WO2008136496A1 - Tôle d'acier revêtue d'un alliage zn-al immergé à chaud, traitée en surface - Google Patents

Tôle d'acier revêtue d'un alliage zn-al immergé à chaud, traitée en surface Download PDF

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Publication number
WO2008136496A1
WO2008136496A1 PCT/JP2008/058320 JP2008058320W WO2008136496A1 WO 2008136496 A1 WO2008136496 A1 WO 2008136496A1 JP 2008058320 W JP2008058320 W JP 2008058320W WO 2008136496 A1 WO2008136496 A1 WO 2008136496A1
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WIPO (PCT)
Prior art keywords
titanium
mass
compound
surface treatment
water
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PCT/JP2008/058320
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English (en)
Japanese (ja)
Inventor
Rie Umebayashi
Nobue Fujibayashi
Satoru Ando
Akira Matsuzaki
Toru Imokawa
Takashi Nakano
Jun Akui
Shinichiro Nitta
Hideo Koumura
Original Assignee
Jfe Steel Corporation
Kansai Paint Co., Ltd.
Jfe Galvanizing & Coating Co., Ltd.
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Priority claimed from JP2008102943A external-priority patent/JP5317516B2/ja
Application filed by Jfe Steel Corporation, Kansai Paint Co., Ltd., Jfe Galvanizing & Coating Co., Ltd. filed Critical Jfe Steel Corporation
Publication of WO2008136496A1 publication Critical patent/WO2008136496A1/fr

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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
    • C23C22/06—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 aqueous acidic solutions with pH less than 6
    • C23C22/34—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 aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
    • 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
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/04—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the coating material
    • C23C2/06—Zinc or cadmium or alloys based thereon
    • 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
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/26—After-treatment
    • 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
    • C23C22/06—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 aqueous acidic solutions with pH less than 6
    • C23C22/40—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 aqueous acidic solutions with pH less than 6 containing molybdates, tungstates or vanadates
    • C23C22/44—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 aqueous acidic solutions with pH less than 6 containing molybdates, tungstates or vanadates containing also fluorides or complex fluorides
    • 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
    • C23C28/02—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 only coatings only including layers of metallic material
    • C23C28/021—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 only coatings only including layers of metallic material including at least one metal alloy layer

Definitions

  • the present invention relates to a surface-treated molten Z n -A 1 alloy-plated steel sheet that is optimal for use in automobiles, home appliances, and building materials.
  • the present invention relates to a surface treatment composition and a surface treatment film formed thereby. This relates to an environmentally-adapted surface-treated steel plate that does not contain any chromium. Background art
  • molten Z n -A 1 alloy-plated steel sheets have been widely used.
  • this hot-dip Zn-A 1 alloy-plated steel sheet mainly the hot-dip Zn-plated steel sheet (hereinafter referred to as GI) having an A1 content of 0.2 mass% or less in the plating layer, the same A1 content Galfan (hereinafter referred to as GF) with an amount of approximately 5% by mass and Galparium steel sheet (hereinafter referred to as GL) with an A1 content of approximately 55% by mass are used.
  • GF has a lower cost than GL and has better corrosion resistance than GI, so demand is particularly high in the field of construction.
  • demand for home appliances is expected to increase as a substitute for heavyweight Zn-plated steel sheets.
  • GF generally has the following problems.
  • a spangle with a tortoiseshell pattern is formed on GF.
  • the shape of this spangle varies depending on the plating conditions (eg, annealing before plating, bath components), cooling conditions after plating (eg, cooling rate), etc.
  • the appearance may be damaged when used naked.
  • spangles may float on the painted surface, which may impair the appearance after painting. For this reason, in recent years, there has been an increasing demand for GF having a beautiful plating layer with a metallic luster without spangle.
  • the plated steel sheet surface is replaced with an aqueous solution containing ions such as Fe, Ni, Co, etc., and Fe, Ni, Co, etc. are deposited on the surface of the plating layer.
  • an aqueous solution containing ions such as Fe, Ni, Co, etc., and Fe, Ni, Co, etc. are deposited on the surface of the plating layer.
  • Patent Document 1 There is a method (for example, Patent Document 1).
  • this method requires a new replacement process, which complicates the manufacturing process. Therefore, a technique for improving blackening resistance at the same time in the chemical conversion treatment step for the purpose of imparting corrosion resistance is required.
  • Patent Document 1 Japanese Patent Application Laid-Open No. 5 9-1 7 7 3 8 1
  • Patent Document 2 Japanese Patent Laid-Open No. 2 0 0 4 — 2 9 5 0
  • Patent Document 3 International Publication No. 2 0 0 3/9 3 5 3 No. 3
  • Patent Document 4 Japanese Patent Laid-Open No. 2 0 0 3-3 0 6 7 7 7 Disclosure of Invention
  • the object of the present invention is to provide a surface-treated molten Zn n -A 1-based alloy that does not contain hexavalent chromium in the surface treatment composition or coating, has excellent blackening resistance and corrosion resistance, and has excellent plating appearance. It is to provide a steel plate with a wall.
  • the plating composition is based on the general A1 concentration of GF, and by containing appropriate amounts of Mg and Ni, spangle-free or very fine spangles are formed. It is possible to obtain a hot-dip Zn-A1 alloy-plated steel sheet that has a beautiful metallic appearance with a high metallic luster and improved blackening resistance.
  • Ni salt or Z and Co salts were added to the treatment liquid. It has been found that adding it is effective. However, if Ni salt, Co salt, etc. are added to the processing solution as they are, the corrosion resistance will be reduced. In order to improve blackening resistance without deteriorating corrosion resistance, it is necessary to add Ni salt, Co salt, etc. to the treatment solution and to form a dense reaction layer on the surface of the adhesive film by treatment. is there.
  • the present invention has been made on the basis of such findings and has the following gist.
  • At least one surface of the steel sheet contains A 1: 1 ⁇ 10 to 10% by mass, Mg: 0.2 to 1.0% by mass, Ni: 0.005 to 0.1% by mass
  • the fluorine-containing compound (C) is at least one selected from zircon ammonium fluoride and zircon hydrofluoric acid.
  • the surface treatment composition (H) further contains an organophosphate compound (D) in a solid content ratio.
  • the surface treatment composition (H) 1 and the panadic acid compound (E) A surface-treated molten Z nA 1 -based alloy-plated steel sheet, characterized by containing 0.1 to 30% by mass.
  • the surface treatment composition (H) 1 is further dispersed in a water-soluble organic resin or / and water.
  • the surface-treated molten Z n -A 1 alloy-plated steel sheet of the present invention is a surface treatment in which a specific titanium-containing aqueous liquid, a nickel compound or / and a cobalt compound, and a fluorine-containing compound are blended at a predetermined ratio.
  • a specific titanium-containing aqueous liquid, a nickel compound or / and a cobalt compound, and a fluorine-containing compound are blended at a predetermined ratio.
  • Fig. 1 is a graph showing the relationship between the Mg content in the plating layer and the plating appearance for a molten Zn-A1 alloy-plated steel sheet having a GF composition plating layer containing an appropriate amount of Ni .
  • Fig. 2 A, Fig. 2 B, and Fig. 2 C are GF-composite molten Zn—A1 alloy-plated steel plates, plated steel containing only Mg in the plating layer, plating layer 4 is a graph showing the component analysis results in the plating layer depth direction for a steel plate containing only N in the steel plate and a steel plate containing Mg and Ni in the plating layer.
  • the molten Zn-A1 alloy-plated steel sheet which is the base of the surface-treated molten ZII-A1 alloy-plated steel sheet (hereinafter referred to as "surface-treated plated steel sheet" for convenience), is at least one of the steel sheets.
  • the balance has a molten Zn—A1-based alloy plating layer consisting of Zn and inevitable impurities. The reason for limiting the plating composition of this molten Z11-1A1 alloy-plated steel sheet and preferred manufacturing conditions will be described in detail later.
  • the surface-treated film formed on the surface of the molten Zn—A 1-based alloy plated layer is a hydrolyzable titanium compound, a hydrolyzable titanium compound low-condensate, or titanium hydroxide.
