TWI224615B - Coating composition for forming titanium oxide film, method of forming titanium oxide film and metal, substrate coated with titanium oxide film - Google Patents

Abstract

The present invention provides: a coating composition for forming a titanium oxide film, comprising (A) a specific titanium-containing aqueous liquid and (B) a phosphoric acid compound; and a coating composition for forming a titanium oxide film, comprising (A) the titanium-containing aqueous liquid, (B) at least one member selected from the group consisting of phosphoric acid compounds, titanium halides and the like and (C) an aqueous organic high molecular compound stable at pH 7 or lower. The present invention further provides a process for forming a titanium oxide film using any of the above coating compositions, and a metal substrate coated with a titanium oxide film.

Description

1224615 A7 --------- B7 _ V. Description of the invention (1) The present invention relates to a newly developed coating agent for forming a titanium oxide film, a method for forming a titanium oxide film, and coating titanium oxide. Metal substrate of the film. In order to improve the corrosion resistance, workability, and the like of metal substrates such as steel plates, aluminum alloys, and aluminum alloys, various surface treatments are usually performed as a base treatment. In recent years, because surface-treated steel sheets require more excellent corrosion resistance, the use of cold-rolled steel sheets on substrates has been replaced by lead-based plated steel sheets, and is gradually increasing. In the past, the surface treatment of a 'wrapped plated steel sheet was generally performed with chromate treatment and phosphate treatment. Chromate treatment has the problem of toxicity of chromium compounds. In particular, 6 " chrome chromate is an extremely harmful substance that has been designated by most public agencies, including IARC (International Agency for Research Review), as a substance that causes human carcinogenesis. Specifically, the chromate treatment has problems such as the volatilization of chromate fumes in the processing procedure, the large cost of wastewater treatment equipment, and the dissolution of chromic acid from the treatment coating film. In addition, in phosphate treatments such as zinc phosphate and iron phosphate, after the phosphate treatment, the chromate post-treatment usually causes the toxicity of chromium compounds, and there are reaction accelerators and metals in phosphate treatment agents. Wastewater treatment such as ions, sludge treatment in which metal ions are eluted from the treated metal. Also, Japanese Patent Laid-Open Publication No. 58-224174, JP-A 6-0-5 (H79, JP-A 60-5, etc.) describe a coated steel sheet, which is referred to as a coated steel sheet. The base material, and it is formed into a silicate coating film, and then an organic oxalate coating film is formed thereon. The coated steel sheet has a paper size that is resistant to Chinese paper and is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) (Please read the notes on the back before filling this page)

J, τ.¾. -4- 1224615 A7 B7 V. Description of the invention (2) Good and good workability, but 'Because the coated steel sheet has a chromate coating film, there is still a problem of toxicity of chromium compounds. The coated steel sheet has insufficient corrosion resistance after removing the chromate coating film. In addition, in order to improve the corrosion resistance and hydrophilicity of aluminum or aluminum alloy substrates, various surface treatments are often applied as a base treatment. For example In general, the blades of the heat exchanger of the air conditioner generally use aluminum or aluminum alloy substrates with light weight, processability and thermal conductivity. In the heat exchanger of the air conditioner, the condensate generated during the cold room becomes water droplets. The connection of water is formed between the blades, and the ventilation path of the air is narrowed, so that the ventilation resistance is increased, and there are problems such as power loss, noise generation, and water droplets scattering. To solve this problem, the blades are made of aluminum or aluminum alloy substrates. The surface is subjected to hydrophilization treatment such as bauxite treatment, water glass coating, and water-based polymer coating to prevent the aforementioned coupling. However, the blades made of hydrophilized aluminum or its alloys The physical coating film is also hydrophilic, and will be corroded in about several months if it is placed in a strong corrosive environment. The method of preventing such blades from rot is based on the viewpoints of tolerance and cost in the past. The surface of the material is treated with chromate as a base treatment. However, chromate treatment has the problem of toxicity of chromium compounds as described above. Moreover, no surface treatment agent or surface treatment method for chromate is used, for example, Known methods include a method of treating aluminum surface with an acidic solution containing titanium salt, hydrogen peroxide, and condensed phosphoric acid (Japanese Patent Laid-Open Publication No. 54-24232); and an alkaline aqueous solution containing titanium ions and a complexing agent. The method of treating the surface of the Ming and washing it with an acidic aqueous solution such as phosphoric acid after washing (please read the precautions on the back before filling this page)

J., Ke 丨. ··· 1224615 A7 ________B7 V. Description of the invention (3) (Japanese Patent Laid-Open Publication No. 54_16〇527); aluminum surface treatment agent containing phosphate ion, titanium compound and fluoride (Special Japanese Patent Publication (please read the precautions on the back before filling this page) Kaiping No. 9-20984); aluminum-based metal surface treatment agent containing condensed phosphoric acid, titanium salt, fluoride and phosphite (Japanese Patent Publication Gazette No. 9-1143752) and so on. However, the aforementioned surface treatment agents or surface treatment methods using titanium compounds have problems such as insufficient stability of the surface treatment agents, inferiority to chromate treatment, poor hydrophilicity, and incomplete durability. From the above situation, it can be seen that surface treatment agents for metal substrates such as steel plates, aluminum, and aluminum alloys need inorganic film forming materials that have no toxicity problems and can form excellent coating films such as corrosion resistance. DISCLOSURE OF THE INVENTION The object of the present invention is to provide a newly developed coating agent for forming a titanium oxide film and a titanium oxide film, which can form a good coating film on metal substrates with good savings, adhesion, and processability. Formation method. Another object of the present invention is to provide a metal substrate coated with a titanium oxide film having excellent corrosion resistance, adhesion, and processability. Other objects and features of the present invention will be made clear by the following description. The present invention provides the following newly developed coating agents for forming a titanium oxide film, a method for forming a titanium oxide film, and a metal substrate coated with a titanium oxide film. 1. A coating agent for forming a titanium oxide film, comprising: (A) one selected from hydrolyzable titanium compounds, low condensates of hydrolyzable titanium compounds, titanium hydroxide, and low condensates of titanium hydroxide; A titanium-containing aqueous solution obtained by mixing at least one titanium compound 'with a hydrogen peroxide solution; and the size of this paper applies the Chinese National Standard (CNS) A4 specification (210X297 mm) -6- 1224615 A7 B7 V. Description of the invention ( 4 (B) Phosphoric acid-based compound 2. The coating agent for forming a titanium oxide film according to the aforementioned item 1, wherein the titanium-containing aqueous solution (A) is a kind of a hydrolyzable titanium compound and / or a low condensation thereof An aqueous solution of peroxytitanic acid obtained by mixing a substance with a hydrogen peroxide solution. 3. The coating agent for forming a titanium oxide film described in item 2 above, wherein the hydrolyzable titanium compound is represented by the general formula (1) Tetraalkoxytitanium, that is, / / Ti (OR) 4 ⑴ (In the formula, R represents an identical or different alkyl group having i to 5 carbon atoms.) 4. Use as described in item 2 above. A coating agent for forming a titanium oxide film, wherein the low condensate of the hydrolyzable titanium compound is represented by the general formula (丨) A compound having a condensation ratio of 2 to 30 as shown in the tetraalkoxytitanium mutual condensation reaction shown; Ti (OR) 4 ⑴ (wherein R represents the same or different carbon atoms having 1 to 5 carbon atoms) 5) As described above, the coating agent for forming a titanium oxide film according to item 2, wherein X solution [the ratio of the raw titanium compound and / or its low condensate to the hydrogen peroxide solution is relative to The former is 10 parts by weight, and the latter is in the range of 0.1 to 100 parts by weight in terms of hydrogen peroxide. 6. The coating agent for forming a titanium oxide film as described in item 2 above, which contains titanium aqueous The liquid (A) is an aqueous solution of perrhenic acid peroxidized by mixing a hydrolyzable amidine compound and / or a low condensate thereof with a hydrogen peroxide solution in the state where a titanium oxide sol is stored. 7. Use as described in item 6 above. In order to form a coating agent for titanium oxide film, the alkane should be appropriate (please read the precautions on the back before filling out this page), one by one-¾. This paper is suitable for financial standards (CNS) Post code: 97) 1224615 A7 ----- B7 V. Description of the invention (5) Titanium oxide sol is anatase type titanium oxide Dispersions. (Please read the precautions on the back before filling in this page) 8. The coating agent used to form the titanium oxide film as described in item 6 above, where the amount of oxidized sol is relative to the hydrolyzable titanium compound and / Or 1 part by weight of the low condensate thereof, and it accounts for about 0.01 to 10 parts by weight as a solid content. 9. The coating agent for forming a titanium oxide film as described in the above item 1, wherein the acid-filling compound (B) is composed of a single-filler acid, a derivative of a single-filler acid and a salt, a condensed linoleic acid, and a condensed phosphoric acid. At least one compound selected from the group consisting of derivatives and salts. 10. The coating agent for forming a titanium oxide film as described in item 1 above, wherein the content ratio of the aqueous solution (A) and the phosphoric acid-based compound (B) containing Qin is relative to the solid content of the former 100. The latter accounts for about 1 to 400 parts by weight. 11 The coating agent for forming a titanium oxide film as described in the above item 1, which is an aqueous solution having a pH of 1 to 7. 12. The coating agent for forming a titanium oxide film according to the above item 1, further comprising a titanium compound, a titanium compound salt, a zirconium compound, a zirconium halide salt, a stone compound, and a stone compound. At least one selected from the group consisting of compound salts! | Chemicals. 13 · A coating agent for forming a titanium oxide film, comprising: (A) selected from a hydrolyzable titanium compound, a low-condensation product of a hydrolyzable titanium compound, titanium hydroxide, and a low-condensation product of titanium hydroxide At least one of the compounds, a titanium-containing aqueous solution obtained by mixing with a hydrogen peroxide solution; (B ') a phosphoric acid-based compound, a titanium halide, a titanium halide salt, a cross halide, a cross halide salt, stone The paper size composed of the halides and the sulfide salts of Xixi is applicable to the Chinese National Standard (CNS) A4 specifications (210X297 mm) -8- 1224615 A7 I · 丨 丨 ———— B7 V. Description of the invention ~ selected from the group At least one compound; and (c) a stable aqueous organic polymer compound having a pH of 7 or less. 14. The coating agent for forming a titanium oxide film as described in item 13, wherein the titanium-containing aqueous solution (A) is a kind of a hydrolyzable titanium compound and / or a low condensation product thereof and a hydrogen peroxide solution. An aqueous solution of peroxytitanic acid obtained by mixing. 15. The coating agent for forming a titanium oxide film as described in the above item 14, wherein the hydrolyzable titanium compound is tetrakis (oxycarbamyl) represented by the general formula (I), namely:

Ti (OR) 4 ⑴ (In the formula, R represents an alkyl group having the same or different carbon number from i to 5). 16. The coating agent for forming a titanium oxide film according to the aforementioned item 2, wherein the low condensate of the hydrolyzable titanium compound is composed of a tetraalkoxytitanium mutual condensation reaction represented by the general formula (0) Compounds with a condensation ratio of 2 ~ 30;

Ti (OR) 4 ⑴ (wherein R represents an alkyl group of the same or different number of carbon atoms of j to 5). 17. The coating agent for forming a titanium oxide film according to the aforementioned item 14, wherein the mixing ratio of the hydrolyzable titanium compound and / or its low condensate with a hydrogen peroxide solution is 10 parts by weight relative to the former, The latter is in the range of about 0.1 to 100 parts by weight in terms of hydrogen peroxide. 18. The coating agent for forming a titanium oxide film according to the foregoing item 14, wherein the titanium-containing aqueous solution (A) is a kind of hydrolyzable titanium compound and / or An aqueous solution of titanic acid is obtained by mixing the low condensate with a hydrogen peroxide solution. This paper size applies to China National Standard (CNS) A4 (210X297 mm) (Please read the precautions on the back before filling this page)

