JP2018144004A - Inorganic compound for photocatalyst, photocatalyst composition, photocatalyst coating film and photocatalyst coating product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an inorganic compound for photocatalyst which can provide a photocatalyst coating having high on-site workability for 1 layer coat type, does not damage a photocatalyst coating film under coating film, demonstrates necessary photocatalyst activity, further improves biological stain resistance and forms a coating film having high transparency, a photocatalyst composition containing the inorganic compound, a photocatalyst coating film and a photocatalyst coating product.SOLUTION: There is provided an inorganic compound for photocatalyst (AB) in which an antibacterial metal (B) of 0.5 to 5 mass% based on an inorganic compound (A) is carried on a particle surface of an inorganic compound (A) having a photocatalytic activity. In the inorganic compound for photocatalyst (AB), the inorganic compound (A) satisfies following (i) condition or satisfies both of following (i) and (ii) conditions. (i) an amount of hydrogen peroxide ([HO]) generated when a suspension containing the inorganic compound (A) is irradiated with an ultraviolet ray with wavelength of 380 nm or less and intensity of 5 mW/cmfor 60 seconds, is 80 μM or less. (ii) an amount of hydroxy radical ([.OH]) generated when the suspension containing the inorganic compound (A) is irradiated with the ultraviolet ray with wavelength of 380 nm or less and intensity of 5 mW/cmfor 60 seconds, is 1.0 μM or less.SELECTED DRAWING: None

Description

  The present invention relates to an inorganic compound for photocatalyst, a photocatalyst composition, a photocatalyst coating film, and a photocatalyst-coated product.

  In recent years, in order to impart antifouling performance to exterior walls of buildings such as houses and buildings, a photocatalyst paint has been put into practical use, and a method of applying the photocatalyst paint to an exterior wall of a building to form a photocatalyst coating film has been applied. This photocatalyst coating material is blended with an inorganic compound material having photocatalytic activity in order to exhibit photocatalytic activity.

Of such inorganic compound materials, titanium dioxide (TiO ₂ ) is most frequently used. When this titanium dioxide is exposed to light (ultraviolet rays), excited electrons and holes are generated, and the generated excited electrons and holes generate superoxide anions (in the presence of oxygen and moisture on the catalyst surface). Active oxygen species such as O ²⁻ ) and hydroxy radicals (• OH) (“•” represents an unpaired electron, meaning that the chemical species attached thereto are radical species) are generated. Holes and generated active oxygen species exhibit important functions (photocatalytic activity) such as a soil decomposition function and a nitrogen oxide removal function.

  However, the active oxygen species may damage the coating film immediately below the photocatalyst coating film when the coating film of the substrate to which the photocatalytic coating material is applied (hereinafter also referred to as “photocatalyst coating film”) is an organic coating film. give. In view of this, a two-layer coat type photocatalyst coating in which a protective layer typified by a silicone resin is provided between the photocatalyst coating and the photocatalyst coating has been proposed (see, for example, Patent Document 1).

  In addition, photocatalyst paints that have been imparted with antifouling performance against dirt due to biological contamination such as mold and algae among dirt on the building outer wall have also been proposed (see, for example, Patent Documents 2 and 3).

JP 2003-73610 A Japanese Patent No. 4110279 Japanese Patent No. 4395886

  The coating film used as a protective layer for a photocatalyst coating film or a two-layer coating type photocatalyst coating material uses silica or silicone resin as its component, and since the coating film is hard and brittle, a minute penetration in the film It is impossible to completely prevent the occurrence of cracks. As a result, it is impossible to prevent the above-mentioned active oxygen species from damaging the coating film directly under the photocatalytic coating film through the through crack. Moreover, the two-layer coat type photocatalyst paint has room for improvement in terms of on-site workability. Therefore, a one-layer coat type photocatalyst coating material that can prevent damage to the coating film directly under the photocatalyst coating film and that does not require a protective layer is desired.

  In addition, as described above, biological contamination such as mold and algae occurs on the outer wall of the building. Therefore, a paint having an anti-algal and anti-fungal function on the outer wall coating film has been proposed. As one, it is common to use an algae and a fungicide. Although it is possible to add such an algae and antifungal agent to the photocatalytic photocatalytic coating film, the film thickness of the photocatalytic coating film is very thin, and the amount of the antialgae and antifungal agent that can be added is limited. It is difficult to impart sufficient antialgae and antifungal properties to the photocatalyst coating film. Examples of the photocatalyst include a photocatalyst composition containing an antibacterial metal or a compound in which an antibacterial metal is supported on an inorganic compound for photocatalyst. However, such a photocatalyst composition may also damage the coating film directly under the photocatalyst coating film.

  The present invention can provide a photocatalyst paint with high on-site workability for a single-layer coating type, exhibits the necessary photocatalytic activity without damaging the coating film directly under the photocatalyst coating film, and further provides biofouling resistance. An object of the present invention is to provide a photocatalyst inorganic compound, a photocatalyst composition containing the inorganic compound, a photocatalyst coating film, and a photocatalyst-coated product, which improve and form a highly transparent coating film.

  As a result of intensive studies to solve the above problems, the present inventors have supported a specific amount of an antibacterial metal (B) on the particle surface of the inorganic compound (A) having photocatalytic activity that satisfies a specific condition. Inorganic compound for photocatalyst can provide a photocatalyst coating with high on-site workability, without damaging the coating directly under the photocatalyst coating, exhibiting the necessary photocatalytic activity, further improving bio-fouling resistance and transparency As a result, the present invention was completed.

That is, the present invention is as follows.
[1]
An inorganic compound for photocatalyst (AB) in which 0.5 to 5% by mass of an antibacterial metal (B) is supported on the particle surface of the inorganic compound (A) having photocatalytic activity,
The inorganic compound (AB) for photocatalyst, wherein the inorganic compound (A) satisfies the following condition (i) or satisfies both the following conditions (i) and (ii):
(I) The amount of hydrogen peroxide generated when the suspension containing the inorganic compound (A) is irradiated with ultraviolet light having a wavelength of 380 nm or less and an intensity of 5 mW / cm ² for 60 seconds ([H ₂ O ₂ ]) Is 80 μM or less;
(Ii) The amount of hydroxy radical ([· OH]) generated when the suspension containing the inorganic compound (A) is irradiated with ultraviolet light having a wavelength of 380 nm or less and an intensity of 5 mW / cm ² for 60 seconds is 1 0.0 μM or less:
[2]
The inorganic compound for photocatalyst (AB) according to [1], wherein the antibacterial metal (B) is at least one selected from the group consisting of copper, silver, gold, platinum, and zinc.
[3]
The inorganic compound for photocatalyst (AB) according to [1] or [2], wherein the inorganic compound (A) having photocatalytic activity is titanium oxide.
[4]
The inorganic compound for photocatalyst (AB) according to any one of [1] to [3], wherein the inorganic compound (A) having photocatalytic activity is an inorganic compound obtained by treating the particle surface with a metal oxide (C).
[5]
The inorganic compound for photocatalyst (AB) according to [4], wherein the specific surface area of the inorganic compound whose particle surface has been treated with the metal oxide (C) is 80 to 180 m ² / g.
[6]
The inorganic compound for photocatalyst (AB) according to [4] or [5], wherein the antibacterial metal (B) is supported on the surface of the inorganic compound obtained by treating the particle surface with the metal oxide (C). .
[7]
The inorganic compound for photocatalysts (AB) according to any one of [4] to [6], wherein the metal oxide (C) is silicon dioxide.
[8]
The photocatalyst composition containing the inorganic compound (AB) for photocatalysts in any one of [1]-[7], and the inorganic compound (D) which does not have photocatalytic activity.
[9]
The ratio of the inorganic compound (A) which has photocatalytic activity is 1-20 mass% with respect to the photocatalyst composition whole quantity, The photocatalyst composition as described in [8].
[10]
The photocatalyst composition according to [8] or [9], wherein the inorganic compound (D) having no photocatalytic activity is silicon dioxide.
[11]
The photocatalyst composition according to any one of [8] to [10], further comprising polymer particles (E).
[12]
The photocatalyst composition according to any one of [8] to [11], further comprising a fluorocarbon surfactant (F).
[13]
The photocatalyst composition according to any one of [8] to [12], further comprising a fading dye (G).
[14]
A step of modifying the metal oxide (C) to the inorganic compound (A) having photocatalytic activity to obtain an inorganic compound whose particle surface is treated with the metal oxide (C); and
The manufacturing method of the inorganic compound for photocatalysts (AB) including the process of carrying | supporting an antibacterial metal (B) to the inorganic compound by which the particle | grain surface was processed with the said metal oxide (C).
[15]
The ratio of the metal oxide (C) that modifies the inorganic compound (A) having photocatalytic activity is 1 to 30% by mass with respect to the inorganic compound (A) having photocatalytic activity,
The proportion of the antibacterial metal (B) to be supported is 0.5 to 5% by mass with respect to the inorganic compound (A) having photocatalytic activity.
[14] The method for producing an inorganic compound for photocatalyst (AB) according to [14].
[16]
The photocatalyst coating film formed from the photocatalyst composition in any one of [8]-[13].
[17]
A photocatalyst-coated product comprising the photocatalyst coating film according to [16].

  If the inorganic compound for photocatalysts of this invention is used, the photocatalyst layer which exhibits a required photocatalytic activity can be provided on it, without damaging a coating film immediately under a photocatalyst coating film, without requiring a protective layer. In addition, it is possible to provide a one-layer coat type photocatalyst coating that can impart bio-contamination resistance and has a highly transparent coating film and excellent on-site workability.

  Hereinafter, a mode for carrying out the present invention (hereinafter simply referred to as “the present embodiment”) will be described in detail. The following embodiments are examples for explaining the present invention, and are not intended to limit the present invention to the following contents. The present invention can be implemented with appropriate modifications within the scope of the gist thereof.

[Inorganic compound for photocatalyst (AB)]
In the inorganic compound for photocatalyst of the present embodiment, 0.1 to 5% by mass of the antibacterial metal (B) is supported on the particle surface of the inorganic compound (A) having photocatalytic activity with respect to the inorganic compound (A). It is an inorganic compound (AB) for photocatalyst.
In addition, the inorganic compound (A) in the inorganic compound for photocatalyst (AB) of the present embodiment satisfies the following condition (i) or both the following conditions (i) and (ii).
(I) An excess generated when the suspension containing the inorganic compound (A) is irradiated with ultraviolet light having a wavelength of 380 nm or less and an intensity of 5 mW / cm ² (hereinafter also referred to as “specific ultraviolet light”) for 60 seconds. The amount of hydrogen oxide (also referred to as [H ₂ O ₂ ]) is 80 μM or less;
(Ii) The amount of hydroxy radicals (also expressed as [· OH]) generated when the suspension containing the inorganic compound (A) is irradiated with ultraviolet light having a wavelength of 380 nm or less and an intensity of 5 mW / cm ² for 60 seconds. The amount is 1.0 μM or less:

The inorganic compound for photocatalysts (AB) of this embodiment can be manufactured by the manufacturing method mentioned later, and the inorganic compound for photocatalysts (AB) can be obtained as a composition containing water or the like. Therefore, the inorganic compound for photocatalyst (AB) of the present embodiment includes a liquid form dissolved or suspended in a solvent such as water, that is, an aspect of a photocatalytic aqueous composition. Moreover, the inorganic compound for photocatalysts (AB) of this embodiment can also be obtained as a powder etc. by performing operation, such as removal of the water of the said photocatalyst aqueous composition, and drying, and may be a solid form.
The inorganic compound for photocatalyst (AB) in the photocatalytic aqueous composition is not particularly limited as long as it is 0.1 to 99.9% by mass relative to the total amount of the photocatalytic aqueous composition, and preferably 0.5 to 50 mass. %, More preferably, it is 1.0-30 mass%, More preferably, it is 1.5-10 mass%.

In the inorganic compound (A) having photocatalytic activity in the inorganic compound for photocatalyst of the present embodiment, an antibacterial metal (B) is supported on the particle surface of the inorganic compound (A). In the present embodiment, the term “support” refers to the fact that the inorganic compound (A) is used as a carrier and the single atom of the antibacterial metal (B) interacts and adheres to the surface of the inorganic compound (A) particles.
Here, the state where the particle surface of the inorganic compound (A) is supported by the antibacterial metal (B) may be the state where the antibacterial metal (B) is directly supported on the particle surface of the inorganic compound (A). The antibacterial metal (B) may be supported on the surface of another substance such as a metal oxide (C) described later.

  The inorganic compound for photocatalyst (AB) of the present embodiment is improved in performance as a photocatalyst and coating film transparency, that is, from the viewpoint of reducing the turbidity of the coating film and exhibiting good dispersibility, the secondary particle diameter thereof. Is preferably in the range of 1 to 400 nm on average (arithmetic average), more preferably in the range of 1 to 100 nm, and still more preferably 40 to 70 nm. When the particle shape of the photocatalyst inorganic compound (AB) has a major axis and a minor axis such as a rod shape, the arithmetic average of the major axis and minor axis is preferably within the above range. The secondary particle diameter of the photocatalyst inorganic compound (AB) is derived as an arithmetic average of 50 arbitrarily selected particles measured by electron microscope observation. The secondary particle diameter refers to the particle diameter when the particles are in the coating film or in the state of particles in the paint.

  The inorganic compound for photocatalyst (AB) of this embodiment can reduce the white turbidity of the photocatalyst coating film which used this inorganic compound for photocatalyst (AB), and can further improve the transparency of a coating film. This is presumably because the refractive index can be lowered by supporting a predetermined amount of the antibacterial metal (B) on the inorganic compound (A) having photocatalytic activity.

(Inorganic compound having photocatalytic activity (A))
The inorganic compound (A) in the inorganic compound for photocatalyst (AB) of the present embodiment satisfies the above-mentioned condition (i) or satisfies both the above-mentioned conditions (i) and (ii).

Of the active oxygen species generated when irradiated with specific ultraviolet light for 60 seconds, the amount of hydroxyl radicals ([· OH]) is 1.0 μM or less, preferably less than 1.0 μM, more preferably Is less than 0.5 μM.
Here, the ultraviolet light means a wavelength region of 400 nm or less. Further, μM represents a micromolar, and 1 μM = 10 ⁻⁶ M = 10 ⁻⁶ mol / L.

  Of the active oxygen species, hydroxy radicals (also referred to as .OH) are radical species that damage the coating film. When the [.OH] is 1.0 μM or less, the inorganic compound (A) has a small amount of .OH generation and can suppress damage to the coating film directly under the photocatalyst coating film. It means that it can be used as an inorganic compound (AB). On the other hand, when an inorganic compound for photocatalyst (AB) obtained from an inorganic compound (A) having a photocatalytic activity with a value of [.OH] greater than 1.0 μM is used for the catalyst coating film, the coating film directly under the photocatalyst coating film is damaged. Tend to give.

In order not to damage the coating film directly under the photocatalyst coating film, the amount of hydrogen peroxide ([H ₂ O ₂ ]) among the above-mentioned active oxygen species generated when irradiated with specific ultraviolet light for 60 seconds is 80 μM or less. Yes, preferably 20 μM or less, more preferably 10 μM or less.
Here, the ultraviolet light means a wavelength region of 400 nm or less. Further, μM represents a micromolar, and 1 μM = 10 ⁻⁶ M = 10 ⁻⁶ mol / L.

Among active oxygen species, hydrogen peroxide (also referred to as H ₂ O ₂ ) is a stable substance compared to radical species such as .OH, and has a longer lifetime than the lifetime of radical species (less than 1 second). And when present in the photocatalytic coating, it travels to a long distance and damages the coating just below the photocatalytic coating. That is, when [H ₂ O ₂ ] is 80 μM or less, the inorganic compound (A) generates a small amount of H ₂ O ₂ and can suppress damage to the coating film directly under the photocatalytic coating film. It means that it can be used as an inorganic compound (AB) for photocatalyst. On the other hand, when an inorganic compound (AB) for photocatalyst obtained from an inorganic compound (A) having a photocatalytic activity with a value of [H ₂ O ₂ ] greater than 80 μM is used for the catalyst coating film, the coating film directly under the photocatalyst coating film is damaged. Tend to give.

  The inorganic compound for photocatalyst (AB) of the present embodiment preferably satisfies the above conditions (i) and (ii) from the viewpoint of more effectively and reliably achieving the effects of the present invention.

In the measurement of [H ₂ O ₂ ], the suspension in the present embodiment is a liquid in which an inorganic compound (A) having photocatalytic activity is suspended in a 0.01 M NaOH aqueous solution, and [.OH]. Is a liquid in which an inorganic compound (A) having photocatalytic activity is suspended in a 0.1 mM coumarin aqueous solution. Specifically, the suspension of the inorganic compound (A) having photocatalytic activity can be prepared under the conditions described in the Examples.

As a method of adjusting [.OH] and [H ₂ O ₂ ] within the above range, for example, as described later, the surface of the inorganic compound (A) particles having photocatalytic activity is modified. And a method for suppressing the amount of active oxygen species. Although the mechanism is not completely elucidated, it is thought that the active species are inactivated or trapped by the surface-modified substance. However, the adjustment method of [.OH] and [H ₂ O ₂ ] is not limited to these.

