KR100674778B1 - Treating solution for surface treatment of metal, a method for surface treatment and metal material - Google Patents

Abstract

The present invention provides a surface treatment treatment liquid and a surface treatment method that do not contain harmful components to the environment, do not generate waste sludge, and can deposit a surface treatment film having excellent corrosion resistance after coating on a metal surface. As an aqueous surface treatment liquid for surface-treating a metal material selected from an iron-based material, a zinc-based material, an aluminum-based material, and a magnesium-based material alone or two or more of them simultaneously, one kind selected from a zirconium compound and a titanium compound The above compound contains 5 to 5000 ppm as the metal element, 0.1 to 100 ppm of free fluorine ions, and is a treatment solution for surface treatment of metal having a pH of 2 to 6. The treatment liquid may further contain a calcium compound, a magnesium compound or a strontium compound, a nitrate muscle, an oxygen acid and / or an oxygen acid salt, a high molecular compound, and a surfactant. A metal material is brought into contact with the treatment liquid or electrolytically treated in the treatment liquid to form a film.

Surface treatment, corrosion resistance, film formation, zirconium compound, titanium compound

Description

Treating solution for surface treatment of metal, a method for surface treatment and metal material

The present invention is solely or two or more of each of the iron-based material, the zinc-based material, the aluminum-based, and the magnesium-based material as represented by the automobile body, alone or two to four kinds thereof. At the same time, the present invention relates to a treatment solution for surface treatment and a surface treatment method capable of simultaneously depositing a surface treatment film having excellent corrosion resistance after coating.

As a method of depositing the surface treatment film excellent in corrosion resistance after coating on a metal surface, the zinc phosphate treatment method and the chromate treatment method are generally used now. The zinc phosphate treatment method can deposit a film excellent in corrosion resistance on the surface of steel, such as a cold rolled steel plate, a galvanized steel plate, and some aluminum alloy surfaces. However, when performing zinc phosphate treatment, the generation of sludge which is a by-product of the reaction cannot be avoided, and depending on the type of aluminum alloy, the resistance for corrosion after coating cannot be sufficiently secured. About an aluminum alloy, it is possible to ensure the performance after sufficient coating by performing chromate treatment. However, from recent environmental regulations, chromate treatments containing harmful hexavalent chromium in treatment liquids have tended to be kept away. Therefore, the invention shown below is proposed as a surface treatment method which does not contain a harmful component in a process liquid.

For example, a compound containing a nitrogen atom having a lone electron pair and a chromium-free coating agent for a metal surface containing the compound and a zirconium compound have been proposed (see Japanese Patent Application Laid-Open No. 2000-204485). This method makes it possible to obtain a surface treatment film which does not contain hexavalent chromium, which is a harmful component, and which is excellent in corrosion resistance and adhesion after coating, by applying the composition. However, since the target metal material is limited to aluminum alloy and forms a surface treatment film by application drying, it is difficult to apply it to a complicated structure such as an automobile body.

Therefore, a number of methods have been proposed as a method of depositing a surface treated film excellent in adhesion and corrosion resistance after coating by chemical reaction (for example, Japanese Patent Application Laid-Open No. 56-136978). (Japanese Patent Application Laid-Open No. 8-176841, Japanese Patent Laid-Open No. 9-25436, and Japanese Patent Application Laid-open No. 9-31404). However, the metal material to be subjected to any method is limited to an aluminum alloy having excellent corrosion resistance of the material itself, and it is impossible to deposit a surface treatment film on the surface of the iron-based material or the zinc-based material.

Also, a surface treatment composition comprising a metal acetylacetonate, a water soluble inorganic titanium compound, or a water soluble inorganic zirconium compound has been proposed in which a method of depositing a surface treated film excellent in corrosion resistance and adhesion after coating has been proposed (Japanese Patent Laid-Open No. 2000-199077). See publication number). By using this method, the applied metal materials have been extended to magnesium, magnesium alloys, zinc and galvanized alloys in addition to aluminum alloys. However, in this method, it is impossible to deposit a surface treatment film on the surface of iron-based materials such as cold rolled steel sheets, and it is impossible to simultaneously process iron-based materials.

Furthermore, a metal surface treatment method using a chromium-free coating type acidic composition, for example, after applying an aqueous solution of a component that can be a film having excellent corrosion resistance to the metal surface, without performing a water washing step A method of surface treatment of a metal for fixing a film by baking drying is proposed (see Japanese Patent Laid-Open No. 5-195244). Since this method does not involve a chemical reaction in the formation of the film, it is possible to coat the metal surface such as a galvanized steel sheet, a cold rolled steel sheet, and an aluminum alloy. However, in the same manner as the invention disclosed in Japanese Patent Laid-Open No. 2000-204485, since a film is formed by coating drying, it is difficult to perform a uniform film treatment on a complex structure such as an automobile body.

Therefore, in the prior art, the treatment liquid does not contain components harmful to the environment and does not generate waste sludge, such as iron-based materials such as cold rolled steel sheets and zinc-based materials such as galvanized steel sheets, such as automobile bodies, and aluminum and It was not possible to simultaneously treat two to four kinds of magnesium-based materials and to perform a surface treatment excellent in corrosion resistance and adhesion.

Disclosure of the Invention

The present invention does not contain components harmful to the environment, which is impossible in the prior art, does not generate waste sludge, and has excellent corrosion resistance after coating on iron, zinc, aluminum and magnesium materials. Provided is a treatment liquid for surface treatment that makes it possible to deposit a treatment film, and also to a metal surface of a structure in which two to four kinds of iron-based materials, zinc-based materials, aluminum-based and magnesium-based materials are combined, such as an automobile body. To provide a treatment solution for surface treatment which enables to simultaneously deposit a surface treatment film having excellent corrosion resistance after coating under the same composition and under the same conditions, and further to provide a surface treatment method using the treatment solution for surface treatment. The purpose.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining the means for solving the said subject, the present inventors came to complete the surface treatment process liquid and the surface treatment method which are not in the prior art.

That is, the present invention is an aqueous surface treatment liquid for surface treatment of a metal material selected from an iron-based material, a zinc-based material, an aluminum-based material, and a magnesium-based material alone or two or more of them simultaneously, from a zirconium compound and a titanium compound. 5 to 5000 ppm of said at least one compound selected as said metal element, 0.1 to 100 ppm of free fluoride ions, and pH of 2 to 6, said surface treatment treatment of metal It is liquid.

