TW201715082A - Surface treating agent, method for surface treating and surface treated metal material - Google Patents

Abstract

The present invention provides a surface treating agent capable of forming a skin film with excellent corrosion resistance and adhesiveness of coating on a surface of a metal regardless of the type of metal, a method for surface treating by applying the surface treating agent on a surface of a metal material to form a skin film, and a surface treated metal material having a skin film on the surface thereof by the method for surface treating. The objective can be attended by a surface treating agent with a pH of 2 or more and 6 or less, the surface treating agent containing at least one of an anionic fluoro-iron (III) complex ion (A) represented by the following formula (I) FeFn[H2O]mXi<SP>-(n-3)</SP> (I) wherein, 3 < n ≤ 6, 0 ≤ m < 3, i=[6-(n+m)]/Z, i ≥ 0, X is ligand capable of being coordinated with iron, Z is the number of dentate of ligand X.

Description

Surface treatment agent, surface treatment method and surface treatment metal material

The present invention relates to a surface treatment agent for forming a film on the surface of a metal material, a surface treatment method for forming a film on the surface of the metal material using the surface treatment agent, and a film having a film formed on the surface thereof by the film formed by the method. Metal material (hereinafter referred to as "surface-treated metal material").

A chemical conversion treatment for the purpose of imparting corrosion resistance has been carried out on metal materials since ancient times. The chemical conversion treatment causes a metal material to contact a chemical called a chemical conversion treatment liquid to form a chemical conversion coating on the surface of the metal material. For the general chemical conversion treatment, for example, zirconium chemical conversion treatment, titanium chemical conversion treatment, hydrazine chemical conversion treatment, vanadium chemical conversion treatment, and the like of Japanese Patent Publications 1 and 2 are known.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2000-199077

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2004-218073

An object of the present invention is to provide a novel surface treatment agent capable of forming a film having excellent corrosion resistance and coating film adhesion on the surface of a metal material regardless of the target metal material, and forming a film on the surface of the metal material using the surface treatment agent. The surface treatment method and the surface treatment of the metal material on the surface of the film formed by the method.

In order to solve the above problems, the results of the research have been focused on, and the following inventions have finally been achieved.

In other words, the present invention provides a surface treatment agent having a pH of 2 or more and 6 or less, and at least one of the anionic fluoroiron (III) complex ion (A) represented by the following formula (I). ,FeF _n [H ₂ O] _m X _i ^-(n-3) (I) where 3<n≦6, 0≦m<3, i=[6-(n+m)]/Z, i≧ 0, X is a ligand capable of coordination with iron, and a number of bases of Z-based ligand X; (2) The surface treatment agent according to (1) above, further comprising a component selected from the group consisting of Zr, Ti, Hf, and Bi a metal component (B) of at least one of Al, Mg, Zn, Ce, Y, In, Mn, W, Mo, and V; (3) a surface treatment agent according to (1) or (2) above Further, the resin (C) which exceeds 01% by mass and does not have 1% by mass based on the total mass of the surface treatment agent as described above; (4) The method according to any one of the above (1) to (3) The surface treatment agent further contains at least one metal component selected from the group consisting of Cu, Sn, and Co in excess of 0 mmol/L and less than 0.01 mmol/L; (5) any one of the above (1) to (4) The surface treatment agent further comprises a surfactant; (6) a surface treatment method comprising the step of contacting the surface treatment agent according to any one of the above (1) to (5) with a metal surface; 7) One The surface treatment method, after the contacting step described in (6) above, further comprises: a phosphate chemical conversion coating forming step of forming a phosphate chemical conversion coating film; (8) a surface treatment method, which is in the above (6) After the contacting step, or the phosphate chemical conversion coating forming step described in (7) above, the method further comprises: forming a zirconium chemical conversion coating film forming a zirconium chemical conversion coating film, and forming a titanium chemical conversion coating film forming the titanium chemical conversion coating film. a step of forming a ruthenium chemical conversion film, a chemical conversion film formation step, or a vanadium chemical conversion film formation step of forming a vanadium chemical conversion film; (9) a surface treatment metal material by the above (6) to (8) Obtained by any of the surface treatment methods described;

According to the present invention, it is possible to provide a novel surface treatment agent capable of forming a film having excellent corrosion resistance and coating film adhesion on the surface of a metal material regardless of the type of the metal material to be used, and forming the surface of the metal material using the surface treatment agent. a surface treatment method of the film, and the surface has The surface of the film formed by the method treats the metal material.

Hereinafter, the present invention will be described in more detail. Further, the scope of the technology of the present invention is not limited to this form. Hereinafter, the surface treatment agent of the present invention, the method for producing the surface treatment agent of the present invention, the surface treatment method for forming a film on the surface of a metal material using the surface treatment agent, and the surface having the surface formed by the method will be described in order. The surface of the film is treated with a metal material.

