US3532611A - Process for the manufacture of surface-treated metallic sheets or the like,with superior coating and anti-corrosive performance - Google Patents

Process for the manufacture of surface-treated metallic sheets or the like,with superior coating and anti-corrosive performance Download PDF

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Publication number
US3532611A
US3532611A US568078A US3532611DA US3532611A US 3532611 A US3532611 A US 3532611A US 568078 A US568078 A US 568078A US 3532611D A US3532611D A US 3532611DA US 3532611 A US3532611 A US 3532611A
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liquid
test
treated
sheets
performance
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US568078A
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English (en)
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Shuichiro Takiguchi
Hirozumi Takada
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JFE Engineering Corp
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Nippon Kokan 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D109/00—Coating compositions based on homopolymers or copolymers of conjugated diene hydrocarbons
    • C09D109/10—Latex
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D113/00—Coating compositions based on rubbers containing carboxyl groups
    • C09D113/02—Latex
    • 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
    • C23C22/73—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 characterised by the process
    • C23C22/74—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 characterised by the process for obtaining burned-in conversion coatings

Definitions

  • modified polymers used in making the emulsion are either acrylonitrile-butadiene or vinylidene chloride having polarizing radicals such as carboxylic, epoxy or amides.
  • a preferred composition for the aqueous emulsion solution is:
  • dispersant liquid containing a minute amount of Formalin and polyoxyethylene octyl phenol ether, (3) a reducing agent such as millet-jelly or sugar.
  • This invention relates to improvements in and relating to a process for the surface-treatment of metallic sheets, bands, plates and the like plan stocks, preferably those of steel, galvanized steel, alloy steel, light metal and the like.
  • a still further object is to provide a process for the manufacture of surface-treated steel sheets adapted for use in place of tinned can sheets and provided with surface coatings highly suitable for canning purposes, and,
  • a unique process which comprises, in combination, selecting a member from the group of, styrene-butadiene rubber, acrylonitrile-butadiene, vinylidene chloride and the like; introducing into said member a polarizing radical such as or the like; preparing an aqueous emulsion of said selected and polarized member; mixing said emulsion with chromic acid and phosphoric acid; preparing an evenly distributed dispersion therefrom; applying said dispersion to a metallic sheet, subjecting the thus treated sheet to a reducing treatment for converting almost all of the hexavalent chromium to trivalent chromium.
  • a reducing agent for chromic acid is preferably added, if the reducing process is not electrolytically carried into effect.
  • polarizing radical As a preferred and representative way of introducing polarizing radical into the main constituent of the treating liquor, taking as an example COOH, specific organic acid such as maleic acid, acrylic acid or the like, which contains both vinyl radical and carboxyl radical, is added to the monomer of the synthetic rubber and subjected to copolymerization.
  • specific organic acid such as maleic acid, acrylic acid or the like, which contains both vinyl radical and carboxyl radical
  • polarizing radicals are given only by way of example, and thus the invention is not limited to these specific radicals. It will be however Well understood from the description to be set forth that the inventive technique is sharply contrasted to known techniques employing non-polarized starting materials for the desired purpose. In the process proposed by the present invention, two or more polarizing radicals can be simultaneously utilized.
  • FIG. 1 is an electro microphotograph taken from a surface-treated steel sheet according to Example 1.
  • FIGS. 2 and 3 are views similar to FIG. 1, illustrating, for comparison, conventional products procured from market, more specifically those subjected to chromic acid and pigmented chromic acid treatment, respectively.
