JP2017048449A - Surface treatment agent, surface treatment method, and surface treated metal material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a novel surface treatment agent capable of forming a coating film on any type of targeted metal materials, the coating film having an excellent corrosion resistance and film adhesion, a surface treatment method forming a coating film on the metal material using the surface treatment agent, and a surface treated metal material having the coating film formed by the method on the surface.SOLUTION: A surface treatment agent of PH 2 - 6 including at least one type of an anionic fluoro iron (III)complex compound ion (A) represented by an equation (I). The surface treatment agent including at least one type of metals selected from Zr Ti, Hf, Bi, Al, Mg, Zn, Ce, Y, In, Mn, W, Mo, and V, and further including water soluble or water dispersible resin of less than 1 mass% based on a total mass of the surface treatment agent. [3<n≤6, 0≤m<3, i=[6-(n+m)]/Z, i≥0, X is a ligand capable of coordinating with iron, and Z is a number of a conformation of the ligand X].SELECTED DRAWING: None

Description

  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 a metal material using the surface treatment agent, and a film having a film formed by the method on the surface. The present invention relates to an attached metal material (hereinafter referred to as “surface-treated metal material”).

  Chemical conversion treatment for the purpose of imparting corrosion resistance to metal materials has been practiced for a long time. This chemical conversion treatment is to bring a metal material into contact with a chemical called a chemical conversion treatment solution to form a chemical conversion film on the surface of the metal material. As general chemical conversion treatments, for example, zirconium chemical conversion treatment, titanium chemical conversion treatment, hafnium chemical conversion treatment, vanadium chemical conversion treatment, and the like disclosed in Patent Documents 1 and 2 are known.

JP 2000-199077 A JP 2004-218073 A

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

ここで、３＜ｎ≦６、０≦ｍ＜３、ｉ＝[６−（ｎ＋ｍ）]／Ｚ、ｉ≧０、Ｘは鉄に配位可能な配位子、Ｚは配位子Ｘの座数である；
（２）Ｚｒ、Ｔｉ、Ｈｆ、Ｂｉ、Ａｌ、Ｍｇ、Ｚｎ、Ｃｅ、Ｙ、Ｉｎ、Ｍｎ、Ｗ、Ｍｏ及びＶから選ばれる少なくとも１種の金属成分（Ｂ）をさらに含有する上記（１）に記載の表面処理剤；
（３）水溶性又は水分散性の樹脂（Ｃ）を前記表面処理剤の全質量を基準として０質量％超１質量％未満でさらに含有する上記（１）又は（２）に記載の表面処理剤；
（４）Ｃｕ、Ｓｎ及びＣｏから選ばれる少なくとも１種の金属成分を０ｍｍｏｌ／Ｌ超０．０１ｍｍｏｌ／Ｌ未満でさらに含有する上記（１）〜（３）のいずれかに記載の表面処理剤；
（５）界面活性剤をさらに含有する上記（１）〜（４）のいずれかに記載の表面処理剤；
（６）上記（１）〜（５）のいずれかに記載の表面処理剤を金属表面に接触させる接触工程を含む表面処理方法；
（７）上記（６）に記載の接触工程後に、リン酸塩化成皮膜を形成させるリン酸塩化成皮膜形成工程をさらに含む、表面処理方法；
（８）上記（６）に記載の接触工程後に、あるいは、上記（７）に記載のリン酸塩化成皮膜形成工程後に、ジルコニウム化成皮膜を形成させるジルコニウム化成皮膜形成工程、チタン化成皮膜を形成させるチタン化成皮膜形成工程、ハフニウム化成皮膜を形成させるハフニウム化成皮膜形成工程、又はバナジウム化成皮膜を形成させるバナジウム化成皮膜形成工程をさらに含む、表面処理方法；
（９）上記（６）〜（８）のいずれかに記載の表面処理方法により得られた表面処理金属材料；
等である。 As a result of researches to solve the above problems, the inventors have reached the following invention.
That is, the present invention
(1) A surface treating agent having a pH of 2 or more and 6 or less containing at least one of the anionic fluoroiron (III) complex compound ions (A) represented by the following formula (I):

Here, 3 <n ≦ 6, 0 ≦ m <3, i = [6- (n + m)] / Z, i ≧ 0, X is a ligand capable of coordinating to iron, Z is a ligand X The number of seats;
(2) The above (1) further containing at least one metal component (B) selected from Zr, Ti, Hf, Bi, Al, Mg, Zn, Ce, Y, In, Mn, W, Mo and V A surface treatment agent according to claim 1;
(3) Surface treatment as described in said (1) or (2) which further contains water-soluble or water-dispersible resin (C) in more than 0 mass% and less than 1 mass% on the basis of the total mass of the said surface treating agent. Agent;
(4) The surface treatment agent according to any one of the above (1) to (3), further containing at least one metal component selected from Cu, Sn, and Co in an amount of more than 0 mmol / L and less than 0.01 mmol / L;
(5) The surface treatment agent according to any one of (1) to (4), further containing a surfactant;
(6) A surface treatment method including a contact step of bringing the surface treatment agent according to any one of (1) to (5) into contact with a metal surface;
(7) A surface treatment method further comprising a phosphate conversion film forming step of forming a phosphate conversion film after the contact step according to (6) above;
(8) A zirconium chemical conversion film forming step for forming a zirconium chemical conversion film, or a titanium chemical conversion film is formed after the contacting step described in (6) above or after the phosphate chemical conversion film forming step described in (7) above. A surface treatment method further comprising a titanium chemical conversion film forming step, a hafnium chemical conversion film forming step of forming a hafnium chemical conversion coating, or a vanadium chemical conversion coating forming step of forming a vanadium chemical conversion coating;
(9) A surface-treated metal material obtained by the surface treatment method according to any one of (6) to (8) above;
Etc.

