WO2007123276A1 - 耐食性、耐黒変性、塗装密着性及び耐アルカリ性に優れる複合皮膜処理亜鉛含有めっき鋼材 - Google Patents
耐食性、耐黒変性、塗装密着性及び耐アルカリ性に優れる複合皮膜処理亜鉛含有めっき鋼材 Download PDFInfo
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- WO2007123276A1 WO2007123276A1 PCT/JP2007/059141 JP2007059141W WO2007123276A1 WO 2007123276 A1 WO2007123276 A1 WO 2007123276A1 JP 2007059141 W JP2007059141 W JP 2007059141W WO 2007123276 A1 WO2007123276 A1 WO 2007123276A1
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C21/00—Alloys based on aluminium
- C22C21/10—Alloys based on aluminium with zinc as the next major constituent
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C18/00—Alloys based on zinc
- C22C18/04—Alloys based on zinc with aluminium as the next major constituent
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
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- 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
- C23C22/05—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 using aqueous solutions
- C23C22/60—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 using aqueous solutions using alkaline aqueous solutions with pH greater than 8
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- 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
- C23C22/05—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 using aqueous solutions
- C23C22/60—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 using aqueous solutions using alkaline aqueous solutions with pH greater than 8
- C23C22/66—Treatment of aluminium or alloys based thereon
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- 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
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
- C23C28/321—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer with at least one metal alloy layer
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- 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
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
- C23C28/322—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer only coatings of metal elements only
- C23C28/3225—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer only coatings of metal elements only with at least one zinc-based layer
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- 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
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
- C23C28/345—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer
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- 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
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- 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
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- 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.]
- Y10T428/12736—Al-base component
- Y10T428/1275—Next to Group VIII or IB metal-base component
- Y10T428/12757—Fe
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- 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
- Y10T428/12785—Group IIB metal-base component
- Y10T428/12792—Zn-base component
- Y10T428/12799—Next to Fe-base component [e.g., galvanized]
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- 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
- Y10T428/12819—Group VB metal-base component
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- 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
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- Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
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- Y10T428/12861—Group VIII or IB metal-base component
- Y10T428/12937—Co- or Ni-base component next to Fe-base component
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- 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
- Y10T428/12861—Group VIII or IB metal-base component
- Y10T428/12951—Fe-base component
- Y10T428/12972—Containing 0.01-1.7% carbon [i.e., steel]
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- 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
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- Y10T428/27—Web or sheet containing structurally defined element or component, the element or component having a specified weight per unit area [e.g., gms/sq cm, lbs/sq ft, etc.]
Definitions
- the present invention is an uncoated or painted steel material for use.
- the present invention relates to a composite film-treated steel material with excellent corrosion resistance, blackening resistance, paint adhesion and alkali resistance.
- the present invention relates to a composite film-treated steel material with excellent corrosion resistance, blackening resistance, paint adhesion and alkali resistance.
- the present invention relates to a zinc-containing galvanized steel material that has been subjected to a composite film treatment that does not contain any chromium and that imparts blackening resistance, paint adhesion, and alkali resistance.
- Plated steel materials including zinc-containing galvanized steel materials, are widely used as components for building materials, automobiles, home appliances, etc. due to the high anticorrosion function of the plating layer metal materials.
- an electrolyte such as salt contained in the atmosphere, oxygen present in a high-temperature and high-humidity environment, and a phenomenon that corrodes white coral by being oxidized by moisture.
- the steel material that appears hot and humid appears to turn black in a specific environment. All of these phenomena are caused by deterioration of the metal material with the adhesive layer, and may be regarded as a problem from the viewpoint of quality and design when incorporated into various products as described above.
- the coating film may be peeled off due to the generation or accumulation of corrosion products, which may cause problems in design and practicality.
- slagging steel is molded and processed, and then washed with a degreasing agent that exhibits strength. In this case, if it is not durable against alkali, it will discolor or corrode prematurely under use.
- a treatment liquid containing chromium such as chromate chromate and phosphate chromate is brought into contact with the surface of the steel plate.
- Surface treatment has been applied by the method. This avoids the above problem by forming what is commonly called a reactive chromate film on the surface of the steel plate.
