WO2018134972A1 - Photocatalyst coating set - Google Patents

Abstract

This photocatalyst coating set comprises: a photocatalyst layer forming composition that includes a titanium oxide photocatalyst and an organic titanium compound; and a protective layer forming composition that includes a hydrolyzable group-containing compound or a polymer thereof. The present invention enables coating of a photocatalytic substance that exhibits excellent adhesiveness to various substrates. Moreover, the present invention enables coating of a photocatalytic substance that has excellent antibacterial and antiviral properties in addition to adhesiveness.

Description

Photocatalyst coating set

The present invention relates to a photocatalyst coating set for supporting a photocatalytic substance on a substrate, a photocatalyst coating film, and a photocatalyst carrier.

Titanium oxide (TiO ₂ ), tungsten oxide (WO) that functions as a catalyst by irradiating light, and has effects such as removal of harmful substances, air purification, deodorization, water purification, sterilization, antibacterial, antifouling, and antifogging ₃ ) Photocatalytic substances such as zinc oxide (ZnO) and cadmium sulfide (CdS) are known. Among them, titanium oxide is a cheap and safe material that is widely used as a white pigment and ultraviolet absorber as a raw material for paints, cosmetics, etc., and is also recognized as a food additive.

The coating film containing the photocatalytic substance has functions such as antifouling, antibacterial, antifungal, deodorizing, and air purification. The coating film can be obtained by directly applying a photocatalyst coating containing an inorganic binder such as titanium dioxide sol or alkali silicate to the substrate and then heat-treating it. However, since the photocatalytic ability of the coating film works in all directions of the coating film, not only the coating film itself but also the substrate on which the coating film is formed may be affected and deteriorate. Therefore, for the purpose of protecting the substrate from the photocatalytic activity and improving the adhesiveness of the photocatalytic substance, it is called an adhesive layer or a protective layer between the substrate and the coating film containing the photocatalytic substance. Techniques for forming an organic layer to protect a substrate from photocatalytic activity are known (Patent Documents 1 to 4, etc.).
Generally, a silicon compound, colloidal silica, or the like is used for the photocatalyst paint and the adhesive layer or the protective layer.

JP 2002-137322 A JP 2001-323189 A JP 2001-205102 A JP 2000-280397 A

However, when the present inventors examined, for example, when the photocatalyst coating surface is touched with a finger, the photocatalytic substance adheres to the finger, or even if the photocatalyst material does not peel off with the finger touch, the adhesive tape is attached to the photocatalyst coating surface and then peeled off. Since there were cases where a large amount of photocatalytic substance adhered to the adhesive layer of the tape and peeled off, it was found that the photocatalyst coating technology does not necessarily provide sufficient adhesion of the photocatalyst to the substrate. In addition, in order to enhance the adhesion of the photocatalytic substance to the base material, if a large amount of a known adhesive is used as the prior art, the adhesive is coated around the photocatalyst, reducing the hydrophilization phenomenon and antibacterial performance. There is a problem that the antiviral performance is significantly reduced.

Accordingly, an object of the present invention is to provide a set capable of performing coating of a photocatalytic substance exhibiting excellent adhesion to various substrates.
Another object of the present invention is to provide a set that can be coated with a photocatalytic substance excellent in antibacterial performance and antiviral properties in addition to the adhesiveness.
Another object of the present invention is to provide a photocatalyst laminate coating film formed using the set, a photocatalyst carrier excellent in adhesion to a substrate, a photocatalyst laminate coating film formed using the set, And the photocatalyst carrier excellent in the adhesiveness to a base material is provided.

The gist of the present invention is as follows.
[1] A set for photocatalyst coating comprising a photocatalyst layer forming composition containing a titanium oxide photocatalyst and an organic titanium compound, and a protective layer forming composition containing a hydrolyzable group-containing compound or a polymer thereof.
[2] Further, the protective layer forming composition contains an acrylic polymer having a number average molecular weight of 20,000 to 5,000,000 and / or a reaction product of the acrylic polymer and a hydrolyzable group-containing compound [1] A set for photocatalyst coating described in 1.
[3] The organic titanium compound comprises an alkoxy titanate compound, a titanium chelate compound, or the alkoxy titanate compound and the titanium chelate compound having a phosphate group, a phosphate ester group, an amino group, an amide group, a lactic acid group or a stearyl group. The set for photocatalyst coating according to the above [1] or [2], wherein one or more compounds selected from the group are oligomerized.
[4] The photocatalyst coating set according to any one of [1] to [3], wherein the hydrolyzable group of the hydrolyzable group-containing compound is an alkoxy group.
[5] The photocatalyst coating set according to any one of [1] to [4], wherein the hydrolyzable group-containing compound is an isocyanate-modified alkoxysilane compound.
[6] The photocatalyst coating set according to any one of [1] to [5], wherein the photocatalyst layer forming composition is a dispersion.
[7] The set for photocatalyst coating according to [6], wherein the dispersion contains water or an organic solvent.
[8] The photocatalyst coating set according to [6] or [7], wherein the organic titanium compound is blended in an amount of 0.01 to 30% by weight in the dispersion.
[9] Any of [5] to [8], wherein the isocyanate-modified alkoxysilane compound is one or more compounds selected from the group consisting of a reaction product of isocyanate and mercaptoalkoxysilane or aminoalkoxysilane and a polymer thereof. A set for photocatalyst coating according to the above.
[10] The photocatalyst coating set according to any one of [1] to [9], wherein the protective layer forming composition contains a hydrophilic or non-hydrophilic organic solvent.
[11] The total solid content of the acrylic polymer having a number average molecular weight of 20,000 to 5,000,000 and the reaction product of the acrylic polymer and the hydrolyzable group-containing compound in the protective layer forming composition is 3 to 40% by weight. %, The set for photocatalyst coating according to [10] above.
[12] The photocatalyst coating set according to any one of [1] to [11], wherein the titanium oxide photocatalyst is anatase titanium oxide or rutile titanium oxide having a primary particle diameter of 10 to 500 nm.
[13] A coating film formed using the photocatalyst coating set according to any one of [1] to [12], wherein the protective layer comprises the protective layer-forming composition, and the protective layer A photocatalyst layered coating film comprising the photocatalyst layer formed on the photocatalyst layer forming composition.
[14] The photocatalyst multilayer coating film according to [13], wherein the photocatalyst forming composition in the photocatalyst layer and the protective layer forming composition in the protective layer are cured.
[15] A photocatalyst carrier on which the photocatalyst multilayer coating film according to [13] or [14] is formed on a substrate surface.