  According to the present invention, regardless of the target metal material type, a novel surface treatment agent capable of forming a film excellent in corrosion resistance and coating film adhesion on the surface of the metal material, and using the surface treatment agent, A surface treatment method for forming a film on the surface, and a surface-treated metal material having a film formed on the surface by the method can be provided.

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

≪Surface treatment agent≫
The surface treating agent according to the present invention contains at least one anionic fluoroiron (III) complex compound ion (A) represented by the above formula (I). In the formula (I), “n” is more than 3 and 6 or less, “m” is 0 or more and less than 3, “X” represents a ligand capable of coordinating with iron, and “i” Is 0 or more and [6- (n + m)] / Z (Z is the dentate of the ligand X). The pH of the surface treatment agent according to the present invention is 2 or more and 6 or less.

  The surface treatment agent according to the present invention is not particularly limited as long as it contains at least one kind of the anionic fluoroiron (III) complex compound ion (A) represented by the above formula (I). Other components may be included. Examples of other components include metal components, water-soluble or water-dispersible resins, and surfactants. Hereinafter, other components will be described.

(Metal component (B))
As a metal component (B) mix | blended with the surface treating agent which concerns on this invention, it selects from Zr, Ti, Hf, Bi, Al, Mg, Zn, Ce, Y, In, Mn, W, Mo, and V, for example. At least one can be mentioned. Among these, when two kinds of metal components are further contained, the combination of the two kinds of metal components includes, for example, Zr and Al, Zr and Bi, Zr and W, Zr and Ce, Ti and V, Ti and Zr. Zn and Al, Bi and Ce, or Zn and Mn. When these metal components (B) are contained, the concentration (metal amount) is preferably 0.01 g / L or more, and more preferably 0.05 g / L or more. In addition, it is preferable that the density | concentration of a metal component is 5.0 g / L or less, and it is more preferable that it is 2.0 g / L or less. When a metal component (B) exists in the said range, corrosion resistance and coating-film adhesiveness improve more.

  Examples of the supply source of the metal component (B) include zirconium sulfate, zirconium oxysulfate, ammonium zirconium sulfate, sodium zirconium sulfate, potassium zirconium sulfate, zirconium nitrate, zirconium oxynitrate, ammonium zirconium nitrate, sodium zirconium nitrate, zirconium nitrate. Zirconium compounds such as potassium, fluorozirconic acid, fluorozirconium complex salt, ammonium zirconium carbonate, potassium zirconium carbonate, zirconyl acetate, zirconyl lactate, titanium sulfate, titanium oxysulfate, titanium ammonium sulfate, titanium nitrate, titanium oxynitrate, ammonium ammonium nitrate, Titanium compounds such as fluorotitanic acid, fluorotitanium complex, titanium lactate, titanium acetylacetonate, Hafnium acid, hafnium sulfate, hafnium silicate, hafnium carbide, hafnium chloride, hafnium fluoride, hafnium oxide and other hafnium compounds, bismuth sulfate, bismuth nitrate, bismuth lactate, bismuth hydroxide, bismuth oxide, bismuth acetate, bismuth trifluoride Bismuth compounds such as bismuth vanadate and bismuth methanesulfonate, aluminum compounds such as aluminum sulfate, aluminum nitrate, aluminum hydroxide, aluminum phosphate, aluminum fluoride, aluminum carbonate, aluminum oxide, magnesium sulfate, magnesium nitrate, hydroxide Magnesium compounds such as magnesium, magnesium chloride, magnesium acetate, magnesium oxide, zinc sulfate, zinc nitrate, zinc hydroxide, zinc phosphate, zinc acetate, zinc oxide, zinc fluoride, Zinc compounds such as zinc fluoride, cerium compounds such as cerium sulfate, cerium nitrate, cerium fluoride, cerium carbonate, cerium chloride, cerium acetate, cerium oxide, yttrium compounds such as yttrium sulfide, yttrium chloride, yttrium fluoride, yttrium oxide, Indium compounds such as indium oxide, indium phosphide, indium antimonide, manganese sulfate, manganese nitrate, manganese carbonate, manganese oxide, manganese dioxide, manganese hydroxide and other manganese compounds, tungsten oxide, tungsten carbide, tungsten fluoride, tungstic acid Tungsten compounds such as sodium, molybdenum compounds such as molybdenum trioxide, sodium molybdate, hexaammonium molybdate, vanadium chloride, vanadium oxide, vanadium carbide, Vanadium compounds such as vanadium fluoride, vanadium pentoxide, and sodium metavanadate can be used, and one or more of these can be used in combination.