The treatment solution for surface treatment may further contain at least one compound selected from the group consisting of calcium compounds, magnesium compounds and strontium compounds. The concentration of these compounds at that time is preferably 5 to 100 ppm in the case of calcium compounds, and 10 to 5000 ppm in the case of magnesium compounds or strontium compounds as these metal elements. It is preferable to contain 1000-50000 ppm of nitrate roots in this process liquid further. Further, at least one oxygen acid selected from HClO ₃ , HBrO ₃ , HNO ₂ , HNO ₃ , HMnO ₄ , HVO ₃ , H ₂ O ₂ , H ₂ WO ₄ , H ₂ MoO ₄ and salts thereof, and It is preferred to contain oxalate. These surface treatment liquids may further contain at least one polymer compound selected from a water-soluble polymer compound and a water-dispersible polymer compound, and are selected from nonionic surfactants, anionic surfactants and cationic surfactants. You may contain at least 1 type of surfactant.

In addition, the present invention is characterized in that each of the metal materials selected from an iron-based material, a zinc-based material, an aluminum-based material and a magnesium-based material alone or two or more thereof is brought into contact with the above-mentioned surface treatment treatment liquid. Metal surface treatment method. In this surface treatment method, at least one element selected from the group consisting of cobalt, nickel, tin, copper, titanium, and zirconium, with or without washing with a metal material after contact with the treatment liquid for surface treatment. It may be brought into contact with an acidic aqueous solution of a compound containing, and may be brought into contact with a treatment liquid containing at least one polymer compound selected from a water-soluble polymer compound and a water-dispersible polymer compound.

In addition, the present invention is the treatment solution for surface treatment described above, wherein each of metal materials selected from an iron-based material, a zinc-based material, an aluminum-based material and a magnesium-based material alone or two or more thereof is used simultaneously, and the metal material is used as a cathode. The surface treatment method of the metal characterized by electrolytic treatment in the middle. In the surface treatment method, at least one kind selected from the group consisting of cobalt, nickel, tin, copper, titanium, and zirconium, without washing or washing with water after electrolytic treatment of the metal material in the treatment solution for surface treatment. It may be brought into contact with an acidic aqueous solution of a compound containing an element, or may be brought into contact with a treatment liquid containing at least one polymer compound selected from a water-soluble polymer compound and a water-dispersible polymer compound.

In addition, the present invention provides the above-mentioned nonionic surfactant, each of which alone or two or more of the metal materials which have not been degreased and cleaned, selected from an iron-based material, a zinc-based material, an aluminum-based material and a magnesium-based material; It is a method which can carry out the degreasing process of a metal surface, and a film formation process simultaneously by contacting with the surface treatment liquid containing at least 1 sort (s) of surfactant chosen from anionic surfactant and cationic surfactant.

The present invention also includes at least one kind of metal element selected from titanium and zirconium formed by the surface treatment method described above on the surface of a metal material selected from an iron material, a zinc material, an aluminum material and a magnesium material. It has a surface treatment film, and the adhesion amount of the said surface treatment film is 30 mg / m <2> or more in the case of the iron metal material surface in conversion of the said metal element, 20 mg / m <2> or more in the case of the zinc-based metal material surface, and aluminum type The metal material surface is 10 mg / m 2 or more, and the magnesium-based metal material surface is 10 mg / m 2 or more.

Brief description of the drawings

1 is a plan view of a test providing plate provided in Examples and Comparative Examples of the present invention. 2 is a front view of the test providing plate.

Best Mode for Carrying Out the Invention

The present invention provides a technique for surface treatment of a metal material selected from an iron-based material, a zinc-based material, an aluminum-based material, and a magnesium-based material alone or two or more thereof at the same time to deposit a surface-treated coating having excellent corrosion resistance after coating. It is about. The iron-based material refers to iron-based metals such as steel sheets such as cold rolled steel sheets and hot rolled steel sheets, cast iron and sintered materials. In addition, zinc type material means zinc die-casting and zinc containing plating. This zinc-containing plating is plated with an alloy and unavoidable impurities of zinc or zinc and another metal (for example, at least one metal such as nickel, iron, aluminum, manganese, chromium, magnesium, cobalt, lead and antimony). The plating method is not limited to, for example, hot dip plating, electroplating, vapor deposition plating, and the like. In addition, an aluminum type material shows the aluminum alloy plate materials, such as a 5000 type aluminum alloy and a 6000 type aluminum alloy, the aluminum alloy die-cast represented by ADC-12, etc. Moreover, magnesium type material means the board | plate material, die-cast, etc. which used magnesium alloy.

The present invention is applied to a structure including the metal material alone in a constituent member, or a structure including two to four kinds of the metal material in a constituent member. In the case where two to four kinds of the metal materials are applied to the structure including the constituent members, the surfaces of the two to four kinds of metal materials can be surface treated at the same time. Here, when surface treatment of two or four kinds of metal materials is carried out simultaneously, dissimilar metals may not be in contact with each other, and dissimilar metals may be formed by a joining method such as welding, bonding, or rivet fixing. It may be in the state where the joint contacted each other.

The treatment solution for surface treatment of the present invention contains 5 to 5000 ppm of at least one compound selected from a zirconium compound and a titanium compound as the metal element, 0.1 to 100 ppm of free fluorine ion, and a pH of 2 to It is a treatment liquid of six. Here, as a zirconium compound used in the present invention, ZrCl ₄ , ZrOCl ₂ , Zr (SO ₄ ) ₂ , ZrOSO ₄ , Zr (NO ₃ ) ₄ , ZrO (NO ₃ ) ₂ , H ₂ ZrF ₆ , H ₂ ZrF ₆ Salts, ZrO ₂ , ZrOBr ₂ , ZrF ₄ and the like. As the titanium compound, salts of TiCl ₄ , Ti (SO ₄ ) ₂ , TiOSO ₄ , Ti (NO ₃ ) ₄ , TiO (NO ₃ ) ₂ , TiO ₂ OC ₂ O ₄ , H ₂ TiF ₆ , H ₂ TiF ₆ , TiO ₂ , TiF ₄ , and the like. In the present invention, a zirconium compound is preferably used.

The concentration of the at least one compound selected from the zirconium compound and the titanium compound used in the present invention is preferably 5 to 5000 ppm as the metal element (that is, as zirconium and / or titanium), more preferably 10 to 3000 ppm. Since the film obtained by using the treatment solution for surface treatment and the surface treatment method of the present invention is an oxide or hydroxide of zirconium or titanium, the concentration of one or more compounds selected from the zirconium compound or titanium compound is zirconium and / or titanium. If it is smaller than 5 ppm, since the main concentration of the coating film becomes small, it is difficult to obtain a sufficient amount of adhesion in a practical treatment time in order to obtain corrosion resistance. In addition, when the concentration is larger than 5000 ppm, a sufficient adhesion amount is obtained, but there is no effect of improving the corrosion resistance any more, which is only economically disadvantageous.

The zirconium compound or titanium compound is relatively dissolved in an acidic solution, but is unstable in an alkaline solution and easily precipitates as an oxide or hydroxide of zirconium or titanium. PH of the process liquid for surface treatments of this invention is 2-6, and more preferable pHs are 3-6. When the metal material to be treated is brought into contact with the treatment solution for surface treatment of the present invention at this pH, dissolution reaction of the metal material to be processed occurs. As the metal material to be dissolved is dissolved, the pH rises at the metal material interface, and oxides or hydroxides of zirconium and titanium are deposited on the surface of the metal material as a film.