  • FIG. 4 is a similar view of a conventional phosphatetreated, zinc coated steel sheet.
  • FIG. 5 is a similar view to FIG. 4, taken from a conventional chromate-treated, zinc coated steel sheet.
  • FIG. 6 is a similar view to FIG. 4, taken from a conventional electrolytically chromate-treated steel sheet.
  • EXAMPLE 1 In the following, a treating liquor for general use is first described. Tinned can sheets can be treated by diluting the general-use liquor with 2-6 parts of water per part of liquor.
  • the treating liquor is a mixture of liquid A and liquid B.
  • Liquid A further comprises liquid I which is a synthetic rubber emulson, liquid II which is a dispersant liquid, and liquid III whch is a reducer solution.
  • Liquid B comprises further liquid IV and liquid V. This preparation can be seen from Table I, to be given hereinafter. Percentages are given by Weight, if not otherwise specified.
  • Synthetic rubber emulsion (Liquid 1) Ingredients Weight, percent ⁇ Styrenc-butadienc rubber, carboxylatcd. 40-60 1 60 80 IW-ater with dispersant 40-60 l Polyoxyethylenc octyl phenol ether 10-30 Dispersant liquid (Liquid II) Water 69. 9-88. 10-20 -40 FQllllfi lllLn 0. 1
  • liquid B 20-40% of CrO 10-30% of ZnO (buffer or intensify ing agent) and of water are throughly mixed while strongly agitating, to obtain liquid IV.
  • liquid IV 20-40% of CrO 10-30% of ZnO (buffer or intensify ing agent) and of water are throughly mixed while strongly agitating, to obtain liquid IV.
  • -90%, preferably 85.0%, industrial H PO and 10-20%, preferably 15%, of water are thoroughly mixed to form said liquid V.
  • said two liquids IV and V are mixed in 5
  • liquid A and liquid B are mixed in a ratio of 20-40%, preferably 30%, and 10-30%, preferably 20%, respectively, with water 50%, with strong agitation, to obtain a homogeneous dispersion ready for use.
  • a metallic strip stock preferably bare steel strip or zinc-coated steel strip
  • the aforementioned liquor according to the conventional dipping process, so that the pick-up quantity become 3-7 g./m. and then cured for a short time, preferably 2-3 minutes at 260-330 C., as measured on the cured strip coil.
  • rigidly attached and stable protecting coatings are formed on the both surfaces of the stock.
  • the thus surface-treated coil is then cut to desired size and subjected to a finish or ornamental coating process with paint or other protecting agent.
  • the aforementioned surface-treated sheets are tested and the results are set forth in following Table II.
  • Table III shows the evaluation standards adopted in Table I.
  • the protecting layer formed by the process according to this invention comprises a highly stable complex com- TABLE IV Commercially Chromic procured Commercial Zinc-galvanized Performance Test acid electrolytically chromium late Inventive treatchromate treated plated Item Conditions products ment steel sheet steel sheet N o. 25 No. 50
  • Repellent nature to paint Alkyd series resin for can use 1O 10 10 10 10 10 Scratch test ..do 10 10 10 10 8 8 Phenolic paint for can use 10 6 6 4 Epoxyphenol series paint for can 10 6 8 6 Bond test use.
  • Epoxy resinous paint for can use 10 G 6 4 paint for can use.
  • Example 1 Polyoxyethylene octyl phenol ether is used as the dispersing agent.
  • Other dispersants can also be utilized with similar results when they do not react with the employed constituting chemicals to gel products.
  • As reducing agent sucrose, glycol, glycerine and/or the like, can be equally employed in place of millet-jelly shown in Example 1, by way of example.
  • the dip process may also be replaced by sprayor other co-nventionel coating processes.
  • the curing temperature can be elevated to as high as 700 C., when measured at the temperature of the heating medium.
  • the curing period can be substantially shortened, for instance, to several seconds.
  • the resin component introduced thereinto polarizing radicals are used in combination with chromic acid (preferably added with reducing agent for the latter) and phosphoric acid
  • the reducing action should preferably be carried into effect so that almost none of the hexavalent chromium component remains, if high performance of bond of paints to be applied later, and highly improved machina'bility are desired.
  • the metallic surface treated with the aforementioned treating liquor has a White-green tone.
