Photocatalytic composition and its manufacturing method

Description: TECHNICAL FIELD [Detailed description of the invention]

【0001】

[Technical field to which the invention belongs]

In the present invention, a photocatalytic composition, particularly an oxycarboxylic acid or a salt thereof, is used to uniformly disperse and stabilize titanium oxide colloid and zirconyl ammonium carbonate in a solution, and this is applied to a substrate to obtain a coating film. The present invention relates to a photocatalytic composition exhibiting excellent photocatalytic activity, alkali resistance, and substrate adhesion resistance.

【0002】

[Conventional technology]

Environmental problems have come to be severely questioned, and titanium oxide photocatalysts are NO._xSince it has actions such as decomposition, sterilization, and antifouling of various harmful gases such as formaldehyde, mercaptan, and hydrogen sulfide, it has been rapidly in the limelight and many studies have been conducted. There are many methods for adhering and supporting a titanium oxide photocatalyst (hereinafter referred to as titanium oxide) to various base materials such as metal, wood, ceramics, paper, cloth, and plastic, depending on the type of base material, application, desired function, and the like. The method is being done. For example, a baking method, a thin-film deposition method, a fixing method using a binder, the above-mentioned combined method, and the like.

【0003】

The strength of the coating film obtained by the baking method or the vapor deposition method is strong. However, since firing at a high temperature is required, it is generally applied to heat-resistant substrates such as ceramics such as glass and pottery, and metals, and the substrates that can be used are limited.

【0004】

With the fixing method using a binder, it is possible to form a film at low temperatures, and it can be used for various base materials, from heat-resistant base materials such as ceramics and metals such as glass and pottery to non-heat-resistant base materials such as wood, paper, cloth, and plastic. Applicable. In order to improve the adhesion between the titanium oxide powder or titanium oxide sol and the base material, the binder used is various metal alkoxides such as colloidal silica, polysiloxane, silica, titanium and aluminum, acrylic resin, acrylic modified resin and urethane. Examples thereof include resin, vinyl chloride resin, acrylic silicon resin, fluororesin, water glass, aluminum phosphate and the like. These binders can be used in cases where an adhesive is applied to the base material in advance and then titanium oxide is applied, and cases where an adhesive such as colloidal silica or various metal alkoxides is contained in the titanium oxide sol. It is roughly divided.

【0005】

In the method of applying the adhesive to the base material in advance, the adhesion strength of titanium oxide to the binder is poor, and titanium oxide itself does not have much film strength, so that the coating of titanium oxide on the surface layer of the film is not often applied.

【0006】

The method of incorporating the adhesive in the titanium oxide sol, which can obtain the coating film strength relatively easily, is easy to apply, inexpensive, and can be expected to have photocatalytic activity. However, in the resin-based binder, the resin as the binder is gradually decomposed due to the photocatalytic effect of titanium oxide, and the titanium oxide is peeled off from the base material. Further, when an inorganic binder is used, the binder is not decomposed by titanium oxide. For example, the titanium oxide coating film obtained by the method of supporting silicon, aluminum alkoxide and their hydrolysis products can be dried. Some show sufficient strength, and many base materials can be applied. However, since these binders are cured as oxides such as silica and alumina, they do not necessarily form a film with high strength and excellent chemical resistance when fired at a low temperature. For example, silicon alkoxide is used as a binder. In this case, silica itself, which is a product, dissolves in strong alkali, so if it is not baked at a high temperature, the film will have poor alkali resistance.

【0007】

For these reasons, a binder that can sufficiently satisfy the requirements such as alkali resistance, photocatalytic ability, coating film strength, and versatility has not been obtained at present.

【0008】

[Problems to be Solved by the Invention]

An object of the present invention is to provide a photocatalyst composition in which an adhesive is stably present in a titanium oxide sol and has excellent alkali resistance and adhesion. Examples of the zirconium-containing surface treatment agent include the invention described in JP-A-4-2204668 and the invention described in JP-A-10-237429. The former has excellent adhesion to a substrate and has high strength. The coating composition is high and has excellent flexibility, and the latter discloses a surface treatment agent having high water wettability. Further, as a photocatalyst composition containing zirconium, JP-A-10-337478 discloses a titanium oxide photocatalyst sol containing ponivinylpyrrolidone, a zirconium compound and a titanium compound, and JP-A-11-179211 discloses. A titanium oxide-based photocatalyst containing titanium oxide and crystalline zirconium titanate is disclosed, and Japanese Patent Application Laid-Open No. 11-209691 discloses a room temperature curing photocatalyst coating material containing organosilane, a zirconia compound, and a titanium compound. .. Further, JP-A-11-188270 discloses a coating liquid having photocatalytic activity using composite titanium oxide fine particles composed of zirconium and titanium, and JP-A-11-229152 discloses an aliphatic monocarboxylic acid Zr and a photocatalyst. Taru TiO₂A method for forming an inorganic film using a thin film precursor is disclosed. Furthermore, the republished patent WO98 / 15600 discloses a photocatalytic coating agent composition containing a zirconium compound.