Yiding I -¾. -9- 1224615 A7 ----- B7 __ V. Description of the Invention (7) 19 · The coating agent for forming a titanium oxide film as described in the aforementioned item 18, wherein the titanium oxide sol It is an aqueous dispersion of anatase titanium oxide. (Please read the precautions on the back before filling this page.) 20 · As described in item 18 of the coating agent used to form the titanium oxide film, the amount of titanium oxide sol is relative to the hydrolyzable titanium compound. And / or 1 part by weight of the low condensate thereof, occupying about 01 to 10 parts by weight as a solid content. 21 · The coating agent for forming a titanium oxide film as described in item 13 above, wherein the acid compound in the fluorene compound (B ') is composed of mono-acid acids, mono-phosphoric acid derivatives and salts, and condensed phosphoric acid At least one compound selected from the group consisting of derivatives, salts of condensed phosphoric acid, and salts. 22. The coating agent for forming a titanium oxide film according to the aforementioned item 13, wherein the compound (B,) is used to constitute a titanium halide, a titanium halide salt, a zirconium compound, a complex compound salt, and a silicon compound. The halide of the halide and silicide salt is fluorine. 23. The coating agent for forming a titanium oxide film according to the aforementioned item 13, wherein the content ratio of the titanium-containing aqueous solution (A) and the compound (B,) is 100% by weight relative to the former's solid content. The latter accounts for about 1 to 400 parts by weight. 24. The coating agent for forming a titanium oxide film according to the aforementioned item 13, wherein the water-based organic polymer compound (C) is composed of an epoxy resin, a phenol resin, an acrylic resin, and ethyl amino acid ester. At least one resin selected from the group consisting of a series resin, a polyvinyl alcohol resin, a polyoxyalkylene chain resin, and an olefin polymerizable unsaturated carboxylic acid copolymer resin. 25. The coating agent for forming a titanium oxide film according to the aforementioned item 13, wherein the content ratio of the aqueous organic polymer compound (C) is 100% relative to the solid content of the titanium-containing aqueous solution (A). The parts by weight account for about 10 to 2000 parts by weight. 26. The coating agent used to form the titanium oxide film as described in item 13 above, which is the paper size applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) -10- 1224615 A7 _____B7 V. Description of the invention (8 ) An aqueous solution of pH 1 ~ 7. (Please read the precautions on the back before filling in this page) 27 · —A method for forming a titanium oxide film is to apply the coating agent used to form a titanium oxide film in the above item 1 or 3 to a metal substrate And dried. 28. A coated metal substrate is a coating film formed on the surface of a metal substrate with a coating agent for forming a titanium oxide film according to the foregoing item 1 or 13. 29. The coated metal substrate according to the aforementioned item 28, wherein the film thickness of the coating film is in the range of 0.001 μm to 100 μm. 30_ The coated metal substrate according to the aforementioned item 28, wherein the metal substrate is a steel plate. 31. The coated metal substrate according to the aforementioned item 28, wherein the metal substrate is a Ming or Shao alloy. The present inventors have conducted special studies to achieve the foregoing objectives. The results show that according to the coating agent I for forming a titanium oxide film containing the titanium-containing aqueous solution (A) and the phosphoric acid-based compound (B), or the foregoing titanium-containing aqueous solution (A), the phosphoric acid-based compound, and / Or titanium! (&Amp;) and (aqueous organic polymer compound coating agent π for forming a titanium oxide film) can form a good and suitable coating on a metal substrate with good corrosion resistance, adhesion, and processability. The film is used as a surface treatment film. The foregoing invention is completed based on such new knowledge. J is %% of the titanium oxide film. Youqi 丨 The coating agent I of the present invention for forming a titanium oxide film contains the aforementioned ( A) An aqueous coating agent containing a titanium-containing aqueous solution and (B) a phosphoric acid-based compound. The component (A) in the coating agent I of the present invention is composed of a hydrolyzable titanium compound, a low condensate of a hydrolyzable titanium compound, Titanium hydroxide and hydroxide This paper is in accordance with the Chinese National Standard (CNS) A4 specification (210X297 mm) -11- V. Description of the invention (9) = at least one kind of ammonium compound selected from the low sulfonium compounds and peroxide The condensed aqueous solution passed from the hydrogen solution 2 can be appropriately selected and used from known ones. The hydrolyzable titanium compound is a titanium compound having a hydrolyzable group which can be directly bonded to a titanium atom, that is, by combining with a titanium atom. Water, water vapor and other moisture Those who produce titanium oxide should have no problem, even if all the hydrolyzable titanium compounds are hydrolyzable groups, and some hydrolyzable groups become hydrolyzed hair groups, it is not necessary. The sex group is not particularly limited as long as it can be formed by reacting with moisture, for example, it can form a salt with a lower silk group or a titanium atom, a group, etc. A group that can form a salt with a titanium atom has a halogen atom ( (Chlorine, etc.), halogen atoms, sulfate ions, etc. Hydrolyzable titanium compounds containing a lower alkoxy group as a hydrolyzable group, for example, a tetraalkoxy titanium, etc. It has a group capable of forming a salt with titanium for hydrolysis. Typical examples of hydrolyzable titanium compounds include titanium chloride and titanium sulfate. The low-condensation product of the hydrolyzable compound is a low-condensation product between the aforementioned hydrolyzable titanium compounds. Even if the low-condensation product is bonded to a titanium atom, The bases are all hydrolyzable groups, and even if some of the hydrolyzable groups become hydroxyl groups that have been hydrolyzed, it does not matter. Low condensates of titanium hydroxide, for example, can be used water-soluble by titanium chloride, sulfuric acid, etc Orthoacid acid (titanium hydroxide gel) obtained by reacting with alkaline aqueous solutions such as ammonia and caustic soda. The aforementioned low-condensation product of hydrolyzable titanium compound or low-condensation of titanium hydroxide This paper applies Chinese national standards (CNS) ) A4 specification (210X297 mm) -12- 1224615 A7 B7 V. Description of the invention (Condensation ratio of 10 compounds can use 2-30 compounds, especially those with a condensation ratio within the range of 2-10 (Please read the precautions on the back before filling this page) The aqueous solution (A) mentioned above can be used if it is a titanium-containing aqueous solution obtained by reacting the aforementioned titanium compound with a nitrogen peroxide solution. There are no particular restrictions. Specifically, those listed below can be used. (1) The coagulation of titanium hydroxide-containing titanium contained in Japanese Patent Laid-Open Publication Nos. Sho 63-35419 and JP-A Hei 1-224220 An aqueous solution of titanic acid obtained by adding a hydrogen peroxide solution to a gel or sol. ， 可 | (2) The aqueous solution for forming a titanium oxide film contained in Japanese Patent Laid-Open Publication Nos. 9-71418 and JP-A No. 10-67516 is a kind of titanium oxide, titanium sulfate, etc. The aqueous solution reacts with alkaline aqueous solutions such as ammonia and caustic soda to precipitate titanium hydroxide gel called orthotitanic acid, followed by decantation method to separate titanium hydroxide gel. After washing with water, peroxide is added to it Yellow transparent viscous liquid obtained from hydrogen solution. .¾. (3) The aqueous solution for forming a titanium oxide film contained in Japanese Patent Laid-Open Publication Nos. 2000-247638 and 2000-247639 is a kind of gasification solution, titanium sulfate Into an aqueous solution of an inorganic titanium compound, a hydrogen peroxide solution is added to form a titanium peroxide hydrate, and a solution obtained by adding an alkaline substance to the solution is left to stand or heated to form a precipitate of a titanium peroxide hydrate polymer. It is obtained by dissolving components other than water and making hydrogen peroxide work. The aqueous solution (A) containing chitin is preferably a peroxytitanic acid aqueous solution (A1) obtained by mixing a hydrolyzable titanium compound and / or a low condensate thereof with a hydrogen peroxide solution.

-13- 1224615

DESCRIPTION OF THE INVENTION The titanium compound is particularly preferably a tetraalkoxytitanium represented by the general formula (1). Ti (OR) 4 ⑴ (Please read the notes on the back before filling out this page) (In this formula, R represents the same or different alkyl group with 1 to 5 carbon atoms). R is an alkyl group having 1 to 5 carbon atoms, which may be methyl, ethyl, n-methyl, isopropyl, n-butyl, isobutyl, second butyl, third butyl, etc. As an example. In addition, as the low-condensation product of the titanium compound, it is preferable to use a compound having a condensation ratio of 2 to 30, which is composed of the compounds of the general formula (engineering) that are subjected to mutual condensation reaction, and the use of the condensation ratio is in the range of 2 to 10 More ideal.

• I-Noisy · Hydrolyzable titanium compound of general formula (1) and / or its low condensate (hereinafter, these will be simply referred to as "hydrolyzable titanium compound (τ)") and hydrogen peroxide solution The mixing ratio is 10 parts by weight with respect to the former, and the latter is in the range of about 0.1 to 100 parts by weight when converted to hydrogen peroxide, and particularly preferably in the range of 1 to 20 parts by weight. If the latter is less than 01 weight summer when converted to hydrogen peroxide, the formation of peroxytitanic acid is incomplete and a white turbid precipitate is produced, which is not ideal. Conversely, if it exceeds 100 parts by weight, unreacted hydrogen peroxide is liable to remain and dangerous active oxygen will be released during storage, which is also not desirable. Although the hydrogen peroxide concentration of hydrogen peroxide is not particularly limited, it is preferably within a range of 3 to 40% by weight from the viewpoint of handling ease. In addition, the aqueous solution of a titanic acid may be generally obtained by mixing a hydrolyzable titanium compound (T) and a hydrogen peroxide solution at a temperature of 1 to 70. (: Prepared by stirring and mixing for about 10 to 20 hours in the range of left and right. When performing this mixing, methanol, ethanol, n-propanol, isopropanol, butoxyethanol (ethylene glyC〇1 monobutyl) may be used as necessary. ether), propylene glycerol monomethyl ether (propylene glyc 〇1 paper size suitable for wealth management (家 M specifications)> <297 public directors) -14-1224615 A7 B7 V. Description of the invention (l2 monomethyl ether) and other water-soluble solvents. (Please read the precautions on the back before filling in this page.) Describe the peroxytitanic acid aqueous solution (A1). It is estimated that the hydrolyzable titanium compound (T) should be mixed with the hydrogen peroxide solution to make the hydrolyzable titanium compound. Hydrogen-containing titanium compound is formed by hydrolysis of water, and then hydrogen peroxide is immediately coordinated with the hydroxyl-containing titanium compound to form peroxytitanic acid. The aqueous solution of peroxytitanic acid is in the range of room temperature, It has high stability and can be stored for a long time.

