Paint composite film comprising anatase-type titanium oxide and method for manufacturing the same

Composite film for coating containing anatase titanium oxide and its manufacturing method

Paint composite film comprising anatase-type titanium oxide and method for manufacturing the same

The present invention relates to a coating composite film containing anatase titanium oxide and a manufacturing method thereof, in particular to excellent photocatalyst activity and antibacterial activity, high film forming ability and strong adhesion to the painted surface, which can reduce the generation of photochemical reactions A composite film for coating containing anatase titanium oxide that causes damage to the inner wall caused by active oxygen and its manufacturing method.

Titanium oxide has anatase and rutile crystal types. Among them, it is known that anatase-type titanium oxide has a strong catalytic activity for chemical reactions, and has a photocatalyst function that absorbs light with energy larger than the energy band gap through the irradiation of light and converts oxygen into active oxygen. The active oxygen exhibits a strong oxidizing effect to oxidize and decompose various objects, and has a self-cleaning effect, a strong antibacterial effect, etc. (for example, refer to Japanese Patent Documents 1 and 2).

For example, the self-cleaning effect of the photocatalyst film is based on the mechanism that the photocatalyst absorbs light energy and converts the absorbed energy into oxygen to generate active oxygen. The generated active oxygen will adhere to the external wall or the adhesive organic pollution on the outside of the window glass. Oxidation and decomposition of substances, rainwater washes away pollutants that are easy to wash away, and keeps the exterior walls or window glass of buildings clean. The self-cleaning effect of this photocatalyst film has been put into practical use.

In addition, the anatase-type titanium oxide film formed on the glass surface generates active oxygen after light absorption and decomposes and removes contaminants adhering to the glass surface. The glass from which the contaminants are removed will restore the original hydrophilicity (hydrophilic effect), so the water attached to the surface will not form droplets or diffuse without generating mist (anti-fog effect). Anatase-type titanium oxide coating is used to coat the surface of car rearview mirrors or traffic signs using this effect. Furthermore, the active oxygen generated by the photocatalyst film will oxidize and decompose nitrogen oxides (NOX) or malodorous substances, so anatase-type titanium oxide film can be used for air cleaning, soundproof walls of highways, home appliances, etc. Deodorizing effect and so on.

Conventional methods for forming anatase titanium oxide coatings include coating method, sol-gel method (Sol-Gel Method), sputtering method, CVD method (Chemical Vapor Deposition Method), plasma spraying method ( Plasma spraying Method). The coating method is to apply a slurry of titanium oxide powder or an aqueous solution of titanium chloride or titanium sulfate on a substrate to be sintered. In the sol-gel method, a sol made by water decomposition of a metal alkoxide is coated on a substrate for sintering. The sputtering method is to sputter an oxide target in a vacuum to form a film on a substrate. The CVD method volatilizes organometallic compounds or halides and decomposes them in a heating furnace to form a film on a substrate. The plasma spraying method melts solid particles in the plasma generated in the atmosphere and sprays them on the surface of the substrate. However, because the coating method requires a high temperature of hundreds of degrees or more to form anatase titanium oxide film, there is a problem that the base material is limited to high-temperature resistant materials, and the sol-gel method also has the problem of removing the sol by sintering. The problematic point that the oxygen or organic substances must be heated to above 400°C.

In recent years, the method for producing anatase-type titanium oxide published in Japanese Patent Literature involves heating an aqueous solution of peroxotitanic acid hydrate (peroxotitanic acid hydrate) produced by treating titanium raw materials with hydrogen peroxide and heating to about 100°C. The aqueous dispersion of anatase-type titanium oxide fine particles can be coated and dried to form an anatase-type titanium oxide photocatalyst film (for example, refer to Japanese Patent Documents 3 to 7).

The anatase-type titanium oxide photocatalyst film obtained by this manufacturing method has the characteristic that as long as it is coated on the substrate and dried, a thin film can be formed and the photocatalyst activity can also be displayed by visible light, but the problem is that the film The strength and adhesion are slightly inferior to conventional photocatalysts fired at high temperatures.

In addition, the active oxygen released by the photocatalyst may also damage the substrate. It can form a photocatalyst film on a substrate that is not attacked by active oxygen like glass, metal, and concrete. However, for example, paint finishes, if coated with a photocatalyst on a substrate that is attacked by active oxygen, it will attack the substrate together with pollutants. , Accelerate the deterioration of the substrate. Therefore, in order to form an anatase-type titanium oxide film on the surface of the substrate that is decomposed by active oxygen, it is necessary to have an undercoat layer that blocks active oxygen.

On the other hand, the intermediate layer coated with anatase titanium oxide is an amorphous titanium oxide film obtained by drying peroxotitanic acid hydrate. Various substrates of titanium film have excellent adhesion.

Furthermore, the photocatalyst cannot exhibit sufficient activity in the absence of light or low light. However, with regard to antibacterial activity, there is a problem that bacteria are prone to multiply especially in dark places. In addition, the coating film of the exterior wall of the building is required to have durability for several years to several decades under very severe environmental conditions. Although the primer layer of amorphous titanium oxide has a certain degree of effect, it is only that There are still shortcomings. Therefore, it is desired to develop a method that can maintain the catalytic activity of anatase-type titanium oxide and further enhance the strength and adhesion of the film.

Prior Art Document Patent Document [Patent Document 1] Japanese Patent Laid-open No. 7-155598 [Patent Document 2] Japanese Patent Laid-Open No. 9-225319 [Patent Document 3] Japanese Patent No. 2875993 [Patent Document 4] Japanese Patent No. No. 3490012 [Patent Document 5] Japanese Patent No. 3490013 [Patent Document 6] Japanese Patent No. 2938376 [Patent Document 7] Japanese Patent No. 3122658 [Patent Document 8] Japanese Patent No. 4452689

Problems to be Solved by the Invention The present invention aims to solve the above-mentioned problems. Its problem is to provide a composite film for coating containing anatase-type titanium oxide and a manufacturing method thereof, which can effectively block the damage of active oxygen to the substrate. Both film formation and adhesion are good, the catalyst efficiency is high, and the manufacturing method is easy and inexpensive. The subject of the first embodiment of the present invention is to provide a composite film for interior decoration containing anatase titanium oxide, which has photocatalytic activity and generates active oxygen even in visible light or weak light, has a self-cleaning effect and is in dark places. It still has strong antibacterial activity.

In addition, in the second embodiment of the present invention, the subject is to provide a composite film for exterior decoration containing anatase-type titanium oxide, which has strong adhesion that can withstand the harsh environmental conditions of building exteriors exposed to sunlight. And the strength of the coating film, it also has a strong self-cleaning effect caused by the action of the photocatalyst, and effectively blocks the active oxygen from attacking the substrate. The problem to be solved by the invention

The composite film for coating containing anatase-type titanium oxide to solve these problems is characterized in that the aqueous solution of peroxytitanic acid is set as A solution, and the A solution is heated to 70 to 200°C in an anatase-type titanium oxide dispersion. The liquid containing noble metal salts or nanocolloids is set as liquid B. After the aforementioned liquid A is applied to the interior surface of the building and dried, the liquid B is applied and dried to form it.

When the weight of peroxytitanic acid is converted to the weight of titanium oxide, and the weight of A liquid is set to 100 parts by weight, the peroxytitanic acid content of the aforementioned A liquid may be in the range of 0.1 to 10 parts by weight. When the weight of the aforementioned B liquid is set to 100 parts by weight, the anatase-type titanium oxide content of the aforementioned B liquid may be in the range of 0.1 to 10 parts by weight.

