JP3038599B2 - Photocatalyst carrying structure and photocatalyst coating agent - Google Patents

Description

TECHNICAL FIELD The present invention relates to a structure supporting a photocatalyst used for antifouling, water purification, deodorization, sterilization, wastewater treatment, water decomposition, growth suppression of algae, various chemical reactions, and the like.

BACKGROUND ART N-type semiconductor titanium oxide is known as a photocatalyst that promotes various chemical reactions such as water decomposition, deodorization, sterilization, water purification, and wastewater treatment by the energy of ultraviolet rays. It is generally said that using a photocatalyst in the form of a powder or suspended in a solution has higher catalytic activity, but in practice it must be used in a form supported on some kind of carrier There are many. In order to make effective use of the energy of the ultraviolet light, it is advantageous that the carrier is in the form of paper or sheet, which allows a large light irradiation area, and that the photocatalyst causes a chemical reaction. In order to increase the contact area with the reactant to be formed, it is preferable that the surface has a porous structure.

Various carrier materials for supporting the photocatalyst have been proposed. For example, (A) nitrocellulose, glass, polyvinyl chloride, plastic, nylon, methacrylic resin, polypropylene and other light-transmitting substances (JP-A-62-66861), ( B)
Polypropylene fiber, ceramic (Japanese Unexamined Patent Publication No. 2-6819)
0), (C) glass, ceramic, nylon, acrylic, polyester (JP-A-5-309267).

However, among these materials, it has been reported that organic materials are mainly decomposed or degraded by the catalytic action when a photocatalyst is supported, and there is a problem in durability (Fumio Otani) , Polymer Processing 42, No. 5,
P18 (1993), Manabu Seino, "Titanium oxide" Gihodo, P16
Five).

Further, even when the carrier material is an inorganic substance such as glass or ceramic, when 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 is reduced. In addition, there was also a problem in durability such that the resin was decomposed and degraded by the photocatalytic action and the photocatalyst was separated.

Therefore, when the carrier material is a heat-resistant inorganic substance, a sputtering method in which no organic substance remains (Japanese Patent Laid-Open No. 60-04440).
53), coating and baking method of organic titanate (Japanese Patent Application Laid-Open No. 60-1182)
36) and spraying and firing method of titania sol (Japanese Patent Laid-Open No.
3544).

However, these methods require the formation of photocatalyst particles on the carrier, crystallization and calcination at a high temperature in order to have adhesiveness with the carrier, and it is difficult to carry a large area, There was a problem that the manufacturing cost was very high.

On the other hand, in order to carry a photocatalyst on glass fiber paper, a method using a metal oxide sol as an adhesive (JP-A-5-3092)
67) has been proposed.

However, the adhesive force of a metal oxide sol such as silica sol is very weak because it is based on Van der Waals' force (Fine Ceramics, Vol. 1, pp. 216-223 198).
0), the adhesiveness and durability were insufficient, and baking treatment at a high temperature was required, so that it could not be applied to all carriers including general-purpose resins which are liable to undergo thermal decomposition.

In addition, in an example in which a photocatalyst powder is supported on a metal oxide gel such as silica or clay mineral, it has been reported that the photocatalytic decomposition reaction of propionaldehyde gas is accelerated by the effect of the carrier as an adsorbent (Symposium “Photocatalyst”). Recent Developments in Reactions, "Preprints, 1994, Workshop on Optical Functional Materials, 2
-11, p.39).

However, there has been no report that a photocatalyst uniformly dispersed in such a metal oxide gel was obtained while maintaining a high catalytic activity and having a carrier excellent in adhesiveness and durability.