【0009】

[Means for solving problems]

The present invention relates to a photocatalytic composition containing oxycarboxylic acid or a salt thereof, zirconyl ammonium carbonate and titanium oxide colloid.

【0010】

BEST MODE FOR CARRYING OUT THE INVENTION

The present invention will be described in detail below.

【0011】

Ammonium zirconyl carbonate (AZC) used in the present invention has a chemical formula (NH), for example.₄)₂ZrO (CO)₃)₂The product name is "Zirconium Ammonium Carbonate, Baycoat 20, Baycoat L" from Nippon Light Metal Co., Ltd., "Zyrconylammonium Carbonate Solution" from Shin Nihon Kinzoku Kagaku Co., Ltd., and the product name from Daiichi Rare Element Chemistry Co., Ltd. It is sold as "Zirconium AC-7", but you may make your own.

【0012】

The titanium oxide colloid used in the present invention may be produced by any known method. For example, a titanium oxychloride solution is neutralized with an alkaline solution such as aqueous ammonia, and the obtained titanium gel is coated with citric acid. , Citric acid, tartrate acid, lactic acid, glycolic acid and other oxycarboxylic acids or salts thereof are added and hydrothermally treated for easy production. Alternatively, it can be produced by adding oxycarboxylic acid or a salt thereof to powdered titanium oxide and wet pulverizing with a ball mill or the like. Alternatively, it can also be produced by hydrolyzing titanium alkoxide. In addition, commercially available titanium sol, for example, hydrochloric acid-stabilized titanium oxide sol, nitric acid-stabilized titanium oxide sol, organic acid-stabilized titanium oxide sol, and alkali-stabilized titanium oxide sol may be used.

【0013】

Regarding the size of the colloidal particles of the present invention, the average particle size is approximately 1 to 500 nm, preferably 2 to 100 nm. If it is 1 nm or less, the photocatalytic activity, that is, the photocatalytic activity is not sufficient, and if it exceeds 500 nm, not only the liquid stability but also the adhesion to the substrate is remarkably deteriorated. In addition, when the photocatalyst composition of the present invention is applied to a base material to form a film, the alkali resistance is significantly deteriorated.

【0014】

Next, regarding the oxycarboxylic acid of the present invention or a salt thereof, as described above, as the oxycarboxylic acid, malic acid, citric acid, tartrate acid, lactic acid, glycolic acid, mandelic acid and the like can be used, and the salt thereof. Examples include lithium salt, sodium salt, potassium salt, calcium salt, ammonium salt, or oxycarboxylic acid and alkaline agent, for example, lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate, potassium carbonate. , Hydroxides and carbonates of alkali metals such as calcium carbonate, or those prepared with ammonia, amines, alkanolamines, etc. can be used, among which aliphatic oxycarboxylic acids or salts thereof can be used. preferable. However, it is not limited to these. Next, the method for producing the photocatalyst composition of the present invention may be described. Zyrconyl ammonium carbonate may be added to the oxycarboxylic acid-containing titanium oxide colloidal solution produced as described above, or the titanium oxide colloidal solution and zirconyl ammonium carbonate may be added. Oxycarboxylic acid or a salt thereof may be added to the mixture. Alternatively, a titanium oxide colloidal solution may be added to a mixture of zirconyl ammonium carbonate and oxycarboxylic acid or a salt thereof. Alternatively, oxycarboxylic acid or a salt thereof and zirconyl ammonium carbonate may be added to powdered titanium oxide and wet-pulverized with a ball mill or the like to produce the product. However, the method most recommended by the present inventors is a method in which ammonium carbonate is added to a titanium oxide colloidal solution stabilized with oxycarboxylic acid or a salt thereof, and the mixture is well stirred. When this method is used, a photocatalytic composition having the highest liquid stability in which each component is uniformly dispersed can be obtained, and when this is applied to a base material, the photocatalytic activity is high, and the adhesion and alkali resistance are excellent. A film can be obtained. Next, regarding the composition ratio of the photocatalyst composition of the present invention, titanium oxide colloid (TiO)₂) Content is 1 to 30% by weight, more preferably 1 to 10% by weight. If it is 1% by weight or less, the manufacturing cost is high, and if it exceeds 30% by weight, the adhesion to the base material is deteriorated and the alkali resistance is also deteriorated.

