US3671205A - Metal materials suitable for organic coating - Google Patents

Metal materials suitable for organic coating Download PDF

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US3671205A
US3671205A US3432A US3671205DA US3671205A US 3671205 A US3671205 A US 3671205A US 3432 A US3432 A US 3432A US 3671205D A US3671205D A US 3671205DA US 3671205 A US3671205 A US 3671205A
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vehicle
resins
layer
film
metal
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Hiromu Uchida
Akimi Umezono
Takao Saito
Tsutomu Enari
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Fuji Iron and Steel Co Ltd
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Fuji Iron and Steel Co Ltd
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    • 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
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/10—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by other chemical means
    • 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
    • B05D2350/00—Pretreatment of the substrate
    • B05D2350/20—Chromatation
    • 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
    • B05D2350/00—Pretreatment of the substrate
    • B05D2350/60—Adding a layer before coating
    • B05D2350/65—Adding a layer before coating metal layer
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S428/00—Stock material or miscellaneous articles
    • Y10S428/906—Roll or coil
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12535—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.] with additional, spatially distinct nonmetal component
    • Y10T428/12542—More than one such component
    • Y10T428/12549—Adjacent to each other
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12535—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.] with additional, spatially distinct nonmetal component
    • Y10T428/12556—Organic component
    • Y10T428/12569—Synthetic resin
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12535—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.] with additional, spatially distinct nonmetal component
    • Y10T428/12611—Oxide-containing component
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12639—Adjacent, identical composition, components
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/1266—O, S, or organic compound in metal component
    • Y10T428/12667—Oxide of transition metal or Al
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12771—Transition metal-base component
    • Y10T428/12806—Refractory [Group IVB, VB, or VIB] metal-base component
    • Y10T428/12826—Group VIB metal-base component
    • Y10T428/12847—Cr-base component
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31511—Of epoxy ether
    • Y10T428/31515—As intermediate layer
    • Y10T428/31522—Next to metal
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31511—Of epoxy ether
    • Y10T428/31529—Next to metal
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31678—Of metal
    • Y10T428/31681—Next to polyester, polyamide or polyimide [e.g., alkyd, glue, or nylon, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31844—Of natural gum, rosin, natural oil or lac

