JPH0860175A - Two-pack type lubricating chromate treatment composition for metal material and treating method - Google Patents

Abstract

PURPOSE: To obtain the composition providing a metal material with a coating film having excellent corrosion resistance and coating adhesivity, comprising an aqueous emulsion containing a lubricant component containing wax, etc., and a specific nonionic surfactant and an emulsifier component and an inorganic chromate component. CONSTITUTION: This two-pack type lubricating chromate treatment comprises (A) an aqueous emulsion of a lubricant component which contains a lubricant component containing wax and at least one such as polytetrafluoroethylene and the emulsifier component containing a nonionic surfactant having at least one aromatic structure in one molecule and at least one of a polyethylene glycol group and a group composed of two or more molecules of ethylene oxides prepared by addition polymerization in which the lubricant component is stably emulsified by the emulsifier component and (B) an inorganic chromate component obtained by combining an aqueous solution of an inorganic chromate component containing a hexavalent chromium ion with an aqueous solution containing a trivalent chromium ion and forms a safe lubricating chromate film having excellent corrosion resistance and coating adhesion on a metal material.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a two-component lubricating chromate treatment composition for metal materials and a treatment method. More specifically, the present invention provides a two-component lubrication for metal material for forming a lubricious chromate film having excellent lubricity and moldability on the surface of the metal material, and at the same time having excellent corrosion resistance. TECHNICAL FIELD The present invention relates to a sex chromate treatment composition and a treatment method.

[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, awareness of environmental conservation on a global scale has increased, 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, (3) JP-A-61-227179,
(4) Japanese Patent Laid-Open No. 61-231177, (5) Japanese Patent Laid-Open No. 61-
279687, (6) JP-A-62-33781, (7)
JP-A-62-83172, (8) JP-A-62-2892
74, (9) JP-A-63-162886, (10) JP-A-2-43040, (11) JP-A-3-39485, and (12) JP-A-3-219086. 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

In the prior arts (2) to (6), after forming a chromate film on the surface of a steel sheet, an acrylic water-based resin as an organic resin is used as a base on the chromate film, and graphite and disulfide are added thereto. Chromate, silica sol, silane coupling to solid lubricants such as molybdenum, or acrylic resins obtained by copolymerizing α, β unsaturated carboxylic acid monomers with other monomers copolymerizable with them. It is disclosed that a surface coating film having excellent corrosion resistance and lubricity is formed by applying a composition containing at least one selected from an agent, a titanate coupling agent, and a fine particle colored pigment. However, when the coating is further overcoated, there is a problem that the coating is water-repellent and oil-repellent, and thus coating failure and adhesion failure are likely to occur.

The prior art (7) 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 blending 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 (8), a coating layer containing a composite material of urethane resin and silicon dioxide or a mixed material thereof as a main component is formed on the plating layer of a zinc-containing metal plated steel sheet, or The present invention is characterized in that a film layer containing a substance or a substance obtained by mixing zinc powder in a mixed substance as a main component is formed. However, there is a problem in that sufficient moldability cannot be obtained only with films of these substances.

In the prior art (9), a chromate film is formed on the surface of a plated steel sheet or a cold rolled steel sheet, and a carboxylated polyolefin resin, a liquid epoxy resin, a fluororesin and silica are further contained on the chromate film. Fluororesin, which forms a characteristic organic composite film,
Since it has both water repellency and oil repellency, it causes problems such as poor coating and poor adhesion when a top coat is applied on this film. 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 (9) 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.

The prior art (10) forms a specific amount of chromate film on a steel plate plated with zinc, a zinc alloy, or an aluminum alloy, and has a hydroxyl group and / or a carboxyl group on both surfaces thereof. And a resin film containing a mixture of a resin having silica, and a fluororesin powder. However, when the top coating is applied on this film, there is a problem that coating failure or adhesion failure occurs.

In the prior art (11), a chromate film is formed on both surfaces of a steel plate plated with zinc, a zinc alloy, or an aluminum alloy in a specific adhesion amount,
A resin mixture obtained by mixing a resin having a hydroxyl group and / or a carboxyl group, silica, and a polyolefin wax having a melting point of 110 ° C. or higher is applied thereon,
Thereby, a steel sheet having excellent powdering resistance during high-speed press forming is manufactured. However, this technique cannot be said to have succeeded in satisfying both lubricity and adhesion at the same time.