It is preferable that the ratio of the weight of the weight of peroxytitanic acid contained in the aforementioned A liquid converted to the weight of titanium oxide and the weight of the aforementioned titanium oxide contained in the liquid B be in the range of 10:1 to 1:10. The aforementioned noble metal salt or nanocolloid is preferably one or more of the salt of copper, silver, gold, and platinum or the nanocolloid group.

When the weight of the precious metal salt or nanocolloid is converted into the weight of the metal, and the weight of the B solution is set to 100 parts by weight, the content of the aforementioned precious metal salt or nanocolloid in the B solution is 1×10^－⁴To 1×10^－⁹Within the range of parts by weight. For the painted surface, the coating amount of the aforementioned A liquid is 1 to 100g/m², The coating amount of the aforementioned B liquid is 1 to 100g/m²Better. The aforementioned painted surfaces are interior surfaces including walls, ceilings, floors, partitions, furniture, and lighting appliances inside buildings.

In addition, the coating composite film containing anatase-type titanium oxide of the present invention is characterized by having a primer layer formed of amorphous titanium oxide formed on the interior surface of a building, and a photocatalyst layer , Which is formed by the precious metal salt or nanocolloid and anatase titanium oxide formed on the above-mentioned undercoat; when the weight of the precious metal salt or nanocolloid is converted into the weight of the metal, the aforementioned When the weight of anatase titanium oxide is set to 100 parts by weight, the content of the aforementioned noble metal salt or nanocolloid is 1×10^－¹To 1×10^－⁸Within the range of parts by weight.

Furthermore, the coating composite film containing anatase-type titanium oxide of the present invention is characterized by having an amorphous solid layer containing a peroxide group, which is formed on the interior surface of a building, and a salt containing noble metal Or nanocolloid anatase titanium oxide layer, which is formed on the aforementioned amorphous solid layer; when the weight of the precious metal salt or nanocolloid is converted into the weight of the metal, the aforementioned anatase titanium oxide When the weight of is set to 100 parts by weight, the content of the aforementioned noble metal salt or nanocolloid is 1×10^－¹To 1×10^－⁸Within the range of parts by weight.

Furthermore, the coating composite film containing anatase-type titanium oxide of the present invention is characterized by having an undercoat layer containing non-crystalline titanium oxide and reinforcing particles having an average particle diameter of 5 to 500 μm and a Mohs hardness of 5 or more And a photocatalyst layer containing anatase-type titanium oxide formed on the undercoat layer; when the mass of the amorphous titanium oxide is set to 100 parts by mass, the mass of the reinforcing particles is 1 to 100 parts by mass.

The aforementioned reinforcing particles can be preferably one or more of particles of feldspar, silica, silica gel, alumina, or titanium dioxide. The coating amount of the aforementioned amorphous titanium oxide on the aforementioned undercoat layer may be 0.1 to 100 g/m². The coating amount of anatase titanium oxide on the aforementioned photocatalyst layer is 0.1 to 50g/m²Better.

The catalyst layer may further contain the amorphous titanium oxide. The coating amount of the aforementioned catalyst layer is characterized in that the total coating amount of the anatase titanium oxide and the coating amount of the amorphous titanium oxide is 0.1 to 50 g/m², The ratio of the mass of anatase titanium oxide to the mass of amorphous titanium oxide is in the range of 1:0 to 1:2 (except for 0).

In addition, the method for producing a coating composite film containing anatase-type titanium oxide of the present invention is characterized in that the aqueous solution of peroxytitanic acid is set to A solution, and the aforementioned A solution is heated to 70 to 200°C to produce anatase-type titanium oxide A liquid in which a salt of a precious metal or a nanocolloid is added to the dispersion is set as liquid B, and the liquid A is applied to the interior surface of the building and dried, and then liquid B is applied and dried to form it.

When the weight of the aforementioned peroxytitanic acid is converted into the weight of titanium oxide, and the weight of the A liquid is set to 100 parts by weight, the peroxytitanic acid content of the aforementioned A liquid may be in the range of 0.1 to 10 parts by weight. When the weight of the aforementioned liquid B is set to 100 parts by weight, the content of anatase-type titanium oxide in the aforementioned liquid B may be in the range of 0.1 to 10 parts by weight.

The ratio of the weight of the weight of peroxytitanic acid contained in the aforementioned A liquid to the weight of titanium oxide to the weight of the aforementioned titanium oxide contained in the aforementioned B liquid is in the range of 10:1 to 1:10. The aforementioned noble metal salts or nanocolloids are preferably copper, silver, gold, and platinum salts or one or more of the nanocolloid group.

When the weight of the precious metal salt or nanocolloid is converted to the weight of the metal, and the weight of the B solution is set to 100 parts by weight, the content of the precious metal salt or nanocolloid in the B solution is 1×10^－⁴To 1×10^－⁹Within the range of parts by weight. For the painted surface, the coating amount of the aforementioned A liquid is 1 to 100g/m², The coating amount of the aforementioned B liquid is 1 to 100g/m²Better. The aforementioned painted surfaces include walls, ceilings, floors, compartment members, furniture, and lighting appliances inside buildings.

In addition, the manufacturing method of the coating composite film containing anatase-type titanium oxide of the present invention is characterized in that it has a peroxytitanic acid aqueous solution process, which is a process of making a peroxytitanic acid aqueous solution and a primer solution from a titanium raw material. The mass of peroxytitanic acid contained in the aforementioned aqueous solution of peroxytitanic acid is converted into the mass of titanium oxide as 100 parts by mass, and the average particle diameter of 5 to 500 μm and Mohs hardness is added to the aforementioned aqueous solution of peroxytitanic acid. 1 to 100 parts by mass of reinforced particles of 5 or more to prepare a primer solution and a process for forming an undercoat layer, which is to apply the primer solution to the surface of the substrate and dry to form the non-crystalline titanium oxide and the reinforcing particles The process of undercoating and photocatalyst solution is to heat the aforementioned aqueous solution of peroxytitanic acid to produce a photocatalyst solution containing anatase titanium oxide dispersion, and the process of forming a photocatalyst layer, which is to coat the aforementioned photocatalyst solution on the aforementioned substrate The coating is dried to form a photocatalyst layer.

The aforementioned reinforcing particles are preferably at least one of feldspar, silica, silica gel, alumina, or titanium dioxide particles. When the mass of peroxy titanic acid is converted to the mass of titanium oxide, and the mass of the aforementioned aqueous solution of peroxy titanic acid is set to 100 parts by mass, the content of peroxy titanic acid contained in the aforementioned aqueous solution of peroxy titanic acid may be 0.1 To 20 parts by mass.

The coating amount of the aforementioned primer solution is preferably 0.1 to 500 g/m by converting the mass of peroxytitanic acid into the mass of titanium oxide²The above-mentioned primer solution is applied to the substrate in a manner of. When the mass of the aforementioned photocatalyst liquid is set to 100 parts by mass, the content of anatase-type titanium oxide contained in the aforementioned photocatalyst liquid is 0.1 to 250 g/m² 。

The coating amount of the aforementioned photocatalyst liquid is preferably 0.1 to 250 g/m based on the mass of titanium oxide²The method of applying the photocatalyst liquid to the undercoat layer. The photocatalyst liquid further contains the aqueous solution of peroxytitanic acid.

