JP6714530B2 - Photocatalyst composition, photocatalyst coating film and photocatalyst coating product - Google Patents

Description

The present invention relates to a photocatalyst composition, a photocatalyst coating film and a photocatalyst coating product.

In recent years, photocatalyst paints have been put into practical use in order to impart antifouling performance to the outer walls of buildings such as houses and buildings, and the photocatalyst paints have been applied to the outer walls of buildings to form photocatalytic coating films. An inorganic compound material having photocatalytic activity is blended in this photocatalytic coating material so as to exhibit photocatalytic activity. The most commonly used inorganic compound material is titanium dioxide (TiO ₂ ). When this titanium dioxide is exposed to light (ultraviolet rays), excited electrons and holes are generated. Due to the generated excited electrons and holes, .O ² -and ・OH (in the presence of oxygen and water on the catalyst surface). "." represents an unpaired electron, which means that the chemical species with this is a radical species.) and other active oxygen species are generated. The holes and the generated active oxygen species exhibit important photocatalytic activities such as a stain decomposition function and a nitrogen oxide removal function. It is also known that when exposed to light, it exerts superhydrophilicity on the surface to wash away stains adhering to the outer wall.

On the other hand, there are various stains on the outer wall of the building, and stains caused by bio-contamination such as mold and algae are no exception, and it has been proposed to prevent bio-contamination such as mold and algae by decomposition by photocatalytic activity. However, it is also considered that the decomposition reaction by the photocatalyst cannot catch up with the growth of mold, algae, etc., and it has been proposed to blend an organic anti-algae/mold agent into the photocatalyst coating material (see Patent Documents 1 and 2). .. A coating film containing an inorganic compound as an antifouling paint has also been proposed (see Patent Documents 3 and 4).

As described above, the active oxygen species are organic in the coating film (hereinafter, also referred to as “coating film directly below the photocatalytic coating film” or “undercoating film”) formed on the base material (base body) to which the photocatalytic coating material is applied. In the case of a coating film, this organic coating film may be damaged. Therefore, a two-layer coat type photocatalyst paint in which a protective layer typified by a silicone resin is provided between the photocatalyst coat and the photocatalyst coat is proposed.

Patent No. 4092434 JP, 2016-808, A Patent No. 4011705 Patent No. 5361513

Patent Document 1 (Japanese Patent No. 4092434) describes a photocatalyst-coated body including a base material, an intermediate layer provided on the base material, and a photocatalyst layer provided on the intermediate layer. There is disclosed a photocatalyst-coated body comprising a silicone-modified resin and an organic antifungal agent, wherein the photocatalyst layer contains photocatalyst particles, inorganic oxide particles, and hydrolyzable silicone in a predetermined ratio. In Examples 29 to 31 of Patent Document 2 (JP-A-2016-808), an aqueous dispersion of a predetermined polymer, aqueous colloidal silica, an inorganic oxide having photocatalytic activity, and a fluorocarbon surfactant are used. , A coated body formed by using an aqueous coating agent containing a discoloring dye and an algae-proofing agent (antifungal agent). Patent Document 3 (Japanese Patent No. 4011705) discloses that at least the base material and the surface layer are contained, the surface layer is hydrophilic and has a self-cleaning ability, and the surface is exposed to occasional rain. A composite material used for reducing nitrogen oxides, ammonia, and/or sulfur dioxide therein, wherein the surface layer comprises a photocatalyst that functions as a catalyst when exposed to light of component (i), and a component ( ii) at least one metal oxide selected from the group consisting of A1 ₂ O ₃ , ZnO, SrO, BaO, MgO, CaO, Rb ₂ O, Na ₂ O, and K ₂ O and a component (iii) SiO ₂ , At least one metal oxide selected from the group consisting of ZrO ₂ , GeO ₂ , and ThO ₂ and at least one metal exhibiting antibacterial properties selected from the group (iv) consisting of Ag and Cu. When the component (iv) is supported on the photocatalyst of (i), the weight of the component (iv) is represented by c, and the weight of the photocatalyst of (i) is represented by b, then c/b is A composite is disclosed that is 0.00001-0.05. Patent Document 4 (Japanese Patent No. 5361513) discloses a photocatalyst-coated body including a substrate, an intermediate layer provided on the substrate, and a photocatalyst layer provided on the intermediate layer. Contains photocatalyst particles composed of a metal oxide that is excited by ultraviolet rays and an ionic copper element, and the intermediate layer contains a weather-resistant resin and a hydroxyphenyltriazine compound. A photocatalyst-coated body characterized by the above is disclosed.

However, none of the examples of the cited documents has demonstrated that the anti-algae and anti-fungal properties can be maintained for a long period of time. Further, in Patent Document 4, if the intermediate layer is not formed between the base material and the photocatalyst layer, the base material (coating directly under the photocatalyst) may be damaged.

Therefore, in the present invention, when it is used as a coating film, it has excellent long-term durability of anti-algal property (antifungal property), excellent weather resistance, and excellent low damage property to a film directly below the photocatalyst (undercoating film). An object of the present invention is to provide a photocatalyst composition, a photocatalyst coating film, and a photocatalyst coating product that can simultaneously satisfy the following conditions.

As a result of intensive studies to solve the above problems, the inventors of the present invention contained an antibacterial metal compound and a non-antibacterial photocatalytically inert inorganic compound in a predetermined ratio, and generated hydrogen peroxide to a predetermined value or less. It has been found that the above problems can be solved by including a photocatalytically active inorganic compound that can be suppressed, and the present invention has been completed.

That is, the present invention is as follows.
[1]
A photocatalyst composition comprising an antibacterial metal compound (A1) and a non-antibacterial inorganic compound (AA) having no antibacterial property,
The non-antibacterial inorganic compound (AA) is a photocatalytically inactive inorganic compound having no photocatalytic activity (
A2) and a photocatalytically active inorganic compound (B) having photocatalytic activity,
The mass ratio (A1/A2) of the antibacterial metal compound (A1) to the photocatalytically inactive inorganic compound (A2) is 0.001 or more and 0.25 or less,
The metal contained in the antibacterial metal compound (A1) is at least one selected from the group consisting of copper and zinc, and the content of the photocatalytically inactive inorganic compound (A2) is the antibacterial metal compound ( 46.1% by mass or more based on the total solid content of the photocatalyst composition excluding A1) 9
9 mass% or less,
The photocatalytically inactive inorganic compound (A2) is silicon dioxide,
A photocatalyst composition in which the photocatalytically active inorganic compound (B) satisfies the following condition (i), or both the following (i) and the following (ii).

(I) In the suspension containing the photocatalytically active inorganic compound (B), a wavelength of 380 nm or less and an intensity of 5 m
The amount of hydrogen peroxide ([H ₂ O ₂ ]) generated when irradiated with UV light of W/cm ² for 60 seconds is 80
μM or less;
(Ii) In the suspension containing the photocatalytically active inorganic compound (B), a wavelength of 380 nm or less and an intensity of 5 m
The amount of hydroxy radicals [.OH] generated when UV light of W/cm ² is irradiated for 60 seconds is
1.0 μM or less:
[ 2 ]
The photocatalyst composition according to the above item [1] , wherein the photocatalytically active inorganic compound (B) is titanium oxide.
[ 3 ]
The photocatalyst composition according to the above [1] or [2] , wherein the particle surface of the photocatalytically active inorganic compound (B) is modified with a metal oxide (C).
[ 4 ]
The photocatalyst composition according to the above item [ 3 ], wherein the metal oxide (C) is silicon dioxide.
[ 5 ]
The content of the photocatalytically active inorganic compound (B) is 1% by mass or more and 20% by mass or less based on the total solid content of the photocatalytic composition excluding the antibacterial metal compound (A1), [1] to
[ 4 ] The photocatalyst composition according to any one of [ 4 ].
[ 6 ]
The photocatalyst composition according to any one of items [1] to [ 5 ] above, further including polymer particles (D).
[ 7 ]
The photocatalyst composition according to the above item [ 6 ], wherein the content of the polymer particles (D) is 40% by mass or less based on the entire photocatalyst composition excluding the antibacterial metal compound (A1).
[ 8 ]
The photocatalyst composition according to any one of items [1] to [ 7 ] above, further containing a fluorocarbon surfactant (E).
[ 9 ]
The photocatalyst composition according to any one of the above items [1] to [ 8 ], further including a fading dye (F).
[ 10 ]
A photocatalyst coating film formed from the photocatalyst composition according to any one of items [1] to [ 9 ].
[ 11 ]
A photocatalyst-coated product comprising the photocatalyst coating according to the above [ 10 ].

The present invention, when used as a coating film, simultaneously exhibits excellent long-term durability of anti-algal properties (antifungal properties), excellent weather resistance, and excellent low damage to the photocatalyst directly undercoat (undercoating). A photocatalyst composition, a photocatalyst coating film, and a photocatalyst coating product that can be filled can be provided.

Hereinafter, modes for carrying out the present invention (hereinafter, simply referred to as “the present embodiment”) will be described in detail. The present embodiment is an example for explaining the present invention, and the present invention is not limited to the embodiment. That is, the present invention can be variously modified without departing from the gist thereof.

In the present specification, the "algae-proofing agent (antifungal agent)" means at least one of an anti-algae agent and an antifungal agent, and the "algae-proofing (mold-proofing)" means anti-algae and anti-mold. At least one of sex. In addition, in the present specification, “long-term durability”, “weather resistance”, and “low damage” refer to, for example, long-term durability, weather resistance of a coating film formed from the photocatalyst composition of the present embodiment, and Refers to low damage.

[Photocatalyst composition (coating agent)]
The photocatalyst composition (coating agent) of the present embodiment is a photocatalyst composition containing an antibacterial inorganic compound (A1) and a non-antibacterial inorganic compound (AA) having no antibacterial property. The compound (AA) includes a photocatalytically inactive inorganic compound (A2) having no photocatalytic activity and a photocatalytically active inorganic compound (B) having photocatalytic activity, and the photocatalytically inactive inorganic material of the antibacterial inorganic compound (A1) The mass ratio (A1/A2) to the compound (A2) is 0.001 or more and 0.25 or less, and the photocatalytically active inorganic compound (B) satisfies the following condition (i), or the following (i) ) And (ii) below.

(I) The amount of hydrogen peroxide ([H ₂ O ₂ ] generated when the suspension containing the photocatalytically active inorganic compound (B) 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 80 μM or less;
(Ii) The amount of hydroxy radicals [.OH] generated when the suspension containing the photocatalytically active inorganic compound (B) was irradiated with ultraviolet light having a wavelength of 380 nm or less and an intensity of 5 mW/cm ² for 60 seconds was 1. 0 μM or less:

The photocatalyst composition of the present embodiment contains the antibacterial metal compound (A1) and the photocatalytically inactive inorganic compound (A2) of the non-antibacterial metal compound in the above-mentioned mass ratio, whereby the antialgal property (antifungal property) is obtained. ) Is excellent in long-term sustainability. Further, the photocatalyst composition of the present embodiment contains a photocatalytically active inorganic compound (B) having a hydrogen peroxide generation amount of the following upper limit value or less under the following measurement conditions (i), so that the coating film directly under the photocatalyst ( Excellent low damage to the base coating). Furthermore, the photocatalyst composition of this embodiment is a photocatalyst inactive inorganic compound (A) containing the antibacterial metal compound (A1) and the photocatalyst inactive inorganic compound (A2) of a non-antibacterial metal compound in the above mass ratio. And the photocatalytically active inorganic compound (B) whose hydrogen peroxide generation amount is at least the following upper limit value under the following measurement conditions (i), the weather resistance is excellent.

[Antibacterial metal compound (A1)]
The photocatalyst composition of this embodiment contains an antibacterial metal compound (A1) having antibacterial properties. The term “having antibacterial properties” as used herein refers to, for example, a minimum concentration (minimum concentration) required when a metal ion of a metal compound is added as a drug to E. coli cells in order to prevent bacterial growth. It has a growth inhibitory concentration (MIC) of 20 mM or less.