  • a titanium-containing aqueous liquid (A) obtained by mixing at least one titanium compound selected from low-condensation products of titanium hydroxide with hydrogen peroxide water, a nickel compound and / or a cobalt compound ( B) and a fluorine-containing compound (C) at a predetermined ratio, and if necessary, an organic phosphate compound (D), a panadic acid compound (E), a zirconium carbonate compound (F), a water-soluble organic compound It is formed by applying and drying a surface treatment composition (H) containing one or more of a resin and / or a water-dispersible organic resin (G) in a predetermined ratio.
  • the titanium-containing aqueous liquid (A) is a hydrolysable titanium compound, a low condensate of a hydrolysable titanium compound, titanium hydroxide, or a low condensate of titanium hydroxide. It is an aqueous liquid containing titanium obtained by mixing hydrogen peroxide water.
  • the hydrolyzable titanium compound is a titanium compound having a hydrolyzable group directly bonded to titanium, and generates titanium hydroxide by reacting with water such as water or water vapor.
  • the hydrolyzable titanium compound may be one in which all of the groups bonded to titanium are hydrolyzable groups, or may be one in which a part of the groups bonded to titanium is a hydrolyzable group.
  • the hydrolyzable group may be hydroxylated by reacting with ice as described above.
  • ice there are no particular limitations as long as it produces titanium, but examples include lower alkoxyl groups and groups that form salts with titanium (for example, halogen atoms such as chlorine, hydrogen atoms, sulfate ions, etc.).
  • hydrolyzable titanium compound containing a lower alkoxyl group as a hydrolyzable group in particular, the general formula T i (OR) 4 (wherein R is the same or different carbon number)
  • a tetraalkoxytitanium represented by 1 to 5 examples include a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butynole group, an iso-butyl group, a sec 1-butyl group, and a tert 1-butyl group. Can be mentioned.
  • hydrolyzable titanium compounds having a group capable of forming a salt with titanium as a hydrolyzable group include titanium chloride and titanium sulfate.
  • the low condensate of the hydrolyzable titanium compound is a low condensate of the above hydrolyzable titanium compounds.
  • the low condensate may be one in which all of the groups bonded to titanium are hydrolyzable groups, or may be one in which some of the groups bonded to titanium are hydrolyzable.
  • hydrolyzable titanium compounds whose hydrolyzable groups form a salt with titanium for example, titanium chloride, titanium sulfate, etc.
  • an aqueous solution of the hydrolyzable titanium compound and an alkaline solution such as ammonia or caustic soda are used.
  • Orthotitanic acid (titanium hydroxide gel) obtained by reaction with a solution can also be used as a low condensate.
  • hydrolyzable titanium compound low condensate and titanium hydroxide low condensate compounds having a degree of condensation of 2 to 30 can be used, and in particular, compounds having a degree of condensation of 2 to 10 are used. It is preferable. When the degree of condensation exceeds 30, a white precipitate is formed when mixed with hydrogen peroxide, and a stable titanium-containing aqueous liquid cannot be obtained. That is, when the degree of condensation is 30 or less, a stable titanium-containing aqueous liquid can be obtained by mixing with hydrogen peroxide.
  • the hydrolyzable titanium compounds, low-condensates of hydrolyzable titanium compounds, low-condensates of hydrous titanium oxide, and titanium hydroxide can be used alone or in combination of two or more.
  • Tetraalkoxy titanium which is a hydrolyzable titanium compound represented by the general formula, is particularly preferred.
  • the reason for this is that tetraalkoxytitanium is volatilized during the process of drying the surface treatment composition by the alcohol produced when hydrolyzed. Therefore, the film performance such as corrosion resistance is not affected, and particularly excellent film performance can be obtained.
  • any conventionally known liquid can be used without particular limitation as long as it is an aqueous liquid containing titanium obtained by mixing the above-described titanium compound or hydrogen peroxide water. . Specifically, the following can be mentioned.
  • Titanium ion hydrogen peroxide complex or titanic acid peroxotitanium hydrate aqueous solution obtained by adding hydrogen peroxide ice to hydrous titanium oxide gel or sol (Japanese Patent Laid-Open No. 6-3-3 5 4 1 9 No. 1 and Japanese Patent Laid-Open No. 1-2 2 4 2 2 0).
  • Titania film-forming liquid obtained by synthesizing a titanium hydroxide gel produced from an aqueous solution and a basic solution of titanium chloride and titanium sulfate by allowing hydrogen peroxide to act on the gel.
  • a titanium hydroxide gel called orthotitanic acid is obtained by reacting an aqueous solution of titanium chloride or titanium sulfate having a salt-forming group with titanium and an alkaline solution such as ammonia or caustic soda. To settle. Next, the titanium hydroxide gel is separated by decantation with water, washed well with water, further added with hydrogen peroxide solution to decompose and remove excess hydrogen peroxide, thereby obtaining a yellow transparent viscous liquid.
  • the ortho-titanic acid thus precipitated is in a gel state polymerized by polymerization of OH and hydrogen bonds, and cannot be used as an aqueous liquid containing titanium as it is.
  • hydrogen peroxide solution is added to this gel, a part of OH is in a peroxidized state, dissolved as peroxotitanate ions or in a kind of sol in which the polymer chain is divided into low molecules, and excess hydrogen peroxide. It decomposes into water and oxygen and can be used as an aqueous liquid containing titanium for forming an inorganic film.
  • this sol contains only oxygen and hydrogen atoms in addition to titanium atoms, when it is changed to titanium oxide by drying or firing, only water and oxygen are generated, so it is necessary for thermal decomposition of sol-gel method and sulfates. Therefore, it is not necessary to remove carbon components and halogen components, and a titanium oxide film having a relatively high density can be formed even at a low temperature.
  • a titanium-containing aqueous liquid (A) using a hydrolyzable titanium compound and Pino or its low condensate as a titanium compound (hereinafter referred to as “hydrolyzable titanium compound a” for convenience of explanation) It can be obtained by reacting with a hydrogen peroxide solution at a reaction temperature of 1 to 70 ° C. for about 10 minutes to 20 hours.
  • the aqueous titanium-containing liquid (A) using the hydrolyzable titanium compound a is obtained by reacting the hydrolyzable titanium compound a with hydrogen peroxide water to hydrolyze the hydrolyzable titanium compound a with water. It is considered that a hydroxyl group-containing titanium compound is produced, and then hydrogen peroxide is coordinated to the hydroxyl group-containing titanium compound. This hydrolysis reaction and coordination by hydrogen peroxide occur at the same time, and it produces a chelate solution that is extremely stable at room temperature and can withstand long-term storage.
  • the titanium hydroxide gel used in the conventional process is partly three-dimensional due to Ti-O-Ti bonds, and what is the titanium-containing aqueous liquid (A) that reacts this gel with hydrogen peroxide? Composition and stability are essentially different.
  • the titanium-containing aqueous liquid (A) using the hydrolyzable titanium compound a is heat-treated or autoclaved at 80 ° C. or higher, a titanium oxide dispersion containing ultrafine particles of crystallized titanium oxide is obtained.
  • the heat treatment or autoclave treatment is less than 80 ° C, crystallization of titanium oxide does not proceed sufficiently. That is, if the heat treatment or autoclave treatment is performed at 803 ⁇ 4 or more, the crystallization of titanium oxide can be sufficiently advanced.
  • the average particle diameter of the titanium oxide ultrafine particles of the titanium oxide dispersion produced in this way is desirably 10 nm or less, preferably about 1 to 6 nm.
  • the film-forming property is lowered (when the film is dried after coating to form a film, a wrinkle occurs at a film thickness of 1 ⁇ HI or more), which is not preferable.
  • the average particle size of the titanium oxide ultrafine particles is 10 nm or less, the film forming property is excellent. This is preferable.
  • the average particle diameter of the titanium oxide ultrafine particles is 1 nm or more, it is preferable because the surface treatment composition can be maintained in a state where the viscosity does not increase. The appearance of this titanium oxide dispersion is translucent.
