JP2018059002A - Photocatalytic composite coating film that transmits visible light and blocks ultraviolet and infrared light, and production method thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a composite coating film that blocks ultraviolet and infrared light and transmits visible light and has photocatalytic activity.SOLUTION: A photocatalytic composite coating film includes: an undercoat layer 2 that contains a fine particle powder of peroxotitanic acid and an infrared blocking agent formed on a substrate 3; and a photocatalytic layer 1 containing anatase-type titanium oxide formed on the undercoat layer. In the photocatalytic composite coating film, the infrared blocking agent is at least one kind selected from antimony oxide, tin oxide, indium oxide, gallium oxide, indium oxide, zinc oxide, titanium oxide, niobium oxide and fluorine.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a photocatalyst composite coating film that transmits visible light and shields ultraviolet rays and infrared rays, and a manufacturing method thereof, and more specifically, contains inorganic compound fine particles that are applied to a substrate surface and shields infrared rays, and peroxotitanic acid. A photocatalyst comprising an undercoat layer and a photocatalyst layer formed on the undercoat layer and containing anatase-type titanium oxide that absorbs and shields ultraviolet rays to generate active oxygen, and transmits visible light and shields ultraviolet rays and infrared rays. The present invention relates to a composite coating film and a method for producing the same.

  Sunlight is a valuable resource that supports all life on the earth, but the energy of visible light is only 45% of solar energy, including 50% infrared and 5% ultraviolet. Infrared rays are heat rays that warm the earth, but in some cases the temperature can rise excessively, and ultraviolet rays can damage and tan the skin, causing skin cancer. Has the problem of being.

  On the other hand, normal glass transmits not only visible light but also infrared light and ultraviolet light. Therefore, excessive infrared light and ultraviolet light irradiation is applied not only to window glass of buildings but also to window glass windows of vehicles such as automobiles and trains. May cause serious problems. For this reason, it is desired to give the glass a function of transmitting only visible light and shielding ultraviolet rays and infrared rays.

As a method for shielding infrared rays and ultraviolet rays while transmitting visible light in sunlight, a transparent film having a function of shielding infrared rays and ultraviolet rays on the glass itself or having a function of shielding infrared rays and ultraviolet rays on the glass. It is conceivable to apply a transparent paint or the like.
However, glass having a function of shielding infrared rays and ultraviolet rays is expensive and difficult to apply to existing buildings.

  Conventionally, zinc oxide and titanium oxide have been used as sun creams as infrared shielding agents for shielding infrared rays. It is also known that metal oxides such as antimony oxide, tin oxide, indium oxide, gallium oxide, iridium oxide, and zinc oxide have an infrared shielding effect. Among them, it is disclosed that compositions such as indium-doped tin oxide, antimony-doped tin oxide, gallium-doped zinc oxide, and fluorine-doped tin oxide exhibit excellent properties (see, for example, cited document 1).

  On the other hand, as an ultraviolet shielding material, many organic compounds have been disclosed in the fields of cosmetic sunscreen and dye / photosensitive material (see, for example, Patent Document 2). However, considering the usage environment of window glass that is exposed to direct sunlight for several years, organic compounds have problems with stability.

  By the way, an anatase type titanium oxide is an inorganic substance having an ultraviolet shielding effect. Anatase-type titanium oxide has a photocatalytic function of absorbing light having energy larger than its band gap and converting oxygen to active oxygen, and exhibits various effects based on the strong oxidizing power of the generated active oxygen. For example, it is known that the photocatalytic film exhibits a self-cleaning action when applied to and formed on the outer wall of a building or the outer surface of a window glass, and exhibits a deodorizing, sterilizing, and air-cleaning action when used on the inner face.

  However, the commercially available “nano-sized titanium oxide powder” has a primary particle size of nanoscale, but the secondary particle is a powder in which thousands of primary particles are associated and has a large particle size. Many of these have problems with visible light transmission. Furthermore, since the active oxygen generated by the photocatalyst oxidizes and decomposes the polymer resin that is the base material of the film or paint, there is a problem that anatase-type titanium oxide cannot be added to the paint or film.

Here, Patent Document 3 discloses a composition comprising anatase-type titanium oxide, an inorganic oxide containing antimony-doped tin oxide, an inorganic material containing silica and alumina, and a polymer resin resin. It is described that the inorganic material protects the active oxygen generated by the absorption of ultraviolet rays by titanium oxide from destroying the resin. However, since all of the disclosed inorganic materials are powders and do not include those that form a film, the ability of these inorganic materials to protect organic resins from active oxygen is not sufficient.
As described above, a coating film for glass that simultaneously shields ultraviolet rays and infrared rays that are satisfactory from the viewpoint of shielding effect, ease of production, and price has not been developed.

JP 2013-87228 A JP 2012-246344 A Japanese Patent No. 5068592 Japanese Patent No. 312658 Japanese Patent No. 3690864 Japanese Patent No. 3490013 Japanese Patent No. 4347814

  The present invention has been made to solve such a problem, and has a photocatalytic activity that transmits visible light, shields infrared rays and ultraviolet rays, and has a self-cleaning action, antifouling action, antibacterial action, and deodorant. It aims at providing the composite coating film which has an effect | action, an air cleaning effect | action, etc.

Another object of the present invention is to provide a composite coating film that is not invaded by active oxygen generated by the photocatalyst.
Moreover, this invention makes it a subject to provide the manufacturing method of the photocatalyst composite coating film which permeate | transmits visible light and shields an ultraviolet-ray and infrared rays by an easy and cheap process, without using high temperature.

A photocatalyst composite coating film that transmits visible light and shields ultraviolet rays and infrared rays of the present invention for solving such problems is applied to the substrate surface, and an undercoat layer containing fine particles of peroxotitanic acid and an infrared shielding agent, A photocatalyst layer containing fine particles of anatase-type titanium oxide formed on the undercoat layer, and the coating amount of the infrared shielding agent on the substrate surface is 0.05 to 20 g / m ² Features.

The infrared shielding agent is preferably at least one selected from antimony oxide, tin oxide, indium oxide, gallium oxide, zinc oxide, titanium oxide, niobium oxide, and fluorine.
The infrared shielding agent may be one or more selected from antimony-doped tin oxide, antimony-doped zinc oxide, gallium-doped zinc oxide, induce-doped tin oxide, and fluorine-doped tin oxide.

The amount of the anatase-type titanium oxide applied to the photocatalyst layer is 0.05 to 20 g / m ² .
The coating amount in terms of titanium oxide of peroxotitanic acid in the undercoat layer is preferably 0.05 to 20 g / m ² .

