WO2002061005A1 - Coating materials for titanium oxide film formation, method of forming titanium oxide film, and metallic base coated with titanium oxide film - Google Patents

Abstract

A coating material for titanium oxide film formation which comprises (A) a specific aqueous liquid containing titanium and (B) a phosphoric acid compound; a coating material for titanium oxide film formation which comprises (A) an aqueous liquid containing titanium, (B') at least one of phosphoric acid compounds, titanium halides, etc., and (C) a water-compatible organic polymer which is stable at a pH of 7 or lower; a method of forming a titanium oxide film which comprises applying either of the coating materials; and a metallic base coated with a titanium oxide film.

Description

 Specification

Coating agent for forming titanium oxide film, method for forming titanium oxide film, and metal substrate coated with titanium oxide film

 The present invention relates to a novel coating material for forming a titanium oxide film, a method for forming a titanium oxide film, and a metal substrate coated with a titanium oxide film. Background technology

 Metallic substrates such as steel plates, aluminum, and aluminum alloys are usually subjected to various surface treatments as base treatments in order to improve corrosion resistance, heat resistance, and the like. In recent years, surface-treated steel sheets have been required to have better corrosion resistance, and thus zinc-coated steel sheets have been increasingly used as base materials instead of cold-rolled steel sheets. Conventionally, chromate treatment and phosphate treatment have been generally performed as surface treatments for zinc-coated steel sheets.

 Chromate treatment has the problem of toxicity of chromium compounds. In particular, hexavalent chromium compounds are extremely harmful, as many public institutions, including the International Agency for Research on Cancer Review (IARC), have designated them as carcinogens for the human body. Specifically, the chromate treatment has problems such as the volatilization of the chromate fume in the treatment process, the need for a large amount of wastewater treatment equipment, and the elution of chromic acid from the treated coating.

 In the case of phosphating with zinc phosphate, iron phosphate, etc., after phosphating, usually post-treatment with chromate is not only a problem of the toxicity of chromium compounds, but also a phosphating agent. There is also a problem of wastewater treatment of reaction accelerators and metal ions in the system, and sludge treatment by elution of metal ions from the metal to be treated.

Japanese Patent Application Laid-Open Nos. 58-224174, 60-501179, and Japanese Patent Publication 60-180180, etc. A coated steel sheet is described in which a plated steel sheet is used as a base material, a chromate film is formed thereon, and an organic silicate film is further formed thereon. This coated steel sheet has excellent performance in corrosion resistance and workability. I However, since the coated steel sheet has a chromate film, there was also a problem of toxicity of the chromium compound. In addition, the steel sheet obtained by removing the chromate film from the coated steel sheet has insufficient corrosion resistance.

 On the other hand, aluminum or aluminum alloy base materials are often subjected to various surface treatments as a base treatment in order to improve corrosion resistance, hydrophilicity, and the like.

 For example, as a fin for a heat exchanger of an air conditioner, an aluminum or aluminum alloy base material excellent in light weight, workability, and heat conductivity is generally used. In the heat exchanger of this air conditioner, condensed water generated during cooling becomes water droplets and forms a water bridge between the fins. There are problems such as noise generation and splashing of water droplets.

 In order to solve this problem, the surface of the fin, which is an aluminum or aluminum alloy base material, is subjected to a hydrophilic treatment such as boehmite treatment, water glass application, or aqueous polymer application to prevent the formation of the bridge. ing. However, fins made of aluminum or its alloy that have been subjected to hydrophilization will be corroded in a few months if placed in a strongly corrosive environment, because the treated film may be hydrophilic. As a method of preventing such fin corrosion, conventionally, a method of performing a chromate treatment on the surface of an aluminum or aluminum alloy base material as a base treatment has been performed in view of corrosion resistance, cost, and the like. However, the chromate treatment has the problem of the toxicity of the chromium compound as described above.

Further, as a surface treatment agent or a surface treatment method that does not use chromate, for example, a method in which an aluminum surface is treated with an acidic solution containing a titanium salt, hydrogen peroxide and condensed phosphoric acid (Japanese Patent Application Laid-Open No. 54-24 / 1979) No. 2332), a method in which an aluminum surface is treated with an alkaline aqueous solution containing titanium ion and a complexing agent, washed with water, and then treated with an acidic aqueous solution of phosphoric acid or the like (Japanese Patent Application Laid-Open No. 54-16005). No. 27), an aluminum surface treating agent containing a phosphate ion, a titanium compound and a fluoride (Japanese Patent Application Laid-Open No. 9-199084), a condensed phosphate, a titanium salt, a fluoride and a phosphorous acid An aluminum-based metal surface treating agent containing a salt (Japanese Patent Application Laid-Open No. Hei 9-1143752) is known. However, the surface treatment agent and method using the titanium compound described above are not sufficient in stability of the surface treatment agent and have lower corrosion resistance than the chromate treatment. There were problems such as insufficient, insufficient hydrophilicity, and insufficient durability.

 From the above-mentioned situation, there is a demand for an inorganic film-forming material capable of forming a film having excellent corrosion resistance and the like without causing a problem of toxicity as a surface treatment agent for a metal substrate such as a steel sheet, aluminum, and an aluminum alloy. . Disclosure of the invention

 An object of the present invention is to provide a novel coating material for forming a titanium oxide film and a method for forming a titanium oxide film, which can form a good film having excellent corrosion resistance, adhesion, and workability on a metal substrate.

 Another object of the present invention is to provide a metal substrate coated with a titanium oxide film having excellent corrosion resistance, adhesion, and workability.

 Other objects and features of the present invention will become apparent from the following description. The present invention provides the following novel coating agent for forming a titanium oxide film, a method for forming a titanium oxide film, and a metal substrate coated with the titanium oxide film.

 1. (A) At least one titanium compound selected from a hydrolyzable titanium compound, a low condensate of a hydrolyzable titanium compound, a titanium hydroxide and a low condensate of titanium hydroxide is mixed with a hydrogen peroxide solution. A titanium-containing aqueous liquid obtained by

 (B) A coating composition for forming a titanium oxide film, comprising a phosphoric acid compound. 2. The coating composition according to the above item 1, wherein the titanium-containing aqueous liquid (A) is an aqueous solution of peroxotitanic acid obtained by mixing a hydrolyzable titanium compound and / or a low-condensate thereof with aqueous hydrogen peroxide.

 3. The hydrolyzable titanium compound has the general formula

 T i (O R) 4 (1)

 (In the formula, R represents the same or different and represents an alkyl group having 1 to 5 carbon atoms.) The coating agent according to the above item 2, which is a tetraalkoxytitanium represented by the formula:

 4. The low-condensation product of the hydrolyzable titanium compound has the general formula

 T i (O R) 4 (1)

(Wherein, R is the same or different and represents an alkyl group having 1 to 5 carbon atoms.) 3. The coating composition according to item 2, which is a compound having a degree of condensation of 2 to 30 obtained by subjecting the tetraalkoxytitaniums to condensation reaction with each other.

 5. The mixing ratio of the hydrolyzable titanium compound and Z or a low-condensate thereof and the aqueous hydrogen peroxide is 0.1 to 100 parts by weight in terms of hydrogen peroxide with respect to the former 10 parts by weight. Item 3. The coating agent according to the above item 2, which is within the range of.

 6. The titanium-containing aqueous liquid (A) is a peroxothiocyanic acid aqueous solution obtained by mixing a hydrolyzable titanium compound and Z or a low condensate thereof with hydrogen peroxide in the presence of a titanium oxide sol. Item 6. The coating agent according to item 2.

 7. The coating agent according to the above item 6, wherein the titanium oxide sol is an aqueous dispersion of an anatase type titanium oxide.

 8. The coating according to the above item 6, wherein the titanium oxide sol is used in an amount of 0.01 to 10 parts by weight on a solid basis with respect to 1 part by weight of the hydrolyzable titanium compound and / or its low-condensate. Agent.

 9. The phosphoric acid compound (B) is at least one compound selected from the group consisting of monophosphoric acids, derivatives and salts of monophosphoric acids, condensed phosphoric acids, and derivatives and salts of condensed phosphoric acids. The coating agent according to the above.

 100. The above item 1 wherein the content ratio of the titanium-containing aqueous liquid (A) and the phosphoric acid compound (B) is 1 to 400 parts by weight based on the former solids content of 100 parts by weight. The coating agent according to the above.

 11. The coating material for forming a titanium oxide film according to item 1, which is an aqueous liquid having ρΗ1 to 7. 12. The above composition further comprising at least one halide selected from the group consisting of titanium halides, titanium halide salts, zirconium halides, zirconium halide salts, silicon halides, and silicon halide salts. Item 1. The coating composition according to item 1.

 1 3. (A) At least one titanium compound selected from a hydrolyzable titanium compound, a low condensate of a hydrolyzable titanium compound, a titanium hydroxide and a low condensate of titanium hydroxide is mixed with aqueous hydrogen peroxide. A titanium-containing aqueous liquid obtained by mixing,

(Β ') phosphoric acid compounds, titanium halides, titanium halide salts, zirconium halides, zirconium octalogenide salts, silicon halides and At least one compound selected from the group consisting of silicon halide salts,

(C) A coating composition for forming a titanium oxide film, which comprises a stable aqueous organic polymer compound at a pH of 7 or less.

14. The coating composition according to the above item 13, wherein the titanium-containing aqueous liquid (A) is an aqueous solution of peroxotitanic acid obtained by mixing a hydrolyzable titanium compound and / or a low-condensation product thereof with aqueous hydrogen peroxide. .