Furthermore, a method of fixing a photocatalyst with a fluororesin has been proposed (Japanese Patent Application Laid-Open No. 6-315614). However, not only is fluororesin expensive, but in order to adhere photocatalyst particles firmly, it is necessary to cover most of the surface of the catalyst particles with fluororesin, and as a result, the catalytic activity is lower than that of powder. There was a problem of doing it. There is an example (EP-0633064) in which a photocatalyst is mixed with a hardly decomposable binder such as a fluororesin or a polyorganosiloxane to support the substrate (EP-0633064), but there are practical problems such as adhesion and long-term durability. It is not enough to solve it.

As described above, in order to support the photocatalyst on the carrier, the problems to be solved are: 1) good adhesion between the photocatalyst and the carrier; 2) support of the photocatalytic activity on the carrier. 3) the carrier and the adhesive are not deteriorated by the supported photocatalyst, the strength is maintained for a long time, and the durability and catalytic activity are maintained.
Points. Further, when used in a high-temperature and high-humidity environment, for example, it is required that the adhesiveness after immersion in boiling water is excellent.

In addition, as a property required for a photocatalyst coating agent for supporting a photocatalyst on a carrier, a photocatalyst coating solution that does not increase in viscosity or sedimentation of particles even when stored for at least one month, preferably three months or more is required. In addition, it is also necessary to carry a photocatalyst without impairing the photocatalytic action when coated on a practical product.

The present inventors have provided a specific adhesive layer between the photocatalytic layer and the carrier, the effect of protecting the underlying carrier from deterioration due to photocatalytic action and the action of firmly adhering the photocatalytic layer to the carrier, and the adhesive layer itself The present inventors have found out that the photocatalyst can be firmly adhered to the carrier for the first time by making the photocatalyst less susceptible to degradation, and have solved the above-mentioned problem.

DISCLOSURE OF THE INVENTION The present inventors have reported that a silicon content of 2
5 to 60% by weight of silicone modified resin such as acrylic-silicone resin, epoxy-silicone resin, colloidal silica
Resin containing 40% by weight or a general formula (1) SiCln ₁ (OH) n ₂ R ¹ n ₃ (OR ² ) n ₄ (1) wherein R ¹ represents an amino group, a carboxyl group Or may be substituted with a chlorine atom) an alkyl group having 1 to 8 carbon atoms, R ² represents an alkyl group having 1 to 8 carbon atoms substituted with an alkyl group having 1 to 8 carbon atoms or an alkoxy group, n ₁ represents an integer from 0 to 2, n ₂ and n ₃ each represent an integer from 0 to 3, n ₄ represents an integer from 2 to 4, and n ₁ + n ₂ +
n ₃ + n ₄ = ₄ is a polycondensation reaction product of the compound represented by the indicating] polysiloxane 3-60 wt% content to resin is strongly bonded photocatalyst, suitable to protect the carrier from the photocatalyst And completed the present invention.

Furthermore, the present inventors have developed a compound represented by the general formula (2) SiR ³ n ₅ (OR ⁴ ) ₄ -n ₅ (2) in order to solve the above-mentioned problem required for the photocatalytic coating agent. In the formula, R ³ represents an alkyl group having 1 to 8 carbon atoms (which may be substituted with an amino group, a chlorine atom, or a carboxyl group), and R ⁴ is substituted with an alkyl group or an alkoxy group having 1 to 8 carbon atoms. It has been an alkyl group having 1 to 8 carbon atoms, n ₅ is the number of one of 0, 1, 2, 3. 1) alkoxysilanes or their hydrolysis products
0.001 to 5% by weight of the seed or two or more kinds, 0.1 to 30% by weight of a metal oxide and / or hydroxide sol as a solid component, and 0.1 to 0.1% of a photocatalyst powder and / or sol as a solid component. The photocatalyst coating solution containing 30% by weight was found to be stable for a long period of time without any increase in viscosity and no sedimentation of the particles, thus completing the present invention.

In addition, the present inventors have found that the photocatalyst supporting structure and the photocatalyst coating agent can be supported on a carrier material such as glass, plastic, metal, fabric, and wood material, and can be used on lenses, adhesive films, blinds, nonwoven fabrics, wood doors, and the like. Also found that application with the photocatalytic coating agent according to the present invention was possible.

