JP2002275653A - Metallic surface treated steel sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce a metallic surface treated steel sheet which has excellent corrosion resistance and hydrophilic properties, and has not environmental problems. SOLUTION: The metallic surface treated steel sheet is obtained by forming a film of a post-treatment agent containing (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, (B) at least one kinds of compound selected from phosphoric compounds, metallic hydrofluoric acids and metallic hydrofluorides, and (C) a water based organic high molecular compound stable at pH <=7 on the surface of a phosphate treatment film on a metallic surface.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a metal surface-treated steel sheet having excellent workability and corrosion resistance obtained by forming a film of a post-treatment agent on a phosphate-treated film on a metal surface, and the metal surface-treated steel sheet And a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, chromate treatment and phosphate treatment are generally performed on cold-rolled steel sheets and galvanized steel sheets for the purpose of improving corrosion resistance and paint adhesion.

[0003] However, the chromate treatment involves a problem of volatilization of chromate fume in the treatment process, a large cost for wastewater treatment equipment, and a problem of elution of hexavalent chromium from the chemical conversion treatment film. There is. Hexavalent chromium compounds are available from IARC (International Agency for R).
esearch on Cancer Review) and many other public institutions have designated it as a carcinogen for the human body and is extremely harmful. In the phosphate treatment, after the phosphate treatment, post-treatment (chromium sealing treatment) is usually performed with a solution containing hexavalent chromium, so that there is a problem of hexavalent chromium.

As treatment methods other than chromate treatment and zinc phosphate treatment, there are (1) a surface treatment method of treating with an aqueous solution containing aluminum biphosphate and then heating at a temperature of 150 to 550 ° C. -28857), (2)
A method of treating with an aqueous solution containing tannic acid (JP-A-51
And (3) a treatment method using sodium nitrite, sodium borate, imidazole, an aromatic carboxylic acid, a surfactant, or a combination thereof.

[0005] However, the method (1) has a problem in that when the paint is applied thereon, the adhesion of the paint is not sufficient, the method (2) has poor corrosion resistance, and the method (3) has a problem.
All have the problem that the corrosion resistance when exposed to a hot and humid atmosphere is poor.

Further, a post-treatment method for a phosphate-treated film which does not have the problem of toxicity due to heavy metals such as chromium compounds and can exhibit paint adhesion and corrosion resistance at least equivalent to that of chromium-sealed phosphate treatment. For example, Japanese Patent Publication No. 7-42423 proposes a treatment composition based on ions containing a metal element such as titanium, zirconium, and hafnium, and a polyalkenylphenol polymer derivative. . However, this treatment composition is intended for post-treatment of an aluminum material, and has little improvement in corrosion resistance and suppresses the generation of white rust even when used for post-treatment of a phosphate treatment film on a galvanized steel sheet. Effect is small.

An object of the present invention is to provide a chromium-sealed phosphate treatment even when the metal to be treated is a steel plate such as a galvanized steel sheet or a cold-rolled steel sheet without the problem of toxicity due to heavy metals such as chromium compounds. The purpose of the present invention is to obtain a metal surface-treated steel sheet exhibiting paint adhesion, workability and corrosion resistance equivalent to or higher than the above.

Another object of the present invention is to provide a method for producing a metal surface-treated steel sheet which is excellent in corrosion resistance, workability and paint adhesion and has no problem in terms of environmental protection.

[0009]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that at least one selected from a hydrolyzable titanium compound, a hydrolyzable titanium compound low-condensate, titanium hydroxide and a titanium hydroxide low-condensate. Aqueous solution containing titanium obtained by reacting a kind of titanium compound with aqueous hydrogen peroxide, at least one compound selected from a phosphoric acid compound, metal hydrofluoric acid and metal hydrofluoride, and an aqueous solution The inventors have found that the above object can be achieved by forming a film made of a post-treatment agent containing an organic polymer compound, and have completed the present invention.

