KR20020068531A - Coating an aluminum alloy substrate - Google Patents

Abstract

The aluminum alloy plate is pretreated with an aqueous solution containing an organic phosphorus compound, preferably a vinylphosphonic acid-acrylic acid copolymer, before coating the plate with a polymer. As the plate passes through the solution, the solution is contaminated with aluminum and other components. The pretreatment solution is returned to its original state by removing aluminum with a cation exchange resin functionalized with sulfate groups, preferably containing styrene-divinyl benzene copolymers. As the plates are washed, the wash water is contaminated with the copolymer. The wash water is concentrated by reverse osmosis or membrane filtration and returned to the pretreatment solution.

Description

Coating of aluminum alloy plate {COATING AN ALUMINUM ALLOY SUBSTRATE}

Aluminum naturally protects itself from corrosion by forming an oxide layer, but the protective layer is not complete. Under moisture and electrolytes, aluminum oxidizes significantly more than pure aluminum.

Therefore, it is necessary to pretreat the aluminum alloy plate or to treat with other chemicals to provide good adhesion to the polymer and improved resistance to corrosion.

In the prior art, chemical conversion coatings are made by "converting" the surface of the metal to a strong adhesive coating of the part that forms the oxidized form of aluminum. Chemical conversion coatings provide high corrosion resistance and improved adhesion to polymer coatings. The chromium-phosphate conversion coating typically provides an aqueous solution containing hexavalent chromium ions, phosphate ions and fluorine ions by contact with aluminum. In recent years, problems have been raised regarding the water pollution of chromium salts and phosphates released by the process. Due to the high solubility and strong oxidative properties of hexavalent chromium ions, expensive waste treatment processes must be adopted to reduce hexavalent chromium ions to trivalent chromium ions for waste disposal.

In the prior art, efforts have been made to produce satisfactory, chromate free conversion coatings for aluminum. For example, some non-chromate conversion coatings include zirconium, titanium, hafnium and / or silicon, and sometimes silicon combined with polymers such as fluorides, surfactants and polyacrylic acid. Despite extensive efforts, no chromate conversion coatings or prior art for adhesion and corrosion resistance of polymer coated aluminum alloy plates are still entirely satisfactory. Polymeric adhesion and resistance to corrosion are important properties for aluminum metal plates to make the body or end of food containers and the ends of beverage containers.

Attempts have also been made in the prior art to pretreat the plate with various organophosphate compounds before coating the aluminum metal plate with a polymer. “Organic compounds” herein include organophosphoric acid, organophosphorous acid, organohypophosphoric acid, and various salts, esters, partial salts, partial esters of such acids. For example, Dutch Patent Application No. 263, 668, filed April 14, 1961, discloses a process of treating a steel sheet with vinylphosphonic acid / acrylic acid prior to coating the alkyd resin enamel. Some organophosphorus treatments can be performed properly but are expensive to implement. Therefore, there is still a need to provide an effective and economical process for treating aluminum alloy plates with organophosphorus compounds prior to polymer coating.

The present invention relates to a process of coating an aluminum alloy plate with a polymer. More specifically, the present invention relates to a process of pretreating an aluminum alloy plate with vinylphosphonic acid-acrylic acid copolymer before coating the plate.

1 is a flow chart for the process of the present invention.

It is a primary object of the present invention to provide an effective and economical process for treating aluminum alloy plates with organophosphorus compounds prior to polymer coating.

To achieve this main purpose, the process of the present invention removes aluminum and other cations from the pretreatment solution to avoid costly treatment of the solution.

Other objects and advantages of the invention will be apparent to those skilled in the art from the following detailed description.

According to the present invention, a process of coating an aluminum alloy plate with an organic polymer is provided. The aluminum alloy plate may be provided in the form of a thin plate, an extrusion, a casting, and preferably in the form of a thin plate.

Various aluminum alloys in the form of a sheet including alloys belonging to AA2000, 3000, 5000, 6000 and 7000 series are effective for carrying out the present invention. Aluminum-magnesium alloys of the AA5000 series are preferred, in particular the AA5042 and AA5182 alloys. The thin plate made of the alloy is suitable for molding into the body or the end of the food container coated with the polymer and the end of the beverage container.