  • Such a titanium oxide dispersion can also be used as the titanium-containing aqueous liquid (A).
  • the surface treatment composition (H) containing the titanium-containing aqueous liquid (A) using the hydrolyzable titanium compound a is applied to the surface of the plated steel sheet and dried (for example, dried by heating at a low temperature).
  • a dense titanium oxide-containing film (surface treatment film) having excellent adhesion can be formed.
  • the heating temperature of the steel sheet after applying the surface treatment composition (H 2) is, for example, preferably 200 ° C. or less, particularly preferably 150 ° C. or less. By heating and drying at such a temperature, the hydroxyl group is reduced. A slight amount of amorphous titanium oxide-containing film can be formed. Further, when the titanium oxide dispersion obtained through the heat treatment or photoclave treatment at 80 ° C. or higher as described above is used as the titanium-containing aqueous liquid (A), only the surface treatment composition (H) is applied. Because it can form a crystalline titanium oxide-containing film, it is useful as a coating material for materials that cannot be heat-treated.
  • a titanium-containing aqueous liquid (A 1) obtained by reacting a hydrolyzable titanium compound a with hydrogen peroxide in the presence of a titanium oxide sol should be used. You can also.
  • the titanium oxide sol is a sol in which amorphous titania fine particles or anatase titania fine particles are dispersed in water (for example, an aqueous organic solvent such as an alcohol or alcohol ether may be added if necessary). is there.
  • this titanium oxide sol conventionally known ones can be used. For example, (i) a titanium oxide aggregate obtained by hydrolyzing a titanium-containing solution such as titanium sulfate sulfate titanyl sulfate,
  • Titanium oxide aggregates obtained by hydrolyzing organic titanium compounds such as titanium alkoxide (iii) Titanium oxide aggregates obtained by hydrolyzing or neutralizing titanium halide solutions such as titanium tetrachloride, etc.
  • An amorphous titania sol in which the titanium oxide aggregates are dispersed in water, or a sol in which the titanium oxide aggregates are calcined to form anatase titanium fine particles, which are dispersed in water, can be used.
  • the temperature is at least higher than the crystallization temperature of anatase.
  • amorphous titania can be converted to anatase titania.
  • aqueous sols of titanium oxide include TKS-20 1 (trade name, manufactured by Tika, anatase crystal form, average particle size 6 nm), TA-15 (trade name, manufactured by Nissan Chemical Co., Ltd., Anatase crystal form), ST S-1 1 (trade name, manufactured by Ishihara Sangyo Co., Ltd., anatase crystal form).
  • the titanium-containing aqueous liquid (A1) if mass ratio X Bruno y between the titanium oxide sol X and titanium peroxide Hydrogen reactant y (reaction product of the hydrolyzable titanium compound a and hydrogen peroxide), A range of 1/9 9 to 9 9 1 is preferred, preferably about ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ . If the mass ratio xZy is less than 1_99, the effect of adding titanium oxide sol cannot be sufficiently obtained in terms of stability, photoreactivity, etc. On the other hand, if it exceeds 991, the film forming property is inferior.
  • the mass ratio xZy is 199 or more, the effect of adding the titanium oxide sol in terms of stability and photoreactivity can be sufficiently obtained, while if it is 9.9 / 1 or less, excellent production is achieved. It is preferable because film properties can be obtained.
  • Titanium-containing aqueous liquid (A 1) reacts hydrolyzable titanium compound a with hydrogen peroxide at a reaction temperature of 1 to 70 ° C for about 10 minutes to 20 hours in the presence of titanium oxide sol. Can be obtained.
  • the formation form and characteristics of the titanium-containing aqueous liquid (A 1) are the same as those of the titanium-containing aqueous liquid (A) using the hydrolyzable titanium compound a described above, but in particular, using a titanium oxide sol.
  • the partial condensation reaction during the synthesis can be prevented from thickening.
  • the reason is considered to be that the condensation reaction product is adsorbed on the surface of the titanium oxide sol, and polymerization in the solution state is suppressed.
  • titanium-containing aqueous liquid (A 1) When the titanium-containing aqueous liquid (A 1) is heat-treated or autoclaved at 80 ° C. or higher, a titanium oxide dispersion containing ultrafine particles of crystallized titanium oxide is obtained. The temperature conditions for obtaining this titanium oxide dispersion, the particle diameter of the crystallized titanium oxide ultrafine particles, the appearance of the dispersion, etc. are also included in the titanium-containing aqueous liquid (A ). Such a titanium oxide dispersion can also be used as the titanium-containing aqueous liquid (A1).
  • the surface treatment composition (H 1) containing the titanium-containing aqueous liquid (A 1) is applied to the surface of the plated steel sheet and dried (for example, heat-dried at a low temperature), so that it is dense with excellent adhesion itself.
  • a titanium oxide-containing film (surface treatment film) can be formed.
  • the heating temperature of the steel sheet after applying the surface treatment composition (H 2) is, for example, preferably 200 ° C. or less, particularly preferably 150 ° C. or less. By heating and drying at such a temperature, the hydroxyl group is reduced. An anatase-type titanium oxide-containing film containing a little can be formed.
  • the titanium-containing aqueous liquid (A) and the titanium-containing aqueous liquid (A 1) using the hydrolyzable titanium compound a have storage stability, corrosion resistance, etc. It is particularly preferable to use these in the present invention.
  • the blending ratio of hydrogen peroxide to at least one titanium compound selected from hydrolysable titanium compounds, hydrolyzable titanium compound low condensates, titanium hydroxide, and titanium hydroxide low condensates is
  • the amount of hydrogen peroxide converted to 10 parts by mass of the titanium compound is 0.1 to 100 parts by mass, desirably 1 to 20 parts by mass.
  • the mixing ratio of hydrogen peroxide water is less than 0.1 parts by mass in terms of hydrogen peroxide, the formation of chelate is not sufficient and white turbid precipitation occurs.
  • the amount exceeds 100 parts by mass unreacted hydrogen peroxide tends to remain, which is not preferable because dangerous active oxygen is released during storage.
  • the mixing ratio of the hydrogen peroxide solution is 0.1 parts by mass or more in terms of hydrogen peroxide, chelate formation is sufficient and no cloudy precipitation occurs.
  • unreacted hydrogen peroxide does not remain, and active oxygen is not released during storage, which is preferable.
  • the hydrogen peroxide concentration in the hydrogen peroxide solution is not particularly limited, but it is preferably about 30 to 30% by mass in terms of the solid content of the produced liquid related to ease of handling and coating workability.
  • titanium-containing aqueous liquid (A) if necessary, other sol or pigment can be added and dispersed.
  • other sol or pigment can be added and dispersed.
  • commercially available titanium oxide sol, titanium oxide powder, my strength, talc, silica, paste, clay and the like can be fisted, and one or more of these can be added.
  • the amount of titanium-containing aqueous liquid (A) added in the surface treatment composition (H) is From the viewpoint of property, the solid content is 10 to 60% by mass.
  • the treatment liquid stability is inferior when the addition amount (solid content ratio) of the titanium-containing aqueous liquid (A) is less than 10% by mass or more than 60% by mass.
  • good preferable lower limit of the addition amount of the titanium-containing permanent liquid-(A) is 1 5 mass 0/0, more preferably from 2 0 wt%, a preferred upper limit is 5 0% by weight .
  • the nickel compound and / or cobalt compound (B) is blended for improving blackening resistance.
  • the nickel compound include nickel acetate, nickel nitrate, nickel sulfate, and the like, as a cobalt compound.
  • examples thereof include cobalt acetate, cobalt nitrate, cobalt sulfate and the like, and one or more of these can be used. Of these, nickel acetate and cobalt acetate are preferred from the viewpoint of achieving both blackening resistance and corrosion resistance.
  • the addition amount of the nickel compound or the cobalt compound (B) in the surface treatment composition (H) is from 0.01 to 1% by mass in terms of solid content from the viewpoint of achieving both blackening resistance and corrosion resistance. Preferably, the content is 0.05 to 0.7% by mass.
