EP1228263A1 - Coating an aluminum alloy substrate - Google Patents
Coating an aluminum alloy substrateInfo
- Publication number
- EP1228263A1 EP1228263A1 EP99964956A EP99964956A EP1228263A1 EP 1228263 A1 EP1228263 A1 EP 1228263A1 EP 99964956 A EP99964956 A EP 99964956A EP 99964956 A EP99964956 A EP 99964956A EP 1228263 A1 EP1228263 A1 EP 1228263A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- aluminum
- solution
- copolymer
- container
- substrate
- 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.)
- Granted
Links
- 238000000576 coating method Methods 0.000 title claims abstract description 26
- 239000011248 coating agent Substances 0.000 title claims abstract description 24
- 239000000758 substrate Substances 0.000 title claims abstract description 23
- 229910000838 Al alloy Inorganic materials 0.000 title claims description 30
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229920001577 copolymer Polymers 0.000 claims abstract description 27
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229920000642 polymer Polymers 0.000 claims abstract description 24
- 150000002903 organophosphorus compounds Chemical class 0.000 claims abstract description 11
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000003729 cation exchange resin Substances 0.000 claims abstract description 9
- 229920002126 Acrylic acid copolymer Polymers 0.000 claims abstract description 6
- JOUOJMIHRPQLAA-UHFFFAOYSA-N ethenylphosphonic acid;prop-2-enoic acid Chemical compound OC(=O)C=C.OP(O)(=O)C=C JOUOJMIHRPQLAA-UHFFFAOYSA-N 0.000 claims abstract description 5
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 36
- 229920005989 resin Polymers 0.000 claims description 16
- 239000011347 resin Substances 0.000 claims description 16
- 125000003700 epoxy group Chemical group 0.000 claims description 11
- 229920000647 polyepoxide Polymers 0.000 claims description 8
- 239000004593 Epoxy Substances 0.000 claims description 7
- -1 aluminum ions Chemical class 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 6
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 5
- 239000004800 polyvinyl chloride Substances 0.000 claims description 5
- 239000007795 chemical reaction product Substances 0.000 claims description 4
- 230000001590 oxidative effect Effects 0.000 claims description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 4
- 229910021645 metal ion Inorganic materials 0.000 claims description 3
- 229920000728 polyester Polymers 0.000 claims description 3
- ZTWTYVWXUKTLCP-UHFFFAOYSA-N vinylphosphonic acid Chemical compound OP(O)(=O)C=C ZTWTYVWXUKTLCP-UHFFFAOYSA-N 0.000 claims description 3
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims 3
- 150000001875 compounds Chemical class 0.000 claims 3
- 239000008199 coating composition Substances 0.000 claims 2
- 239000000243 solution Substances 0.000 abstract description 29
- 229910045601 alloy Inorganic materials 0.000 abstract description 5
- 239000000956 alloy Substances 0.000 abstract description 5
- 239000007864 aqueous solution Substances 0.000 abstract description 4
- 238000001223 reverse osmosis Methods 0.000 abstract description 3
- 239000012528 membrane Substances 0.000 abstract description 2
- 238000000108 ultra-filtration Methods 0.000 abstract description 2
- 230000003716 rejuvenation Effects 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- 238000005260 corrosion Methods 0.000 description 6
- 230000007797 corrosion Effects 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 150000007513 acids Chemical class 0.000 description 4
- 229910001430 chromium ion Inorganic materials 0.000 description 4
- 238000007739 conversion coating Methods 0.000 description 4
- 229920000620 organic polymer Polymers 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 239000011324 bead Substances 0.000 description 3
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 239000000314 lubricant Substances 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000012607 strong cation exchange resin Substances 0.000 description 3
- 238000011282 treatment Methods 0.000 description 3
- 229910000861 Mg alloy Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 description 2
- 235000013361 beverage Nutrition 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000005098 hot rolling Methods 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000002203 pretreatment Methods 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-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
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- 229920002125 SokalanĀ® Polymers 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 230000001464 adherent effect Effects 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- BUSBFZWLPXDYIC-UHFFFAOYSA-N arsonic acid Chemical group O[AsH](O)=O BUSBFZWLPXDYIC-UHFFFAOYSA-N 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000007744 chromate conversion coating Methods 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical class [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 229910000151 chromium(III) phosphate Inorganic materials 0.000 description 1