According to the photocatalyst coating set according to the present invention, a protective layer is formed on the surface of a substrate using the protective layer-forming composition, and the photocatalyst layer-forming composition is formed on the surface of the protective layer. Since the layer is formed, the surface of the base material can be protected from the photocatalytic ability as compared with the case where the photocatalytic layer is directly formed on the surface of the base material. Moreover, by using a specific resin for each of the protective layer and the photocatalyst layer, the adhesiveness between the protective layer and the photocatalyst layer in the photocatalyst coating film formed is remarkably improved. The photocatalytic substance does not easily peel off even if it is touched with a finger or is peeled off with an adhesive tape.
In addition, the present invention facilitates the movement of electrons by bonding photocatalytic substance particles (hereinafter also referred to as photocatalyst particles) using an organic titanium compound having high electrical conductivity. By using a material that does not hinder movement, the balance between film-forming properties (adhesiveness), antibacterial properties, antiviral properties, and hydrophilic properties is excellent.
Therefore, using the photocatalyst coating set according to the present invention, a photocatalyst carrier formed by forming a photocatalyst coating film on the surface of various members such as a member used in a living environment has no harmful substances on these substrates. Actions such as removal, air purification, deodorization, water purification, sterilization, antibacterial, antifouling, and antifogging can be imparted. Further, the photocatalyst carrier can be used in a wide range of applications by being bonded to various members with an adhesive, a pressure-sensitive adhesive, or heat lamination as required, as well as being used alone.

(Photocatalyst coating set)
A set for photocatalyst coating according to the present invention (hereinafter referred to as a set of the present invention) contains a composition for forming a photocatalyst layer containing a titanium oxide photocatalyst and an organic titanium compound, and a hydrolyzable group-containing compound or a polymer thereof. And a composition for forming a protective layer.

In the present invention, the composition for forming a photocatalyst layer is a composition for forming a layer containing a photocatalyst (photocatalyst layer) on the surface of the protective layer.

The titanium oxide photocatalyst contained in the photocatalyst layer forming composition may be any titanium oxide photocatalyst having ultraviolet responsiveness or visible light responsiveness. The titanium oxide of the titanium oxide photocatalyst may be completely crystalline or may contain imperfect crystalline, that is, amorphous. The crystal form of titanium oxide may be a single phase of anatase, rutile, or brookite, and two or more of these may be mixed. Moreover, in order to express a high photocatalytic ability, it is preferable that a titanium oxide is an anatase single phase, a rutile single phase, or these mixed phases.

Specific examples of the titanium oxide-based photocatalyst include anatase-type and rutile-type crystalline titanium dioxide, crystalline titanium dioxide carrying a metal such as platinum, copper, and iron, peroxotitanium, peroxotitanic acid, and titanate metal. Salt. These can be used in the form of a powder or a dispersion of powder, particularly a dispersion using water or ethanol as a dispersion medium. As the powder, those having a primary particle diameter determined by an electron microscope (SEM, TEM) in the range of 10 to 500 nm are preferably used.

Commercially available materials for the titanium oxide photocatalyst powder or dispersion include ST-21, ST-41, STS-21, MPT-623 (all trade names) manufactured by Ishihara Sangyo Co., Ltd., Showa Denko FP6 , Lumiresh (registered trademark) series and the like.

The content of the titanium oxide photocatalyst in the composition for forming a photocatalyst layer is preferably 0.1 to 30% by weight, more preferably 1 to 10% by weight, from the viewpoint of efficiently exhibiting photocatalytic activity.

The organic titanium compound contained in the photocatalyst layer forming composition refers to a titanium compound containing an organic group, and examples thereof include a titanium alkoxide compound, a titanium chelate compound, a titanium acylate compound, and a titanium oligomer compound.

Examples of the titanium alkoxide compound include:
General formula (1):
Ti (OR ¹ ) ₄ (1)
[Wherein, R ¹ independently represents the same or different alkyl group. ]
The thing represented by is mentioned.

Examples of the alkyl group represented by R ¹ in the general formula (1) include those having 1 to 8 carbon atoms, such as methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl. Group, t-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group and the like.

Examples of the titanium alkoxide compound represented by the general formula (1) include tetramethoxy titanate, tetraethoxy titanate, tetrapropoxy titanate, tetraisopropyl titanate, tetrabutoxy titanate, tetranormal butyl titanate, and tetraoctyl titanate. it can.
As a commercial item of the said titanium alkoxide compound, "Orgatics" series by Matsumoto Fine Chemical Co., Ltd., etc. are mentioned.

Further, the titanium alkoxide compound may be an alkoxy titanate compound having a phosphate group, a phosphate ester group, an amino group, an amide group, a lactic acid group or a stearic acid group. Examples of commercially available titanium alkoxide compounds having such groups include titanate coupling agents “Plenact” series manufactured by Ajinomoto Fine Techno Co., Ltd., and the like.

The titanium chelate compound may be a titanium compound containing a chelating agent capable of coordinating with a titanium atom. For example, phthalic acid, trimellitic acid, trimesic acid, hemimellitic acid, pyromellitic acid Hydroxy polyvalent carboxylic acids such as polyvalent carboxylic acid, malic acid, citric acid, ethylenediaminetetraacetic acid, nitrilotripropionic acid, carboxyiminodiacetic acid, carboxymethyliminodipropionic acid, diethylenetriaminopentaacetic acid, triethylenetetraminohexaacetic acid, imino Nitrogen-containing polyvalent carboxylic acids such as diacetic acid, iminodipropionic acid, hydroxyethyliminodiacetic acid, hydroxyethyliminodipropionic acid, and methoxyethyliminodiacetic acid.
As a commercial item of the said titanium chelate compound, the "Orga Tix" series by Matsumoto Fine Chemical Co., Ltd., etc. are mentioned.

The titanium acylate compound is a titanium compound whose substituent is an acylate group. Examples of acylate groups include tetraacylate groups such as lactate and stearate, phthalic acid, trimellitic acid, trimesic acid, hemimellitic acid, pyromellitic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, sebacine Polycarboxylic acid compounds such as acid, maleic acid, fumaric acid, cyclohexanedicarboxylic acid or their anhydrides, ethylenediaminetetraacetic acid, nitrilotripropionic acid, carboxyiminodiacetic acid, carboxymethyliminodipropionic acid, diethylenetriaminopentaacetic acid And nitrogen-containing polycarboxylic acids such as triethylenetetraminohexaacetic acid, iminodiacetic acid, iminodipropionic acid, hydroxyethyliminodiacetic acid, hydroxyethyliminodipropionic acid, and methoxyethyliminodiacetic acid. Examples of the amino group include aniline, phenylamine, diphenylamine, and the like. At least one selected from these compounds is preferable, and any one or two is more preferable. Further, diisopropoxybisacetylacetone and triethanolaminate isopropoxide containing two kinds of these substituents may be mentioned. The alkoxy group and acylate group are preferably aliphatic from the viewpoint of polymerization activity.

Examples of the titanium acylate compound include titanium isostearate.
As a commercial item of the said titanium chelate compound, the "Orga Tix" series by Matsumoto Fine Chemical Co., Ltd., etc. are mentioned.

In addition, the organic titanium compound may be one obtained by oligomerizing one or more compounds selected from the group consisting of the titanium alkoxide compound, the alkoxy titanate compound, and the titanium acylate compound. Specifically, an oligomer formed by reacting the one or more compounds may be used.

These organic titanium compounds can be used alone or in admixture of two or more.

