JP2002275644A - Metallic surface treatment composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a metallic surface treatment composition which enables the obtainment of corrosion resistance and lubricity by single treatment without incorporating heavy metals such as hexavalent chromium into a film. SOLUTION: The metallic surface treatment composition which can deposit a lubricating film is obtained by blending (A) a water based solution containing titanium obtained by reacting at least one kind of titanium compound selected from hydrolyzable titanium compounds, hydrolyzable titanium compound low condensation products, titanium hydroxide and titanium hydroxide low condensation products with a hydrogen peroxide solution with (B) at least one kind of compound selected from phosphoric compounds, metallic hydrofluoric acids and metallic hydrofluorides, (C) a water based organic high molecular compound stable at pH <=7, and (D) a lubricant.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an organic composite coated steel sheet based on a galvanized steel sheet used for automobile bodies and home electric appliances, which is excellent in press formability and corrosion resistance. Things.

[0002]

2. Description of the Related Art In the fields of automobile bodies and home electric appliances, there is a demand for excellent press-formable materials and a problem of destruction of an ozone layer of a fluorocarbon solvent used in a degreasing process. Development of a possible organic composite coated steel sheet has been promoted. For example, Japanese Patent Application Laid-Open No. 64-8033 discloses a Zn-Ni alloy-plated steel sheet having a chromate layer on its surface, and an organic layer comprising an amine-modified epoxy resin containing silica or chromate as a second layer on the chromate layer. An organic composite coated steel sheet coated with a film is disclosed in JP-A-5-65666, in which a zinc-based plated steel sheet has a chromate layer on the surface, and an aqueous resin, silica, and a polar group-provided molecular weight of 1000 to 4000 on the upper layer. Polyolefin wax dispersion having a softening temperature of 150 ° C. or less (particle size: 3.0 μm)
Below) and a Teflon (registered trademark) dispersion (particle diameter: 3.0 μm or less), an organic composite coated steel sheet having an organic coating, and JP-A-6-57440 discloses:
Organic composite having a chromate layer on the surface of a zinc-based or aluminum-based plated steel sheet and an organic coating containing a fine powder of carboxyl-modified epoxy resin or polyvinyl butyral resin, silica, polyethylene wax and polytetrafluoroethylene resin on the upper layer A coated steel sheet is disclosed.

[0003] In each of these methods, a lubricating organic film is formed on a steel plate which has been subjected to chromate treatment. However, since this chromate treatment uses hexavalent chromium which is a pollution control substance, In the treatment process, chromate salts have an adverse effect on the human body, it is difficult to dispose of chromium sludge after wastewater treatment, and hexavalent chromium may be eluted from products after chromate treatment. Have a problem. For this reason, as the use control standards for chromic acids have become stricter, the management of chromate treatment plants, wastewater treatment, and secondary contamination by chromate treatment have become problems, and in response to this, each plant has closed drainage relations. In addition, measures are taken to minimize the emission of chromium ions to the outside. Also, in the process of degreasing the rust-preventive oil and press oil attached to the chromate-treated steel sheet by the user, when using an alkaline degreasing solution, the elution of chromium into the degreasing solution is considerably increased,
Degreasing treatment of the degreasing solution is required.

[0004] In view of such circumstances, in order to prevent the generation of white rust on a zinc-based plated steel sheet, many pollution-free treatment techniques not based on chromate treatment have been proposed. Among them, several methods using an organic compound or an organic resin have been proposed. For example, Japanese Patent Application Laid-Open No. S71-71233 discloses a method using tannic acid.
Japanese Patent Application Laid-Open No. 8-325 discloses a method using a thermosetting paint obtained by mixing an epoxy resin, an amino resin and tannic acid.
No. 760 discloses a method using a mixed composition of an aqueous resin and a polyphenol carboxylic acid.
No. 7 discloses a method using a treating agent obtained by mixing a heterocyclic compound such as a benzothiazole compound and tannic acid, and JP-A-11-36079 discloses an aqueous resin, silica particles,
Examples thereof include a method using a composition containing aminoalkylenephosphonic acid and / or alkylmethane-1-hydroxy-1,1-diphosphonic acid, lithium silicate and ammonium metavanadate.

[0005] However, in each of these, a lubricating film is formed on the undercoating film.
Two separate processes are required. Development of a metal surface treatment composition having corrosion resistance and lubricity in one treatment is desired because of problems such as shortening of the process and disposal of the treatment solution.

An object of the present invention is to solve the above-mentioned problems of the prior art, and to provide a metal surface having excellent corrosion resistance and lubricity in a single treatment without containing a heavy metal such as hexavalent chromium in a film. It is an object of the present invention to provide a treatment composition, and to provide a method for forming a surface treatment film using the metal surface treatment composition and an organic coated steel sheet.

[0007]

Means for Solving the Problems The present inventors have proposed, as a metal anticorrosive, at least one selected from an aqueous liquid containing a specific titanium, a phosphoric acid compound, a metal hydrofluoric acid and a metal hydrofluoride. The present inventors have found that a metal surface treatment composition containing one compound, an aqueous organic polymer compound and a lubricant achieves the above object, and have completed the present invention.

Thus, according to the present invention, (A) at least one titanium compound selected from a hydrolyzable titanium compound, a low condensate of a hydrolyzable titanium compound, titanium hydroxide and a low condensate of titanium hydroxide, and peroxide Aqueous liquid containing titanium obtained by reacting with hydrogen water, (B) at least one compound selected from phosphoric acid compounds, metal hydrofluoric acid and metal hydrofluoride, (C) PH7 or less A metal surface treatment composition capable of forming a lubricating film, characterized by comprising a stable aqueous organic polymer compound and (D) a lubricant.

The present invention also provides a method for forming a surface-treated film, which comprises applying the metal surface-treating composition to a substrate and subjecting it to a heat treatment if necessary.

Further, the present invention provides an organic-coated steel sheet characterized in that the surface of a zinc-based plated steel sheet is coated with a surface-treated film of the metal surface-treating composition.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The metal surface treatment composition of the present invention comprises:
At least one selected from an aqueous liquid (A) containing titanium, a phosphoric acid compound, a metal hydrofluoric acid, and a metal hydrofluoride.
It contains a compound (B), an aqueous organic polymer compound (C) and a lubricant (D).

Aqueous Liquid Containing Titanium (A) The aqueous liquid containing titanium (A) used in the metal surface treatment composition of the present invention comprises a hydrolyzable titanium compound, a hydrolyzable titanium compound low condensate, It is an aqueous liquid containing titanium obtained by reacting at least one titanium compound selected from titanium and titanium hydroxide low-condensate with hydrogen peroxide water. The aqueous liquid is not particularly limited as long as it is as described above, and a conventionally known aqueous liquid can be appropriately selected and used.

The above-mentioned hydrolyzable titanium compound is a titanium compound having a hydrolyzable group directly bonded to titanium, and produces titanium hydroxide by reacting with water such as water or steam. In the hydrolyzable titanium compound, all of the groups bonded to titanium may be hydrolyzable groups, or one part thereof may be a hydrolyzed hydroxyl group.