[H ₂ O ₂ ] can be measured using a lucigenin chemiluminescence method. To a quartz cell (optical path (length) 1 cm × width 1 cm) placed on a magnetic stirrer in a dark box, 3.5 mL of 0.01 M NaOH aqueous solution is added to adjust to pH 9, and further 15 mg of an inorganic compound ( A) powder (for example, obtained by drying a sol; the same applies hereinafter) is charged and suspended to obtain a suspension. Next, using the LED (Hamamatsu Photonics, model number “LC-L2”, wavelength: 365 nm, intensity 5 mW / cm ² ) as a light source, the cell containing the suspension was irradiated with ultraviolet light for 60 seconds. Do. After irradiation, 50 μL of a 0.7 mM lucigenin solution is added, and chemiluminescence generated by H ₂ O ₂ is passed through a bandpass filter, and then detected with an electron-cooled photomultiplier tube.

[.OH] can be measured using a coumarin fluorescent probe method. First, a 0.1 mM aqueous solution of coumarin is prepared, and a suspension is obtained by suspending 15 mg of a powder of an inorganic compound (A) such as TiO ₂ and 35 mL of an aqueous solution of coumarin in a quartz cell having the same dimensions as described above. This suspension is irradiated with LED light having a wavelength of 365 nm and an intensity of 5 mW / cm ² for 60 seconds. Next, in order to separate a metal compound (photocatalyst) powder such as TiO ₂ from the suspension, 0.5 g of KCl is added to the suspension after the irradiation and left in a dark place for 24 hours. Thereafter, the supernatant is taken as a sample, and fluorescence is measured with a fluorescence spectrophotometer (850 type, manufactured by HITACHI). OH is quantified by comparing the fluorescence intensity of a known concentration of coumarin with the fluorescence intensity of the sample.

The inorganic compound (A) having photocatalytic activity of the present embodiment is preferably an inorganic compound obtained by treating the particle surface with a metal oxide (C). The treatment of the particle surface means that the particle surface is modified with a metal oxide (C). When the inorganic compound (A) is modified with the metal oxide (C), part or all of the inorganic compound (A) is covered with the metal oxide (C).
When the modification treatment is not performed, the amount of active oxygen species such as H ₂ O ₂ and .OH generated is increased, and the coating film immediately below the photocatalyst coating film tends to be damaged. Examples of the substance to be modified include metal oxides (C) such as silicon dioxide, aluminum, copper oxide, and iron oxide. Among these, silicon dioxide is preferable.
Here, when the inorganic compound (A) having photocatalytic activity is an inorganic compound obtained by treating the particle surface with the metal oxide (C), the antibacterial metal (B) is supported on the particle surface of the inorganic compound (A). The state where the antibacterial metal (B) is directly supported on the particle surface of the inorganic compound (A) is also antibacterial on the surface of the metal oxide (C) via the metal oxide (C). It also includes a state in which the conductive metal (B) is supported.

Examples of the inorganic compound (A) having photocatalytic activity include TiO ₂ , ZnO, SrTiO ₃ , CdS, GaP, InP, GaAs, BaTiO ₃ , BaTiO ₄ , BaTi ₄ O ₉ , K ₂ NbO ₃ , Nb ₂ O _5. Fe ₂ O ₃ , Ta ₂ O ₅ , K ₃ Ta ₃ Si ₂ O ₃ , WO ₃ , SnO ₂ , Bi ₂ O ₃ , BiVO ₄ , NiO, Cu ₂ O, SiC, MoS ₂ , InPb, RuO ₂ , and CeO ₂ Etc.
As the inorganic compound (A) having photocatalytic activity, TiO ₂ is preferable from the viewpoint of safety and cost. TiO ₂ has anatase, rutile, and brookite crystal structures, any of which can be used.

  In the inorganic compound for photocatalyst (AB) of the present embodiment, the metal oxide (C) is preferably supported with an antibacterial metal (B). By forming such a state, compared with the state in which the antibacterial metal (B) is supported on the inorganic compound (A) having photocatalytic activity and further coated with the metal oxide (C), Since the antibacterial metal (B) is present on the outermost surface of the photocatalyst inorganic compound (AB) particles, it exhibits an effect of biofouling resistance.

The specific surface area of the inorganic compound (hereinafter, simply referred to as “inorganic compound (A ′)”) obtained by treating the particle surface of the inorganic compound (A) having photocatalytic activity with the metal oxide (C) is preferably 80 to 180 m ^2. / g, and more preferably from 90～160M ² / g, more preferably from 100-150 ² / g.
By setting the specific surface area to 80 to 180 m ² / g, the particle surface area increases, and the number of points for supporting the antibacterial metal (B) increases. It can carry | support on the surface of the inorganic compound (A) and / or metal oxide (C) which has, and improves biofouling resistance.
Moreover, by setting the specific surface area to 80 to 180 m ² / g, the photocatalytic activity of the inorganic compound (A) having photocatalytic activity is also sufficient.
Therefore, by setting the specific surface area to 80 to 180 m ² / g, both biofouling resistance and photocatalytic activity can be achieved.

As a method for obtaining the inorganic compound (A ′) having the specific surface area as described above, for example, a method of adjusting the amount of the metal oxide (C) for treating the particle surface of the inorganic compound (A) having photocatalytic activity, And a method of controlling the reaction concentration, temperature, time and the like.
The specific surface area can be measured by a BET method in which gas molecules such as nitrogen (N ₂ ) and argon (Ar) are adsorbed on solid particles and the specific surface area of the solid particles is measured from the amount of adsorbed gas molecules.
In the present embodiment, the ratio of the metal oxide (C) that modifies the inorganic compound (A) having photocatalytic activity is adjusted to the above specific surface area range with respect to the inorganic compound (A) having photocatalytic activity. , Preferably it is 1-30 mass%, More preferably, it is 5-25 mass%, More preferably, it is 10-20 mass%. Specifically, the ratio of the metal oxide (C) that modifies the inorganic compound (A) having photocatalytic activity is the same as that in Example 3. It can be calculated according to the method described in the quantification of the surface modification product.

(Antimicrobial metal (B))
The antibacterial metal (B) in the present embodiment refers to, for example, a metal having a minimum inhibitory concentration (MIC) of metal ions for E. coli cells of 20 mM or less. The minimum inhibitory concentration (MIC) is the minimum concentration of a drug (referred to here as a metal ion) necessary to inhibit the growth of bacteria.

Examples of the antibacterial metal (B) of the present embodiment include heavy metals such as mercury, silver, gold, palladium, platinum, cadmium, cobalt, nickel, copper, zinc, thallium, lead, and manganese. Among these, from the viewpoints of safety and practicality, copper, silver, gold, platinum, and zinc are preferable, and copper, silver, and gold are more preferable.
These heavy metals may be used alone or in combination of two or more.

    The supported amount of the antibacterial metal (B) in the inorganic compound for photocatalyst (AB) of the present embodiment is 0.5 to 5% by mass with respect to the mass of the inorganic compound (A) having photocatalytic activity, preferably 0. 0.5 to 2% by mass, more preferably 0.5 to 1% by mass. Specifically, the amount of the antibacterial metal (B) supported can be measured by the method described in Examples. When the amount of the antibacterial metal (B) supported is less than 0.5% by mass, the effect of biofouling resistance tends to be lowered. When the amount of the antibacterial metal (B) supported is larger than 5% by mass, coloring by the metal occurs and the coating film appearance tends to be not excellent.

[Method of producing inorganic compound for photocatalyst (AB)]
The inorganic compound for photocatalyst (AB) of this embodiment is
A step of modifying the metal oxide (C) to the inorganic compound (A) having photocatalytic activity to obtain an inorganic compound whose particle surface is treated with the metal oxide (C);
A step of supporting the antibacterial metal (B) on the inorganic compound whose particle surface is treated with the metal oxide (C) is included.

A method of directly supporting the antibacterial metal (B) on the inorganic compound (A) having a photocatalytic activity by the order of supporting the antibacterial metal (B) after modifying the metal oxide (C); In comparison, the antibacterial metal (B) itself is prevented from becoming metal colloidal particles, and the antibacterial metal (A) or the metal oxide (C) has an antibacterial metal (C) surface efficiently. B) can be carried.
The reason why metal colloidal particles can be suppressed and the antibacterial metal (B) can be supported is that the inorganic compound (A) having photocatalytic activity modified with the metal oxide (C) has a larger specific surface area. This is probably because the antibacterial metal (B) is easily supported.
In addition, since the antibacterial metal (B) is present on the outermost surface of the inorganic compound for photocatalyst (AB) particles, the inorganic compound for photocatalyst (AB) exhibits the effect of biofouling resistance.

  As a method for supporting the antibacterial metal (B), for example, a water-soluble compound containing the antibacterial metal (B) is used, and the water-soluble compound is reduced with a reducing agent in a liquid containing the inorganic compound (A). And a method of depositing the antibacterial metal (B) on the surface of the inorganic compound (A) or metal oxide (C) having photocatalytic activity.

  As the reducing agent, for example, one or more selected from the group consisting of citric acid, ascorbic acid, tannic acid, diborane, borohydride, formaldehyde, ethanol and the like can be preferably mentioned. If the water-soluble compound containing the antibacterial metal (B) remains without being reduced, the antibacterial metal (B) has water solubility, so that the antibacterial compound is easily eluted from the coating film, and is resistant to biofouling. Since the sustainability tends to be inferior, the reducing agent may be appropriately selected.

  As a water-soluble compound containing an antibacterial metal (B), a salt of an antibacterial metal (B) cation and an anion can be used.

  The method for modifying the metal oxide (C) to the inorganic compound (A) having photocatalytic activity is not particularly limited. For example, a compound (for example, a compound that is a raw material for the metal oxide (C) in an aqueous composition containing titanium oxide) For example, in the case of modification with silicon dioxide, a method of reacting sodium silicate, tetraethoxysilane, etc.) under a heating condition of 70 to 90 ° C., and the like.

  As a method for modifying silicon dioxide, for example, a silicon compound is added to a titanium oxide slurry, and a hydrous oxide is precipitated by neutralization or the like. As the silicon compound, a water-soluble alkali metal silicate such as sodium silicate can be used. Among them, sodium silicate is preferable because it is colorless and the titanium oxide sol is not colored. The treatment amount of the hydrous oxide of silicon is preferably 3 to 25% by mass, more preferably 5 to 20% by mass with respect to titanium oxide. When the treatment amount is less than the above range, the amount of active oxygen species is increased, and the coating film immediately below the photocatalyst coating film is damaged, which is not preferable. On the other hand, when the treatment amount is larger than the above range, titanium oxide is aggregated conversely, the viscosity of the sol tends to increase, the dispersibility is deteriorated, and it is difficult to obtain a product having excellent transparency, which is not preferable.

In the production method of the present embodiment, the ratio of the metal oxide (C) that modifies the inorganic compound (A) having photocatalytic activity is preferably 1 to 30% by mass with respect to the inorganic compound (A) having photocatalytic activity. Yes, more preferably 5 to 25% by mass, still more preferably 10 to 20% by mass.
In the production method of the present embodiment, the amount of the antibacterial metal (B) supported is 0.5 to 5% by mass, preferably 0.5 to 2%, based on the mass of the inorganic compound (A) having photocatalytic activity. It is mass%, More preferably, it is 0.5-1 mass%. Specifically, the amount of the antibacterial metal (B) supported can be measured by the method described in Examples.

[Photocatalyst composition]
The inorganic compound (AB) for photocatalyst of this embodiment can be blended with an inorganic compound (D) that does not have photocatalytic activity to form a photocatalytic composition. That is, one of the present embodiments is a photocatalyst composition containing the inorganic compound for photocatalyst (AB) of the present embodiment and the inorganic compound (D) having no photocatalytic activity.
In the photocatalyst composition of the present embodiment, the proportion of the inorganic compound (A) having photocatalytic activity in the photocatalyst composition is preferably 1 to 20% by mass from the viewpoint of the coating film appearance. By being in this range, the performance as a photocatalyst and the transparency of the coating film are combined. Moreover, the ratio of the inorganic compound (A) having photocatalytic activity is more preferably 3 to 15% by mass, and further preferably 7 to 15% by mass.

(Inorganic compound (D))
Examples of the inorganic compound (D) having no photocatalytic activity include silicon dioxide (silica) particles, aluminum oxide (alumina) particles, calcium silicate particles, magnesium oxide particles, antimony oxide particles, zirconium oxide particles, and composites thereof. Examples thereof include oxide particles. These are used singly or in combination of two or more. Among these, from the viewpoint that there are many surface hydroxyl groups, the surface area of the inorganic compound particles is increased, and the bond between the inorganic compound particles or the bond between the inorganic compound and the polymer particles can be strengthened, silicon dioxide particles, aluminum oxide Particles, antimony oxide particles, and composite oxide particles thereof are preferable, and colloidal silica particles in which silica having silicon dioxide as a basic unit is dispersed in a solvent are more preferable.

  As colloidal silica, one prepared by a sol-gel method can be used, and a commercially available product can also be used. For preparation by the sol-gel method, Werner Stober et al; Colloid and Interface Sci. , 26, 62-69 (1968), Rickey D .; Badley et al; Lang muir 6, 792-801 (1990), Color Material Association Journal, 61 [9] 488-493 (1988), and the like.

  Examples of colloidal silica include acidic colloidal silica and basic colloidal silica using water as a dispersion medium, and colloidal silica using a water-soluble solvent as a dispersion medium.

  Examples of the acidic colloidal silica include commercially available products such as Snowtechs (registered trademark) -O, manufactured by Nissan Chemical Industries, Snowtex-OS, Adelite (registered trademark) AT-20Q, manufactured by Asahi Denka Kogyo Co., Ltd., and Clariant. Examples include clebosol (registered trademark) 20H12 and clebosol 30CAL25 manufactured by Japan Corporation.

  Examples of basic colloidal silica include silica stabilized by addition of alkali metal ions, ammonium ions, amines, and the like. Specifically, SNOWTEX-NS, SNOWTEX manufactured by Nissan Chemical Industries, Ltd. -20, Snowtex-30, Snowtex-C, Snowtex-C30, Snowtex-CM40, Snowtex-N, Snowtex-N30, Snowtex-K, Snowtex-XL, Snowtex-YL, Snowtex -ZL, Snowtex PS-M, Snowtex PS-L, etc .; manufactured by Asahi Denka Kogyo Co., Ltd., Adelite AT-20, Adelite AT-30, Adelite AT-20N, Adelite AT-30N, Adelite AT-20A, Adelite AT -30A, Adelite AT-40, Adela Clarant Japan Co., Ltd. clebosol 30R9, clebosol 30R50, clebosol 50R50, etc .; DuPont Ludox (trademark) HS-40, Ludox HS-30, Ludox LS, Ludox SM-30, etc. Can do.

  Examples of colloidal silica using a water-soluble solvent as a dispersion medium include MA-ST-M (methanol dispersion type having a particle size of 20 to 25 nm) and IPAST (isopropyl having a particle size of 10 to 15 nm) manufactured by Nissan Chemical Industries, Ltd. Alcohol dispersion type), EG-ST (ethylene glycol dispersion type with particle diameter of 10 to 15 nm), EG-ST-ZL (ethylene glycol dispersion type with particle diameter of 70 to 100 nm), NPC-ST (particle diameter of 10 to 10 nm) 15 nm ethylene glycol monopropyl ether dispersion type).

These colloidal silicas may be used alone or in combination of two or more.
Colloidal silica may contain alumina, sodium aluminate or the like as a minor component. Colloidal silica may contain an inorganic base (such as sodium hydroxide, potassium hydroxide, lithium hydroxide, or ammonia) or an organic base (such as tetramethylammonium) as a stabilizer.

The average particle size of the inorganic compound (D) is preferably 100 nm or less, more preferably 50 nm or less, and even more preferably 20 nm or less. Further, inorganic oxide particles having an average particle size of 10 nm or less are more preferable from the viewpoint that the resulting photocatalyst coating film has very high transparency.
The particle diameter (number average particle diameter) of the inorganic compound (D) can be measured according to the method described in the following examples.
In the photocatalyst composition of the present embodiment, the proportion of the inorganic compound (D) having no photocatalytic activity is preferably 40 to 99% by mass with respect to the total amount of the photocatalyst composition, from the viewpoint of the hydrophilicity and weather resistance of the coating film. Yes, more preferably 40 to 90% by mass, still more preferably 45 to 85% by mass.

(Polymer particles (E))
The photocatalyst composition of the present embodiment preferably further includes polymer particles (E).
As the polymer particles (E) that can be used in the photocatalyst composition of the present embodiment, all synthetic resins and natural resins can be used. Further, the form thereof may be a form of pellets or a form dissolved or dispersed in a solvent, and is not particularly limited, but a form of a resin paint for coating is preferable.

Examples of resin paints include oil-based paints, lacquers, solvent-based synthetic resin paints (acrylic resins, epoxy resins, urethane resins, fluororesins, silicone-acrylic resins, alkyd resins, aminoalkyd resins, vinyl. Resin-based, unsaturated polyester resin-based, chlorinated rubber-based, etc.), water-based synthetic resin coatings (emulsion-based, water-based resin-based, etc.), solvent-free synthetic resin coatings (powder coatings, etc.), inorganic coatings, electrical insulation coatings, etc. be able to.
Among these resin coatings, silicone resins and fluorine resins that are hardly decomposable with respect to the photocatalyst, and a combination resin coating of a silicone resin and a fluorine resin are preferably used.

  Examples of such silicone resins include alkoxysilanes and / or organoalkoxysilanes, their hydrolysis products (polysiloxanes) and / or colloidal silica, and acrylic-silicone resins having a silicone content of 1 to 80% by mass. , An epoxy-silicone resin, a urethane-silicone resin, an alkoxysilane and / or an organoalkoxysilane, a hydrolysis product thereof (polysiloxane) and / or a resin containing 1 to 80% by mass of colloidal silica. These silicone resins may be any of a solvent-soluble type, a dispersion type, and a powder type, and may contain additives such as a crosslinking agent and a catalyst.