， 可 I. 啜 · In addition, in the state in which a titanium oxide sol is stored, a hydrolyzable titanium compound (T) and a hydrogen peroxide solution are mixed to obtain a titanium peroxide acid aqueous solution (A2). The titanium oxide film has improved residual resistance and the like, and the effect is ideal. The reason is presumably that in the preparation of the aqueous solution, the hydrolyzable titanium compound (T) will be adsorbed on the titanium oxide sol particles, and the adsorbed hydrolyzable titanium compound (T) will be condensed with the radicals generated on the surface of the particles. The reaction results in chemical binding, and the hydrolyzable titanium compound itself undergoes a condensation reaction and becomes polymerized. After mixing with a hydrogen peroxide solution, the obtained aqueous solution is stabilized and can be significantly prevented from being stored. Gelation or thickening occurs. The titanium oxide sol is one in which amorphous titanium oxide particles and anatase titanium oxide particles are dispersed in water. Among the titanium oxide sols, an aqueous solution of anatase-type titanium oxide is preferred in terms of surname resistance. The titanium oxide sol may contain an aqueous organic solvent such as an alcohol-based or alcohol-ether-based solvent, in addition to water. The titanium oxide sol may be a conventionally known one. For example, it is possible to use amorphous titanium oxide particles that have dispersed the aggregates in water, or this paper size applies the Chinese National Standard (CNS) A4 specification (210X297 cm) -15- 5. Description of the invention (l3) roasting The titanium oxide agglomerates to form an anatase-type titanium oxide particle and disperse it :: the medium. Amorphous titanium oxide is calcined at a temperature that is at least higher than the crystallization temperature of anatase, usually at a temperature of 2GG ° C or higher. The aforementioned oxidized agglomerates are exemplified by: ⑴ obtained by hydrolyzing blood organic compounds such as titanium sulfate and titanium sulfate, and ⑺ obtained by hydrolyzing organic titanium compounds such as titanium filaments, (3) Four gasification and other self-chemical titanium solution hydrolyzed or neutralized and so on. The commercially available products of titanium oxide sol are described, for example, "TKs_2〇i" (aqueous sol of anatase-type titanium oxide particles manufactured by TAYCA Corporation, trade name, average particle diameter of 6 nm); rTKS_2. 3 "(aqueous sol of anatase-type titanium oxide particles manufactured by Tayca Co., Ltd. with a trade name and an average particle diameter of 6 nm);" TA-15 "(manufactured by Jassan Chemical Co., Ltd., trade name, anatase type Aqueous sol of titanium oxide particles); rSTS-11 "(aqueous sol of anatase-type hafnium oxide particles, manufactured by Ishihara Industry Co., Ltd., trade name). When the hydrolyzable titanium compound (T) is mixed with a hydrogen peroxide solution, the amount of the titanium oxide sol used is usually 1% of that of the hydrolyzable titanium compound (T), which accounts for about 0.001 ~ 1 in terms of solid content. 10 parts by weight, ideally occupying a range of about 0.1 to 8 parts by weight. If the amount of the titanium oxide sol is less than 0.01 parts by weight, the effects of improving the storage stability of the coating agent and the corrosion resistance of the titanium oxide film obtained after adding the titanium oxide sol cannot be obtained; otherwise, it exceeds 10 Parts by weight make the coating agent poor in film forming properties, which are not ideal. The titanium-containing aqueous solution (A) can also be mixed with a hydrolyzable titanium compound (T) and a hydrogen peroxide solution in the state where a titanium oxide sol is stored as required. The paper size is applicable to Chinese national standard (WS) A4. Specifications (21〇χ297mm) -16- 1224615 A7 _____B7 V. Faxian Ming (14) ^ s The combined aqueous solution of peroxytitanic acid, which is then heated or hot-pressed at a temperature above 80〇Γ A dispersion of oxidized microparticles having an average particle diameter of 10 nmw is formed and then used. The appearance of the dispersion is usually translucent. When the temperature of the heat treatment or hot pressing treatment is lower than 801, the titanium oxide cannot be completely crystallized. The titanium oxide fine particles obtained by the aforementioned treatment have a particle diameter of not more than 10 nm, and are preferably in the range of 1 to 6 nm. If the particle diameter is larger than 10 nm, the film forming property is reduced, and cracks occur when the film thickness is larger than km, and the effect is not satisfactory. When the titanium-containing aqueous solution (A) is the aforementioned aqueous solution (A1), an amorphous titanium oxide film containing several warp groups is usually formed under the aforementioned dry conditions. This amorphous titanium oxide film has the advantage of having good gas barrier properties. In the case of a titanium-containing aqueous solution (A2), an anatase-type titanium oxide film containing several hydroxyl groups will usually be formed under the aforementioned dry conditions. The phosphoric acid-based compound (B) in the coating agent I of the present invention has the effect of improving the corrosion resistance of the obtained coating film. The compound (B) may include, for example, linoleic acid, polyphosphoric acid, triscale acid, hypophosphorous acid, low phosphoric acid, trimetaphosphoric acid, diphosphite, diphosphoric acid, pyrophosphite, pyrophosphoric acid, metaphosphite Derivatives and salts of monophosphates such as phosphoric acid, metaphosphoric acid, orthophosphoric acid, monoscale acids, etc .; Condensed phosphoric acids such as trimer acid, tetraphosphoric acid, hexaphosphate, and derivatives and salts of condensed phosphoric acid ... . These compounds can be used alone or in combination of two or more. Examples of the alkali compound used to form a phosphoric acid-based compound include organic or inorganic test compounds containing lithium, sodium, ammonium, and the like. This paper size applies to China National Standard (CNS) A4 specification (210X297 mm) -17- ------------------- 嘹: ...——...:-Order .. ......... 啜 (Please read the precautions on the back before filling in this page) 1224615 A7 _______ B7 V. Description of the Invention (I5) osmic acid compounds (B) should be used for those who have solubility in water. If the phosphoric acid-based compound (B) exhibits effects such as excellent storage qualitative properties of the coating agent and corrosion resistance of the coating film, sodium pyrophosphate, sodium tripolyphosphate, sodium tetraphosphate, and The use of phosphoric acid, ammonium metaphosphate and sodium hexametaphosphate is particularly desirable. The content ratio of the titanium-containing aqueous solution (A) and the phosphoric acid-based compound (B) is 100 parts by weight relative to the solid content of the former, and the latter preferably accounts for about 1 to 400 parts by weight. If the component (B) is less than 1 part by weight, the corrosion resistance will be reduced. On the other hand, if the component (B) exceeds 400 parts by weight, the film-forming properties will be poor, and the corrosion resistance will be reduced. The phosphoric acid-based compound (B) has a more preferable content ratio, which is about 10 to 200 parts by weight based on 100 parts by weight of the titanium-containing aqueous solution (A). The coating agent J for forming a titanium oxide film of the present invention is produced by mixing a titanium-containing aqueous solution (A) and a phosphoric acid-based compound (B) according to a common method. In the coating agent of the present invention, the phosphoric acid-based compound (B) has an acidic phosphate ion capable of binding to the compound (B) and a titanium ion to form a complex structure between the two. Such a complex structure can be easily formed only by mixing two components. For example, it can be formed by leaving it at room temperature (2 (rc) for about 5 minutes to 1 hour.) When the mixture is heated, for example, It is about 30 ~ 70. (: The complex structure is formed by heating for about 1 ~ 30 minutes. The coating agent I used to form the titanium oxide film of the present invention is a kind of water-based composition which is stable in the neutral or acidic field. The pH of the liquid is generally in the range of 丨 ~ ?. Especially in the acidic field, it has good storage stability and is preferably in the range of ρΗι ~ 5. The coating agent j of the present invention may also contain such as 曱The standard of this paper applies to the Zhongguanjia standard ⑽) A4 size ⑵QX297 public Chu) ------------------ Order --------------- (Please read the notes on the back before filling this page) -18- 1224615 κι ___ B7 V. Description of the invention (16) Alcohol, ethanol, isopropanol, ethylene glycol, propylene glycol and other hydrophilic solvents. The coating agent I of the present invention may be used after being diluted with water or a hydrophilic solvent, if necessary. The coating agent for forming a titanium oxide film according to the present invention may contain titanium halide, titanium halide salt, hafnium halide, hafnium halide salt, silicon halide, silicon halide salt as required. At least one kind of halide is selected from the group to further improve the corrosion resistance of the obtained coating film. The halogen used to form the phantom is exemplified by fluorine, gas, iodine, and the like. From the standpoint of excellent storage stability of the coating agent, corrosion resistance of the coating film, and moisture resistance, fluorine is particularly suitable as the tooth element. Examples of the salts used to form the compounds include sodium, potassium, lithium, and ammonium. For salt formation, potassium and sodium are preferred. The foregoing halides are preferably titanium compounds such as titanium hydrofluoric acid; titanium iide salts such as potassium potassium fluoride and titanium ammonium fluoride; zirconium dental compounds such as hydrofluoric acid; ammonium fluoride and potassium zirconium fluoride, etc. Zirconium dentate salts; Silicon fluoride and other silicon dentate salts; Silicon fluoride and other silicon dentate salts ... In the coating agent I of the present invention, the content ratio when the aforementioned halide is contained is usually 100 parts by weight with respect to the solid content of the titanium-containing aqueous solution (A), accounting for about 1 to 400 parts by weight, and 10 to 200 parts by weight. It is particularly preferable to be in a range of parts by weight. The coating agent I of the present invention may further include a basic neutralizing agent such as ammonia, an organic basic compound, an alkali metal hydroxide, or an alkaline earth metal hydroxide, if necessary. The aforementioned organic basic compounds are preferably ethanolamine and triethylamine, and the aforementioned alkali metal hydroxides are preferably lithium hydroxide, sodium hydroxide, and hydrogen. The paper size is applicable to the Chinese National Standard (QJS) A4 specification (21 × 297). %) —F… (Please read the notes on the back before filling this page),? -19- A7 ----------- B7 V. Description of the invention (17) &quot; --- Potassium oxide Wait. (Please read the precautions on the reverse side before filling out this page) The coating agent 1 of the present invention may contain various additives as necessary. Examples of such additives include thickeners, antibacterial agents, rust inhibitors, titanium oxide sols, titanium oxide pigments, rust inhibitor pigments, coloring pigments, and surfactants. Examples of the rust inhibitor include tannic acid, phytic acid, benzotriazol, and the like. The aforementioned physical pigments include mica, talc, stone spar, barium sulfate, clay, and the like. The coating agent π for forming a titanium oxide film according to the present invention is an aqueous organic compound containing the aforementioned aqueous solution (A), a phosphoric acid-based compound, and / or a titanium compound (B) and (C). Aqueous coating agent for molecular compounds. The titanium-containing aqueous solution (A) in the coating agent π of the present invention is appropriately selected from the rhenium-containing aqueous solution in the coating agent I of the present invention and the same. In the coating agent Π of the present invention, at least one compound selected from the group consisting of a phosphoric acid-based compound, a titanium compound, a titanium compound, a hammer compound, a #halide salt, a silicide, and a silicon compound salt (B,) are those which can improve the remaining resistance of the coating film. Examples of the phosphoric acid-based compound in the compound (B,) include phosphorous acid, polyphosphoric acid, triphosphoric acid, hypophosphorous acid, low phosphoric acid, trimetaphosphoric acid, diphosphite, diphosphoric acid, pyrophosphite, pyrophosphoric acid, and metaphosphoric acid. Monophosphoric acid such as phosphorous acid, metaphosphoric acid, orthophosphoric acid, derivatives and salts of monophosphoric acid; Condensed phosphoric acid such as tripolyphosphoric acid, tetraphosphoric acid, hexaphosphoric acid, and derivatives and salts of condensed phosphoric acid ... . Examples of the alkali compound used to form a salt of a phosphoric acid-based compound include organic or inorganic alkali compounds containing lithium, sodium, potassium, ammonium, and the like. The phosphoric acid-based compound described above is preferably used for those having solubility in water. In addition, if the acid-filling compound exhibits excellent storage stability of the coating agent, the Chinese paper standard (CNS) A4 specification (210X297 mm) applies to this paper size -20- to 4615 A7

