JP2009039687A - Composition for forming photocatalyst layer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a chemical for forming a photocatalyst layer not requiring the process of heating at a high temperature and capable of being applied at a site. <P>SOLUTION: A composition for forming a photocatalyst layer contains photocatalyst particles and/or a photocatalyst sol, a silica sol in which colloidal silica particles are dispersed, an aluminum compound and zirconium acetate. Preferably, 0.1-6 wt.% of the photocatalyst particles and/or sol, 0.1-5 wt.% of the silica sol in which colloidal silica is dispersed, 0.1-5 wt.% of zirconium acetate and 0.1-9 wt.% of the aluminum compound are contained in terms of oxide against the whole composition for forming the photocatalyst layer. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a composition for forming a photocatalyst layer used for water purification, deodorization, antifouling, sterilization, wastewater treatment, growth control of algae, various chemical reactions, and the like, in particular, a composition for photocatalyst layer formation that can be cured at room temperature. .

Conventionally, a photocatalyst carrying structure in which a photocatalyst is carried on a carrier for the purpose of antibacterial, antifungal and decomposition of harmful substances by the action of the photocatalyst is known.
The photocatalyst layer can be formed by coating the photocatalyst layer forming coating solution on the surface of the carrier or adhesive layer by a printing method, a sheet forming method, a spray spraying method, a dip coating method, a spin coating method, and the like, followed by drying and curing. it can. Although the preferable temperature at the time of drying and curing varies depending on the carrier material and the resin material in the adhesive layer, it is usually about 50 ° C to 300 ° C.
However, until now, since heating at a high temperature is required for drying and curing, although it can be manufactured in a factory, it cannot be easily dried and cured after coating on site.
Accordingly, a photocatalyst-supporting structure that can be cured at room temperature has been developed. For example, room temperature curing is possible by using a binder. For example, in Patent Documents 1 and 2, as a binder, at least one selected from the group consisting of an organomonosilane containing a methyl group and an organosilane oligomer containing a methyl group, and as a curing catalyst, an acid, an alkali, a zinc compound, It describes that a paint containing a composition containing at least one selected from the group consisting of a titanium compound and a zirconium compound and titanium oxide for photocatalyst is prepared, applied onto a substrate, and dried and cured at room temperature. .
Further, in Patent Document 3, various binders such as colloidal silica, polysiloxane, silica, titanium, and aluminum, acrylic resin, acrylic modified resin, urethane resin, vinyl chloride resin, acrylic silicon resin, fluorine resin, It describes that it is cured at room temperature by using water glass, aluminum phosphate or the like.
However, using these binders alone is not sufficient as a photocatalyst layer, and further development has been desired.

JP 11-209691 A JP 2000-63704 A JP 2002-136869 A

  It is an object of the present invention to provide a photocatalyst layer-forming agent that can be applied in the field without requiring heating at a high temperature.

The present inventors have found that by using zirconium acetate as a zirconium compound, coating at room temperature is possible, so that on-site coating is possible, and the present invention has been completed.
That is, the present invention
(1) A photocatalyst layer and / or sol, a silica sol in which colloidal silica particles are dispersed, an aluminum compound and zirconium acetate,
(2) The composition for forming a photocatalyst layer according to (1), which can be formed at room temperature,
(3) The aluminum compound is selected from the group consisting of aluminum oxide, oxide hydroxide, hydroxide, oxynitrate, oxycarbonate, alkoxide having 1 to 4 carbon atoms, and hydrolyzate of the alkoxide. The composition for forming a photocatalyst layer according to (1) or (2), which is one type or a mixture of two or more types,
(4) 0.1 to 6% by weight of photocatalyst particles and / or sol in terms of oxide as a solid content and 0.1 to 10% of silica sol silica sol in which colloidal silica particles are dispersed with respect to the entire composition for forming a photocatalyst layer The photocatalyst layer according to any one of (1) to (3) above, comprising 5% by weight, 0.1 to 5% by weight of zirconium acetate, and 0.1 to 9% by weight of an aluminum compound Forming composition,
About.