 Hereinafter, the present invention will be described in detail.

In the present invention, the resin used for the adhesive layer of the photocatalyst supporting structure contains silicon-modified resin such as acryl-silicon resin and epoxy-silicon resin having a silicon content of 2 to 60% by weight, and 5 to 40% by weight of colloidal silica. Resin,
And a resin containing 3 to 60% by weight of polysiloxane.

Silicon-modified resin such as acryl-silicon resin having a silicon content of less than 2% by weight and polysiloxane content of 2
Less than 5% by weight of resin and colloidal silica content
When the resin content is less than the above, adhesion to the photocatalyst layer becomes poor, and the adhesion layer is deteriorated by the photocatalyst, and the photocatalyst layer is easily peeled. On the other hand, acrylic with a silicon content exceeding 60% by weight
With a silicon-modified resin such as a silicone resin, the adhesion between the adhesive layer and the carrier is poor, and the hardness of the adhesive layer is low, so that the wear resistance is poor.

In the case of a resin having a polysiloxane content of more than 60% by weight or a resin having a colloidal silica content of more than 40% by weight, the adhesive layer becomes porous, the underlying carrier is degraded by a photocatalyst, and the resin adheres to the carrier. Adhesion between the layer and the photocatalyst becomes poor, and the photocatalyst is easily peeled off from the carrier.

When the adhesive layer resin is a silicon-modified resin such as an acrylic-silicone resin or an epoxy-silicone resin, the method of introducing silicon into the resin is a transesterification reaction, a graft reaction using a silicon macromer or a reactive silicon monomer,
There are various methods such as a hydrosilylation reaction and a block copolymerization method,
In the present invention, products made by any method can be used.

As a resin into which silicon is introduced, an acrylic resin or an epoxy resin is the most excellent in terms of film formability, toughness, and adhesion to a carrier, but even resins such as alkyd resin, urethane resin, and polyester resin can be used. Can be used. These resins can be used either in a type dissolved in a solvent or in an emulsion type. There is no problem even if additives such as a crosslinking agent are included.

When the adhesive layer resin contains a polysiloxane and the polysiloxane is a hydrolyzate of a silicon alkoxide having an alkoxy group having 1 to 5 carbon atoms or a product of the hydrolyzate, the adhesiveness and durability are poor. A more improved supporting structure can be obtained. When the carbon number of the alkoxy group in the silicon alkoxide is 6 or more, it is expensive and has a very low hydrolysis rate, so that it is difficult to cure the resin in a resin, and the adhesiveness and durability deteriorate.

Polysiloxane obtained by hydrolyzing silicon alkoxide partially containing chlorine can be used.However, when polysiloxane containing a large amount of chlorine is used, the carrier is corroded by chlorine ions as an impurity, and adhesiveness is deteriorated. Make it worse.

As a method for introducing the polysiloxane into the resin, a method of mixing the resin in the state of a silicon alkoxide monomer and hydrolyzing it with water in the air at the time of forming the adhesive layer, in advance, a product obtained by partially hydrolyzing the silicon alkoxide with the resin There are various methods, such as mixing and further hydrolyzing with moisture in the air at the time of forming the protective film, but any method may be used as long as it can be uniformly mixed with the resin. In order to change the hydrolysis rate of silicon alkoxide, a small amount of an acid or base catalyst may be added.

As the resin into which polysiloxane is introduced, acrylic resin, acrylic-silicone resin, epoxy-silicone resin, silicon-modified resin, urethane resin, epoxy resin,
Polyester resin, alkyd resin, etc. can be used,
Silicon-modified resins including acrylic-silicon resins and epoxy-silicon resins are most excellent in terms of durability.