The hydrolyzable group is not particularly limited as long as it forms titanium hydroxide by reacting with water as described above. For example, a lower alkoxyl group or a group which forms a salt with titanium (for example, , A halogen atom (eg, chlorine), a hydrogen atom, a sulfate ion, etc.).

As the hydrolyzable titanium compound containing a lower alkoxyl group as a hydrolyzable group, a compound represented by the general formula Ti (OR) ₄ (wherein R is the same or different and represents an alkyl group having 1 to 5 carbon atoms) ) Is preferred. Examples of the alkyl group having 1 to 5 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, an iso-butyl group, a sec-butyl group, and a tert-butyl group. No.

As the hydrolyzable titanium compound having a group capable of forming a salt with titanium as a hydrolyzable group, representative examples include titanium chloride and titanium sulfate.

The hydrolyzable titanium compound low condensate is a low condensate of the above hydrolyzable titanium compounds. The low-condensate may be either a group in which all of the groups bonded to titanium are hydrolyzable or a part of which is a hydrolyzed hydroxyl group.

Also, orthotitanic acid (titanium hydroxide gel) obtained by reacting an aqueous solution of titanium chloride or titanium sulfate with an alkaline solution such as ammonia or caustic soda can be used as a low condensate.

The degree of condensation of the low condensate of the hydrolyzable titanium compound or the low condensate of titanium hydroxide is 2 to 30.
As the aqueous liquid (A), it is preferable to use a compound having a condensation degree in the range of 2 to 10,
As long as it is an aqueous liquid containing titanium obtained by reacting the above-described titanium compound with aqueous hydrogen peroxide, a conventionally known aqueous liquid can be used without particular limitation.
Specifically, the following can be mentioned.

A titanyl ion hydrogen peroxide complex or a titanic acid (peroxotitanium hydrate) aqueous solution obtained by adding aqueous hydrogen peroxide to a gel or sol of hydrous titanium oxide is disclosed in JP-A-63-35419 and JP-A-Hei. -224220).

Liquids for forming a titania film obtained by reacting a hydrogen peroxide solution on a titanium hydroxide gel produced from an aqueous solution of titanium chloride or titanium sulfate and a basic solution (Japanese Patent Application Laid-Open Nos. -67516).

In the above-mentioned liquid for forming a titania film, an aqueous solution of titanium chloride or titanium sulfate having a group capable of forming a salt with titanium is reacted with an alkaline solution such as ammonia or caustic soda to form a hydroxide called orthotitanic acid. Precipitate the titanium gel. Subsequently, the titanium hydroxide gel is separated by decantation using water, washed well with water, and further added with hydrogen peroxide solution to decompose and remove excess hydrogen peroxide, whereby a yellow transparent viscous liquid can be obtained.

The precipitated orthotitanic acid is in a gel state polymerized by polymerization of OH and hydrogen bonds, and cannot be used as an aqueous liquid containing titanium as it is. When hydrogen peroxide solution is added to this gel, a part of OH becomes a peroxidized state and dissolves as peroxotitanate ions, or it becomes a kind of sol in which the polymer chain is divided into low molecules, and excess peroxidation occurs. Hydrogen is decomposed into water and oxygen to be used as an aqueous liquid containing titanium for forming an inorganic film.

Since this sol contains only oxygen atoms and hydrogen atoms in addition to titanium atoms, when it is changed to titanium oxide by drying or calcination, only water and oxygen are generated, which is necessary for the sol-gel method and thermal decomposition of sulfates and the like. It is not necessary to remove a carbon component or a halogen component, and a crystalline titanium oxide film having a relatively high density can be formed even at a lower temperature than before.

Hydrogen peroxide is added to an aqueous solution of an inorganic titanium compound such as titanium chloride or titanium sulfate to form peroxotitanium hydrate, and a basic substance is added thereto. After a precipitate of the titanium hydrate polymer is formed, at least a dissolved component other than water derived from the titanium-containing raw material solution is removed, and a solution for forming titanium oxide obtained by further reacting with hydrogen peroxide (particularly, Kai 2000-247638 and JP 2000-247639
Reference).

As the aqueous liquid (A) used in the present invention, an aqueous liquid containing titanium obtained by the above-mentioned known method can be used. In addition, a method of producing the aqueous liquid by adding a titanium compound to a hydrogen peroxide solution. The aqueous liquid containing titanium obtained by the above can be used. The titanium compound contains a group which is hydrolyzed by the general formula Ti (OR) ₄ (where R is the same or different and represents an alkyl group having 1 to 5 carbon atoms). It is preferable to use a hydrolyzable titanium compound or a low-condensate of the hydrolyzable titanium compound.

The mixing ratio of the hydrolyzable titanium compound and / or a low-condensate thereof (hereinafter, these are simply referred to as “hydrolyzable titanium compound a”) and hydrogen peroxide water are as follows. It is preferably in the range of 0.1 to 100 parts by weight, particularly 1 to 20 parts by weight in terms of hydrogen peroxide, based on 10 parts by weight of a. If the amount is less than 0.1 part by weight in terms of hydrogen peroxide, chelate formation is not sufficient and cloudy precipitation occurs.
On the other hand, if it exceeds 100 parts by weight, unreacted hydrogen peroxide is apt to remain, and dangerous active oxygen is released during storage.

The concentration of hydrogen peroxide in the aqueous hydrogen peroxide solution is not particularly limited, but is preferably in the range of 3 to 30% by weight in view of the ease of handling and the solid content of the product liquid related to coating workability.

The aqueous liquid (A) comprising the hydrolyzable titanium compound a is prepared by reacting the hydrolyzable titanium compound a with hydrogen peroxide at a reaction temperature of 1 to 70 ° C. for 10 minutes to 20 minutes.
It can be produced by reacting for hours.

The aqueous liquid (A) using the hydrolyzable titanium compound (a) is prepared by reacting the hydrolyzable titanium compound (a) with aqueous hydrogen peroxide to hydrolyze the hydrolyzable titanium compound with water. It is presumed that a hydroxyl group-containing titanium compound is generated, and then hydrogen peroxide is coordinated to the generated hydroxyl group-containing titanium compound, and a product obtained by this hydrolysis reaction and coordination by hydrogen peroxide occurring at the same time. And a chelating solution having extremely high stability at room temperature and enduring long-term storage is produced. The titanium hydroxide gel used in the conventional manufacturing method is partially three-dimensionalized by Ti-O-Ti bonds, and is essentially different in composition and stability from a product obtained by reacting this gel with a hydrogen peroxide solution.