For the effect of obtaining the corrosion resistance of the coating film, sodium pyrophosphate and tripolyphosphate (please read the precautions on the back before filling this page) sodium, sodium tetraphosphate, metaphosphoric acid, ammonium metaphosphate, six The use of sodium metaphosphate is particularly desirable. Among the aforementioned compounds (B '), the halogens used to form the titanium halide, titanium halide salt, zirconium halide, hafnium halide salt, silicon halide, silicon halide salt, and examples thereof include fluorine, gas, and iodine. . From the viewpoint of excellent storage stability of coating agent, corrosion resistance of coating film, moisture resistance, etc., it is particularly suitable as a pigment. Examples of the salt used to form the dentate include sodium, potassium, lithium, and ammonium. For salt formation, potassium and sodium are preferred. # · 述 述 || Compounds, titanium halides such as titanium hydrofluoric acid should be used; titanium halides such as potassium fluoride and titanium ammonium fluoride; zirconium dentates such as hafnium hydrofluoric acid; zirconium ammonium fluoride Samarium compound salts such as potassium fluoride; Silicon halide compounds such as hydrofluoric acid; Silicon fluoride compounds such as sodium fluoride, ammonium silicon fluoride, and potassium silicon fluoride. In the coating agent π for forming a titanium oxide film according to the present invention, the titanium-containing aqueous solution (A) and at least one (β,) such as a discic acid-based compound and a titanium compound form a complex between the two. structure. Such a complex structure can be easily formed only by mixing the two components. For example, it can be formed by leaving it at about 5 knives for 1 hour at room temperature (20 ° F). When the mixture is heated, for example, a complex structure is formed by heating at about 30 to 70 ° C for about 1 to 30 minutes. The content ratio of the titanium-containing aqueous solution (A) and the compound (b,) in the coating agent Π of the present invention is relative to the solid content of the former, and the latter accounts for about 1 to 400 parts by weight. The range of 1 ～ 200 parts by weight is particularly ideal. 0 This paper size is suitable for towel standard (Norway) A4 specification (QX297). -21- Like 4615 V. Description of the invention (l9 ▲ This invention is used to form oxidation The water-soluble organic molecular compound (C) in the coating agent n of the convergence film, if the pH is below 7, it is recognized as U 1 / P / M, and it is stable when dissolved in water or divided. Those in the case of agglomeration, thickening, gelation, etc. are not limited, and known ones can be used. The aqueous organic polymer compound (c) can be used in the form of an aqueous solution, an aqueous dispersion, or an emulsion. The method of dissolving, dispersing or emulsifying the organic polymer compound in water can be performed by a known method. Specific examples of the water-based organic polymer compound (c) include, for example, those which can be separately dissolved or water-dispersible. Functional groups (such as hydroxyl °, At least one of the following: an amino group, an amine group, an imine group, a sulfide group, a phosphine group, etc.), and those that have neutralized some or all of the functional groups of the compound. The molecular compound (c) is an acidic resin such as a resin containing rhenium, and is neutralized with amine compounds such as ethanolamine and triethylamine; ammonia water; alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide; If it is a basic resin such as an amine group-containing resin, it is neutralized with fatty SiL such as acetic acid and lactic acid, mineral acid such as eelic acid, etc. The aqueous organic polymer compound (C) includes, for example,% oxygen system Resin, phenol-based resin, acrylic resin, urethane-based resin, polyvinyl alcohol-based resin, polyoxyalkylene bond-containing resin, olefin polymerizable unsaturated carboxylic acid copolymer-based resin, nylon-based resin, polymer Glycerin, carboxymethyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, etc .. Among the above-mentioned water-based organic polymer compounds (C), epoxy resins, resins, and acrylic resins are preferred. Resin, urethane resin, poly Women's alcohol-based resins, polyoxyalkylene bond-containing resins, and ethylenically polymerizable unsaturated carboxyl paper standards are applicable to Chinese National Standard (CNS) A4 specifications (210 x 297). (Please read the precautions on the back before filling this page). -22- 1224615 V. Description of the invention (20 acid copolymer resins, etc.) ′ 〇 'JT uses the hydrophilic one as the coating agent for the water-based organic polymer compound (state). A coating film with both hydrophilicity 'and = as a hydrophilizing treatment agent for ms alloy blades. The aforementioned epoxy resin is a cationic epoxy resin that can be used to add an amine to an epoxy resin; Epoxy resin, epoxy urethane modified epoxy resin, etc. „Epoxy resin, etc. The aforementioned cationic epoxy waxes include, for example, epoxy compounds and W monoamines or polyamines, secondary monoamines or Addition of polyamine, grade 1-2 mixed polyamine (refer to US Patent No. 3984299), addition of epoxy compound and grade 2 monoamine or polyamine with ketimated industrial grade amine group Finished product (refer to US Pat. No. 4,017,438) An epoxy compound by etherification with the compound already having a ketiminized amino group of the i-th stage reaction product (refer to Japanese Patent Publication Laid-Open Publication No. Sho 59-43013) and the like. The aforementioned epoxy compound has a number average molecular weight in the range of 400 to 4,000, especially in the range of 800 to 2000, and an epoxy equivalent in the range of 190 to 2000, especially in the range of 400 to 1,000. The insider is better. Such an epoxy compound, for example, can be obtained by the reaction of various compounds with epigasol. Examples of the dopant compound include bis (4-hydroxyphenyl) -2,2-propane, 4,4-dihydroxydiphenyl ketone, and bis (4-hydroxyphenyl) -1,1-ethyl Alkane, bis (4-hydroxyphenyl) isobutane, bis (4-hydroxy-third butylphenyl) -2,2-propane, bis (2-hydroxynaphthyl) methane, 1,5-dihydroxy Naphthalene, bis (2,4-dihydroxyphenyl) pinene, tetrakis (4-hydroxyphenyl) · 1,2,2-ethane, 4,4-dihydroxydiphenylhydrazone, phenol novolac resin, fluorene Phenol novolac resin, etc. This paper size applies to Chinese National Standard (CNS) A4 specification U10X297 mm) Page order -23- 丄 4615 A7-~ -—— _ β7_ V. Description of the invention (21) A description of phenol resins A polymer obtained by subjecting a polymer compound to water / combination is used, and the polymer compound is obtained by heating and adding and condensing a phenol component and methyl ether in the presence of a reaction catalyst. As the aforementioned phenol component as a starting material, a bifunctional phenol compound, a trifunctional phenol compound, a tetrafunctional or higher phenol compound, or the like can be used. Examples of the 2-functional phenol compound system include o-cresol, p-cresol, p-tertiary butylphenol, p-ethylphenol, 2, stubble phenol, and 2,5-stub phenol. Phenol, m-cresol, m-ethylphenol, 3,5-phenol, m-oxyphenol and the like are exemplified, and bisphenol A and bisphenol F are exemplified as the 4-functional phenol compound. These phenol compounds can be used singly or in combination of two or more kinds. The aforementioned acrylic resin may be a single polymer or copolymer of a monomer having a hydrophilic group such as a carboxyl group, an amine group, or a hydroxyl group, and a copolymer of a monomer having a hydrophilic group and other copolymerizable monomers. example. These resins are obtained by emulsion polymerization, suspension polymerization or solution polymerization, and if necessary, neutralization and water-based polymerization. In addition, the obtained resin may be further modified if necessary. Examples of the carboxyl group-containing monomer include acrylic acid, fluorenyl acrylic acid, maleic acid, maleic anhydride, crotonic acid, and decomposed aconitic acid. Examples of the nitrogen-containing monomer include: N, N-dimethylaminoethyl (m) acrylate, N, N-diethylamineethyl (m) acrylate, and N-third butylamine Ethyl (m-) acrylic acid esters and other nitrogen-containing alkyl (m-) acrylates; propylammonium, methacrylamine, N_methyl (m-acryl), N-ethyl (m-) ) Acrylamide, N-Hydroxyfluorenyl (m-acrylamide), N-Phenoxyfluorenyl (m-acrylamide), N-Butoxyfluorenyl (m-) acrylamide, N, N-dimethyl (Intermediate) Acrylamide, N, N-Diamidinopropyl (m) Acrylamide, n, N-Diamidine This paper is sized to the Chinese National Standard (CNS) A4 (210X297 mm) 'f ( Please read the precautions on the back before filling this page), τ · A7 ------- B7 V. Description of the invention (22) Ethyl (m-) acrylamide and other polymerizable amidine groups; 2_ethylene Aromatic nitrogen-containing monomers, such as pyridine, 2-vinyl, and 2-vinyl, respectively; and, acrylamine, etc. As examples of the hydroxyl-containing monomer, there are: 2-hydroxyethyl (m) propylene, hydroxypropyl (m) acrylate, 2,3_hydroxybutyl (m) propylene, S , Monoesters of polyhydric alcohols such as 4-hydroxybutyl (m) acrylate and polyethylene glycol mono (m) acrylate, and acrylic acid or methacrylic acid; and Among the monoesters, compounds that cause ε-caprolactone to undergo ring-opening polymerization ... For other copolymerizable monomers, for example: methyl (m-) acrylate, ethyl (m-) acrylate, n-propyl (m-) acrylate, isopropyl (m-) acrylate, n-butyl ( M) acrylate, isobutyl (m) acrylate, second butyl (m) acrylate, 2-ethylhexyl (m) acrylate, n-octyl (m) acrylate, lauryl (m) acrylate Esters, tridecyl (m) acrylates, octadecyl (m) acrylates, isostearyl (m) acrylates and other alkyl (m) acrylates having a carbon number of SJ to 24; and, styrene , Vinyl acetate and so on. These compounds may be used singly or in combination of two or more kinds. In this specification, "(m) acrylic acid ester" means acrylic acid or m-acrylic acid. The urethane resin is described as a polyurethane resin made from a polyol such as polyester polyol, polyether polyol, and diisocyanate. Chain extension of low molecular weight compounds with more than 2 active hydrogen, such as amines, to extend the chain and make it in water. This paper applies Chinese National Standard (CNS) A4 (210X297). (Please read first Note on the back, please fill out this page again), order — 囔 · -25- 1224615 A7 B7 V. Description of the invention (23) Stable dispersion or dissolution. Such amine ethyl acetate-based resins can be widely used, for example, Japanese Patent Publications No. 42-24192, No. 42-24194, No. 42-5118, No. 49-986, No. 49-33 No. 104, No. 50-5015027, No. 53-29175, etc. As a method for stably dispersing or dissolving the polyurethane resin in water, the following method can be used. (1) Hydrophilicity is imparted by introducing an ionic group such as an amine group or a tertiary group into the branch or end of a polyurethane resin to impart hydrophilicity, and then it is dispersed or dissolved in water by self-emulsification. (2) The polyurethane g resin after completion of the reaction, or a polyurethane resin with terminal isocyanate blocked by a blocking agent, is forcibly dispersed in water using an emulsifier and mechanical shear force. Examples of the blocking agent include oxime, ethanol, phenol, thiol, amine, and sodium bisulfite. (3) A polyurethane resin with a terminal isocyanate group is mixed with water, an emulsifier, and a chain extender, and mechanical dispersion is used to simultaneously disperse and quantify the polymer. (4) A polyurethane resin prepared by using a water-soluble polyol such as polyethylene glycol as a raw material polyol of a polyurethane resin, dispersed or dissolved in water. The water-based resin 'obtained by the method of dispersing or dissolving the aforementioned polyurethane resin can be used alone or in combination of two or more kinds. Diisocyanates which can be used in the synthesis of the aforementioned polyurethane resins include aromatic, alicyclic and aliphatic diisocyanates. Specifically, this paper is translated into Chinese National Standard (CNS) A4 size (210X297 mm) (Please read the precautions on the back before filling out this page) Order — 囔 · -26- I224615 A7 B7 V. Description of the invention (24 Examples include: hexamethylene diisocyanate, tetramethylene diisocyanate, 3'3-dimethoxy-4,4 diphenyl diisocyanate, p-xylylene Diisocyanate, m-xylylene diisocyanate, 13- (methyl diisocyanate) cyclohexyl_, 1,4- (diisocyanate) cyclohexanone, 4,4 '-Cyclohexanone diisocyanate, 4,4, methylenebis (cyclohexyl isocyanate), isophorone diisocyanate, 2,4-methylphenyl diisocyanate , 2,6-Methylphenylene diisocyanate, p-phenylene monoisocyanate, dibenzoyl diisocyanate, m-phenylene diisocyanate, 2,4-naphthalene Diisocyanate, 3,3, -dimethyl_4,4, biphenyl diisocyanate ^ 4,4_biben ^^ isomeric acid salt ... Phenyl diisocyanate, 2,6-methylenephenyl diisocyanate, hexamethylene diisocyanate, and isophorone diisocyanate are particularly desirable. Examples of commercially available polyurethane-based resins include: "Hydra" "Sound # · /, 彳 卜 7 y" HW_330 "," Hydra "HW-340," Hydra "HW-350 "(All are manufactured by Daikoku Ink Chemical Industry Co., Ltd., trade names)," SUPERFLEX100 "," SUPERFLEX150 "," SUPERFLEXF-3438D "(all are manufactured by Daiichi Pharmaceutical Co., Ltd., trade names), etc. Polyvinyl alcohol resin is preferably polyethenol with a degree of saponification of more than 87%, and a degree of saponification of more than 98%, so-called fully saponified polyvinyl alcohol is particularly desirable. Also, the number average molecular weight is preferably 300. Within the range of 0 to 100, 000. As the aforementioned polyoxyalkylene chain-containing resin, those having a polyoxyethylene homing chain or a polyoxypropylene chain can be suitably used, for example, polyethylene glycol, polypropylene glycol, The polyoxyethylene chain and the polyoxypropylene chain are combined to form a block, and the block polyoxidation is reduced to two papers. The standard is suitable for financial affairs. (_ A 视 格 ⑽χ297 public variable) ------------ --- 嚓…:, …… —— 、 玎 --------------------- 嘬 (Please read the precautions on the back before filling this page) -27 -丄 厶 厶 HO 丄) A7 '^ ----- B7 V. Description of the invention (2τγ ----- ~ alcohols, etc., and then mention the polymerizable unsaturated fluorene copolymer resin, which is good to use; olefins such as hydrazone and fluorene 6 and ( (M) A copolymer of a polymerized 2-unsaturated carboxylic acid such as acrylic acid, maleic acid, and the like, and a polymerizable unsaturated compound is added to an aqueous dispersion of the copolymer to perform emulsification polymerization, and then cross-linked within the particles to form At least one water-dispersible resin or water-soluble resin selected from the two resins. The copolymer of an olefin and a polymerizable unsaturated carboxylic acid is a copolymer of one or more dilute hydrocarbons and one or more polymerizable unsaturated carboxylic acids. In this copolymer, the content of the monomer is 3 to 60% by weight of the aforementioned non-combined carboxylic acid, and desirably falls within a range of 40% by weight. It can be dispersed in water by neutralizing the acid groups in the copolymer with a test substance. The polymerizable unsaturated compound is added to the aqueous dispersion of the copolymer to emulsify and polymerize it, and the polymerizable unsaturated compound in the crosslinked resin formed by cross-linking in the particles may be the aforementioned water-dispersible or water-soluble The vinyl monomers and the like listed in the description of the acryl-based acrylic resin are examples, and one or two or more of them may be appropriately selected and used. The content ratio of the aqueous organic polymer compound (C) is about 10 to 2000 parts by weight relative to 100 parts by weight of the solid content of the titanium-containing aqueous solution (A). The stability of the coating agent, From the viewpoints of the corrosion resistance of the obtained titanium oxide film, it is particularly preferable to be in the range of 100 to 1,000 parts by weight. The coating agent Π for forming a titanium oxide film of the present invention can be prepared by mixing the necessary components by a general method. The coating agent Π of the present invention is an aqueous liquid in a stable state in the neutral or acidic field, and its pH is usually 1 paper size applicable to the Chinese National Standard (CNS) A4 specification (210X297 public director) ... ...--------------— Order —......... (Please read the notes on the back before filling out this page) -28- V. Description of the invention ( 26) in the range of ~ 7. In particular, it has good storage stability in the acidic field, and should be within the range of 5 '. The coating agent Π of the present invention may contain a hydrophilic solvent such as f-alcohol, ethanol, isopropanol, ethylene glycol, and propylene glycol, if necessary. The coating 11 of the present invention can be used with water or a hydrophilic solvent if necessary. 2. Coating agent of this month] [[wherein, if necessary, it may further contain basic formulas such as ammonia, organic chemical compounds, alkali metal hydroxides, alkaline earth metal hydroxides and the like. The organic test compounds can be exemplified by ethanolamine and triethylamine, and the test metal hydroxides can be exemplified by M hydroxide, sodium hydroxide, and hydrogen hydroxide. The coating agent I [of the present invention may further contain various additives as necessary. Examples of such additives include thickeners, antibacterial agents, rust inhibitors, titanium oxide sols, titanium oxide powders, extender pigments, rust preventive pigments, coloring pigments, and surfactants. The aforementioned rust inhibitors include tannic acid, phytic acid, benzotriazole and the like. The physical pigments described are mica, talc, stone spar, barium sulfate, clay and so on. The coating agent for forming a titanium oxide film according to the present invention] and π are excellent in storage stability. In addition, the coating agent can form a titanium oxide-containing coating film having excellent corrosion resistance, adhesion, and processability on a metal substrate. Benefit .... Method for forming a chemical drink film and gold eyebrow coated with titanium oxide film The method for forming a titanium oxide film of the present invention is by coating the coating agent I or Π of the present invention on a metal substrate And dried. Thereby, a metal substrate coated with a titanium oxide film is obtained. This coated metal substrate can be used directly as a rust-proof coated metal substrate. As for the metal substrate to which the titanium oxide film forming method of the present invention is applicable, as long as the paper size is in accordance with the Chinese National Standard (CNS) A4 specification (210X297 mm) -29- 1224615 A7 B7 V. Description of the invention (27 疋 At least the surface is metal The substrate is not particularly limited. For example, if the surface is made of iron, aluminum, zinc, copper, tin, or an alloy containing any of these metals, a steel plate substrate and aluminum or aluminum are particularly used. An alloy substrate is preferred. The aforementioned steel substrate may be, for example, a hot-dip galvanized steel plate, an electro-galvanized steel plate, an iron-zinc alloy plated steel plate, a nickel-zinc alloy plated steel plate, an aluminum-zinc alloy plated steel plate, or the like. For the aluminum-zinc alloy plated steel plate, commercially available products called "Jiaerbalim" Transliteration: twq Xiru "and Γ Jiaerfang" Transliteration: Fanger 7 7〆 "can be used. In addition, the steel base As the material, a zinc-based plated steel plate subjected to conversion treatment such as chromate treatment, zinc phosphate treatment, and composite oxide film treatment can be used. Furthermore, if the steel plate base material is an overlapped steel plate, it does not matter. The material is not particularly limited, but can be used for heat exchange The blade is a representative example. The heat exchanger blade used as the base material may be a component before being assembled on the heat exchanger, or may be in a state of being installed on a heat exchanger, and it can be used by any publicly known person. (Please read the precautions on the back before filling this page). Order 丨 The method of coating the coating agent I or Π of the present invention on a metal substrate. _ 吕 | , Spray coating, spray coating, roll coating, electrodeposition and other known methods for coating. The drying conditions of the coating agent are usually suitable for the heating conditions where the material reaches the most south / m degree of about 60 to 2 50 C. It is allowed to dry for 2 seconds to about 30 minutes. In addition, the thickness of the dried coating film of the coating agent is usually about 0.001 μm to 10 μm, and particularly preferably from 0.1 μm to 3 μm. 〇〇〇1μιη, the low water resistance and water resistance are poor, and if it exceeds 10μηι, the coating film is broken and the corrosion resistance is reduced, and the effect is not satisfactory. Thus, by the method for forming a titanium oxide film of the present invention, Available in metal

