JP5145021B2 - Photocatalyst-containing coating composition - Google Patents

Description

  The present invention relates to a photocatalyst-containing coating composition, and particularly to a photocatalyst-containing coating composition that has good adhesion and does not require an adhesive layer.

  An n-type semiconductor titanium oxide is known as a photocatalyst that causes various chemical reactions such as water decomposition, deodorization, sterilization, water purification, and wastewater treatment to proceed by ultraviolet energy. Although it is generally said that the photocatalyst is used in the form of powder or suspended in a solution, its catalytic activity is generally higher, but in practice it must be used in the form of being supported on some support. There are many.

Various support materials for supporting a photocatalyst have been proposed. For example, (A) nitrocellulose, glass, polyvinyl chloride, plastic, nylon, methacrylic resin, polypropylene and other light transmitting materials, (B) polypropylene fiber, ceramic, ( C) Glass, ceramic, nylon, acrylic, polyester, etc.
However, among these materials, those mainly composed of organic substances have been reported to be decomposed or deteriorated due to their catalytic action when carrying a photocatalyst, which has a problem in durability.

Even if the carrier material is an inorganic substance such as glass or ceramic, if an organic polymer resin is used as an adhesive to support the photocatalyst, the surface of the photocatalyst particles is covered with the resin, so that the catalytic activity decreases. In addition, the resin suffered degradation due to photocatalytic action, and the photocatalyst peeled off.
Therefore, when the carrier material is a heat-resistant inorganic substance, a sputtering method in which no organic substance remains, an organic titanate coating-firing method, a titania sol spraying-firing method, or the like is employed.

  However, these methods require the generation of photocatalyst particles on the carrier, crystallization, and adhesion with the carrier, so that firing at a high temperature is necessary, and it is difficult to carry a large area. There was a problem that the manufacturing cost was very high.

On the other hand, a method of using a metal oxide sol as an adhesive for supporting the photocatalyst on glass fiber paper has also been proposed.
However, the adhesive strength of metal oxide sols such as silica sol is very weak because of the van der Waals force, the adhesiveness and durability are insufficient, and the baking process at high temperature is necessary. In other words, it has not been applicable to all carriers including general-purpose resins that easily undergo thermal decomposition.

Further, in an example in which the photocatalyst powder is supported on a metal oxide gel such as silica or clay mineral, there is a report that the photocatalytic decomposition reaction of propionaldehyde gas is promoted by the effect as an adsorbent of the carrier.
However, there has been no report that a photocatalyst dispersed uniformly in such a metal oxide gel has a carrier having excellent adhesion and durability while maintaining high catalytic activity.

  Furthermore, a method for fixing the photocatalyst with a fluororesin has also been proposed. However, not only is fluororesin expensive, but in order to firmly adhere photocatalyst particles, it is necessary to cover most of the catalyst particle surface with fluororesin, and as a result, the catalytic activity is lower than when powdered. There was a problem to say. There is an example (Patent Document 1) in which a photocatalyst is mixed with a hard-to-decompose binder such as a fluororesin or polyorganosiloxane and is carried on a substrate (Patent Document 1). However, there are practical problems such as adhesion and long-term durability. Insufficient solution.

As described above, the problems that must be solved in order to support the photocatalyst on the carrier are as follows: 1) the adhesiveness between the photocatalyst and the carrier is good, and 2) the photocatalytic activity is supported on the carrier. 3) that the carrier and the adhesive are not deteriorated by the supported photocatalyst and that the strength is maintained over a long period of time, and durability and catalytic activity are maintained. Further, when used in a high temperature and high humidity environment, for example, it is required to have excellent adhesion after being immersed in boiling water.
In addition, as a characteristic required for a photocatalyst coating agent for supporting a photocatalyst on a carrier, a photocatalyst coating liquid that does not increase in viscosity and does not settle particles even when stored for at least 1 month, preferably 3 months or more is required. It is also necessary to carry a photocatalyst without lowering the photocatalytic action when the photocatalyst is coated on a practical product.

In order to solve the above-mentioned problems, the inventors of the present invention provide a silicon-modified resin such as an acrylic-silicon resin or an epoxy-silicon resin having a silicon content of 2 to 60% by weight and colloidal silica between the photocatalyst layer and the carrier. 3 to 60% by weight of a polysiloxane which is a polycondensation reaction product of a resin represented by ˜40% by weight or a compound represented by the general formula SiCln ₁ (OH) n ₂ R ¹ n ₃ (OR ² ) n ₄ The adhesive layer containing the resin to perform was provided (patent document 2).
However, in this method, by providing the catalyst layer via the adhesive layer, the adhesion to the carrier is improved, but on the other hand, the photocatalyst layer is likely to crack due to the stress caused by the difference in expansion and contraction, It was not enough in terms of transparency.

In addition, as a photocatalytic coating agent using a silicon compound, (a) (R ¹ ) _n Si (OR ² ) _4-n (wherein R ¹ is the same or different when two exist, and has 1 to 10 carbon atoms) R ² is the same or different and represents an alkyl group having 1 to 5 carbon atoms or an acyl group having 1 to 6 carbon atoms, and n is an integer of 1 to 2). (B) a trifunctional and / or bifunctional organosiloxane oligomer having an SiO bond and a weight average molecular weight of 300 to 100,000, There is also a coating composition containing (c) a photocatalyst (Patent Document 3).
The technique of Patent Document 3 is not intended to be used alone as a photocatalyst coating layer, but is used in combination with an undercoat layer or a primer layer as necessary, and all examples are provided with an undercoat layer. It is. In terms of performance, transparency and boiling resistance were not sufficient.

JP-A-7-171408 Japanese Patent No. 3038599 JP 2001-192616 A

  In the present invention, 1) the adhesion to the carrier is good, 2) the photocatalytic activity is not lowered by being supported on the carrier, and 3) the carrier is not deteriorated by the supported photocatalyst and the strength is maintained for a long time. And providing a photocatalyst coating agent that satisfies durability and catalytic activity, 4) does not require an adhesive layer, and 5) does not lower transparency.

  As a result of diligent research to solve the above problems, the inventors of the present invention use a siloxane having an epoxy group as a siloxane as a monomer, and mix the condensed product with a metal oxide sol or the like. The present inventors have found that the above problems can be achieved and have completed the present invention.

That is, the present invention
(1) (a) Formula (I)
R _n SiX _4-n (I)
(In the formula, R represents an organic group having an epoxy group, X represents a hydroxyl group or a hydrolyzable group. N represents 1 or 2, and when n is 2, each R may be the same or different, (When n is 2 or more, each X may be the same or different.), (B) a photocatalyst, and (c) a metal oxide and / or metal water. Containing oxides, the composition of each component as a solid content, the entire solid content,
(A) = 5-90 mass%
(B) = 5 to 70% by weight
(C) = 5-50% by weight
A photocatalyst-containing coating composition, characterized in that
(2) The photocatalyst-containing coating composition according to (1), wherein the photocatalyst is a titanium oxide,
(3) The composition for photocatalyst coating according to (1), wherein the metal oxide is alumina.

