abstract description 36
- 239000011248 coating agent Substances 0.000 claims abstract description 34
- 239000006185 dispersion Substances 0.000 claims abstract description 30
- 239000006229 carbon black Substances 0.000 claims abstract description 29
- 239000002270 dispersing agent Substances 0.000 claims abstract description 24
- 229920005989 resin Polymers 0.000 claims abstract description 19
- 239000011347 resin Substances 0.000 claims abstract description 19
- 239000007788 liquid Substances 0.000 claims abstract description 10
- 239000002253 acid Substances 0.000 claims abstract description 8
- NVVZQXQBYZPMLJ-UHFFFAOYSA-N formaldehyde;naphthalene-1-sulfonic acid Chemical compound O=C.C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 NVVZQXQBYZPMLJ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000007800 oxidant agent Substances 0.000 claims abstract description 7
- 229910052751 metal Inorganic materials 0.000 claims description 13
- 239000002184 metal Substances 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000004615 ingredient Substances 0.000 claims description 4
- 239000000758 substrate Substances 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 3
- 229910021645 metal ion Inorganic materials 0.000 abstract description 7
- 238000005260 corrosion Methods 0.000 abstract description 5
- 230000007797 corrosion Effects 0.000 abstract description 5
- 238000003860 storage Methods 0.000 abstract description 4
- 230000001464 adherent effect Effects 0.000 abstract description 3
- 229940105289 carbon black Drugs 0.000 description 21
- 235000019241 carbon black Nutrition 0.000 description 21
- 239000000049 pigment Substances 0.000 description 12
- 238000012360 testing method Methods 0.000 description 11
- 238000007654 immersion Methods 0.000 description 6
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 5
- -1 X = NH4) Chemical class 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 4
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 3
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 3
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 229920000126 latex Polymers 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- PRAMZQXXPOLCIY-UHFFFAOYSA-N 2-(2-methylprop-2-enoyloxy)ethanesulfonic acid Chemical compound CC(=C)C(=O)OCCS(O)(=O)=O PRAMZQXXPOLCIY-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 2
- 229940063559 methacrylic acid Drugs 0.000 description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- FFJCNSLCJOQHKM-CLFAGFIQSA-N (z)-1-[(z)-octadec-9-enoxy]octadec-9-ene Chemical compound CCCCCCCC\C=C/CCCCCCCCOCCCCCCCC\C=C/CCCCCCCC FFJCNSLCJOQHKM-CLFAGFIQSA-N 0.000 description 1
- SQAINHDHICKHLX-UHFFFAOYSA-N 1-naphthaldehyde Chemical compound C1=CC=C2C(C=O)=CC=CC2=C1 SQAINHDHICKHLX-UHFFFAOYSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- 229940044192 2-hydroxyethyl methacrylate Drugs 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- VHSHLMUCYSAUQU-UHFFFAOYSA-N 2-hydroxypropyl methacrylate Chemical compound CC(O)COC(=O)C(C)=C VHSHLMUCYSAUQU-UHFFFAOYSA-N 0.000 description 1
- GWZMWHWAWHPNHN-UHFFFAOYSA-N 2-hydroxypropyl prop-2-enoate Chemical compound CC(O)COC(=O)C=C GWZMWHWAWHPNHN-UHFFFAOYSA-N 0.000 description 1
- LNQVOBNVXUVSEA-UHFFFAOYSA-N 4,5-dihydro-1h-imidazol-3-ium;dodecanoate Chemical compound C1CN=C[NH2+]1.CCCCCCCCCCCC([O-])=O LNQVOBNVXUVSEA-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-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
- 229910000640 Fe alloy Inorganic materials 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 229910001297 Zn alloy Inorganic materials 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000010960 cold rolled steel Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- POULHZVOKOAJMA-UHFFFAOYSA-M dodecanoate Chemical compound CCCCCCCCCCCC([O-])=O POULHZVOKOAJMA-UHFFFAOYSA-M 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N formaldehyde Substances O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 1
- 229960004279 formaldehyde Drugs 0.000 description 1
- 239000006232 furnace black Substances 0.000 description 1