  In the photocatalyst composition of the present embodiment, from the viewpoint of weather resistance, the proportion of the polymer particles (E) having no photocatalytic activity is preferably 0 to 40% by mass, more preferably, relative to the total amount of the photocatalyst composition. It is 0-30 mass%, More preferably, it is 0-20 mass%.

(Fluorocarbon surfactant (F))
It is preferable that the photocatalyst composition of this embodiment further contains a fluorocarbon surfactant (F). This further improves the wettability to the organic base material and the like when coating with the aqueous coating agent composition of the present embodiment or the aqueous coating material containing the same, and further suppresses appearance troubles such as repellency. be able to. Furthermore, the uniformity of the coating film is further improved. Although it is not certain as these reasons, it is presumed that the surface tension of the aqueous coating agent composition can be lowered by containing the component (F) (however, the action of this embodiment is limited to these). Not.)

  Although it does not specifically limit as (F) component, Amphoteric surfactant is preferable. Examples of amphoteric surfactants include nonionic amphoteric surfactants, anionic amphoteric surfactants, and cationic amphoteric surfactants. Preferable specific examples include amphoteric surfactants having a C 3-20 perfluoroalkyl group.

  Specific examples of the amphoteric surfactant having a C 3-20 perfluoroalkyl group include perfluoroalkyl sulfonate, perfluoroalkyl carboxylate, perfluoroalkyl amine oxide, perfluoroalkyl ethylene oxide adduct, negative Examples include perfluoroalkyl compounds having an ionic group and a cationic group. Among these, from the viewpoint of lowering the surface tension of the paint, perfluoroalkylethylene oxide adducts and perfluoroalkyl compounds having an anionic group and a cationic group are preferred.

As a perfluoroalkyl carboxylate, a commercial item can also be used, for example. Examples of commercially available perfluoroalkyl carboxylates include “Surflon S-211” manufactured by AGC Seimi Chemical Co., Ltd.
As the perfluoroalkylamine oxide, for example, a commercially available product can be used. Examples of commercially available perfluoroalkylamine oxides include “Surflon S-241” manufactured by AGC Seimi Chemical Co., Ltd.
As a perfluoroalkyl ethylene oxide adduct, a commercial item can also be used, for example. Examples of commercially available products such as perfluoroalkylethylene oxide adducts include “Megafac F-444” manufactured by DIC and “Surflon S-242” manufactured by AGC Seimi Chemical.
As a perfluoroalkyl compound having an anionic group and a cationic group, for example, a commercially available product can be used. Commercially available products such as perfluoroalkyl compounds having an anionic group and a cationic group include “Surflon S-231”, “Surflon S-232”, and “Surflon S-233” manufactured by AGC Seimi Chemical Co., Ltd. Etc.
These amphoteric surfactants having a perfluoroalkyl group may be used alone or in combination of two or more.

  The content of the component (F) in the aqueous coating agent composition is not particularly limited, but is preferably 0.0001 to 0.50 mass%, more preferably 0.01 to 0.10 mass%. By making content of (F) component more than the said lower limit, the uniformity of the coating film obtained improves further. By making content of (F) component below the said upper limit, the weather resistance of the coating film obtained further improves.

It is preferable that the photocatalyst composition of this embodiment further contains a fading dye (G). As a result, troubles such as forgetting to paint, overlapping painting, and uneven painting can be prevented.
(G) As a component, the thing which loses color by irradiation of sunlight and does not impair the design of the ground is preferable. Although the time until the color loss varies depending on the season, the irradiation direction, etc., the period until the color loss is confirmed visually is usually 20 days or less, more preferably 10 days or less, and even more preferably 3 days. It is as follows.

The component (G) is not particularly limited as long as it has the property of being decolored by irradiation with sunlight. Preferred examples include methylene blue, crystal violet, malachite green, brilliant blue FCF, erythrosin, new coxin, phloxine. , Rose Bengal, Acid Red, and First Green FCF. Among these, methylene blue is more preferable from the viewpoint of good color developability and fast decolorization rate. These may be used alone or in combination of two or more.
Although content of (G) component in a water-system coating agent composition is not specifically limited, Preferably it is 0.0002-0.01 mass%, More preferably, it is 0.001-0.007 mass%. By setting the content of the component (G) in the aqueous coating agent composition within the above range, the color developability and color fading of the coating film are further improved. Color development here refers to the property of coloring to the extent that the painted and unpainted surfaces are visually distinguished from the difference in color, and fading is the color that does not impair the design of the base material. Refers to the nature of

Although content of (G) component in the coating film obtained from an aqueous coating agent composition is not specifically limited, Preferably it is 0.01-0.5 mass%, More preferably, it is 0.05-0.2. It is mass%, More preferably, it is 0.1-0.2 mass%. By making content of (G) component more than the said lower limit, the coloring property of a coating film improves further, and the fading property of a coating film improves further by setting it as the said upper limit or less.

[Photocatalytic coating]
The photocatalyst composition of this embodiment can form a photocatalyst coating film. That is, one of the embodiments is a photocatalyst coating film formed from the photocatalyst composition of the embodiment.
Although the film thickness of the photocatalyst coating film of this embodiment is not specifically limited, It is preferable that it is 0.05-50 micrometers, It is more preferable that it is 0.1-10 micrometers, It is that it is 0.2-2.0 micrometers. Further preferred. When the thickness is 50 μm or less, good transparency can be ensured, and when the thickness is 0.05 μm or more, functions such as antifouling property and photocatalytic activity can be expressed more effectively.

  The photocatalyst coating film of the present embodiment may contain a dispersion stabilizer from the viewpoint of dispersion stability of each particle contained therein. Examples of the dispersion stabilizer include various water-soluble oligomers selected from the group consisting of polycarboxylic acids and sulfonates, polyvinyl alcohol, hydroxyethyl cellulose, starch, maleated polybutadiene, maleated alkyd resin, polyacrylic acid (salt ), Various synthetic or natural polymer materials represented by polyacrylamide and acrylic resins, and the like. A dispersion stabilizer is used individually by 1 type or in mixture of 2 or more types.

  In addition, the photocatalyst coating film of the present embodiment has components added to and blended with ordinary paints and molding resins, for example, a solvent, a thickener, a leveling agent, and a thixotropic agent, depending on the application and method of use. , Antifoaming agent, Freezing stabilizer, Matting agent, Crosslinking reaction catalyst, Pigment, Curing catalyst, Crosslinking agent, Filler, Anti-skinning agent, Dispersant, Wetting agent, Light stabilizer, Antioxidant, UV absorber , Rheology control agent, antifoaming agent, film forming aid, rust preventive agent, dye, plasticizer, lubricant, reducing agent, preservative, antifungal agent, deodorant, anti-yellowing agent, antistatic agent or A charge adjusting agent or the like may be contained. As described above, it is presumed that adding an anti-algal fungicide to the photocatalyst coating does not give an anti-algal anti-fungal performance, but adding it does not seem to affect other coating performance.

  The photocatalyst coating film of this embodiment is obtained by applying the photocatalyst composition to the surface of a substrate or a coating covering the substrate and drying it. Examples of the base material on which the photocatalyst composition is applied include organic substrates represented by synthetic resins, natural resins, fibers, inorganic substrates represented by metals, ceramics, glass, stone, cement, concrete, and combinations thereof. Is mentioned.

  Examples of the synthetic resin include thermoplastic resins and curable resins (thermosetting resins, photocurable resins, moisture curable resins, and the like). Specific examples thereof include, for example, silicone resin, acrylic resin, methacrylic resin, fluororesin, alkyd resin, aminoalkyd resin, vinyl resin, polyester resin, styrene-butadiene resin, polyolefin resin, polystyrene resin, polyketone resin, polyamide resin, Polycarbonate resin, polyacetal resin, polyether ether ketone resin, polyphenylene oxide resin, polysulfone resin, polyphenylene sulfone resin polyether resin, polyvinyl chloride resin, polyvinylidene chloride resin, urea resin, phenol resin, melamine resin, epoxy resin, urethane resin And silicone-acrylic resin. Examples of the natural resin include cellulose resins, isoprene resins typified by natural rubber, protein resins typified by casein, and the like.

  When the substrate is a resin plate or fiber, the surface thereof may be subjected to a surface treatment such as a corona discharge treatment, a flame treatment, or a plasma treatment, but these surface treatments are not essential.

  The photocatalyst coating film of the present embodiment can be applied by any method according to the use of the photocatalyst composition. Examples of the application method include spray spraying, flow coating, roll coating, brush coating, dip coating, spin coating, screen printing, casting, gravure printing, and flexographic printing.

  The photocatalyst coating film of this embodiment is obtained by applying a photocatalyst composition and then drying to remove volatile components. At this time, for example, after drying at a low temperature of 20 ° C. to 80 ° C., heat treatment at 20 ° C. to 500 ° C., more preferably 40 ° C. to 250 ° C. may be performed as desired, and ultraviolet irradiation or the like is performed. Also good.

[Photocatalyst coating products]
The photocatalyst-coated product of the present embodiment is a product including the photocatalyst coating film of the present embodiment, and includes a substrate and the photocatalyst coating film formed on the substrate. The photocatalyst-coated product may be the same as the known embodiment except that the photocatalyst coating film of the present embodiment is provided. Specific examples of the photocatalyst-coated product of the present embodiment include, for example, building materials, building exteriors, building interiors, window frames, window glass, structural members, building facilities such as houses, vehicle illumination lamp covers, window glass, mechanical devices, Exterior of goods, dustproof cover and painting, display equipment, its covers, traffic signs, various display devices, display objects such as advertising towers, sound insulation walls for roads and railways, bridges, exterior and painting of guardrails, tunnel interior and painting , Electronic parts used outside such as insulators, solar battery covers, solar water heater heat collection covers, etc., and exterior parts of electrical equipment, especially exteriors such as transparent members, greenhouses and greenhouses. This photocatalyst-coated product may be obtained by applying a photocatalyst composition on the surface of a substrate and drying it to form a photocatalyst coating film on the substrate, but the production method is not limited thereto. For example, the substrate and the photocatalyst coating film may be molded at the same time, and more specifically, may be integrally molded.

  In addition, after the photocatalyst coating film of the present embodiment is formed on a substrate, the photocatalyst coating film is adhered to another substrate by adhesion, fusion, or the like in a state where the photocatalyst coating film is peeled off or adhered to the substrate. You may let them.

As mentioned above, although the form for implementing this invention was demonstrated, this invention is not limited to the said this embodiment. The present invention can be variously modified without departing from the gist thereof.

  The following production examples, examples, and comparative examples, as well as production examples and production comparative examples, will specifically describe the present invention, but these do not limit the scope of the present invention. Various physical properties were measured by the following methods.

1. Measurement of quantitative [H ₂ O _2] in the H ₂ O ₂ was performed using a lucigenin chemiluminescence method.
First, to a quartz cell (optical path (length) 1 cm × width 1 cm) placed on a magnetic stirrer in a dark box, 3.5 mL of 0.01 M NaOH aqueous solution was added to adjust to pH 9, and further 15 mg of A powder of the inorganic compound (A) obtained by drying the sol was added and suspended to obtain a suspension.
Next, using the LED (Hamamatsu Photonics, model number “LC-L2”, wavelength: 365 nm, intensity 5 mW / cm ² ) as a light source, the cell containing the suspension was irradiated with ultraviolet light for 60 seconds. Went. After irradiation, 50 μL of a 0.7 mM lucigenin solution was added, and chemiluminescence generated by H ₂ O ₂ was passed through a bandpass filter, and then detected with an electron-cooled photomultiplier tube. [H ₂ O ₂ ] was derived from the detected amount of chemiluminescence.

2. Hydroxyl radical quantification [.OH] was measured using a coumarin fluorescent probe method.
First, a 0.1 mM coumarin aqueous solution was prepared, and 15 mg of an inorganic compound (A) obtained by drying the sol and 35 mL of the coumarin aqueous solution were suspended in a quartz cell (optical path (length) 1 cm × width 1 cm). Suspension was obtained. This suspension was irradiated with LED light having a wavelength of 365 nm and an intensity of 5 mW / cm ² for 60 seconds.
Next, in order to separate the inorganic compound (A) powder, 0.5 g of KCl was added to the suspension after the irradiation, and the mixture was allowed to stand in the dark for 24 hours.
Thereafter, the supernatant was taken as a sample, and the fluorescence was measured with a fluorescence spectrophotometer (850 type, manufactured by HITACHI). By comparing the fluorescence intensity of the coumarin having a known concentration with the fluorescence intensity of the sample, .OH was quantified, and the value of [.OH] was derived.

3. Quantification of surface-modified product Using a fluorescent X-ray analyzer, quantification was performed by the FP method in which quantitative analysis was performed according to the theory and the fundamental constant Fundamental Parameter (FP).

4). Particle size (secondary particle size of inorganic compound for photocatalyst (AB))
The secondary particle size of the inorganic compound for photocatalyst (AB) was determined by observing 50 arbitrarily selected particles by observation with an electron microscope and calculating them as an arithmetic average thereof.
(Number average particle diameter of inorganic compound (D) and polymer particles (E))
The sample was appropriately diluted by adding a solvent so that the solid content in the sample was 1 to 20% by mass, and the measurement was performed using a wet particle size analyzer (Microtrac UPA-9230 manufactured by Nippon Nikkiso).

5. Film thickness of coating film Film thickness measurement system (SPECTRA COOP, trade name "HandyLambda II THICKNESS") equipped with halogen light source (MORITEX, trade name "MHF-D100LR") It measured using.

6). Paintability The test plate surface state was observed and photographed with a scanning electron microscope (manufactured by JEOL Ltd., NeoScope JCM-5000), and the photocatalyst coating rate was calculated as the coating rate.
[Evaluation criteria]
○: The coating rate was 80% or more.
(Triangle | delta): The coating rate was 80 to 50%.
X: The coating rate was 50% or less.

7). Photocatalytic activity (pigment degradation activity)
It calculated | required based on JISR1703-2. The test piece purification conditions were irradiation for 24 hours at an illuminance of 1 mW / cm ² , the methylene blue adsorption conditions were irradiation for an adsorption time of 24 hours at an adsorption liquid concentration of 0.02 mM, and the decomposition measurement conditions for methylene blue were illuminance of 1 mW / cm ² and the test liquid concentration. Absorption spectrum of the test solution collected after irradiation with 0.01 mM, injection volume of 35 mL was measured with a spectrophotometer, and a degradation activity index (nM / min) was calculated. The absorbance measurement wavelength was 664 nm.
[Evaluation criteria]
A: Decomposition activity index was 10 nM / min or more.
○: Decomposition activity index was 7 nM / min or more and less than 10 nM / min.
(Circle) (triangle | delta): The decomposition activity index was 5 nM / min or more and less than 7 nM / min.
X: The decomposition activity index was less than 5 nM / min.

8). Deterioration observation of the coating film directly under the photocatalyst coating film After embedding the sample in an epoxy resin (trade name, Quetol 812), an ultrathin section having a thickness of 50 to 60 nm was obtained with a ULTRACUT-N type microtome (trade name) manufactured by Reichert, Germany. After being prepared and loaded on a mesh with a support film, carbon deposition was performed to make a sample for speculum, and the cross section of the coating film was observed with TEM (Hitachi HF2000 type, acceleration voltage: 125 kV). The deterioration state of the coating film was evaluated.
[Evaluation criteria]
○: Deterioration of the coating film directly under the photocatalyst coating film was not observed.
○ Δ: Slight deterioration of the coating film directly under the photocatalyst coating film was observed, but it was judged that there was no problem as a whole.
Δ: Some deterioration of the coating film directly under the photocatalyst coating film was observed.
X: Deterioration of the coating film directly under the photocatalyst coating film was observed as a whole.

9. Algae-proof, mold-proof (short term)
The test specimen was placed in a petri dish containing algae and placed in a thermostatic bath maintained at a constant temperature, and the test was conducted. Judgment was made 4 weeks after the start of the test. In addition, the mold resistance test was conducted in accordance with JIS Z2911: 2010. The determination was made 2 weeks after the start of the test.
[Evaluation criteria]
○: Growth of algae and mold was not observed.
Δ: Slight growth of algae and mold was observed, but it was judged that there was no problem overall.
X: Growth of algae and mold was clearly seen.

10. Algae-proof, mold-proof (long-term)
In the neighborhood of Choshi City, Chiba Prefecture, an outdoor exposure test was conducted at 90 ° north of the specimen on land where lawns grow. Judgment was made one year after exposure.
[Evaluation criteria]
A: Growth of algae and mold was not observed by visual observation and microscopic observation (40 times).
Δ: Growth of algae and mold was not observed by visual observation, but growth was not observed by microscopic observation (40 times).
X: Growth of algae and mold was observed by visual observation.

11. Transparency (coating opacity)
The color difference was measured in a state where black paper was laid under a glass plate (manufactured by Testpiece Corp., flat plate glass; 60 mm * 60 mm * 2 mm). Thereafter, it was applied with a dip coater (DC4200, manufactured by Aiden, elevating speed: 10 mm / sec when descending, 10 mm / sec when raising), and dried for 2 days after coating. Then, the color difference of the test body which left it for 10 days under the fluorescent lamp adjusted to illumination intensity 5000Lx and decolored the coloring agent was measured. The color difference (lightness difference ΔL) before and after coating was evaluated. The color difference was obtained from a standard plate using a color guide (BYK Gardner). The lower the color difference ΔL, the higher the transparency and the better the appearance.
[Evaluation criteria]
○: Color difference ΔL was less than 1.6.
Δ: Color difference ΔL was 1.6 to less than 3.0.
X: The color difference ΔL was 3.0 or more.

