JP4242827B2 - Metal surface treatment composition, surface treatment liquid, surface treatment method, and surface-treated metal material - Google Patents

Description

  The present invention provides a surface treatment composition and a surface treatment treatment liquid capable of depositing a surface treatment film excellent in corrosion resistance after coating or bare corrosion resistance on the surface of a metal material represented by building materials and home appliances. And a surface treatment method, and a metal material obtained by the treatment method.

  As a technique for depositing a surface treatment film having excellent corrosion resistance after coating on a metal surface, a zinc phosphate treatment method and a chromate treatment method are generally used. The zinc phosphate treatment method can deposit a film having excellent corrosion resistance on steel such as hot-rolled steel sheets and cold-rolled steel sheets, and galvanized steel sheets.

  However, when the zinc phosphate treatment is performed, generation of sludge as a by-product of the reaction is inevitable. In addition, it is possible to ensure sufficient post-painting performance by applying chromate treatment, but chromate treatment containing harmful hexavalent chromium in the treatment liquid is in the direction of being avoided from recent environmental regulations. .

  Therefore, as a recent technology, a technology has been developed in which corrosion resistance is imparted by coating the surface of a material with a metal thin film such as zirconium, and further, no harmful components are contained in the processing liquid and generation of sludge is suppressed. . As these surface treatment methods, the following methods have been proposed.

  For example, Patent Document 1 describes a compound containing a nitrogen atom having a lone electron pair, and a non-chromium coating agent for a metal surface containing the compound and a zirconium compound. The purpose of this method is to obtain a surface-treated film excellent in corrosion resistance and adhesion after coating without applying hexavalent chromium, which is a harmful component, by applying the composition.

  However, the target metal material is limited to an aluminum alloy, and a surface treatment film is formed by coating and drying, so that it is difficult to apply to a complicated structure.

  Therefore, as a method of depositing a surface treatment film having excellent adhesion and corrosion resistance after coating by a chemical conversion reaction, Patent Document 2 discloses a surface treatment agent using cerium, zirconium, phosphoric acid, a fluorine compound, and a treatment bath. Are listed.

  However, as in the invention described in Patent Document 1, this method is also limited to aluminum or an aluminum alloy, which is excellent in the corrosion resistance of the material itself, and is applied to the surface of an iron-based material or a zinc-based material. It was impossible to deposit a surface treatment film.

  Patent Document 3 discloses a method for depositing a surface treatment film having excellent corrosion resistance and adhesion after coating with a surface treatment composition comprising a metal acetylacetonate and a water-soluble inorganic titanium compound or a water-soluble inorganic zirconium compound. Is described. By using this method, the metal material applied was expanded to magnesium, magnesium alloy, zinc, and galvanized alloy in addition to aluminum alloy.

  However, with this method, it was impossible to deposit a surface treatment film on the surface of an iron-based metal material such as a hot-rolled steel sheet or a cold-rolled steel sheet.

  Furthermore, Patent Document 4 describes a metal surface treatment method using a chromium-free coating-type acidic composition. In the metal surface treatment method, an aqueous solution of a component that can be a film having excellent corrosion resistance is applied to the metal surface, and then the film is fixed by baking and drying without performing a water washing step. Therefore, since a chemical reaction is not accompanied with the production | generation of a membrane | film | coat, it is possible to give a membrane | film | coat process to metal surfaces, such as a hot rolled steel plate, a cold rolled steel plate, a galvanized steel plate, and an aluminum alloy.

  However, similarly to the invention described in Patent Document 1, since a film is generated by coating and drying, it is difficult to perform a uniform film treatment on a complicated structure.

  Further, Patent Document 5 discloses a metal chemical conversion treatment method containing zirconium ions and / or titanium ions and fluorine ions in a treatment bath. By using this method, the target metal material can be applied to iron, aluminum and zinc.

  However, there is a constraint that the iron ion concentration in the chemical conversion treatment agent must be controlled by the oxidizing agent during the treatment.

Therefore, in the prior art, it is a processing solution that does not contain components harmful to the environment, and it is excellent in corrosion resistance and adhesion, and also in operability, for metal materials such as iron-based metal materials and zinc-based metal materials. It was impossible to perform surface treatment.
JP 2000-204485 A JP-A-2-25579 JP 2000-199077 A JP-A-5-195244 JP 2004-43913 A

  The present invention is a treatment liquid that does not contain components harmful to the environment, which has been difficult in the prior art, and is used for building materials, hot-rolled steel sheets and cold-rolled steel sheets such as cold-rolled steel sheets used in home appliances, Surface treatment composition and surface treatment capable of depositing a surface treatment film with excellent corrosion resistance after coating or bare corrosion resistance on the surface of metal materials such as zinc-based metal materials such as galvanized steel sheets The object is to provide a treatment liquid, a surface treatment method, and a surface-treated metal material.

  As a result of intensive studies on means for solving the above problems, the present inventors have completed a surface treatment composition, a surface treatment solution, a surface treatment method, and a surface treatment metal material that are not present in the prior art. It was.

  Such a subject is achieved by the present invention of the following (1) to (17).

(1) The following component (A), component (B), and component (C):
(A) a compound containing at least one element selected from the group consisting of Ti, Zr, Hf, and Si (B) Y and / or a compound containing a lanthanoid element (C) nitric acid and / or a nitric acid compound, K1 = B / A which is a ratio of the total mass concentration B of the Y and / or lanthanoid elements in the component (B) to the total mass concentration A of the elements in the component (A) is 0.05 ≦ K1 ≦ 50, and K2 = C / A, which is a ratio of the total mass concentration C in terms of NO ₃ of nitrogen atoms in the component (C) to the total mass concentration A, is 0.01 ≦ K2 ≦ 200. A composition for surface treatment of a metal containing iron and / or zinc.

(2) Further, the following component (D):
(D) The composition for surface treatment as described in (1) above, which contains at least one fluorine-containing compound.

(3) The following component (A), component (B), and component (C):
(A) a compound containing at least one element selected from the group consisting of Ti, Zr, Hf, and Si (B) Y and / or a compound containing a lanthanoid element (C) nitric acid and / or a nitric acid compound, K1 = B / A which is a ratio of the total mass concentration B of the Y and / or lanthanoid elements in the component (B) to the total mass concentration A of the elements in the component (A) is 0.05 ≦ K1 ≦ 50, and K2 = C / A, which is the ratio of the total mass concentration C in terms of NO ₃ of nitrogen atoms in the component (C) to the total mass concentration A, is 0.01 ≦ K2 ≦ 200, A treatment liquid for surface treatment of a metal containing iron and / or zinc, wherein the total mass concentration A is 10 ppm ≦ A ≦ 10000 ppm.