When the mass of the aforementioned photocatalyst liquid is set to 100 parts by mass and the mass of peroxytitanic acid contained in the aforementioned photocatalyst liquid is converted into the mass of titanium oxide, the mass of anatase-type titanium oxide is added to the mass of peroxytitanic acid The total mass is 0.1 to 20 parts by mass, and the ratio of the mass of anatase-type titanium oxide to the mass of peroxytitanic acid is in the range of 1:0 to 1:2. Invention effect

The coating composite film containing anatase-type titanium oxide of the present invention is made of titanium raw material and hydrogen peroxide to make liquid A (peroxytitanic acid aqueous solution), and in the anatase titanium oxide dispersion liquid made by heating liquid A at 70 to 200°C Add precious metal as B solution, apply A solution on the interior surface and dry, then apply B solution and dry it. It is easy and inexpensive to manufacture. The heating temperature of A liquid is also much lower than that of sol-gel method or titanium oxide coating method.

In addition, the photocatalyst film of the present invention is characterized in that the raw materials of the primer liquid and the photocatalyst liquid are both water, and are produced below the boiling point of water. If the primer liquid and the photocatalyst liquid are sequentially coated and dried, the film can be formed. Therefore, it is easy to make.

Furthermore, in the present invention, by coating and drying the amorphous titanium oxide layer formed by liquid A, a high-density film with good film formability and adhesion to various substrates is formed, and it is compatible with the anatase type The anatase titanium oxide layer formed by the titanium oxide dispersion liquid (B solution) also has good adhesion, which makes up for the insufficient adhesion of the anatase titanium oxide layer, and shows a good primer for the active oxygen generated by the photocatalyst reaction The role.

Furthermore, the photocatalyst composite film of the present invention has a strong catalytic effect, and also has a photocatalytic effect by indoor light. In addition, when exposed to light, it exhibits the function of photochemically active catalyst, generates active oxygen, and has self-cleaning, antibacterial, antifungal, and antiviral activities, as well as deodorization and formaldehyde decomposition.

In addition, according to the first embodiment of the present invention, the anatase-type titanium oxide layer formed by adding precious metals to the solution B and drying after coating, exhibits a photochemically active catalyst function even if it is irradiated by visible light or weak light. , It produces active oxygen and has strong self-cleaning effect and strong antibacterial, antifungal and antiviral activity, and it also shows deodorant effect and formaldehyde decomposition effect. The precious metal contained in it still shows strong antibacterial, antifungal, and anti- Virus activity compensates for the weakness that photocatalyst cannot show activity in dark places, and shows the excellent characteristics of composite film for interior decoration.

In addition, according to the second embodiment of the present invention, reinforcing particles having an average particle diameter of 5 to 500 μm and a Mohs hardness of 5 or more are blended in an undercoat layer of amorphous titanium oxide excellent in film strength and adhesion to strengthen The recesses are formed between the particles to protect the photocatalyst layer, thereby improving the strength and wear resistance of the photocatalyst layer, and show the excellent characteristics of the coating composite film for exterior decoration. In addition, amorphous titanium oxide is added to the photocatalyst layer to further improve the strength and wear resistance of the photocatalyst layer.

Hereinafter, a composite film for coating containing anatase-type titanium oxide in an embodiment of the present invention and its manufacturing method will be described in detail. [Composite Film for Coating] The composite film for coating of the present invention containing anatase-type titanium oxide is the aqueous solution of peroxytitanic acid as A solution, and the anatase-type titanium oxide dispersion prepared by heating the A solution at 70 to 200°C is set as Liquid B and Liquid A are coated on the substrate and dried to form a primer layer with good film-forming properties and adhesion, so that the substrate and the photocatalyst layer are adhered and the substrate is protected by active oxygen. Coat the primer layer Liquid B is dried and has a photocatalyst layer containing anatase titanium oxide.

(Preparation of peroxytitanic acid aqueous solution) In the present invention, the peroxytitanic acid aqueous solution used as the A solution can be used in any method as long as it does not hinder the implementation of the present invention. As published in Japanese Patent Document 5, the aqueous solution containing the titanium raw material is added with more than the reaction equivalent of hydrogen hydroxide water, and then ammonia water is added to neutralize it, and the obtained yellow solution is left to precipitate the peroxytitanate. It is filtered and washed, suspended in water and added with hydrogen peroxide to obtain a yellow and transparent aqueous solution of peroxytitanic acid (liquid A). The dried liquid A is coated to form an amorphous solid having a peroxy group.

In addition, as disclosed in Japanese Patent Document 5, an aqueous titanium oxide gel produced by adding an alkaline component to an aqueous solution containing a titanium raw material can be used. Here, it is preferable to fully wash with water until the substance used to form the precipitate is not detected. If the substance used to form the precipitate remains, the produced peroxytitanic acid aqueous solution (A solution) and the anatase titanium oxide dispersion in the next stage will cause coagulation, resulting in the size of the titanium oxide particle size of the anatase titanium oxide dispersion If it becomes larger, the coating agent becomes unstable, and the adhesion or density may deteriorate. Hydrogen peroxide was added to the obtained titanium hydroxide gel and reacted overnight to obtain a yellow viscous liquid peroxytitanic acid aqueous solution (A solution). In addition, methods for producing various peroxytitanic acid aqueous solutions (A liquid) are published in Japanese Patent Document 7.

When the concentration of the peroxytitanic acid aqueous solution (A solution) is 100 parts by weight, the weight of peroxytitanic acid converted to titanium oxide is preferably 0.1 to 10 parts by weight. If the content of peroxytitanic acid converted to titanium oxide is less than 0.1 parts by weight, a sufficient thickness of the primer layer cannot be formed, and if the content of peroxytitanic acid is higher than 10 parts by weight, the viscosity of the aqueous solution of peroxytitanic acid will increase, making handling difficult.

The peroxytitanic acid aqueous solution (A solution) is coated and solidified to obtain a peroxytitanic acid layer. However, peroxy titanic acid (peroxy titanic acid), the molecular formula is TiO₃3H₂O, when heated, it will release oxygen and water and change into titanium oxide. In fact, peroxytitanic acid is an unstable compound, and it changes into amorphous titanium oxide by releasing oxygen and water over time at room temperature. The composite film for interior decoration of the present invention is not a peroxy titanic acid layer, but an amorphous titanium oxide layer in actual use.

(Preparation of anatase titanium oxide dispersion) Aqueous solution of peroxytitanic acid (A solution) at 70°C to 200°C for 1 to 40 hours, preferably at 80°C to 120°C for 3 to 30 hours, the best example Then, heat treatment is applied at 90°C to less than 100°C for 5 to 20 hours to prepare anatase titanium oxide dispersion. If the heating temperature is lower than 70°C, it takes too much time for the reaction. Heating to a temperature higher than 200°C will cause excessive and rapid reaction and make control difficult, and the equipment will only become larger without a symmetrical effect. As published in Japanese Patent Document 5, the X-ray analysis spectrum of a film formed by applying a solution heat-treated with an aqueous solution of peroxytitanic acid and curing it has a peak based on anatase titanium oxide.

[First Embodiment] The first embodiment of the present invention relates to a composite film for interior decoration containing a noble metal and anatase-type titanium oxide. Here, the so-called interior is not particularly limited as long as it is the equipment or components installed on the inner surface of the building, but for example, it may include walls, ceilings, floors, doors, partition panels, furniture, lighting fixtures, cooking Counter, bathroom, toilet, etc.

Generally speaking, the interiors of buildings are not exposed to harsh outdoor air conditions like the exteriors. The strength of the coating film is not so required, but a more beautiful degree. In addition, most of the materials are susceptible to active oxygen. Therefore, it is necessary to take countermeasures. Furthermore, the interior of the building is substantially not irradiated by ultraviolet rays, and the amount of visible light that is exposed to it is less than that of the exterior. Therefore, an anatase-type titanium oxide composite film with higher activity than conventional photocatalysts is required. In addition to the usual pollutants, the pollutants that should be treated in the interior include malodor, formaldehyde, cigarette smoke, etc. Therefore, there is a need for anti-active bacteria, especially strong anti-active bacteria in the dark.