- IKZBVTPSNGOVRJ-UHFFFAOYSA-K chromium(iii) phosphate Chemical compound [Cr+3].[O-]P([O-])([O-])=O IKZBVTPSNGOVRJ-UHFFFAOYSA-K 0.000 description 1
- 229920001688 coating polymer Polymers 0.000 description 1
- 238000005097 cold rolling Methods 0.000 description 1
- 210000003298 dental enamel Anatomy 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000007765 extrusion coating Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000005374 membrane filtration Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 238000007746 phosphate conversion coating Methods 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
- C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/86—Regeneration of coating baths
-
- 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
- B05D7/14—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 to metal, e.g. car bodies
- B05D7/16—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 to metal, e.g. car bodies using synthetic lacquers or varnishes
-
- 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
- B05D7/51—One specific pretreatment, e.g. phosphatation, chromatation, in combination with one specific coating
-
- 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
- B05D2202/00—Metallic substrate
- B05D2202/20—Metallic substrate based on light metals
- B05D2202/25—Metallic substrate based on light metals based on Al
-
- 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
- B05D7/52—Two layers
Definitions
- the present invention relates to a process for coating an aluminum alloy substrate with a polymer. More particularly, the invention relates to a process for pretreating an aluminum alloy substrate with a vinyl phosphonic acid-acrylic acid copolymer before polymer coating the substrate.
- chemical conversion coatings have been formed on aluminum alloys by "converting" a surface of the metal into a tightly adherent coating, part of which consists of an oxidized form of aluminum. Chemical conversion coatings provide high corrosion resistance and improved adhesion for polymer coatings.
- a chromium-phosphate conversion coating is typically provided by contacting aluminum with an aqueous solution containing hexavalent chromium ions, phosphate ions and fluoride ions.
- concerns have arisen regarding the pollution effects of chromates and phosphates discharged into waterways by such processes. Because of the high solubility and strongly oxidizing character of hexavalent chromium ions, expensive waste treatment procedures must be employed to reduce the hexavalent chromium ions to trivalent chromium ions for waste disposal.
- chromate-free conversion coatings for aluminum.
- some chromate-free conversion coatings contain zirconium, titanium, hafnium and/or silicon, sometimes combined with fluorides, surfactants and polymers such as polyacrylic acid.
- non-chromate conversion coating or primer for improving the adhesion and corrosion resistance of polymer coated aluminum alloy substrates.
- Polymer adhesion and corrosion resistance are important characteristics in aluminum alloy sheet used for making food container bodies and ends and beverage container ends. Attempts have also been made in the prior art to pretreat substrates with various organophosphorus compounds before coating them with a polymer.
- organophosphorus compounds includes organophosphoric acids, organophosphinic acids, organophosphonic acids, as well as various salts, esters, partial salts, and partial esters of such acids.
- Dutch Patent Application No. 263,668, filed April 14, 1961 discloses a process wherein steel sheets are treated with a vinylphosphonic acid/acrylic acid copolymer before coating with an alkyd resin enamel.
- organophosphorus pretreatments may perform adequately, they are expensive to implement. Accordingly, there still remains a need to provide an efficient and economical process for pretreating an aluminum alloy substrate with an organophosphorus compound before applying a polymer coating.
- a principal objective of the present invention is to provide an efficient and economical process for pretreating an aluminum alloy substrate with an organophosphorus compound before applying a polymer coating.
- the aluminum alloy substrate may be provided in the form of a sheet plate, extrusion or casting and is preferably a sheet.
- Aluminum alloys available in sheet form are suitable for practice of the present invention, including alloys belonging to the AA2000, 3000, 5000, 6000 and 7000 series.
- Aluminum-magnesium alloys of the AA5000 series and particularly the AA5042 and AA5182 alloys are preferred.
- Sheet made from these alloys is useful for shaping into polymer coated food container bodies or ends, and beverage container ends.
- Aluminum alloys suitable for container end panels such as AA5182 are provided as an ingot or billet or slab by casting techniques known in the art. Before working, the ingot or billet is subjected to elevated temperature homogenization. The alloy stock is then hot rolled to provide an intermediate gauge sheet.