The content of the organic titanium compound in the composition for forming a photocatalyst layer is preferably 0.01 to 30% by weight, and preferably 0.01 to 10% by weight, from the viewpoint of hydrophilicity and antibacterial / antiviral performance.

Examples of the solvent for the photocatalyst layer forming composition include water, an organic solvent, and a water-containing organic solvent. Examples of the organic solvent include methanol, ethanol, isopropyl alcohol, and the like. Further, the ratio of water to the organic solvent in the water-containing organic solvent is not particularly limited. Among these, water is preferable as the solvent from the viewpoint of improving the dispersibility of the photocatalyst.
The content of the solvent in the composition for forming a photocatalyst layer is preferably 50 to 95% by weight, more preferably 70 to 95% by weight from the viewpoints of improving the dispersibility of the photocatalyst and drying properties. .

The composition for forming a photocatalyst layer contains optional components such as a silicon compound, a reactive silicon compound, colloidal silica, aluminum, a zirconium alkoxysilane compound, a filler, an adhesive, and a dispersant, as necessary. Also good.

The composition for forming a photocatalyst layer can be prepared by mixing the titanium oxide photocatalyst, the organic titanium compound, a solvent, and optionally the optional components.
In addition, the photocatalyst layer forming composition is heated at a predetermined temperature to react with the titanium alkoxide compound, the alkoxy titanate compound, the titanium acylate compound, etc. contained as an organic titanium compound to oligomerize. You may let them.

In the present invention, the composition for forming a protective layer is a composition that is adhered to a photocatalyst layer and forms a protective layer between the photocatalyst layer and the base material to prevent deterioration of the base material due to photocatalytic activity. .

The protective layer-forming composition contains a hydrolyzable group-containing compound or a polymer thereof.

Examples of the hydrolyzable group in the hydrolyzable group-containing compound include an alkoxy group, a ketoxime group, an alkenyloxy group, an aryloxy group, a mercapto group, an acyloxy group, an amino group, an aminoxy group, an amide group, an isocyanate group, and a halogen. Can be mentioned. Among these hydrolyzable groups, alkoxy groups, alkenyloxy groups, acyloxy groups, and halogens are preferable because of their high activity, and alkoxy groups such as methoxy groups and ethoxy groups are more preferable because they are mildly hydrolyzable and easy to handle. .

Examples of the hydrolyzable group-containing compound include an isocyanate-modified alkoxysilane compound, an amino-modified alkoxysilane compound, and a mercapto-modified alkoxysilane compound.

Of these, isocyanate-modified alkoxysilane compounds are preferred from the viewpoint of mild hydrolyzability and easy handling. The isocyanate-modified alkoxysilane compound refers to a reaction product of isocyanate and alkoxysilane.

The isocyanate is not particularly limited as long as it is a crosslinking agent containing an isocyanate group, and examples thereof include non-yellowing or non-yellowing polyisocyanate, aliphatic isocyanate, and alicyclic isocyanate.
Examples of the non-yellowing or non-yellowing polyisocyanate include aromatic polyisocyanates such as tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, xylylene diisocyanate, and tolidine diisocyanate, and commercially available products include Mitsui Chemicals, Inc. “XDI system”, “IPDI system”, “HDI system” and the like manufactured by the company can be mentioned.
Aliphatic isocyanates include trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate (HDI), 2,2,4-trimethylhexamethylene diisocyanate, propylene diisocyanate, butylene diisocyanate, 2-methyl- 1,5-pentamethylene diisocyanate (MPDI) and the like, and commercially available products include “Takenate” series manufactured by Mitsui Chemicals, Inc.
Cycloaliphatic isocyanates include isophorone diisocyanate (IPDI), hydrogenated tolylene diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated diphenylmethane diisocyanate, 1,3-cyclopentane diisocyanate, 1,4-cyclohexane diisocyanate, 1,3-cyclohexane. Examples thereof include diisocyanate, methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, norbornane diisocyanate and the like.

Examples of the alkoxysilane used in the isocyanate-modified alkoxysilane compound include mercaptoalkoxylanes having a mercapto group, such as γ-mercaptopropylmethyldiethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ -Mercaptopropyltriethoxysilane and the like; aminoalkoxysilanes having primary and secondary amino groups, such as γ-aminopropylmethyldiethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropyltrimethoxysilane, γ- Aminopropyltriethoxysilane, N- (β-aminoethyl) -N ′-(γ-trimethoxysilylpropyl) -ethylenediamine, N- (β-aminoethyl) -γ-aminopropyltrimethoxy Sisilane, N- (β-aminoethyl) -γ-aminopropylmethyldiethoxysilane, N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane, N- (β-aminoethyl) -γ-aminopropyl Triethoxysilane, 1,3-diaminoisopropyltrimethoxysilane, γ-N-phenylaminopropyltrimethoxysilane, γ-N-phenylaminopropyltriethoxysilane, bis (trimethoxysilylpropyl) amine, etc .; having an epoxy group Alkoxysilanes such as γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, 3,4-epoxycyclohexylethyltrimethoxysilane, 3,4-epoxycyclohexylethylmethyldimethoxysilane, γ-glycidoxyp Propylmethyldiisopropenoxysilane and the like; alkoxysilane having an isocyanate group, such as γ-isocyanatopropylmethyldiethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropyltriethoxy Silane etc. are mentioned.

Further, the degree of polymerization of the polymer of the isocyanate-modified alkoxysilane compounds is not particularly limited.

The isocyanate-modified alkoxysilane compound or polymer thereof is one or more selected from the group consisting of a reaction product of isocyanate and mercaptoalkoxysilane or aminoalkoxysilane and a polymer thereof from the viewpoint of weather resistance and radical resistance. A compound is preferred.

The protective layer-forming composition may further contain an acrylic polymer having a number average molecular weight of 20,000 to 5,000,000 and / or a reaction product of the acrylic polymer and a hydrolyzable group-containing compound. By containing these compounds, there is an advantage that weather resistance, radical resistance and the like are improved.

The acrylic polymer is a polymer of acrylic acid ester or methacrylic acid ester, and may be any one used for a coating agent.
The number average molecular weight of the acrylic polymer is from 20,000 to 5,000,000, preferably from 20,000 to 500,000, more preferably from 50,000 to 300,000 from the viewpoints of workability and film formability.

As the acrylic polymer having a number average molecular weight of 20,000 to 5,000,000, a commercially available product can be used. For example, “Dianar BR” series manufactured by Mitsubishi Rayon Co., Ltd. can be used.

As a reaction product of the acrylic polymer with a hydrolyzable group-containing compound, for example, the acrylic polymer having a number average molecular weight of 20,000 to 5,000,000 and an alkoxy group-containing silane coupling agent are reacted in an organic solvent. Things.
Examples of the alkoxy group-containing silane coupling agent include acrylic silanes, aminosilanes, epoxy silanes, isocyanate silanes, and mercaptosilanes. The degree of the reaction is not particularly limited as long as it is a partial reaction.

