WO2011065581A1 - Composition de traitement de surface, et tôle d'acier traitée en surface - Google Patents

Composition de traitement de surface, et tôle d'acier traitée en surface Download PDF

Info

Publication number
WO2011065581A1
WO2011065581A1 PCT/JP2010/071534 JP2010071534W WO2011065581A1 WO 2011065581 A1 WO2011065581 A1 WO 2011065581A1 JP 2010071534 W JP2010071534 W JP 2010071534W WO 2011065581 A1 WO2011065581 A1 WO 2011065581A1
Authority
WO
WIPO (PCT)
Prior art keywords
titanium
surface treatment
water
treatment composition
organic resin
Prior art date
Application number
PCT/JP2010/071534
Other languages
English (en)
Japanese (ja)
Inventor
金子里江
藤林亘江
窪田隆広
中野多佳士
阿久井潤
Original Assignee
Ｊｆｅスチール株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ｊｆｅスチール株式会社 filed Critical Ｊｆｅスチール株式会社
Priority to CN201080053499.2A priority Critical patent/CN102666920B/zh
Publication of WO2011065581A1 publication Critical patent/WO2011065581A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08—Anti-corrosive paints
    • 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
    • C23C22/62—Treatment of iron 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
    • 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

Definitions

  • the present invention is a surface treatment composition and a surface-treated steel sheet suitable for use in automobiles, home appliances, and building materials, and uses an environment-adaptive surface treatment composition that does not contain any hexavalent chromium in the composition or coating film.
  • the present invention relates to a surface-treated steel sheet.
  • the chromate treatment uses hexavalent chromium which is a pollution control substance.
  • This hexavalent chromium is treated in a closed system in the treatment process, and the sealing action by the organic film formed on the upper layer causes the chromate film to contain Since the elution of chromium from can be made almost zero, the human body and the environment are not substantially polluted by hexavalent chromium.
  • laws and regulations that emphasize the conventional work environment and wastewater treatment, but also laws and regulations that emphasize environmental load and environmental harmony are beginning.
  • Patent Documents 1 and 2 propose a surface treatment agent containing Al, a phosphoric acid compound, silica, and a water-based organic resin emulsion, and a metal material coated therewith.
  • Patent Document 3 proposes a galvanized steel sheet in which an organic coating layer is formed after an amorphous film is formed by applying and drying a mixed aqueous solution of polyphosphate primary phosphate and metal oxide sol. Has been.
  • Patent Documents 4 and 5 a composite oxide film layer containing oxide fine particles, phosphoric acid and / or a phosphoric acid compound, and one or more metals selected from Mg, Mn, and Al is used as a lower layer.
  • a steel sheet having an organic film formed thereon is proposed.
  • Patent Documents 6 and 7 propose an inorganic rich film mainly composed of Mg-phosphate, colloidal silica, and a phosphonic acid compound.
  • Patent Document 8 proposes a two-layer coating in which an inorganic rich coating mainly composed of primary phosphate and colloidal silica is disposed as a lower layer, and a silicate coating and / or a silicon resin is disposed as an upper layer.
  • Patent Document 9 discloses that at least one titanium compound selected from hydrolyzable titanium compounds, low-condensates of hydrolyzable titanium compounds, titanium hydroxide, and low-condensates of titanium hydroxide is hydrogen peroxide.
  • a surface treatment composition containing a titanium-containing aqueous liquid obtained by mixing with water, an organic phosphoric acid, a water-soluble or water-dispersible organic resin, a vanadic acid compound, a zirconium fluoride compound, and a zirconium carbonate compound.
  • Patent Documents 6 and 7 have extremely low corrosion resistance levels and are difficult to apply as chromate coating substitutes.
  • the two-layer coating of Patent Document 8 has a corrosion resistance level applicable as a chromate coating substitute, but has a problem in terms of cost because it uses expensive silicate or silicon resin.
  • the coatings produced by these technologies are subject to a phenomenon of black discoloration (black discoloration) in a humid environment, making it difficult to apply to heat exchangers that are subject to dew condensation, and the storage environment during product transportation. Are also impractical and impractical.
  • Patent Document 9 improves the adhesion resistance when the fluoride contained therein improves the water-resistant adhesion and the corrosion resistance after alkaline degreasing, but has a relatively thick organic resin layer on the upper layer. I will invite you.
  • the adhesion of the organic resin layer is an important performance, but the conventional phosphating treatment that is performed as a base treatment has a crystalline film. Crystals are destroyed by strict processing, and the adhesion of the organic resin layer tends to be lowered.
  • the phosphate film is destroyed when the steel sheet is processed, and the organic resin layer is easily peeled off starting from this portion.
  • the plating metal on the substrate reacts with the treatment liquid to form a very thin, insoluble phosphate to prevent corrosion resistance and paint adhesion.
  • the adhesion and corrosion resistance when processed are likely to deteriorate.
  • an organic resin-coated steel sheet having an organic resin layer with a thickness of 100 ⁇ m or more since the film strength is high, a strong shearing force acts on the interface between the organic resin layer and its base during deformation, and the organic resin layer Peeling easily occurs.
  • Japanese Patent Application No. 2008-335387 has proposed a surface treatment composition capable of obtaining excellent adhesion properties, particularly when a thick organic resin layer having a thickness of 100 ⁇ m or more is deformed.
  • This surface treatment composition comprises at least one titanium compound selected from hydrolyzable titanium compounds, low-condensates of hydrolysable titanium compounds, titanium hydroxide, and low-condensates of titanium hydroxide with a hydrogen peroxide solution.
  • the film formed from the above-mentioned surface treatment composition has a relatively brittle nature. It was found that there was a problem that the film was scratched and the corrosion resistance was likely to be lowered.
  • the object of the present invention is to solve the above-mentioned problems, and does not contain hexavalent chromium at all, and provides excellent corrosion resistance, heat discoloration resistance and blackening resistance, and contact with a metal roll after forming a surface treatment film. Excellent adhesion to the organic resin layer formed on the upper layer of the surface treatment film, particularly a thick organic resin layer having a thickness of 100 ⁇ m or more is formed, and is severely processed.
  • An object of the present invention is to provide a surface-treated composition and a surface-treated steel sheet that can obtain excellent adhesion even when added.
  • Another object of the present invention is to provide an organic resin-coated steel sheet using such a surface-treated steel sheet.
  • the inventors of the present invention have studied a film composition that can solve the above-described problems, and as a result, on the surface of a metal material (preferably a zinc-based plated steel sheet or an aluminum-based plated steel sheet), a specific titanium-containing aqueous liquid.
  • a surface treatment film by a surface treatment composition in which a zirconium carbonate compound, an organic phosphate compound, a metal phosphate, silicon oxide, and a water-soluble organic resin and / or a water-dispersible organic resin are added in a predetermined ratio.
  • a surface treatment composition in which a zirconium carbonate compound, an organic phosphate compound, a metal phosphate, silicon oxide, and a water-soluble organic resin and / or a water-dispersible organic resin are added in a predetermined ratio.
  • a thick organic resin layer having a thickness of 100 ⁇ m or more is formed, and excellent adhesion can be obtained even when severe processing is applied.
  • the surface treatment film formed by the surface treatment composition of the present invention has a high level of barrier properties by being composed of a specific inorganic component, it has excellent corrosion resistance and blackening resistance comparable to a chromate film, In addition, it has excellent heat discoloration that hardly causes coloration or discoloration by heating. Furthermore, the scratch resistance when a metal roll or the like comes into contact after the surface treatment film is formed, and an organic resin layer, particularly a thick organic resin layer having a thickness of 100 ⁇ m or more is formed on the surface treatment film, Excellent adhesion is obtained even when harsh processing is applied.
  • the surface-treated steel sheet and the organic resin-coated steel sheet of the present invention are excellent in corrosion resistance, blackening resistance, heat discoloration resistance and scratch resistance, and are thick enough to have adhesion of the organic resin layer, particularly 100 ⁇ m or more. Excellent adhesion of organic resin layer.