- the material may be hot rolled at a metal entry temperature of about 700Ā°-975Ā°F to provide an intermediate product having a thickness of about 0.100 inch to 0.150 inch.
- This material is cold rolled to provide a sheet ranging in thickness from about 0.006 to 0.015 inch.
- AA5182 aluminum alloy sheet in the H19 temper.
- Aluminum alloy 5042 sheet for end panels is preferably in the HI 9 temper.
- Aluminum alloys such as AA5042 are provided as an ingot that is homogenized. This is followed by hot rolling to an intermediate gauge of about 0.100 inch to 0.150 inch.
- the intermediate gauge product is annealed, followed by hot rolling and then cold rolling to a final gauge product having a thickness of about 0.006 to 0.015 inch.
- the sheet is coated with a polymer and then drawn and redrawn into food container bodies.
- the natural oxide coating on an aluminum alloy sheet surface is generally sufficient for practice of our invention.
- the natural oxide coating ordinarily has a thickness of approximately 30-50 angstroms.
- the oxide coating can be grown by treatments such as anodic oxidation or hydrothermal treatment in water, water vapor or aqueous solutions.
- Aluminum alloy sheet of the invention is generally cleaned with an alkaline surface cleaner to remove any residual lubricant adhering to the surface, and then rinsed with water. Cleaning can be avoided if the residual lubricant content is negligible.
- the cleaned sheet surface is then pretreated in a first container with a composition comprising an aqueous solution of an organophosphorus compound.
- the solution preferably contains about 1-20 g/L of a vinyl phosphonic acid-acrylic acid copolymer (VPA-AA copolymer). Solutions containing about 4-10 g/L of the copolymer are preferred.
- the copolymer usually comprises about 5-50 mole % vinylphosphonic acid, preferably about 20-40 mole %.
- the VPA-AA copolymer may have a molecular weight of about 20,000 to 100,000, preferably about 50,000 to 80,000.
- a particularly preferred VPA-AA copolymer contains about 30 mole % VPA and about 70 mole % AA.
- the solution has a temperature of about 100Ā°-200Ā°F, more preferably about 120Ā°-180Ā°F.
- a particularly preferred solution has a temperature of about 170Ā°F.
- the sheet surface may be dipped into the composition or the composition may be roll coated or sprayed onto the sheet surface.
- a preferred continuous cleaning and pretreating line is operated at about 500-1500 feet per minute.
- a contact time of about 6 seconds between the sheet surface and the composition is sufficient when the line is operated at 1000 feet per minute.
- the VPA-AA copolymer reacts with the oxide or hydroxide coating to form a layer on the sheet surface.
- Aluminum alloy sheet passing through the pretreatment solution contaminates the solution with ions of various elements, including aluminum, magnesium, iron, chromium and manganese.
- the pretreatment solution loses effectiveness when the aluminum concentration rises above about 150-200 ppm.
- the resin may be provided as pellets, beads, fibers, or particles and preferably is a hard, spherical gel type bead.
- the resin has a minimum total capacity in the hydrogen form, wet, of 1.9 meq/m.L.
- a preferred resin has an average particle size of about 650 microns, a specific gravity of about 1.22-1.23, and a bulk density of about 49.9 lb/ft 3 .
- the resin is preferably a gel comprising a styrene-divinylbenzene copolymer functionalized with acid groups, preferably sulfonate groups.
- the copolymer may be functionalized with phosphonic acid or arsonic acid groups.
- a particularly preferred cation exchange resin is sold by The Dow Chemical Company of Midland, Michigan under the trademark DOWEX G-26(H). Less preferably, the cation exchange resin may comprise ethylene copolymerized with an unsaturated carboxylic acid such as acrylic acid.
- the pretreatment solution After the pretreatment solution passes through the second container, it contains a reduced concentration of aluminum.
- the aluminum concentration in the treated solution is less than about 75 ppm, more preferably less than about 25 ppm, and optimally about 10 ppm or less.
- the treated solution, containing the organophosphorus compound and a reduced concentration of aluminum, is returned to the first container.
- the pretreated sheet may be rinsed with water to remove excess VPA-AA copolymer.
- the rinse water preferably has a temperature of about 170Ā°-180Ā°F.