By using zirconium acetate, it has sufficient film strength even at film formation at room temperature, and has high photocatalytic activity and excellent transparency, so that it can be applied on site.
Moreover, the photocatalyst carrying structure of the present invention has the following characteristics.
1) Since a transparent material that transmits visible light can be obtained, the decorative properties of a wide range of carriers such as general-purpose resins and natural fibers are not impaired.
2) The photocatalyst is firmly adhered to the carrier, has high photocatalytic activity, and the carrier is not deteriorated by photocatalytic action or the photocatalyst is not detached.
3) Can be used under light irradiation for a long time, has good evaluation in alkali resistance test, and maintains high adhesion even after accelerated weathering test with sunshine carbon arc weather meter. It can be used in the environment of

I. Photocatalyst layer forming composition The photocatalyst layer forming composition of the present invention is a coating liquid for forming a photocatalyst layer, and includes photocatalyst particles and / or sol, silica sol in which colloidal silica particles are dispersed, and zirconium acetate. Containing. Preferably, an aluminum compound is further contained.
The zirconium compound, aluminum compound and photocatalyst are preferably used in the form of a sol. When a sol is used, an acid or alkali peptizer can be added to the photocatalyst coating solution for stabilization. In addition, in order to improve adhesion and operability, 5% by weight or less of a surfactant or the like can be added to the sol suspension with respect to the photocatalyst.
The amount of each component contained in the composition for forming a photocatalyst layer is 0.1 to 5% by weight of silica sol in which colloidal silica particles are dispersed in terms of oxide as a solid content with respect to the whole composition, Alternatively, the sol is preferably 0.1 to 6% by weight, the zirconium compound is 0.1 to 5% by weight, and the aluminum compound is preferably 0.1 to 9% by weight.

(photocatalyst)
Specific examples of the photocatalyst include 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, and the} like, and these photocatalysts include Pt, Rh, RuO ₂ , Nb, Cu, Sn, Ni, What added metals or metal oxides, such as Fe, can be used. Among these, in view of durability, cost, and photocatalytic activity, those containing titanium oxide (TiO ₂ ) as a main component are preferable, and anatase type titanium oxide is particularly preferable. Further, not only titanium oxide that exhibits catalytic activity with light containing a large amount of ultraviolet rays such as sunlight, but also titanium oxide that exhibits catalytic activity in indoor light with little ultraviolet rays by doping a noble metal or the like can be used.

(Colloidal silica)
Although the colloidal silica particle used for this invention is not specifically limited, It is preferable that the spherical colloidal silica particle is the colloidal silica particle couple | bonded in the elongate shape. As a specific example of the shape, when the spherical colloidal silica particles are seen in the pearl of the pearl necklace, a shape like a part of the pearl necklace can be exemplified. That is, a particle in which 3 or more, preferably 5 or more, more preferably 7 or more spherical silica particles are connected can be exemplified. In addition, the shape of each spherical colloidal particle need not be clear, and it may be partially elongated in a cylindrical shape, and the spherical colloidal particles need to be bonded. Rather, it is preferable that the whole particle has an elongated shape.
In the elongated shape, the length is preferably in the range of 50 to 400 nm, the thickness is preferably in the range of 10 to 50 nm, and the thickness is preferably uniform throughout. Furthermore, the elongated shape preferably extends in a two-dimensional direction starting from a certain spherical colloidal silica particle. Moreover, as long as it has an elongated shape as a whole, it may have a somewhat branched structure.
When the spherical colloidal silica particles are bonded in a necklace shape as described above, the average particle diameter of the spherical colloidal silica particles is preferably in the range of 10 to 50 nm.
Specifically, as the colloidal silica particles having the above-described characteristics, the ratio D1 / D2 of the measured particle diameter (D1 nm) by the dynamic light scattering method and the measured particle diameter (D2 nm) by the nitrogen gas adsorption method is 5 or more. The D1 is 40 to 300 nm, and exemplifies elongated amorphous colloidal silica particles having a uniform thickness in the range of 5 to 20 nm by electron microscopy and having an extension in only one plane. be able to. Examples of a method for producing such a sol in which colloidal silica particles are dispersed include the methods described in JP-A-1-317115 and JP-A-7-118008.