- the chromate film obtained by these treatments is mainly composed of trivalent chromium. Although the toxic hexavalent chromium is hardly dissolved, the corrosion resistance is not sufficient. If the damage is large, the corrosion resistance of the steel plate will decrease.
- a coating type chromate treatment obtained by applying a treatment liquid containing hexavalent chromium to a material by roll coating or the like and drying it contains a large amount of hexavalent chromium in the film to be formed. Therefore, the chromate film has excellent corrosion resistance even if it is damaged due to processing or scratches, but hexavalent chromium may be eluted from the cuprate film.
- the chromate-treated film containing hexavalent chromium has an adverse effect if it accumulates in the human body due to its toxicity. It can be said that there is a problem from the viewpoint of conservation.
- Japanese Patent Application Laid-Open No. 2 0 2-3 3 2 5 7 4 describes a chromate alternative technique for coating the surface of a steel material with a treatment liquid not containing chromate.
- a treatment solution containing zirconium carbonate complex ion, vanadyl ion, dimercapto succinic acid, etc. is applied and heated and dried to form a dense three-dimensional film and adsorbed on the surface metal.
- a technology that has excellent corrosion resistance due to its high ability to be applied has been proposed.
- the inventors processed zinc-containing steel with an aqueous solution having a specific composition, so that excellent corrosion resistance, blackening resistance, paint adhesion and It was found that a composite film-treated zinc-containing galvanized steel material having alkali resistance was obtained, and the present invention was completed.
- the present invention provides a basic zirconium compound, vanadyl (V o 2 + ) A composite film formed by applying a treatment solution of pH 7 to l 4 containing a compound, phosphate compound, cobalt compound, organic acid and water to the surface of a steel plate and drying it.
- the composite film is composed of 10 to 45 mass% of Vr, 10 to 45 mass% of P, 5 to 100 mass% of P, 0.1 to 20 mass% of Co,
- the present invention relates to a zinc-plated galvanized steel material that is excellent in corrosion resistance, blackening resistance, paint adhesion, and aluminum resistance, characterized by containing an organic acid in a proportion of 10 to 90% by mass.
- the total film mass of the above film is preferably 50 to 200,000 m / m 2 , and is preferably 100 to 150 O mg / m 2 , corrosion resistance, blackening resistance Particularly preferred for improving coating adhesion and alkali resistance.
- the composite film-treated zinc-containing steel material according to the present invention has extremely excellent performances in all of corrosion resistance, blackening resistance, paint adhesion, and alkali resistance, and therefore the present invention has an extremely significant industrial significance. .
- the composite film in the present invention is formed from a pH 7 to 14 treatment solution containing a basic zirconium compound, a vanadyl (vo 2 + ) -containing compound, a phosphoric acid compound, a cobalt compound, an organic acid and water.
- a basic zirconium compound is a compound that supplies the Zr element in the composite film.
- Basic zirconium compound is not particularly limited, for example, carbonate with [Z r (C_ ⁇ 3) 2 (OH) 2] or [Z r (C_ ⁇ 3) 3 (OH)] as a cationic Zirconium compounds, ammonium salts containing these cations, potassium salts, sodium salts, and the like.
- the compound containing vanadyl (V0 2 + ) supplies V element in the composite film. It is a compound.
- the vanadyl (V0 2 + )-containing compound is not particularly limited.
- an oxovanadium cation and an inorganic acid anion or formic acid such as hydrochloric acid, nitric acid, phosphoric acid or sulfuric acid, acetic acid, propionic acid, It can be a salt with an organic acid anion such as butyric acid or oxalic acid.
- a chelate of an organic acid and a vanadyl compound such as vanadyl glycolate or vanadyl dehydroascorbate may be used.
- the elemental V is 10 to 45% by mass with respect to 2100% by mass. If V is less than 10% by mass, corrosion resistance and alkali resistance may be reduced. When V is more than 45% by mass, blackening resistance and paint adhesion deteriorate.
- the amount of V in the composite film is preferably 15 to 30% by mass, more preferably 20 to 25% by mass with respect to Zr 100% by mass.
- Phosphoric acid compounds are compounds that supply element P in the composite film.
