JPH0860381A - Two-pack lubricative chromating solution for metallic material surface and chromating method - Google Patents

Abstract

PURPOSE: To form a chromate film excellent in corrosion resistance and lubricity on the surface of a metallic material in a single coating stage. CONSTITUTION: A processing soln. at >=pH 2.5 is prepared from a chromate component soln. contg. a chromium(III) compd. sol and a lubricant component- contg. soln., and the processing soln. is applied on the surface of a metallic material and dried to form a chromate film excellent in corrosion resistance and lubricity.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a two-liquid type lubricating chromate treatment liquid composition for metal surface and a treatment method. More specifically, the present invention is a surface of a metal material, a lubricating film having excellent moldability and corrosion resistance,
The present invention relates to a two-pack type lubricative chromate treatment liquid composition used for simultaneously and integrally forming a chromate film having excellent spot weldability, coatability for top coat paint, etc. in one step, and a treatment method using the same. is there.
The metal material with the lubricious chromate film formed on the surface can be processed without applying a processing oil such as press oil, and therefore the press working environment can be cleaned and after the press processing. Since the degreasing step of is unnecessary,
The productivity can be improved by the process saving.

[0002]

2. Description of the Related Art A metal material is processed into a plate shape, a tubular shape, a bar shape or the like by a rolling device of a steel manufacturer such as a steel material, and further, according to each application in home appliances, automobiles, building material manufacturers, etc. It is assembled after being processed into a desired shape and size by a method such as pressing or forging. Most of such forming processing is performed after forming a lubricating film including a combination of an oil lubricant such as press oil, a solid lubricant such as lime soap, and a zinc phosphate film on the processed surface of the metal material. It has been subjected. At the site where such molding is performed, oil stains and dust are scattered in the molding apparatus and its peripheral portion, which creates an unfavorable environment from the viewpoints of pollution prevention and occupational safety and health.

On the other hand, sacrificial corrosion protection by zinc-based plating of steel is the most effective and economical. Therefore, at present, 10 million tons, which is 10% of the annual crude steel production of 100 million tons in Japan, is zinc-based. It is produced as a plated steel sheet and used in a wide range of fields such as building materials, automobiles and home appliances. The mechanism of sacrificial corrosion protection by zinc is that a battery is formed under the condition that two metals, zinc and steel, are in contact with each other.
This is because zinc, which is a more base metal, serves as an anode and iron is made into a cathode to prevent anodic dissolution due to formation of a local battery when iron alone is used to prevent corrosion of steel. Therefore, the anticorrosion effect is lost when the zinc in contact with the steel disappears. Therefore, it is necessary to suppress corrosion of the zinc layer in order to maintain its action and effect for a long period of time. As a countermeasure for this, chromate treatment is applied after zinc plating.

When forming such a zinc-plated steel sheet that has been subjected to such chromate treatment, press oil or the like is applied as a lubricant and is subjected to forming such as pressing, and it remains after forming. Dirt such as press oil and metal powder is degreased with a chlorine-based solvent such as trichlorethylene, then painted and the like, sent to the assembly process and finished as a final product.

However, in recent years, there has been an increasing demand for environmental protection on a global scale, and there is an opportunity to regulate or completely abolish the use of chlorine-based solvents, chlorofluorocarbon-based solvents and the like. Therefore, it is necessary to form a chromate film having lubricity on a metal material in advance, and to form a lubricious chromate film that can be molded without applying a lubricant such as press oil, that is, without applying oil. Development is urgent.

Various methods have been proposed to meet these demands. As conventional techniques relating to these techniques, there are (1) JP-A-61-60766 and (2) JP-A-6-60676.
1-227178, JP 61-227179, JP 61-231177, JP 61-279687, JP 62-33781, (3) JP 63-83172,
(4) JP-A-62-289274, (5) JP-A-63-
162886, (6) JP-A-2-43040, JP-A-3
There is a technique disclosed in 39485 and the like. Below, these conventional techniques will be outlined.

That is, the prior art (1) relates to an aqueous composition containing an organic-inorganic composite reaction product composed of a water-soluble or water-dispersible organic resin, an alkoxysilane compound, and silica and a lubricant as main components. Is. The film formed from this composition has an organic-inorganic composite reaction product as a main constituent, and has problems such as poor flexibility and poor adhesion to metal materials, and insufficient moldability. Have

The prior art (2) is based on an acrylic water-based resin as an organic resin, on which fine particles of graphite, molybdenum disulfide or the like, or these and paraffin oil,
A composition containing a mixture of silicone oil and one or more of neopentyl polyol fatty acid ester is used. When the coating is further overcoated, the coating is water repellent. Since it has oil repellency, it has a problem that it tends to cause poor coating and poor adhesion.

