WO2010082415A1 - Surface-treated metallic material and method of treating metal surface - Google Patents

Abstract

A surface-treated metallic material having excellent corrosion resistance and excellent suitability for coating by electrodeposition, and a method of metal surface treatment for producing the material.  The surface-treated metallic material, which is obtained by treating a surface of a metallic material, comprises the metallic material and, formed on the surface, a surface treatment coating film comprising an amorphous coating film and semiconductor particles having a maximum average particle diameter of 5-300 nm, wherein the surface treatment coating film has a proportion of surface coverage by the semiconductor particles of 10-90%, the semiconductor particles are exposed on the surface of the surface treatment coating film, and the semiconductor particles are present at a density of 5-10,000 particles/µm2.

Description

Surface treatment metal material and metal surface treatment method

The present invention relates to a surface-treated metal material in which a surface-treated film having excellent corrosion resistance is formed on the surface of a metal material typified by an automobile body, and a metal surface treatment method for producing the surface-treated metal material.

As a method for depositing a surface treatment film having excellent corrosion resistance after coating on a metal surface, a zinc phosphate treatment method or a chromate treatment method is currently generally used.
Here, in the zinc phosphate treatment method, a film having excellent corrosion resistance can be deposited on the surface of steel such as hot rolled steel sheet and cold rolled steel sheet, galvanized steel sheet and some aluminum alloys.
However, when zinc phosphate treatment is performed, the generation of sludge, which is a by-product of the reaction, is unavoidable, and depending on the type of aluminum alloy, sufficient resistance to yarn rust after coating cannot be ensured. .
Moreover, it is possible to ensure sufficient performance after coating by applying chromate treatment to the aluminum alloy.
However, due to recent environmental regulations, chromate treatment containing hexavalent chromium harmful to the treatment liquid is in a direction to be avoided.
Therefore, various methods have been proposed as surface treatment methods that do not contain harmful components in the treatment liquid.

For example, Patent Document 1 discloses a chemical conversion treatment agent composed of “at least one selected from the group consisting of zirconium, titanium, and hafnium, fluorine, and an adhesion and corrosion resistance imparting agent, wherein the adhesion and corrosion resistance imparting agent includes: ,
1 to 5000 ppm (metal ion concentration) of at least one metal ion (A) selected from the group consisting of zinc, manganese, and cobalt ions,
Alkaline earth metal ions (B) 1 to 5000 ppm (metal ion concentration),
Periodic Table III metal ions (C) 1-1000ppm (metal ion concentration),
Copper ion (D) 0.5-100 ppm (metal ion concentration), and
Silicon-containing compound (E) 1 to 5000 ppm (as silicon component)
A chemical conversion treatment agent characterized by being at least one selected from the group consisting of: And "a surface-treated metal having a chemical conversion film formed on the surface thereof by the chemical conversion treatment agent according to claim 1 or 2" ([Claim 1] and [Claim 3]. ]).

Moreover, in patent document 2, this applicant says "The following component (A), component (B), and component (C):
(A) Compound containing at least one element selected from the group consisting of Ti, Zr, Hf and Si (B) Naphthalenesulfonic acid, naphthalenesulfonic acid-formaldehyde condensate, styrenesulfonic acid, polystyrenesulfonic acid, vinylamine, polyvinyl At least one compound selected from the group consisting of amine, allylamine, polyallylamine and derivatives thereof (C) Selected from the group consisting of Ag, Al, Cu, Fe, Mn, Mg, Ni, Co, Zn, Ca and Sr K1 = B / A, which is a ratio of the total mass concentration B of the component (B) and the total mass concentration A of the element in the component (A), 0.01 ≦ K1 ≦ 50 is satisfied, and the total mass concentration A of the elements in the compound of the component (A) is 5 to 100 0 mg / L, and the total mass concentration of the metal element in the compound is 1 ~ 50000mg / L, the metal surface treatment processing solution of the component (C). "A metal surface treatment method comprising a treatment liquid contact step of bringing a treatment liquid for metal surface treatment according to any one of claims 4 to 10 into contact with a metal material." And "On the surface of an iron-based metal material." A surface formed by the metal surface treatment method according to any one of claims 12 to 17 and containing the element of the component (A) and having an adhesion amount in terms of the element of 20 mg / m ² or more. A metal material having a treated coating layer has been proposed ([Claim 4] [Claim 12] [Claim 18]).

Further, Patent Document 3 discloses a metal surface treatment solution for cationic electrodeposition coating having a pH of 1.5 to 6.5, which contains zirconium ions, copper ions, and other metal ions,
The other metal ions are at least one selected from the group consisting of tin ions, indium ions, aluminum ions, niobium ions, tantalum ions, yttrium ions, and cerium ions,
The concentration of the zirconium ions is 10 to 10,000 ppm,
The concentration ratio of copper ions to zirconium ions is 0.005 to 1 in terms of mass,
A metal surface treatment solution for cationic electrodeposition coating, wherein the concentration ratio of the other metal ions to copper ions is 0.1 to 1000 in terms of mass. "A metal surface treatment method including a step of performing a surface treatment on a metal substrate using the metal surface treatment liquid according to any one of claims 1 to 4.", and "The method according to claim 5." A metal substrate on which a film is formed by surface treatment obtained by the method "is described ([Claim 1] [Claim 5] [Claim 6]).

JP 2004-218073 A JP 2005-264230 A JP 2008-174832 A

As a result of intensive studies on the surface-treated metal (metal material, metal substrate) surface-treated with the chemical conversion treatment agent (metal surface treatment solution) described in Patent Documents 1 to 3 described above Depending on the type of metal material such as iron-based metal material, zinc-based metal material, and aluminum-based metal material, the corrosion resistance cannot be improved, or bag structures (for example, transportation structures such as automobile bodies) It has been clarified that there is a case where the throwing power of the paint at the time of wearing is deteriorated (hereinafter referred to as “the throwing ability with electrodeposition coating”).

Therefore, an object of the present invention is to provide a surface-treated metal material that is excellent in both corrosion resistance and electrodeability with electrodeposition coating, and a metal surface treatment method for producing the same.

As a result of continuing earnest research to achieve the above object, the present inventor has newly found that the physical state and the chemical state of the surface of the electrodeposited material have a great influence on the wearability of the electrodeposition coating. By forming a surface treatment film on the surface of the metal material in which a semiconductor particle containing copper, tin or the like is present in a predetermined form with a predetermined coverage in an amorphous film containing zirconium, Ti or the like, corrosion resistance and The present invention has been completed by finding that the surface-treated metal material is excellent in both of the reversibility with electrodeposition coating.
In addition, the present inventor brings the surface treatment liquid into contact with the surface of the metal material at a predetermined flow rate, so that the semiconductor particles containing copper, tin, etc. in the amorphous film containing zirconium, Ti, etc. have a predetermined density, etc. The present invention was completed by finding that the surface treatment film existing in (1) was formed on the surface of the metal material.
That is, the present invention provides the following (1) to (13).

(1) A surface-treated metal material obtained by surface-treating a metal material,
The surface of the metal material has an amorphous film and a surface-treated film containing semiconductor particles having a maximum average particle diameter of 5 to 300 nm,
The surface coverage of the semiconductor particles in the surface treatment film is 10 to 90%,
The semiconductor particles are exposed from the surface of the surface treatment film,
A surface-treated metal material having a semiconductor particle density of 5 to 10,000 particles / μm ² .

(2) The amorphous film contains at least one element selected from the group consisting of Zr, Ti and Hf,
The surface-treated metal material according to (1), wherein the semiconductor particles contain at least one element selected from the group consisting of Sn, In, Te, and Cu.

(3) The element conversion amount of the element contained in the amorphous film is 5 to 200 mg / m ² ;
The surface-treated metal material according to the above (2), wherein the amount of the element-converted adhesion of the element contained in the semiconductor particles is 1 to 100 mg / m ² .

(4) The metal material according to any one of (1) to (3), wherein the metal material is at least one metal material selected from the group consisting of iron-based metal materials, zinc-based metal materials, and aluminum-based metal materials. Surface treatment metal material.

(5) First to third surface-treated metal materials having a size of 150 mm in length and 70 mm in width and having a hole with a diameter of 8 mm at a position 50 mm from the lower end of the center in the horizontal direction, and a size of 150 mm in length and 70 mm in width The fourth surface-treated metal materials are installed in parallel in this order at intervals of 20 mm,
Each of the first to fourth surface-treated metal materials is immersed in an electrodeposition coating bath from the lower end to a position of 95 mm,
A counter electrode is installed on the surface of the first surface-treated metal material where the second surface-treated metal material is not installed, and electrodeposition coating is performed under the following conditions (a) to (c):
A coating thickness ratio (A / G) of the surface on the counter electrode side (A surface) of the first surface-treated metal material and the surface on the counter electrode side (G surface) of the fourth surface-treated metal material is 3.0. A surface-treated metal material that can be:
(A) Electrodeposition paint temperature: 28 ° C
(B) Electrolytic conditions: A voltage is applied linearly from 0 V to 230 V over 30 seconds and then held at 230 V for 150 seconds. (C) Firing conditions: 170 ° C., 20 minutes

(6) The metal material contains at least one element selected from the group consisting of Zr, Ti, and Hf, and contains at least one element selected from the group consisting of Sn, In, Te, and Cu. A metal surface treatment method for obtaining a surface-treated metal material according to any one of the above (1) to (5) by contacting a surface treatment solution at a flow rate of 1 to 10 cm / sec.