The present invention also provides:
(4) (A) Formula (I)
R _n SiX _4-n (I)
(In the formula, R represents an organic group having an epoxy group, X represents a hydroxyl group or a hydrolyzable group. N represents 1 or 2, and when n is 2, each R may be the same or different, A step of condensing the organosilicon compound represented by (4-n) of 2 or more in the presence of water and a silanol condensation catalyst in a solvent; and (B ) In any one of the above (1) to (3), which comprises the step of mixing the condensate of the organosilicon compound obtained in step (A), the photocatalyst, and the metal oxide and / or metal hydroxide in a solvent. A method for producing the photocatalyst-containing coating composition according to claim 1,
(5) The method for producing a photocatalytic coating composition according to (4), wherein the organosilicon compound is 3-glycidoxypropyltrimethoxysilane, and the silanol condensation catalyst is titanium oxide, and (6) The present invention relates to a substrate carrying the photocatalyst coating composition according to any one of (1) to (3) above.

In the present invention, by using a combination of an organosilicon compound having an epoxy group and a metal oxide and / or metal hydroxide sol, especially an alumina sol,
(1) Adhesive layer is unnecessary, (2) Adhesion with the carrier is good, (3) The film can be thickened, (4) Good hydrophilicity, (5) Transparency Can be obtained.

(1) Photocatalyst-containing coating composition The photocatalyst-containing coating composition of the present invention is usually in a solvent,
(A) Formula (I)
R _n SiX _4-n (I)
(In the formula, R represents an organic group having an epoxy group, X represents a hydroxyl group or a hydrolyzable group. N represents 1 or 2, and when n is 2, each R may be the same or different, (When n is 2 or more, each X may be the same or different.), (B) photocatalyst, and (c) metal oxide and / or hydroxylation It is a composition containing a product, and may contain other components as long as the effects of the present invention are not impaired.
Each of the components (a) to (c) is blended as a solid content in the following ratio with respect to the mass of the entire solid content.
(A) = 5-90 mass%, preferably 10-70 mass%
(B) = 5-70 mass%, preferably 5-50 mass%
(C) = 5-50% by mass, preferably 5-40% by mass

  As the solvent used in the present invention, those described in the method for preparing the composition are used.

Below, each component of the photocatalyst containing coating composition of this invention is explained in full detail.
1) Organosilicon compound and condensate thereof The organosilicon compound of the present invention has the formula (I)
R _n SiX _4-n is a compound represented by (I).
In formula (I), R shows the organic group which has an epoxy group, and has 1 or 2 in a compound.

  The reason why the organosilicon compound having an epoxy group is suitable in the present invention is considered to be that the epoxy group is ring-opened and reacted, thereby contributing to improvement in adhesion to the substrate.

  Here, the “organic group” is not limited as long as it is an organic group that can have at least one epoxy group (oxirane ring) in the terminal, side chain, or skeleton, and may be substituted carbon. It refers to a hydrogen group or an optionally substituted heterocyclic group. The hydrocarbon group may contain oxygen, nitrogen or silicon.

Examples of the “hydrocarbon group” include an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an aryl group, an arylalkyl group, an arylalkenyl group, and an arylcycloalkyl group.
The “alkyl group” is preferably a linear or branched alkyl group having 1 to 10 carbon atoms, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group. N-pentyl group, isopentyl group, neopentyl group, 2-methylbutyl group, 2,2-dimethylpropyl group, n-hexyl group, isohexyl group n-heptyl group, n-octyl group, nonyl group, isononyl group, decyl group Etc.
The “cycloalkyl group” is preferably a cycloalkyl group having 3 to 10 carbon atoms, and examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group.

An “alkenyl group” is a hydrocarbon group having a carbon-carbon double bond at any one or more positions. A straight chain or branched chain alkenyl group having 2 to 10 carbon atoms is preferable, for example, an ethenyl group, a prop-1-en-1-yl group, a prop-2-en-1-yl group, and a prop-1-ene- 2-yl group, but-1-en-1-yl group, but-2-en-1-yl group, but-3-en-1-yl group, but-1-en-2-yl group, butane -3-en-2-yl group, penta-1-en-1-yl group, penta-4-en-1-yl group, penta-1-en-2-yl group, penta-4-en-2 -Yl group, 3-methyl-but-1-en-1-yl group, hexa-1-en-1-yl group, hexa-5-en-1-yl group, hepta-1-en-1-yl Group, hepta-6-en-1-yl group, octa-1-en-1-yl group, octa-7-en-1-yl group and the like.
The “cycloalkenyl group” is a cyclic hydrocarbon group having a carbon-carbon double bond at any one or more positions. A cycloalkenyl group having 3 to 10 carbon atoms is preferable, for example, a 1-cyclopenten-1-yl group, a 2-cyclopenten-1-yl group, a 1-cyclohexen-1-yl group, a 2-cyclohexen-1-yl group, 3-cyclohexen-1-yl group etc. are mentioned.

The “aryl group” is preferably an aryl group having 6 to 14 carbon atoms, and examples thereof include a phenyl group, a naphthyl group, an anthracen-1-yl group, and a phenanthren-1-yl group.
The “arylalkyl group” is preferably a C _6-14 aryl C _1-10 alkyl group, and is a benzyl group, a phenethyl group, a 3-phenyl-n-propyl group, a 4-phenyl-n-butyl group, a 5-phenyl-n. -Pentyl group, 8-phenyl-n-octyl group, naphthylmethyl group and the like.
The “arylalkenyl group” is preferably a C _{6-14 arylC 2-10} alkenyl group, such as a styryl group, 3-phenyl-prop-1-en-1-yl group, 3-phenyl-prop-2-ene. -1-yl group, 4-phenyl-but-1-en-1-yl group, 4-phenyl-but-3-en-1-yl group, 5-phenyl-pent-1-en-1-yl group 5-phenyl-pent-4-en-1-yl group, 8-phenyl-oct-1-en-1-yl group, 8-phenyl-oct-7-en-1-yl group, naphthylethenyl group, etc. Can be mentioned.
The “arylcycloalkyl group” is preferably a C _{6-14 arylC 3-10} cycloalkyl group, for example, a 3-phenylcyclopropyl group, a 3-phenylcyclobutyl group, a 4-phenylcyclopentyl group, a 4-phenylcyclohexyl group. , 4-naphthylcyclohexyl group and the like.