≪ surface treatment agent≫

The surface treatment agent of the present invention contains at least one of the anionic fluoroiron (III) complex ion (A) represented by the above formula (I). Further, in the formula (I), "n" is more than 3 and is 6 or less, "m" is 0 or more and is less than 3, and "X" is a ligand which can be coordinated to iron, and "i" is 0. The above is [6-(n+m)]/Z (the number of bases of the Z-based ligand X). Further, the pH of the surface treatment agent of the present invention is 2 or more and 6 or less.

The surface treatment agent of the present invention is not particularly limited as long as it contains at least one of the anionic fluoroiron (III) complex ion (A) represented by the above formula (I), and may contain other components as needed. Examples of the other components include a metal component, a water-soluble or water-dispersible resin, a surfactant, and the like. Hereinafter, other components will be described.

(Metal composition (B))

The metal component (B) to be blended in the surface treatment agent of the present invention may, for example, be selected from the group consisting of Zr, Ti, Hf, Bi, Al, Mg, Zn, Ce, Y, In, Mn, W, Mo, and V. At least one. In the case of further containing two kinds of metal components, examples of the combination of the two metal components include Zr and Al, Zr and Bi, Zr and W, Zr and Ce, Ti and V, Ti and Zr, and Zn. And Al, Bi and Ce, or Zn and Mn. When the metal component (B) is contained, the concentration (metal amount) is preferably 0.01 g/L or more, more preferably 0.05 g/L or more. Further, the concentration of the metal component is preferably 5.0 g/L or less, more preferably 2.0 g/L or less. When the metal component (B) is present in this range, the corrosion resistance and the coating film adhesion are further improved.

Examples of the supply source of the metal component (B) include zirconium acid, zirconium sulfate, ammonium zirconium sulfate, sodium zirconium sulfate, potassium zirconium sulfate, zirconium nitrate, zirconium nitrate, ammonium zirconium nitrate, sodium zirconium nitrate, and zirconium nitrate. Zirconium compounds such as potassium, fluorozirconic acid, fluorozirconium salt, ammonium zirconium carbonate, potassium zirconium carbonate, zirconium acetate, zirconium nitrate, etc.; titanium sulfate, titanium oxysulfate, titanium ammonium sulfate, titanium nitrate, titanium oxynitrate, titanium ammonium nitrate, a titanium compound such as fluorotitanic acid, fluorotitanium salt, titanium lactate or titanium acetonate; a ruthenium compound such as ruthenium phosphate, ruthenium sulfate, ruthenium ruthenate, ruthenium carbide, ruthenium chloride, ruthenium fluoride or ruthenium oxide; Barium nitrate, barium lactate, barium hydroxide, barium oxide, barium acetate, barium trifluoride, barium vanadate, barium methanesulfonate, etc.; aluminum sulfate, aluminum nitrate, aluminum hydroxide, aluminum phosphate, aluminum fluoride, Aluminum compound such as aluminum carbonate or aluminum oxide; magnesium compound such as magnesium sulfate, magnesium nitrate, magnesium hydroxide, magnesium chloride, magnesium acetate, magnesium oxide, zinc sulfate, zinc nitrate, zinc hydroxide, zinc phosphate, zinc acetate, zinc oxide, fluorine Zinc, a zinc compound such as zinc chloride; barium sulfate, barium nitrate, barium fluoride, barium carbonate, barium chloride, barium acetate, barium oxide or the like; barium sulfide, barium chloride, barium fluoride, barium oxide and the like; Indium compounds such as indium oxide, indium phosphide, indium antimonide; manganese compounds such as manganese sulfate, manganese nitrate, manganese carbonate, manganese oxide, manganese dioxide, manganese hydroxide; tungsten oxide, tungsten carbide, tungsten fluoride, sodium tungstate Such tungsten compounds; molybdenum compounds such as molybdenum trioxide, sodium molybdate, hexammonium heptamolybdate; vanadium chloride, vanadium oxide, vanadium carbide, vanadium fluoride, vanadium pentoxide, vanadate, etc. Among them, one type or a combination of two or more types can be used.

Further, in the surface treatment agent of the present invention, at least one metal component selected from the group consisting of Cu, Sn, and Co may be blended in the metal component. When these metal components are formulated, it is preferably less than 0.01 mmol/L.

Examples of the supply source of the metal component include copper nitrate, copper sulfate, copper chloride, copper oxide, copper fluoride, tin chloride, tin oxide, tin sulfate, tin fluoride, cobalt chloride, cobalt nitrate, and oxidation. Cobalt, cobalt hydroxide, cobalt sulfate, cobalt fluoride, and the like.

(Water-soluble or water-dispersible resin (C))

In addition, the resin (C) to be used in the surface treatment agent of the present invention is not particularly limited as long as it is water-soluble or water-dispersible, and for example, a hydroxyl group, a sulfonic acid group, an amine group, a carbonyl group or a guanamine group can be used. Further, in addition to the water-soluble or water-dispersible resin of at least one of the polyoxyethylene groups, tannins, amine-modified tannins, and the like may be used. When such a resin (C) is added, the concentration is preferably less than 1% by mass based on the total mass of the surface treatment agent, more preferably 0.0001 g/L or more and less than 10 g/L, and 0.01 g/ L or above Below 1.0 g/L is particularly good {the total value of the resin (C) in the presence of a complex number}. If it is within this range, an appropriate amount of the water-soluble or water-dispersible resin (C) is taken into the iron film, and more excellent corrosion resistance (for example, a salt warm water immersion test) can be exhibited. Further, the "water-soluble or water-dispersible resin" is a resin which is dissolved when 0.1 g of a resin is stirred and mixed in 100 g of water at 20 ° C or a uniformly dispersed resin (including a resin which forms an emulsion).