(7) The surface treatment liquid contains 1 to 10,000 ppm of at least one element selected from the group consisting of Zr, Ti and Hf, and at least one selected from the group consisting of Sn, In, Te and Cu The metal surface treatment method according to the above (6), which contains 1 to 5000 ppm of one element and has a pH of 2.0 to 6.0.

(8) Zr contained in the surface treatment liquid is zirconium sulfate, zirconium oxysulfate, ammonium zirconium sulfate, zirconium nitrate, zirconium oxynitrate, zirconium nitrate ammonium, zirconium sulfate, zirconium oxysulfate, ammonium zirconium sulfate, zirconium nitrate, oxy The metal surface treatment method according to the above (6) or (7), which is contained as at least one selected from the group consisting of zirconium nitrate, ammonium zirconium nitrate, fluorozirconic acid, and fluorozirconium complex salt.

(9) Ti contained in the surface treatment liquid is titanium sulfate, titanium oxysulfate, ammonium ammonium sulfate, titanium nitrate, titanium oxynitrate, titanium ammonium nitrate, titanium sulfate, titanium oxysulfate, ammonium titanium sulfate, titanium nitrate, oxy The metal surface treatment method according to any one of the above (6) to (8), which is contained as at least one selected from the group consisting of titanium nitrate, ammonium titanium nitrate, fluorotitanic acid, and fluorotitanium complex salt.

(10) The Sn contained in the surface treatment liquid is any one of the above (6) to (9), which is contained as at least one selected from the group consisting of tin nitrate, tin sulfate and tin fluoride. Metal surface treatment method.

(11) The In contained in the surface treatment liquid is contained as at least one selected from the group consisting of indium nitrate, indium sulfate, indium sulfamate, indium fluoride, indium oxide and indium hydroxide ( 6) The metal surface treatment method according to any one of (10).

(12) Te contained in the surface treatment liquid is at least one selected from the group consisting of telluric acid, potassium tellurate, sodium tellurate, telluric acid, potassium tellurite, sodium tellurite and tellurium dioxide. The metal surface treatment method according to any one of the above (6) to (11), which is contained as:

(13) Cu contained in the surface treatment liquid is selected from the group consisting of copper nitrate, copper sulfate, copper chloride, copper carbonate, basic copper carbonate, copper oxide, copper acetate, copper hydroxide, copper fluoride and copper sulfide. The metal surface treatment method according to any one of the above (6) to (12), which is contained as at least one selected.

According to the present invention, as shown below, it is possible to provide a surface-treated metal material that is excellent in both corrosion resistance and removability with electrodeposition coating, and a metal surface treatment method for producing the same.

The reason why the surface-treated metal material of the present invention exhibits such an effect is not clear, but the present inventor presumes as follows.
In other words, the amorphous film in the surface treatment film makes the corrosion resistance good, and the electrocoating with the electrodeposition coating is good due to the semiconductor particles existing in a predetermined form (exposure) with a predetermined coverage, particle diameter and density in the amorphous film. It is thought that it is.

In particular, it is considered as follows about the reversibility with electrodeposition coating.
First, in the cationic electrodeposition, when a predetermined potential is applied so that the metal material (object to be processed) becomes a cathode, the pH of the metal material surface (interface) increases, so that the paint aggregates and precipitates.
On the surface of the metal material after the surface treatment using a zinc phosphate-based metal surface treatment solution, which has good electrodeposition coating performance, a film in which insulating zinc phosphate crystals are deposited in the form of particles is formed. Is formed.
Therefore, when a predetermined voltage is applied, the insulating crystal becomes a resistance, and the current is concentrated in the gap between the crystals. As a result, the current density is locally high and the pH of the metal material surface is greatly increased. Thus, it is considered that the electrodeposition paint is easily aggregated and deposited.
Further, when the agglomerated and deposited paint is fused as a coating film, it is considered that due to the high resistance of the coating film, the current sequentially goes to a place where the resistance is low, and as a result, a high throwing power is exhibited.

On the other hand, a uniform and smooth amorphous film is formed on the surface of the metal material after the surface treatment using the zirconium-based metal surface treatment liquid, which is poor in circulation performance with electrodeposition coating.
Therefore, when a predetermined voltage is applied, the above-mentioned current concentration is unlikely to occur, so that the electrodeposition paint is less likely to agglomerate. Conceivable.

Therefore, it is considered that the presence of semiconductor particles in a predetermined manner in the amorphous film that ensures corrosion resistance causes the same action (current concentration) as the zinc phosphate film described above, and also exhibits high removability with electrodeposition coating. It is done.

Further, the surface-treated metal material of the present invention is very useful because the coating film adhesion is improved.
Furthermore, according to the metal surface treatment method of the present invention, a metal surface treatment solution that does not contain environmentally harmful components is used for a wide range of metal materials such as iron-based metal materials, zinc-based metal materials, and aluminum-based metal materials. In addition, since the surface adjustment step and the post-treatment step are not required, the treatment step can be shortened and space can be saved.

FIG. 1 is a schematic view showing an example of a cross-sectional structure of the surface-treated metal material of the present invention. FIG. 2 is a schematic view showing another example of the cross-sectional structure of the surface-treated metal material of the present invention. FIG. 3 is an SEM image of the surface treatment film measured in Comparative Example 1, Example 1 and Example 2. FIG. 4 is a sketch drawing of a box used for the throwing power test of electrodeposition coating (four-sheet box test).

Hereinafter, the surface-treated metal material of the present invention and the metal surface treatment method of the present invention (hereinafter simply referred to as “the treatment method of the present invention”) will be described in detail.

[Surface-treated metal material of the present invention]
The surface-treated metal material according to the first aspect of the present invention is a surface-treated metal material obtained by surface-treating a metal material, and has an amorphous film and a maximum average particle size of 5 to 300 nm on the surface of the metal material. A surface treatment film containing the semiconductor particles, the surface coverage of the semiconductor particles in the surface treatment film is 10 to 90%, the semiconductor particles are exposed from the surface of the surface treatment film, The surface-treated metal material has a semiconductor particle density of 5 to 10,000 particles / μm ² .

Next, the surface-treated metal material according to the first aspect of the present invention will be described with reference to FIGS. 1 and 2, and the surface-treated metal material according to the first aspect of the present invention is described in these drawings. It is not limited to the embodiment.
Here, FIG. 1 is a schematic diagram showing an example of the cross-sectional structure of the surface-treated metal material of the present invention, and FIG. 2 is a schematic diagram showing another example of the cross-sectional structure of the surface-treated metal material of the present invention. .

1 and 2, the surface-treated metal material 30 of the present invention has a surface-treated film 34 containing an amorphous film 32 and semiconductor particles 33 on the surface of the metal material 31.

<Metal material>
Although the said metal material 31 is not specifically limited, It applies suitably to an iron-type metal material, a zinc-type metal material, and an aluminum-type metal material.

Although the said iron-type metallic material is not specifically limited, For example, steel plates, such as a cold rolled steel plate and a hot rolled steel plate; Cast iron; Sintered material;
Although the said zinc-type metal material is not specifically limited, For example, zinc die-casting, zinc containing plating, etc. are mentioned. Zinc-containing plating is plated with zinc or zinc and other metals (for example, alloys of at least one of nickel, iron, aluminum, manganese, chromium, magnesium, cobalt, lead, antimony, and inevitable impurities). is there. The plating method is not particularly limited, and examples thereof include hot dipping, electroplating, and vapor deposition plating.
The aluminum-based metal material is not particularly limited, and examples thereof include aluminum alloy plate materials such as a 5000-series aluminum alloy and a 6000-series aluminum alloy; an aluminum alloy die-cast represented by ADC-12;

In the present invention, two or more kinds of metal materials can be surface-treated at the same time. When two or more kinds of metal materials are simultaneously surface-treated, the surface treatment may be performed in a state in which different kinds of metals are not in contact with each other, and in a state in which different kinds of metals are joined and contacted by a joining method such as welding, adhesion, or riveting. May be processed.

<Surface treatment film>
The surface treatment film 34 is a mixed film in which the semiconductor particles 33 are present in the amorphous film 32 in a predetermined form (exposed) with a predetermined coverage, particle diameter, and density.
In the present invention, the method for forming the surface treatment film 34 is not particularly limited. As shown in the treatment method of the present invention, which will be described later, a predetermined surface treatment liquid is brought into contact with the metal material 31 to form the metal material 31. It is preferable that the surface is formed by chemical conversion treatment.