When the adhesive layer is a resin containing colloidal silica,
The particle size of the colloidal silica is preferably 10 nm or less.
When the thickness 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 of introducing the colloidal silica into the resin is to mix the resin solution and the colloidal silica solution, and then apply and dry to form an adhesive layer.However, the resin is dispersed in the state where the colloidal silica is dispersed. A polymerized and synthesized product may be applied and dried before use. Further, in order to improve the adhesiveness and dispersibility between the colloidal silica and the resin, the colloidal silica may be treated with a silane coupling agent before use.

Examples of the resin into which colloidal silica is introduced include acrylic resin, acrylic-silicone resin, epoxy-silicone resin, silicon-modified resin, urethane resin, epoxy resin, polyester resin, and alkyd resin. A resin or a silicon-modified resin including an epoxy-silicon resin is most excellent in durability.

As the colloidal silica, any silica sol produced by cation exchange of a sodium silicate solution or silica sol produced by hydrolyzing silicon alkoxide can be used.

Further, for the purpose of suppressing the deterioration due to the photocatalytic action in the adhesive layer resin, the durability can be improved by mixing a light stabilizer and / or an ultraviolet absorber. As a light stabilizer that can be used, a hindered amine type is preferable, but other substances can also be used. As the ultraviolet absorber, a triazole type or the like can be used. The addition amount is 0.005 wt% or more and 10 wt% or less with respect to the resin, preferably 0.01 wt%.
% To 5 wt% or less. When the surface of the adhesive layer is treated with a silane-based or titanium-based coupling agent, the adhesiveness to the photocatalyst layer may be improved.

As a method of supporting the adhesive layer on the carrier, a method of coating a resin solution by a printing method, a sheet forming method, a spray spraying method, a dip coating method, a spin coating method, or the like and drying the resin solution can be used. The drying temperature varies depending on the type of the solvent and the resin, but is generally preferably 150 ° C. or lower. If the thickness of the adhesive layer is 0.1 μm or more, the photocatalyst layer can be firmly adhered to form a highly durable photocatalyst supporting structure. In addition, in the case of a coating method that requires the adhesive layer to be dried and cured in a short time, such as a gravure printing method,
It is also preferable to add 0.1 to 10% by weight of a hardening agent such as a silicon-based hardening agent to the solid content of the adhesive layer depending on the required hardening speed.

The metal oxide gel or hydroxide gel in the photocatalyst layer has an effect of fixing the photocatalyst powder and firmly adhering to the adhesive layer. As shown in the examples, this photocatalyst-supporting structure has adhesiveness, It has excellent long-term durability and weather resistance. Since this metal oxide gel or hydroxide gel is porous, it has an adsorptive property and also has an effect of enhancing photocatalytic activity. The content of the metal oxide gel or metal hydroxide gel in the photocatalyst layer is preferably 25 to 95% by weight. If it is less than 25% by weight, the adhesion to the adhesive layer will be insufficient, and if it exceeds 95% by weight, the photocatalytic activity will be insufficient.

The specific surface area of the metal oxide gel or metal hydroxide gel preferably 0.99 ° C. after drying 50 m ² / g or more, further preferably in 100 m ² / g or more, the adhesive becomes stronger, the catalytic activity Also improve.

Preferred examples of the metal component include oxide gels and hydroxide gels of metals such as silicon, aluminum, titanium, zirconium, magnesium, niobium, tantalum, tungsten, and tin.

In addition, by using an oxide or hydroxide gel containing two or more metals selected from silicon, aluminum, titanium, zirconium, and niobium as the metal component, the photocatalyst after immersion in boiling water It is possible to increase the adhesion of the layer. Examples of combinations of metal components having excellent boiling water resistance include silicon-aluminum, silicon-titanium, silicon, zirconium, silicon-niobium, aluminum-titanium, aluminum-
Preferred are zirconium, aluminum-niobium, aluminum-tantalum, titanium-zirconium, titanium-niobium, titanium-tantalum, silicon-aluminum-zirconium, silicon-aluminum-titanium, and more preferably silicon-aluminum, silicon-titanium, silicon -Zirconium, silicon-
An oxide gel or a hydroxide gel of titanium-aluminum, silicon-aluminum-zirconium, or the like can be given.