Examples of the water-soluble or water-dispersible resin (C) include PVA derivatives such as polyvinyl alcohol, carboxyl modified PVA, hydroxy modified PVA, stanol modified PVA, polyethylene glycol, polyacrylic acid, and poly Urethane resin, polyester resin, epoxy resin, polypropylene decylamine or polypropylene decylamine polymer, polyethylenimine or polyethylenimine polymer, diallylamine or two Cellulose derivatives such as allylamine polymer, carboxymethylcellulose, hydroxyethylcellulose, hydroxypropylmethylcellulose, polyvinylpyrrolidone, polyimine resin, vinylsulfonic acid resin The polyallylamine or polyallylamine polymer is equivalent to the resin commonly used for the surface treatment of metals. Further, a known phenol resin can be used, and more specifically, a general phenol resin as a metal surface treatment agent is used. For example, a water-soluble polymer of the following general formula (II) can be used. Further, these resins may be used alone or in combination of two or more. The combination of the two resins may, for example, be diallylamine and polyethylenimine, an epoxy resin and a polyurethane resin, or a polyvinyl alcohol and a polyallylamine.

In the formula (II), n represents an average degree of polymerization of 2 to 50, and the substituent X represents a hydrogen atom, a hydroxyl group, a C ₁ to C ₅ alkyl group, a hydroxy group substituted C ₁ to C ₅ alkyl group, and C ₆ to C ₁₂ An aryl group, a benzyl group, a benzylidene group, an unsaturated hydrocarbon group in which a benzene ring in the formula (II) is fused to form a naphthalene ring, or a group represented by the following formula (III): R ¹ and R ² in the formula (III) each independently represent a hydrogen atom, a hydroxyl group, a C ₁ to C ₅ alkyl group, or a hydroxy-substituted C ₁ to C ₁₀ alkyl group, and the formula (II) and the formula (III) The substituents Y ¹ and Y ² in each of them independently represent a hydrogen atom or a Z group represented by the following formula (IV) or formula (V):

, R ⁷ in the formula (IV) and formula ^{(V) 3, R 4,} R 5, R 6 and R ⁷ independently of one another each line represents a C ₁ to C ₁₀ alkyl substituted with hydroxy or C ₁ to C ₁₀ alkyl The average number of substitutions of the aforementioned Z groups of the respective benzene rings in the water-soluble polymer molecule is from 0.2 to 1.0.

(surfactant (D))

The surfactant (D) formulated in the surface treatment agent of the present invention may be either nonionic, cationic, anionic or amphoteric. Examples of the nonionic surfactant include polyoxyethylene ethyl phenyl ether, polyoxyethylene ethyl ether, polyoxyethyl alcohol ester, and polyoxyethyl sorbitan fatty acid. Polyethylene glycol type nonionic surfactant such as ester, polyoxyethylene-polyoxypropylene block polymer, polyol type nonionic surfactant such as sorbitan fatty acid ester, fatty acid alkanolamine, etc. Amidino-type nonionic surfactant and the like. Examples of the cationic surfactant include a amine salt type cationic surfactant such as a higher alkylamine salt or a polyoxyalkylene higher alkylamine, and a 4-stage ammonium salt type cation interface such as an alkyltrimethylammonium salt. Active agent, etc. The anionic surfactant may, for example, be a higher alkyl ether sulfate salt to which ethylene oxide is added. Among these, it is preferable that the HLB value (calculated by the Griffin method) is 6 or more and 18 or less, and more preferably 10 or more and 14 or less. Further, these surfactants may be contained alone or in combination of two or more. By blending such a surfactant with the surface treating agent of the present invention, the chemical conversion treatment and the degreasing treatment can be carried out in one step. The concentration of the surfactant is preferably in the range of 0.1 to 10.0 g/L, more preferably in the range of 0.5 to 5.0 g/L.

<Liquidity>

The surface treatment agent of the present invention is preferably a pH of 2.0 to 6.0, more preferably a pH of 3.0 to pH 4.0. In this range, a tin film having excellent corrosion resistance can be obtained. Further, the pH in the present specification is a value of a liquid at 25 ° C measured by a pH meter.

制造 Surface treatment agent manufacturing method≫

The surface treatment agent of the present invention, that is, a surface treatment agent containing at least one anionic fluoroiron (III) complex ion (A) represented by the above formula (I), for example, (1) water-insoluble iron The source is dissolved in a surface treatment agent to dissolve the trivalent iron to form a fluorine-containing compound, and if necessary, an oxidizing agent, the above ligand X, and the like are sequentially added and mixed, and (2) a water-soluble iron source is added thereto. Water (an aqueous liquid medium such as an alcohol may be added as needed), and after mixing, the fluorine-containing compound may be added, and if necessary, an oxidizing agent, the above-mentioned ligand X, and the like may be sequentially added and mixed, whereby it can be produced. Hereinafter, each raw material (ligand, oxidizing agent, iron source, fluorine-containing compound) will be described in detail.