  • the addition amount of the nickel compound or the cobalt compound (B) is less than 0.01% by mass, the effect of improving blackening resistance cannot be sufficiently obtained, while 1% by mass. If it exceeds 0 , the corrosion resistance will decrease.
  • the fluorine-containing compound (C) is added to increase the reactivity between the treatment liquid (surface treatment composition) and the plating surface and form a dense reaction layer.
  • Examples of the fluorine-containing compound (C) include zircon ammonium fluoride, potassium zircon fluoride, zircon hydrofluoric acid, titanium ammonium fluoride, hydrofluoric acid, and ammonium hydrofluoride.
  • zircon ammonium fluoride potassium zircon fluoride
  • zircon hydrofluoric acid titanium ammonium fluoride
  • titanium ammonium fluoride hydrofluoric acid
  • ammonium hydrofluoride a type or two or more types can be used.
  • the addition amount of the fluorine-containing compound (C) in the surface treatment composition (H) is 1 to 80% by mass in terms of the solid content. If the addition amount of the fluorine-containing compound (C) is less than 1% by mass, the reactivity between the treatment liquid and the plating surface is poor, so that sufficient corrosion resistance cannot be obtained and blackening resistance is not improved. On the other hand, if it exceeds 80% by mass, the etching performance of the processing solution will increase, resulting in excessive etching of the plating surface, and on the contrary, the corrosion resistance will deteriorate.
  • the addition amount of the fluorine-containing compound (C) in the surface treatment composition (H) is 1 to 80% by mass in terms of the solid content. If the addition amount of the fluorine-containing compound (C) is less than 1% by mass, the reactivity between the treatment liquid and the plating surface is poor, so that sufficient corrosion resistance cannot be obtained and blackening resistance is not improved. On the other hand, if it exceeds 80% by mass,
  • the preferable lower limit of the addition amount of the fluorine-containing compound (C 3) is 3% by mass, more preferably 10% by mass, and particularly preferably 20% by mass. / 0 .
  • it preferred upper limit is 7 0 mass 0/0, more preferably 6 0 mass%.
  • the surface treatment composition (H) used in the present invention essentially comprises the titanium-containing aqueous liquid (A), nickel compound or cobalt compound (B), and fluorine-containing compound (C) as described above.
  • One or more kinds can be contained.
  • organic phosphate compound (D) examples include 1-hydroxymethane-1,1-diphosphonic acid, 1-hydroxyethane-1,1-diphosphonic acid, 1-hydroxypropane-1,1-diphosphonic acid and the like.
  • Group-containing organic phosphorous acid 2-hydroxyphosphonoacetic acid, 2-phosphonoptane 1, 2, 4 and 1, carboxyl group-containing organic phosphorous acid such as tri-force norlevonic acid, and salts thereof are suitable. 1 type or 2 types or more of these can be used.
  • the organophosphate compound (D) has the effect of improving the storage stability of the titanium-containing aqueous liquid (A), and 1-hydroxyxetane 1,1-diphosphonic acid is particularly effective. Therefore, it is particularly preferable to use this.
  • the amount of the organic phosphate compound (D) added in the surface treatment composition (H) is 10 to 60% by mass in terms of the solid content. Is preferable from the viewpoint of water resistance and the like.
  • the amount of the organic phosphate compound (D) is less than 10% by mass, the effect of improving the storage stability of the titanium-containing aqueous liquid (A) is small.
  • the amount of the organic phosphate compound (D) added is 10% by mass or more, the effect of improving the storage stability of the titanium-containing aqueous liquid (A) can be sufficiently obtained, while 60% by mass. If it is less than / 0 , phosphoric acid will not be present in excess, and water resistance will not deteriorate.
  • a more preferable addition amount of the organic phosphate compound (D) is 20 to 50% by mass.
  • Examples of the panadic acid compound (E) include lithium metapanadate, potassium metapanadate, sodium metapanadate, and ammonium metapanadate. And one or more of these can be used. Of these, ammonium metavanadate is preferred from the standpoint of adhesion to water.
  • Panajin acid compounds in the addition amount of (E) is 0 in the percentage of solids. 1-3 0 weight 0/0 and it forces S, Al force Li degreasing corrosion resistance after Preferable from the point. If the amount of vanadate compound (E) added is less than 0.1% by mass, the effect of improving the corrosion resistance after alkali degreasing is insufficient. On the other hand, if it exceeds 30% by mass, sufficient corrosion resistance cannot be exhibited because V is excessively present. That is, the amount of vanadic acid compound (E) added is 0.1 mass. If this is the case, the effect of improving the corrosion resistance after degreasing can be sufficiently obtained. On the other hand, if it is 30% by mass or less, V does not exist in excess, so that sufficient corrosion resistance can be exhibited. . A more preferable addition amount of the panadic acid compound (E) is 0.5 to 20% by mass.
  • zirconium carbonate compound (F 2) examples include salts of zirconium carbonate such as sodium, potassium, lithium, and ammonium, and one or more of these can be used. Of these, ammonium zirconium carbonate is preferred from the viewpoint of water resistance and the like.
  • the addition amount of the zirconium carbonate compound (F) in the surface treatment composition (H) is preferably 0.1 to 20% by mass in terms of solid content from the viewpoint of corrosion resistance and the like. If the added amount of the zirconium carbonate compound (F) is less than 0.1% by mass, the effect of improving the corrosion resistance is insufficient. On the other hand, if it exceeds 20% by mass, Zr is excessively present and sufficient corrosion resistance cannot be exhibited. That is, if added pressure of zirconium carbonate compound (F) to zero. 1 mass% or more, the corrosion resistance improvement effect is sufficiently obtained, whereas, if 2 0 wt% or less, Z r is present in excess Therefore, sufficient corrosion resistance can be achieved. A more preferable addition amount of the zirconium carbonate compound (F) is 0.2 to 15% by mass.
  • the water-soluble organic resin or Z and the water-dispersible organic resin (G) are organic resins that can be dissolved or dispersed in water. Conventionally known methods for water-solubilizing or dispersing organic resins in water The method can be applied. Specifically, as an organic resin, functional groups that can be water-soluble or water-dispersed independently (for example, hydroxyl groups, polyoxyalkyls). Containing a ren group, a strong lpoxyl group, an amino group, a sulfido group, a phosbuin group, etc.) and, if necessary, some or all of these functional groups may be converted to an acidic resin (carboxyl group).
  • functional groups that can be water-soluble or water-dispersed independently (for example, hydroxyl groups, polyoxyalkyls). Containing a ren group, a strong lpoxyl group, an amino group, a sulfido group, a phosbuin group, etc
  • Containing resins ethanolamine, triethylamine and other amine compounds; ammonia water; lithium hydroxide, sodium hydroxide, potassium hydroxide neutralized alkali metal hydroxide, etc., base
  • a resin such as an amino group-containing resin
  • fatty acids such as acetic acid and lactic acid
  • those neutralized with a mineral acid such as phosphoric acid
  • water-soluble or water-dispersible organic resins include epoxy resins, phenol resins, acryl resins, urethane resins, olefin reinforced rubonic acid resins, nylon resins, resins having a polyoxyalkylene chain, Examples thereof include polyvinyl alcohol, polyglycerin, canolepoxymethylenorescenellose, hydroxymethinoresenorelose, and hydroxyxetylcellulose.
  • One or more organic resins can be used.
  • the storage stability of the surface treatment composition can be obtained by using at least one organic resin selected from water-soluble or water-dispersible acryl-based resins, urethane resins, and epoxy resins.
  • a water-soluble or water-dispersible acryl resin or urethane resin as a main component from the viewpoint of the balance between the storage stability of the surface treatment composition and the coating film performance.
  • an urethane resin having a Tg of less than 50 ° C. in order to ensure the paint adhesion of the processed part.
  • a water-soluble or water-dispersible acrylic resin is synthesized by a conventionally known method, for example, an emulsion polymerization method, a suspension polymerization method, or a polymer having a hydrophilic group by solution polymerization, and neutralized or made aqueous as necessary. Or the like.
