JP2001172770A - Method for producing surface treated metallic sheet and surface treated metallic sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a surface treated metallic sheet excellent in the maintainability of the working environment and moreover excellent in corrosion resistance, formability and adhesion for a coating film and to provide a surface treated metallic sheet produced by using the production method. SOLUTION: Using a treating solution consisting of a binder composed of an inorganic compound, electrically conductive powder and/or metallic ions, a pretreating film composed of sollike hydrated oxide, electrically conductive substance and metal is deposited directly on a metallic sheet or no a plated metallic sheet, and, after water-washing, the same is dried, or without executing water washing, the same is dried as it is.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a surface-treated metal sheet and a surface-treated metal sheet prepared by using the method. More specifically, the present invention relates to a method for producing a surface-treated metal sheet capable of improving the corrosion resistance, moldability, and coating film adhesion of the metal sheet, and a surface-treated metal sheet produced using the method.

[0002]

2. Description of the Related Art Metal sheets such as cold-rolled steel sheets and aluminum alloy sheets are inexpensive and have excellent mechanical properties, but when used in a rolled state, they are easily rusted.
In terms of corrosion resistance and coating adhesion when painted,
Many troubles occur in practical use. Therefore, the metal plate after rolling is subjected to a surface treatment such as plating or anodizing treatment. In addition, in order to obtain sufficient corrosion resistance, a coating is often further applied thereon. In order to improve the adhesion between the coating and the metal plate by this coating, surface treatment such as phosphate treatment or chromate treatment is applied directly on the metal plate or on the plating applied to the metal plate. Is done.

[0003] However, such conventional surface treatments have a number of disadvantages inherent in them, and improvements are required. For example, in the conventional chromate treatment of galvanized steel sheet, zinc reacts with a chemical conversion treatment agent in a treatment tank to generate sludge, and it is necessary to improve work environment conservation and economy. As a remedy, a coating type chromate treatment that does not require a treatment tank has been developed, but it is not satisfactory in characteristics such as environmental protection and moldability, and further improvement is required.

[0004]

SUMMARY OF THE INVENTION In the present invention, in order to solve the above-mentioned drawbacks of the prior art, a surface treatment which is excellent in the preservation of working environment and excellent in corrosion resistance, molding workability and coating film adhesion. An object of the present invention is to provide a method for manufacturing a metal plate and a surface-treated metal plate prepared by using the method.

[0005]

According to a first aspect of the present invention, there is provided a method for producing a surface-treated metal sheet, comprising: at least one kind of a binder comprising an inorganic compound; at least one kind of a conductive powder; In an aqueous solution having a pH of 2 to 11 consisting of at least one of the following, after performing a cathode treatment on the metal plate to form a film composed of a sol-like hydrated oxide, a conductive substance, and a metal on the metal plate, Then, it is characterized by drying as it is after washing or without washing. The method for producing a surface-treated metal sheet according to claim 2 includes at least one kind of a binder composed of an inorganic compound;
In an aqueous solution having a pH of 2 to 11 and at least one kind of conductive powder, a metal plate was subjected to cathodic treatment to form a film composed of a sol-like hydrated oxide and a conductive material on the metal plate. After that, it is characterized in that it is dried as it is without or after washing with water. The method for producing a surface-treated metal plate according to claim 3, wherein the binder comprising the inorganic compound is any one of an alkali metal salt, an acidic metal salt, a colloid metal oxide, a metal alkoxide, a metal acylate, and an organic / inorganic hybrid resin. There is a feature. The method for producing a surface-treated metal plate according to claim 4, wherein the conductive powder is titanium, zinc,
It is characterized by being any one of powder of tin, nickel, copper, aluminum and carbon, or an alloy powder composed of two or more of these. The method for producing a surface-treated metal sheet according to claim 5, wherein the metal ion supply substance is an ion derived from any of aluminum, chromium, molybdenum, tungsten, titanium, zirconium, vanadium, cerium, zinc, tin, nickel, cobalt, and copper. Characterized in that it is a supply material of 7. The surface-treated metal sheet according to claim 6, wherein the sol-like hydrated oxide having a thickness of 0.05 to 3 μm and a conductive material are formed on the metal sheet by using any one of the above-described methods for producing a surface-treated metal sheet. And a film comprising:

[0006]

DETAILED DESCRIPTION OF THE INVENTION In the present invention, a metal or a metal plate is plated directly or on a metal plate by using a binder and a conductive powder made of an inorganic compound, or a processing solution containing a metal ion. It has been found that the object of the present invention can be achieved by forming a film made of a sol-like hydrated oxide and a conductive substance on a plate.