  The “heterocyclic group” is preferably a 5- to 11-membered heterocyclic group containing 1 to 3 heteroatoms selected from a nitrogen atom, an oxygen atom and a sulfur atom in addition to a carbon atom, such as a 2-furyl group, 3-furyl group, 2-thienyl group, 3-thienyl group, pyrrol-1-yl group, pyrrol-2-yl group, pyrrol-3-yl group, pyridin-2-yl group, pyridine -3-yl group, pyridin-4-yl group, pyrazin-2-yl group, pyrazin-3-yl group, pyrimidin-2-yl group, pyrimidin-4-yl group, pyrimidin-5-yl group, pyridazine- 3-yl group, pyridazin-4-yl group, 1,3-benzodioxol-4-yl group, 1,3-benzodioxol-5-yl group, 1,4-benzodioxan-5-yl Group, 1,4-benzodioxan-6-yl group, 3,4-dihydride -2H-1,5-benzodioxepin-6-yl group, 3,4-dihydro-2H-1,5-benzodioxepin-7-yl group, 2,3-dihydrobenzofuran-4-yl group 2,3-dihydrobenzofuran-5-yl group, 2,3-dihydrobenzofuran-6-yl group, 2,3-dihydrobenzofuran-7-yl group, benzofuran-4-yl group, benzofuran-5-yl group Benzofuran-6-yl group, benzofuran-7-yl group, benzothiophen-4-yl group, benzothiophen-5-yl group, benzothiophen-6-yl group, benzothiophen-7-yl group, quinoxaline-2 -Yl group, quinoxalin-5-yl group, quinoxalin-6-yl group, indol-4-yl group, indol-5-yl group, indol-6-yl group, indole 7-yl group, isoindol-4-yl group, isoindol-5-yl group, isoindol-6-yl group, isoindol-7-yl group, isobenzofuran-4-yl group, isobenzofuran-5 Yl group, isobenzofuran-6-yl group, isobenzofuran-7-yl group, chromen-5-yl group, chromen-6-yl group, chromen-7-yl group, chromen-8-yl group, imidazole-1 -Yl group, imidazol-2-yl group, imidazol-4-yl group, imidazol-5-yl group, pyrazol-1-yl group, pyrazol-3-yl group, pyrazol-4-yl group, thiazol-2- Yl, thiazol-4-yl, thiazol-5-yl, oxazol-2-yl, oxazol-4-yl, oxazol-5-yl, isooxy Sazol-3-yl group, isoxazol-4-yl group, isoxazol-5-yl group, pyrimidin-2-yl group, pyrimidin-4-yl group, pyrimidin-5-yl group, pyridin-2-yl group , Pyridin-3-yl group, pyridin-4-yl group, pyrrolidin-2-yl group, pyrrolidin-3-yl group, benzimidazol-1-yl group, benzimidazol-2-yl group, benzothiazol-2- Yl group, benzoxazol-2-yl group, quinolin-2-yl group, quinolin-3-yl group, quinolin-4-yl group, isoquinolin-1-yl group, isoquinolin-3-yl group, isoquinolin-4- Yl group, 1,3,4-thiadiazol-2-yl group, morpholin-4-yl group and the like.

In formula (I), X represents a hydroxyl group or a hydrolyzable group.
A hydrolyzable group is, for example, a group that can be hydrolyzed to form a silanol group or a siloxane condensate by heating at 25 ° C. to 100 ° C. in the presence of no catalyst and excess water. Specifically, an alkoxy group, an acyloxy group, a halogen group, an isocyanate group and the like can be mentioned, and an alkoxy group having 1 to 6 carbon atoms or 1 to 8 carbon atoms (of a carbonyl group). Acyloxy groups) are preferred.

  Examples of the alkoxy group having 1 to 6 carbon atoms include a methyloxy group, an ethyloxy group, a propyloxy group, an isopropyloxy group, an n-butyloxy group, an isobutyloxy group, a t-butyloxy group, and a hexyloxy group. Examples of the acyloxy group of 1 to 8 include an acetyloxy group and a benzoyloxy group. Examples of the halogen include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Examples of the isocyanate group include an isocyanate group bonded to an alkyl group, an isocyanate group bonded to a cycloalkyl group, an isocyanate group bonded to an aryl group, an isocyanate group bonded to an alkyl group substituted with a cycloalkyl group, and an aryl group. And an isocyanate group bonded to the alkyl group.

Examples of the organosilicon compound represented by the formula (I) are as follows.
Glycidyltrimethoxysilane,
Glycidyltrichlorosilane,
Glycidyl triacetyloxysilane,
Glycidyl tribenzoyloxysilane,
3-glycidoxymethyltrimethoxysilane,
3-glycidoxymethyl triacetyloxysilane,
3-glycidoxymethyltribenzyloxysilane 3-glycidoxypropyltrimethoxysilane,
3-glycidoxypropyltriethoxysilane,
3-glycidoxypropylmethyldiethoxysilane,
3-glycidoxypropylmethyldimethoxysilane,
3-glycidoxypropyl chlorodimethoxysilane,
2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane and the like.
These compounds can be used individually by 1 type or in mixture of 2 or more types.

  The condensate of the organosilicon compound is not particularly limited as long as it is a condensation degree capable of forming a sol, but the average particle size is preferably 50 nm or less, and more preferably 20 nm or less. The condensate can be produced by the method described in the section on preparation of the composition.

2) Photocatalyst Any form of the photocatalyst used in the present invention can be used as long as it shows photocatalytic activity such as powder, sol, and solution. When using a sol-like photocatalyst, if the particle diameter is 20 nm or less, preferably 10 nm or less, the transparency is improved and the linear transmittance is increased. Particularly preferred when applied to the body. In addition, in the case where a color or pattern is printed on the base carrier, if the transparent photocatalyst layer is applied, the base color or pattern is not impaired.

The _{photocatalyst, TiO 2, ZnO, SrTiO 3} , CdS, GaP, InP, GaAs, BaTiO 3, KNbO 3, Fe 2 O 3, Ta 2 O 5, WO 3, SnO 2, Bi 2 O 3, NiO, Cu ₂ O, SiC, SiO ₂ , MoS ₂ , InPb, RuO ₂ , CeO _2, etc., and these photocatalysts, metals such as Pt, Rh, RuO ₂ , Nb, Cu, Sn, Ni, Fe and their metals What added the oxide of these can be used. In addition, these photocatalysts obtained by adding a metal such as Pt, Rh, RhO ₂ , Nb, Cu, Sn, Ni, and Fe using a photocatalytic reduction action can be used. The higher the content of the photocatalyst, the higher the catalytic activity. However, from the viewpoint of adhesiveness, the content is preferably 70% by weight or less based on the total solid content.
As the photocatalyst, not only the ultraviolet responsive type but also a visible light responsive type photocatalyst can be used. For example, metal oxide doped type, oxygen defect type, nitrogen (nitrogen compound) type doped titanium oxide, etc. Can be mentioned.