(Amorphous film)
The amorphous film 32 is a main component constituting the surface treatment film 34 and is considered to be a part that ensures good corrosion resistance as described above.
In the present invention, the amorphous film preferably contains at least one element selected from the group consisting of Zr, Ti, and Hf, and contains these elements as oxides and / or hydroxides. More preferred.
Of these, zirconium oxides and / or hydroxides are preferable because a uniform and dense film structure can be obtained and the surface-treated metal material of the present invention has better corrosion resistance.

In the present invention, the amount of the element in terms of the element contained in the amorphous film is preferably 5 to 200 mg / m ² , more preferably 10 to 100 mg / m ² .
When the adhesion amount is within this range, the corrosion resistance of the surface-treated metal material of the present invention becomes better.

Furthermore, in the present invention, the film thickness of the amorphous film 32 is not particularly limited, but is preferably 3 to 300 nm, more preferably 20 to 200 nm.

(Semiconductor particles)
The semiconductor particles 33 are other main components constituting the surface treatment film 34 and, as described above, are considered to be portions that ensure good removability with electrodeposition coating.
In the present invention, the semiconductor particle 33 has a particle size described later among substances having an electric conductivity of about 10 ³ to 10 ⁻¹⁰ S / cm between the metal and the insulator.

In the present invention, the semiconductor particle 33 preferably contains at least one element selected from the group consisting of Sn, In, Te and Cu, and contains these elements as oxides. More preferably, as shown in FIG. 2, it is more preferable that these elements are contained as the core 35 and the periphery is covered with the oxide.
The presence or absence of the core 35 shown in FIG. 2 can be measured by X-ray photoelectron spectroscopy.

Further, in the present invention, the amount of the element contained in the semiconductor particles in terms of element is preferably 1 to 100 mg / m ² , more preferably 3 to 60 mg / m ² .
When the amount of adhesion is within this range, the surface-treated metal material of the present invention has better electrodeability with electrodeposition coating.

In the present invention, the maximum average particle size of the semiconductor particles 33 is 5 to 300 nm, and preferably 50 to 200 nm.
Here, the maximum average particle diameter refers to a value obtained by measuring the maximum particle diameter of all the particles present in the measurement range of 1 μm ² using a scanning electron microscope and calculating the average of those measured values.

In the present invention, the surface coverage of the semiconductor particles 33 in the surface treatment film 34 is 10 to 90%, preferably 20 to 80%, and more preferably 30 to 70%. .
Here, the surface coverage in the surface treatment film 34 can also be referred to as the abundance ratio of the semiconductor particles 33 in the surface treatment film 34. In the present invention, the surface treatment film of the surface treatment metal material 30. The surface on which the surface 34 is formed is observed with a scanning electron microscope to measure the geometric measurement area of the surface treatment film 34 and the semiconductor particles 33, and the ratio thereof (the semiconductor particles 33 / the surface treatment film 34). ). When the surface treatment film 34 is formed on the entire surface of the metal material 31, the surface coverage of the surface treatment film 34 is equal to the coverage of the semiconductor particles 33 on the surface of the metal material 31. The same.

The maximum average particle diameter and surface coverage of the semiconductor particles can be adjusted by the elements forming the semiconductor particles.
Specifically, when the semiconductor particles contain Te as a main component, it becomes easy to make the maximum average particle size in the range of 5 to 100 nm and the surface coverage in the range of 60 to 90%.
Similarly, when the semiconductor particles contain In as a main component, it becomes easy to make the maximum average particle size in the range of 80 to 180 nm and the surface coverage in the range of 50 to 70%.
Similarly, when the semiconductor particles contain Sn as a main component, it becomes easy to make the maximum average particle size in the range of 120 to 200 nm and the surface coverage in the range of 40 to 60%.
Similarly, when the semiconductor particle Cu is contained as a main component, it becomes easy to make the maximum average particle size in the range of 150 to 300 nm and the surface coverage in the range of 10 to 50%.
In addition, by using the semiconductor particles in various proportions, the maximum average particle diameter and the surface coverage can be appropriately adjusted within the range other than the above. For example, the maximum average particle size can be reduced by containing Te, and the maximum average particle size can be increased by containing copper.

In addition, the maximum average particle diameter and surface coverage of the semiconductor particles are the composition, pH, temperature, concentration of the semiconductor particles described later, and the contact time of the processing liquid in the processing method of the present invention described later. Can be adjusted.
Specifically, the surface coverage can be lowered by adding a chelating agent described later to the processing solution of the present invention described later. Moreover, the maximum average particle diameter can be reduced and the surface coverage can be lowered by adding an organic substance to be described later, for example, an amino group-containing compound.
In addition, when the treatment is performed in a relatively high pH region (pH of about 3.5 or more), it is possible to increase the maximum average particle diameter and increase the surface coverage.
Similarly, when the treatment is performed in a relatively high temperature range (about 40 ° C. or more), the maximum average particle size can be increased and the surface coverage can be increased.
Similarly, when the treatment is performed at a higher concentration of the semiconductor particles, it is possible to increase the maximum average particle size and increase the surface coverage.
Similarly, if the treatment time is increased (about 120 seconds or more), it is possible to increase the maximum average particle size and increase the surface coverage.

Further, the surface coverage of the semiconductor particles can be adjusted by the material of the metal material 31.
Specifically, when the metal material 31 is an iron-based metal material, the surface coverage can easily be set in the range of 40 to 60%.
Similarly, when the metal material 31 is a zinc-based metal material, the surface coverage can easily be in the range of 60 to 90%.
Similarly, when the metal material 31 is an aluminum-based metal material, the surface coverage can easily be in the range of 10 to 40%.

In the present invention, at least a part of the semiconductor particles 33 are exposed from the surface of the surface treatment film 34, and the density thereof is 5 to 10,000 particles / μm ² .
Here, the existence of the semiconductor particles 33 exposed from the surface of the surface treatment film 34 means that the elements contained in the amorphous film 32 and the elements contained in the semiconductor particles 33 are energy dispersive X-ray spectroscopy. It can be confirmed by analyzing by law.
The density is a value obtained by observing the surface of the surface-treated metal material 30 on which the surface-treated film 34 is formed with a scanning electron microscope and measuring the number of the semiconductor particles 32 present at 1 μm ^2. is there.

The density can be adjusted by the elements forming the semiconductor particles.
Specifically, when the semiconductor particles contain Te as a main component, it becomes easy to set the density to a range of 1000 to 10,000 particles / μm ² .
Similarly, when the semiconductor particles contain Sn as a main component, it becomes easy to set the density to a range of 100 to 1000 particles / μm ² .
Similarly, when the semiconductor particles contain In as a main component, it becomes easy to set the density to a range of 100 to 500 particles / μm ² .
Similarly, when the semiconductor particle Cu is contained as a main component, it becomes easy to set the density in the range of 5 to 100 particles / μm ² .
Moreover, the density can be appropriately adjusted in a range other than the above by using the semiconductor particles in various proportions. For example, the density can be increased by adding Te, and the density can be decreased by adding copper.
Furthermore, when the treatment is performed in a relatively high pH region (pH of about 3.5 or more), the density can be reduced.
Similarly, when processing is performed in a relatively high temperature range (about 40 ° C. or higher), the density can be reduced.
Further, when the treatment is performed with the concentration of the semiconductor particles increased, the density can be increased.
Similarly, the density can be increased by increasing the processing time (about 120 seconds or more).

Next, the surface-treated metal material according to the second aspect of the present invention has a size of 150 mm in length and 70 mm in width, and has a hole having a diameter of 8 mm at a position 50 mm from the lower end of the center in the horizontal direction. A surface-treated metal material and a fourth surface-treated metal material having a size of 150 mm in length and 70 mm in width are installed in parallel in this order at intervals of 20 mm,
Each of the first to fourth surface-treated metal materials is immersed in an electrodeposition coating bath from the lower end to a position of 95 mm,
A counter electrode is installed on the surface of the first surface-treated metal material where the second surface-treated metal material is not installed, and electrodeposition coating is performed under the following conditions (a) to (c):
A coating thickness ratio (A / G) of the surface on the counter electrode side (A surface) of the first surface-treated metal material and the surface on the counter electrode side (G surface) of the fourth surface-treated metal material is 3.0. A surface-treated metal material that can be:
(A) Electrodeposition paint temperature: 28 ° C
(B) Electrolytic conditions: A voltage is applied linearly from 0 V to 230 V over 30 seconds and then held at 230 V for 150 seconds. (C) Firing conditions: 170 ° C., 20 minutes

Next, the surface-treated metal material according to the second aspect of the present invention will be described with reference to FIG.
FIG. 4 is a sketch drawing of a box used for the throwing power test of electrodeposition coating (four-sheet box test).

As shown in FIG. 4, the four-box 1 is assembled by first to third surfaces having a length of 150 mm and a width of 70 mm, and a hole having a diameter of 8 mm at a position 50 mm from the lower end of the center in the horizontal direction. The treated metal materials 12 to 14 and the fourth surface treated metal material 15 having a size of 150 mm in length and 70 mm in width were arranged in parallel in this order with an interval of 20 mm.
Next, the both sides and lower surface of the surface-treated metal materials 12 to 15 are closed with the vinyl chloride plates 21 to 23, and the vinyl chloride plates 21 to 23 and the surface-treated metal materials 12 to 15 are fixed with the adhesive tape. It was.
In the four-box 1, the first to fourth four surface-treated metal materials 12 to 15 are the same kind of metal material that has been subjected to the same surface treatment, but the surface is not yet treated. A surface treatment may be applied to a box similarly assembled using a metal material.

