US3829371A - Method for coating the surface of a metallic material - Google Patents

Method for coating the surface of a metallic material Download PDF

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Publication number
US3829371A
US3829371A US00121527A US12152771A US3829371A US 3829371 A US3829371 A US 3829371A US 00121527 A US00121527 A US 00121527A US 12152771 A US12152771 A US 12152771A US 3829371 A US3829371 A US 3829371A
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US
United States
Prior art keywords
coating
film
acid
metallic
aqueous
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Expired - Lifetime
Application number
US00121527A
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English (en)
Inventor
S Miki
T Nishida
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Henkel Corp
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Amchem Products Inc
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Assigned to AMCHEM PRODUCTS, INC. A CORP. OF DEL. reassignment AMCHEM PRODUCTS, INC. A CORP. OF DEL. MERGER (SEE DOCUMENT FOR DETAILS). Assignors: AMCHEM PRODUCTS, INC. (MERGED INTO), HHC, INC. (CHANGED TO)
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Expired - Lifetime legal-status Critical Current

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Classifications

    • 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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/44—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications
    • C09D5/4484—Anodic paints
    • 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
    • Y10T428/31692—Next to addition polymer from unsaturated monomers
    • Y10T428/31696—Including polyene monomers [e.g., butadiene, etc.]

Definitions

  • the present invention relates to a method for coating the surface of a'metallic material. More particularly, it relates to a method for forming a uniform and smooth film of polymer firmly adhered on the surface of a metallic material, particularly of a ferriferous or zinciferous material, in a short time.
  • a method for coating the surface of a metallic mate,- rial which comprises immersing the metallic surface in an aqueous composition comprising a film-forming polymer, an acid and an oxidizing agent, passing a direct electric current between the metallic surface, as a primary electrode, and a secondary electrode and withdrawing the metallic surface from the aqueous composition, followed by baking the coated surface.
  • the material to be coated on the surface by the method of this invention is a metallic one, particularly a ferriferous or zinciferous one.
  • Thefterm"ferriferous herein used is intended to mean iron, steel and other iron alloys wherein iron is the principal constituenttsuch as especially coldand'hot-rolled steel alloys with minor amounts of carbon, silicon'and manganese) but excludes the so-called stainless steel.
  • the term zinciferous is' intended to mean not only'zinc'and zinc-alloys wherein zinc is the principal con- "Ice stituent but also galvanized metal, especially both hotdipped and electrogalvanized iron steel. 1
  • the aqueous composition used for coating in th method of this invention comprises a film-forming polymer, an acid and an oxidizing agent as theessential components.
  • the film-forming polymer is normally used in the form of an aqueous dispersion stable over a period of at least 24 hours at a pH range of about 1.6 to about 5.0.
  • aqueous dispersion which is commercially available are styrene-butadiene copolymer emulsion (Hycar LX 407 manufactured by Nihon Geon Co., Lt.; Pliolite 491 manufactured by Goodyear Rubber & Chemical Corp.), acrylic copolymer emulsion (Hycar LX 814 manufactured by Nihon Geon Co., Ltd.
  • Polysol AP 300 manufactured by Kobunshi Kagaku Kogyo Co., Ltd.
  • ethylene-vinyl acetate copolymer emulsion Polysol EVA P 1 manufactured by Kobunshi Kagaku Kogyo Co., Ltd
  • polyethylene emulsion Poly-em 40 manufactured by Gulf Oil Corp.
  • polyacrylic acid emulsion (Primal ASE-60 manufactured by Nihon Acryl Co., Ltd.), etc.
  • the acid there may be utilized various kinds of acids such as mineral acids (e.g. hydrochloric acid, hydrofluoric acid, sulfuric acid, phosphoric acid), organic acids (e.g. acetic acid) and their mixtures, provided that the effective and sufiicient liberation of a metallic ion (e.g. Fe ion, Zn ion) from the surface of the metallic material can be assured in the aqueous composition.
  • mineral acids e.g. hydrochloric acid, hydrofluoric acid, sulfuric acid, phosphoric acid
  • organic acids e.g. acetic acid
  • hydrofluoric acid e.g. hydrofluoric acid.
  • the most preferred oxidizing agent is hydrogen peroxide.
  • oxidizing agent is hydrogen peroxide.
  • chromium trioxide potassium dichromate
  • potassium permanganate potassium permanganate
  • potassium nitrate potassium nitrate
  • ammonium persulfate a variety of oxidizing agents can be also used, for instance, chromium trioxide, potassium dichromate, potassium permanganate, potassium nitrate and ammonium persulfate. These oxidizing agents may be used alone or in combination.
  • the concentrations of the said essential components in the aqueous composition for coating are varied more or less with their kinds.
  • the aqueous coatin composition includes about 5 to about 550 g./l. of polymer particles (i.e. resin solid), about 0.01 to about. 0.50 g. equivalent/l. of the acid and about 0.01 to about 0.30 g. equivalent/l. of an oxidizing agent.
  • a composition includ ing 5 to 550 g./l. of polymer particles, 0.4 to 5.0 g./l. of fluoride ion and 0.3 to 3.0 g./l. of hydrogen peroxide is a typical example of suitable ones fIt is preferred that such aqueous composition has a pH within the range of about 1.6 to about 5.0.
  • any waterdispersible pigment may be incorporated into the aqueous coating composition to provide-a" decorative effect upon and also to improve the corrosion'resistance of the treated metallic surface.