Suitable aluminum alloys for end panels of containers such as AA5182 are provided in the form of ingots, slabs, and planks by casting techniques known in the art. Prior to operation, the ingot or slab needs temperature uniformity. For example, the material is stretched to a high temperature at a metal input temperature of about 700-975 ° F. to obtain an intermediate product with a thickness of about 0.100 inch to 0.150 inch. The material is stretched to low temperature to obtain a sheet having a thickness of about 0.006 inches to 0.015 inches. In the present invention, an AA5182 aluminum alloy plate of H19 hardness is preferred. Aluminum alloy plate AA5182 for the end panel is preferably H19 hardness.

Aluminum alloys such as AA5042 are provided in the form of uniform ingots. The ingot is stretched at high temperature with an intermediate gauge of about 0.100 inch to 0.15 inch. Typically, the intermediate gauge is slow cooled and then stretched at high temperatures and at low temperatures with a final gauge product having a thickness of about 0.006 to 0.015 inches. The sheet is stretched after being coated with a polymer and stretched back to the food container body. In the present invention, an AA5042 aluminum alloy plate of H2x hardness is preferred.

Natural oxide layers on the aluminum alloy sheet surface are generally sufficient for the practice of the present invention. The native oxide layer typically has a thickness of about 30-50 Angstroms. For a better protective layer against corrosion, the oxide layer can be grown by treatment such as anodizing or hydrothermal treatment in water, steam or aqueous solution.

The aluminum sheet of the invention is generally washed with an alkaline surface detergent and rinsed with water to remove residual lubricant adhering to the surface. Such cleaning may be avoided if the residual lubricant content is negligible.

The washed thin surface is pretreated in a first vessel having a composition consisting of an aqueous solution of an organophosphorus compound. The solution preferably comprises about 1-20 g / L of vinylphosphonic acid-acrylic acid copolymer (VPA-AA copolymer). Solutions containing about 4-10 g / L copolymer are preferred. The copolymer generally comprises about 5-50 mole%, preferably about 20-40 mole%, of vinylphosphonic acid. The VPA-AA copolymer may have a molecular weight of about 20,000 to 100,000, preferably about 50,000 to 80,000. Particularly preferred VPA-AA copolymers contain about 30 mole percent VPA and about 70 mole percent AA. The solution has a temperature of about 100-200 ° F., more preferably about 120-180 ° F. Particularly preferred solutions have a temperature of about 170 ° F.

The thin surface can be dipped into the composition or the composition can be coated or sprayed onto the thin surface. Preferred continuous wash and pretreatment lines are treated at about 500-1500 feet per minute. When the line runs at 1000 feet per minute, a contact time between the sheet surface and the composition of about 6 seconds is sufficient. The VPA-AA copolymer reacts with oxides or hydroxides to form a layer on the sheet surface.

The thin aluminum alloy sheet passing through the treatment solution contaminates the solution with various ions including aluminum, magnesium, iron, chromium and magnesium salts. The treatment solution loses its effectiveness when the aluminum concentration is above about 150-200 ppm. Accordingly, the present invention provides a process for removing aluminum ions and other metals from the treatment solution.

At least one portion of the treatment solution is delivered to a second vessel containing a cation exchange resin. The resin is supplied in the form of pellets, beads, fibers or particles and is preferably a hard spherical gel type of beads. The resin has a minimum capacity in a wet hydrogen form of 1.9 meq / mL. Preferred resins have 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 .

Preference is given to gels consisting of styrene-divinylbenzene copolymers, wherein the resins have acid groups, preferably sulfuric acid groups. As an alternative, the copolymer can be functionalized with phosphonic acid (phosphoric acid) or arsenic acid groups. Particularly preferred cation exchange resins are sold by Dow Chemical Company of Midland, Michigan under the DOWEX G-26 (H) trademark.

Slightly less preferred, the cationic resin may consist of ethylene copolymerized with unsaturated fatty acids such as acrylic acid.

After the treatment solution has passed through the second vessel, the solution has a reduced aluminum concentration. The aluminum concentration in the treated solution is 75 ppm or less, preferably about 35 ppm or less and the optimum is 10 ppm or less. The treated solution containing the organophosphorus compound and the reduced aluminum concentration is returned to the first vessel.