12 Weather resistance (color difference after exposure to SWOM5000 hours)
Using the sunshine weather meter manufactured by Suga Test Instruments Co., Ltd., an exposure test (black panel temperature: 63 ° C., rainfall: 18 minutes / 2 hours) The color difference before exposure was used as a standard, and the state change before and after exposure was evaluated as ΔE *. The color difference was obtained from a standard plate using a color guide (BYK Gardner). The lower the color difference ΔE *, the better the appearance and the better the weather resistance.
[Evaluation criteria]
○: ΔE * was less than 2.
○ Δ: ΔE * was 2 or more and less than 3.
Δ: ΔE * was 3 or more and less than 5.
X: ΔE * was 5 or more.

[Production Example 1] Silica-modified rutile type titanium oxide 700 mL of a titanium tetrachloride aqueous solution having a concentration of 200 g / L as TiO ₂ and a sodium hydroxide aqueous solution having a concentration of 100 g / L as Na ₂ O, and the pH of the system being 5 to 9 Were added in parallel in water to maintain Thereafter, the pH of the system was adjusted to 7, then filtered, and washed until the filtrate had a conductivity of 100 μS / cm, to obtain a titanium oxide wet cake 1 having a solid content concentration of 28.3 mass%. This titanium oxide wet cake 1 had a rutile structure, and its average particle size was 8 nm.
The obtained rutile-type titanium oxide wet cake 1 was diluted with pure water to prepare a 1 mol / L slurry. 1 L of this slurry was charged into a 3 L flask, 1 L of 1N nitric acid was added so that the molar ratio of titanium oxide and nitric acid (titanium oxide / nitric acid) was 1, and the mixture was heated to a temperature of 95 ° C. The acid heat treatment was performed by maintaining the temperature for 2 hours. Next, the acid-heated slurry is cooled to room temperature, neutralized with 28% aqueous ammonia (pH = 6.7), filtered, and washed until the filtrate has a conductivity of 100 μS / cm. A titanium oxide wet cake 2 having a solid content of 25% by mass was obtained.
To the obtained titanium oxide wet cake 2, a 10% by mass sodium hydroxide aqueous solution was added, repulped, and then dispersed for 3 hours with an ultrasonic washer, pH = 10.5, solid content concentration 10% by mass. An alkaline titanium oxide sol was obtained. This alkaline titanium oxide sol 2L was charged into a 3 L flask, heated to a temperature of 70 ° C., 69.4 ml of a sodium silicate aqueous solution having a concentration of 432 g / L as SiO ₂ was added, and then heated to 90 ° C. After aging for 1 hour, 10% sulfuric acid was added to adjust the pH to 6, and the surface of titanium oxide was surface treated with a hydrous oxide of silicon.
The obtained titanium oxide sol was cooled to room temperature, 5.4 L of pure water was added, impurities were removed and concentrated using a desalting and concentrating device, pH = 7.3, solid content concentration 29% by mass A neutral rutile-type titanium oxide sol having a conductivity of 1.18 mS / cm was obtained. It contained 15 wt% of silicon oxide hydroxide with SiO ₂ basis relative to Ti _2. The average particle diameter of titanium oxide in this sol was 60 nm. The specific surface area of the silica-modified rutile type titanium oxide was 145 m ² / g.

[Production Example 2] Silica-modified anatase-type titanium oxide Titanium ore is reacted with sulfuric acid, and the resulting titanium sulfate solution is hydrolyzed with heating to form an agglomerated metatitanic acid as an aqueous slurry of 30% by mass in terms of TiO _2. The slurry was neutralized with aqueous ammonia to pH 7, and then filtered and washed to remove sulfate radicals to obtain a dehydrated cake. Nitric acid was added to the obtained dehydrated cake and peptized to obtain an acidic titanium oxide sol having a pH of 1.5 consisting of titanium oxide fine particles (secondary particle diameter 7 nm) containing an anatase type crystal structure. The obtained acidic titanium oxide sol is diluted with pure water to make 600 ml of titanium oxide sol of 200 g / L in terms of TiO ₂ , heated to 70 ° C., and then a sodium silicate aqueous solution 20 having a concentration of 432 g / L in terms of SiO _2. .8 ml was added simultaneously with 20% sulfuric acid and then aged for 30 minutes. Next, the pH was adjusted to 8 with a 10% by mass aqueous sodium hydroxide solution, the pH was adjusted to 6 with a 2% aqueous sulfuric acid solution, filtered and washed to obtain a wet cake. The wet cake was repulped into pure water and then ultrasonically dispersed to obtain a titanium oxide sol (solid content concentration 20% by mass, pH = 7.5) stable in the neutral range. In this sample, the aggregated silica was deposited on the surface of the titanium oxide fine particles in a porous state, and the content thereof was 7 parts by mass in terms of SiO _{2 with} respect to 100 parts by mass of TiO ₂ . The specific surface area of the silica-modified rutile titanium oxide was 90 m ² / g.

[Production Example 1], [Production Example 2], [Commercial product 1] (Ishihara Sangyo Co., Ltd., anatase-type titanium oxide ST-01), and [Commercial product 2] (Teika Co., Ltd., rutile type) Table 1 shows [H ₂ O ₂ ] and [.OH] of titanium oxide MT150A).

[Example 1] Silver-supported titanium oxide 400 g of the titanium oxide aqueous dispersion (solid content: 2% by mass) obtained in [Production Example 1] and [Production Example 2] was charged into a 500 mL flask and heated to 80 ° C. Warmed up. When the temperature reaches 80 ° C., an aqueous silver nitrate solution (concentration of 5% by mass) is added in an amount of 1.26 g to 5.04 g depending on the supported amount, and immediately thereafter trisodium citrate aqueous solution (concentration of 10% by mass) is added to 0.85 g. 3.4 g and 3.18 g to 12.72 g of an aqueous tannic acid solution (concentration 1% by mass) were added. After the addition, the mixture was stirred for 1 hour, and after stirring, cooled to room temperature was used as a composite. The average secondary particle diameter of titanium oxide in the obtained composite was about 60 nm.
From the titanium oxide aqueous dispersion obtained in [Production Example 1], a silver-supporting silica-modified rutile type titanium oxide was obtained. From the titanium oxide aqueous dispersion obtained in [Production Example 2], a silver-supporting silica-modified anatase-type titanium oxide was obtained.

[Example 2] Copper-supported titanium oxide 400 g of the titanium oxide aqueous dispersion (solid content: 2% by mass) obtained in [Production Example 1] and [Production Example 2] was charged into a 500 mL flask and heated to 80 ° C. Warmed up. When the temperature reached 80 ° C., 0.11 g to 0.22 g of an aqueous copper chloride solution (concentration of 5% by mass) was added depending on the amount supported, and immediately thereafter trisodium citrate aqueous solution (concentration of 10% by mass) was added to 0.85 g. To 3.4 g and 3.18 g to 12.72 g of a tannic acid aqueous solution (concentration 1% by mass) were added. After the addition, the mixture was stirred for 1 hour, and after stirring, cooled to room temperature was used as a composite. The average secondary particle diameter of titanium oxide in the obtained composite was 60 to 70 nm.
From the titanium oxide aqueous dispersion obtained in [Production Example 1], a copper-supported silica-modified rutile type titanium oxide was obtained. From the titanium oxide aqueous dispersion obtained in [Production Example 2], a copper-supported silica-modified anatase-type titanium oxide was obtained.

[Example 3] Gold-supported titanium oxide 400 g of the titanium oxide aqueous dispersion (solid content: 2% by mass) obtained in [Production Example 1] and [Production Example 2] was charged into a 500 mL flask and heated to 80 ° C. Warmed up. When the temperature reached 80 ° C., 0.08 g to 0.33 g of a chloroauric acid aqueous solution (concentration of 5% by mass) was added depending on the supported amount, and immediately after that, a trisodium citrate aqueous solution (concentration of 10% by mass) was added to 0.03 g. 85 g to 3.4 g and 3.18 g to 12.72 g of a tannic acid aqueous solution (concentration 1% by mass) were added. After the addition, the mixture was stirred for 1 hour, and after stirring, cooled to room temperature was used as a composite. The average secondary particle diameter of titanium oxide in the obtained composite was around 60 nm.
From the titanium oxide aqueous dispersion obtained in [Production Example 1], a gold-supporting silica-modified rutile type titanium oxide was obtained. From the titanium oxide aqueous dispersion obtained in [Production Example 2], a gold-supporting silica-modified anatase-type titanium oxide was obtained.

[Example 4] Silver-copper-supported titanium oxide 400 g of the titanium oxide aqueous dispersion (solid content 2% by mass) obtained in [Production Example 1] and [Production Example 2] was charged into a 500 mL flask, 80 Warmed to ° C. When the temperature reached 80 ° C., 1.89 g to 2.52 g of an aqueous silver nitrate solution (concentration of 5% by mass) was added depending on the supported amount, and immediately after that an aqueous solution of trisodium citrate (concentration = 10%) was added to 1.28 g to 1.7 g and 4.77 g to 6.36 g of an aqueous tannic acid solution (concentration = 1%) were added. After the addition, the mixture is stirred for 45 minutes, and then an aqueous copper chloride solution (concentration 5 mass%) is added in an amount of 0.11 g to 0.16 g depending on the supported amount, and immediately after that, an aqueous tannic acid solution (concentration 1 mass%) 3.18 g 4.77 g was added. After the addition, the mixture was stirred for 45 minutes, and the mixture was cooled to room temperature after stirring to obtain a composite. The average secondary particle diameter of titanium oxide in the obtained composite was about 60 nm.
From the titanium oxide aqueous dispersion obtained in [Production Example 1], a silver-copper-supported silica-modified rutile type titanium oxide was obtained. Silver-copper-supported silica-modified anatase-type titanium oxide was obtained from the titanium oxide aqueous dispersion obtained in [Production Example 2].

[Example 5] Copper-gold-supported titanium oxide 400 g of the titanium oxide aqueous dispersion (solid content 2% by mass) obtained in [Production Example 1] and [Production Example 2] was charged into a 500 mL flask, 80 Warmed to ° C. When the temperature reached 80 ° C., 0.17 g of chloroauric acid aqueous solution (concentration 5% by mass) was added, and immediately after that 1.7 g of trisodium citrate aqueous solution (concentration 10% by mass) and tannic acid aqueous solution (concentration 1% by mass) ) Was added to 6.36 g. After the addition, the mixture was stirred for 45 minutes, and then 0.11 g of an aqueous copper chloride solution (concentration 5 mass%) was added, and immediately after that 3.18 g of an aqueous tannic acid solution (concentration 1 mass%) was added. After the addition, the mixture was stirred for 45 minutes, and the mixture was cooled to room temperature after stirring to obtain a composite. The average secondary particle diameter of titanium oxide in the obtained composite was about 60 nm.
From the titanium oxide aqueous dispersion obtained in [Production Example 1], a copper-gold supported silica-modified rutile type titanium oxide was obtained. From the titanium oxide aqueous dispersion obtained in [Production Example 2], copper-gold supported silica modified anatase type titanium oxide was obtained.

[Example 6] Silver-gold-supported titanium oxide 400 g of the titanium oxide aqueous dispersion (solid content 2% by mass) obtained in [Production Example 1] and [Production Example 2] was charged into a 500 mL flask, 80 Warmed to ° C. When the temperature reached 80 ° C., an aqueous silver nitrate solution (concentration of 5% by mass) was added in an amount of 1.26 g to 2.52 g depending on the amount supported, and immediately thereafter trisodium citrate aqueous solution (concentration of 10% by mass) was added from 0.85 g to 1.7 g and 3.18 g to 6.36 g of a tannic acid aqueous solution (concentration 1% by mass) were added. After the addition, the mixture was stirred for 45 minutes, and then 0.17 g of an aqueous chloroauric acid solution (concentration 5% by mass) was added, and immediately after that 6.36 g of an aqueous tannic acid solution (concentration 1% by mass) was added. After the addition, the mixture was stirred for 45 minutes, and the mixture was cooled to room temperature after stirring to obtain a composite. The average secondary particle diameter of titanium oxide in the obtained composite was about 60 nm.
From the titanium oxide aqueous dispersion obtained in [Production Example 1], a silver-gold supported silica modified rutile type titanium oxide was obtained. From the titanium oxide aqueous dispersion obtained in [Production Example 2], a silver-gold supported silica modified anatase type titanium oxide was obtained.

[Comparative Example 1] Copper-supported rutile type titanium oxide [Commercially available product 2] (rutile titanium oxide MT150A manufactured by Teika Co., Ltd.) 400 g of an aqueous dispersion (solid content: 2% by mass) was charged into a 500 mL flask and heated to 80 ° C. Warm up. When the temperature reached 80 ° C., 0.11 g to 0.22 g of an aqueous copper chloride solution (concentration of 5% by mass) was added depending on the amount supported, and immediately thereafter trisodium citrate aqueous solution (concentration of 10% by mass) was added to 0.85 g. To 3.4 g and 3.18 g to 12.72 g of a tannic acid aqueous solution (concentration 1% by mass) were added. After the addition, the mixture was stirred for 1 hour, and after stirring, cooled to room temperature was used as a composite. The average secondary particle diameter of titanium oxide in the obtained composite was 200 nm.

[Production Example 3] Synthesis of polymer emulsion particles (E1) aqueous dispersion A reactor having a reflux condenser, a dropping tank, a thermometer and a stirrer was charged with 830 g of ion-exchanged water and a 10% by mass dodecylbenzenesulfonic acid aqueous solution 40. After charging 0.0 g, the temperature in the reactor was heated to 80 ° C. with stirring. In this reactor, 90.7 g of dimethyldimethoxysilane and 83.5 g of methyltrimethoxysilane and 10 g of water were simultaneously dropped over about 2 hours while maintaining the temperature in the reactor at 80 ° C. did. At that time, 2 g of a 10% by mass aqueous solution of dodecylbenzenesulfonic acid was added when 1 hour had passed after the mixed solution composed of dimethyldimethoxysilane and methyltrimethoxysilane was dropped. After dropping a total amount of a mixed liquid composed of dimethyldimethoxysilane and methyltrimethoxysilane, the temperature in the reactor was maintained at 80 ° C. and stirring was continued for about 30 minutes, and then 14.8 g of a 10% by mass aqueous solution of dodecylbenzenesulfonic acid. And the temperature in the reactor was maintained at 80 ° C., and stirring was continued for 2.5 hours.
Next, 26.4 g of 0.5% by weight aqueous solution of ammonium persulfate was added, 0.1 g of n-butyl acrylate, 36.7 g of phenyltrimethoxysilane, 27.8 g of tetraethoxysilane, and 3-methacryloxypropyltri A mixture of 1.1 g of methoxysilane with 10 g of water added, 0.1 g of diethyl acrylamide, 0.9 g of acrylic acid, reactive emulsifier (trade name “Adekaria Soap SR-1025”, Asahi Denka Co., Ltd. ), 25% solid content aqueous solution) 4.5 g, reactive emulsifier (trade name “AQUALON KH-1025”, Daiichi Kogyo Seiyaku Co., Ltd., 25% aqueous solution solid content) 2.3 g, ammonium persulfate A mixture of 120 g of 5% by mass aqueous solution and 256.4 g of ion-exchanged water was added for about 2 hours with the temperature in the reactor kept at 80 ° C. It was dropped at the same time Te. Further, the temperature in the reactor was maintained at 80 ° C. and stirring was continued for about 2 hours, and then the mixture was cooled to room temperature and filtered through a 100-mesh wire mesh. The solid content was adjusted to 10.0% by mass with ion-exchanged water, and an aqueous dispersion of polymer emulsion particles (E-1) having a number average particle diameter of 20 nm was obtained as polymer particles.

[Production Example 4] Synthesis of polymer emulsion particles (E2) aqueous dispersion A reactor having a reflux condenser, a dropping tank, a thermometer, and a stirrer was charged with 850 g of ion-exchanged water, 10% by mass of dodecylbenzenesulfonic acid aqueous solution 10. After adding 0.0 g, the temperature in the reactor was heated to 80 ° C. with stirring. In this reactor, a mixed solution consisting of 140.0 g of dimethyldimethoxysilane, 20.0 g of phenyltrimethoxysilane, and 5.0 g of methyltrimethoxysilane was added for about 2 hours while maintaining the temperature in the reactor at 80 ° C. It was dripped over. Thereafter, the temperature in the reactor was maintained at 80 ° C., and stirring was continued for 30 minutes.
Next, 16.8 g of a 10% by mass dodecylbenzenesulfonic acid aqueous solution was added, and then the temperature in the reactor was maintained at 80 ° C. and stirring was continued for 2 hours. Then, 6.6 g of a 2 mass% ammonium persulfate aqueous solution was added thereto, and then a mixed solution composed of 26.8 g of phenyltrimethoxysilane, 28.6 g of tetraethoxysilane, and 1.1 g of 3-methacryloxypropyltrimethoxysilane; 0.9 g of acrylic acid, reactive emulsifier (manufactured by ADEKA, “ADEKA rear soap SR-1025”; solid content 25% by mass aqueous solution) 2.3 g, reactive emulsifier (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., “AQUALON KH- 1025 "; 25 mass% solid content aqueous solution) 2.3 g, 30 g of 2.0 mass% ammonium persulfate aqueous solution, and 170.0 g of ion-exchanged water, the temperature in the reactor was kept at 80 ° C. In the state, it was dripped simultaneously over about 2 hours. Further, the temperature in the reactor was maintained at 80 ° C. and stirring was continued for about 1 hour, followed by cooling to room temperature, adjusting the pH to 8 by adding 25% aqueous ammonia solution to the reaction solution, and then adding 100 mesh. Filtered through a wire mesh. The solid content was adjusted to 10.0% by mass with ion-exchanged water, and an aqueous dispersion of a polymer (E2) having a number average particle diameter of 119 nm was obtained as a polymer.