- the rinse water is concentrated by removing excess water so that the VPA-AA copolymer can be recycled. Some preferred concentrating techniques include reverse osmosis and membrane filtration. After concentration, the rinse water may be transferred to the first container in order to recover VPA-AA copolymer values.
- the primed sheet is coated with a polymer composition that preferably includes an organic polymer dispersed in an organic solvent.
- a polymer composition that preferably includes an organic polymer dispersed in an organic solvent.
- Three preferred coating polymers are the epoxies, polyvinyl chloride and polyesters.
- the suitable epoxies include phenolic-modified epoxies, polyester-modified epoxies, epoxy-modified polyvinyl chloride, and cross linkable epoxies.
- the polymer composition may be clear or it may contain pigment particles.
- the pigment particles are preferably titanium dioxide, alumina or silica. We prefer titanium dioxide particles in the 0.5 to 10 microns median particle size range.
- the primed sheet may be coated by electrocoating, slot coating, extrusion coating, flow coating, spray coating, or other continuous coating processes.
- the polymer coated sheet is dried, coiled, and then finally shaped into container bodies or container end panels. As shown schematically in the Figure, there is provided a coil of
- AA5182-H19 aluminum-magnesium alloy sheet 10 having a thickness of about 8.8 mils (224 microns).
- the sheet 10 is cleaned with an alkaline surface cleaner in a vat 20 to remove any residual lubricant on the sheet surface.
- the cleaned sheet is then rinsed in a deionized water bath 30.
- the cleaned and rinsed sheet is pretreated in a first container 40 with a solution comprising about 10 g/L of a VPA-AA copolymer containing about 30 mole percent VPA and about 70 mole percent AA units, dissolved in water.
- the solution has a temperature of about 170Ā°F (77Ā°C) and it initially contains about 10 ppm aluminum.
- the VPA-AA copolymer reacts with an aluminum oxide or hydroxide coating on the sheet surface to form a layer comprising a reaction product of the copolymer and the oxide or hydroxide.
- the pretreated sheet is then rinsed with water 50 to remove excess
- the rinse water 50 preferably has a temperature of about 170Ā°-180Ā°F.
- the rinsed sheet is roll coated with a polymer composition 60 that preferably includes an organic polymer and pigment particles dispersed in an organic solvent.
- the organic polymer is preferably an epoxy resin.
- suitable epoxies include phenolic-modified epoxies, polyester-modified epoxies, epoxy-modified polyvinyl chloride, and cross linkable epoxies.
- the polymer coated sheet is dried in a hot air dryer 70 and then recoiled as a coated sheet product 80.
- portions of the solution are periodically transferred from the first container 40 to a second container 100 holding a cation exchange resin.
- a particularly preferred resin is sold by Dow Chemical Company of Midland, Michigan under the trademark DOWEX G-26 (H) strong cation exchange resin.
- the strong cation exchange resin is sold as hard spherical beads with a 650 micron dry mesh size.
- the strong cation exchange resin is a gel comprised of a styrene-divinyl benzene copolymer functionalized with sulfonate groups.
- Treatment with the resin produces a treated solution having an aluminum concentration that is optimally less than about 10 ppm.
- the treated solution is returned through a pipe 110 from the second container 100 to the first container 40.
- the cation exchange resin eventually becomes saturated with metal salts.
- the resin is regenerated by washing with a strong acid solution 120, such as 6-10 vol.% HC1 or 6-12 vol.% sulfuric acid in water.
- Metal salts 130 washed from the second container 100 are discarded. Used rinse water from the water rinse 50 is also recycled to recover
- VPA-AA copolymer values The used rinse water is first sent to a concentrator 140 where water is removed, for example by reverse osmosis or membrane ultrafiltration. The concentrated rinse water is then returned to the first container 40.
- the cation exchange process of our invention maintains aluminum concentrations at acceptable levels in the pretreatment solution.
- a 200 mL aliquot of the pretreatment solution at 140Ā°F containing 10 g/L VPA-AA copolymer, 350 ppm aluminum, and other metals was placed in a 250 mL Ehrlenmeyer flask containing 40 mL wet volume of the DOWEX G-26(H) resin in the hydrogen form.
- the flask was placed in a water bath and held at 140Ā°F (60Ā°C) for 16-20 hours.
