EP1228263B1 - Beschichtung von aluminiumlegierungssubstraten - Google Patents

Beschichtung von aluminiumlegierungssubstraten Download PDF

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Publication number
EP1228263B1
EP1228263B1 EP99964956A EP99964956A EP1228263B1 EP 1228263 B1 EP1228263 B1 EP 1228263B1 EP 99964956 A EP99964956 A EP 99964956A EP 99964956 A EP99964956 A EP 99964956A EP 1228263 B1 EP1228263 B1 EP 1228263B1
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EP
European Patent Office
Prior art keywords
aluminum
solution
copolymer
container
coating
Prior art date
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Expired - Lifetime
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EP99964956A
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English (en)
French (fr)
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EP1228263A1 (de
Inventor
Joseph D. Alcoa Technical Center Guthrie
Alfred M. Dennis
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Howmet Aerospace Inc
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Alcoa Inc
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Filing date
Publication date
Priority claimed from US09/074,136 external-priority patent/US6020030A/en
Application filed by Alcoa Inc filed Critical Alcoa Inc
Publication of EP1228263A1 publication Critical patent/EP1228263A1/de
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Publication of EP1228263B1 publication Critical patent/EP1228263B1/de
Anticipated expiration legal-status Critical
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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.
  • 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. For example, the material may be hot rolled at a metal entry temperature of about 371°-524°C (700°-975°F) to provide an intermediate product having a thickness of about 0.254 cm to 0.381 cm (0.100 inch to 0.150 inch). This material is cold rolled to provide a sheet ranging in thickness from about 0.0152 to 0.0381 cm (0.006 to 0.015 inch). We prefer AA5182 aluminum alloy sheet in the H19 temper. Aluminum alloy 5042 sheet for end panels is preferably in the H 19 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 0.254 to 0.381 cm (0.100 inch to 0.150 inch). Typically, the intermediate gauge product is annealed, followed by hot rolling and then cold rolling to a final gauge product having a thickness of about 0.0152 to 0.0381 cm (0.006 to 0.015 inch). The sheet is coated with a polymer and then drawn and redrawn into food container bodies. We prefer AA5042 aluminum alloy sheet in the H2x temper.
  • 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 3-5 nm (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 38°-93°C (100°-200°F), more preferably about 49°-82°C (120°-180°F).
  • a particularly preferred solution has a temperature of about 77°C (170°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 152-457 meters per minute (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 (305 meters 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. Accordingly, we provide a process for removing ions of aluminum and other metals from the pretreatment solution.
  • 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 ⁇ m (microns), a specific gravity of about 1.22-1.23, and a bulk density of about 0.7999 kg/L (49.9 lb/ft 3 ).
  • the resin is preferably a gel comprising a styrene-divinylbenzene copolymer functionalized with acid groups, preferably suifonate 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 DOWER G-26(H).
  • 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 77°-82°C (170°-180°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 ⁇ m (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.
  • a coil of AA5182-H 19 aluminum-magnesium alloy sheet 10 having a thickness of about (8.8 mils) 224 ⁇ m (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 77°C (170°F) 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 VPA-AA copolymer.
  • the rinse water 50 preferably has a temperature of about 77°-82°C (170°-180°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 ⁇ m (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.% HCl 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 60°C (140°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 60°C (140°F) for 16-20 hours.
  • the resin was prepared by washing with 400-600 mL of 6 vol.% HCI, followed by rinsing with 600-800 mL of deionized water.

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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)

Claims (10)

  1. Verfahren zum Vorbehandeln eines Aluminiumlegierungsbleches das einen Oberflächenabschnitt aufweist, um die Haftung einer Polymerbeschichtung auf dem Oberflächenabschnitt zu verbessern, welches Verfahren umfasst:
    a) in einem ersten Behälter Vorbehandeln eines Aluminiumlegierungsbleches, das einen Aluminiumoxid- oder Aluminiumhydroxid aufweisenden Oberflächenabschnitt aufweist, mit einer Vorbehandlungslösung, im Wesentlichen bestehend aus Wasser und einer phosphororganischen Verbindung, wodurch eine Lage erzeugt wird, die ein Reaktionsprodukt der Verbindung und des Oxids oder Hydroxids aufweist; und Kontaminieren der Lösung mit Aluminium-Ionen;
    b) Überführen mindestens eines Teils der Lösung in einen zweiten Behälter, der ein Kationen-Austauschharz enthält, das ein Polymer aufweist; und darin auf dem Harz Aluminium-Ionen adsorbieren, wodurch eine Behandlungslösung erzeugt wird, die die Verbindung enthält und eine verringerte Konzentration an Aluminium-Ionen hat; und
    c) Zurückführen der behandelten Lösung in den ersten Behälter.
  2. Verfahren nach Anspruch 1, bei welchem das Blech eine Aluminiumlegierung der Reihe AA2000, 3000, 5000, 6000 oder 7000 umfasst, und ferner umfassend:
    d) Beschichten der Lage mit einer Beschichtungszusammensetzung, die ein Polymer aufweist, das ausgewählt ist aus der Gruppe, bestehend aus Polyvinylchlorid, Epoxiden und Polyestern.
  3. Verfahren nach Anspruch 1, bei welchem das Harz ein mit SulfonatGruppen funktionalisiertes Styrol/Divinylbenzol-Copolymer aufweist.
  4. Verfahren nach Anspruch 1, bei welchem die behandelte Lösung weniger als etwa 75 ppm Aluminium-Ionen enthält.
  5. Verfahren nach Anspruch 1, bei welchem die behandelte Lösung weniger als etwa 25 ppm Aluminium-Ionen enthält.
  6. Verfahren nach Anspruch 1, ferner umfassend:
    e) nach Schritt a) Spülen des Substrats mit Wasser, wodurch ein Spülwasser erzeugt wird, das die phosphororganische Verbindung und Aluminium-Ionen enthält,
    f) Einengen des Spülwassers, indem das Wasser daraus entfernt wird, und
    g) Zurückführen mindestens eines Teils des in Schritt f) behandelten Spülwassers in den ersten Behälter.
  7. Verfahren nach Anspruch 1, bei welchem die phosphororganische Verbindung ein Vinylphosphonsäure/Acrylsäure-Copolymer aufweist.
  8. Verfahren nach Anspruch 7, bei welchem das Copolymer eine relative Molekülmasse von etwa 20.000 bis 100.000 hat.
  9. Verfahren nach Anspruch 7, bei welchem die Vorbehandlungslösung etwa 1 bis 20 g/l des Copolymers aufweist.
  10. Verfahren nach Anspruch 7, bei welchem die Vorbehandlungslösung in Schritt a) eine Temperatur von etwa 49° bis 93°C (120° bis 200°F) hat.
EP99964956A 1998-05-07 1999-11-03 Beschichtung von aluminiumlegierungssubstraten Expired - Lifetime EP1228263B1 (de)