Examples of the metal contained in the antibacterial metal compound (A1) of the present embodiment include heavy metals such as mercury, silver, gold, palladium, platinum, cadmium, cobalt, nickel, copper, zinc, thallium, lead and manganese. .. These metals can be used alone or in combination of two or more. Among these metals, at least one selected from the group consisting of copper, silver, gold, platinum, and zinc is preferable from the viewpoint of excellent safety and practicality, and the group consisting of copper, silver, and gold. More preferably, it is at least one selected from the above.

The antibacterial metal compound (A1) of the present embodiment is preferably in the form of a metal oxide. Since the antibacterial metal compound (A1) of the present embodiment is in the form of a metal oxide, the solubility in water is high. It is small and may exist in the coating film formed from the photocatalyst composition (photocatalyst coating film) continuously or in the long term, and has long-term resistance to biofouling (for example, algae resistance, mold resistance, etc.). Persistence tends to be even better.

The metal oxide is not particularly limited, but examples thereof include copper oxide, silver oxide, and zinc oxide. These metal oxides may be used alone or in combination of two or more. Among these, at least one selected from the group consisting of copper oxide, silver oxide, and zinc oxide is preferable, and copper oxide is more preferable, from the viewpoint of further excellent long-term sustainability.

[Non-antibacterial inorganic compound (AA)]
The photocatalyst composition of the present embodiment contains a non-antibacterial inorganic compound (AA), and the non-antibacterial inorganic compound (AA) is a photocatalytically inactive inorganic compound (A2) having no photocatalytic activity and a photocatalyst having a photocatalytic activity. And an active inorganic compound (B). The phrase “having no photocatalytic activity” as used herein means that neither an oxidation reaction nor a reduction reaction occurs due to light irradiation.

[Photocatalytically inactive inorganic compound (A2)]
The non-antibacterial photocatalytically inactive inorganic compound (A2) of the present embodiment is not particularly limited, and examples thereof include silicon dioxide (silica), aluminum oxide (alumina), calcium silicate, magnesium oxide, antimony oxide, zirconium oxide and Inorganic oxides such as these complex oxides can be mentioned. Among these, at least one inorganic oxide selected from the group consisting of silicon dioxide, aluminum oxide, antimony oxide, and complex oxides thereof is preferable from the viewpoint of having many surface hydroxyl groups. More preferably.

The inorganic compound used as the non-antibacterial photocatalytically inactive metal compound (A2) of the present embodiment is preferably present as colloidal particles such as a hydrate. That is, by being an inorganic compound (preferably an inorganic oxide) colloidal particle, further complexation with other components such as the photocatalytically active inorganic compound (B) and polymer particles (D) described later becomes possible, and the present embodiment When the photocatalyst composition in the form is used as an aqueous coating agent, the stability is further improved.

The silicon dioxide is preferably colloidal silica. Examples of the colloidal silica include colloidal silica, which is a dispersion of silica having silicon dioxide as a basic unit in water or a water-soluble solvent.

The method for producing colloidal silica is not particularly limited, and for example, it can be prepared by a sol-gel method. When prepared by the sol-gel method, Werner Stober et al. Journal of Colloid And Interface Science, vol. 26, pp. 62-69 (1968) and Rickey D. et al. Badley et al. Langmuir 6, 792-801 (1990), "Coloring Material Association Magazine", 61 [9] 488-493 (1988), and the like.

The colloidal silica may be, for example, acidic colloidal silica or basic colloidal silica in a state of being dispersed in an aqueous dispersion. As the acidic colloidal silica having water as a dispersion medium, commercially available products may be used, and examples of the commercially available products include "Snowtex (trademark)-OXS" and "Snowtex-OS" manufactured by Nissan Chemical Industries, Ltd., "Snowtex-O", "Snowtex-O-40", "Snowtex-OL" and "Snowtex-OYL", Asahi Denka Co., Ltd. product "Adelite (trademark) AT-20Q", Clariant Japan company product " "Clevozole (trademark) 20H12" and "Clevozole 30CAL25" and the like can be mentioned.

Examples of the basic colloidal silica include colloidal silica stabilized by addition of alkali metal ions, ammonium ions, amines and the like. These may be commercially available products, and examples of commercially available products include "Snowtex-XS", "Snowtex-S", "Snowtex-30", "Snowtex-50", manufactured by Nissan Chemical Industries, Ltd., "Snowtex-20L", "Snowtex-XL", "Snowtex-YL", "Snowtex-ZL", "Snowtex-NXS", "Snowtex-NS", "Snowtex-N", "Snowtex-N", "Snowtex-N40", "Snowtex-CXS", "Snowtex-C", "Snowtex-CM", "Snowtex-PS-S" and "Snowtex PS-M"; Asahi Denka Kogyo KK product Adelite AT-20", "Adelite AT-30", "Adelite AT-20N", "Adelite AT-30N", "Adelite AT-20A", "Adelite AT-30A", "Adelite AT-40" and "Adelite AT-40" AT-50"; "Clevosol 30R9", "Clevozole 30R50", "Clevozole 50R50" manufactured by Clariant Japan Ltd., "Ludox (trademark) HS-40", "Ludox HS-30", "Ludox LS" and "Ludox LS" and "Ludox LS" and "Ludox LS". Ludox SM-30" and the like.

As the colloidal silica having a water-soluble solvent as a dispersion medium, a commercially available product may be used, and as the commercially available product, for example, a product “MA-ST-M (dispersion type of methanol having a particle diameter of 20 to 25 nm) manufactured by Nissan Chemical Industries, Ltd.” may be used. , "IPAST (dispersion type of isopropyl alcohol having a particle size of 10 to 15 nm)", "EG-ST (dispersion type of ethylene glycol having a particle size of 10 to 15 nm)", "EG-ST-ZL (ethylene having a particle size of 70 to 100 nm) Glycol dispersion type)", "NPC-ST (ethylene glycol monopropyl ether dispersion type having a particle diameter of 10 to 15 nm)" and the like.

These colloidal silica can be used individually by 1 type or in combination of 2 or more types. These colloidal silicas may further contain a small amount of alumina, sodium aluminate or the like. The colloidal silica may also contain an inorganic base (eg, sodium hydroxide, potassium hydroxide, lithium hydroxide, ammonia, etc.) or an organic base (eg, tetramethylammonium, etc.) as a stabilizer.

The number average particle diameter of the non-antibacterial inorganic compound (A2) of the present embodiment is preferably 1.0 to 400 nm, more preferably 1.0 to 100 nm, and further preferably 1.0 to 30 nm. .. When the number average particle diameter of the non-antibacterial inorganic compound (A2) is 1 nm or more, the storage stability of the photocatalyst composition (water-based coating agent) tends to be further improved, and the number average particle diameter is 400 nm. By the following, the transparency of the obtained coating film tends to be further improved. The number average particle diameter can be measured using a wet particle size analyzer.

The content of the non-antibacterial photocatalytically inactive inorganic compound (A2) is the whole solid content of the photocatalyst composition excluding the antibacterial metal compound (A1) (or the coating excluding the antibacterial metal compound when forming the coating film). with respect to the total film) (100 mass%), preferably at most 99.9 mass% or more 46.1% by weight, more preferably at most 46.1% by weight to 99% by weight, 46.1 wt % To 85% by mass is more preferable. When the content is 46.1 % by mass or more, the biofouling resistance (eg, algae-proofing property and mold-proofing property) in forming a coating film tends to be further improved, and is 99.9% by mass. By being the following, the weather resistance when forming a coating film tends to be further improved.

The mass ratio (A1)/(A2) of the antibacterial metal compound (A1) to the photocatalytically inactive inorganic compound (A2) in the photocatalyst composition of the present embodiment is preferably 0.001 or more and 0.25 or less. , 0.004 or more and 0.15 or less, more preferably 0.005 or more and 0.05 or less. When the mass ratio is 0.001 or more, the biofouling resistance (mold resistance, algae resistance) tends to be further excellent, and when it is 0.25 or less, the coating film due to coloring, whitening, etc. Poor appearance tends to be suppressed, and an excellent appearance tends to be maintained.

[Photocatalytically active inorganic compound (B)]
The photocatalyst composition of this embodiment contains a photocatalytically active inorganic compound (B) having photocatalytic activity. As a result, the coating film formed from the photocatalyst composition of the present embodiment can have photocatalytic activity, and can be exposed to light to exhibit photocatalytic activity and hydrophilicity.

The photocatalytically active inorganic compound (B) of the present embodiment satisfies the following condition (i) or both the following (i) and (ii) conditions. The photocatalytically active inorganic compound (B) of the present embodiment is excellent in low damage to the coating directly under the photocatalyst (base coating) by satisfying the following condition (i). By satisfying both conditions of (ii), the low damage tends to be more excellent.

(I) The amount of hydrogen peroxide ([H ₂ O ₂ ] generated when the suspension containing the photocatalytically active inorganic compound (B) 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 80 μM or less;
(Ii) The amount of hydroxy radicals [.OH] generated when the suspension containing the photocatalytically active inorganic compound (B) was irradiated with ultraviolet light having a wavelength of 380 nm or less and an intensity of 5 mW/cm ² for 60 seconds was 1. 0 μM or less:

The “suspension” used herein refers to, for example, a suspension prepared under the conditions described in the examples.

The photocatalytically active inorganic compound (B) of the present embodiment has a hydrogen peroxide amount [H ₂ O ₂ ] of 80 μM or less among the amount of active oxygen species generated when the specific ultraviolet light is irradiated for 60 seconds, and is preferable. Is 20 μM or less, more preferably 10 μM or less. When the amount of hydrogen peroxide [H ₂ O ₂ ] is 80 μM or less, damage to the coating film (undercoating film) directly under the photocatalyst can be suppressed. The "specific ultraviolet light" referred to in the present specification means ultraviolet light having a wavelength region of 380 nm or less and an intensity of 5 mW/cm ² , "μM" represents micromolar, and 1 μM=10. ^-6 M=10 ^-6 mol/L.

Among the active oxygen species, hydrogen peroxide (H ₂ O ₂ ) is a stable substance compared to radical species such as hydroxy radical (.OH), and compared to the life of the radical species (1 second or less). It has a long life, and it seems to move to a long distance and damage the coating directly below the photocatalytic coating. On the other hand, in the photocatalytically active inorganic compound (B) of the present embodiment, the hydrogen peroxide amount (hydrogen peroxide generation amount) [H ₂ O ₂ ] can be made relatively small at 80 μM or less. The damage of can be suppressed.

The photocatalytically active inorganic compound (B) of the present embodiment has a hydroxy radical amount [.OH] of 1.0 μM or less in the amount of active oxygen species generated when the specific ultraviolet light is irradiated for 60 seconds. It is preferably less than 1.0 μM, more preferably less than 0.5 μM (or less). Hydroxy radicals (.OH) have the effect of damaging the underlying coating film. On the other hand, when the amount of hydroxy radicals (amount of hydroxy radicals generated) [.OH] is 1.0 μM or less, damage to the coating film directly under the photocatalyst tends to be further suppressed.

From the viewpoint that the photocatalytically active inorganic compound (B) of the present embodiment more effectively and reliably exhibits the effects of the present invention (particularly weather resistance and low damage to the underlying coating film), the condition (i) and (ii) It is preferable that both of the conditions of 1) are satisfied.

The method for adjusting the amount of each active oxygen species ([H ₂ O ₂ ] and [.OH]) described above to be less than (or less than) the specific value is not particularly limited, but, for example, a photocatalytically active inorganic compound (described later) ( Examples thereof include a method of applying a modification treatment to the particle surface of B). By modifying the particle surface of the photocatalytically active inorganic compound (B), the amount of each active oxygen species can be reduced to the above specified value or less by the reason that the surface-modified photocatalytically active inorganic compound deactivates the active oxygen species. It is thought that it can be trapped. However, the present invention is not limited to this factor.