  • the polymer having a hydrophilic group is, for example, an unsaturated monomer having a hydrophilic group such as a strong lpoxyl group, an amino group, a hydroxyl group, or a polyoxyalkylene group. Can be obtained by polymerizing the unsaturated monomer.
  • the water-soluble or water-dispersible acrylic resin is preferably one obtained by copolymerizing styrene from the viewpoint of corrosion resistance, etc.
  • the amount of styrene in the total unsaturated monomer is 10 to 60% by mass, particularly 15%. It is preferably ⁇ 50% by mass.
  • the T g (glass transition point) of the resin is preferably 30 to 80 ° C, particularly 40 to 70 ° C, from the viewpoint of the toughness of the resulting film.
  • carboxyl group-containing unsaturated monomer examples include acrylic acid, methacrylic acid, maleic acid, maleic anhydride, crotonic acid ', and itaconic acid.
  • nitrogen-containing unsaturated monomer such as the amino group-containing unsaturated monomer
  • examples of the nitrogen-containing unsaturated monomer include N, N-dimethylaminoethyl (meth) acrylate, N, N-jetylaminoethyl (meth) atalyte.
  • Nitrogen-containing alkyl (meth) acrylates such as N-tert-butylaminoethyl (meth) acrylate; N-methyl (meth) allylamide, N-ethyl (meth) Acrylamide, N—Methylol (meth) atrylamide, N—Methoxymethyl (meth) atrylamide, N—Butoxymethyl (meth) atrylamide, N, N—dimethyl (meth) acrylamide, N— Polymerizable amides such as dimethylaminopropyl (meth) atrylamide and N, N-dimethylaminoethyl (meth) atrylamide
  • 2-vinylpyridine 1 one Bulle one 2-pyrrolidone, aromatic nitrogen-containing monomers such as 4 one Bulle pyridine.
  • hydroxyl group-containing unsaturated monomer examples include 2-hydroxyxetyl (meth) acrylate, hydroxypropyl (meth) acrylate, 2,3-dihydroxypropyl (meth) acrylate, and 4-hydroxypropyl.
  • Mono-esterified products of polyhydric alcohols such as (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, and acrylic acid or methacrylic acid;
  • a compound obtained by ring-opening polymerization of ⁇ -force prolacton to a monoesterified product of polyhydric alcohol and acrylic acid or methacrylic acid can be used.
  • unsaturated monomers include methyl (meth) acrylate, ethyl (meth) acrylate, ⁇ -propyl (meth) acrylate, isopropyl (meth) acrylate, II Butyl (meth) acrylate, Isoptyl (meth) acrylate, tert-Pinitole (meth) acrylate, 2-Ethenolehexinoleacrylate, n-octyl (meth) acrylate, Lauryl (Metal) C1-C2 alkyl (meth) acrylates such as acrylate, tridecyl (meth) acrylate, octadecyl (meth) acrylate, isostearyl (meth) acrylate, etc. Bini And the like.
  • the unsaturated monomer mentioned above can use 1 type (s) or 2 or more types.
  • (meta) acrylate means “attalate or metaacrylate”.
  • a chain extension which is a low molecular weight compound having two or more active hydrogens such as a diol and diamine, if necessary, is a polyurethane composed of a polyol such as a polyester polyol and a polyether polyol and a diisocyanate.
  • a polyol such as a polyester polyol and a polyether polyol and a diisocyanate.
  • those conventionally known can be used widely (for example, Japanese Examined Patent Publication No. 4 2-2 4 1 92 2)
  • No. 4 2-2 4 1 9 4 Publication Japanese Patent Publication No. 4 2-5 1 1 8 Publication, Japanese Patent Publication No. 4 9-9 8 6 Publication, Japanese Patent Publication No. 4 9-3 3 1 0 4 Publication, Special Publication No. 5-0-1 5 0 2 7 and JP 5 3-2 9 1 7 5).
  • a method of imparting hydrophilicity by introducing an ionic group such as a hydroxyl group, an amino group, or a carboxyl group into the side chain or terminal of a polyurethane polymer, and dispersing or dissolving in water by self-emulsification.
  • polyurethane resin those obtained by different methods among the above-described dispersion or dissolution methods can be mixed and used.
  • diisocyanate examples include fragrance Aliphatic, cycloaliphatic or aliphatic diisocyanates, such as hexamethylene diisocyanate, tetramethylene diisocyanate, 3, 3 '— dimethyoxy 4, 4' Direndisorbate, ⁇ -Xylylene diisocyanate, m-Xylylene diisocyanate, 1, 3— (Diisocyanatomethyl) Dioxyhexanone, 1, 4— (Diisocyanatomethyl) Cyclohexanone, 4,4'-diisocyanatocyclohexanone, 4,4'-methylenebis (cyclohexenole isocyanate), isophorone diisocyanate, 2, 4 1-tolylene diisocyanate, 2, 6-tolylene diisocyanate P-phenylene diisocyanate, di-methane diisocyanate, m-phenylene diisocyanates, 1, 3— (Diisocyanato
  • 2,4-tolylene diisocyanate 2,6-tolylene diisocyanate, hexamethylene diisocyanate, and isophorone diisocyanate are particularly preferable.
  • polyurethane-based resins include Hydran (registered trademark) AP-1 0, AP-2 0, AP-3 0, Neudran HW-3 30, HW-3400, H W- 3 5 0 (Brand name, manufactured by Dainippon Ink and Chemicals, Inc.), Superflex (registered trademark) 1 1 0, 1 5 0, 6 0 0, E 2 25 0 0, F-3 4 3 8 D (both trade names, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.).
  • the hydran AP—10 (T: 27.0, Tg: less than 50 ° C), Tg: 2 7.C), HW-340 (Tg: 7 ° C), Superflex 1 1 0 (D. ⁇ : 4 6 ° 0, 1550 (Tg: 40 ° C), E—
  • the epoxy resin is preferably a cationic epoxy resin obtained by adding amine to an epoxy resin, such as acryl modification or urethane modification. Epoxy resins, etc. can be suitably used.
  • Cationic epoxy resins include, for example, adducts of epoxy compounds and primary mono- or polyamines, secondary mono- or polyamines, primary and secondary mixed polyamines (for example, US Pat.
  • Epoxy compounds and secondary mono- or poly having ketiminated primary amino groups Min (For example, see US Patent No. 4 0 1 7 4 3 8); etherification reaction product of an epoxy compound and a hydroxyl compound having a ketiminated primary amino group (for example, JP-A-5-9-43013)).
  • Epoxy resins have a number average molecular weight of 400-400, particularly 80-200, and an epoxy equivalent of 190-200, in particular 400-1000. Is preferred.
  • Such an epoxy resin can be obtained, for example, by a reaction between a polyphenol compound and propyl hydrin.
  • polyphenol compound examples include bis (4-hydroxyphenyl) -1,2-propane, 4 , 4-dihydroxybenzophenone, bis (4-hydroxyoxyphenenole) 1-1, 1-ethane, bis (4-hydroxyoxyphenenole) 1-1, 1-isobutane, bis (4-hydroxy-tert-tert —Butinolephenol 2) 2-Propane, Bis (2—Hydroxynaphthol) Methane, 1,5-Dihydroxynaphthalene, Bis (2,4-Dihydroxyphenyl) Methane, Tetra (4-Hydroxyphenyl) 1, 1, 2, 2-Ethane, 4, 4-Dihydroxydiphenenolesnorehon, Fenenorenovolak, Cresol Novolac and the like.
  • the amount of water-soluble organic resin or Z and water-dispersible organic resin (G) added in the surface treatment composition (H) is 30% by mass or less, particularly 1 to 20% by mass in terms of solid content. It is preferable. If the added amount of water-soluble organic resin or water-dispersible organic resin (G) exceeds 30% by mass, the pariacity due to the inorganic component is reduced, so it is necessary to increase the coating adhesion amount. Conductivity will fall. That is, the amount of water-soluble organic resin or / and water-dispersible organic resin (G) added is 30 mass. /. In the following cases, since the pariacity due to the inorganic component can be maintained, there is no need to increase the coating amount, and therefore the conductivity is good.