-30- 1224615 A7 I ---------------- B7 _ 5. Description of the invention (28) Formation on substrate-corrosion, adhesion, processability, fingerprint resistance, etc. Good titanium oxide coating. X, the coating agent I of the present invention or]! A titanium oxide coating film can also be formed by coating on a substrate other than a metal substrate and drying it. The substrate other than the metal substrate is not particularly limited. For example, such as: Polyethylene resin, polyethylene terephthalate, acrylic resin, silicon resin, polyester resin, fluorine resin, epoxy resin, polyethylene resin , Plastic substrates made of resins consisting of two or more resins such as resistant resins, butyric acid resins, cellulose resins, and ageing resins; inorganic substrates such as glass and cement; pulp substrates such as paper and fiber; and , Substrates with surface treatment or primer applied to these plastic substrates, inorganic substrates, and pulp substrates. The substrate coating method can be performed by a known method such as dip coating, shower coating, spray coating, roll coating, or electrodeposition method, for example. The drying condition of the coating agent is generally suitable for drying the material for 2 seconds to about 30 minutes under heating conditions where the maximum temperature reaches about 20 to 2500c. In addition, the thickness of the dry coating film of the coating agent is generally preferably about 0.001 μm to 10 μm. On the substrate on which the titanium oxide coating film is formed through the coating agent I or π of the present invention, an upper coating film may be formed as required. The composition for forming the upper coating film can be appropriately selected according to the purpose, and various coating compositions can be used. The coating composition can be exemplified by a lubricating coating film-forming composition, the residual coating film-forming composition, a primer coating, and a colored top coating. It is also possible to apply a lubricious coating film-forming composition, a highly corrosion-resistant coating film-forming composition, or a primer coating and then dry it, and then apply a color-coated top coating thereon. Aluminum or aluminum alloy base material covered with the coating agent I or π of the present invention The paper size is applicable to China National Standard (CNS) A4 specification (210 × 297 mm)