  In addition, as a metal component, you may mix | blend the at least 1 sort (s) of metal component chosen from Cu, Sn, and Co with the surface treating agent which concerns on this invention. When these metal components are blended, it is preferably less than 0.01 mmol / L.

  Examples of the metal component supply source include copper nitrate, copper sulfate, copper chloride, copper oxide, copper fluoride, tin chloride, tin oxide, tin sulfate, tin fluoride, cobalt chloride, cobalt nitrate, cobalt oxide, and water. Examples thereof include cobalt oxide, cobalt sulfate, and cobalt fluoride.

(Water-soluble or water-dispersible resin (C))
Further, the resin (C) to be blended in the surface treatment agent according to the present invention is not particularly limited as long as it is water-soluble or water-dispersible, and examples thereof include a hydroxyl group, a sulfonic acid group, an amino group, a carbonyl group, In addition to water-soluble or water-dispersible resins having at least one group selected from amide groups and polyoxyethylene groups, tannins, amine-modified tannins, and the like can be used. When these resins (C) are added, the concentration is preferably less than 1% by mass based on the total mass of the surface treatment agent, more preferably from 0.0001 g / L to less than 10 g / L, and 0.01 g / L. It is particularly preferably 1.0 g / L or less {total value when a plurality of resins (C) are present}. Within the above range, as a result of incorporating an appropriate amount of the water-soluble or water-dispersible resin (C) into the iron film, more excellent corrosion resistance (for example, a salt warm water immersion test) can be exhibited. The “water-soluble or water-dispersible resin” means a resin that dissolves or uniformly disperses (resin that forms an emulsion) when 0.1 g of resin is stirred and mixed in 100 g of water at 20 ° C. Means).

式（ＩＩ）中、ｎは２〜５０の平均重合度を表し、置換基Ｘは、水素原子、ヒドロキシル基、Ｃ_１〜Ｃ_５アルキル基、ヒドロキシ置換Ｃ_１〜Ｃ_５アルキル基、Ｃ_６〜Ｃ_１２アリール基、ベンジル基、ベンザル基、式（ＩＩ）中のベンゼン環に縮合してナフタレン環を形成する不飽和ハイドロカーボン基、又は下記式（ＩＩＩ）で示される基：

を表し、式（ＩＩＩ）中のＲ^１及びＲ^２は、それぞれ相互に独立に、水素原子、ヒドロキシル基、Ｃ_１〜Ｃ_５アルキル基、又はヒドロキシ置換Ｃ_１〜Ｃ_１０アルキル基を表し、式（ＩＩ）及び式（ＩＩＩ）における置換基Ｙ^１及びＹ^２は、それぞれ相互に独立に、水素原子、又は下記式（ＩV）若しくは式（Ｖ）で示されるＺ基：

を表わし、式（ＩV）及び式（Ｖ）におけるＲ^３、Ｒ^４、Ｒ^５、Ｒ^６及びＲ^７は、それぞれ相互に独立に、Ｃ_１〜Ｃ_１０アルキル基又はヒドロキシ置換Ｃ_１〜Ｃ_１０アルキル基を表し、この水溶性重合体分子中の各ベンゼン環における前記Ｚ基の置換数の平均値は０．２〜１．０である。 Examples of the water-soluble or water-dispersible resin (C) include PVA derivatives such as polyvinyl alcohol, carboxy-modified PVA, hydroxy-modified PVA, and silanol-modified PVA, polyethylene glycol, polyacrylic acid, polyurethane resin, polyester resin, and epoxy. Resin, polyacrylamide or polyacrylamide polymer, polyethyleneimine or polyethyleneimine polymer, diallylamine or diallylamine polymer, cellulose derivatives such as carboxymethylcellulose, hydroxyethylcellulose, hydroxypropylmethylcellulose, polyvinylpyrrolidone, polyimide resin, vinylsulfonic acid resin, poly Examples thereof include resins commonly used for surface treatment of metals such as allylamine or polyallylamine polymers. In addition, a known phenol resin, more specifically, a general phenol resin used as a metal surface treatment agent, for example, a water-soluble polymer represented by the following general formula (II) can be used. These resins may be used alone or in combination of two or more. Examples of the combination of the two resins include diallylamine and polyethyleneimine, epoxy resin and polyurethane resin, or polyvinyl alcohol and polyallylamine.