Examples of the photocatalytically active inorganic compound (B) of this embodiment include titanium oxide (TiO ₂ ), strontium titanate (SrTiO ₃ ), gallium phosphide (GaP), indium phosphide (InP), gallium arsenide (GaAs). ), barium titanate (BaTiO ₃ , BaTiO ₄ , BaTi ₄ O ₉ ), potassium niobate (K ₂ NbO ₃ ), niobate (Nb ₂ O ₅ ), iron oxide (Fe ₂ O ₃ ), tantalum pentoxide ( Ta ₂ O ₅ ), K ₃ Ta ₃ Si ₂ O ₃ , tungsten oxide (WO ₃ ), tin oxide (SnO ₂ ), bismuth oxide (Bi ₂ O ₃ ), bismuth vanadate (BiVO ₄ ), silicon carbide (SiC) ), molybdenum disulfide (MoS ₂ ), indium lead (InPb), ruthenium dioxide (RuO ₂ ), and cesium dioxide (CeO ₂ ), at least one element selected from the group consisting of Nb, Ta, and V. Layered oxides having (for example, JP-A-62-074452, JP-A-02-172535, JP-A-07-024329, JP-A-08-087999, JP-A-08-089800, and JP-A-08-0889800). 08-089804, JP-A 09-248465, JP-A 10-099694, JP-A 10-244165 and the like).

These photocatalytically active inorganic compounds (B) can be used alone or in combination of two or more. Among these, from the viewpoint of more effectively and reliably exhibiting the action and effect of the present invention, an inorganic oxide having photocatalytic activity (photocatalytic inorganic oxide (B)) is preferable, and from the viewpoint of excellent safety and cost, It is more preferably titanium oxide. Examples of the crystal structure of titanium oxide include anatase type, rutile type, and brookite type, and of these, the rutile type is preferable.
Yes.

The particle surface of the photocatalytically active inorganic oxide (B) of the present embodiment is preferably modified with a metal oxide (or modifier) (C). By modifying the surface of the particles with a modifier, the amount of active oxygen species such as H ₂ O ₂ and .OH generated can be further reduced, and damage to the base coating film can be further suppressed. Examples of the metal oxide (modifier) include metal oxides such as silicon dioxide, aluminum, copper oxide, and iron oxide.

These metal oxides may be used alone or in combination of two or more. Of these, silicon dioxide is preferable. By using silicon dioxide as the metal oxide, the pH of a composition such as an aqueous dispersion or an aqueous sol containing the photocatalytically active inorganic compound (B) can be kept neutral, and the photocatalytically active inorganic compound (B) can be maintained. Since the particles are less likely to aggregate and the morphology of the particles can be stably maintained, the appearance characteristics of the coating film (for example, low cloudiness) tend to be further improved.
As a method of modifying silicon dioxide, for example, when titanium oxide is used as the photocatalytically active inorganic compound (A), a silicon compound is added to a slurry of titanium oxide and neutralized to precipitate a hydrous oxide of silicon. There is a method. Examples of the silicon compound include water-soluble alkali metal silicates such as sodium silicate, which is colorless and is preferably sodium silicate from the viewpoint of not coloring the titanium oxide sol. The amount of hydrous oxide of silicon to be treated is preferably 3% by mass or more and 25% by mass or less, more preferably 5% by mass or more and 20% by mass or less, based on the oxide based on titanium oxide. If the treatment amount is less than 3% by mass, the amount of active oxygen species increases, and the coating film (undercoating film) directly below the photocatalytic coating film may be damaged. On the other hand, if the treatment amount exceeds 25% by mass, titanium oxide may agglomerate, the viscosity of the sol tends to increase, the dispersibility may deteriorate, and the transparency may become insufficient.

The metal oxide (C) may be in the form of supporting an antibacterial metal. When the photocatalytically active inorganic compound (B) is surface-modified with the metal oxide (C) having such a form, the photocatalytically active inorganic compound (B) is loaded with an antibacterial metal, and thus has a biofouling resistance (algae resistance). , Mold resistance, etc.) tends to be more excellent. Examples of the antibacterial metal include heavy metals such as mercury, silver, gold, palladium, platinum, cadmium, cobalt, nickel, copper, zinc, thallium, lead and manganese. These antibacterial metals can be used alone or in combination of two or more. Among these, at least one selected from the group consisting of copper, silver, gold, platinum, and zinc is preferable from the viewpoint of excellent safety and practicality, and selected from the group consisting of copper, silver, and gold. More preferably, it is at least one kind.

The photocatalytically active inorganic oxide (B) of the present embodiment has a viewpoint of further improving the photocatalytic performance, further reducing the transparency of the coating film, especially the white turbidity of the coating film, and further improving the dispersibility. Therefore, the primary average particle diameter (arithmetic average) thereof is preferably in the range of 1 to 400 nm, and more preferably in the range of 1 to 100 nm. More preferably, it is in the range of 40 to 70 nm. When the particle shape of the photocatalytically active inorganic oxide (B) has a major axis and a minor axis such as a rod shape, the arithmetic mean of the major axis and the minor axis is preferably within the above range. The primary average particle diameter of the photocatalytically active inorganic oxide (B) may be derived as an arithmetic average of, for example, 50 particles selected arbitrarily and observed by an electron microscope.

The content of the photocatalytically active inorganic compound (B) is the total solid content of the photocatalyst composition excluding the antibacterial metal compound (A1) (or the entire coating film excluding the antibacterial metal compound (A1) when forming a coating film). It is preferably 1% by mass or more and 20% by mass or less, more preferably 5% by mass or more and 15% by mass or less, and further preferably 10% by mass or more and 15% by mass or less with respect to (100% by mass). preferable. By setting the content of the photocatalytically active inorganic compound (B) within the above range, the biofouling resistance (algae resistance, mold resistance) and transparency tend to be further excellent.

In the present embodiment, the content of the non-antibacterial photocatalytically inactive inorganic compound (A2) is 40% by mass or more and 99% by mass or more based on the entire solid content of the photocatalytic composition excluding the antibacterial metal compound (A1). The content of the photocatalytically active inorganic compound (B) is preferably 1% by mass or more and 20% by mass or less based on the total solid content of the photocatalytic composition excluding the antibacterial metal compound (A1). It is preferable. When the content of the non-antibacterial photocatalytically inactive metal compound (A2) and the content of the photocatalytically active inorganic compound (B) simultaneously satisfy the above ranges, weather resistance and biofouling resistance (algae resistance, protection against (Moldiness) and transparency can be satisfied at the same time in a more balanced manner.

<Polymer particles (D)>
The photocatalyst composition of the present embodiment preferably further contains polymer particles (D) from the viewpoint of further excellent weather resistance.

The polymer particles (D) are not particularly limited and include, for example, at least one selected from the group consisting of synthetic resins and natural resins. The form of the polymer particles (D) is not particularly limited and may be a form of pellets or a form dissolved or dispersed in a solvent, but a form of a resin paint for coating. preferable.

Examples of resin paints include oil paints, lacquers, solvent-based synthetic resin paints (acrylic resin-based, epoxy resin-based, urethane resin-based, fluororesin-based, silicone resin-based, silicone-acrylic resin-based, alkyd resin-based, aminoalkyd Resin-based, vinyl resin-based, unsaturated polyester resin-based, chlorinated rubber-based paints, etc., water-based synthetic resin paints (emulsion-based, water-based resin-based paints, etc.), solvent-free synthetic resin paints (powder paints, etc.), inorganic substances At least one selected from the group consisting of paints and electrically insulating paints can be mentioned.

Among these resin paints, a silicone resin-based paint and/or a fluororesin-based paint, which are hardly decomposable to a photocatalyst, are preferable, and a resin paint of a combination type of a silicone resin-based paint and a fluororesin-based paint Is more preferable.

Examples of the silicone-based resin contained in the resin coating include, for example, a copolymer containing a structural unit derived from alkoxysilane and/or organoalkoxysilane, a hydrolysis product of alkoxysilane and/or organoalkoxysilane (polysiloxane), and A mixture of these resins and colloidal silica, and further a structure derived from an acryl-silicone resin, an epoxy-silicone resin, a urethane-silicone resin, an alkoxysilane and/or an organoalkoxysilane, which has a silicone content of 1 to 80% by mass. Examples thereof include copolymers containing units, or hydrolysis products (polysiloxanes) of alkoxysilanes and/or organoalkoxysilanes, and mixtures of these resins with colloidal silica. These silicone resins may be of any type dissolved in a solvent, dispersion type, or powder type, and may contain additives such as a crosslinking agent and a catalyst.

The content of the polymer particles (D) is the entire solid content of the photocatalyst composition excluding the antibacterial metal compound (A1) (or the entire coating film excluding the antibacterial metal compound (A1) when forming a coating film). With respect to (100 mass %), it is preferably more than 0 mass% and 40 mass% or less, more preferably more than 0 mass% and 30 mass% or less, more than 0 mass% and 20 mass%. The following is more preferable. When the content of the polymer particles (D) is within the above range, the biofouling resistance (algae resistance, mold resistance) tends to be further excellent.

<Fluorocarbon surfactant (E)>
The photocatalyst composition of the present embodiment preferably further contains a fluorocarbon surfactant (E). The photocatalyst composition of the present embodiment contains a fluorocarbon surfactant (E), so that when it is used as a water-based coating agent or a water-based paint containing the water-based coating agent, it is applied to a substrate (for example, an organic substrate). There is a tendency that the wettability is further improved, problems in appearance due to cissing and the like can be further suppressed, and the uniformity of the coating film is further improved. It is considered that this factor is due to the fact that the inclusion of the fluorocarbon surfactant (E) can reduce the surface tension of the water-based coating agent, but the present invention is not limited to this factor.

The fluorocarbon surfactant (E) is not particularly limited, but examples thereof include an amphoteric surfactant, and the amphoteric surfactant is preferable from the viewpoint of improving the uniformity of the coating film with a small addition amount. .. Examples of the amphoteric surfactant include nonionic amphoteric surfactants, anionic amphoteric surfactants, and cationic amphoteric surfactants. These amphoteric surfactants may be used alone or in combination of two or more. Among these, from the viewpoint of easy availability, an amphoteric surfactant having a perfluoroalkyl group having 3 to 20 carbon atoms is preferable.

The amphoteric surfactant having a perfluoroalkyl group having 3 to 20 carbon atoms is not particularly limited, and examples thereof include perfluoroalkyl sulfonates and perfluoroalkyl carboxylates (for example, "Surflon S, a product of AGC Seimi Chemical Co., Ltd." -211"), perfluoroalkylamine oxide (for example, "Surflon S-241" manufactured by AGC Seimi Chemical Co., Ltd.), perfluoroalkylethylene oxide adduct, and perfluoro having an anionic group and a cationic group. Examples thereof include alkyl compounds. These amphoteric surfactants may be used alone or in combination of two or more. Among these, perfluoroalkylethylene oxide adducts and perfluoroalkyl compounds having an anionic group and a cationic group are preferable from the viewpoint of further reducing the surface tension of the photocatalyst composition (paint).

The perfluoroalkyl ethylene oxide adduct is not particularly limited and, for example, a commercially available product may be used. Examples of the commercially available product include DIC's product “Megafuck F-444” and AGC Seimi Chemical's product “Surflon S”. -242" and the like. These commercially available products may be used alone or in combination of two or more.

The perfluoroalkyl compound having an anionic group and a cationic group is not particularly limited, and, for example, a commercially available product may be used, and the commercially available product is "Surflon S-231" manufactured by AGC Seimi Chemical Co., Ltd. , "Surflon S-232", "Surflon S-233" and the like. These commercially available products may be used alone or in combination of two or more.