The counter electrode (not shown) is a stainless steel plate (SUS304) 70 × 150 × 0.55 mm sealed on one side with an insulating tape. The surface of the electrodeposition paint is immersed in a surface treated metal material 12-15 and the counter electrode is 95 mm. Controlled to a position.

As shown in the above (a) to (c), the electrodeposition coating was performed while maintaining the temperature of the electrodeposition paint at 28 ° C. and stirring with a stirrer. All of the four surface-treated metal materials 12 to 15 were short-circuited, and a coating film was electrolytically deposited by a cathode electrolysis method using a rectifier with the counter electrode as an anode. The electrolysis was performed by applying a voltage linearly from 0V to 230V over 30 seconds in the cathode direction and then maintaining 230V for 150 seconds.
After the electrolysis, each of the surface-treated metal materials 12 to 15 was washed with water and baked at 170 ° C. for 20 minutes to form a coating film. The counter electrode side of the surface-treated metal material 12 closest to the counter electrode is the A surface, the counter electrode side of the surface-treated metal material 15 furthest from the counter electrode is the G surface, and the coating thickness of the A surface and the G surface is measured. The ratio of G was calculated.

The surface-treated metal material according to the second aspect of the present invention has a coating thickness ratio (A / G) of 3.0 or less.
Here, at least the surface-treated metal material according to the first aspect of the present invention described above has a coating film thickness ratio (A / G) of 3.0 or less. Regardless of the aspect 1, if the coating film thickness ratio (A / G) is 3.0 or less, the surface-treated metal material is excellent in both corrosion resistance and reversibility with electrodeposition coating. I found.

[Treatment method of the present invention]
The treatment method of the present invention contains at least one element selected from the group consisting of Zr, Ti and Hf in the metal material, and at least one selected from the group consisting of Sn, In, Te and Cu Metal surface treatment method for obtaining the surface-treated metal material of the present invention described above by contacting a surface treatment liquid containing an element (hereinafter referred to formally as "treatment liquid of the present invention") at a flow rate of 1 to 10 cm / second. It is.
Here, the flow rate refers to the flow rate of the surface treatment liquid brought into contact with the surface of the metal material. For example, in the case of dipping treatment, the flow rate can be adjusted by the dipping rate.
Specifically, the speed of the surface treatment liquid at the contact interface can be adjusted by oscillating the pump for circulating the treatment liquid of the present invention or the metal material that is the object to be treated.

<Metal material>
As the metal material, as described above, an iron-based metal material, a zinc-based metal material, and an aluminum-based metal material are preferably exemplified.
In addition, it is desirable that the surface of the metal material to be brought into contact with the treatment liquid of the present invention is previously cleaned to remove metal powder, oil, dirt, and the like generated by wear or molding.
The cleaning method is not particularly limited, and a conventionally known method such as degreasing treatment or alkali cleaning can be used.

<Contact method>
The method of bringing the treatment liquid of the present invention into contact with the metal material is not particularly limited as long as the flow rate of the surface treatment liquid is in the range of 1 to 10 cm / second, and examples include immersion treatment.
Here, the temperature of the treatment liquid of the present invention at the time of contact (treatment temperature) is preferably 30 to 60 ° C.
The contact time is preferably about 2 to 600 seconds, although it depends on the material and structure of the metal material, the concentration of the treatment liquid of the present invention, and the treatment temperature. For example, in the case of a complex structure typified by an automobile body, liquid replacement inside the bag structure is necessary, and therefore it is preferable that the contact is made for 30 to 120 seconds.

The metal material surface-treated by the treatment method of the present invention forms the above-mentioned surface-treated film excellent in corrosion resistance and electrodeposition with electrodeposition coating.
This is because when the flow rate of the surface treatment liquid is 1 to 10 cm / second, the pH at the interface between the treatment liquid of the present invention and the metal material can be maintained in a relatively high range (3.5 or more). This is considered to be because the etching reaction occurring at this interface proceeds gently.
Moreover, after a surface treatment film is formed, it can be subjected to electrodeposition coating without being dried after being washed with water or deionized water as needed.

<The treatment liquid of the present invention>
The treatment liquid of the present invention contains at least one element selected from the group consisting of Zr, Ti and Hf, and contains at least one element selected from the group consisting of Sn, In, Te and Cu. It is a surface treatment liquid.

In addition, the treatment liquid of the present invention contains 1 to 10,000 ppm of at least one element selected from the group consisting of Zr, Ti and Hf from the viewpoint of further improving the corrosion resistance and the ability of electrodeposition coating, and Sn. It is preferable to contain 1 to 5000 ppm of at least one element selected from the group consisting of In, Te and Cu.

In the present invention, from the viewpoint of depositing a uniform and dense amorphous film, Zr contained in the treatment liquid of the present invention is zirconium sulfate, zirconium oxysulfate, zirconium ammonium sulfate, zirconium nitrate, zirconium oxynitrate, ammonium zirconium nitrate, It is preferably contained as at least one selected from the group consisting of zirconium sulfate, zirconium oxysulfate, ammonium zirconium sulfate, zirconium nitrate, zirconium oxynitrate, ammonium zirconium nitrate, fluorozirconic acid, and fluorozirconium complex salt.
Of these, fluorozirconic acid and fluorozirconium complex salts are more preferable for the reason of improving the stability of the treatment liquid of the present invention.

Similarly, from the viewpoint of depositing a uniform and dense amorphous film, Ti contained in the treatment liquid of the present invention is titanium sulfate, titanium oxysulfate, ammonium titanium sulfate, titanium nitrate, titanium oxynitrate, ammonium titanium nitrate, titanium sulfate. It is preferably contained as at least one selected from the group consisting of titanium oxysulfate, ammonium ammonium sulfate, titanium nitrate, titanium oxynitrate, ammonium ammonium nitrate, fluorotitanic acid and fluorotitanium complex.
Of these, fluorotitanic acid and fluorotitanium complex salts are more preferable for the reason of improving the stability of the treatment liquid of the present invention.

Further, from the viewpoint of easily exposing and dispersing the semiconductor particles from the surface of the surface treatment film, Sn contained in the treatment liquid of the present invention is selected from the group consisting of tin nitrate, tin sulfate and tin fluoride. It is preferable to contain as at least one kind.

Similarly, from the viewpoint of easily exposing and dispersing the semiconductor particles from the surface of the surface treatment film, In contained in the treatment liquid of the present invention is indium nitrate, indium sulfate, indium sulfamate, indium fluoride, It is preferably contained as at least one selected from the group consisting of indium oxide and indium hydroxide.

Similarly, from the viewpoint of easily exposing and dispersing the semiconductor particles from the surface of the surface treatment film, Te contained in the treatment liquid of the present invention is telluric acid, potassium tellurate, sodium tellurate, tellurite. And at least one selected from the group consisting of potassium tellurite, sodium tellurite and tellurium dioxide.

Similarly, from the viewpoint of easily exposing and dispersing the semiconductor particles from the surface of the surface treatment film, Cu contained in the treatment liquid of the present invention is copper nitrate, copper sulfate, copper chloride, copper carbonate, basic It is preferably contained as at least one selected from the group consisting of copper carbonate, copper oxide, copper acetate, copper hydroxide, copper fluoride and copper sulfide.

(Fluorine compound)
In the present invention, the treatment liquid of the present invention preferably contains a fluorine compound from the viewpoint of promoting an etching reaction occurring at the interface between the treatment liquid of the present invention and the metal material.
Specific examples of the fluorine compound include hydrofluoric acid, ammonium fluoride, ammonium hydrogen fluoride, germanium fluoride, potassium fluoride, potassium hydrogen fluoride, iron fluoride, sodium fluoride, and hydrogen fluoride. Sodium etc. are mentioned, These may be used individually by 1 type and may use 2 or more types together.

From the same viewpoint, it is preferable that the treatment liquid of the present invention contains ions that are relatively easily reduced together with the fluorine compound.
Further, from the same viewpoint, it is preferable to treat the treatment liquid of the present invention in the relatively high pH range (3.5 or more) in the presence of an oxidizing substance such as nitrate ions.
This is because, at a high pH, the etching reaction occurring at the interface between the treatment liquid of the present invention and the metal material proceeds gently, and an amorphous film is likely to be formed. Further, due to the electron emission accompanying this etching reaction, Sn or Cu is reduced, and a metal nucleus is formed on the surface. That is, by suppressing the etching reaction and allowing an oxidizing substance to coexist, the growth of the amorphous film and the growth of oxides and hydroxides around the metal core proceed, so the surface treatment of the cross-sectional structure shown in FIG. A metal material can be obtained.