In the formula (II), n represents an average degree of polymerization of 2 to 50, and the substituent X is a hydrogen atom, a hydroxyl group, a C _{1 to} C ₅ alkyl group, a hydroxy substituted C _{1 to} C ₅ alkyl group, C ₆ to C ₁₂ aryl group, a benzyl group, benzal group, a group represented by unsaturated hydrocarbon groups fused to a benzene ring in the formula (II) to form a naphthalene ring, or the following formula (III):

R ¹ and R ² in formula (III) each independently represent a hydrogen atom, a hydroxyl group, a C ₁ -C ₅ alkyl group, or a hydroxy-substituted C ₁ -C ₁₀ alkyl group, The substituents Y ¹ and Y ² in (II) and formula (III) are each independently a hydrogen atom, or a Z group represented by the following formula (IV) or formula (V):

R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ in formula (IV) and formula (V) are each independently a C ₁ -C ₁₀ alkyl group or a hydroxy-substituted C ₁ -C _10. Represents an alkyl group, and the average number of substitutions of the Z group in each benzene ring in the water-soluble polymer molecule is 0.2 to 1.0.

(Surfactant (D))
The surfactant (D) to be blended in the surface treatment agent according to the present invention may be nonionic, cationic, anionic or amphoteric. Nonionic surfactants include, for example, polyethylene glycols such as polyoxyethylene alkylphenyl ether, polyoxyethylene alkyl ether, polyoxyethylene fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene-polyoxypropylene-block polymer, etc. And non-ionic surfactants such as polyhydric alcohol type nonionic surfactants such as sorbitan fatty acid esters and amide type nonionic surfactants such as fatty acid alkylolamides. Examples of the cationic surfactant include amine salt type cationic surfactants such as higher alkylamine salts and polyoxyethylene higher alkylamines, and quaternary ammonium salt type cationic surfactants such as alkyltrimethylammonium salts. Can be mentioned. Examples of the anionic surfactant include higher alkyl ether sulfate salts to which ethylene oxide is added. Among these, the HLB value (calculated by the Griffin method) is preferably 6 or more and 18 or less, and more preferably 10 or more and 14 or less. These surfactants may be contained alone or in combination of two or more. By blending such a surfactant with the surface treatment agent of the present invention, it is possible to perform the degreasing treatment together with the chemical conversion treatment in one step. The concentration of the surfactant is preferably in the range of 0.1 to 10.0 g / L, and more preferably in the range of 0.5 to 5.0 g / L.

<Liquid>
The surface treatment agent according to the present invention preferably has a pH of 2.0 to 6.0, and more preferably has a pH of 3.0 to 4.0. When it is in the range, an iron film having excellent corrosion resistance can be obtained. In addition, pH in this specification is a value in the liquid of 25 degreeC measured with the pH meter.

≪Method for producing surface treatment agent≫
The surface treatment agent according to the present invention, that is, the surface treatment agent containing at least one of the anionic fluoroiron (III) complex compound ions (A) represented by the above formula (I) is, for example, (1) water-insoluble (2) is dissolved in a fluorine-containing compound that is stabilized as dissolved trivalent iron in a surface treatment agent, and if necessary, an oxidizing agent, the ligand X and the like are sequentially added and mixed. ) After adding and mixing a water-soluble iron source to water (optionally an aqueous liquid medium such as alcohol may be added), the fluorine-containing compound is added, and if necessary, an oxidizing agent, It can manufacture by adding the said ligand X etc. sequentially and mixing. Hereinafter, each raw material (ligand, oxidizing agent, iron source, fluorine-containing compound) will be described in detail.

(Ligand)
The ligand X is a component for preventing precipitation of iron (including an iron compound) in an aqueous solution. The ligand X is not particularly limited as long as it can coordinate with dissolved trivalent iron. For example, at least selected from the group consisting of aminocarboxylic acid, hydroxycarboxylic acid, sulfonic acid, and phosphonic acid One kind can be mentioned. Specifically, EDTA (ethylenediaminetetraacetic acid), HEDTA (hydroxyethylethylenediaminetriacetic acid), NTA (nitrilotriacetic acid), DTPA (diethylenetriaminepentaacetic acid), TTHA (triethylenetetraminehexaacetic acid), DHEG (dihydroxyethylglycine) , EDTMP (ethylenediaminetetramethylenephosphonic acid), NTMP (nitrilotrimethylenephosphonic acid), HEDP (hydroxyethylidene diphosphonic acid), iminodiacetic acid, tricine, tartaric acid, malic acid, citric acid, glycolic acid, lactic acid, gluconic acid, mucus Acid, quinic acid, taurine and the like can be mentioned. These ligands X may be used individually by 1 type, and may be used in combination of 2 or more type. Here, the abundance of the ligand X can be measured by a general method such as high performance liquid chromatography using a column for anion analysis, derivatization-solvent extraction-GC / MS method, or the like.

(Oxidant)
Examples of the oxidizing agent include perchloric acid, hypochlorous acid, dissolved oxygen, ozone, permanganic acid, hydrogen peroxide, and the like. These oxidizing agents may be used alone. And two or more kinds may be used in combination.

(Iron source)
As the iron supply source, 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 may be used. The iron (trivalent dissolved iron) concentration 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 0.5 g / L or more and 5.0 g / L or less. More preferably, it is 0.7 g / L or more and 2.0 g / L or less. If it is within this range, an iron film that exhibits more excellent corrosion resistance and coating film adhesion is easily obtained. Here, the abundance of iron in the surface treatment agent of the present invention can be measured by a general method, for example, by performing a titration method and an ICP emission spectroscopic analysis method.