The photocatalyst layer may further contain peroxotitanic acid.
The coating amount of the photocatalyst layer on the substrate surface is a total coating amount of 0.05 to 20 g / m ^2, which is the sum of the coating amount of anatase titanium oxide and the mass of peroxotitanic acid converted to titanium oxide. The ratio of the mass of anatase-type titanium oxide to the mass of peroxotitanic acid converted to titanium oxide is in the range of 1: 0 to 1: 2 (excluding 0).

The method for producing a photocatalytic composite coating film that transmits visible light and shields ultraviolet rays and infrared rays according to the present invention includes a peroxotitanic acid aqueous solution production process for producing a peroxotitanic acid aqueous solution from a titanium raw material, and a mass of the peroxotitanic acid aqueous solution of 100. An undercoat liquid production process for producing an undercoat liquid by adding 0.05 to 20 parts by mass of fine particles of an infrared shielding agent with respect to parts by mass, and the undercoat liquid on the surface of the substrate. An undercoat layer forming step in which an application amount is 0.05 to 20 g / m ² and dried at a temperature of less than 70 ° C. to form an undercoat layer containing peroxotitanic acid and an infrared shielding agent; A photocatalyst for producing a photocatalyst liquid containing an aqueous dispersion of anatase-type titanium oxide fine particles by heating an aqueous titanic acid solution to 70 ° C. to 200 ° C. It has a liquid manufacturing process and a photocatalyst composite coating film manufacturing process which forms a photocatalyst composite coating film by apply | coating a photocatalyst liquid on an undercoat layer, and drying.

In the undercoat liquid manufacturing process, the infrared shielding agent may be at least one selected from antimony oxide, tin oxide, indium oxide, gallium oxide, zinc oxide, titanium oxide, niobium oxide, and fluorine.
In the undercoat liquid manufacturing process, the infrared shielding agent is preferably at least one selected from antimony-doped tin oxide, antimony-doped zinc oxide, gallium-doped zinc oxide, indium-doped tin oxide, and fluorine-doped tin oxide.

In the peroxotitanic acid aqueous solution manufacturing step, the content of peroxotitanic acid contained in the peroxotitanic acid aqueous solution is such that when the mass of the peroxotitanic acid aqueous solution is 100% by mass, the mass of peroxotitanic acid is the mass of titanium oxide. It is preferably 0.1 to 10% by mass in terms of conversion.
In the undercoat layer forming step, the undercoat liquid is applied to the substrate surface so that the mass of peroxotitanic acid converted to titanium oxide in the peroxotitanic acid aqueous solution is 0.05 to 20 g / m ^2. It is preferable to do.

In the photocatalyst composite coating film production process, the content of the anatase-type titanium oxide contained in the photocatalyst solution is preferably 0.1 to 10% by mass when the mass of the photocatalyst solution is 100% by mass.
In the photocatalyst composite coating film production step, it is preferable to apply the photocatalyst solution to the surface of the undercoat layer so that the amount of the anatase-type titanium oxide applied is 0.05 to 20 g / m ² .

In the photocatalyst liquid production step, the photocatalyst liquid further contains a peroxotitanic acid aqueous solution.
In the photocatalyst solution production step, when the mass of the photocatalyst solution is 100 parts by mass and the mass of peroxotitanic acid contained in the photocatalyst solution is converted to the mass of titanium oxide, the mass of anatase-type titanium oxide, 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 peroxotitanic acid is in the range of 1: 0 to 1: 2 (excluding 0). it can.

  The photocatalyst composite coating film that transmits visible light and shields ultraviolet rays and infrared rays of the present invention transmits visible light and shields ultraviolet rays and infrared rays, so that harmful ultraviolet rays and excess infrared rays can be shielded while taking in sunlight. it can. This prevents sunburn on the skin and reduces summer cooling costs. It is especially effective for vehicles such as large glass buildings, cars, and trains.

Since the composite coating film of the present invention exhibits a photocatalytic action, when applied to the outer surface of a building, the active oxygen generated by the photocatalyst exhibits a self-cleaning action on the outer wall, and the appearance of the building can be kept beautiful. When applied indoors, the coated surface is kept clean and beautiful, and also exhibits sterilization, deodorization, and air cleaning actions.
Furthermore, the strength of the photocatalyst layer can be increased by adding peroxytitanic acid to the photocatalyst layer.

  Moreover, according to the manufacturing method of this invention, a photocatalyst composite coating film can be easily manufactured at 70 degreeC200 degreeC, More preferably, at 100 degrees C or less. In addition, the raw material can be a cheaper raw material, such as titanium tetrachloride, than the conventionally used Arco shore titanium, and can be manufactured inexpensively and easily. Moreover, the composite coating film of this invention can be apply | coated also to the existing glass structure.

It is a longitudinal cross-sectional view of the photocatalyst composite coating film which permeate | transmits visible light based on one Example of this invention, and shields an ultraviolet-ray and infrared rays. It is a block diagram which shows the manufacturing method of the photocatalyst composite coating film which permeate | transmits the visible light of this invention, and shields an ultraviolet-ray and infrared rays.

(About fine particle powder)
In the present invention, “fine particles” are “particles having a size smaller than the wavelength of visible light (380 to 780 nm) and having a size that allows the dispersion to transmit visible light even when dispersed in transparent solutions having different refractive indexes”. Used to mean. In general, “fine particle powder” corresponds to “powder composed of particles having a size of 1 μm or less”.
The titanium oxide fine particles used in the present invention are, for example, anatase type titanium oxide described in Patent Document 5 and having a particle diameter of 8 to 20 nm, and a transparent coating film is formed by applying and drying an aqueous dispersion. Peroxotitanic acid is an aqueous solution, and forms an amorphous transparent coating film by coating and drying. Moreover, the coating film of a photocatalyst can be strengthened by adding peroxotitanic acid to titanium oxide fine particles. As the fine particle powder of the infrared shielding agent, a commercially available product can be purchased.

Below, the photocatalyst composite coating film which permeate | transmits visible light and shields ultraviolet rays and infrared rays which concern on embodiment of this invention, and its manufacturing method are demonstrated in detail with reference to an accompanying drawing.
FIG. 1 is a longitudinal sectional view of a photocatalyst composite coating film that transmits visible light and shields ultraviolet rays and infrared rays according to one embodiment of the present invention.
As shown in FIG. 1, the photocatalyst composite film of the present invention is applied on an undercoat layer 2 containing fine particles of peroxotitanic acid and an infrared shielding agent applied on a transparent substrate 3, and on the undercoat layer 2. A photocatalyst composite coating film 1 containing anatase-type titanium oxide fine particles.

(Infrared shielding agent)
The infrared shielding agent used in the present invention is not particularly limited as long as it is an inorganic compound that transmits incident visible light but shields it by reflecting or / and absorbing infrared light. Many metal oxides are known to have such properties. Preferred examples include metal oxides containing antimony oxide, tin oxide, indium oxide, gallium oxide, iridium oxide, zinc oxide, titanium oxide, and niobium oxide. Not exclusively.