(4) Furthermore, the following component (D):
(D) The treatment liquid for surface treatment according to the above (3), which contains at least one fluorine-containing compound and has a free fluorine ion concentration D of 0.001 ppm ≦ D ≦ 300 ppm.

  (5) The treatment liquid for surface treatment according to the above (3) or (4), which has a pH of 6.0 or less.

(6) Further, it is selected from the group consisting of HCl, H ₂ SO ₄ , HClO ₃ , HBrO ₃ , HNO ₂ , HMnO ₄ , HVO ₃ , H ₂ O ₂ , H ₂ WO ₄ , H ₂ MoO ₄ and their salts. The treatment liquid for surface treatment according to any one of (3) to (5) above, which contains 10 to 20000 ppm of at least one kind.

  (7) Further, selected from the group consisting of ethylenediaminetetraacetic acid, gluconic acid, heptogluconic acid, glycolic acid, citric acid, succinic acid, fumaric acid, aspartic acid, tartaric acid, malonic acid, malic acid, salicylic acid, and salts thereof. The treatment liquid for surface treatment according to any one of the above (3) to (6), containing 1 to 10000 ppm of at least one kind.

  (8) The surface treatment treatment liquid according to any one of (3) to (7), further comprising a water-soluble polymer compound and / or a water-dispersible polymer compound.

  (9) The surface according to any one of (3) to (8), further comprising at least one selected from the group consisting of a nonionic surfactant, an anionic surfactant, and a cationic surfactant. Treatment liquid for treatment.

  (10) It contains iron and / or zinc, which has a treatment liquid contact step of bringing the surface treatment liquid according to any one of (3) to (8) into contact with a metal material containing iron and / or zinc. Metal surface treatment method.

  (11) A treatment liquid contact step in which the surface treatment liquid according to (9) is brought into contact with a metal material containing iron and / or zinc, and the metal material is subjected to degreasing treatment and film formation treatment at the same time. Surface treatment method of metal containing iron and / or zinc.

  (12) The surface treatment method according to (10) or (11), wherein the metal material containing iron and / or zinc is a metal material cleaned by degreasing treatment.

  (13) The surface treatment method according to any one of (10) to (12), wherein in the treatment liquid contact step, electrolytic treatment is performed using the metal material containing iron and / or zinc as a cathode.

(14) Furthermore, after the treatment liquid contact step,
The above (10) to (13), comprising a step of bringing the metal material containing iron and / or zinc into contact with an aqueous solution containing at least one selected from the group consisting of cobalt, nickel, tin, copper, titanium, and zirconium. ).

(15) Furthermore, after the treatment liquid contact step,
The method according to any one of (10) to (13), further including a step of bringing the metal material containing iron and / or zinc into contact with an aqueous solution containing a water-soluble polymer compound and / or a water-dispersible polymer compound. Surface treatment method.

(16) The element of the component (A) formed on the surface of the metal material containing iron by the surface treatment method according to any one of (10) to (15), and in terms of the element A metal material containing iron having a surface treatment coating layer having an adhesion amount of 20 mg / m ² or more.

(17) containing the element of the component (A) formed on the surface of the metal material containing zinc by the surface treatment method according to any one of (10) to (15), and in terms of the element A metal material containing zinc having a surface treatment coating layer having an adhesion amount of 15 mg / m ² or more.

  The metal surface treatment composition, surface treatment liquid, surface treatment method, and surface treatment metal material of the present invention are treatment baths that do not contain components harmful to the environment, which are difficult in the prior art. This is an epoch-making technology that makes it possible to deposit a surface-treated film with excellent corrosion resistance after coating on the surface.

  Hereinafter, the metal surface treatment composition of the present invention (hereinafter also simply referred to as “the composition of the present invention”), the metal surface treatment solution of the present invention (hereinafter also simply referred to as “the treatment liquid of the present invention”), Details of the metal surface treatment method of the present invention (hereinafter also simply referred to as “the treatment method of the present invention”) and the metal material containing iron and / or zinc of the present invention (hereinafter also simply referred to as “the metal material of the present invention”) Explained. First, the composition and the treatment liquid of the present invention will be described.

At the time of use, the composition of the present invention is diluted with water or dissolved in water to obtain the treatment liquid of the present invention.
The object of the surface treatment with the treatment liquid of the present invention is an iron-based metal material or a zinc-based metal material.
The iron-based metal material is not particularly limited as long as it contains iron, and examples thereof include steel plates such as cold rolled steel plates and hot rolled steel plates, cast iron, and sintered materials.
The zinc-based metal material is not particularly limited as long as it contains zinc, but for example, indicates a material that has been subjected to zinc die casting or zinc-containing plating. Furthermore, zinc-containing plating means zinc or an alloy of zinc and other metals such as nickel, iron, aluminum, manganese, chromium, magnesium, cobalt, lead and antimony, and unavoidable impurities. There is no limitation on the plating method, for example, electroplating, hot dipping, vapor deposition plating or the like.

The present invention performs surface treatment on the surface of such a metal material. Moreover, the metal material to be processed can be surface-treated singly or in combination of two or more. Here, when two or more kinds of metal materials are processed at the same time, if at least one of the metal materials is iron or a zinc-based metal material, the other metal materials are aluminum, magnesium, nickel and alloys thereof. Anything is acceptable. Further, different metals may not be in contact with each other, or different metals may be in contact with each other by a joining method such as welding, adhesion, riveting, or the like.
The operation of the present invention will be described in detail below.