(coordination base)

The ligand X is used to prevent the composition of the iron (including the iron compound) in the aqueous solution. The ligand X is not particularly limited as long as it can be disposed in the form of a dissolved trivalent iron, and is, for example, at least one selected from the group consisting of an aminocarboxylic acid, a hydroxycarboxylic acid, a sulfonic acid, and a phosphonic acid. Specifically, for example, EDTA (ethylenediaminetetraacetic acid), HEDTA (hydroxyethylethylenediaminetriacetic acid), NTA (nitrotriacetic acid), DTPA (diethylenetriaminepentaacetic acid), TTHA (triethyl) Tetraamine hexaacetic acid), DHEG (dihydroxyethylglycine), EDTMP (B Diamine tetramethylenesulfonic acid), NTMP (nitrotrimethylenephosphonic acid), HEDP (hydroxyethylidene diphosphonic acid), imidodiacetic acid, tris(hydroxymethyl)methylglycine ( Tricine), tartaric acid, malic acid, citric acid, glycolic acid, lactic acid, gluconic acid, mucic acid, quinic acid, taurine, and the like. These ligands X may be used alone or in combination of two or more. Here, the amount of the ligand X present can be measured by a general method, for example, a high-speed liquid chromatography using an anion analysis column, a derivative-solvent extraction GC/MS method, or the like.

(oxidant)

Examples of the oxidizing agent include perchloric acid, hypochlorous acid, dissolved oxygen, ozone, permanganic acid, and hydrogen peroxide. These oxidizing agents may be used singly or in combination of two or more.

(iron source)

As the supply source of iron, for example, a water-insoluble iron source such as iron powder or iron oxide, or a soluble iron salt such as iron nitrate, iron sulfate or iron chloride can be used. The concentration of iron (trivalent dissolved iron) in the surface treatment agent of the present invention is preferably 0.1 g/L or more and 10.0 g/L or less, and more preferably 0.5 g/L or more and 5.0 g/L or less. 0.7 g/L or more and 2.0 g/L or less are particularly preferable. When it is in this range, it is easy to obtain a tin film which exhibits more excellent corrosion resistance and coating film adhesion. Here, the amount of iron present in the surface treatment agent of the present invention can be measured by a general method, and can be measured, for example, by titration and ICP emission spectrometry.

(fluorine-containing compound)

The fluorine component in the fluorine-containing compound is an etching component of a metal material and a component which stabilizes iron in an aqueous solution. The fluorine component is soluble in fluorine (dissolved fluorine) in water. The fluorine-containing compound, that is, the supply source of fluorine, may, for example, be hydrofluoric acid, fluorotitanic acid, fluorozirconic acid, fluoroantimonic acid, ammonium fluoride, acidic ammonium fluoride, sodium fluoride, sodium hydrogen difluoride or fluorine. Potassium, potassium hydrogen difluoride, etc., but not limited to these. Moreover, the amount of fluorine present in the surface treatment agent of the present invention can be measured by a general method, and examples thereof include a chelating agent (for example, ethylenediaminetetraacetic acid (EDTA)) which easily forms a chelate complex with iron. It is added to the surface treatment agent, and the free fluoride ion is determined by ion chromatography.

Here, the iron system can obtain a maximum of six coordination positions (positive octahedral structure), and it is necessary to coordinate more than three fluorines for one iron. At this time, the rest of the system can be coordinated with water (hydroxide ions). Although it depends on the coordination number of the above-mentioned fluorine, it is better that the water system has a coordination ratio of less than 3 times the molar concentration of iron. For example, when fluorine is coordinated to iron at 4 times Mo, the remaining coordination number of iron is at most 2, and the remaining groups are coordinated with water and ligand X. Therefore, in order to form the anionic fluoroiron (III) complex ion (A) represented by the above formula (I), that is, in order to coordinate one iron with more than three fluorines, fluorine (dissolved fluorine) to iron (Trivalent dissolved iron) is greater than 3 times the molar concentration, and preferably 6 times the molar concentration or less. It is better to be more than 4 times the molar concentration. When iron and fluorine are present in the above-mentioned concentration, it is easy to obtain an iron film which exhibits more excellent corrosion resistance and coating film adhesion. On the other hand, in the coordination of these, when fluorine is less than 3 times the molar concentration of iron, the stability of the trivalent iron ion is impaired and an insoluble iron salt is generated. Therefore, in the agent, the molar ratio of fluorine (dissolved fluorine) to iron (soluble trivalent dissolved iron) exceeds 3 and is 15 In the following (except for 4 or more and more preferably 10 or less), it is suitable to exert the effects of the present invention.