(Fluorine-containing compound)
The fluorine component in the fluorine-containing compound is a component that stabilizes the etching component of the metal material and iron in an aqueous solution. The fluorine component is fluorine that can be dissolved in water (dissolved fluorine). Fluorine-containing compounds, that is, fluorine sources include, for example, hydrofluoric acid, fluorotitanic acid, fluorozirconic acid, fluorosilicic acid, ammonium fluoride, acidic ammonium fluoride, sodium fluoride, sodium dihydrofluoride, fluorine. Examples thereof include, but are not limited to, potassium fluoride and potassium hydrogen difluoride. The amount of fluorine present in the surface treatment agent of the present invention can be measured by a general method. For example, a chelating agent that easily forms a chelate complex with iron (for example, ethylenediaminetetraacetic acid (EDTA) or the like) is surfaced. When added to the treatment agent, the liberated fluorine ions can be measured by ion chromatography.

  Here, iron can take a maximum of six coordination (regular octahedral structure), and it is necessary to coordinate more than three fluorines to one iron. In this case, the remainder can be coordinated by water (hydroxide ions). Although depending on the coordination number of the fluorine, it is preferable that water is coordinated to less than 3 times the molar concentration with respect to iron. For example, when fluorine is coordinated four times with respect to iron, the remaining coordination number of iron is 2 at the maximum, and the residue is coordinated with water and ligand X. Therefore, in order to form the anionic fluoroiron (III) complex compound ion (A) represented by the above formula (I), that is, to coordinate more than 3 fluorine atoms to one iron, fluorine (dissolved type) Fluorine) is preferably more than 3 times the molar concentration and 6 times the molar concentration or less with respect to iron (trivalent dissolved iron). More preferably, it is 4 times or more molar concentration or more. When fluorine is present at a concentration relative to iron, an iron coating that exhibits better corrosion resistance and coating film adhesion is easily obtained. On the other hand, in these coordinations, when the fluorine is 3 times or less the molar concentration with respect to iron, the stability of the trivalent iron ions is impaired and an insoluble iron salt is produced. From the above, in the agent, fluorine (dissolved fluorine) is present in a molar ratio of more than 3 to 15 or less (more preferably 4 or more or more than 10) with respect to iron (trivalent dissolved iron). ) Is preferable for achieving the effects of the present invention.

  On the other hand, each ligand X has a unique locus. For example, EDTA can be hexadentate and the value of Z in the above formula (I) is 6. Therefore, the coordination number of the ligand X is preferably 0 or more. Moreover, since the ligand X has a chelating power with iron stronger than that of fluorine or water, it coordinates with iron preferentially.

≪Surface treatment method≫
The surface treatment agent according to the present invention is used for surface treatment of a metal material. Here, the surface treatment method essentially includes a chemical conversion film forming step of forming an iron film on the metal material by bringing the metal material into contact with the surface treatment agent described above.

  Hereinafter, the surface treatment method will be described in detail. The metal material used for the surface treatment method is not particularly limited, and examples thereof include iron materials, galvanized materials, and aluminum materials. As more specific examples, cold-rolled steel sheet, hot-rolled steel sheet, black leather sheet, hot-dip galvanized steel sheet, electrogalvanized steel sheet, galvannealed steel sheet, aluminum-plated steel sheet, aluminum-zinc alloyed steel sheet , Zinc-nickel alloyed plated steel sheets, aluminum plates, aluminum alloy plates, etc., or heat history materials obtained by subjecting these materials to heat treatment (for example, high heat treatment, welding treatment, etc.).

  The contact method of the said metal material and a surface treating agent is not specifically limited, What is necessary is just the method applied in a normal chemical conversion treatment method. For example, an immersion treatment method, a spray treatment method, an electrolytic treatment method, a pouring treatment method, and the like can be given. Among these, the immersion treatment method is preferable.

  The contact temperature between the metal material and the surface treatment agent is preferably 25 to 55 ° C, more preferably 35 to 45 ° C, but is not limited to these temperatures. Further, the contact time between the metal material and the surface treatment agent is preferably 30 to 300 seconds, more preferably 60 to 180 seconds, but the treatment time is not limited thereto.

  In addition, the surface treatment method according to the present invention is another method such as phosphate chemical conversion treatment using zinc phosphate, zirconium chemical conversion treatment, titanium chemical conversion treatment, hafnium chemical conversion treatment, vanadium chemical conversion treatment after the chemical conversion film forming step. Chemical conversion treatment may be performed. Further, the surface treatment method according to the present embodiment performs the phosphate chemical conversion treatment as the second chemical conversion treatment after the chemical conversion film forming step, and subsequently the zirconium chemical conversion treatment, the titanium chemical conversion treatment, the hafnium chemical conversion treatment, and the vanadium chemical conversion treatment. A third chemical conversion treatment such as the above may be performed. Thus, the corrosion resistance and coating film adhesion of the metal material can be further improved by performing another chemical conversion treatment, or the second and third chemical conversion treatments, after the chemical conversion film forming step.