The composition of this invention contains the following component (A), component (B), and component (C).
Component (A) is a compound containing at least one element selected from the group consisting of Ti, Zr, Hf, and Si. Examples of such compounds include TiCl ₄ , Ti (SO ₄ ) ₂ , TiOSO ₄ , Ti (NO ₃ ) ₄ , TiO (NO ₃ ) ₂ , Ti (OH) ₄ , TiO ₂ OC ₂ O ₄ , H ₂ TiF ₆ , H ₂ TiF ₆ salt, TiO, TiO ₂ , Ti ₂ O ₃ , TiF ₄ , ZrCl ₄ , ZrOCl ₂ , Zr (OH) ₂ Cl ₂ , Zr (OH) ₃ Cl, Zr (SO ₄ ) ₂ , ZrOSO ₄ , Zr (NO ₃ ) ₄ , ZrO (NO ₃ ) ₂ , Zr (OH) ₄ , H ₂ ZrF ₆ , H ₂ ZrF ₆ salt, H ₂ (Zr (CO ₃ ) ₂ (OH) ₂ ), H ₂ (Zr (CO ₃ ) ₂ (OH) ₂ ) salt, H ₂ Zr (OH) ₂ (SO ₄ ) ₂ , H ₂ Zr (OH) ₂ (SO ₄ ) ₂ salt, ZrO ₂ , ZrOBr ₂ , ZrF ₄ , HfCl ₄ , Hf (SO ₄ ) ₂ , H ₂ HfF ₆ , H ₂ HfF ₆ salt, HfO ₂ , HfF ₄ , H ₂ SiF ₆ , H ₂ SiF ₆ salt, and Al ₂ O ₃ (SiO ₂ ) ₃ may be mentioned. Two or more of these may be used in combination.

  Component (B) is a compound containing Y and / or a lanthanoid element. That is, it is a compound containing at least one selected from the group consisting of Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu. Such compounds include oxides, sulfates, nitrates, and chlorides of these elements. Specifically, for example, yttrium chloride, lanthanum chloride, cerium chloride, praseodymium chloride, neodymium chloride, promethium chloride, samarium chloride, europium chloride, gadolinium chloride, terbium chloride, dysprosium chloride, holmium chloride, erbium chloride, thulium chloride, chloride Ytterbium, lutetium chloride, yttrium sulfate, lanthanum sulfate, cerium sulfate, praseodymium sulfate, neodymium sulfate, promethium sulfate, samarium sulfate, europium sulfate, gadolinium sulfate, terbium sulfate, dysprosium sulfate, holmium sulfate, erbium sulfate, thulium sulfate, ytterbium sulfate, Lutetium sulfate, yttrium nitrate, lanthanum nitrate, cerium nitrate, praseodymium nitrate, neodymium nitrate, promethium nitrate, samarium nitrate, glass Europium, gadolinium nitrate, terbium nitrate, dysprosium nitrate, holmium nitrate, erbium nitrate, thulium nitrate, ytterbium nitrate, lutetium nitrate, yttrium oxide, lanthanum oxide, cerium oxide, praseodymium oxide, neodymium oxide, promethium oxide, samarium oxide, europium oxide, Examples include gadolinium oxide, terbium oxide, dysprosium oxide, holmium oxide, erbium oxide, thulium oxide, ytterbium oxide, and lutetium oxide. Moreover, these may use 2 or more types together.

  Component (C) is nitric acid and / or a nitric acid compound. As such a thing, nitric acid, metal nitrate, etc. are mentioned, for example. Examples of the metal nitrate include iron nitrate, manganese nitrate, nickel nitrate, cobalt nitrate, silver nitrate, sodium nitrate, potassium nitrate, magnesium nitrate, and calcium nitrate. Moreover, these may use 2 or more types together.

  The composition of the present invention is used by diluting with water or dissolving in water for the surface treatment of metal. That is, a metal surface treatment solution is prepared and used. To prepare the metal surface treatment solution, water is added to the surface treatment composition, and the total mass concentration A of the elements (Ti, Zr, Hf, and Si) in the component (A) is 10 ppm to 10,000 ppm. To be in the range.

“The total mass concentration A of the elements in the component (A)” means “the concentration of the elements in the component (A) in the composition of the present invention (in some cases, a treatment liquid)”. Show.
The same applies to “total mass concentration B” and “total mass concentration C”.

The present invention relates to the total of the Y and / or lanthanoid elements in the component (B) relative to the total mass concentration A of the elements in the component (A) in the surface treatment composition and the surface treatment solution. K1 = B / A which is the ratio of the mass concentration B is 0.05 ≦ K1 ≦ 50, and the ratio of the total mass concentration C in terms of NO ₃ of nitrogen atoms in the component (C) to the total mass concentration A is calculated. Where K2 = C / A is 0.01 ≦ K2 ≦ 200.

Here, the component (A) is a substance having excellent acid resistance and alkali resistance, and is a main component of the surface treatment film of the present invention.
Further, the component (B) has an effect of promoting film deposition of the component (A). Furthermore, the component (B) can also be contained in the surface treatment film, which can be expected to improve the corrosion resistance after coating and the bare corrosion resistance.
The component (C) has a function of maintaining the stability of the treatment liquid by increasing the solubility of the component (A) and the component (B) in the treatment liquid for surface treatment. Further, the component (C) has an effect of assisting film deposition of the component (A) although not as much as the component (B).

Here, if K1 = B / A is too small, the proportion of component (B) is small, so that the effect of promoting film deposition of component (A) by component (B) cannot be expected. Therefore, compared with the case where K1 which is the ratio of the total mass concentration of the component (A) and the component (B) is 0.05 ≦ K1 ≦ 50, the coating amount of the component (A) is reduced, and the metal material to be processed Corrosion resistance may decrease.
On the other hand, if K1 is too large, the reaction starting point itself of the component (A) on the surface of the metal material to be treated is reduced, and although it has an accelerating effect by the component (B), it is a main component of the film and imparts corrosion resistance to the film. Since the coating amount of the component (A) is reduced, it does not show excellent corrosion resistance but may adversely affect the adhesion.

Moreover, even if K2 = C / A is too small, the corrosion resistance of the metal material to be treated can be obtained, but the stability of the treatment liquid of the treatment liquid for surface treatment may be impaired. May cause problems. Furthermore, since the ratio of the component (C) in the treatment liquid is low, the auxiliary effect of depositing the film of the component (A) by the component (C) cannot be expected.
Further, in order to maintain the stability of the treatment liquid of the present invention, it is sufficient that K2 = C / A is in the range of 0.01 ≦ K2 ≦ 200, and even if K2 is too large, the corrosion resistance is improved. It is only economically disadvantageous.

  The total mass concentration A of the component (A) used in the treatment liquid of the present invention is preferably adjusted from 10 ppm to 10,000 ppm, more preferably from 50 ppm to 5000 ppm. If the total mass concentration A is too small, even if the K1 and the K2 are within the specified range, the coating main component concentration is low, so that a sufficient amount of adhesion is obtained in a practical processing time to obtain corrosion resistance. It becomes difficult. On the other hand, if the total mass concentration A is too large, a sufficient amount of adhesion can be obtained, but there is no further effect of improving the corrosion resistance, which is economically disadvantageous.