 15. The hydrolyzable titanium compound has the general formula

 T i (OR) * (1)

 (Wherein R is the same or different and represents an alkyl group having 1 to 5 carbon atoms.) The coating agent according to the above item 14, which is a tetraalkoxytitanium represented by the formula:

 16. The low-condensation product of the hydrolyzable titanium compound has the general formula

 T i (OR) 4 (1)

 (In the formula, R is the same or different and represents an alkyl group having 1 to 5 carbon atoms.) A compound having a condensation degree of 2 to 30 obtained by subjecting tetraalkoxytitanium represented by Item 15. The coating agent according to the above item 14.

 17. The mixing ratio of the hydrolyzable titanium compound and / or its low condensate and aqueous hydrogen peroxide is in the range of 0.1 to 100 parts by weight in terms of hydrogen peroxide for the latter 10 parts by weight. Item 15. The coating agent according to the above item 14, wherein

 18. The titanium-containing aqueous liquid (A) is a peroxotitanic acid aqueous solution obtained by mixing a hydrolyzable titanium compound and Z or a low condensate thereof with a hydrogen peroxide solution in the presence of a titanium oxide sol. Item 15. The coating agent according to Item 14.

 19. The coating agent according to the above item 18, wherein the titanium oxide sol is an aqueous dispersion of anatase type titanium oxide.

 20. The coating composition according to the above item 18, wherein the titanium oxide sol is used in an amount of 0.01 to 10 parts by weight in terms of solid content with respect to 1 part by weight of the hydrolyzable titanium compound and / or its low condensate.

21. If the phosphoric acid compound in the compound (Β ') is a group consisting of monophosphates, derivatives and salts of monophosphates, condensed phosphoric acids, derivatives and salts of condensed phosphoric acids Item 14. The coating agent according to Item 13, which is at least one compound selected from the group consisting of:

22. In the compound (3 ′), the titanium halide, the titanium halide salt, the zirconium halide, the zirconium halide salt, the silicon halide, and the halogen constituting the silicon halide salt are fluorine. The coating agent according to the item.

 23. The content of the titanium-containing aqueous liquid (Α) and the compound (Β ′) is 100 to 100 parts by weight of the solid content of the former, and the latter is 1 to 400 parts by weight according to the above item 13. Coating agent as described.

 2 4. The aqueous organic high molecular compound (C) is an epoxy resin, phenol resin, acryl resin, urethane resin, polyvinyl alcohol resin, polyoxyalkylene chain-containing resin, and olefin monopolymerizable unsaturated carboxylic acid. Item 14. The coating agent according to Item 13, which is at least one resin selected from the group consisting of copolymer resins. 25. The above item, wherein the content 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 component of the titanium-containing aqueous liquid (Α). 13. The coating agent according to item 13.

 26. The coating agent according to the above item 13, which is an aqueous liquid having ρΗ1 to 7.

 27. A method for forming a titanium oxide film, which comprises applying the coating material for forming a titanium oxide film according to the above item 1 or 13 to a metal substrate and drying.

 28. A coated metal substrate in which a coating of the coating material for forming a titanium oxide film according to item 1 or 13 is formed on the surface of the metal substrate.

 29. The coated metal substrate according to the above item 28, wherein the coating has a thickness of 0.001 to 10111.

 30. The coated metal substrate according to the above item 28, wherein the metal substrate is a steel plate.

 31. The coated metal substrate according to the above item 28, wherein the metal substrate is aluminum or an aluminum alloy.

The present inventor has made intensive studies to achieve the above object. As a result, the titanium oxide-containing coating agent I containing the titanium-containing seven-part liquid (液) and the phosphate compound (系), or the titanium-containing aqueous liquid (Α), the phosphate compound and the Ζ or titanium For forming titanium oxide film containing halides (Β ') and (C) aqueous organic polymer It has been found that the coating material 11 has good corrosion resistance, adhesion, workability, and the like on a metal substrate, and can form a film suitable as a base treatment film.

 The present invention has been completed based on these new findings. Coating agent for forming titanium oxide film

 The coating agent I for forming a titanium oxide film of the present invention is an aqueous coating agent containing the (A) titanium-containing aqueous liquid and (B) a phosphate compound.

 At least one titanium compound selected from the group consisting of a hydrolyzable titanium compound, a low condensate of a hydrolyzable titanium compound, titanium hydroxide and a low condensate of titanium hydroxide, which is the component (A) in the coating composition I of the present invention; As a titanium-containing aqueous liquid obtained by mixing the above with a hydrogen peroxide solution, a known one can be appropriately selected and used.

 The hydrolyzable titanium compound is a titanium compound having a hydrolyzable group directly bonded to a titanium atom, and generates titanium hydroxide by reacting with water such as water or water vapor. In the hydrolyzable titanium compound, it does not matter whether all of the groups bonded to the titanium atom are hydrolyzable groups or if some of the hydrolyzable groups are hydrolyzed hydroxyl groups. Absent.

 The hydrolyzable group is not particularly limited as long as it reacts with water to generate a hydroxyl group, and examples thereof include a lower alkoxyl group and a group that forms a salt with a titanium atom. Examples of the group that forms a salt with a titanium atom include an octogen atom (such as chlorine), a hydrogen atom, and a sulfate ion.

 Examples of the hydrolyzable titanium compound containing a lower alkoxyl group as the hydrolyzable group include tetraalkoxy titanium.

 Representative hydrolyzable titanium compounds having a group capable of forming a salt with titanium as the hydrolyzable group include titanium chloride and titanium sulfate. The low condensate of the hydrolyzable titanium compound 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 the titanium atom are hydrolyzable groups, or a group in which some of the hydrolyzable groups are hydrolyzed hydroxyl groups.

Examples of low condensation products of titanium hydroxide include, for example, aqueous solutions of titanium chloride, titanium sulfate, etc. Ortho titanic acid (titanium hydroxide gel) obtained by the reaction of the solution with an aqueous alkali solution such as ammonia or caustic soda can be used.

 The degree of condensation in the low-condensation product of the hydrolyzable titanium compound or the low-condensation product of titanium hydroxide can be a compound having a degree of condensation of 2 to 30, and particularly a compound having a degree of condensation of 2 to 10 can be used. preferable.

 As the aqueous liquid (A), a conventionally known aqueous liquid containing titanium obtained by reacting the titanium compound with aqueous hydrogen peroxide can be used without particular limitation. . Specifically, the following can be used.

 (1) A peroxotitanic acid aqueous solution described in JP-A-63-35419 and JP-A-224220, which is obtained by adding aqueous hydrogen peroxide to a hydrous titanium oxide gel or sol.

 (2) The reaction of an aqueous solution of titanium chloride, titanium sulfate, etc. with an alkaline aqueous solution of ammonia, caustic soda, etc., as described in JP-A-9-71418 and JP-A-10-67516, An aqueous liquid for forming a titanium oxide film, which is a yellow transparent viscous liquid obtained by precipitating a titanium hydroxide gel, then separating the titanium hydroxide gel by decantation, washing with water, and adding hydrogen peroxide solution to the gel.

 (3) peroxotitanium hydrate by adding aqueous hydrogen peroxide to an aqueous solution of an inorganic titanium compound such as titanium chloride or titanium sulfate described in JP-A-2000-247638 and JP-A-2000-247639. A solution obtained by adding a basic substance thereto is left or heated to form a precipitate of a peroxotitanium hydrate polymer, and after removing dissolved components other than water, hydrogen peroxide is removed. An aqueous liquid for forming a titanium oxide film obtained by acting. As the titanium-containing aqueous liquid (A), it is preferable to use an aqueous solution of peroxotitanic acid (A 1) obtained by mixing a hydrolyzable titanium compound and Z or a low condensate thereof with aqueous hydrogen peroxide.

 As the titanium compound, a general formula

 T i (O R) 4 (1)

(Wherein, R is the same or different and represents an alkyl group having 1 to 5 carbon atoms.). Examples of the alkyl group having 1 to 5 carbon atoms represented by R include a methyl group, an ethyl group, an n-propyl group, and an iso-propyl Group, η-butyl group, iso-butyl group, sec-butyl group, tert-butyl group and the like.

 As the low condensate of the titanium compound, those having a condensation degree of 2 to 30 obtained by subjecting the compounds of the general formula (1) to a condensation reaction with each other are preferably used. It is more preferred to use one.

 The mixing ratio of the hydrolyzable titanium compound of the general formula (1) and Z or a low condensate thereof (hereinafter, these are simply referred to as “hydrolysable titanium compound (T)”) and the hydrogen peroxide solution are as follows. The amount of the former is preferably from 0.1 to 100 parts by weight, particularly from 1 to 20 parts by weight, based on 10 parts by weight of the former. If the amount of the latter is less than 0.1 part by weight in terms of hydrogen peroxide, the formation of peroxotitanic acid becomes insufficient and cloudy precipitation occurs, which is not preferable. 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, which is not preferable.

 The hydrogen peroxide concentration of the hydrogen peroxide solution is not particularly limited, but is preferably in the range of 3 to 40% by weight from the viewpoint of easy handling.

 The aqueous solution of peroxotitanic acid is usually a hydrolyzable titanium compound.

(T) can be prepared by mixing with aqueous hydrogen peroxide under stirring at a temperature of about 1 to 70 ° C for about 10 minutes to 20 hours. At the time of this mixing, a water-soluble solvent such as methanol, ethanol, n-propanol, iso-isopropanol, ethylene glycol monobutyl ether, and propylene glycol monomethyl ether can be used, if necessary.

 The aqueous solution of peroxotitanic acid (A 1) is obtained by mixing a hydrolyzable titanium compound (T) with aqueous hydrogen peroxide, whereby the hydrolyzable titanium compound is hydrolyzed with water to produce a hydroxyl-containing titanium compound. It is presumed that hydrogen peroxide is obtained by immediate coordination of hydrogen peroxide to this hydroxyl-containing titanium compound to form peroxotitanic acid. This aqueous solution of peroxotitanic acid has high stability at room temperature and withstands long-term storage.