The hydrolyzable group-containing compound, the polymer thereof, the acrylic polymer having a number average molecular weight of 20,000 to 5,000,000, and the reaction product of the acrylic polymer and the hydrolyzable group-containing compound in the protective layer forming composition The total solid content is preferably 3 to 40% by weight, more preferably 3 to 20% by weight from the viewpoint of antibacterial / antiviral properties and film-forming properties.

Examples of the solvent for the protective layer forming composition include hydrophilic or non-hydrophilic organic solvents. Examples of the hydrophilic organic solvent include alcohol-based organic solvents. Examples of the non-hydrophilic organic solvent include ethyl acetate and butyl acetate.

The content of the solvent in the protective layer forming composition is preferably 70 to 95% by weight from the viewpoint of workability.

The protective layer forming composition may contain optional components such as a silane coupling agent and a dispersing agent, if necessary.

The protective layer-forming composition comprises the hydrolyzable group-containing compound or polymer thereof, and, if necessary, an acrylic polymer having a number average molecular weight of 20,000 to 5,000,000 and / or hydrolyzable with the acrylic polymer. It can be prepared by mixing a reaction product with a group-containing compound and further the optional component in the solvent.
Among these, from the viewpoint of workability, the photocatalyst layer forming composition is preferably a dispersion.

The amounts of the photocatalyst layer forming composition and the protective layer forming composition in the set of the present invention are appropriately determined according to the surface area of the substrate for forming the coating film and the desired thickness of each layer. There is no particular limitation.

(Photocatalyst laminated coating)
The photocatalyst laminated coating film according to the present invention is a coating film formed using the photocatalyst coating set, and is formed on the protective layer formed of the protective layer forming composition and the protective layer. And a photocatalyst layer comprising the photocatalyst layer forming composition.

As a method of forming the photocatalyst multilayer coating film, after forming the protective layer forming composition contained in the set into a thin film, the photocatalyst layer forming composition is applied to the surface, dried and reacted. Thus, an integral coating film having a protective layer and a photocatalyst layer can be formed.

When the protective layer forming composition is formed into a thin film, for example, the protective layer forming composition may be applied to the surface of the substrate until a predetermined thickness is reached. As a base material, what consists of a synthetic resin film, a synthetic resin sheet, glass, a woven fabric, a nonwoven fabric, paper, a plastic, a stone, a metal, a ceramic tile, a gypsum board, wood etc. can be employ | adopted suitably.

For the application, a known method such as air spray, brush, or roll can be used.

The photocatalyst composition in the photocatalyst layer and the protective layer composition in the protective layer are preferably cured.
The curing reaction may be carried out at 20 to 80 ° C., preferably 20 to 40 ° C., for 0.1 to 24 hours, preferably 0.5 to 24 hours.

(Photocatalyst carrier)
The photocatalyst carrier according to the present invention is a photocatalyst carrier on which the photocatalyst laminated coating film is formed on the surface of a substrate.
Specifically, a photocatalyst carrier obtained by coating a photocatalyst on the surface of a substrate using the photocatalyst coating set,
The protective layer-forming composition is attached to the surface of the base material, and the photocatalyst layer-forming composition is attached to the surface of the protective layer-forming composition, followed by a curing reaction. It is a photocatalyst carrier.

As the substrate, a material made of synthetic resin film, synthetic resin sheet, glass, woven fabric, non-woven fabric, paper, plastic, stone, metal, ceramic tile, gypsum board, wood, etc. can be suitably employed.

As a method for attaching the protective layer forming composition to the surface of the substrate, a known method such as air spray, brush, roll, or the like can be used.

The protective layer-forming composition adhered to the substrate surface as described above can be dried to form a protective layer. As drying conditions, it is sufficient that the solvent disappears to such an extent that the composition for forming a protective layer does not flow. For example, the drying may be performed at 20 to 40 ° C.

As a method for attaching the photocatalyst layer forming composition to the surface of the protective layer forming composition, a known method such as an air spray, a brush, or a roll can be used.

Examples of methods for curing the photocatalyst-forming composition include moisture curing and wet heat curing.

The photocatalyst carrier obtained as described above is not only used alone, but can be developed for a wide range of applications by being bonded to various members by an adhesive, a pressure-sensitive adhesive, heat lamination, or the like as required.
The present invention will be described in more detail with reference to the following examples. However, the examples do not define the scope of the present invention.

(Example 1: Ultraviolet light type 1)
A titanate coupling agent “Plenact 44” was added to 200 g (concentration 10%) of an aqueous dispersion of ultraviolet light titanium oxide “ST-21” (primary particle diameter 20 nm as measured by electron microscope (SEM, TEM), manufactured by Ishihara Sangyo Co., Ltd.). 1 g (manufactured by Ajinomoto Fine Techno Co., Ltd.) was added and mixed uniformly.
Next, 0.5 g of a titanium chelate compound “Orgatics TC-310” (titanium lactate, manufactured by Matsumoto Fine Chemical Co., Ltd.) was blended and dispersed.
Next, the dispersion was allowed to stand in an oven at 50 ° C. for 3 days, and a portion of the alkoxy titanate was reacted and partially oligomerized to prepare a photocatalyst dispersion (photocatalyst layer forming composition).

Next, a protective agent was prepared by the following procedure.
Mercaptoalkoxysilane “KBM803” (3-mercaptopropyltrimethoxysilane, Shin-Etsu Chemical) to 10 g of trimethylolpropane hydrogenated XDI compound (“Takenate (registered trademark) D-120N” manufactured by Mitsui Chemicals, Inc.), which is an aliphatic isocyanate compound 8 g of Kogyo Co., Ltd. was reacted in a 200 g solution of ethyl acetate at 80 ° C. for 24 hours. The reaction was completed when the NCO% disappeared.
Next, 0.5 g of epoxy silane “KBM402” (3-glycidoxypropylmethyldiethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.) was added to the reaction solution.
In addition, a 10% ethyl acetate solution and an acrylic alkoxy partial reactant solution (acrylic silane “KBM503”) of an acrylic resin “Dyanal (registered trademark) BR80” (manufactured by Mitsubishi Rayon Co., Ltd., weight average molecular weight 95,000) previously dissolved and partially reacted. (3-methacryloxypropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.) 0.5 g reacted with 10% ethyl acetate acrylic resin solution at 50 ° C. for 24 hours) 40 g of each was added to the above reaction solution for protection An agent (composition for forming a protective layer) was completed.

Next, using the obtained photocatalyst dispersion liquid and the protective agent, a test body on which a coating film containing a photocatalyst was formed was prepared by the following procedure.
On a 100 μm thick PET film (Toyobo Co., Ltd.), a protective agent was applied uniformly with an air spray gun, dried at room temperature for 30 minutes, and then the photocatalyst dispersion liquid was applied on the air spray gun. The film was applied uniformly at 50 ° C. and dried and reacted for 24 hours to form a film.
The thickness of the protective layer in the coating film formed on the PET film was about 1 to 10 μm, and the thickness of the photocatalyst layer formed on the protective layer was about 1 μm.