Moreover, it is preferable that the composition of this invention and a process liquid further contain at least 1 sort (s) of a fluorine-containing compound as a component (D). For example, hydrofluoric acid, H ₂ TiF ₆ , H ₂ TiF ₆ salt, TiF ₄ , H ₂ ZrF ₆ , H ₂ ZrF ₆ salt, ZrF ₄ , H ₂ HfF ₆ , H ₂ HfF ₆ salt, HfF ₄ , H ₂ SiF ₆ , HBF ₄ , HBF ₄ salt, NaHF ₂ , KHF ₂ , NH ₄ HF ₂ , NaF, KF, and NH ₄ F. These fluorine-containing compounds may be used in combination of two or more.

  In addition, when component (D) is added to the treatment liquid of the present invention, it is preferable to adjust at least one fluorine-containing compound of component (D) so that the free fluorine ion concentration D is 0.001 ppm to 300 ppm, More preferably, it is preferably adjusted to be 0.1 ppm to 100 ppm. The free fluorine ion concentration D here refers to the fluorine ion concentration measured using a commercially available ion electrode. If the free fluorine ion concentration D is too large, the etching reaction of the material surface by HF becomes excessive, and it tends to be difficult to deposit a coating amount sufficient to obtain corrosion resistance on the surface of the metal material to be treated. Moreover, although the corrosion resistance of the metal material to be treated can be obtained even if the free fluorine ion concentration D due to the fluorine-containing compound of the component (D) is too small, the stability of the treatment liquid of the surface treatment liquid may be impaired. There is a possibility of causing troubles in continuous operation.

  Moreover, it is preferable that the process liquid of this invention deposits a film | membrane by the chemical conversion reaction accompanying the etching of a raw material metal. Therefore, it is preferably used at a pH of 6.0 or less, which is a pH region where an etching reaction can generally occur, more preferably at a pH of 5.0 or less, and even more preferably at a pH of 4.0 or less.

  Here, when it is necessary to adjust the pH of the treatment liquid of the present invention, there is no particular restriction on the agent to be used, and any of them may be used. For example, acids such as hydrochloric acid, sulfuric acid, boric acid, and organic acids, lithium hydroxide, potassium hydroxide, sodium hydroxide, calcium hydroxide, magnesium hydroxide, barium hydroxide, alkali metal salts, ammonia, ammonium salts, and There are alkalis such as amines.

  Moreover, the metal contained in the raw material eluted by the etching reaction of the raw material, and the metal or compound contained in tap water and industrial water may be mixed into the treatment liquid of the present invention. This is because the film deposition of the component (A) is not affected by other metal elements or compounds due to the effect of the component (B) promoting the film deposition of the component (A).

In addition, an anionic component is preferably added to the treatment liquid of the present invention in order to further accelerate the film formation reaction. Examples of anion components that can be used in the treatment liquid for surface treatment of the present invention include HCl, H ₂ SO ₄ , HClO ₃ , HBrO ₃ , HNO ₂ , HMNO ₄ , HVO ₃ , H ₂ O ₂ , and H ₂ WO _4. , H ₂ MoO ₄ and salts thereof. There are no particular restrictions on the concentration of these anionic components added, but a sufficient effect is exhibited with an addition amount of about 10 ppm to 20000 ppm.

  Furthermore, when the treatment load of the metal material to be treated on the treatment liquid of the present invention is high, it is preferable to add a chelating agent capable of chelating metal ions eluted by the etching reaction. Examples of chelating agents that can be used in the treatment liquid of the present invention include ethylenediaminetetraacetic acid (EDTA), gluconic acid, heptogluconic acid, glycolic acid, citric acid, succinic acid, fumaric acid, aspartic acid, tartaric acid, malonic acid, Examples include malic acid, salicylic acid, and salts of these chelating agents. The content of these chelating agents is not particularly limited, but a sufficient effect is exhibited with an addition amount of about 1 ppm to 10000 ppm.

  Moreover, it is preferable to add a water-soluble polymer compound and / or a water-dispersible polymer compound having an ionic reactive group in the molecule to the treatment liquid of the present invention. Examples of such compounds include polyvinyl alcohol, poly (meth) acrylic acid, copolymers of acrylic acid and methacrylic acid, acrylic monomers such as ethylene and (meth) acrylic acid and (meth) acrylate. Copolymer, ethylene and vinyl acetate copolymer, polyurethane, amino-modified phenol resin, polyester resin, epoxy resin, polyamidoamine, polyamine, polyamine derivative, polyallylamine, polyallylamine derivative, polyamidoamine derivative, polyvinylamine , Polyvinylamine derivatives, tannin and tannic acid and salts thereof, and phytic acid. The concentration of the compound added is not particularly limited, but is preferably about 1 ppm to 10000 ppm, and such an added amount exhibits a sufficient effect.

  Moreover, it is preferable to add at least one surfactant selected from the group consisting of a nonionic surfactant, an anionic surfactant and a cationic surfactant to the treatment liquid of the present invention. When the surface treatment of the metal material is performed using the surface treatment solution, it is possible to form a good film without degreasing the treated metal material in advance and cleaning it as described later. That is, this surface treatment liquid can be used as a degreasing chemical treatment surface treatment agent.

  The treatment method of the present invention is a surface treatment method for a metal containing iron and / or zinc, which has a treatment liquid contact step of bringing the treatment liquid of the present invention into contact with a metal material containing iron and / or zinc.

In the surface treatment method of the present invention, it is only necessary to bring the treatment liquid of the present invention into contact with the metal material containing iron and / or zinc. As a result, a film made of an oxide and / or hydroxide of the element (A) is deposited on the surface of the metal material, and a surface-treated film layer having excellent adhesion and corrosion resistance is formed.
For this contact treatment, any method such as spray treatment, dipping treatment and pouring treatment can be used, and this contact method does not affect the performance.
It is chemically difficult to obtain a metal hydroxide contained in the film of the component (A) as a pure hydroxide. Generally, a form in which hydrated water is attached to the metal oxide is also water. It is in the category of oxides. Therefore, the metal hydroxide eventually becomes an oxide when heated. The structure of the surface treatment film layer in the present invention is a state in which an oxide and a hydroxide are mixed when dried at room temperature or low temperature after the surface treatment, and further when oxidized at a high temperature after surface treatment. It is thought that it is in the state which has many things or oxides.