When the aqueous liquid (A) using the hydrolyzable titanium compound a is subjected to a heat treatment or an autoclave treatment at 80 ° C. or higher, a titanium oxide dispersion liquid containing ultra-fine particles of crystallized titanium oxide is obtained. If it is lower than 80 ° C., crystallization of titanium oxide does not proceed sufficiently. In the titanium oxide dispersion thus produced, the particle diameter of the ultrafine titanium oxide particles is 10 nm or less, preferably in the range of 1 nm to 6 nm. The appearance of the dispersion is translucent. When the particle diameter is larger than 10 nm, the film forming property is reduced (1 μm).
m or more), which is not preferable. This dispersion can likewise be used.

The aqueous liquid (A) comprising the hydrolyzable titanium compound a is applied to a steel sheet material and dried or heat-treated at a low temperature to form a dense titanium oxide film having excellent adhesion by itself. it can.

As the heat treatment temperature, for example, it is preferable to form the titanium oxide film at a temperature of 200 ° C. or lower, particularly 150 ° C. or lower.

The aqueous liquid (A) using the hydrolyzable titanium compound a forms an amorphous titanium oxide film containing some hydroxyl groups at the above-mentioned temperature.

Further, the titanium oxide dispersion liquid which has been subjected to a heat treatment at 80 ° C. or higher can form a crystalline titanium oxide film only by coating, and thus is useful as a coating material of a material which cannot be subjected to a heat treatment.

In the present invention, as the aqueous liquid (A), a hydrolyzable titanium compound and / or a low-condensate of a hydrolyzable titanium compound and hydrogen peroxide water as described above are further used in the presence of a titanium oxide sol. An aqueous liquid containing titanium obtained by the reaction (hereinafter, abbreviated as "aqueous liquid (A-1)") can be used. As the hydrolyzable titanium compound and / or the low-condensate of the hydrolyzable titanium compound (hydrolysable titanium compound a), the above-mentioned general formula Ti (OR)
₄ (wherein R is the same or different and represents an alkyl group having 1 to 5 carbon atoms), a titanium monomer containing a group that becomes a hydroxyl group by hydrolysis and a low-condensate of the hydrolyzable titanium compound. It is preferred to use.

In the above-mentioned titanium oxide sol, amorphous titania and anatase-type titania fine particles contain water (if necessary,
For example, a sol dispersed in an aqueous organic solvent such as an alcohol-based or alcohol-ether-based solvent may be used.

As the above-mentioned titanium oxide sol, a conventionally known one can be used. Examples of the titanium oxide sol include (1) those obtained by hydrolyzing a titanium-containing solution such as titanium sulfate or titanyl sulfate;
Titanium oxide aggregates such as those obtained by hydrolyzing an organic titanium compound such as titanium alkoxide and (3) those obtained by hydrolyzing or neutralizing a titanium halide solution such as titanium tetrachloride are dispersed in water. Amorphous titania sol or anatase type titanium fine particles obtained by firing the titanium oxide aggregates and dispersing them in water can be used. Amorphous titania can be converted to anatase-type titania by firing at least at a temperature higher than the crystallization temperature of anatase, for example, at a temperature of 400 ° C. to 500 ° C. or higher. As an aqueous sol of the titanium oxide, for example, TKS-201 (manufactured by Teica Co., Ltd., trade name, anatase crystal form, average particle diameter 6n)
m), TA-15 (manufactured by Nissan Chemical Co., Ltd., trade name, anatase type crystal form), STS-11 (manufactured by Ishihara Sangyo Co., Ltd., trade name, anatase type crystal form) and the like.

The weight ratio of the titanium oxide sol to the titanium hydrogen peroxide reactant when used for reacting the hydrolyzable titanium compound a with aqueous hydrogen peroxide is 1/99 to 9
9/1, preferably in the range of about 10/90 to 90/10. When the weight ratio is less than 1/99, the effect of adding titanium oxide sol such as stability and photoreactivity is not seen, and 99/1
Exceeding the range is not preferred because the film-forming properties are poor.

The mixing ratio of the hydrolyzable titanium compound a and the hydrogen peroxide solution is 0.1 to 100 parts by weight, particularly 1 to 20 parts by weight in terms of hydrogen peroxide, based on 10 parts by weight of the hydrolyzable titanium compound a. Is preferably within the range. If the amount is less than 0.1 part by weight in terms of hydrogen peroxide, chelate formation is not sufficient and cloudy precipitation occurs. On the other hand, if it exceeds 100 parts by weight, unreacted hydrogen peroxide is apt to remain, and dangerous active oxygen is released during storage.

The hydrogen peroxide concentration of the aqueous hydrogen peroxide solution is not particularly limited, but is preferably in the range of 3 to 30% by weight from the viewpoint of the ease of handling and the solid content of the product liquid related to coating workability.

The aqueous liquid (A-1) is prepared by reacting the hydrolyzable titanium compound a with aqueous hydrogen peroxide in the presence of a titanium oxide sol at a reaction temperature of 1 to 70 ° C. for 10 minutes to 20 hours. Can be manufactured.

The aqueous liquid (A-1) is produced by reacting the hydrolyzable titanium compound a with aqueous hydrogen peroxide, whereby the hydrolyzable titanium compound a is hydrolyzed with water to form a hydroxyl group-containing titanium compound. Next, it is presumed that hydrogen peroxide is coordinated to the generated hydroxyl group-containing titanium compound, and the hydrolysis reaction and the coordination by hydrogen peroxide occur at the same time, resulting in stability at room temperature. Produces a chelating solution that is extremely high and can withstand long-term storage. The titanium hydroxide gel used in the conventional manufacturing method is Ti-OT
The gel is partially three-dimensionalized by i-bonds, and the gel and the hydrogen peroxide solution are essentially different in composition and stability. In addition, by using the titanium oxide sol, it is possible to prevent a partial condensation reaction from occurring during the synthesis to increase the viscosity. It is considered that the reason for this is that the condensation reaction product is adsorbed on the surface of the titanium oxide sol, thereby preventing polymerization in a solution state.

Further, the aqueous liquid (A-1) containing titanium was
When a heat treatment or an autoclave treatment is carried out at 0 ° C. or more, a titanium oxide dispersion containing crystallized ultrafine particles of titanium oxide is obtained. If it is lower than 80 ° C., crystallization of titanium oxide does not proceed sufficiently. In the titanium oxide dispersion thus produced, the particle diameter of the ultrafine titanium oxide particles is 10 nm or less, preferably in the range of 1 nm to 6 nm. The appearance of the dispersion is translucent. The particle size is 10
If it is larger than nm, the film-forming property is deteriorated (breakage occurs at 1 μm or more), which is not preferable. This dispersion can likewise be used.

The aqueous liquid (A-1) containing titanium is applied to a steel sheet material by drying or by heat treatment at a low temperature,
By itself, a dense titanium oxide film having excellent adhesion can be formed.

It is preferable to form the titanium oxide film at a temperature of, for example, 200 ° C. or lower, particularly 150 ° C. or lower.

The aqueous liquid (A-1) containing titanium forms an anatase-type titanium oxide film containing a small amount of hydroxyl groups at the above-mentioned temperature.