(Zirconium acetate and aluminum compounds)
Zirconium acetate is a compound represented by ZrO (C ₂ H ₃ O ₂ ) ₂ or the like, and is commercially available as, for example, zircosol ZA (manufactured by Daiichi Rare Element Chemical Industries, Ltd., registered trademark).
Examples of the aluminum compound include aluminum oxide, oxide hydroxide, hydroxide, nitrate, oxynitrate, carbonate, oxycarbonate, oxalate, oxysuccinate, acetate, oxyacetate, and 1 to 6 carbon atoms. 1 type, or 2 or more types of mixtures chosen from the group which consists of a alkoxide of this, and the hydrolysis product of this alkoxide is preferable.
Preferred specific examples of aluminum compounds include aluminum oxide, aluminum oxide hydroxide, aluminum hydroxide, hydrated aluminum oxide, boehmite, aluminum nitrate, aluminum oxynitrate, aluminum carbonate, aluminum oxycarbonate, aluminum oxalate, aluminum oxyoxalate, and acetic acid. Examples thereof include aluminum, aluminum oxyacetate, aluminum triisopropoxide, aluminum tributoxide, aluminum butoxide acetylacetonate, aluminum butoxide lactate, a hydrolysis product of aluminum butoxide, a hydrolysis product of aluminum isopropoxide, and the like.
As the zirconium acetate or aluminum compound, a sol having an average particle diameter of 2 nm to 50 nm, preferably 2 nm to 20 nm is preferably used. When using a particle having such a particle size, the transparency of the photocatalyst layer is improved and the parallel light transmittance is increased. Therefore, particularly when applied to a glass substrate or a plastic molded body that requires transparency. preferable. Further, in the case where a color or pattern is printed on the base carrier, such a transparent photocatalyst layer does not impair the base color or pattern.

(Other ingredients)
When the silicon compound is contained in the photocatalyst complex, it is preferable to contain 0.001 to 5% by weight of the silicon compound in terms of oxide as a solid content with respect to the entire composition for forming the photocatalyst layer. As the silicon compound, for example, a hydrolyzate of silicon alkoxide having an alkoxy group having 1 to 5 carbon atoms or the hydrolyzate product is preferable. When the number of carbon atoms of the alkoxy group of the silicon alkoxide exceeds 6, the hydrolysis rate becomes very slow. Polysiloxane obtained by hydrolyzing silicon alkoxide partially containing chlorine can also be used. However, when polysiloxane containing a large amount of chlorine is used, the carrier is corroded by chlorine ions as impurities. Or the adhesiveness may decrease.

II. Preparation Method of Photocatalyst Layer Forming Composition As a preparation method of the photocatalyst layer forming composition, zirconium acetate, an aluminum compound, a photocatalyst, colloidal silica sol and the like may be usually mixed. Examples of the solvent used include alcohols such as water, methanol, ethanol, propyl alcohol, isopropyl alcohol, butanol and t-butanol, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, acetylacetone and cyclohexanone, diethyl ether, methyl Cellsolve, ethers such as tetrahydrofuran, aromatic hydrocarbons such as benzene, toluene, xylene, halogenated hydrocarbons such as dichloromethane and chloroform, esters such as saxane ethyl, propyl acetate, butyl acetate, pentane, hexane, cyclohexane, etc. Of saturated hydrocarbons. Moreover, these 2 types or more can also be mixed and used. Of these, water-alcohol solvents are particularly preferred.

III Coating and photocatalyst layer The photocatalyst layer is formed by coating the photocatalyst layer forming composition on the surface of the adhesive layer by a printing method, a sheet molding method, a spray spraying method, a dip coating method, a spin coating method, etc., and drying and curing. Can be formed. The drying and curing have been performed at a temperature of about 50 ° C. to about 300 ° C., but the photocatalyst layer forming composition of the present invention varies depending on the carrier material and the resin material in the adhesive layer, but at low temperatures. It can be dried and cured, and can be dried and cured at room temperature or below as well as 40 ° C. or below.
The photocatalyst layer after coating on the substrate contains a photocatalyst component, colloidal silica particles, zirconia acetate and, if necessary, an aluminum compound.
The content of each component in the photocatalyst layer after drying is 5% to 60% by weight of the photocatalyst component, 10 to 80% by weight of colloidal silica, and 5 to 40% of the zirconium component in terms of oxide with respect to the entire photocatalyst layer. It is preferable that the aluminum content is 10 to 80% by weight.