  • the surface treatment composition of the present invention comprises a titanium-containing aqueous liquid (A), a zirconium carbonate compound (B), an organic phosphate compound (C), a metal phosphate (D), silicon oxide (E), and a water-soluble organic resin. And / or a water-dispersible organic resin (F).
  • This surface treatment composition does not contain hexavalent chromium (except for hexavalent chromium as an inevitable impurity).
  • the titanium-containing aqueous liquid (A) contains at least one titanium compound selected from hydrolyzable titanium compounds, hydrolyzable titanium compound low condensates, titanium hydroxide and titanium hydroxide low condensates. It is an aqueous liquid containing titanium obtained by mixing with hydrogen oxide 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 a part of the groups bonded to titanium may be hydrolyzable groups.
  • the hydrolyzable group is not particularly limited as long as it generates titanium hydroxide by reacting with moisture as described above.
  • a lower alkoxyl group or a group that forms a salt with titanium for example, Halogen atoms such as chlorine, hydrogen atoms, sulfate ions, etc.).
  • the hydrolyzable titanium compound containing a lower alkoxyl group as the hydrolyzable group is particularly represented by the general formula Ti (OR) 4 (wherein R represents the same or different alkyl group having 1 to 5 carbon atoms). Tetraalkoxy titanium is preferred.
  • the alkyl group having 1 to 5 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, an iso-butyl group, a sec-butyl group, and a tert-butyl group.
  • Typical examples of the hydrolyzable titanium compound having a group capable of forming a salt with titanium as a hydrolyzable group include titanium chloride and titanium sulfate.
  • the low condensate of a hydrolysable titanium compound is a low condensate of the above-mentioned hydrolysable titanium compounds.
  • the low condensate may be one in which all of the groups bonded to titanium are hydrolyzable groups, or a part of the groups bonded to titanium may be hydrolyzable.
  • hydrolyzable titanium compounds whose hydrolyzable group forms 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 the reaction can also be used as a low condensate.
  • the low condensate of the hydrolyzable titanium compound and the low condensate of titanium hydroxide a compound having a condensation degree of 2 to 30 can be used, and a compound having a condensation degree of 2 to 10 is particularly preferable. If 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 hydrolysable titanium compounds, titanium hydroxide, and low condensates of titanium hydroxide can be used alone or in combination of two or more thereof. Tetraalkoxy titanium which is a hydrolyzable titanium compound represented by the formula is particularly preferable.
  • tetraalkoxytitanium does not affect the film performance such as corrosion resistance because the alcohol produced when hydrolyzed volatilizes in the process of drying the surface treatment composition, and has particularly excellent film performance. It is because it is 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 and hydrogen peroxide solution. Specifically, the following can be mentioned.
  • a liquid for forming a titania film obtained by synthesizing a titanium hydroxide gel produced from an aqueous solution of titanium chloride or titanium sulfate and a basic solution with a hydrogen peroxide solution (Japanese Patent Laid-Open No. 9-71418, (See Kaihei 10-67516).
  • titanium hydroxide gel called ortho titanic acid is precipitated 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.
  • the titanium hydroxide gel is separated by decantation with water, washed thoroughly with water, further added with hydrogen peroxide water, and excess hydrogen peroxide is decomposed and removed, whereby a yellow transparent viscous liquid can be obtained.
  • the precipitated orthotitanic acid is in a gel state polymerized by polymerization of OH or 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 a peroxotitanate ion or in a kind of sol state in which the polymer chain is divided into low molecules, and excess hydrogen peroxide Is decomposed 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 carbon components necessary for thermal decomposition such as sol-gel method and sulfate Further, it is not necessary to remove the halogen component, and a titanium oxide film having a relatively high density can be formed even at a low temperature.
  • (Iii) Hydrogen peroxide is added to an aqueous solution of an inorganic titanium compound such as titanium chloride or titanium sulfate to form a peroxotitanium hydrate, and then the solution obtained by adding a basic substance is allowed to stand or be heated.
  • a titanium oxide forming solution obtained by forming a precipitate of a titanium hydrate polymer, and then removing hydrogen and other dissolved components derived from at least a titanium-containing raw material solution (Japanese Patent Application Laid-Open 2000-247638, JP-A-2000-247639).
  • the titanium-containing aqueous liquid (A) using a hydrolyzable titanium compound and / or a low condensate thereof as a titanium compound contains hydrolyzable titanium compound a. It can be obtained by reacting with hydrogen oxide water at a reaction temperature of 1 to 70 ° C. for about 10 minutes to 20 hours.
  • the hydrolyzable titanium compound a is hydrolyzed with water by reacting the hydrolyzable titanium compound a with hydrogen peroxide.
  • the titanium hydroxide gel used in the conventional manufacturing method is partially three-dimensionalized by Ti—O—Ti bonds, and the titanium-containing aqueous liquid (A) obtained by reacting this gel with hydrogen peroxide is composition and stable. Sex is essentially different.
  • the titanium-containing aqueous liquid (A) using the hydrolyzable titanium compound a is heated or autoclaved at 80 ° C. or higher, a titanium oxide dispersion liquid containing crystallized ultrafine particles of titanium oxide is obtained. If the heat treatment or autoclave treatment is performed at 80 ° C. or higher, the crystallization of titanium oxide can be sufficiently advanced.
  • the average particle size of the titanium oxide ultrafine particles of the titanium oxide dispersion thus produced is 10 nm or less, preferably about 1 to 6 nm. When the average particle diameter of the titanium oxide ultrafine particles is 10 nm or less, the film-forming property is excellent (when the film is dried after coating to form a film, cracking does not occur when the film thickness is 1 ⁇ m or more).
  • 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 plate and dried (for example, heat-dried at a low temperature), thereby adhering to itself.
  • a dense titanium oxide-containing film (surface treatment film) having excellent properties can be formed.
  • the heating temperature of the steel sheet after the application of the surface treatment composition (H) is, for example, preferably 200 ° C. or lower, particularly preferably 150 ° C. or lower.
  • Amorphous) titanium oxide-containing film can be formed.
  • the crystal can be obtained by simply applying the surface treatment composition (H). It is useful as a coating material for materials that cannot be heat-treated.
  • a titanium-containing aqueous liquid (A1) obtained by reacting the hydrolyzable titanium compound a with hydrogen peroxide in the presence of a titanium oxide sol can also be used.
  • the titanium oxide sol is a sol in which amorphous titania fine particles and / or anatase type 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).
  • an aqueous organic solvent such as an alcohol or alcohol ether may be added if necessary.
  • this titanium oxide sol conventionally known ones can be used.
  • An amorphous titania sol dispersed in water, or a sol in which the titanium oxide aggregates are calcined to form anatase-type titanium fine particles and this is dispersed in water can be used.
  • the amorphous titania can be converted to anatase titania by firing at a temperature at least higher than the crystallization temperature of anatase, for example, at a temperature of 400 ° C. to 500 ° C. or higher.
  • the aqueous sol of titanium oxide include, for example, TKS-201 (trade name, manufactured by Teika, anatase crystal form, average particle diameter 6 nm), TA-15 (trade name, manufactured by Nissan Chemical Co., anatase crystal form).
  • STS-11 trade name, manufactured by Ishihara Sangyo Co., Ltd., anatase crystal form).
  • the mass ratio x / y between the titanium oxide sol x and the titanium hydrogen peroxide reactant y is 1 /
  • the range of 99 to 99/1, preferably about 10/90 to 90/10 is appropriate. If the mass ratio x / y is 1/99 or more, the effect of adding the titanium oxide sol is sufficiently obtained in terms of stability, photoreactivity, and the like, and if it is 99/1 or less, excellent film formation is achieved. It is preferable because of its property.
  • the titanium-containing aqueous liquid (A1) can be obtained by reacting the 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 a titanium oxide sol.
  • the production form and characteristics of the titanium-containing aqueous liquid (A1) are the same as those of the titanium-containing aqueous liquid (A) using the hydrolyzable titanium compound a described above, but in particular, by using a titanium oxide sol. , It is possible to suppress a partial condensation reaction during the synthesis to increase the viscosity. The reason is considered to be that the condensation reaction product is adsorbed on the surface of the titanium oxide sol, and polymerization in a solution state is suppressed.