Definitions

  • This invention relates to metal articles, such as metal sheets, which are surface-coated with a chromiumcontaining layer or film, wherein the chromium-containing layer or film is in turn coated with a protective film or adsorbed layer of a water-soluble vehicle.
  • the chromium-containing layer or film comprises as major component hydrated chromium oxide and is formed by chromic acid treatment of the metallic substratum proper or of a plated surface of the metallic substratum.
  • the protective film or adsorbed layer of the Water-soluble vehicle is in turn formed by treating the chromium-containing layer or film with an aqueous solution of the water-soluble vehicle.
  • One of the objects of this invention is to provide metal materials which remain perfectly free from rusting during the forming operation and are of excellent lacquerability as final product.
  • the second feature of this invention relates to a metal material which is produced by applying a film of oil onto the said metal material treated in accordance with the first-feature to prevent abrasion and scratches Without deteriorating adhesion of paint to the base.
  • the immersion chromate treatment includes irnmersion treatment of materials in an aqueous solution containing as major components one or several of the following sodium dichromate, potassium, dichromate, sodium chromate and chromic anhydride with addition of sulfuric acid, sulfates, nitric acid and fluoric compounds.
  • the electrolytic chromate treatment includes a cathodic electrolytic treatment of materials in an aqueous solution of chromic anhydride or sodium dichromate with or without additives such as sulfuric acid, sulfates, fluoric compounds, nitric acid manganates, tungstatcs and molybdates.
  • the electrolytic chromic acid treatment includes a cathodic electrolytic treatment and a chromium plating of steel in an aqueous solution of chromic anhydride with additives such as phosphoric acid, sulfuric acid, boric acid, sulfonic acid, acetic acid, chloric acid, bromic acid, fiuoric acid and their salts and fluoric compounds.
  • the :film obtained by the chromic acid treatment is generally considered to be in a form of hydrate oxides (xCr2O3'yCrO3-xH2O) containing trivalent chromium and hexavalent chromium, but the film obtained by the electrolytic chromic acid treatment of steel is considered to be composed of an upper layer of trivalent hydrated chromium oxide and a lower layer of metallic chromium.
  • the hydrated chromium oxide film formed on the metal lbase or on a metal coated thereon is corrosion resistant but is exceedingly chemically active so that organic substances especially oily substances coming into contact with the coating film immediately after the film formation are strongly adsorbed to the film.
  • the characteristic required of the substances to be adsorbed on the hydrated chromium oxide film to prevent strong adsorption of other substances in the subsequent processes are not only that they should not interfere with the lacquer adhesion and that they themselves polymerize into the lacquer film, but also that they should be water soluble substances so that they can be adsorbed uniformly while the hydrated chromium oxide film formed is still wet after washing with Water and is free from other contaminations.
  • FIGS. l to 4 illustrate several embodiments of metal pieces with coatings according to the invention.
  • FIG. 1 shows the cross-section of a metal material of this invention
  • FIG. 2 show the cross-section of a metal material of this invention when the metal base is covered by a plated layer
  • FIG. 3 shows the cross-section in which an oil film is applied to the metal material shown in FIG. 1
  • FIG. 4 shows the cross-section in which an oil film is applied to the metal material in FIG. 2.
  • FIG. l 1 is a metal base
  • 2 is a hydrated chromium oxide film
  • 3 is a thin layer of a water soluble vehicle
  • FIG. 2 shows in 4 an intermediate layer of coated metal between the metal base 1 and the film 2.
  • FIG. 3 illustrates an embodiment in which an oil film 5 is applied as a top coating to the material shown in FIG. l
  • FIG. 9 is a similar showing for a modificaion of material according to FIG. 2.
  • the Water soluble vehicles of this invention which are resins capable of yielding Water soluble paints by themselves, are compatible With the paint applied to the metal materials and polymerize into a coating film proper after lacquering; as a result adhesion of the paint applied is improved.
  • the thin layer of Water soluble vehicle formed on the surface of the film of hydrated chromium oxide not only strongly adheres, but also becomes practically insoluble after the drying, and is by no means affected by such oily substances as lubricants applied to it, and thus degreasing is possible with ease without interfering with the adhesion of the organic coating.
  • the water soluble vehicles of this invention are classified into 5 groups as shown below.
  • Oleoresinous water soluble vehicles Resins prepared by mixing rosin, ester gum, alkyl, phenol resin, coumarone resin, cyclopentadiene resin, petroleum resin, cashew nut shell oil, or epoxy resin to anhydrous castor oil, tung oil, linseed oil or soybean oil, and by then reacting with maleic acid; and resins prepared by replacing maleic acid by fumaric, itaconic, acrylic or citraconic acid.