The content of the fluorocarbon surfactant (E) is the total solid content of the photocatalyst composition excluding the antibacterial metal compound (A1) (or the entire coating film excluding the antibacterial metal compound (A1) when forming a coating film). It is preferably 1% by mass or more and 6% by mass or less, more preferably 2% by mass or more and 5% by mass or less, and further preferably 3% by mass or more and 4% by mass or less with respect to (100% by mass). .. When the content of the fluorocarbon surfactant (E) is 1% by mass or more, the uniformity of the resulting coating film tends to be further improved, and the content of the fluorocarbon surfactant (E) is 6 When it is at most mass%, the weather resistance of the resulting coating film will tend to be further improved.

<Fadeable dye (F)>
The photocatalyst composition of the present embodiment preferably further contains a fading dye (F). The photocatalyst composition of the present embodiment can prevent problems such as forgetting to paint, overlapping coating, and uneven coating by including the fading dye (F).

The fading dye (F) is not particularly limited, and examples thereof include dyes that are discolored by irradiation of sunlight and do not impair the design of the base material or the base coating film. The time until the fading dye (F) loses color varies depending on the season, the direction of irradiation, etc., but normally the period until visual confirmation of discoloration is preferably 20 days or less, more preferably 10 days. It is not more than one day, and more preferably not more than 3 days.

As a typical fading dye (F), at least selected from the group consisting of methylene blue, crystal violet, malachite green, brilliant blue FCF, erythrosine, new coccin, phloxine, rose bengal, acid red, and fast green FCF. There is one kind. Among these, methylene blue is preferable from the viewpoints of good color development and a high rate of color loss. These fading dyes (F) can be used alone or in combination of two or more.

The content of the fading dye (F) is the whole solid content of the photocatalyst composition excluding the antibacterial metal compound (A1) (or the photocatalyst composition excluding the antibacterial metal compound (A1) when forming a coating film). ) (100 mass %), preferably 0.01 mass% or more and 0.5 mass% or less, more preferably 0.05 mass% or more and 0.2 mass% or less, and 0.1 mass% or less. % Or more and 0.2 mass% or less is more preferable. When the content of the discolorable dye (F) is 0.01% by mass or more, the color developability in forming a coating film tends to be further improved, and the content is 0.5% by mass or less. When it exists, there is a tendency that the fading property in forming a coating film is further improved. As used herein, the term "colorability" refers to the property of developing color to the extent that it can be visually distinguished from the difference in color between the painted surface and the unpainted surface, and the "fading property" as used herein means It is the property of fading to the extent of a color that does not impair the design of the base material or base coating film.

The photocatalyst composition of the present embodiment may further contain an organic antialgal agent (antifungal agent). As the algae-proofing agent (antifungal agent), for example, at least selected from the group consisting of organic iodine compounds, alcohol compounds, nitrile compounds, disulfide compounds, thiocarbamate compounds, urea compounds and nitrogen-containing ring compounds. There is one kind. Among these, urea compounds and/or nitrogen-containing ring compounds are preferable. Examples of the nitrogen-containing ring compound include at least one selected from the group consisting of thiazoline compounds, isothiazoline compounds, triazine compounds, and imidazole compounds. Among these, at least one selected from the group consisting of isothiazoline compounds, triazine compounds and imidazole compounds is preferable, and at least one selected from the group consisting of isothiazoline compounds and triazine compounds. Is more preferable. In particular, a triazine-based compound is preferable from the viewpoint of excellent algae resistance, and at least one selected from the group consisting of thiazoline-based compounds, isothiazoline-based compounds, and imidazole-based compounds is preferable from the viewpoint of excellent antifungal properties. From the viewpoint of excellent anti-algal and antifungal properties, it is more preferable to use an isothiazoline compound containing a chlorine atom in the molecule. These algae inhibitors (antifungal agents) can be used alone or in combination of two or more.

As the thiazoline-based compound, a commercially available product may be used, and examples of the commercially available product include Nippon Soda's product "Milcut-180", "Biocut-LC3", and Daiwa Chemical Industry's product "Amorden ALK". To be

As the isothiazoline-based compound, a commercially available product may be used. Examples of the commercially available product include "Biocut-TR120", a product of Nippon Soda Co., Ltd., "PROXEL GXL", "PROXEL BDN", a product of Arch Chemicals, a product of Dow Chemical Co., Ltd. "KLARIX 4000", "ROZONE 2000", "ROCIMA 252", "ROCIMA 200", "ROCIMA 345", "ROCIMA 350", "ROCIMA 553", "BIOBAN 551S", "Scene M-8" and the like can be mentioned. ..

As the triazine-based compound, a commercially available product may be used, and examples of the commercially available product include Nippon Bio Soda Co., Ltd. products "Biocut-N35", "DP-2159", and "DP-2615". Examples include "DP-2618", "DP-2623", "Amorden NBP-8", "Amorden NBPconc" manufactured by Daiwa Chemical Industry Co., Ltd., "San Alga 1907" manufactured by Sankyo Kasei Co., Ltd., and the like.

As the imidazole compound, a commercially available product may be used, and examples of the commercially available product include Nippon Bio Soda Co., Ltd. products "Biocut-N35", "Biocut-AF40", "DX-2", and Dow Chemical Co. "ROCIMA 363" etc. are mentioned.

The photocatalyst composition of the present embodiment may contain a dispersion stabilizer from the viewpoint of stabilizing the dispersibility of particles constituting each component. Examples of the dispersion stabilizer include various water-soluble oligomers selected from the group consisting of polycarboxylic acid and sulfonate, polyvinyl alcohol, hydroxyethyl cellulose, starch, maleated polybutadiene, maleated alkyd resin, polyacrylic acid (salt ), polyacrylamide, and various synthetic or natural polymer substances such as acrylic resin. The dispersion stabilizers may be used alone or in combination of two or more.

The photocatalyst composition of the present embodiment, depending on its application and method of use, etc., components added and blended with usual paints and molding resins, for example, solvents, thickeners, leveling agents, thixotropic agents, defoaming agents. Agents, freeze stabilizers, matting agents, crosslinking reaction catalysts, pigments, curing catalysts, crosslinking agents, fillers, anti-skin agents, dispersants, wetting agents, light stabilizers, antioxidants, UV absorbers, rheology control Agents, defoaming agents, film forming aids, rust preventives, dyes, plasticizers, lubricants, reducing agents, preservatives, antifungal agents, deodorants, anti-yellowing agents, antistatic agents or antistatic agents. Etc. may be included.

[Photocatalyst coating]
The photocatalyst coating film of this embodiment is formed from the photocatalyst composition of this embodiment.

The film thickness of the photocatalyst coating film of this embodiment is not particularly limited. The film thickness is preferably 0.05 μm or more and 50 μm or less, more preferably 0.1 μm or more and 10 μm or less, and further preferably 0.2 μm or more and 2.0 μm or less. When the film thickness is 0.05 μm or more, there is a tendency that the antifouling property including antialgae and antifungal property and the photocatalytic activity can be more effectively exhibited, and when the film thickness is 50 μm or less, the transparency is Can be further improved.

[Coating film directly under photocatalyst (base coating)]
From the viewpoint of more effectively exhibiting the effects of the present invention, the photocatalyst coating film of the present embodiment is preferably formed as a base coating film (coating film directly under the photocatalyst) formed on a substrate (base material). The base coating film is, for example, silicone paint, acrylic-silicone paint, silicone-alkyd paint, acrylic paint, fluorine-based paint, urethane paint, acrylic urethane paint, epoxy paint, vinyl chloride paint, vinyl acetate paint, phthalic acid paint, alkyd. It is formed from resin paint such as paint. Among these, from the viewpoint of further excellent weather resistance, it is preferably formed from at least one selected from the group consisting of silicone paints, acrylic-silicone paints, and fluorine-based paints.

[Method for producing photocatalytic coating film]
The photocatalyst coating film of the present embodiment can be obtained, for example, by coating and forming a photocatalyst composition (photocatalyst coating agent) on a base coating film and solidifying to form a film. Examples of the coating method include a spraying method, a flow coating method, a roll coating method, a brush coating method, a dip coating method, a spin coating method, a screen printing method, a casting method, a gravure printing method, and a flexographic printing method. After coating and forming, a solidified film is obtained by drying and removing volatile matter. At this time, for example, after drying at a low temperature of 20° C. to 80° C., if desired, a heat treatment of preferably 20° C. to 500° C., more preferably 40° C. to 250° C. may be performed, and ultraviolet irradiation or the like may be performed. Good.

[Photocatalyst coating products]
The photocatalyst-coated product (painted body) of the present embodiment may have a photocatalyst coating film. The coated body is, for example, a substrate (base material), a base coating film arranged (formed) on the base body (base material), and the photocatalytic coating of the present embodiment arranged (formed) on the base coating film. It may be composed of a membrane. Specific examples of the photocatalyst coated product of the present embodiment include, for example, building materials, building exteriors, building interiors, window frames, window glasses, structural members, building equipment such as houses, covers for vehicle lighting, window glasses, mechanical devices, and the like. Exterior of articles, dust-proof covers and coatings, display equipment, covers, traffic signs, various display devices, display materials such as advertising towers, sound insulation walls for roads and railways, exterior and coating of bridges, guardrails, tunnel interiors and coatings. Examples include exterior parts of electronic and electric devices used outside, such as insulators, solar cell covers, and solar water heater heat collection covers, especially exterior parts of transparent members, vinyl houses, greenhouses, and the like. The method for producing this photocatalyst-coated product is not particularly limited, but, for example, a composition (coating agent) for forming a base coating film and a photocatalyst composition were applied to the surface of a substrate (base material) in the above order. Examples of the method include subsequent drying to form a multilayer coating film on the substrate (base material). The substrate (base material) and the base coating film and the photocatalyst coating film may be simultaneously molded, or may be integrally molded.

Further, after the photocatalyst coating film of the present embodiment is formed on a certain substrate, the photocatalyst coating film is peeled from the substrate or adhered to the substrate, and then adhered to another substrate by adhesion, fusion, or the like. You may let me.

Although the embodiments for carrying out the present invention have been described above, the present invention is not limited to the above embodiments. The present invention can be variously modified without departing from the gist thereof.

The present invention will be specifically described with reference to the following examples, reference examples and comparative examples, but these do not limit the scope of the present invention. Various physical properties were measured by the methods described below.

1. Quantification Quantification [H ₂ O _2] in the [H ₂ O _2] was performed using lucigenin chemiluminescence method.
First, to a quartz cell (optical path (length) 1 cm×width 1 cm) installed on a magnetic stirrer in a dark box, 3.5 mL of 0.01 M NaOH aqueous solution was added to adjust pH to 9, and further 15 mg of sol was added thereto. The powder of the photocatalytically active inorganic compound (B) obtained by drying was added and suspended to obtain a suspension.
Next, using an LED (Hamamatsu Photonics (Hamamatsu Photonics), model “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. I went. After the irradiation, 50 μL of 0.7 mM lucigenin solution was added, and the chemiluminescence generated by H ₂ O ₂ was passed through a bandpass filter and then detected by an electron-cooled photomultiplier tube. [H ₂ O ₂ ] was derived from the detected amount of chemiluminescence.

2. Quantification of [.OH] [.OH] was measured using the coumarin fluorescent probe method.
First, a 0.1 mM coumarin aqueous solution was prepared, and a photocatalytically active inorganic compound (B) powder obtained by drying 15 mg of a sol in the quartz cell and 35 mL of a coumarin aqueous solution were suspended to obtain a suspension. It was 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 metal compound (photocatalyst) powder such as TiO ₂ from the suspension, 0.5 g of KCl was added to the suspension after the irradiation, and the mixture was left standing for 24 hours in the dark. Then, the supernatant was taken as a sample, and the fluorescence was measured with a Fluorescence spectrophotometer (Model 850, manufactured by HITACHI) (at this time, it was confirmed that the light scattering at the time of fluorescence measurement by the addition of KCl did not affect). [.OH] was quantified by comparing the fluorescence intensity of coumarin of known concentration with the fluorescence intensity of the above sample.