As the aqueous liquid (A) of the present invention, the aqueous liquid and the aqueous liquid (A-1) using the hydrolyzable titanium compound a have excellent properties such as storage stability and corrosion resistance. Preferably, one is used.

In the aqueous liquid (A) containing titanium, other pigments and sols can be added and dispersed as needed. Examples of the additives include commercially available titanium oxide sol, titanium oxide powder, and the like, mica, talc, silica, barita, clay, and the like.

Compound (B) The compound which is the component (B) of the metal surface treatment composition of the present invention is at least one compound selected from a phosphoric acid compound, a metal hydrofluoric acid and a metal hydrofluoride. It is.

Examples of the phosphoric acid compounds include phosphorous acid, strong phosphoric acid, triphosphoric acid, hypophosphorous acid, hypophosphoric acid,
Monophosphoric acids such as trimetaphosphoric acid, diphosphoric acid, diphosphoric acid, pyrophosphoric acid, pyrophosphoric acid, metaphosphoric acid, metaphosphoric acid, phosphoric acid (orthophosphoric acid), and phosphoric acid derivatives, and salts thereof, and tripolyphosphoric acid , Tetraphosphoric acid, hexaphosphoric acid, condensed phosphoric acids such as condensed phosphoric acid derivatives, and salts thereof. These compounds can be used alone or in combination of two or more. Also,
Examples of the alkali compound forming the above-mentioned salt include organic or inorganic alkali compounds such as lithium, sodium, potassium, and ammonium. further,
It is preferable to use a water-soluble phosphoric acid compound.

Examples of the phosphoric acid compound include sodium pyrophosphate, sodium tripolyphosphate, sodium tetraphosphate, metaphosphoric acid, ammonium metaphosphate,
It is preferable to use sodium hexametaphosphate, since sodium hexametaphosphate and the like exhibit excellent effects such as storage stability of the coating agent and rust prevention of the coating film.

In the present invention, the above-mentioned blend of the aqueous liquid (A) containing titanium and the phosphate compound is prepared by coordinating the acidic phosphate group ion bound to the phosphate compound with the titanium ion. It is considered that a complex structure is formed between the two.

Such a reaction can be easily carried out by simply mixing the two components. For example, by leaving the mixture at room temperature (20 ° C.) for about 5 minutes to about 1 hour, When forcibly heating, for example, heating can be performed at about 30 to about 70 ° C. for about 1 minute to about 30 minutes.

The above-mentioned metal hydrofluoric acid and metal hydrofluoride include, for example, zirconium hydrofluoric acid, titanium hydrofluoric acid, hydrosilicofluoric acid, zirconium fluoride, titanium fluoride, Examples thereof include silicofluoride. Examples of the metal hydrofluoric acid salt include, for example, sodium, potassium, lithium, and ammonium. Among them, potassium and sodium are preferable, and specific examples thereof include potassium zirconium fluoride, potassium titanium fluoride, Examples thereof include sodium silicofluoride and potassium silicofluoride.

The phosphoric acid compound, the metal hydrofluoric acid and the metal hydrofluoride can be used singly or as a mixture of two or more kinds. The compounding ratio of the compound (B) is determined based on the aqueous liquid containing titanium. The amount is preferably from 1 to 400 parts by weight, particularly preferably from 10 to 200 parts by weight, based on 100 parts by weight of the solid content of (A).

Aqueous Organic Polymer Compound (C) The metal surface treatment composition of the present invention contains an aqueous organic polymer compound (C) in addition to the above components. The aqueous organic polymer compound (C) itself is free from aggregation and sedimentation of the organic resin component dissolved or dispersed in water at a pH of 7 or less, and does not cause thickening or abnormal gelation. Any conventionally known aqueous liquid can be used as long as the aqueous liquid has excellent stability.

The aqueous organic polymer compound (C) is water-soluble,
Those having a form of water dispersibility or emulsion can be used. Water soluble organic polymer compound in water,
As a method of dispersing and emulsifying, a conventionally known method can be used. In particular,
As the organic polymer compound, a compound containing a functional group (for example, at least one kind of a hydroxyl group, a carboxyl group, an amino (imino) group, a sulfide group, a phosphine group, etc.) which can be made water-soluble or water-dispersible by itself, and if necessary. When some or all of these functional groups are acidic resins (such as carboxyl group-containing resins), amine compounds such as ethanolamine and triethylamine; ammonia water; lithium hydroxide;
Those neutralized with an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide, or a basic resin (such as an amino group-containing resin), a fatty acid such as acetic acid or lactic acid; A sum can be used.

Examples of the aqueous organic polymer compound (C) include an epoxy resin, a phenol resin, an acrylic resin, a urethane resin, an olefin-carboxylic acid resin, a nylon resin, and a polyoxyalkylene chain. Resins, polyvinyl alcohol, polyglycerin, carboxymethylcellulose, hydroxymethylcellulose, hydroxyethylcellulose and the like can be mentioned.

As the epoxy resin, a cationic epoxy resin obtained by adding an amine to an epoxy resin; a modified epoxy resin such as an acrylic-modified or a urethane-modified resin can be preferably used. As a cationic epoxy resin,
For example, an adduct of an epoxy compound with a primary mono- or polyamine, a secondary mono- or polyamine, a mixed primary and secondary polyamine, and the like (for example, U.S. Pat.
No. 99); an adduct of an epoxy compound and a secondary mono- or polyamine having a ketiminated primary amino group (see, for example, U.S. Pat. No. 4,017,438); And etherification reaction products with a hydroxyl compound having a secondary amino group (for example, see JP-A-59-43013).

The epoxy compound has a number average molecular weight of 4
In the range of from 0.00 to 4,000, in particular from 800 to 2,000, and the epoxy equivalent is in the range from 190 to 2,000, in particular 4
Those in the range of 00 to 1,000 are suitable. Such an epoxy compound can be obtained, for example, by reacting a polyphenol compound with epilurylhydrin. Examples of the polyphenol compound include bis (4-hydroxyphenyl) -2,2-propane,
4-dihydroxybenzophenone, bis (4-hydroxyphenyl) -1,1-ethane, bis (4-hydroxyphenyl) -1,1-isobutane, bis (4-hydroxy-tert-butylphenyl) -2,2-propane ,
Bis (2-hydroxynaphthyl) methane, 1,5-dihydroxynaphthalene, bis (2,4-dihydroxyphenyl) methane, tetra (4-hydroxyphenyl)-
Examples thereof include 1,1,2,2-ethane, 4,4-dihydroxydiphenylsulfone, phenol novolak, and cresol novolak.

As the above-mentioned phenolic resin, those obtained by making a polymer compound obtained by heating and adding and condensing a phenol component and formaldehydes in the presence of a reaction catalyst into water, can be suitably used. As the phenol component as a starting material, a bifunctional phenol compound, a trifunctional phenol compound, a phenol compound having four or more functional groups, and the like can be used. For example, as the bifunctional phenol compound, o-cresol, As trifunctional phenol compounds such as p-cresol, p-tert-butylphenol, p-ethylphenol, 2,3-xylenol, and 2,5-xylenol, phenol, m-cresol, m-ethylphenol, 3,5-
Bifunctional phenol compounds such as xylenol and m-methoxyphenol include bisphenol A and bisphenol F. These phenol compounds can be used alone or in combination of two or more.