Hereinafter, the present invention will be described in detail. First, as a metal sheet applicable to the present invention, in addition to a cold-rolled steel sheet in an as-rolled state, a hot-dip coated steel sheet, an electroplated steel sheet,
Includes plated steel sheets such as composite plated steel sheets and vapor-deposited plated steel sheets. Metals to be plated include zinc, tin, aluminum, nickel, copper, chromium, and alloys thereof. In addition to the cold-rolled steel sheet and the plated steel sheet, an aluminum sheet, an aluminum alloy sheet, a copper sheet, a copper alloy sheet, a stainless steel sheet and the like can be mentioned.

Next, the processing liquid used for forming the pretreatment film will be described. As the binder composed of an inorganic compound contained in the treatment liquid, those generally used as binders for inorganic paints can be applied as they are. Examples include silicates such as sodium silicate, potassium silicate, and lithium silicate; alkali metal salts such as zirconium salts including alkali zirconium; acidic metal salts such as aluminum phosphate; aluminum, tin, nickel, and cobalt. Colloidal metal oxides such as zinc, vanadium, zirconium, metal alkoxides such as tetrabutyl zirconate and tetrabutyl titanate, and other metal salts such as silicon acylate, silicon acetate, and aluminum stearate. Metal acylates, metal acylates such as alkyl metals such as triethylaluminum, organopolysiloxanes such as silicone resins, organoalkoxysilanes such as methyltrimethoxysilane, tetrabutyl Zirconia Silicon, including Rujirukoneto and silicone resin, and organic / inorganic hybrid resins such as acrylic silicates and the like, including silicic acid amine and an acrylic resin.

As the conductive powder contained in the processing liquid, any conductive powdery substance can be used, and it is not particularly limited. From the economic viewpoint, titanium and zinc are used. , Tin, nickel, copper, aluminum, carbon, or an alloy powder thereof is preferably used. The fine particles preferably have a maximum diameter of about 3 μm from the fine particles in the state of the colloidal region.

[0010] Further, the processing solution further contains ion supply substances such as aluminum, chromium, molybdenum, tungsten, titanium, zirconium, vanadium, cerium, and the like.
Zinc, tin, nickel, cobalt, copper and the like may be contained. Among them, zinc, tin, nickel, cobalt, copper, etc. are present in the processing liquid as these ions,
Depending on the pH of the aqueous solution, it may be present as zincate ions or stannate ions. For metals other than these metals, chromate ions, molybdate ions,
Tungstate ions, titanate ions, vanadate ions, or oxysalts of these metals, or compounds of these ions are present in the processing solution. The ion supply substance used in the present invention can be applied as long as it can be dissolved in the processing solution, and is not limited to the above metal compounds. By treating in a treatment liquid containing a binder made of the above-mentioned inorganic compound and conductive powder, or in a treatment liquid further containing these ion-supplying substances, a film made of sol and a conductive substance is formed. The addition of metal ions densifies the sol that forms the film, improves the adhesion with the organic / inorganic hybrid film that is formed on the sol, promotes the formation of a strong main treatment film, and improves corrosion resistance, moldability, Improves properties such as coating adhesion.

Next, a method of forming a film will be described. One or more binders composed of the inorganic compound, one or more conductive powders, and one or more ion donors are dissolved in water at a concentration of 5 to 300 g / l to obtain a treatment liquid. At this time, the concentration of the conductive powder is 5 to 100.
g / l. If it is less than 5 g / l, no improvement in corrosion resistance is observed, and if it exceeds 100 g / l, the treatment liquid becomes unstable, which is not preferable. When the concentration of all the components in the treatment liquid is less than 5 g / l, the deposition efficiency of the film is remarkably reduced. Will be The pH of the treatment liquid is preferably in the range of 2 to 11, and more preferably in the range of 3 to 10. p
When H is less than 2 or more than 11, the efficiency of forming a hydrated oxide decreases. The pH is adjusted by adding an organic or inorganic acidic or alkaline solution.