In addition, an aqueous solution of peroxotitanic acid (A 2) obtained by mixing a hydrolyzable titanium compound (T) with aqueous hydrogen peroxide in the presence of a titanium oxide sol provides storage stability of the aqueous solution and a titanium oxide film obtained. It is preferable because the corrosion resistance of the steel is improved. So The reason is that, in the preparation of the aqueous solution, the hydrolyzable titanium compound (T) is adsorbed on the titanium oxide sol particles, and the adsorbed hydrolyzable titanium compound (T) is condensed with hydroxyl groups generated on the surface of the particles. And the hydrolyzable titanium compound itself is condensed and polymerized, and then mixed with aqueous hydrogen peroxide to stabilize the obtained aqueous solution and store it. It is presumed that gelation and thickening in the inside were significantly prevented.

 The titanium oxide sol is a sol in which amorphous titanium oxide fine particles and anatase type titanium oxide fine particles are dispersed in water. As the titanium oxide sol, an aqueous solution of an anatase-type titanium oxide is preferable from the viewpoint of corrosion resistance. The titanium oxide sol may contain, for example, an aqueous organic solvent such as an alcohol-based solvent or an alcohol ether-based solvent as required, in addition to water.

 As the titanium oxide sol, a conventionally known one can be used. As the titanium oxide sol, for example, amorphous titanium oxide fine particles in which a titanium oxide aggregate is dispersed in water, or an anatase type titanium oxide fine particle obtained by calcining the titanium oxide aggregate to be used in water are used. can do. Amorphous titanium oxide can be converted to an anatase-type titanium oxide by firing at a temperature at least equal to the crystallization temperature of anatase, usually at a temperature of 200 ° C or higher. it can. Examples of the above-mentioned oxidized titanium aggregates include (1) those obtained by hydrolyzing inorganic titanium compounds such as titanium sulfate and titanyl sulfate, and (2) those obtained by hydrolyzing organic titanium compounds such as titanium alkoxide. And (3) those obtained by hydrolyzing or neutralizing a titanium halide solution such as titanium tetrachloride.

Commercially available titanium oxide sols include, for example, “TK S—201” (trade name, manufactured by Tika Co., Ltd., aqueous sol of anatase-type titanium oxide fine particles having an average particle diameter of 6 nm), and “TK S—201”. 203 (product name, manufactured by Tika Co., Ltd., aqueous sol of anatase-type titanium oxide fine particles with an average particle diameter of 6 nm), “TA-15” (product made by Nissan Ideraku Co., Ltd.) Name, aqueous sol of anatase-type titanium oxide fine particles), “STS-1 lj (trade name, manufactured by Ishihara Sangyo Co., Ltd., aqueous sol of anatase-type titanium oxide fine particles)” and the like. When mixing the hydrolyzable titanium compound (T) and the aqueous hydrogen peroxide, the amount of the titanium oxide sol to be used is usually 0 parts by weight based on 1 part by weight of the hydrolyzable titanium compound (T). 0.1 to 10 parts by weight, preferably 0.1 to 8 parts by weight. If the amount of the titanium oxide sol is less than 0.01 part by weight, the effect of adding the titanium oxide sol, such as improvement in the storage stability of the coating agent and the corrosion resistance of the obtained titanium oxide film, cannot be obtained. Exceeding this is not preferable because the film forming properties of the coating agent are inferior. The titanium-containing aqueous liquid (A) is prepared by mixing a hydrolyzable titanium compound (T) with a hydrogen peroxide solution in the presence of a titanium oxide sol, if necessary, and then adding an aqueous solution of 80 ° It can be used as a dispersion liquid of titanium oxide fine particles having an average particle diameter of 1 O nm or less by heat treatment or autoclave treatment at a temperature of C or higher. The appearance of this dispersion is usually translucent.

 If the temperature of the heat treatment or autoclave treatment is lower than 80 ° C, crystallization of titanium oxide does not proceed sufficiently. The titanium oxide fine particles obtained by the above treatment have a particle size of 1 O nm or less, preferably in the range of 1 nm to 6 nm. When the particle diameter is larger than 1 O nm, the film-forming property is deteriorated, and when the film thickness is 1 zm or more, unevenness occurs, which is not preferable.

 When the titanium-containing aqueous liquid (A) is the aqueous liquid (A 1), an amorphous titanium oxide film containing a small amount of hydroxyl groups is usually formed under the above drying conditions. The amorphous titanium oxide film has an advantage that the gas barrier property is excellent. In the case of the titanium-containing aqueous liquid (A 2), an anatase type titanium oxide film containing a small amount of a hydroxyl group is usually formed under the above drying conditions.

The phosphoric acid compound (B) in the coating composition I of the present invention has an effect of improving the corrosion resistance of the obtained coating film. Examples of the compound (B) include phosphorous acid, strong phosphoric acid, triphosphoric acid, hypophosphorous acid, hypophosphoric acid, trimetaphosphoric acid, diphosphoric acid, diphosphoric acid, pyrophosphoric acid, and pyrophosphoric acid Monophosphoric acids such as metaphosphoric acid, metaphosphoric acid, metaphosphoric acid, and orthophosphoric acid; derivatives and salts of monophosphoric acids; condensed phosphoric acids such as tripolyphosphoric acid, tetraphosphoric acid, and hexanoic acid; and derivatives and salts of condensed phosphoric acids. I can do it. One or more of these compounds can be used. Examples of the alkaline compound that forms a salt of a phosphoric acid compound include lithium and natrium. Organic or inorganic alkali compounds containing thorium, potassium, ammonium and the like can be mentioned.

 As the phosphoric acid compound (B), it is preferable to use a compound that is soluble in water.

 As the phosphoric acid compound (B), use of sodium pyrophosphate, sodium tripolyphosphate, sodium tetraphosphate, metaphosphoric acid, ammonium metaphosphate, sodium hexametaphosphate, etc. is particularly preferable. It is preferable because the resulting coating film exhibits excellent effects such as corrosion resistance.

 It is preferable that the content ratio of the titanium-containing aqueous liquid (A) and the phosphoric acid compound (B) is about 1 to 400 parts by weight with respect to the former solid content of 100 parts by weight.

 When the amount of the component (B) is less than 1 part by weight, the corrosion resistance and the like are reduced. On the other hand, when the amount of the component (B) is more than 400 parts by weight, the film-forming properties are poor and the corrosion resistance and the like are undesirably reduced. The content ratio of the phosphoric acid compound (B) is more preferably about 100 to 200 parts by weight based on 100 parts by weight of the titanium-containing aqueous liquid (A).

 The coating agent I for forming a titanium oxide film of the present invention is produced by mixing a titanium-containing aqueous liquid (A) and a phosphoric acid compound (B) by an ordinary method. In the coating composition I of the present invention, it is considered that the phosphate compound (B) forms a complex structure between the acidic compound and the acidic phosphate group ion bound to the compound (B) by coordinating with the titanium ion. Can be Such a complex structure is easily formed by simply mixing both components, and is formed, for example, by allowing to stand at room temperature (20) for about 5 minutes to about 1 hour. When the mixture is heated, a complex structure is formed, for example, by heating at about 30 to about 70 for about 1 to 30 minutes.

 The coating agent I for forming a titanium oxide film of the present invention is an aqueous liquid that is stable in a neutral or acidic region, and its pH is usually in the range of 1 to 7. In particular, the storage stability is good in an acidic region, and it is preferable that ρΗ1-5. The coating composition I of the present invention may contain a hydrophilic solvent such as, for example, methanol, ethanol, isopropyl alcohol, ethylene glycol, and propylene dalicol, if necessary. The coating composition I of the present invention can be used by diluting it with water or a hydrophilic solvent, if necessary.

The coating agent I for forming a titanium oxide film of the present invention may have, if necessary, In order to further improve the edibility, at least one octa-logenide selected from the group consisting of titanium halide, titanium halide salt, zirconium halide, zirconium halide salt, silicon halide and silicon halide salt is used. Can be contained.

 Examples of the halogen constituting the halide include fluorine, chlorine, and iodine. As octogen, fluorine is particularly preferred since it has excellent properties such as storage stability of the coating agent, corrosion resistance of the coating film, and moisture resistance. Examples of the compound that forms a halide salt include sodium, potassium, lithium, and ammonium. Potassium and sodium are preferred as salts. Examples of the halide include titanium halides such as titanium hydrofluoric acid; titanium halide salts such as potassium titanium fluoride and titanium ammonium fluoride; zirconium halides such as zirconium hydrofluoric acid; and zirconium fluoride. Preferred are zirconium halide salts such as ammonium and potassium zirconium fluoride, silicon halides such as hydrosilicofluoric acid, and silicon halide salts such as sodium silicofluoride, ammonium silicofluoride and silicofluoride rim.

 In the case where the octylogenate is contained in the coating composition I of the present invention, the content is usually about 1 to 400 parts by weight based on 100 parts by weight of the solid content of the titanium-containing aqueous liquid (A). It is preferably in the range, in particular in the range from 10 to 200 parts by weight.

 The coating composition I of the present invention may further contain, if necessary, a basic neutralizing agent such as ammonia, an organic basic compound, an alkaline metal hydroxide, or an alkaline earth metal hydroxide. Can be. Preferred examples of the organic basic compound include ethanolamine and triethylamine, and preferred examples of the alkali metal hydroxide include lithium hydroxide, sodium hydroxide, and potassium hydroxide.

The coating composition I of the present invention may further contain various additives, if necessary. Examples of the additive include a thickener, an antibacterial agent, an antioxidant, a titanium oxide sol, a titanium oxide powder, an extender pigment, an antioxidant pigment, a coloring pigment, and a surfactant. Examples of the protective agent include tannic acid, phytic acid, benzotriazole and the like. The extender includes, for example, my power, talc, sili power, barium sulfate, clay and the like. The coating agent II for forming a titanium oxide film of the present invention contains the titanium-containing aqueous liquid (A), a phosphate compound and / or a titanium octalogenide (等 ′), and (C) an aqueous organic polymer compound. Aqueous coating agent.