Examples of the acrylic resin include a homopolymer or a copolymer of a monomer having a hydrophilic group such as a carboxyl group, an amino group, and a hydroxyl group, and a copolymer of a monomer having a hydrophilic group with another monomer. And copolymers with possible monomers. These are resins obtained by emulsion polymerization, suspension polymerization or solution polymerization, and, if necessary, neutralized and made aqueous or modified resins.

Examples of the carboxyl group-containing monomer include acrylic acid, methacrylic acid, maleic acid, maleic anhydride, crotonic acid and itaconic acid.

Examples of the nitrogen-containing monomer include nitrogen-containing alkyl (meth) acrylates such as N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, and Nt-butylaminoethyl (meth) acrylate. ) Acrylate; acrylamide, methacrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-methylol (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide,
N, N-dimethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, N, N
Polymerizable amides such as -dimethylaminoethyl (meth) acrylamide; 2-vinylpyridine, 1-vinyl-2-
Aromatic nitrogen-containing monomers such as pyrrolidone and 4-vinylpyridine; and allylamine.

As the hydroxyl group-containing monomers, 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, 2,3-dihydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth)
Acrylate and polyethylene glycol mono (meth)
Monoesters of polyhydric alcohols such as acrylates with acrylic acid or methacrylic acid; compounds obtained by ring-opening polymerization of ε-caprolactone with monoesters of the polyhydric alcohols with acrylic acid or methacrylic acid, and the like.

Other monomers include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl C1-C24 such as (meth) acrylate, 2-ethylhexyl acrylate, n-octyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, octadecyl (meth) acrylate, and isostearyl (meth) acrylate Alkyl (meth) acrylate; styrene, vinyl acetate and the like. These compounds can be used alone or in combination of two or more. In the present invention, “(meth) acrylate” means acrylate or methacrylate.

As the urethane resin, a polyurethane comprising a polyol such as a polyester polyol and a polyether polyol and a diisocyanate may be a chain which is a low molecular weight compound having two or more active hydrogens such as a diol and a diamine, if necessary. Those obtained by elongating a chain in the presence of an elongating agent and stably dispersing or dissolving in water can be suitably used, and known ones can be widely used (for example, JP-B-42-24192, JP-B-42-24194, No. 42-5118, No. 49-986, No. 4
9-33104, JP-B-50-15027 and JP-B-53-29175). As a method for stably dispersing or dissolving the polyurethane resin in water, for example, the following method can be used.

(1) A method of imparting hydrophilicity by introducing an ionic group such as a hydroxyl group, amino group or carboxyl group into a side chain or terminal of a polyurethane polymer, and dispersing or dissolving in water by self-emulsification.

(2) The reaction-completed polyurethane polymer or terminal isocyanate group is replaced with an oxime, alcohol,
A method in which a polyurethane polymer blocked with a blocking agent such as phenol, mercaptan, amine, and sodium bisulfite is forcibly dispersed in water using an emulsifier and mechanical shearing force. Further, a method of mixing a urethane polymer having a terminal isocyanate group with water / emulsifier / chain extender and simultaneously dispersing and increasing the molecular weight using mechanical shearing force.

(3) A method in which a water-soluble polyol such as polyethylene glycol is used as a polyol as a main raw material of polyurethane and dispersed or dissolved in water as a water-soluble polyurethane.

The above-mentioned dispersion or dissolution method is not limited to a single method, and a mixture obtained by each method can also be used for the polyurethane resin.

Examples of the diisocyanate which can be used for synthesizing the polyurethane resin include aromatic, alicyclic and aliphatic diisocyanates, and specific examples thereof include hexamethylene diisocyanate, tetramethylene diisocyanate, and 3,3′-dimethoxy-isocyanate. 4,4′-biphenylene diisocyanate, p-xylylene diisocyanate,
m-xylylene diisocyanate, 1,3- (diisocyanatomethyl) cyclohexanone, 1,4- (diisocyanatomethyl) cyclohexanone, 4,4'-diisocyanatocyclohexanone, 4,4'-methylenebis (cyclohexyl isocyanate) , Isophorone diisocyanate, 2,4-tolylene diisocyanate, 2,6-
Tolylene diisocyanate, p-phenylene diisocyanate, diphenylmethane diisocyanate, m-phenylene diisocyanate, 2,4-naphthalene diisocyanate, 3,3'-dimethyl-4,4'-biphenylene diisocyanate, 4,4'-biphenylene diisocyanate, and the like. . Of these, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, hexamethylene diisocyanate, and isophorone diisocyanate are particularly preferred.

Commercially available polyurethane resins include Hydran HW-330, HW-340 and HW-340.
-350 (all manufactured by Dainippon Ink and Chemicals, Incorporated),
Superflex 100, 150, F-3438
D (all manufactured by Daiichi Kogyo Seiyaku Co., Ltd.).

As the polyvinyl alcohol resin,
It is preferably polyvinyl alcohol having a saponification degree of 87% or more, and particularly preferably so-called completely saponified polyvinyl alcohol having a saponification degree of 98% or more, and having a number average molecular weight of 3,000 to 100,000.
Is preferably within the range.

As the resin having a polyoxyalkylene chain, those having a polyoxyethylene chain or a polyoxypropylene chain can be suitably used. For example, polyethylene glycol, polypropylene glycol, the above polyoxyethylene chain and the above polyoxypropylene chain can be used. Blocked polyoxyalkylene glycol in which a chain is bonded in a block shape can be exemplified.

As the olefin-carboxylic acid resin, a copolymer of an olefin such as ethylene or propylene and a polymerizable unsaturated carboxylic acid, and a polymerizable unsaturated compound are added to a dispersion of the copolymer to emulsify. At least one kind of water-dispersible or water-soluble resin selected from two kinds of resins which are polymerized and crosslinked in the particles can be used.

The above copolymer comprises olefin and (meth)
It is a copolymer with one or more of unsaturated carboxylic acids such as acrylic acid and maleic acid. In the copolymer, the content of the unsaturated carboxylic acid is 3 to 60% by weight,
The content is preferably in the range of 5 to 40% by weight, and the copolymer can be dispersed in water by neutralizing the acid group in the copolymer with a basic substance.

The above resin is added to an aqueous dispersion of a copolymer,
It is a crosslinked resin formed by adding a polymerizable unsaturated compound, performing emulsion polymerization, and further performing intra-particle crosslinking. Examples of the polymerizable unsaturated compound include the vinyl monomers listed in the description of the water-dispersible or water-soluble acrylic resin.
The species or two or more species can be appropriately selected and used.