[0012] The ionicity of the binder comprising the above-mentioned inorganic compound may be affected by the pH of the processing solution. For example, in a treatment solution having a pH of 4, the hydrated aluminum sol is positively charged, while the silica sol is negatively charged. When both are mixed, they are often positively charged. In these cases, it is preferable to use a cathodic electrolytic treatment for deposition of the film. As described above, in order to select an optimal method for depositing a film, it is necessary to check the ionicity of the binder made of an inorganic compound in advance. Further, in order to maintain the treatment liquid stably or to improve the deposition state of the film, a commonly used surfactant can be added.

The above-mentioned film can be obtained by immersing the metal plate in the treatment solution and then drying and solidifying the metal plate. However, the metal plate is subjected to a cathode treatment in the treatment solution. You can also get. The current density is 0.1 ~
A range of 50 A / dm ² is preferred. The temperature of the processing solution is 2
A range from 0 to 50C is preferred. Although the processing time depends on the thickness of the film, a range of 0.5 to 10 seconds is practical. According to the Hull cell test, the temperature of the processing solution is on the low temperature side,
As for the current density, a sol is easily formed on the high temperature side, but a brittle sol tends to be formed. Further, since the current density and the processing time are related to the film thickness of the film, it is preferable to select a practical temperature range and current density of the processing solution in consideration of the film thickness of the film generated by the Hull cell test in advance. The thickness of the treated film obtained as described above is preferably 0.05 to 3 μm. If the thickness is less than 0.05 μm, the effect of improving the properties is not so small.

After the treatment film is formed on the metal plate as described above, it is dried as it is or immediately after washing with water. Regarding the presence or absence of water washing after forming the film, when acids or alkalis are added for adjusting the pH of the processing solution, these acids and alkalis remain in the film and decrease the corrosion resistance and coating film adhesion. Therefore, it is preferable to wash with water.

The surface-treated metal plate obtained by forming the coating of the present invention on the above-described plated steel plate, aluminum alloy plate, stainless steel plate, or copper alloy plate is not only used as a surface-treated plate for coating undercoating but also coated. It can be applied to any unpainted applications as it is, and since the surface treatment film has conductivity, it can also be applied to applications requiring conductivity.

[0016]

The present invention will be described in more detail with reference to the following examples. (Example) [Metal plate] As a substrate used for the surface-treated metal plate of the present invention, a metal plate shown in Table 1 having a thickness of 0.3 mm was buff-polished, and then subjected to electrolytic alkali degreasing treatment and pickling treatment. Used metal plate. In Table 1, the cold-rolled steel sheet is SS,
Each hot-dip coated steel sheet (galvanized steel sheet, Zn-5% Al alloy coated steel sheet, aluminum-coated steel sheet)
n (H), Zn-5% Al (H), Al (H), electroplated steel sheet (galvanized steel sheet, Zn-2% Co-0.5
% Mo plated steel sheet, nickel plated steel sheet, tin plated steel sheet, copper plated steel sheet, chrome plated steel sheet)
n (E), Zn-2% Co (E), Ni (E), Sn
(E), Cr (E), vacuum-deposited galvanized steel sheet
(V), the aluminum alloy plate is made of AlS, and the copper plate is made of Cu
In S, a stainless steel plate is shown by SUS. These metal plates were buffed before being subjected to the surface treatment of the present invention, and then subjected to electrolytic alkali degreasing treatment and pickling treatment to clean their surfaces.

On the metal plate whose surface was cleaned as described above, a film was formed using the treatment liquid shown in Table 1 under the conditions shown in Table 2.

[0018]

[Table 1]

[0019]

[Table 2]

[Evaluation of Characteristics] The corrosion resistance, coating film adhesion, and moldability of the surface-treated metal plate obtained as described above were evaluated under the following conditions. As comparative materials, commercially available materials, cold-rolled steel plate subjected to phosphoric acid treatment and chromate treatment (comparative material 1), tin-plated steel plate subjected to coating type chromate treatment (comparative material 2), and electricity A galvanized steel sheet subjected to a coating type chromate treatment (Comparative Material 3) was evaluated under the same conditions. [Corrosion resistance] An organic solvent-based acrylic resin paint is applied to the surface-treated metal plate so that the thickness after baking and curing becomes 15 μm.
Baked. After performing a salt spray test on the coated metal plate in accordance with JIS Z 2371 for 500 hours, the state of occurrence of blisters generated on the surface was visually observed and evaluated by the following rating. ：: No problem in practical use ×: Blister is recognized on the surface to the extent that there is a problem in practical use.