IV. Structure carrying a photocatalyst A structure carrying a photocatalyst according to the present invention has a structure in which an adhesive layer is provided between a photocatalyst layer and a carrier. The adhesive layer provided between the photocatalyst layer and the carrier has the effect of protecting the underlying carrier from deterioration due to photocatalysis and the effect of firmly adhering the photocatalyst layer to the carrier, and the adhesive layer itself is photocatalytic. It is characterized by being less susceptible to deterioration due to.

  The carrier is not particularly limited as long as it can carry a photocatalyst through an adhesive layer. For example, it is possible to obtain a structure provided with the adhesive layer and the photocatalyst layer even if the ceramic, inorganic material, carrier material is an organic polymer that cannot be heated, or a metal that is easily oxidized and corroded by heat or water. it can. Further, as the carrier shape, any complicated shape such as a film shape, a sheet shape, a plate shape, a tubular shape, a fiber shape, and a net shape can be used. The thickness of the carrier is preferably 10 μm or more because it can be firmly supported. Furthermore, in order to improve the adhesion between the carrier and the adhesive layer, a carrier whose surface has been subjected to easy adhesion treatment such as discharge treatment or primer treatment can be used.

The material of the adhesive layer is not particularly limited as long as it can protect the carrier from deterioration due to photocatalysis and can firmly fix the photocatalyst layer. Specifically, (1) the silicon content is converted into oxide. 2 to 10% by weight of a silicon-modified resin such as (acrylic silicone resin, epoxy silicone resin, polyester silicone resin), (2) a resin containing 3 to 90% by weight of polysiloxane in terms of oxide, or (3 ) A resin containing 5 to 90% by weight of colloidal silica in terms of oxide can be used. These resins are suitable for firmly bonding the photocatalyst and protecting the carrier from the photocatalyst.
Silicon-modified resins such as acrylic silicon resins with a silicon content of less than 2% by weight in terms of oxides, resins with a polysiloxane content of less than 3% by weight in terms of oxides, and colloidal silica content in oxides If converted to less than 5% by weight of resin, adhesion to the photocatalyst layer becomes poor. Further, the adhesive layer is deteriorated by the photocatalyst, and the photocatalyst layer is easily peeled off. Silicon-modified resin such as acrylic-silicone resin whose silicon content is more than 10% by weight in terms of oxide, resin whose polysiloxane content is more than 90% by weight in terms of oxide, colloidal silica content is oxide If the resin exceeds 90% by weight, the adhesion to the carrier is lowered.
Examples of the resin into which silicon is introduced include acrylic resin, epoxy resin, polyester resin, alkyd resin, and urethane resin. Among these, acrylic resins, epoxy resins, and polyester resins are particularly preferable in terms of film formability, toughness, and adhesion to the carrier. These resins can be used in either a solution form or an emulsion type. Moreover, additives, such as a crosslinking agent, may be contained.
When the polysiloxane contained in the resin of the adhesive layer is a hydrolyzate of silicon alkoxide having an alkoxy group having 1 to 5 carbon atoms or the hydrolyzate product, the support having improved adhesion and durability A structure can be obtained. When the number of carbon atoms of the alkoxy group of the silicon alkoxide exceeds 6, the hydrolysis rate is very slow, making it difficult to cure in the resin, resulting in poor adhesion and durability. Polysiloxane obtained by hydrolyzing silicon alkoxide partially containing chlorine can also be used. However, when polysiloxane containing a large amount of chlorine is used, the carrier is corroded by chlorine ions as impurities. Or the adhesiveness may decrease.