3) Metal oxide or hydroxide The metal oxide or hydroxide used in the present invention has an effect of fixing the photocatalyst and firmly adhering to the substrate, and has activity as a photocatalyst. Is not included. When this metal oxide or hydroxide is used as a raw material, it is preferably used in a sol state. The metal oxide or hydroxide sol gels after being applied to the substrate. If it is less than 5% by weight, the adhesion with the adhesive layer is insufficient, and if it exceeds 50% by weight, the photocatalytic activity becomes insufficient.
Preferred examples of the metal component include silicon, aluminum, titanium, zirconium, magnesium, niobium, tantalum, tungsten, and tin. In particular, aluminum is preferable.
In addition, an oxide or hydroxide containing two or more metals selected from silicon, aluminum, titanium, zirconium, and niobium can be used as the metal component.

  The metal oxide or metal hydroxide sol used as a raw material may be a commercially available one. For example, as described in Japanese Patent No. 3609262, (1) a hydrated metal oxide is converted to a monobasic acid or a salt thereof. Or by dialysis after adding a metal tetrachloride compound to low-temperature water, or (3) adding a metal alkoxide to an aqueous hydrochloric acid solution.

Examples of commercially available silica sols include, for example, Nissan Chemical Industries, Ltd., methanol silica sol and isopropanol silica sol; Catalyst Kasei Kogyo Co., Ltd., Oscar. Examples of the alumina sol include alumina sol 520, 100, and 200 manufactured by Nissan Chemical Industries, Ltd .; alumina clear sol, alumina sol 10, and 132 manufactured by Kawaken Fine Chemical Co., Ltd.
These metal oxide or metal hydroxide sols can be used alone or in combination of two or more, and alumina sol is particularly preferable.

4) Other components In the composition of the present invention, a filler may be added and dispersed separately for coloring and thickening of the resulting coating film. Examples of such fillers include water-insoluble organic pigments and inorganic pigments, particulate, fibrous or scale-like ceramics, metals or alloys other than pigments, and oxides and hydroxides of these metals. , Carbides, nitrides, sulfides and the like.

  Specific examples of the filler include iron, copper, aluminum, nickel, silver, zinc, ferrite, carbon black, stainless steel, silicon dioxide, titanium oxide for pigment, aluminum oxide, chromium oxide, manganese oxide, iron oxide, and oxidation. Zirconium, cobalt oxide, synthetic mullite, aluminum hydroxide, iron hydroxide, silicon carbide, silicon nitride, boron nitride, clay, diatomaceous earth, slaked lime, gypsum, talc, barium carbonate, calcium carbonate, magnesium carbonate, barium sulfate, bentonite, Mica, Zinc green, Chrome green, Cobalt green, Viridian, Guinea green, Cobalt chromium green, Shale green, Green earth, Manganese green, Pigment green, Ultramarine, Bitumen, Pigment green, Rock ultramarine, Cobalt blue, Cerulean blue, Boric acid Copper, molybdenum blue, copper sulfide, cobalt purple Mars Purple, Manganese Purple, Pigment Violet, Lead Oxide, Calcium Leadate, Zinc Yellow, Lead Sulfide, Chrome Yellow, Ocher, Cadmium Yellow, Strontium Yellow, Titanium Yellow, Resurge, Pigment Yellow, Cuprous Oxide, Cadmium Red, Selenium Red , Chrome vermilion, bengara, zinc white, antimony white, basic lead sulfate, titanium white, lithopone, lead silicate, zircon oxide, tungsten white, lead, zinc white, bunchison white, lead phthalate, manganese white, lead sulfate Graphite, bone black, diamond black, thermatomic black, vegetable black, potassium titanate whisker, molybdenum disulfide, and the like. These fillers can be used alone or in admixture of two or more. The amount of the filler used is usually 300 parts by weight or less with respect to 100 parts by weight of the total solid content of the composition.

  Furthermore, the composition of the present invention may optionally contain a known dehydrating agent such as methyl orthoformate, methyl orthoacetate, tetraethoxysilane; polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene fatty acid ester, Dispersants such as polycarboxylic acid type polymer surfactant, polycarboxylate, polyphosphate, polyacrylate, polyamide ester salt, polyethylene glycol; methylcellulose, ethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, etc. Thickeners such as celluloses, castor oil derivatives, ferrosilicates; ammonium carbonate, ammonium bicarbonate, ammonium nitrite, sodium borohydride, calcium azide In addition to inorganic foaming agents, azo compounds such as azobisisobutyronitrile, hydrazine compounds such as diphenylsulfone-3,3'-disulfohydrazine, organic foaming agents such as semicarbazide compounds, triazole compounds, and N-nitroso compounds In addition, other additives such as a surfactant, a silane coupling agent, a titanium coupling agent, and a dye may be blended.

  Moreover, a leveling agent can be mix | blended in order to improve the coating property of a composition more. Among such leveling agents, examples of fluorine-based leveling agents (trade names; the same applies hereinafter) include BM1000 and BM1100 of BM-CHEMIE; Fuka 772 and Fuka 777 of Fuka Chemicals; Examples include the Floren series manufactured by Kagaku Co., Ltd .; the FC series manufactured by Sumitomo 3M Co., Ltd .; the Fluoronal TF series manufactured by Toho Chemical Co., Ltd., etc. Examples of silicone leveling agents include BYK series manufactured by BYK Chemie Corporation; Sshmego series from Sshmegmann; Fuka 30, Fuka 31, Fuka 34, Efka 35, Efka 36, Efka 39, Efka 83, Efka 86, Efka 88, etc. from Efka Chemicals can be mentioned. Ester-based The coupling agent, for example, Kafinoru of Nissin Chemical Industry Co., Kao Corp. Emulgen, and the like Homogenol.

  Moreover, you may blend other resin with the composition used for this invention. Examples of other resins include acrylic-urethane resins, epoxy resins, polyesters, acrylic resins, fluororesins, acrylic resin emulsions, epoxy resin emulsions, polyurethane emulsions, and polyester emulsions.

(2) Preparation method of composition for photocatalyst coating In order to prepare the composition of this invention, the following two processes are performed. That is,
First Step Formula (I)
R _n SiX _4-n (I)
(In the formula, R represents an organic group having an epoxy group, X represents a hydroxyl group or a hydrolyzable group. N represents 1 or 2, and when n is 2, each R may be the same or different, (When n is 2 or more, each X may be the same or different.) The organic silicon compound represented by (4) is condensed in a solvent in the presence of water and a silanol condensation catalyst.
Second Step A photocatalyst-containing coating composition is produced by mixing the condensate of the organosilicon compound obtained in step (A), a photocatalyst, and a metal oxide and / or hydroxide in a solvent.

  In the second step, the photocatalyst and the metal oxide and / or hydroxide may be added to the liquid of the condensate of the organosilicon compound, or the mixed liquid of the photocatalyst and the metal oxide and / or hydroxide. Alternatively, a liquid of a condensate of an organosilicon compound may be added. The solvent used here can be the same as that used in the first step. The form of the condensate, photocatalyst, metal oxide and metal hydroxide of the organosilicon compound is not particularly limited, but is preferably used in the form of a sol.