3. Quantification of surface modified material Quantification was carried out by the FP method, in which quantitative analysis was carried out using a theoretical X and fundamental constant Fundamental Parameter (FP) using a fluorescent X-ray analyzer.

4. Number average particle diameter It was measured by using a wet particle size analyzer (Microtrac UPA-9230 manufactured by Nikkiso Japan Co., Ltd.) by appropriately adding a solvent so that the solid content in the sample becomes 1 to 20% by mass.

5. Film thickness of coating film The film thickness of the coating film was measured by a film thickness measuring device (manufactured by SPECTRA/COOP, product name "HanGyLambGa II THICKNESS") equipped with a halogen light source device (manufactured by MORITEX, product name "MHF-G100LR"). Was measured using.

6. The coatability test plate was observed and photographed with a scanning electron microscope (NeoScope JCM-5000, manufactured by JEOL Ltd.), and the photocatalyst coating rate was calculated. The evaluation criteria are as follows.

◯: The coating rate is 80% or more Δ: The coating rate is 50% or more and less than 80% ×: The coating rate is less than 50%

7. Transparency (whiteness of coating film)
The color difference was measured when a black paper was laid under a glass plate (a normal plate glass manufactured by Test Piece Co., Ltd.; 60 mm×60 mm×2 mm). Then, the photocatalyst composition was applied with a dip coater (DC4200 manufactured by Aiden Co., Ltd., ascending/descending speed: descending 10 mm/sec, ascending 10 mm/sec), and dried for 2 days after coating. After that, the specimen was left under a fluorescent lamp adjusted to an illuminance of 5000 Lx for 10 days to decolorize the colorant, and the color difference was measured. The color difference (brightness difference ΔL) before and after coating was evaluated. The evaluation criteria are as follows.

⊚: Color difference ΔL=less than 0.8 ○: Color difference ΔL=0.8 or more and less than 1.6 Δ: Color difference ΔL=1.6 or more and less than 3.0 ×: Color difference ΔL=3.0 or more

8. Photocatalytic activity (dye decomposition activity)
The decomposition activity index was determined according to JIS R1703-2. The test piece purification conditions were irradiation at an illuminance of 1 mW/cm ² for 24 hours, methylene blue adsorption conditions were an adsorbent concentration of 0.02 mM and an adsorption time of 24 hours.Methylene blue decomposition measurement conditions were illuminance of 1 mW/cm ² , test solution concentration of 0.01 mM and injection amount. The absorption spectrum of 35 mL of the test solution collected after irradiation was measured with a spectrophotometer. The absorbance measurement wavelength was 664 nm. The evaluation criteria are as follows.

◎: Degradation activity index is 10 nM/min or more ○: Degradation activity index is 5 nM/min or more and less than 10 nM/min ×: Degradation activity index is less than 5 nM/min

9. Deterioration observation of the coating film (undercoating film) directly under the photocatalyst coating film After embedding the sample in an epoxy resin (trade name, Quetol 812), a 50 to 60 nm film was obtained using a product "ULTRACUT-N type microtome (trade name)" manufactured by Reichert in Germany. After making an ultrathin section with a thickness and loading it on a mesh with a support film, carbon deposition is performed and it is used as a speculum sample, and the cross section of the coating film is observed by TEM (HF2000 type manufactured by Hitachi, accelerating voltage: 125 kV). Then, the deterioration state of the base coating film was evaluated. The evaluation criteria are as follows.

⊚: No deterioration of the base coating film was observed. ◯: A slight deterioration of the base coating film was observed, but there was no problem overall. Δ: Some deterioration of the base coating film was observed. Deterioration of the underlying coating film was generally observed

10. Anti-algal and anti-mold (short term)
After placing each test plate in a petri dish containing algae, the petri dish containing the test plate was placed in a constant temperature bath kept at a constant temperature to carry out the test. The judgment was made 4 weeks after the start of the test. The evaluation criteria are as follows.

A: Growth of algae was not observed. B: Slight growth of algae was observed, but there was no problem overall.: Growth of algae was clearly observed.

As for mold resistance, a mold resistance test was carried out in accordance with JIS Z2911:2010. The judgment was made two weeks after the start of the test. The evaluation criteria are as follows.

◯: No mold growth was observed Δ: A slight mold growth was observed, but there was no problem overall ×: Mold growth was clearly observed

11. Anti-algal, anti-mold (long-term)
An outdoor exposure test was carried out on each test plate on the land where there is a forest and lawn growing near Choshi City, Chiba Prefecture, at 90° north face. The judgment was made 6 years after the exposure. The evaluation criteria are as follows.

◯: No growth of algae and mold was observed in both visual observation and microscopic observation (40 times). Δ: Growth of algae and mold was not observed by visual observation, but growth was observed in microscopic observation (40 times). X: Growth of algae and mold was observed by visual observation

12. Weather resistance (color difference after exposure to SWOM 5000 hours)
An exposure test (black panel temperature 63° C., rainfall 18 minutes/2 hours) was performed using the product "Sunshine Weather Meter" manufactured by Suga Test Instruments Co., Ltd., and the color difference between before exposure of the test plate and after 5000 hours of exposure was measured. , A color guide (product of BYK GarDner) was used to determine the color difference from the standard plate, and the color difference before and after exposure was used as the standard, and the change in state before and after exposure was evaluated as ΔE. The evaluation criteria are as follows.

◯: ΔE* is less than 3 ×: ΔE* is 3 or more.

[Reference Example 1] Silica-modified rutile type titanium oxide (B-1)
700 mL of an aqueous titanium tetrachloride solution having a concentration of 200 g/L as TiO ₂ and an aqueous sodium hydroxide solution having a concentration of 100 g/L as Na ₂ O were added in parallel to water so as to maintain the pH of the system at 5-9. Then, after adjusting the pH of the system to 7, the system was filtered and washed until the conductivity of the filtrate reached 100 μS/cm to obtain titanium oxide wet cake 1 having a solid content concentration of 28.3 mass %. The titanium oxide fine particles had a rutile structure, and the average particle diameter 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 further added so that the molar ratio of titanium oxide/nitric acid was 1/L, and the mixture was heated to a temperature of 95° C. and kept at this temperature for 2 hours. Then, an acid heat treatment was performed. Then, the slurry after the acid heat treatment was cooled to room temperature, neutralized (pH=6.7) with 28% ammonia water, filtered, and washed until the filtrate had a conductivity of 100 μS/cm. Titanium oxide wet cake 2 having a solid content concentration of 25 mass% was obtained.
An aqueous solution of sodium hydroxide having a concentration of 10% was added to the obtained titanium oxide wet cake 2, repulped, and then dispersed for 3 hours with an ultrasonic cleaner to have a pH of 10.5 and a solid content concentration of 10 mass. % Alkaline titanium oxide sol was obtained. 2 L of this alkaline titanium oxide sol was charged into a 3 L flask, the temperature was raised to 70° C., 69.4 ml of an aqueous sodium silicate solution having a concentration of 432 g/L as SiO 2 was added, and then the temperature was raised to 90° C. for 1 hour. After aging, 10% sulfuric acid was added to adjust the pH to 6, and the surface of titanium oxide was surface-treated with 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 concentrator, pH=7.3, solid content concentration 29 mass %, A neutral rutile-type titanium oxide sol having an electrical conductivity of 1.18 mS/cm was obtained. It contained 15 wt% of silicon oxide hydroxide with SiO ₂ basis relative to TiO _2. The average particle size of titanium oxide in this sol was 60 nm.

[Reference Example 2] Preparation of silica-modified anatase-type titanium oxide (B-2) Aggregated metatitanic acid produced by reacting titanium ore with sulfuric acid and heating and hydrolyzing the obtained titanium sulfate solution was converted into TiO ₂ 30 A mass% aqueous slurry was prepared, which was neutralized to pH 7 with aqueous ammonia, and then filtered and washed to remove sulfate radicals. Nitric acid was added to the obtained dehydrated cake to perform deflocculation treatment to obtain acidic titanium oxide sol having a pH of 1.5 and comprising titanium oxide fine particles (primary particle diameter 7 nm) containing an anatase type crystal structure. The obtained acidic titanium oxide sol was diluted with pure water to obtain 600 ml of titanium oxide sol having a TiO ₂ conversion of 200 g/L, heated to 70° C., and then an aqueous solution of sodium silicate having a SiO ₂ conversion concentration of 432 g/L. 20.8 ml was added at the same time as 20% sulfuric acid and then aged for 30 minutes. Next, the pH was adjusted to 8 with a 10% aqueous sodium hydroxide solution, the pH was adjusted to 6 with a 2% aqueous sulfuric acid solution, and filtration and washing were performed to obtain a wet cake. This wet cake was repulped in pure water and then ultrasonically dispersed to obtain a titanium oxide sol (solid content concentration 20% by mass, pH=7.5) that was stable in the neutral range. In this sample, agglomerated silica was adhered to 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 .

[Reference Example 3] Preparation of silver-supported silica-modified rutile type titanium oxide (B-3)
400 g of the titanium oxide aqueous dispersion (solid content=2%) obtained in [Reference Example 1] was charged into a 500 mL flask and heated to 80° C., and when this temperature was reached, an aqueous silver nitrate solution (concentration=5%) 1.26 g to 5.04 g was added according to the supported amount, and immediately after that, 0.85 g to 3.4 g of trisodium citrate aqueous solution (concentration = 10%) and tannic acid aqueous solution (concentration = 1%) were added. 18g-12.72g was added. After the addition, the mixture was stirred for 1 hour, cooled to room temperature after stirring, and used as a synthetic product. The average particle size of titanium oxide in the obtained composite was about 80 nm.

Reference Example 1, Reference Example 2, Reference Example 3, commercial product 1 (manufactured by Ishihara Sangyo Co., Ltd., anatase type titanium oxide ST-01), and commercial product 2 (manufactured by Teika Co., Ltd., rutile titanium oxide MT150A). Table 1 shows [H ₂ O ₂ ] and [.OH]. Note that [Reference Example 3] uses the titanium oxide obtained in [Reference Example 1], and [H ₂ O ₂ ] and [.OH] are the same as in [Reference Example 1].

[Reference Example 4] Synthesis of Polymer Emulsion Particle (C-1) 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 10% by weight of dodecylbenzenesulfonic acid. After adding 40 g of an aqueous solution and 20 g of water, the temperature in the reactor was heated to 80° C. under stirring. A mixture of 90.7 g of dimethyldimethoxysilane and 83.5 g of methyltrimethoxysilane and 10 g of water were simultaneously added dropwise to this reactor over about 2 hours while maintaining the temperature in the reactor at 80°C. .. At that time, 2 hours after the addition of a mixed solution of dimethyldimethoxysilane and methyltrimethoxysilane, 2 g of a 10% by weight aqueous dodecylbenzenesulfonic acid solution was added. After the total amount of a mixed solution of dimethyldimethoxysilane and methyltrimethoxysilane was dropped, 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 wt% dodecylbenzenesulfonic acid aqueous solution was added. Was charged, the temperature in the reactor was maintained at 80° C., and stirring was continued for 2.5 hours. Next, 26.4 g of a 0.5 wt% aqueous solution of ammonium persulfate was added, and 0.1 g of n-butyl acrylate, 36.7 g of phenyltrimethoxysilane, 27.8 g of tetraethoxysilane, and 3-methacryloxypropyltrimethoxy. Mixed liquid consisting of 1.1 g of silane, 10 g of water, 0.1 g of diethyl acrylamide, 0.9 g of acrylic acid, reactive emulsifier (trade name "Adekaria Soap SR-1025", manufactured by Asahi Denka Co., Ltd., solid content 25%) Aqueous solution) 4.5 g, reactive emulsifier (trade name "Aqualon KH-1025", manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., solid content 25% aqueous solution) 2.3 g, 0.5% by weight aqueous solution of ammonium persulfate 120 g, and A mixed solution of 256.4 g of ion-exchanged water was added dropwise at the same time while keeping the temperature in the reactor at 80° C. over about 2 hours. Furthermore, the temperature in the reactor was maintained at 80° C. and stirring was continued for about 2 hours, then cooled to room temperature and filtered through a 100 mesh wire mesh. The solid content was adjusted to 10.0 mass% with ion-exchanged water to obtain an aqueous dispersion of polymer emulsion particles (BB) having a number average particle diameter of 20 nm as polymer particles.