【0015】

Zyrconyl ammonium carbonate (ZrO)₂) / Titanium oxide colloid (TiO₂) Is 95/5 ~ 5/95. It is preferably 80/20 to 30/70. Above 95/5, the adhesion is good, but the photocatalytic activity is extremely low. On the other hand, below 5/95, the photocatalytic activity is good, but the adhesion to the substrate and the alkali resistance are significantly reduced.

【0016】

Then oxycarboxylic acid or a salt thereof / (zirconyl ammonium carbonate (ZrO)₂) And titanium oxide colloid (TiO₂)) The molar ratio to) is 0.01 to 1.0, preferably 0.05 to 0.5. If it is 0.01 or less, a homogeneous composition cannot be obtained and the adhesion is deteriorated. On the other hand, when the composition is 1.0 or more, although a homogeneous composition can be obtained, the addition of a large amount of oxycarboxylic acid is not preferable because the strength is lowered due to the presence of a large amount of oxycarboxylic acid in the coating film. Also, oxycarboxylic acid or a salt thereof / (zirconyl ammonium carbonate (ZrO)₂) And titanium oxide colloid (TiO₂)) = 0.5 to 1.0 (molar ratio), it is desirable to bake and use the coating film at 200 to 500 ° C rather than drying it at 100 ° C.

【0017】

There is no particular problem with the drying temperature even if it is dried at room temperature, but it is preferable to dry at 50 ° C or higher if possible. If it is a heat-resistant substrate, it can be fired at 150 ° C. or higher, more preferably 200 ° C. to 500 ° C. to obtain a strong film having higher adhesion. The photocatalytic composition of the present invention can be easily produced by the method described in detail above and exhibits excellent adhesion to various substrates, but in order to further enhance the effect, silica alkoxide and silica sol , Silicon-modified resin, silane coupling agent, etc. can also be added. Also, to increase photocatalytic activity, Pt, Rh, RhO₂, Nb, Ni, Fe and other metals can also be added. Further, Cu, Ag and the like can be contained for the purpose of antibacterial. Speaking of the method of using the photocatalyst composition of the present invention, it is applied to various substrates such as ceramics, glass, plastic, rubber, wood, paper, cloth and metal by any method such as a dipping method, a spinner coating method and a roller coating method. By drying, a film having high photocatalytic activity and excellent adhesion and alkali resistance can be easily obtained. Hereinafter, the present invention will be described in more detail with reference to examples of the present invention, but the present invention is not limited to these examples. Unless otherwise specified,% indicates all weight%.

【0018】

[Example]

(Example 1) Titanium oxychloride aqueous solution (TiO₂= 2%) 2000g, ammonia water (NH₃= 2%) 2212g (NH₃/ Cl equivalent ratio = 1.3) was added under stirring to form a titanium gel. Chlorine ions in the filtrate are titanium gel (TiO).₂) With filtered water until it becomes 100ppm or less, and TiO₂= 10%, NH₃= 0.30% gel was obtained.

【0019】

This gel (TiO₂= 10%, NH₃= 0.30%) 400g, lactic acid / TiO₂Add 45.1 g of lactic acid and 54.9 g of ion-exchanged water so that (molar ratio) = 1.0, put this in an autoclave, perform hydrothermal treatment at 150 ° C for 6 hours, and perform a crystalline titanium oxide colloidal solution (TiO).₂= 8.0%) was obtained. Anatase-type titanium oxide peaks were observed by X-ray diffraction, and the crystallite size determined from the Debai-Scherer equation using the first peak was 6 nm. The obtained titanium oxide colloidal solution (TiO₂= 8%) 100g, zirconyl ammonium carbonate (manufactured by Daiichi Rare Element Chemistry Co., Ltd., trade name: Zircozol AC-7 (ZrO)₂= 13%)) 41.0 g was added with stirring to the photocatalytic composition of the present invention (TiO).₂= 5.7%, ZrO₂= 3.8%, lactic acid / (ZrO₂+ TiO₂) (Mole ratio) = 0.70, ZrO₂/ TiO₂(Weight ratio) = 40/60) was obtained. This photocatalyst composition is applied to a transparent glass plate (20 cm).²) Was spinner-coated, dried at 100 ° C., and then calcined at 400 ° C. for 30 minutes to obtain a photocatalyst material coated with 1.2 mg (dry weight) of the photocatalyst composition of the present invention.