- the phosphoric acid compound is not particularly limited, but may be phosphoric acid and its ammonium salt. More specifically, for example, orthophosphoric acid, pyrophosphoric acid, metaphosphoric acid, polyphosphoric acid, phytic acid, phosphonic acid, ammonium phosphate, ammonium dihydrogen phosphate, ammonium dihydrogen phosphate, sodium phosphate, phosphoric acid Examples include potassium.
- the elemental P is present in an amount of 5 to 100% by mass with respect to 1 "10% by mass. If P is less than 5% by mass, the corrosion resistance decreases, and the mass is 100% by mass.
- the amount of P in the composite film is preferably 10 to 70% by mass with respect to Zr 100% by mass, and the blackening resistance, coating film adhesion, and alkali resistance decrease. More preferably, it is 10 to 40% by mass, and particularly preferably 12 to 20% by mass.
- Cobalt compound is a compound that supplies Co element in the composite film.
- the cobalt compound is not particularly limited, and may be, for example, cobalt carbonate, cobalt nitrate, cobalt sulfate, or cobalt acetate.
- the elemental Co is 0.1 to 20% by mass with respect to Zr 100% by mass.
- Co is less than 0.1% by mass, blackening resistance decreases, and when Co is more than 20% by mass, corrosion resistance, alkali resistance and coating film adhesion decrease.
- the amount of Co in the composite film is preferably 0.5 to 10% by mass, more preferably 0.5 to 5% by mass, and particularly preferably 0.8 to 0% by mass with respect to Zr 100 mass. 1. 5% by mass.
- the composite coating in the present invention contains an organic acid.
- organic acids include, but are not limited to, glycolic acid, lingoic acid, tartaric acid, oxalic acid, citrate, ascorbic acid, lactic acid, dehydrobenzoic acid, dehydroascorbic acid, gallic acid
- acids, tannic acid, and phytic acid include acids, tannic acid, and phytic acid. In some cases, ammonium salts of these organic acids can be used.
- organic acids 1 "It is 10 to 90% by mass with respect to 100% by mass.
- the organic acid is less than 10% by mass with respect to Zr 100% by mass, the corrosion resistance and paint adhesion are slightly inferior.
- the preservability of the processing solution will be reduced, ie, the organic acid includes vanadyl (vo 2 + ) -containing compounds, basic zirconium compounds, phosphoric acid.
- the organic acid with respect to Zr 100 mass% in the composite film If more than 90% by mass, paint adhesion and alkali resistance will decrease.
- the amount of the organic acid in the composite film is preferably 10 to 70% by mass, preferably 10 to 50% by mass, particularly preferably 15 to 10% by mass of Zr. ⁇ 30% by mass.
- the composite film-treated zinc-containing steel material of the present invention comprises a basic zirconium compound, vanadyl (vo 2 + ) in an amount to supply Zr, V, P, Co elements and organic acid in the composite film at the above-mentioned ratio. It can be produced by applying an aqueous solution containing a containing compound, a phosphorylated compound, a cobalt compound, and an organic acid to the surface of the steel plate and drying it by heating to form a film.
- the treatment solution is preferably pH 7-14. Within this pH range, the basic zirconium compound can be stably water-solubilized.
- the pH of the treatment liquid is preferably 8 to 11, and particularly preferably 8 to 10.
- the following substances can be used as pH adjusting agents. For example, ammonia water, triethylamine, triethanolamine, phosphoric acid, nitric acid, hydrofluoric acid, carbonic acid, ammonium fluoride, etc., pH adjusters must significantly reduce the stability of the processing solution. There is no particular limitation.
- the formed film is a composite film having a dense three-dimensional structure, excellent barrier properties, and improved corrosion resistance.
- One reason for the formation of such a composite film is that organic acids and metal ions are coordinated by complex formation, and a dense three-dimensional structure is formed mainly by Zr—O. This is because V, organic acid, P, and Co are mixed with each other, and zinc that has been taken in by etching of the mating surface is taken in. In the dense three-dimensional structure of Z r — O, some Z r may be replaced with other elements. Furthermore, etching of the plating surface with an organic acid during the formation of the composite film increases the adhesion at the interface between the film and the plating surface, thereby improving the corrosion resistance and paint adhesion.