  Here, a general zirconium chemical conversion treatment agent can be used for the zirconium chemical conversion treatment. Moreover, a general titanium chemical conversion treatment agent can be used for the titanium chemical conversion treatment. A general hafnium chemical conversion treatment agent can be used for the hafnium chemical conversion treatment, and a general vanadium chemical conversion treatment agent can be used for the vanadium chemical conversion treatment. In these chemical conversion treatments, for example, using a treatment liquid having a pH of 3.0 to 6.0 containing 0.005 to 5.0 g / L of zirconium ions, titanium ions, hafnium ions and / or vanadium ions, 25 to 55 is used. It is carried out by dipping or spraying at 10 ° C. for 10 to 300 seconds.

  Furthermore, a general phosphate chemical conversion treatment can be similarly used for the phosphate chemical conversion treatment. The phosphate chemical conversion treatment uses, for example, a treatment solution having a pH of 3.0 to 6.0 containing 0.1 to 50 g / L of phosphate ions and 0.01 to 3.0 g / L of zinc ions, It is carried out by dipping or spraying at 25 to 55 ° C. for 10 to 300 seconds.

  In the surface treatment method according to the present invention, it is preferable to perform a degreasing step of cleaning the metal material in advance by a degreasing treatment before the chemical conversion film forming step. The method of degreasing is not particularly limited, and a conventionally known method can be applied. In addition, after performing a degreasing process and a chemical conversion film formation process, you may perform said another chemical conversion treatment. Moreover, after performing a degreasing process and a chemical conversion film formation process, you may perform a 2nd chemical conversion treatment and a 3rd chemical conversion treatment.

  Moreover, the surface treatment method according to the present invention may perform a coating step using a paint after the chemical conversion film forming step, after the other chemical conversion treatment, or after the third chemical conversion treatment. The coating method is not particularly limited, and conventionally known methods such as electrodeposition coating (for example, cationic electrodeposition coating), solvent coating, and powder coating can be applied. In addition, when applying the electrodeposition coating method using an electrodeposition paint, the chemical conversion treatment agent used in the said chemical conversion film formation process which is the previous process, said another chemical conversion treatment, or said 3rd chemical conversion treatment. It is preferable to control the sodium ion concentration therein to less than 500 ppm on a mass basis.

  The surface treatment method according to the present invention includes, in addition to the chemical conversion film formation step, the degreasing step; the other chemical conversion treatment; the second chemical conversion treatment and the third chemical conversion treatment; the coating step; Step and the other chemical conversion treatment; the degreasing step, the second chemical conversion treatment and the third chemical conversion treatment; the degreasing step and the coating step; the another chemical conversion treatment and the coating step; the second chemical conversion treatment. The third chemical conversion treatment and the 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, In the case of containing water, a water washing step may be included after each step. Thus, when a water washing process is included after each process, the surface treatment method may abbreviate | omit a part of water washing process and may abbreviate | omit all the water washing processes.

≪Surface treatment metal material obtained by surface treatment≫
Next, a metal material having a chemical conversion film obtained by chemical conversion treatment with the surface treatment agent according to the present invention, that is, a surface-treated metal material will be described in detail. The chemical conversion film formed on the surface of the surface-treated metal material according to the present embodiment is an iron film. This film can be formed regardless of the metal material type. Here, the thickness of the iron film is preferably 0.001 to 1.0 μm.

  Furthermore, the surface-treated metal material according to the present invention may have a zirconium chemical conversion coating, a titanium chemical conversion coating, a hafnium chemical conversion coating, or a vanadium chemical conversion coating on the iron coating. In this case, the thickness of the chemical conversion film is preferably 0.005 to 0.2 μm, and more preferably 0.01 to 0.1 μm.

  Moreover, the surface treatment metal material which concerns on this invention may have a phosphate chemical conversion film on this iron film. In this case, the thickness of the phosphate chemical film is preferably 0.1 to 10 μm, and more preferably 1.0 to 3.0 μm. When the surface-treated metal material according to the present invention has a phosphate chemical film, a zirconium chemical film, a titanium chemical film, a hafnium chemical film, or a vanadium chemical film on the iron film, A zirconium chemical conversion film, a titanium chemical conversion treatment film, a hafnium chemical conversion treatment film, or a vanadium chemical conversion treatment film is formed on the phosphate chemical conversion film.

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

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

  In the cationic electrodeposition coating, for example, while maintaining the temperature of the paint at about 26 to 30 ° C. and stirring the paint, the surface-treated metal material is straightened from 0 V to 200 V over 30 seconds using a rectifier. Specifically, a voltage is applied in the cathode direction, and then held at 200 V for 150 seconds. The metal material coated on the surface in this manner is washed with water and baked to form a coating film. Note that the baking is performed at 170 ° C. for 20 minutes, for example.

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

  In addition, the thickness of a coating film can be calculated | required by measuring using an electromagnetic film thickness meter or an eddy current film thickness meter. More specifically, when the coating film is formed on the surface of a magnetic metal material (iron, iron-based alloy, etc.), it is measured using an electromagnetic film thickness meter. Moreover, when a coating film is formed on the surface of a non-magnetic metal material (aluminum, aluminum alloy, etc.), it measures using an eddy current film thickness meter. After the measurement, several arbitrary points on the coating film are measured to obtain the average thickness.

  Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited to these.

<Metal material>
The following metal materials were prepared (all manufactured by Partec Co., Ltd.)
-Cold-rolled steel sheet: SPC (SPCC-SD) 70 x 150 x 0.8 mm
・ High-tensile hot-rolled steel sheet: SPH (SPH-590) 70 x 150 x 1.2 mm
・ Heat history steel plate: baked SPH (steel plate fired at 400 ° C. for 20 minutes in a muffle furnace; size is the same as SPH)
・ Black skin steel plate: SPHC 70 × 150 × 2.3mm
Electrogalvanized steel sheet: EG (zinc basis weight 20 g / m ² ; on both sides) 70 × 150 × 0.8 mm
· Hot-dip galvanized steel sheet: GI (zinc basis weight 90 g / m ² ; both sides) 70 × 150 × 0.8 mm
Alloyed galvanized steel sheet: GA (zinc basis weight 45 g / m ² ; on both sides) 70 × 150 × 0.8 mm
Aluminum alloy plate: AL (A6061P) 70 x 150 x 1.0 mm

<Surface treatment>
The surface of each metal material was degreased by spraying a degreasing agent (Nihon Parkerizing Co., Ltd .; FC-E2001) heated to 40 ° C. for 120 seconds. After the degreasing treatment, the surface was washed with spray water for 30 seconds. Subsequently, a metal material in which an iron film was formed on the surface by immersing in a surface treatment agent of Examples 1 to 44 and Comparative Examples 1 and 3 described later at 40 ° C. for 120 seconds, then washing with water and drying at room temperature. Was made. Moreover, the metal material which carried out the said degreasing process and the spray water washing process is used for the zirconium chemical conversion liquid of the comparative example 4 [50 g / L zirconium chemical conversion liquid (The chemical conversion processing agent by Nippon Parkerizing Co., Ltd .; PLM-1000 is used)]. A zirconium chemical conversion treatment was performed by immersion at 35 ° C. for 120 seconds to produce a metal material on which a zirconium chemical conversion film was formed. Further, the metal material subjected to the degreasing treatment and the spray water washing treatment was subjected to the zinc phosphate chemical conversion treatment solution of Comparative Example 5 [50 g / L of zinc phosphate chemical conversion treatment solution (Zinc phosphate chemical conversion treatment agent manufactured by Nihon Parkerizing Co., Ltd .; PB -SX35 used)] was immersed for 120 seconds at 35 ° C. to perform a zinc phosphate conversion treatment, and a metal material having a zinc phosphate conversion coating formed thereon was produced.

  In addition, after forming an iron film by immersing in the surface treatment agent of Example 1 at 40 ° C. for 120 seconds and then washing with water, zirconium conversion treatment was performed using the zirconium chemical conversion treatment liquid of Comparative Example 4, A metal material on which a composite film including a film and a zirconium chemical conversion film was formed was produced. Moreover, after forming an iron film by immersing in the surface treating agent of Example 1 at 40 ° C. for 120 seconds and then washing with water, a 3.0 g / L surface conditioning solution (a surface conditioning agent manufactured by Nihon Parkerizing Co., Ltd.) ; Using PL-X) at room temperature for 30 seconds to perform surface treatment, followed by zinc phosphate chemical conversion treatment using the zinc phosphate chemical conversion solution of Comparative Example 5, and iron film and zinc phosphate chemical conversion A metal material on which a composite film including the film was formed was produced.

<Cation electrodeposition coating>
A metal material having each film was used as a cathode, and an electrodeposition paint (manufactured by Kansai Paint Co., Ltd .; GT-100) was used for constant voltage cathodic electrolysis for 180 seconds to form a coating film on the entire surface of the metal plate. Then, it washed with water, baked at 170 degreeC for 20 minute (s), and produced each test board, and implemented the following salt warm water immersion tests, the combined cycle test, and the coating-film adhesiveness test. The coating thickness was adjusted to 20 μm.

<Salt warm water immersion test>
Each test plate was cross-cut with a cutter, immersed in a 5% by 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) peel test was performed on the cross cut portion of the test plate, the maximum peel width on both sides from the cross cut was measured, and evaluated according to the following evaluation criteria.
<Evaluation criteria>
A: Maximum peel width on both sides is less than 3.0 mm ○: Maximum peel width on both sides is 3.0 mm or more and less than 5.0 mm Δ: Maximum peel width on both sides is 5.0 mm or more and less than 10.0 mm ×: Maximum peel width on both sides is 10. 0mm or more <Composite cycle test>
Each test plate was cross-cut with a cutter, put into a combined cycle tester, and combined cycle test was performed 100 cycles according to JASO-M609-91. The maximum swollen width on both sides from the crosscut after 100 cycles was measured and evaluated according to the following evaluation criteria.
<Evaluation criteria>
◎: Both sides maximum swelling width is less than 5.0 mm ○: Both sides maximum swelling width is 5.0 mm or more and less than 10.0 mm Δ: Both sides maximum swelling width is 10.0 mm or more and less than 15.0 mm ×: Both sides maximum swelling width is 15. 0mm or more