  The metal oxide can be further doped with a small amount of metal oxide or fluorine. Particularly preferable specific examples include antimony-doped tin oxide (ATO), antimony-doped zinc oxide, gallium-doped zinc oxide, indium oxide-doped tin oxide (ITO), and fluorine-doped titanium oxide (FTO).

The amount of the infrared shielding agent contained in the ultraviolet ray and infrared shielding photocatalyst composite film of the present invention is preferably 0.05 to 20 g / m ² , more preferably 0.1 to 15 parts by mass. If the amount of the infrared shielding agent is less than 0.05 parts by mass, sufficient infrared shielding effect may not be exhibited, and if it exceeds 20 parts by mass, the infrared shielding effect does not increase any more, and the strength of the undercoat layer decreases. This is not preferable.

(Peroxotitanic acid)
The peroxotitanic acid used in the present invention may be any one produced by any method as long as it does not hinder the practice of the present invention.
For example, as described in Patent Document 4, an aqueous solution of titanium raw material containing hydrogen hydroxide water in excess of the reaction equivalent is added and then neutralized by adding aqueous ammonia, and the resulting yellow solution is left to stand for peroxotitanium. The acid salt is precipitated, and the precipitate is collected by filtration, washed, suspended in water and added with aqueous hydrogen peroxide to obtain a yellow transparent peroxotitanic acid aqueous solution. Peroxotitanic acid, which is applied and dried at 70 ° C. or lower, is an amorphous solid that absorbs peroxo groups in FT-IR and forms a strong coating film with strong adhesion.

(Anatase type titanium oxide)
An anatase-type titanium oxide dispersion can be produced by heat treating a peroxotitanic acid aqueous solution at 70 to 200 ° C. for 2 to 40 hours.
As described in Patent Document 5, an X-ray analysis spectrum of a film formed by applying and solidifying a heat-treated peroxotitanic acid aqueous solution has a peak based on anatase-type titanium oxide. According to the cited document 5, the particle size of the dispersed anatase-type titanium oxide is 8 to 20 nm.

The undercoat layer is preferably applied so that the mass of peroxotitanic acid contained in the undercoat solution is 0.05 to 20 / m ² in terms of the mass of titanium oxide. More preferably, it is 15 to 15 g / m ² . May in terms of titanium oxide coated amount of peroxotitanate can not show a sufficient effect as an undercoat layer is less than 0.05 g / m ^2, even beyond 20 g / m ² becomes hard to be produced, The effect may not be improved only by reducing the film formability.

The coating amount of the anatase-type titanium oxide fine powder in the photocatalyst layer is preferably 0.05 to 20 g / m ² , and more preferably 0.1 to 15 g / m ² . The anatase type coating amount of less than 0.05 g / m ² of titanium oxide, it may not exhibit sufficient photocatalytic activity, be applied beyond 20 g / m ^2, it becomes hard to be with a coating deposited It is not preferable because the photocatalytic activity may not be further increased only by the decrease in properties.

In another embodiment of the present invention, the film formation property and film strength of the photocatalyst layer can be increased by further adding peroxotitanic acid to the photocatalyst layer made of anatase-type titanium oxide fine powder.
The coating amount of the photocatalyst layer of this example is 0.05 to 20 g / m ² in which the total coating amount of the anatase-type titanium oxide and the mass of the peroxotitanate layer converted to titanium oxide is 0.05 to 20 g / m ² . Preferably there is. The total was less than the coating amount is 0.05 g / m ^2, may not exhibit sufficient photocatalytic activity, be applied beyond 20 g / m ^2, by itself or photocatalyst to with paint becomes very Activity may not increase.

  The ratio of the mass of anatase-type titanium oxide and the mass of peroxotitanic acid in the photocatalyst layer is preferably in the range of 1: 0 to 1: 2 (excluding 0). If the ratio of peroxotitanic acid is too small, the film formability and strength of the photocatalyst layer may not be increased, and the ratio of the mass of anatase-type titanium oxide and the mass of peroxotitanic acid is 1: 2. If exceeded, the photocatalytic effect and the ultraviolet shielding effect may be lowered.

(Production method)
Below, the manufacturing method of the photocatalyst film composite film which concerns on one Example of this invention is demonstrated.
FIG. 2 is a block diagram showing a method for producing a photocatalyst composite coating film that transmits visible light and shields ultraviolet rays and infrared rays according to the present invention.
As shown in FIG. 2, the present invention includes a peroxotitanic acid aqueous solution production process for producing a peroxotitanic acid aqueous solution from a titanium material, and an undercoat liquid for producing an undercoat liquid by mixing a peroxotitanic acid aqueous solution and an infrared shielding agent. A manufacturing process, a photocatalyst liquid manufacturing process for manufacturing an aqueous dispersion of anatase-type titanium oxide fine powder by heating a peroxotitanic acid aqueous solution, an undercoat layer forming process for applying and drying an undercoat liquid on a substrate, And a photocatalyst composite coating film production step in which a photocatalyst solution is applied on the undercoat layer and dried.

(Peroxotitanic acid aqueous solution manufacturing process)
The peroxotitanic acid aqueous solution used for the production of the undercoat layer in the present invention can be used by any method as long as it does not hinder the practice of the present invention. For example, as described in Patent Document 6, the aqueous solution containing titanium raw material is added with an excess of hydrogen peroxide solution over the reaction equivalent, then neutralized by adding aqueous ammonia, and the resulting yellow solution is allowed to stand. When peroxotitanate is precipitated, the precipitate is collected by filtration, washed, suspended in water and added with aqueous hydrogen peroxide, a yellow transparent peroxotitanate aqueous solution is obtained.
The coating film obtained by applying and drying a peroxotitanic acid aqueous solution is an amorphous solid that exhibits absorption based on a peroxo group in an infrared absorption spectrum.

  The content of peroxotitanic acid contained in the peroxotitanic acid aqueous solution is 0.1 to 10 when the mass of the peroxotitanic acid aqueous solution is 100% by mass and the mass of peroxotitanic acid is converted to the mass of titanium oxide. It is preferable that it is mass%. If the content of peroxotitanic acid is less than 0.1% by mass, the amount of peroxotitanic acid may be too small to form an undercoat layer having a sufficient thickness. On the other hand, although it is preferable that the concentration of the peroxotitanic acid aqueous solution is high, it may be difficult to produce a peroxotitanic acid having a peroxotitanic acid concentration exceeding 10% by mass.