Reference Example 5 Synthesis of Polymer Emulsion Particle (C-2) Aqueous Dispersion In a reactor having a reflux condenser, a dropping tank, a thermometer and a stirrer, 850 g of ion-exchanged water and 10% by mass of dodecylbenzenesulfonic acid were added. After adding 10.0 g of the aqueous solution, the temperature in the reactor was heated to 80° C. under stirring. A mixture of 140.0 g of dimethyldimethoxysilane, 20.0 g of phenyltrimethoxysilane, and 5.0 g of methyltrimethoxysilane was placed in this reactor for about 2 hours while maintaining the temperature in the reactor at 80°C. It dripped over. Then, the temperature in the reactor was maintained at 80° C. and stirring was continued for 30 minutes. Next, after adding 16.8 g of a 10% by mass dodecylbenzenesulfonic acid aqueous solution, the temperature in the reactor was maintained at 80° C. and stirring was continued for 2 hours. After adding 6.6 g of a 2 mass% ammonium persulfate aqueous solution thereto, a mixed solution of 26.8 g of phenyltrimethoxysilane, 28.6 g of tetraethoxysilane, and 1.1 g of 3-methacryloxypropyltrimethoxysilane, Acrylic acid 0.9 g, reactive emulsifier (made by AGEKA, "Adecaria Soap SR-1025"; solid content 25 mass% aqueous solution) 2.3 g, reactive emulsifier (made by Dai-ichi Kogyo Seiyaku Co., Ltd., "Aqualon KH-1025") 2.3 g of solid content 25% by weight aqueous solution), 30 g of 2.0% by weight aqueous solution of ammonium persulfate, and 170.0 g of ion-exchanged water, while maintaining the temperature in the reactor at 80° C. It dripped simultaneously over 2 hours. Furthermore, the temperature in the reactor was maintained at 80° C. and stirring was continued for about 1 hour, then cooled to room temperature, 25% aqueous ammonia solution was added to the reaction solution to adjust the pH to 8, and then 100 mesh It was filtered through a wire mesh. The solid content was adjusted to 10.0 mass% with ion-exchanged water to obtain an aqueous dispersion of a polymer (E2) having a number average particle diameter of 119 nm as a polymer.

Reference Example 6 Synthesis of Polymer Emulsion Particles (C-3) 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 10% by mass of dodecylbenzenesulfonic acid. After adding 5.6 g of the aqueous solution, the temperature in the reactor was heated to 80° C. under stirring. A mixture of 110.0 g of dimethyldimethoxysilane, 73.0 g of phenyltrimethoxysilane and 29.4 g of methyltrimethoxysilane was placed in this reactor for about 2 hours while maintaining the temperature in the reactor at 80°C. It dripped over. Then, the temperature in the reactor was maintained at 80° C. and stirring was continued for 30 minutes. Next, after adding 5.6 g of a 10 mass% dodecylbenzenesulfonic acid aqueous solution, the temperature in the reactor was maintained at 80° C. and stirring was continued for 2 hours. After adding 6.6 g of a 2% by mass aqueous ammonium persulfate solution thereto, 22.5 g of methyl methacrylate, 11.2 g of n-butyl acrylate, 12.3 g of phenyltrimethoxysilane, 28.6 g of tetraethoxysilane and 38.6. -A mixed solution consisting of 1.1 g of methacryloxypropyltrimethoxysilane, 0.9 g of acrylic acid, 1.2 g of a reactive emulsifier ("ADEKA REASOAP SR-1025" manufactured by ADEKA; solid content 25 mass% aqueous solution), 1.2 g of reactive emulsifier (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., "Aqualon KH-1025"; solid content 25% by weight aqueous solution), 2.0% by weight ammonium persulfate aqueous solution 30 g, ion-exchanged water 286.4 g And were simultaneously added dropwise over a period of about 2 hours while maintaining the temperature in the reactor at 80°C. Furthermore, the temperature in the reactor was maintained at 80° C. and stirring was continued for about 1 hour, then cooled to room temperature, 25% aqueous ammonia solution was added to the reaction solution to adjust the pH to 8, and then 100 mesh It was filtered through a wire mesh. The solid content was adjusted to 10.0 mass% with ion-exchanged water to obtain an aqueous dispersion of a polymer (E3) having a number average particle diameter of 155 nm as a polymer.

[Example 1]
Copper oxide (manufactured by CIK Nanotech Co., Ltd., solid content 15.3%) (antibacterial metal compound (A1-1) 0.37 g, and silica-modified rutile titanium oxide (solid content=5. 5%) (photocatalytically active inorganic compound (B-1)) 59.56 g and water-dispersed colloidal silica having a number average particle diameter of 8 nm (trade name "Snowtex NS", manufactured by Nissan Chemical Industries, Ltd., solid content 20 mass) %) (non-antibacterial photocatalytic inactive metal compound (A2-1)) 120.6 g, and fluorocarbon surfactant (D-1) (AGC Seimi Chemical Co., Ltd., "Surflon S-232") 0.99 g , 140 g of a fading dye (E) whose solid content was adjusted to 1.0% by mass with ion-exchanged water (“Methylene Blue” manufactured by Kishida Chemical Co., Ltd.) and 656.54 g of water were mixed and stirred to obtain a photocatalyst composition ( F-1) was obtained.

[Example 2]
A photocatalyst composition (F-2) was obtained in the same manner as in Example 1 except that the addition amount of the antibacterial metal compound (A1-1) was set to 0.93 g instead of 0.37 g. ..

[Example 3]
A photocatalyst composition (F-3) was obtained in the same manner as in Example 1 except that the addition amount of the antibacterial metal compound (A1-1) was changed to 0.37 g and changed to 1.86 g. ..

[Example 4]
A photocatalyst composition (F-4) was obtained in the same manner as in Example 1 except that the amount of the antibacterial metal compound (A1-1) added was 3.73 g instead of 0.37 g. ..

[Example 5]
A photocatalyst composition (F-5) was obtained in the same manner as in Example 1 except that the addition amount of the antibacterial metal compound (A1-1) was changed to 0.37 g and changed to 5.59 g. ..

[Example 6]
0.47 g of copper oxide (manufactured by CIK Nanotech Co., Ltd., solid content 15.3%) (antibacterial metal compound (A1-1)) and silica-modified rutile titanium oxide (solid content=5) prepared in Reference Example 1 0.5%) (photocatalytically active inorganic compound (B-1)) and 59.56 g of water-dispersed colloidal silica having a number average particle diameter of 8 nm (trade name "Snowtex NS", manufactured by Nissan Chemical Industries, Ltd., solid content 20). (% by mass) (non-antibacterial photocatalytically inactive metal compound (A2-1)) 104.0 g, and polymer emulsion particles (C-1) aqueous dispersion (solid content 8.5% by weight) shown in Reference Example 4. 38.7 g, fluorocarbon surfactant (D-1) (manufactured by AGC Seimi Chemical Co., Ltd., "Surflon S-232") 0.99 g, and fading property in which the solid content was adjusted to 1.0% by mass with ion-exchanged water. A photocatalyst composition (F-6) was obtained by mixing 140 g of the dye (E) (“Methylene blue” manufactured by Kishida Chemical Co., Ltd.) and 634.44 g of water with stirring.

[Example 7]
A photocatalyst composition (F-7) was obtained in the same manner as in Example 6 except that the addition amount of the antibacterial metal compound (A1-1) was changed to 0.43 g, and changed to 0.93 g. ..

[Example 8]
A photocatalyst composition (F-8) was obtained in the same manner as in Example 6 except that the addition amount of the antibacterial metal compound (A1-1) was changed to 0.47 g and changed to 1.86 g. ..

[Example 9]
1.86 g of copper oxide (manufactured by CIK Nanotech Co., Ltd., solid content 15.3%) (antibacterial metal compound (A1-1)) and silica-modified rutile titanium oxide (solid content=5) prepared in Reference Example 1 0.5%) (non-antibacterial photocatalytically active inorganic compound (B-1)) 59.56 g and water-dispersed colloidal silica having a number average particle diameter of 8 nm (trade name "Snowtex NS", manufactured by Nissan Chemical Industries, Ltd.) , Solid content 20 mass%) (non-antibacterial photocatalytically inactive metal compound (A2-1)) 90.4 g, and polymer emulsion particles (C-1) aqueous dispersion (solid content 8. 5 wt%) 70.9 g, fluorocarbon surfactant (D-1) (AGC Seimi Chemical Co., "Surflon S-232") 0.99 g, and ion-exchanged water to a solid content of 1.0 wt %. A photocatalyst composition (F-9) was obtained by mixing 140 g of the adjusted fading dye (E) ("Methylene blue" manufactured by Kishida Chemical Co., Ltd.) and 614.44 g of water with stirring.

[Example 10]
1.86 g of copper oxide (manufactured by CIK Nanotech Co., Ltd., solid content 15.3%) (antibacterial metal compound (A1-1)) and silica-modified rutile titanium oxide (solid content=5) prepared in Reference Example 1 0.5%) (non-antibacterial photocatalytically active inorganic compound (B-1)) 59.56 g and water-dispersed colloidal silica having a number average particle diameter of 8 nm (trade name "Snowtex NS", manufactured by Nissan Chemical Industries, Ltd.) , Solid content 20 mass%) (non-antibacterial photocatalytically inactive metal compound (A2-1)) 65.7 g, and polymer emulsion particles (C-1) aqueous dispersion (solid content 8. 5 wt.%) 128.71 g, fluorocarbon surfactant (D-1) (AGC Seimi Chemical Co., "Surflon S-232") 0.99 g, and ion-exchanged water to a solid content of 1.0 wt. A photocatalyst composition (F-10) was obtained by mixing 140 g of the adjusted fading dye (E) ("Methylene blue" manufactured by Kishida Chemical Co., Ltd.) and 585.05 g of water with stirring.

[Example 11]
0.93 g of copper oxide (manufactured by CIK Nanotech Co., Ltd., solid content 15.3%) (antibacterial metal compound (A1-1)) and silica-modified anatase-type titanium oxide (solid content=5) prepared in Reference Example 2 0.5%) (non-antibacterial photocatalytically active inorganic compound (B-2)) 59.56 g and water-dispersed colloidal silica having a number average particle diameter of 8 nm (trade name "Snowtex NS", manufactured by Nissan Chemical Industries, Ltd.) , Solid content 20% by mass) (non-antibacterial photocatalytic inactive metal compound (A2-1)) 120.6 g, and fluorocarbon surfactant (D-1) (AGC Seimi Chemical Co., Ltd., "Surflon S-232"). ) 0.99 g, 140 g of fading dye (E) (manufactured by Kishida Chemical Co., Ltd., "methylene blue") in which the solid content is adjusted to 1.0% by mass with ion-exchanged water, and 656.54 g of water are mixed and stirred. To obtain a photocatalyst composition (F-11).

[Example 12]
A photocatalyst composition (F-12) was obtained in the same manner as in Example 11 except that the amount of the antibacterial metal compound (A1-1) added was changed to 0.93 g to 1.86 g. ..