The compounding ratio of the aqueous organic polymer compound (C) is 10 to 2,000 parts by weight, especially 100 to 1,000 parts by weight, per 100 parts by weight of the solid content of the aqueous liquid (A) containing titanium.
The amount within the range of 0 parts by weight is preferable from the viewpoints of stability of the liquid, anticorrosion property and the like.

Lubricant (D) By adding a lubricant which is the component (D) of the metal surface treatment composition of the present invention to the metal surface treatment composition, press formability is remarkably improved. Further, compared to a metal surface treatment composition without a lubricant, a good press-moldability with a lower film thickness can be obtained. The amount of the lubricant is preferably 1 to 50 parts by weight based on 100 parts by weight of the total solid content of the aqueous liquid (A) containing titanium and the aqueous organic polymer compound (C). If the amount of the lubricant exceeds 50 parts by weight, the adhesion to an electrodeposition paint or the like is deteriorated. Further, in order to obtain higher press formability and paint adhesion, the content is preferably in the range of 5 to 40 parts by weight.

As the lubricant, fine powder of fluororesin (eg, ethylene tetrafluoride resin, ethylene tetrafluoride-hexafluoropropylene copolymer resin, ethylene tetrafluoride-perfluoroalkyl vinyl ether copolymer resin, tetrafluoroethylene resin) Ethylene-ethylene copolymer resin, ethylene trifluoride chloride resin,
Fine powder such as vinylidene fluoride resin), polyolefin wax (eg, polyethylene wax, polypropylene wax, etc.), lubricant containing polyolefin and fluororesin mixed in one particle, graphite, boron nitride, carbon fluoride It is preferable to use at least one lubricant selected from the group consisting of In particular, the lubricating properties are markedly improved by the complex addition of polyolefin wax and fluororesin fine powder.

As the above-mentioned polyolefin wax, those produced by a coordination anion polymerization method using a Ziegler catalyst are preferably used, and among them, polyethylene wax is particularly preferred because it is most excellent in lubricity. Among polyethylene waxes, those having a molecular weight of 700 to 4500 and a softening point of 100 ° C. to 140 ° C. show particularly excellent lubricity, and further have a molecular weight of 1000 to 1000.
Those having 3500 and a softening point of 110 ° C to 130 ° C show the most excellent lubricity.

Since the metal surface treatment composition of the present invention becomes a stable liquid in a neutral or acidic region, it is particularly preferable that the pH is
7, particularly preferably in the range of 1 to 5.

The metal surface treatment composition of the present invention may further comprise, if necessary, for example, a thickener,
Surfactants, antibacterial agents, rust inhibitors (tannic acid, phytic acid, benzotriazole, etc.), coloring pigments, extender pigments,
It may contain pigments such as rust preventive pigments.

Also, the metal surface treatment composition of the present invention includes:
If necessary, it can be used after being diluted with a hydrophilic solvent such as methanol, ethanol, isopropyl alcohol, ethylene glycol or propylene glycol.

Next, a method for producing an organic-coated steel sheet will be described.

Organically Coated Steel Sheet The metal surface treatment composition of the present invention is coated on a zinc-based plated steel sheet and dried to produce an organically coated steel sheet having lubricity.

As the base sheet of the galvanized steel sheet, a cold-rolled steel sheet for general working (CQ) to a cold-rolled steel sheet for deep drawing (D
Q), all cold-rolled steel sheets for soft working, including cold-rolled steel sheets for deep and deep drawing (DDQ) and cold-rolled steel sheets for ultra-deep drawing (EDDQ), are applicable. The method may be either box annealing or continuous annealing. Further, as the original sheet, a high-strength steel sheet having a baking hardenability and a relatively low strength level, a general high-strength steel sheet exceeding 390 MPa, a descaled hot-rolled steel sheet, or the like can be used. In addition,
Particularly, when a cold-rolled steel sheet for soft working having excellent press formability such as a cold-rolled steel sheet for deep and deep drawing (DDQ) and a cold-rolled steel sheet for ultra-deep drawing (EDDQ) is used as a base material of a galvanized steel sheet, Excellent action and effect can be obtained.

As the plating layer of the zinc-based plated steel sheet, Z
n plating, Zn-Ni alloy plating (Ni content 10-1)
5 wt%), Zn-Fe alloy plating (Fe content 5 to 2)
5 wt% or Fe content 60 to 90 wt%), Zn-
Mn alloy plating (Mn content 30-80 wt%), Zn
-Co alloy plating (Co content 3 to 15 wt%), Zn
-Cr alloy plating (Cr content 5-30 wt%), Zn
-Al alloy plating (Al content: 3 to 60 wt%). For the purpose of improving corrosion resistance, the above-mentioned plating components may contain alloying elements such as Co, Fe, Ni, and Cr, oxides and salts such as silica, alumina, and hardly soluble chromates, and polymers. .

[0091] Of the above-mentioned plating layers, two or more of the same or different plating layers may be plated to form a multilayer plating. As the plating method, any method that can be used among the electrolysis method, the melting method, and the gas phase method can be adopted, but the electrolysis method is most advantageous from the viewpoint of the selectivity of the material of the base steel sheet.

The coating on the galvanized steel sheet can be performed, for example, by the following method. That is,
The metal surface treatment composition of the present invention is applied by a known coating method such as a roll coater, a curtain roll coater, or a spray, or a galvanized steel sheet is immersed in these coating liquids, and then rolls or air spraying is performed. In this method, a film is formed by controlling the amount of adherence, and then the film is dried. Drying may be performed at normal temperature, but is usually performed by heating the steel sheet to about 60 ° C. or more, preferably 80 to 200 ° C., using a hot air oven or an induction heating device.

The coating amount of the metal surface treatment composition is usually 0.1 to 5 μm, preferably 0.3 to 3 μm as a dry film thickness.
Range.

[0094]

According to the present invention having the above-described structure, the following effects are considered to be obtained.

In the present invention, the metal surface treatment composition having the above-mentioned structure is applied to a metal substrate such as a steel plate, for example.
By forming a surface treatment film by heating, the phosphoric acid compound, metal hydrofluoric acid, metal hydrofluoride, etc. which are the component (B) constituting the metal surface treatment composition are used as metal etching agents. On the other hand, it is presumed that the aqueous liquid (A) containing titanium and the aqueous organic high molecular compound (C) form a film having excellent adhesion to the material, small oxygen permeability and small water vapor permeability, Has extremely high corrosion resistance and durability. Further, constituting a metal surface treatment composition (D)
In order to impart excellent lubricity to the coating film as a component lubricant, by using the metal surface treatment composition of the present invention,
A lubricated steel sheet having excellent corrosion resistance and lubricity can be obtained by one treatment.

[0096]

The present invention will be described more specifically below with reference to examples and comparative examples. Hereinafter, “parts” and “%” mean “parts by weight” and “% by weight”, respectively. The present invention is not limited to the following examples.