[Production Example 5] Synthesis of polymer emulsion particle (E3) aqueous dispersion A reactor having a reflux condenser, a dropping tank, a thermometer and a stirrer was charged with 850 g of ion-exchanged water and an aqueous solution of dodecylbenzenesulfonic acid 5 of 10% by mass. After charging .6 g, the temperature in the reactor was heated to 80 ° C. with stirring. In this reactor, 110.0 g of dimethyldimethoxysilane, 73.0 g of phenyltrimethoxysilane, and 29.4 g of methyltrimethoxysilane were mixed for about 2 hours with the temperature in the reactor kept at 80 ° C. It was dripped over. Thereafter, the temperature in the reactor was maintained at 80 ° C., and stirring was continued for 30 minutes.
Next, 5.6 g of a 10% by mass dodecylbenzenesulfonic acid aqueous solution was added, and then the temperature in the reactor was maintained at 80 ° C. and stirring was continued for 2 hours. After charging 6.6 g of a 2% by mass aqueous ammonium persulfate solution, 22.5 g of methyl methacrylate, 11.2 g of n-butyl acrylate, 12.3 g of phenyltrimethoxysilane, 28.6 g of tetraethoxysilane, and A mixed solution composed of 1.1 g of 3-methacryloxypropyltrimethoxysilane, 0.9 g of acrylic acid, reactive emulsifier (manufactured by ADEKA, “ADEKA rear soap SR-1025”; solid content 25% by mass aqueous solution) 1.2 g , Reactive emulsifier (Daiichi Kogyo Seiyaku Co., Ltd., “Aqualon KH-1025”; solid content 25% by weight aqueous solution) 1.2 g, ammonium persulfate 2.0% by weight aqueous solution 30 g, and ion-exchanged water 286.4 g. The mixed solution was simultaneously added dropwise over about 2 hours while maintaining the temperature in the reactor at 80 ° C. Further, the temperature in the reactor was maintained at 80 ° C. and stirring was continued for about 1 hour, followed by cooling to room temperature, adjusting the pH to 8 by adding 25% aqueous ammonia solution to the reaction solution, and then adding 100 mesh. Filtered through a wire mesh. The solid content was adjusted to 10.0% by mass with ion-exchanged water, and an aqueous dispersion of a polymer (E3) having a number average particle diameter of 155 nm was obtained as a polymer.

[Production Example 1]
Of the silver-supported silica-modified rutile titanium oxide prepared in Example 1, silver-supported silica-modified rutile titanium oxide having a silver support amount of 1% by mass with respect to titanium oxide was used as the inorganic compound for photocatalyst (AB1).
163.8 g of inorganic compound for photocatalyst (AB1) and basic colloidal silica, water-dispersed colloidal silica (D1) having a number average particle diameter of 8 nm (trade name “Snowtex NS”, manufactured by Nissan Chemical Industries, Ltd., 120.6 g of solid content 20% by mass), 0.99 g of fluorocarbon surfactant (F) (manufactured by DIC, “Megafac F-444”), which is a perfluoroalkylethylene oxide adduct, and solid with ion-exchanged water The photocatalytic composition (H-1) was prepared by mixing and stirring 140 g of a fading dye (G) (manufactured by Kishida Chemical Co., “Methylene Blue”) whose amount was adjusted to 1.0% by mass and 656.2 g of water. Was made.
A glass plate having a size of 10 cm × 10 cm, in which an acrylic silicone resin was applied in advance to a thickness of 100 μm on another surface (front surface) of a glass plate on which one side (back surface) was subjected to white printing, was prepared. The said photocatalyst composition (H-1) was apply | coated to the single side | surface (surface) of this glass plate by the spray method. Then, the test plate (I-1) in which the photocatalyst coating film was formed was obtained by drying the apply | coated photocatalyst composition (H-1) at normal temperature for 1 hour. Various evaluation results of this test plate (I-1) are shown in Table 2.

[Production Example 2]
Of the silver-supported silica-modified rutile titanium oxide prepared in Example 1, silver-supported silica-modified rutile titanium oxide having a silver support amount of 2% by mass with respect to titanium oxide was used as the inorganic compound for photocatalyst (AB2).
163.8 g of photocatalyst inorganic compound (AB2) and water-dispersed colloidal silica (D1) having a number average particle diameter of 8 nm (trade name “Snowtex NS”, manufactured by Nissan Chemical Industries, Ltd., solid content 20% by mass) 6 g, 0.99 g of fluorocarbon surfactant (F) (manufactured by DIC, “Megafac F-444”), and a fading dye (G) (solid content adjusted to 1.0 mass% with ion-exchanged water) (G) ( A photocatalyst composition (H-2) was prepared by mixing and stirring 140 g of “Methylene Blue” manufactured by Kishida Chemical Co., Ltd.) and 656.2 g of water.
A glass plate having a size of 10 cm × 10 cm, in which an acrylic silicone resin was applied in advance to a thickness of 100 μm on another surface (front surface) of a glass plate on which one side (back surface) was subjected to white printing, was prepared. The said photocatalyst composition (H-2) was apply | coated to the single side | surface (surface) of this glass plate by the spray method. Then, the test plate (I-2) in which the photocatalyst coating film was formed was obtained by drying the apply | coated photocatalyst composition (H-2) at normal temperature for 1 hour. Various evaluation results of this test plate (I-2) are shown in Table 2.

[Production Example 3]
Of the copper-supported silica-modified rutile titanium oxide prepared in Example 2, copper-supported silica-modified rutile titanium oxide having a copper support amount of 1% by mass with respect to titanium oxide was used as the inorganic compound for photocatalyst (AB3).
163.8 g of inorganic compound for photocatalyst (AB3) and water-dispersed colloidal silica (D1) having a number average particle diameter of 8 nm (trade name “Snowtex NS”, manufactured by Nissan Chemical Industries, Ltd., solid content 20% by mass) 6 g, 0.99 g of fluorocarbon surfactant (F) (manufactured by DIC, “Megafac F-444”), and a fading dye (G) (solid content adjusted to 1.0 mass% with ion-exchanged water) (G) ( A photocatalyst composition (H-3) was prepared by mixing and stirring 140 g of “Methylene Blue” manufactured by Kishida Chemical Co., Ltd.) and 656.2 g of water.
A glass plate having a size of 10 cm × 10 cm, in which an acrylic silicone resin was applied in advance to a thickness of 100 μm on another surface (front surface) of a glass plate on which one side (back surface) was subjected to white printing, was prepared. The said photocatalyst composition (H-3) was apply | coated to the single side | surface (surface) of this glass plate with the spray method. Then, the test plate (I-3) in which the photocatalyst coating film was formed was obtained by drying the apply | coated photocatalyst composition (H-3) at normal temperature for 1 hour. Various evaluation results of this test plate (I-3) are shown in Table 2.

[Production Example 4]
Of the gold-supported silica-modified rutile titanium oxide prepared in Example 3, gold-supported silica-modified rutile titanium oxide having a gold support amount of 1% by mass relative to titanium oxide was used as the inorganic compound for photocatalyst (AB4).
163.8 g of inorganic compound for photocatalyst (AB4) and water-dispersed colloidal silica (D1) having a number average particle diameter of 8 nm (trade name “Snowtex NS”, manufactured by Nissan Chemical Industries, Ltd., solid content 20% by mass) 6 g, 0.99 g of fluorocarbon surfactant (F) (manufactured by DIC, “Megafac F-444”), and a fading dye (G) (solid content adjusted to 1.0 mass% with ion-exchanged water) (G) ( A photocatalyst composition (H-4) was prepared by mixing 140 g of “Methylene Blue” manufactured by Kishida Chemical Co., Ltd.) and 656.2 g of water and stirring.
A glass plate having a size of 10 cm × 10 cm, in which an acrylic silicone resin was applied in advance to a thickness of 100 μm on another surface (front surface) of a glass plate on which one side (back surface) was subjected to white printing, was prepared. The said photocatalyst composition (H-4) was apply | coated to the single side | surface (surface) of this glass plate by the spray method. Then, the test plate (I-4) in which the photocatalyst coating film was formed was obtained by drying the apply | coated photocatalyst composition (H-4) at normal temperature for 1 hour. Various evaluation results of this test plate (I-4) are shown in Table 2.

[Production Example 5]
Of the gold-supported silica-modified rutile titanium oxide prepared in Example 3, gold-supported silica-modified rutile titanium oxide having a gold support amount of 2 mass% with respect to titanium oxide was used as the inorganic compound for photocatalyst (AB5).
163.8 g of inorganic compound for photocatalyst (AB5) and water-dispersed colloidal silica (D1) having a number average particle diameter of 8 nm (trade name “Snowtex NS”, manufactured by Nissan Chemical Industries, Ltd., solid content 20 mass%) 6 g, 0.99 g of fluorocarbon surfactant (F) (manufactured by DIC, “Megafac F-444”), and a fading dye (G) (solid content adjusted to 1.0 mass% with ion-exchanged water) (G) ( A photocatalyst composition (H-5) was produced by mixing and stirring 140 g of “Methylene Blue” manufactured by Kishida Chemical Co., Ltd.) and 656.2 g of water.
A glass plate having a size of 10 cm × 10 cm, in which an acrylic silicone resin was applied in advance to a thickness of 100 μm on another surface (front surface) of a glass plate on which one side (back surface) was subjected to white printing, was prepared. The said photocatalyst composition (H-5) was apply | coated to the single side | surface (surface) of this glass plate by the spray method. Thereafter, the coated photocatalyst composition (H-5) was dried at room temperature for 1 hour to obtain a test plate (I-5) on which a photocatalyst coating film was formed. Various evaluation results of this test plate (I-5) are shown in Table 2.

[Production Example 6]
Of the silver-copper-supported silica-modified rutile titanium oxide prepared in Example 4, a silver-copper-supported silica-modified silica-modified rutile titanium oxide having a silver / copper support amount of 1% by mass / 0.5% by mass relative to titanium oxide. Used as an inorganic compound for photocatalyst (AB6).
163.8 g of photocatalyst inorganic compound (AB6) and water-dispersed colloidal silica (D1) having a number average particle diameter of 8 nm (trade name “Snowtex NS”, manufactured by Nissan Chemical Industries, Ltd., solid content 20 mass%) 6 g, 0.99 g of fluorocarbon surfactant (F) (manufactured by DIC, “Megafac F-444”), and a fading dye (G) (solid content adjusted to 1.0 mass% with ion-exchanged water) (G) ( A photocatalyst composition (H-6) was produced by mixing and stirring 140 g of “Methylene Blue” manufactured by Kishida Chemical Co., Ltd.) and 656.2 g of water.
A glass plate having a size of 10 cm × 10 cm, in which an acrylic silicone resin was applied in advance to a thickness of 100 μm on another surface (front surface) of a glass plate on which one side (back surface) was subjected to white printing, was prepared. The said photocatalyst composition (H-6) was apply | coated to the single side | surface (surface) of this glass plate by the spray method. Then, the test plate (I-6) in which the photocatalyst coating film was formed was obtained by drying the apply | coated photocatalyst composition (H-6) at normal temperature for 1 hour. The various evaluation results of this test plate (I-6) are shown in Table 2.

[Production Example 7]
Of the silver-copper-supported silica-modified rutile titanium oxide prepared in Example 4, the silver-copper-supported silica-modified silica-modified rutile-type oxide having a silver / copper support amount of 0.75% by mass / 0.75% by mass with respect to titanium oxide. Titanium was used as the inorganic compound for photocatalyst (A7).
163.8 g of inorganic compound for photocatalyst (A7) and water-dispersed colloidal silica (D1) having a number average particle diameter of 8 nm (trade name “Snowtex NS”, manufactured by Nissan Chemical Industries, Ltd., solid content 20 mass%) 6 g, 0.99 g of fluorocarbon surfactant (F) (manufactured by DIC, “Megafac F-444”), and a fading dye (G) (solid content adjusted to 1.0 mass% with ion-exchanged water) (G) ( A photocatalyst composition (H-7) was prepared by mixing and stirring 140 g of “Methylene Blue” manufactured by Kishida Chemical Co., Ltd.) and 656.2 g of water.
A glass plate having a size of 10 cm × 10 cm, in which an acrylic silicone resin was applied in advance to a thickness of 100 μm on another surface (front surface) of a glass plate on which one side (back surface) was subjected to white printing, was prepared. The said photocatalyst composition (H-7) was apply | coated to the single side | surface (surface) of this glass plate by the spray method. Thereafter, the coated photocatalyst composition (H-7) was dried at room temperature for 1 hour to obtain a test plate (I-7) on which a photocatalyst coating film was formed. Various evaluation results of this test plate (I-7) are shown in Table 2.

[Production Example 8]
Of the copper-gold supported silica modified rutile type titanium oxide prepared in Example 5, the copper / gold supported silica modified rutile type titanium oxide having a copper / gold supported amount of 0.5% by mass / 1% by mass with respect to titanium oxide. Used as an inorganic compound for photocatalyst (AB8).
163.8 g of inorganic compound for photocatalyst (AB8) and water-dispersed colloidal silica (D1) having a number average particle diameter of 8 nm (trade name “Snowtex NS”, manufactured by Nissan Chemical Industries, Ltd., solid content 20 mass%) 6 g, 0.99 g of fluorocarbon surfactant (F) (manufactured by DIC, “Megafac F-444”), and a fading dye (G) (solid content adjusted to 1.0 mass% with ion-exchanged water) (G) ( A photocatalyst composition (H-8) was prepared by mixing and stirring 140 g of “Methylene Blue” manufactured by Kishida Chemical Co., Ltd.) and 656.2 g of water.
A glass plate having a size of 10 cm × 10 cm, in which an acrylic silicone resin was applied in advance to a thickness of 100 μm on another surface (front surface) of a glass plate on which one side (back surface) was subjected to white printing, was prepared. The said photocatalyst composition (H-8) was apply | coated to the single side | surface (surface) of this glass plate by the spray method. Then, the test plate (I-8) in which the photocatalyst coating film was formed was obtained by drying the apply | coated photocatalyst composition (H-8) at normal temperature for 1 hour. Various evaluation results of this test plate (I-8) are shown in Table 2.

[Production Example 9]
Of the silver-gold supported silica modified rutile type titanium oxide prepared in Example 6, the silver / gold supported silica modified rutile type titanium oxide having a silver / gold supported amount of 0.5 mass% / 1 mass% with respect to titanium oxide. Used as an inorganic compound for photocatalyst (AB9).
163.8 g of inorganic compound for photocatalyst (AB9) and water-dispersed colloidal silica (D1) having a number average particle diameter of 8 nm (trade name “Snowtex NS”, manufactured by Nissan Chemical Industries, Ltd., solid content 20 mass%) 6 g, 0.99 g of fluorocarbon surfactant (F) (manufactured by DIC, “Megafac F-444”), and a fading dye (G) (solid content adjusted to 1.0 mass% with ion-exchanged water) (G) ( A photocatalyst composition (H-9) was prepared by mixing and stirring 140 g of “Methylene Blue” manufactured by Kishida Chemical Co., Ltd.) and 656.2 g of water.
A glass plate having a size of 10 cm × 10 cm, in which an acrylic silicone resin was applied in advance to a thickness of 100 μm on another surface (front surface) of a glass plate on which one side (back surface) was subjected to white printing, was prepared. The said photocatalyst composition (H-9) was apply | coated to the single side | surface (surface) of this glass plate by the spray method. Thereafter, the coated photocatalyst composition (H-9) was dried at room temperature for 1 hour to obtain a test plate (I-9) on which a photocatalyst coating film was formed. Various evaluation results of this test plate (I-9) are shown in Table 2.

[Production Example 10]
Of the silver-gold supported silica modified rutile titanium oxide prepared in Example 6, the silver / gold supported silica modified rutile titanium oxide having a silver / gold supported amount of 1% by mass / 1% by mass with respect to titanium oxide was used for the photocatalyst. Used as an inorganic compound (AB10).
163.8 g of inorganic compound for photocatalyst (AB10) and water-dispersed colloidal silica (D1) having a number average particle diameter of 8 nm (trade name “Snowtex NS”, manufactured by Nissan Chemical Industries, Ltd., solid content 20% by mass) 6 g, 0.99 g of fluorocarbon surfactant (F) (manufactured by DIC, “Megafac F-444”), and a fading dye (G) (solid content adjusted to 1.0 mass% with ion-exchanged water) (G) ( A photocatalyst composition (H-10) was prepared by mixing and stirring 140 g of “Methylene Blue” manufactured by Kishida Chemical Co., Ltd.) and 656.2 g of water.
A glass plate having a size of 10 cm × 10 cm, in which an acrylic silicone resin was applied in advance to a thickness of 100 μm on another surface (front surface) of a glass plate on which one side (back surface) was subjected to white printing, was prepared. The said photocatalyst composition (H-10) was apply | coated to the single side | surface (surface) of this glass plate by the spray method. Then, the test plate (I-10) in which the photocatalyst coating film was formed was obtained by drying the apply | coated photocatalyst composition (H-10) at normal temperature for 1 hour. Various evaluation results of this test plate (I-10) are shown in Table 2.