- the resin was prepared by washing with 400-600 mL of 6 vol.% HC1, followed by rinsing with 600-800 mL of deionized water.
- the pretreatment solution was filtered and the resin was rinsed with 25 mL of deionized water.
- the solution was analyzed and the results are presented below in the Table. All concentrations were corrected to reflect a volume of 200 mL, for comparison.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Chemical Treatment Of Metals (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Laminated Bodies (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Paints Or Removers (AREA)
Abstract
Description
Claims
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US09/074,136 US6020030A (en) | 1998-05-07 | 1998-05-07 | Coating an aluminum alloy substrate |
PCT/US1999/025894 WO2001032955A1 (en) | 1998-05-07 | 1999-11-03 | Coating an aluminum alloy substrate |
Publications (2)
Publication Number | Publication Date |
---|---|
EP1228263A1 true EP1228263A1 (en) | 2002-08-07 |
EP1228263B1 EP1228263B1 (en) | 2004-04-07 |
Family
ID=22273976
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP99964956A Expired - Lifetime EP1228263B1 (en) | 1998-05-07 | 1999-11-03 | Coating an aluminum alloy substrate |
Country Status (19)
Country | Link |
---|---|
EP (1) | EP1228263B1 (en) |
JP (1) | JP2003513773A (en) |
KR (1) | KR100610579B1 (en) |
CN (1) | CN1187473C (en) |
AT (1) | ATE263853T1 (en) |
AU (1) | AU3097600A (en) |
BR (1) | BR9917547A (en) |
CA (1) | CA2397674C (en) |
CZ (1) | CZ299666B6 (en) |
DE (1) | DE69916339T2 (en) |
DK (1) | DK1228263T3 (en) |
ES (1) | ES2219101T3 (en) |
HU (1) | HUP0203608A3 (en) |
NO (1) | NO20022089L (en) |
PL (1) | PL354493A1 (en) |
PT (1) | PT1228263E (en) |
SK (1) | SK286005B6 (en) |
TR (1) | TR200201197T2 (en) |
WO (1) | WO2001032955A1 (en) |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7416831B2 (en) * | 2004-08-20 | 2008-08-26 | Eastman Kodak Company | Substrate for lithographic printing plate precursor |
WO2011145594A1 (en) * | 2010-05-21 | 2011-11-24 | č²“ååå¦č¬åę Ŗå¼ä¼ē¤¾ | Chromium-free metal surface treatment agent, and metal surface treatment method using same |
CA2984597C (en) * | 2015-05-01 | 2020-06-16 | Novelis Inc. | Continuous coil pretreatment process |
JP7463379B2 (en) * | 2019-01-02 | 2024-04-08 | ćććŖć¹ć»ć¤ć³ć³ć¼ćć¬ć¤ććć | Systems and methods for laminating can end stock |
KR102273220B1 (en) * | 2019-12-10 | 2021-07-05 | ź¹ģ¤ģ | Aluminum alloy for enamel coating and method for manufacturing die casted aluminum alloy frying pan |
CN115867616A (en) * | 2020-06-10 | 2023-03-28 | čÆŗē»“å°éęÆå ¬åø | Pretreatment composition for bonding to metal substrate and method for preparing same |
Family Cites Families (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
BE566276A (en) * | 1957-08-19 | 1958-04-15 | ||
US2909455A (en) * | 1958-09-24 | 1959-10-20 | Amchem Prod | Method of coating a succession of aluminum surfaces |
BE602685A (en) * | 1960-04-16 | 1900-01-01 | ||
ZA728674B (en) * | 1972-05-26 | 1973-09-26 | Amchem Prod | Stabilization of acidic aqueous coating compositions containing an organic coating-forming material |
US4012351A (en) * | 1972-11-20 | 1977-03-15 | Amchem Products, Inc. | Stabilization of acidic aqueous coating compositions containing an organic coating-forming material |
JPS53125238A (en) * | 1977-04-09 | 1978-11-01 | Nippon Paint Co Ltd | Regenerating method for surface treating liquid for aluminum and its alloy |