As the treatment solution for surface treatment of the present invention, free fluorine ions are present therein. In order to make free fluorine ion exist, a fluorine compound is added to the surface treatment liquid. As a source of this free fluorine ion, hydrofluoric acid, a salt of H ₂ ZrF ₆ , H ₂ ZrH ₆ , a salt of H ₂ TiF ₆ , a H ₂ TiF ₆ , a salt of H ₂ SiF ₆ , a H ₂ SiF ₆ , HBF ₄ , Salts of HBF ₄ , NaHF ₂ , KHF ₂ , NH ₄ HF ₂ , NaF, KF, NH ₄ F and the like. Free fluorine ion has the effect | action which improves the stability of a zirconium compound and a titanium compound in the process liquid for surface treatment. Furthermore, the free fluorine ion has an effect of promoting dissolution reaction in an acidic solution to any material of iron-based material, zinc-based material, aluminum-based material and magnesium-based material which is the metal material to be subjected to the surface treatment of the present invention. Therefore, the addition of a fluorine compound and the presence of free fluorine ions make it possible to increase the stability of the treatment solution for surface treatment of the present invention and to increase the reactivity to the metal material to be treated.

The present applicant has previously used a titanium compound, a zirconium compound, and a fluorine-containing compound for the surface treatment composition and the surface treatment liquid for treating the surface of a metal containing at least one kind of iron or zinc. The ratio A / B of the total molar weight A of the metal elements in the composition for the composition and the treatment solution for the surface treatment and the molar weight B when the total fluorine atoms in the fluorine-containing compound is converted into HF is set to a specific range, that is, 0.06 to 0.18. It was proposed (WO02 / 103080). According to the present invention, by defining the concentration of metal elements, pH, and free fluorine ions of a titanium compound or a zirconium compound, it is selected from an iron-based material, a zinc-based material, an aluminum-based material, and a magnesium-based material even outside the above specific ranges. It is possible to surface-treat a metal material individually or simultaneously two or more types thereof.

Since the iron-based material, the zinc-based material, the aluminum-based, and the magnesium-based materials are different in reactivity, it has not been possible to simultaneously surface-treat two or more kinds of the metal materials in the prior art. In the present invention, since the balance between the stability and the reactivity of the treatment solution for surface treatment can be changed freely by adjusting the concentration of free fluorine ions, iron-based materials, zinc-based materials, aluminum-based materials and magnesium-based materials having different reactivity. It is possible to surface-treat two or more kinds of at the same time or individually.

The concentration of free fluorine ions herein refers to the concentration of fluorine ion measured using a commercially available ion electrode. It is preferable that the concentration of free fluorine ion in the process liquid for surface treatment of this invention is 0.1-100 ppm, More preferably, it is 2-70 ppm. When the concentration of free fluorine ion is higher than 100 ppm, dissolution reaction of the metal material to be treated is promoted, but since the zirconium compound and titanium compound in the surface treatment solution are very stable, the pH at the interface of the metal material to be treated is very stable. Even if it rises, it becomes difficult to precipitate as a film. Moreover, when smaller than 0.1 ppm, the effect on the improvement of stability and reactivity of the surface treatment process liquid is small, and it becomes meaningless to contain free fluorine ion.

The free fluorine ion in the present invention plays a role of stably maintaining the component eluted by dissolution of the metal material to be treated in the surface treatment solution, in addition to improving the stability and reactivity of the surface treatment solution. . In the case of zinc phosphate treatment, which is one of the prior arts, sludge occurs because, for example, iron ions eluted from an iron-based metal material produce phosphoric acid and iron phosphate, which is an insoluble salt. Even in the treatment solution for surface treatment of the present invention, phosphate root may be included in the treatment liquid, but sludge may occur when the concentration of the phosphate muscle exceeds 1.0 g / L. In addition, when the throughput of the metal material to be treated is remarkably large with respect to the capacity of the treatment bath, for example, inorganic acids such as sulfuric acid and hydrochloric acid; Organic acids such as acetic acid, oxalic acid, tartaric acid, citric acid, succinic acid, gluconic acid, and phthalic acid; You may add 1 type, or 2 or more types of chelating agents etc. which can chelate an eluting component.

The treatment solution for surface treatment of the present invention may include at least one or more selected from the group consisting of calcium compounds, magnesium compounds and strontium compounds. The present invention provides two to four kinds of iron-based materials, zinc-based materials, aluminum-based, and magnesium-based materials by setting the concentration of free fluorine ions in an aqueous solution containing a zirconium compound and a titanium compound at a specific concentration in a certain range. It is possible to perform surface treatment simultaneously or individually. Here, the metal element (calcium, magnesium or strontium) contained in the calcium compound, magnesium compound or strontium compound is intended to maintain the free fluorine ion concentration in the aqueous solution by generating salts of fluorine and fluoride in the aqueous solution. Has action. By this action, even if the surface treatment of various kinds of metal materials to be treated simultaneously does not depend on the use ratio and always maintains a constant free fluorine concentration, the optimum coating amount for each metal material is obtained. .

Examples of calcium compounds, magnesium compounds or strontium compounds that can be used in the present invention include oxides, hydroxides, chlorides, sulfates, nitrates and carbonates of these metal elements. In addition to the calcium compound, the magnesium compound and the strontium compound, any compound having a function of maintaining a constant free fluorine concentration in the fluorine-containing aqueous solution can be used in the present invention regardless of whether it is an inorganic substance or an organic substance.

It is preferable that the density | concentration of the magnesium compound or strontium compound used for this invention is 10-5000 ppm as said metal element, More preferably, it is 100-3000 ppm. In the case of a calcium compound, since solubility of calcium fluoride is remarkably small, 5-100 ppm is preferable as calcium, More preferably, it is 5-50 ppm. Here, when the concentration of the compound is larger than the upper limit, the stability of the treatment solution for surface treatment may be impaired, resulting in problems in continuous operation. In addition, when the concentration of the compound is smaller than the lower limit, there is a concern that the adhesion amount of the coating film of the present invention on the iron-based material is particularly lowered.

In addition, 1000-50000 ppm of nitrates can be added to the surface treatment liquid of this invention, More preferably, 1000-30000 ppm can be added. Nitrate acts as an oxidizing agent to promote the film deposition reaction in the present invention and to increase the solubility of the calcium compound, magnesium compound or strontium compound in the treatment solution for surface treatment. Therefore, even when the concentration of the nitrate is less than 1000 ppm, it is possible to deposit a film having excellent corrosion resistance, but when the concentration of the calcium compound, magnesium compound or strontium compound is high, the stability of the treatment solution for surface treatment is impaired. There is concern. In addition, the concentration of the nitrate is 50000 ppm is sufficient, even if the addition of nitrate more than that will be economically disadvantageous.