  • the'pi'gment include phthalo cyanine blue, phthalocyanine green, carbon black, iron oxide red, iron-oxide yellow, quinacridone red, lead chro mate, etc.
  • these pigments provide excellent a nonionic or anionic surface active agent and with some amount of water and dispersed by the aid of a high speed 3 mixer like .Cowles Mixer, the said essential components are added to the resulting dispersion under further agitation and finally the bath solid content is adjusted by adding extra water thereto.
  • coalescing agent i.e. ethyleneglycol monobutylether
  • the method of this invention includes the steps of immersing a metallic surface as an anode and an appropriate electrode as a cathode in the aqueous coatin composition set up in a bath and of applying a direct electric current through these electrodes.
  • the bath voltage may be from about 2 to about 100 volts, preferably less than 50 volts.
  • the immersion time is normally from about to about 100 seconds, preferably less than 60 seconds.
  • the thickness or weight of the resinous coating formed on the metallic surface from the immersion-electrolysis bath can be controlled by varying the time of applying an electric current and also by varying the voltage.
  • the application of direct electric current i.e. passing a direct electric current through the aqueous coating composition is carried out as in the case of an ordinary electro-deposition coating. Nevertheless, the purpose of the application of electric energy is no more than the acceleration of the coating speed. For example, this procedure has nothing to do with the throwing power as defined in the electro-deposition coating but the throwing performance is solely dependent upon the behaviors of the essential components, i.e., the film-forming polymer, the acid and the oxidizing agent, in the aqueous coating composition.
  • the coated surface is withdrawn from the aqueous coating composition and baked usually at about 1'20 to about 250 C. for about 5 to about 30 minutes, depending upon the fusion characteristics of the polymer (i.e. resin).
  • EXAMPLE 1 Component Styrene-butadiene copolymer emulsion (Hycar LX 407 manufactured by Nihon Geon Co., Ltd., resin solid, 48%) g.. 180 Hydrogen peroxide -..g- 2 Hydrofluoric acid -g 3 Tap water ml To make 1000 Hycar LX 407 was diluted with water, and the dilution was admixed with hydrofluoric acid and hydrogen peroxide with a good agitation. A steel panel, previously cleaned in a conventional alkali metal silicate solution,
  • Resin emulsion used 2. Styrene-butadiene copolymer emulsion- (Pliolite 491" manufactured by Goodyear Rubber & Chemical Corp.; resin solid, 56 percent).
  • Acrylic copolymer emulsion (Hycar LX 814" manufactured by Nihon Geon. 00., Ltd.; resin solid, 48%).
  • EXAMPLES 9-12 The coating of a steel panel was carried out in the same manner as in Example 1 but using a coating composition comprising d-Iycar LX 407 g.), hydrogen peroxide (2 g.; 0.11 g. equivalent/l.) and an acid (as shown in Table 2) in tap water (to make 1000 ml.). The thickness of the film thus formed on the surface of the panel is shown in Table 2. r
  • EXAMPLES 19-21 The coating of a steel panel was carried out in the same manner as in Example 18 but using a different coating composition while passing a direct electric current at 20 Table 6 with or without passing a direct electric current. The film appearance and thickness formed on clean steel panels are shown in Tables 6 and 7.
  • the test panel was impacted by a balling W ball with 1,000 g. weight from 50 cm. height, deforming the specimen.
  • the paint surface was scribed with parallel lines approximately 1 mm. apart and cut through to bare metal. Duplicate lines were scribed at right angles to make a cross-hatch pattern. Scotch brand cellophane tape was pressed smoothly over the scribed area. After several seconds, the tape was pulled back rapidly so that the tape was turned back upon itself approximately 180 from its original pressed position. The results are shown in the degree of failure noted; e.g. none, slight, moderate or heavy loss of paint.
  • a method for coating the surface of a metallic material which comprises immersing the metallic surface in an aqueous composition comprising a dispersion of a filmforming polymer, an acid, and an oxidizing agent, passing a direct electric current between the metallic surface and a secondary electrode, such that the metallic surface is anodic and the secondary electrode is cathodic and withdrawing the thus-coated metallic surface from the aqueous composition followed by baking the coated surface.
  • Hycar LX 814 (220)-- Iron oxide red (50) Demol-P (2.5) 4. 5 3 29
  • the comparison test was carried out using the aqueous coating compositions described in Examples 18 6.
  • 8T1ie areth aaarain to claim 1', wherein the'a'cidis hydrofluoric acid, hydrochloric acid, sulfuric acid; phosphoric acid or acetic acid.
  • the-oxidizing agent is. hydrogen peroxide, chromium trioxide, potassium dichromate, potassium permanganate, sodium nitrate or ammonium persulfate. 7 j;
  • aqueous composition contains a water-dispersible pigment.
  • a method for coating the surface of a ferriferous or zinciferous material which comprises immersing the surface in an aqueous composition of a dispersion of a filmforming polymer having a pH of from about 1.6 to about 5.0 and comprising from about 0.01 to about 0.50 g. equivalent/l. of an acid selected from the group consisting of hydrofluoric acid, hydrochloric acid, sulfuric acid, phosphoric acidand aceticacid anafiam about OIOTto about 0.30 g. equivalent/l.
  • an oxidizing agent selected from the group consisting of hydrogen peroxide, chromium trioxide; potassium dichromate, potassium permanganate, sodium nitrate and ammonium persulfate, the film forniing polymer being contained in a concentration of from about 5 to about 550 g./1.”