US5103550A (en) * | 1989-12-26 | 1992-04-14 | Aluminum Company Of America | Method of making a food or beverage container |
US5277788A (en) * | 1990-10-01 | 1994-01-11 | Aluminum Company Of America | Twice-anodized aluminum article having an organo-phosphorus monolayer and process for making the article |
US5368974A (en) * | 1993-05-25 | 1994-11-29 | Eastman Kodak Company | Lithographic printing plates having a hydrophilic barrier layer comprised of a copolymer of vinylphosphonic acid and acrylamide overlying an aluminum support |
JP3620893B2 (en) * | 1995-07-21 | 2005-02-16 | ę„ę¬ćć¼ć«ć©ć¤ćøć³ć°ę Ŗå¼ä¼ē¤¾ | Surface treatment composition for aluminum-containing metal and surface treatment method |
US6020030A (en) * | 1998-05-07 | 2000-02-01 | Aluminum Company Of America | Coating an aluminum alloy substrate |
-
1999
- 1999-11-03 CN CNB998169935A patent/CN1187473C/en not_active Expired - Fee Related
- 1999-11-03 AU AU30976/00A patent/AU3097600A/en not_active Abandoned
- 1999-11-03 SK SK593-2002A patent/SK286005B6/en not_active IP Right Cessation
- 1999-11-03 DK DK99964956T patent/DK1228263T3/en active
- 1999-11-03 CZ CZ20021422A patent/CZ299666B6/en not_active IP Right Cessation
- 1999-11-03 PL PL99354493A patent/PL354493A1/en not_active IP Right Cessation
- 1999-11-03 EP EP99964956A patent/EP1228263B1/en not_active Expired - Lifetime
- 1999-11-03 DE DE69916339T patent/DE69916339T2/en not_active Expired - Fee Related
- 1999-11-03 KR KR1020027005773A patent/KR100610579B1/en active IP Right Grant
- 1999-11-03 JP JP2001535632A patent/JP2003513773A/en active Pending
- 1999-11-03 BR BR9917547-9A patent/BR9917547A/en not_active Application Discontinuation
- 1999-11-03 AT AT99964956T patent/ATE263853T1/en not_active IP Right Cessation
- 1999-11-03 PT PT99964956T patent/PT1228263E/en unknown
- 1999-11-03 WO PCT/US1999/025894 patent/WO2001032955A1/en active IP Right Grant
- 1999-11-03 CA CA002397674A patent/CA2397674C/en not_active Expired - Fee Related
- 1999-11-03 ES ES99964956T patent/ES2219101T3/en not_active Expired - Lifetime
- 1999-11-03 TR TR2002/01197T patent/TR200201197T2/en unknown
- 1999-11-03 HU HU0203608A patent/HUP0203608A3/en unknown
-
2002
- 2002-05-02 NO NO20022089A patent/NO20022089L/en not_active Application Discontinuation
Non-Patent Citations (1)
Title |
---|
See references of WO0132955A1 * |
Also Published As
Publication number | Publication date |
---|---|
PL354493A1 (en) | 2004-01-26 |
HUP0203608A3 (en) | 2005-05-30 |
SK5932002A3 (en) | 2002-12-03 |
ES2219101T3 (en) | 2004-11-16 |
KR20020068531A (en) | 2002-08-27 |
SK286005B6 (en) | 2008-01-07 |
DK1228263T3 (en) | 2004-08-09 |
DE69916339T2 (en) | 2005-03-17 |
KR100610579B1 (en) | 2006-08-09 |
HUP0203608A2 (en) | 2003-03-28 |
WO2001032955A1 (en) | 2001-05-10 |
EP1228263B1 (en) | 2004-04-07 |
NO20022089L (en) | 2002-05-08 |
TR200201197T2 (en) | 2002-08-21 |
CZ20021422A3 (en) | 2003-01-15 |
CZ299666B6 (en) | 2008-10-08 |
CN1187473C (en) | 2005-02-02 |
ATE263853T1 (en) | 2004-04-15 |
BR9917547A (en) | 2002-06-25 |
PT1228263E (en) | 2004-07-30 |
CA2397674A1 (en) | 2001-05-10 |
CN1375018A (en) | 2002-10-16 |
AU3097600A (en) | 2001-05-14 |
DE69916339D1 (en) | 2004-05-13 |
JP2003513773A (en) | 2003-04-15 |
CA2397674C (en) | 2006-07-04 |
NO20022089D0 (en) | 2002-05-02 |
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