The prior art (12) uses 6 as an inorganic compound.
PH 5 or less containing a valent chromium ion, or a hexavalent chromium ion and a trivalent chromium ion, a specific acrylic polymer emulsion as an organic compound, and a lubricant dispersion dispersed with a nonionic emulsifier as a lubricating component. Disclosed is a metal surface treatment composition having excellent lubricity.
This prior art (12) has good treatment liquid stability, corrosion resistance, coating adhesion, and workability, but weldability is not yet sufficiently secured.

[0015]

DISCLOSURE OF THE INVENTION The present invention solves the above-mentioned problems of the prior art, and improves the surface treatment step and the molding workability required in the prior art to improve the corrosion resistance. A coating that can simultaneously achieve two steps, a lubricant treatment step and a single step, has excellent corrosion resistance, coating adhesion, weldability, and can impart sufficient lubricity to metal materials. The present invention aims to provide a novel two-pack type lubricous chromate treatment composition for metal materials and a treatment method for forming it on the surface of a metal material.

[0016]

The two-component type lubricating chromate treatment composition for metallic materials of the present invention comprises a lubricant component containing the following components: (A) wax and at least one selected from polytetrafluoroethylene. And an emulsifier containing a nonionic surfactant having at least one aromatic ring structure per molecule, a polyethylene glycol group, and at least one member selected from the group consisting of two or more molecules of addition-polymerized ethylene oxide. And a lubricant component aqueous emulsion in which the lubricant component is stably emulsified by the emulsifier component, and (B) an aqueous solution of an inorganic chromate component containing hexavalent chromium ions and trivalent chromium ions. It is characterized by that.

In the aqueous emulsion of the two-component type lubricating chromate treatment composition for metallic materials of the present invention, the content of the nonionic surfactant is 0.5 to 20 relative to 100 parts by weight of the lubricant component. It is preferably part by weight.

The inorganic chromate component of the two-component type lubricating chromate treatment composition for metallic materials of the present invention is 5 to 3
At least one selected from silica sol, colloidal silica, and fumed silica having a particle size of 00 nm.
It may further contain a seed.

The inorganic chromate component of the two-component type lubricating chromate treatment composition for metallic materials of the present invention may further contain at least one selected from phosphoric acid and fluoride.

The method for treating a lubricious chromate film on a metallic material according to the present invention comprises mixing an aqueous emulsion of a lubricant component of the two-component type lubricating chromate treatment composition for metallic material of the present invention with an aqueous solution of an inorganic chromate component. And adjusting the pH to less than 3.0 to prepare a treatment liquid, applying the treatment liquid to the surface of the metal material, and drying it to form a lubricious chromate film on the surface of the metal material. It is characterized by that.

In the treatment liquid used in the above method, the total chromium ion concentration (total concentration of hexavalent chromium ions and trivalent chromium ions) is preferably 1 to 100 g / liter.

[0022]

The function of the present invention will be described in detail below. The metal material targeted by the present invention mainly includes, but is not limited to, a steel material, a steel plate, a zinc-based plated steel sheet, an aluminum alloy material, and a stainless steel material.

The two-component type lubricating chromate treatment liquid for metal materials in the present invention is composed of (A) a lubricant component aqueous emulsion and (B) an inorganic chromate component aqueous solution.

Therefore, the lubricating component aqueous emulsion (A) will be described first. The lubricant component contains at least one selected from wax and polytetrafluoroethylene (hereinafter referred to as PTFE), and is used as an aqueous emulsion with the following specific emulsifier component.

The emulsifier component used in the present invention is at least one aromatic ring structure (eg, benzene ring, naphthalene ring, diphenyl ring, etc.) per molecule, polyethylene glycol group, and addition-polymerized two or more molecules of ethylene. It contains a nonionic surfactant having at least one member selected from the group consisting of oxides.

The nonionic surfactant used in the present invention is not particularly limited in addition to the above matters, and any one or more selected from the above-mentioned nonionic emulsifiers can be used. At least 1 contained in such a nonionic surfactant
The individual aromatic ring structure acts as a lipophilic group, and the polyethylene glycol or ethylene oxide adduct acts as a hydrophilic group. It is further preferable that the lipophilic group and the hydrophilic group are bonded by a bonding method other than the ester bond.