The prior art (3) is a composition comprising an organic resin selected from an epoxy resin, a polyester resin and an acrylic resin and an amino resin or polyisocyanate as a curing component, a conductive substance, a chromium compound,
And a composition prepared by mixing a lubricating substance as a coating liquid. In this method, when the conductive substance is carbon black or graphite, the color tone of the film is only black, and the use is limited. Further, if the conductive substance is a metal powder, a semiconductor oxide, or iron phosphide, the moldability is not sufficiently exhibited.

In the prior art (4), a coating layer containing a urethane resin and a silicon dioxide composite material or a mixed material thereof as a main component is formed on the surface of a metal material, or the composite material or the mixed material is formed. It is characterized in that a coating layer containing a substance containing zinc powder as a main component is formed on the surface of the metal material. However, there is a problem that sufficient moldability cannot be obtained only with these substances.

The prior art (5) forms an organic composite film containing a carboxylated polyolefin resin, a liquid epoxy resin, a fluororesin, and silica on the surface of a metal material. Since it has both water repellency and oil repellency, it causes problems such as poor coating and poor adhesion when the top coat is applied on this film. In addition, when a coating type chromate is used as a base treatment to form a chromate film and then the resin composition disclosed in the prior art (5) is applied, since the resin composition is water-based, this composition At the time of coating, there is a problem that the chromium compound from the undercoat elutes into the treatment liquid, impairing the stability of the resin composition.

[0012]

DISCLOSURE OF THE INVENTION The present invention solves the above-mentioned problems of the prior art, and a base treatment step required for improving corrosion resistance in the prior art and a lubricity treatment step for improving molding workability. A two-component lubricative chromate for metal surface, which can perform two steps of (1) and (2) simultaneously in a single step, and can form a film excellent in corrosion resistance, spot weldability, and adhesion to the top coating. It is intended to provide a treating composition and a treating method using the same.

[0013]

The present inventors have solved these problems of the conventional lubricity imparting technology, and
In the conventional technology, by performing two steps, which are the base treatment step required to improve the corrosion resistance and the lubricity imparting step that imparts moldability, in one step, the surface of the metal material can be treated without impairing the production efficiency. In order to newly develop a processing technology that simultaneously imparts lubricity and corrosion resistance, etc. As a result, a chromate treatment liquid having a pH of 2.5 or more, which was prepared from a two-component composition consisting of a chromate component liquid containing a trivalent chromium compound sol and a lubricant component containing liquid, was applied to the surface of the metal material, Then, it was found that a chromate film treatment with high lubricity can be formed on the surface of the metal material by drying in one step, and the present invention has been completed.

The two-component type lubricating chromate treatment liquid composition for the surface of a metal material of the present invention is characterized by comprising a chromate component liquid containing a sol of a trivalent chromium compound and a lubricant component containing liquid. Is.

In the composition of the present invention, the weight ratio of total chromium contained in the chromate component liquid to the lubricant component in the lubricant component-containing liquid is in the range of 50: 1 to 1: 100. preferable.

In the composition of the present invention, the lubricant component-containing liquid is an aqueous solution of a water-soluble lubricating polymer compound, an aqueous emulsion of a water-insoluble lubricating polymer compound, and 50
It is preferably composed of at least one selected from aqueous emulsions of waxes having a melting point of 150 ° C.

In the composition of the present invention, it is preferable that the sol of the trivalent chromium compound contains at least one sol selected from trivalent chromium oxide and chromium hydroxide.

The method for treating the surface of a metal material with lubricious chromate according to the present invention comprises applying a treatment liquid prepared from the above-mentioned two-pack type composition and adjusted to a pH of 2.5 or more to the surface of the metal material. The formed treatment liquid layer is dried to form a lubricious chromate film.