When the specific surface area of these oxide gels or hydroxide gels is 50 m ² / g or more, the adhesiveness is high, the catalytic activity is improved, and excellent adhesiveness is obtained even after immersion in boiling water. In actual use, a gel obtained by mixing and drying a sol for forming a gel or a complex oxide gel prepared by a method such as a coprecipitation method may be used. For the composite with the photocatalyst, it is desirable to mix uniformly in the state of the sol before forming the gel, or to mix the raw material before preparing the sol.

The method of preparing the gel includes a method of hydrolyzing a metal salt, a method of neutralizing decomposition, a method of ion exchange, a method of hydrolyzing a metal alkoxide, and the like.The photocatalyst powder is uniformly dispersed in the gel. Any method can be used as long as it can be obtained in a state where it is placed. However, if a large amount of impurities are present in the gel, the adhesiveness and catalytic activity of the photocatalyst will be adversely affected. Therefore, a gel with a small amount of impurities is preferred.

In addition, while maintaining high catalytic activity by adding a silicon-modified resin or a silane coupling agent to the photocatalyst layer in an amount of 10 to 50% by weight, after immersion in boiling water for 15 minutes, a crosscut tape specified in JIS K5400 Excellent adhesion having an evaluation score of 6 or more can be obtained in the adhesion test by the method.

The silicon-modified resin or silane coupling agent added to the photocatalyst layer has an effect of increasing the adhesion of the photocatalyst layer in boiling water. As the silicon-modified resin, a commercially available silicon-acrylic or silicone-epoxy resin can be used, and any of those dissolved in a solvent or dispersed in water as an emulsion can be used. is there. Examples of the silane coupling agent include general formulas: RSi (Y) ₃ and (R) ₂ Si (Y) ₂ (where R represents an organic functional group and Y represents a chlorine atom or an alkoxy group). Can be used. In the above general formula, R represents a methyl group, an ethyl group, a vinyl group, a γ-glycidoxypropyl group, a γ-methacryloxypropyl group, a γ- (2-aminoethyl) aminopropyl group, a γ-chloropropyl group , Γ-mercaptopropyl group, γ-aminopropyl group, γ-acryloxypropyl group and the like.
Any of C _{1 to} C ₅ alkoxy groups such as an ethoxy group, β-methoxyethoxy group, and β-ethoxyethoxy group can be used.

The addition amount of the silicon-modified resin or the silane coupling agent is desirably 10 to 50% by weight as a solid content in the photocatalyst layer. When the amount is less than 10% by weight, the adhesion after the boiling water test is reduced, and when the amount is more than 50% by weight, the photocatalytic activity is significantly reduced. As a method of adding a silicon-modified resin or a silane coupling agent to the photocatalyst layer, a method of adding a photocatalyst powder or a sol to a liquid or a metal oxide or a metal oxide for forming a metal oxide gel to be added together with the photocatalyst is used. Various methods such as a method of adding a hydroxide to a sol solution are possible. It is particularly preferable to add an emulsion-type silicon-modified resin to the sol solution, since the adhesion of the photocatalyst layer in boiling water can be significantly increased without substantially reducing the photocatalytic activity.

Further, an additive such as a cross-linking agent may be included in the silicon-modified resin or the silane coupling agent.

As the photocatalyst used in the present invention, any one such as powder, sol, solution, etc. can be used as long as it is fixed to the adhesive layer and shows photocatalytic activity when dried at the drying temperature of the photocatalytic layer. When using a sol photocatalyst, the particle size should be 20
When the thickness is 10 nm or less, preferably 10 nm or less, the transparency of the photocatalyst layer is improved and the linear transmittance is increased. Therefore, it is particularly preferable when the composition is applied to a glass substrate or a plastic molded product requiring transparency. Further, in the case where a color or pattern is printed on a base carrier, applying such a transparent photocatalyst layer does not impair the base color or pattern.