  • titanium-containing aqueous liquid (A1) when heated or autoclaved at 80 ° C. or higher, a titanium oxide dispersion containing ultrafine particles of crystallized titanium oxide is obtained.
  • the titanium-containing aqueous liquid (A) using the hydrolyzable titanium compound a described above also describes 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. It is the same.
  • Such a titanium oxide dispersion can also be used as the titanium-containing aqueous liquid (A1).
  • the surface treatment composition (G) containing the titanium-containing aqueous liquid (A1) is applied to the surface of the plated steel sheet and dried (for example, By heating and drying at a low temperature, it is possible to form a dense titanium oxide-containing film (surface-treated film) having excellent adhesion by itself.
  • the heating temperature of the steel sheet after the application of the surface treatment composition (G) is, for example, 200 ° C. or less, particularly preferably 150 ° C. or less. By heating and drying at such a temperature, anatase-type oxidation containing some hydroxyl groups. A titanium-containing film can be formed.
  • the titanium-containing aqueous liquid (A) and the titanium-containing aqueous liquid (A1) using the hydrolyzable titanium compound a are excellent in storage stability, corrosion resistance, and the like. It is particularly preferable to use these in the present invention.
  • the compounding ratio of hydrogen peroxide water to at least one titanium compound selected from hydrolyzable titanium compounds, hydrolyzable titanium compound low condensates, titanium hydroxide, titanium hydroxide low condensates is titanium compounds It is preferably 0.1 to 100 parts by mass, more preferably 1 to 20 parts by mass in terms of hydrogen peroxide with respect to 10 parts by mass. If the blending ratio of hydrogen peroxide water is 0.1 parts by mass or more in terms of hydrogen peroxide, chelate formation is sufficient so that no cloudy precipitation occurs. On the other hand, if it is 100 parts by mass or less, unreacted This is preferable because no hydrogen peroxide remains, and no active oxygen is released during storage.
  • the hydrogen peroxide concentration in the hydrogen peroxide solution is not particularly limited, but it is preferably about 3 to 30 mass% from the viewpoint of ease of handling and the solid content of the produced liquid related to the coating workability.
  • sols and pigments can be added and dispersed in the titanium-containing aqueous liquid (A) as necessary.
  • the additive include commercially available titanium oxide sol, titanium oxide powder, mica, talc, barita, clay, and the like, and one or more of these can be added.
  • the content of the titanium-containing aqueous liquid (A) in the surface treatment composition is preferably 1 to 100 g / L, preferably 5 to 50 g / L in terms of solid content from the viewpoint of the stability of the treatment liquid. .
  • the surface treatment composition of the present invention further improves the corrosion resistance by adding the zirconium carbonate compound (B) to the titanium-containing aqueous liquid (A), and an organic resin layer (an organic resin layer formed by lamination or coating).
  • the corrosion resistance after coating with the organic resin layer is significantly improved.
  • the organophosphate compound (C) increases the reactivity with the steel sheet to improve the corrosion resistance, and also improves the storage stability of the surface treatment composition.
  • metal phosphate (D) and silicon oxide (E) an organic resin layer formed as an upper layer, particularly a thick organic resin layer having a thickness of 100 ⁇ m or more (for example, formed by lamination).
  • the adhesion of the organic resin layer) during deformation of the steel sheet is improved.
  • a water-soluble organic resin and / or water-dispersible organic resin (F) the scratch resistance of the surface treatment film is improved, and even when roll contact occurs after the surface treatment film is formed, excellent corrosion resistance is achieved. It expresses.
  • the zirconium carbonate compound (B) ammonium zirconium carbonate, zirconium oxycarbonate and the like are suitable, and improvement of corrosion resistance can be achieved by using at least one of these.
  • the compounding amount of the zirconium carbonate compound (B) is 10 to 300 parts by mass, preferably 50 to 100 parts by mass with respect to 100 parts by mass of the solid content of the titanium-containing aqueous liquid (A).
  • the blending amount of the zirconium carbonate compound (B) is less than 10 parts by mass with respect to 100 parts by mass of the solid content of the titanium-containing aqueous liquid (A), the effect of improving the corrosion resistance is small. Tend to deteriorate.
  • organic phosphoric acid compound (C) examples include hydroxyl groups such as 1-hydroxymethane-1,1-diphosphonic acid, 1-hydroxyethane-1,1-diphosphonic acid, and 1-hydroxypropane-1,1-diphosphonic acid.
  • Group-containing organic phosphorous acid; carboxyl group-containing organic phosphorous acid such as 2-hydroxyphosphonoacetic acid and 2-phosphonobutane-1,2,4-tricarboxylic acid, and salts thereof are preferred. 1 type (s) or 2 or more types can be used.
  • the organic phosphoric acid compound (C) has the effect of improving the corrosion resistance and the storage stability of the titanium-containing aqueous liquid (A). Among them, 1-hydroxyethane-1,1-diphosphonic acid is particularly effective. Therefore, it is particularly preferable to use this.
  • the compounding amount of the organic phosphoric acid compound (C) is 50 to 200 parts by mass, particularly 70 to 150 parts by mass with respect to 100 parts by mass of the solid content of the titanium-containing aqueous liquid (A). It is preferable from the point.
  • the compounding amount of the organic phosphoric acid compound (C) is less than 50 parts by mass with respect to 100 parts by mass of the solid content of the titanium-containing aqueous liquid (A), the storage stability of the surface treatment composition is inferior and the corrosion resistance is reduced. It is done. On the other hand, when it exceeds 200 mass parts, water-resistant adhesiveness is inferior.
  • Metal phosphate (D) and silicon oxide (E) are blended in order to improve adhesion to an organic resin layer formed as an upper layer by laminating or the like, particularly a thick organic resin layer having a thickness of 100 ⁇ m or more. It is something to be made.
  • silicon oxide (E) include amorphous silica such as liquid phase silica produced by a liquid phase reaction method and gas phase silica produced by a dry method, and one or more of these are used. be able to. Specifically, as liquid phase silica, SNOWTEX (registered trademark) O, N, 20, 30, 40, C, S manufactured by Nissan Chemical Industries, Ltd., as gas phase silica, Nippon Aerosil Co., Ltd.
  • AEROSIL registered trademark 130, 200, 200V, 200CF, 300, 300CF, etc. manufactured by the company can be used.
  • vapor-phase silica produced by a dry method is very preferable from the viewpoint of adhesion to the organic resin layer, and good performance can be obtained.
  • metal phosphate (D) there are no special restrictions on the type of metal phosphate (D), but among them, aluminum salts, magnesium salts, and manganese salts are effective.
  • aluminum salt there is an advantage that the solubility of the phosphate is lowered and the effect in a humid environment is sustained. 1 type (s) or 2 or more types can be used for said metal phosphate.
  • the metal phosphate (D) it is preferable to apply a commercially available aqueous solution in which the phosphoric acid / metal cation component ratio is rich in phosphoric acid in advance so that it can exist as an aqueous solution.
  • the metal phosphate (D) and the silicon oxide (E) are mixed in advance, It is preferable to add in the form of this mixture. More excellent adhesion and corrosion resistance can be obtained when added in a premixed state than when added separately. Although this reason is not necessarily clear, it is thought that it is because the cohesive force of the film obtained by the surface treatment composition is increased by the effect of the phosphoric acid component. Moreover, the storage stability of the surface treatment composition is improved by mixing by this method.
  • the metal phosphate aqueous solution is obtained by adding the gas phase silica to the metal phosphate aqueous solution and stirring vigorously.
  • a silicon oxide dispersion liquid in which vapor phase silica is dispersed may be prepared in advance and mixed with other components.
  • the surface treatment composition may be prepared by vigorously stirring the vapor phase silica and the metal phosphate aqueous solution together with other compounding components and water.
  • vapor phase silica when vapor phase silica is dispersed in the surface treatment composition with a sand mill or the like, aggregation occurs in about one week to several weeks, and a precipitate is generated.
  • gas phase silica having a low bulk specific gravity it has been found that it is effective to use gas phase silica having a low bulk specific gravity in order to prevent such aggregation and improve storage stability (chemical solution stability). It was. Specifically, it is preferable to use gas phase silica having a bulk specific gravity of 40 g / L or less.
  • the bulk specific gravity of the vapor phase silica can be adjusted by controlling the deaeration conditions after the production by the dry method, whereby a vapor phase silica having a small bulk specific gravity can be obtained.