[0019]

The structure of the present invention will be described in detail below. The metal materials targeted by the present invention are mainly steel plates, zinc-containing metal plated steel plates, aluminum-containing metal plated steel plates, aluminum-based metal materials, stainless steel plates, etc., but are not limited thereto. The chromate treatment liquid of the present invention comprises a trivalent chromium compound sol-containing chromate component liquid and a lubricant component-containing liquid. When preparing a treatment liquid from this two-component composition,
The pH of the treatment liquid is adjusted to 2.5 or higher. The type of the trivalent chromium compound sol to be used is not particularly limited, but for example, a chromium oxide sol called chromia sol or a chromium hydroxide sol can be used. More preferably, the sol of the trivalent chromium compound is stably dispersed in water with chromic acid, but other dispersion stabilizers such as phosphoric acid, chromic anhydride, hydrofluoric acid, borofluoric acid, and fluorosilicic acid are used. Inorganic acids such as hydrofluoric acid, titanium hydrofluoric acid, and zircon hydrofluoric acid, organic acids such as formic acid, acetic acid, citric acid, tartaric acid, malic acid, acrylic acid, methacrylic acid, and maleic acid, acrylic acid, methacrylic acid At least one selected from a homopolymer or a copolymer of an acid and a carboxylic acid having vinyl polymerizability such as maleic acid is used. As a preferred form of these trivalent chromium compound sols, JP-A-6-15834 previously disclosed by the present inventors is disclosed.
The sol of the trivalent chromium compound described in Japanese Patent No. 5 can be used. The chromate component liquid containing the trivalent chromium compound sol preferably has a pH of 2.5 or higher.

By using these trivalent chromium compound sols, it is possible to stably mix the lubricant component-containing liquid and the trivalent chromium compound sol-containing chromate component liquid, and therefore the chromate treatment liquid in the present invention. Is applied to the surface of the metal material and the coating liquid layer is dried to improve the uniformity of the lubricating chromate film to be formed,
A chromate film having high corrosion resistance and lubricity, which is the object of the present invention, can be obtained.

The treatment liquid used in the lubricating chromate treatment method of the present invention is prepared from the two-component treatment composition of the present invention and has a pH adjusted to 2.5 or higher.
If the pH is less than 2.5, dissolution of the trivalent chromium compound sol is caused and the stability of the chromate treatment liquid is lowered, which is not preferable. If the pH is 2.5 or more, the chromate treatment solution of the present invention is stable. Therefore, there is no upper limit to the pH value of the treatment liquid, but the pH value is preferably 12 or less, more preferably 10 or less. In general, if the pH is 10 or less, the chromate treatment liquid of the present invention is sufficiently stable,
If the pH exceeds 10, the effect of stabilizing the chromate treatment solution reaches saturation, resulting in wasteful consumption of alkali components, which may be uneconomical.

There is no particular limitation on the ratio of the trivalent chromium compound sol-containing chromate component to the lubricant component in the two-component composition and the chromate treatment liquid in the present invention, but the total chromium (as metal chromium): The weight ratio of the lubricant component is 5
It is preferably in the range of 0: 1 to 1: 100. If this ratio exceeds 50: 1, the resulting chromate film may deteriorate in lubrication performance, and it may be 1: 1.
If it is less than 00, the effect of improving the corrosion resistance of the obtained chromate film may be deteriorated and may be unsatisfactory.

The type of the lubricant component usable in the present invention is not limited, and widely known lubricant components such as graphite, molybdenum disulfide, fats and oils can be used. As a particularly preferable lubricant component, at least one selected from an aqueous solution of a water-soluble polymer resin, an aqueous emulsion of a non-water-soluble polymer resin, and an aqueous emulsion of wax having a melting point of 50 to 150 ° C. is used.

When graphite, molybdenum disulfide, or the like is used as a lubricant component in the chromate treatment liquid of the present invention, the resulting chromate film has a black appearance, and the metal material on which this film is formed is processed. In this case, the degree of coloring changes depending on the degree of molding process, resulting in uneven appearance, which is not preferable. Further, when oils and fats are used as a lubricant component, degreasing is required when coating is applied in the subsequent step, which may be disadvantageous in the step, which is not preferable.

In the present invention, the kind of the water-soluble polymer resin used as the lubricant component is not particularly limited, and widely known water-soluble polymer resins can be used. Specific examples thereof include polyacrylic acid, polymethacrylic acid, water-soluble polycarboxylic acids such as a copolymer of maleic acid and methyl vinyl ether, polyacrylic amide, acrylic amide and a compound having another vinyl group. There are copolymers with and polyethers such as polyethylene glycol.