  • Organic and inorganic pigments or the like conventional coloring agents can be added to the coating liquor, if ornamental elfects are wanted. These agents should also be used in the form of finely divided particles so as not to injure the desired bonding performance of the coated layer according to the invention.
  • the treated sheet products can be used for various and numerous purposes without applying ornamental color paint layers. Although this invention can be well applied to tinned or zinc-coated steel sheets, it is a advantageous that the sheet products, as treated according to this invention, can well be produced at a considerably more economical base than the tinned sheets and be used in place of thereof. Thus, by adopting the present invention, highly economical can sheets may be produced in place of tinned iron sheets.
  • EXAMPLE 2 In place of carboxylic radicals, epoxy, acid amide and/ or CONHCH OH radicals are introduced into styrenebutadiene rubber, and further treatments are carried into effect under similar operating conditions as set forth in Example 1 with similar results.
  • EXAMPLE 3 40% of acrylonitrile-butadiene introduced with carboxylic radicals and 60% of water added with a minor quantity of conventional dispersant, as employed broadly in the rubber industry, are thoroughly mixed together while agitating, so as to produce 60 parts of synthetic rubber emulsion.
  • a dispersant solution is prepared as in the case of Example 1, from of polyoxyethylene octyl phenol ether, 89.9% of water and 0.1% of Formalin (37%).
  • a reducing liquid is prepared from millet-jelly, 50%, and Water, 50%, as before.
  • EXAMPLE 4 60 parts of vinylidene chloride, introduced therein with epoxy radicals as polarizing radicals, and 40 parts of water, added with a small amount of conventional dispersant as in the preceding examples, are thoroughly mixed together to form a synthetic rubber emulsion, while a dispersant solution comprising 30% of a conventional dispersant, as was employed in Example 1, 69.9% of water and Formalin (37%) 0.1%, is prepared as before. Further, sugar 40% and water 60% are intimately agitated to form a reducing liquid. Then, these three kinds of liquids are combined together at a ratio of 70:15:15, so as to produce a kind of liquid A, in the aforementioned meaning.
  • liquid B is prepared as was shown in aforementioned Example 1, the percentages being capable of varing within limits listed in aforementioned Table I.
  • FIG. 1 shows an electromicroscopic photograph of the product prepared in Example 1 X5000).
  • FIGS. 26 are similar views to FIG. 1, taken from comparative conventional products. From comparison of these photographs, it may be easily ascertained that the inventive productive product (with no pigment added thereto) represents a highly even and fine film structure. There are shown in FIG. 1, a number of small spots which are believed at present to comprise fine particles. However, there is no evidence for discriminating them from recessed spots.
  • acrylonitrilebutadiene rubber, vinylidene chloride and the like used as the starting material should have a mutual solubility to chromic acid.
  • a process for the surface treatment of metallic sheet stock comprising preparing an aqueous mixture comprising:
  • said dispersant liquid comprises an aqueous solution containing 0.1 Weight percent of 37% Formalin and to weight percent polyoxyethylene octyl phenol ether.
  • a process for the surface treatment of metallic sheet stock comprising preparing an aqueous mixture comprising:
US568078A 1965-05-25 1966-05-23 Process for the manufacture of surface-treated metallic sheets or the like,with superior coating and anti-corrosive performance Expired - Lifetime US3532611A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3873349A (en) * 1971-03-12 1975-03-25 Nippon Kokan Kk Process of treating surfaces of metals
US5006413A (en) * 1989-09-05 1991-04-09 E. I. Du Pont De Nemours And Company Waterbased methylol (meth)acrylamide acrylic polymer and polyurethane containing coating composition
US5314945A (en) * 1990-12-03 1994-05-24 E. I. Du Pont De Nemours And Company Waterbased coating compositions of methylol(meth)acrylamide acrylic polymer, polyurethane and melamine crosslinking agent
US11383329B2 (en) * 2017-03-23 2022-07-12 Bayerische Motoren Werke Aktiengesellschaft Method for producing a workpiece composite, and workpiece composite