The metal material containing iron and / or zinc is preferably cleaned by degreasing. The method of degreasing is not particularly limited, and a conventionally known method can be used.
In addition, as mentioned above, when the treatment liquid of the present invention contains the surfactant, a good film can be obtained without degreasing and cleaning the metal material containing iron and / or zinc in advance. Can be formed. That is, in this case, the degreasing treatment and the film chemical conversion treatment of the metal material containing iron and / or zinc are simultaneously performed in the treatment liquid contact step.

There are no particular limitations on the use conditions of the treatment liquid of the present invention.
The reactivity of the treatment liquid of the present invention is K1 = B / A, which is the ratio of the total mass concentration B to the total mass concentration A, and K2 = the ratio of the total mass concentration C to the total mass concentration A = It can be freely controlled by changing C / A.
Further, even when at least one of the component (D) fluorine-containing compounds is used, it is possible to control by changing the free fluorine ion concentration D. Therefore, the treatment temperature and treatment time can be changed in any way in combination with the reactivity of the treatment bath.

In the treatment method of the present invention, the metal material containing iron and / or zinc can be electrolytically treated with the treatment liquid of the present invention in contact with the cathode.
In this case, a reduction reaction of hydrogen occurs at the interface of the metal material containing iron and / or zinc as the cathode, and the pH rises. As the pH increases, the stability of the compound containing the element (A) at the cathode interface decreases, and a surface-treated film is deposited as an oxide or a hydroxide containing water.

  After the treatment liquid of the present invention is brought into contact with the metal material containing iron and / or zinc or subjected to the electrolytic treatment by contact, at least selected from the group consisting of cobalt, nickel, tin, copper, titanium, and zirconium It can be made to contact with the processing liquid containing at least 1 sort (s) among the acidic aqueous solution containing 1 type, or a water-soluble polymer compound and a water-dispersible polymer compound. Thereby, the effect of the present invention can be further enhanced.

  The surface-treated film layer obtained by the present invention is a thin film and exhibits excellent coating performance. If there is an abnormality in the surface state of the metal material to be treated, there may be a minute defect in the surface treatment film layer. Therefore, an acidic aqueous solution containing at least one selected from the group consisting of cobalt, nickel, tin, copper, titanium, and zirconium, or at least one selected from a water-soluble polymer compound and a water-dispersible polymer compound. By contacting with a treatment liquid containing a polymer compound, the defect portion is covered and the corrosion resistance is further enhanced.

  Here, the source of at least one selected from the group consisting of cobalt, nickel, tin, copper, titanium, and zirconium is not particularly limited, but the metal element oxides, Oxides, fluorides, complex fluorides, chlorides, nitrates, oxynitrates, sulfates, oxysulfates, carbonates, oxycarbonates, phosphates, oxyphosphates, oxalates, oxysuccinates, and organic A metal compound or the like can be used. The pH of the acidic aqueous solution containing the metal element is preferably 2 to 6, and acids such as phosphoric acid, nitric acid, sulfuric acid, hydrofluoric acid, hydrochloric acid, and organic acids, sodium hydroxide, hydroxide It can be adjusted with alkali such as potassium, lithium hydroxide, alkali metal salt, ammonia, ammonium salt, and amines.

  Examples of at least one polymer compound selected from the water-soluble polymer compound and the water-dispersible polymer compound include polyvinyl alcohol, poly (meth) acrylic acid, and a copolymer of acrylic acid and methacrylic acid. , Copolymers of ethylene and acrylic monomers such as (meth) acrylic acid and (meth) acrylate, copolymers of ethylene and vinyl acetate, polyurethane, amino-modified phenolic resins, polyester resins, epoxy resins, Polyamidoamine, polyamine, polyamine derivatives, polyallylamine, polyallylamine derivatives, polyamidoamine derivatives, polyvinylamine, polyvinylamine derivatives, tannin, tannic acid and salts thereof, phytic acid, and the like can be used.

  As described above in detail, the present invention provides a coating layer composed of an oxide and / or hydroxide of the component (A) on the surface of the metal material to be treated, or the coating layer of the component (A) and the component. By providing a coating layer in which the coating layer composed of the oxide and / or hydroxide of the metal element (B) is provided, the corrosion resistance of the metal material can be drastically improved. Here, the film made of the oxide and / or hydroxide of the component (A) has a chemically stable property that is hardly affected by acid or alkali.

  Here, in a corrosive environment under an actual metal coating film, the pH decreases in the anode portion where the metal elution occurs, and the pH increases in the cathode portion where the reduction reaction occurs. Therefore, the surface treatment film inferior in acid resistance and alkali resistance dissolves in a corrosive environment and loses its effect. The film made of the oxide and / or hydroxide of the component (A) in the present invention is not easily affected by acid or alkali, and the present invention forms a uniform surface treatment film with a thin film on the surface of the metal to be treated. Therefore, the excellent effect is maintained even in a corrosive environment.

  In addition, the metal element oxides and hydroxides contained in the film form a network structure through the metal and oxygen, so that a very good barrier film is obtained. Although the corrosion of a metal material differs depending on the environment in which it is used, it is generally an oxygen demand type corrosion in the presence of water and oxygen, and the corrosion speed is accelerated by the presence of components such as chloride. Here, since the film layer of the present invention has a barrier effect against water, oxygen, and corrosion promoting components, it can exhibit excellent corrosion resistance.

  In the composition of this invention and the process liquid of this invention, the said component (C) is contained in addition to the said component (A) and the said component (B), and these quantitative ratios are made into the specific range. For this reason, a chemical conversion reaction is accompanied when the surface treatment film is deposited. With the chemical conversion reaction, the adhesion of the film becomes extremely high.

Here, in order to increase the corrosion resistance of ferrous metal materials such as cold rolled steel sheets, hot rolled steel sheets, cast iron and sintered materials using the barrier effect, the amount of surface treatment coating layer deposited is determined by the component ( In terms of element A), it is preferably 20 mg / m ² or more, more preferably 30 mg / m ² or more, and further preferably 40 mg / m ² or more.

Moreover, in order to improve the corrosion resistance of zinc-based metallic materials such as zinc, galvanized steel sheet, and electrogalvanized steel sheet, the amount of surface treatment coating layer deposited is 15 mg / m ² or more in terms of element of component (A). And more preferably 20 mg / m ² or more.
When the adhesion amount is too small, the barrier effect cannot be sufficiently exhibited, and it becomes difficult to obtain excellent corrosion resistance.

Furthermore, there is no particular limitation on the upper limit of the amount of iron-based metal material and zinc-based metal material, but if the amount is too large, cracks are likely to occur in the surface-treated film layer, and a uniform film is obtained. It becomes difficult. Therefore, the adhesion amount of both the iron-based material and the zinc-based material is preferably 1 g / m ² or less, more preferably 800 mg / m ² or less, in terms of the element of component (A).