In the present invention, the mechanism of action of the water-soluble polymer resin to enhance the lubricity of the chromate film containing it is still unknown, and it does not go beyond speculation. By doing so, the surface tension of the chromate treatment liquid is reduced, filling the metal base or minute recesses on the surface of the chromate film to enhance the smoothness of the surface, and the polymer resin contained in the chromate film aggregates the chromate film. The effect of increasing the strength and the strength of the film is considered, and it is presumed that these effects are due to the effect of reducing the friction coefficient of the chromate film formed by the combined effect.

Further, in the present invention, examples of an aqueous emulsion of a water-insoluble polymer resin used as a lubricant component and an aqueous emulsion of a wax having a melting point of 50 to 150 ° C. will be specifically described. There is no particular limitation on the type of the water-insoluble polymer resin aqueous emulsion used in the present invention, and a resin emulsion polymerized by emulsion polymerization, solution polymerization, or the like can be used. As such a resin, preferably an aqueous emulsion of a water-insoluble polymer resin such as an acrylic ester resin, a polyolefin resin, an alkyd resin, a polyester resin, an epoxy resin, a urethane resin, or a fluorine resin is used. Can be used. Particularly preferred is the use of polytetrafluoroethylene (hereinafter referred to as PTFE).

Since PTFE has a very low coefficient of friction in itself and is widely known as a low friction material, it is also known to be used as a lubricant component.
The effect of the emulsifier does not last sufficiently in the chromate treatment liquid having a pH of less than this. Therefore, in the chromate treatment liquid containing this, the emulsion particles of PTFE are easily aggregated and the stability as the treatment liquid is extremely insufficient. Becomes However, in the present invention, the action of the emulsifier continues in the chromate treatment liquid containing the trivalent chromium compound sol and having a pH of 2.5 or more, and the stability of the treatment liquid is increased to the extent that it can be practically used.
This is the advantage and advantage of the chromate treatment liquid in the present invention.

The wax emulsion used in the present invention is not particularly limited, but preferable types of wax emulsion include aqueous emulsions of olefin wax such as paraffin, microcrystalline and polyethylene. Particularly preferable wax is a wax having a melting point of 50 to 150 ° C. A wax having a melting point of less than 50 ° C. may have insufficient lubricity, and a wax having a melting point of more than 150 ° C. may be difficult to emulsify. Therefore, it was formed from a chromate treatment liquid containing this wax emulsion. The chromate film inevitably contains a non-uniform lubricant component in the film, resulting in insufficient lubricity.

Similar to the above, wax has a low coefficient of friction of itself and is widely known as a low friction material. It is also known to be used as a lubricant component, but it has a pH of less than 2.5. The action of the emulsifier does not last sufficiently in the chromate treatment liquid that it has, and the emulsion particles of the wax tend to aggregate in the chromate treatment liquid containing this, and the stability as a treatment liquid must be extremely insufficient. . However, in the chromate treatment liquid containing the trivalent chromium compound sol of the present invention and having a pH of 2.5 or more, the action of the emulsifier continues and the stability of the treatment liquid is increased to the extent that it can be put to practical use. The advantages and advantages of the chromate treatment liquid of the present invention are also exhibited here.

In the method of the present invention, the chromate treatment liquid
A basic compound is used to adjust the pH to 2.5 or higher. The type of the basic compound is not particularly limited, but in order to obtain a film having excellent coating performance, lithium,
The use of alkali metal oxides, hydroxides, carbonates and the like such as sodium and potassium deteriorates the coatability of the obtained chromate film, especially the water-resistant secondary adhesion, and is not preferred. Therefore, the basic compound used in the present invention is preferably a volatile one. Specific examples of particularly preferable basic compounds include ammonia, aqueous ammonia, and highly volatile relatively low molecular weight amines.

As another additional component that can be contained in the chromate-treating solution of the present invention, generally known phosphoric acid,
Examples include acids such as chromic acid, metal ions such as zinc ions, nickel ions, cobalt ions, iron ions, and aluminum ions, and various oxide sols such as silica sol, alumina sol, titania sol, and zirconia sol, or hydroxide sol. It may be used alone or as a mixture of two or more thereof. Further, these may be contained in the chromate component liquid of the two-pack type composition, or may be added during preparation of the chromate treatment liquid.