(Metal ions)
Moreover, in this invention, even if the process liquid of this invention contains the metal ion which elutes from a metal material during the continuous operation of surface treatment, it does not become a problem.
Specifically, metal ions eluted by the etching reaction occurring at the interface between the treatment liquid of the present invention and the metal material, for example, Fe, Zn, Al, etc., are contained, but contain Zr, Sn, etc. By controlling the amount within the above-described range, problems such as sludge generation can be suppressed.
In some cases, the corrosion resistance can be further improved by positively adding metal ions and eutectating the metal. For example, polyvalent metal ions such as Mg, Si, Ca, V, Mn, Co, Ni, Y, Ag, Ba, Bi, and Ce can be added.

(Metal chelating agent)
Furthermore, in this invention, it is preferable that the processing liquid of this invention contains a metal chelating agent.
The metal chelating agent basically has the effect of increasing the stability of the treatment liquid of the present invention.
In particular, when the amount of liquid brought in from the previous step (for example, degreasing, etc.) of the treatment liquid contact step in the metal treatment method of the present invention (for example, a washing step or a line where the amount of water tends to be insufficient), the pH increases. The stability of the processing solution may be impaired due to the tendency.
Therefore, it is preferable to contain a metal chelating agent in such a case.

Specific examples of the metal chelating agent include oxalic acid, tartaric acid, citric acid, malic acid, malonic acid, organic phosphonic acid, nitrilodiacetic acid (NTA), ethylenediaminetetraacetic acid (EDTA), and hydroxyethylenediamine. Examples include triacetic acid (HEDTA) and salts thereof. These may be used alone or in combination of two or more.
Of these, malic acid, malonic acid, organic phosphonic acid, HEDTA, and salts thereof, which do not affect the precipitation of Zr, Sn, etc., that is, the formation of the above-described surface treatment film, are preferable.

In the present invention, the content of the chelating agent is preferably 5 to 5000 mg / L, and more preferably 10 to 1000 mg / L.

(Other organic substances)
From the viewpoint of further improving the corrosion resistance and improving the paint adhesion, the treatment liquid of the present invention can be added with an organic substance such as a resin within the range that does not impair the object of the present invention.
Specific examples of organic substances include amino group-containing compounds (for example, vinylamine, polyvinylamine, allylamine, polyallylamine, polyethyleneimine, etc.), vinyl alcohol, polyvinyl alcohol, urethane resin, polyester, acrylic acid, and polyacrylic acid. , Phenol, polyphenol, bisphenol, saccharides and derivatives thereof.

The pH of the treatment liquid of the present invention is preferably 2.0 to 6.0, more preferably 2.5 to 5.0, and still more preferably 3.0 to 4.5.
When the pH is within this range, the deposition efficiency of Zr, Sn, etc. is improved, and the generation of sludge during continuous operation of the surface treatment can be suppressed.

In the present invention, when it is necessary to adjust the pH of the treatment liquid, the chemical used is not particularly limited.
Specific examples of such agents include acids such as hydrochloric acid, sulfuric acid, nitric acid, hydrofluoric acid, boric acid, and organic acids; lithium hydroxide, potassium hydroxide, sodium hydroxide, calcium hydroxide, Examples include alkalis such as magnesium hydroxide, barium hydroxide, alkali metal salts, aqueous ammonia, ammonium hydrogen carbonate, ammonium salts, and amines.

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

First, the metal material, the cleaning in the surface treatment method of the metal material, the contact with the treatment liquid, and the subsequent electrodeposition coating will be described.
In addition, various test methods (evaluation methods) of each metal material after the surface treatment using each metal surface treatment solution and the preparation of each metal surface treatment solution will be described later. The results are shown in Tables 1 to 3 below.

〔Metal material〕
As the metal material, cold-rolled steel plate (size: 70 × 150 × 0.8 mm, trade name: SPCC (JIS 3141), manufactured by Partec), alloyed hot-dip galvanized steel plate (size: 70 × 150 × 0.8 mm, Product name: SGCC F06 MO (JIS G3302), manufactured by Partec Co., Ltd.) and aluminum alloy plate (size: 70 x 150 x 1.0 mm, product name: A5052P (JIS 4000), manufactured by Partec Co., Ltd.) It was.
Hereinafter, the cold-rolled steel sheet is abbreviated as “SPC”, the galvannealed steel sheet as “GA”, and the aluminum alloy sheet as “AL”.

[Cleaning]
Using a degreasing agent (trade name: Fine Cleaner E2001 (A agent 13g / L, B agent 7g / L), manufactured by Nippon Parkerizing Co., Ltd.), spray the surface of each metal material at a liquid temperature of 40 ° C for 120 seconds. Degreased.
Thereafter, it was washed with spray water for 30 seconds.
In addition, about the box mentioned later used for the evaluation of the circulation property with electrodeposition coating, it was degreased by immersing for 180 seconds at a liquid temperature of 40 ° C. using the same degreasing agent as described above. In this case, the washing with water was also performed by immersing for 60 seconds and rocking well.

[Processing liquid contact]
Prepare a treatment solution for each metal surface treatment having the composition described later, and stir at a predetermined temperature for 1 hour to confirm the degree of stability such as pH and the occurrence of precipitation, and leave the treatment solution to appear (initial appearance). Was observed.
Then, the surface treatment of each metal material and the box described later was performed under the following surface treatment conditions 1 or 2.
After the surface treatment, the surface of each metal material was washed with tap water at room temperature for 30 seconds, and further washed with deionized water at room temperature for 30 seconds.

<Surface treatment condition 1>
(1) Processing temperature: 35 ° C
(2) Treatment time: 90 seconds (3) Contact method: Immersion (4) Flow rate during contact: 10 cm / second <Surface treatment condition 2>
(1) Processing temperature: 40 ° C
(2) Treatment time: 90 seconds (3) Contact method: Immersion (4) Flow rate during contact: 2 cm / second

[Electrodeposition coating]
After the above deionized water washing, an electrodeposition paint (trade name: GT-10HT, manufactured by Kansai Paint Co., Ltd.) was applied to a metal material that was not dried, and constant voltage cathode electrolysis was performed for 180 seconds to deposit a coating film.
Thereafter, it was washed with water and baked at 170 ° C. for 20 minutes to perform electrodeposition coating to form a coating film. The film thickness of the coating film was adjusted to 20 μm by controlling the voltage.

Example 1
A treatment liquid 1 for metal surface treatment was prepared, and the surface treatment film layer was formed by performing surface treatment of the three kinds of metal materials cleaned by the above-described method and a box described later.
Here, in preparing the metal surface treatment solution 1, the following components (A) to (C) were first added in this order so as to have the following concentrations, followed by stirring at room temperature for 20 minutes. Subsequently, it heated to predetermined temperature (35 degreeC), pH was adjusted to 4.5 using aqueous ammonia, and the metal surface treatment processing liquid 1 was obtained.
Further, the surface treatment using the metal surface treatment solution 1 was performed under the surface treatment condition 1 described above.
Thereafter, the metal material after the surface treatment was washed with water, deionized water, and electrodeposition coating was performed without drying, thereby forming a coating film.

<Metal surface treatment liquid 1>
(A) Fluorozirconic acid: 100 ppm as Zr
(B) Copper nitrate: 30 ppm as Cu
(C) Zinc nitrate: 500 ppm as Zn

(Example 2)
A treatment liquid 2 for metal surface treatment was prepared, and the surface treatment film layer was formed by performing the surface treatment of the three kinds of metal materials cleaned by the above-described method and the box described below.
Here, in preparing the metal surface treatment solution 2, the following components (A) to (D) were first added in this order so as to have the following concentrations, followed by stirring at room temperature for 20 minutes. Subsequently, it heated to predetermined temperature (40 degreeC), pH was adjusted to 3.0 using aqueous ammonia, and the metal surface treatment processing liquid 2 was obtained.
The surface treatment using the metal surface treatment solution 2 was performed under the surface treatment condition 2 described above.
Thereafter, the metal material after the surface treatment was washed with water, deionized water, and electrodeposition coating was performed without drying, thereby forming a coating film.

<Metal surface treatment liquid 2>
(A) Fluorotitanic acid: 50 ppm as Ti
(B) Potassium tellurite: 50 ppm as Te
(C) Zinc nitrate: 200 ppm as Zn
(D) Aluminum nitrate: 20 ppm as Al

(Example 3)
A metal surface treatment solution 3 was prepared, and surface treatment was performed on the three types of metal materials cleaned by the above-described method and a box described later to form a surface treatment film layer.
Here, in preparing the metal surface treatment solution 3, the following components (A) to (F) were first added in this order so as to have the following concentrations, followed by stirring at room temperature for 20 minutes. Subsequently, it heated to predetermined temperature (35 degreeC), pH was adjusted to 4.0 using ammonia water, and the metal surface treatment processing liquid 3 was obtained.
Further, the surface treatment using the metal surface treatment liquid 3 was performed under the surface treatment condition 1 described above.
Thereafter, the metal material after the surface treatment was washed with water, deionized water, and electrodeposition coating was performed without drying, thereby forming a coating film.