[Production Example 11]
163.8 g of inorganic compound for photocatalyst (AB1) and water-dispersed colloidal silica (D1) having a number average particle diameter of 8 nm (trade name “Snowtex NS”, manufactured by Nissan Chemical Industries, Ltd., solid content 20% by mass) 0 g, 38.7 g of a polymer emulsion particle (E1) aqueous dispersion shown in Production Example 3 (solid content: 8.5% by mass) and a fluorocarbon surfactant (F) (manufactured by DIC, “Megafac F-444 ”) 0.99 g, 140 g of a fading dye (G) (“ Methylene Blue ”manufactured by Kishida Chemical Co., Ltd.) whose solid content was adjusted to 1.0% by mass with ion-exchanged water, and 530.2 g of water were mixed. The photocatalyst composition (H-11) was produced by stirring.
A glass plate having a size of 10 cm × 10 cm, in which an acrylic silicone resin was applied in advance to a thickness of 100 μm on another surface (front surface) of a glass plate on which one side (back surface) was subjected to white printing, was prepared. The said photocatalyst composition (H-11) was apply | coated to the single side | surface (surface) of this glass plate with the spray method. Then, the test plate (I-11) in which the photocatalyst coating film was formed was obtained by drying the apply | coated photocatalyst composition (H-11) at normal temperature for 1 hour. Various evaluation results of this test plate (I-11) are shown in Table 2.

[Production Example 12]
163.8 g of inorganic compound for photocatalyst (AB2) and water-dispersed colloidal silica (D1) having a number average particle diameter of 8 nm (trade name “Snowtex NS”, manufactured by Nissan Chemical Industries, Ltd., solid content 20 mass%) 0 g, 38.7 g of a polymer emulsion particle (E1) aqueous dispersion shown in Production Example 3 (solid content: 8.5% by mass) and a fluorocarbon surfactant (F) (manufactured by DIC, “Megafac F-444 ”) 0.99 g, 140 g of a fading dye (G) (“ Methylene Blue ”manufactured by Kishida Chemical Co., Ltd.) whose solid content was adjusted to 1.0% by mass with ion-exchanged water, and 530.2 g of water were mixed. The photocatalyst composition (H-12) was produced by stirring.
A glass plate having a size of 10 cm × 10 cm, in which an acrylic silicone resin was applied in advance to a thickness of 100 μm on another surface (front surface) of a glass plate on which one side (back surface) was subjected to white printing, was prepared. The said photocatalyst composition (H-12) was apply | coated to the single side | surface (surface) of this glass plate by the spray method. Then, the test plate (I-12) in which the photocatalyst coating film was formed was obtained by drying the apply | coated photocatalyst composition (H-12) at normal temperature for 1 hour. Various evaluation results of this test plate (I-12) are shown in Table 2.

[Production Example 13]
163.8 g of inorganic compound for photocatalyst (AB3) and water-dispersed colloidal silica (D1) having a number average particle diameter of 8 nm (trade name “Snowtex NS”, manufactured by Nissan Chemical Industries, Ltd., solid content 20 mass%) 0 g, 38.7 g of a polymer emulsion particle (E1) aqueous dispersion shown in Production Example 3 (solid content: 8.5% by mass) and a fluorocarbon surfactant (F) (manufactured by DIC, “Megafac F-444 ”) 0.99 g, 140 g of a fading dye (G) (“ Methylene Blue ”manufactured by Kishida Chemical Co., Ltd.) whose solid content was adjusted to 1.0% by mass with ion-exchanged water, and 530.2 g of water were mixed. The photocatalyst composition (H-13) was produced by stirring.
A glass plate having a size of 10 cm × 10 cm, in which an acrylic silicone resin was applied in advance to a thickness of 100 μm on another surface (front surface) of a glass plate on which one side (back surface) was subjected to white printing, was prepared. The said photocatalyst composition (H-13) was apply | coated to the single side | surface (surface) of this glass plate by the spray method. Then, the test plate (I-13) in which the photocatalyst coating film was formed was obtained by drying the apply | coated photocatalyst composition (H-13) at normal temperature for 1 hour. Various evaluation results of this test plate (I-13) are shown in Table 2.

[Production Example 14]
163.8 g of inorganic compound for photocatalyst (AB4) and water-dispersed colloidal silica (D1) having a number average particle diameter of 8 nm (trade name “Snowtex NS”, manufactured by Nissan Chemical Industries, Ltd., solid content 20 mass%) 0 g, 38.7 g of a polymer emulsion particle (E1) aqueous dispersion shown in Production Example 3 (solid content: 8.5% by mass) and a fluorocarbon surfactant (F) (manufactured by DIC, “Megafac F-444 ”) 0.99 g, 140 g of a fading dye (G) (“ Methylene Blue ”manufactured by Kishida Chemical Co., Ltd.) whose solid content was adjusted to 1.0% by mass with ion-exchanged water, and 530.2 g of water were mixed. The photocatalyst composition (H-14) was produced by stirring.
A glass plate having a size of 10 cm × 10 cm, in which an acrylic silicone resin was applied in advance to a thickness of 100 μm on another surface (front surface) of a glass plate on which one side (back surface) was subjected to white printing, was prepared. The said photocatalyst composition (H-14) was apply | coated to the single side | surface (surface) of this glass plate by the spray method. Then, the test plate (I-14) in which the photocatalyst coating film was formed was obtained by drying the apply | coated photocatalyst composition (H-14) at normal temperature for 1 hour. Various evaluation results of this test plate (I-14) are shown in Table 2.

[Production Example 15]
163.8 g of mass% inorganic compound for photocatalyst (AB6) and water-dispersed colloidal silica (D1) having a number average particle diameter of 8 nm (trade name “Snowtex NS”, manufactured by Nissan Chemical Industries, Ltd., solid content 20 mass%) 104.0 g, 38.7 g of the polymer emulsion particles (E1) aqueous dispersion (solid content 8.5% by mass) shown in Production Example 3, and a fluorocarbon surfactant (F) (manufactured by DIC, “Megafac F -444 "), 0.99 g, 140 g of a fading dye (G) (manufactured by Kishida Chemical Co.," methylene blue ") whose solid content was adjusted to 1.0 mass% with ion-exchanged water, and 530.2 g of water. By mixing and stirring, a photocatalyst composition (H-15) was produced.
A glass plate having a size of 10 cm × 10 cm, in which an acrylic silicone resin was applied in advance to a thickness of 100 μm on another surface (front surface) of a glass plate on which one side (back surface) was subjected to white printing, was prepared. The said photocatalyst composition (H-15) was apply | coated to the single side | surface (surface) of this glass plate by the spray method. Then, the test plate (I-15) in which the photocatalyst coating film was formed was obtained by drying the apply | coated photocatalyst composition (H-15) at normal temperature for 1 hour. Various evaluation results of this test plate (I-15) are shown in Table 2.

[Production Example 16]
Of the silver-supported silica-modified anatase-type titanium oxide prepared in Example 1, silver-supported silica-modified anatase-type titanium oxide having a silver support amount of 1% by mass with respect to titanium oxide was used as the inorganic compound for photocatalyst (AB11).
163.8 g of inorganic compound for photocatalyst (AB11) and water-dispersed colloidal silica (D1) having a number average particle diameter of 8 nm (trade name “Snowtex NS”, manufactured by Nissan Chemical Industries, Ltd., solid content 20% by mass) 6 g, 0.99 g of fluorocarbon surfactant (F) (manufactured by DIC, “Megafac F-444”), and a fading dye (G) (solid content adjusted to 1.0 mass% with ion-exchanged water) (G) ( A photocatalyst composition (H-16) was produced by mixing and stirring 140 g of “Methylene Blue” manufactured by Kishida Chemical Co., Ltd.) and 656.2 g of water.
A glass plate having a size of 10 cm × 10 cm, in which an acrylic silicone resin was applied in advance to a thickness of 100 μm on another surface (front surface) of a glass plate on which one side (back surface) was subjected to white printing, was prepared. The said photocatalyst composition (H-16) was apply | coated to the single side | surface (surface) of this glass plate by the spray method. Thereafter, the coated photocatalyst composition (H-16) was dried at room temperature for 1 hour to obtain a test plate (I-16) on which a photocatalyst coating film was formed. Various evaluation results of this test plate (I-16) are shown in Table 2.

[Production Example 17]
Of the copper-supported silica-modified anatase-type titanium oxide prepared in Example 2, copper-supported silica-modified anatase-type titanium oxide having a copper support amount of 1% by mass with respect to titanium oxide was used as the inorganic compound for photocatalyst (AB12).
163.8 g of inorganic compound for photocatalyst (AB12) and water-dispersed colloidal silica (D1) having a number average particle diameter of 8 nm (trade name “Snowtex NS”, manufactured by Nissan Chemical Industries, Ltd., solid content 20 mass%) 6 g, 0.99 g of fluorocarbon surfactant (F) (manufactured by DIC, “Megafac F-444”), and a fading dye (G) (solid content adjusted to 1.0 mass% with ion-exchanged water) (G) ( A photocatalyst composition (H-17) was prepared by mixing 140 g of “Methylene Blue” manufactured by Kishida Chemical Co., Ltd.) and 656.2 g of water and stirring.
A glass plate having a size of 10 cm × 10 cm, in which an acrylic silicone resin was applied in advance to a thickness of 100 μm on another surface (front surface) of a glass plate on which one side (back surface) was subjected to white printing, was prepared. The said photocatalyst composition (H-17) was apply | coated to the single side | surface (surface) of this glass plate by the spray method. Then, the test plate (I-17) in which the photocatalyst coating film was formed was obtained by drying the apply | coated photocatalyst composition (H-17) at normal temperature for 1 hour. Various evaluation results of this test plate (I-17) are shown in Table 2.

[Production Example 18]
Of the silver-copper-supported silica-modified anatase-type titanium oxide prepared in Example 4, a silver-copper-supported silica-modified anatase-type titanium oxide having a silver / copper support amount of 1% by mass / 0.5% by mass with respect to titanium oxide. Used as an inorganic compound for photocatalyst (AB13).
163.8 g of inorganic compound for photocatalyst (AB13) and water-dispersed colloidal silica (D1) having a number average particle diameter of 8 nm (trade name “Snowtex NS”, manufactured by Nissan Chemical Industries, Ltd., solid content 20% by mass) 6 g, 0.99 g of fluorocarbon surfactant (F) (manufactured by DIC, “Megafac F-444”), and a fading dye (G) (solid content adjusted to 1.0 mass% with ion-exchanged water) (G) ( A photocatalyst composition (H-18) was prepared by mixing and stirring 140 g of “Methylene Blue” manufactured by Kishida Chemical Co., Ltd.) and 656.2 g of water.
A glass plate having a size of 10 cm × 10 cm, in which an acrylic silicone resin was applied in advance to a thickness of 100 μm on another surface (front surface) of a glass plate on which one side (back surface) was subjected to white printing, was prepared. The said photocatalyst composition (H-18) was apply | coated to the single side | surface (surface) of this glass plate by the spray method. Then, the test plate (I-18) in which the photocatalyst coating film was formed was obtained by drying the apply | coated photocatalyst composition (H-18) at normal temperature for 1 hour. Various evaluation results of this test plate (I-18) are shown in Table 2.

[Production Example 19]
Example 1 163.8 g of inorganic compound for photocatalyst (AB1) 163.8 g and water-dispersed colloidal silica (D1) having a number average particle diameter of 8 nm (trade name “Snowtex NS”, manufactured by Nissan Chemical Industries, Ltd., solid content 20 (Mass%) 93.0 g, polymer emulsion particles (E1) aqueous dispersion 64.4 g (solid content 8.5 mass%) shown in Production Example 3, and fluorocarbon surfactant (F) (manufactured by DIC, “ Megafa F-444 ”) 0.99 g, 140 g of a fading dye (G) (“ Methylene Blue ”manufactured by Kishida Chemical Co., Ltd.) whose solid content was adjusted to 1.0 mass% with ion-exchanged water, and 515.5 g of water Were mixed and stirred to prepare a photocatalyst composition (H-19).
A glass plate having a size of 10 cm × 10 cm, in which an acrylic silicone resin was applied in advance to a thickness of 100 μm on another surface (front surface) of a glass plate on which one side (back surface) was subjected to white printing, was prepared. The said photocatalyst composition (H-19) was apply | coated to the single side | surface (surface) of this glass plate by the spray method. Then, the test plate (I-19) in which the photocatalyst coating film was formed was obtained by drying the apply | coated photocatalyst composition (H-19) at normal temperature for 1 hour. Various evaluation results of this test plate (I-19) are shown in Table 2.

[Production Example 20]
Example 1 163.5 g of a mass% inorganic compound for photocatalyst (AB1) and water-dispersed colloidal silica (D1) having a number average particle diameter of 8 nm (trade name “Snowtex NS”, manufactured by Nissan Chemical Industries, Ltd., solid content 20 (Mass%) 65.7 g, polymer emulsion particles (E1) aqueous dispersion 128.7 g (solid content 8.5 mass%) shown in Production Example 3, and fluorocarbon surfactant (F) (manufactured by DIC, “ Megafa F-444 ”) 0.99 g, 140 g of a fading dye (G) (“ Methylene Blue ”manufactured by Kishida Chemical Co., Ltd.) whose solid content was adjusted to 1.0 mass% with ion-exchanged water, and 515.5 g of water Were mixed and stirred to prepare a photocatalyst composition (H-20).
A glass plate having a size of 10 cm × 10 cm, in which an acrylic silicone resin was applied in advance to a thickness of 100 μm on another surface (front surface) of a glass plate on which one side (back surface) was subjected to white printing, was prepared. The said photocatalyst composition (H-20) was apply | coated to the single side | surface (surface) of this glass plate by the spray method. Then, the test plate (I-20) in which the photocatalyst coating film was formed was obtained by drying the apply | coated photocatalyst composition (H-20) at normal temperature for 1 hour. Various evaluation results of this test plate (I-20) are shown in Table 2.

[Production Example 21]
Example 1 163.5 g of a mass% inorganic compound for photocatalyst (AB1) and water-dispersed colloidal silica (D1) having a number average particle diameter of 8 nm (trade name “Snowtex NS”, manufactured by Nissan Chemical Industries, Ltd., solid content 20 (Mass%) 52.0 g, polymer emulsion particles (E1) aqueous dispersion 160.9 g (solid content 8.5 mass%) shown in Production Example 3, and fluorocarbon surfactant (F) (manufactured by DIC, “ Megafa F-444 ") 0.99 g, 140 g of a fading dye (G) (Methylene Blue, manufactured by Kishida Chemical Co., Ltd.) whose solid content was adjusted to 1.0 mass% with ion-exchanged water, and 482.61 g of water Were mixed and stirred to prepare a photocatalyst composition (H-21).
A glass plate having a size of 10 cm × 10 cm, in which an acrylic silicone resin was applied in advance to a thickness of 100 μm on another surface (front surface) of a glass plate on which one side (back surface) was subjected to white printing, was prepared. The said photocatalyst composition (H-21) was apply | coated to the single side | surface (surface) of this glass plate with the spray method. Then, the test plate (I-21) in which the photocatalyst coating film was formed was obtained by drying the apply | coated photocatalyst composition (H-21) at normal temperature for 1 hour. Various evaluation results of this test plate (I-21) are shown in Table 2.

[Production Example 22]
Example 1 273.5 g of inorganic compound (AB1) for mass% photocatalyst and water-dispersed colloidal silica (D1) having a number average particle diameter of 8 nm (trade name “Snowtex NS”, manufactured by Nissan Chemical Industries, Ltd., solid content 20 82.1 g (mass%), polymer emulsion particles (E1) aqueous dispersion 64.4 g (solid content 8.5 mass%) shown in Production Example 3, and fluorocarbon surfactant (F) (manufactured by DIC, “ MegaFuck F-444 ") 0.99 g, 140 g of fading dye (G) (Methylene Blue, manufactured by Kishida Chemical Co., Ltd.) whose solid content was adjusted to 1.0 mass% with ion-exchanged water, and 439.0 g of water Were mixed and stirred to prepare a photocatalyst composition (H-22).
A glass plate having a size of 10 cm × 10 cm, in which an acrylic silicone resin was applied in advance to a thickness of 100 μm on another surface (front surface) of a glass plate on which one side (back surface) was subjected to white printing, was prepared. The said photocatalyst composition (H-22) was apply | coated to the single side | surface (surface) of this glass plate by the spray method. Then, the test plate (I-22) in which the photocatalyst coating film was formed was obtained by drying the apply | coated photocatalyst composition (H-22) at normal temperature for 1 hour. Various evaluation results of this test plate (I-22) are shown in Table 3.

[Production Example 23]
Example 1 273.5 g of inorganic compound (AB1) for mass% photocatalyst and water-dispersed colloidal silica (D1) having a number average particle diameter of 8 nm (trade name “Snowtex NS”, manufactured by Nissan Chemical Industries, Ltd., solid content 20 (Mass%) 68.45 g, polymer emulsion particles (E1) aqueous dispersion 96.6 g (solid content 8.5 mass%) shown in Production Example 3, and fluorocarbon surfactant (F) (manufactured by DIC, “ Megafa F-444 ") 0.99g, 140g of fading dye (G) (" Methylene Blue "manufactured by Kishida Chemical Co., Ltd.) whose solid content was adjusted to 1.0 mass% with ion-exchanged water, and 420.5g of water Were mixed and stirred to prepare a photocatalyst composition (H-23).
A glass plate having a size of 10 cm × 10 cm, in which an acrylic silicone resin was applied in advance to a thickness of 100 μm on another surface (front surface) of a glass plate on which one side (back surface) was subjected to white printing, was prepared. The said photocatalyst composition (H-22) was apply | coated to the single side | surface (surface) of this glass plate by the spray method. Thereafter, the coated photocatalyst composition (H-23) was dried at room temperature for 1 hour to obtain a test plate (I-23) on which a photocatalyst coating film was formed. Table 3 shows various evaluation results of the test plate (I-23).