The effects of the above-mentioned additional components will be described with reference to specific examples. For example, chromic acid has the effect of improving the corrosion resistance of the film obtained by the self-repairing property based on hexavalent chromium ions, and phosphoric acid enhances the reactivity of the chromate treatment liquid with respect to the metal substrate and improves the water resistance of the chromate film. This has the effect of improving the corrosion resistance of the material to be treated. Further, there is no established theory about the action mechanism of the silica sol contained in the chromate treatment solution, but the effect is obviously the improvement of corrosion resistance.

Next, the chromate treatment method of the present invention will be described. The above-mentioned chromate treatment liquid is applied onto the surface of the metal material, and this coating liquid layer is dried. There is no limitation on this coating method, and after the coating is performed by a generally known method such as dipping or showering, a method of removing excess treatment liquid by air, rolls or the like, roll coating method, spray coating method And the like.

There is no limitation on the method of drying the coating liquid layer and the drying conditions, and an appropriate drying method such as hot air or high frequency induction heating can be used. Further, the heating temperature and the heating time are not limited, and the drying condition can be selected according to the kind, application, productivity and economical efficiency of the metal material.

The amount of the chromate film formed on the surface of the metallic material by the method of the present invention is not limited, and any amount of the film can be appropriately selected, but the total amount of chromium deposited (calculated as metallic chromium) is preferably 2. ˜500 mg / m ² , and it is preferable to adjust so that the lubricant component adhesion amount is 1 to 3000 mg / m ² , and more preferably the chromium adhesion amount is 5 to 200 mg / m ² , and the lubricant component adhesion amount is 2 to 1000
It is mg / m ² . If the amount of deposited chromium is less than 5 mg / m ² , the corrosion resistance of the obtained chromate film may be insufficient, and if the amount of attached lubricant component is less than 2 mg / m ² , the lubricating performance of the obtained film may be insufficient. Sometimes there is. On the other hand, when the amount of deposited chromium exceeds 200 mg / m ² , the corrosion resistance reaches saturation, wasting the processing liquid, and is not economical.
Further, if the amount of the lubricant component adhered exceeds 1000 mg / m ² , not only the lubrication performance reaches saturation, but also problems such as deterioration of spot weldability may occur.

[0037]

EXAMPLES The present invention will be described in detail with reference to the following examples, but the scope of the present invention is not particularly limited by these examples.

Example 1 Chromate Treatment Liquid A From an aqueous solution in which chromic anhydride was dissolved, 19.2 g / liter of trivalent chromium ions (Cr ³⁻ ) and hexavalent chromium ions (Cr ⁶⁺ ) were obtained by the partial reduction method. An acidic chromium compound aqueous solution (250 mL) containing 28.8 g / liter was prepared. Next, this liquid was placed in a heating and pressurizing container, water was further added to make it 1 kg, and the mixture was kept at 150 ° C. for 2 hours and then cooled to room temperature. As a result, a chromate component solution containing a trivalent chromium compound sol stabilized by chromic acid was obtained. To 250 g of this chromate component liquid, the lubricant component-containing liquid a shown in Table 1 was added in an amount of 120 g, water was further added, and the pH was adjusted to 2.5 with ammonia water to obtain 1 liter of the chromate treatment liquid. Prepared. This processing solution is 1 at room temperature
No abnormality was found even after storage for months.

Example 2 Chromate Treatment Liquid B By the same method as in the chromate treatment liquid A, trivalent chromium ion was 10 g / liter and hexavalent chromium ion was 10 g / liter.
An acidic chromium compound aqueous solution (500 mL) containing 10 g / liter of phosphate ion (PO ₄ ³⁻ ) was prepared. Next, this liquid was placed in a heating and pressurizing container, water was further added to 1 kg, and the mixture was kept at 120 ° C. for 3 hours and then cooled to room temperature. As a result, a chromate component solution containing a trivalent chromium compound sol stabilized by phosphoric acid and chromic acid was obtained. To 500 g of this chromate component liquid, 8 g of the lubricant component-containing liquid b shown in Table 1 was added,
Further, water was added and the pH was adjusted to about 4 with aqueous ammonia to prepare 1 liter of the chromate treatment liquid. No abnormalities were observed even when this treatment liquid was stored at room temperature for 1 month.