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- MTNDZQHUAFNZQY-UHFFFAOYSA-N imidazoline Chemical compound C1CN=CN1 MTNDZQHUAFNZQY-UHFFFAOYSA-N 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- SHXXPRJOPFJRHA-UHFFFAOYSA-K iron(iii) fluoride Chemical compound F[Fe](F)F SHXXPRJOPFJRHA-UHFFFAOYSA-K 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229940070765 laurate Drugs 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- PSZYNBSKGUBXEH-UHFFFAOYSA-M naphthalene-1-sulfonate Chemical compound C1=CC=C2C(S(=O)(=O)[O-])=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-M 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229940096017 silver fluoride Drugs 0.000 description 1
- REYHXKZHIMGNSE-UHFFFAOYSA-M silver monofluoride Chemical compound [F-].[Ag+] REYHXKZHIMGNSE-UHFFFAOYSA-M 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000012430 stability testing Methods 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 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
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
- C09K23/12—Sulfonates of aromatic or alkylated aromatic compounds
-
- 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
- C09D5/08—Anti-corrosive paints
- C09D5/088—Autophoretic paints
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
Definitions
- This invention relates to a water-borne autodepositing coating composi ⁇ tion that has an excellent storage stability and that, when brought into contact with an electrochemically active metal surface, e.g., a surface of iron, zinc, iron alloy, or zinc alloy, efficiently coats the metal surface with a high-quality resin coating.
- This water-borne autodepositing coating composition is an acidic aqueous coating composition that contains water-dispersible or water-soluble organic coating-forming resin, pigment, acid, and oxidizing agent as essential components and may contain metal ions as an optional component.
- Autodepositing coating compositions are acidic compositions containing organic coating-forming resin that are able to form a resin coating on the surface of an active metal brought into contact with the coating composition.
- Autodepos ⁇ iting coating compositions are disclosed, inter alia, in Japanese Patent Publica- tion Numbers Sho 47-17630 [17,630/1972], Sho 48-14412 [14,412/1973], Sho 52-21006 [21 ,006/1977], Sho 52-35692 [35,692/1977], Sho 53-15093 [15,093/ 1978], Sho 53-16010 [16,010/1978], and Sho 53-44949 [44,949/1978] and Jap ⁇ anese Patent Application Laid Open [Kokai] Numbers Sho 60-58474 [58,474/ 1985], Sho 61-168673 [168,673/1986], and Sho 61-246267 [246,267/1986].
- pigment can be added to autodepositing coat ⁇ ing compositions in order, for example, to increase the corrosion resistance or impart the desired tinctorial strength or degree of color.
- Japanese Patent Pub- lication Numbers Sho 54-13453 [13,453/1979] and Sho 59-275 [275/1984] dis ⁇ close management of the specific amount of pigment used based on the specific type of pigment used and the desired coating color.
- Japanese Patent Publi ⁇ cation Number Sho 52-35692 [35692/1977] discloses the formation of colored coatings by immersion of the substrate in autodepositing coating compositions containing various types of pigments.
- Japanese Patent Publica ⁇ tion Number Sho 53-44949 teaches that there are no specific restrictions on type as long as the pigment is stable in the bath.
- Japanese Patent Application Laid Open Number Sho 60-58474 discloses a dispersant for maintaining the pigment particles in a dispersed state and teaches that the pigment dispersion should be selected in such a manner that the dispersant concentration in the aqueous phase of the autodepositing coating composition does not exceed the critical mi ⁇ celle concentration (“CMC").
- CMC critical mi ⁇ celle concentration
- United States Patent Number 4,177,180 discloses autodepositing coating compositions in which the pigment particles are dispersed and stabilized by non- ionic dispersant and also discloses a method for the preparation of such compo ⁇ sitions.
- United States Patent Number 4,177,180 also states that a uni ⁇ form coating appearance cannot be obtained when a colored coating is pro ⁇ quizzed using pigment dispersed in the form of an autodepositing coating compo- sition.
- the invention takes as its object the introduction of a black pigment-con ⁇ taining autodepositing coating composition that is able to generate a black coat ⁇ ing of uniform appearance, that exhibits a very good storage stability, and that forms a strongly adherent and highly corrosion-resistant coating.