【0020】

(Example 2) Titanium oxide gel (TiO) obtained in the same manner as in Example 1.₂= 10%, NH₃= 0.30%) 400g, lactic acid / TiO₂Add 36.1 g of lactic acid and 63.9 g of ion-exchanged water so that (molar ratio) = 0.8, put this in an autoclave, perform hydrothermal treatment at 150 ° C for 6 hours, and perform a crystalline titanium oxide colloidal solution (TiO).₂= 8.0%) was obtained. The obtained titanium oxide colloidal solution (TiO₂= 8%) 100g, zirconyl ammonium carbonate (manufactured by Daiichi Rare Element Chemistry Co., Ltd., trade name: Zircozol AC-7 (ZrO)₂= 13%)) 41.0 g was added with stirring to the photocatalytic composition of the present invention (TiO).₂= 5.7%, ZrO₂= 3.8%, lactic acid / (ZrO₂+ TiO₂) (Mole ratio) = 0.56, ZrO₂/ TiO₂(Weight ratio) = 40/60) was obtained. By the same method as in Example 1, this photocatalyst composition was applied to a transparent glass plate (20 cm).²) Was spinner-coated, dried at 100 ° C., and then calcined at 300 ° C. for 30 minutes to obtain a photocatalyst material coated with 1.2 mg (dry weight) of the photocatalyst composition of the present invention.

【0021】

(Example 3) Titanium oxide gel (TiO) obtained in the same manner as in Example 1.₂= 10%, NH₃0.30%) 400g, lactic acid / TiO₂Add 22.5 g of lactic acid and 77.5 g of ion-exchanged water so that (molar ratio) = 0.5, put this in an autoclave, perform hydrothermal treatment at 150 ° C for 6 hours, and perform a crystalline titanium oxide colloidal solution (TiO).₂= 8.0%) was obtained. The obtained titanium oxide colloidal solution (TiO₂= 8%) 100g, zirconyl ammonium carbonate (manufactured by Daiichi Rare Element Chemistry Co., Ltd., trade name: Zircozol AC-7 (ZrO)₂= 13%)) 41.0 g was added with stirring to the photocatalytic composition of the present invention (TiO).₂= 5.7%, ZrO₂= 3.8%, lactic acid / (ZrO₂+ TiO₂) (Mole ratio) = 0.35, ZrO₂/ TiO₂(Weight ratio) = 40/60) was obtained. By the same method as in Example 1, this photocatalyst composition was applied to a transparent glass plate (20 cm).²) Was spinner-coated and dried at 100 ° C. for 10 minutes to obtain a photocatalyst material coated with 1.2 mg (dry weight) of the photocatalyst composition of the present invention.

【0022】

(Example 4) The crystalline titanium oxide colloidal solution (TiO) obtained in Example 3₂= 8.0%) with extra-cleaning treatment, lactic acid / TiO₂(Mole ratio) = 0.2, TiO₂= 8.0% titanium oxide colloidal solution was obtained. The amount of lactic acid in the titanium oxide colloidal solution was quantified by using liquid chromatography. The obtained titanium oxide colloidal solution (TiO₂= 8%) 100g, zirconyl ammonium carbonate (manufactured by Daiichi Rare Element Chemistry Co., Ltd., trade name: Zircozol AC-7 (ZrO)₂= 13%)) 41.0 g was added with stirring to the photocatalytic composition of the present invention (TiO).₂= 5.7%, ZrO₂= 3.8%, lactic acid / (ZrO₂+ TiO₂) (Mole ratio) = 0.14, ZrO₂/ TiO₂(Weight ratio) = 40/60) was obtained. By the same method as in Example 1, this photocatalyst composition was applied to a transparent glass plate (20 cm).²) Was spinner-coated and dried at 100 ° C. for 10 minutes to obtain a photocatalyst material coated with 1.2 mg (dry weight) of the photocatalyst composition of the present invention.

【0023】

(Example 5) Similar to Example 4, the crystalline titanium oxide colloidal solution (TiO) obtained in Example 3 was obtained.₂= 8.0%) with extra-cleaning treatment, lactic acid / TiO₂(Mole ratio) = 0.05, TiO₂= 8.0% titanium oxide colloidal solution was obtained. The amount of lactic acid in the titanium oxide colloidal solution was quantified by using liquid chromatography. The obtained titanium oxide colloidal solution (TiO₂= 8%) 100g, zirconyl ammonium carbonate (manufactured by Daiichi Rare Element Chemistry Co., Ltd., trade name: Zircozol AC-7 (ZrO)₂= 13%)) 41.0 g was added with stirring to the photocatalytic composition of the present invention (TiO).₂= 5.7%, ZrO₂= 3.8%, lactic acid / (ZrO₂+ TiO₂) (Mole ratio) = 0.04, ZrO₂/ TiO₂(Weight ratio) = 40/60) was obtained. By the same method as in Example 1, this photocatalyst composition was applied to a transparent glass plate (20 cm).²) Was spinner-coated and dried at 100 ° C. for 10 minutes to obtain a photocatalyst material coated with 1.2 mg (dry weight) of the photocatalyst composition of the present invention.