On the other hand, the ligand X has an inherent number of bases, respectively. For example, the EDTA system can be coordinated to the 6-dentate group, and the Z value described in the above formula (I) is 6. Therefore, the coordination number of the ligand X is preferably 0 or more. Further, since the chelating power of the ligand X and iron is stronger than that of fluorine or water, the iron is preferentially coordinated.

≪Surface treatment method≫

The surface treatment agent of the present invention is used for surface treatment of a metal material. Here, the surface treatment method is required to have a chemical conversion film forming step of forming a metal film on the metal material by contacting the metal material with the surface treatment agent described above.

Hereinafter, the surface treatment method will be described in detail. The metal material used in the surface treatment method is not particularly limited, and examples thereof include iron materials, zinc plating materials, and aluminum materials. More specific examples include cold-rolled steel sheets, hot-rolled steel sheets, black-sheathed steel sheets, molten zinc-based plated steel sheets, electric zinc-based plated steel sheets, alloyed molten zinc-based plated steel sheets, aluminum-plated steel sheets, and aluminum. - a zinc-alloyed plated steel sheet, a zinc-nickel alloyed plated steel sheet, an aluminum sheet, an aluminum alloy sheet, or the like, or a heat history material to which heat treatment (for example, high heat treatment, welding treatment, etc.) is applied to the materials.

The method of contacting the metal material with the surface treatment agent is not particularly limited, and may be any method suitable for use in a general chemical conversion treatment method. For example, an immersion treatment method, a spray treatment method, and electricity Solution processing, vertical flow processing, etc. Among these, an immersion treatment method is preferred.

The contact temperature of the above metal material with the surface treatment agent is preferably 25 to 55 ° C, more preferably 35 to 45 ° C, but is not limited to such a temperature. Further, the contact time between the metal material and the surface treatment agent is preferably from 30 to 300 seconds, more preferably from 60 to 180 seconds, but is not limited to the treatment time.

Further, the surface treatment method of the present invention is carried out by using a phosphate chemical conversion treatment such as zinc phosphate or the like, zirconium chemical conversion treatment, titanium chemical conversion treatment, hydrazine chemical conversion treatment, vanadium chemical conversion treatment, etc., after the chemical conversion coating film formation step. Other chemical conversion treatments. Further, in the surface treatment method of the present embodiment, after the chemical conversion film formation step, the phosphate chemical conversion treatment as the second chemical conversion treatment is performed, and then the zirconium chemical conversion treatment, the titanium chemical conversion treatment, and the hydrazine chemical conversion treatment can be performed. The third chemical conversion treatment of vanadium chemical conversion treatment. As described above, after the chemical conversion film formation step, the corrosion resistance and the coating film adhesion of the metal material can be further improved by the other chemical conversion treatment or the second and third chemical conversion treatments.

Here, a zirconium chemical conversion treatment can be carried out using a general zirconium chemical conversion treatment agent. Further, as the titanium chemical conversion treatment, a general titanium chemical conversion treatment agent can be used. The hydrazine chemical conversion treatment can use a general hydrazine chemical conversion treatment agent, and the vanadium chemical conversion treatment can use a general vanadium chemical conversion treatment agent. Such chemical conversion treatments are, for example, a treatment liquid having a pH of 3.0 to 6.0 containing zirconium ions, titanium ions, strontium ions and/or vanadium ions of 0.005 to 5.0 g/L, at 25 to 55 ° C, 10 to 300 seconds. The clock is dipped or sprayed Sprinkle it.

Further, for the phosphate chemical conversion treatment, a general phosphate chemical conversion treatment can be used. The phosphate chemical conversion treatment uses, for example, a treatment liquid having a phosphate ion of 0.1 to 50 g/L, a zinc ion of 0.01 to 3.0 g/L, and a pH of 3.0 to 6.0, and is impregnated at 25 to 55 ° C for 10 to 300 seconds. Or spray it.

The surface treatment method of the present invention is preferably carried out before the step of forming the chemical conversion coating film, and the degreasing step of preliminarily purifying the metal material by degreasing treatment is preferred. The method of the degreasing treatment is not particularly limited, and a conventionally known method can be applied. Further, the above-described other chemical conversion treatment may be carried out after the degreasing step and the chemical conversion coating forming step. Further, the second chemical conversion treatment and the third chemical conversion treatment may be performed after the degreasing step and the chemical conversion coating forming step.

Further, the surface treatment method of the present invention may be carried out after the chemical conversion film formation step, after the other chemical conversion treatment described above, or after the third chemical conversion treatment. The coating method is not particularly limited, and a conventionally known method such as electrodeposition coating (for example, cationic electrodeposition coating), solvent coating, powder coating, or the like can be used. Further, when the electrodeposition coating method using an electrodeposition coating material is used, the chemical conversion coating agent used in the preceding step, the other chemical conversion treatment, or the chemical conversion treatment agent used in the third chemical conversion treatment is used. The sodium ion concentration is preferably controlled on a mass basis to less than 500 ppm.