Production Example 1 of Titanium-Based Aqueous Solution Ammonia water (1: 9) was added dropwise to a solution of 5 cc of a 60% titanium tetrachloride solution made up to 500 cc with distilled water to precipitate titanium hydroxide. After washing with distilled water, hydrogen peroxide water 30
% Solution was added and stirred to obtain a titanium-based aqueous liquid (A1) containing titanium and containing a translucent yellowish solid having a solid content of 2%.

Production Example 2 A mixture of 10 parts of tetra-iso-propoxytitanium and 10 parts of iso-propanol was stirred at 20 ° C. for 1 hour in a mixture of 10 parts of 30% hydrogen peroxide and 100 parts of deionized water. It was dropped. Thereafter, the mixture was aged at 25 ° C. for 2 hours, and was a yellowish, transparent, slightly viscous titanium-based aqueous liquid having a solid content of 2% (A
2) was obtained.

Production Example 3 Preparation of Titanium-Based Aqueous Liquid (A2) Titanium n-butoxytitanium was used in place of tetraiso-propoxytitanium in the same production conditions as in the preparation example of titanium-based aqueous liquid (A3). ) Got.

Production Example 4 Titanium-isopropoxytitanium trimer was used in place of tetraiso-propoxytitanium trimer in the production example of titanium-based aqueous liquid (A2). An aqueous liquid (A4) was obtained.

Production Example 5 In the production example of the titanium-based aqueous liquid (A2), a hydrogen peroxide solution was added dropwise at 50 ° C. over 1 hour using a 3 times amount of hydrogen peroxide solution, and further added at 60 ° C.
For 3 hours to obtain a titanium-based aqueous liquid (A5) having a solid content of 2%.

Production Example 6 A titanium-based aqueous solution (A3) was heated at 95 ° C. for 6 hours.
White-yellow translucent titanium-based aqueous liquid having a solid content of 2% (A6)
I got

Production Example 7 A mixture of 10 parts of tetra-iso-propoxytitanium and 10 parts of iso-propanol was mixed with TKS-203 (Taika).
1 part in a mixture of 5 parts (solid content), 10 parts of 30% hydrogen peroxide solution and 100 parts of deionized water.
The mixture was added dropwise with stirring at 0 ° C. for 1 hour. Then 10
Aged at 24 ° C. for 24 hours, yellow transparent, slightly viscous solid 2
% Titanium-based aqueous liquid (A7).

Production Example 8 Production of Acrylic Resin 180 parts of isopropyl alcohol was placed in a 1 L four-necked flask equipped with a thermometer, a stirrer, a cooler, and a dropping funnel. C. and adjusted to a monomer mixture consisting of 140 parts of ethyl acrylate, 68 parts of methyl methacrylate, 15 parts of styrene, 15 parts of Nn-butoxymethylacrylamide, 38 parts of 2-hydroxyethyl acrylate and 24 parts of acrylic acid. Dropwise over about 2 hours with a catalyst consisting of 6 parts of 2,2'-azobis (2,4-dimethylvaleronitrile). When the reaction was continued at the same temperature for 5 hours after the completion of the dropwise addition, the polymerization rate was almost 100%, the solid content was about 63%, and the acid value was about 67.
A colorless and transparent resin solution is obtained. This resin solution 500
To this part, 108 parts of dimethylaminoethanol was mixed, and after adding water, the mixture was sufficiently stirred to obtain an aqueous acrylic resin dispersion (C1) having a solid content of 30%.

Production Example 9 of Amine-Modified Epoxy Resin A reactor equipped with a stirrer, a reflux condenser, a thermometer, and a liquid dropping device was charged with Epicoat 1009 resin (epoxy resin manufactured by Shell Chemical Co .; molecular weight 3,750). 880g
(0.5 mol) and methyl isobutyl ketone / xylene =
After adding 1,000 g of a 1/1 (weight ratio) mixed solvent,
The mixture was stirred and heated to dissolve uniformly. Thereafter, the temperature was cooled to 70 ° C., and 70 g of di (n-propanol) amine collected in the liquid dropping device was dropped over 30 minutes. During this time, the reaction temperature was maintained at 70 ° C. After completion of the dropwise addition, the mixture was kept at 120 ° C. for 2 hours to complete the reaction, thereby obtaining an amine-modified epoxy resin having a solid content of 66%. The obtained resin 1,00
25 g of 88% formic acid was mixed with 0 g, and the mixture was sufficiently stirred after the addition of water to obtain an aqueous dispersion of an amine-modified epoxy resin (C2) having a solid content of 30%.

Preparation of Metal Surface Treatment Composition Example 1 50 parts of a 2% titanium-based aqueous liquid (A1), 5 parts of a 20% zirconium hydrofluoric acid, and a 30% aqueous dispersion of an acrylic resin (C
1) 10 parts, polyethylene powder a (weight average molecular weight 9,
000, melting point 90 ° C., particle size 2-5 μm) and 0.5 part of deionized water were mixed to obtain a metal surface treatment composition.

Examples 2 to 11 and Comparative Examples 1 to 3 Each metal surface treatment composition was obtained by blending in the same manner as in Example 1 except that the composition was changed as shown in Table 1 below. .

Preparation of Test Specimen An electrogalvanized steel sheet having a thickness of 0.8 mm was sprayed with a 2% aqueous solution of alkaline degreasing agent “CC-561B” manufactured by CB Chemical Co., Ltd. at a liquid temperature of 65 ° C. for 20 seconds. After degreasing, the resultant was sprayed with hot water having a liquid temperature of 60 ° C. for 20 seconds to perform hot water washing. The metal surface treatment compositions obtained in Examples and Comparative Examples were applied onto the degreased steel sheet so that the dry film weight became 0.8 g / m ^2, and the atmosphere temperature was set to 250 ° C. for 20 seconds (the maximum temperature of the steel sheet was reached). (Temperature: 120 ° C.) and dried to prepare each test coated plate.

Each of the prepared test coated plates was evaluated using the following test methods, and the results shown in Table 1 were obtained.

Test Method Coating Appearance: The appearance of the treated film was visually determined and evaluated according to the following criteria. ：: uniform and without unevenness Δ: partially unevenness X: unevenness over the entire surface

[0111] Corrosion resistance: A salt spray test specified in JIS Z2371 was performed for up to 120 hours on the test coated plate in which the end face and the back face of the test coated plate were sealed, and the degree of rust on the treated film surface was evaluated according to the following criteria. ◎: No white rust was observed, ：: White rust was less than 5% of the coating area, Δ: White rust was 5% or more and less than 30% of the coating area, ×: White The degree of rusting is 30% or more of the coating area.

Lubricity: According to a tensile tester, surface pressure: 5
Under a condition of 0 kg / cm ² and a drawing speed of 100 m / min, a flat test piece was pulled out, a dynamic friction coefficient at that time was examined, and lubricity was evaluated according to the following criteria. ：: dynamic friction coefficient of less than 0.10, ：: dynamic friction coefficient of 0.10 or more and less than 0.15, Δ: dynamic friction coefficient of 0.15 or more and less than 0.25, ×: dynamic friction coefficient of 0.25 or more.