(Undercoat liquid manufacturing process)
An undercoat liquid is produced by adding fine particles of an infrared shielding agent to a peroxotitanic acid aqueous solution. The amount of the infrared shielding agent contained in the undercoat liquid is preferably 0.1 to 20 parts by mass when the mass of the undercoat liquid is 100 parts by mass. If the amount of the infrared shielding agent is 0.05 parts by mass or less, sufficient infrared shielding effect may not be exhibited, and even if it exceeds 20 parts by mass, the infrared shielding effect does not increase any more, and the strength of the undercoat layer May decrease, which is not preferable.

(Photocatalyst liquid production process)
The step of producing an aqueous dispersion of anatase-type titanium oxide fine powder, which is a photocatalyst solution in the present invention, is carried out by using a peroxotitanic acid aqueous solution at 70 ° C. to 200 ° C. for 2 to 40 hours, preferably 80 to 120 ° C. for 3 to 3 hours. A dispersion of anatase-type titanium oxide fine powder can be produced by heating treatment at 90 ° C. to less than 100 ° C. for 5 to 20 hours as a most preferred example. When the heating temperature is 70 ° C. or lower, the reaction takes too much time, which is not preferable. Even when heated to 200 ° C. or higher, the reaction becomes too fast and difficult to control, and a pressurizing device that suppresses boiling of water is large. It just has no effect.
As described in Patent Document 5, an X-ray analysis spectrum of a film formed by applying and solidifying a heat-treated peroxotitanic acid aqueous solution has a peak based on anatase-type titanium oxide.

  The content of the anatase-type titanium oxide contained in the photocatalyst solution is preferably 0.1 to 10% by mass when the mass of the photocatalyst solution is 100% by mass. If the content of the anatase-type titanium oxide is less than 0.1% by mass, the amount of the anatase-type titanium oxide may be too small to form a photocatalyst layer having a sufficient thickness. It may be difficult to produce an anatase-type titanium oxide aqueous solution exceeding 1%.

(Undercoat layer manufacturing process)
An undercoat liquid can be applied to a substrate and dried at 70 ° C. or lower to produce an undercoat layer. The amount of the undercoat liquid applied is preferably such that the mass of peroxotitanic acid converted to titanium oxide is 0.05 to 20 g per square meter of the surface area of the substrate. It is more preferable to apply so as to be 0.1 to 15 g. If the surface area of the substrate is less than 0.05 g per square meter, an undercoat layer having a sufficient thickness and strength may not be formed, and it is difficult to apply uniformly. In addition, in order to apply an amount of more than 20 g per square meter, it is necessary to apply several times, so that the film-forming property of the manufactured coating film becomes poor and the coating film becomes non-uniform. It is not preferable.

(Photocatalyst composite coating film manufacturing process)
A photocatalyst liquid can be applied onto the undercoat layer and dried to form a photocatalyst composite coating film. The photocatalyst solution is preferably applied to the undercoat layer so that the mass of titanium oxide is 0.05 to 20 g per square meter of the surface area of the substrate. More preferably, it is 15 g. If it is less than 0.05 g / m ² , a photocatalyst layer having a sufficient thickness and strength may not be formed, and it is difficult to apply uniformly. In addition, in order to apply an amount exceeding 20 g / m ² per square meter, it is necessary to apply a plurality of times, so that the produced coating film becomes non-uniform, and there is a risk of tearing the coating film. This is also not preferable.

[Production Example 1]
<Production of 5.0 mass% concentration of peroxotitanic acid aqueous solution>
To a solution of 39.6 mL of a 60% (mass / volume) aqueous solution of titanium tetrachloride in 4000 mL with distilled water, 440 mL of 2.5% (mass / volume) ammonia water was added dropwise to precipitate titanium hydroxide. The precipitate was collected by filtration and washed with distilled water, and then 80 mL of 30% (mass / volume) hydrogen peroxide water was added to the titanium hydroxide suspension to 80 mL by adding distilled water and stirred. The mixture was allowed to stand at 7 ° C. for 24 hours to decompose excess hydrogen peroxide solution, and water was further added to obtain 200 g of a peroxotitanic acid aqueous solution having a concentration of 5% by mass in terms of titanium oxide.

[Production Example 2]
<Production of 1.0 mass% concentration of peroxotitanic acid aqueous solution>
Titanium hydroxide was precipitated by dropwise addition of 440 mL of 2.5% (mass / volume) ammonia water to a solution of 39.6 mL of 60% (mass / volume) aqueous solution of titanium tetrachloride in 4000 mL with distilled water. . The precipitate was collected by filtration, washed with distilled water, and then added with 80 mL of 30% (mass / volume) hydrogen peroxide water to a titanium hydroxide suspension to which 720 mL was added by adding distilled water and stirred. The mixture was allowed to stand at 7 ° C. for 24 hours to decompose excess hydrogen peroxide solution, and water was further added to obtain 1000 g of a peroxotitanic acid aqueous solution having a concentration of 1.0% by mass in terms of titanium oxide. The 0.1 mass% peroxotitanic acid aqueous solution was prepared by diluting a 1.0 mass% peroxotitanic acid aqueous solution with water.

[Production Example 3]
<Production of 10 mass% concentration of peroxotitanic acid aqueous solution>
Titanium hydroxide was precipitated by dropwise addition of 440 mL of 2.5% (mass / volume) ammonia water to a solution of 39.6 mL of 60% (mass / volume) aqueous solution of titanium tetrachloride in 4000 mL with distilled water. The precipitate was collected by filtration, washed with distilled water, 30% (mass / volume) hydrogen peroxide water and 80 mL were added and stirred. The mixture was allowed to stand at 7 ° C. for 24 hours to decompose excess hydrogen peroxide solution, and water was further added to obtain 100 g of a peroxotitanic acid aqueous solution having a concentration of 10% by mass in terms of titanium oxide.

[Production Example 4]
<Manufacture of 1.0 mass% concentration anatase type titanium oxide dispersion>
The 1.0 mass% peroxotitanic acid aqueous solution 1000 g obtained in Production Example 1 was sealed in a pressure-resistant glass container and boiled in a water bath for 12 hours (98 to 100 ° C.). 1000 g of anatase-type titanium oxide aqueous dispersion was obtained. The 0.1 mass% anatase-type titanium oxide dispersion was prepared by diluting a 1.0 mass% anatase-type titanium oxide dispersion with water.

[Production Example 5]
<Manufacture of 5.0 mass% concentration anatase type titanium oxide dispersion>
200 g of the 5.0 mass% peroxotitanic acid aqueous solution obtained in Production Example 2 was sealed in a pressure-resistant glass container and boiled in a water bath for 12 hours (98 to 100 ° C.). 200 g of an anatase-type titanium oxide aqueous dispersion was obtained.