Specific examples of the group having at least one aromatic ring structure will be explained. For example, phenols,
Groups having one benzene nucleus such as alkylated phenols, polynuclear aromatic groups such as naphthalene and anthracene, styrenated phenols, polyvinylphenols, phenols and aldehydes such as formaldehyde and acetaldehyde. , A group having a plurality of benzene nuclei by addition of mononuclear aromatic compounds such as condensation products with ketones such as acetone and methyl ethyl ketone, and condensation polymerization, and polynuclear aromatic compounds such as naphthalene and bisphenol There are a group obtained by condensation polymerization of a compound and an aldehyde such as formaldehyde and acetaldehyde, or a ketone such as acetone and methyl ethyl ketone, and a group having a plurality of benzene nuclei, and a composite group thereof.

The method used for emulsification is not particularly limited and may be any emulsification method that is generally used, that is, a method using a polar group, a method using an emulsifier, a mechanical method, or the like. Emulsions can be used.

The lubricant component used in the present invention may contain a conventionally known lubricant such as graphite, molybdenum disulfide, fats and oils in addition to the above wax and / or PTFE. When a lubricant component containing graphite, molybdenum disulfide, etc. is used by being contained in the treatment liquid of the present invention, the film formed is colored black, and when the metal material forming this film is processed, depending on the degree of molding processing. May change the degree of coloring and cause uneven appearance. Further, when oils and fats are used as a lubricating component, it is necessary to degrease when coating in the subsequent step, which may be disadvantageous in the step.

The wax used in the present invention is not particularly limited, but specific examples of preferable waxes include waxes such as paraffin, microcrystalline and polyethylene waxes, which can be used as emulsions. Especially preferred is a melting point of 50-
It is a wax at 150 ° C. Waxes with a melting point of less than 50 ° C may result in insufficient lubricity,
A wax having a melting point higher than that may be difficult to emulsify, and a coating formed from a coating treatment liquid containing such a wax emulsion inevitably contains a non-uniform lubricant component in the coating. Since it contains, the lubricity may be insufficient. The PTFE used in the present invention is also not particularly limited, but a commercially available PTFE powder or the like emulsified in water, or an emulsion produced by emulsion polymerization can be used.

To stabilize the aqueous lubricant component emulsion (A) in the present invention, an emulsifier component containing the above-mentioned nonionic surfactant is used, which contains other nonionic and / or anionic emulsifiers. You may stay. In this way, an aqueous emulsion of the lubricant component stably dispersed in water can be obtained. Examples of other nonionic surfactants that can be used include higher alcohol ethylene oxide adducts, fatty acid ethylene oxide adducts, polyhydric alcohol fatty acid ester ethylene oxide adducts, higher alkylamine ethylene oxide adducts, fatty acid amide ethylene oxide adducts. Polyethylene glycol type such as polypropylene glycol ethylene oxide adduct, glycerol fatty acid ester type, fatty acid ester type of pentaerythritol and sorbitan, alkyl ether type of polyhydric alcohol, fatty acid amide type of alkanolamines, etc. Nonionic surface active Agents and the like.

Examples of anionic emulsifiers that can be used in the present invention include higher alcohol sulfate ester salts, higher alkyl ether sulfate ester salts, sulfated oils, sulfated fatty acid esters, sulfated ester salts such as sulfated olefins, and the like.
Examples include sulfonate type alkylbenzene sulfonate, alkylnaphthalene sulfonate, paraffin sulfonate, igepon T, aerosol OT and other sulfonate types, and higher alcohol phosphate ester type and other phosphate ester salt type anionic surfactants. .

The action and effect of the nonionic emulsifier (and optionally anionic emulsifier) used in the lubricant component aqueous emulsion of the present invention will be described below. The treatment liquid in the method of the present invention contains trivalent chromium ions and hexavalent chromium ions derived from the inorganic chromate component aqueous solution (B), and the pH thereof is adjusted to less than 3.0 before use. The trivalent chromium ions contained here are polyvalent cations and tend to neutralize the charge on the surface of the emulsion particles. In general, neutralizing the surface charge of a particle tends to destabilize the dispersion of the particle and agglomerate.