The performance evaluation of the photocatalytic ability of the obtained specimen under ultraviolet irradiation was performed according to the following procedure.
Ultraviolet irradiation was performed for 4 hours with a metal halide lamp of 80 mw / cm ² , and the contact angle after 10 seconds was measured with a contact angle tester manufactured by Kyowa Interface Science.
As a result of the test, it was found that the contact angle was 10 ° or less, which was applicable to antifouling properties and antifogging properties and was at a practical level.

Moreover, in order to evaluate the adhesive strength of the photocatalyst in a test body, finger touch and tape peeling were performed.
Regarding finger touch, when the photocatalyst coating surface of the test body was pressed with the whole hand, the photocatalyst particles were not attached to the hand. In addition, after a transparent cellophane tape was attached to the photocatalyst coating surface, a test was performed to peel the tape so that the tape angle was 90 ° or more. Was not recognized, and it was found that the adhesive strength was at a practical level.

(Example 2: Ultraviolet light type 2)
200 g of an aqueous dispersion of ultraviolet light titanium oxide “ST-21”, 0.5 g of titanate coupling agent “Plenact 46B” (manufactured by Ajinomoto Fine-Techno Co., Ltd.) and titanium chelate compound “Orgatyx TC-401” (triethanol) 0.5 g (aminate, manufactured by Matsumoto Fine Chemical Co., Ltd.) was added and uniformly mixed and dispersed.
Next, the obtained dispersion was left in an oven at 50 ° C. for 3 days, and a part of alkoxytitanate was reacted to be oligomerized to prepare a photocatalyst dispersion.

Next, a protective agent was prepared by the following procedure.
Mercaptoalkoxysilane “KBM802” (3-mercaptopropylmethyldimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.) 8 g is added to 10 g of trimethylolpropane hydrogenated XDI compound, which is an aliphatic isocyanate compound, at 80 ° C. for 24 hours, 200 g of ethyl acetate solution Reacted in. Further, 0.5 g of epoxy silane “KBM403” (3-glycidoxypropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.) was added. 10% ethyl acetate solution and acrylic alkoxy partial reactant solution (acrylic silane “KBM503”) 0 of acrylic resin “Dyanal (registered trademark) BR85” (Mitsubishi Rayon Co., Ltd., weight average molecular weight 280000) previously dissolved and partially reacted 0.5 g was reacted with a 10% ethyl acetate acrylic resin solution at 50 ° C. for 24 hours) 40 g of each was added to the reaction solution to complete the protective agent.

Next, using the obtained photocatalyst dispersion liquid and the protective agent, a test body on which a coating film containing a photocatalyst was formed was prepared by the following procedure.
Apply a protective agent on a 100 μm thick PET film (Toyobo Co., Ltd.) with an air spray gun so that it is uniform, and after drying at room temperature for 30 minutes, make the photocatalyst dispersion uniform with an air spray gun. The film was formed into a film by drying and curing reaction at 50 ° C. for 24 hours.
The thickness of the protective layer in the coating film formed on the PET film was about 1 to 10 μm, and the thickness of the photocatalyst layer formed on the protective layer was about 1 μm.

The performance evaluation of the photocatalytic activity of the obtained test specimen under ultraviolet irradiation and the adhesive strength of the photocatalyst in the test specimen were evaluated in the same manner as in Example 1.
As a result of the test, it was found that the contact angle was 10 ° or less, which was a practical level applicable to antifouling properties and antifogging properties.
As for film formability, when the photocatalyst particles are not attached to the hand and a transparent cellophane tape is attached to the surface and then peeled so that the tape has an angle of 90 ° or more, a tape adhesion is performed. It was found that the photocatalyst particles were not noticeably adhered to the surface (which could be visually confirmed), and the adhesive strength was at a practical level.

(Example 3: Ultraviolet light type 3)
Add 200g of titanate coupling agent "Plenact 44" to 200g aqueous dispersion of UV light titanium oxide "ST-21" and mix uniformly, then blend 0.5g of titanium chelate compound "Orgatyx TC-310" And dispersed. Next, the dispersion was allowed to stand in an oven at 50 ° C. for 3 days, and a part of the alkoxy titanate was reacted to be oligomerized to prepare a photocatalyst dispersion.

Next, a protective agent was prepared by the following procedure.
10 g of a trimethylolpropane IPDI compound (“Takenate (registered trademark) D140N” manufactured by Mitsui Chemicals), which is an aliphatic isocyanate compound, was reacted with 8 g of mercaptoalkoxysilane “KBM803” at 80 ° C. for 24 hours in a 200 g solution of ethyl acetate. Further, 1 g of epoxy silane “KBM403” was added. 50% of 10% ethyl acetate solution of acrylic resin “Dyanal (registered trademark) BR85” and acrylic alkoxy partial reactant solution (0.5 g of acrylic silane “KBM503”) dissolved in advance and partially reacted in 10% ethyl acetate acrylic resin solution 40 g each was reacted at 24 ° C.) was added to the reaction solution to complete the protective agent.

Next, using the obtained photocatalyst dispersion liquid and the protective agent, a test body on which a coating film containing a photocatalyst was formed was prepared by the following procedure.
Apply a protective agent on a 100 μm thick PET film (Toyobo Co., Ltd.) with an air spray gun so that it is uniform, and after drying at room temperature for 30 minutes, make the photocatalyst dispersion uniform with an air spray gun. The film was formed into a film by drying and curing reaction at 50 ° C. for 24 hours.
The thickness of the protective layer in the coating film formed on the PET film was about 1 to 10 μm, and the thickness of the photocatalyst layer formed on the protective layer was about 1 μm.

The performance evaluation of the photocatalytic activity of the obtained test specimen under ultraviolet irradiation and the adhesive strength of the photocatalyst in the test specimen were evaluated in the same manner as in Example 1.
As a result of the test, it was found that the contact angle was 10 ° or less, which was a practical level applicable to antifouling properties and antifogging properties. As for film formability, the photocatalyst particles are not attached to the hand, and in a test where the transparent cellophane tape is attached to the surface and then peeled so that the tape angle is 90 ° or more, the photocatalyst is applied to the tape adhesive surface. No noticeable particle adhesion (which can be visually confirmed) was observed, and it was found that the adhesion strength was at a practical level.

(Comparative Example 1: Ultraviolet light type 4)
1 g of methyl-based silicone resin emulsion “SILRES (registered trademark) BS45” (manufactured by Asahi Kasei Wacker Silicone Co., Ltd.) was added to 200 g of an aqueous dispersion of ultraviolet light titanium oxide “ST-21” and mixed uniformly, and then aminosilane “KBM603” 0.5 g each of (N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.) and acrylic silane “KBM503” were blended and dispersed to prepare a dispersion. Next, the dispersion was left in an oven at 50 ° C. for 3 days, and a part of alkoxysilane was reacted to be oligomerized to prepare a photocatalyst dispersion.