Thus, according to the present invention, (A) hydrolyzable titanium compound, hydrolyzable titanium compound low condensate, titanium hydroxide and titanium hydroxide low condensate Aqueous liquid containing titanium obtained by reacting at least one selected titanium compound with aqueous hydrogen peroxide, (B) at least one selected from phosphoric acid compounds, metal hydrofluoric acid and metal hydrofluoride A metal surface-treated steel sheet is provided, which is formed by forming a film of a post-treatment agent containing one kind of compound and (C) an aqueous organic polymer compound stable at pH of 7 or less.

Further, a post-treatment agent is applied to the surface of the phosphatized film on the metal surface so that the dry film thickness is 0.05 to 5.0 g / m 2.
^{2. A} method for producing a metal surface-treated steel sheet, characterized in that the method is applied and dried so as to be 2.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION The metal surface-treated steel sheet of the present invention is obtained by applying a post-treatment agent to the surface of a phosphate-treated film of a phosphate-treated steel sheet and drying it.

First, the post-treatment agent will be described.

Post-Treatment Agent The post-treatment agent used in the present invention is at least one compound selected from an aqueous liquid (A) containing titanium, a phosphoric acid compound, a metal hydrofluoric acid and a metal hydrofluoride. (B) and an aqueous organic polymer compound (C).

Aqueous Liquid Containing Titanium (A) The aqueous liquid containing titanium (A) used in the post-treatment agent includes a hydrolyzable titanium compound, a low-condensate of a hydrolyzable titanium compound, titanium hydroxide and titanium hydroxide. It is an aqueous liquid containing titanium obtained by reacting at least one titanium compound selected from low condensates with aqueous hydrogen peroxide. 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 generates 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 produces 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 the hydrolyzable group, a compound represented 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) ) 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.

Typical hydrolyzable titanium compounds having a group capable of forming a salt with titanium as a hydrolyzable group 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.

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

The degree of condensation of the low condensate of the above hydrolyzable titanium compound or 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 bonding, 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 baking, only water and oxygen are generated, so it 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 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 in view of the ease of handling and the solid content of the product liquid related to the coating workability.

The aqueous liquid (A) using the hydrolyzable titanium compound a is prepared by reacting the hydrolyzable titanium compound a with hydrogen peroxide solution 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 a hydrogen peroxide solution, whereby the hydrolyzable titanium compound is hydrolyzed 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) comprising the hydrolyzable titanium compound a is subjected to a heat treatment or an autoclave treatment at 80 ° C. or higher, a titanium oxide dispersion containing crystallized ultrafine titanium oxide particles 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, it is preferable to form the titanium oxide film at a temperature of, for example, 200 ° C. or less, particularly 150 ° C. or less.

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 in the presence of a titanium oxide sol are further used. 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 in view 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 a hydrogen peroxide solution 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 to hydrolyze the hydrolyzable titanium compound a 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 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 required. 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 post-treatment agent is at least one compound selected from phosphoric acid compounds, metal hydrofluoric acids and metal hydrofluorides.

Examples of the above-mentioned 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, the mixture is allowed to stand at room temperature (20 ° C.) for about 5 minutes to about 1 hour, and the mixture can be mixed. 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 alone or in combination of two or more. The compounding ratio of the compound (B) is 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).

[0060] aqueous organic high molecular compound (C) post-treatment agent is an aqueous organic high molecular compound (C) is blended in addition to components described above. The aqueous organic polymer compound (C) is P
An organic polymer compound (C) which is excellent in stability of an aqueous solution of an organic polymer compound (C) itself which does not cause aggregation and sedimentation of an organic resin component dissolved or dispersed in water at H7 or less, and does not cause an increase in viscosity or abnormal gelation. If so, conventionally known ones can be used.