  • the adhesion of the organic resin layer is improved by blending the metal phosphate (D) and the silicon oxide (E).
  • the surface polarity of the surface treatment film is changed by blending the silicon oxide and the metal phosphate. It is thought that this is because it acts on the adhesiveness advantageously. Since silicon oxide increases the polarity, it has the effect of increasing the adhesion with the resin layer and the adhesive layer when the organic resin layer is directly applied to the upper layer or when the organic resin film is brought into close contact with the adhesive. On the other hand, if the polarity is too high, it becomes easy to take in moisture in a humid environment, which is disadvantageous for swelling.
  • nonpolar phosphoric acid metal phosphate
  • metal phosphate nonpolar phosphoric acid
  • secondary aggregation of silicon oxide forms surface irregularities on the order of submicrons, and the formation of such surface irregularities increases the effective area at the adhesion interface, thus effectively acting on adhesion. It is considered a thing.
  • the influence on the texture due to the incorporation of the metal phosphate is not sufficiently clear, it is considered that the texture is affected by acting on the secondary aggregation of silicon oxide.
  • the compounding amount of the metal phosphate (D) is 5 to 20 mass% as a ratio in the total solid content of the surface treatment composition, and the compounding amount of silicon oxide (E) is in the total solid content of the surface treatment composition.
  • the ratio is 32 to 40 mass%.
  • the blending amount of silicon oxide (E) is less than 32 mass% in the total solid content of the surface treatment composition, formation of irregularities on the order of submicron is insufficient, and the upper organic resin layer and Sufficient adhesion cannot be obtained.
  • it exceeds 40 mass% good adhesion can be obtained, but the surface treatment film becomes brittle, so the film is scratched by roll contact etc., and of course the bare corrosion resistance as well as the scratched part after coating with organic resin Corrosion progresses and blistering occurs.
  • the water-soluble organic resin and / or water-dispersible organic resin (F) is an organic resin that can be dissolved or dispersed in water, and a conventionally known method for water-solubilizing or dispersing the organic resin in water.
  • the method can be applied.
  • the organic resin contains a functional group (for example, a hydroxyl group, a polyoxyalkylene group, a carboxyl group, an amino (imino) group, a sulfide group, a phosphine group, etc.) that can be water-soluble or water-dispersed independently.
  • amine compounds such as ethanolamine and triethylamine if acidic resin (carboxyl group-containing resin, etc.); ammonia water; lithium hydroxide, sodium hydroxide, water Neutralized with alkali metal hydroxides such as potassium oxide, and basic resins (amino group-containing resins, etc.), fatty acids such as acetic acid and lactic acid; neutralized with mineral acids such as phosphoric acid, etc. Can be used.
  • water-soluble or water-dispersible organic resins include epoxy resins, phenolic resins, acrylic resins, urethane resins, olefin-carboxylic acid resins, nylon resins, resins having a polyoxyalkylene chain, and polyvinyl alcohol. , Polyglycerin, carboxymethylcellulose, hydroxymethylcellulose, hydroxyethylcellulose and the like.
  • the said organic resin can use 1 type (s) or 2 or more types.
  • a water-soluble or water-dispersible acrylic resin is prepared by a conventionally known method, for example, an emulsion polymerization method, a suspension polymerization method, a polymer having a hydrophilic group by solution polymerization, and neutralized or made aqueous if necessary. Or the like.
  • the polymer having a hydrophilic group includes, for example, an unsaturated monomer having a hydrophilic group such as a carboxyl group, an amino group, a hydroxyl group, and a polyoxyalkylene group, and, if necessary, other unsaturated monomers. It can be obtained by polymerizing the monomer.
  • the water-soluble or water-dispersible acrylic resin is preferably obtained by copolymerizing styrene from the viewpoint of corrosion resistance, and the amount of styrene in the total unsaturated monomer is 10 to 60 mass%, particularly 15 to 50 mass%. It is preferable. Further, the Tg (glass transition point) of the acrylic resin obtained by copolymerization is preferably 30 to 80 ° C., particularly 35 to 70 ° C. from the viewpoint of the toughness of the resulting film.
  • Examples of the carboxyl group-containing unsaturated monomer include acrylic acid, methacrylic acid, maleic acid, maleic anhydride, crotonic acid, and itaconic acid.
  • Examples of the nitrogen-containing unsaturated monomer such as the amino group-containing unsaturated monomer include N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, Nt- Nitrogen-containing alkyl (meth) acrylates such as butylaminoethyl (meth) acrylate; acrylamide, methacrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-methylol (meth) acrylamide, N-methoxymethyl Polymerization of (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-dimethyla
  • hydroxyl group-containing unsaturated monomer examples include 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, 2,3-dihydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, polyethylene glycol mono Monoesterified product of polyhydric alcohol such as (meth) acrylate, polypropylene glycol mono (meth) acrylate and acrylic acid or methacrylic acid; ⁇ -caprolactone is opened to monoesterified product of polyhydric alcohol and acrylic acid or methacrylic acid. Examples include a ring-polymerized compound.
  • unsaturated monomers include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, 1 carbon number such as tert-butyl (meth) acrylate, 2-ethylhexyl acrylate, n-octyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, octadecyl (meth) acrylate, isostearyl (meth) acrylate To 24 alkyl (meth) acrylates; vinyl acetate and the like.
  • the unsaturated monomer mentioned above can use 1 type (s) or 2 or more types.
  • (meth) acrylate” means “acrylate or methacrylate”.
  • the urethane-based resin examples include a chain extender which is a low molecular weight compound having two or more active hydrogens such as a diol and a diamine as needed, and a polyurethane composed of a polyol and a diisocyanate such as polyester polyol and polyether polyol.
  • a chain extender which is a low molecular weight compound having two or more active hydrogens such as a diol and a diamine as needed
  • a polyurethane composed of a polyol and a diisocyanate such as polyester polyol and polyether polyol.
  • Those which are chain-extended in the presence and stably dispersed or dissolved in water can be suitably used, and conventionally known ones can be widely used (for example, Japanese Patent Publication No. 42-24192, Japanese Patent Publication No. 42-24194, (See JP-B-42-5118, JP-B-49-986, JP-B-49-33104, JP-B
  • a method for stably dispersing or dissolving the polyurethane resin in water for example, the following method can be used.
  • a blocking agent such as oxime, alcohol, phenol, mercaptan, amine, sodium bisulfite, etc.
  • diisocyanate examples include aromatic, alicyclic or aliphatic diisocyanates. Specifically, hexamethylene diisocyanate, tetramethylene diisocyanate, 3,3′-dimethoxy-4, 4'-biphenylene diisocyanate, p-xylylene diisocyanate, m-xylylene diisocyanate, 1,3- (diisocyanatomethyl) cyclohexanone, 1,4- (diisocyanatomethyl) cyclohexanone, 4,4'-diisocyanato Cyclohexanone, 4,4'-methylenebis (cyclohexyl isocyanate), isophorone diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, p-phenylene diisocyanate, diphenylmethane di Isocyanate
  • 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, hexamethylene diisocyanate, and isophorone diisocyanate are particularly preferable.
  • commercially available polyurethane resins include Hydran (registered trademark) HW-330, HW-340, HW-350 (both trade names, manufactured by Dainippon Ink and Chemicals), Superflex (registered trademark) 100, 150, E-2500, F-3438D (all trade names, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) and the like.
  • a cationic epoxy resin obtained by adding an amine to an epoxy resin a modified epoxy resin such as acrylic modified or urethane modified
  • a modified epoxy resin such as acrylic modified or urethane modified
  • examples of cationic epoxy resins include adducts of epoxy compounds with primary mono- or polyamines, secondary mono- or polyamines, and primary and secondary mixed polyamines (see, for example, US Pat. No. 3,984,299).
  • An adduct of an epoxy compound and a secondary mono- or polyamine having a ketiminated primary amino group see, for example, US Pat. No. 4,017,438); an epoxy compound having a ketiminated primary amino group
  • Examples include etherification reaction products with hydroxyl compounds (see, for example, JP-A-59-43013).
  • the epoxy resin preferably has a number average molecular weight of 400 to 4000, particularly 800 to 2000, and an epoxy equivalent of 190 to 2000, particularly 400 to 1000.
  • Such an epoxy resin can be obtained, for example, by a reaction between a polyphenol compound and epirulhydrin, and examples of the polyphenol compound include bis (4-hydroxyphenyl) -2,2-propane, 4,4.