Subsequently, the test body which formed the coating film containing a photocatalyst using the protective agent produced in Example 1 was produced in the following procedures.
Apply a protective agent on a 100 μm thick PET film (Toyobo Co., Ltd.) with an air spray gun so that it is uniform, and after drying at room temperature for 30 minutes, make the photocatalyst dispersion uniform with an air spray gun. The film was formed into a film by drying and curing reaction at 50 ° C. for 24 hours.
The thickness of the protective layer in the coating film formed on the PET film was about 1 to 10 μm, and the thickness of the photocatalyst layer formed on the protective layer was about 1 μm.

The performance evaluation of the photocatalytic activity of the obtained test specimen under ultraviolet irradiation and the adhesive strength of the photocatalyst in the test specimen were evaluated in the same manner as in Example 1.
As a test result, it was confirmed that the contact angle was 60 °, which was not applicable to antifouling properties and antifogging properties, and was not at a practical level.
On the other hand, with regard to film formability, photocatalyst particles are not attached to the hand, and in a test in which a transparent cellophane tape is attached to the surface and peeled at 90 ° or more, the photocatalyst particles are noticeable on the tape adhesive surface (confirmed visually). It was found that it was at a practical level.

(Comparative Example 2: Ultraviolet light type 5)
1 g of silicon emulsion “IE-7170” (manufactured by Toray Dow Corning Co., Ltd.) was added to 200 g of an aqueous dispersion of ultraviolet light titanium oxide “ST-21” and mixed uniformly, then epoxy silane “KBM403”, mercaptoalkoxysilane 0.5 g of “KBM803” was added and dispersed. Next, the dispersion was left in an oven at 50 ° C. for 3 days, and a part of alkoxysilane was reacted to be oligomerized to prepare a photocatalyst dispersion.

Subsequently, the test body which formed the coating film containing a photocatalyst using the protective agent produced in Example 2 was produced in the following procedures.
Apply a protective agent on a 100 μm thick PET film (Toyobo Co., Ltd.) with an air spray gun so that it is uniform, and after drying at room temperature for 30 minutes, make the photocatalyst dispersion uniform with an air spray gun. The film was formed into a film by drying and curing reaction at 50 ° C. for 24 hours.
The thickness of the protective layer in the coating film formed on the PET film was about 1 to 10 μm, and the thickness of the photocatalyst layer formed on the protective layer was about 1 μm.

The performance evaluation of the photocatalytic activity of the obtained test specimen under ultraviolet irradiation and the adhesive strength of the photocatalyst in the test specimen were evaluated in the same manner as in Example 1.
As a result of the test, it was confirmed that the contact angle was 30 °, which was not applicable to antifouling properties and antifogging properties and was not at a practical level.
It was confirmed that the photocatalyst particles were attached to the hand in terms of finger touch. Moreover, also in the test which adheres a transparent cellophane tape to the surface and peels at 90 ° or more, the adhesion of the photocatalyst particles (which can be visually confirmed) was recognized on the tape adhesive surface, and it was confirmed that the adhesive strength was not at a practical level.

(Comparative Example 3: Ultraviolet light type 6)
An aqueous dispersion 200 g of ultraviolet light titanium oxide “ST-21” was prepared.
Subsequently, the test body which formed the coating film containing a photocatalyst using the protective agent produced in Example 1 was produced in the following procedures.
Apply a protective agent on a 100 μm thick PET film (Toyobo Co., Ltd.) with an air spray gun so that it is uniform, and after drying at room temperature for 30 minutes, make the photocatalyst dispersion liquid uniform with an air spray gun. It was applied, dried at 50 ° C. for 24 hours, and cured to form a film.
The thickness of the protective layer in the coating film formed on the PET film was about 1 to 10 μm, and the thickness of the photocatalyst layer formed on the protective layer was about 1 μm.

The performance evaluation of the photocatalytic activity of the obtained test specimen under ultraviolet irradiation and the adhesive strength of the photocatalyst in the test specimen were evaluated in the same manner as in Example 1.
As a result of the test, it was found that the contact angle is 10 ° or less, which is a practical level applicable to antifouling properties and antifogging properties.
On the other hand, in terms of finger touch, photocatalyst particles were attached to the hand, and were noticeably adhered in the transparent cellophane tape adhesion test, confirming that the adhesive strength was not at a practical level.

Table 1 shows the results relating to contact angles, tape peelability, and finger touch in Examples 1 to 3 and Comparative Examples 1 to 3.
The evaluation criteria for tape peelability and finger touch are as follows.
[Tape peelability]
○: The photocatalytic material is hardly visually confirmed on the tape peeling surface.
Δ: The photocatalytic material can be visually confirmed on the tape peeling surface. The adhesion rate is less than 50% of the release tape surface.
X: The photocatalytic material can be visually confirmed on the tape peeling surface. Adhesion rate is 50% or more of the release tape surface.
(Finger touch)
A: Almost no photocatalytic material can be visually confirmed on the finger.
Δ: The photocatalytic material can be visually confirmed on the finger. Adhesion area is less than 70%.
X: The photocatalytic material can be visually confirmed on the finger. The adhesion area is 70% or more.

From the results shown in Table 1, the coating films prepared in Examples 1 to 3 all exhibited excellent photocatalytic activity because the contact angle was 10 ° or less, and the coating surface was pointed to the surface. It does not peel off only by touching with, and even when an adhesive tape is attached, the photocatalyst cannot be visually confirmed to peel off, which indicates that the adhesive strength of the photocatalyst is high.

(Example 4: Visible light type 1)
1 g of titanate compound “Plenact 44” was added to 200 g of an aqueous dispersion of copper-supported visible light responsive photocatalyst “Lumiresh (registered trademark)” (manufactured by Showa Denko KK), and then mixed with titanium chelate compound “OrgaTix TC”. -310 "0.5 g was dispersed. Next, the dispersion was allowed to stand in an oven at 50 ° C. for 3 days, and a part of the alkoxy titanate was reacted to be oligomerized to obtain a photocatalyst dispersion.

Next, a protective agent was prepared by the following procedure.
Trimethylolpropane hydrogenated XDI compound “Takenate (registered trademark) D-120N” was reacted with 10 g of mercaptoalkoxysilane “KBM803” 8 g at 80 ° C. for 24 hours in a 200 g ethyl acetate solution. The reaction was completed when the NCO% disappeared.
Next, 0.5 g of epoxy silane “KBM402” was added to the reaction solution. In addition, 10% ethyl acetate solution of acrylic resin “Dianal (registered trademark) BR80” and acrylic alkoxy partial reactant solution (0.5 g of acrylic silane “KBM503”) dissolved in advance and partially reacted (10% ethyl acetate acrylic resin solution) 40 g of each was added to the above reaction solution to complete the protective agent.