Example 3 Chromate Treatment Liquid C By the same method as that for the chromate treatment liquid A, trivalent chromium ions 8 g / liter, hexavalent chromium ions 8 g / liter, and zinc ions 0.4 g / liter as metal ions, An acidic chromium compound aqueous solution (500 mL) containing 10 g / l of phosphate ions was prepared. This solution was placed in a heating and pressurizing vessel, urea (9 g) was further added, and water was added to adjust the pressure to 1 kg, and the mixture was kept at 120 ° C. for 2 hours, and then cooled to room temperature. As a result, a chromate component solution containing a trivalent chromium compound sol stabilized by phosphoric acid and chromic acid was obtained. To 625 g of this chromate component liquid, Table 1
The lubricant component-containing liquid c shown in (4) was added in an amount of 200 g, water was further added, and the pH was adjusted to about 7 with aqueous ammonia to prepare 1 liter of the chromate treatment liquid. No abnormalities were observed even when this treatment liquid was stored at room temperature for 1 month.

[0041]

[Table 1]

Example 4 Chromate Treatment Liquid D By the same method as in the chromate treatment liquid A, trivalent chromium ions of 3.6 g / liter and hexavalent chromium ions of 8.4 g were used.
Acidic chrome compound aqueous solution (50
0 mL) was prepared. This aqueous solution was put in a beaker, and 24 g of silica sol (Note 1) as SiO ₂ was added and dispersed as an oxide sol. Put this solution in a heating and pressurizing container, add urea (9g), and add water to make 1Kg.
The temperature was kept at 0 ° C. for 2 hours and then cooled to room temperature. As a result, a chromate component liquid containing a trivalent chromium compound sol stabilized with phosphoric acid was obtained. This chromate component liquid 25
The lubricant component-containing liquid b shown in Table 1 was added to 0 g in an addition amount of 250 g, water was further added, and the pH was adjusted to about 8 with ammonia water.
To 1 liter of chromate treatment liquid. No abnormalities were observed even when this treatment liquid was stored at room temperature for 1 month. [Note 1] Nissan Chemical, trademark: Snowtex O, SiO
₂ Contains 20%

Example 5 Chromate Treatment Solution E Chromium carbonate was dissolved in an aqueous solution (500 mL) containing 10 g / liter of phosphate ion (PO ₄ ³⁻ ) to prepare an acidic chromium compound aqueous solution containing 1 g of trivalent chromium ion. did. This solution was placed in a heating and pressurizing vessel, urea (9 g) was further added, and water was added to 1 Kg to maintain the temperature at 110 ° C. for 3 hours, and then cooled to room temperature. As a result, a chromate component solution containing a trivalent chromium compound sol stabilized by phosphoric acid was obtained. The pH of this chromate component liquid was about 6.5. To 400 g of this chromate component liquid,
1.5 g of ammonium dichromate and 320 g of Table 1
The lubricant component-containing liquid c shown in 1 above and water were added to prepare 1 liter of the chromate treatment liquid. This processing solution is 1 at room temperature
No abnormality was found even after storage for months.

Example 6 Chromate Treatment Liquid F The same trivalent chromium compound sol as in the chromate treatment liquid E was formed, and 800 g of this aqueous dispersion liquid was added with 3 g of ammonium dichromate and 32 g of the lubricant shown in Table 1. Ingredient a and water were added to prepare 1 liter of a chromate treatment liquid. No abnormalities were observed even when this treatment liquid was stored at room temperature for 1 month.

Example 7 Chromate Treatment Solution G Acid chromium containing 30 g / liter of trivalent chromium ions, 30 g / liter of hexavalent chromium ions, and 26 g / liter of phosphate ions was prepared in the same manner as the chromate treating solution A. A compound aqueous solution (600 mL) was prepared. Next, this solution was placed in a heating and pressurizing apparatus, urea (30 g) was further added, water was added to 1 Kg, and the mixture was maintained at 120 ° C. for 2 hours and then cooled to room temperature. As a result, a chromate component liquid containing a trivalent chromium compound sol stabilized by phosphoric acid and chromic acid was obtained. This chromate component liquid 6
0.72 g of the lubricant component b shown in Table 1 was added to 00 g, water was further added, and the pH was adjusted to about 7 with aqueous ammonia to prepare 1 liter of the chromate treatment liquid. No abnormalities were observed even when this treatment liquid was stored at room temperature for 1 month.

Comparative Example 1 Comparative Chromate Treatment Liquid H By the same method as for the chromate treatment liquid A, trivalent chromium ions of 4.8 g / liter and hexavalent chromium ions of 7.2 g / liter were used.
1 liter of an aqueous solution of a chromium compound containing 1 liter was prepared. The pH of this chromium compound aqueous solution was about 1.2. No abnormalities were observed even when this treatment liquid was stored at room temperature for 1 month.