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 acryl-modified resin 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 formaldehyde 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 composed of 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, an amino group or a carboxyl group into a side chain or a 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 polyurethane resin is not limited to a single dispersion or dissolution method as described above, and a mixture obtained by each method can also be used.

Examples of the diisocyanate which can be used for synthesizing the polyurethane resin include aromatic, alicyclic and aliphatic diisocyanates, and specifically, hexamethylene diisocyanate, tetramethylene diisocyanate, and 3,3'-dimethoxy- 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 above 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.

The olefin-carboxylic acid resin includes a copolymer of an olefin such as ethylene and propylene and a polymerizable unsaturated carboxylic acid, and a polymerizable unsaturated compound added to a dispersion of the copolymer to emulsify the copolymer. 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 mixing 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.

Since the post-treatment agent becomes a stable liquid in a neutral or acidic region, the pH is preferably in the range of 1 to 7, particularly 1 to 5.

The post-treatment agent may be, if necessary, for example, in addition to the above-mentioned components, a thickener, a surfactant, a bactericide, a rust inhibitor (tannic acid, phytic acid, benzotriazole, etc.), coloring Pigments such as pigments, extender pigments, rust-preventive pigments and the like can be contained.

The post-treatment agent can be used by diluting it with a hydrophilic solvent such as methanol, ethanol, isopropyl alcohol, ethylene glycol or propylene glycol, if necessary.

The metal on which the phosphate treatment film to which the post-treatment agent of the present invention is applied is not particularly limited as long as the surface is a metal. Aluminum, zinc, copper, tin, and alloys containing some of these metals can be mentioned. Representative examples include, for example, an iron plate, a zinc-plated steel plate, an aluminum plate, and an aluminum-plated steel plate. it can. Examples of the galvanized steel sheet include a galvanized steel sheet, an electrogalvanized steel sheet, an iron-zinc alloy-coated steel sheet, a nickel-zinc alloy-coated steel sheet, and an aluminum-coated steel sheet.
Zinc alloy-plated steel sheets and the like can be mentioned.

The phosphating film is formed by subjecting the above metal surface to a known phosphating treatment such as an iron phosphate treatment or a zinc phosphate treatment by a dipping method or a roll coating method. A phosphate-treated film was formed on the surface thereof. The film weight of the phosphate treatment film on the metal surface is not particularly limited, but usually,
A range of 0.05 to 5 g / m ² , preferably 1 to 3 g / m ² is suitable from the viewpoint of workability, paint adhesion and the like.

Next, a method for post-treatment of a phosphate treatment film using the post-treatment agent of the present invention will be described.

In the post-treatment method of the present invention, the above-mentioned post-treatment agent of the present invention is applied to the surface of the phosphate-treated film formed on the surface of the metal, followed by drying to perform post-treatment.

When applying the post-treatment agent of the present invention to the surface of the phosphating film formed on the surface of the metal,
Depending on the amount of application, the viscosity of the post-treatment agent is usually 5 to 10 with water.
It is adjusted within a range of about 0 mPa · s, and is applied by a coating method such as roll coating, spray coating, brush coating, flow coating, dip coating, and squeezing to remove excess liquid by squeezing after liquid coating. Then, by heating and drying, the phosphate treatment film can be subjected to a post-treatment. The application amount of the post-treatment agent is usually 0.05 to 5.0 g / m ² , preferably 0.1 to ² g in terms of dry film weight.
g / m ² is suitable in terms of corrosion resistance, workability, paint adhesion, and the like. The drying conditions are not particularly limited as long as the applied post-treatment agent can be dried. In general, it is preferable to heat at an ambient temperature of 100 to 250 ° C. for about 10 to 100 seconds (the maximum temperature of the steel sheet is about 80 to 150 ° C.).