  • the blending amount of the water-soluble organic resin and / or the water-dispersible organic resin (F) is 2 to 10 mass% as a ratio in the total solid content of the surface treatment composition. If the blending amount of the water-soluble organic resin and / or water-dispersible organic resin (F) is less than 2 mass% in the total solid content of the surface treatment composition, the brittleness of the surface treatment film cannot be improved and the surface treatment is performed. The film is scratched by contact with the roll after the film is formed, and the corrosion starts from the scratched part after the organic resin coating as well as the bare corrosion resistance. On the other hand, if it exceeds 10 mass%, the heat discoloration and post-processing adhesion will be reduced.
  • the pH of the surface treatment composition is preferably adjusted to 7-12. If the pH is less than 7 or more than 12, aggregation of the surface treatment composition occurs with time, and a film cannot be formed.
  • the surface treatment composition of the present invention 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, a thickener, A surfactant, a lubricity-imparting agent (polyethylene wax, fluorine-based wax, carnauba wax, etc.), a rust inhibitor, a color pigment, an extender pigment, a rust preventive pigment, and a dye can be contained.
  • 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, a thickener, A surfactant, a lubricity-imparting agent (polyethylene wax, fluorine-based wax, carnauba wax, etc.), a rust inhibitor, a color pigment, an extender pigment, a rust preventive pigment, and a dye can
  • the surface treatment composition of this invention can be diluted with hydrophilic solvents, such as methanol, ethanol, isopropyl alcohol, an ethylene glycol type solvent, a propylene glycol type solvent, for example as needed, and can be used.
  • hydrophilic solvents such as methanol, ethanol, isopropyl alcohol, an ethylene glycol type solvent, a propylene glycol type solvent, for example as needed, and can be used.
  • the surface treatment composition of the present invention preferably has a solid content of about 2 to 10 mass% from the viewpoint of storage stability and stability during coating.
  • the surface treatment composition of the present invention can be used as a surface treatment agent for various metal materials, but is particularly suitable as a surface treatment agent for zinc-based plated steel sheets and aluminum-based plated steel sheets described later.
  • the surface-treated steel sheet of the present invention has a surface-treated composition as described above, that is, a titanium-containing aqueous liquid (A), a zirconium carbonate compound (B), and an organic phosphate compound on the surface of a zinc-based plated steel sheet or an aluminum-based plated steel sheet. Formed by applying and drying a surface treatment composition containing (C), metal phosphate (D), silicon oxide (E), and water-soluble organic resin or / and water-dispersible organic resin (F) And having a surface-treated film having a predetermined coating amount. This surface-treated film does not contain hexavalent chromium (except for hexavalent chromium as an inevitable impurity). Further, the titanium-containing aqueous liquid (A) and the surface treatment composition may further contain other additive components as mentioned above, if necessary.
  • Examples of the galvanized steel sheet used as the base of the surface-treated steel sheet of the present invention include a galvanized steel sheet, a Zn—Ni alloy plated steel sheet, a Zn—Fe alloy plated steel sheet (electroplated steel sheet, galvannealed steel sheet), Zn -Cr alloy plated steel sheet, Zn-Mn alloy plated steel sheet, Zn-Co alloy plated steel sheet, Zn-Co-Cr alloy plated steel sheet, Zn-Cr-Ni alloy plated steel sheet, Zn-Cr-Fe alloy plated steel sheet, Zn-Al Alloy-plated steel sheets (for example, Zn-5 mass% Al alloy-plated steel sheets, Zn-55 mass% Al alloy-plated steel sheets), Zn-Mg alloy-plated steel sheets, Zn-Al-Mg alloy-plated steel sheets, and plating of these plated steel sheets Zinc-based composite plated steel sheet (for example, Zn-SiO2 dispersion plated steel sheet) in which metal
  • an aluminum system plated steel plate used as the base of the surface treatment steel plate of this invention an aluminum plating steel plate, an Al-Si alloy plating steel plate, etc. can be used.
  • the steel plate surface may be previously plated with lightness such as Ni, and various plating as described above may be performed thereon.
  • a plating method any feasible method among an electrolytic method (electrolysis in an aqueous solution or electrolysis in a nonaqueous solvent), a melting method, and a gas phase method can be adopted.
  • alkali degreasing, solvent degreasing, surface conditioning treatment (alkaline surface conditioning) is performed on the surface of the plating film as necessary in order to prevent film defects and unevenness from occurring. Treatment or acidic surface conditioning treatment) can be performed.
  • an iron group metal ion (one or more of Ni ion, Co ion, Fe ion) is previously applied to the plating surface as necessary.
  • Surface adjustment treatment with an acidic or alkaline aqueous solution containing can also be performed.
  • iron group metal ions one or more of Ni ions, Co ions, Fe ions
  • These metals can be contained in an amount of 1 mass ppm or more.
  • the adhesion amount of the surface treatment film formed by the surface treatment composition is 0.03 to 0.5 g / m 2 . If the coating amount is less than 0.03 g / m 2 , the corrosion resistance is inferior. On the other hand, if it exceeds 0.5 g / m 2 , the coating tends to break, and the adhesion during severe processing after coating with an organic resin is reduced.
  • the surface treatment composition as described above that is, the titanium-containing aqueous liquid (A), the zirconium carbonate compound (B), on the surface of the zinc-based plated steel sheet or the aluminum-based plated steel sheet,
  • a surface treatment composition (treatment liquid) containing an organic phosphate compound (C), metal phosphate (D), silicon oxide (E) and a water-soluble organic resin or / and a water-dispersible organic resin (F)
  • a surface treatment composition containing an organic phosphate compound (C), metal phosphate (D), silicon oxide (E) and a water-soluble organic resin or / and a water-dispersible organic resin (F)
  • the titanium-containing aqueous liquid (A) and the surface treatment composition may further contain other additive components as mentioned above, if necessary.
  • the means for applying the surface treatment composition (treatment liquid) is optional, for example, spray + roll squeezing, roll coater, etc.
  • the drying method after application is also, for example, a hot air method, induction heating method, electric furnace method, etc. Is optional.
  • the drying temperature (steel plate temperature) of the applied surface treatment composition (treatment liquid) is preferably about 60 to 200 ° C. When the drying temperature is 60 ° C. or higher, film formation is sufficient and a film having excellent corrosion resistance and the like is obtained. On the other hand, if the drying temperature is 200 ° C. or less, cracks are not generated in the film due to heat, so that a sufficient effect of improving corrosion resistance is obtained.
  • a more preferable drying temperature is 60 to 140 ° C., and a further preferable temperature is 60 to 100 ° C.
  • the organic resin-coated steel sheet of the present invention is obtained by forming an organic resin layer on the surface-treated film of the surface-treated steel sheet as described above.
  • the method for forming the organic resin layer is arbitrary, and for example, a method of applying and drying a coating composition, a method of laminating an organic resin film, and the like can be applied.
  • the surface treatment film of the present invention is particularly excellent in adhesion of a thick organic resin layer having a thickness of 100 ⁇ m or more
  • the organic resin-coated steel sheet of the present invention has an organic resin layer thickness of 100 ⁇ m or more. Is particularly useful.
  • the organic resin layer may contain various additives including non-chromium rust preventive additives, solid lubricants, color pigments and the like.
  • titanium-containing aqueous liquid (A) and components (B) to (F) used in the surface treatment composition are shown below.
  • Tianium-containing aqueous liquid T2 A mixture of 10 parts by mass of tetraiso-propoxytitanium and 10 parts by mass of iso-propanol was dropped into a mixture of 10 parts by mass of 30 mass% hydrogen peroxide and 100 parts by mass of deionized water while stirring at 20 ° C. over 1 hour. . Thereafter, aging was carried out at 25 ° C. for 2 hours to obtain a yellow transparent, slightly viscous titanium-containing aqueous liquid T2.
  • Production Example 3 (Titanium-containing aqueous liquid T3) A titanium-containing aqueous liquid T3 was obtained under the same production conditions as in Production Example 2 except that tetra-n-butoxy titanium was used instead of tetraiso-propoxy titanium used in Production Example 2.
  • Production Example 4 (Titanium-containing aqueous liquid T4)
  • a tetramer of tetraiso-propoxytitanium low condensation product of tetraiso-propoxytitanium
  • titanium was used instead of tetraiso-propoxytitanium used in Production Example 2
  • a contained aqueous liquid T4 was obtained.
  • Production Example 5 (Titanium-containing aqueous liquid T5) A titanium-containing aqueous liquid was produced under the same production conditions as in Production Example 2, except that hydrogen peroxide was used in 3 times the amount of Production Example 2, dropped at 50 ° C over 1 hour, and further aged at 60 ° C for 3 hours. T5 was obtained.