Further, the treatment solution for surface treatment of the present invention includes at least one selected from the group consisting of HClO ₃ , HBrO ₃ , HNO ₃ , HNO ₂ , HMnO ₄ , HVO ₃ , H ₂ O ₂ , H ₂ WO ₄ and H ₂ MoO ₄ . One type of oxygen acid and / or salts of these oxygen acids can be added. The oxygen acid or its salt acts as an oxidizing agent for the material to be treated to promote the film forming reaction in the present invention. Although there is no restriction | limiting in particular in the addition concentration of said oxygen acid or these salts of these oxygen acids, The effect as an oxidizing agent is exhibited fully by the addition amount about 10-5000 ppm.

Moreover, you may add at least 1 sort (s) of high molecular compound chosen from the water-soluble high molecular compound and the water dispersible high molecular compound to the process liquid for surface treatments of this invention. Although the metal material surface-treated using the surface treatment process liquid of this invention has sufficient corrosion resistance, when additional functions, such as lubricity, are needed, a polymeric compound is selected and added according to the objective function, and the physical property of a film is carried out. You may modify this. As said water-soluble high molecular compound and water-dispersible high molecular compound, polyvinyl alcohol, poly (meth) acrylic acid, the copolymer of acrylic acid and methacrylic acid, acrylic monomers, such as ethylene and (meth) acrylic acid and (meth) acrylate, for example. The high molecular compound generally used for surface treatment of metals, such as a copolymer of a copolymer, a copolymer of ethylene and vinyl acetate, a polyurethane, an amino modified phenol resin, a polyester resin, and an epoxy resin, can be used.

To treat the surface of the metal using the surface treatment liquid of the present invention, the surface may be degreased by a general method, and the cleansed metal material may be brought into contact with the surface treatment liquid. As a result, a film made of an oxide and / or a hydroxide of a metal element selected from zirconium and titanium is deposited on the surface of the metal material, thereby forming a surface treated film layer having good adhesion and corrosion resistance. This contact treatment can use any method such as spray treatment, dipping treatment and pouring treatment, and this contact method does not affect performance. It is chemically difficult to obtain the hydroxide of the metal as a pure hydroxide, and in general, the form in which hydrated water adheres to the oxide of the metal is also included in the category of hydroxide. Accordingly, the hydroxide of the metal becomes an oxide finally by applying heat. The structure of the surface-treated coating layer in the present invention is a state in which oxides and hydroxides are mixed when dried at room temperature or low temperature after surface treatment, or in which only oxides or oxides are large when dried at high temperature after surface treatment. I think it is.

There is no restriction | limiting in particular in the use condition of the process liquid for surface treatments in this invention. The reactivity of the surface treatment liquid of the present invention can be freely adjusted by changing the concentration of the zirconium compound or the titanium compound and the free fluorine concentration in the treatment solution for the surface treatment. Therefore, the treatment temperature and treatment time can be changed in any way in combination with the reactivity of the treatment bath.

Moreover, at least 1 type of surfactant chosen from the group of a nonionic surfactant, anionic surfactant, and cationic surfactant can be added to the said surface treatment liquid, and it can be used for surface treatment. In the case of surface treatment of a metal material using this surface treatment treatment liquid, a good film can be formed without degreasing the treated metal material in advance and cleaning. In other words, the treatment solution for surface treatment can be used as a surface treatment agent for use in both degreasing properties.

In addition, when treating the surface of metal using the surface treatment liquid of this invention, it is also possible to employ | adopt the method of electrolyzing in the surface treatment liquid using the to-be-processed metal material as a cathode. Here, when electrolytic treatment is performed using the metal material to be treated as a cathode, a reduction reaction of hydrogen occurs at the cathode interface and the pH rises. With the rise of pH, the stability of a zirconium compound and / or a titanium compound in a cathode interface falls, and a surface treatment film precipitates as a hydroxide containing an oxide or water.

Further, the metal material to be treated may be washed with or without water after contact with the treatment liquid for surface treatment or after electrolytic treatment in the treatment liquid for surface treatment, and may be selected from the group consisting of cobalt, nickel, tin, copper, titanium and zirconium. The effect of the present invention can be further enhanced by contacting with an acidic aqueous solution of a compound containing at least one element selected or a treatment liquid containing at least one polymer compound selected from a water-soluble polymer compound and a water dispersible polymer compound. .

Although the surface-treated coating layer obtained by this invention shows the outstanding coating performance in a thin film, depending on the surface state of a to-be-processed metal material, a fine defect part may exist in a surface-treated coating layer. Therefore, an acidic aqueous solution of a compound containing at least one element selected from the group consisting of cobalt, nickel, tin, copper, titanium and zirconium, or at least one polymer compound selected from a water-soluble polymer compound and a water-dispersible polymer compound By contacting with the processing liquid containing the above, the above-mentioned fine defect part is coat | covered and corrosion resistance becomes high further.

The compound containing at least one element selected from the group consisting of cobalt, nickel, tin, copper, titanium and zirconium described above is not particularly limited, but oxides, hydroxides, fluorides and complexes of the above-described metal elements are easily available. Fluorides, chlorides, nitrates, oxynitrates, sulfates, oxysulfates, carbonates, oxycarbonates, phosphates, oxyphosphates, oxalates, oxyoxalates and organometallic compounds. In addition, 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 acid, and sodium hydroxide, potassium hydroxide, lithium hydroxide, and alkali metal salts. And alkali such as ammonium salts and amines.

Moreover, as at least 1 type of high molecular compound chosen from said water-soluble high molecular compound and water-dispersible high molecular compound, a polyvinyl alcohol, poly (meth) acrylic acid, the copolymer of acrylic acid and methacrylic acid, ethylene, and (meth) Copolymers of acrylic monomers such as acrylic acid and (meth) acrylates, copolymers of ethylene and vinyl acetate, polyurethanes, amino-modified phenol resins, polyester resins, epoxy resins, tannins and tannic acids and salts thereof, and phytic acid (phytic acid) can be used.

The present invention makes it possible to dramatically increase the corrosion resistance of a metal material by providing a surface treated film layer of an oxide and / or a hydroxide of a metal element selected from zirconium and / or titanium on the surface of the metal material to be treated. Here, the oxides and hydroxides of the metal elements are hardly eroded by acids or alkalis and have chemically stable properties. In the corrosive environment of the metal, the pH decreases in the anode portion where the metal is eluted, and in the cathode portion in which the reduction reaction occurs. Therefore, the surface treatment film which is inferior in acid resistance and alkali resistance melt | dissolves in a corrosive environment, and the effect loses. Since the main component of the surface treatment film layer in this invention is hard to corrode by acid and alkali, the outstanding effect also persists in a corrosive environment.