As the photocatalyst in the photocatalyst layer, TiO ₂ , ZnO, SrTiO ₃ , C
dS, GaP, InP, GaAs, BaTiO 3, KNbO 3, Fe 2 O 3, Ta 2 O 5, W
O ₃ , SnO ₂ , Bi ₂ O ₃ , NiO, Cu ₂ O, SiC, SiO ₂ , MoS ₂ , InP
b, RuO ₂ , CeO ₂ etc., and Pt, R
Metals such as h, RuO ₂ , Nb, Cu, Sn, Ni, and Fe and oxides of these metals added can be used.
In addition, Pt,
Any material to which a metal such as Rh, RhO ₂ , Nb, Cu, Sn, Ni, and Fe is added can be used. The content of the photocatalyst in the photocatalyst layer increases as the content of the photocatalyst increases, but is preferably 75% by weight or less from the viewpoint of adhesiveness.

The photocatalyst coating solution according to the present invention has a silicon compound content of 0.00
Contains 1% to 5% by weight, 0.1 to 30% by weight of a metal oxide and / or hydroxide sol as a solid component, and 0.1 to 30% by weight of a photocatalyst powder and / or sol as a solid component. It is characterized by doing.

As the silicon compound to be added to the coating solution for the photocatalyst layer of the present invention, general formula (2): SiR ³ n ₅ (OR ⁴ ) ₄ -n ₅ formula (2) [where R ³ is Represents an alkyl group having 1 to 8 carbon atoms (which may be substituted with an amino group, a chlorine atom, or a carboxyl group), and R ⁴ has 1 to 8 carbon atoms substituted with an alkyl group having 1 to 8 carbon atoms or an alkoxy group. Represents an alkyl group of 8, and n ₅ represents any number of 0, 1, 2, and 3. 1) alkoxysilanes or their hydrolysis products
Species or mixtures of two or more can be used. In the general formula (2), R ³ represents a methyl group, an ethyl group, a vinyl group, a γ-glycidoxypropyl group, a γ-methacryloxypropyl group, a γ- (2-aminoethyl) aminopropyl group, a γ- There are a chloropropyl group, a γ-mercaptopropyl group, a γ-aminopropyl group, a γ-acryloxypropyl group and the like, and -OR ⁴ is a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, an n- C ₁ -C ₈ alkoxy groups such as a butoxy group, β-memethoxyethoxy group, β-ethoxyethoxy group and 2-ethylhexyloxy group are preferred. Examples of the silicon compound represented by the general formula (2) include tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, and one or a mixture of two or more of their hydrolysis products. Are preferred.

By adding a small amount of the above silicon compound to the coating solution for the photocatalyst layer, a stable photocatalyst coating solution with little increase in viscosity and little sedimentation of particles can be obtained even after long-term storage. The silicon compound is preferably added in an amount of 0.001 to 5% by weight as a solid content in the coating solution for the photocatalyst layer. When the amount is less than 0.001% by weight, the stability of the coating solution for photocatalyst layer during long-term storage decreases, and when the amount is more than 5% by weight, the photocatalytic activity decreases significantly. As a method of adding the silicon compound to the coating solution of the photocatalyst layer, a method of adding the silicon compound to the solution of the photocatalyst powder or sol, and a method of adding a metal oxide and / or
Alternatively, various methods such as a method of adding a hydroxide sol to a liquid are possible. Further, a partially hydrolyzed silicon compound may be added. Since the silicon compound added to the coating solution for the photocatalyst layer also has the effect of increasing the adhesion of the photocatalyst layer in boiling water, the amount of the silicon compound added when the above-described silane coupling agent or the like is added is reduced. It is possible to reduce.