Subsequently, the test body which formed the coating film containing a photocatalyst using the said protective agent was produced in the following procedures.
A protective agent is applied on a PET film (made by Toyobo Co., Ltd.) with a thickness of 100 μm so as to be uniform with an air spray gun, dried at room temperature for 30 minutes, and then the photocatalyst dispersion liquid is applied thereon with an air spray gun. A uniform coating was applied, followed by drying and curing reaction at 50 ° C. for 24 hours to form a film.
The thickness of the protective layer in the coating film formed on the PET film was about 1 to 10 μm, and the thickness of the photocatalyst layer formed on the protective layer was about 1 μm.

Antibacterial and antiviral performance was evaluated for the photocatalytic ability of the obtained specimen under visible light irradiation.
The antibacterial / antiviral performance was evaluated according to JIS R 1702, 1756. Specifically, the fluorescent lamp illuminance was 1000 LUX (sharp cut of 400 nm or less), the bacteria were irradiated for 8 hours, and the viruses were 4 hours. Multidrug-resistant Staphylococcus aureus (MRSA) and multidrug-resistant Pseudomonas aeruginosa (MDRP) were used as test bacteria, and bacterial phage QB and bacterial phage φ6 were used as test viruses. The measured antibacterial activity value and antiviral activity value both indicate that the higher the value, the stronger the activity.
As a result of the test, the antibacterial activity value is 3 to 4 and the antiviral activity value is 4 to 5, exceeding the normally required “2” (99% bacteria, killing the virus) and having high antibacterial and antibacterial properties. The virus performance was confirmed to be at a practical level.

Moreover, when the adhesive strength of the photocatalyst in the obtained test body was evaluated in the same manner as in Example 1, the photocatalyst particles were not attached to the hand in terms of finger touch, and a transparent cellophane tape was attached to the surface and peeled at 90 ° or more. In the test, the photocatalyst particles were not noticeably adhered (which can be visually confirmed) on the tape adhesive surface, and the adhesive strength was found to be at a practical level.

(Example 5: Visible light type 2)
To 200 g of an aqueous dispersion of a copper-supported visible light responsive photocatalyst “Lumireche (registered trademark)”, 0.5 g of a titanate coupling agent “Plenact 46B” and 0.5 g of a titanium chelate compound “Orgatyx TC-410” were added. Uniformly mixed into a dispersion. Next, the dispersion was allowed to stand in an oven at 50 ° C. for 3 days, and a part of the alkoxy titanate was reacted to be oligomerized to prepare a photocatalyst dispersion.

Next, a protective agent was prepared by the following procedure.
10 g of trimethylolpropane hydrogenated XDI compound “Takenate (registered trademark) D-120N” was reacted with 8 g of mercaptoalkoxysilane “KBM802” at 80 ° C. for 24 hours in a solution of 200 g of ethyl acetate. Furthermore, 10% ethyl acetate solution and acrylic alkoxy partial reactant solution (acrylic silane “KBM503” 0.5 g) of acrylic resin “Dyanal (registered trademark) BR85” in which 0.5 g of epoxy silane “KBM403” was previously dissolved and partially reacted. 40 g of each was reacted with a 10% ethyl acetate acrylic resin solution at 50 ° C. for 24 hours to complete the protective agent.

Subsequently, the test body which formed the coating film containing a photocatalyst using the said protective agent was produced in the following procedures.
A protective agent is applied on a PET film (made by Toyobo Co., Ltd.) with a thickness of 100 μm so as to be uniform with an air spray gun, dried at room temperature for 30 minutes, and then the photocatalyst dispersion liquid is applied thereon with an air spray gun. A uniform coating was applied, followed by drying and curing reaction at 50 ° C. for 24 hours to form a film.
The thickness of the protective layer in the coating film formed on the PET film was about 1 to 10 μm, and the thickness of the photocatalyst layer formed on the protective layer was about 1 μm.

The photocatalytic ability and photocatalytic adhesive strength of the obtained test specimen under visible light irradiation were evaluated in the same manner as in Example 4.

As a result of the test, the antibacterial activity value is 3 to 4 and the antiviral activity value is 4 to 5, exceeding the normally required “2” (99% of bacteria and viruses are killed), and high antibacterial and antiviral performance It was confirmed that it was a practical level.
In addition, in the finger touch, the photocatalyst particles are not attached to the hand, and in the test in which a transparent cellophane tape is attached to the surface and peeled at 90 ° or more, the photocatalyst particles are noticeably adhered (which can be visually confirmed) to the tape adhesive surface. In other words, it was found that the adhesive strength was at a practical level.

(Example 6: visible light type 3)
To 200 g of an aqueous dispersion of a copper-supported visible light responsive photocatalyst “Lumireche (registered trademark)” 0.5 g of a titanate compound titanate compound “Plenact 44” was added and mixed uniformly, and then a titanium chelate compound “Orgatics TC-310” 0.5 g was added to form a dispersion. Next, the dispersion was allowed to stand in an oven at 50 ° C. for 3 days, and a part of the alkoxy titanate was reacted to be oligomerized to prepare a photocatalyst dispersion.

Next, a protective agent was prepared by the following procedure.
10 g of trimethylolpropane IPDI compound “Takenate (registered trademark) D140N” was reacted with 8 g of mercaptoalkoxysilane “KBM803” at 80 ° C. for 24 hours in a solution of 200 g of ethyl acetate. Further, 1 g of epoxy silane “KBM403” was added. 10% ethyl acetate solution of acrylic resin “Dyanal (registered trademark) BR85” previously dissolved and partially reacted and 0.5 g of acrylic alkoxy partial reaction product (acrylic silane “KBM503”) in 10% ethyl acetate acrylic resin solution at 50 ° C. For 24 hours)
40 g of each solution was added to the reaction solution to complete the protective agent.

Subsequently, the test body which formed the coating film containing a photocatalyst using the said protective agent was produced in the following procedures.
A protective agent is applied on a PET film (made by Toyobo Co., Ltd.) with a thickness of 100 μm so as to be uniform with an air spray gun, dried at room temperature for 30 minutes, and then the photocatalyst dispersion liquid is applied thereon with an air spray gun. It was applied so as to be uniform, and dried and cured at 50 ° C. for 24 hours.
The thickness of the protective layer in the coating film formed on the PET film was about 1 to 10 μm, and the thickness of the photocatalyst layer formed on the protective layer was about 1 μm.

The photocatalytic ability and photocatalytic adhesive strength of the obtained test specimen under visible light irradiation were evaluated in the same manner as in Example 4.

As a result of the test, the antibacterial activity value is 3-4, and the antiviral activity value is 4-5, which exceeds 2 (99% of bacteria and viruses are killed) which is normally required, and has high antibacterial and antiviral performance. Confirmed that the level.
In addition, in the finger touch, the photocatalyst particles are not attached to the hand, and in the test in which a transparent cellophane tape is attached to the surface and peeled at 90 ° or more, the photocatalyst particles are noticeably adhered (which can be visually confirmed) to the tape adhesive surface. It was found that the adhesive strength was at a practical level.