In addition, the oxides and hydroxides of the metal elements form a network structure in which the metal and the oxygen are mediated, which results in a very good barrier coating. Corrosion of metal materials also varies depending on the environment used, but is generally oxygen demanded corrosion in the presence of water and oxygen, and the corrosion rate is promoted by the presence of a component such as chloride. Here, since the surface treatment film layer of this invention has a barrier effect with respect to water, oxygen, and a corrosion promoting component, it can exhibit the outstanding corrosion resistance.

Here, in order to improve the corrosion resistance of iron-based materials such as cold rolled steel sheet, hot rolled steel sheet, cast iron and sintered material by using the barrier effect, an adhesion amount of 30 mg / m 2 or more is required in terms of the metal element. Preferably, it is an adhesion amount of 40 mg / m <2> or more, More preferably, 50 mg / m <2> or more. In addition, in order to increase the corrosion resistance of zinc-based materials such as zinc or galvanized steel sheets and alloyed hot dip galvanized steel sheets, an adhesion amount of 20 mg / m 2 or more is required in terms of the above metal elements, and preferably an adhesion amount of 30 mg / m 2 or more. . Further, in order to increase the corrosion resistance of aluminum-based materials such as aluminum castings and aluminum alloy plates, an adhesion amount of 10 mg / m 2 or more is required in terms of the above metal elements, and preferably an adhesion amount of 20 mg / m 2 or more. In order to increase the corrosion resistance of magnesium-based materials such as magnesium alloy plates and magnesium castings, an adhesion amount of 10 mg / m 2 or more is required in terms of the metal element, and an adhesion amount of 20 mg / m 2 or more is preferable. Although there is no restriction | limiting in particular about the upper limit of adhesion amount, When an adhesion amount exceeds 1 g / m <2>, a crack will generate | occur | produce easily in a surface treatment film layer, and the operation | work which obtains a uniform film becomes difficult. Therefore, the upper limit of the adhesion amount in all of the iron-based material, the zinc-based material, and the aluminum-based material is 1 g / m 2, more preferably 800 mg / m 2.

An Example is given to the following with a comparative example, and the effect of the surface treatment process liquid and surface treatment method of this invention is demonstrated concretely. In addition, the to-be-processed material, the degreasing agent, and the coating material used in the Example are arbitrarily selected from the material which is marketed, and do not limit the practical use of the surface treatment process liquid and surface treatment method of this invention.

[Experimental Edition]

Cold rolled steel sheets, hot-dip galvanized steel sheets, aluminum alloy sheets, and magnesium alloy sheets were used as test plates for the examples and comparative examples. The symbol and description of this test plate are shown below. In addition, in the evaluation of the appearance after the surface treatment, a test providing plate in a state in which three kinds of SPC, GA, and Al metal materials were joined by spot welding was used. For the evaluation of the adhesion amount of the surface-treated coating layer, an individual test donor plate of SPC, GA, Al, and Mg, and a test donor plate in a state in which three kinds of metal materials of SPC, GA, and Al were joined by spot welding were used. For evaluation of coating performance, a series of tests from surface treatment, painting, and coating performance evaluation were conducted using a test provision plate in which three kinds of metal materials, SPC, GA, and Al were joined by spot welding. BRIEF DESCRIPTION OF THE DRAWINGS The top view of the test provision board which spot-welded three types of metal materials of SPC, GA, and Al, and FIG. 2 is the front view. 1 represents a spot weld.

SPC (cold rolled steel: JIS-G-3141)

GA (Double Sided Alloy Hot-dip Galvanized Steel Sheet: Plating Amount 45 g / m2)

Al (aluminum alloy plate: 6000 aluminum alloy)

Mg (magnesium alloy plate: JIS-H-4201)

[Processing Step]

The process of an Example and a comparative example is as follows.

Examples 1-4, Example 7 and Comparative Examples 1-4: Alkali degreasing → washing | cleaning → coating | film | coat chemical conversion treatment → washing water → pure water washing → drying

Example 5 Alkaline Degreasing → Washing → Electrolytic Chemical Treatment → Water Washing → Pure Water → Drying

Example 6 Film Chemical Treatment (Combination with Degreasing Chemical) → Water Wash → Pure Water → Drying

Example 8: Alkaline degreasing → washing → coating chemical treatment → washing → post treatment → pure washing → drying

Example 9 Coating Chemical Treatment (Combination with Degreasing Chemical) → Water Washing → After Treatment → Pure Washing → Drying

Comparative Example 5: Alkali degreasing → washing → surface adjustment → zinc phosphate treatment → washing with water → pure washing → drying

In the above, alkaline degreasing was performed by diluting fine cleaner L 4460 (registered trademark: Nippon Parkerizing Co., Ltd.) with tap water at 2% in 40 ° C. for 120 seconds in both Examples and Comparative Examples. Was used. Water washing and pure water washing after the coating treatment were sprayed onto the treated plate for 30 seconds at room temperature in both the Examples and Comparative Examples.

Example 1

An aqueous solution having a zirconium concentration of 200 ppm was prepared using a zirconium oxynitrate reagent and nitric acid. After heating this aqueous solution to 45 degreeC, pH is adjusted to 3.0 using sodium hydroxide reagent and hydrofluoric acid, and also the free fluorine ion measured by a fluorine ion meter (IM-55G; Doa Denpa Kogyo Co., Ltd. product). The concentration was adjusted to 1 ppm to obtain a treatment solution for surface treatment. The total fluorine concentration in the treatment solution for surface treatment after adjusting the free fluorine ion concentration was 50 ppm.

The test-providing plate subjected to washing with water after degreasing was immersed in the surface treatment solution for 120 seconds for surface treatment.

Example 2

An aqueous solution having a zirconium concentration of 100 ppm, a magnesium concentration of 5000 ppm, a strontium concentration of 2000 ppm, and a muscle of 28470 ppm was prepared using a zirconium oxynitrate reagent, a magnesium nitrate reagent, and a strontium nitrate reagent. After heating this aqueous solution to 50 degreeC, pH was adjusted to 4.0 using the ammonia water reagent and hydrofluoric acid, and also the free fluorine ion concentration measured by a fluorine ion meter (IM-55G; product made from Doadenpa Kogyo Co., Ltd.). Was adjusted to 80 ppm to obtain a treatment solution for surface treatment. The total fluorine concentration in the treatment solution for surface treatment after adjusting the free fluorine ion concentration was 2000 ppm.

The test providing plate subjected to water washing after degreasing was immersed in the surface treatment solution for 60 seconds to perform a surface treatment.