[Production Example 24]
Example 1 273.5 g of inorganic compound (AB1) for mass% photocatalyst and water-dispersed colloidal silica (D1) having a number average particle diameter of 8 nm (trade name “Snowtex NS”, manufactured by Nissan Chemical Industries, Ltd., solid content 20 (Mass%) 27.35 g, polymer emulsion particles (E1) aqueous dispersion 193.2 g (solid content 8.5 mass%) shown in Production Example 3, and fluorocarbon surfactant (F) (manufactured by DIC, “ Megafa F-444 ") 0.99 g, fading dye (G) (Methylene Blue, manufactured by Kishida Chemical Co., Ltd.) whose solid content was adjusted to 1.0 mass% with ion-exchanged water, and 364.98 g of water Were mixed and stirred to prepare a photocatalyst composition (H-24).
A glass plate having a size of 10 cm × 10 cm, in which an acrylic silicone resin was applied in advance to a thickness of 100 μm on another surface (front surface) of a glass plate on which one side (back surface) was subjected to white printing, was prepared. The said photocatalyst composition (H-24) was apply | coated to the single side | surface (surface) of this glass plate by the spray method. Then, the test plate (I-24) in which the photocatalyst coating film was formed was obtained by drying the apply | coated photocatalyst composition (H-24) at normal temperature for 1 hour. Various evaluation results of this test plate (I-24) are shown in Table 3.

[Production Example 25]
Example 1 163.8 g of inorganic compound for photocatalyst (AB1) 163.8 g and acidic colloidal silica, water-dispersed colloidal silica (D2) having a number average particle size of 8 nm (trade name “Snowtex OS”, Nissan Chemical Industries ( Co., Ltd., solid content 20% by mass) 120.6 g, fluorocarbon surfactant (F) (manufactured by DIC, “Megafac F-444”) 0.99 g, and the solid content with ion-exchanged water is 1.0. A photocatalytic composition (H-25) was prepared by mixing and stirring 140 g of a fading dye (G) (manufactured by Kishida Chemical Co., “methylene blue”) adjusted to mass% and 574.6 g of water.
A glass plate having a size of 10 cm × 10 cm, in which an acrylic silicone resin was applied in advance to a thickness of 100 μm on another surface (front surface) of a glass plate on which one side (back surface) was subjected to white printing, was prepared. The said photocatalyst composition (H-25) was apply | coated to the single side | surface (surface) of this glass plate by the spray method. Thereafter, the coated photocatalyst composition (H-25) was dried at room temperature for 1 hour to obtain a test plate (I-25) on which a photocatalyst coating film was formed. Various evaluation results of this test plate (I-25) are shown in Table 3.

[Production Example 26]
Example 1 163.8 g of inorganic compound for photocatalyst (AB1) 163.8 g and acidic colloidal silica, water-dispersed colloidal silica (D3) having a number average particle size of 25 nm (trade name “Snowtex O-40”, Nissan Chemical Co., Ltd.) 120.6 g manufactured by Kogyo Co., Ltd., solid content 20% by mass), 0.99 g of fluorocarbon surfactant (F) (manufactured by DIC, “Megafac F-444”), and the amount of solid content is 1 with ion-exchanged water. The photocatalytic composition (H-26) was prepared by mixing and stirring 140 g of the fading dye (G) (Kishida Chemical Co., “methylene blue”) adjusted to 0.0 mass% and 574.6 g of water. .
A glass plate having a size of 10 cm × 10 cm, in which an acrylic silicone resin was applied in advance to a thickness of 100 μm on another surface (front surface) of a glass plate on which one side (back surface) was subjected to white printing, was prepared. The said photocatalyst composition (H-26) was apply | coated to the single side | surface (surface) of this glass plate by the spray method. Then, the test plate (I-26) in which the photocatalyst coating film was formed was obtained by drying the apply | coated photocatalyst composition (H-26) at normal temperature for 1 hour. Table 3 shows various evaluation results of the test plate (I-26).

[Production Example 27]
Example 1 163.8 g of inorganic compound for photocatalyst (AB1) 163.8 g and water-dispersed colloidal silica (D2) having a number average particle diameter of 8 nm (trade name “Snowtex OS”, manufactured by Nissan Chemical Industries, Ltd., solid content 20 (Mass%) 104.0 g, the polymer emulsion particles (E1) shown in Production Example 3 (38.7 g) (solid content 8.5% by mass), fluorocarbon surfactant (F) (manufactured by DIC Corporation, “ MegaFuck F-444 ") 0.99 g, 140 g fading dye (G) (" Methylene Blue "manufactured by Kishida Chemical Co., Ltd.) whose solid content was adjusted to 1.0 mass% with ion-exchanged water, and 552.5 g water Were mixed and stirred to prepare a photocatalyst composition (H-27).
A glass plate having a size of 10 cm × 10 cm, in which an acrylic silicone resin was applied in advance to a thickness of 100 μm on another surface (front surface) of a glass plate on which one side (back surface) was subjected to white printing, was prepared. The said photocatalyst composition (H-27) was apply | coated to the single side | surface (surface) of this glass plate by the spray method. Then, the test plate (I-27) in which the photocatalyst coating film was formed was obtained by drying the apply | coated photocatalyst composition (H-27) at normal temperature for 1 hour. Various evaluation results of this test plate (I-27) are shown in Table 3.

[Production Example 28]
Example 1 163.8 g as an inorganic compound (AB1) for mass% photocatalyst, water-dispersed colloidal silica (D2) having a number average particle diameter of 25 nm (trade name “Snowtex O-40”, manufactured by Nissan Chemical Industries, Ltd., 104.0 g of solid content (20% by mass), 38.7 g of polymer emulsion particles (E1) aqueous dispersion shown in Production Example 3 (8.5% by mass of solid content), and fluorocarbon surfactant (F) (DIC Corporation) Manufactured by “Megafac F-444”), 0.99 g, 140 g of a fading dye (G) (“Methylene Blue” manufactured by Kishida Chemical Co., Ltd.) having a solid content adjusted to 1.0% by mass with ion-exchanged water, water 552.5 g was mixed and stirred to prepare a photocatalyst composition (H-28).
A glass plate having a size of 10 cm × 10 cm, in which an acrylic silicone resin was applied in advance to a thickness of 100 μm on another surface (front surface) of a glass plate on which one side (back surface) was subjected to white printing, was prepared. The photocatalyst composition (H-28) was applied to one surface (surface) of this glass plate by a spray method. Then, the test plate (I-28) in which the photocatalyst coating film was formed was obtained by drying the apply | coated photocatalyst composition (H-28) at normal temperature for 1 hour. Table 3 shows various evaluation results of this test plate (I-28).

[Production Example 29]
Example 1 163.8 g of inorganic compound for photocatalyst (AB1) 163.8 g and water-dispersed colloidal silica (D1) having a number average particle diameter of 8 nm (trade name “Snowtex NS”, manufactured by Nissan Chemical Industries, Ltd., solid content 20 (Mass%) 104.0 g, polymer emulsion particles (E2) aqueous dispersion 32.9 g (solid content 10.0 mass%) shown in Production Example 4, and fluorocarbon surfactant (F) (manufactured by DIC, “ Megafa F-444 ") 0.99 g, fading dye (G) (Methylene Blue, manufactured by Kishida Chemical Co., Ltd.) having a solid content adjusted to 1.0 mass% with ion-exchanged water, and 558.3 g of water Were mixed and stirred to prepare a photocatalyst composition (H-29).
A glass plate having a size of 10 cm × 10 cm, in which an acrylic silicone resin was applied in advance to a thickness of 100 μm on another surface (front surface) of a glass plate on which one side (back surface) was subjected to white printing, was prepared. The said photocatalyst composition (H-29) was apply | coated to the single side | surface (surface) of this glass plate by the spray method. Then, the test plate (I-29) in which the photocatalyst coating film was formed was obtained by drying the apply | coated photocatalyst composition (H-29) at normal temperature for 1 hour. Various evaluation results of this test plate (I-29) are shown in Table 3.

[Production Example 30]
Example 1 163.8 g of inorganic compound for photocatalyst (AB1) 163.8 g and water-dispersed colloidal silica (D1) having a number average particle diameter of 8 nm (trade name “Snowtex NS”, manufactured by Nissan Chemical Industries, Ltd., solid content 20 (Mass%) 104.0 g, polymer emulsion particles (E3) aqueous dispersion 32.9 g (solid content 10.0 mass%) shown in Production Example 5, and fluorocarbon surfactant (F) (manufactured by DIC, “ Megafa F-444 ") 0.99 g, fading dye (G) (Methylene Blue, manufactured by Kishida Chemical Co., Ltd.) having a solid content adjusted to 1.0 mass% with ion-exchanged water, and 558.3 g of water Were mixed and stirred to prepare a photocatalyst composition (H-30).
A glass plate having a size of 10 cm × 10 cm, in which an acrylic silicone resin was applied in advance to a thickness of 100 μm on another surface (front surface) of a glass plate on which one side (back surface) was subjected to white printing, was prepared. The said photocatalyst composition (H-30) was apply | coated to the single side | surface (surface) of this glass plate by the spray method. Then, the test plate (I-30) in which the photocatalyst coating film was formed was obtained by drying the apply | coated photocatalyst composition (H-30) at normal temperature for 1 hour. Table 3 shows various evaluation results of the test plate (I-30).

[Production Example 31]
163.8 g of inorganic compound for photocatalyst (AB1) and basic colloidal silica, water-dispersed colloidal silica (D1) having a number average particle diameter of 8 nm (trade name “Snowtex NS”, manufactured by Nissan Chemical Industries, Ltd., Fluorocarbon surfactant (F2) (“Surflon S-232” manufactured by AGC Seimi Chemical Co., Ltd.), which is a perfluoroalkyl compound having a solid content of 20% by mass) 120.6 g and an anionic group and a cationic group 0.99 g, 140 g of a fading dye (G) (manufactured by Kishida Chemical Co., “methylene blue”) whose solid content is adjusted to 1.0 mass% with ion-exchanged water, and 656.2 g of water are mixed and stirred. This produced the photocatalyst composition (H-31).
A glass plate having a size of 10 cm × 10 cm, in which an acrylic silicone resin was applied in advance to a thickness of 100 μm on another surface (front surface) of a glass plate on which one side (back surface) was subjected to white printing, was prepared. The said photocatalyst composition (H-31) was apply | coated to the single side | surface (surface) of this glass plate by the spray method. Thereafter, the coated photocatalyst composition (H-31) was dried at room temperature for 1 hour to obtain a test plate (I-31) on which a photocatalyst coating film was formed. Various evaluation results of this test plate (I-31) are shown in Table 2.

[Production Example 32]
163.8 g of inorganic compound for photocatalyst (AB3) and water-dispersed colloidal silica (D1) having a number average particle diameter of 8 nm (trade name “Snowtex NS”, manufactured by Nissan Chemical Industries, Ltd., solid content 20% by mass) 6 g, 0.99 g of a fluorocarbon surfactant (F2) (“Surflon S-232” manufactured by AGC Seimi Chemical Co., Ltd.), and a fading dye (G) whose solid content is adjusted to 1.0 mass% with ion-exchanged water ( A photocatalyst composition (H-32) was produced by mixing and stirring 140 g of “Methylene Blue” manufactured by Kishida Chemical Co., Ltd.) and 656.2 g of water.
A glass plate having a size of 10 cm × 10 cm, in which an acrylic silicone resin was applied in advance to a thickness of 100 μm on another surface (front surface) of a glass plate on which one side (back surface) was subjected to white printing, was prepared. The said photocatalyst composition (H-32) was apply | coated to the single side | surface (surface) of this glass plate by the spray method. Then, the test plate (I-32) in which the photocatalyst coating film was formed was obtained by drying the apply | coated photocatalyst composition (H-32) at normal temperature for 1 hour. Various evaluation results of this test plate (I-32) are shown in Table 2.

[Production Example 33]
163.8 g of inorganic compound for photocatalyst (AB1) and water-dispersed colloidal silica (D1) having a number average particle diameter of 8 nm (trade name “Snowtex NS”, manufactured by Nissan Chemical Industries, Ltd., solid content 20% by mass) 0 g, 38.7 g of the polymer emulsion particles (E1) aqueous dispersion shown in Production Example 3 (solid content: 8.5% by mass), fluorocarbon surfactant (F2) (“Surflon S-232 manufactured by AGC Seimi Chemical Co., Ltd.) ”) 0.99 g, 140 g of a fading dye (G) (“ Methylene Blue ”manufactured by Kishida Chemical Co., Ltd.) whose solid content was adjusted to 1.0% by mass with ion-exchanged water, and 530.2 g of water were mixed. The photocatalyst composition (H-33) was produced by stirring.
A glass plate having a size of 10 cm × 10 cm, in which an acrylic silicone resin was applied in advance to a thickness of 100 μm on another surface (front surface) of a glass plate on which one side (back surface) was subjected to white printing, was prepared. The said photocatalyst composition (H-33) was apply | coated to the single side | surface (surface) of this glass plate by the spray method. Thereafter, the coated photocatalyst composition (H-33) was dried at room temperature for 1 hour to obtain a test plate (I-33) on which a photocatalyst coating film was formed. Various evaluation results of this test plate (I-33) are shown in Table 2.

[Production Example 34]
Example 2 163.8 g of photocatalyst inorganic compound (AB3) and water-dispersed colloidal silica (D1) having a number average particle diameter of 8 nm (trade name “Snowtex NS”, manufactured by Nissan Chemical Industries, Ltd., solid content of 20% by mass ) 104.0 g, 38.7 g of the polymer emulsion particles (E1) aqueous dispersion shown in Production Example 3 (solid content 8.5% by mass), fluorocarbon surfactant (F2) (manufactured by AGC Seimi Chemical Co., Ltd., “Surflon”) S-232 ”) 0.99 g, 140 g of a fading dye (G) (“ Methylene Blue ”manufactured by Kishida Chemical Co., Ltd.) whose solid content was adjusted to 1.0 mass% with ion-exchanged water, and 530.2 g of water. The photocatalyst composition (H-34) was prepared by mixing and stirring.
A glass plate having a size of 10 cm × 10 cm, in which an acrylic silicone resin was applied in advance to a thickness of 100 μm on another surface (front surface) of a glass plate on which one side (back surface) was subjected to white printing, was prepared. The said photocatalyst composition (H-34) was apply | coated to the single side | surface (surface) of this glass plate by the spray method. Thereafter, the coated photocatalyst composition (H-34) was dried at room temperature for 1 hour to obtain a test plate (I-34) on which a photocatalyst coating film was formed. Various evaluation results of this test plate (I-34) are shown in Table 2.

[Production Comparative Example 1]
[Commercially available product 1] (Ishihara Sangyo Co., Ltd., anatase-type titanium oxide ST-01) as an inorganic compound for photocatalyst (AB14), 163.8 g, water-dispersed colloidal silica (D1) having a number average particle diameter of 8 nm (trade name) “Snowtex NS”, manufactured by Nissan Chemical Industries, Ltd., solid content 20% by mass) 120.6 g, fluorocarbon surfactant (F) (manufactured by DIC, “Megafac F-444”) 0.99 g, A photocatalytic composition is prepared by mixing and stirring 140 g of a fading dye (G) (manufactured by Kishida Chemical Co., “methylene blue”) whose solid content is adjusted to 1.0% by mass with ion-exchanged water and 656.2 g of water. (H-31) was produced.
A glass plate having a size of 10 cm × 10 cm, in which an acrylic silicone resin was applied in advance to a thickness of 100 μm on another surface (front surface) of a glass plate on which one side (back surface) was subjected to white printing, was prepared. The said photocatalyst composition (H-31) was apply | coated to the single side | surface (surface) of this glass plate by the spray method. Thereafter, the coated photocatalyst composition (H-31) was dried at room temperature for 1 hour to obtain a test plate (I-31) on which a photocatalyst coating film was formed. Various evaluation results of this test plate (I-31) are shown in Table 3.

[Production Comparative Example 2]
[Commercially available product 2] 163.8 g of rutile titanium oxide MT150A manufactured by Teika Co., Ltd. as an inorganic compound for photocatalyst (AB15), water-dispersed colloidal silica (D1) having a number average particle diameter of 8 nm (trade name “Snowtex”) NS ", Nissan Chemical Industries, Ltd., solid content 20% by mass) 120.6 g, Fluorocarbon Surfactant (F) (DIC," Megafac F-444 ") 0.99 g, and ion-exchanged water The photocatalytic composition (H-) was prepared by mixing and stirring 140 g of the fading dye (G) (manufactured by Kishida Chemical Co., “Methylene Blue”) whose solid content was adjusted to 1.0% by mass by water and 656.2 g of water. 32) was produced.
A glass plate having a size of 10 cm × 10 cm, in which an acrylic silicone resin was applied in advance to a thickness of 100 μm on another surface (front surface) of a glass plate on which one side (back surface) was subjected to white printing, was prepared. The said photocatalyst composition (H-32) was apply | coated to the single side | surface (surface) of this glass plate by the spray method. Then, the test plate (I-32) in which the photocatalyst coating film was formed was obtained by drying the apply | coated photocatalyst composition (H-32) at normal temperature for 1 hour. Various evaluation results of this test plate (I-32) are shown in Table 3.