As such a silicon alkoxide, for example, a compound represented by the following formula can be preferably used.
^{_{SiCln 1 (OH) n 2 R}} 1 n 3 (OR 2) n 4
Here, R ¹ is methyl, ethyl, propyl, isopropyl, butyl, s-butyl, t-butyl, hexyl, octyl, aminomethyl, aminoethyl, carboxymethyl, carboxyethyl, chloromethyl, chloroethyl, chloropropyl group, etc. An alkyl group having 1 to 8 carbon atoms (which may be substituted with an amino group, a carboxyl group or a chlorine atom).
R ² is an alkyl group having 1 to 8 carbon atoms such as methyl, ethyl, propyl, isopropyl, butyl, s-butyl, t-butyl, hexyl group, or methoxymethyl, ethoxymethyl, propoxymethyl, isopropoxymethyl, butoxy An alkyl group having 1 to 8 carbon atoms substituted with an alkoxy group such as methyl, methoxyethyl, ethoxymethyl, propoxyethyl, methoxypropyl, or methoxybutyl group. N ₁ , n ₂ and n ₃ represent 0, 1 or 2, n ₄ represents an integer of 2 to 4, and n ₁ + n ₂ + n ₃ + n ₄ = 4.
Preferable specific examples of the silicon alkoxide represented by the above formula include Si (OCH ₃ ) ₄ , Si (OC ₂ H ₅ ) ₄ , Si (OC ₃ H ₇ ) ₄ , Si (OC ₄ H ₉ ) ₄ , Si (OC ₅ H ₁₁ ) ₄ , Si (OC ₆ H ₁₃ ) ₄ , SiCH ₃ (OCH ₃ ) ₃ , SiCH ₃ (OC ₂ H ₅ ) ₃ , SiCH ₃ (OC ₃ H ₇ ) ₃ , SiCH ₃ (OC ₃₎ H ₇ ) ₃ , SiCH ₃ (OC ₄ H ₉ ) ₃ , SiCl (OCH ₃ ) ₃ , SiCl (OC ₂ H ₅ ) ₃ , SiCl (OC ₃ H ₇ ) ₃ , SiCl (OC ₄ H ₉ ) ₃ , SiCl (OC ₆ H ₁₃ ) ₃ , SiCl (OH) (OCH ₃ ) ₂ , SiCl (OH) (OC ₂ H ₅ ) ₂ , SiCl (OH) (OC ₃ H ₇ ) ₂ , SiCl (OH) (OC _{4 H 9) 2, SiCl 2 (} OCH 3) 2, SiCl 2 (OC 2 H 5) may be mentioned _2.

There are various methods for introducing silicon of these silicon-modified resins, such as transesterification, grafting reaction using silicon macromers and reactive silicon monomers, hydrosilylation reaction, block copolymerization method, etc. Can also be used.
For example, as a method for introducing polysiloxane into a resin, (1) a method in which silicon alkoxide is mixed with a resin solution in a monomer state and hydrolyzed with moisture in the air when forming an adhesive layer; There are various methods such as mixing the partially hydrolyzed product with the resin and further hydrolyzing with moisture in the air when forming the adhesive layer. Any method can be used as long as it can be mixed with the resin uniformly.
Further, in order to adjust the hydrolysis rate of silicon alkoxide, a small amount of acid or base catalyst may be added. The amount of polysiloxane added to the resin is preferably 3 to 90% by weight in terms of oxide in order to firmly adhere the photocatalyst layer to the carrier.
Any resin such as an acrylic resin, an epoxy resin, a polyester resin, a urethane resin, or an alkyd resin can be used as the resin into which polysiloxane is introduced. Among these, an acrylic resin, an epoxy resin, a polyester resin, or a mixed resin thereof is preferable in terms of durability and alkali resistance when a silicon-modified resin is used.

When the adhesive layer contains colloidal silica, the particle diameter of the colloidal silica is preferably 10 nm or less. When the particle diameter is 10 nm or more, the resin in the adhesive layer is not only easily deteriorated by the photocatalyst but also the adhesion between the photocatalyst layer and the adhesive layer is deteriorated.
The simplest method for introducing colloidal silica into the resin is to form a protective film by mixing a resin solution and a colloidal silica solution, followed by coating and drying. In addition, a polymer obtained by polymerizing a resin in a state where colloidal silica is dispersed can also be used.