Example 3

Aqueous solution containing 1000 ppm zirconium, 2000 ppm titanium, 5 ppm calcium, and 1000 ppm nitric acid was prepared using hexafluorozirconic acid (IV) solution, titanium (IV) sulfate solution, calcium sulfate reagent, and nitric acid. It prepared. After heating this aqueous solution to 40 degreeC, the pH is adjusted to 5.0 using potassium hydroxide reagent and hydrofluoric acid, and also the free fluorine ion measured by the fluorine ion meter (IM-55G; Doa Denpa Kogyo Co., Ltd. product). The concentration was adjusted to 25 ppm to obtain a treatment solution for surface treatment. The total fluorine concentration in the treatment solution for surface treatment after adjusting the free fluorine ion concentration was 2250 ppm.

The test providing plate subjected to water washing after degreasing was immersed in the surface treatment solution for 90 seconds to perform a surface treatment.

Example 4

An aqueous solution of 5000 ppm titanium, 5000 strontium concentration, 7080 ppm nitrate muscle, and 40 ppm nitrite muscle was prepared using an aqueous hexafluorotitanic acid (IV) solution, a strontium nitrate reagent, and a sodium nitrite reagent. After heating this aqueous solution to 35 degreeC, the pH is adjusted to 4.0 using a triethanolamine reagent and hydrofluoric acid, and also the free fluorine ion measured by a fluorine ion meter (IM-55G; product made from Doadenpa Co., Ltd.). The concentration was adjusted to 10 ppm to obtain a treatment solution for surface treatment. The total fluorine concentration in the treatment solution for surface treatment after adjusting the free fluorine ion concentration was 11900 ppm.

The surface treatment was sprayed on the test providing plate subjected to water washing after degreasing with a spray for 120 seconds.

Example 5

Using zirconium oxynitrate reagent, aqueous hexafluorotitanic acid (IV) solution, magnesium nitrate reagent, nitric acid, sodium chlorate reagent, 5 ppm zirconium, 5 ppm titanium, 100 ppm magnesium, 30520 ppm nitrate An aqueous solution having 100 ppm of chloric acid root was prepared. After heating this aqueous solution to 30 degreeC, pH was adjusted to 6.0 using an ammonia water reagent and hydrofluoric acid, and also the free fluorine concentration measured by a fluorine-ion meter (IM-55G; Doa Denpa Kogyo Co., Ltd. product). It was set as the processing liquid for surface treatments adjusted to 0.5 ppm. The total fluorine concentration in the treatment solution for surface treatment after adjusting the free fluorine ion concentration was 12 ppm.

After degreasing, the test plate subjected to washing with water was used as a cathode, a carbon electrode was used for the anode, and surface treatment was performed by electrolysis for 5 seconds under an electrolytic condition of 5 A / dm 2 in the surface treatment solution.

Example 6

A zirconium oxynitrate reagent, magnesium oxide reagent, nitric acid, and hydrogen peroxide reagent were used to prepare an aqueous solution containing 150 ppm of zirconium, 10 ppm of magnesium, 5200 ppm of nitrate, and 10 ppm of hydrogen peroxide. After heating this aqueous solution to 50 degreeC, pH was adjusted to 5.0 using an ammonia water reagent and hydrofluoric acid, and also the free fluorine ion concentration measured by a fluorine ion meter (IM-55G; product made from Doadenpa Kogyo Co., Ltd.). Was adjusted to 50 ppm, and 2 g / L of polyoxyethylene nonylphenyl ether (12 mol of ethylene oxide added mole number) which is a nonionic surfactant was further added to obtain a treatment solution for surface treatment. The total fluorine concentration in the treating solution for surface treatment after adjusting the free fluorine ion concentration was 170 ppm.

The surface-treated treatment liquid was sprayed with a spray for 90 seconds onto the test-providing plate as it was, without performing degreasing treatment, to perform degreasing and surface treatment.

Example 7

Using titanium (IV) sulfate solution, calcium nitrate reagent, magnesium nitrate reagent, potassium permanganate reagent, titanium concentration is 100 ppm, calcium concentration is 50 ppm, magnesium concentration is 5000 ppm, muscle nitrate is 25660 ppm, permanganic acid is 10 ppm An aqueous solution was prepared. Furthermore, a water-soluble acrylic polymer compound (Jurima AC-10L: manufactured by Nippon Kayaku Co., Ltd.) was added to the aqueous solution so that the solid content concentration was 1%, and heated to 50 ° C. Then, the pH was adjusted with sodium hydroxide reagent and hydrofluoric acid. It adjusted to 3.0, adjusted the free fluorine concentration measured by a fluorine meter (IM-55G; Toa Denpa Kogyo Co., Ltd.) to 95 ppm, and used it as the surface treatment liquid. The total fluorine concentration in the treatment solution for surface treatment after adjusting the free fluorine ion concentration was 2000 ppm.

The test providing plate subjected to water washing after the degreasing treatment was immersed in the treatment solution for surface treatment for 60 seconds to perform surface treatment.

Example 8

An aqueous solution of 1% water-soluble acrylic polymer compound (Jurima AC-10L: manufactured by Nippon Kayaku Co., Ltd.) at a solid content concentration and 2 g / L as the phosphate reagent was prepared as a phosphate root. After warming this aqueous solution to 40 degreeC, pH was adjusted to 4.5 with the ammonia water reagent, and the after-treatment liquid was produced. The test providing plate subjected to the film formation and the water washing by the surface treatment of Example 5 was immersed in the post-treatment solution for 30 seconds to perform post-treatment.

Example 9

Using an aqueous solution of hexafluorozirconic acid (IV) and a cobalt nitrate reagent, an aqueous solution having a zirconium concentration of 50 ppm and a cobalt concentration of 50 ppm was prepared. The aqueous solution was further heated to 40 ° C, and the pH was adjusted with an ammonia solution. Adjusting to 5.0 to prepare a post-treatment liquid. The test providing plate subjected to the film formation and the water washing by the surface treatment of Example 6 was immersed in the post-treatment solution for 30 seconds to perform post-treatment.

Comparative Example 1

An aqueous solution having a zirconium concentration of 500 ppm, a magnesium concentration of 1000 ppm, and a root of 6780 ppm was prepared using a zirconium oxynitrate reagent, a magnesium nitrate reagent, and nitric acid. After warming this aqueous solution to 45 degreeC, pH was adjusted to 4.0 with the sodium hydroxide reagent, and it was set as the treatment liquid for surface treatment. It was 0 ppm when the free fluorine ion concentration in the said process liquid for surface treatments was measured with the commercially available fluorine meter (IM-55G; the Toadenpa Kogyo Co., Ltd. product).

After the degreasing, the test plate subjected to washing with water was immersed in the surface treatment solution for 120 seconds to perform surface treatment.

Comparative Example 2

Titanium (IV) aqueous solution was used to adjust the aqueous solution of 2000 ppm of titanium. After the aqueous solution was warmed to 50 ° C., the pH was adjusted to 3.5 with an ammonia water reagent and hydrofluoric acid, and the free fluorine concentration measured by a fluoride meter (IM-55G; manufactured by Doadenpa Co., Ltd.) was 400 ppm. It adjusted to the surface treatment liquid.