囔… (Please read the precautions on the back before filling out this page), Yiding—-31- V. Description of the Invention (29) There is a coating film with excellent durability, hydrophilicity, adhesion, processability, etc., and By irradiating it with light, hydrophilicity can be further improved. When the coated earth material coated with the coating agent of the present invention on an aluminum or aluminum alloy substrate is used as a blade for a heat exchanger, a hydrophilic treatment coating film may be formed on the coating film as needed. The above-mentioned hydrophilized coating film is one having a surface having sufficient coating film strength due to hydrophilicity, water resistance, and excellent adhesion to the surface-treated coating. The formation of the hydrophilized coating film is generally carried out appropriately by applying and drying the hydrophilized composition. The hydrophilizing composition is preferably one containing a hydrophilic coating film-forming adhesive. The ideal hydrophilic coating film-forming adhesives include, for example: (1) organic resin-based adhesives composed of a hydrophilic organic resin as the main component and combined with a crosslinking agent as needed; (2) Organic resin · colloidal silica based binder formed by hydrophilic organic resin and colloidal silica as the main component and combined with a crosslinking agent as needed; (3) alkali metal silicate and anionic or Water glass-based adhesives such as mixtures of non-ionic water-based organic resins. Among these adhesives, an organic resin-based adhesive (1) and an organic resin-colloidal silica-based adhesive are preferably used. The ability to implement the invention Next, the present invention will be described more specifically with reference to manufacturing examples, examples, and comparative examples. However, the present invention is not limited by the following examples. The "parts" and "%" described in each example are based on weight. Preparation example of titanium-containing aqueous solution (A) 1 This paper size is in accordance with Chinese National Standard (CNS) A4 specification (210X297 mm) -32- 1224615 A7 ___ B7 V. Description of the invention (3〇) 5cc of titanium 60% aqueous solution and distilled water were adjusted to 500CC, 10% ammonia water was dropped, and titanium hydroxide was precipitated. After washing the precipitate with distilled water, 10cc of a 30% solution of hydrogen peroxide solution was added and stirred to prepare a yellow translucent viscous liquid containing titanium peroxytitanic acid and 2% solids (1 ) 70cc. Production Example 2 A mixture of 10 parts of titanium tetraisopropoxide and 10 parts of isopropanol was dripped into 10 parts of a 30% hydrogen peroxide solution and deionized water 100 at 20 t while stirring for 1 hour. Parts of the mixture. Then 25. 〇Curing for 2 hours to prepare a yellow transparent titanium peroxytitanate aqueous solution (2) with a slight viscosity and a solid content of 2%. Manufacturing Example 3 A titanium-containing aqueous solution having a solid content of 2% was prepared in the same manner as in Manufacturing Example 2 except that tetraisopropoxy titanium in Manufacturing Example 2 was replaced with tetra-n-butoxy titanium in the same amount. (3). Manufacturing Example 4 A solid content of 2% was obtained in the same manner as in Manufacturing Example 2 except that the tetraisopropoxy titanium in Manufacturing Example 2 was changed to a terpolymer using the same amount of titanium tetraisopropoxy titanium. The titanium aqueous solution (4). Manufacturing Example 5 The same manufacturing method as in Manufacturing Example 2 was carried out except that a three-fold amount of a hydrogen peroxide solution was used and dripped at 5 (Γ (: it took 1 hour to drip, and then matured at 6 (rc for 3 hours). A titanium-containing aqueous hydrazone with a solid content of 2% was prepared in the manner of Example 2. Manufacturing Example 6 The paper size is applicable to the Chinese National Standard (CNS) A4 specification (21〇 &gt; &lt; 297mm) (Please read the back first Please pay attention to this page and fill in this page) Order ·-囔--33- 1224615 A7 B7 ___ V. Description of the invention (31) I (Please read the precautions on the back before filling this page) The titanium-containing material obtained in Manufacturing Example 3 The aqueous solution was further subjected to a heating treatment at 95 ° C for 6 hours to obtain a titanium yellow aqueous solution (6) having a solid content of 2% as a white-yellow translucent titanium oxide dispersion. Production Example 7 Tetraisopropoxy A mixture of 10 parts of base titanium and 10 parts of isopropanol was dropped at 10 ° C and stirring for 1 hour to an anatase type of "TKS-203" (manufactured by TAYCA Corporation) with a trade name and an average particle diameter of 6 nm. Aqueous sol of titanium oxide microparticles) in a mixture of 5 parts (solid content), 10 parts of 30% hydrogen peroxide solution and 100 parts of deionized water. The maturation was carried out for 24 hours, and a yellow transparent titanium-containing aqueous solution (7) with a little viscosity and a solid content of 2% was prepared. The main application is a coating agent for forming a titanium oxide film. Example 1 After mixing 50 parts of the titanium-containing aqueous solution (1) obtained in Manufacturing Example 1, 50 parts of 10% metaphosphoric acid and 45 parts of deionized water, a coating for forming a titanium oxide film according to the present invention was prepared. Cloth agent. Examples 2 to 16 and Comparative Examples 1 to 2 According to the composition shown in Table 1, the coating agent of the present invention and a comparative coating agent were prepared in the same manner as in Example 1. This paper The scale is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) -34 · 1224615 A7B7 V. Description of the invention (32) Table 1 Example 1 2 3 4 5 6 7 8 9 (A) Composition (1) (2) (3) (4) (5) (6) ⑺ 50 50 50 50 50 50 50 50 50 (B) 10% metaphosphoric acid 5 5 10 5 5 10% sodium pyrophosphate 5 10% sodium tripolyphosphate 5 10% Sodium tetraphosphate 5 10% Sodium hexametaphosphate 5 40% Zirconium cyanide L acid 10% Zirconium ammonium fluoride 10% Ammonia water 10% Lithium hydroxide deionized water 45 45 45 45 45 45 45 45 45 (Please read the notes on the back before filling in this page) This paper size applies to Chinese National Standard (CNS) A4 (210X297 mm) -35- 1224615 A7B7 V. Description of the invention (33) Table 1 (continued) ) Examples Comparative Example 10 11 12 13 14 15 16 1 2 (A) component ⑴ 50 (2) 50 50 50 50 50 (3) (4) (5) 50 (6) 50 ⑺ 50 (B) component 10% Metaphosphoric acid 5 5 5 5 5 5 5 10% sodium pyrophosphate 10% sodium tripolyphosphate 10% sodium tetraphosphate 10% sodium hexametaphosphate 40% zirconium cyanofluoric acid 2 2 2 10% ammonium zirconium fluoride 1 10% ammonia 1 10% lithium hydroxide 3 Deionized water 45 45 45 45 45 45 45 45 45 45 (Please read the precautions on the back before filling out this page) Performance test utilization of coating agent I for forming titanium oxide film of the present invention Each coating agent obtained in Examples 1 to 16 and Comparative Examples 1 to 2 was subjected to coating treatment on a metal substrate, and the corrosion resistance of the prepared coating substrate was examined. (1) Coating treatment of aluminum plate The aluminum plate (A1050) with a thickness of 0.1 mm is degreased with an aqueous solution having a concentration of 2% by dissolving an alkali degreaser (produced by CBCHEMICAL Co., Ltd. under the trade name "ChemiCleaner561B"). After washing with water, each coating agent is applied with a roller to make the dry coating weight reach 0.2 g / m2, and it is fired for 20 seconds to make the material reach the temperature of the paper. The Chinese national standard (CNS) A4 specification (210X297 mm) is applied. ) -36- 1224615 A7 B7 5. Description of the invention (34) The temperature reaches 100 ° C, and a titanium oxide coating film is formed. (2) Corrosion resistance of coated panels (Please read the precautions on the back before filling in this page.) For each of the aforementioned coated panels, measure in accordance with the salt spray test method of JIS Z2371. The test time is divided into 120 hours, 240 hours, 360 hours, and 480 hours, and is evaluated according to the following criteria. a. .. There is no white rust or air bubbles on the coating surface; b .. A little white rust or air bubbles are generated; c. .. White rust or air bubbles are obviously generated. The test results are shown in Table 2. Table 2 Coating agent test time 120hr 240hr 360hr 480hr Example 1 aabc Example 2 aaab Example 3 aabb Example 4 aabb Example 5 aaab Example 6 aaab Example 7 aaab Example 8 aaab Example 9 aaab Example 10 aaab example 11 aabc example 12 aabc example 13 aaab example 14 aaab example 15 aaab example 16 aaab comparative example 1 bccc comparative example 2 bbcc This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) -37- 1224615 A7 ____B7 V. Description of the invention (35) (3) Coating treatment of steel plate The thickness of 0.6-leg SEM zinc steel plate (single-sided boat coating amount is 20g / m2), with alkali degreaser dissolved (CB Chemical Co., Ltd., Japan, product name: "ChemiCleaner561B") degreasing solution with a concentration of 2%, after washing with water, each coating agent is applied with a roller to make the dry coating weight reach 1.0 g / m. And baked for 20 seconds so that the temperature of the material reached 100. [While forming a titanium oxide coating film. (4) Residual resistance of coated panels The test coated panels that sealed the end and inner surfaces of the aforementioned coated panels were measured in accordance with the salt water spray test method of JIS Z2371. The test time is divided into three stages of 24 hours, 48 hours, and 72 hours, and the evaluation is based on the following criteria. a ... no white rust is generated; b ... the degree of white rust is less than 5% of the area of the coating film; c ... the degree of white record exceeds the area of the coating film but not yet reached; d ... the degree of white record exceeds the coating The area of the film is less than that; e. The generation of white scale exceeds 50% of the area of the coating film. The test results are not shown in Table 3. This paper size applies to China National Standard (CNS) A4 specification (210X297 mm) (Please read the precautions on the back before filling this page) Order — -38- 1224615 A7 B7 V. Description of the invention (36) Table 3 Coating agent Test time 24hr 48hr 72hr Example 1 abc Example 2 aab Example 3 abb Example 4 abb Example 5 aab Example 6 aab Example 7 aab Example 8 aab Example 9 aab Example 10 aab Example 11 abc Implementation Example 12 abc Example 13 aab Example 14 aab Example 15 aab Example 16 aab Comparative example 1 cbd Comparative example 2 ccd (Please read the precautions on the back before filling out this page) (5) Covering the steel sheet 0.6 Li of galvanized steel sheet (plating adhesion amount of 20g / m2 on one side) is degreased with alkali, and sprayed with "Preparan" transliteration: (produced by PAKERIZING Co., Ltd., trade name) and then Surface adjustment. Next, "PALBOND3308" (trade name, zinc phosphate aqueous solution, manufactured by PARKERIZING Co., Ltd.) was spray-washed, washed with water, and dried to obtain a zinc phosphate-treated plated steel sheet. The adhesion amount of the zinc phosphate-treated coating film was 1.5 g / m2. Spray each coating agent on the surface of the aforementioned plated steel plate with zinc phosphate treatment to make the dry coating weight reach 1.0 g / m2, and bake for 20 seconds so that the paper size of the material applies the Chinese national standard (CNS ) A4 specification (210X297 mm) -39- 1224615 A7 B7 V. Description of the invention (37 When the temperature reaches 100 ° C, a titanium oxide coating film is formed. (6) Corrosion resistance of the covering plate The test coated plate sealed at the inner part and the inner part was measured according to the salt water spray test method of JIS Z2371. The test time was divided into three stages of 24 hours, 48 hours, and 72 hours, and evaluated according to the following criteria. A ... No white rust Produced; b ... the generation of white rust is less than 5% of the coating film area; c ... the generation of white rust is more than 5% but less than 10% of the coating film area; d ... the generation of white rust exceeds the coating film area 10% but less than 50%; e ... The degree of white recording exceeds the area of the coating film. The test results are shown in Table 4. (Please read the precautions on the back before filling this page) • Order —. 管 _ 本Paper size applies to China National Standard (CNS) A4 (21〇297mm) -4 0- ^ 4615 A7 B7 V. Description of the invention (38) Table 4 Test time of coating agent 24hr 48hr 72hr Example 1 abc Example 2 aab Example 3 abb — Example 4 abb _ implementation He 5 aab Example 6 aab implementation Example 7 aab Example 8 aab Example 9 aab Example 10 aab Example 11 abc Example 12 abc Example 13 aab Example 14 aab — Example 15 aab Example 16 aa bb Comparative Example 1 hbcc Comparative Example 2 bbc Da A Organic High Breaking Compound (C) Preparation Example 8 (Please read the precautions on the back before filling this page) Order | -Tube-In a thermometer with a stirrer, condenser, dripping funnel Put 180 parts of isopropanol in a mouth flask, and after nitrogen substitution, the temperature in the flask was adjusted to 85 ° C, and 140 parts of ethyl acrylate, 68 parts of methyl methacrylate, and 15 parts of styrene , 15 parts of N-n-butoxymethacrylamide, 2 monomer mixture consisting of 38 parts of ethyl acrylic acid and 24 parts of acrylic acid, and catalyst 2,2-azobis (2, 4_dimethylvaleronitrile) 6 parts together takes about 2 hours plus After dripping, if the reaction is continued for another 5 hours at the same temperature, a polymerization rate of nearly 100%, a solid content of about 63%, and an acid value of about this paper are applicable to China National Standard (CNS) A4 specifications. (210X297mm) -41- 1224615 A7 __B7_ V. Description of the invention (39) 67mgKOH / g colorless transparent resin solution. By mixing 108 parts of diammonium alcohol with respect to 500 to the resin solution, and adding water and stirring well, an acrylic resin aqueous dispersion (ci) having a solid content of 30% was prepared. Production Example 9 To a reaction device having a mixing device, a reflux condenser, a thermometer, and a droplet device, "EPIKOTE1009" (epoxy resin manufactured by SHELL Chemical Co., Ltd., trade name, molecular weight 3750) i880g (0.5 mol) and After 1000 g of a mixed solvent of methyl isobutyl ketone / xylylene = 1/1 (weight ratio), the mixture was heated with stirring and uniformly dissolved. After that, it was cooled to 70 ° C., and 70 g of bis (n-propanol) amine, which was evenly divided in the droplet device, was dropped for 30 minutes. Meanwhile, the reaction temperature was maintained at 70 ° C. After the completion of the drop, the temperature was 120 °. C was held for 2 hours and the reaction was completed to prepare an amine-modified epoxy resin with a solid content of 66%. 25 parts of 88% osmic acid was mixed with 1,000 g of the obtained resin, and water was added sufficiently By stirring, an amine-modified epoxy resin aqueous dispersion (C2) having a solid content of 30% is prepared. Example 17 of the main puming used to form a fluorinated cloth agent π of a vaporized titanium film Example 17 will be prepared in Production Example 1 The titanium-containing aqueous solution (D 50 parts, 20% hydrofluoric acid, 30% acrylic resin aqueous dispersion (ci) 10 parts, and deionized water 35 parts were mixed to prepare the invention for forming Coating agents for titanium oxide films. Examples 18 to 27 and Comparative Examples 3 to 5 According to the composition shown in Table 5, the coating agent of the present invention and a comparative coating were prepared in the same manner as in Example 17. Cloth agent. This paper size is applicable to Chinese National Standard (CNS) M specification (2lox297 mm) ——.....— 9 ^ ------------------ Order— -------- * line · (please first Read the notes on the back and fill in this page) -42- 1224615 A7B7 V. Description of the invention (4〇) Table 5 Implementation &Example; Example 17 18 19 20 21 22 23 (A) Ingredient (1) 50 50 50 50 50 ⑵ 50 (3) 50 (4) (5) ⑹ ⑺ (B) 20% zirconium hydrofluoric acid 5 2.5 10 40% titanium hydrofluoric acid 10 20 40% silicic acid 2.5 10% metaphosphoric acid 10 (C) 30 % Acrylic resin water dispersion (C1) 10 20 30% amine modified epoxy resin water dispersion (C2) 15 25 "SaranLatex L-411" 10 20 "KURARAYRS polymer RS-105" 25 DI water 35 25 37.5 15 37.5 15 10 (Please read the notes on the back before filling out this page) This paper size applies to Chinese National Standard (CNS) A4 (210X297 mm) -43- 1224615 A7 B7 V. Description of the invention (41) Table 5 ( Continued)