Moreover, the surface treatment method of the present invention is not limited to the above In addition to the conversion coating forming step, the method includes: the degreasing step; the other chemical conversion treatment; the second chemical conversion treatment and the third chemical conversion treatment; the coating step; the degreasing step and the other chemical conversion The degreasing step, the second chemical conversion treatment, and the third chemical conversion treatment; the degreasing step and the coating step; the other chemical conversion treatment and the coating step; the second chemical conversion treatment, and the 3 chemical conversion treatment and the above coating step; the degreasing step, the other chemical conversion treatment and the coating step; or the degreasing step, the second chemical conversion treatment, the third chemical conversion treatment, and the coating step At this time, a water washing step may be separately included after each step. Thus, when the water washing step is included after each step, the surface treatment method may omit a part of the water washing step, or may omit all the water washing steps.

表面 Surface treatment of metal materials by surface treatment≫

Next, a metal material having a chemical conversion film obtained by chemical conversion treatment with the surface treatment agent of the present invention, that is, a surface-treated metal material, will be described in detail. The chemical conversion coating film formed on the surface of the metal material on the surface of the present embodiment is a tin film. The film system can be formed regardless of the kind of the metal material. Here, the thickness of the iron film is preferably 0.001 to 1.0 μm.

Furthermore, the surface-treated metal material of the present invention may have a zirconium chemical conversion coating film, a titanium chemical conversion treatment film, a ruthenium chemical conversion treatment film or a vanadium chemical conversion treatment film on the iron film. At this time, the thickness of the chemical conversion coating film is preferably 0.005 to 0.2 μm, and is 0.01 to More preferably 0.1 μm.

Further, the surface-treated metal material of the present invention may have a phosphate chemical conversion film on the iron film. At this time, the thickness of the phosphate chemical conversion film is preferably 0.1 to 10 μm, more preferably 1.0 to 3.0 μm. Further, when the surface-treated metal material of the present invention has a phosphate chemical conversion coating film, a zirconium chemical conversion coating film, a titanium chemical conversion treatment film, a chemical conversion treatment film or a vanadium chemical conversion treatment film on the iron film, the phosphate can be used in the phosphate film. A zirconium chemical conversion coating film, a titanium chemical conversion treatment film, a chemical conversion treatment film or a vanadium chemical conversion treatment film is formed on the chemical conversion film.

The content of the iron element in the iron film of the present invention can be determined from the spectrum of the composition distribution in the depth direction by an ion etching method by an X-ray photoelectron spectroscopy apparatus (ESCA).

In order to evaluate the corrosion resistance of the above film, the surface of the surface-treated metal material obtained by the above treatment method can be applied. The coating method is not particularly limited, and a conventionally known method such as electrodeposition coating (for example, cationic electrodeposition coating), solvent coating, powder coating, or the like can be applied. As the cationic electrodeposition coating system, a conventionally known method can be applied. For example, a cationic electrodeposition coating composition containing an addition amine epoxy resin as a coating material and a blocked polyisocyanate curing agent as a hardening component, which is a surface-treated metal material obtained by impregnating the surface treatment agent of the present invention, is used. Further, the surface-treated metal material may be washed with water or may be impregnated without washing before immersion. Further, the surface of the metal material after washing or not washing may be dried before being immersed, or may be immersed in the above without drying. coating.

Further, in the above-described cationic electrodeposition coating system, for example, the temperature of the coating material is maintained at about 26 to 30 ° C, and the surface of the metal material is treated with a rectifier for 30 seconds from 0 V to 200 V in a state of stirring the coating material toward the cathode. The voltage was applied in the direction and thereafter held at 200 V for 150 seconds. In this manner, the metal material coated on the surface is subjected to water washing and baking to form a coating film. Further, the baking system is carried out, for example, at 170 ° C for 20 minutes.

The coating film coated with the metal material preferably has an average thickness of from 1 to 50 μm, more preferably from 7 to 25 μm.

Further, the thickness of the coating film can be determined by measurement using an electromagnetic film thickness meter or a vortex type film thickness meter. More specifically, when the coating film is formed on the surface of a metal material (iron, iron-based alloy, or the like) of a magnetic material, it is measured using an electromagnetic film thickness meter. Further, when the coating film is formed on the surface of a non-magnetic metal material (aluminum, aluminum alloy, or the like), it is measured using a vortex type film thickness meter. After the measurement, any portion of the coating film was measured at a plurality of points to obtain an average thickness.

[Examples]

Hereinafter, the examples are presented to specifically illustrate the invention. However, the invention is not limited thereto.

<Metal material>

Prepare the following metal materials (all made by Paltek Co., Ltd.)