After the degreasing, the test providing plate subjected to water washing was immersed in the surface treatment solution for 90 seconds to perform surface treatment.

Comparative Example 3

Alchrom 713 (trademark: Nihon Parkerizing Co., Ltd.), a commercially available chromatic chromate treatment drug, was diluted with tap water to 3.6%, and further acidity and free acidity were added. Was adjusted to the center of the catalog value.

The test serving plate subjected to water washing after degreasing was immersed in the chromate treatment liquid heated to 35 ° C. for 60 seconds to perform chromate treatment.

Comparative Example 4

Palcote 3756 (trademark: Nippon Parkerizing Co., Ltd.), a commercially available non-chromate treatment agent, was diluted with tap water at 2%, and the acidity and free acidity were further adjusted to the center of the catalog value. The test providing plate subjected to water washing after degreasing was immersed in the bichromate treatment liquid heated at 40 ° C. for 60 seconds to perform a bichromate treatment.

Comparative Example 5

After spraying the test plate subjected to washing with water after degreasing, spraying a solution of preparene ZN (registered trademark: Nihon Parkerizing Co., Ltd.), which is a surface adjustment agent, with tap water at 0.1% with a spray for 30 seconds at room temperature, After dilution of L 3020 (registered trademark: Nippon Parker Co., Ltd.) with tap water to 4.8% and further adding 200 ppm of sodium hydrogen fluoride reagent as fluorine, the acidity and free acidity were adjusted to the center of the catalog value. The zinc phosphate coating was deposited by immersing in a 42 ° C zinc phosphate chemical treatment solution.

[Evaluation of Surface Treatment Coating]

The external appearance of the test-providing plate after the surface treatment of Examples and Comparative Examples was visually evaluated. The results are shown in Table 1. In addition, the adhesion amount of the surface treatment film layer was measured by the fluorescent X-ray analyzer (Stem 3270; Rigaku Denki Kogyo Co., Ltd. product). The results are shown in Tables 2 and 3. In addition, the adhesion amount of the surface treatment film layer was measured about the case where each metal material was processed individually without bonding (without joining), and the case where it welded with spot welding (with sum).

Table 1 shows the external appearance evaluation result of the surface treatment film obtained by the Example and the comparative example. In the example, it was possible to obtain a uniform coating with respect to all metal material species of all test plates. Moreover, the appearance that the surface treatment film was deposited also in the spot weld part of the test provision plate used in the Example was observed. On the other hand, in the comparative example, it was impossible to deposit a uniform film with respect to the whole test plate. In particular, in Comparative Examples 3, 4, and 5, no film was deposited at the spot welds. In addition, Comparative Example 5 is a zinc phosphate treatment liquid used when simultaneously processing a cold rolled steel sheet, a galvanized steel sheet, and an aluminum alloy. However, cold rolling is performed under the conditions in which each test piece is joined by welding as in this test. The exposed part of the metal material called the lack of hiding was shown on the steel plate.

Table 2 and Table 3 show the measurement results of the adhesion amount of the surface treatment film obtained in the Example and the comparative example. In the Example, the target adhesion amount could be obtained with respect to all the metal material types of all the test-providing plates. In addition, the adhesion amount of the surface treatment film layer in an Example was constant irrespective of the presence or absence of the test plate joining for a test. On the other hand, in the comparative example, as apparent from the film appearance evaluation result, it was impossible to deposit a uniform film with respect to the whole test plate.

[Evaluation of Coating Performance]

(Production of coating performance evaluation version)

In order to evaluate the coating performance of the surface treatment plates of Examples and Comparative Examples,

Cationic electrodeposition coating → pure water washing → baking → middle coating → baking → coating → baking

Painting was carried out in the step of. Cationic electrodeposition coating, intermediate coating, and overcoat are as follows.

Cationic electrodeposition coating: epoxy based cationic electrodeposition coating (Erecron 9400: manufactured by Kansai Paint Co., Ltd.), voltage 200 V, film thickness of 20 µm, 20 minutes at 175 ° C.

Intermediate lacquer coating coating: Amino alkyd paint (Amirak TP-37 gray: Kansai Paint Co., Ltd.), spray coating, film thickness 35 μm, 140 ° C. for 20 minutes

Coating: Amino alkyd paint (Amirak TM-13 white: Kansai Paint Co., Ltd.), spray coating, film thickness 35 μm, 140 ° C. for 20 minutes

(Painting performance evaluation)

Coating performance evaluation of the Example and the comparative example was performed. The results are shown in Tables 4 and 5. Evaluation items and symbol are shown below. In addition, the coating film at the time of electrodeposition coating completion is called an electrodeposition coating film, and the coating film at the time of completion of an overcoat coating is called a 3 coats coating film.

① SST: salt spray test (electrodeposit coating)

② SDT: Salt Water Test (Electrode Coating Film)

③ 1st ADH: 1st adhesion (3 coats coating)

④ 2nd ADH: Water resistance 2nd adhesion (3 coats coating)

SST: 5% brine was sprayed for 840 hours (according to JIS-Z-2371) on the electrodeposition paint board which the crosscut was put into the sharp cutter. Both maximum swelling widths from the crosscut portions were measured after the completion of spraying.

SDT: The electrodeposition coating plate was immersed in 5 wt% of NaCl aqueous solution heated to 50 degreeC for 840 hours. After the immersion, the entire surface of the test piece washed with water and dried at room temperature with a tap water was peeled off with a rubber tape, and the peeling area of the coating film on each metal material was visually determined.

1st ADH: 3 coats 100 checkerboard grids of 2 mm intervals were drawn with a sharp cutter. The cellophane tape peeling of the checkerboard portion was performed and the number of peelings of the checkerboard scale was counted.

2nd ADH: 3 coats paint plate was immersed in 40 ℃ deionized water for 240 hours. After dipping, 100 checkerboard scales of 2 mm intervals were drawn with a sharp cutter. The cellophane tape peeling of the checkerboard portion was performed and the number of peelings of the checkerboard scale was counted.

Table 4 shows the coating performance evaluation results of the electrodeposition coating film. The examples showed good corrosion resistance for the entire test plate. On the other hand, in Comparative Example 1, since no free fluorine ions are included in the treatment solution for surface treatment, the surface treatment film is not sufficiently precipitated and corrosion resistance is poor. In Comparative Example 2, since the free fluorine ion concentration in the treatment solution for surface treatment was high, the amount of coating on the SPC was particularly small, resulting in poor corrosion resistance. Examples 5 and 6 showed better coating performance than the comparative example, but compared with other examples, the corrosion resistance after electrodeposition coating was slightly inferior. However, as shown in Examples 8 and 9, the post-treatment further improved the corrosion resistance.