[Example 13]
0.93 g of copper oxide (manufactured by CIK Nanotech Co., Ltd., solid content 15.3%) (antibacterial metal compound (A1-1)) and silver-supported (supported amount 1%) silica-modified rutile prepared in Reference Example 3 Type titanium oxide (solid content = 2%) (non-antibacterial photocatalytically active inorganic compound (B-3)) 163.82 g and water-dispersed colloidal silica having a number average particle diameter of 8 nm (trade name "Snowtex NS", Nissan Chemical Industry Co., Ltd., solid content 20 mass%) (non-antibacterial photocatalytic inactive metal compound (A2-1)) 120.6 g and fluorocarbon surfactant (D-1) (manufactured by AGC Seimi Chemical Co., "Surflon S-232") 0.99 g, 140 g of fading dye (E) whose solid content is adjusted to 1.0% by mass with ion-exchanged water ("Methylene Blue" manufactured by Kishida Chemical Co., Ltd.), and water 552.28 g A photocatalyst composition (F-13) was obtained by mixing and stirring.

[Example 14]
A photocatalyst composition (F-14) was obtained in the same manner as in Example 13 except that the addition amount of the antibacterial metal compound (A1-1) was changed to 0.93 g and changed to 1.86 g.

[Example 15]
1.86 g of copper oxide (manufactured by CIK Nanotech Co., Ltd., solid content 15.3%) (antibacterial metal compound (A1-1)) and silver-supported (supported amount 1%) silica-modified rutile prepared in Reference Example 3 Type titanium oxide (solid content = 2%) (non-antibacterial photocatalytically active inorganic compound (B-3)) 163.8 g, and water-dispersed colloidal silica having a number average particle diameter of 8 nm (trade name "Snowtex NS", Nissan Chemical Industry Co., Ltd., solid content 20 mass%) (non-antibacterial photocatalytic inactive metal compound (A2-1)) 104.0 g, and polymer emulsion particles (C-1) water dispersion shown in Reference Example 4 Body (solid content 8.5% by weight) 38.7 g, fluorocarbon surfactant (D-1) (AGC Seimi Chemical Co., "Surflon S-232") 0.99 g, and the solid content by ion exchange water. A photocatalyst composition (F-15) was obtained by mixing 140 g of the fading dye (E) (“Methylene blue” manufactured by Kishida Chemical Co., Ltd.) adjusted to 1.0% by mass and 530.2 g of water with stirring.

[Example 16]
1.86 g of copper oxide (manufactured by CIK Nanotech Co., Ltd., solid content 15.3%) (antibacterial metal compound (A1-1)) and silica-modified rutile titanium oxide (solid content=5) prepared in Reference Example 1 0.5%) (non-antibacterial photocatalytically active inorganic compound (B-1)) 59.56 g and water-dispersed colloidal silica having a number average particle diameter of 8 nm (trade name "Snowtex OS", manufactured by Nissan Chemical Industries, Ltd.) , Solid content 20 mass%) (non-antibacterial photocatalytically inactive metal compound (A2-2)) 120.6 g, fluorocarbon surfactant (D-1) (AGC Seimi Chemical Co., "Surflon S-232") ) 0.99 g, 140 g of fading dye (E) (manufactured by Kishida Chemical Co., Ltd., "methylene blue") in which the solid content is adjusted to 1.0% by mass with ion-exchanged water, and 656.54 g of water are mixed and stirred. To obtain a photocatalyst composition (F-16).

[Example 17]
1.86 g of copper oxide (manufactured by CIK Nanotech Co., Ltd., solid content 15.3%) (antibacterial metal compound (A1-1)) and silica-modified rutile titanium oxide (solid content=5) prepared in Reference Example 1 0.5%) (non-antibacterial photocatalytically active inorganic compound (B-1)) 59.56 g, and water-dispersed colloidal silica having a number average particle diameter of 25 nm (trade name "Snowtex O-40", Nissan Chemical Industries, Ltd. ), solid content 20% by mass) (non-antibacterial photocatalytically inactive metal compound (A2-3)) 120.6 g, and fluorocarbon surfactant (D-1) (manufactured by AGC Seimi Chemical Co., "Surflon S-. 232"), 0.99 g, 140 g of fading dye (E) (manufactured by Kishida Chemical Co., Ltd., "methylene blue") whose solid content is adjusted to 1.0% by mass with ion-exchanged water, and 656.54 g of water are mixed and stirred. By doing so, a photocatalyst composition (F-17) was obtained.

[Example 18]
1.86 g of copper oxide (manufactured by CIK Nanotech Co., Ltd., solid content 15.3%) (antibacterial metal compound (A1-1)) and silver-supported (supported amount 1%) silica-modified rutile prepared in Reference Example 3 Type titanium oxide (solid content=2%) (non-antibacterial photocatalytically active inorganic compound (B-3)) 163.82 g and water-dispersed colloidal silica having a number average particle diameter of 8 nm (trade name "Snowtex OS", Nissan Chemical Industry Co., Ltd., solid content 20% by mass) (non-antibacterial photocatalytic inactive metal compound (A2-2)) 120.6 g and fluorocarbon surfactant (D-1) (manufactured by AGC Seimi Chemical Co., "Surflon S-232") 0.99 g, 140 g of fading dye (E) whose solid content is adjusted to 1.0% by mass with ion-exchanged water ("Methylene Blue" manufactured by Kishida Chemical Co., Ltd.), and water 552.28 g A photocatalyst composition (F-18) was obtained by mixing and stirring.

[Example 19]
1.86 g of copper oxide (manufactured by CIK Nanotech Co., Ltd., solid content 15.3%) (antibacterial metal compound (A1-1)) and silver-supported (supported amount 1%) silica-modified rutile prepared in Reference Example 3 Type titanium oxide (solid content=2%) (non-antibacterial photocatalytically active inorganic compound (B-3)) 163.82 g and water-dispersed colloidal silica having a number average particle diameter of 25 nm (trade name “Snowtex O-40”) Manufactured by NISSAN CHEMICAL INDUSTRIES CO., LTD., solid content 20% by mass (non-antibacterial photocatalytic inactive metal compound (A2-3)) 120.6 g, and fluorocarbon surfactant (D-1) (AGC Seimi Chemical Co., Ltd. Manufactured by "Surflon S-232") 0.99 g, 140 g of fading dye (E) (manufactured by Kishida Chemical Co., Ltd., "methylene blue") having a solid content adjusted to 1.0% by mass with ion-exchanged water, and water 552. A photocatalyst composition (F-19) was prepared by mixing and stirring 0.28 g with.

[Example 20]
1.86 g of copper oxide (manufactured by CIK Nanotech Co., Ltd., solid content 15.3%) (antibacterial metal compound (A1-1)) and silica-modified rutile titanium oxide (solid content=5) prepared in Reference Example 1 0.5%) (non-antibacterial photocatalytically active inorganic compound (B-1)) 59.56 g and water-dispersed colloidal silica having a number average particle diameter of 8 nm (trade name "Snowtex NS", manufactured by Nissan Chemical Industries, Ltd.) , Solid content 20% by mass) (non-antibacterial photocatalytically inactive metal compound (A2-1)) 104.0 g, and polymer emulsion particles (C-2) aqueous dispersion (solid content 10. 0 wt%) 32.9 g, fluorocarbon surfactant (D-1) (manufactured by AGC Seimi Chemical Co., "Surflon S-232") 0.99 g, and ion-exchanged water to a solid content of 1.0% by mass. A photocatalyst composition (F-20) was obtained by mixing 140 g of the adjusted fading dye (E) (manufactured by Kishida Chemical Co., Ltd., "methylene blue") and 640.24 g of water with stirring.

[Example 21]
32.9 g of the polymer emulsion particle (C-3) water dispersion (solid content 10.0% by weight) shown in Reference Example 6 instead of the polymer emulsion particle (C-2) water dispersion shown in Reference Example 5. A photocatalyst composition (F-21) was obtained in the same manner as in Example 20 except that the above was mixed.
Prepared.

[Example 22]
1.86 g of copper oxide (manufactured by CIK Nanotech Co., Ltd., solid content 15.3%) (antibacterial metal compound (A1-1)) and silica-modified rutile titanium oxide (solid content=5) prepared in Reference Example 1 0.5%) (non-antibacterial photocatalytically active inorganic compound (B-1)) 59.56 g and water-dispersed colloidal silica having a number average particle diameter of 8 nm (trade name "Snowtex NS", manufactured by Nissan Chemical Industries, Ltd.) , Solid content 20% by mass) (non-antibacterial photocatalytically inactive inorganic compound (A2-1)) 120.6 g and fluorocarbon surfactant (D-2) (manufactured by DIC, "Megafuck F-444"). By mixing and stirring 0.99 g, 140 g of the fading dye (E) whose solid content was adjusted to 1.0% by mass with ion-exchanged water (“Methylene Blue” manufactured by Kishida Chemical Co., Ltd.), and 656.54 g of water. A photocatalyst composition (F-22) was obtained.

[Example 23]
1.86 g of copper oxide (manufactured by CIK Nanotech Co., Ltd., solid content 15.3%) (antibacterial metal compound (A1-1)) and silica-modified rutile titanium oxide (solid content=5) prepared in Reference Example 1 0.5%) (non-antibacterial photocatalytically active inorganic compound (B-1)) 59.56 g and water-dispersed colloidal silica having a number average particle diameter of 8 nm (trade name "Snowtex NS", manufactured by Nissan Chemical Industries, Ltd.) , Solid content 20% by mass) (non-antibacterial photocatalytically inactive metal compound (A2-1)) 104.0 g, and polymer emulsion particles (C-1) aqueous dispersion (solid content 8. 5% by weight) 38.7 g, fluorocarbon surfactant (D-2) (manufactured by DIC, "Megafuck F-444") 0.99 g, and the solid content is adjusted to 1.0% by weight with ion-exchanged water. The photocatalyst composition (F-23) was obtained by mixing 140 g of the fading dye (E) (“Methylene Blue” manufactured by Kishida Chemical Co., Ltd.) and 634.44 g of water with stirring.

[Example 24]
0.93 g of copper oxide (manufactured by CIK Nanotech Co., Ltd., solid content 15.3%) (antibacterial metal compound (A1-1)) and silver-supported (supported amount 1%) silica-modified rutile prepared in Reference Example 3 Type titanium oxide (solid content = 2%) (non-antibacterial photocatalytically active inorganic compound (B-3)) 163.82 g and water-dispersed colloidal silica having a number average particle diameter of 8 nm (trade name "Snowtex NS", Nissan Chemical Industry Co., Ltd., solid content 20 mass%) (non-antibacterial photocatalyst inorganic compound (A2-1)) 120.6 g and fluorocarbon surfactant (D-2) (manufactured by DIC, "Megafuck F"). -444"), 0.99 g, 140 g of the fading dye (E) (manufactured by Kishida Chemical Co., Ltd., "methylene blue") having a solid content adjusted to 1.0% by mass with ion-exchanged water, and 552.28 g of water. A photocatalyst composition (F-24) was obtained by stirring.

[Example 25]
1.86 g of copper oxide (manufactured by CIK Nanotech Co., Ltd., solid content 15.3%) (antibacterial metal compound (A1-1)) and silver-supported (supported amount 1%) silica-modified rutile prepared in Reference Example 3 Type titanium oxide (solid content = 2%) (non-antibacterial photocatalytically active inorganic compound (B-3)) 163.8 g, and water-dispersed colloidal silica having a number average particle diameter of 8 nm (trade name "Snowtex NS", Nissan Chemical Industry Co., Ltd., solid content 20 mass%) (non-antibacterial photocatalytically inactive inorganic compound (A2-1)) 104.0 g, and polymer emulsion particles (C-1) water dispersion shown in Reference Example 4 Body (solid content 8.5% by weight) 38.7 g, fluorocarbon surfactant (D-2) (manufactured by DIC, "Megafuck F-444") 0.99 g, and ion-exchanged water to give a solid content of 1 A photocatalyst composition (F-25) was prepared by mixing and stirring 140 g of the fading dye (E) (“Methylene blue” manufactured by Kishida Chemical Co., Ltd.) adjusted to 0.0% by mass and 530.2 g of water with stirring.