<Metal surface treatment liquid 3>
(A) Fluorozirconic acid: 300 ppm as Zr
(B) Titanium nitrate: 50 ppm as Ti
(C) Copper nitrate: 10 ppm as Cu
(D) Aluminum nitrate: 200 ppm as Al
(E) Zinc nitrate: 2000 ppm as Zn
(F) Ferrous sulfate: 100 ppm as Fe

Example 4
A metal surface treatment treatment solution 4 was prepared, and surface treatment was performed on the three types of metal materials cleaned by the above-described method and a box described later to form a surface treatment film layer.
Here, in preparing the metal surface treatment solution 4, the following components (A) to (E) were first added in this order so as to have the following concentrations, followed by stirring at room temperature for 20 minutes. Subsequently, it heated to predetermined temperature (35 degreeC), pH was adjusted to 3.5 using aqueous ammonia, and the metal surface treatment processing liquid 4 was obtained.
Further, the surface treatment using the metal surface treatment solution 4 was performed under the surface treatment condition 1 described above.
Thereafter, the metal material after the surface treatment was washed with water, deionized water, and electrodeposition coating was performed without drying, thereby forming a coating film.

<Metal surface treatment liquid 4>
(A) Fluorotitanic acid: 100 ppm as Ti
(B) Zirconium nitrate: 100 ppm as Zr
(C) Tin chloride: 20 ppm as Sn
(D) Zinc nitrate: 500 ppm as Zn
(E) Aluminum nitrate: 10 ppm as Al

(Example 5)
A treatment liquid 5 for metal surface treatment was prepared, and the surface treatment film layer was formed by performing surface treatment of the three kinds of metal materials cleaned by the above-described method and a box described later.
Here, in preparation of the metal surface treatment solution 5, first, the following components (A) to (E) were added in this order so as to have the following concentrations, followed by stirring at room temperature for 20 minutes. Subsequently, it heated to predetermined temperature (40 degreeC), pH was adjusted to 4.0 using aqueous ammonia, and the metal surface treatment processing liquid 5 was obtained.
Further, the surface treatment using the metal surface treatment solution 5 was performed under the surface treatment condition 2 described above.
Thereafter, the metal material after the surface treatment was washed with water, deionized water, and electrodeposition coating was performed without drying, thereby forming a coating film.

<Metal surface treatment liquid 5>
(A) Fluorozirconic acid: 100 ppm as Zr
(B) Basic copper carbonate: 50 ppm as Cu
(C) Zinc nitrate: 500 ppm as Zn
(D) Aluminum nitrate: 20 ppm as Al
(E) Colloidal silica (Snowtex O, manufactured by Nissan Chemical Industries): 200 ppm

(Example 6)
A treatment liquid 6 for metal surface treatment was prepared, and the surface treatment film layer was formed by performing surface treatment of the three kinds of metal materials cleaned by the above-described method and a box described later.
Here, in preparation of the metal surface treatment solution 6, first, the following components (A) to (E) were added in this order so as to have the following concentrations, followed by stirring at room temperature for 20 minutes. Subsequently, it heated to predetermined temperature (35 degreeC), pH was adjusted to 4.0 using ammonia water, and the metal surface treatment processing liquid 6 was obtained.
Further, the surface treatment using the metal surface treatment liquid 6 was performed under the surface treatment condition 1 described above.
Thereafter, the metal material after the surface treatment was washed with water, deionized water, and electrodeposition coating was performed without drying, thereby forming a coating film.

<Metal surface treatment liquid 6>
(A) Fluorotitanic acid: 100 ppm as Ti
(B) Indium nitrate: 20 ppm as In
(C) Copper nitrate: 30 ppm as Cu
(D) Zinc nitrate: 2000 ppm as zinc
(E) Ferrous sulfate: 50 ppm as Fe

(Example 7)
A metal surface treatment solution 7 was prepared, and the surface treatment film layer was formed by performing the surface treatment of the three types of metal materials cleaned by the above-described method and the box described below.
Here, in preparing the metal surface treatment solution 7, the following components (A) to (D) were first added in this order so as to have the following concentrations, followed by stirring at room temperature for 20 minutes. Subsequently, it heated to predetermined temperature (35 degreeC), pH was adjusted to 4.0 using ammonia water, and the metal surface treatment processing liquid 7 was obtained.
Further, the surface treatment using the metal surface treatment solution 7 was performed under the surface treatment condition 1 described above.
Thereafter, the metal material after the surface treatment was washed with water, deionized water, and electrodeposition coating was performed without drying, thereby forming a coating film.

<Metal surface treatment liquid 7>
(A) Fluorozirconic acid: 200 ppm as Zr
(B) Copper nitrate: 20 ppm as Cu
(C) Zinc nitrate: 2000 ppm as Zn
(D) Diallylamine salt polymer (PAS-20CL, manufactured by Nittobo): 50 ppm

(Example 8)
A surface treatment film 8 was prepared by preparing a metal surface treatment solution 8 and subjecting the three kinds of metal materials cleaned by the above-described method and a surface treatment of a box to be described later.
Here, in preparation of the metal surface treatment solution 8, first, the following components (A) to (C) were added in this order so as to have the following concentrations, followed by stirring at room temperature for 20 minutes. Subsequently, it heated to predetermined temperature (35 degreeC), pH was adjusted to 3.0 using aqueous ammonia, and the metal surface treatment processing liquid 8 was obtained.
Further, the surface treatment using the metal surface treatment solution 8 was performed under the surface treatment condition 1 described above.
Thereafter, the metal material after the surface treatment was washed with water, deionized water, and electrodeposition coating was performed without drying, thereby forming a coating film.

<Metal surface treatment liquid 8>
(A) Fluorozirconic acid: 200 ppm as Zr
(B) Sodium tellurate: 50 ppm as Te
(C) Diallyldimethylammonium salt polymer (PAS-H1L, manufactured by Nittobo): 50 ppm

Example 9
A metal surface treatment treatment liquid 9 was prepared, and surface treatment was performed on the three types of metal materials cleaned by the above-described method and a box described below to form a surface treatment film layer.
Here, in preparation of the metal surface treatment solution 9, the following components (A) to (D) were first added in this order so as to have the following concentrations, followed by stirring at room temperature for 20 minutes. Subsequently, it heated to predetermined temperature (35 degreeC), pH was adjusted to 4.5 using aqueous ammonia, and the metal surface treatment processing liquid 9 was obtained.
Further, the surface treatment using the metal surface treatment liquid 9 was performed under the surface treatment condition 1 described above.
Thereafter, the metal material after the surface treatment was washed with water, deionized water, and electrodeposition coating was performed without drying, thereby forming a coating film.

<Metal surface treatment liquid 9>
(A) Fluorotitanic acid: 100 ppm as Ti
(B) Basic copper carbonate: 50 ppm as Cu
(C) Sodium ethylenediaminetetraacetate: 50 ppm
(D) Tannic acid: 100 ppm

(Example 10)
A treatment liquid 10 for metal surface treatment was prepared, and surface treatment of the three types of metal materials cleaned by the above-described method and a box described later was performed to form a surface treatment film layer.
Here, in preparation of the metal surface treatment solution 10, the following components (A) to (C) were first added in this order so as to have the following concentrations, followed by stirring at room temperature for 20 minutes. Subsequently, it heated to predetermined temperature (35 degreeC), pH was adjusted to 3.5 using aqueous ammonia, and the metal surface treatment processing liquid 10 was obtained.
Further, the surface treatment using the metal surface treatment solution 10 was performed under the surface treatment condition 1 described above.
Thereafter, the metal material after the surface treatment was washed with water, deionized water, and electrodeposition coating was performed without drying, thereby forming a coating film.

<Treatment solution 10 for metal surface treatment>
(A) Fluorozirconic acid: 100 ppm as Zr
(B) Potassium tellurite: 50 ppm as Te
(C) Sodium nitrilotriacetate: 100 ppm

Example 11
A metal surface treatment solution 11 was prepared, and surface treatment was performed on the three types of metal materials cleaned by the above-described method and a box described later, thereby forming a surface treatment film layer.
Here, in preparation of the metal surface treatment solution 11, the following components (A) to (D) were first added in this order so as to have the following concentrations, followed by stirring at room temperature for 20 minutes. Subsequently, it heated to predetermined temperature (35 degreeC), pH was adjusted to 4.0 using aqueous ammonia, and the metal surface treatment processing liquid 11 was obtained.
Further, the surface treatment using the metal surface treatment solution 11 was performed under the surface treatment condition 1 described above.
Thereafter, the metal material after the surface treatment was washed with water, deionized water, and electrodeposition coating was performed without drying, thereby forming a coating film.

<Treatment solution 11 for metal surface treatment>
(A) Fluorozirconic acid: 100 ppm as Zr
(B) Fluorotitanic acid: 20 ppm as Ti
(C) Copper nitrate: 50 ppm as Cu
(D) γ-aminopropyltriethoxysilane: 100 ppm

(Example 12)
A treatment liquid 12 for metal surface treatment was prepared, and surface treatment of the three types of metal materials cleaned by the above-described method and a box described later was performed to form a surface treatment film layer.
Here, in preparing the metal surface treatment solution 12, the following components (A) to (D) were first added in this order so as to have the following concentrations, followed by stirring at room temperature for 20 minutes. Subsequently, it heated to predetermined temperature (35 degreeC), pH was adjusted to 3.0 using ammonia water, and the metal surface treatment processing liquid 12 was obtained.
Further, the surface treatment using the metal surface treatment liquid 12 was performed under the surface treatment condition 1 described above.
Thereafter, the metal material after the surface treatment was washed with water, deionized water, and electrodeposition coating was performed without drying, thereby forming a coating film.