The method of the first step is as follows.
The organosilicon compound, water and silanol condensation catalyst are mixed in a solvent. Although there will be no restriction | limiting in particular if the usage-amount of a silanol condensation catalyst is a range used as a catalyst, Usually, it is 0.001-0.2 mol with respect to 1 mol of organosilicon compounds.
The water to be used is not particularly limited as long as it is sufficient to hydrolyze the organosilicon compound, but it is usually 1 to 10 moles per mole of the organosilicon compound.

The reaction temperature is 0 to 100 ° C., and the reaction time is 1 hour to 10 days.
As the solvent, water, ethanol solvents such as methanol, ethanol, n-propanol, and n-butanol can be used singly or in combination of two or more. In addition, a solvent such as an ester solvent such as methyl acetate or ethyl acetate; a ketone solvent such as acetone or diethyl ketone; an ether solvent such as diethyl ether or tetrahydrofuran;

The silanol condensation catalyst used in the present invention includes at least one compound selected from the group consisting of metal oxides, metal hydroxides, metal alkoxides, partial hydrolysis products of metal alkoxides, acid catalysts, and the like. Of these, metal oxides are preferable, and titanium oxide fine particles are particularly preferable.
Below, each silanol condensation catalyst is explained in full detail.

The 1) the metal oxide in the metal oxide is not particularly _limited, is like _{TiO 2, ZrO 2, Al 2} O 3, in particular of the TiO ₂ fine particles are preferable.
Hereinafter, particularly, but describes the preparation method of nanoparticles of TiO _2, preparation method is not limited thereto. Other metal oxides can be similarly prepared.

Titanium oxide nanoparticles obtained by mixing a titanium chelate compound in which a hydrolyzable group and a chelate ligand are bonded to a titanium atom, and a large excess of water with respect to the titanium chelate compound, Usually used in a state dispersed in an organic solvent.
The titanium chelate compound is not particularly limited as long as it is a titanium compound in which a hydrolyzable group and a chelate ligand are bonded to a titanium atom.
The valence of the titanium atom which is the central metal atom is usually 2 to 4, preferably 4.

The hydrolyzable group is not particularly limited as long as it is a group that reacts with water and decomposes. Specific examples include an alkoxyl group which may have a substituent, an acyloxy group which may have a substituent, a halogen atom, an isocyanate group, a cyano group, an amino group, an amide group, and the like.
Examples of the alkoxyl group which may have a substituent include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, a sec-butoxy group, a t-butoxy group, an n-pentyloxy group, Examples include n-hexyloxy group.
Examples of the acyloxy group which may have a substituent include an acetoxy group, a propionyloxy group, an n-propylcarbonyloxy group, an isopropylcarbonyloxy group, and an n-butylcarbonyloxy group.
Examples of the substituent for the alkoxyl group and acyloxy group include a halogen atom, a carboxyl group, an amide group, an imide group, an ester group, and a hydroxyl group.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

Among these, an alkoxyl group which may have a substituent, an acyloxy group which may have a substituent, a halogen atom or an isocyanate group are preferable, and an alkoxyl group which may have a substituent is more preferable. Particularly preferred are alkoxy groups having 1 to 4 carbon atoms.
The chelate ligand is not particularly limited as long as it can bind to a metal to form a chelate, and may be a neutral ligand or an anion. What is necessary is just to couple | bond with the metal atom at at least one place, and it may be a monodentate ligand or a polydentate ligand. For example, even if it is a bidentate ligand, it does not need to be bound to one metal atom by bidentate.
Specific examples of the chelate ligand include the following. However, it illustrates as a chelate compound which can become a chelate ligand.

Saturated aliphatic dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid and sebacic acid; β-diketones such as acetylacetone, benzoylacetone and hexafluoroacetylacetone; Β-ketoesters such as methyl acetate and ethyl acetoacetate; glycols such as ethylene glycol; glycolic acids such as oxyacetic acid; ethylenediaminetetraacetic acid (EDTA) and its sodium salt, ethylenediamine, 1,3-propanediamine, diethylenetriamine, penta Nitrogen-containing compounds such as methyldiethylenetriamine, hexamethyltriethylenetetramine, tris [2- (dimethylamino) ethyl] amine, tri (pyridinylmethyl) amine;
Furancarboxylic acid, thiophenecarboxylic acid, nicotinic acid, isonicotinic acid, phenanthroline, diphenanthroline, substituted phenanthroline, 2,2 ': 6', 2 "-terpyridine, pyridineimine, bridged aliphatic diamine, 4-4'-di (5-nonyl) -2,2′-bipyridine, bipyridine coordinated with O, S, Se, Te, alkyliminopyridine, alkylbipyridinylamine, alkyl-substituted tripyridine, di (alkylamino) alkylpyridine, ethylenediaminedi Pyridine, other heterocyclic compounds;

Sulfur-containing compounds such as mercapto alcohols such as 2-mercaptoethanol; dithiols such as ethanedithiol; mercaptoamines such as 2-mercaptoethylamine; dithioketones such as 2,4-pentanedithione;
These can be used alone or in combination of two or more. There is no restriction | limiting in particular as a manufacturing method of a titanium chelate compound, For example, the method etc. which add a predetermined amount chelate compound to the organic solvent solution of the titanium alkoxide compound mentioned later etc. are mentioned. The addition amount of the chelate compound is usually 1 to 5 times mol, preferably 1 to 3 times mol for 1 mol of the titanium alkoxide compound.

The method for producing a dispersion of titanium oxide which is a hydrolysis product of a titanium chelate compound is described in detail in WO 2006-87986 pamphlet, and can be performed based on this.
The content of titanium oxide in the dispersion is 0.1 to 10% by weight, preferably 0.1 to 5% by weight, in terms of titanium oxide, with respect to the entire dispersion.

  The dispersion is a dispersion of titanium oxide particles having the property that fine particles of titanium oxide, which is a hydrolysis product of a titanium chelate compound, are stably dispersed without agglomerating in an aqueous solvent or an organic solvent. is there. Here, the state of being stably dispersed without agglomeration represents a state in which the dispersoid of a hydrolysis product such as a titanium chelate compound in an organic solvent is not coagulated and separated non-uniformly, preferably Represents a transparent and homogeneous state. Here, transparent means a state in which the transmittance in visible light is high. Specifically, the concentration of the dispersoid is 0.5% by weight in terms of oxide, the optical path length of the quartz cell is 1 cm, and the control sample is This is a state in which an organic solvent is used and the transmittance is preferably 80 to 100%, expressed by spectral transmittance measured under the condition that the wavelength of light is 550 nm.