A metal oxide added to the coating solution for the photocatalyst layer and / or
Alternatively, the hydroxide sol is applied as a solid component to the coating solution.
It is desirable to add 0.1 to 30% by weight of the photocatalyst powder and / or sol to the coating solution as a solid component in an amount of 0.1 to 30% by weight, respectively.

The metal oxide and / or hydroxide sol has a poor function of adhering the photocatalyst to the substrate when added in an amount of 0.1% by weight or less, and the powder and / or sol of the photocatalyst and / or sol added simultaneously when the addition is 30% by weight or more. The amount decreases and the photocatalytic activity decreases. When the amount of the photocatalyst powder and / or sol is 0.1% by weight or less, the photocatalytic activity is low,
When the content is not less than% by weight, the amount of the metal oxide and / or hydroxide sol to be fixed to the base material is small, so that it is easy to peel off.

In the photocatalyst coating liquid of the present invention, since an adhesive layer is provided between the photocatalyst layer and the carrier, a coating liquid for the adhesive layer applied on the carrier can be used in combination. The coating liquid for the adhesive layer may be a silicone-modified resin having a silicon content of 2 to 60% by weight, a resin containing 3 to 60% by weight of polysiloxane or a resin containing 5 to 40% by weight of colloidal silica as a resin solid content. ~
Solutions containing 50% by weight can be used.

As the resin used in the coating solution for the adhesive layer, it is preferable to use the above-mentioned resin that can be used for the adhesive layer alone or as a mixture. The resin solid content is 1 to 50% by weight as an organic solvent solution or an aqueous emulsion. It is desirable to use a coating solution of With a coating liquid having a resin solid content of 1% or less, the adhesive layer becomes too thin, and adhesion of the photocatalyst layer becomes difficult. With a coating liquid having a resin solid content of 50% by weight or more, the adhesive layer becomes too thick, which is good. Not only does not give a good coating, but also the viscosity becomes too high and handling becomes difficult.

To form the photocatalyst layer on the adhesive layer, a suspension in which the photocatalyst is dispersed in a metal oxide sol or a metal hydroxide sol solution can be coated by the same coating method as that for forming the adhesive layer. . The photocatalyst may be dispersed in the state of a precursor solution of a metal oxide sol or a metal hydroxide sol, and may be hydrolyzed or neutralized and decomposed at the time of coating to form a sol or a gel. When using a sol, an acid or alkali peptizer may be added for stabilization. In addition, a surfactant or a silane coupling agent of 5% by weight or less with respect to the photocatalyst may be added to the sol suspension to improve adhesion and operability. The drying temperature at the time of forming the photocatalytic layer varies depending on the material of the carrier and the material of the resin in the adhesive layer, but is preferably from 50 ° C to 200 ° C.

As for the thickness of the photocatalyst layer, the thicker the photocatalyst layer, the higher the activity. Even at 5 μm or less,
It exhibits high catalytic activity and translucency, so that the catalyst layer is not conspicuous and is preferred. However, when the thickness is less than 0.1 μm, although the translucency is improved, since the ultraviolet ray utilized by the photocatalyst is transmitted,
High activity cannot be expected. When the thickness of the photocatalyst layer is 0.1 μm or more and 5 μm or less, and the photocatalyst particles having a crystal particle diameter of 40 nm or less and a metal oxide gel or a metal hydroxide gel having a specific surface area of 100 m ² / g or more are used, The total light transmittance of the adhesive layer at a total wavelength of 550 nm is 70% or more. The structure supported so that the total light transmittance at a wavelength of 550 nm is 70% or more can be used as illumination for transmitted visible light when the carrier is transparent, and can be used on the carrier even when the carrier is opaque. Since the pattern is not impaired, it is useful in terms of decorativeness.