 As the titanium-containing aqueous liquid (Α) in the coating composition II of the present invention, the same one as the titanium-containing aqueous liquid in the coating composition I of the present invention can be appropriately selected and used.

 At least one selected from the group consisting of a phosphate compound, a titanium halide, a titanium halide salt, a zirconium halide, a zirconium halide salt, a silicon octalogenide, and a silicon halide salt in the present coating composition II.

One kind of compound (Β ′) has an effect of improving the corrosion resistance of the obtained coating film.

 Examples of the phosphoric acid compound in the above compound (Β ′) include, for example, phosphorous acid, strong phosphoric acid, triphosphoric acid, hypophosphorous acid, hypophosphoric acid, trimetaphosphoric acid, diphosphoric acid, nilinic acid, and pyrophosphoric acid. Monophosphoric acids such as phosphorous acid, pyrophosphoric acid, metaphosphoric acid, metaphosphoric acid, and orthophosphoric acid; derivatives and salts of monophosphoric acids; condensed phosphoric acids such as tripolyphosphoric acid, tetraphosphoric acid, and hexaphosphoric acid; derivatives of condensed phosphoric acids; Salts and the like. In addition, examples of the alkali compound that forms a salt of a phosphoric acid compound include an organic or inorganic alkali compound containing lithium, sodium, potassium, ammonium, or the like.

 It is preferable to use a water-soluble compound as the above-mentioned phosphoric acid compound. In addition, as the phosphoric acid compound, sodium pyrophosphate, sodium tripolyphosphate, sodium tetraphosphate, metaphosphoric acid, ammonium metaphosphate, sodium hexametaphosphate, and the like can be used. It is preferable because the resulting coating film exhibits excellent effects such as corrosion resistance.

Examples of the halogen constituting the titanium halide, the titanium halide salt, the zirconium halide, the zirconium halide salt, the silicon halide, and the silicon halide salt in the compound (Β ′) include fluorine, chlorine, and iodine. Can be As octogen, fluorine is particularly preferred since it has excellent properties such as storage stability of the coating agent, corrosion resistance and moisture resistance of the coating film. Those which form halide salts include, for example, sodium, potassium, lithium, and ammonium. And the like. Potassium and sodium are preferred as salts.

 Examples of the halide include titanium halides such as titanium hydrofluoric acid; titanium halide salts such as potassium titanium fluoride and titanium ammonium fluoride; zirconium halides such as zirconium hydrofluoric acid; and zirconium fluoride. Preferred are zirconium halide salts such as ammonium and potassium zirconium fluoride, silicon halides such as hydrosilicofluoric acid, and silicon halide salts such as sodium silicofluoride, ammonium silicofluoride and silicofluoride rim.

 In the coating agent II for forming a titanium oxide film of the present invention, the titanium-containing aqueous liquid (A) and at least one of the phosphoric acid compound and the titanium halide (Β ′) form a complex structure between the two. It is thought that there is. Such a complex structure is easily formed by simply mixing both components, and is formed, for example, by allowing the mixture to stand at room temperature (20 "C) for about 5 minutes to about 1 hour. In the case of heating, for example, the complex structure is formed by heating at about 30 to about 70 ° C. for about 1 to 30 minutes. ) And the compound (Β ') are in the range of about 1 to 400 parts by weight, especially about 100 to 200 parts by weight for the former, 100 parts by weight of solids. It is preferred that

 The aqueous organic polymer compound (C) in the coating composition II for forming a titanium oxide film of the present invention has a ρ of about 7 or less, and when dissolved or dispersed in water, causes aggregation, thickening, gelation, and the like. As long as it does not occur and is in a stable state, a known material can be used without limitation.

 As the aqueous organic polymer compound (C), those having the form of an aqueous solution, an aqueous dispersion or an emulsion can be used. As a method for making the organic polymer compound water-soluble, dispersed or emulsified in water, a known method can be used.

Specific examples of the aqueous organic polymer compound (C) include, for example, at least one functional group that can be independently water-soluble or water-dispersible (for example, at least one of a hydroxyl group, a carboxyl group, an amino group, an imino group, a sulfide group, a phosphine group, and the like). Species), and those in which some or all of the functional groups of the compound are neutralized. Neutralization in this case is When the aqueous organic polymer compound (C) is an acidic resin such as a carboxyl group-containing resin, amine compounds such as ethanolamine and triethylamine; ammonia water; alkali metal water such as lithium hydroxide, sodium hydroxide, and potassium hydroxide; If the resin is neutralized with an oxide or the like, or is a basic resin such as an amino-containing resin, it is neutralized with a fatty acid such as acetic acid or lactic acid; or a mineral acid such as phosphoric acid.

 • Examples of the aqueous organic polymer compound (C) include an epoxy resin, a phenol resin, an acrylic resin, a urethane resin, a polyvinyl alcohol resin, a resin containing a polyoxyalkylene chain, and an olefin monopolymerizable resin. Saturated carboxylic acid copolymer resins, nylon resins, polyglycerin, carboxymethyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, and the like. Among the above-mentioned aqueous organic polymer compounds (C), preferred are epoxy resins, phenol resins, acrylic resins, urethane resins, polyvinyl alcohol resins, resins containing polyoxyalkylene chains, and olefin polymerization. And unsaturated carboxylic acid copolymer resins.

 In addition, according to the coating agent using a highly hydrophilic compound as the aqueous organic polymer compound (C), a coating film having both corrosion resistance and hydrophilicity can be formed, and fins made of aluminum or aluminum alloy are subjected to hydrophilic treatment. It is suitable as an agent.

 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 epoxy resin or a urethane-modified epoxy resin can be preferably used. Examples of the cationic epoxy resin include, 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, US Pat. No. 3,984,299). Adduct of an epoxy compound and a secondary mono- or polyamine having a ketiminated primary amino group (for example, see US Pat. No. 4,174,38); an epoxy compound And an etherification reaction product of a ketimine-containing hydroxyl compound having a primary amino group (for example, see JP-A-59-43013).

The epoxy compound has a number average molecular weight of 400 to 4,000, particularly 800 to 2,000, and an epoxy equivalent of 190 to 2,000, In particular Those within the range of 400 to 1,000 are suitable. Such an epoxy compound can be obtained, for example, by reacting a polyphenol compound with epichlorohydrin. Examples of the polyphenol compound include bis (4-hydroxyphenyl) -1,2,2-propane, 4,4-dihydroxybenzophenone, bis (4-hydroxyphenyl ^ /)-1,1-ethane, and bis (4 —Hydroxyphenyl) 1,1-isobutane, bis (4-hydroxy-1-tert-butylphenyl) 1,2,2-propane, bis (2-hydroxynaphthyl) methane, 1,5-dihydroxynaphthalene, bis ( 2,4-dihydroxyphenyl) methane, tetra (4-hydroxyphenyl) -11,1,2,2-ethane, 4,4-dihydroxydiphenylsulfone, phenol nopolak, cresol nopolak and the like.

 As the phenolic resin, those obtained by heating and adding and condensing a phenol component and formaldehydes in the presence of a reaction catalyst to obtain a water-soluble polymer compound 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, or the like can be used. Examples of the bifunctional phenol compounds include trifunctional phenols such as o-cresol, p-cresol, ρ-tert-butylphenol, p-ethylphenol, 2,3-xylenol, and 2,5-xylenol. Enol ^; Examples of compounds include phenol, m-cresol, m-ethylphenol, 3,5-xylenol, and m-methoxyphenol, and examples of tetrafunctional phenol compounds include bisphenol A and bisphenol F. can do. These phenol compounds can be used alone or in combination of two or more.

 The acrylic resin includes, for example, a homopolymer or copolymer of a monomer having a hydrophilic group such as a hydroxyl group, an amino group, or a hydroxyl group, and a monomer copolymerizable with a monomer having a hydrophilic group. Copolymers with monomers and the like can be mentioned. These resins are obtained by emulsion polymerization, suspension polymerization or solution polymerization, and if necessary, neutralization and aqueous conversion. Further, the obtained resin may be further modified if necessary.

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

 Examples of the nitrogen-containing monomer include nitrogen-containing monomers such as N, N-dimethylaminoethyl (meth) acrylate, N, N-getylaminoethyl (meth) acrylate, and N-t-butylaminoethyl (meth) acrylate. Alkyl (meth) acrylate; acrylamide, methacrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-methylol (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-butoxy Polymerizable amides such as methyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, N, N-dimethylaminoethyl (meth) acrylamide; 2- Vinylpyridine, 1-vinyl-2-pyrrolidone, 4- Aromatic nitrogen-containing monomers such as Nirubirijin; Ariruamin like.

 Examples of the hydroxyl group-containing monomer include 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, 2,3-dihydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and polyethylene. Monoester of polyhydric alcohol and acrylic acid or methacrylic acid, such as glycol mono (meth) acrylate; ε-force prolactone is released from the monoester of polyhydric alcohol with acrylic acid or methacrylic acid. Ring-polymerized compounds are exemplified.

Other copolymerizable monomers include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, η-propyl (meth) acrylate, isop pill (meth) acrylate, η-butyl (me) Acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, octadecyl ( Alkyl (meth) acrylates having 1 to 24 carbon atoms, such as meth) acrylate and isostearyl (meth) acrylate; styrene, vinyl acetate and the like. These compounds can be used alone or in combination of two or more. In the present specification, “(meth) acrylate” means acrylate or methacrylate.