  • Production Example 6 (Titanium-containing aqueous liquid T6) The titanium-containing aqueous liquid T3 produced in Production Example 3 was further heat-treated at 95 ° C. for 6 hours to obtain a white yellow translucent titanium-containing aqueous liquid T6.
  • Production Example 7 (Titanium-containing aqueous liquid T7) A mixture of 10 parts by mass of tetraiso-propoxytitanium and 10 parts by mass of iso-propanol was mixed with 5 parts by mass (solid content) of “TKS-203” (trade name, manufactured by Teika Co., Ltd.), 10 mass% hydrogen peroxide solution 10 The mixture was added dropwise to a mixture of parts by mass and 100 parts by mass of deionized water at 10 ° C. with stirring for 1 hour. Thereafter, the mixture was aged at 10 ° C. for 24 hours to obtain a yellow transparent, slightly viscous titanium-containing aqueous liquid T7.
  • Silicon oxide (E) is added to the aqueous solution of metal phosphate (D) at the solid content blending ratio shown in Table 3, Table 5, Table 7, and Table 9 and stirred vigorously, and silicon oxide is added to the metal phosphate aqueous solution. A dispersed mixture was obtained.
  • Tables 7 and 8 No. 77 comparative examples contain only silicon oxide E4.
  • D1 primary aluminum phosphate
  • D2 primary magnesium phosphate
  • D3 primary manganese phosphate / silicon oxide
  • E1 Aerosil 300 (trade name, manufactured by Nippon Aerosil Co., Ltd., vapor phase silica, bulk specific gravity; 50 g / L)
  • E2 Aerosil 200 (trade name, manufactured by Nippon Aerosil Co., Ltd., vapor phase silica, bulk specific gravity; 35 g / L)
  • E3 Snowtex O (trade name, manufactured by Nissan Chemical Industries, colloidal silica)
  • E4 Aerosil 300CF (trade name, manufactured by Nippon Aerosil Co., Ltd., vapor phase silica, bulk specific gravity; 35 g / L)
  • Water-soluble or water-dispersible organic resin (F) Of the water-soluble or water-dispersible organic resins, water-dispersible acrylic resins F1 to F5 were produced according to Production Examples 8 to 12 shown below, and commercially available products were used for F6 to F13. In the following production examples, “part” and “%” are based on mass.
  • Production Example 8 Water-dispersible acrylic resin F1 265 parts deionized water, 9 parts Aqualon RN-50 (Note 1), Aqualon RN-2025 (Note 2) 87 in a 2-liter four-necked flask equipped with a reflux condenser, stirrer, thermometer, and dropping funnel 5% (28.9 parts) of a pre-emulsion obtained by forcibly emulsifying monomer mixture liquid 1 (first stage) having the following composition was added, and the temperature was raised after nitrogen substitution.
  • Monomer mixture 1 Deionized water 166.5 parts Aqualon RN-50 6.6 parts Aqualon RN-2025 53 parts Styrene 35 parts Methyl methacrylate 163.5 parts 2-Ethylhexyl acrylate 105 parts 2-Hydroxyethyl methacrylate 5 parts Methacrylic acid 3 parts Acrylonitrile 38.
  • the monomer mixed solution 2 (second stage) having the following composition was dropped over 1 hour from the end of dropping of the first stage pre-emulsion.
  • ⁇ Monomer mixture 2 >> Styrene 15 parts Methyl methacrylate 84.5 parts 2-Ethylhexyl acrylate 22.5 parts 2-hydroxyethyl methacrylate 4.25 parts Methacrylic acid 6 parts Acrylonitrile 15 parts ⁇ -Methacryloxypropyltrimethoxysilane 2.75 parts The temperature is kept at 60 ° C. for 1 hour, and then the temperature is lowered to 40 ° C. or less.
  • Production examples 9 to 12 water-dispersible acrylic resins F2 to F5
  • water-dispersible acrylic resins F2 to F5 were obtained in the same manner as in Production Example 8, except that the monomer composition of the first and second stages was changed to the blending ratio shown in Table 2.
  • Table 2 also shows the characteristic values of each water-dispersible acrylic resin.
  • F6 Superflex E-2500 (trade name, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., aqueous polyurethane resin)
  • F7 Superflex 150 (trade name, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., water-based polyurethane resin)
  • F8 Superflex 420 (trade name, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., water-based polyurethane resin)
  • F9 Superflex 300 (trade name, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., water-based polyurethane resin)
  • F10 Bironal MD-1100 (trade name, manufactured by Toyobo Co., Ltd., water-based polyester resin)
  • F11 Adeka Resin EM-0718 (trade name, manufactured by ADEKA, water-based epoxy resin)
  • F12 MODEPICS 303 (trade name, manufactured by Arakawa Chemical Industries, Ltd., water-based epoxy resin)
  • the plated steel plate shown in Table 1 was used as the base steel plate of the surface-treated steel plate.
  • Surface treatment composition in which components (B) to (F) and distilled water are appropriately blended and mixed with the titanium-containing aqueous liquid (A) described above, and the solid content is adjusted to 2 to 10 mass% and the pH is adjusted to 8.
  • the product was applied to the surface of the plated steel sheet and dried after 5 seconds so as to reach a predetermined drying temperature (maximum plate temperature) to prepare a surface-treated steel sheet.
  • the surface-treated steel sheet thus obtained is wound with a paper roll wrapped around a rubber roll (48 mm ⁇ ⁇ 205 mm) and scratched on the surface of the coating once without rotating the roll with a load of 690 g (including the roll's own weight). It processed and it was set as the test material 1.
  • the comparative example 46 does not perform the scratching process.
  • test materials 1 were evaluated for heat discoloration resistance, water adhesion resistance, corrosion resistance, and blackening resistance by the following test methods (1) to (4). Furthermore, after applying a general adhesive for a polyvinyl chloride film to the test material 1 so that the dry film thickness becomes 3 ⁇ m, the furnace temperature is heated in a heating furnace having a temperature of 100 ° C., and then a polyvinyl chloride film having a film thickness of 250 ⁇ m. Is pressed against the surface of the test material with a roll so that the steel plate temperature becomes 230 ° C., and a polyvinyl chloride film (organic resin layer) is adhered by thermocompression bonding, and an organic resin-coated steel plate (this is “test material 2”). And).
  • Adhesion after processing (peeling strength after processing) Using a test piece of 30 mm ⁇ 120 mm cut out from the specimen 2, draw a double line at 50 mm intervals perpendicular to the length direction at the center of the test piece in the length direction. Both ends in the vertical direction were grasped with a clamp of a tensile tester, and stretched in a uniaxial direction until the distance between the two lines reached 60 mm. Using the stretched test piece as a sample, the organic resin layer between the spread two wires was provided with a cut reaching the steel plate so as to have a width of 20 mm.
  • One end of the organic resin layer provided with this incision is forcibly peeled off, the end of the peeled organic resin layer is gripped by one clamp of a tensile tester, a steel plate is gripped by the other clamp of the tensile tester, and the peeling speed is 50 mm.
  • peel strength is 40 N / 20 mm width or more
  • B Peel strength is 30 N / 20 mm width or more and less than 40 N / 20 mm width
  • X Peel strength is less than 30 N / 20 mm width
  • Corrosion resistance (scratch resistance) A 50 mm ⁇ 100 mm test piece cut out from the test material 2 was used, a cross cut was made on the surface of the test piece, and a salt spray test was conducted for 1000 hours in accordance with the provisions of JIS-Z-2371-2000. The one-sided corrosion width from the crosscut was measured. The evaluation criteria are as follows. A: The average corrosion width from the cut portion is less than 5 mm. O: The average corrosion width from the cut portion is 5 mm or more and less than 10 mm. X: The average corrosion width from the cut portion is 10 mm or more. The film formed on the surface of the surface-treated steel sheet.
  • the scratch resistance is inferior, the coating is scraped off and a large number of scratches reaching the plated surface are formed. Since there is no film in the scratched part, the adhesion with the organic resin layer is poor, and water easily enters. Therefore, salt water that has entered from the cross cut portion penetrates into the scratch portion, and corrosion progresses. As a result, when the scratch resistance is inferior, the corrosion width from the cross cut portion increases. Therefore, the evaluation of the one-sided average corrosion width from the cross cut is an evaluation of scratch resistance.
  • Storage stability The surface treatment composition having a solid content of 8 mass% was aged at 40 ° C. for 2 weeks, and the precipitation state and viscosity of the solid content were visually evaluated. The evaluation criteria are as follows. ⁇ : No solid content precipitation and no change in viscosity ⁇ : Slight solid content precipitation or small viscosity change ⁇ : Many solid content precipitations or large viscosity change ⁇ : Many solid content precipitations Large change in viscosity (8) Storage stability (II) The surface treatment composition having a solid content of 8 mass% was maintained at 30 ° C., and the solid precipitation state was visually evaluated every week. The evaluation criteria are as follows. ⁇ : No precipitation after 4 weeks ⁇ : Precipitation occurs after 4 weeks ⁇ : Precipitation occurs after 2 to 3 weeks ⁇ : Precipitation occurs after 1 week