[Coating Adhesion] An organic solvent-based acrylic resin coating was applied to the surface-treated metal plate so as to have a thickness of 15 μm after baking and curing, followed by baking. The coated metal plate was drawn into a cylindrical cup shape at a draw ratio of 2.2, the coating on the side surface of the cup was forcibly peeled off with an adhesive tape, the degree of peeling of the coating was visually observed, and evaluated by the following rating. ：: No problem in practical use ×: Blister is recognized on the surface to the extent that there is a problem in practical use.

[Molding processability] An organic solvent-based acrylic resin paint was applied to a surface-treated metal plate so as to have a thickness of 15 μm after baking and curing, and baked. The coated metal plate was subjected to a DuPont impact tester (shape of impact applied portion: hemisphere having a radius of 1/2 inch, weight of impact applied portion: 500 g, drop height: 50).
cm), the coating film in the processed portion was forcibly peeled off with an adhesive tape, the degree of peeling of the coating film was visually observed, and evaluated according to the following rating. ：: No problem in practical use ×: Blister is recognized on the surface to the extent that there is a problem in practical use. Table 3 shows the above results.

[0023]

[Table 3]

As shown in Table 3, the surface-treated metal sheet coated with the treated film of the present invention has excellent corrosion resistance, coating film adhesion, and moldability.

[0025]

The present invention provides a binder comprising an inorganic compound,
Forming a film composed of sol-like hydrated oxide and a conductive substance directly on a metal plate or on a plated metal plate using a processing solution comprising a conductive powder or a metal ion. A method for producing a surface-treated metal sheet, and a surface-treated metal sheet using the method, the production method of the present invention is excellent in the preservation of working environment, and the surface-treated metal sheet using the production method has corrosion resistance. Excellent in molding processability and coating film adhesion.

 ──────────────────────────────────────────────────続 き Continuing from the front page (72) Inventor Katsumi Kanda 1296-1, Higashi-Toyoi, Kudamatsu-shi, Yamaguchi Prefecture Toyo Kohan Co., Ltd. F-term (Reference) 4K022 AA02 BA02 BA15 BA16 BA20 BA26 BA33 BA34 DA06 DA07 DA09 DB01 DB02 EA02 4K026 AA02 AA07 AA08 AA09 AA10 AA12 AA13 AA22 BA02 BA03 BA08 BB06 BB08 BB09 CA15 CA18 CA23 CA27 CA29 CA30 CA31 CA32 CA33 CA37 CA39 CA41 DA01 DA03 DA11 DA12 DA16

Claims (6)

[Claims] 1. A binder comprising at least one inorganic compound,
In a pH 2 to 11 aqueous solution containing at least one kind of conductive powder and at least one kind of metal ion supplying substance, the metal plate is subjected to cathodic treatment, and the sol-like hydrated oxide and conductive material are formed on the metal plate. A method for producing a surface-treated metal plate, comprising: forming a film made of a conductive substance, followed by washing with water or drying without washing with water. 2. A binder comprising at least one inorganic compound,
In an aqueous solution having a pH of 2 to 11 and at least one kind of conductive powder, a metal plate was subjected to cathodic treatment to form a film composed of a sol-like hydrated oxide and a conductive material on the metal plate. A method for producing a surface-treated metal sheet, characterized by drying after washing with water or without washing. 3. The binder according to claim 1, wherein the binder comprising the inorganic compound is any one of an alkali metal salt, an acidic metal salt, a colloid metal oxide, a metal alkoxide, a metal acylate, and an organic / inorganic hybrid resin. The method for producing a surface-treated metal sheet according to the above. 4. The method according to claim 1, wherein the conductive powder is any one of titanium, zinc, tin, nickel, copper, aluminum, and carbon, or an alloy powder of two or more of these. Or the method for producing a surface-treated metal sheet according to item 2. 5. The metal ion supply material according to claim 1, wherein the metal ion supply material is an ion supply material derived from any of aluminum, chromium, molybdenum, tungsten, titanium, zirconium, vanadium, cerium, zinc, tin, nickel, cobalt and copper. Item 2. A method for producing a surface-treated metal sheet according to Item 1. 6. A sol-like hydrated oxide having a thickness of 0.05 to 3 μm and a conductive substance on a metal plate by using the method for producing a surface-treated metal plate according to any one of claims 1 to 5. A surface-treated metal plate formed by forming a film consisting of