Examples Comparative Example 24 25 26 27 3 4 5 (A) component 0) 50 (2) (3) 50 (4) 50 (5) 50 ⑹ 50 (7) 50 (B) component 20% zirconium hydrofluoric acid 5 10 5 40% titanium hydrofluoric acid 5 40% silicon hydrofluoric acid 5 5 10% metaphosphoric acid (C) component 30% acrylic resin aqueous dispersion (C1) 20 20 30% amine modified epoxy resin aqueous dispersion (C2 ) 20 80 "SaranLatex L-411" 45 "KURARAYRS Polymer RS-105" 25 40 Deionized water 20 25 20 5 30 15 In the aforementioned Table 5, "SaranLatex L-411" and "KURARAYRS (Please read the precautions on the back first) Fill out this page again) Polymer RS-105 "is shown below.

SaranLatex L-411: manufactured by Asahi Kasei Corporation, trade name, vinylidene chloride resin, solid content 50%. KURARAY RS polymer RS-105: manufactured by Kurary Co., Ltd., trade name, polyvinyl alcohol, solid content 10%. The performance test of the coating agent Π for forming a titanium oxide film of the present invention uses each coating agent prepared in Examples 17 to 27 and Comparative Examples 3 to 5 to perform a rust-proof coating treatment on a steel plate substrate, and inspects the obtained results. Coating film appearance, adhesion and corrosion resistance of coated steel plates. (1) Anti-rust coating place of steel plate base material Various plated steel plates having a plate thickness of 0.8 were used as the base material. Used plating This paper is sized for Chinese National Standard (CNS) A4 (210X297 mm) -44-1224615 A7 B7 5. Description of the invention (42) There are 6 types of steel plates. ⑴Dianzhong Zhongci steel plate: 20g / m2 of mineral deposits, and is called "EG"; (⑴) ^: Minci steel plate: 60g / m2 of mineral deposits, and is called "HDG" · (Hi) Zinc-iron alloy cladding steel sheet: 10% Fe in the ore layer, 60g / m2 plating deposit, and is called "Zn-Fe"; (iv) Zinc-nickel alloy cladding steel sheet: 12% in the coating, (G) Zinc-aluminum alloy plated steel plate: 8% of the amount of the coating, 150g / m2, and called "Zn-12" "% A1"; (vi) Zinc-aluminum alloy coated steel plate · The amount of Ai in the coating is 55%, the bond adhesion amount is 250g / m2, and it is referred to as "Zη · 55% Α1". Spray a 20% solution of alkali degreaser ("ChemiCleaner561B", manufactured by CBCHEMICAL Co., Ltd.) at a liquid temperature of 65 ° C for 20 seconds to remove fat, and then spray 60 ° C. It was washed in warm water for 20 seconds. On the degreased mineral-coated steel plate, each coating agent was sprayed so that the dry coating film weight reached 0.5 g / m2, and the ambient temperature was 250 ° C. Dry for 15 seconds (the material reaches a temperature of 100 ° C) to form an anti-rust coating film. Coated steel sheet. (2) Performance test of coated steel sheet For each coated steel sheet prepared as described above, the coating film appearance, adhesion, and corrosion resistance were tested according to the following test methods. Test method Coating film appearance ·· Visually and according to The following standards are used to evaluate the uniformity of the coating film. This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) (Please read the precautions on the back before filling this page) Order | -45- 1224615 A7 5 、 Explanation of invention (43) (Please read the notes on the back before filling in this page) a: No unevenness and uniform appearance; b: Some unevenness; c: All unevenness. Adhesion · The coating film was subjected to the checkerboard adhesion method (space interval 1 mm) described in jIS [5400-85.2], and the adhesion was evaluated according to the following criteria: a: the coating film was completely free of peeling; b: the coating film was peeling, but The peeling area is less than 5%; c: The peeling area is more than 5% but less than 20%; d: The peeling area is more than 20% but less than 50%; e: The peeling area is more than 50%. End face and inside are sealed and divided into 24 The salt spray test specified in JIS Z2371 was performed at three stages of hours, 48 hours, and 72 hours, and the corrosion resistance was evaluated according to the following criteria: a: No white rust or air bubbles on the coating surface; b: Less than white rust or air bubbles 10% of the area of the coating film; c: The degree of white rust or air bubbles exceeds 10% but not more than 30% of the area of the coating film; d: The degree of white rust or air bubbles exceeds 30% of the area of the coating film but not more Up to 50%; e: the degree of white rust or air bubbles exceeds 50% of the area of the coating film. The test results are shown in Table 6. This paper size applies to Chinese National Standard (CNS) A4 (210X297 mm) -46- 1224615 A7 B7 V. Description of the invention (44) Table 6 Coating agent plating steel sheet coating film appearance adhesiveness surplus 24hr 48hr 72hr Implementation Example 17 EG aaabc Example 18 EG aaabc Example 19 EG aaaab Example 20 HDG aaaaa Example 21. HDG aaaaa Example 22 Zn-Fe aaaab Example 23 Zn-Fe aaaab Example 24 Zn-Ni aaaab Example 25 Zn -12% A1 aaaaa Example 26 Zn-55% A1 aaaaa Example 27 Zn-55% A1 aaaaa Comparative example 3 EG abbcd Comparative example 4 HDG ababc Comparative example 5 Zn-Fe abbcd (Please read the notes on the back before filling (This page) Example 28 of the coating agent Π for forming a titanium oxide film of the present invention Example 28 The titanium-containing aqueous solution (1) obtained in the mixed production example 1 50 parts, 20 parts zirconium hydrofluoric acid 5 parts, "AC10LP "(Made by Benhwa Pharmaceutical Co., Ltd., an aqueous polyacrylic acid solution, a weight average molecular weight of 25,000, an acid value of 779 mgKOH / g, and a solid content of 10%) and 30 parts of deionized water. Titanium film Coating agent. Example 2 9 to 3 3 and Comparative Examples 6 to 7 According to the composition shown in Table 7, the coating agent of the present invention and a comparative coating agent were prepared in the same manner as in Example 28. This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) -47- 1224615 A7B7 V. Description of the invention (45) Table 7 Examples Comparative Examples 28 29 30 31 32 33 6 7 (A) Ingredients (1) 50 50 (2) 50 ⑶ 50 (4) 50 (5) 50 (6) 50 (B) 20% zirconium hydrofluoric acid 5 40% titanium hydrofluoric acid 10 40% silicon hydrofluoric acid 2.5 5 10% metaphosphoric acid 10 5 (C) Ingredients "AC10LP" 30 50 "DENKAPOVALK-05" 20 30 "PEG6000S" 40 30 40 85 Deionized water 15 20 7.5 10 10 5 15 In the aforementioned Table 7, "AC10LP", "DENKAPOVALK-05 (Please Please read the notes on the back before filling out this page) and "PEG6000S" are shown below. AC10LP: manufactured by Japan Chemical Co., Ltd., trade name, polyacrylic acid aqueous solution, weight average molecular weight 25000, acid value 779 mgKOH / g, solid content 10%. DENKA POVAL K-05: manufactured by Denki Chemical Industry Co., Ltd., trade name, polyvinyl alcohol, saponification degree of 99%, polymerization degree of 550, and solid content of 10%. PEG6000S: manufactured by Sanyo Chemical Industries, Ltd., trade name, polyethylene glycol, average molecular weight 8300, and solid content 10%. The performance test of the coating agent U for forming a titanium oxide film of the present invention uses each coating agent prepared in Examples 28 to 33 and Comparative Examples 6 to 7 to perform an antirust coating treatment on an aluminum substrate, and inspects the obtained Coating film appearance, hydrophilicity and #resistance of coated aluminum plate. (1) The rust-proof coating treatment of the aluminum base material is made of aluminum plate (A1050) with a thickness of 0.1 liters with an alkali degreasing agent (the paper size of this paper applies the Chinese National Standard (CNS) A4 specification (210X297 mm)- 48- 1224615 A7 ___ B7 V. Description of the invention (46) I CBCHEMICAL Co., Ltd. (trade name "chemiCleaner561B") in a concentration of 2% aqueous solution for degreasing, after washing with water, each coating at 30t: It was dip-coated in the agent for 30 seconds to achieve a dry film thickness of 5 μm, and baked at 160 ° C. for 10 minutes to form a rust-preventive coating film, and a coated aluminum plate was prepared. (2) Performance test of the test coated plate For each of the foregoing coated aluminum plates, the test of the appearance, hydrophilicity and resistance of the coating film was performed according to the following test methods. Coating film appearance: The uniformity of the anti-rust coating film was evaluated visually and based on the following criteria. a: No unevenness and uniform appearance; b: Partial unevenness; c: Full unevenness. Hydrophilicity: Hydrophilicity was evaluated based on the water contact angle after the coated aluminum plate was immersed in running water (flowing amount was 15 kg / hr per 1 lm2 of coated plate) for 72 hours. For comparison, an initial test plate before the test was measured for water contact angle (initial hydrophilicity). The water contact angle is at 80 ° C: After drying the coated plate for 5 minutes, 0.04cc of deionized water was dripped on the coated surface of the coated aluminum plate with a syringe to form water droplets. Then, the product was manufactured by Kyowa Scientific Co., Ltd. The Tanger meter "Transliteration: 3 ^ Xixi Xi &gt; Xi ,, Xiaoxi Yixiyi"]:) (:: type of eight or eight "measures the contact angle of water droplets. The larger the water contact angle, the more hydrophilic The larger the remaining resistance: For each of the foregoing coated aluminum plates, and measured in accordance with the salt spray test method specified in 13 Z2371. The test time is divided into two stages of 120 hours and 240 hours, and the corrosion resistance is evaluated according to the following criteria. A: Coating There is no white rust and air bubbles on the surface; ------------ This paper is suitable for standard size (CNS) A4 (210X297 mm) ~--49-