Topcoat paint adhesion: Magiclon # 1000 white (manufactured by Kansai Paint Co., thermosetting acrylic resin paint, white) was applied to the test coated plate so that the dry film thickness became 30 μm, and baked at 150 ° C. for 20 minutes. A topcoat was obtained. On the obtained top-coated board, 11 cuts each in the vertical and horizontal directions reaching the substrate with a knife were cut in a grid pattern on the coating surface.
100 squares of mm square were created. A cellophane pressure-sensitive adhesive tape was adhered to the grid, and the tape was instantaneously peeled off. The degree of peeling of the upper layer coating film was evaluated according to the following criteria. ：: No peeling of the upper coating film was observed at all. ○: 1 to 2 peeling of the upper coating film was observed. △: 3 to 10 peeling of the upper coating film were observed. ×: Peeling of the upper coating film 10 or more are observed.

[0114]

[Table 1]

──────────────────────────────────────────────────続 き Continued on the front page (51) Int. Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C09D 7/12 C09D 7/12 4K044 185/00 185/00 201/00 201/00 C10M 107/02 C10M 107 / 02 107/38 107/38 125/10 125/10 125/16 125/16 125/18 125/18 125/24 125/24 129/18 129/18 139/00 139/00 145/00 145/00 149/14 149/14 C23C 22/23 C23C 22/23 22/36 22/36 26/00 26/00 A 28/00 28/00 C (72) Inventor Osamu Isozaki 4--17 Higashi-Yawata, Hiratsuka City, Kanagawa Prefecture No. 1 Kansai Paint Co., Ltd. F-term (reference) 4D075 CA06 CA09 CA33 DB05 DC12 EC01 4F100 AA04B AB03A AB18A AH08B AK03B AK17B AK21B AK24B AK33B AK51B AK53B AK70B AL01B AL06 BA02 BA07 CA19B EHB AJB AJB AJB EJA42B AA20C BB02C CA01A CB02C CB07C CB08C CB12C CB14C CD01A CE13C EA08A EA17C FA0 1 FA04 LA06 PA23 QA01 QA12 RA06 4J038 CB022 CB061 CB062 CB071 CB072 CB091 CB092 CC021 CC022 CD122 CD132 CE021 CE022 CF021 CF022 CG011 CG012 CG061 CG062 CG141 HA0327 CG141 DB031 DG02 012 PA19 PC02 4K026 AA07 AA12 AA13 AA22 BA03 BB08 BB09 CA13 CA18 CA24 CA25 CA28 CA39 DA02 DA03 DA06 DA11 EB11 4K044 AA02 AB02 BA10 BA12 BA17 BA20 BA21 BB03 BC01 BC02 BC05 CA11 CA16 CA18 CA53 CA62

Claims (17)

[Claims] (A) reacting at least one titanium compound selected from a hydrolyzable titanium compound, a hydrolyzable titanium compound low-condensate, titanium hydroxide and a titanium hydroxide low-condensate with hydrogen peroxide water. Aqueous liquid containing titanium obtained by the reaction, (B) at least one compound selected from phosphoric acid compounds, metal hydrofluoric acid and metal hydrofluoride,
A metal surface treatment composition capable of forming a lubricating film, characterized by comprising (C) an aqueous organic polymer compound having a pH of 7 or less and (D) a lubricant. 2. The aqueous liquid (A) contains titanium obtained by reacting a hydrolyzable titanium compound and / or a low-condensate of a hydrolyzable titanium compound with hydrogen peroxide in the presence of a titanium oxide sol. The metal surface treatment composition according to claim 1, which is an aqueous liquid (A-1). 3. The metal surface treatment composition according to claim 1, wherein the aqueous liquid (A) is produced by adding a titanium compound to a hydrogen peroxide solution. 4. The metal surface treatment composition according to claim 1, wherein the hydrolyzable titanium compound is a titanium monomer containing a group that is hydrolyzed to become a hydroxyl group. . 5. The method according to claim 1, wherein the low-condensation product of the hydrolyzable titanium compound is a low-condensation product of a titanium monomer having a group that becomes a hydroxyl group by hydrolysis. The metal surface treatment composition as described in the above. 6. The hydrolyzable titanium compound represented by the general formula Ti
(OR) _{4 wherein} R is the same or different and has 1 carbon atom
The metal surface treatment composition according to any one of claims 1 to 4, wherein the composition has an alkyl group of 1 to 5). 7. The metal surface treatment composition according to claim 1, wherein the low condensate has a degree of condensation of 2 to 30. 8. The method according to claim 1, wherein the mixing ratio of the titanium compound to the hydrogen peroxide solution is 0.1 to 100 parts by weight of hydrogen peroxide per 10 parts by weight of the titanium compound.
The metal surface treatment composition according to any one of claims 1 to 3. 9. Compound (B) is phosphoric acid, metaphosphoric acid,
Condensed phosphoric acid, condensed metaphosphoric acid, phosphate, metaphosphate, condensed phosphate, condensed metaphosphate, zirconium hydrofluoric acid, titanium hydrofluoric acid, hydrofluorosilicic acid, zirconium fluoride, titanium The metal surface treatment composition according to claim 1, wherein the composition is at least one compound selected from a fluoride salt and a silicofluoride salt. 10. The compounding ratio of the compound (B) is 1 to 4 with respect to 100 parts by weight of the solid content of the aqueous liquid (A) containing titanium.
The metal surface treatment composition according to claim 1 or 9, which is 00 parts by weight. 11. The aqueous organic polymer compound (C) is at least one of an epoxy resin, a phenol resin, an acrylic resin, a urethane resin, a polyvinyl alcohol resin, a polyalkylene glycol resin, and an olefin-carboxylic acid resin. The metal surface treatment composition according to claim 1, wherein the composition is an aqueous organic polymer compound selected from one kind of resin. 12. The compounding ratio of the aqueous organic polymer compound (C) is 10 to 2,000 parts by weight based on 100 parts by weight of the solid content of the aqueous liquid (A) containing titanium. Item 12. The metal surface treatment composition according to item 1 or 11. 13. The lubricant (D) is a polyolefin wax and / or a fine powder of a fluororesin, and the compounding ratio thereof is the total solid content of the aqueous liquid (A) containing titanium and the aqueous organic polymer compound (C). 1 to 50 for 100 parts by weight
The metal surface treatment composition according to claim 1, which is in parts by weight. 14. The metal surface treatment composition according to claim 1, wherein the metal surface treatment composition is an aqueous liquid having a pH of 1 to 7. 15. A surface-treated coating formed by applying the metal surface-treating composition according to any one of claims 1 to 14 to a substrate and subjecting the composition to a heat treatment if necessary. Method. 16. The method according to claim 1, wherein the surface of the galvanized steel sheet is
An organic-coated steel sheet, which is coated with a surface-treated film of the metal surface-treating composition according to any one of the above items 14. 17. The film thickness of the surface treatment film is 0.1 to 5 μm.
The organic coated steel sheet according to claim 16, wherein m is m.