Since the comparative example 3 is the chromate treatment agent for aluminum alloys, and the comparative example 4 is the non-chromate treatment agent for aluminum alloys, although Al corrosion resistance was excellent, the corrosion resistance of the other test provision board is clearly inferior to an Example. Comparative Example 5 is a zinc phosphate treatment currently used generally as a base for cationic electrodeposition coating. However, also in the comparative example 5, it was a result inferior compared with an Example in the conditions which joined each test piece by welding like this test.

Table 5 shows the results of the adhesion evaluation of the 3 coats plate. The Example showed good adhesiveness with respect to the whole test plate. Although the 1st ADH was a favorable result also in the comparative example, there was no level which showed favorable adhesiveness with respect to the whole test plate in the 2nd ADH similarly to the corrosion resistance of an electrodeposition coating film. In Comparative Example 5, sludge, which was a by-product of zinc phosphate treatment, was generated in the treatment bath after the surface treatment. However, in the Example, the generation of sludge was not recognized at any level.

From the above results, by using the treatment solution for surface treatment and the surface treatment method of the present invention, SPC, GA, and Al are simultaneously treated without changing the treatment bath and treatment conditions to precipitate a surface treated film excellent in adhesion and corrosion resistance. It is clear that it is possible. Moreover, by using this invention, it became possible to deposit the surface treatment film excellent in corrosion resistance also on a weld part. Moreover, since the surface treatment method of this invention only needs to contact a to-be-processed metal material and the surface treatment liquid, the surface treatment film is precipitated also in the site | part where an agitation effect cannot be expected like the inside of a sealing structure part, and corrosion resistance is improved. It is possible to plan.

According to the treatment liquid for surface treatment of the present invention and the surface treatment method using the treatment liquid, iron-based materials, zinc-based materials, aluminum without generating sludge in a treatment bath containing no harmful components to the environment, which were not possible in the prior art. The surface treatment film excellent in the corrosion resistance after coating can be deposited on the metal surface which becomes two or four types of system type and magnesium type material simultaneously or individually. In addition, a surface treated film can be deposited without performing the surface adjustment process of a to-be-processed metal material, In that case, a process process can be shortened and space saving can be carried out.

Claims (17)

As an aqueous surface treatment liquid for surface-treating a metal material selected from an iron-based material, a zinc-based material, an aluminum-based material, and a magnesium-based material alone or two or more of them simultaneously, one kind selected from a zirconium compound and a titanium compound The above compound contains 5 to 5000 ppm as the metal element, and contains 0.1 to 100 ppm of free fluorine ions, and has a pH of 2 to 6; The method of claim 1, further comprising at least one compound selected from the group consisting of calcium compounds, magnesium compounds and strontium compounds, wherein the concentration of the compound is 5 to 100 ppm, magnesium in the case of the calcium compound as the metal element. In the case of a compound or a strontium compound, a treatment solution for surface treatment of a metal which is 10 to 5000 ppm. The treatment liquid for treating the surface of metal according to claim 1 or 2, further comprising 1000 to 50000 ppm of nitrate. The method according to claim 1 or 2, further comprising HClO ₃ , HBrO ₃ , HNO ₂ , HNO ₃ , HMnO ₄ , HVO ₃ , H ₂ O ₂ , H ₂ WO ₄ and H ₂ MoO ₄ and salts thereof. A treatment liquid for surface treatment of a metal containing at least one oxygen acid, oxygen acid salt or oxygen acid and oxygen acid salt selected. The treatment liquid for treating the surface of metal according to claim 1 or 2, further comprising at least one polymer compound selected from water-soluble polymer compounds and water-dispersible polymer compounds. The treatment liquid for treating the surface of metal according to claim 1, further comprising at least one type of surfactant selected from nonionic surfactants, anionic surfactants and cationic surfactants. Each of the metal materials selected from iron-based materials, zinc-based materials, aluminum-based materials and magnesium-based materials alone or two or more thereof are brought into contact with the surface treatment treatment liquid according to claim 1, And said contact treatment is a spray treatment, dipping treatment or pouring treatment. 8. The method according to claim 7, wherein at least one element selected from the group consisting of cobalt, nickel, tin, copper, titanium and zirconium is further washed with or without washing with a metal material after contact with the treatment solution for surface treatment. A method for surface treatment of metals, comprising contacting with an acidic aqueous solution of a compound. The treatment liquid according to claim 7, further comprising a treatment liquid comprising at least one polymer compound selected from a water-soluble polymer compound and a water-dispersible polymer compound, without washing or washing with water after contacting the metal material with the treatment solution for surface treatment. A surface treatment method of a metal, characterized in that the contact. The surface treatment according to claim 1, wherein each of metal materials selected from an iron material, a zinc material, an aluminum material, and a magnesium material is used alone or two or more thereof at the same time, with the metal material as the cathode and the carbon electrode as the anode. Electrolytic treatment in a solution treatment solution, characterized in that the metal surface treatment method. The at least one element according to claim 10, further selected from the group consisting of cobalt, nickel, tin, copper, titanium, and zirconium, with or without water washing after electrolytic treatment of the metal material in the treatment solution for surface treatment. Method for surface treatment of metals, comprising contacting with an acidic aqueous solution of a compound comprising a. The treatment solution according to claim 10, wherein the metal material is rinsed or not washed after the electrolytic treatment in the treatment solution for surface treatment, and further includes at least one polymer compound selected from water-soluble polymer compounds and water-dispersible polymer compounds. And contacting with the metal. A single or two or more kinds of metal materials which have not been degreased and clarified selected from an iron-based material, a zinc-based material, an aluminum-based material and a magnesium-based material are brought into contact with the surface treatment treatment liquid according to claim 6 at the same time. With And said contact treatment is a spray treatment, dipping treatment or pouring treatment. A surface treatment film containing at least one kind of metal element selected from titanium and zirconium formed by the surface treatment method according to any one of claims 7 to 13 on the surface of the iron-based metal material, and the adhesion amount of the surface treatment film A metal material, characterized in that 30 mg / ㎡ or more in terms of the metal element. A surface treatment film containing at least one kind of metal element selected from titanium or zirconium formed by the surface treatment method according to any one of claims 7 to 13 on the surface of the zinc-based metal material, A metal material, characterized in that the adhesion amount of 20 mg / ㎡ or more in terms of the metal element. A surface treatment film layer containing at least one kind of metal element selected from titanium or zirconium formed by the surface treatment method according to any one of claims 7 to 13 on the surface of the aluminum-based metal material, and further comprising A metal material characterized in that the adhesion amount is 10 mg / m 2 or more in terms of the metal element. A surface treatment film layer containing at least one kind of metal element selected from titanium or zirconium formed by the surface treatment method according to any one of claims 7 to 13 on the surface of the magnesium-based metal material, A metal material characterized in that the adhesion amount is 10 mg / m 2 or more in terms of the metal element.

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