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Wood Science & Technology (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Laminated Bodies (AREA)
  • Paints Or Removers (AREA)

Abstract

L'invention divulgue une composition de traitement de surface qui présente une excellente résistance à la corrosion, une excellente résistance à la décoloration thermique, une excellente résistance au noircissement, une excellente résistance aux rayures, une excellente adhérence post-traitement à une couche de résine organique qui est formée sur celle-ci. La composition de traitement de surface contient (A) une solution aqueuse contenant du titane qui est produite en mélangeant au moins un composé de titane sélectionné parmi un composé de titane hydrolysable, un produit faiblement condensé d'un composé de titane hydrolysable, l'hydroxyde de titane et un produit faiblement condensé d'hydroxyde de titane avec du peroxyde d'hydrogène aqueux, (B) un composé de carbonate de zirconium, (C) un composé d'acide phosphorique organique, (D) un sel de phosphate de métal, (E) de l'oxyde de silicium, et (F) une résine organique soluble dans l'eau et/ou une résine organique dispersible dans l'eau, dans une proportion spécifiée.
PCT/JP2010/071534 2009-11-25 2010-11-25 Composition de traitement de surface, et tôle d'acier traitée en surface WO2011065581A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201080053499.2A CN102666920B (zh) 2009-11-25 2010-11-25 表面处理组合物及表面处理钢板

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2009-267086 2009-11-25
JP2009267086A JP5600416B2 (ja) 2009-11-25 2009-11-25 表面処理組成物及び表面処理鋼板

Publications (1)

Publication Number Publication Date
WO2011065581A1 true WO2011065581A1 (fr) 2011-06-03

Family

ID=44066684

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2010/071534 WO2011065581A1 (fr) 2009-11-25 2010-11-25 Composition de traitement de surface, et tôle d'acier traitée en surface

Country Status (4)

Country Link
JP (1) JP5600416B2 (fr)
CN (1) CN102666920B (fr)
TW (1) TWI463036B (fr)
WO (1) WO2011065581A1 (fr)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013226796A (ja) * 2012-03-30 2013-11-07 Nisshin Steel Co Ltd 塗装金属素形材と熱可塑性樹脂組成物の成形体とが接合された複合体およびその製造方法
JP2013226842A (ja) * 2012-03-30 2013-11-07 Nisshin Steel Co Ltd 塗装金属素形材
JP2014141021A (ja) * 2013-01-24 2014-08-07 Nisshin Steel Co Ltd 塗装金属素形材、複合体およびそれらの製造方法
JP2014532815A (ja) * 2011-11-03 2014-12-08 ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ 酸基を有するポリマーとＴｉもしくはＺｒ化合物とを含む、金属表面を不動態化するための調製物
JP2015074743A (ja) * 2013-10-10 2015-04-20 共栄社化学株式会社 水系脱錆塗料
CN114423886A (zh) * 2019-09-20 2022-04-29 日本制铁株式会社 无取向性电磁钢板