  Examples are given below together with comparative examples to specifically explain the effects of the surface treatment liquid and the surface treatment method of the present invention. In addition, the to-be-treated material, the degreasing agent, and the paint used in the examples are arbitrarily selected from commercially available materials, and the actual use of the surface treatment liquid and the surface treatment method of the present invention. It is not intended to limit.

(Test plate)
The abbreviations and breakdown of the test plates used in the examples and comparative examples are shown below.
・ SPC (Cold rolled steel sheet: JIS-G-3141)
EG (electrogalvanized steel sheet: plating basis weight 20 g / m ² )

(Processing process)
In Examples 1 to 5 and Comparative Examples 1 to 3, surface treatment was performed in the following treatment steps.
Alkaline degreasing → Washing → Chemical conversion treatment → Washing → Pure water washing → Drying.

In Example 6, surface treatment was performed by the following treatment steps.
Alkaline degreasing → Washing → Chemical conversion treatment → Washing → Post treatment → Pure water washing → Drying.

In Example 7, the surface treatment was performed by the following treatment steps.
Alkaline degreasing → water washing → electrochemical conversion treatment → water washing → pure water washing → drying.

Moreover, the comparative example 4 processed in the following process steps.
Alkaline degreasing → Washing → Surface conditioning → Zinc phosphate treatment → Washing → Pure water washing → Drying.

  For alkaline degreasing, tap water in both Examples and Comparative Examples was Fine Cleaner L4460A (registered trademark: manufactured by Nihon Parkerizing Co., Ltd.) 2% and Fine Cleaner L4460B (registered trademark: manufactured by Nihon Parkerizing Co., Ltd.) 1.4%. And then used by spraying on the plate to be treated at 40 ° C. for 120 seconds.

The washing with water and the washing with pure water after the film treatment were sprayed on the plate to be treated for 30 seconds at room temperature in both the examples and the comparative examples.
The drying was performed by leaving it in a room temperature room.

<Example 1>
A surface treatment composition having a total mass concentration ratio K1 = B / A = 0.1 and a total mass concentration ratio K2 = C / A = 0.01 was prepared using an aqueous zirconium sulfate solution, lanthanum sulfate, and nitric acid. The surface treatment composition was diluted with ion-exchanged water, the zirconium element mass concentration was adjusted to 8000 ppm, and a surface treatment solution having a pH of 3.2 was prepared using sodium hydroxide. The test plate that had been degreased and washed with water was immersed in the surface treatment solution heated to 50 ° C. for 180 seconds for surface treatment.

<Example 2>
A surface treatment composition having a total mass concentration ratio K1 = B / A = 2.0 and a total mass concentration ratio K2 = C / A = 50 was prepared using an aqueous hexafluorozirconium solution, samarium nitrate and nitric acid. The surface treatment composition is diluted with ion-exchanged water so that the mass concentration of zirconium element is 100 ppm, and the free fluorine ion concentration is 25 ppm by using hydrofluoric acid and ammonia (fluorine ion meter: manufactured by Toa Denpa Kogyo Co., Ltd.) IM-55G), a surface treatment solution having a pH of 3.6 was prepared. The test plate that had been degreased and washed with water was immersed in the surface treatment solution heated to 45 ° C. for 150 seconds for surface treatment.

<Example 3>
A surface treatment composition having a total mass concentration ratio K1 = B / A = 5.0 and a total mass concentration ratio K2 = C / A = 20 was prepared using an aqueous zirconium nitrate solution, hafnium oxide, gadolinium oxide, and potassium nitrate. . The surface treatment composition is diluted with ion-exchanged water so that the total mass concentration of the zirconium element and hafnium elements is 50 ppm. To this liquid is added 100 ppm of succinic acid, and further potassium fluoride, hydroxide A treatment liquid for surface treatment having a free fluorine ion concentration of 20 ppm (fluorine ion meter: IM-55G manufactured by Toa Denpa Kogyo Co., Ltd.) and a pH of 4.0 was prepared using lithium. The test plate that had been degreased and washed with water was immersed in the surface treatment solution heated to 60 ° C. for 120 seconds for surface treatment.

<Example 4>
Using a zirconium nitrate aqueous solution, a lanthanum chloride aqueous solution, erbium oxide, sodium nitrate, and sodium nitrate, a total mass concentration ratio K1 = B / A = 35 and a total mass concentration ratio K2 = C / A = 100 Adjusted. The composition for surface treatment is diluted with ion-exchanged water so that the mass concentration of zirconium element is 20 ppm, and the concentration of free fluorine ions is 15 ppm by using hydrofluoric acid and calcium hydroxide (fluorine ion meter: Toa Denpa Kogyo Co., Ltd.) IM-55G manufactured), a treatment liquid for surface treatment having a pH of 3.0 was prepared. The test plate that had been degreased and washed with water was sprayed for 120 seconds with the above-mentioned surface treatment solution heated to 55 ° C. for surface treatment.

<Example 5>
Using a titanium nitrate aqueous solution, a hexafluorosilicic acid aqueous solution, praseodymium oxide and potassium nitrate, the total mass concentration ratio K1 = B / A = 0.4 and the total mass concentration ratio K2 = C / A = 8.0. I adjusted things. The surface treatment composition is diluted with ion-exchanged water so that the total mass concentration of the titanium element mass concentration and the silicon element mass concentration is 2500 ppm. Further, using ammonium fluoride and ammonia, the free fluorine ion concentration is 100 ppm (fluorine Ion meter: IM-55G manufactured by Toa Denpa Kogyo Co., Ltd.), a surface treatment solution having a pH of 2.9 was prepared. The test plate that had been degreased and washed with water was subjected to surface treatment by spraying for 300 seconds with the above-mentioned surface treatment solution heated to 65 ° C.

<Example 6>
Using a zirconium nitrate aqueous solution, a hexafluorotitanium aqueous solution, lanthanum chloride and iron nitrate, the total mass concentration ratio K1 = B / A = 1.0 and the total mass concentration ratio K2 = C / A = 0.5 The composition was adjusted. The surface treatment composition is diluted with ion-exchanged water so that the total mass concentration of the zirconium element mass concentration and the titanium element mass concentration is 200 ppm, and the free fluorine ion concentration is 50 ppm using ammonium fluoride and potassium hydroxide. Fluorine ion meter: IM-55G manufactured by Toa Denpa Kogyo Co., Ltd.), a surface treatment treatment solution having a pH of 4.2 was prepared. The test plate that had been degreased and washed with water was immersed in the surface treatment solution heated to 60 ° C. for 200 seconds for surface treatment, and then washed with water and subjected to post-treatment. As the post-treatment liquid used at this time, an aqueous solution having a titanium mass concentration of 200 ppm and a nickel mass concentration of 50 ppm as a metal element was prepared using a hexafluorotitanium aqueous solution and nickel nitrate, and the aqueous solution was further heated to 45 ° C. Then, the one whose pH was adjusted to 4.5 with sodium hydroxide was used.