  • the surface treatment composition (H) may further include, for example, an etching agent such as a silane coupling agent, resin fine particles, and an inorganic phosphate compound, a heavy metal compound other than the components specified by the present invention, an increased viscosity Agents, surfactants, lubricity-imparting agents (polyethylene wax, fluorine wax, carnauba wax, etc.), antifungal agents, coloring pigments, constitutional facial materials, antifungal pigments, dyes, and the like.
  • an etching agent such as a silane coupling agent, resin fine particles, and an inorganic phosphate compound, a heavy metal compound other than the components specified by the present invention
  • an increased viscosity Agents such as a silane coupling agent, resin fine particles, and an inorganic phosphate compound, a heavy metal compound other than the components specified by the present invention
  • an increased viscosity Agents such as a silane coupling agent, resin fine particles, and an inorganic phosphate compound,
  • the surface treatment composition (H) can be used, for example, methanol, ethanol as necessary. It can be used after diluting with a hydrophilic solvent such as ethylene glycol, isopropyl alcohol, ethylene glycol solvent, or propylene glycol solvent.
  • a hydrophilic solvent such as ethylene glycol, isopropyl alcohol, ethylene glycol solvent, or propylene glycol solvent.
  • the adhesion amount of the surface treatment film formed by the surface treatment composition (H) is set to 0.05 to 1.0 g / m 2 , preferably 0.1 to 0.8 g / m 2 .
  • the coating amount is less than 0.05 g / in 2 , the corrosion resistance is inferior.
  • it exceeds 1.0 g / m 2 the coating tends to break and the corrosion resistance decreases.
  • the Mg added to the molten Z n -A 1 alloy-plated layer of this molten Z n to A 1 alloy-plated steel sheet is mainly a metallic luster with no spangles or very fine spandal formed.
  • Ni that is added to the same plating layer in order to obtain a certain beautiful plating appearance is mainly aimed at improving the blackening resistance.
  • the effect of improving blackening resistance due to the addition of Ni is estimated to be obtained by the concentration of Ni in the outermost layer of the plating layer when an appropriate amount of Mg coexists. Further, by controlling the cooling rate after plating within an appropriate range, it is possible to more appropriately cause Ni concentration at the outermost layer portion of the plating layer.
  • plating layer The reason for limiting the component composition of the molten Z EL—A 1-based alloy plating layer (hereinafter simply referred to as “plating layer”) will be described below.
  • a 1 content in the plating layer is less than 1.0% by mass, a Fe 1 Zn alloy layer is formed thick on the plating eyebrow substrate interface, and workability deteriorates.
  • a 1 content is 10 mass. If it exceeds / 0 , the eutectic structure of Zn and A 1 cannot be obtained, and the A 1 lithiated layer increases and the sacrificial anticorrosive action decreases, so that the corrosion resistance of the end face is inferior.
  • a top dross mainly composed of A 1 is likely to occur in the plating bath, resulting in a problem that the plating appearance is impaired.
  • the A 1 content in the plating layer is 1.0 to 10% by mass, preferably 3 to 7% by mass.
  • one of the aims to limit the composition of the adhesive is to eliminate the spangle peculiar to the molten Z ⁇ -A 1 alloy alloy of the GF composition (zero spangle) or to form a very fine spangle.
  • the present inventors have adjusted the relationship between the plating composition and the plating appearance. The following experiments were conducted to test
  • a 1 (4 to 5 wt. / 0) of GF composition Mg and N i the molten Z n -A 1 alloy plated bath containing added singly, melting steel in these plating baths Z n — A 1 type alloy was attached, and the plating appearance (particularly spangle size, degree of dross adhesion, color tone, gloss) of the obtained plated steel sheet was visually observed.
  • the plating layer with Ni added did not show any changes in the plating appearance within the experimental range of the present inventors, and showed a plating appearance almost equivalent to that of normal GF, but added Mg.
  • the plating layer changed the spangle size, color tone, luster, etc. depending on the amount added.
  • the Mg content is 0.2 mass. If it is less than 0 , the blackening resistance also decreases. As will be described later, 0.2 mass of Mg coexists with Ni in the plating layer. If it is less than 0 , it is presumed that Ni is not concentrated on the outermost surface layer of the adhesive layer, and as a result, the blackening resistance is lowered. On the other hand, when the Mg content exceeds 1.0% by mass, the color tone gradually changes from grayish white to gray and dross adhesion increases. In addition, if the Mg content exceeds 1.0% by mass, cracks are likely to occur in the plating layer, resulting in a problem that workability is lowered. Moreover, when there is too much Mg, blackening-proof property is also inferior.
  • the Mg content in the plating layer has a lower limit of 0.2% by mass in order to obtain a beautiful plating appearance and excellent blackening resistance, preventing dross adhesion and color tone deterioration, and further reducing workability.
  • the upper limit is 1.0 mass from the viewpoint of preventing the above. / 0 .
  • Mg mainly contributed to the improvement of the appearance of adhesion
  • N i mainly contributed to the improvement of blackening resistance. It was found that coexistence with Mg is indispensable for improving the blackening resistance. In other words, Mg has the effect of forming a beautiful plating appearance, and N It was found that coexistence with i indirectly promotes the blackening resistance improvement effect by Ni. This was clarified by analyzing the plating layer in the depth direction by glow discharge luminescence surface analysis (GD S) for plated steel sheets with different blackening resistance. An example of the analysis result is shown below.
  • GD S glow discharge luminescence surface analysis
  • the samples (1) to (3) above were analyzed mainly from the outermost surface to a depth of about 200 nm (2000 A). The result is shown in Fig.2.
  • a GDS analysis device was used to discharge for 30 seconds in the depth direction with a diameter of 4 mm ⁇ and a current of 20 mA.
  • a concentration peak of Mg is seen at the same position as Zn in the outermost layer (outermost surface).
  • the concentration peak of 1 is inside (base side) of the Zn and Mg concentration peaks.
  • the sample containing only Ni with poor blackening resistance (2) In the thickening layer of the plating layer, A 1 is observed after Zn of the outermost layer, and the concentration of Ni The enrichment peak is inside the A 1 concentration peak (base side).
  • Ni is concentrated in the outermost layer part in order to have a black layer with excellent blackening resistance. It was found that the coexistence of Mg was necessary. It was also found that the Ni concentration was affected by the cooling rate after plating.
  • Ni concentration in the outermost layer portion of the plating layer exists between the outermost surface of the plating and a depth of about 30 nm (30 O A).
  • a 1 and Mg are more oxidizable than Zn
  • Ni is an element that is less oxidizable.
  • Blackening is due to the fact that the strong oxidative component elements diffuse (move / concentrate) to the outermost surface of the plating layer and take part of oxygen from the zinc oxide formed on the outermost surface of the plating layer.
  • the concentrated layer in the sample with poor blackening resistance (1) has Mg concentrated in the outermost layer deprived of oxygen of zinc oxide.
  • a 1 is concentrated on the surface side of the surface of Ni, so A 1 with strong oxidization also takes up oxygen in zinc oxide. It is conceivable that each was converted to oxygen-deficient zinc oxide.
  • Ni which is weakly oxidizable, concentrates in the outermost layer portion of the plating layer of the sample with excellent blackening resistance (3), and this coexists as a barrier layer Mg, A 1 It is considered that the blackening resistance was improved by suppressing the diffusion (migration / concentration) to the outermost layer.
  • Ni be concentrated in the outermost layer portion of the adhesive layer to play the role of a barrier layer.
  • This concentration of Ni in the outermost layer portion of the adhesive layer is It is thought that it is caused by the coexistence of Mg. However, coexist with Mg
  • the mechanism by which Ni moves to and concentrates in the outermost layer of the striking layer is not always clear at present.
  • the N i content is less than 0.005 wt% in the coating layer, less enrichment of plated layer outermost layer of the N i even coexist M g, the effect of improving the blackening resistance is not obtained .