However, the composite film-based peroxytitanic acid aqueous solution for interior decoration containing anatase titanium oxide of the present invention is set as liquid A, and noble metal is added to the anatase titanium oxide dispersion produced by heating the A liquid at 70°C to 200°C The solution is set to B solution, and the A solution is applied to the substrate on the interior surface and dried to form a primer layer with good film-forming and adhesive properties, so that the substrate and the photocatalyst layer are adhered and the substrate is protected by active oxygen. The upper coating B liquid is dried to form a composite film for interior decoration containing anatase titanium oxide and noble metal and has photocatalytic and sterilization effects.

The first embodiment of the present invention is characterized in that a noble metal salt or nanocolloid is added to the anatase-type titanium oxide dispersion liquid as the B liquid. The noble metal used preferably contains one or more selected from the group consisting of copper, silver, gold, and platinum, and more preferable examples include silver salt and platinum salt. These precious metals exhibit strong antibacterial, antifungal and antiviral activities.

(Preparation of peroxytitanic acid aqueous solution) In the present invention, the peroxytitanic acid aqueous solution used as liquid A can be used by any method as long as it does not hinder the implementation of the present invention. As published in Japanese Patent Document 5, in the aqueous solution containing the titanium raw material, more than the reaction equivalent of hydrogen hydroxide water is added, and then ammonia water is added to neutralize the obtained yellow solution to precipitate the peroxytitanate. Filter, wash, suspend in water and add hydrogen peroxide to obtain a yellow and transparent aqueous solution of peroxytitanic acid (liquid A). The coated and dried liquid A forms an amorphous solid with peroxy groups.

In addition, as published in Japanese Patent Document 5, the titanium hydroxide gel produced by adding an alkaline component to an aqueous solution containing a titanium raw material can be sufficiently washed with water until the substance used to form a precipitate is not detected. Substances used to form precipitates remain. The produced peroxytitanic acid aqueous solution (A solution) and the next stage anatase titanium oxide dispersion will cause coagulation, and the resulting anatase titanium oxide dispersion will have titanium oxide particles that change in size. If it is too large, the coating agent becomes unstable, and the adhesion or density may deteriorate. After adding hydrogen peroxide to the obtained titanium hydroxide gel and reacting overnight, a yellow viscous liquid peroxytitanic acid aqueous solution (liquid A) will be obtained. In addition, methods for producing various peroxytitanic acid aqueous solutions (A liquid) are published in Japanese Patent Document 7.

When the concentration of the peroxytitanic acid aqueous solution (A solution) is 100 parts by weight, the weight of peroxytitanic acid converted to titanium oxide is preferably 0.1 to 10 parts by weight. If the content of peroxytitanic acid converted to titanium oxide is less than 0.1 parts by weight, a sufficient thickness of the primer layer cannot be formed, and if the content of peroxytitanic acid is higher than 10 parts by weight, the viscosity of the aqueous solution of peroxytitanic acid will increase, making handling difficult.

(Preparation of anatase titanium oxide dispersion) Aqueous solution of peroxytitanic acid (A solution) at 70°C to 200°C for 40 to 2 hours, preferably at 80°C to 120°C for 3 to 30 hours, the best example Then, heat treatment is performed at 90°C to less than 100°C for 5 to 20 hours to prepare anatase-type titanium oxide dispersion. If the heating temperature is lower than 70°C, it is not good that the reaction takes too much time. Heating to higher than 200°C will cause excessive and rapid reaction and make handling difficult, and the equipment will only become larger without a symmetrical effect. As published in Japanese Patent Documents 3 and 4, the X-ray analysis spectrum of a film formed by applying a solution heat-treated with an aqueous solution of peroxytitanic acid and curing it has a peak based on anatase titanium oxide.

(Addition of noble metal salts or nanocolloids) The present invention is characterized in that a solution in which noble metal salts or nanocolloids are added to the anatase-type titanium oxide dispersion is set as B solution. The noble metal used preferably contains one or more selected from the group consisting of copper, silver, gold, and platinum, and more preferable examples include silver salt and platinum salt. These precious metals exhibit strong antibacterial, antifungal and antiviral activities.

The noble metal is the anion of the noble metal salt of the cation. The salt of strong acid includes hydrochloride, nitrate, perchlorate, sulfate, phosphate, tetrafluoroborate and hexafluorophosphate. In addition Examples of weak acid salts include acetate, formate, and carbonate, but they are not limited to these. In addition, the platinum salt may include Hexachloroplatinic acid, Tetrachloroplatinate, and salts of these. If the purpose of the present invention can be met, the noble metal nanocolloid can be any known noble metal nanocolloid.

The concentration of anatase titanium oxide in liquid B. When the weight of liquid B is set to 100 parts by weight, the weight of titanium oxide is preferably 0.1 to 10 parts by weight. If the weight of titanium oxide is less than 0.1 parts by weight, it is difficult to form a sufficient thickness. If the photocatalyst film is higher than 10 parts by weight, the viscosity of anatase-type titanium oxide increases, making handling difficult.

When the weight of the precious metal salt or nanocolloid is converted to the weight of the metal, and the B solution is set to 100 parts by weight, the concentration of the precious metal salt or nanocolloid in the B solution is 1×10^－⁴To 1×10^－⁹It is preferably within the range of parts by weight. The amount of precious metals is less than 1×10^－⁹The concentration of parts by weight may not show sufficient antibacterial activity, and adding more than 1×10^－⁴Parts by weight, compared to the increased amount, the effect is not relatively enhanced. Here, when the weight of the noble metal salt or nanocolloid is converted into the weight of the metal, and the weight of the aforementioned anatase-type titanium oxide is 100 parts by weight, the content of the noble metal salt or nanocolloid is 1× 10^－¹To 1×10^－⁸Within the range of parts by weight.

(Process of coating peroxytitanic acid aqueous solution (A solution) and drying) The coating method of the process of applying peroxytitanic acid aqueous solution (A solution) and drying can be any method as long as it can achieve the purpose of the present invention. The coating amount is not particularly limited, but it can be 1.0 to 100ml/m². Less than 1.0 to 100ml/m²There may be cases where the thickness of the peroxy titanic acid film is insufficient, even if the coating thickness is higher than 1.0 to 100 ml/m²The effect is not relatively increased, so it is not good. The coating can be carried out once or divided into multiple times. In addition, if the drying temperature is higher than 70°C, the peroxytitanic acid will change into anatase crystals. For example, the drying temperature is lower than 40°C.

The coating method of the process in which the coating B liquid is dried can be any method if it can achieve the purpose of the invention. The coating amount is not particularly limited, but it can be 1.0 to 100ml/m². Less than 1.0 to 100ml/m², When used in interior walls, the thickness of anatase titanium oxide may be insufficient, even if the coating thickness is higher than 1.0 to 100ml/m²The effect has not increased relatively, so it is not good. The coating can be carried out once or divided into several times. In addition, drying is preferably performed at less than 60°C.

The ratio of liquid A to liquid B is preferably such that the weight of peroxytitanic acid contained in liquid A is converted to the weight of titanium oxide and the ratio of the weight of titanic acid contained in liquid B is 10:1 to 1:10 The range is more preferably in the range of 4:1 to 1:4. If liquid B is lower than 1/10 of liquid A, the anatase titanium oxide film cannot exhibit sufficient activity as a photoactive catalyst. In addition, when liquid A is lower than 1/10 of liquid B, the peroxytitanic acid film cannot The active oxygen generated by the titanium oxide film exhibits a sufficient coating effect and cannot exhibit the characteristics of a composite film.