- the invention provides a water-borne autodepositing coating composition that has a pH of 1.6 to 5 and comprises, preferably consists essentially of, or still more preferably consists of: water, a water-dispersible or water-soluble organic coating-forming resin, a liquid dispersion of carbon black that was separately prepared and was mixed with other constituents of the auto- deposition composition in the course of making the autodeposition composition, acid, and oxidizing agent, and, optionally, metal ions, wherein said liquid disper ⁇ sion of carbon black, before it was mixed with all of the other ingredients of the autodepositing composition, comprised, preferably consisted essentially of, or more preferably consisted of, water, carbon black, and a dispersant that is a naphthalenesulfonate-formaldehyde condensate conforming to formula (I):
- X Na, V-;Ca, or NH 4 and n is an integer with a value of at least 1.
- Description of Preferred Embodiments The most important characteristic feature of the invention is the use, as the liquid dispersion of carbon black incorporated into the water-borne autode ⁇ positing coating composition, of an aqueous carbon black dispersion in which the carbon black is dispersed in water using a naphthalenesulfonate-formalde- hyde condensate conforming to formula (I).
- the degree of condensation of the naphthalenesulfonate acid-formaldehyde condensate in formula (I), which is indicated by the subscript n in formula (I), is preferably 10 to 30 based on dispersibility considerations.
- the carbon black concentration in the liquid dispersion of carbon black is also not critical, but a 15 to 50 % dispersion is preferred.
- the coating compo ⁇ sition preferably contains 0.5 to 7.5 grams per liter (hereinafter usually abbrevi ⁇ ated as "g L") of carbon black and more preferably contains 1.0 to 1.5 g/L of car- bon black.
- the generally known channel blacks and furnace blacks may be used as the carbon black in the present invention.
- the heretofore known autodepositing coating compositions are well suit ⁇ ed for use as the autodepositing coating composition employed in the present invention, except for the change in the source of at least some of any carbon black previously used.
- no new restrictions apply to the organic coating-forming resins usable by the present invention, and those resins hereto ⁇ fore known for this purpose may be used for the present invention.
- Examples thereof are urethane resins, epoxy resins, polyester resins, and polymeric resins composed of one or more monomers selected from methyl acrylate, ethyl acryl- ate, n-butyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-ethyl- hexyl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, 2- hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, glycidyl acrylate, gly- cidyl methacrylate, acrylamide, methacrylamide, acrylonitrile, styrene, ethylene, butadiene, vinyl chloride, vinylidene chloride, vinyl acetate, acrylic acid, metha- crylic acid, and the like.
- Japanese Patent Application Laid Open Number Sho 60-58474 discloses coating compositions that contain dispersed vinylidene chloride-based copolymer, for example, copolymer composed of 50 to 70 weight % of vinylidene chloride; approximately 5 to 35 weight % of vinyl chloride; ap- proximately 5 to 20 weight % of vinylic compound comprising at least 1 selection from acrylic acid, methacrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, ethyl methacrylate, acrylamide, methacrylamide, acrylonitrile, and methacryloni- trile; and approximately 0.1 to 5 weight % of sulfoethyl methacrylate.
- dispersed vinylidene chloride-based copolymer for example, copolymer composed of 50 to 70 weight % of vinylidene chloride; approximately 5 to 35 weight % of vinyl chloride; ap- proximately 5 to 20 weight
- the pre ⁇ ferred vinylidene chloride-based copolymer disclosed therein contains approxi- mately 15 to 20 weight % of vinyl chloride, 2 to 5 weight % of butyl acrylate, 3 to 10 weight % of acrylonitrile, and approximately 1 to 2 weight % of sulfoethyl methacrylate (for example, DaranTM latices from W R. Grace & Company, Ser- feneTM latices from Morton Chemical, and HaloflexTM 202 from Imperial Chemical Industries).
- the resin concentration in the water-borne autodepositing coating compo ⁇ sition of the present invention is preferably 5 to 550 g/L and more preferably 50 to 100 g/L.