- the plated steel material on which the composite film is formed on the surface is not particularly limited as long as the plating layer contains zinc.
- a plated steel material having a plating layer made of zinc and inevitable impurities may be used.
- a plated steel material with a plating layer containing Al, Mg, Si, Ti, Ni, Fe, etc. as an alloy component with zinc is used. May be used.
- a particularly preferred plating layer contains, in addition to zinc (and inevitable impurities), at least one of A 1 of 60% by mass or less, Mg of 10% by mass or less, and Si of 2% by mass or less. To do.
- the plating layer of the plated steel material may be formed by any plating method.
- the plating layer may be formed by any one of fusion plating, electric plating, vapor deposition plating, dispersion plating, vacuum plating, and the like.
- examples of the melt adhesion method include a flux method, a Sendzimir method, and a method of ensuring wettability by performing pre-plating such as Ni, and any of them may be used.
- the steel plate is sprayed with water spray, air spray, sprayed with sodium phosphate aqueous solution, zinc powder, zinc phosphate powder, magnesium hydrogen phosphate. You may spray powder or those aqueous solution.
- the surface may be adjusted with cobalt sulfate or a nickel sulfate solution as a pretreatment after the plating and after the composite film treatment.
- any method for applying the treatment liquid to the surface of the plated steel material any method such as a spray method, a dipping method, a roll coating method, a shower ringer method, an air-knife method, and the like can be used.
- the surfactant is added to the treatment liquid as long as the original performance is not impaired.
- an organic solvent may be added.
- lubricants and fillers in the treatment liquid such as molybdenum disulfide, dulphite, tungsten disulfide, boron nitride, graphite fluoride, cerium fluoride, melamine cyanurate, fluororesin wax, polyolefin wax,
- colloidal silica, vapor phase silica or the like it is possible to prevent scratches and wear during processing of the composite film-treated zinc-containing tempered steel material of the present invention.
- the range of the total film mass of the composite film on the surface of the plated steel material is preferably about 50 to 20 OmgZm2. Within this range, it is possible to obtain a composite film-treated zinc-containing galvanized steel material having good corrosion resistance, blackening resistance, paint adhesion and alkali resistance, which is the object of the present invention.
- a particularly preferable total coating amount range of the composite membrane is 100 to 1500 mg / m 2 . If it is less than 100 mgZm 2 , the corrosion resistance, blackening resistance and alkali resistance may be lowered. If it exceeds 1 5 0 OmgZm 2 , the film becomes brittle and the alkali resistance and paint adhesion may be reduced.
- the plated steel material When the plated steel material is treated with the treatment liquid, it is preferably heat-dried in the range of 50 ° C. to 200 ° C. at the ultimate plate temperature.
- the heating method is not particularly limited, and any method such as hot air, direct fire, induction heating, infrared, electric furnace or the like can be used.
- Table 1 shows the composition ratios of Zr, V, P, Co, and organic acid of the composite film produced.
- the compounds used in the treatment liquid are as shown in the following symbols.
- a 2 Sodium zirconium carbonate
- V B1: Vanadyl acetate
- Treatment liquid that contains Zr, V, P, Co, and organic acid, and the ratio of V and organic acid to Zr 100% by mass is outside the scope of the present invention (both V and organic acid are large)
- the composite coating is prepared by applying a treatment solution whose components are diluted with deionized water to a predetermined concentration and applying it to the surface of the steel with a roll coater so that a predetermined dry coating amount is obtained, and immediately using a hot air dryer. Then, it was dried by heating so that the ultimate plate temperature was 80 ° C.
- the pH of the treatment solution was 9. Table 2 shows the processing conditions and test evaluation results for the prepared specimens.
- the steel used for shirring is represented by the following symbols.
- a salt spray test according to JISZ 2 3 7 1 was performed on the flat and cross-cut specimens up to 2400 hours. Corrosion resistance was determined based on the area ratio of white birch generation after the salt spray test.
- Cross-cut specimen (including cut and surrounding white coral)
- composition of composite film (compound is the compound used in the treatment liquid)
- the composite film-treated zinc-containing tempered steel material according to the present invention has corrosion resistance (evaluation with flat plate test pieces and cross-cut processing test pieces), blackening resistance, paint adhesion, and alkali resistance. It is clear that it has good performance.