  • ⁇ 1 is 0.005 mass% or more
  • Mg is less than 0.2 mass%
  • Ni content is 0.1 mass. If it exceeds / 0 , there is an effect of improving blackening resistance. However, it is not preferable because A 1—Mg-based dross containing Ni is generated in the plating bath and the plating appearance due to dross adhesion is impaired.
  • the Ni content in the adhesive layer is set to 0.005 to 0.1 mass%, and as described above, the Mg content is set to 0.2 to 1.0. Mass%.
  • a misch metal containing Ce and Pino or La can be contained in the plating layer. Although this misch metal containing Ce and Z or La is not effective for zero spangle formation, it increases the fluidity of the plating bath, prevents the occurrence of fine unplated pinholes, and reduces the plating surface. Smoothes the surface.
  • the content of misch metal is less than 0.005 mass% in terms of the total amount of Ce and La, pinhole suppression effects cannot be obtained sufficiently, and surface smoothing is not effective.
  • the total amount of Ce and La exceeds 0.05% by mass, it will be present as undissolved suspended matter in the plating bath, which will adhere to the plating surface and impair the plating appearance. That is, if the content of misch metal is 0.00'5 mass% or more in terms of the total amount of Ce and La, a pinhole suppression effect can be sufficiently obtained, and surface smoothing can be achieved, On the other hand, the total amount of Ce and La is 0.05 mass.
  • the misch metal containing C e and ⁇ or La is 0.005 to 0.05 mass in terms of the total amount of C e and La. / 0 , preferably 0.007 to 0.02 mass%.
  • an appropriate amount of Mg and Ni is contained in the plating layer having the GF composition, and an appropriate amount of misch metal containing Ce and / ⁇ or La can be added as necessary.
  • molten Zn-A1-based alloy steel sheet can be obtained, for example, under the following production conditions.
  • the steel plate used as the base steel plate may be appropriately selected from known steel plates according to the application, and it is not necessary to specifically limit the steel plate.
  • This steel plate (underlying steel plate) is immersed in a molten Z n -A 1 alloy plating bath and subjected to thermal immersion (molten) plating, then cooled by pulling up from the plating bath and molten on the surface of the steel plate.
  • a 1-type alloy plating layer is formed.
  • the plated layer is, A 1:. 1 0 to 1 0 weight 0/0, M g:. 0 2 ⁇ 1 ⁇ 0 Weight 0/0, N i:.
  • the bath composition of the molten Z n -A 1 alloy plating bath is substantially the same as the alloy plating layer composition.
  • Ni is concentrated in the outermost layer portion of the molten Zn-A1-based alloy plating layer.
  • the inventors of the present invention have prepared a Mg, Ni content in the molten Zn-A 1 alloy plating layer, a cooling rate after plating, and a concentration of plating component elements in the plating layer and outermost layer.
  • Mg and Ni are indispensable for improving the blackening resistance, that is, for Ni concentration in the outermost layer of the plating layer, as described above.
  • the cooling rate up to 250 ° C after fitting was greatly affected by this Ni concentration.
  • Metals such as A1, Mg, Ni, etc. in the molten Zn—A1 alloy plating layer gradually diffuse toward the outermost surface of the plating layer during solidification and normal temperature after plating.
  • Concentration of Mg and Ni on the outermost surface of the plating layer which has been particularly noted in our experiments, has a large cooling rate up to 250 ° C after plating. It was found that it affected. On the other hand, the cooling rate in the temperature range below 250 ° C had little effect on the concentration of Mg and Ni. Specifically, the cooling rate of the plated steel sheet pulled up from the molten Zn-A 1 alloy alloy bath is 1 to 15 ° C / sec, preferably 2 to 10 ° CZ sec. It was found that the Ni concentration in the outermost surface layer of the plating layer can be more effectively promoted by controlling to the upper limit.
  • the cooling rate of the plated steel sheet pulled up from the plating bath to 250 ° C is less than 2 seconds, the Ni layer is sufficiently concentrated in the outermost layer of the plating layer, but an alloy layer grows in the plating layer. As a result, it becomes a tortoiseshell pattern and the appearance deteriorates, and the workability deteriorates.
  • the cooling rate is 15 and exceeds seconds, the Mg content in the plating layer is in the range of 0.2 to 1.0% by mass, and the Ni content is in the range of 0.05 to 0.1% by mass. Even in the surrounding area, the concentration of Ni in the outermost layer of the plating layer is reduced, and the blackening resistance is not significantly affected.
  • the cooling rate of the plated steel sheet pulled up from the plating bath to 250 ° C is 15 ° C or less, Ni is sufficiently concentrated in the outermost layer of the plating layer, which is effective for blackening resistance. Indicates.
  • the cooling rate is 1 ° C / second or more, the alloy layer does not grow in the plating layer, so that a tortoiseshell pattern is not deteriorated and the appearance is not deteriorated. Therefore, the cooling rate of the steel sheet for lifting from the molten Z n -A 1 alloy alloy bath to 250 ° C is 1 to 15 ° CZ seconds, preferably 2 to 10 ° CZ seconds. It is preferable.
  • the plating bath temperature is preferably in the range of 39.degree.
  • the plating bath temperature is less than 390 ° C, the viscosity of the plating bath increases, and the plating surface tends to be uneven.
  • it exceeds 500 ° C dross in the plating bath tends to increase. That is, if the plating bath temperature is 3900 ° C or higher, the viscosity of the plating bath is properly maintained, so that the plating surface is not likely to be uneven, whereas if it is 5500 or less, The dross in the plating bath is unlikely to increase.
  • a titanium-containing aqueous liquid (A) as described above, a nickel compound or a noble metal is coated on the surface of the molten Z n -A 1 alloy-plated steel sheet.
  • cobalt compound (B), fluorine-containing compound (C) is an essential component, and if necessary, organophosphate compound (D), panadic acid compound (E), zirconium carbonate compound (F),
  • a surface treatment composition (ii) (treatment solution) containing one or more of a water-soluble organic resin or a water-dispersible organic resin (G) is applied and then dried without washing.
  • the titanium-containing aqueous liquid (A) and the surface treatment composition (H) may further contain other additive components as mentioned above, if necessary.
  • the method for applying the surface treatment composition may be any method that allows the treatment liquid to adhere to the surface of the plated steel sheet, for example, spray + roll squeezing, mouth coater, dipping.
  • the drying method after application is arbitrary, for example, a hot air method, an induction heating method, or an electric iron method.
  • the drying temperature (steel plate temperature) of the applied surface treatment composition (treatment liquid) is preferably about 40 to 200 ° C.
  • the drying temperature is less than 40 ° C, the film formation is insufficient and the corrosion resistance is poor.
  • the effect of improving the performance such as corrosion resistance corresponding to the drying temperature cannot be obtained. That is, if the drying temperature is 40 ° C or higher, the film formation is sufficient and the corrosion resistance is excellent, while if it is 200 ° C or lower, the performance such as corrosion resistance corresponding to the drying temperature is sufficiently improved. The effect is obtained.
  • the titanium-containing aqueous liquid (A) and components (B) to (G) used for the surface treatment composition are shown below.
  • Titanium tetrachloride 60 mass Ammonia water (1: 9) was added dropwise to a solution in which 5 cc of / 0 solution was made 500 cc with distilled water to precipitate a low condensation product of titanium hydroxide. After washing with distilled water, 10 cc of a 30% by mass solution of hydrogen peroxide was added and stirred to obtain a yellow translucent viscous titanium-containing aqueous liquid T 1 containing titanium.
  • Production Example 3 (Titanium-containing aqueous liquid T 3) A titanium-containing aqueous liquid T3 was obtained under the same production conditions as in Production Example 2 except that tetra-n-butoxytitanium was used instead of tetra-iso-propoxytitanium used in Production Example 2. ,
  • the production conditions were the same as in Production Example 2 except that 3 times the amount of hydrogen peroxide water was added to Production Example 2 and added dropwise at 50 ° C over 1 hour and further aged at 60 ° C for 3 hours. A titanium-containing aqueous liquid T5 was obtained.