 Examples of the urethane resin include a polyurethane resin obtained from a polyol such as polyester polyol or polyether polyol and diisocyanate, and a low molecular weight compound having two or more active hydrogens such as diol and diamine, if necessary. It is preferable to use those obtained by elongating a chain in the presence of a chain extender and stably dispersing or dissolving in water. Examples of such urethane-based resins include, for example, Japanese Patent Publication No. Sho 42-241, Japanese Patent Publication Sho 42-241, Japanese Patent Publication Sho 42-511, and Japanese Patent Publication Sho 49-9. No. 86, No. 493-1330, No. 50-150, No. 27, No. 53-291, No. 5, etc. Can be widely used.

 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 resin, and dispersing or dissolving in water by self-emulsification.

 (2) A method of forcibly dispersing a polyether resin having completed the reaction or a polyether resin in which terminal isocyanate groups are blocked with a blocking agent, using an emulsifier and mechanical shearing force. Examples of the blocking agent include oxime, alcohol, phenol, mercaptan, amine, and sodium bisulfite.

 (3) A method in which a polyurethane resin having a terminal isocyanate group is mixed with water, an emulsifier, and a chain extender, and dispersion and high molecular weight are simultaneously performed using mechanical shearing force.

 (4) A method of dispersing or dissolving a polyurethane resin obtained using a water-soluble polyol such as polyethylene glycol as a raw polyol for the polyurethane resin in water.

 The aqueous resin obtained by the method for dispersing or dissolving the polyurethane resin described above can be used alone or as a mixture of two or more.

Examples of the diisocyanate that can be used for synthesizing the polyurethane-based resin include aromatic, alicyclic, and aliphatic diisocyanates. Specifically, for example, —Dimethoxy-1,4'-biphenylenediisocyanate, p-xylylenediisocyanate, m-xylylenediisocyanate, 1,3- (diisocyanatomethyl) cyclohexanone, 1,4 -— (diisocyanate) Methyl) cyclohexanone, 4,4 diisocyanatocyclohexanone, 4,4'-methylenebis (cyclohex ^ / isocyanate), isophorone diisocyanate, 2,4-tolylene diisocyanate, 2,6-trirangene Isocyanate, p-phenylene diisocyanate, diphenylmethane diisocyanate, m-phenylene diisocyanate, 2,4-naphthylene diisocyanate, 3,3'-dimethyl-4, 4'-biphenylene diisocyanate, 4,4'-biphenylene diisocyanate, and the like. Of these, 2,4-tolylene diisocyanate and 2,6-tolylene are particularly preferred.

 Commercially available polyurethane resins include, for example, "Hydran HW-330", "Hydran HW-340", and "Hydran HW-350" (all manufactured by Dainippon Ink and Chemicals, Inc.) , Product name), “Superflex 100”, “Superflex 150”, “Superflex F—34438D” (all manufactured by Dai-ichi Kogyo Pharmaceutical Co., Ltd.) Can be mentioned.

 The polyvier alcohol-based resin is preferably a polyvier alcohol having a degree of genification of 87% or more, and particularly preferably a so-called completely saponified polyvinyl alcohol having a degree of saponification of 98% or more. It is also preferable that the number average molecular weight is in the range of 3,000 to 10,000,000.

 As the above polyoxyalkylene chain-containing resin, those having a polyoxyethylene chain or a polyoxypropylene chain can be suitably used. For example, polyethylene glycol, polypropylene glycol, or a polyoxyethylene chain and a polyoxypropylene chain in a block form can be used. And a blocked polyoxyalkylene glycol bonded to.

Examples of the above-mentioned olefin monopolymerizable unsaturated carboxylic acid copolymer resin include a copolymer of an olefin such as ethylene and propylene and a polymerizable unsaturated sulfonic acid such as (meth) acrylic acid and maleic acid; The polymerizable unsaturated compound is added to the combined aqueous dispersion. In addition, at least one kind of water-dispersible resin or water-soluble resin selected from two kinds of resins obtained by emulsion polymerization and further intra-particle crosslinking can be suitably used.

 The copolymer of an olefin and a polymerizable unsaturated carboxylic acid is a copolymer of one or more olefins and one or more polymerizable unsaturated carboxylic acids. In the copolymer, the monomer content of the unsaturated carboxylic acid is suitably in the range of 3 to 60% by weight, preferably 5 to 40% by weight. The copolymer can be dispersed in water by neutralizing the acid groups in the copolymer with a basic substance.

 The polymerizable unsaturated compound in the crosslinked resin obtained by adding a polymerizable unsaturated compound to an aqueous dispersion of the above-mentioned copolymer and subjecting it to emulsion polymerization and further cross-linking within the particles is, for example, the above-mentioned water-dispersible or water-soluble The pierced monomers listed in the description of the acryl-based resin can be used, and one or more kinds can be appropriately selected and used.

 The content ratio of the aqueous organic polymer compound (C) is 100 to 2,000 parts by weight, preferably 100 to 1.0 parts by weight, based on 100 parts by weight of the solid content of the titanium-containing aqueous liquid (A). The amount within the range of 100 parts by weight is preferable from the viewpoint of the stability of the coating agent, the corrosion resistance of the obtained titanium oxide film, and the like.

 The coating agent II for forming a titanium oxide film of the present invention can be prepared by mixing each essential component by a conventional method. The coating agent II of the present invention is an aqueous liquid that is stable in a neutral or acidic region, and its pH is usually in the range of 1 to 7. In particular, the storage stability is good in the acidic region, and the pH is preferably in the range of 1 to 5. The present coating composition II may contain, if necessary, a hydrophilic solvent such as methanol, ethanol, isopropyl alcohol, ethylene glycol, or propylene glycol. The coating composition II of the present invention can be used by diluting it with water or a hydrophilic solvent, if necessary.

 The coating composition II of the present invention may further contain, if necessary, a basic neutralizing agent such as ammonia, an organic basic compound, an alkaline metal hydroxide, or an alkaline earth metal hydroxide. Can be. Examples of the organic basic compound include ethanolamine and triethylamine, and examples of the alkali metal hydroxide include lithium hydroxide, sodium hydroxide, and potassium hydroxide.

The coating composition II of the present invention may further contain various additives, if necessary. Examples of additives include thickeners, antibacterial agents, antibacterial agents, titanium oxide sols, Examples thereof include titanium oxide powder, extender pigments, sun protection pigments, coloring pigments, and surfactants. Examples of the protective agent include tannic acid, phytic acid, benzotriazole and the like. Examples of the extender pigment include my power, talc, sili power, barium sulfate, and clay.

 The coating agents I and II for forming a titanium oxide film of the present invention have excellent storage stability. Further, the coating agent can form a coating containing titanium oxide having good corrosion resistance, adhesion, workability, and the like on a metal substrate. Method for forming titanium oxide film and metal substrate coated with titanium oxide film

 The method for forming a titanium oxide film of the present invention is carried out by applying the above-mentioned coating agent I or II of the present invention to a metal substrate and drying it. Thus, a metal substrate covered with the titanium oxide film is obtained. This coated metal substrate can be used as it is as a protection metal substrate.

 The metal substrate to which the method for forming a titanium oxide film of the present invention is applied is not particularly limited as long as the substrate has at least a metal surface. For example, a base material whose surface is iron, aluminum, zinc, copper, tin, or an alloy containing any one of these metals can be given. In particular, it is preferable to use a rope base material and an aluminum or aluminum alloy base material.

 Examples of the steel sheet substrate include a hot-dip galvanized steel sheet, an electro-zinc plated steel sheet, an iron-zinc alloy plated steel sheet, a nickel-zinc alloy plated steel sheet, and an aluminum-zinc alloy plated steel sheet. . Further, as the aluminum-zinc alloy-coated steel sheet, for example, those sold under the trade names “Galvalume” and “Galphan” can be mentioned. Further, a zinc-coated steel sheet which has been subjected to a chemical conversion treatment such as a chromate treatment, a zinc phosphate treatment, and a composite oxide film treatment can also be used as the steel sheet substrate. Further, the steel sheet base material may be a steel sheet assembled.

The aluminum or aluminum alloy substrate is not particularly limited, but a typical example is a fin for a heat exchanger. As the heat exchanger fin as the base material, even a member before being assembled into the heat exchanger, It may be in a state assembled in a heat exchanger, and any known one can be used.

 As a method for applying the coating agent I or II of the present invention to a metal substrate, for example, a known method such as dip coating, shower coating, spray coating, roll coating, and electrodeposition coating can be used. it can. As for the drying condition of the coating agent, it is usually preferable to dry the coating material under heating conditions at which the maximum temperature of the material reaches about 60 to 250 ° C. for about 2 seconds to about 30 minutes.

 Further, the dry film thickness of the coating agent is usually preferably about 0.01 to 10 m, particularly preferably 0.1 to 3 m. If it is less than 0.001 m, the performance such as corrosion resistance and water resistance will be inferior. On the other hand, if it exceeds 10 m, the coating will be cracked or the corrosion resistance will be reduced, which is not preferable.

 Thus, according to the method for forming a titanium oxide film of the present invention, a titanium oxide film having good corrosion resistance, adhesion, workability, fingerprint resistance and the like can be formed on a metal substrate.

 Further, the coating agent I or II of the present invention can be applied to a substrate other than a metal substrate and dried to form a titanium oxide film.

 The substrate other than the metal substrate is not particularly limited. For example, polyvinyl chloride resin, polyethylene terephthalate, acrylic resin, silicone resin, polyester resin, fluorine resin, epoxy resin, polyethylene resin, nylon resin, petital resin, cellulose resin, phenol resin, etc. , A plastic substrate composed of a resin in which two or more of these resins are combined; an inorganic substrate such as glass or cement; a pulp substrate such as paper or fiber; a plastic substrate, an inorganic substrate, or a pulp substrate And a substrate to which a surface treatment or a primer has been applied.

 As a method of applying to the above-mentioned base material, it can be applied by a known method such as dip coating, shower coating, spray coating, roll coating, and electrodeposition coating. As for the drying condition of the coating agent, it is generally preferable to dry the coating material for about 2 seconds to about 30 minutes under heating conditions at which the maximum temperature of the material reaches about 20 to 250 ° C. The dry coating film thickness of the coating agent is usually preferably about 0.001-1.