[Second Embodiment] The inventor found that during the durability test of the prototype, even the prototype of the photocatalyst layer with insufficient strength and adhesion during the development of the test was applied to the photocatalyst layer on a substrate with a rough surface. , It still has better wear resistance than the photocatalyst layer coated on a smooth surface. Inspired by this, when trial-produced a photocatalyst composite film with a primer layer with a rough surface, it was found that the wear resistance was higher than expected.

Figure 1 is a schematic cross-sectional view of the photocatalyst composite film of the present invention, Figure 1(a) is a view of the photocatalyst composite film just after coating, and Figure 1(b) is a view showing a state where a part of the convex part of the photocatalyst composite film is worn and peeled , Figure 2 is a plan view showing the state of Figure 1(b). As shown in Fig. 1(a), the photocatalyst composite film 10 of the present invention is formed by coating and drying a primer layer 2 containing reinforcing particles 3 on a substrate 6, and then coating and drying the photocatalyst layer 1.

The photocatalyst composite film 10 is a thin film whose wear continues to expand. As shown in Figure 1(b), it becomes a local loss of the photocatalyst layer 1 on the top of the convex portion 4 and the undercoat layer 2 is exposed to form the photocatalyst composite of the exposed portion 7.membrane20. Film 20. However, as shown in FIG. 2, the area ratio of the exposed portion 7 of the photocatalyst composite film 20 is small, and the active oxygen diffuses and moves, so it is presumed that the contaminants in the exposed portion 7 can also be decomposed.

The inventor of the present invention estimated that when the state shown in FIG. 1(b) is reached, the convex portion 4 formed by solid particles and amorphous titanium oxide protects the anatase-type titanium oxide in the concave portion 5, so the photocatalyst composite film 20 The further expansion of the wear and tear was delayed, and it was conceived to mix reinforcing particles 3 in the undercoat layer 2 to form a rough surface on the undercoat layer 2, leading to the completion of the present invention. Generally, in order to form a rough surface primer layer, a new process must be added. However, the advantage of the present invention is that since the primer layer 2 is already provided, only reinforcing particles 3 need to be added, so there is no need to increase the number of processes.

Hereinafter, the photocatalyst composite film of the second embodiment and its manufacturing method will be described. The photocatalyst composite film 10 of the present invention has an undercoat layer 2 containing amorphous titanium oxide and reinforcing particles 3 and a photocatalyst layer 1 containing anatase type titanium oxide coated on the undercoat layer 2.

The reinforcing particles 3 used in the present invention have an average particle diameter (JIS Z 8901:2006 2006 3.1) of 5 to 500 μm, a Mohs hardness of 5 or more, and a rough surface can be formed on the primer layer 2. be usable. Examples of desirable reinforcing particles include one or more of natural minerals containing feldspar and silica, and inorganic powders containing silica, alumina or titanium dioxide. The reinforcing particles of the present invention are not limited to these. The shape of the reinforcing particles is not particularly limited as long as it can form a rough surface on the primer layer 2, and particles of any shape can be used.

The size of the reinforcing particles 3 preferably has an average particle diameter in the range of 5 to 500 μm, more preferably 10 to 300 μm, and most preferably 15 to 200 μm. For particles with an average particle size of less than 5μm, the size of the formed protrusion 4 is too small to adequately protect the photocatalyst layer 1, and for particles with an average particle size of more than 5μm, there will be a strong adhesion to the substrate 6 by the primer layer 2 Difficulty, causing the reinforcing particles 3 to peel off. The content of the reinforcing particles 3 is preferably when the mass of the amorphous titanium oxide forming the primer layer 2 is set to 100 parts by mass, and the mass of the reinforcing particles 3 is 1 to 100 parts by mass, more preferably 2 to 50 parts by mass , The best is 5 to 20 parts by mass. If the mass of the reinforcing particles 3 is less than 1 part by mass, sufficient protrusions 4 cannot be formed, and if the mass of the reinforcing particles 3 exceeds 100 parts by mass, the area of the protected recesses becomes smaller, which is not preferable.

The photocatalyst composite film of the present invention is a thin film formed on a rough surface, so it is difficult to actually measure the film thickness and coating amount of the coating film. Therefore, in the embodiments of the present invention, the coating amount is based on the titanium oxide (TiO₂, Calculated by the molar mass of 80) or the mass of peroxytitanic acid converted to the mass of titanium oxide (hereinafter, "converted to TiO₂"Quality" description) to calculate.

Converted TiO coated on the undercoat layer 2 of the present invention₂Mass, preferably 0.1 to 100g/m², More preferably 0.2 to 50g/m², The best is 0.5 to 20g/m². The aforementioned conversion TiO of the undercoat layer 2₂The mass is less than 0.1 g/m², Unable to exert sufficient adhesion and/or barrier function of active oxygen, even if it exceeds 100g/m²The thickness is not expected to increase the adhesion and/or the barrier function of active oxygen, which is not economically good.

The coating amount of titanium oxide of the photocatalyst layer 1 of the present invention is preferably 0.1 to 50 g/m², More preferably 0.2 to 20g/m², The best is 1 to 10g/m². When the titanium oxide coating amount of the photocatalyst layer 1 is less than 0.1 g/m²At this time, sufficient photocatalyst activity cannot be displayed and it is easy to wear out. The coating amount of titanium oxide on the photocatalyst layer 1, even if the coating amount exceeds 50g/m², The activity and strength of the photocatalyst still increase very little, and the economy is not good.

In addition, in the present invention, an amorphous titanium oxide film can be prepared in the photocatalyst layer 1 to increase the strength of the photocatalyst composite film 10. Furthermore, the coating amount of the photocatalyst layer 1 of the other examples is when the mass of the amorphous titanium oxide and the mass of the anatase titanium oxide are added together (hereinafter, the total TiO₂Mass" description), preferably 0.1 to 50g/m², More preferably 0.2 to 20g/m², The best is 1 to 10g/m². "Convert and add TiO₂Mass" less than 0.1 g/m²When the photocatalyst cannot show enough activity, it is easy to wear out, even if it exceeds 50g/m², The photocatalyst activity and strength increase very little, and the economy is not good. In addition, the ratio of the mass of the anatase titanium oxide contained in the photocatalyst liquid to the mass of the amorphous titanium oxide film is preferably in the range of 1:0 to 1:2 (except for 0), and more preferably 4:1 to 2:3, preferably 3:2 to 1:1. The mass ratio of the amorphous titanium oxide film to the anatase titanium oxide exceeds 1:2, and the photocatalyst activity of the photocatalyst composite film is not well reduced.

When the finished product of the present invention is coated on a glossy outer wall surface, the finished product of the present invention does not substantially absorb visible light, so when the average particle size of the reinforcing particles 3 contained in the primer layer is small, it is applied to the outer surface. The luster of the base material of the wall is rarely damaged. However, as the average particle diameter of the reinforcing particles 3 becomes larger, it has a brightening effect caused by irregular reflection.

(Manufacturing method) Hereinafter, the manufacturing method of the photocatalyst composite film of the 2nd Embodiment of this invention is demonstrated. The photocatalyst composite film 10 of the first embodiment of the present invention may have a peroxy titanic acid aqueous solution process, which is a process of making a peroxy titanic acid aqueous solution and a primer solution from a titanium raw material, which is a process of making a peroxy titanic acid aqueous solution and strengthening The process of forming the primer liquid and the primer layer of the particles 3 is to coat the primer liquid on the surface of the substrate 6 and dry to form the primer layer 2. The photocatalyst liquid and the photocatalyst layer forming process of the titanium-type titanium oxide dispersion liquid are formed by coating the photocatalyst liquid on the undercoat layer 2 and drying to form the photocatalyst layer 1. In addition, when the photocatalyst composite film is used in a very severe environment, an aqueous solution of peroxytitanic acid can be added to the anatase-type titanium oxide dispersion to further strengthen the photocatalyst layer 1.