  • Polyesters prepared from polyalcohols such as glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, diglycerol, dipentaerythritol, epichlorohydrin, allylglycidylether, phenylglycidylether and epoxy resins, and dibasic acids, such as phthalic, maleic, furmaric, succinic, adipic, itaconic and citraconic acids; polyesters prepared by employing instead of above dibasic acids polybasic acids, such as benzenetricarboxylic acid, benzenetetracarboxylic acid, phosphoric acid, additives of rosin and maleic acid anhydride and maleic oils; and polyesters having polyoxymethylene bondings prepyleneglycol;
  • polyalcohols such as glycerin, trimethylolethane, trimethylolpropane, pentaerythri
  • Water soluble acrylic resin vehicles Copolymers of acrylic or methacrylic acid with methyl acrylate, ethyl acrylate or methyl crotonate; copolymers of alkyl esters of acrylic or methacrylic acid with vinyltoluene; and hydroxymethylated copolymers of acrylamide or methacrylamide with N-vinyllactam; and copolymers of N-methylolamides with ethyl acrylate.
  • the water soluble vehicles shown above from (l) through (5) may be used either singly or in combination of more than two.
  • the adsorbed quantity can be arbitrarily varied by controlling the vehicle concentration in the aqueous solution.
  • the preferred concentration is 0.1 to 48% by Weight, or 3 to 100 mg./m.2 in the adsorbed quantity of vehicle.
  • These quantities are remarkably small in comparison with those conventionally adopted for water soluble paints, for example 10 to 20% by Weight in the concentration of vehicle and 50 to 500 mg./dm..2.
  • the application of vehicles in the present invention is not for the purpose of undercoating nor as primer in the conventional lacquering. That is to say, the applied quantity of vehicles, 3 to 100 mg./m.2, is suicient to form a thin layer of the vehicles, and baking is not required, but mere removal of water by ordinary drying methods is sufficient.
  • the layer is extremely thin, or less than 0.1M, so that it is colorless and transparent without affecting the appearance. It does not act as a coating lilm but exhibits only a sealing effect toward adsorption of oily substances.
  • the lower limit of the adsorbed vehicle 3 m.g./m.2, is considered the minimum quantity necessary to completely cover the whole surface. With vehicle below this quantity, a desirable effect cannot -be expected.
  • the adsorbed quantity 3 mg./m.2 of the water soluble vehicle corresponds to a concentration of 0.1% by weight in a solution. Below this concentration, lacquer adhesion is not sufficient when a lubricant, for example, is applied to a metal material.
  • the adsorbed quantity of vehicle above the upper limit Ing/m.2 makes the vehicle layer so thick that non-uniform squeezing with rollers may often result which is unfavorable for good appearance.
  • the absorbed quantity 100 mg./m.2 of the water soluble vehicle corresponds to a concentration of 8% by weight in a solution.
  • a solution of higher concentration, hence increased quantity absorbed, does not enhance the desired eiTect, but degrades the appearance and is liable to cause incomplete drying.
  • the amount of the water soluble vehicle should be limited to 3 to 100 mg./m.2.
  • the metal materials of this invention are suited to bending or drawing, for example, where lubricants are applied during the processing and they are degreased afterward and the materials are coated with paint. More particularly, the thin layer of the vehicle strongly adheres to the hydrated chromium oxide layer, and the vehicle layer is practically insoluble and in addition does not adsorb lubricants, so that the degreasing can be conducted completely.
  • the vehicle layer is compatible with ordinary baking paints such as, for example, alkyl, melamine-alkyd, epoxy, epoxymelaminealkyd, acryl and vinyl paints. This is due to the property of the vehicle layer to polymerize into the applied organic coatings and to increase the adhesive strength of the coating layer.
  • the thin layer of vehicle on the metal materials of this invention is practically insoluble and can never be removed by the ordinary solvent degreasing process such as trichlene degreasing and by the emulsion degreasing, -but is partly removed from the surface when treated with a powerful alkaline degreasing agent containing sodium hydroxide or sodium silicate. In this case, however, along with the complete removal of greases, a part of the vehicle still remains on the metal surface and further improves the adhesion of paints.
  • oils to be used in this invention include D.O.S. (di- 2-ethyl-hexylsebacate), cotton seed oil, linseed oil and others.
  • EXAM-PLE l In an aqueous solution containing 60 ⁇ g./l. of' chromic anhydride and 0.55 g./1. of sulfuric acid, a cold rolled steel sheet was treated electrolytically as cathode to form on the steel sheet a duplicate layer of hydrated chromium oxide and metallic chromium, washed with water, and immediately dipped for 2 seconds into a 4% aqueous solution by weight of a water soluble oleoresinous vehicle which 'was obtained by heating a mixture consisting of 75 parts of anhydrous castor oil, 5 parts of an epoxy resin (Epikote #812) and 20 parts of maleic acid anhydride, squeezed with rollers to control the adsorbed amount of the vehicle to 30 mg./m.2 and then dried at room temperature.
  • a water soluble oleoresinous vehicle which 'was obtained by heating a mixture consisting of 75 parts of anhydrous castor oil, 5 parts of an epoxy resin (Epikote
  • EXAMPLE 2 A cold rolled steel sheet was treated, as in Example 1, electrolytically in chromic acid solution, Washed with water, then immediately a 0.5% aqueous solution by Weight of a water soluble alkyd resin vehicle, which was obtained by heating a mixture consisting of 40 partsof anhydrous castor oil, parts of trimethylolpropane, and 45 parts of phthalic acid, was sprayed on for 2 seconds, and then the sheet was squeezed with rollers to control the adsorbed amount of the vehicle to 10 mg./m.2, the material vwas then dried at 50 C. with hot air, and finally cotton seed oil was applied electrostatically in an amount of 8 mg./m.2.