[Production Comparative Example 3]
163.8 g of silica-modified rutile type titanium oxide of [Production Example 1] as an inorganic compound for photocatalyst (AB16), water-dispersed colloidal silica (D1) having a number average particle diameter of 8 nm (trade name “Snowtex NS”, Nissan Chemical Co., Ltd.) 120.6 g manufactured by Kogyo Co., Ltd., solid content 20% by mass), 0.99 g of fluorocarbon surfactant (F) (manufactured by DIC, “Megafac F-444”), and the amount of solid content is 1 with ion-exchanged water. The photocatalytic composition (H-33) was prepared by mixing and stirring 140 g of the fading dye (G) (manufactured by Kishida Chemical Co., “Methylene Blue”) adjusted to 0.0 mass% and 656.2 g of water. .
A glass plate having a size of 10 cm × 10 cm, in which an acrylic silicone resin was applied in advance to a thickness of 100 μm on another surface (front surface) of a glass plate on which one side (back surface) was subjected to white printing, was prepared. The said photocatalyst composition (H-33) was apply | coated to the single side | surface (surface) of this glass plate by the spray method. Thereafter, the coated photocatalyst composition (H-33) was dried at room temperature for 1 hour to obtain a test plate (I-33) on which a photocatalyst coating film was formed. Various evaluation results of this test plate (I-33) are shown in Table 3.

[Production Comparative Example 4]
163.8 g of silica-modified anatase-type titanium oxide of [Production Example 2] as an inorganic compound for photocatalyst (AB17), water-dispersed colloidal silica (D1) having a number average particle diameter of 8 nm (trade name “Snowtex NS”, Nissan Chemical Co., Ltd.) 120.6 g manufactured by Kogyo Co., Ltd., solid content 20% by mass), 0.99 g of fluorocarbon surfactant (F) (manufactured by DIC, “Megafac F-444”), and the amount of solid content is 1 with ion-exchanged water. The photocatalytic composition (H-34) was prepared by mixing and stirring 140 g of the fading dye (G) (manufactured by Kishida Chemical Co., “Methylene Blue”) adjusted to 0.0 mass% and 656.2 g of water. .
A glass plate having a size of 10 cm × 10 cm, in which an acrylic silicone resin was applied in advance to a thickness of 100 μm on another surface (front surface) of a glass plate on which one side (back surface) was subjected to white printing, was prepared. The said photocatalyst composition (H-34) was apply | coated to the single side | surface (surface) of this glass plate by the spray method. Thereafter, the coated photocatalyst composition (H-34) was dried at room temperature for 1 hour to obtain a test plate (I-34) on which a photocatalyst coating film was formed. Various evaluation results of this test plate (I-34) are shown in Table 3.

[Production Comparative Example 5]
A silver-supporting silica-modified rutile titanium oxide having a silver support of 6% by mass, prepared in the same manner as in [Example 1], was used as the inorganic compound for photocatalyst (AB18).
163.8 g of inorganic compound for photocatalyst (AB18) and water-dispersed colloidal silica (D1) having a number average particle diameter of 8 nm (trade name “Snowtex NS”, manufactured by Nissan Chemical Industries, Ltd., solid content 20 mass%) 6 g, 0.99 g of fluorocarbon surfactant (F) (manufactured by DIC, “Megafac F-444”), and a fading dye (G) (solid content adjusted to 1.0 mass% with ion-exchanged water) (G) ( A photocatalyst composition (H-35) was prepared by mixing and stirring 140 g of “Methylene Blue” manufactured by Kishida Chemical Co., Ltd.) and 656.2 g of water.
A glass plate having a size of 10 cm × 10 cm, in which an acrylic silicone resin was applied in advance to a thickness of 100 μm on another surface (front surface) of a glass plate on which one side (back surface) was subjected to white printing, was prepared. The said photocatalyst composition (H-35) was apply | coated to the single side | surface (surface) of this glass plate by the spray method. Then, the test plate (I-35) in which the photocatalyst coating film was formed was obtained by drying the apply | coated photocatalyst composition (H-35) at normal temperature for 1 hour. Table 3 shows various evaluation results of the test plate (I-35).

[Production Comparative Example 6]
A silver-supported silica-modified rutile type titanium oxide having a silver support of 0.1% by mass, prepared in the same manner as in [Example 1], was used as the inorganic compound for photocatalyst (AB19).
163.8 g of photocatalyst inorganic compound (AB19) and water-dispersed colloidal silica (D1) having a number average particle diameter of 8 nm (trade name “Snowtex NS”, manufactured by Nissan Chemical Industries, Ltd., solid content 20% by mass) 6 g, 0.99 g of fluorocarbon surfactant (F) (manufactured by DIC, “Megafac F-444”), and a fading dye (G) (solid content adjusted to 1.0 mass% with ion-exchanged water) (G) ( A photocatalyst composition (H-36) was prepared by mixing and stirring 140 g of “Methylene Blue” manufactured by Kishida Chemical Co., Ltd.) and 656.2 g of water.
A glass plate having a size of 10 cm × 10 cm, in which an acrylic silicone resin was applied in advance to a thickness of 100 μm on another surface (front surface) of a glass plate on which one side (back surface) was subjected to white printing, was prepared. The said photocatalyst composition (H-36) was apply | coated to the single side | surface (surface) of this glass plate by the spray method. Then, the test plate (I-36) in which the photocatalyst coating film was formed was obtained by drying the apply | coated photocatalyst composition (H-36) at normal temperature for 1 hour. Various evaluation results of this test plate (I-36) are shown in Table 3.

[Production Comparative Example 7]
Of the copper-supported rutile type titanium oxide of [Comparative Example 1], a copper-supported rutile type titanium oxide having a copper support amount of 1% by mass with respect to titanium oxide was used as the inorganic compound for photocatalyst (AB20).
163.8 g of inorganic compound for photocatalyst (AB20) and water-dispersed colloidal silica (D1) having a number average particle diameter of 8 nm (trade name “Snowtex NS”, manufactured by Nissan Chemical Industries, Ltd., solid content 20 mass%) 6 g, 0.99 g of fluorocarbon surfactant (F) (manufactured by DIC, “Megafac F-444”), and a fading dye (G) (solid content adjusted to 1.0 mass% with ion-exchanged water) (G) ( A photocatalyst composition (H-37) was prepared by mixing and stirring 140 g of “Methylene Blue” manufactured by Kishida Chemical Co., Ltd.) and 656.2 g of water.
A glass plate having a size of 10 cm × 10 cm, in which an acrylic silicone resin was applied in advance to a thickness of 100 μm on another surface (front surface) of a glass plate on which one side (back surface) was subjected to white printing, was prepared. The said photocatalyst composition (H-37) was apply | coated to the single side | surface (surface) of this glass plate by the spray method. Then, the test plate (I-37) in which the photocatalyst coating film was formed was obtained by drying the apply | coated photocatalyst composition (H-37) at normal temperature for 1 hour. Various evaluation results of this test plate (I-37) are shown in Table 3.

[Production Comparative Example 8]
Example 1 163.8 g of inorganic compound for photocatalyst (AB1) 163.8 g and water-dispersed colloidal silica (D1) having a number average particle diameter of 8 nm (trade name “Snowtex NS”, manufactured by Nissan Chemical Industries, Ltd., solid content 20 (Mass%) 120.6 g, hydrocarbon surfactant (F ′) (trade name “Perex OT-P”, manufactured by Kao Corporation) 0.99 g, and water 656.2 g are mixed and stirred. This produced the photocatalyst composition (H-38). No fading dye (G) was used.
A glass plate having a size of 10 cm × 10 cm, in which an acrylic silicone resin was applied in advance to a thickness of 100 μm on another surface (front surface) of a glass plate on which one side (back surface) was subjected to white printing, was prepared. The said photocatalyst composition (H-38) was apply | coated to the single side | surface (surface) of this glass plate by the spray method. Then, the test plate (I-38) in which the photocatalyst coating film was formed was obtained by drying the apply | coated photocatalyst composition (H-38) at normal temperature for 1 hour. Various evaluation results of this test plate (I-38) are shown in Table 3.

[Production Comparative Example 9]
Production Example 59.56 g of photocatalyst inorganic compound (AB16) and water-dispersed colloidal silica (D2) having a number average particle diameter of 8 nm (trade name “Snowtex OS”, manufactured by Nissan Chemical Industries, Ltd., solid content 20 mass%) 52.0 g, 160.9 g of the polymer emulsion particles (E2) aqueous dispersion shown in Production Example 4 (solid content: 10.0% by mass), and fluorocarbon surfactant (F) (manufactured by DIC, “Megafac F -444 "), 0.99 g, 140 g of a fading dye (G) (manufactured by Kishida Chemical Co.," Methylene Blue ") whose solid content was adjusted to 1.0% by mass with ion-exchanged water, and 586.55 g of water, The photocatalyst composition (H-39) was produced by mixing and stirring.
A glass plate having a size of 10 cm × 10 cm, in which an acrylic silicone resin was applied in advance to a thickness of 100 μm on another surface (front surface) of a glass plate on which one side (back surface) was subjected to white printing, was prepared. The said photocatalyst composition (H-39) was apply | coated to the single side | surface (surface) of this glass plate by the spray method. Then, the test plate (I-39) in which the photocatalyst coating film was formed was obtained by drying the apply | coated photocatalyst composition (H-39) at normal temperature for 1 hour. Various evaluation results of this test plate (I-39) are shown in Table 3.

[Production Comparative Example 10]
Example 1 826.5 g of inorganic compound for photocatalyst (AB1) 826.5 g and water-dispersed colloidal silica (D2) having a number average particle size of 8 nm (trade name “Snowtex NS”, manufactured by Nissan Chemical Industries, Ltd., solid content 20 22.8 g (mass%), polymer emulsion particles (E1) aqueous dispersion 73.8 g (solid content 8.5 mass%) shown in Production Example 3, and fluorocarbon surfactant (F) (manufactured by DIC, “ 0.99 g of MegaFuck F-444 ") and 140 g of a fading dye (G) (Methylene Blue, manufactured by Kishida Chemical Co., Ltd.) whose solid content was adjusted to 1.0% by mass with ion-exchanged water and stirred. Thus, a photocatalyst composition (H-40) was produced.
A glass plate having a size of 10 cm × 10 cm, in which an acrylic silicone resin was applied in advance to a thickness of 100 μm on another surface (front surface) of a glass plate on which one side (back surface) was subjected to white printing, was prepared. The said photocatalyst composition (H-40) was apply | coated to the single side | surface (surface) of this glass plate with the spray method. Then, the test plate (I-40) in which the photocatalyst coating film was formed was obtained by drying the apply | coated photocatalyst composition (H-40) at normal temperature for 1 hour. Table 3 shows various evaluation results of this test plate (I-40).

[Production Comparative Example 11]
104.0 g of water-dispersed colloidal silica (D2) having a number average particle size of 8 nm (trade name “Snowtex OS”, manufactured by Nissan Chemical Industries, Ltd., solid content 20 mass%) and 104.0 g of the polymer emulsion particles shown in Production Example 4 (E2) 65.4 g of water dispersion (solid content: 10.0% by mass), 0.99 g of fluorocarbon surfactant (F) (manufactured by DIC, “Megafac F-444”), solid with ion-exchanged water The photocatalytic composition (H-41) was prepared by mixing and stirring 140 g of the fading dye (G) (Kishida Chemical Co., Ltd., “methylene blue”) whose amount was adjusted to 1.0% by mass, and 689.0 g of water. Was made.
A glass plate having a size of 10 cm × 10 cm, in which an acrylic silicone resin was applied in advance to a thickness of 100 μm on another surface (front surface) of a glass plate on which one side (back surface) was subjected to white printing, was prepared. The said photocatalyst composition (H-41) was apply | coated to the single side | surface (surface) of this glass plate by the spray method. Then, the test plate (I-41) in which the photocatalyst coating film was formed was obtained by drying the apply | coated photocatalyst composition (H-41) at normal temperature for 1 hour. Table 3 shows various evaluation results of the test plate (I-41).

[Production Comparative Example 12]
Among the silver-supported titanium oxides produced in Example 1, silver is supported on a titanium oxide aqueous dispersion not modified with silica in the same manner as described above, and thereafter, in the same manner as described in [Production Example 1]. Silica-modified silver-supported titanium oxide (silver supported amount of 1% by mass) was used as an inorganic compound for photocatalyst (AB1 ′).
163.8 g of inorganic compound for photocatalyst (AB1 ′) and water-dispersed colloidal silica (D1) having a number average particle diameter of 8 nm (trade name “Snowtex NS”, manufactured by Nissan Chemical Industries, Ltd., solid content 20 mass%) 120 .6 g, fluorocarbon surfactant (F) (manufactured by DIC, “Megafac F-444”) 0.99 g, and a fading dye (G) (solid content adjusted to 1.0 mass% with ion-exchanged water) (G) ( A photocatalyst composition (H-42) was prepared by mixing and stirring 140 g of “Methylene Blue” manufactured by Kishida Chemical Co., Ltd.) and 656.2 g of water.
A glass plate having a size of 10 cm × 10 cm, in which an acrylic silicone resin was applied in advance to a thickness of 100 μm on another surface (front surface) of a glass plate on which one side (back surface) was subjected to white printing, was prepared. The said photocatalyst composition (H-42) was apply | coated to the single side | surface (surface) of this glass plate by the spray method. Then, the test plate (I-42) in which the photocatalyst coating film was formed was obtained by drying the apply | coated photocatalyst composition (H-42) at normal temperature for 1 hour. Various evaluation results of this test plate (I-42) are shown in Table 3.

  If the inorganic compound for photocatalysts (AB) of this invention is used, the photocatalyst layer which exhibits required photocatalytic activity can be provided on a coating film directly under a photocatalyst coating film, without requiring a protective layer. The inorganic compound for photocatalyst (AB) of the present invention can provide anti-algal and anti-fungal properties by providing anti-bacterial properties, is excellent in on-site workability, and has a highly transparent one-layer coat type photo-catalytic coating. Can be provided. The photocatalyst coating film of the present invention is excellent in self-cleaning properties, and has industrial applicability in fields such as architectural exteriors, interior materials, exterior display applications, automobiles, and displays.

Claims (17)

An inorganic compound for photocatalyst (AB) in which 0.5 to 5% by mass of an antibacterial metal (B) is supported on the particle surface of the inorganic compound (A) having photocatalytic activity,
The inorganic compound (AB) for photocatalyst, wherein the inorganic compound (A) satisfies the following condition (i) or satisfies both the following conditions (i) and (ii):
(I) The amount of hydrogen peroxide generated when the suspension containing the inorganic compound (A) is irradiated with ultraviolet light having a wavelength of 380 nm or less and an intensity of 5 mW / cm ² for 60 seconds ([H ₂ O ₂ ]) Is 80 μM or less;
(Ii) The amount of hydroxy radical ([· OH]) generated when the suspension containing the inorganic compound (A) is irradiated with ultraviolet light having a wavelength of 380 nm or less and an intensity of 5 mW / cm ² for 60 seconds is 1 0.0 μM or less:   The inorganic compound (AB) for photocatalysts according to claim 1, wherein the antibacterial metal (B) is at least one selected from the group consisting of copper, silver, gold, platinum, and zinc.   The inorganic compound (AB) for photocatalyst according to claim 1 or 2, wherein the inorganic compound (A) having photocatalytic activity is titanium oxide.   The inorganic compound for photocatalysts (AB) as described in any one of Claims 1-3 whose inorganic compound (A) which has photocatalytic activity is an inorganic compound which processed the particle | grain surface with the metal oxide (C). The inorganic compound (AB) for photocatalysts of Claim 4 whose specific surface area of the inorganic compound which processed the particle | grain surface with the said metal oxide (C) is 80-180 m < ² > / g.   The inorganic compound (AB) for photocatalysts according to claim 4 or 5, wherein the antibacterial metal (B) is supported on the surface of the inorganic compound whose particle surface is treated with the metal oxide (C).   The inorganic compound (AB) for photocatalysts as described in any one of Claims 4-6 whose metal oxide (C) is silicon dioxide.   The photocatalyst composition containing the inorganic compound (AB) for photocatalysts as described in any one of Claims 1-7, and the inorganic compound (D) which does not have photocatalytic activity.   The photocatalyst composition of Claim 8 whose ratio of the inorganic compound (A) which has photocatalytic activity is 1-20 mass% with respect to the photocatalyst composition whole quantity.   The photocatalyst composition according to claim 8 or 9, wherein the inorganic compound (D) having no photocatalytic activity is silicon dioxide.   The photocatalyst composition according to any one of claims 8 to 10, further comprising polymer particles (E).   The photocatalyst composition according to any one of claims 8 to 11, further comprising a fluorocarbon surfactant (F).   The photocatalyst composition according to any one of claims 8 to 12, further comprising a fading dye (G). A step of modifying the metal oxide (C) to the inorganic compound (A) having photocatalytic activity to obtain an inorganic compound whose particle surface is treated with the metal oxide (C); and
The manufacturing method of the inorganic compound for photocatalysts (AB) including the process of carrying | supporting an antibacterial metal (B) to the inorganic compound by which the particle | grain surface was processed with the said metal oxide (C). The ratio of the metal oxide (C) that modifies the inorganic compound (A) having photocatalytic activity is 1 to 30% by mass with respect to the inorganic compound (A) having photocatalytic activity,
The proportion of the antibacterial metal (B) to be supported is 0.5 to 5% by mass with respect to the inorganic compound (A) having photocatalytic activity.
The manufacturing method of the inorganic compound (AB) for photocatalysts of Claim 14.   The photocatalyst coating film formed from the photocatalyst composition as described in any one of Claims 8-13.   The photocatalyst coating product provided with the photocatalyst coating film of Claim 16.