If necessary, an upper layer film can be formed on the substrate on which the titanium oxide film is formed by the coating agent I or II of the present invention. The composition forming this upper layer coating is It may be appropriately selected according to the conditions, and various coating compositions can be used. Examples of the coating composition include a lubricating coating forming composition, a highly corrosion resistant coating forming composition, a primer coating, and a colored top coating. 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 color top coat may be applied thereon.

 The aluminum or aluminum alloy substrate coated with the coating agent I or II of the present invention has a coating excellent in corrosion resistance, hydrophilicity, adhesion, workability, and the like. Further, hydrophilicity can be improved.

 If the coated substrate obtained by coating the coating agent of the present invention on an aluminum or aluminum alloy substrate is to be used as a fin for a heat exchanger, if necessary, the surface of the coated film may be further hydrophilized. A treatment film can be formed.

 The surface of the hydrophilic treatment film is hydrophilic, has sufficient film strength, has good water resistance, and has good adhesion to the underlayer treatment film. The formation of the above-mentioned hydrophilized coating film can be suitably performed usually by applying and drying the hydrophilized composition. As the hydrophilic treatment composition, a composition containing a hydrophilic film-forming binder is preferable. Preferred hydrophilic film-forming binders include, for example, (1) an organic resin-based binder comprising a hydrophilic organic resin as a main component and, if necessary, a crosslinking agent; and (2) a hydrophilic organic resin and a colloidal silicone. Organic resin composed mainly of force and optionally combined with a cross-linking agent. Colloidal silica-based binder. (3) Water glass-based, which is a mixture of formed alkali silicate and anionic or nonionic aqueous organic resin. Pinda and the like can be mentioned. Among these binders, an organic resin-based binder (1) and an organic resin-colloidal silica-based binder (2) are more preferable. BEST MODE FOR CARRYING OUT THE INVENTION

Next, the present invention will be described more specifically with reference to Production Examples, Examples and Comparative Examples. However, the present invention is not limited to the following examples. “Parts” and “%” in each example are based on weight. Preparation of titanium-containing aqueous liquid (A) Production Example 1

 10% aqueous ammonia was added dropwise to an aqueous solution obtained by converting 5 cc of a titanium tetrachloride aqueous solution 5 cc with distilled water to 500 cc to precipitate titanium hydroxide. After washing the precipitate with distilled water, add 10 cc of a 30% solution of hydrogen peroxide and stir to obtain a titanium-containing aqueous liquid (1) 70 cc, a yellow translucent viscous liquid with a solid content of 2% containing peroxotitanic acid. I got Production Example 2

 A mixture of 10 parts of tetra-iso-propoxytitanium and 10 parts of iso-propanol was added to a mixture of 10 parts of 30% hydrogen peroxide solution and 100 parts of deionized water at 20 ° C for 1 hour. The mixture was added dropwise while stirring. Thereafter, the mixture was aged at 25 for 2 hours to obtain a titanium-containing aqueous liquid (2), which is a yellow transparent, slightly viscous peroxotitanic acid aqueous solution having a solid content of 2%.

Production Example 3

 In Preparation Example 2, a titanium-containing aqueous liquid (3) having a solid content of 2% was obtained in the same manner as in Preparation Example 2, except that the same amount of tetra-n-butoxytitanium was used instead of tetra-iso-propoxytitanium. .

Production Example 4

 In Preparation Example 2, a titanium-containing aqueous liquid having a solid content of 2% (4%) was prepared in the same manner as in Preparation Example 2, except that the same amount of a trimer of tetra-iso-propoxytitanium was used instead of tetra-iso-propoxytitanium. ).

Production Example 5

 In Preparation Example 2, a 3% amount of hydrogen peroxide was used.5 (TC was added dropwise over 1 hour, and then aged at 60 ° C for 3 hours. Thus, a titanium-containing aqueous liquid (5) was obtained.

Production Example 6

 The titanium-containing aqueous liquid obtained in Production Example 3 was further subjected to a heat treatment at 95 to 6 hours to obtain a titanium-containing aqueous liquid (6) having a solid content of 2% as a white-yellow translucent titanium oxide dispersion. Production Example 7

A mixture of 10 parts of tetra-iso-propoxytitanium and 10 parts of iso-propanol was mixed with “TKS-203” (manufactured by Tika Co., Ltd., trade name; Aqueous sol of titanium oxide fine particles of type 5) (as solid content) in a mixture of 10 parts of 30% hydrogen peroxide water and 100 parts of deionized water at 10 over 1 hour It was added dropwise with stirring. Thereafter, aging was performed at 10 ° C. for 24 hours to obtain an aqueous liquid (7) containing 2% of titanium, which was transparent and yellow and had a slightly viscous solid content. Example of coating agent I for forming titanium oxide film of the present invention

Example 1

 50 parts of the titanium-containing aqueous liquid (1) obtained in Production Example 1, 5 parts of 10% metaphosphoric acid, and 45 parts of deionized water were mixed to obtain a coating material for forming a titanium oxide film of the present invention.

Examples 2 to: L6 and Comparative Examples 1 to 2

 Based on the compositions shown in Table 1, in the same manner as in Example 1, a coating agent of the present invention and a coating agent for comparison were obtained.

 table 1

 Example

 1 2 3 4 5 6 7 8 9

 (1) 50

 (2) 50 50 50 50 50 50

(A) (3) 50

 (4) 50

 (Five)

 (6)

 (7)

 赠 Phosphoric acid 5 5 10 5 5

 Sodium

 Torriho. Lilin 5

 Pum

 Larynic acid 5

 Sodium

 Puki Tallinn 5

 Translation

 Hiroshi Luconi

 Gong Shi's Condominium

 10% ammonia water

 7 Literary Lithium

本発明酸化チタン膜形成用塗布剤 Iの性能試験 Deo K 45 45 45 45 45 40 45 45 45

Performance test of the coating agent I for forming a titanium oxide film of the present invention

 Using each coating agent obtained in Examples 1 to 16 and Comparative Examples 1 and 2, a coating treatment of a metal substrate was performed, and the corrosion resistance of the obtained coated substrate was examined.

 (1) Coating treatment of aluminum plate

A 0.1% thick aluminum plate (A1500) was dissolved in an alkaline degreasing agent (Nippon Shii-Bee Chemical Co., Ltd., trade name "Chem Cleaner 561B") at a concentration of 2%. degreased using an aqueous solution, washed with water, each coating agent dry coating weight 0. and roller coating so that ² g / m 2, 2 as the material reaches the temperature becomes 1 0 0 ° C 0 After baking for 2 seconds, a titanium oxide film was formed.

 (2) Corrosion resistance of coated plate

The above coated plates were measured in accordance with the salt spray test method of JISZ2371. The test time has four stages of 120 hours, 240 hours, 360 hours and 480 hours. And evaluated according to the following criteria.

 a ... No white rust or blistering is observed on the painted surface.

 b ... A little white rust or blistering occurs

 c: White rust or blisters are remarkably generated.

 Table 2 shows the test results.

 Table 2

(3) Steel sheet coating

An electrogalvanized steel sheet with a thickness of 0.6 mm (coating weight on one side: 20 g / m ² ) was replaced with an alkaline degreasing agent (trade name “Chem Cleaner 56 1 B” manufactured by Nippon CB Chemical Co., Ltd.) the using concentration of 2% aqueous solution of defatted, washed with water, each coating agent dry coating weight 1. 0 g / m ² and made so by roller coating, material temperature reached 1 0 0 ° C And baked for 20 seconds to form a titanium oxide film.

 (4) Corrosion resistance of coated plate

The test coated plate in which the end surface and the back surface of each of the coated plates were sealed was measured according to the salt spray test method of JISZ2371. Testing time is 24 hours, 48 hours And three hours of 72 hours, and evaluated according to the following criteria.

 a: No occurrence of white mackerel is observed.

 b: The degree of whitening is less than 5% of the coating film area,

 c: The degree of white mackerel generation is 5% or more of the coating film area and less than 10%,

 d: The occurrence of white mackerel is 10% or more of the coating film area and less than 50%,

 e: The degree of whitening is 50% or more of the coating film area.

 Table 3 shows the test results.

 Table 3

(5) Steel sheet coating

Alkaline degreasing the surface of a 0.6 mm-thick electro-zinc-plated steel sheet (coating weight 20 g / m ^{2 on} one side), followed by “Preparet Z” (trade name, manufactured by Nippon Parkerizing Co., Ltd.) The surface was adjusted by spray painting. Then, after spray-coating “Pal Pond 338” (trade name, aqueous zinc phosphate solution, manufactured by Nippon Parkerizing Co., Ltd.), the coated steel sheet was subjected to zinc phosphate treatment by washing with water and drying. The adhesion amount of the zinc phosphate treated coating was 1.5 g Zm ² . The plated steel sheet surface subjected to the zinc phosphate treatment, dry coating weight each of said coating agent is 1. 0 g / m was spray-coated at ^2, material temperature reached Ensure a 1 0 0 By baking for 20 seconds, a titanium oxide film was formed.

(6) Corrosion resistance of coated plate

 The test coated plate in which the end face and the back face of each coated plate were sealed was measured according to the salt spray test method of JIS Z 2371. The test time was set in three stages of 24 hours, 48 hours and 72 hours, and evaluated according to the following criteria.

 a: No whitening is observed.

 b: The degree of whitening is less than 5% of the coating film area,

 c: The degree of whitening is 5% or more of the coating film area and less than 10%,

 d: The degree of whitening is 10% or more of the coating film area and less than 50%,

 e: The degree of whitening is 50% or more of the coating film area.

 Table 4 shows the test results.