  Although the particle diameter of the titanium oxide particle contained in a dispersion liquid is not specifically limited, Usually, 1-100 nm, Preferably it is 1-50 nm, More preferably, it is the range of 1-20 nm. The titanium oxide particles are preferably monodispersed.

2) Metal hydroxide Although it does not specifically limit as a metal hydroxide, Ti (OH) ₄ , Zr (OH) ₄ , Al (OH) ₃ etc. are mentioned.

3) Metal alkoxides The metal alkoxides are not particularly limited, but titanium, zirconium, aluminum, silicon, iron, germanium, indium, tin, tantalum, and the like can be obtained because an organic thin film having excellent transparency can be obtained. Preference is given to alkoxides of at least one metal selected from the group consisting of zinc, tungsten and lead.
The number of carbon atoms of the alkoxy group of the metal alkoxide is not particularly limited, but one having 1 to 4 carbon atoms is more preferable from the viewpoint of the concentration of the contained oxide, the ease of detachment of organic substances, the availability, and the like.

Specific examples of metal alkoxides used in the present invention include Si (OCH ₃ ) ₄ , Si (OC ₂ H ₅ ) ₄ , Si (OC ₃ H ₇ -i) ₄ , Si (OC ₄ H ₉ -t) _4. Silicon alkoxides such as Ti (OCH ₃ ) ₄ , Ti (OC ₂ H ₅ ) ₄ , Ti (OC ₃ H ₇ -i) ₄ , Ti (OC ₄ H ₉ ) _{4 and} other titanium alkoxides; Ti [OSi (CH ₃ ) ₃ ] ₄ , tetrakistrialkylsiloxytitanium such as Ti [OSi (C ₂ H ₅ ) ₃ ] ₄ ; Zr (OCH ₃ ) ₄ , Zr (OC ₂ H ₅ ) ₄ , Zr (OC ₃ H ₇ ) ₄ Zr (OC ₄ H ₉ ) _{4 and} other zirconium alkoxides; Al (OCH ₃ ) ₄ , Al (OC ₂ H ₅ ) ₄ , Al (OC ₃ H ₇ -i) ₄ , Al (OC ₄ H ₉ ) _{3 and the} like Aluminum Al Coxide; Germanium alkoxide such as Ge (OC ₂ H ₅ ) ₄ ; In (OCH ₃ ) ₃ , In (OC ₂ H ₅ ) ₃ , In (OC ₃ H ₇ -i) ₃ , In (OC ₄ H ₉ ) ₃ Indium alkoxides such as Sn (OCH ₃ ) ₄ , Sn (OC ₂ H ₅ ) ₄ , Sn (OC ₃ H ₇ -i) ₄ , Sn (OC ₄ H ₉ ) ₄ etc. Tin alkoxides; Ta (OCH ₃ ) ₅ , tantalum alkoxides such as Ta (OC ₂ H ₅ ) ₅ , Ta (OC ₃ H ₇ -i) ₅ , Ta (OC ₄ H ₉ ) ₅ ; W (OCH ₃ ) ₆ , W (OC ₂ H ₅ ) ₆ , W (OC ₃ H ₇ -i) ₆ , tungsten alkoxides such as W (OC ₄ H ₉ ) ₆ ; zinc alkoxides such as Zn (OC ₂ H ₅ ) ₂ ; lead alkoxides such as Pb (OC ₄ H ₉ ) ₄ ; Etc. It is. These metal alkoxides can be used alone or in combination of two or more.

In the present invention, as a metal alkoxide, a reaction of a composite alkoxide obtained by reaction of two or more metal alkoxides, one or more metal alkoxides, and one or two or more metal salts. It is also possible to use a composite alkoxide obtained by the above and a combination thereof.
The composite alkoxide obtained by the reaction of two or more kinds of metal alkoxides includes a complex alkoxide obtained by the reaction of an alkali metal or alkaline earth metal alkoxide and a transition metal alkoxide, or a complex salt by a combination of Group 3B elements. The compound alkoxide obtained by the form of this can be illustrated.

Specific _{examples, BaTi (OR) 6, SrTi} (OR) 6, BaZr (OR) 6, SrZr (OR) 6, LiNb (OR) 6, LiTa (OR) 6 , and, combinations thereof, LiVO ( OR) ₄ , MgAl ₂ (OR) ₈ , (RO) ₃ SiOAl (OR ′) ₂ , (RO) ₃ SiOTi (OR ′) ₃ , (RO) ₃ SiOZr (OR ′) ₃ , (RO) ₃ SiOB ( OR ′) ₂ , (RO) ₃ SiONb (OR ′) ₄ , (RO) ₃ SiOTa (OR ′) _4, etc., and reaction products of the above metal alkoxides and polycondensates thereof. Here, R and R ′ represent an alkyl group or the like.

  Examples of the composite alkoxide obtained by reaction of one or more metal alkoxides with one or more metal salts include compounds obtained by reaction of metal salts with metal alkoxides. .

  Examples of the metal salt include chlorides, nitrates, sulfates, acetates, formates, oxalates, and the like, and examples of the metal alkoxides include those similar to the metal alkoxides described above.

4) Partial hydrolysis product of metal alkoxide The partial hydrolysis product of metal alkoxide is obtained before the metal alkoxide is completely hydrolyzed, and exists in an oligomer state.
As a method for producing a partial hydrolysis product of a metal alkoxide, 0.5 to 2.0 times less water than the above exemplified metal alkoxide is used in an organic solvent, and the organic solvent reflux temperature is from −100 ° C. A method of hydrolyzing within a range can be preferably exemplified. Specifically, for example, it can be produced by a method described in JP-A-2007-125548.

5) Acid catalyst Acid catalysts include mineral acids such as hydrochloric acid, nitric acid, boric acid, borohydrofluoric acid, organic acids such as acetic acid, formic acid, oxalic acid, carbonic acid, trifluoroacetic acid, p-toluenesulfonic acid, and methanesulfonic acid. An acid etc. can be illustrated. Furthermore, photoacid generators that generate an acid upon irradiation with light, specifically, diphenyliodonium hexafluorophosphate, triphenylphosphonium hexafluorophosphate, and the like can be exemplified.

6) Other silanol condensation catalysts Examples of other silanol condensation catalysts include carboxylic acid metal salts, carboxylic acid ester metal salts, carboxylic acid metal salt polymers, carboxylic acid metal salt chelates, titanate esters, and titanate ester chelates. be able to.

(3) Coating method of photocatalyst coating composition on carrier As a method of supporting the photocatalyst coating composition of the present invention on a carrier, a resin solution is printed, sheet molding, spray spraying, dip coating, spin coating A method of coating by a coating method or the like and drying can be used. The drying temperature is appropriately selected depending on the type of solvent and resin.