At the same time, hexavalent chromium ions present in the treatment liquid are strong oxidants, and the treatment liquid pH is 3.0.
Should be kept below. For this reason, when the aqueous solution of inorganic chromate component (B) is mixed with the aqueous emulsion of lubricant component (A), a sudden pH change occurs, which causes a sudden change in the zeta (ζ) potential on the particle surface and destabilization of dispersion. A tendency to agglomerate occurs. In order to prevent such dispersion instability of emulsion particles and maintain a stable dispersion state in the treatment liquid in the present invention, it is particularly effective to use an emulsifier containing a nonionic surfactant. .

PTFE, wax and the like used as the lubricant component in the present invention have a very low coefficient of friction themselves and are widely known as low friction materials, and they should be emulsified and used as a lubricant component. Is also known, but the action of the emulsifier does not sufficiently continue in the chromate treatment liquid having a pH of less than 3.0, and the chromate treatment liquid containing this tends to have emulsion particles that are highly stable as a treatment liquid. It has to be insufficient. However, in the present invention, the lubricant component aqueous emulsion (A) stably emulsified by the above-mentioned nonionic surfactant-containing emulsifier is the same as the chromate component aqueous solution (B) containing hexavalent chromium ions and trivalent chromium ions. The effect of the emulsifier is maintained even in the treatment liquid which is mixed and has a pH of less than 3.0, and the stability of the treatment liquid is improved to such an extent that it can be put to practical use. This is exactly the advantage and advantage of the treatment liquid obtained from the two-component composition of the present invention.

A coating formed on the surface of a metal material by applying the chromate treatment liquid of the present invention containing at least one selected from wax and PTFE as a lubricant component to the surface of the metal material and then drying the solution is It does not significantly change the appearance of the generally known chromate film, and has a yellow to nearly colorless appearance. That is, since the change in the appearance color tone due to the degree of processing is extremely small, the appearance quality is not deteriorated, and such a product is practically preferable.

Next, the inorganic chromate component aqueous solution (B) contained in the lubricating chromate treatment composition for metal materials in the present invention will be explained. The concentrations of hexavalent chromium ions and trivalent chromium ions contained in the inorganic chromate component aqueous solution (B) are not particularly limited, but all chromium ions (hexavalent chromium ions + 3
The (valent chromium ion) concentration is preferably 1 to 100 g / liter. If it is less than 1 g / liter, the corrosion resistance of the obtained coating may be insufficient, and even if it exceeds 100 g / liter, the corrosion resistance of the obtained coating reaches saturation, which is not economical. Further, the weight ratio of trivalent chromium ion / 6 hexavalent chromium ion is 2/8 to 7 /
It is preferably within the range of 3. If this ratio is less than 2/8, the water resistance of the resulting coating may be insufficient due to the excessively high content of hexavalent chromium in the formed coating, and if it exceeds 7/3. 6 in the formed film
Since the content of valent chromium decreases excessively, the corrosion resistance of the resulting coating may be insufficient. The source of hexavalent chromium ions is not particularly limited, but, for example, chromic acid, dichromic acid and salts thereof can be used. Examples of the trivalent chromium ion source include, but are not limited to, chromium nitrate, chromium phosphate, chromium fluoride, and reduced products of chromic acid.

In order to keep the lubricating chromate treatment liquid for metal materials of the present invention stable, it is effective to stabilize the trivalent chromium ions contained in the treatment liquid. For that purpose, it is necessary to adjust the pH of the treatment liquid to less than 3.0.
There is no particular limitation on the type of acid used to adjust the pH of the treatment liquid to less than 3.0. Specifically showing the type of pH adjusting acid particularly preferred for use in the film treatment liquid of the present invention,
Inorganic acids such as phosphoric acid, chromic acid, dichromic acid, hydrofluoric acid and complex hydrofluoric acid, organic carboxylic acids such as formic acid, acetic acid, glycolic acid, citric acid, tartaric acid, malic acid, acrylic acid, methacrylic acid and maleic acid Examples thereof include homopolymers or copolymers of carboxylic acids having vinyl polymerizability such as acrylic acid, methacrylic acid and maleic acid. When using one or more selected from these acids,
It is preferable because it does not impair the coatability and corrosion resistance of the resulting film. These acids may be contained in the aqueous solution of the inorganic chromate component, or may be added during the preparation of the treatment liquid.