<Production Process of Peroxytitanic Acid Aqueous Solution> The same as in the first embodiment.

<Preparation process of primer solution> The reinforcing particles 3 having an average particle diameter of 5 to 500 μm and a Mohs hardness of 5 or more are added to the aqueous solution of peroxytitanic acid to prepare a primer solution. The amount of the reinforcing particles 3 contained in the primer solution is preferably 0.01 to 20 parts by mass, more preferably 0.02 to 10 parts by mass when the mass of the peroxytitanic acid aqueous solution is set to 100 parts by mass. When the content of the reinforcing particles 3 is less than 0.01 parts by mass, it is impossible to form a surface with sufficient roughness on the primer layer 2, and when it exceeds 20 parts by mass, the fluidity of the primer liquid may decrease, making coating difficult or difficult. / And the case where the content of the reinforcing particles 3 is relatively increased and the strength of the undercoat layer 2 is reduced.

<Undercoat layer forming process> A predetermined amount of undercoat liquid is applied to form an undercoat layer. The undercoat layer initially forms a layer of peroxytitanic acid, but over time it releases oxygen and water and changes to a layer of amorphous titanium oxide. The method of applying the primer liquid can be any method if it can achieve the purpose of the invention, and it can be applied once or divided into several times. In addition, if the drying temperature is higher than 70°C, the peroxytitanic acid gradually changes into anatase crystals, and the strength and adhesion are lowered. Therefore, it is better to proceed at lower than 40°C.

The coating amount of the primer liquid is based on the peroxy titanic acid contained in the primer liquid.₂Mass" is 0.1 to 500g/m²The way of coating is better. "Convert TiO₂Mass" less than 0.1g/m²Then, a sufficient primer layer 2 cannot be formed, the adhesion with the photocatalyst layer 1 cannot be sufficiently strengthened, and the active oxygen cannot be sufficiently blocked from the substrate 6 generated by the photocatalyst. In addition, even if the coating is "converted to TiO₂Mass" more than 500g/m²The amount of coating, the cost and labor of coating increase, but the effect is not relatively increased, so it is not good.

<Process of photocatalyst solution> The aqueous solution of peroxytitanic acid can be heated at 70°C to 200°C for 0.2 to 40 hours, preferably at 80°C to 120°C for 3 to 30 hours, and the best example is at 90°C to 200°C. Heat treatment at 100°C for 1 to 20 hours to produce a photocatalyst solution containing anatase titanium oxide. If the heating temperature is less than 70°C, the reaction will take too much time, which is not good. Heating above 200°C will make it difficult to react too quickly, and an autoclave is necessary, but the equipment becomes larger and the relative effect cannot be achieved.

The anatase-type titanium oxide concentration of the photocatalyst liquid is preferably 0.1 to 20 parts by mass, and more preferably 0.5 to 10 parts by mass when the mass of the photocatalyst liquid is 100 parts by mass. If the mass of titanium oxide is less than 0.1 parts by mass, it is difficult to form a photocatalyst film with a sufficient thickness. If the mass of titanium oxide exceeds 20 parts by mass, the viscosity of anatase-type titanium oxide may increase, which may make handling difficult. The X-ray analysis spectrum of a film formed by applying a solution heat-treated with an aqueous solution of peroxytitanic acid and curing it has a peak based on anatase-type titanium oxide, as disclosed in Japanese Patent Documents 1 and 2.

<Photocatalyst layer formation process> The photocatalyst liquid is coated on the undercoat layer and dried to form a photocatalyst layer. The coating method can be any method if it can achieve the purpose of the present invention. The coating may be performed once or divided into multiple times. The drying method is not particularly limited, but it is preferably performed at less than 60°C. The coating amount of the photocatalyst layer 1 of the present invention is preferably that the amount of anatase titanium oxide is 0.1 to 250 g/m². The coating amount of the photocatalyst layer 1 is less than 0.1g/m²In the case of insufficient thickness, the photocatalyst layer cannot be formed, even if the coating exceeds 250g/m², The cost and labor of coating increase, and the relative increase in photocatalyst activity and strength is small, which is not good.

In addition, the photocatalyst layer 1 of the present invention may also contain an amorphous titanium oxide film. In the photocatalyst solution of other embodiments, when the mass of the photocatalyst solution is set to 100 parts by mass, the mass of anatase-type titanium oxide and the "converted TiO" of peroxytitanic acid₂The total mass of "mass" is preferably 0.1 to 20 parts by mass, and more preferably 0.5 to 5 parts by mass. When the aforementioned total mass is less than 0.1 parts by mass, a sufficient thickness of the primer layer cannot be formed, and when it exceeds 20 parts by mass , The viscosity of the photocatalyst liquid increases and it becomes difficult to handle.

The coating amount of the catalyst layer 1 of this embodiment is "converted and added to TiO₂Mass" is 0.1 to 250g/m²Better. When "converted and added TiO₂Mass" less than 0.1g/m²When the photocatalyst layer of sufficient thickness cannot be formed, the coating exceeds 250g/m², The cost and labor of coating increase, and the relative increase in photocatalyst activity and strength is small, which is not good. In addition, the mass of anatase titanium oxide contained in the photocatalyst liquid is₂The ratio of "quality" is preferably in the range of 1:0 to 1:2, more preferably 4:1 to 2:3, and most preferably 3:2 to 1:1. Example

Hereinafter, the present invention will be described in detail with examples. [Example 1] <The first process> Preparation of peroxytitanic acid aqueous solution (A solution) 39.6ml of 60% (weight/volume) titanium tetrachloride aqueous solution diluted with distilled water to 4000ml of solution was dropped into 2.5% (weight/volume) ) 440ml of ammonia water to precipitate water titanium oxide. After filtering the precipitate and washing with distilled water, add distilled water to 720ml of aqueous titanium oxide suspension, add 30% (weight/volume) of hydrogen peroxide 80ml and stir. Leave it at 7°C for 24 hours to decompose excess hydrogen peroxide to obtain 1000 ml of yellow viscous liquid.

<Second process> Preparation of liquid B. When the peroxytitanic acid aqueous solution obtained in the first process is sealed in a pressure-resistant glass container and boiled in a water bath for 12 hours (98 to 100°C), a light yellow translucent is produced 1.00% (weight/volume) of anatase titanium oxide dispersion. For 100ml of 1.00% (weight/volume) anatase-type titanium oxide dispersion, add 0.1ml of silver nitrate aqueous solution containing 0.1% (weight/volume) of silver as metallic silver to make 1×10^－⁶% (Weight/volume) Ag-containing liquid B after mixing.

<3rd process> A process in which an aqueous solution of peroxytitanic acid (A liquid) is applied to the interior surface and dried. The aqueous solution of peroxytitanic acid (A liquid) produced in the first process is 10ml/m²The amount was coated on a glass slide with a sprayer and dried at 25°C to form a peroxy titanic acid layer.

<The 4th process> The process of applying liquid B and drying it on the dried glass slide made by the third process, and 10ml/m of the liquid B produced by the second process.²The amount was dried at 40°C to obtain a sample coated with anatase-type titanium oxide-containing composite film for interior decoration according to the first embodiment of Example 1.