Comparative Example 2 Comparative Chromate Treatment Liquid I In the same manner as in the chromate treatment liquid A, trivalent chromium ion 6 g / liter, hexavalent chromium ion 4 g / liter, phosphate ion 1 g / liter, and silica sol (Note) 1 liter of a chromium compound aqueous solution containing 40 g / liter of 1) as SiO ₂ was prepared. The pH of this chromium compound aqueous solution was about 1.7. This processing solution is 1 at room temperature
No abnormality was found even after storage for months.

Comparative Example 3 Comparative Chromate Treatment Liquid J By the same method as for the chromate treatment liquid A, trivalent chromium ion 2.5 g / liter and hexavalent chromium ion 2.5 g
/ L and a chromium compound aqueous solution containing 2.5 g / L of phosphate ions were prepared. The pH of this chromium compound aqueous solution was about 1.5. No abnormalities were observed even when this treatment liquid was stored at room temperature for 1 month.

Comparative Example 4 Comparative Chromate Treatment Liquid K Chromium containing 5 g / liter of trivalent chromium ions, 5 g / liter of hexavalent chromium ions, and 5 g / liter of phosphate ions was prepared in the same manner as the chromate treatment liquid A. A compound aqueous solution (500 mL) was prepared. The pH of this chromium compound aqueous solution was about 1.5. The lubricant component c shown in Table 1 was added to this chromium compound aqueous solution in an amount of 100 g, and diluted with water to 1 liter. This treatment liquid
When it was stored at room temperature for 1 month, it gelled and became unusable.

Examples 8 to 26 and Comparative Examples 5 to 12 (I) Preparation of Test Plate Commercially available galvanized steel sheet (EG), hot dip galvanized steel sheet (GI), galvannealed steel sheet (GA), 5%
Alkaline degreasing agent (trade name: FC-, manufactured by Nippon Parkerizing Co., Ltd.) in advance using aluminum / zinc plated steel plate (GF) and aluminum plated steel plate (AlS) as test plates.
4336, concentration = 20 g / liter, degreaser temperature = 60
Degreasing at ℃, degreasing time = 10 seconds, degreasing method = spray,
Then, it was washed with water and drained. As shown in Table 2, various test solutions prepared by using any one of the chromate-treated solutions A, B, C, D, E, F, G and the comparative chromate-treated solutions H, I, J and K were tested. On the plate surface, use a roll coater to apply a wet coating amount of 5 ml / m ² , and apply 100
It dried at 5 degreeC (achievement board temperature) for 5 seconds. Table 2 shows the details of the test plate treatment.

[0051]

[Table 2]

(II) Performance test (1) Corrosion resistance According to JIS-Z, various treated steel sheets produced under the above conditions were used.
According to each test plate type, salt spray test according to −2731 is performed for 200 hours for EG and GI materials, 120 hours for GA, 300 hours for GF material, 400 hours for AlS material, and 400 hours for corrosion. The generated area was visually evaluated. <Evaluation criteria> Excellent 5 ... less than 5% of rust occurrence area ↑ 4 ... 5% or more and less than 10% of rust occurrence area 3 ... Rust occurrence area of 10% or more and less than 15% ↓ 2 ... Rust occurrence area of 15% or more, 25% Less than 1… Rust generation area 25% or more

(2) Workability Using various processed steel sheets produced under the above conditions, using a high-speed cylindrical deep-drawing tester, a drawing speed = 10 m / min, blank diameter = 88 mmφ, punch diameter = 40 mmφ (drawing ratio = 2.
2) Under the conditions, the wrinkle holding load was sequentially increased in increments of 0.5 Ton, and the wrinkle holding load at the limit of rupture was measured.

(3) Dynamic Friction Coefficient The dynamic friction coefficient was measured with a Bowden tester under a load of 100 g for the examples according to the present invention and a load of 50 g for the comparative examples.