<Example 7>
Using a hexafluorozirconium aqueous solution, yttrium sulfate and nitric acid, a surface treatment composition having a total mass concentration ratio K1 = B / A = 3.0 and a total mass concentration ratio K2 = C / A = 3.0 was prepared. . The composition for surface treatment is diluted with ion-exchanged water so that the mass concentration of zirconium element is 200 ppm, 50 ppm of EDTA is added to this liquid, and the concentration of free fluorine ions is 80 ppm using hydrofluoric acid and sodium hydroxide. Fluorine ion meter: IM-55G manufactured by Toa Denpa Kogyo Co., Ltd.), a surface treatment treatment solution having a pH of 2.8 was prepared. A test plate that had been degreased and washed with water was used as a cathode, and a carbon electrode was used as the anode, and surface treatment was performed by electrolysis for 10 seconds in the surface treatment solution at room temperature under an electrolysis condition of 5 A / dm ² .

<Comparative Example 1>
A surface treatment composition having a total mass concentration ratio K1 = B / A = 0.01 and a total mass concentration ratio K2 = C / A = 10 was prepared using an aqueous zirconium nitrate solution, holmium nitrate, and nitric acid. The surface treatment composition was diluted with ion-exchanged water so that the mass concentration of zirconium element was 100 ppm, and further, a surface treatment solution having a pH of 3.0 was prepared using sodium hydroxide. The test plate that had been degreased and washed with water was immersed in the surface treatment solution heated to 55 ° C. for 180 seconds for surface treatment.

<Comparative example 2>
A surface treatment composition having a total mass concentration ratio K1 = B / A = 5.0 and a total mass concentration ratio K2 = C / A = 200 was prepared using an aqueous hexafluorozirconium solution, europium oxide, and sodium nitrate. The surface treatment composition is diluted with ion-exchanged water so that the zirconium element has a mass concentration of 4 ppm, and further uses potassium fluoride and potassium hydroxide to give 20 ppm free fluorine ions (fluorine ion meter: IM made by Toa Denpa Kogyo Co., Ltd.) -55G), a surface treatment solution having a pH of 3.8 was prepared. The test plate that had been degreased and washed with water was immersed in the surface treatment solution heated to 60 ° C. for 120 seconds for surface treatment.

<Comparative Example 3>
A surface treatment composition having a total mass concentration ratio K1 = B / A = 70 and a total mass concentration ratio K2 = C / A = 50 was prepared using an aqueous hexafluorotitanium solution, gallium sulfate, potassium nitrate, and ammonium nitrate. The surface treatment composition is diluted with ion-exchanged water so that the mass concentration of titanium element is 50 ppm, and further, the concentration of free fluorine ions is 400 ppm by using ammonium fluoride and ammonia (fluorine ion meter: IM-manufactured by Toa Denpa Kogyo Co., Ltd. 55G), a surface treatment solution having a pH of 2.8 was prepared. The test plate that had been degreased and washed with water was sprayed for 150 seconds with the surface treatment solution heated to 50 ° C. to perform surface treatment.

<Comparative example 4>
A test plate that has been degreased and washed with water is sprayed with a solution prepared by diluting Preparen ZN (registered trademark: manufactured by Nippon Parkerizing Co., Ltd.) 0.1% with tap water at room temperature for 30 seconds. After that, Palbond L3020 (registered trademark: manufactured by Nihon Parkerizing Co., Ltd.) was diluted to 4.8% with tap water, and after adding 200 ppm of sodium hydrogen fluoride reagent as fluorine, the total acidity and free acidity were cataloged. It was immersed in a 43 ° C. zinc phosphate chemical treatment solution adjusted to the center of the value to deposit a zinc phosphate coating.

(Evaluation of surface treatment film and adhesion amount measurement)
The appearance of the test plate after the surface treatment of the examples and comparative examples was visually evaluated, and the amount of the surface treatment coating layer deposited was measured using a fluorescent X-ray analyzer (system 3270; manufactured by Rigaku Denki Kogyo Co., Ltd.). It was measured.

(Preparation of paint performance evaluation board)
In order to evaluate the coating performance of the surface treatment board of an Example and a comparative example, it applied by the process shown below. Cationic electrodeposition coating → pure water washing → baking → intermediate coating → baking → top coating → baking.

  Cationic electrodeposition coating: Epoxy-based cationic electrodeposition coating (Electron 9400: manufactured by Kansai Paint Co., Ltd.), voltage 200 V, film thickness 20 μm, baked at 175 ° C. for 20 minutes

  Intermediate coating: Aminoalkyd paint (Amirac TP-37 Gray: manufactured by Kansai Paint Co., Ltd.), spray coating, film thickness 35 μm, baking at 140 ° C. for 20 minutes

  Top coating: Aminoalkyd paint (Amirac TM-13 white: manufactured by Kansai Paint Co., Ltd.), spray coating, film thickness 35 μm, baking at 140 ° C. for 20 minutes

(Painting performance evaluation)
Evaluation of the coating performance of the examples and comparative examples was performed according to JIS standards. The evaluation items are shown below. The coating film upon completion of electrodeposition coating is referred to as an electrodeposition coating film, and the coating film upon completion of top coating is referred to as a 3 coats coating film.
(i) Salt spray test: electrodeposition coating
(ii) Adhesion test: 3coats coating film

(Salt spray test (SST test))
5% salt water was sprayed for 720 hours (according to JIS-Z-2371) onto an electrodeposition coated plate with a crosscut cut with a sharp cutter. After completion of spraying, the maximum swollen width on both sides from the cross-cut portion was measured and evaluated according to the following evaluation criteria.
<Maximum swollen width on both sides>
Less than 5mm: ◎
5 mm or more and less than 7 mm: ○
8 mm or more and less than 9 mm: △
9mm or more: ×

(Adhesion test (cross-cut method))
Using a sharp cutter on the 3coats coating film, 25 cuts were made in accordance with JIS-K-5600-5-6 by making 6 cuts in the vertical and horizontal directions at intervals of 2 mm. The grid part was peeled off with tape and evaluated by an evaluation method according to the JIS standard.