- test pieces with a total coating mass of 100 to 1500 mg / m 2 showed excellent results for all evaluations of corrosion resistance, blackening resistance, paint adhesion, and alkali resistance. It was.
- none of the plated steel materials of the comparative examples could satisfy all the performances of corrosion resistance, blackening resistance, paint adhesion, and alkali resistance.
Abstract
Description
Claims
Priority Applications (11)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
NZ572946A NZ572946A (en) | 2006-04-20 | 2007-04-20 | Zinc-plated steel material coated with composite film excellent in corrosion resistance, unsusceptibility to blackening, coating adhesion, and alkali resistance |
JP2008512199A JP5258557B2 (ja) | 2006-04-20 | 2007-04-20 | 耐食性、耐黒変性、塗装密着性及び耐アルカリ性に優れる複合皮膜処理亜鉛含有めっき鋼材 |
EP07742576A EP2011900B1 (en) | 2006-04-20 | 2007-04-20 | Zinc-plated steel material coated with composite film excellent in corrosion resistance, unsusceptibility to blackening, coating adhesion, and alkali resistance |
CN2007800137854A CN101421435B (zh) | 2006-04-20 | 2007-04-20 | 耐腐蚀性、抗变黑性、涂装密合性和耐碱性优异的复合皮膜处理含锌镀覆钢材 |
MX2008013219A MX2008013219A (es) | 2006-04-20 | 2007-04-20 | Material de acero galvanizado con zinc revestido con pelicula mixta excelente para resistencia a la corrosion, no susceptible a ennegrecimiento, adhesion de revestimiento y resistencia alcalina. |
KR1020087028190A KR101161101B1 (ko) | 2006-04-20 | 2007-04-20 | 내식성, 내흑변성, 도장 밀착성 및 내알칼리성이 우수한 복합 피막 처리 아연 함유 도금 강재 |
BRPI0710818-4A BRPI0710818B1 (pt) | 2006-04-20 | 2007-04-20 | Material de aço laminado contendo zinco revestido de compósito, superior em resistência à corrosão, resistência ao enegrecimento, adesão do revestimento e resistência ao álcali |
KR1020117018024A KR101257596B1 (ko) | 2006-04-20 | 2007-04-20 | 내식성, 내흑변성, 도장 밀착성 및 내알칼리성이 우수한 복합 피막 처리 아연 함유 도금 강재 |
US12/226,388 US8263232B2 (en) | 2006-04-20 | 2007-04-20 | Composite coated zinc-containing plated steel material superior in corrosion resistance, blackening resistance, coating adhesion, and alkali resistance |
ES07742576T ES2391988T3 (es) | 2006-04-20 | 2007-04-20 | Material de acero chapado que contiene cinc revestido con material compuesto que tiene excelentes características de resistencia a la corrosión, resistencia al ennegrecimiento, adherencia del revestimiento y resistencia a los álcalis |
AU2007241748A AU2007241748B2 (en) | 2006-04-20 | 2007-04-20 | Zinc-plated steel material coated with composite film excellent in corrosion resistance, unsusceptibility to blackening, coating adhesion, and alkali resistance |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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JP2006-116751 | 2006-04-20 | ||
JP2006116751 | 2006-04-20 |
Publications (1)
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WO2007123276A1 true WO2007123276A1 (ja) | 2007-11-01 |
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PCT/JP2007/059141 WO2007123276A1 (ja) | 2006-04-20 | 2007-04-20 | 耐食性、耐黒変性、塗装密着性及び耐アルカリ性に優れる複合皮膜処理亜鉛含有めっき鋼材 |
Country Status (14)
Country | Link |
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US (1) | US8263232B2 (ja) |
EP (1) | EP2011900B1 (ja) |
JP (1) | JP5258557B2 (ja) |
KR (2) | KR101161101B1 (ja) |