(4) Applications Structures coated with the photocatalyst-containing composition of the present invention are architectural paints, wallpaper, window glass, blinds, curtains, carpets, lighting fixtures, lighting lamps, black lights, ship bottoms / fishing net antifouling paints, water It can be used for processing fillers, agricultural films, herbicidal sheets, packaging materials, and the like. In addition, a photocatalyst carrier that can be used even in a high-temperature and high-humidity environment is also possible.
The shape of the glass that can be used as the carrier may be any complicated shape such as a plate shape, a tubular shape, a spherical shape, or a fibrous shape. If the size is 10 μm or more, it can be firmly supported. Moreover, depending on uses, such as a constructed window glass, a showcase, and glasses, it can also be set as photocatalyst carrying glass by processing into processed glass.

Glass carrying a photocatalyst layer according to the present invention includes window glass, instrument cover glass, lighting fixtures, illumination lamps, black light, water treatment fillers, cameras, spectacle lenses, etc., antibacterial, deodorant, antifouling, etc. It can be used for any use scene that requires the effect of.
The plastic molded article carrying the photocatalyst layer according to the present invention requires antibacterial, deodorizing, antifouling, etc., including wallpaper, interior boards, furniture, electrical equipment, vehicle parts, cameras, glasses lenses, etc. Can be used for many use situations.
The shape of the plastic molded body may be any complicated shape such as a film shape, a plate shape, a tubular shape, a spherical shape, or a fibrous shape. If the size is 10 μm or more, it can be firmly supported. In addition, depending on applications such as construction materials, home appliances, and glasses that have already been constructed, the processed plastic molded product can be processed into the photocatalyst-supported plastic molded product of the present invention. It can be said that it is wide.

Fabrics that can be used as carriers include natural fibers such as hair, silk, cotton, and linen, regenerated fibers such as rayon and acetate, synthetic fibers such as nylon, acrylic, polyamide, polyester, polyacrylonitrile, and polyvinyl chloride, and aramid. Examples include woven fabrics, knitted fabrics, and non-woven fabrics composed of heat-resistant fibers alone or blended fibers. Also, fabrics treated with water repellents such as silicon water repellents, fluorine water repellents such as perfluoroalkyl acrylate, zirconium salt water repellents, ethylene urea water repellents, and durability as required. Water-repellent processed fabrics that use ethyleneimine-based, epoxy-based, and melamine-based crosslinkers together to improve, artificial leather made of fibrillated composite fibers of polyamide and polyester, woven fabrics, non-woven fabrics, knitted fabrics, etc. Synthetic leather or the like in which a polyurethane resin layer is formed on a base material such as cloth via a polyurethane adhesive can also be used. Moreover, it can also be set as the photocatalyst carrying | support cloth of this invention by processing to processed cloths, such as an umbrella, a tent, a bag.
The fabric carrying the photocatalyst layer according to the present invention has many uses such as antibacterial, deodorizing, and antifouling effects, such as interior products such as curtains and wallpaper, daily necessaries such as tents, umbrellas, and tablecloths, and food packaging. It can also be used in the agricultural field such as nursery sheets as a material.

Examples of the metal carrying the photocatalyst layer according to the present invention include various metals such as stainless steel, brass, brass, aluminum alloy and titanium alloy in addition to simple metals such as aluminum, iron and copper. Depending on the shape and material of the metal used, a photocatalyst layer according to the present invention may be provided on a metal sheet or plate coated with a normal paint, a colored color steel plate, a color aluminum sash, or the like to form a photocatalyst carrier. Can do. In this case, it is preferable that the light transmittance of the photocatalyst layer is high and transparent, since the hue of the underlying paint is not impaired.
The metal shape may be any complicated shape such as a plate shape, a tubular shape, a spherical shape, a fiber shape, and a sheet shape. If the size is 10 microns or more, it can be firmly supported. Moreover, depending on uses, such as a constructed window frame, furniture, a showcase, and a spectacle frame, it can also be set as the photocatalyst carrying metal of this invention by processing to a processed metal.
The metal carrying the photocatalyst layer according to the present invention requires window frames, furniture, decorations, interior panels, exterior panels, fillers for water treatment, strainers, filters, etc., such as antibacterial, deodorizing, and antifouling effects. Can be used for many usage scenes.

The shape of the wood and wood material provided with the photocatalyst layer according to the present invention can be any complicated shape such as a plate shape, a spherical shape, and a sheet shape. In addition, if the size is 10μm or more, it can be firmly supported. In addition to the finished walls, ceiling boards, pillars, processed wood and wood materials such as furniture and woodwork, The photocatalyst-supporting wood and wood material of the invention can also be used.
The wood and wood material carrying the photocatalyst layer according to the present invention can be used in many usage scenes that require antibacterial, deodorizing, antifouling and other effects such as building materials, furniture, woodwork, interior materials and interior materials.
The plastic film provided with the photocatalyst carrying structure according to the present invention makes use of its antifouling, antibacterial, and deodorizing functions to form a film in which an adhesive is applied to the surface not carrying the photocatalyst, so that automobiles and various transport equipment Can be affixed to the inside of glass windows, building glass windows, frozen and refrigerated showcases and greenhouses, etc. to decompose trace amounts of harmful substances in the interior space, prevent contamination of the glass surface, and prevent scattering It is possible to make a film having high transparency that is effective for the above. Moreover, what formed into a film the photocatalyst support structure which concerns on this invention in the thin plastic film can be used also as a wrap film for food packaging. Resins that can be used for this plastic film include polyethylene terephthalate resin, polycarbonate resin, polyacrylate resin, polymethyl methacrylate resin, polyethylene resin, polypropylene resin, polyamide resin, polyimide resin, polystyrene resin, polyvinyl chloride resin, polyfluoride resin. A highly transparent synthetic resin having a linear transmittance of light having a wavelength of 550 nm of 50% or more when molded into a film such as vinylidene resin, fluorinated ethylene-propylene copolymer resin, or fluorinated ethylene-ethylene copolymer resin. Either film or sheet can be used. In addition, since the photocatalyst-supporting structure according to the present invention is transparent on the surface of an opaque material in which an adhesive layer and a release film are provided on the back surface of a wallpaper or a decorative sheet and a pattern is printed on the surface, the underlying wallpaper or decorative sheet Since it does not impair the pattern or pattern printed on the film, it can be preferably used.

  These synthetic resin films or sheets can be surface-treated to improve the adhesion of the photocatalyst-supporting structure, and the surface on which the photocatalyst layer is applied can be surfaced by corona discharge treatment or UV-ozone treatment. It is also possible to preferably use a material that is physically oxidized in a very small amount or is thinly coated with a surface treatment agent such as silicon to improve the familiarity with the photocatalyst layer. Furthermore, as shown in the examples, it is possible to form a thin film for providing heat ray reflection / shielding function or ultraviolet light reflection / shielding function on the front or back surface of these base materials, and to provide antifouling / antibacterial properties. -In addition to being able to be a heat ray reflective film or UV cut film having a deodorizing function, the photocatalyst-supporting structure according to the present invention has extremely high durability and photocatalytic activity, so it has extremely high added value. High product.

  EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited to an Example.

上記各成分の固形分を固形分全体に対する割合で示すと以下のとおりである。

[Examples 1 to 3]
<Preparation of photocatalyst layer forming coating solution>
Dissolve 303.03 g of diisopropoxybisacetylacetonate titanium (manufactured by Nippon Soda Co., Ltd., T-50, solid content in terms of titanium oxide: 16.5% by weight) in 584.21 g of ethanol solvent, and then ion-exchange with stirring. 112.76 g of water (10-fold mol / mol of titanium oxide) was slowly added dropwise to cause hydrolysis. One day later, the solution was filtered to obtain a yellow transparent titanium oxide nanodispersion [A-1] having a titanium oxide equivalent concentration of 5% by weight. The average particle size of titanium oxide was 4.1 nm and was monodispersed. As the organosilicon compound, 3-glycidoxypropyltrimethoxysilane [B-1] (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-403) was used. [C-1] was prepared by mixing 427.25 g of the above [A-1] and 572.75 g of [B-1] so that the element ratio (Ti / Si = 1/9) was obtained, and stirring for 12 hours. Furthermore, aluminum sol 10A (10% boehmite alumina colloid aqueous solution manufactured by Kawaken Fine Chemical Co., Ltd.) [D-1] is used as the aluminum compound, and nitric acid acidic titania sol dispersion (crystal particle diameter 8 nm) [E-1] is used as the photocatalyst. 1] Liquid, [D-1] liquid, and [E-1] liquid were mixed and prepared to obtain a photocatalyst layer-forming coating liquid [F-1].
<Composition of coating solution for forming photocatalyst layer>

It is as follows when solid content of each said component is shown in the ratio with respect to the whole solid content.

<Preparation of photocatalyst layer>
The film-forming solution [F-1] obtained above was formed into a film on the carrier [TA-1] using a bar coater, and dried at 100 ° C. for 30 minutes in a hot-air circulating drier. A photocatalyst layer of 1 μm to 10 μm was obtained.
Carrier [TA-1] is a soda lime glass plate.

<Performance test of photocatalyst carrying structure>
(1) Photocatalytic activity evaluation test The photocatalyst-supporting structure obtained above was cut into a size of 70 mm x 70 mm and placed in a 4 liter Pyrex (registered trademark) glass container. A mixed gas of air and aldehyde was added to the container so that the aldehyde concentration was 200 ppm. Next, the sample was irradiated with light from a black light (FL15BLB, manufactured by Toshiba Lighting & Technology Co., Ltd.) with an ultraviolet intensity of ² mW / cm ² for 24 hours, and the aldehyde gas concentration inside the container was measured by gas chromatography. Photocatalytic activity was evaluated. The evaluation results are shown in Table 3 below.

The evaluation criteria are as follows.
Performance evaluation by reduction of aldehyde gas concentration after irradiation for 24 hours 200 ppm or more A
100-200ppm B
100ppm or less C

(2) Measurement of haze ratio Using the carrier before supporting the adhesive layer and the photocatalyst layer as a reference, the total light transmittance at a wavelength of 550 nm and the haze ratio of each sample were recorded by a self-recording spectrophotometer (U-manufactured by Hitachi, Ltd.). 4000 type). The haze ratio (%) is calculated from the formula “(total light transmittance−linear transmittance) × 100 / total light transmittance”.
The evaluation results are shown in Table 3 below. The photocatalyst carrier structures of Examples 1 to 3 and Comparative Examples 1 to 3 formed on [TA-1] all exhibited excellent transparency with a haze ratio of 1% or less.

(3) Tape peeling test On the surface of each sample, 25 squares were formed at intervals of 2 mm by cuts, and adhesion was evaluated by a cross-cut tape method test specified in JIS K5400. Evaluations were made as ○ for those that did not peel, and × for those that did not peel. The evaluation results are shown in Table 3 below.

(4) Finger Friction Test A sample surface was rubbed with a finger, and the sample that was not peeled off was evaluated as ◯, and the sample that was peeled off was evaluated as ×. The evaluation results are shown in Table 2 below.

(5) Pencil hardness test It was performed according to JIS K5600-5-4. The evaluation results are shown in Table 3 below.

(6) Boiling test A tape peeling test was conducted after immersing the photocatalyst-supporting structure in boiling ion-exchanged water and tap water for 15 minutes. The evaluation results are shown in Table 3 below.

(7) Contact angle test After the sample was irradiated with light of black light (FL15BLB, manufactured by Toshiba Lighting & Technology Co., Ltd.) with an ultraviolet intensity of ² mW / cm ² for 48 hours, the amount of water drops was 0 using a solid-liquid interface analysis system DropMaster700 manufactured by Kyowa Interface Chemical Co., Ltd. A contact angle of 4 μL was measured. The evaluation results are shown in Table 3 below.

Claims (5)

(A) Formula (I)
R _n SiX _4-n (I)
(In the formula, R represents an organic group having an epoxy group, X represents a hydroxyl group or a hydrolyzable group. N represents 1 or 2, and when n is 2, each R may be the same or different, (When n is greater than or equal to 2, each X may be the same or different.) A condensate of an organosilicon compound represented by (b) a photocatalyst, and (c) a titanium atom with a hydrolyzable group Containing titanium oxide nanoparticles obtained by mixing a titanium chelate compound in which a chelate ligand is bound with a large excess of water with respect to the titanium chelate compound, and alumina , The composition of each of the above components is (a) = 5 to 90% by mass, (b) = 5 to 70% by weight, and (c) = 5 to 50% by weight with respect to the entire solid content. A composition for coating containing a photocatalyst. The photocatalyst-containing coating composition according to claim 1, wherein the photocatalyst is a titanium oxide. (A) Formula (I)
R _n SiX _4-n (I)
(In the formula, R represents an organic group having an epoxy group, X represents a hydroxyl group or a hydrolyzable group. N represents 1 or 2, and when n is 2, each R may be the same or different, (When n is 2 or more, each X may be the same or different.) In a solvent, water and a titanium atom, a hydrolyzable group, a chelate ligand, A step of condensing in the presence of titanium oxide nanoparticles obtained by mixing a titanium chelate compound formed by bonding a large excess of water with respect to the titanium chelate compound , and (B) a step in a solvent ( The method for producing a photocatalyst-containing coating composition according to claim 1, comprising a step of mixing the condensate of the organosilicon compound obtained in A), a photocatalyst, and alumina . The method for producing a photocatalyst-containing coating composition according to claim 3 , wherein the organosilicon compound is 3-glycidoxypropyltrimethoxysilane, and the silanol condensation catalyst is titanium oxide. A substrate carrying the composition for photocatalyst coating according to claim 1 or 2 .