  • an alkyd coating (hammer finish) was applied by baking to 25u thickness.
  • the cross-cut Erichsen test resulted in 0/ 100 in number. of peeled squares, while the same test of a sample, to which no vehicle was applied, resulted in 100/100 in number of peeled squares.
  • Example 3 After the lapse of a month, the samples in Example 2 were pressed, ⁇ using press oil #620 in a drawing ratio of 2.0, into a cylinder of 40 mm. diameter with a at bottom. After a week, these samples were degreased by dipping in cold trichlene for a minute and then by exposing to trichlene vapor for 2 minutes. A melamine-alkyd paint was applied to 30p. thickness by baking.
  • EXAMPLE 4 An electroytic tin plate was electrolytically treated as cathode in a 3% solution of sodium dichromate to form thereon a hydrated chromium oxide film, washed with water and immediately dipped for a second in a 0.2% aqueous solution of the vehicle consisting of parts of water soluble alkyd vehicle and 20 parts of hexamethoxymethylmelamine, the former being obtained by heating a mixture consisting of 60 parts of linseed oil, 10 parts of glycerine and 30 parts of maleic acid.
  • the wet plate was squeezed with rollers to control the adsorbed amount of the vehicle to 5 mg./m.2, dried at room temperature, and D.O.S. (di-2-ethylhexylsebacate) was applied in an amount of 5 mg./m.2 using mineral spirit as solvent.
  • aqueous solution was sprayed onto the coated sheet, containing 6% by weight of vehicle which consisted of 40 parts of partially butoxylated methylolurea and 60 parts of the water soluble alkyd resin employed in Example 2, then the sheet was squeezed with rollers to control the adsorbed amount of the vehicle to 70 mg./m.2, dried by blowing hot air at 60 C., cotton seed oil was applied electrostatically in an amount of 3 mg./m.2 and then Valvoline 861Q (trade name, rust preventive oils, available from Daikyo Petroleum Co. of Japan) in an amount of 5 g./m.2. After three months the sample was pressed in a drawing ratio of 2.0 into a cylinder of 40 mm. diameter with a at bottom.
  • EXAMPLE 6 v A zinc plated steel sheet was treated by the electrolytic chromate process in an aqueous solution containing 30 g./l. of chromatic anhydride and 0.2 g./l. of sulfuric acid to form on it a lm composed mainly of hydrated chrominium oxide.
  • a 1% aqueous solution of Resydrol P411, an alkyd resin modified by phenolic resin was sprayed on, and sheet was squeezed With rollers, to control the adsorbed amount of vehicle to 15 mg./m.2, the sheet was then dried.
  • machine oil #120 was applied in an amount of 5 g./m.2. ⁇ After 3 months degreasing was conducted for 1 minute by dipping in cold trichlene and then for another minute with trichlene vapor, and a melamine-alkyd resin coating was baked to 25p. thickness.
  • the cross-cut Erichen test on the above product showed /100 in number of peeled squares, while a similar sample to which no vehicle was applied proved to be 38/100.
  • EXAMPLE 7 A cold rolled steel sheet was first plated with chromium to 0.025# thickness, and then treated by the electrolytic chromate process in a solution containing 60 g./l. of chromic anhydride, g./l. of acetic acid and 0.5 g./l. of sodium fluorosilicate to form a lm composed mainly of hydrated chromium oxide. Immediately after washing with water, the sheet was dipped for l second into an aqueous solution containing 1% by Weight of water soluble acrylic resin vehicle consisting of a copolymer of N-methylolamide and ethyl acrylate.
  • the sheet was then squeezed with rollers to control the adsorbed amount of the vehicle to mg./m.2, and then dried at room temperature.
  • This sample was pressed, with #640 press oil, into a cylindrical vessel of 80 mm. diameter and 60 mm. depth, which was degreased for 1 minute by dipping in cold trichlene and for another minute with alkali (NaOH 2%, 60 C.), and then a phthalic acid alkyd coating was baked to 15p thickness.
  • the sheet was dipped for 1 second in a 4% by weight aqueous solution of the vehicle consisting of 70 parts of the ⁇ water soluble alkyd resin vehicle employed in Example 2 and 30 parts of the water soluble acrylic resin vehicle employed in Example 7, squeezed with rollers to control the adsorbed amount of the vehicle to 45 mg./m.2, dried at 60 C., and then D.O.S. (di 2 ethylhexylsebacate) was applied in an amount of 5 mg./m.2.
  • alkyd white coating and acrylic white coating were baked respectively to 30p. thickness, and the crosscut Erichsen test of the coating film of these samples proved to be 0/100 in number of peeled squares.
  • EXAMPLE 10 A cold rolled steel sheet was chromium plated in an aqueous solution containing g./l. of chromic anhydride and 1.5 g./l. of sulfuric acid to form a metallic chromium layer of 0.32 g./m.2 on the sheet andl a hyldrated chromium oxide iilm of 8 mg. Cr./m.2 on the metallic chromium layer.
  • a metal sheet or coil receptive to organic coatings comprising:
  • a protective, water-soluble film on said chromiumcontaining layer said film being formed from at least one member of the group consisting of oleoresinous resins, alkyd resins, aminoalkyd resins, phenolalkyd resins and acrylic resins.
  • said watersoluble lm essentially consisting of at least one member of the group consisting of oleoresinous resins, alkyd resins, aminoalkyd resins, phenolalkyd resins and acrylic resins.
  • a method of forming a metal sheet into a metal object which comprises:

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Paints Or Removers (AREA)
  • Electrochemical Coating By Surface Reaction (AREA)
  • Chemical Treatment Of Metals (AREA)
US3432A 1969-01-22 1970-01-16 Metal materials suitable for organic coating Expired - Lifetime US3671205A (en)

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Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3773544A (en) * 1970-06-02 1973-11-20 Steel Corp Fluorocarbon polymer coated substrate
US3860398A (en) * 1972-12-05 1975-01-14 Toyo Seikan Kaisha Ltd Can produced from chromium-coated steel plate
US3977839A (en) * 1973-11-21 1976-08-31 The Empire Plating Company Coated metal article and method of coating
US3981691A (en) * 1974-07-01 1976-09-21 Minnesota Mining And Manufacturing Company Metal-clad dielectric sheeting having an improved bond between the metal and dielectric layers
US4269904A (en) * 1978-06-05 1981-05-26 Nippon Steel Corporation Manganese surface coated steel materials
US4298661A (en) * 1978-06-05 1981-11-03 Nippon Steel Corporation Surface treated steel materials
US4369221A (en) * 1981-03-13 1983-01-18 Transformer Service (Ohio), Inc. Protective coating laminate
US4411964A (en) * 1980-12-24 1983-10-25 Nippon Kokan Kabushiki Kaisha Composite coating steel sheets having good corrosion resistance paintability and corrosion resistance after paint coating
US4525425A (en) * 1981-05-11 1985-06-25 El-Chem Corporation Water and oil repellent metal oxide-organic combination coating systems and method of making same
US4614691A (en) * 1984-10-01 1986-09-30 Toyo Kohan Co., Ltd. Method for production of metal sheet covered with polyester resin film
US4853297A (en) * 1987-04-06 1989-08-01 Usui Kokusai Sangyo Kaisha Ltd. Multilayer coated corrosion resistant metal pipe
US4961994A (en) * 1987-12-16 1990-10-09 General Electric Company Protective coated composite material
US5002837A (en) * 1988-07-06 1991-03-26 Kabushiki Kaisha Kobe Seiko Sho Zn-Mg alloy vapor deposition plated metals of high corrosion resistance, as well as method of producing them
US5094924A (en) * 1988-10-19 1992-03-10 Kenzo Matsui Polyester resin film laminated steel sheet for drawn and ironed can

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA993831A (en) * 1971-07-07 1976-07-27 Iwakichi Kawaguchi Chromate treated metal sheet and a process therefor

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3773544A (en) * 1970-06-02 1973-11-20 Steel Corp Fluorocarbon polymer coated substrate
US3860398A (en) * 1972-12-05 1975-01-14 Toyo Seikan Kaisha Ltd Can produced from chromium-coated steel plate
US3977839A (en) * 1973-11-21 1976-08-31 The Empire Plating Company Coated metal article and method of coating
US3981691A (en) * 1974-07-01 1976-09-21 Minnesota Mining And Manufacturing Company Metal-clad dielectric sheeting having an improved bond between the metal and dielectric layers
US4269904A (en) * 1978-06-05 1981-05-26 Nippon Steel Corporation Manganese surface coated steel materials
US4298661A (en) * 1978-06-05 1981-11-03 Nippon Steel Corporation Surface treated steel materials
US4411964A (en) * 1980-12-24 1983-10-25 Nippon Kokan Kabushiki Kaisha Composite coating steel sheets having good corrosion resistance paintability and corrosion resistance after paint coating
US4369221A (en) * 1981-03-13 1983-01-18 Transformer Service (Ohio), Inc. Protective coating laminate
US4525425A (en) * 1981-05-11 1985-06-25 El-Chem Corporation Water and oil repellent metal oxide-organic combination coating systems and method of making same
US4614691A (en) * 1984-10-01 1986-09-30 Toyo Kohan Co., Ltd. Method for production of metal sheet covered with polyester resin film
US4853297A (en) * 1987-04-06 1989-08-01 Usui Kokusai Sangyo Kaisha Ltd. Multilayer coated corrosion resistant metal pipe
US4961994A (en) * 1987-12-16 1990-10-09 General Electric Company Protective coated composite material
US5002837A (en) * 1988-07-06 1991-03-26 Kabushiki Kaisha Kobe Seiko Sho Zn-Mg alloy vapor deposition plated metals of high corrosion resistance, as well as method of producing them
US5094924A (en) * 1988-10-19 1992-03-10 Kenzo Matsui Polyester resin film laminated steel sheet for drawn and ironed can

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DE2002599A1 (de) 1970-07-30
DE2002599B2 (de) 1978-02-16
JPS5235620B1 (it) 1977-09-10

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