  • the titanium-containing aqueous liquid T 3 produced in Production Example 3 was further heat-treated at 9 5 for 6 hours to obtain a white yellow translucent titanium-containing aqueous liquid T 6.
  • a mixture of 10 parts by mass of tetra-iso-propoxytitanium and 10 parts by mass of iso-propanol was added to “TKS-203” (trade name, manufactured by Tika Co., Ltd., titanium oxide sol), 5 parts by mass (solid content), 30
  • the mixture was added dropwise to a mixture of 10% by mass of hydrogen peroxide water and 10 parts by mass of deionized water with stirring at 10 ° C. over 1 hour. Thereafter, the mixture was aged for 24 hours at 10 ° C. to obtain a yellow transparent, slightly viscous titanium-containing aqueous solution T7.
  • G1 Superflex E-2500 (trade name, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., water-based polyurethane resin, T g: 42 ° C)
  • G 2 Pyronal MD— 1 1 00 (trade name, manufactured by Toyobo Co., Ltd., water-based polyester resin)
  • Ade force resin EM— 07 1 8 (trade name, AD E K A), water-borne epoxy resin)
  • G 4 Hydran AP—10 (trade name, manufactured by Dainippon Ink & Chemicals, water-based polyurethane resin, T g: 27 ° C)
  • G 5 Hydran AP-30 (trade name, manufactured by Dainippon Ink & Chemicals, water-based polyurethane resin, T g: 61 ° C)
  • G 6 Hydran HW-340 (trade name, manufactured by Dainippon Ink & Chemicals, water-based polyurethane resin, T g: 7 ° C)
  • G 7 Hydran HW-3 50 (trade name, manufactured by Dainippon Ink & Chemicals, water-based polyurethane resin, T g: 5 7 ° C)
  • G 8 Superflex 110 (trade name, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., water-based polyurethane resin, T g: 46 ° C)
  • G 9 Superflex 1 30 (trade name, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., waterborne poly (Urethane resin, T g: 9 6 ° C)
  • G 10 Superflex 600 (trade name, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., aqueous polyurethane resin, T g: 70 ° C)
  • water-dispersible acrylic resins of G 11 to G 15 were produced according to Production Examples 8 to 12 shown below.
  • Table 1 shows the monomer composition and characteristic values of the water-dispersible acryl resins of G 11 to G 15. In the following production examples, “part” and “%” are based on mass.
  • Aqualon RN-50 Product name, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., nonionic emulsifier, solid content 60%
  • a water-dispersible acrylic resin of G 1 to G 15 was obtained in the same manner as in Production Example 8 except that the monomer composition in the first and second stages was changed to the blending ratio shown in Table 1.
  • the plated steel sheets shown in Table 2 were used as the base steel sheets for the surface-treated plated steel sheets.
  • Surface treatment appropriately blending the above-mentioned titanium-containing product liquid (A) and components (B) to (G)
  • the physical composition was applied to the surface of the steel plate and dried to obtain a maximum plate temperature of 80 ° C in 5 to 20 seconds.
  • These test materials were evaluated for corrosion resistance, blackening resistance and paint adhesion by the following test methods. The results are shown in Tables 3 to 5 together with the composition of the surface treatment composition applied to each specimen and the coating conditions.
  • Degreasing agent “Palclean N 364 S” (trade name, manufactured by Nihon Parkerizing Co., Ltd.) dissolved in water and adjusted to a concentration of 2% and a liquid temperature of 60 ° C for 2 minutes Spray spraying (spraying pressure: 1 kgf / cm 2 ) was performed. Thereafter, the test material was washed with tap water for 30 seconds and dried by blowing compressed air.
  • a salt spray test of JIS—Z—2 3 7 1—2 00 00 was performed on the specimen with the end and the back surface tape-sealed, and the test time when the white haze generation area ratio was 5% was measured.
  • the evaluation criteria are as follows.
  • ⁇ 144 hours or more, less than 240 hours
  • ⁇ 72 hours or more, less than 144 hours
  • the evaluation criteria are as follows.
  • Melamine alkyd resin paint (trade name “Delicon (registered trademark) # 700”, manufactured by Dainippon Paint Co., Ltd.) with or without pre-treatment so that the dry film thickness is 30 ⁇ 2 ⁇ m It was applied and dried at 1300C for 30 minutes.
  • Treatment method 2 minutes spray treatment (1 kgf / cm 2 )
  • cellophane adhesive tape (trade name “CT 24”, manufactured by Nichipan Co., Ltd.) was applied to the grid area, and the cell number after the cellophane adhesive tape was peeled was evaluated.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Chemical Treatment Of Metals (AREA)

Abstract

L'invention propose une tôle d'acier revêtue d'alliage Zn-Al immergé à chaud, traitée en surface, exempte de chrome, qui présente d'excellentes caractéristiques en termes de résistance à la corrosion, de résistance au noircissement et d'aspect de surface du placage. Selon l'invention, une tôle d'acier qui a sur la surface une couche de placage d'alliage Zn-Al immergé à chaud contenant Al : 1,0 à 10%, Mg : 0,2 à 1,0% et Ni : 0,005 à 0,1% est traitée en surface avec une composition de traitement de surface contenant une solution aqueuse contenant du titane spécifique, un composé de nickel et/ou un composé de cobalt et un composé contenant du fluor à un rapport spécifique pour former un film de traitement de surface sur la surface. Une excellente résistance au noircissement est obtenue grâce au composé Ni et/ou Co contenu dans le film de traitement de surface et à la composition de placage optimisée. En outre, la composition de traitement de surface présente une réactivité améliorée en raison du composé contenant du fluor pour former une couche de réaction dense sur la surface du placage et le composé contenant du fluor confère des propriétés de barrière supérieures au film de traitement de surface lui-même, ce qui permet d'obtenir une excellente résistance à la corrosion.
PCT/JP2008/058320 2007-04-27 2008-04-24 Tôle d'acier revêtue d'un alliage zn-al immergé à chaud, traitée en surface WO2008136496A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2007-119966 2007-04-27
JP2007119966 2007-04-27
JP2008102943A JP5317516B2 (ja) 2007-04-27 2008-04-10 表面処理溶融Ｚｎ−Ａｌ系合金めっき鋼板
JP2008-102943 2008-04-10

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WO2008136496A1 true WO2008136496A1 (fr) 2008-11-13

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108690944A (zh) * 2018-06-12 2018-10-23 武汉钢铁有限公司 耐黑变性和耐蚀性优异的热浸镀钢板制造方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS59177381A (ja) * 1983-03-26 1984-10-08 Nippon Steel Corp 耐黒変性に優れた溶融亜鉛系メツキ鋼板の製造法
JP2001335960A (ja) * 2000-05-23 2001-12-07 Yuken Industry Co Ltd 亜鉛系めっき材の耐候性改善方法
JP2004238638A (ja) * 2002-12-09 2004-08-26 Kansai Paint Co Ltd 表面処理組成物および表面処理金属板
JP2005036304A (ja) * 2003-07-01 2005-02-10 Nippon Steel Corp 外観に優れた溶融Ｚｎ−Ｍｇ−Ａｌ系めっき鋼板の製造方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS59177381A (ja) * 1983-03-26 1984-10-08 Nippon Steel Corp 耐黒変性に優れた溶融亜鉛系メツキ鋼板の製造法
JP2001335960A (ja) * 2000-05-23 2001-12-07 Yuken Industry Co Ltd 亜鉛系めっき材の耐候性改善方法
JP2004238638A (ja) * 2002-12-09 2004-08-26 Kansai Paint Co Ltd 表面処理組成物および表面処理金属板
JP2005036304A (ja) * 2003-07-01 2005-02-10 Nippon Steel Corp 外観に優れた溶融Ｚｎ−Ｍｇ−Ａｌ系めっき鋼板の製造方法

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108690944A (zh) * 2018-06-12 2018-10-23 武汉钢铁有限公司 耐黑变性和耐蚀性优异的热浸镀钢板制造方法

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