<Coating adhesion test>
Each test plate was cut with a cutter in a grid pattern (10 × 10 = 100) at intervals of 1 mm, and then immersed in boiling water for 1 hour. Subsequently, the moisture on the surface was wiped off, a tape peeling test using cello tape (registered trademark) was performed on a grid-like cut wound, the number of grids that did not peel was measured, and the following evaluation criteria According to the evaluation.
<Evaluation criteria>
◎: 100 pieces ○: 80 to 99 pieces △: 1 to 79 pieces ×: 0 pieces

<Preparation of surface treatment agents of Examples 1-44 and Comparative Examples 1-3>
Iron powder or iron (II) sulfate is dissolved in a hydrofluoric acid aqueous solution, and various solutions are prepared in which the concentration of iron and the molar concentration of hydrofluoric acid to the molar concentration of iron (times) are shown in Table 1. did. In addition, after iron powder or iron (II) sulfate is dissolved in a hydrofluoric acid aqueous solution, hydrogen peroxide (used in the preparation of the surface treatment agents of Examples 1 to 43 and Comparative Examples 1 to 3) and various coordinations The child X, various metal compounds, various resins, and the like are sequentially added and mixed with stirring. The concentration of iron, various metal compounds, various resins, etc .; the ratio of the molar concentration of hydrofluoric acid to the molar concentration of iron (times); In addition, various ratios of the molar concentration of the ligand X to the molar concentration of iron (times) were prepared as shown in Table 1. Then, pH of various solution or various liquid mixture was adjusted to the value shown in Table 1, and the various surface treating agents of Examples 1-44 and Comparative Examples 1-3 were obtained.

In Examples 32 to 44, the following resins were used as the water-soluble or water-dispersible resin (C).
(C1) Water-based urethane resin (Superflex E-2000; manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)
(C2) Phenol resin (in formula (II), n = 5, X = hydrogen, Y ¹ = —CH ₂ N (CH ₃ ) ₂ , Z group substitution number average value = 1.0)
(C3) novolak resin (novolak phenol resin having a methylol group with a ratio of F / P (phenols / aldehydes) of 0.84)
(C4) Amine-modified tannin (formaldehyde condensate of aluminum tannate (100 parts by mass; manufactured by Fuji Chemical Co., Ltd.) and monoethanolamine (15 parts by mass))
(C5) Aluminum tannate (C6) Polydiallylamine hydrochloride (weight average molecular weight: about 110000)
(C7) Polyethyleneimine (weight average molecular weight: about 1300)
(C8) 99% saponified product of polyvinyl acetate (weight average molecular weight: about 50000)
(C9) Water-based epoxy resin (Adeka Resin EP-4100; manufactured by ADEKA Corporation)

  Tables 2 to 4 show the results of a salt warm water immersion test, a combined cycle test, and a coating film adhesion test performed on each test plate. As shown in Tables 2 to 4, the surface treatment agent according to the present invention of Examples 1 to 44 is excellent for difficult-to-convert materials (black leather plate and heat history steel plate) regardless of the target metal material type. An iron film having high corrosion resistance and coating film adhesion could be formed.

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

  Moreover, the test plate surface-treated with the surface treating agent of Comparative Example 2 also had insufficient corrosion resistance and coating film adhesion.

  Furthermore, the test plate surface-treated with the surface treating agent of Comparative Example 3 also had insufficient corrosion resistance and coating film adhesion.

Claims (8)

A surface treatment agent having a pH of 2 or more and 6 or less, containing at least one kind of anionic fluoroiron (III) complex compound ion (A) represented by the following formula (I).

Here, 3 <n ≦ 6, 0 ≦ m <3, i = [6- (n + m)] / Z, i ≧ 0, X is a ligand capable of coordinating to iron, Z is a ligand X The number of seats.   The surface according to claim 1, further comprising at least one metal component (B) selected from Zr, Ti, Hf, Bi, Al, Mg, Zn, Ce, Y, In, Mn, W, Mo and V. Processing agent.   The surface treatment agent according to claim 1 or 2, further comprising a water-soluble or water-dispersible resin (C) in an amount of less than 1% by mass based on the total mass of the surface treatment agent.   The surface treating agent according to any one of claims 1 to 3, further containing at least one metal component selected from Cu, Sn, and Co at less than 0.01 mmol / L.   The surface treatment method including the contact process which makes the surface treatment agent in any one of Claims 1-4 contact a metal surface.   A zirconium conversion coating forming step for forming a zirconium conversion coating, a titanium conversion coating forming step for forming a titanium conversion coating, a hafnium conversion coating forming step for forming a hafnium conversion coating, or a vanadium conversion coating after the contacting step according to claim 5. A surface treatment method further comprising a vanadium chemical conversion film forming step of forming a film.   A surface treatment method further comprising a phosphate conversion film forming step of forming a phosphate conversion film after the contacting step according to claim 5.   A surface-treated metal material obtained by the surface treatment method according to claim 5.