[Production Example 6]
<Production of 10% by mass concentration of anatase-type titanium oxide dispersion>
100 g of the 10% by mass peroxotitanic acid aqueous solution obtained in Production Example 3 was sealed in a pressure-resistant glass container and boiled in a water bath for 12 hours (98 to 100 ° C.) to give a pale yellow translucent 10% by mass anatase-type titanium oxide. 100 g of an aqueous dispersion was obtained.

[Production Example 7]
<Production of infrared shielding agent-1, antimony-doped tin oxide: ATO>
To 9.0 parts by mass of tin oxide fine particles (SN-100P, Ishihara Sangyo, particle size 0.01 to 0.03 μm), 1.0 part by mass of antimony trioxide powdered in an agate mortar was added, and the mixture was stirred and mixed with a stirrer. As a result, 10.0 parts by mass of antimony-doped tin oxide was produced.
[Production Example 8]
<Production of infrared shielding agent-2, indium-doped tin oxide: ITO>
To 1.0 part by mass of tin oxide fine particles (SN-100P, Ishihara Sangyo, particle size 0.01 to 0.03 μm), 1.0 part by mass of indium oxide powdered with an agate mortar was added, and the mixture was stirred and mixed with a stirrer. Thus, 10 parts by mass of indium-doped tin oxide was produced.

[Example 1]
<Undercoat liquid manufacturing process-1>
5 g of the infrared shielding agent produced in Production Example 7 was added to 100 g of the peroxotitanic acid aqueous solution having a concentration of 5.0% by mass produced in Production Example 1, and stirred with a stirrer to produce 105 g of an undercoat solution.
<Undercoat layer manufacturing process-2>
The undercoat liquid 105 g was applied to a clean glass plate having an area of 1 square meter using a spray coater and dried at 40 ° C. or lower to produce an undercoat layer.
<Photocatalyst composite coating film manufacturing process>
100 g of the 5.0 mass% concentration anatase-type titanium oxide dispersion produced in Production Example 5 is uniformly applied to the undercoat layer having an area of 1 square meter using a spray coater and dried at 40 ° C. or lower. The photocatalyst composite coating film of Example 1 was produced.

[Examples 2 to 10]
As in Example 1, but as shown in Table 1, the concentration (mass%), liquid amount (g), component amount (g / m ² ) of the peroxotitanic acid aqueous solution constituting the coating film, and the undercoat liquid Infrared shielding agent (g / m ² ), liquid amount (g), photocatalyst liquid concentration (mass%), liquid amount (g), component amount (g / m ² ) The photocatalyst composite coating films of Examples 2 to 10 were produced.

[Comparative Examples 1-6]
As in Example 1, but as shown in Table 1, the concentration (mass%), liquid amount (g), component amount (g / m ² ) of the peroxotitanic acid aqueous solution constituting the coating film, and undercoat Change the concentration of the infrared shielding agent (g / m ² ), the amount of liquid (g), the concentration of the photocatalyst liquid (% by mass), the amount of liquid (g), and the amount of ingredients (g / m ² ). The photocatalyst composite coating films of Comparative Examples 1 to 6 were produced.

[Example 11]
As in Example 1, except that the infrared shielding agent (ITO) produced in Production Example 8 was used instead of the infrared shielding agent (ATO) produced in Production Example 7, the photocatalyst composite coating film of Example 11 was produced.

[Example 12]
<Undercoat liquid manufacturing process and undercoat layer manufacturing process>
Same as Production Example 1.
<Photocatalyst composite coating film manufacturing process>
On the undercoat layer having an area of 1 square meter, 70 g of the 5.0 mass% anatase-type titanium oxide dispersion produced in Production Example 5 and the 5.0 mass% aqueous peroxotitanic acid solution produced in Production Example 1 were prepared. 30 g was mixed, applied using a spray coater, and dried at 40 ° C. or lower to produce a photocatalyst composite coating film of Example 12.

(Preparation of test specimen)
The glass piece for test was washed using an automatic washing machine until it was no longer watered even after draining and then dried with a hot air dryer (60 ° C.). The coating composition of Examples 1-12 and Comparative Examples 1-6 was apply | coated to this glass piece for a test using the spray coater, and it dried naturally at room temperature dark place for 10 days, and created the sample piece for a test.

(Visible light transmission)
The intensity of visible light (VIS ₀ ) transmitted through the glass piece coated with the composite coating film of the present invention and the intensity of visible light (VIS) transmitted through the glass piece not coated with the composite coating film were measured, and the formula (1) Was used to calculate the visible light shielding rate (%).
(Formula 1) Visible light shielding rate (%) = (VIS / VIS ₀ ) × 100
Visible light shielding rate of 80% or more was evaluated as ◯, 60 to less than 80% as Δ, less than 60% as ×, and Δ or more as acceptable.

(Infrared shielding test)
Using an infrared lamp and an infrared measuring instrument, the infrared intensity (IR) transmitted through the glass piece coated with the composite coating of the present invention and the infrared intensity (IR ₀ ) transmitted through the glass piece not coated with the composite coated film. Was measured, and the infrared shielding rate (%) was calculated using the formula (2).
(Formula 2) Infrared shielding rate (%) = {(IR ₀ −IR) / IR ₀ } × 100
Infrared shielding rate of 80% or more was evaluated as ◯, 60 to less than 80% as Δ, less than 60% as ×, and Δ or more as acceptable.

(UV shielding test)
Using a medium-pressure ultraviolet lamp (output wavelength: 200 to 600 nm) and an ultraviolet ray measuring instrument, the intensity (UV) of ultraviolet rays transmitted through the glass piece coated with the composite coating film of the present invention, and the glass piece not coated with the composite coating film The intensity of the transmitted ultraviolet rays (UV ₀ ) was measured, and the infrared shielding rate (%) was calculated using Equation (3).
(Formula 3) Ultraviolet ray shielding rate (%) = {(UV ₀ −UV) / UV ₀ } × 100
Infrared shielding rate of 80% or more was evaluated as ◯, 60 to less than 80% as Δ, less than 60% as ×, and Δ or more as acceptable.

(Photocatalytic activity test)
Add 15 mL of water, 1 mL of 0.01M ammonia water and a few drops of phenolphthalein indicator to a glass petri dish with a diameter of 7 cm, cover the petri dish with the sample coating surface of the test piece facing down, and turn on a 10 W UV lamp from above. Irradiation was performed, and the time until oxygen peroxide generated by the photocatalyst oxidized ammonia and the color of phenolphthalein disappeared was measured.
Since there is a slight time lag before the photocatalyst is activated, the phenolphthalein color disappearance time of less than 20 minutes is marked as ◯, 20 minutes or more but less than 30 minutes as △, and more than 30 minutes Was evaluated as x, and Δ or higher was regarded as acceptable.