【0024】

(Example 6) Anatase-type titanium oxide powder (manufactured by Taki Chemical Co., Ltd., trade name: Tynoc A-100 (TiO)₂= 84%, particle size 1.4 μm)) 100 g, lactic acid / TiO₂(Mole ratio) = 0.10, 9.5 g of lactic acid, 30.5 g of ion-exchanged water, zirconyl ammonium carbonate (manufactured by Nippon Light Metal Co., Ltd., trade name: Baycoat 20 (ZrO)₂= 20%)) 280 g was added, mixed, and then pulverized by a pulverizer to obtain the photocatalytic composition (TiO) of the present invention.₂= 20.0%, ZrO₂= 13.3%, lactic acid / (ZrO₂+ TiO₂) (Mole ratio) = 0.07, ZrO₂/ TiO₂(Weight ratio) = 40/60, titanium oxide particle size 0.1 μm) was obtained. This photocatalytic composition is TiO₂After diluting with ion-exchanged water so that = 8%, a transparent glass plate (20 cm) is used in the same manner as in Example 1.²) Was spinner-coated and dried at 100 ° C. for 10 minutes to obtain a photocatalyst material coated with 2.5 mg (dry weight) of the photocatalyst composition of the present invention.

【0025】

(Comparative Example 1) Titanium oxide gel (TiO) obtained in the same manner as in Example 1.₂= 10%, NH₃Add ion-exchanged water = 100g to 400g of = 0.30%), put this in an autoclave, perform hydrothermal treatment at 150 ° C for 6 hours, and perform a crystalline titanium oxide colloidal solution (TiO).₂= 8.0%) was obtained. The obtained titanium oxide colloidal solution (TiO₂= 8%) 100g, zirconyl ammonium carbonate (manufactured by Daiichi Rare Element Chemistry Co., Ltd., trade name: Zircozol AC-7 (ZrO)₂= 13%)) 41.0 g was added with stirring to the photocatalytic composition (TiO).₂= 5.7%, ZrO₂= 3.8%, oxycarboxylic acid / (ZrO₂+ TiO₂) (Mole ratio) = 0, ZrO₂/ TiO₂(Weight ratio) = 40/60) was obtained. By the same method as in Example 1, this photocatalyst composition was applied to a transparent glass plate (20 cm).²) Is spinner coated, dried at 100 ° C for 10 minutes, and glass plate (area = 20 cm).²), A photocatalyst material coated with 1.2 mg (dry weight) of the photocatalyst composition was obtained.

【0026】

(Comparative Example 2) Titanium oxide colloidal solution (TiO) obtained in Example 3₂= 8%, lactic acid / TiO₂Using (molar ratio) = 0.5), a transparent glass plate (20 cm) was used in the same manner as in Example 1.²) Is spinner coated, dried at 100 ° C for 10 minutes, dried at 100 ° C, and then fired at 500 ° C for 30 minutes to obtain a photocatalyst material coated with 1.0 mg (dry weight) of the photocatalyst composition. It was.

【0027】

Table 1 shows a comparison of the coating film strengths of Examples 1 to 6 and Comparative Examples 1 and 2. The film strength was evaluated based on the following general paint test method. General paint test method (JIS K 5400) Pencil hardness: Section 8-4 Pencil scratch value tester method [0028]

[table 1]

<img file="JP2002136869A_D0001.tif" />【0029】

* Does not contain zirconyl ammonium carbonate (Example 7) Titanium oxide gel (TiO) obtained in the same manner as in Example 1.₂= 10%, NH₃= 0.30%) 400g, citric acid / TiO₂Add 31.6 g of citric acid monohydrate and 68.4 g of ion-exchanged water so that (molar ratio) = 0.3, put this in an autoclave, and perform hydrothermal treatment at 150 ° C for 6 hours to crystallize oxidation. Titanium colloid solution (TiO₂= 8.0%) was obtained. Anatase-type titanium oxide peaks were observed by X-ray diffraction, and the crystallite size determined from the Debai-Scherer equation using the first peak was 6 nm. The obtained titanium oxide colloidal solution (TiO₂= 8%) In 100g, zirconyl ammonium carbonate solution (ZrO, manufactured by Shin Nihon Kinzoku Kagaku Co., Ltd.)₂= 13%)) 3.2 g and 2.1 g of ion-exchanged water were added under stirring to obtain the photocatalytic composition (TiO) of the present invention.₂= 7.6%, ZrO₂= 0.4%, citric acid / (ZrO₂+ TiO₂) (Mole ratio) = 0.29, ZrO₂/ TiO₂(Weight ratio) = 5/95) was obtained. By the same method as in Example 1, this photocatalyst composition was applied to a transparent glass plate (20 cm).²) Was spinner-coated, dried at 100 ° C. for 10 minutes, and then calcined at 500 ° C. for 30 minutes to obtain a photocatalyst material coated with 1.2 mg (dry weight) of the photocatalyst composition of the present invention.