Particularly preferred acids are phosphoric acid, hydrofluoric acid,
Complex fluorides such as hydrosilicofluoric acid can be mentioned.
These acids and trivalent chromium ions are preferably used so that the equivalence ratio of trivalent chromium ions / acid is 1/3 or more. When the equivalence ratio is less than 1/3, the acid ratio is excessive. Therefore, the water resistance of the obtained coating may be lowered, and thus the corrosion resistance may be deteriorated.

The two-component type lubricating chromate treatment composition for metallic materials of the present invention has at least one selected from colloidal silica, silica sol and fumed silica having a particle diameter of 5 to 300 nm in the aqueous chromate component solution. Seeds can be included. The particle diameter of the silica sol that can be used is preferably within the range of 5 to 300 nm. A film formed by using a treatment liquid containing silica having a particle size of more than 300 nm may have irregularities on the surface of the film, which may impair the glossiness of the appearance. Further, when a coating treatment liquid containing a silica sol having a particle diameter of less than 5 nm is used, the specific surface area of the silica sol becomes excessive and the stability of the treatment liquid may be impaired. The silica may be added when preparing the chromate treatment liquid.

In the present invention, the effect of silica contained in the lubricating chromate treatment liquid for metal materials will be described. Generally, as the effect of silica contained in the chromate treatment liquid, mainly the effect of improving corrosion resistance and the effect of improving fingerprint resistance are known. Silica also exhibits the same effect in the lubricating chromate treatment liquid for metal materials of the present invention.

Further, the content ratio of the lubricant component contained in the lubricating chromate treatment liquid for metal materials in the present invention is 1/50 to 10 by weight ratio of lubricant component / inorganic chromate component.
When the weight ratio of the lubricant component is less than 1/50, which is preferably within the range of 0/1, the lubricating performance of the obtained coating may be insufficient. Further, if it exceeds 100/1, the corrosion resistance and weldability of the obtained film may be deteriorated.

In the aqueous solution of the chromate component of the two-component type lubricating chromate treatment composition for metal materials of the present invention, in addition to the above components, for example, zinc, iron, nickel, cobalt, aluminum contained in a usual chromate liquid, Titanium, may contain a metal such as zirconium as a soluble salt, also, in the lubricant component aqueous emulsion, polyacrylic acid, maleic acid-methyl vinyl ether copolymer, a water-soluble polymer such as polyacrylic amide,
It may contain an acrylic acid ester-based copolymer emulsion, styrene, an acrylic acid ester-based copolymer emulsion, an epoxy resin emulsion, an ethylene / acrylic acid copolymer emulsion, a polyester resin emulsion and the like. In particular, the addition of an epoxy resin emulsion having a bisphenol skeleton is effective in improving the coating adhesion of the obtained film. The above-mentioned additional components may be added at the time of preparing the treatment liquid.

Next, the method for forming the lubricating film of the present invention will be described. In this treatment method, a treatment liquid having a pH of less than 3.0 is prepared from the two-component composition of the present invention, which is applied to the surface of the metal material and dried. The coating and drying methods are not limited, and a treatment liquid layer may be formed by a method such as commonly known dipping and showering, and the coating amount of the treatment liquid may be adjusted by air, rolls, or the like, or roll coating. A desired coating can be applied by any method such as a coating method and a spray coating method. The amount of the coating formed by the method of the present invention is not limited, but the total amount of trivalent chromium ions and hexavalent chromium ions deposited on the surface of the metal material is within the range of 5 to 150 mg / m ² (calculated as metal chromium). Preferably there is. If the total amount of trivalent chromium ions and hexavalent chromium ions deposited is less than 5 mg / m ² , the corrosion resistance of the resulting coating may be insufficient, and it is 150
Even if it exceeds mg / m ² , the corrosion resistance of the obtained coating may be saturated and it may not be economical.