  Tables 1 and 2 show the appearance evaluation results of the surface treatment films obtained in Examples and Comparative Examples, and the adhesion amount of the surface treatment film. In the example, a uniform film could be obtained for both the SPC material and the EG material, and the target film adhesion amount could be obtained. On the other hand, in Comparative Example 1, the total concentrated mass ratio K1 was small, so that the surface treatment film could not be deposited on both the SPC material and the EG material. In Comparative Example 2, since the content of the component (A) was small, the surface treatment film could not be deposited on both the SPC material and the EG material. In Comparative Example 3, since the total mass concentration ratio K1 was large and the free fluorine ion concentration D was high, the surface treatment film could not be deposited on both the SPC material and the EG material. Further, since Comparative Example 4 is a conventional zinc phosphate treatment, a surface treatment film could be formed on both the SPC material and the EG material.

  Table 3 shows the coating performance evaluation results (salt spray test) of the electrodeposition coating film. In the examples, both the SPC material and the EG material showed good corrosion resistance. On the other hand, in Comparative Example 1, since the total concentrated mass ratio K1 was small in K1, the film promoting effect of the component (A) by the component (B) was not sufficiently obtained. As a result, both the SPC material and the EG material were inferior in corrosion resistance because a large amount of the surface treatment film was not deposited. In Comparative Example 2, since the content of component (A) was small, the targeted film adhesion amount was not obtained for both the SPC material and the EG material, and the corrosion resistance was inferior. Further, in Comparative Example 3, the total mass concentration ratio K1 was large and K1 was high, and the free fluorine ion concentration D was high, so that the targeted coating amount was not obtained for both the SPC material and the EG material, and the corrosion resistance was inferior. Comparative Example 4 is a zinc phosphate treatment that is currently commonly used as a cationic electrodeposition coating base. The Examples showed excellent coating performance at all levels as compared with Comparative Example 4.

  Table 4 shows the evaluation results of the adhesion of the 3coats plate. The examples showed good adhesion to all the test plates. The comparative example did not have the level which shows favorable adhesiveness with respect to a test board in all the comparative examples except the comparative example 4 similarly to the corrosion resistance of an electrodeposition coating board.

  From the above results, by using the surface treatment composition, the surface treatment solution, the surface treatment method, and the surface treatment metal material that are the products of the present invention, it is possible to deposit a surface treatment film excellent in adhesion and corrosion resistance. Clearly it is possible.

Claims (14)

Following components (A), component (B), Ingredient (C) and component (D):
(A) Compound containing at least one element selected from the group consisting of Ti, Zr, Hf, and Si (B) Compound containing Y and / or lanthanoid element (C) Nitric acid and / or nitric acid compound
(D) containing at least one fluorine-containing compound ;
K1 = B / A which is a ratio of the total mass concentration B of the Y and / or lanthanoid elements in the component (B) to the total mass concentration A of the elements in the component (A) is 0.05 ≦ K1 ≦ 50,
K2 = C / A, which is the ratio of the total mass concentration C in terms of NO ₃ of nitrogen atoms in the component (C) to the total mass concentration A, is 0.01 ≦ K2 ≦ 200,
The total mass concentration A is Ri 10 ppm ≦ A ≦ 10000 ppm der,
The free fluorine ion concentration D is 0.001 ppm ≦ D ≦ 300 ppm,
Treatment liquid for surface treatment of metal containing iron and / or zinc. The treatment liquid for surface treatment according to claim 1 , wherein the pH is 6.0 or less. Further, at least one selected from the group consisting of HCl, H ₂ SO ₄ , HClO ₃ , HBrO ₃ , HNO ₂ , HMnO ₄ , HVO ₃ , H ₂ O ₂ , H ₂ WO ₄ , H ₂ MoO ₄ and salts thereof. The treatment liquid for surface treatment according to claim 1 or 2 , comprising 10 to 20000 ppm of seeds. Furthermore, at least one selected from the group consisting of ethylenediaminetetraacetic acid, gluconic acid, heptogluconic acid, glycolic acid, citric acid, succinic acid, fumaric acid, aspartic acid, tartaric acid, malonic acid, malic acid, salicylic acid, and salts thereof. The processing liquid for surface treatment in any one of Claims 1-3 which contains 1-10000 ppm. Furthermore, a water-soluble polymer compound and / or water-dispersible polymer compound, for surface treatment treatment solution according to any one of claims 1-4. Further, nonionic surface active agents, containing at least one selected from the group consisting of anionic surfactants and cationic surfactants, surface treatment for treatment liquid according to any one of claims 1 to 5. A surface treatment method for a metal containing iron and / or zinc, comprising a treatment liquid contact step of bringing the treatment liquid for surface treatment according to any one of claims 1 to 5 into contact with a metal material containing iron and / or zinc. The surface treatment liquid according to claim 6 is brought into contact with a metal material containing iron and / or zinc, and the process comprises a treatment liquid contact step of simultaneously performing a degreasing treatment and a film forming treatment on the metal material. Or the surface treatment method of the metal containing zinc. The surface treatment method according to claim 7 or 8 , wherein the metal material containing iron and / or zinc is a metal material cleaned by a degreasing treatment. The surface treatment method according to any one of claims 7 to 9 , wherein in the treatment liquid contact step, electrolytic treatment is performed using the metal material containing iron and / or zinc as a cathode. Furthermore, after the treatment liquid contact step,
A metallic material containing iron and / or zinc, cobalt, nickel, tin, copper, titanium, and a step of contacting an aqueous solution containing at least one selected from the group consisting of zirconium, more of claims 7-10 A surface treatment method according to claim 1. Furthermore, after the treatment liquid contact step,
The surface treatment method according to any one of claims 7 to 10 , further comprising a step of bringing the metal material containing iron and / or zinc into contact with an aqueous solution containing a water-soluble polymer compound and / or a water-dispersible polymer compound. . The metal-containing surface containing iron contains the element of the component (A) formed by the surface treatment method according to any one of claims 7 to 12 , and the attached amount in terms of the element is 20 mg / A metal material containing iron having a surface treatment coating layer of m ² or more. The metal material surface containing zinc contains the element of the component (A) formed by the surface treatment method according to any one of claims 7 to 12 , and the element conversion amount is 15 mg / A metal material containing zinc having a surface treatment coating layer of m ² or more.