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62100561A (ja) * 1985-10-28 1987-05-11 Nisshin Steel Co Ltd 電磁鋼板絶縁皮膜形成用組成物及び電磁鋼板絶縁皮膜形成方法
JPS6369984A (ja) * 1986-07-16 1988-03-30 サ−マテツク・インタ−ナシヨナル・インコ−ポレイテツド 改良被覆部品、コ−テイング及びその適用方法
GB2215740B (en) * 1988-02-08 1992-06-03 Brent Chemicals Int Composition and process for treating metal surfaces

Citations (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2163984A (en) * 1935-12-09 1939-06-27 Petkovic Valentin Anton Process for the preparation of a rust-preventing coating on metallic objects
US2798017A (en) * 1954-06-07 1957-07-02 Hercules Powder Co Ltd Coating composition for metals
US2812296A (en) * 1953-06-16 1957-11-05 United States Steel Corp Electrochemical method for coating steel surfaces and the product thereof
US2846342A (en) * 1955-09-30 1958-08-05 Leo P Curtin Bonding coats for metal
US3053693A (en) * 1958-05-29 1962-09-11 Pennsalt Chemicals Corp Metal coating with hexavalent chromium compound
US3063877A (en) * 1960-10-10 1962-11-13 Amchem Prod Method and solutions for treating metal surfaces
US3094441A (en) * 1958-09-03 1963-06-18 Curtin Leo Vincent Chromic phosphate bonding coats for metal
US3162550A (en) * 1961-05-08 1964-12-22 Union Oil Co Process of preventing corrosion of ferrous metal by an aqua ammonia solution
US3175964A (en) * 1960-01-23 1965-03-30 Yawata Iron & Steel Co Surface treatment of metal article by water-soluble (film-forming) material
US3248350A (en) * 1962-09-14 1966-04-26 Hooker Chemical Corp Water insoluble coating of methyl vinyl ether-maleic anhydride copolymer, hydroxyethyl cellulose and phosphoric acid
US3276916A (en) * 1961-09-22 1966-10-04 Lubrizol Corp Inhibition of corrosion of metal surfaces
US3346522A (en) * 1963-05-23 1967-10-10 Pennsalt Chemicals Corp Aqueous solution containing a resin and sucrose for use with solutions of hexavalentchromium coating compounds
US3370992A (en) * 1963-10-14 1968-02-27 Diamond Shamrock Corp Pretreatment of a metal surface for conversion coating
US3437574A (en) * 1964-08-31 1969-04-08 Kansai Paint Co Ltd Anticorrosive treatment of zinc and metallic materials coated with zinc

Patent Citations (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2163984A (en) * 1935-12-09 1939-06-27 Petkovic Valentin Anton Process for the preparation of a rust-preventing coating on metallic objects
US2812296A (en) * 1953-06-16 1957-11-05 United States Steel Corp Electrochemical method for coating steel surfaces and the product thereof
US2798017A (en) * 1954-06-07 1957-07-02 Hercules Powder Co Ltd Coating composition for metals
US2846342A (en) * 1955-09-30 1958-08-05 Leo P Curtin Bonding coats for metal
US3053693A (en) * 1958-05-29 1962-09-11 Pennsalt Chemicals Corp Metal coating with hexavalent chromium compound
US3094441A (en) * 1958-09-03 1963-06-18 Curtin Leo Vincent Chromic phosphate bonding coats for metal
US3175964A (en) * 1960-01-23 1965-03-30 Yawata Iron & Steel Co Surface treatment of metal article by water-soluble (film-forming) material
US3063877A (en) * 1960-10-10 1962-11-13 Amchem Prod Method and solutions for treating metal surfaces
US3162550A (en) * 1961-05-08 1964-12-22 Union Oil Co Process of preventing corrosion of ferrous metal by an aqua ammonia solution
US3276916A (en) * 1961-09-22 1966-10-04 Lubrizol Corp Inhibition of corrosion of metal surfaces
US3248350A (en) * 1962-09-14 1966-04-26 Hooker Chemical Corp Water insoluble coating of methyl vinyl ether-maleic anhydride copolymer, hydroxyethyl cellulose and phosphoric acid
US3346522A (en) * 1963-05-23 1967-10-10 Pennsalt Chemicals Corp Aqueous solution containing a resin and sucrose for use with solutions of hexavalentchromium coating compounds
US3370992A (en) * 1963-10-14 1968-02-27 Diamond Shamrock Corp Pretreatment of a metal surface for conversion coating
US3437574A (en) * 1964-08-31 1969-04-08 Kansai Paint Co Ltd Anticorrosive treatment of zinc and metallic materials coated with zinc

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3873349A (en) * 1971-03-12 1975-03-25 Nippon Kokan Kk Process of treating surfaces of metals
US5006413A (en) * 1989-09-05 1991-04-09 E. I. Du Pont De Nemours And Company Waterbased methylol (meth)acrylamide acrylic polymer and polyurethane containing coating composition
US5314945A (en) * 1990-12-03 1994-05-24 E. I. Du Pont De Nemours And Company Waterbased coating compositions of methylol(meth)acrylamide acrylic polymer, polyurethane and melamine crosslinking agent
US11383329B2 (en) * 2017-03-23 2022-07-12 Bayerische Motoren Werke Aktiengesellschaft Method for producing a workpiece composite, and workpiece composite

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Publication number Publication date
DE1521907A1 (de) 1969-11-06
GB1152951A (en) 1969-05-21
DE1521907B2 (de) 1977-02-03

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