Moreover, in order to improve the adhesiveness and dispersibility of colloidal silica and resin, colloidal silica treated with a silane coupling agent can also be used.
The amount of colloidal silica added to the resin is preferably 5 to 90% by weight in terms of oxide in order to firmly adhere the photocatalytic layer to the support.
Any resin such as an acrylic resin, an epoxy resin, a urethane resin, a polyester resin, or an alkyd resin can be used as a resin for introducing colloidal silica. Among these resins, acrylic resins, epoxy resins, and polyester resins are particularly preferable because when they are silicon-modified resins, those having excellent durability and alkali resistance can be obtained.
Colloidal silica may be any silica sol obtained by cation exchange of an aqueous sodium silicate solution or silica sol obtained by hydrolyzing silicon alkoxide.
Furthermore, in the present invention, a resin containing both polysiloxane and colloidal silica can be used as the adhesive layer. In that case, if the total content of the polysiloxane and colloidal silica in the adhesive layer is within the range of the content showing the improvement in alkali resistance in terms of oxide, the same excellent alkali resistance will be exhibited. be able to

  When the resin used for the adhesive layer is a resin containing colloidal silica or a resin containing polysiloxane, the particle diameter of the colloidal silica or polysiloxane is preferably 10 nm or less. If the particle diameter of colloidal silica or polysiloxane exceeds 10 nm, the dispersibility deteriorates and the translucency of the adhesive layer decreases, so the total light transmittance at a total wavelength of 550 nm of the adhesive layer and the photocatalyst layer is 70. % Or less.

In addition, a light stabilizer and / or an ultraviolet absorber can be further added to the adhesive layer resin for the purpose of suppressing deterioration due to photocatalytic action. As the light stabilizer that can be used, a hindered amine system is preferable, but other substances can also be used. As the ultraviolet absorber, triazole or the like can be used. These addition amounts are 0.005 weight%-10 weight% with respect to resin, Preferably they are 0.01 weight%-5 weight%. It is also preferable to improve the adhesion with the photocatalyst layer by treating the adhesive layer with a silane or titanium coupling agent.
The thickness of the adhesive layer is preferably about 0.1 μm to 20 μm in order to obtain good adhesion with the photocatalyst layer. When the thickness of the adhesive layer is 0.1 μm or less, the function of firmly bonding the photocatalytic layer is weakened. On the other hand, there is no particular problem when the thickness is 20 μm or more, but there are few merits to make it 20 μm or more in consideration of actual coating.

  The structure carrying the photocatalyst of the present invention includes architectural paint, wallpaper, window glass, blinds, curtains, carpets, lighting fixtures, lighting lights, road lights, tunnel lighting lights, highway and Shinkansen sound insulation walls, black lights, ship bottoms. -Can be used for fishing net antifouling paints, water treatment fillers, agricultural bi-films, grass protection sheets, packaging materials, etc. In particular, when used in a hot and humid environment or an outdoor environment, it exhibits excellent durability and transparency.

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

1) Production of photocatalyst carrying structure Photocatalyst carrying structures of Examples 1 to 6 and Comparative Examples 1 to 4 having configurations as shown in Table 1 were produced as follows.

(1) Carrier (TA-1) Soda lime glass plate (TA-2) Acrylic paint plate

(2) Adhesive layer A solution for forming an adhesive layer in which the silicon-modified resin or the like (PS-1) and the resin solution (J-1) were mixed and the concentration was adjusted was obtained. This solution was applied and formed on a soda lime glass carrier (TA-1) or an acrylic coating plate (TA-2) by a dipping method. It was dried at room temperature for 60 minutes to form an adhesive layer with a thickness of 1 μm.
(PS-1) Polyethoxysiloxane (Colcoat ethyl silicate 40)
(J-1) Acrylic silicon resin xylene solution having a silicon content of 3% by weight