The method of drying after coating is also not particularly limited, and a method of drying such as hot air or high frequency induction heating can be used depending on the application, productivity and economy, and the heating temperature and heating time are also applicable. Also, there is no particular limitation, and appropriate drying conditions can be selected depending on the metal material, application, productivity, and economic efficiency.

[0046]

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

Examples 1 to 12 and Comparative Examples 1 to 6 (1) Method for Preparing Inorganic Chromate Component Aqueous Solution An inorganic chromate component aqueous solution I having the composition shown in Table 1 was prepared by first dissolving 200 g of chromic anhydride in 500 g of water. Then, methanol is added to this aqueous solution to partially reduce chromic acid so that the weight ratio of hexavalent chromium ion / trivalent chromium ion is 7
After setting to / 3, water was added to adjust the total amount to 1 kg. In addition, the inorganic chromate component aqueous solutions II to VI shown in Table 1 are used.
Were prepared to have the compositions shown in Table 1 by the same procedure as the aqueous solution I of chromate component.

(2) Lubricant Component An aqueous emulsion was prepared so as to have the composition shown in Table 2. (3) Preparation of Chromate Treatment Liquid One of the inorganic chromate component aqueous solutions I to IV shown in Table 1:
385 g was mixed with 16 g of one kind of the lubricant component-containing aqueous emulsions a to c shown in Table 2, and then water was added to make 1 liter to prepare a chromate treatment liquid having a composition shown in Table 3. Prepared.

(4) Preparation of test plate Commercially available galvanized steel sheet (EG), hot-dip galvanized steel sheet (GI), alloyed hot-dip galvanized steel sheet (GA), 5%
The aluminum / zinc plated steel sheet (GF) or the aluminum plated steel sheet (AS) was used as a test plate. This test plate was preliminarily treated with an alkaline degreasing agent (trade name: fine cleaner 4336, concentration = 20, manufactured by Nippon Parkerizing Co., Ltd.).
g / liter, degreasing agent temperature = 60 ° C., degreasing time = 10
Second, degreasing method = spraying method), followed by washing with water,
After draining, in each of Examples 1 to 12 and Comparative Examples 1 to 6, each treatment liquid was applied to the test plate using a roll coater so that the WET coating amount was 5 ml / m ^2.
It was dried at 00 ° C. (achieved plate temperature) for 5 seconds. Table 3 shows the processing details of the test plate.

(5) Performance test (a) Corrosion resistance Using various treated steel sheets produced under the above conditions, JIS-Z
According to each material, the 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 AS material, and 400 hours for AS material. It was evaluated by. <Evaluation criteria> Excellent 5 ... Rust generation area: less than 5% ↑ 4 ... Rust generation area: 5% or more and less than 10% 3 ... Rust generation area: 10% or more, less than 15% ↓ 2 ... Rust generation area: 15% Above, less than 25% Poor 1 ... Rust generation area: 25% or more

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

(C) Dynamic friction coefficient Bowden tester (Conditions: pressure contactor = SUJ-2, 10 mm
φ, sliding speed 10 mm / sec, room temperature), the dynamic friction coefficient was measured under a load of 100 g for the product of the example according to the present invention and a load of 50 g for the product of the comparative example.

(D) Weldability With respect to the electrogalvanized nickel alloy-plated steel sheet, if spot welding is continuously carried out under the following conditions, the weld terminal gradually deteriorates and the weldability deteriorates. Can be evaluated. That is, 30 × 10 for every 100 hit points
Welded another test piece of 0 mm and the tensile strength of the test piece was 4
I recorded the number of hits until I could maintain 00kg. <Welding conditions> Pressurizing force: 200 kg Current: 8.5 kA Energizing time: 10 cycles Electrode shape: R40 (radius type) Electrode material: Chrome-copper

(E) Paintability Various treated steel sheets produced under the conditions shown in Table 1 were coated with melamine and alkyd paint (trade name: Dericon # manufactured by Dainippon Paint Co., Ltd.).
700) is bar-coated so that the coating film thickness is 25 μm,
A coated plate was prepared by baking and drying at 140 ° C. for 30 minutes.
A coating performance test was carried out on the coated plate produced as described above under the following conditions.