- the coating composition according to the invention should have a pH of 1.6 to 5.0: A high-quality coating will not usually be formed when compo ⁇ sitions with a pH outside this range are used.
- the heretofore known water-borne autodepositing coating compositions usable by the present invention also contain acid and oxidizing agent as essential components, and may contain metal ions as an optional component.
- water-borne autodepositing coating compositions is the water-borne autodepos- iting coating composition, disclosed in Japanese Patent Application Laid Open Number Sho 49-108135 [108,135/1974], of dispersed resin at approximately 5 to 550 g/L as solids concentration; any suitable acid that can supply hydrogen ions to the composition, but preferably approximately 0.4 to 5.0 g/L of hydrofluor ⁇ ic acid; oxidizing agent, whose type is not critical, but which is preferably hydro ⁇ gen peroxide at not more than approximately 3.0 g/L; and metal compound cap- s able of furnishing metal ions, for example, approximately 1 to 50 g/L in the case of ferric fluoride.
- Another example is the coating composition disclosed in Jap ⁇ anese Patent Publication Number Sho 53-44949, which contains dispersed resin at approximately 5 to 550 g/L as solids concentration, approximately 0.4 to 5.0 g/L of hydrofluoric acid as acid, not more than approximately 3.0 g/L of hydrogen ⁇ o peroxide as oxidizing agent, and a metal compound, for example, approximately 0.1 to 10.0 g/L in the case of silver fluoride.
- Hydrogen peroxide 0.10 g/L and deionized water sufficient to make a total of 1 L.
- the organic coating-forming resin is a vinylidene chloride-based resin
- the carbon black dispersion contained dispersant as reported in Table 1 in the quantity noted in Table 1 ; the carbon black, a furnace black, was adjusted to a concentration of 25 weight % in the dispersion.
- C) were evaluated for each autodepositing coating composition prepared for the examples and comparison examples, except that for those of the comparison examples for which the compatibility was unsatisfactory, the accelerated stability was not measured.
- the compatibility was evaluated using the following scale: + + excellent dispersion x poor dispersion (production of aggregates or viscosity increase during preparation of the dispersion)
- the accelerated stability was evaluated using the following scale.
- Preliminarily cleaned cold-rolled steel panels (70 x 150 x 1 mm) were coated by immersion for 180 seconds in the respective baths of the water-borne autodepositing coating compositions described above.
- the baths were main ⁇ tained at approximately 20° C to 22° C.
- the panels were dried in an oven at 110° C for 20 minutes and were thereafter subjected to evaluation testing.
- the thickness of the coating on each test panel was approx ⁇ imately 20 microns for all the examples and for the comparison example with lignosulfate dispersant, the only comparison example which had a satisfactory coating performance.
- This dispersant had a hydrophile-lipophile balance value of 16.
- This dispersant had a hydrophile-lipophile balance value of 14.
- “Comp.” means “Composition”; “Amt.” means “Amount”; “Dis.” means “Dispersant”; “C.B.” means “Carbon Black”; “N F C” means naphthalene-formaldehyde condensate; "AP-EO” means “alkyl phenol-ethylene oxide adduct”; “Imid.” means “imidazoline”; “POE” means “polyoxyethylene”; and “Styr.” means “styrenated”.
- a cross cut was scribed through the paint film to the base metal, followed by salt-spray testing according to Japanese Industrial Standard Z-2371 for 500 hours. This was followed by tape peeling. Evaluation consisted of measuring the width of peel from the scribed cross (maximum on one side in mm).
- the solids in the water-borne autodepositing coating composition of the invention do not precipitate, separate, or aggregate during storage. Moreover, when the water-borne autodepositing coating composition of the invention is brought into contact with an active metal surface, for example, the surface of a ferrous, zinciferous, aluminiferous, or magnesium-containing metal, it forms on said metal surface a black resin coating that is strongly adherent, highly corro ⁇ sion resistant, and uniform in appearance.