[Example 26]
1.86 g of zinc oxide (manufactured by CIK Nanotech Co., Ltd., solid content 30.2%) (antibacterial metal compound (A1-2)) and silica-modified rutile type titanium oxide (solid content=5) prepared in Reference Example 1 0.5%) (non-antibacterial photocatalytically active inorganic compound (B-1)) 59.56 g and water-dispersed colloidal silica having a number average particle diameter of 8 nm (trade name "Snowtex NS", manufactured by Nissan Chemical Industries, Ltd.) , Solid content 20% by mass) (non-antibacterial photocatalytically inactive inorganic compound (A2-1)) 120.6 g, fluorocarbon surfactant (D-1) (AGC Seimi Chemical Co., Ltd., "Surflon S-232") ) 0.99 g, 140 g of fading dye (E) (manufactured by Kishida Chemical Co., Ltd., "methylene blue") in which the solid content is adjusted to 1.0% by mass with ion-exchanged water, and 656.54 g of water are mixed and stirred. To obtain a photocatalyst composition (F-26).

[Example 27]
A photocatalyst composition (F-27) was obtained in the same manner as in Example 26 except that the amount of the antibacterial metal compound (A1-2) was changed to 1.86 g and was set to 3.73 g.

[Example 28]
1.86 g of zinc oxide (manufactured by CIK Nanotech Co., Ltd., solid content 30.2%) (antibacterial metal compound (A1-2)) and silica-modified rutile type titanium oxide (solid content=5) prepared in Reference Example 1 0.5%) (non-antibacterial photocatalytically active inorganic compound (B-1)) 59.56 g and water-dispersed colloidal silica having a number average particle diameter of 8 nm (trade name "Snowtex NS", manufactured by Nissan Chemical Industries, Ltd.) , Solid content 20% by mass) (non-antibacterial photocatalytically inactive inorganic compound (A2-1)) 104.0 g, and polymer emulsion particles (C-1) aqueous dispersion (solid content 8. 5% by weight) 38.7 g, fluorocarbon surfactant (D-1) (manufactured by AGC Seimi Chemical Co., "Surflon S-232") 0.99 g, and ion-exchanged water to a solid content of 1.0% by mass. A photocatalyst composition (F-28) was obtained by mixing 140 g of the adjusted fading dye (E) (manufactured by Kishida Chemical Co., Ltd., "methylene blue") and 634.44 g of water with stirring.

[Example 29]
1.86 g of zinc oxide (manufactured by CIK Nanotech Co., Ltd., solid content 30.2%) (antibacterial metal compound (A1-2)) and silver-supported (supported amount 1%) silica-modified rutile prepared in Reference Example 3 Type titanium oxide (solid content = 2%) (non-antibacterial photocatalytically active inorganic compound (B-3)) 163.82 g and water-dispersed colloidal silica having a number average particle diameter of 8 nm (trade name "Snowtex NS", Nissan Chemical Industry Co., Ltd., solid content 20 mass%) (non-antibacterial photocatalyst inorganic compound (A2-1)) 120.6 g, fluorocarbon surfactant (D-1) (AGC Seimi Chemical Co., "surflon S-232"), 0.99 g, 140 g of the fading dye (E) (manufactured by Kishida Chemical Co., Ltd., "methylene blue") having a solid content adjusted to 1.0% by mass with ion-exchanged water, and 552.28 g of water. A photocatalyst composition (F-29) was obtained by mixing and stirring.

[Example 30]
1.86 g of zinc oxide (manufactured by CIK Nanotech Co., Ltd., solid content 30.2%) (antibacterial metal compound (A1-2)) and silver-supported (supported amount 1%) silica-modified rutile prepared in Reference Example 3 Type titanium oxide (solid content = 2%) (non-antibacterial photocatalytically active inorganic compound (B-3)) 163.8 g, and water-dispersed colloidal silica having a number average particle diameter of 8 nm (trade name "Snowtex NS", Nissan Chemical Industry Co., Ltd., solid content 20 mass%) (non-antibacterial photocatalytically inactive inorganic compound (A2-1)) 104.0 g, and polymer emulsion particles (C-1) water dispersion shown in Reference Example 4 Body (solid content 8.5% by weight) 38.7 g, fluorocarbon surfactant (D-1) (AGC Seimi Chemical Co., "Surflon S-232") 0.99 g, and the solid content by ion exchange water. A photocatalyst composition (F-30) was prepared by mixing 140 g of the fading dye (E) (“Methylene blue” manufactured by Kishida Chemical Co., Ltd.) adjusted to 1.0% by mass and 530.2 g of water with stirring.

[Comparative Example 1]
0.09 g of copper oxide (manufactured by CIK Nanotech Co., Ltd., solid content 15.3%) (antibacterial metal compound (A1-1)) and silica-modified rutile titanium oxide (solid content=5) prepared in Reference Example 1 0.5%) (non-antibacterial photocatalytically active inorganic compound (B-1)) 59.56 g and water-dispersed colloidal silica having a number average particle diameter of 8 nm (trade name "Snowtex NS", manufactured by Nissan Chemical Industries, Ltd.) , Solid content 20% by mass) (non-antibacterial photocatalytically inactive inorganic compound (A2-1)) 120.6 g, fluorocarbon surfactant (D-1) (AGC Seimi Chemical Co., Ltd., "Surflon S-232") ) 0.99 g, 140 g of fading dye (E) (manufactured by Kishida Chemical Co., Ltd., "methylene blue") in which the solid content is adjusted to 1.0% by mass with ion-exchanged water, and 656.54 g of water are mixed and stirred. To obtain a photocatalyst composition (F-31).

[Comparative example 2]
A photocatalyst composition (F-32) was obtained in the same manner as in Comparative Example 1 except that the amount was 41 g instead of the antibacterial metal compound (A1-1) being 0.09 g.

[Comparative Example 3]
1.86 g of copper oxide (manufactured by CIK Nanotech Co., Ltd., solid content 15.3%) (antibacterial metal compound (A1-1)), and commercially available titanium oxide (Anatase type titanium oxide ST manufactured by Ishihara Sangyo Co., Ltd.) -01, solid content 5.5%) (non-antibacterial photocatalytically active inorganic compound (B-4)) 59.56 g, and water-dispersed colloidal silica having a number average particle diameter of 8 nm (trade name "Snowtex NS", Nissan Chemical Industry Co., Ltd., solid content 20 mass%) (non-antibacterial photocatalytic inactive metal compound (A2-1)) 120.6 g and fluorocarbon surfactant (D-1) (manufactured by AGC Seimi Chemical Co., "Surflon S-232"), 0.99 g, 140 g of fading dye (E) (manufactured by Kishida Chemical Co., Ltd., "methylene blue") whose solid content is adjusted to 1.0% by mass with ion-exchanged water, and 656.54 g of water. A photocatalyst composition (F-33) was obtained by mixing and stirring.

[Comparative Example 4]
Instead of the commercially available titanium oxide of Comparative Example 3, commercially available titanium oxide (Rutile titanium oxide MT150A manufactured by Teika Co., Ltd., solid content 5.5%) (non-antibacterial photocatalytically active inorganic compound (B-5 )) A photocatalyst composition (F-34) was obtained in the same manner as in Comparative Example 3 except that the amount was 59.56 g.

[Comparative Example 5]
0.1 g of copper oxide (manufactured by CIK Nanotech Co., Ltd., solid content: 15.3%) (antibacterial metal compound (A1-1)) and commercially available titanium oxide (“STS-11” manufactured by Ishihara Sangyo Co., Ltd.) Solid content = 5.5%) (non-antibacterial photocatalytically active inorganic compound (B-6)) 77.7 g, and water-dispersed colloidal silica having a number average particle diameter of 30 nm (trade name "Snowtex 50", Nissan Chemical Co., Ltd.). 50.5 g (manufactured by Kogyo Co., Ltd., solid content: 48% by mass) (non-antibacterial photocatalytically inactive inorganic compound (A2-4)), and polyether-modified silicone surfactant (D") (trade name "KF -643", manufactured by Shin-Etsu Chemical Co., Ltd.) and 850.1 g of water were mixed and stirred to obtain a photocatalyst composition (F-35).

[Production of photocatalytic coating]
A glass plate having a size of 10 cm×10 cm was prepared by coating an acrylic silicone resin with a film thickness of 100 μm on another surface (front surface) of a glass plate having one surface (back surface) white-printed. Each photocatalyst composition (F-1 to F-35) was applied to one surface (front surface) of this glass plate by a spray method. Then, the coated photocatalyst compositions (F-1 to F-35) were dried at room temperature for 1 hour to obtain test plates (G-1 to G-35) having a photocatalyst coating film formed thereon.

Tables 2 and 3 show various evaluation results of the test plates (G-1 to G-35).

The photocatalyst composition of the present embodiment is excellent in long-term durability of algae-proof property (antifungal property), weather resistance, and low damage to the underlying coating film during coating, and therefore, the coating film directly under the photocatalyst coating film (primer coating Since a protective layer can be formed on a film without needing it, it has excellent self-cleaning properties and can be applied to building exteriors, interior materials, exterior display applications, automobiles, displays and the like.

Claims (11)

A photocatalyst composition comprising an antibacterial metal compound (A1) and a non-antibacterial inorganic compound (AA) having no antibacterial property,
The non-antibacterial inorganic compound (AA) is a photocatalytically inactive inorganic compound having no photocatalytic activity (
A2) and a photocatalytically active inorganic compound (B) having photocatalytic activity,
The mass ratio (A1/A2) of the antibacterial metal compound (A1) to the photocatalytically inactive inorganic compound (A2) is 0.001 or more and 0.25 or less,
The metal contained in the antibacterial metal compound (A1) is at least one selected from the group consisting of copper and zinc, and the content of the photocatalytically inactive inorganic compound (A2) is the antibacterial metal compound ( 46.1% by mass or more based on the total solid content of the photocatalyst composition excluding A1) 9
9 mass% or less,
The photocatalytically inactive inorganic compound (A2) is silicon dioxide,
A photocatalyst composition in which the photocatalytically active inorganic compound (B) satisfies the following condition (i) or both the following (i) and (ii) conditions are satisfied.

(I) In the suspension containing the photocatalytically active inorganic compound (B), a wavelength of 380 nm or less and an intensity of 5 m
The amount of hydrogen peroxide ([H ₂ O ₂ ]) generated when irradiated with UV light of W/cm ² for 60 seconds is 80
μM or less;
(Ii) In the suspension containing the photocatalytically active inorganic compound (B), a wavelength of 380 nm or less and an intensity of 5 m
The amount of hydroxy radicals [.OH] generated when UV light of W/cm ² is irradiated for 60 seconds is
1.0 μM or less: The photocatalyst composition according to claim 1 , wherein the photocatalytically active inorganic compound (B) is titanium oxide. Particle surface of the photocatalytic activity inorganic compound (B) is a metal oxide (C), has been modified process, the photocatalytic composition as claimed in claim 1 or 2. The photocatalyst composition according to claim 3 , wherein the metal oxide (C) is silicon dioxide. The content of the photocatalytic activity inorganic compound (B) is, overall solid content of the photocatalytic composition excluding the antimicrobial metal compound (A1) with respect to, 20 mass% or less 1 wt%, claim 1-4
The photocatalyst composition according to any one of 1. Further comprising polymer particles (D), the photocatalytic composition according to any one of claims 1-5. The photocatalyst composition according to claim 6 , wherein the content of the polymer particles (D) is 40% by mass or less based on the entire photocatalyst composition excluding the antibacterial metal compound (A1). Fluorocarbon further comprises a surfactant (E), the photocatalytic composition according to any one of claims 1-7. Fading dye (F) further comprises, photocatalyst composition according to any one of claims 1-8. It formed from the photocatalyst composition according to any one of claim 1 to 9 photocatalytic coating. A photocatalyst coating product, comprising the photocatalyst coating according to claim 10 .