(I) Primary Adhesion <Gourd-eye Erichsen Test> After making 100 scoring cuts of 1 mm square on the surface of the coating film with a cutter knife,
5 mm of extruded spots were extruded by an Erichsen tester, and the number of remaining spots in the coating film after peeling with a cellophane tape was evaluated.

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

(Ii) Secondary Adhesion The coated plate was immersed in boiling water for 4 hours and then an adhesion test was conducted under the following conditions. <Eye-opening eye test> After making 100 cut-outs in 1 mm square on the coating surface with a cutter knife,
5 mm of the crevices were pushed out by an Erichsen tester, and the number of residual crevices of the coating film after peeling with a cellophane tape was evaluated. That is, the larger the number of remaining coating films, the better the coating adhesion.

<DuPont Impact Test> After the DuPont impact was applied to the surface of the coating film under the conditions of a 1/2 inch φ impact shape, 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 observed. evaluated.

(Iii) Corrosion resistance test after coating Put a cross cut on the coated surface until reaching the metal base,
After subjecting this to a salt spray test (JIS-Z2371) for 500 hours, the width of peeling of the coating film from the cross-cut portion was measured in mm. That is, the smaller the number of mm, the better the corrosion resistance after painting.

The results of the above tests are shown in Table 4.

[0061]

[Table 1]

[0062]

[Table 2]

[0063]

[Table 3]

[0064]

[Table 4]

As is clear from Table 4, in Examples 1 to 12 using the chromate treatment liquid prepared from the two-pack type composition of the present invention, the films formed had a small coefficient of friction and were easy to process. It also showed excellent weldability, bare corrosion resistance, and paintability. On the other hand, the films formed in Comparative Examples 1 to 5 which are the conventional techniques have a large friction coefficient and are significantly inferior in workability, and cannot be processed without applying a lubricating oil such as a press oil. there were. Further, the film formed in Comparative Example 6 had a small friction coefficient and excellent workability, but because of its large insulating property, spot welding,
The paintability was significantly inferior.

[0066]

As is apparent from the above description, the two-component type lubricating chromate treatment composition for metal materials of the present invention and the treatment method using the treatment liquid containing the same have a friction coefficient on various metal material surfaces. A chromate film that is small and has excellent lubricity, weldability, bare corrosion resistance, and paintability can be efficiently formed, and the press working environment can be greatly improved, which is a great practical effect. Is.

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Claims (6)

[Claims] 1. The following components: (A) a lubricant component containing at least one selected from wax and polytetrafluoroethylene, at least one aromatic ring structure per molecule, a polyethylene glycol group, and an addition. An emulsifier component containing a nonionic surfactant having at least one member selected from the group consisting of polymerized two or more molecules of ethylene oxide, wherein the lubricant component is stably emulsified by the emulsifier component. A two-component type lubricating chromate treatment composition for metal materials, comprising an aqueous emulsion of a lubricant component and (B) an aqueous solution of an inorganic chromate component containing hexavalent chromium ions and trivalent chromium ions. 2. The metallic material according to claim 1, wherein the content of the nonionic surfactant in the aqueous emulsion is 0.5 to 20 parts by weight with respect to 100 parts by weight of the lubricant component. Liquid lubricating chromate treatment composition. 3. The aqueous solution of the inorganic chromate component is 5 to
The two-component lubricative chromate treatment composition for metal materials according to claim 1 or 2, further containing at least one selected from silica sol, colloidal silica, and fumed silica having a particle diameter of 300 nm. 4. The two-component lubricous chromate for metal materials according to claim 1, wherein the aqueous solution of the inorganic chromate component further contains at least one selected from phosphoric acid and fluoride. Treatment composition. 5. A lubricant component aqueous emulsion of the two-component type lubricative chromate treatment composition for metal materials according to claim 1, and an inorganic chromate component aqueous solution are mixed, and the pH is adjusted. It is characterized in that the treatment liquid is prepared by adjusting it to less than 3.0, the treatment liquid is applied to the surface of a metal material, and this is dried to form and adhere a lubricious chromate film on the surface of the metal material. Lubricating chromate coating method for metallic materials. 6. The method for treating a lubricious chromate film on a metal material according to claim 5, wherein the treatment liquid has a total chromium ion concentration of 1 to 100 g / liter.