- an active metal surface for example, the surface of a ferrous, zinciferous, aluminiferous, or magnesium-containing metal
Abstract
Description
Claims
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP95910274A EP0746424A4 (en) | 1994-02-23 | 1995-02-22 | Water-borne autodepositing coating compositions |
US08/696,958 US5760112A (en) | 1994-02-23 | 1995-02-22 | Water-borne autodepositing coating compositions |
AU18451/95A AU682937B2 (en) | 1994-02-23 | 1995-02-22 | Water-borne autodepositing coating compositions |
MX9603497A MX9603497A (en) | 1994-02-23 | 1995-02-22 | Water-borne autodepositing coating compositions. |
BR9506849A BR9506849A (en) | 1994-02-23 | 1995-02-22 | Composition of self-depositing coating and process of forming a self-depositing coating on a metal substrate |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP6049687A JPH07233341A (en) | 1994-02-23 | 1994-02-23 | Self-deposition type water-based coating composition |
JP6/049687 | 1994-02-23 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1995023038A1 true WO1995023038A1 (en) | 1995-08-31 |
Family
ID=12838102
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US1995/001935 WO1995023038A1 (en) | 1994-02-23 | 1995-02-22 | Water-borne autodepositing coating compositions |
Country Status (8)
Country | Link |
---|---|
EP (1) | EP0746424A4 (en) |
JP (1) | JPH07233341A (en) |
AU (1) | AU682937B2 (en) |
BR (1) | BR9506849A (en) |
CA (1) | CA2183994A1 (en) |
MX (1) | MX9603497A (en) |
WO (1) | WO1995023038A1 (en) |
ZA (1) | ZA951347B (en) |
Cited By (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0909799A1 (en) * | 1997-03-17 | 1999-04-21 | Toyo Ink Manufacturing Co. Ltd. | Electrocoagulation printing ink |
US6130289A (en) * | 1998-01-27 | 2000-10-10 | Lord Corporation | Aqueous phenolic dispersion |
US6383307B1 (en) | 1998-01-27 | 2002-05-07 | Lord Corporation | Aqueous metal treatment composition |
US6476119B1 (en) | 1998-01-27 | 2002-11-05 | Lord Corporation | Aqueous primer or coating |
US8618210B2 (en) | 2003-08-25 | 2013-12-31 | Dow Global Technologies, Llc | Aqueous polymer dispersions and products from those dispersions |
US8852739B2 (en) | 2010-02-23 | 2014-10-07 | Evonik Carbon Black Gmbh | Carbon black, method for the production thereof, and use thereof |
US8915998B2 (en) | 2008-11-27 | 2014-12-23 | Evonik Carbon Black Gmbh | Pigment granulate, method for producing the same and use thereof |
US8946329B2 (en) | 2003-08-25 | 2015-02-03 | Dow Global Technologies Llc | Coating compositions |
US9169406B2 (en) | 2003-08-25 | 2015-10-27 | Dow Global Technologies Llc | Coating compositions |
US9422444B2 (en) | 2012-12-28 | 2016-08-23 | Dow Global Technologies Llc | Coating compositions |
US9938413B2 (en) | 2012-12-28 | 2018-04-10 | Dow Global Technologies Llc | Coating composition and articles made therefrom |
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US3671476A (en) * | 1969-03-01 | 1972-06-20 | Sumitomo Light Metal Ind | Electrodeposition color coating composition and method for electrodeposition color coating of metal therewith |
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SU637415A1 (en) * | 1977-07-12 | 1978-12-15 | Киевский Филиал По Специальным Видам Печати Всесоюзного Научно-Исследовательского Института Комплексных Проблем Полиграфии | Ink for intaglio or flexography printing |
US4177180A (en) * | 1975-09-15 | 1979-12-04 | Amchem Products, Inc. | Composition comprising resin and pigment for autodeposition |
WO1985002838A1 (en) * | 1983-12-27 | 1985-07-04 | Sandoz Ltd | Water reducing agent utilized in mortar and concrete |