‧ Cold rolled steel plate: SPC (SPCC-SD) 70 × 150 × 0.8mm

‧ High-tension hot-rolled steel sheet: SPH (SPH-590) 70 × 150 × 1.2mm

‧Heat history steel plate: Baked SPH (SPH is fired in a MUFFLE FURNACE at 400 ° C for 20 minutes; the size is the same as SPH)

‧Black leather plate: SPHC 70×150×2.3mm

‧Electrical zinc plated steel plate: EG (zinc per unit area weight 20g/m ² ; both sides are) 70×150×0.8mm

‧Fused zinc plated steel plate: GI (zinc per unit area weight 90g/m ² ; both sides are) 70×150×0.8mm

‧ Alloyed zinc plated steel plate: GA (zinc per unit area weight 45g/m ² ; both sides are) 70 × 150 × 0.8mm

‧ Aluminum alloy plate: AL (A6061P) 70 × 150 × 1.0mm

<surface treatment>

The degreasing treatment was carried out by spraying a degreaser (manufactured by Japan PARKERIZING Co., Ltd.; FC-E2001) which was heated to 40 ° C for 120 seconds on the surface of each metal material. After the degreasing treatment, the surface was sprayed with water for 30 seconds. Then, the surface treatment agents of Examples 1 to 44 and Comparative Examples 1 to 3, which will be described later, were immersed at 40 ° C for 120 seconds, and then washed with water and dried at room temperature to prepare a metal material having a surface formed with a tin film. Further, the metal material of the degreasing treatment and the spray washing treatment was immersed in a zirconium chemical conversion treatment liquid of Comparative Example 4 at 35 ° C [50 g/L of zirconium chemical conversion treatment liquid (chemical conversion treatment agent manufactured by Japan PARKERIZING Co., Ltd.) The zirconium chemical conversion treatment was carried out using PLM-1000) for 120 seconds to prepare a metal material in which a zirconium chemical conversion coating film was formed. Further, the above The metal material of the degreasing treatment and the spray washing treatment was immersed in the zinc phosphate chemical conversion treatment liquid of Comparative Example 5 at 35 ° C [50 g/L zinc phosphate chemical conversion treatment liquid (phosphoric acid zinc chemical conversion treatment agent manufactured by Japan PARKERIZING Co., Ltd.) The chemical conversion treatment of zinc phosphate is carried out using PB-SX35)] to prepare a metal material in which a zinc phosphate chemical conversion film is formed.

Further, the surface treatment agent of Example 1 was immersed at 40 ° C for 120 seconds, and then washed with water to form an iron film, and then zirconium chemical conversion treatment liquid of Comparative Example 4 was used to carry out zirconium chemical conversion treatment to prepare iron-containing alloy. A metal material of a composite film of a film and a zirconium chemical conversion film. Furthermore, the surface treatment agent of Example 1 was immersed at 40 ° C for 120 seconds, and then washed with water to form an iron film, and then immersed in a surface conditioning liquid of 3.0 g/L at normal temperature (manufactured by Japan PARKERIZING Co., Ltd.) Surface conditioning agent; surface treatment was carried out using PL-X) for 30 seconds, and then zinc phosphate chemical conversion treatment liquid of Comparative Example 5 was used to carry out chemical conversion treatment of zinc phosphate to prepare a composite film containing a coating film containing iron film and zinc phosphate. The metal material of the film.

<Cationic electrodeposition coating>

A metal film having each film was used as a cathode, and an electrodeposition coating (manufactured by Kansai Paint Co., Ltd.; GT-100) was used, and a constant voltage cathodic electrolysis was performed for 180 seconds to form a coating film on the entire surface of the metal plate. Thereafter, the mixture was washed with water, and calcined at 170 ° C for 20 minutes to prepare each test plate, and the following salt warm water immersion test, composite cycle test, and coating film adhesion test were carried out. Further, the coating film thickness was adjusted to 20 μm.

<Salt warm water immersion test>

Each of the test plates was subjected to cross-cutting with a cutter, and immersed in a 5 mass% NaCl aqueous solution at 55 ° C for 240 hours (10 days), followed by washing with water and air drying. Next, a Cellotape (registered trademark) peeling test was performed on the cross-cut portion of the test plate, and the maximum peel width from both sides of the cross-cut was measured, and evaluated based on the evaluation criteria shown below.

<Evaluation criteria>

◎: The maximum peel width on both sides is less than 3.0mm

○: The maximum peel width on both sides is 3.0 mm or more and less than 5.0 mm.

△: The maximum peeling width on both sides is 5.0 mm or more and less than 10.0 mm

×: The maximum peel width on both sides is 10.0 mm or more

<Composite cycle test>

The cross-cut was applied to each test plate by a cutter, placed in a compound cycle test machine, and a compound cycle test was performed for 100 cycles in accordance with JASO-M 609-91. The maximum expansion widths on both sides of the cross-cut after the 100-cycle execution were measured, and evaluated based on the evaluation criteria shown below.

<Evaluation criteria>

◎: The maximum expansion width on both sides is less than 5.0mm

○: The maximum expansion width on both sides is 5.0mm or more and less than 10.0mm

△: The maximum expansion width on both sides is 10.0mm or more and less than 15.0mm

×: The maximum expansion width on both sides is 15.0 mm or more

<Coating film adhesion test>

After incision was applied to each test plate in a checkerboard shape (10 × 10 = 100) at intervals of 1 mm, and then immersed in boiling water for 1 hour. Then, the moisture on the surface was wiped off, and the check mark of the checkerboard shape was subjected to a tape peeling test using Cellotape (registered trademark), and the number of the unpeeled checkerboard was measured, and evaluated based on the evaluation criteria shown below.