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103011358B (zh) * 2012-12-20 2014-03-05 山东大学 聚合硫酸钛无机高分子絮凝剂及其制备方法与应用
JP6085369B2 (ja) * 2013-09-02 2017-02-22 日本パーカライジング株式会社 金属材料用表面処理剤、表面処理金属材料およびその製造方法
ES2755359T3 (es) * 2013-11-14 2020-04-22 Nippon Steel Nisshin Co Ltd Solución de tratamiento de conversión química y lámina de acero químicamente convertida
CN104109473A (zh) * 2014-06-19 2014-10-22 锐展(铜陵)科技有限公司 一种起动机铝合金外壳用表面处理剂
CN115261852B (zh) 2015-03-31 2024-05-28 日本制铁株式会社 热浸镀锌系钢板
CN107829082A (zh) * 2017-11-07 2018-03-23 北京安邦之星科技有限公司 环保镀锌层用皮膜剂、制备方法及包含该皮膜剂的防锈膜
CN110294963B (zh) * 2019-08-12 2022-02-08 厦门欧化实业有限公司 水性uv免处理表印油墨及其加工方法、加工设备
EP4136174A4 (fr) * 2020-04-15 2023-12-20 Henkel AG & Co. KGaA Composition de revêtement anti-noircissement
CN112538294B (zh) * 2020-12-04 2022-10-11 攀钢集团攀枝花钢铁研究院有限公司 环保型锌铝镁镀层表面处理剂及其制备方法和使用方法

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
JP2005148684A (ja) * 2003-11-20 2005-06-09 Seiko Epson Corp トナーの製造方法
JP2006009121A (ja) * 2004-06-29 2006-01-12 Kansai Paint Co Ltd 金属表面処理組成物および金属表面処理鋼板
JP2008115442A (ja) * 2006-11-07 2008-05-22 Nippon Steel Corp 加熱時の耐変色性、加熱後耐食性に優れたアルミめっき鋼材およびその水系処理薬剤。
JP2008169470A (ja) * 2006-12-13 2008-07-24 Jfe Steel Kk 平板部耐食性、耐黒変性およびプレス成形後の外観と耐食性に優れた表面処理亜鉛系めっき鋼板、並びに亜鉛系めっき鋼板用水系表面処理液
JP2009191284A (ja) * 2008-02-12 2009-08-27 Kansai Paint Co Ltd 金属表面処理剤

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000028109A1 (fr) * 1998-11-08 2000-05-18 Nkk Corporation Feuille d'acier traitee en surface presentant une excellente resistance a la corrosion et son procede de production
JP4041368B2 (ja) * 2002-08-30 2008-01-30 新日本製鐵株式会社 耐熱性および耐食性に優れた亜鉛系メッキ鋼板

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
JP2005148684A (ja) * 2003-11-20 2005-06-09 Seiko Epson Corp トナーの製造方法
JP2006009121A (ja) * 2004-06-29 2006-01-12 Kansai Paint Co Ltd 金属表面処理組成物および金属表面処理鋼板
JP2008115442A (ja) * 2006-11-07 2008-05-22 Nippon Steel Corp 加熱時の耐変色性、加熱後耐食性に優れたアルミめっき鋼材およびその水系処理薬剤。
JP2008169470A (ja) * 2006-12-13 2008-07-24 Jfe Steel Kk 平板部耐食性、耐黒変性およびプレス成形後の外観と耐食性に優れた表面処理亜鉛系めっき鋼板、並びに亜鉛系めっき鋼板用水系表面処理液
JP2009191284A (ja) * 2008-02-12 2009-08-27 Kansai Paint Co Ltd 金属表面処理剤

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014532815A (ja) * 2011-11-03 2014-12-08 ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ 酸基を有するポリマーとＴｉもしくはＺｒ化合物とを含む、金属表面を不動態化するための調製物
JP2013226796A (ja) * 2012-03-30 2013-11-07 Nisshin Steel Co Ltd 塗装金属素形材と熱可塑性樹脂組成物の成形体とが接合された複合体およびその製造方法
JP2013226842A (ja) * 2012-03-30 2013-11-07 Nisshin Steel Co Ltd 塗装金属素形材
JP2014141021A (ja) * 2013-01-24 2014-08-07 Nisshin Steel Co Ltd 塗装金属素形材、複合体およびそれらの製造方法
JP2015074743A (ja) * 2013-10-10 2015-04-20 共栄社化学株式会社 水系脱錆塗料
CN114423886A (zh) * 2019-09-20 2022-04-29 日本制铁株式会社 无取向性电磁钢板
CN114423886B (zh) * 2019-09-20 2023-09-29 日本制铁株式会社 无取向性电磁钢板

Also Published As

Publication number Publication date
JP5600416B2 (ja) 2014-10-01
CN102666920B (zh) 2014-07-30
TW201131018A (en) 2011-09-16
TWI463036B (zh) 2014-12-01
JP2011111638A (ja) 2011-06-09
CN102666920A (zh) 2012-09-12

Similar Documents

Publication Publication Date Title
JP5600417B2 (ja) 表面処理組成物及び表面処理鋼板
JP5600416B2 (ja) 表面処理組成物及び表面処理鋼板
JP5431721B2 (ja) 亜鉛系めっき鋼板又はアルミニウム系めっき鋼板用表面処理組成物及び表面処理鋼板
JP4972240B2 (ja) 表面処理鋼板
JP5160866B2 (ja) 表面処理溶融Ｚｎ−Ａｌ系合金めっき鋼板
TWI261610B (en) Coating composition for forming titanium oxide film, method of forming titanium oxide film and metal substrate coated with titanium oxide film
JP4575047B2 (ja) 金属表面処理組成物および金属表面処理鋼板
KR101162401B1 (ko) 표면처리강판
JP5317516B2 (ja) 表面処理溶融Ｚｎ−Ａｌ系合金めっき鋼板
JP5577782B2 (ja) 表面処理鋼板
JP2006022370A (ja) 表面処理鋼板
JP5097311B2 (ja) 表面処理鋼板及び有機樹脂被覆鋼板
JPWO2002061005A1 (ja) 酸化チタン膜形成用塗布剤、酸化チタン膜形成方法及び酸化チタン膜で被覆された金属基材
JP4916913B2 (ja) 表面処理鋼板及び有機樹脂被覆鋼板
JP2009287078A (ja) 高耐食性表面処理鋼板
JP5490657B2 (ja) 高耐食性表面処理鋼板
JP5101271B2 (ja) 表面処理鋼板
JP5441109B2 (ja) 高耐食性表面処理鋼板
JP5222491B2 (ja) 表面処理鋼板
JP2002275653A (ja) 金属表面処理鋼板
JP2002275642A (ja) 耐食性に優れた塗装鋼板
JP5649394B2 (ja) 高耐食性表面処理鋼板
WO2008136496A1 (fr) Tôle d'acier revêtue d'un alliage zn-al immergé à chaud, traitée en surface
KR100963734B1 (ko) 표면처리강판

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 201080053499.2

Country of ref document: CN

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 10833424

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 10833424

Country of ref document: EP

Kind code of ref document: A1