The post-treated phosphate treatment film obtained by the post-treatment method of the present invention has excellent corrosion resistance and workability, and can be used as it is as a rust-proof steel sheet.
It has excellent coating film adhesion, and it is possible to further form an upper layer film on a metal plate having a post-treated phosphate treatment film. The composition for forming the upper layer film may be appropriately selected depending on the purpose, and various coating compositions can be used. As the coating composition, for example,
Examples include a lubricating film forming composition, a highly corrosion resistant film forming composition, a primer coating, and a colored topcoat. The composition for forming a lubricating film, the composition for forming a highly corrosion-resistant film or a primer paint may be applied and dried, and then a colored top coat may be applied thereon.

[0093]

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

In the present invention, a titanium-based rust preventive is constituted by applying a post-treatment agent having the above-mentioned structure on a phosphate-treated steel sheet and heating to form a titanium-based anticorrosive film (B) The components phosphoric acid compound, metal hydrofluoric acid, metal hydrofluoride, etc. act as metal etchants, while aqueous liquid (A) containing titanium and aqueous organic polymer compound (C) With, excellent adhesion to the material,
It is presumed that a film having low oxygen permeability and low water vapor permeability is formed, and it is supposed that the film has a function of further increasing the corrosion prevention effect by the phosphate treatment, and a metal surface treated steel sheet having extremely high corrosion protection and durability can be obtained.

[0095]

EXAMPLES Hereinafter, the present invention will be described more specifically 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 prepared by diluting 5 cc of a 60% titanium tetrachloride solution with 500 cc of 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 Titanium-based aqueous liquid (A3) having a solid content of 2% under the same production conditions using tetra-n-butoxytitanium instead of tetra-iso-propoxytitanium in the production example of titanium-based aqueous liquid (A2) ) Got.

Production Example 4 Titanium-isopropoxytitanium trimer was used in place of tetraiso-propoxytitanium 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), 3 times the amount of hydrogen peroxide was added dropwise at 50 ° C. over 1 hour, and the temperature was further increased to 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 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 maintained at 120 ° C. for 2 hours to complete the reaction, whereby the solid content was 66%
An amine-modified epoxy resin was obtained. The obtained resin 1,0
25 parts of 88% formic acid was mixed with 00 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%.

Manufacturing Example 10 of Zinc Phosphate Treated Steel Sheet A plated steel sheet obtained by subjecting a cold-rolled steel sheet having a thickness of 0.8 mm to zinc plating or various zinc alloy platings was used as a base material. Table 2 below shows the types and abbreviations of the plated steel sheets used.
Shown in

After the surface of the plated steel sheet was alkali-degreased, the surface was adjusted (spray treatment using “Preparen Z” manufactured by Nippon Parkerizing Co., Ltd.) and further treated with zinc phosphate (manufactured by Nippon Parkerizing Co., Ltd.). After performing spray treatment using "Palbond 3308", various types of plated steel sheets subjected to zinc phosphate treatment were obtained by washing with water and drying. The adhesion amount of the zinc phosphate treated film was 1.5 g / m ² .

Production of Metal Surface-treated Steel Sheet Example 1 50 parts of 2% titanium treating agent (A1), 5 parts of 20% zirconium hydrofluoric acid, 30% aqueous dispersion of acrylic resin (C1)
10 parts and 35 parts of deionized water were blended to obtain a post-treatment agent of Example 1. The obtained post-treatment agent has a dry film amount of 0.2 g on the surface of the galvanized steel sheet subjected to the zinc phosphate treatment.
/ M ² and the material temperature is 100 in 5 seconds.
C. to obtain a surface-treated steel sheet.

Examples 2 to 11 and Comparative Examples 1 to 3 Each surface-treated steel sheet was obtained in the same manner as in Example 1, except that the post-treatment agent was mixed and the type of plated steel sheet shown in Table 1 was used. .

Various tests were carried out on the test plates obtained as described above according to the following test methods. The test results are shown in Table 1 below. The types of the plated steel sheets used in Table 1 are described by abbreviations shown in Table 2 below.