(4) Weldability When the spot welding of the test plate is continuously performed on the electrogalvanized nickel alloy-plated steel plate under the following conditions, the welding terminal gradually deteriorates and the weldability deteriorates. The weldability of the test plate can be judged by the degree. That is, 100 RBI
Another test piece of 30 × 100 mm was welded for each point, and the number of hit points was recorded until the tensile strength of the test piece could be maintained at 400 kg. <Welding conditions> Pressurizing force …… 200kg Current ……… 8.5kA Energizing time… 10 cycles Electrode shape… R40 (radius type) Electrode material… Chromium-copper <Evaluation standard> Excellent 5… 5000 points or more ↑ 4… 4000- Less than 5000 points 3 ... 3000 to less than 4000 points ↓ 2 ... 2000 to less than 3000 points Poor 1 ... Less than 2000 points

(5) Paintability A melamine alkyd paint (trade name: Dericon # 700) manufactured by Dainippon Paint Co., Ltd. was applied to various treated steel plates prepared under the conditions shown in Table 1 to give a coating film thickness of 25 μm. Thus, bar coating was performed and baking was performed at 140 ° C. for 30 minutes to dry the coated plate. A coating performance test was carried out using the coated plate prepared as described above under the following conditions.

(A) Primary adhesion <Gobang eye Erichsen test> After making 100 Gobang-like cuts of 1 mm square on the coating surface of the coated plate with a cutter knife, the Gobang eye spots were measured by an Erichsen tester. 5 mm
It was evaluated by the number of residual cross stitches in the coating film after extrusion and peeling with cellophane tape.

<DuPont Impact Test> A DuPont impact was applied to a coated plate under conditions of a firing needle shape of 1/2 inch φ, a load of 500 g, and a distance of 50 cm, and then cellophane tape was peeled off to visually evaluate the remaining state of the coating film. did.

(B) Secondary Adhesion The coated plate was immersed in boiling water for 4 hours, and then an adhesion test was conducted under the following conditions. <Gourd-eye Erichsen test> After making 100 gouge-like cuts of 1 mm square on the coating surface of the coated plate with a cutter knife, push out 5 mm with a goba-in-place Erichsen tester and peel off cellophane tape. The coating film was evaluated according to the number of residual stitches. That is, the larger the number of remaining coating films, the better the coating adhesion.

<DuPont Impact Test> After a DuPont impact was applied to a coated plate under the conditions of a firing needle shape of 1/2 inch φ, a load of 500 g, and a distance of 50 cm, cellophane tape was peeled off and the remaining state of the coating film was visually evaluated. .

(C) Corrosion resistance test after coating After applying a cross-cut until reaching the metal base on the coated surface and performing a salt spray test (JIS-Z2371) for 500 hours, the width of the coating film peeled from the cross-cut portion is in mm. It was measured at. In other words, the smaller the number of mm, the better the corrosion resistance after painting.

The test results are shown in Table 3.

[Table 3]

As is clear from Examples 4 to 26 (Table 3), the film formed by using the chromate treatment liquid according to the present invention has a small coefficient of friction, excellent workability, weldability and bareness. It also showed excellent corrosion resistance and paintability.
On the other hand, in Comparative Examples 5 to 11 according to the related art, the coefficient of friction was large and the workability was significantly inferior, and it was impossible to process without applying lubricating oil such as press oil. Further, the comparative chromate treatment liquid K other than the present invention was not only poor in stability, but the comparative example using this treatment liquid had a relatively large coefficient of friction and poor workability.

[0064]

The treatment liquid obtained from the two-component type lubricating chromate treatment composition for surface treatment of metallic materials of the present invention has a small friction coefficient, excellent lubricity, weldability and bare corrosion resistance on the surface of various metallic materials. A chromate film having excellent paintability can be efficiently formed, and the press working environment can be greatly improved.

Claims (5)

[Claims] 1. A two-component type lubricating chromate treatment composition for a metal material surface, which comprises a chromate component liquid containing a sol of a trivalent chromium compound and a lubricant component containing liquid. 2. The weight ratio of chromium contained in the chromate component liquid to the lubricant component contained in the lubricant component-containing liquid is in the range of 50: 1 to 1: 100. Composition. 3. The lubricant component-containing liquid is selected from an aqueous solution of a water-soluble lubricating polymer compound, an aqueous emulsion of a water-insoluble lubricating polymer compound, and an aqueous emulsion of wax having a melting point of 50 to 150 ° C. The composition according to claim 1, which comprises at least one of 4. The composition according to claim 1, wherein the sol of the trivalent chromium compound contains at least one sol selected from trivalent chromium oxide and chromium hydroxide. 5. A treatment liquid prepared from the two-component composition according to any one of claims 1 to 4 and having a pH adjusted to 2.5 or more is applied to the surface of the metal material, A method for treating a surface of a metal material with lubricious chromate, which comprises drying the formed treatment liquid layer to form a lubricious chromate film.