 Table 4

水性有機高分子化合物 （c) の調製 製造例 8

Preparation of aqueous organic polymer compound (c) Production Example 8

 Place 180 parts of isopropyl alcohol in a 1-L four-neck flask equipped with a thermometer, stirrer, cooler, and dropping funnel. After purging with nitrogen, adjust the temperature in the flask to 85, and add 140 parts of ethyl acrylate. , Methyl methacrylate 68 parts, styrene 15 parts, Nn-butoxymethylacrylamide 15 parts, 2-hydroxyethyl acrylate 38 parts and acrylic acid 24 parts were mixed with the catalyst 2,2'-azobis (2,2). It was added dropwise over 6 hours together with 6 parts of 4-dimethylperonitrile. When the reaction was continued at the same temperature for 5 hours after the completion of the dropwise addition, a colorless and transparent resin solution having a polymerization rate of almost 100%, a solid content of about 63%, and an acid value of about 67 mgKOHZg was obtained. To 500 parts of this resin solution, 108 parts of dimethylaminoethanol were mixed, water was added, and the mixture was sufficiently stirred to obtain an aqueous acrylic resin dispersion (C1) having a solid content of 30%.

Production Example 9

 In a reactor equipped with a stirrer, reflux condenser, thermometer, and liquid dropping device, “Epicoto 1009” (trade name, manufactured by Shell Chemical Company, epoxy resin with a molecular weight of 3,750) 1,880 g (0. After adding 1,000 g of a mixed solvent of 5 mol) and methylisobutylketone noxylene = 11 (weight ratio), 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 a 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 at 2 hours to complete the reaction, thereby obtaining an amine-modified epoxy resin having a solid content of 66%. To 1,000 g of the obtained resin, 25 parts of 88% formic acid were mixed, and water was added thereto. The mixture was thoroughly stirred to obtain a 30% solids content aqueous amine-modified epoxy resin dispersion (C2). Obtained. Example of coating agent 11 for forming titanium oxide film of the present invention

Example 17

Mix the titanium-containing aqueous liquid obtained in Production Example 1 (1) 50 parts, 20% zirconium hydrofluoric acid 5 parts, 30% acrylic resin aqueous dispersion (C1) 10 parts and deionized water 35 parts. Thus, a coating material for forming a titanium oxide film of the present invention was obtained. Examples 18 to 27 and Comparative Examples 3 to 5

 Based on the compositions shown in Table 5, in the same manner as in Example 17, a coating agent of the present invention and a coating agent for comparison were obtained.

 Table 5

 Example

 17 18 19 20 21 22 23

 (1) 50 50 50 50 50

 (2) 50

 (A) (3) 50

 (Four)

 (Five)

 (6)

 (7)

 20% コ coni 贿 is 5 2. 5 10

(Β'Conveyor fiber 10 20

 The fiber is Fiber 2.5

 Leg taric acid 10

 Recitation K dispersion 10 20 liquid (C1)

 (ai famine f raw; Lf xy tree 15 25

 Jumping Night (C2)

 `` Saran L-411 '' 10 20

“Kuraray RS Ho. Lima-RS-105” 25

35 25 37.5 15 37.5 15 10

(Table 5)

 In Table 5 above, "Saran Latex L-411" and "Kuraray RS Polymer-RS-105" indicate the following.

 Saran Latex L-411: manufactured by Asahi Kasei Kogyo Co., Ltd., trade name, vinylidene chloride resin, solid content 50%.

 Kuraray RS Polymer RS-105: Kuraray Co., Ltd., trade name, polyvinyl alcohol, solid content 10%. Performance test of coating agent for forming titanium oxide film of the present invention II

 Using each of the coating agents obtained in Examples 17 to 27 and Comparative Examples 3 to 5, a steel sheet substrate was subjected to a protective coating treatment, and the coated film appearance, adhesion, and corrosion resistance of the obtained coated steel sheet were examined. (1) Protection coating of steel substrate

Various plated steel sheets with a thickness of 0.8 mm were used as the base material. The following six types of plated steel sheets were used. (i) Electro-galvanized steel sheet: coating weight 20 g / m ² , which is called “EG”

(ii) Hot-dip galvanized steel sheet: coating weight of 60 g / m ² , called “HDGJ”

(iii) Steel sheet coated with zinc-iron alloy: 10% Fe content during plating, 60g / m coating weight This is called "Zn-Fe".

(iv) Zinc-nickel alloy coated steel sheet: Ni content in plating is 12%, coating weight is 30 g / m ² , which is called ΓΖη-Ν i J

(v) Zinc-aluminum alloy coated steel sheet: A1 content in plating is 12%, plating coverage is 150 gZm ² , which is called “Zn—12% A1”.

(vi) Zinc-aluminum alloy coated steel sheet: A1 content in plating is 55%, plating deposition amount is 250 g / m ² , which is called “Zn—55% A1”.

The surface of each of the above-mentioned plated steel sheets is sprayed with a 2% concentration aqueous solution of an alkaline degreasing agent (trade name “Chem Cleaner 561 B”, manufactured by Nippon Chibi Chemical Co., Ltd.) at a liquid temperature of 65 for 20 seconds. After degreasing, it was washed by spraying 60 warm water for 20 seconds. This degreased plated steel sheet, each coating agent dry coating weight was spray painted so that Do and 0. 5 gZm ^2, 15 seconds at ambient temperature 250 (Material temperature reached 10 o) and dried, anti鲭被film Was formed to obtain a coated steel sheet.

(2) Performance test of coated steel sheet

 With respect to each coated steel sheet obtained above, a coating film appearance, adhesion, and corrosion resistance were tested based on the following test methods.

 Test method

 Coating appearance: The uniformity of the coating was evaluated visually based on the following criteria.

 a: uniform appearance without unevenness,

 b: Partially uneven,

 c: Unevenness is present on the entire surface.

 Adhesion: The coating was subjected to the cross-cut tape method (clearance interval lmm) described in 8.5.2 of JIS K5400, and the adhesion was evaluated according to the following criteria.

 a: No peeling of the coating was observed.

 b: Peeling of the coating is observed, but the peeling area is less than 5%,

c: Peeling area is 5% or more and less than 20%, d: Peeling area is 20% or more and less than 50%,

 e: Peeling area is 50% or more.

 Corrosion resistance: Sealed the end face and the back face of the coated steel sheet, and performed the salt spray test specified in JISZ 2371 in three stages of 24 hours, 48 hours and 72 hours, and evaluated the corrosion resistance according to the following criteria .

 a No white or blistering is observed on the painted surface.

 b The degree of whitening or blistering is less than 10% of the coating area,

 c The degree of whitening or swelling is 10% or more and less than 30% of the coating area, d The degree of whitening or swelling is 30% or more of the coating area and less than 50%, e The degree of blistering is 50% or more of the coating area.

 Table 6 shows the test results.

 Table 6

本発明酸化チタン膜形成用塗布剤 11の例

Example of coating agent 11 for forming titanium oxide film of the present invention

Example 2 8

50 parts of titanium-containing aqueous liquid obtained in Production Example 1 (1) 50 parts, 20% zirconium hydrofluoric acid 5 parts, “AC10 LP” (manufactured by Nippon Kayaku Co., Ltd., polyacrylic acid aqueous solution, weight average Average molecular weight 25,000, acid value 779 mg KOHZ g, solid content 10%) 30 parts and 15 parts of deionized water was mixed to obtain a coating composition for forming a titanium oxide film of the present invention.

Examples 29 to 33 and Comparative Examples 6 to 7

 Based on the compositions shown in Table 7, in the same manner as in Example 28, a coating agent of the present invention and a coating agent for comparison were obtained.

 In Table 7 above, “AC 10LP”, “DENKA POVAL K-05” and “P EG6000 S” indicate the following.

 AC 10LP: manufactured by Nippon Kayaku Co., Ltd., trade name, aqueous solution of polyacrylic acid, weight average molecular weight 25,000, acid value 779 mgKOH / g, solid content 10%.

 Denka Bhopal K_05: manufactured by Denki Kagaku Kogyo Co., Ltd., trade name, polyvinyl alcohol, kendani degree 99%, polymerization degree 550, solid content 10%.

 PEG6000 S: manufactured by Sanyo Chemical Industries, Ltd., trade name, polyethylene glycol, average molecular weight 8,300, solid content 10%. Performance test of coating agent for forming titanium oxide film of the present invention II

Using each coating agent obtained in Examples 28 to 33 and Comparative Examples 6 to 7, an aluminum-based The material was subjected to a heat-resistant coating treatment, and the appearance, hydrophilicity and corrosion resistance of the coating film of the obtained coated aluminum plate were examined.

 (1) Aluminum base metal coating treatment

 Aluminum plate (A1500) with a thickness of 0.1 mm dissolved in an alkaline degreasing agent (Nippon Chibi Chemical Co., Ltd., trade name "Chemcleaner 56 1B") at a concentration of 2% After degreased and rinsed with an aqueous solution of the above, dip-coating is applied to each coating agent at 30 ° C for 30 seconds to a dry film thickness of 5 / m, and baked at 160 ° C for 10 minutes. Thus, a water-proof coating was formed to obtain a coated aluminum plate.

 (2) Performance test of test coated plate

 With respect to each of the coated aluminum plates described above, the coating film appearance, hydrophilicity, and corrosion resistance were tested based on the following test methods.

 Coating appearance: The uniformity of the anti-corrosion coating was visually evaluated based on the following criteria. a: uniform appearance without unevenness,

 b: There is unevenness for 5 minutes.

 c: Unevenness is present on the entire surface.