【0030】

(Example 8) Titanium oxide gel (TiO) obtained in the same manner as in Example 1.₂= 10%, NH₃= 0.30%) 400g, tartaric acid / TiO₂Add 45.1 g of tartaric acid and 54.9 g of ion-exchanged water so that (molar ratio) = 0.6, put this in an autoclave, perform hydrothermal treatment at 150 ° C for 6 hours, and perform a crystalline titanium oxide colloidal solution (TiO).₂= 8.0%) was obtained. Anatase-type titanium oxide peaks were observed by X-ray diffraction, and the crystallite size determined from the Debai-Scherer equation using the first peak was 6 nm. The obtained titanium oxide colloidal solution (TiO₂= 8%) In 100g, zirconyl ammonium carbonate solution (ZrO, manufactured by Shin Nihon Kinzoku Kagaku Co., Ltd.)₂= 13%)) 15.4 g and 9.6 g of ion-exchanged water were added under stirring to obtain the photocatalytic composition (TiO) of the present invention.₂= 6.4%, ZrO₂= 1.6%, tartaric acid / (ZrO₂+ TiO₂) (Mole ratio) = 0.52, ZrO₂/ TiO₂(Weight ratio) = 20/80) was obtained. By the same method as in Example 1, this photocatalyst composition was applied to a transparent glass plate (20 cm).²) Was spinner-coated, dried at 100 ° C. for 10 minutes, and then calcined at 300 ° C. for 30 minutes to obtain a photocatalyst material coated with 1.2 mg (dry weight) of the photocatalyst composition of the present invention.

【0031】

(Example 9) Titanium oxide gel (TiO) obtained in the same manner as in Example 1.₂= 10%, NH₃= 0.30%) 400g, glycolic acid / TiO₂Add 27.2 g of glycolic acid (70%) and 72.8 g of ion-exchanged water so that (molar ratio) = 0.5, put this in an autoclave, and perform hydrothermal treatment at 150 ° C for 6 hours to crystallize oxidation. Titanium colloid solution (TiO₂= 8.0%) was obtained. Anatase-type titanium oxide peaks were observed by X-ray diffraction, and the crystallite size determined from the Debai-Scherer equation using the first peak was 6 nm. The obtained titanium oxide colloidal solution (TiO₂= 8%) In 100g, zirconyl ammonium carbonate solution (ZrO, manufactured by Shin Nihon Kinzoku Kagaku Co., Ltd.)₂= 13%)) 26.4 g and 16.5 g of ion-exchanged water were added under stirring to obtain the photocatalytic composition (TiO) of the present invention.₂= 5.6%, ZrO₂= 2.4%, glycolic acid / (ZrO₂+ TiO₂) (Mole ratio) = 0.39, ZrO₂/ TiO₂(Weight ratio) = 30/70) was obtained. By the same method as in Example 1, this photocatalyst composition was applied to a transparent glass plate (20 cm).²) Was spinner-coated, dried at 100 ° C. for 10 minutes, and then calcined at 200 ° C. for 30 minutes to obtain a photocatalyst material coated with 1.2 mg (dry weight) of the photocatalyst composition of the present invention.

【0032】

(Example 10) Titanium oxide gel (TiO) obtained in the same manner as in Example 1.₂= 10%, NH₃= 0.30%) 400g, tetramethylammonium hydroxide (TMAOH) / TiO₂Add 22.8 g of tetramethylammonium hydroxide aqueous solution (10% product) and 77.2 g of ion-exchanged water so that (molar ratio) = 0.05, put this in an autoclave, and perform hydrothermal treatment at 150 ° C for 6 hours. Do and crystallize titanium oxide colloidal solution (TiO₂= 8.0%) was obtained. Anatase-type titanium oxide peaks were observed by X-ray diffraction, and the crystallite size determined from the Debai-Scherer equation using the first peak was 12 nm. The obtained titanium oxide colloidal solution (TiO₂= 8%) 100g, diammonium citrate / TiO₂Add 2.3 g of diammonium citrate and 36.2 g of ion-exchanged water so that (molar ratio) = 0.1, mix well, and then zirconyl ammonium carbonate solution (manufactured by Shin Nihon Kinzoku Kagaku Co., Ltd.) ZrO₂= 13%)) 61.5 g was added with stirring to the photocatalytic composition of the present invention (TiO).₂= 4.0%, ZrO₂= 4.0%, 2 ammonium citrate / (ZrO₂+ TiO₂) (Mole ratio) = 0.06, ZrO₂/ TiO₂(Weight ratio) = 50/50) was obtained. By the same method as in Example 1, this photocatalyst composition was applied to a transparent glass plate (20 cm).²) Was spinner-coated and dried at 100 ° C. for 10 minutes to obtain a photocatalyst material coated with 1.3 mg (dry weight) of the photocatalyst composition of the present invention.