[Example 2] <The first process> Preparation of A solution of 60% (weight/volume) titanium tetrachloride aqueous solution 5.00ml diluted with distilled water to 500ml solution was added 30% (weight/volume) hydrogen peroxide 20ml and stirred to make a brown Transparent liquid, 10% ammonia water (1 part by volume of concentrated ammonia water: 9 parts by volume of water) was dropped into the solution and the pH value was 7, to make a yellow transparent solution. The obtained solution was left at 25°C for a whole day and night, resulting in a yellow precipitate. After filtering the precipitate and washing, add distilled water to make about 150ml, put in 25g each of cation exchange resin (amberlite IR-120B, H type) and anion exchange resin (amberlite IRA-410, OH type) for 30 minutes. After filtering and removing the ion exchange resin, distilled water was used to make 180 ml, cooled with ice water, and 20 ml of 30% (weight/volume) hydrogen peroxide was added for cooling. In this way, 200 ml of a transparent yellow liquid A liquid was obtained after 1 hour. The second process to the fourth process were performed in the same manner as in Example 1, and the sample of Example 2 coated with the composite film for interior decoration containing anatase-type titanium oxide was obtained.

[Example 3] <1st process> Preparation of A solution The same method as in Example 1 was used to obtain A solution. <Second process> Preparation of liquid B. When the peroxytitanic acid aqueous solution obtained in the first process is sealed in a pressure-resistant glass container and boiled in a water bath for 12 hours (98 to 100°C), a light yellow translucent is produced 1.00% (weight/volume) of anatase titanium oxide dispersion. For 100ml of anatase-type titanium oxide dispersion of 1.00% (weight/volume), 0.1ml of an aqueous solution containing 0.001% (weight/volume) of platinum nanocolloid (refer to Japanese Patent Document 8) as metallic platinum is added to make it contain Metal Platinum 1×10^－⁸(Weight/volume) 1.00% (weight/volume) solution B of platinum nanocolloid. The third process and the fourth process were performed in the same manner as in Example 1, and the sample of Example 3 coated with the composite film for interior decoration containing anatase-type titanium oxide was obtained.

[Comparative Example 1] 10ml/m of liquid B obtained in the second process of Example 1²The amount was coated on a glass slide, dried at 40° C., and heat-treated to obtain a sample coated with the anatase-type titanium oxide composite layer of Comparative Example 1.

[Comparative Example 2] 10ml/m of the aqueous solution (liquid A) obtained in the first process of Example 1²The amount was coated on a glass slide and dried at 40° C. to obtain a sample coated with the anatase-type titanium oxide composite film of Comparative Example 2 in this way.

[Comparative Example 3] As in Example 1, except that silver nitrate was not added in the second process, a sample coated with an anatase-type titanium oxide composite film was obtained.

[Example 4] <The first process> Preparation of the primer solution, 39.6ml of titanium tetrachloride 60% (weight/volume) aqueous solution diluted with distilled water to 4000ml of solution, drop 2.5% (weight/volume) ammonia water 440ml to make Water titanium oxide precipitates. After filtering the precipitate and washing it with distilled water, add distilled water to a 720 ml aqueous titanium oxide suspension, and add 80 ml of 30% (weight/volume) hydrogen peroxide and stir. After leaving it at 7°C for 24 hours to decompose excess hydrogen peroxide, water was added to obtain 1.00 kg of a yellow viscous aqueous solution of peroxytitanic acid. The "calculated mass of titanium" of the peroxytitanic acid in 100 parts by mass of the peroxytitanic acid aqueous solution was 1.00 part by mass. 0.1 parts by mass of silicon powder having an average particle diameter of 20 μm was added to 100 parts by mass of the aqueous solution of peroxytitanic acid , and stirred to obtain a primer liquid.

<Second process> In the process of primer coating, the primer liquid produced in the first process is stirred at the same time, and the sprayer is used to spray 20g/m on the other side.²Coated on the melamine decorative plywood and dried at 25°C to make a rough base coat. The mass of silica when the "mass of peroxytitanic acid in the undercoat layer" is set to 100 parts by mass is 10 parts by mass.

<3rd process> Process of photocatalyst The peroxytitanic acid aqueous solution obtained in the first process is sealed in a pressure-resistant glass container and boiled in a water bath for 12 hours (98 to 100°C), and a light yellow translucent is obtained Photocatalyst liquid. When the mass of the photocatalyst liquid is set to 100 parts by mass, the mass of anatase-type titanium oxide is 1.0 part by mass.

<4th process> The photocatalyst composite film process uses 10ml/m of the photocatalyst liquid produced in the third process²The amount of was coated on the undercoat layer obtained in the second process and dried at 40° C. to obtain the sample of Example 1 coated with the photocatalyst composite film containing anatase titanium oxide of Example 1. The coating amount of anatase titanium oxide in the photocatalyst layer of the prepared sample is 1.0g/m² 。

[Example 5] The same as Example 1, except that in the fourth process, the primer solution obtained in the first process of Example 1 and the photocatalyst solution obtained in the third process were 1:1 (mass, strengthening particles 3 The quality is too small, so ignored), mixed, coated on the primer layer obtained in the second process and dried to produce the photocatalyst composite film of Example 2.

[Comparative Example 4] As in Example 1, except that no reinforcing particles were added to the undercoat layer, a photocatalyst composite film of Comparative Example 1 without a rough surface was produced. [Comparative Example 5] In the same manner as in Example 5, the photocatalyst composite film of Comparative Example 2 in which the photocatalyst layer contains amorphous titanium oxide without the rough surface without adding reinforcing particles was produced.

[Comparative Example 6] Coating only 10ml/m on the melamine decorative plywood²The photocatalyst liquid can be dried. [Comparative Example 7] Only the primer liquid was applied to the melamine decorative plywood and dried to form a primer layer.

[Test Example 1] Nitrogen Oxide Removal Test Sample: Test Pieces of Examples 1 to 3 and Comparative Examples 1 and 2, and Glass Piece Test Method: JIS R 1701-1: 2004, Air Purification Performance of Fine Ceramics-Photocatalyst Materials Test method-Part 1: Nitrogen oxide removal performance 6. 1, 6. 2 Test unit: Japan Environmental Technology Research Institute (Co., Ltd.)

Table 1 shows the measurement results of the samples of Examples 1 to 3 and Comparative Examples of the first embodiment. Examples 1 to 3, which have a photocatalyst layer and a primer layer, show an excellent nitrogen oxide removal effect. Although Comparative Example 1 had a photocatalyst layer of anatase-type titanium oxide, the film-forming properties were poor, and therefore, the nitrogen oxide removal effect was inferior to those of Examples 1 to 3. Comparative Example 2 without a photocatalyst layer and the glass sheet do not have the effect of removing nitrogen oxides. Table 1<tables><img wi="240" he="324" file="tw201800238a_d0001.tif" img-content="drawing" img-format="jpg" orientation="portrait" inline="no" /></tables>: Yes ×: No

Table 2 shows the measurement results of the samples of Examples 4 and 5 and Comparative Examples 4 to 7 of the second embodiment. As shown in Example 4 of Table 2, the photocatalyst function (NO removal effect) exhibited by the photocatalyst composite film of the second embodiment of the present invention is compared with that of the conventional photocatalyst composite film shown in Comparative Example 4. The photocatalyst composite film containing amorphous titanium oxide shown in Example 5 is equivalent to the sample having only the photocatalyst layer shown in Comparative Example 6. In another embodiment of the present invention, in the photocatalyst composite film of the sample containing the primer liquid in the photocatalyst layer of the example, the function of the photoactive catalyst is reduced. Table 2<tables><img wi="292" he="316" file="tw201800238a_d0002.tif" img-content="drawing" img-format="jpg" orientation="portrait" inline="no" /></tables>