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 EP1228263A1 (de) 2002-08-07
EP1228263B1 true EP1228263B1 (de) 2004-04-07

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EP99964956A Expired - Lifetime EP1228263B1 (de) 1998-05-07 1999-11-03 Beschichtung von aluminiumlegierungssubstraten

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EP (1) EP1228263B1 (de)
JP (1) JP2003513773A (de)
KR (1) KR100610579B1 (de)
CN (1) CN1187473C (de)
AT (1) ATE263853T1 (de)
AU (1) AU3097600A (de)
BR (1) BR9917547A (de)
CA (1) CA2397674C (de)
CZ (1) CZ299666B6 (de)
DE (1) DE69916339T2 (de)
DK (1) DK1228263T3 (de)
ES (1) ES2219101T3 (de)
HU (1) HUP0203608A3 (de)
NO (1) NO20022089L (de)
PL (1) PL354493A1 (de)
PT (1) PT1228263E (de)
SK (1) SK286005B6 (de)
TR (1) TR200201197T2 (de)
WO (1) WO2001032955A1 (de)

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US7416831B2 (en) * 2004-08-20 2008-08-26 Eastman Kodak Company Substrate for lithographic printing plate precursor
JPWO2011145594A1 (ja) * 2010-05-21 2013-07-22 貴和化学薬品株式会社 クロムフリー金属表面処理剤及びこれを使用する金属表面処理方法
CN107532308A (zh) 2015-05-01 2018-01-02 诺维尔里斯公司 连续卷材预处理方法
CN113382867A (zh) 2019-01-02 2021-09-10 诺维尔里斯公司 用于层压罐盖料的系统和方法
KR102273220B1 (ko) * 2019-12-10 2021-07-05 김준수 에나멜 코팅용 알루미늄 합금 및 다이캐스팅법에 의해 제조된 알루미늄 합금 프라이팬의 제조방법

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NL228877A (de) * 1957-08-19 1900-01-01
US2909455A (en) * 1958-09-24 1959-10-20 Amchem Prod Method of coating a succession of aluminum surfaces
NL263668A (de) * 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 (ja) * 1995-07-21 2005-02-16 日本パーカライジング株式会社 アルミニウム含有金属用表面処理組成物及び表面処理方法
US6020030A (en) * 1998-05-07 2000-02-01 Aluminum Company Of America Coating an aluminum alloy substrate

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WO2001032955A1 (en) 2001-05-10
CZ299666B6 (cs) 2008-10-08
PT1228263E (pt) 2004-07-30
ES2219101T3 (es) 2004-11-16
ATE263853T1 (de) 2004-04-15
JP2003513773A (ja) 2003-04-15
SK286005B6 (sk) 2008-01-07
KR20020068531A (ko) 2002-08-27
CN1187473C (zh) 2005-02-02
PL354493A1 (en) 2004-01-26
DE69916339D1 (de) 2004-05-13
CA2397674C (en) 2006-07-04
DE69916339T2 (de) 2005-03-17
CN1375018A (zh) 2002-10-16
DK1228263T3 (da) 2004-08-09
SK5932002A3 (en) 2002-12-03
TR200201197T2 (tr) 2002-08-21
NO20022089D0 (no) 2002-05-02
CZ20021422A3 (cs) 2003-01-15
HUP0203608A3 (en) 2005-05-30
BR9917547A (pt) 2002-06-25
HUP0203608A2 (hu) 2003-03-28
EP1228263A1 (de) 2002-08-07
CA2397674A1 (en) 2001-05-10
AU3097600A (en) 2001-05-14
NO20022089L (no) 2002-05-08
KR100610579B1 (ko) 2006-08-09

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