【0033】

(Example 11) Titanium oxide gel (TiO) obtained in the same manner as in Example 1.₂= 10%, NH₃= 0.30%) 400g, sodium tartrate / TiO₂Add 23.0 g of sodium tartrate dihydrate and 77.0 g of ion-exchanged water so that (molar ratio) = 0.2, put this in an autoclave, and perform hydrothermal treatment at 150 ° C for 6 hours to crystallize oxidation. Titanium colloidal solution (TiO₂= 8.0%) was obtained. Anatase-type titanium oxide peaks were observed by X-ray diffraction, and the crystallite size determined from the Debai-Scherer equation using the first peak was 5 nm. The obtained titanium oxide colloidal solution (TiO₂= 8%) In 100g, zirconyl ammonium carbonate solution (ZrO, manufactured by Shin Nihon Kinzoku Kagaku Co., Ltd.)₂= 13%)) 143.6 g and 89.7 g of ion-exchanged water were added under stirring to obtain the photocatalytic composition (TiO) of the present invention.₂= 2.4%, ZrO₂= 5.6%, sodium tartrate / (ZrO₂+ TiO₂) (Mole ratio) = 0.08, ZrO₂/ TiO₂(Weight ratio) = 70/30) was obtained. By the same method as in Example 1, this photocatalyst composition was applied to a transparent glass plate (20 cm).²) Was spinner-coated and dried at 70 ° C. for 10 minutes to obtain a photocatalyst material coated with 1.2 mg (dry weight) of the photocatalyst composition of the present invention.

【0034】

(Comparative Example 3) Titanium oxide colloidal solution (TiO) obtained in Example 8₂= 8.0%) 100g, silica sol (manufactured by Nissan Chemical Industries, Ltd., trade name: Snowtex ST-OL (SiO)₂= 20.0%)) 10.0 g and 15.0 g of ion-exchanged water were added and mixed, and the photocatalyst composition (TiO) was added.₂= 6.4%, SiO₂= 1.6%, SiO₂/ TiO₂(Weight ratio) = 20/80) was obtained.

【0035】

Transparent glass plate (20 cm) by the same method as in Example 1.²) Was spinner-coated, dried at 100 ° C. for 10 minutes, and then calcined at 500 ° C. for 30 minutes to obtain a photocatalyst material coated with 1.0 mg (dry weight) of the photocatalyst composition.

【0036】

(Comparative Example 4) Titanium oxide colloidal solution (TiO) obtained in Example 9₂= 8.0%) 100g, silica sol (manufactured by Tama Chemical Co., Ltd., trade name: Silicate 40 (SiO)₂= 40.0%)) 20.0 g and 80.0 g of ion-exchanged water were added and mixed, and the photocatalyst composition (TiO) was added.₂= 4.0%, SiO₂= 4.0%, SiO₂/ TiO₂(Weight ratio) = 50/50) was obtained.

【0037】

Transparent glass plate (20 cm) by the same method as in Example 1.²) Was spinner-coated, dried at 100 ° C. for 10 minutes, and then calcined at 300 ° C. for 30 minutes to obtain a photocatalyst material coated with 1.0 mg (dry weight) of the photocatalyst composition.

【0038】

Table 2 shows the evaluation results of the alkali resistance tests of Examples 7 to 11 and Comparative Examples 3 to 4. The evaluation of the alkali resistance of the coating film was carried out based on the following general paint test method. General paint test method (JIS K 5400) Alkali resistance test: Sections 8-21<img file="JP2002136869A_D0002.tif" />【0039】

[Table 2]