(Comparative Example 4: Visible light type 4)
1 g of a methyl silicone resin emulsion “SILRES (registered trademark) BS45” was added to 200 g of an aqueous dispersion of a copper-supported visible light responsive photocatalyst “Lumiresh (registered trademark)”, and then mixed uniformly. Then, aminosilane “KBM603”, acrylic silane “KBM503” and 0.5 g of each were blended and dispersed. Next, the dispersion was left in an oven at 50 ° C. for 3 days, and a part of alkoxysilane was reacted to be oligomerized to prepare a photocatalyst dispersion.

Subsequently, the test body which formed the coating film containing a photocatalyst using the protective agent produced in Example 1 was produced in the following procedures.
Apply a protective agent on a 100 μm thick PET film (Toyobo Co., Ltd.) with an air spray gun so that it is uniform, and after drying at room temperature for 30 minutes, make the photocatalyst dispersion uniform with an air spray gun. The film was formed into a film by drying and curing reaction at 50 ° C. for 24 hours.
The thickness of the protective layer in the coating film formed on the PET film was about 1 to 10 μm, and the thickness of the photocatalyst layer formed on the protective layer was about 1 μm.

The photocatalytic ability and adhesive strength of the photocatalyst under visible light irradiation of the obtained specimen were evaluated in the same manner as in Example 4.
As a result, it was found that the film-forming property was at a practical level for both tape peeling and finger touch, but the antibacterial and antiviral properties were low and not at a practical level.

(Comparative Example 5: Visible light type 5)
1 g of silicon emulsion “IE-7170” was added to 200 g of an aqueous dispersion of Showa Denko copper-supported visible light responsive photocatalyst “Lumireche (registered trademark)” and mixed uniformly, then epoxy silane “KBM403”, mercaptoalkoxysilane “KBM803” “0.5 g of each was blended and dispersed. Next, the dispersion was left in an oven at 50 ° C. for 3 days, and a part of alkoxysilane was reacted to be oligomerized to prepare a photocatalyst dispersion.
Subsequently, the test body was produced using the protective agent produced in Example 2.
Apply a protective agent on a PET film (Toyobo) with a thickness of 100μ so that it is uniform with an air spray gun, and after drying at room temperature for 30 minutes, apply the photocatalyst dispersion liquid so that it is uniform with an air spray gun. Then, the film was dried and cured at 50 ° C. for 24 hours to form a film. Antibacterial / antiviral evaluation, tape peeling, and finger touch were evaluated in the same manner as in Example 1. As a result of the measurement, antibacterial and antiviral performance is low anti-activity value, and as for film formability, photocatalyst particles are attached to the tape when peeling, and photocatalyst particles are in hand, and both performances are put to practical use. It turns out that it is not a level.

(Comparative Example 6: visible light type 6)
An aqueous dispersion 200 g of Showa Denko copper-supported visible light responsive photocatalyst “Lumiresh (registered trademark)” was prepared.
Subsequently, the test body which formed the coating film containing a photocatalyst using the protective agent produced in Example 1 was produced in the following procedures.
A protective agent is applied on a PET film (made by Toyobo Co., Ltd.) with a thickness of 100 μm so as to be uniform with an air spray gun, dried at room temperature for 30 minutes, and then the photocatalyst dispersion liquid is applied thereon with an air spray gun. A uniform coating was applied, followed by drying and curing reaction at 50 ° C. for 24 hours to form a film.
The thickness of the protective layer in the coating film formed on the PET film was about 1 to 10 μm, and the thickness of the photocatalyst layer formed on the protective layer was about 1 μm.

The photocatalytic ability and adhesive strength of the photocatalyst under visible light irradiation of the obtained specimen were evaluated in the same manner as in Example 4.
As a result, it was found that the antibacterial / antiviral performance was high in antibacterial activity, but the film forming property was not at a practical level in terms of tape peeling and finger touch.

Table 2 shows the evaluation results regarding antibacterial activity, antiviral activity, tape peelability, and finger touch in Examples 4 to 6 and Comparative Examples 4, 5, and 6.

From the results shown in Table 2, the coating films prepared in Examples 4 to 6 have high antibacterial activity and antiviral activity, and the photocatalyst does not peel off even when touched with a finger or attached with an adhesive tape. Therefore, it turns out that it is the thing excellent in the adhesive strength of a photocatalyst.

Claims (15)

A set for photocatalyst coating comprising a photocatalyst layer forming composition containing a titanium oxide photocatalyst and an organic titanium compound, and a protective layer forming composition containing a hydrolyzable group-containing compound or a polymer thereof. The photocatalyst according to claim 1, wherein the protective layer-forming composition further comprises an acrylic polymer having a number average molecular weight of 20,000 to 5,000,000 and / or a reaction product of the acrylic polymer and a hydrolyzable group-containing compound. Set for coating. The organic titanium compound is selected from the group consisting of an alkoxy titanate compound having a phosphate group, a phosphate ester group, an amino group, an amide group, a lactic acid group or a stearyl group, a titanium chelate compound, or the alkoxy titanate compound and the titanium chelate compound. The set for photocatalyst coating of Claim 1 or 2 which is what oligomerized 1 or more types of compounds which are obtained. The set for photocatalyst coating according to any one of claims 1 to 3, wherein the hydrolyzable group of the hydrolyzable group-containing compound is an alkoxy group. The set for photocatalyst coating according to any one of claims 1 to 4, wherein the hydrolyzable group-containing compound is an isocyanate-modified alkoxysilane compound. The photocatalyst coating set according to any one of claims 1 to 5, wherein the photocatalyst layer forming composition is a dispersion. The set for photocatalyst coating according to claim 6, wherein the dispersion contains water or an organic solvent. The set for photocatalyst coating according to claim 6 or 7, wherein the organic titanium compound is blended in an amount of 0.01 to 30% by weight in the dispersion. 9. The photocatalytic coating according to claim 5, wherein the isocyanate-modified alkoxysilane compound is at least one compound selected from the group consisting of a reaction product of isocyanate and mercaptoalkoxysilane or aminoalkoxysilane and a polymer thereof. Set. The photocatalyst coating set according to any one of claims 1 to 9, wherein the protective layer-forming composition contains a hydrophilic or non-hydrophilic organic solvent. The total solid content of the acrylic polymer having a number average molecular weight of 20,000 to 5,000,000 and the reaction product of the acrylic polymer and the hydrolyzable group-containing compound in the protective layer forming composition is 3 to 40% by weight. The set for photocatalyst coatings of Claim 10. The photocatalyst coating set according to any one of claims 1 to 11, wherein the titanium oxide photocatalyst is anatase type titanium oxide or rutile type titanium oxide having a primary particle diameter of 10 to 500 nm. A coating film formed using the photocatalyst coating set according to any one of claims 1 to 12, wherein the protective layer is formed of the protective layer forming composition, and is formed on the protective layer. A photocatalyst layered coating film comprising a photocatalyst layer comprising the composition for forming a photocatalyst layer. The photocatalyst multilayer coating film according to claim 13, wherein the photocatalyst forming composition in the photocatalyst layer and the protective layer forming composition in the protective layer are cured. A photocatalyst carrier on which the photocatalyst multilayer coating film according to claim 13 or 14 is formed on a substrate surface.