<Metal surface treatment liquid 12>
(A) Fluorozirconic acid: 100 ppm as Zr
(B) Sodium tellurite: 50 ppm as Te
(C) Copper nitrate: 20 ppm as Cu
(D) Polyethyleneimine (SP-006, manufactured by Nippon Shokubai Co., Ltd.): 20 ppm

(Comparative Example 1)
A metal surface treatment treatment liquid 13 was prepared, and the surface treatment film layer was formed by performing the surface treatment of the three types of metal materials cleaned by the above-described method and the box described below.
Here, in preparing the metal surface treatment solution 13, the following components (A) to (D) were first added in this order so as to have the following concentrations, followed by stirring at room temperature for 20 minutes. Subsequently, it heated to predetermined temperature (35 degreeC), pH was adjusted to 3.5 using aqueous ammonia, and the metal surface treatment processing liquid 13 was obtained.
Further, the surface treatment using the metal surface treatment liquid 13 was performed under the surface treatment condition 1 described above.
Thereafter, the metal material after the surface treatment was washed with water, deionized water, and electrodeposition coating was performed without drying, thereby forming a coating film.

<Treatment liquid 13 for metal surface treatment>
(A) Fluorozirconic acid: 100 ppm as Zr
(B) Titanium nitrate: 100 ppm as Ti
(C) Zinc nitrate: 2000 ppm as Zn
(D) Aluminum nitrate: 200 ppm as Al

(Comparative Example 2)
A metal surface treatment solution 14 was prepared, and the surface treatment film layer was formed by performing the surface treatment of the three types of metal materials cleaned by the above-described method and the box described below.
Here, in preparation of the metal surface treatment solution 14, first, the following components (A) and (B) were added in this order so as to have the following concentrations, followed by stirring at room temperature for 20 minutes. Subsequently, it heated to predetermined temperature (40 degreeC), pH was adjusted to 3.5 using aqueous ammonia, and the metal surface treatment processing liquid 14 was obtained.
The surface treatment using the metal surface treatment solution 14 was performed under the surface treatment condition 2 described above.
Thereafter, the metal material after the surface treatment was washed with water, deionized water, and electrodeposition coating was performed without drying, thereby forming a coating film.

<Metal surface treatment liquid 14>
(A) Zirconium nitrate: 1000 ppm as Zr
(B) Magnesium nitrate: 2000 ppm as Mg

(Comparative Example 3)
A metal surface treatment solution 15 was prepared, and the surface treatment film layer was formed by performing the surface treatment of the three types of metal materials cleaned by the above-described method and the box described below.
Here, preparation of the metal surface treatment solution 15 was performed by first adding the following component (A) so as to have the following concentration and stirring at room temperature for 20 minutes. Subsequently, it heated to predetermined temperature (40 degreeC), pH was adjusted to 7.0 using nitric acid water, and the metal surface treatment processing liquid 15 was obtained.
Further, the surface treatment using the metal surface treatment solution 15 was performed under the surface treatment condition 1 described above.
Thereafter, the metal material after the surface treatment was dried without being washed with water by the method described above, and then electrodeposition coating was performed to form a coating film.

<Metal surface treatment liquid 15>
(A) Sodium tellurite: 2000 ppm as Te

(Comparative Example 4)
A treatment liquid 16 for metal surface treatment was prepared, and the surface treatment film layer was formed by performing the surface treatment of the three types of metal materials cleaned by the above-described method and the box described below.
Here, in preparing the metal surface treatment solution 16, the following components (A) to (D) were first added in this order so as to have the following concentrations, followed by stirring at room temperature for 20 minutes. Subsequently, it heated to predetermined temperature (35 degreeC), pH was adjusted to 7.0 using aqueous ammonia, and the metal surface treatment processing liquid 16 was obtained.
Further, the surface treatment using the metal surface treatment liquid 16 was performed under the surface treatment condition 1 described above.
Thereafter, the metal material after the surface treatment was washed with water, deionized water, and electrodeposition coating was performed without drying, thereby forming a coating film.

<Metal surface treatment liquid 16>
(A) Fluorozirconic acid: 100 ppm as Zr
(B) Sodium tellurite: 50 ppm as Te
(C) Colloidal silica (Snowtex C, manufactured by Nissan Chemical Co., Ltd.): 200 ppm
(D) Zinc nitrate: 2000 ppm as Zn

(Comparative Example 5)
Using the metal surface treatment liquid 13, three types of metal materials cleaned by the above-described method and a surface treatment of a box described later were performed to form a surface treatment film layer.
The surface treatment using the metal surface treatment solution 13 was performed by applying the above-described surface treatment condition 1 and then applying a 0.1% fine particle tin oxide dispersion and drying.
Thereafter, the metal material after the surface treatment was washed with water, deionized water, and electrodeposition coating was performed without drying, thereby forming a coating film.

(Comparative Example 6)
Using the above-described metal surface treatment liquids 12 and 14, the surface treatment film layer was formed by performing surface treatment of the three types of metal materials cleaned by the above-described method and the box described below.
First, the surface treatment using the metal surface treatment solution 12 was performed under the surface treatment condition 2 described above, and copper and tellurium were precipitated in the form of particles.
Next, surface treatment was performed using the metal surface treatment solution 14 under the following conditions.
Thereafter, the metal material after the surface treatment was dried without being washed with water by the method described above, and then electrodeposition coating was performed to form a coating film.
(1) Processing temperature: 50 ° C
(2) Treatment time: 300 seconds (3) Contact method: Immersion (4) Flow velocity during contact: 5 cm / second

(Comparative Example 7)
A metal surface treatment solution 17 was prepared, and the surface treatment film layer was formed by performing the surface treatment of the three types of metal materials cleaned by the above-described method and the box described below.
Here, in preparation of the metal surface treatment solution 17, first, the following component (A) was added so as to have the following concentration, followed by stirring at room temperature for 20 minutes. Subsequently, it heated to predetermined temperature (35 degreeC), and the metal surface treatment process liquid 17 of pH 8.0 was obtained, without adjusting pH.
Further, the surface treatment using the metal surface treatment liquid 17 was performed under the surface treatment condition 1 described above.
Thereafter, the metal material after the surface treatment was dried without being washed with water by the method described above, and then electrodeposition coating was performed to form a coating film.

<Metal surface treatment liquid 17>
(A) Zirconia sol (ZR-40BL, manufactured by Nissan Chemical Industries): 1000 ppm

(Comparative Example 8)
Using a 5% aqueous solution of a zinc phosphate chemical conversion treatment agent (Palbond (registered trademark) L3020, manufactured by Nihon Parkerizing Co., Ltd.), surface treatment was performed under the following conditions.
Thereafter, the metal material after the surface treatment was dried without being washed with water by the method described above, and then electrodeposition coating was performed to form a coating film.
(1) Processing temperature: 35 ° C
(2) Treatment time: 120 seconds (3) Contact method: Immersion (4) Flow velocity during contact: 10 cm / second

[Metal adhesion after surface treatment]
The metal adhesion amount (mg / m ² ) in the surface-treated metal material after the surface treatment was quantified with a fluorescent X-ray analyzer (ZSX Primus, manufactured by Rigaku Corporation).
The metal material used for the measurement was washed with water after the surface treatment, washed with deionized water, and dried in cold air.

[Surface condition of surface treatment film]
Using a field emission scanning electron microscope (S-4700-TYPEII, manufactured by Hitachi, Ltd.), surface analysis of the surface-treated metal material after surface treatment was performed, and the maximum average of semiconductor particles in the surface-treated film (amorphous film) Particle size, surface coverage and density were measured.
3A to 3C show SEM images (30000 times) of the surface treatment films measured in Comparative Example 1, Example 1 and Example 2, respectively.
Further, the ratio of metal to oxide (hydroxide) in the semiconductor particles was measured by X-ray photoelectron spectroscopy (ESCA-850M, manufactured by Shimadzu Corporation).
In Tables 1 to 3 below, in Comparative Example 4, since the semiconductor particles could not be confirmed, the maximum average particle diameter was described as “None”, and in Comparative Example 5, the semiconductor particles were formed on the amorphous film. Therefore, the coverage is described as “over 90% on the film”, and in Comparative Example 6, since the semiconductor particles were hidden in the amorphous film, the coverage was described as “concealment”.

[Film thickness of electrodeposition coating]
The film thickness of the metal material after electrodeposition coating is shown as follows: when the metal material is SPC or GA, an electromagnetic film thickness meter (LZ-200, manufactured by Kett Science Laboratory), and when the metal material is AL, the vortex It measured using the electric current type film thickness meter, and confirmed that it was 20 micrometers.