[Corrosion resistance test]
A 50 W medium pressure ultraviolet lamp (output wavelength: 200 to 600 nm) was irradiated for 200 hours from a distance of 50 cm from the test specimen, and the appearance of the specimen was compared before and after irradiation. By visual inspection, no change before and after UV irradiation was evaluated as ◯, slightly colored as △, colored or turbid as x, and Δ or higher as acceptable.

[Adhesion test]
Using a cutter knife, the coating on the surface of the test piece was scratched in a grid pattern with 1 mm length and width, and 100 1 mm square coating blocks were formed, and cellophane tape (manufactured by Nichiban) was applied to the surface and then peeled. The number of paint film blocks peeled off was counted. The peeled coating block was evaluated as 0, 0 or less as Δ, 6 or more as x, and Δ or more as acceptable.

The test results are shown in Table 2.

As shown in Table 2, in Examples 1 to 4 and Comparative Examples 1 and 2, the amount of photocatalyst applied was changed to change the ultraviolet shielding rate, photocatalytic activity, and film formability (corrosion resistance, adhesion, and visible light transmission). ).
As shown in Comparative Example 1, when the photocatalyst coating amount was 0.01 g / m ² , although weak photocatalytic activity was observed, the ultraviolet shielding effect did not pass. On the other hand, as shown in Example 2, when the coating amount of the photocatalyst was 0.05 g / m ² , the UV shielding effect was slightly weak, but the photocatalytic activity was sufficient.

Further, as shown in Example 4, when the photocatalyst application amount is 20 g / m ² , the photocatalyst of 20 g / m ² must be applied several times to increase the work amount, and the film formation is not limited. However, the visible light permeability, corrosion resistance, and adhesion were in the acceptable range, but there was a tendency to slightly decrease.
Moreover, as shown in Comparative Example 2, when a photocatalyst of 30 g / m ² was applied, the film formability became insufficient, and the corrosion resistance and adhesion became unacceptable.

Examples 1, 5 to 8, and Comparative Examples 3 and 4 were obtained by comparing the film formability (corrosion resistance, adhesion, and visible light transmittance) by changing the coating amount of peroxotitanic acid in the undercoat solution. It is.
As shown in Comparative Example 3, when the coating amount of peroxotitanic acid was 0.01 g / m ² , the thickness of the undercoat layer was insufficient, and the corrosion resistance and adhesion showing film forming properties were rejected. As shown in Example 5, when the coating amount of peroxotitanic acid was 0.05 g / m ² , the corrosion resistance and adhesion were within the acceptable range.

On the other hand, as shown in Example 8, since the coating amount of peroxotitanic acid must be repeated several times in order to achieve 20 g / m ² , visible light permeability, corrosion resistance, and adhesion are within the acceptable range. There was a tendency to be somewhat inferior.
Moreover, as shown in Comparative Example 4, when 30 g / m ² of peroxotitanic acid was applied, the film formability was insufficient, and the corrosion resistance and adhesion became unacceptable.

Examples 1, 9, and 10 and Comparative Examples 5 and 6 compare the infrared shielding effect and film formability by changing the coating amount of the infrared shielding agent in the undercoat solution. As shown in Comparative Example 5, the coating amount of 0.05 g / m ² of infrared shielding agent, but the coating amount of the infrared shielding agent is insufficient, the 0.1 g / m ² as shown in Example 9 coated amount Then, the infrared shielding rate became the acceptable range.

As shown in Example 10, when an infrared shielding agent having an infrared shielding agent coating amount of 20 g / m ² is applied, the film forming property of the undercoat layer tends to be slightly lowered although it is within the acceptable range. As shown in Comparative Example 6, when an infrared shielding agent having an infrared shielding agent amount of 30 g / m ² was applied, the film forming property was insufficient, and the corrosion resistance and adhesion were rejected.

1 Photocatalyst composite coating layer 2 Undercoat layer 3 Substrate

A photocatalyst composite coating film that transmits visible light and shields ultraviolet rays and infrared rays of the present invention for solving such problems is applied to the substrate surface, and an undercoat layer containing fine particles of peroxotitanic acid and an infrared shielding agent, A photocatalyst layer containing fine particles of anatase-type titanium oxide formed on the undercoat layer,
The coating amount to the substrate surface of the infrared ray shielding agent, 0.05 g / ^{m 2} to 20 g / ^{m 2} (where 0.05 g / ^{m 2} are excluded) der is, in terms of titanium oxide of the peroxotitanate layer the coating amount of the said substrate, a 0.05 g / ^{m 2} to 20 g / ^{m 2,} before
The coating amount to the base anatase titanium oxide serial photocatalyst layer, characterized in that a 0.05 g / ^{m 2} to 20 g / ^{m 2.}

The infrared shielding agent, oxidation antimony, tin oxide, indium oxide, gallium oxide, zinc oxide, titanium oxide, niobium oxide, and fluorine that the at least one selected from doped metal oxides preferred.
The infrared shielding agent may be one or more selected from antimony-doped tin oxide, antimony-doped zinc oxide, gallium-doped zinc oxide, induce-doped tin oxide, and fluorine-doped tin oxide.

The method for producing a photocatalyst composite coating film that transmits visible light and shields ultraviolet rays and infrared rays of the present invention includes a peroxotitanic acid aqueous solution production process for producing a peroxotitanic acid aqueous solution from a titanium raw material, and a mass of the peroxotitanic acid aqueous solution of 100. relative to the weight parts, the undercoat liquid process of manufacturing the undercoat liquid by adding fine particles of 0.05 part by mass to 20 parts by weight of the infrared-screening agent, the undercoating liquid was coated fabric substrate surface, An undercoat layer forming step of forming an undercoat layer containing the peroxotitanic acid and the infrared shielding agent by drying at a temperature of less than 70 ° C; and heating the peroxotitanic acid aqueous solution to 70 ° C to 200 ° C to anatase A photocatalyst solution production process for producing a photocatalyst solution containing an aqueous dispersion of titanium oxide fine particles,
The photocatalyst solution, have a, a photocatalyst composite coating film manufacturing process for forming a photocatalyst composite coating film by applying and drying on the undercoat layer,
In the undercoat layer forming step, the infrared coating weight of screening agent is 0.05 g / ^{m 2} to 20 g / ^{m 2} (where 0.05 g / ^{m 2} are excluded) is, the peroxotitanate in terms of titanium oxide mass, the undercoat solution was applied to the substrate surface such that the 0.05 g / m ² to 20 g / m ^2, in the photocatalyst composite coating film manufacturing process, the coating amount of the photocatalyst solution, titanium oxide the mass, characterized by applying the photocatalyst liquid solution so that 0.05 g / ^{m 2} to 20 g / ^{m 2} on the undercoat layer.