(3) Photocatalyst layer The following were used for the photocatalyst.
(T-1) Nitric acid acidic titanium oxide sol (crystal particle diameter: 8 nm)
The following silica sol was used.
(S-1) Snowtex ST-UP (manufactured by Nissan Chemical Co., Ltd., registered trademark)
The following aluminum compounds were used.
Alumina sol-520 (Nissan Chemical Co., Ltd.) (A-1)
The following zirconium compounds were used.
(Z-1) Zircozol ZA30 (Zircon Acetate, registered trademark) manufactured by Daiichi Rare Elemental Chemical Co., Ltd.
(Z-2) Zircozole ZN (Zirconic nitrate manufactured by Daiichi Rare Elemental Chemicals, registered trademark)
(Z-3) Nano Use ZR-30AL (Nissan Chemical Co., Ltd. acid zirconia sol, registered trademark)

The photocatalyst, silica sol, aluminum compound and zirconium compound are prepared in an appropriate range of pH 1.5 to 9, mixed, a predetermined amount of a surfactant is added, and a photocatalyst complex solution (photocatalyst layer forming composition) is prepared. Obtained.
The obtained photocatalyst complex solution was applied and formed on the adhesive layer by dipping. The photocatalyst layer was dried at the same temperature as the adhesive layer and was formed to a thickness of 0.5 μm.

2) Performance test of photocatalyst carrying structure The following performance test was conducted using the photocatalyst carrying structure obtained above.
(1) Evaluation Test of Catalytic Activity The photocatalyst carrying structure obtained above was cut into a size of 70 mm × 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, after irradiating the sample with light of a black light (FL15BLB, manufactured by Toshiba Lighting & Technology Co., Ltd.) with an ultraviolet intensity of ² mW / cm ² for 3 hours, the aldehyde gas concentration inside the container was measured by gas chromatography, Photocatalytic activity was evaluated.
As a result, the photocatalyst carrying structures of Examples 1 to 6 and Comparative Examples 1 to 4 showed an excellent photocatalytic activity with a reduction amount of aldehyde gas of 100 ppm or more.

(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 measurement results are shown in Table 2 below. The photocatalyst carrier structures of Examples 1 to 4 and Comparative Examples 1 and 3 formed on TA-1 all showed excellent transparency with a haze ratio of 3% 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 defined 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 2.

(4) Finger Friction Test The sample surface was rubbed with a finger and evaluated as “◯” for those that did not peel, “Δ” for those that had scratches, and “x” for those that had peeled. The evaluation results are shown in Table 2 below.

(5) Boiling test After dipping the photocatalyst carrying structure in boiling ion exchange water for 1 hour, a tape peeling test and a finger friction test were conducted to evaluate durability. The results are shown in Table 2 below.

From Table 2, the photocatalyst-supported structures of Examples 1 to 6 containing the zirconia compound (Z-1) have excellent durability without peeling or scratching in the tape peeling and finger friction tests even after the boiling test. Had. In comparison, the structures of Comparative Examples 1 to 4 containing the zirconia compounds (Z-2) and (Z-3) were good in the tape peeling test, but peeling and scratching occurred in the finger friction test. The result was inferior in durability.

Claims (4)

A composition for forming a photocatalyst layer, comprising: photocatalyst particles and / or sol; silica sol in which colloidal silica particles are dispersed; an aluminum compound; and zirconium acetate. The composition for forming a photocatalyst layer according to claim 1, which can be formed at room temperature. The aluminum compound is selected from the group consisting of an oxide of aluminum, an oxide hydroxide, a hydroxide, an oxynitrate, an oxycarbonate, an alkoxide having 1 to 4 carbon atoms, and a hydrolyzate of the alkoxide, or The composition for forming a photocatalyst layer according to claim 1 or 2, wherein the composition is a mixture of two or more kinds. 0.1 to 6% by weight of photocatalyst particles and / or sol and 0.1 to 5% by weight of silica sol silica sol in which colloidal silica particles are dispersed in terms of oxide as a solid content with respect to the entire composition for forming a photocatalyst layer The composition for forming a photocatalyst layer according to any one of claims 1 to 3, comprising 0.1 to 5% by weight of zirconium acetate and 0.1 to 9% by weight of an aluminum compound.