Optionally, the treated sheet is washed with water to remove excess VPA-AA copolymer. The wash water preferably has a temperature of about 170-180 ° F. The wash water is concentrated by removing excess water so that the VPA-AA copolymer can be reused. Preferred concentration techniques include reverse osmosis and membrane filtration. After concentration, the wash water can be delivered to the first vessel to recover the VPA-AA copolymer value.

The prepared thin plate is preferably coated with a polymer composition comprising an organic polymer dispersed in an organic solvent. Three preferred coating polymers are epoxy, polyvinyl chloride and polyester. Suitable resins are epoxy with phenol groups, epoxy with polyester and epoxy crosslinked with polyvinyl chloride with epoxy. The polymer composition may be transparent or may comprise dye particles. The dye particles are preferably titanium dioxide, aluminum or silica. Particles of 0.5 to 10 micron median are preferred in the present invention.

As an alternative, the prepared sheet may be coated by electrocoating, slot coating, extrusion coating, flow coating, spray coating, or other continuous coating process. Can be.

The polymer coated sheet is dried and rolled and finally formed into a vessel body or vessel end panel.

As schematically shown in the figure, a wound about 8.8 millimeter (224 micron) thick AA5182-H19 aluminum-magnesium alloy sheet 10 is provided. The thin plate 10 is washed with an alkaline surface cleaner in the keg 20 to remove residual lubricant on the thin plate surface. The washed thin plates are rinsed in an ion removal bath (30).

The washed and rinsed thin plate is processed in a first vessel 40 having a solution consisting of about 10 g / L of a VPA-AA copolymer comprising about 70 mole% AA and 30 mole% VPA dissolved in water. The solution has a temperature of about 170 ° F. (77 ° C.) and initially has an aluminum concentration of about 10 ppm. The VPA-AA copolymer reacts with aluminum oxide or aluminum hydroxide on the surface of the sheet to form a layer consisting of the reaction product of the copolymer and the oxide or hydroxide.

The preheated thin plate is then washed with water 50 to remove excess VPA-AA copolymer. The wash water 50 preferably has a temperature of 170-180 ° F.

The washed thin plates are preferably roll coated with a polymer coat 60 comprising pigment particles and organic polymer dispersed in an organic solvent. The organic polymer is preferably an epoxy resin. Suitable resins are epoxy with phenol groups, epoxy with polyester and epoxy crosslinked with polyvinyl chloride with epoxy.

The polymer coated sheet is dried in a hot air dryer 70 and rewound with the coated sheet product 80.

In order to maintain a low concentration of metal ions in the pretreatment solution, a portion of the solution is periodically transferred from the first vessel 40 to the second vessel 100 having the cation exchange resin. Particularly preferred resins are sold by Dow Chemical Company of Midland, Michigan, under the DOWEX G-26 (H) strong cation exchange resin brand. Strong cation exchange resins are gels composed of styrene-divinyl benzene with sulfate groups. Treatment with the resin results in a treated solution having an optimal aluminum concentration of about 10 ppm or less. The treated solution is returned through the tube 110 from the second vessel 100 to the first vessel 40.

The cation exchange resin is subsequently saturated with a metal salt. The resin is washed and regenerated with a strong acidic solution 120 such as 6-10% by volume HCl or 6-12% by volume sulfuric acid aqueous solution. The metal salt 130 from the second vessel 100 is discarded.

The wash water used from the wash water 50 is also recycled to recover the VPA-AA copolymer value. The used wash water is first sent to a concentrator 140 where the water is removed, for example by reverse osmosis or membrane filtration. The concentrated wash water is returned to the first vessel 40 again.

The cation exchange process of the present invention maintains the aluminum concentration in the pretreatment solution at a satisfactory level. 200 mL of 140 ° F. pretreatment solution containing 10 g / L VPA-AA copolymer, 350 ppm aluminum and other metals was placed in a 250 mL Erlenmeyer flask containing 40 mL wet capacity of DOWEX G-26 (H) resin in hydrogen form. The flask was placed in a water bath to maintain 140 ° F. (60 ° C.) for 16-20 hours. The resin was prepared by washing with 400-600 mL of 6 volume% HCl and then rinsing with 600-800 mL of non-ionized water.

After 16-20 hours of contact time, the treatment solution was filtered and the resin was washed with 25 mL of non-ionized water. The solution is analyzed and the results are shown in the table below. All concentrations were corrected to reflect a volume of 200 mL for comparison.