Test Method Coating Appearance: The uniformity of the post-treated coating on the test plate was visually evaluated based on the following criteria. ：: Uniform appearance without unevenness Δ: Slight unevenness observed X: Unevenness is noticeable.

Topcoat paint adhesion: "Magiclon 1000 White" (manufactured by Kansai Paint Co., Ltd., acrylic-melamine resin paint, white) was applied to the test plate so that the dry film thickness became 30 μm, and the coating was applied at 160 ° C. for 20 minutes. After baking for a minute, a coated plate was obtained. This coated plate was immersed in boiling water of about 98 ° C for 2 hours, pulled up and left at room temperature for 24 hours. Thus, 100 squares of 1 mm square were formed. The degree of peeling of the upper layer coating film when the cellophane adhesive tape was closely adhered to the cross-cut portion and the tape was instantaneously peeled was evaluated based on the peeling area with respect to the area of 100 squares according to the following criteria. 5: No peeling of the coating film is observed at all. 4: Peeling of the coating film is observed, but the peeling area is less than 10%. 3: The peeling area is 10% or more and less than 25%. 2: The peeling area is 25% or more. Less than 50% 1: Peeling area is 50% or more.

Corrosion resistance: A test plate was cut into a size of 70 mm × 150 mm, the end face and the back face of the test plate were sealed, and the salt water spray test specified in JIS Z2371 was performed according to 24.
Time, 48 hours, and 72 hours were evaluated, and the degree of generation of white rust on the coating film surface was evaluated according to the following criteria. 5: No occurrence of white rust is observed 4: White rust occurrence is less than 10% of coating film area 3: White rust occurrence is 10% or more and less than 25% of coating film area 2: White rust occurrence The extent is 25% or more and less than 50% of the coating film area 1: The degree of white rust generation is 50% or more of the coating film area.

[0113]

[Table 1]

[0114]

[Table 2]

[0115]

[Table 3]

Continuation of the front page (72) Inventor Osamu Isozaki 4-171-1, Higashi-Hachiman, Hiratsuka-shi, Kanagawa F-term (reference) in Kansai Paint Co., Ltd. 4K022 AA01 AA32 BA15 BA22 BA33 CA28 DA06 DA09 DB01 4K026 AA02 AA06 AA07 AA09 AA10 AA12 AA13 BA03 BA04 BA12 BB06 BB08 BB09 BB10 CA13 CA14 CA23 CA25 CA28 DA02 DA03 EB02 EB08 4K044 AA02 AA06 AB02 BA11 BA17 BA21 BB05 BB06 BC02 BC04 BC05 CA11 CA15 CA16 CA18 CA53

Claims (14)

[Claims] 1. A phosphating film on a metal surface,
(A) Titanium obtained by 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 (B)
At least one compound selected from a phosphoric acid compound, metal hydrofluoric acid and metal hydrofluoride, and (C) PH
A metal surface-treated steel sheet formed by forming a film of a post-treatment agent containing an aqueous organic polymer compound that is stable at 7 or less. 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-treated steel sheet according to claim 1, which is an aqueous liquid (A-1). 3. The metal surface-treated steel sheet 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-treated steel sheet 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-treated steel sheet according to 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-treated steel sheet according to any one of claims 1 to 4, wherein: 7. The metal surface-treated steel sheet 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.
4. The metal surface-treated steel sheet according to any one of items 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-treated steel sheet according to claim 1, wherein the steel sheet 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-treated steel sheet 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-treated steel sheet according to claim 1, which 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. A metal surface-treated steel sheet according to item 1 or 11. 13. The metal surface-treated steel sheet according to claim 1, wherein the titanium-based rust preventive is an aqueous liquid having a pH of 1 to 7. 14. A metal surface, characterized in that a post-treatment agent is applied on the phosphatized film on the metal surface so that the dry film thickness becomes 0.05 to 5.0 g / m ² and dried. Manufacturing method of treated steel sheet.