<Evaluation criteria>

◎: 100

○: 80 to 99

△: 1 to 79

×: 0

<Preparation of Surface Treatment Agents of Examples 1 to 44 and Comparative Examples 1 to 3>

The iron powder or iron (II) sulfate was prepared by dissolving in an aqueous solution of hydrofluoric acid. The ratio of the molar concentration of hydrofluoric acid to the concentration of iron and the molar concentration of iron was shown in the various solutions in Table 1. Further, after dissolving iron powder or iron (II) sulfate in a hydrofluoric acid aqueous solution, hydrogen peroxide was sequentially added (used in the preparation of the surface treatment agents of Examples 1 to 43 and Comparative Examples 1 to 3), and various a ligand X, various metal compounds, various resins, and the like, followed by stirring and mixing to prepare a concentration of iron, various metal compounds, various resins, etc.; a ratio of the molar concentration of hydrofluoric acid to the molar concentration of iron (double); The ratio of the molar concentration of the ligand X to the molar concentration of iron (doubles); various mixtures shown in Table 1. Thereafter, the pHs of various solutions or various mixed solutions were adjusted to the values shown in Table 1, and various surface treatment agents of Examples 1 to 44 and Comparative Examples 1 to 3 were obtained.

Further, Examples 32 to 44 were based on the following resins. Water-soluble or water-dispersible resin (C).

(C1) Aqueous urethane resin (Superflex E-2000; manufactured by First Industrial Pharmaceutical Co., Ltd.)

(C2) phenol resin (in the formula (II), n = 5, X = hydrogen, Y ¹ = -CH ₂ N(CH ₃ ) ₂ , average value of Z group substitution = 1.0)

(C3) Novolac resin (F/P (phenolic/aldehyde) ratio of 0.84 of a novolac phenol resin having a methylol group)

(C4) Amine-modified tannin (aluminum tannic acid (100 parts by mass; manufactured by Fuji Chemical Industry Co., Ltd.) and monoethanolamine (15 parts by mass) of formaldehyde condensate)

(C5) Aluminum tannic acid

(C6) Polydiallylamine hydrochloride (weight average molecular weight: about 110,000)

(C7) Polyethylenimine (weight average molecular weight: about 1300)

(C8) 99% saponified polyvinyl acetate (weight average molecular weight: about 50,000)

(C9) Aqueous epoxy resin (Adeka Resin EP-4100; manufactured by ADEKA Co., Ltd.)

Tables 2 to 4 show the results of the salt warm water immersion test, the composite cycle test, and the coating film adhesion test performed on each test plate. As shown in Tables 2 to 4, the surface treatment agents of the present invention of Examples 1 to 44 are regardless of the kind of the metal material of the object, even for materials which are difficult to chemically convert (black skin) Steel sheets and thermal history steel sheets can also form iron films with excellent corrosion resistance and coating film adhesion.

On the other hand, the surface-treated test panel using the surface treatment agent of Comparative Example 1 was insufficient in corrosion resistance and coating film adhesion.

Further, the surface-treated test panel using the surface treatment agent of Comparative Example 2 was also insufficient in corrosion resistance and coating film adhesion.

Further, the surface-treated test panel using the surface treatment agent of Comparative Example 3 was also insufficient in corrosion resistance and coating film adhesion.

Claims (8)

The surface treatment agent having a pH of 2 or more and 6 or less is at least one of an anionic fluoroiron (III) complex ion (A) represented by the following formula (I); and FeF _n [H ₂ O] _m X _i ^-(n-3) (I) wherein 3<n≦6, 0≦m<3, i=[6-(n+m)]/Z, i≧0, X system can be coordinated to iron The number of bases of the ligand and Z-based ligand X. The surface treatment agent according to claim 1, further comprising at least one selected from the group consisting of Zr, Ti, Hf, Bi, Al, Mg, Zn, Ce, Y, In, Mn, W, Mo, and V. Metal component (B). The surface treatment agent according to claim 1 or 2 further contains a water-soluble or water-dispersible resin (C) which is less than 1% by mass based on the total mass of the surface treatment agent. The surface treatment agent according to any one of claims 1 to 3, further comprising a metal component of at least one selected from the group consisting of Cu, Sn, and Co of less than 0.01 mmol/L. A surface treatment method comprising the step of contacting a surface treatment agent according to any one of claims 1 to 4 to a metal surface. A surface treatment method, after the contacting step described in claim 5, further comprises: a zirconium chemical conversion coating forming step for forming a zirconium chemical conversion coating film, a titanium chemical conversion coating forming step for forming a titanium chemical conversion coating film, and forming Chemical conversion film formation after chemical conversion film a step, or a vanadium chemical conversion coating forming step of forming a vanadium chemical conversion coating. A surface treatment method, after the contacting step described in claim 5, further comprises: a phosphate chemical conversion coating forming step of forming a phosphate chemical conversion coating. A surface-treated metal material obtained by the surface treatment method according to any one of claims 5 to 7.