......----- (Please read the precautions on the back before filling this page) Order — 1224615 A7 B7 V. Description of the invention (47 b: The degree of white rust or air bubbles does not reach the area of the coating film 10%; the degree of white rust or air bubbles exceeds 10% but less than 30% of the area of the coating film; d. The degree of white rust or air bubbles exceeding the area of the film but not more than 50%; e: white rust or The degree of air bubble generation exceeds 50% of the area of the coating film. The test results are shown in Table 8. Table 8 Hydrophilic water contact angle at the initial stage of the appearance of the coating film of the hydrophilic water contact angle 120hr 240hr Example 28 a &lt; 5 ° 20-30 ° aa example 29 a &lt; 5 ° 20-30 ° aa example 30 a &lt; 5 ° 20-30 ° ab example 31 a &lt; 5 ° 20-30 ° ab example 32 a & lt 5 ° 20-30 ° aa Example 33 a &lt; 5 ° 20-30 ° ab Comparative Example 6 a &lt; 5 ° 40-50 ° bc Comparative Example 7 a &lt; 5 ° &gt; 50 ° ce (please first Read the precautions on the back and fill in this page again),-| Tubes, forming methods, and metal substrates coated with titanium oxide film can cause the following special effects. (1) The coating agent of the present invention has excellent Store Stability. The reason is that the titanium-containing aqueous solution (A) itself is in a stable state, and the aqueous solution (A) and phosphoric acid-based compounds, titanium dental compounds (b) or (B,) can form a stable (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, a metal substrate can be formed with a residue resistance, adhesion, durability, and processability. And hydrophilicity, and the size of coated paper containing titanium oxide is applicable to Chinese National Standard (CNS) A4 specification (210X297 mm) -50- ^ 24615 A7 ^ ----------------- B7 V. Invention Explanation (48) ~~ ---- Film. The recommended residual resistance or durability is good. The reasons are: its adhesion to the substrate is good, and because it is a fine titanium oxide film, it has oxygen permeability or water vapor. Permeability is low, and 鳞 &lt; (B,), such as scaly acid-based compounds, titanium dendrites, has a function as a preservative and corrosion inhibitor for metals, and scaly acid-based compounds, titanium halides, etc. (B or B, ) Can be protected by titanium oxide, etc. (3) The coated metal substrate obtained by using the titanium oxide film forming method of the present invention can be It is directly used for rust-proof coating the substrate. (4) The heat exchanger blades formed by applying the coating agent of the present invention to the surface of an aluminum or aluminum alloy substrate to form a coating film can be prevented from occurring in a cold room. The condensed water forms a water connection between the leaves. Therefore, it is possible to prevent corrosion of the blade made of aluminum or aluminum alloy. (Please read the precautions on the back before filling out this page) ir—next This paper size applies to China National Standard (CNS) A4 (210X297 mm) -51-

Claims (1)

1224615 A8 B8 C8 ____D8 VI. Application for Patent Scope No. 91101041 Patent Application for Amendment of Patent Scope April 30, 1993 1 · A coating agent for forming a titanium oxide film, comprising: (A) containing An aqueous titanium solution is at least one kind of titanium compound selected from hydrolyzable titanium compounds, low-fine compounds of hydrolyzable compounds, and low-condensation products of hydrogen hydroxide and low-temperature condensation compounds, and mixed with a hydrogen peroxide solution. The winner; and (B) a phosphate compound. 2. The coating agent for forming a titanium oxide film according to item 1 of the application, wherein the titanium-containing aqueous solution (A) is a solution of a hydrolyzable titanium compound and / or a low condensation product thereof and a hydrogen peroxide solution. An aqueous solution of peroxytitanic acid obtained by mixing. 3. As the coating agent for forming a titanium oxide film according to item 2 of the application, wherein the hydrolyzable titanium compound is a tetraalkoxy titanium represented by the general formula, namely: Ti (OR) 4 (i) ( In the formula, R represents an identical or different alkyl group having 1 to 5 carbon atoms). 4. The coating agent for forming a titanium oxide film according to item 2 of the patent application range, wherein the low condensate of the hydrolyzable titanium compound is an interactive condensation reaction of tetraalkoxytitanium represented by the general formula (1) The composition is a compound having a condensation ratio of 2 to 30; Ti (OR) 4 (i) (in the formula, R represents the same or different radicals having 1 to 5 broken atoms). China National Standard (CMS) A4 Specification (2l0X297々iff ------ -52- 1224615 6. Scope of patent application 5. The coating agent for forming a titanium oxide film according to item 2 of the scope of patent application, wherein the mixing ratio of the hydrolyzable titanium compound and / or its low condensate to the hydrogen peroxide solution is relative. The former is 10 parts by weight, and the latter is in the range of 0.1 to 100 parts by weight when converted into hydrogen peroxide. 6. The coating agent for forming a titanium oxide film according to item 2 of the patent application range, wherein the titanium-containing aqueous solution (A) is a kind of hydrolyzable titanium compound and / Or its low condensate and a hydrogen peroxide solution to obtain an aqueous solution of titanic acid. 7. The coating agent for forming a titanium oxide film according to item 6 of the application, wherein the titanium oxide sol is an aqueous dispersion of anatase titanium oxide. 8. The coating agent for forming a titanium oxide film according to item 6 of the application, wherein the amount of the titanium oxide sol is 1 part by weight relative to 1 part by weight of the hydrolyzable iridium compound and / or its low condensate. Ingredients account for 001 to 10 parts by weight. 9. As the coating agent for forming a titanium oxide film according to item 1 of the scope of patent application, wherein the phosphoric acid-based compound (B) is composed of monophosphoric acid, monophosphoric acid derivative and salt, condensed phosphoric acid, and condensation At least one compound selected from the group consisting of phosphate derivatives and salts. 10. As the coating agent for forming a titanium oxide film according to item i of the application, wherein the content ratio of the titanium-containing aqueous solution (A) and the phosphoric acid-based compound (β) is 100% relative to the former solid content The latter accounts for 1 to 400 parts by weight. 11. The coating agent for forming an oxidized film as described in item 1 of the scope of patent application, which is an aqueous solution with a pH of 1 to 7. The size of this paper is suitable ^ 1 ^ standard (〇 ^) A4 gauge & (210X297)--53- Patent application range 12 · As the coating agent for forming a titanium oxide film according to item 丨 of the patent application range, it further includes a titanium halide, a titanium halide salt, a hafnium halide, a onanium salt, and a silicon halide. And at least one halide selected from the group consisting of silicide salts. —A coating agent for forming a titanium oxide film, comprising: (A) a titanium-containing aqueous solution, comprising a hydrolyzable titanium compound, a low-condensation product of a hydrolyzable titanium compound, titanium hydroxide, and titanium hydroxide At least one titanium compound selected from the low condensates is obtained by mixing with a hydrogen peroxide solution; (B) a phosphoric acid-based compound, a titanium halide, a titanium halide salt, a hafnium halide, a hafnium halide salt, silicon At least one compound selected from the group consisting of a halide and a silicon halide salt; and (C) a stable aqueous organic polymer compound having a pH of 1 to 7. 14 · The coating agent for forming a titanium oxide film according to item 3 of the patent application, wherein the titanium-containing aqueous solution (A) is a kind of a hydrolyzable titanium compound and / or a low condensate thereof and hydrogen peroxide The solution was mixed to obtain an aqueous solution of peroxytitanic acid. 15. The coating agent for forming a titanium oxide film according to item 14 of the application, wherein the hydrolyzable titanium compound is a tetraalkoxy titanium represented by the general formula (丨), namely: Ti (OR) 4 ⑴ (In the formula, 'R' represents the same or different alkyl group having 5 carbon atoms). 16. · Coating for forming a titanium oxide film according to item 14 of the scope of patent application -54- 1224615 AB CD VI. Patent application scope agent, in which the low condensate of the hydrolyzable titanium compound is a condensation ratio of tetrakis-oxytitanium represented by the general formula (i) and the condensation rate is 2 ~ 30 compounds; Ti (OR) 4 (i) (where 'R is the same or different radicals having 1 to 5 carbon atoms). 17. The coating agent for forming a titanium oxide film according to item 14 of the application, wherein the mixing ratio of the hydrolyzable titanium compound and / or its low condensate and hydrogen peroxide solution is 10 weight relative to the former. The latter is in the range of 0.1 to 100 parts by weight in terms of hydrogen peroxide. 18. · A coating agent for forming a titanium oxide film according to item 14 of the application, wherein the titanium-containing aqueous solution (A) is a kind of hydrolyzable titanium compound and / Or its low condensate and hydrogen peroxide solution to obtain an aqueous solution of titanic acid. 19. The coating agent for forming a titanium oxide film as claimed in claim 18, wherein the titanium oxide sol is an aqueous dispersion of anatase-type titanium oxide. 20. The coating agent for forming a titanium oxide film according to item 18 of the scope of patent application, wherein the amount of the titanium oxide sol to be used is relative to the hydrolyzable titanium compound and / or its low condensate. The composition accounts for 0.001 to 10 parts by weight. 21 · A coating agent for forming a titanium oxide film according to item 13 of the patent application, wherein the phosphoric acid-based compound in the compound (B,) is composed of an inscription, an acid-derived derivative, and a salt At least one compound selected from the group consisting of derivatives, salts of condensed discic acids, condensed phosphoric acids, and salts (size of A4 (⑵χ297)) ------ -55- 1224615 A8 B8 C8 _________ D8 Sixth, the scope of patent application. 22. The coating agent for forming a titanium oxide film according to item 13 of the patent application, wherein the compound (B,) is used to form a titanium compound, a titanium halide salt, a compound, a complex compound salt, The halides of shixi halides and shixi halides are fluorine. 23. The coating agent for forming a titanium oxide film according to item 13 of the patent application, wherein the content ratio of the titanium-containing aqueous liquid (A) and the compound (B ') is 100 weight relative to the solid content of the former The latter accounts for 1 to 400 parts by weight. 24. The coating agent for forming a titanium oxide film according to item 13 of the application, wherein the water-based organic polymer compound (C) is made of epoxy resin, phenol resin, acrylic resin, ethyl carbamate At least one resin selected from the group consisting of an ester-based resin, a polyvinyl alcohol-based resin, a polyoxyalkylene chain-containing resin, and an olefin polymerizable unsaturated acid copolymer resin. 25. The coating agent for forming a titanium oxide film according to item 13 of the scope of the patent application, wherein the content ratio of the aqueous organic polymer compound (C) is 100% with respect to the solid content of the titanium-containing aqueous solution (A) Part by weight accounts for 10 to 2000 parts by weight. 26. A coating agent for forming a titanium oxide film according to item 13 of the scope of the patent application, which is an aqueous liquid having a pH of 1 to 7. , National Standard (CN S) A4 Specification (2 1 〇 X 297 mm) -56-