In the undercoat liquid manufacturing process, the infrared shielding agent is at least one selected from antimony oxide, tin oxide, indium oxide, gallium oxide, zinc oxide, titanium oxide, niobium oxide, and fluorine- doped metal oxide. be able to.
In the undercoat liquid manufacturing process, the infrared shielding agent is preferably at least one selected from antimony-doped tin oxide, antimony-doped zinc oxide, gallium-doped zinc oxide, indium-doped tin oxide, and fluorine-doped tin oxide.

Moreover, according to the manufacturing method of this invention, a photocatalyst composite coating film can be easily manufactured at 70 to 200 degreeC, More preferably, at 100 degrees C or less. Moreover, raw materials than alkoxy titanium has been used conventionally can be used inexpensive materials, for example titanium tetrachloride, can be inexpensively and easily manufactured. Moreover, the composite coating film of this invention can be apply | coated also to the existing glass structure.

(Peroxotitanic acid)
The peroxotitanic acid used in the present invention may be any one produced by any method as long as it does not hinder the practice of the present invention.
For example, as described in Patent Document 4, the titanium raw material aqueous solution containing reactive equivalent from the excess of hydrogen peroxide solution was added, then neutralized by adding aqueous ammonia, the resulting yellow solution was allowed to peroxotitanic the The acid salt is precipitated, and the precipitate is collected by filtration, washed, suspended in water and added with aqueous hydrogen peroxide to obtain a yellow transparent peroxotitanic acid aqueous solution. Peroxotitanic acid, which is applied and dried at 70 ° C. or lower, is an amorphous solid that absorbs peroxo groups in FT-IR and forms a strong coating film with strong adhesion.

The test results are shown in Table 2.

[Comparative Examples 1-6]
  As in Example 1, but as shown in Table 1, the concentration (mass%), liquid amount (g), and component amount (g / m) of the peroxotitanic acid aqueous solution constituting the coating film ² ) And an infrared shielding agent (g / m) of the concentration of the undercoat liquid ² ), Liquid amount (g), photocatalyst liquid concentration (% by mass), liquid amount (g), component amount (g / m) ² And photocatalyst composite coating films of Comparative Examples 1 to 6 were produced.

The test results are shown in Table 2.

Conventionally, zinc oxide and titanium oxide have been used as sun creams as infrared shielding agents for shielding infrared rays. Further, it is known that metal oxides such as antimony oxide, tin oxide, indium oxide, gallium oxide, iridium oxide, and zinc oxide have an infrared shielding effect. Among them, it is disclosed that compositions such as indium-doped tin oxide, antimony-doped tin oxide, gallium-doped zinc oxide, and fluorine-doped tin oxide exhibit excellent properties (see, for example, Patent Document 1).

Here, Patent Document 3 discloses a composition comprising anatase-type titanium oxide, an inorganic oxide containing antimony-doped tin oxide, an inorganic material containing silica and alumina, and a polymer resin resin. It is described that the inorganic material protects the active oxygen generated by the absorption of ultraviolet rays by titanium oxide from destroying the resin. However, since all of the disclosed inorganic materials are powders and do not include those that form a film, the ability of these inorganic materials to protect organic resins from active oxygen is not sufficient.
As described above, a coating film for glass that simultaneously shields ultraviolet rays and infrared rays that are satisfactory from the viewpoint of shielding effect, ease of production, and price has not been developed .

The infrared shielding agent is preferably at least one selected from antimony oxide, tin oxide, indium oxide, gallium oxide, zinc oxide, titanium oxide, niobium oxide, and fluorine.
The infrared shielding agent may be antimony-doped tin oxide, antimony-doped zinc oxide, gallium-doped zinc oxide, is one or more selected from Inju undoped tin oxide, and fluorine doped tin oxide.

The metal oxide can be further doped with a small amount of metal oxide or fluorine. As a particularly preferred embodiment, the antimony-doped tin oxide (ATO), antimony-doped zinc oxide, gallium-doped zinc oxide, can be exemplified oxidized indicator-menu Mudopu tin oxide (ITO), and fluorine-doped titanium oxide (FTO).

(Anatase type titanium oxide)
An anatase-type titanium oxide dispersion can be produced by heat treating a peroxotitanic acid aqueous solution at 70 to 200 ° C. for 2 to 40 hours.
As described in Patent Document 5, an X-ray analysis spectrum of a film formed by applying and solidifying a heat-treated peroxotitanic acid aqueous solution has a peak based on anatase-type titanium oxide. According to Patent Document 5, the particle size of the dispersed anatase-type titanium oxide is 8 to 20 nm.

Below, the manufacturing method of the photocatalyst film composite film which concerns on one Example of this invention is demonstrated.
FIG. 2 is a block diagram showing a method for producing a photocatalyst composite coating film that transmits visible light and shields ultraviolet rays and infrared rays according to the present invention.
As shown in FIG. 2, the present invention includes a peroxotitanic acid aqueous solution production process for producing a peroxotitanic acid aqueous solution from a titanium material, and an undercoat liquid for producing an undercoat liquid by mixing a peroxotitanic acid aqueous solution and an infrared shielding agent. A manufacturing process, a photocatalyst liquid manufacturing process for manufacturing an aqueous dispersion of anatase-type titanium oxide fine powder by heating a peroxotitanic acid aqueous solution, an undercoat layer forming process for applying and drying an undercoat liquid on a substrate , And a photocatalyst composite coating film production step in which a photocatalyst solution is applied on the undercoat layer and dried.

[Comparative Examples 1-6]
As in Example 1, except as shown in Table 1, the concentration (mass%) of the peroxotitanic acid aqueous solution constituting the coating film, liquid volume and (g), the component amount (g / m ^2), an undercoat solution Infrared shielding agent (g / m ² ), liquid amount (g), photocatalyst liquid concentration (mass%), liquid amount (g), component amount (g / m ² ) The photocatalyst composite coating films of Examples 1 to 6 were produced.

Using a cutter knife, scratch the coating on the surface of the test piece in a grid pattern at intervals of 1 mm in length and width, form 100 1 mm square coating blocks, apply cellophane tape (made by Nichiban) to the surface, peel off, and peel off. The number of paint film blocks was counted. The peeled coating block was evaluated as 0, 0 or less as Δ, 6 or more as x, and Δ or more as acceptable.

A photocatalyst composite coating film that transmits visible light and shields ultraviolet rays and infrared rays of the present invention for solving such problems is applied to the substrate surface, and an undercoat layer containing fine particles of peroxotitanic acid and an infrared shielding agent, A photocatalyst layer containing fine particles of anatase-type titanium oxide formed on the undercoat layer,
The coating amount to the substrate surface of the infrared ray shielding agent, 0.05 g / ^{m 2} to 20 g / ^{m 2} (where 0.05 g / ^{m 2} are excluded) is, oxidation of peroxotitanate contained in the undercoat layer the coating amount to the substrate in terms of titanium, a 0.05 g / ^{m 2} to 20 g / ^{m 2,} the coating amount to the base of anatase type titanium oxide of the photocatalyst layer is 0.05 g / ^{m 2} to It is characterized by being 20 g / m ² .