[Test Example 2] Active oxygen barrier test sample: 0.1 mol of methylene blue (methylene blue) ethanol solution was sprayed evenly on a 10 cm×10 cm surface ground wood chip to make an active oxygen barrier test piece. According to the methods of Examples 1 to 3 and Comparative Examples 1 and 2, but instead of the glass sheet, the above-mentioned active oxygen blocking test piece was used to make the sample for the active oxygen blocking test, and the sample was dried at 25°C for 2 days in the dark . Test method 1. Make a standard color film coated with 0.1 mol methylene blue and its 2 times and 4 times diluted solutions. 2. Instead of the glass sheet, use the above-mentioned active oxygen blocking test sheet. 10cm away from the sample, irradiate it with a fluorescent lamp with an illuminance of 5000 lux. Observe the hue change of the test sheet and evaluate it with the following 5 levels. 4: No change 3: Become the same hue as the standard hue diluted by 2 times 2: Become the hue equal to the standard hue diluted by 4 times 1: Blue almost disappeared 0: Blue completely disappeared

Table 3 shows the measurement results of the samples of Examples 1 to 3 and Comparative Examples of the first embodiment. Comparative Example 1 with a catalyst layer but no primer layer shows that the methylene blue fades quickly and the active oxygen does not reach the substrate. Examples 1 to 3 with a catalyst layer and a primer layer show that the fading speed of methylene blue is slow, and the primer layer prevents the active oxygen from attacking. table 3<tables><img wi="316" he="318" file="tw201800238a_d0003.tif" img-content="drawing" img-format="jpg" orientation="portrait" inline="no" /></tables>: Yes ×: No

Table 4 shows the measurement results of the samples of Examples 4 to 6 and Comparative Examples of the second embodiment. The samples of Examples 4 to 6 all showed excellent active oxygen attack prevention effects. Table 4<tables><img wi="316" he="318" file="tw201800238a_d0004.tif" img-content="drawing" img-format="jpg" orientation="portrait" inline="no" /></tables>: Yes ×: No

[Test Example 3] Antibacterial test sample: Test pieces of Examples 1, 3 and Comparative Example 3 Test unit: Kyoto Institute of Microbiology, Japan Test method: Light irradiation film adhesion method (bright condition, dark condition) Test strain :According to Staphylococcus aurens NBRC-12732 "Light-irradiated film adhesion method of the Antimicrobial Technology Council", the bacteria liquid in the bacterial liquid dropped on the fluorescent lamp irradiation (550lx, 10cm)/non-irradiation test piece is measured after 24 hours. Bacteria count.

Results: The results are shown in Table 5. The test piece of Example 1 containing the catalyst layer, the primer layer and the noble metal has antibacterial activity regardless of the light and dark conditions, but the test pieces of Comparative Examples 1 and 3 that do not contain noble metal have the antibacterial activity under the light condition , But did not show antibacterial activity under dark conditions. table 5<tables><img wi="397" he="238" file="tw201800238a_d0005.tif" img-content="drawing" img-format="jpg" orientation="portrait" inline="no" /></tables>

[Abrasion resistance test] Preparation of test piece Use melamine decorative plywood with a thickness of 1.5mm as the base material. It is the same as Example 1, except that 0.01 parts by mass of red pigment is added to 100 parts by mass of the photocatalyst liquid in the second process. The red photocatalyst layer is made, and after coating and drying, it is punched with a circular punch for abrasion resistance test. (Measurement of wear resistance) Abrasion resistance test was conducted based on JIS K 5600 (wear ring), but the film was too thin to measure the correct amount of change in mass, so the red emission from the scanning part of the wear ring was measured The number of rotations of the wear ring until the powder of the photocatalyst layer cannot be seen in red. The test is performed 10 times and the arithmetic average of the measured values is performed, rounding up to the nearest decimal point.

For Examples 4 and 5 and Comparative Examples 1 to 4 of the second embodiment of the present invention, a nitrogen oxide removal test was performed. The results are shown in Table 6. Table 6<tables><img wi="300" he="314" file="tw201800238a_d0006.tif" img-content="drawing" img-format="jpg" orientation="portrait" inline="no" /></tables>

(Review of the average particle size of the reinforced particles) &lt;Examples 6 to 9&gt; The same as in Example 1, except that as shown in Table 2, the average particle size of the silica contained in the undercoat layer was changed to produce examples 4 to 6 Photocatalyst composite film. &lt;Comparative Examples 8, 9&gt; The same as in Example 1, except that as shown in Table 2, the average particle size of the silica contained in the primer layer was changed to produce the photocatalyst composite films of Comparative Examples 5 and 6.

For Examples 4, 6 to 9 and Comparative Examples 8, 9 abrasion resistance test and nitrogen oxide removal test were performed. The results are shown in Table 7. Table 7<tables><img wi="280" he="366" file="tw201800238a_d0007.tif" img-content="drawing" img-format="jpg" orientation="portrait" inline="no" /></tables>

As shown in Table 7, if the average particle size of the reinforced particles in Comparative Example 8 is 1 μm, the abrasion resistance cannot be sufficiently enhanced. However, as shown in Examples 4, 6 to 9, if the average particle size of the reinforced particles is 5 to 500 μm If it is, it shows obvious abrasion resistance strengthening effect. In addition, when the particle size of the reinforcing particles is 1000 μm (Comparative Example 9), the reinforcing particles fall off and the wear resistance is reduced.

(Review of the amount of reinforced particles) &lt;Examples 10 to 12&gt; The same as in Example 1, except that as shown in Table 3, the amount of silica contained in the undercoat layer was changed to produce the photocatalyst composite films of Examples 7 to 9. &lt;Comparative Examples 10 and 11&gt; The same as in Example 1, except that as shown in Table 3, the amount of silica contained in the undercoat layer was changed to produce the photocatalyst composite films of Comparative Examples 7 and 8.

For Examples 7 to 9 and Comparative Examples 7 and 8, the abrasion resistance test and the nitrogen oxide removal test were performed. The results are shown in Table 3. Table 8<tables><img wi="294" he="220" file="tw201800238a_d0008.tif" img-content="drawing" img-format="jpg" orientation="portrait" inline="no" /></tables>

As shown in Table 8, when the mass of the primer layer is set to 100 parts by mass, and the mass of the reinforcing particles is less than 0.5 parts by mass (Comparative Example 10), the reinforcing effect of sufficient abrasion resistance does not appear. 1. As shown in 10 to 12, if more than 1 to 100 parts by mass of reinforcing particles are added, a significant abrasion resistance strengthening effect appears. However, if the amount of the reinforcing particles exceeds 200 parts by mass (Comparative Example 11), the reinforcing particles are not sufficiently fixed, and the abrasion resistance test cannot be performed. Even if it is 100 parts by mass, too large reinforcing particles cannot be sufficiently fixed, but it is judged that reinforcing particles with a small average particle diameter or reinforcing particles with a mixture of large and small diameters can be used when there are few aggregation voids.

<p>1Photocatalyst layer</p><p>2Undercoating</p><p>3Enhanced particles</p><p>4Protrusion</p><p>5Concave</p><p>6Substrate</p><p>7Exposed part</p><p>10Photocatalyst composite film</p><p>20Photocatalyst composite film (partial wear)</p>

Figure 1 is a schematic cross-sectional view of the photocatalyst composite film of the present invention. Figure 1(a) is a view just after the photocatalyst composite film is coated, and Figure 1(b) is a view showing a state where a part of the protruding part of the photocatalyst composite film is worn and peeled . Fig. 2 is a plan view showing the state of Fig. 1(b).

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