<img file="JP2002136869A_D0003.tif" />【0040】

* Does not contain zirconyl ammonium carbonate (Example 12) Titanium oxide gel (TiO) obtained in the same manner as in Example 1.₂= 10%, NH₃= 0.30%) 400g, malic acid / TiO₂Add 20.1 g of malic acid and 79.9 g of ion-exchanged water so that (molar ratio) = 0.3, put this in an autoclave, perform hydrothermal treatment at 150 ° C for 6 hours, and perform a crystalline titanium oxide colloid solution (crystalline titanium oxide colloid solution). TiO₂= 8.0%) was obtained. Anatase-type titanium oxide peaks were observed by X-ray diffraction, and the crystallite size determined from the Debai-Scherer equation using the first peak was 6 nm. The obtained titanium oxide colloidal solution (TiO₂= 8%) 100g, zirconyl ammonium carbonate (manufactured by Nippon Light Metal Co., Ltd., trade name: Baycoat 20 (ZrO)₂= 20%)) 10 g and 15 g of ion-exchanged water were added under stirring to obtain the photocatalytic composition (TiO) of the present invention.₂= 6.4%, ZrO₂= 1.6%, malic acid / (ZrO₂+ TiO₂) (Mole ratio) = 0.26, ZrO₂/ TiO₂(Weight ratio) = 20/80) was obtained. Silica-deposited PET film (40 cm)²) Was coated with a spinner and dried at 100 ° C. for 10 minutes to obtain a photocatalyst material coated with 2.5 mg (dry weight) of the photocatalyst composition of the present invention.

【0041】

(Example 13) The crystalline titanium oxide colloidal solution (TiO) obtained in Example 12₂= 8%) 100g, zirconyl ammonium carbonate (manufactured by Nippon Light Metal Co., Ltd., trade name: Baycoat 20 (ZrO)₂= 20%)) 40 g and 60 g of ion-exchanged water were added under stirring to obtain the photocatalytic composition (TiO) of the present invention.₂= 4.0%, ZrO₂= 4.0%, malic acid / (ZrO₂+ TiO₂) (Mole ratio) = 0.18, ZrO₂/ TiO₂(Weight ratio) = 50/50) was obtained. Silica-deposited PET film (40 cm)²) Was coated with a spinner and dried at 100 ° C. for 10 minutes to obtain a photocatalyst material coated with 2.6 mg (dry weight) of the photocatalyst composition of the present invention.

【0042】

(Example 14) The crystalline titanium oxide colloidal solution (TiO) obtained in Example 12₂= 8%) 100g, Zyrconyl ammonium carbonate (Nippon Light Metal Co., Ltd. Baycoat 20 (ZrO)₂= 20%)) 93.3 g and 140 g of ion-exchanged water were added under stirring to obtain the photocatalytic composition (TiO) of the present invention.₂= 2.4%, ZrO₂= 5.6%, malic acid / (ZrO₂+ TiO₂) (Mole ratio) = 0.12, ZrO₂/ TiO₂(Weight ratio) = 70/30) was obtained. Silica-deposited PET film (40 cm)²) Was coated with a spinner and dried at 100 ° C. for 10 minutes to obtain a photocatalyst material coated with 2.7 mg (dry weight) of the photocatalyst composition of the present invention.

【0043】

(Example 15) The crystalline titanium oxide colloidal solution (TiO) obtained in Example 12₂= 8%) 20g, zirconyl ammonium carbonate (manufactured by Nippon Light Metal Co., Ltd., trade name: Baycoat 20 (ZrO)₂= 20%)) 152 g and 228 g of ion-exchanged water were added under stirring to obtain the photocatalytic composition (TiO) of the present invention.₂= 0.4%, ZrO₂= 7.6%, malic acid / (ZrO₂+ TiO₂) (Mole ratio) = 0.02, ZrO₂/ TiO₂(Weight ratio) = 95/5) was obtained. Silica-deposited PET film (40 cm)²) Was coated with a spinner and dried at 100 ° C. for 10 minutes to obtain a photocatalyst material coated with 2.6 mg (dry weight) of the photocatalyst composition of the present invention. The photocatalytic ability was measured using the coating films prepared in Examples 12 to 15. The gas used was acetaldehyde, and after enclosing 100 ppm of acetaldehyde gas in a closed container containing a photocatalytic material, the ultraviolet intensity was 1.0 mW / cm.²The photocatalytic ability was evaluated from the difference between the initial concentration and the concentration after 120 minutes of black light irradiation. The results are shown in Table 3.

【0044】

[Table 3]

<img file="JP2002136869A_D0004.tif" />【0045】

[Effect of the invention]

The present invention is excellent when a photocatalytic composition, particularly an oxycarboxylic acid or a salt thereof, is used to uniformly disperse and stabilize titanium oxide colloid and zirconyl ammonium carbonate in a solution, and this is applied to a substrate such as plastic. Demonstrates photocatalytic ability, alkali resistance, and substrate adhesion resistance.