Claims (16)

An undercoat layer coated on the substrate surface and containing fine particles of peroxotitanic acid and an infrared shielding agent, and a photocatalyst layer containing fine particles of anatase-type titanium oxide formed on the undercoat layer,
A photocatalyst composite coating film that transmits visible light and shields ultraviolet rays and infrared rays, wherein the amount of the infrared shielding agent applied to the substrate surface is 0.05 to 20 g / m ² .   2. The visible light according to claim 1, wherein the infrared shielding agent is one or more selected from antimony oxide, tin oxide, indium oxide, gallium oxide, zinc oxide, titanium oxide, niobium oxide, and fluorine. Photocatalyst composite coating that transmits UV light and shields ultraviolet and infrared rays.   The said infrared shielding agent is 1 or more chosen from antimony dope tin oxide, antimony dope zinc oxide, gallium dope zinc oxide, induce dope tin oxide, and fluorine dope tin oxide, The Claim 2 characterized by the above-mentioned. A photocatalytic composite coating that transmits visible light and blocks ultraviolet and infrared rays. The coating amount to the substrate surface of the anatase-type titanium oxide of the photocatalyst layer is transparent to visible light according to any one of claims 1 to 3, wherein the range of 0.05 to 20 g / m ² A photocatalytic composite coating that blocks ultraviolet and infrared rays. The coating amount to the substrate surface in terms of titanium oxide peroxotitanate layer, visible light according to any one of claims 1 to 3, wherein the range of 0.05 to 20 g / m ² Photocatalyst composite coating that transmits UV light and shields ultraviolet and infrared rays.   2. The photocatalyst composite coating film that transmits visible light and blocks ultraviolet rays and infrared rays according to claim 1, wherein the photocatalyst layer further contains the peroxotitanic acid. The coating amount of the photocatalyst layer on the surface of the substrate is a total coating amount of 0.05 to 20 g / m with the coating amount of the anatase type titanium oxide and the mass converted to the titanium oxide of the peroxotitanic acid layer. ^2, the mass of anatase type titanium oxide of the photocatalyst layer, and the mass of peroxotitanate, the ratio of, 1: 0 to 1: claims, characterized in that a second range (where 0 is excluded) Item 7. A photocatalytic composite coating film that transmits visible light according to Item 6 and blocks ultraviolet rays and infrared rays. A method for producing a photocatalyst composite coating film, comprising:
A peroxotitanic acid aqueous solution production process for producing a peroxotitanic acid aqueous solution from a titanium raw material;
An undercoat liquid production step of producing an undercoat liquid by adding 0.05 to 20 parts by mass of infrared shielding agent fine particles to 100 parts by mass of the peroxotitanic acid aqueous solution;
The undercoat liquid is applied to the substrate surface so that the amount of the infrared shielding agent applied is 0.05 to 20 g / m ² and dried at a temperature of less than 70 ° C. to shield the peroxotitanic acid and the infrared shielding. An undercoat layer forming step of forming an undercoat layer containing an agent;
A photocatalyst solution production process for producing a photocatalyst solution comprising an aqueous dispersion of anatase-type titanium oxide fine particles by heating the peroxotitanic acid aqueous solution to 70 ° C. to 200 ° C .;
A photocatalyst composite coating film production step of applying the photocatalyst solution on the undercoat layer and drying to form a photocatalyst composite coating film,
A method for producing a photocatalyst composite coating film that transmits visible light and shields ultraviolet rays and infrared rays.   In the undercoat liquid manufacturing process, the infrared shielding agent is at least one selected from antimony oxide, tin oxide, indium oxide, gallium oxide, zinc oxide, titanium oxide, niobium oxide, and fluorine. The manufacturing method of the photocatalyst composite coating film which permeate | transmits the visible light of Claim 8, and shields an ultraviolet-ray and infrared rays.   In the undercoat liquid production process, the infrared shielding agent is at least one selected from antimony-doped tin oxide, antimony-doped zinc oxide, gallium-doped zinc oxide, indium-doped tin oxide, and fluorine-doped tin oxide. The manufacturing method of the photocatalyst composite coating film which permeate | transmits visible light of Claim 9, and shields an ultraviolet-ray and infrared rays.   In the undercoat liquid manufacturing step, the content of peroxotitanic acid contained in the peroxotitanic acid aqueous solution is that the mass of the peroxotitanic acid aqueous solution is 100% by mass, and the mass of the peroxotitanic acid is converted to the mass of titanium oxide. The method for producing a photocatalyst composite coating film that transmits visible light and shields ultraviolet rays and infrared rays according to claim 8, wherein the content is 0.1 to 10% by mass. In the undercoat layer forming step, the undercoat liquid is applied to the surface of the substrate so that the mass of the peroxotitanic acid converted to titanium oxide is 0.05 to 20 g / m ^2. Item 9. A method for producing a photocatalyst composite coating film which transmits visible light according to Item 8 and shields ultraviolet rays and infrared rays.   In the photocatalyst solution production step, the content of anatase-type titanium oxide contained in the photocatalyst solution is 0.1 to 10% by mass when the mass of the photocatalyst solution is 100% by mass. The manufacturing method of the photocatalyst composite coating film which permeate | transmits the visible light of Claim 8, and shields an ultraviolet-ray and infrared rays. In the photocatalyst composite coating film production process, the photocatalyst solution is applied on the undercoat layer so that the amount of titanium oxide is 0.05 to 20 g / m ^2. The manufacturing method of the photocatalyst composite coating film which permeate | transmits the visible light of Claim 8, and shields an ultraviolet-ray and infrared rays.   9. The method for producing a photocatalyst composite coating film that transmits visible light and blocks ultraviolet rays and infrared rays according to claim 8, wherein in the photocatalyst solution production step, the photocatalyst solution further contains the aqueous peroxotitanic acid solution.   In the photocatalyst solution production step, when the mass of the photocatalyst solution is 100 parts by mass and the mass of peroxotitanic acid contained in the photocatalyst solution is converted to the mass of titanium oxide, the mass of anatase-type titanium oxide, and peroxotitanium The sum of the mass of the acid is 0.1 to 20 parts by mass, and the ratio of the mass of the anatase-type titanium oxide and the mass of peroxotitanic acid is in the range of 1: 0 to 1: 2 (excluding 0). The method for producing a photocatalyst composite coating film according to claim 15, which transmits visible light and shields ultraviolet rays and infrared rays.

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