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US3709743A (en) * | 1969-11-28 | 1973-01-09 | Celanese Coatings Co | Acidic deposition process |
US4297259A (en) * | 1979-04-18 | 1981-10-27 | Diamond Shamrock Corporation | Synthetic polymer emulsifier |
-
1994
- 1994-02-23 JP JP6049687A patent/JPH07233341A/en active Pending
-
1995
- 1995-02-17 ZA ZA951347A patent/ZA951347B/en unknown
- 1995-02-22 CA CA002183994A patent/CA2183994A1/en not_active Abandoned
- 1995-02-22 EP EP95910274A patent/EP0746424A4/en not_active Withdrawn
- 1995-02-22 MX MX9603497A patent/MX9603497A/en unknown
- 1995-02-22 BR BR9506849A patent/BR9506849A/en not_active Application Discontinuation
- 1995-02-22 WO PCT/US1995/001935 patent/WO1995023038A1/en not_active Application Discontinuation
- 1995-02-22 AU AU18451/95A patent/AU682937B2/en not_active Ceased
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3671476A (en) * | 1969-03-01 | 1972-06-20 | Sumitomo Light Metal Ind | Electrodeposition color coating composition and method for electrodeposition color coating of metal therewith |
US4001159A (en) * | 1973-04-23 | 1977-01-04 | Sumitomo Chemical Company, Limited | Aqueous dispersion of olefin-acrylate copolymer |
US3998773A (en) * | 1975-03-14 | 1976-12-21 | The Dow Chemical Company | Hydraulic cement composition |
US4177180A (en) * | 1975-09-15 | 1979-12-04 | Amchem Products, Inc. | Composition comprising resin and pigment for autodeposition |
SU637415A1 (en) * | 1977-07-12 | 1978-12-15 | Киевский Филиал По Специальным Видам Печати Всесоюзного Научно-Исследовательского Института Комплексных Проблем Полиграфии | Ink for intaglio or flexography printing |
WO1985002838A1 (en) * | 1983-12-27 | 1985-07-04 | Sandoz Ltd | Water reducing agent utilized in mortar and concrete |
Cited By (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0909799A1 (en) * | 1997-03-17 | 1999-04-21 | Toyo Ink Manufacturing Co. Ltd. | Electrocoagulation printing ink |
EP0909799A4 (en) * | 1997-03-17 | 1999-05-06 | ||
US6130289A (en) * | 1998-01-27 | 2000-10-10 | Lord Corporation | Aqueous phenolic dispersion |
US6383307B1 (en) | 1998-01-27 | 2002-05-07 | Lord Corporation | Aqueous metal treatment composition |
US6476119B1 (en) | 1998-01-27 | 2002-11-05 | Lord Corporation | Aqueous primer or coating |
US9169406B2 (en) | 2003-08-25 | 2015-10-27 | Dow Global Technologies Llc | Coating compositions |
US8946329B2 (en) | 2003-08-25 | 2015-02-03 | Dow Global Technologies Llc | Coating compositions |
US8618210B2 (en) | 2003-08-25 | 2013-12-31 | Dow Global Technologies, Llc | Aqueous polymer dispersions and products from those dispersions |
US9416291B2 (en) | 2003-08-25 | 2016-08-16 | Dow Global Technologies Llc | Coating compositions |
US8915998B2 (en) | 2008-11-27 | 2014-12-23 | Evonik Carbon Black Gmbh | Pigment granulate, method for producing the same and use thereof |
US8852739B2 (en) | 2010-02-23 | 2014-10-07 | Evonik Carbon Black Gmbh | Carbon black, method for the production thereof, and use thereof |
US9422444B2 (en) | 2012-12-28 | 2016-08-23 | Dow Global Technologies Llc | Coating compositions |
US9938413B2 (en) | 2012-12-28 | 2018-04-10 | Dow Global Technologies Llc | Coating composition and articles made therefrom |
Also Published As
Publication number | Publication date |
---|---|
CA2183994A1 (en) | 1995-08-31 |
AU1845195A (en) | 1995-09-11 |
EP0746424A4 (en) | 1998-06-10 |
BR9506849A (en) | 1997-09-30 |
AU682937B2 (en) | 1997-10-23 |
JPH07233341A (en) | 1995-09-05 |
ZA951347B (en) | 1995-10-24 |
EP0746424A1 (en) | 1996-12-11 |
MX9603497A (en) | 1997-05-31 |
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