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  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Paints Or Removers (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Chemical Treatment Of Metals (AREA)
US00121527A 1970-03-06 1971-03-05 Method for coating the surface of a metallic material Expired - Lifetime US3829371A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP1910270A JPS5413453B1 (enrdf_load_stackoverflow) 1970-03-06 1970-03-06

Publications (1)

Publication Number Publication Date
US3829371A true US3829371A (en) 1974-08-13

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Family Applications (1)

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US00121527A Expired - Lifetime US3829371A (en) 1970-03-06 1971-03-05 Method for coating the surface of a metallic material

Country Status (5)

Country Link
US (1) US3829371A (enrdf_load_stackoverflow)
JP (1) JPS5413453B1 (enrdf_load_stackoverflow)
CA (1) CA928248A (enrdf_load_stackoverflow)
FR (1) FR2081754B1 (enrdf_load_stackoverflow)
GB (1) GB1351634A (enrdf_load_stackoverflow)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5688560A (en) * 1993-11-09 1997-11-18 Henkel Corporation Process for coating metal surfaces
US5760112A (en) * 1994-02-23 1998-06-02 Henkel Corporation Water-borne autodepositing coating compositions
WO2014151311A1 (en) * 2013-03-15 2014-09-25 Henkel Ag & Co. Kgaa Electrodeposition of an autodepositable polymer

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1592993A (enrdf_load_stackoverflow) * 1967-12-04 1970-05-19

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5688560A (en) * 1993-11-09 1997-11-18 Henkel Corporation Process for coating metal surfaces
US5760112A (en) * 1994-02-23 1998-06-02 Henkel Corporation Water-borne autodepositing coating compositions
WO2014151311A1 (en) * 2013-03-15 2014-09-25 Henkel Ag & Co. Kgaa Electrodeposition of an autodepositable polymer
US9115442B2 (en) 2013-03-15 2015-08-25 Henkel Ag & Co. Kgaa Electrodeposition of an autodepositable polymer

Also Published As

Publication number Publication date
DE2110578B2 (de) 1977-03-10
GB1351634A (en) 1974-05-01
FR2081754B1 (enrdf_load_stackoverflow) 1974-04-05
DE2110578A1 (de) 1971-09-16
FR2081754A1 (enrdf_load_stackoverflow) 1971-12-10
JPS5413453B1 (enrdf_load_stackoverflow) 1979-05-31
CA928248A (en) 1973-06-12

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Date Code Title Description
AS Assignment

Owner name: AMCHEM PRODUCTS, INC. A CORP. OF DEL.

Free format text: MERGER;ASSIGNORS:AMCHEM PRODUCTS, INC. (MERGED INTO);HHC, INC. (CHANGED TO);REEL/FRAME:004102/0461

Effective date: 19810320