CN (1) | CN101421435B (ja) |
AU (1) | AU2007241748B2 (ja) |
BR (1) | BRPI0710818B1 (ja) |
ES (1) | ES2391988T3 (ja) |
MX (1) | MX2008013219A (ja) |
MY (1) | MY145935A (ja) |
NZ (1) | NZ572946A (ja) |
RU (1) | RU2418098C2 (ja) |
TW (1) | TW200809006A (ja) |
WO (1) | WO2007123276A1 (ja) |
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JP2010150626A (ja) * | 2008-12-26 | 2010-07-08 | Nippon Parkerizing Co Ltd | 亜鉛めっき加工用後処理剤およびこれを用いて表面処理した亜鉛めっき加工材 |
CN102459700A (zh) * | 2009-05-19 | 2012-05-16 | 汉高股份有限及两合公司 | 用于金属底物的微碱性薄无机防腐涂层 |
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- 2007-04-20 US US12/226,388 patent/US8263232B2/en active Active
- 2007-04-20 AU AU2007241748A patent/AU2007241748B2/en active Active
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- 2007-04-20 MY MYPI20084144A patent/MY145935A/en unknown
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- 2007-04-20 ES ES07742576T patent/ES2391988T3/es active Active
- 2007-04-20 WO PCT/JP2007/059141 patent/WO2007123276A1/ja active Application Filing
- 2007-04-20 JP JP2008512199A patent/JP5258557B2/ja active Active
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WO2009143144A1 (en) | 2008-05-19 | 2009-11-26 | Henkel Ag & Co. Kgaa | Midly alkaline thin inorganic corrosion protective coating for metal substrates |
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JP2010150626A (ja) * | 2008-12-26 | 2010-07-08 | Nippon Parkerizing Co Ltd | 亜鉛めっき加工用後処理剤およびこれを用いて表面処理した亜鉛めっき加工材 |
CN102459700A (zh) * | 2009-05-19 | 2012-05-16 | 汉高股份有限及两合公司 | 用于金属底物的微碱性薄无机防腐涂层 |
AU2009346389B2 (en) * | 2009-05-19 | 2016-08-18 | Henkel Ag & Co. Kgaa | Mildly alkaline thin inorganic corrosion protective coating for metal substrates |
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AU2014222132B2 (en) * | 2013-02-28 | 2015-11-19 | Nihon Parkerizing Co., Ltd. | Aluminium-zinc plated steel sheet and method for producing the same |
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JPWO2016093286A1 (ja) * | 2014-12-10 | 2017-08-03 | 新日鐵住金株式会社 | 亜鉛めっき鋼板用表面処理剤 |
KR101918879B1 (ko) | 2014-12-10 | 2018-11-14 | 신닛테츠스미킨 카부시키카이샤 | 아연 도금 강판용 표면 처리제 |
JP2017197784A (ja) * | 2016-04-25 | 2017-11-02 | 新日鐵住金株式会社 | めっき溶接形鋼及びめっき溶接形鋼の製造方法 |
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Also Published As
Publication number | Publication date |
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AU2007241748B2 (en) | 2010-12-16 |
US20090202859A1 (en) | 2009-08-13 |
JPWO2007123276A1 (ja) | 2009-09-10 |
ES2391988T3 (es) | 2012-12-03 |
EP2011900A1 (en) | 2009-01-07 |
KR101161101B1 (ko) | 2012-06-29 |
BRPI0710818B1 (pt) | 2018-01-23 |
TW200809006A (en) | 2008-02-16 |
TWI374198B (ja) | 2012-10-11 |
RU2418098C2 (ru) | 2011-05-10 |
AU2007241748A1 (en) | 2007-11-01 |
KR20110094226A (ko) | 2011-08-22 |
EP2011900B1 (en) | 2012-07-25 |
RU2008145739A (ru) | 2010-05-27 |
MX2008013219A (es) | 2008-10-22 |
JP5258557B2 (ja) | 2013-08-07 |
NZ572946A (en) | 2011-07-29 |
KR101257596B1 (ko) | 2013-04-26 |
CN101421435A (zh) | 2009-04-29 |
CN101421435B (zh) | 2012-07-18 |
EP2011900A4 (en) | 2011-05-25 |
MY145935A (en) | 2012-05-31 |
US8263232B2 (en) | 2012-09-11 |
KR20090008366A (ko) | 2009-01-21 |
BRPI0710818A2 (pt) | 2011-08-23 |
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