Hydrophilicity: The hydrophilicity was evaluated by the water contact angle after immersing the coated aluminum plate in running tap water (the amount of flowing water was 15 kg / hr per 1 m ² of the coated plate) for 72 hours. For comparison, the water contact angle of the initial test plate before this test was also measured (initial hydrophilicity). The water contact angle was determined by drying the coated aluminum plate at 80 ° C for 5 minutes, then dropping 0.04 cc of deionized water with a syringe onto the coated surface of the coated aluminum plate to form a water droplet. Was measured using Kyowa Kagaku Co., Ltd. “Contacta Gourmet Ichiyoichi DC AA”. The greater the water contact angle, the greater the hydrophilicity. Corrosion resistance: The above coated aluminum plates were measured according to the salt spray test method of JISZ2371. The test time was set in two stages of 120 hours and 240 hours, and the corrosion resistance was evaluated according to the following criteria.

 a: No white or blistering is observed on the painted surface,

 b: The degree of whitening or blistering is less than 10% of the coating area,

c: The degree of whitening or swelling is 10% or more of the coating film area and less than 30%, d: The degree of whitening or swelling is 30% or more of the coating film area and less than 50%, e: The degree of whitening or blistering is 50% or more of the coating film area.

 Table 8 shows the test results.

 Table 8

本発明の酸化チタン膜形成用塗布剤、 酸化チタン膜形成方法及び酸化チタン膜 で被覆された金属基材によれば、 次のような格別な効果が得られる。

According to the coating material for forming a titanium oxide film, the method for forming a titanium oxide film, and the metal substrate coated with the titanium oxide film of the present invention, the following special effects can be obtained.

 (1) The coating composition of the present invention has excellent storage stability. The reason is that the titanium-containing aqueous liquid (A) itself is stable, and that the aqueous liquid (A) forms a stable complex with (B) or (Β ′) such as a phosphoric acid compound, titanium octa-genide or the like. It is thought to be due to formation.

 (2) According to the method for forming a titanium oxide film using the coating agent for forming a titanium oxide film of the present invention, titanium oxide having excellent corrosion resistance, adhesion, durability, workability, hydrophilicity and the like is formed on a metal substrate. Can be formed.

 This film is excellent in corrosion resistance and durability because it has excellent adhesion to the substrate, because it is a dense titanium oxide film, it has low oxygen permeability and water vapor permeability, phosphoric acid compounds, titanium halides, etc. ( (Ii) or (Β ') functions as an etchant and corrosion inhibitor for metals, phosphoric acid compounds, titanium halides, etc.

It is considered that ((or B ′) is protected by titanium oxide. It is considered that this film has excellent adhesion because the titanium oxide in the film contains a hydroxyl group.

(3) The coated metal substrate obtained by applying the method for forming a titanium oxide film of the present invention can be suitably used as it is as a heat-resistant coated substrate. (4) According to the fin for a heat exchanger in which the coating agent of the present invention is coated on the surface of an aluminum or aluminum alloy base material to form a coating, water bridge formation between the fins due to condensed water generated during cooling can be prevented. . Therefore, the corrosion of the fins made of aluminum or aluminum alloy can be prevented.

Claims

The scope of the claims 1. (A) At least one titanium compound selected from a hydrolyzable titanium compound, a low condensate of a hydrolyzable titanium compound, a titanium hydroxide and a low condensate of titanium hydroxide is mixed with a hydrogen peroxide solution. A titanium-containing aqueous liquid obtained by  (B) A coating composition for forming a titanium oxide film, comprising a phosphoric acid compound. 2. The coating composition according to claim 1, wherein the titanium-containing aqueous liquid (A) is an aqueous solution of peroxotitanic acid obtained by mixing a hydrolyzable titanium compound and Z or a low-condensate thereof with a hydrogen peroxide solution. 3. The hydrolyzable titanium compound has the general formula  T i (O R) 4 (1)  (Wherein R is the same or different and represents an alkyl group having 1 to 5 carbon atoms.) The coating agent according to claim 2, wherein the coating agent is a tetraalkoxytitanium. 4. The low-condensation product of the hydrolyzable titanium compound has the general formula  T i (O R) 4 (1)  (In the formula, R is the same or different and represents an alkyl group having 1 to 5 carbon atoms.) A compound having a condensation degree of 2 to 30 obtained by subjecting tetraalkoxy titanium represented by 3. The coating composition according to claim 2, wherein: 5. The mixing ratio of the hydrolyzable titanium compound and / or its low-condensate and aqueous hydrogen peroxide is such that the former is 10 parts by weight, and the latter is 0.1 to 100 parts by weight in terms of hydrogen peroxide. 3. The coating composition according to claim 2, which is within the range of part. 6. The titanium-containing aqueous liquid (A) is a peroxothiconic acid aqueous solution obtained by mixing a hydrolyzable titanium compound and / or a low-condensate thereof with hydrogen peroxide in the presence of a titanium oxide sol. Item 6. The coating agent according to item 2. 7. The coating composition according to claim 6, wherein the titanium oxide sol is an aqueous dispersion of anatase-type titanium oxide. 5 8. The use amount of the titanium oxide sol according to claim 6, wherein the amount of the solid content is 0.01 to: 0 parts by weight of L with respect to 1 part by weight of the hydrolyzable titanium compound and Z or a low condensate thereof. Coating agent. 9. The phosphoric acid compound (B) is at least one compound selected from the group consisting of monophosphoric acids, derivatives and salts of monophosphoric acids, 10 condensed phosphoric acids, derivatives and salts of condensed phosphoric acids. The coating agent according to 1. 10. The content ratio of the titanium-containing aqueous liquid (A) and the phosphoric acid compound (B) is 100 to 100 parts by weight of the solid content of the former, and 1 to 400 parts by weight of the latter. Described in 15 Coating agent. 2. The coating composition for forming a titanium oxide film according to claim 1, which is an aqueous liquid having a pH of 1 to 7. 12. The composition further contains at least one halide selected from the group consisting of titanium halides, titanium halide salts, zirconium halides, zirconium octalogenates, silicon halides, and silicon halide salts. The coating agent according to claim 1. 13. (A) At least one titanium compound selected from a hydrolyzable titanium compound, a low condensate of a hydrolyzable titanium compound, water 25 Aqueous liquid containing titanium obtained by mixing with (Β ′) at least one member selected from the group consisting of a phosphoric acid compound, titanium octogenide, titanium halide salt, zirconium octogenogen, zirconium halide salt, silicon halide and silicon halide salt Compounds, row To  (C) A coating agent for forming a titanium oxide film, which comprises a stable aqueous organic polymer compound having a pH of 7 or less. 14. The coating agent according to claim 13, wherein the titanium-containing aqueous liquid (A) is an aqueous solution of peroxotitanic acid obtained by mixing a hydrolyzable titanium compound and / or a low-condensation product thereof with aqueous hydrogen peroxide. 15. The hydrolyzable titanium compound has the general formula  T i (OR) 4 (1)  15. The coating agent according to claim 14, wherein R is the same or different and represents an alkyl group having 1 to 5 carbon atoms. 16. The low-condensation product of the hydrolyzable titanium compound has the general formula  T i (OR) 4 (1)  (In the formula, R is the same or different and represents an alkyl group having 1 to 5 carbon atoms.) A compound having a condensation degree of 2 to 30 obtained by subjecting tetraalkoxytitanium represented by 15. The coating composition according to claim 14, wherein: 17. The mixing ratio of the hydrolyzable titanium compound and / or its low-condensate and the aqueous hydrogen peroxide is within the range of 0.1 to 100 parts by weight of hydrogen peroxide in terms of the former 10 parts by weight. 15. The coating composition according to claim 14, wherein 18. The claim that the aqueous titanium-containing liquid (A) is an aqueous solution of peroxotitanic acid obtained by mixing a hydrolyzable titanium compound and Z or a low condensate thereof with a hydrogen peroxide solution in the presence of a titanium oxide sol. Item 15. The coating agent according to Item 14. 19. The coating composition according to claim 18, wherein the titanium oxide sol is an aqueous dispersion of anatase-type titanium oxide. 20. The use according to claim 18, wherein the titanium oxide sol is used in an amount of 0.01 to 10 parts by weight in terms of solid content with respect to 1 part by weight of the hydrolyzable titanium compound and / or a low-condensation product thereof. Coating agent. 21. The phosphoric acid compound in the compound (Β ′) is at least one compound selected from the group consisting of monophosphates, derivatives and salts of monophosphates, condensed phosphoric acids, derivatives and salts of condensed phosphoric acids 14. The coating composition according to claim 13. 22. The compound (Β '), wherein the titanium halide, the titanium halide salt, the zirconium halide, the zirconium halide salt, the silicon halide and the halogen constituting the silicon halide salt are fluorine. The coating agent according to any one of the above. 23. The method according to claim 13, wherein the content ratio of the titanium-containing aqueous liquid (Α) and the compound (Β ′) is 1 to 400 parts by weight based on the solid content of 100 parts by weight. Coating agent as described. 2 4. When the aqueous organic polymer compound (C) is an epoxy resin, phenol resin, acryl resin, urethane resin, polyvinyl alcohol resin, polyoxyalkylene chain-containing resin and olefin monopolymerizable unsaturated carboxylic acid. 14. The coating agent according to claim 13, which is at least one resin selected from the group consisting of polymer resins. 25. The content 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 component of the titanium-containing aqueous liquid (Α). 13. The coating agent according to item 13. 26. The coating composition according to claim 13, which is an aqueous liquid having ρΗ1 to 7. 27. A method for forming a titanium oxide film, comprising applying the coating material for forming a titanium oxide film according to claim 1 to a metal substrate, and drying. 28. A coated metal substrate having a coating of the coating material for forming a titanium oxide film according to claim 1 formed on a surface of the metal substrate. 29. The coated metal substrate according to claim 28, wherein the coating has a thickness of 0.001 to 10 zm. 30. The coated metal substrate according to claim 28, wherein the metal substrate is a steel plate. 31. The coated metal substrate according to claim 28, wherein the metal substrate is aluminum or an aluminum alloy.