[Paint adhesion (adhesion)]
The painted surface of the electrodeposited metal material was cut into a grid so that there were 100 grids.
Subsequently, after immersing in boiling water for 1 hour, water was wiped and tape peeling was performed.
The paint adhesion was evaluated by observing the state of the grid after peeling and the number of grids that were not peeled. It can be evaluated that the closer to 100, the better the paint adhesion.

[Corrosion resistance]
The coated surface of the electrodeposited metal material was cross-cut and subjected to a salt spray test (JIS-Z2371), and the one-side swollen width of the cross-cut portion after 1000 hours was measured.
In general, it can be evaluated as good if it is 3 mm or less for a cold-rolled steel sheet, good if it is 3 mm or less for an galvannealed steel sheet, and good if it is 2 mm or less for an aluminum alloy sheet.

[Circuitability with electrodeposition coating]
FIG. 4 is a sketch drawing of a box used for the throwing power test of electrodeposition coating (four-sheet box test).
As shown in FIG. 4, four metal plates 12 to 15 of the same kind were prepared, and a hole 10 having a diameter of 8 mm was formed in three of the metal plates 12 to 14 among them. The position of the hole 10 was 50 mm from the center in the lateral direction and from the lower end.
The four metal plates 12 to 15 were assembled with a clearance of 20 mm as shown in FIG.
The both sides and the lower surface of the metal plates 12 to 15 were closed with the vinyl chloride plates 21 to 23, and the vinyl chloride plates 21 to 23 and the metal plates 12 to 15 were fixed with the adhesive tape, and the four-sheet box 1 was assembled.

The assembled box was subjected to the surface treatment shown in each of the above experimental examples, and electrodeposition coating was performed without drying.
Here, as the counter electrode, a stainless steel plate (SUS304) 70 × 150 × 0.55 mm whose one surface was sealed with an insulating tape was used. The liquid level of the electrodeposition paint was controlled at a position where the metal plates 12 to 15 and the counter electrode were immersed 90 mm.
Electrodeposition coating was carried out with the temperature of the electrodeposition paint maintained at 28 ° C. and stirring with a stirrer. After all of the four metal plates 12 to 15 were short-circuited, a coating film was electrolytically deposited by a cathode electrolysis method using a rectifier with the counter electrode as an anode. The electrolysis was performed by applying a voltage linearly from 0 V to 230 V in the direction of the cathode over 30 seconds, and then maintaining 230 V for 150 seconds.
After the electrolysis, each of the metal plates 12 to 15 was washed with water and baked at 170 ° C. for 20 minutes to form a coating film. The counter electrode side of the metal plate 12 closest to the counter electrode is the A surface, the counter electrode side of the metal plate 15 furthest from the counter electrode is the G surface, the coating thickness of the A surface and the G surface is measured, and the ratio of A / G is determined. It was used as an indicator of the throwing power of electrodeposition coating.
Here, the film thickness of the coating film in the four-box test is as follows. When the metal material is SPC or GA, the electromagnetic film thickness meter (LZ-200, manufactured by Kett Science Laboratory Co., Ltd.) is used. It measured using the electric current type film thickness meter.
In this coating material, the G-side coating film thickness is preferably 7 μm or more, and an A / G ratio of 2.0 to 2.5 is judged to be good.

From the results shown in Tables 1 to 3 above, a surface-treated metal material having a surface-treated film in which semiconductor particles are present in a predetermined form (exposed) with a predetermined coverage, particle diameter and density in the amorphous film (implementation) It can be seen that Examples 1 to 12) are excellent in both corrosion resistance and reversibility with electrodeposition coating, and excellent in paint adhesion.

1 Box 10 Hole 12 Test plate (metal plate after painting) No. 1 1 (outside: A side)
13 Test plate (metal plate after painting) No. 2
14 Test plate (metal plate after painting) No. 3
15 Test plate (metal plate after painting) No. 4 (Inside: G side)
21 Side partition plate 22 Side partition plate 23 Bottom partition plate 30 Surface treatment metal material 31 Metal material 32 Amorphous film 33 Semiconductor particle 34 Surface treatment film 35 Core

Claims (13)

1. A surface-treated metal material obtained by surface-treating a metal material,
   The surface of the metal material has an amorphous film and a surface-treated film containing semiconductor particles having a maximum average particle size of 5 to 300 nm,
   The surface coverage of the semiconductor particles in the surface treatment film is 10 to 90%,
   The semiconductor particles are exposed from the surface of the surface treatment film,
   A surface-treated metal material, wherein the semiconductor particles have a density of 5 to 10,000 particles / μm ² .
2. The amorphous film contains at least one element selected from the group consisting of Zr, Ti and Hf;
   The surface-treated metal material according to claim 1, wherein the semiconductor particles contain at least one element selected from the group consisting of Sn, In, Te, and Cu.
3. The amount of the element-converted adhesion of the element contained in the amorphous film is 5 to 200 mg / m ² ;
   The surface-treated metal material according to claim ² , wherein the amount of the element-converted adhesion of the element contained in the semiconductor particles is 1 to 100 mg / m ² .
4. The surface-treated metal material according to any one of claims 1 to 3, wherein the metal material is at least one metal material selected from the group consisting of iron-based metal materials, zinc-based metal materials, and aluminum-based metal materials.
5. First to third surface-treated metal materials having a length of 150 mm and a width of 70 mm and having a hole with a diameter of 8 mm at a position 50 mm from the lower end of the center in the horizontal direction, and a fourth having a length of 150 mm and a width of 70 mm The surface-treated metal materials are installed in parallel in this order with an interval of 20 mm,
   Each of the first to fourth surface-treated metal materials is immersed in an electrodeposition coating bath from the lower end to a position of 95 mm,
   A counter electrode is installed on the surface side of the first surface-treated metal material where the second surface-treated metal material is not installed, and electrodeposition coating is performed under the following conditions (a) to (c):
   The coating thickness ratio (A / G) of the surface on the counter electrode side (A surface) of the first surface-treated metal material and the surface on the counter electrode side (G surface) of the fourth surface-treated metal material is 3.0. A surface-treated metal material that can be:
   (A) Electrodeposition paint temperature: 28 ° C
   (B) Electrolytic conditions: A voltage is applied linearly from 0 V to 230 V over 30 seconds and then held at 230 V for 150 seconds. (C) Firing conditions: 170 ° C., 20 minutes
6. Surface treatment liquid containing at least one element selected from the group consisting of Zr, Ti and Hf in the metal material and containing at least one element selected from the group consisting of Sn, In, Te and Cu The metal surface treatment method for obtaining the surface-treated metal material according to any one of claims 1 to 5, wherein the surface-treated metal material is contacted at a flow rate of 1 to 10 cm / sec.
7. The surface treatment liquid contains 1 to 10,000 ppm of at least one element selected from the group consisting of Zr, Ti and Hf, and contains at least one element selected from the group consisting of Sn, In, Te and Cu The metal surface treatment method according to claim 6, which contains 1 to 5000 ppm and has a pH of 2.0 to 6.0.
8. Zr contained in the surface treatment solution is zirconium sulfate, zirconium oxysulfate, ammonium zirconium sulfate, zirconium nitrate, zirconium oxynitrate, zirconium nitrate ammonium, zirconium sulfate, zirconium oxysulfate, ammonium zirconium sulfate, zirconium nitrate, zirconium oxynitrate, The metal surface treatment method according to claim 6 or 7, comprising at least one selected from the group consisting of ammonium zirconium nitrate, fluorozirconic acid, and fluorozirconium complex salt.
9. Ti contained in the surface treatment liquid is titanium sulfate, titanium oxysulfate, titanium ammonium sulfate, titanium nitrate, titanium oxynitrate, titanium ammonium nitrate, titanium sulfate, titanium oxysulfate, ammonium titanium sulfate, titanium nitrate, titanium oxynitrate, The metal surface treatment method according to any one of claims 6 to 8, which is contained as at least one selected from the group consisting of titanium ammonium nitrate, fluorotitanic acid and fluorotitanium complex salt.
10. 10. The metal surface treatment method according to claim 6, wherein Sn contained in the surface treatment liquid is contained as at least one selected from the group consisting of tin nitrate, tin sulfate and tin fluoride.
11. The In contained in the surface treatment liquid is contained as at least one selected from the group consisting of indium nitrate, indium sulfate, indium sulfamate, indium fluoride, indium oxide, and indium hydroxide. The metal surface treatment method according to any one of the above.
12. Te contained in the surface treatment liquid is contained as at least one selected from the group consisting of telluric acid, potassium tellurate, sodium tellurite, telluric acid, potassium tellurite, sodium tellurite and tellurium dioxide. The metal surface treatment method according to any one of claims 6 to 11.
13. Cu contained in the surface treatment liquid is selected from the group consisting of copper nitrate, copper sulfate, copper chloride, copper carbonate, basic copper carbonate, copper oxide, copper acetate, copper hydroxide, copper fluoride and copper sulfide. The metal surface treatment method according to any one of claims 6 to 12, which is contained as at least one kind.

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