While the invention has been described with reference to several selected embodiments, those skilled in the art will recognize that the invention does not depart from the spirit and scope of the appended claims.

Claims (22)

(a) supplying an aluminum alloy plate having a surface portion composed of aluminum oxide or aluminum hydroxide; (b) In a first vessel, the plate is pretreated with an aqueous pretreatment solution consisting essentially of water and an organic acid compound to form a layer consisting of a reaction product of the compound and the oxide or hydroxide, the plate containing the solution Contaminated with aluminum; (c) transferring at least a portion of the pretreatment solution to a second vessel containing a cation exchange resin to adsorb aluminum onto the resin and produce a treated solution having a reduced aluminum concentration; (d) returning the treated solution from the second vessel to the first vessel; And (e) coating said layer with a coating composition consisting of a polymer selected from the group consisting of polyvinyl chloride, epoxy and polyester; Coating the aluminum alloy plate with a polymer consisting of. The method of claim 1, (f) after step (b), washing the plate with water to produce wash water containing the organophosphorus compound and aluminum; (g) concentrating the wash water by removing water from the wash water; More organized into processes. The method of claim 2, (h) returning at least a portion of the wash water treated in step (g) to the first vessel; More organized into processes. The process according to claim 1, wherein the organophosphorus compound is composed of a vinylphosphonic acid-acrylic acid copolymer. 5. The process of claim 4 wherein the copolymer consists of about 5-50 mole percent vinylphosphonic acid. The process of claim 4, wherein the copolymer has a molecular weight of about 20,000 to 100,000. 5. The process according to claim 4, wherein said pretreatment solution consists of about 1-20 g / L of said copolymer. 5. The process according to claim 4, wherein in step (b) the pretreatment solution has a temperature of about 120-200 ° F (49-93 ° C). The process according to claim 1, wherein the resin is composed of styrene-divinyl benzene copolymers. The process according to claim 1, wherein the resin is functionalized with a sulfate group. (a) in a first vessel an aluminum alloy plate having a surface portion consisting of aluminum oxide or aluminum hydroxide with a solution consisting essentially of water and an organic acid compound, thereby forming a layer consisting of the reaction product of said compound and said oxide or hydroxide And contaminating the solution with aluminum ions; (b) transfer at least a portion of the solution to a second vessel comprising a cation exchange resin comprised of a polymer functionalized with a sulfate group, adsorbing aluminum on the resin to produce a treated solution containing the compound and having a reduced aluminum concentration. Process of doing; And (c) returning the treated solution to the first vessel; A step of pretreating the aluminum alloy plate having a surface portion coated with a polymer in order to improve the adhesion consisting of. The method of claim 11, (d) coating said layer with a coating composition consisting of a polymer selected from the group consisting of polyvinyl chloride, epoxy and polyester; More organized into processes. 12. The process according to claim 11, wherein the resin is composed of styrene-divinyl benzene copolymers. The process according to claim 11, wherein the plate is made of an aluminum alloy of AA2000, 3000, 5000, 6000 or 7000 series. The process according to claim 11, wherein the plate is made of an aluminum alloy of AA5000 series. The process of claim 1, wherein step (b) is performed without anodizing the plate. 12. The process of claim 11, wherein step (a) is performed without anodizing the plate. The process of claim 1 wherein the treated solution contains less than about 75 ppm aluminum. 12. The process according to claim 11, wherein said treated solution contains less than about 75 ppm aluminum. The process of claim 1, wherein the treated solution contains less than about 25 ppm aluminum. The process of claim 11, wherein the treated solution contains less than about 25 ppm aluminum. (a) In a first container, an aluminum alloy plate having a surface portion composed of aluminum oxide or aluminum hydroxide in a solution consisting essentially of water and vinylphosphonic acid-acrylic acid copolymer is pretreated with the copolymer without anodizing Contaminating the solution with aluminum by forming a layer composed of a reaction product of the oxide or hydroxide; (b) delivering at least a portion of the solution to a second vessel containing a cation exchange resin and adsorbing aluminum on the resin to produce a treated solution containing the copolymer and to have a reduced aluminum concentration; And (c) returning the treated solution to the first vessel; Process of processing the aluminum alloy plate having a surface portion coated with a polymer in order to improve the adhesion composed of.