The structure provided with the adhesive layer and the photocatalyst layer can be obtained in any complicated shape such as a film shape, a plate shape, a tubular shape, a fibrous shape, and a net shape. The size is 10
If it is at least μm, it can be firmly supported. As a carrier material, a structure provided with this adhesive layer and photocatalyst layer can be obtained even for an organic polymer that cannot be heated when it is carried or a metal that is easily oxidized and corroded by heat or water. Shows durability. To improve the adhesion between the carrier and the adhesive layer,
A carrier whose surface has been subjected to a discharge treatment or a primer treatment may be used.

The structure supporting the photocatalyst according to the present invention, as shown in the examples, architectural coatings, wallpaper, window glass, blinds,
It can be used for curtains, carpets, lighting fixtures, lighting lamps, black lights, antifouling paints for ship bottoms and fishing nets, fillers for water treatment, agricultural film, grass-proof sheets, packaging materials and the like. In addition, a photocatalyst carrier that can be used even under a high-temperature and high-humidity environment can be used.

In the structure according to the present invention provided with an adhesive layer and a photocatalytic layer,
Light of black light with UV intensity 3mW / cm ² at temperature 40 ℃,
Even after irradiation for 500 hours at 90% relative humidity, JIL K54
A material having high durability such that the adhesion by the crosscut tape method of No. 00 maintains an evaluation score of 6 or more can also be obtained. In the accelerated weathering test using a sunshine weather meter, even when the test time is 500 hours, there is also a material showing excellent weather resistance such that the adhesion by the cross-cut tape method of JIL K5400 maintains an evaluation score of 6 points or more. Have been obtained. 20 ° C
Conductivity at 200μS / cm after immersion in boiling water for 15 minutes, the adhesion by the cross-cut tape method specified in JIL K5400, a product exhibiting a high boiling water resistance with an evaluation score of 6 or more is also obtained. In addition, since all of the samples show high photocatalytic activity, they can have characteristics sufficient for the various uses described above.

The shape of the glass that can be used as a carrier is plate-like,
The glass provided with the adhesive layer and the photocatalyst layer can be obtained in any complicated shape such as a tubular shape, a spherical shape, and a fibrous shape. Also,
If the size is 10 μm or more, it can be firmly supported. In addition, depending on applications such as a window glass, a showcase, and glasses which have been completed, the photocatalyst-carrying glass of the present invention can be obtained by treating a processed glass.

The glass supporting the photocatalyst according to the present invention is a window glass,
It can be used in all kinds of use situations where effects such as antibacterial, deodorant, and antifouling are required, such as instrument cover glass, lighting equipment, lighting, black light, and filler for water treatment, as well as cameras and spectacle lenses.

The plastic molded article supporting the photocatalyst according to the present invention requires effects such as antibacterial, deodorizing, and antifouling effects, such as wallpaper, interior boards, furniture, electric equipment, vehicle parts, cameras, eyeglass lenses, and the like. Can be used in many situations.

Regardless of the shape of the plastic molded body, such as a film, a plate, a tube, a sphere, a fiber, or any other complicated shape, a plastic molded body provided with the adhesive layer and the photocatalyst layer can be obtained. If the size is 10 μm or more, it can be firmly supported. In addition, depending on applications such as completed building materials, home appliances, and glasses, the photocatalyst-carrying plastic molded article of the present invention can be obtained by processing the processed plastic molded article, so that the application range is extremely large. It can be said that it is wide.

As the fabric used in the present invention, wool, silk, cotton, natural fibers such as hemp, rayon, recycled fibers such as acetate,
A woven fabric, a knitted fabric, a nonwoven fabric, or the like made of a synthetic fiber such as nylon, acrylic, polyamide, polyester, polyacrylonitrile, or polyvinyl chloride, or a heat-resistant fiber such as aramid alone or a blended fiber can be used. In addition, fabrics treated with a water repellent such as a silicon water repellent, a fluorine water repellent such as perfluoroalkyl acrylate, a zirconium salt-based water repellent, an ethylene urea water repellent, etc. Water-repellent fabrics using a cross-linking agent such as ethyleneimine-based, epoxy-based, or melamine-based to improve the quality, artificial leather, woven fabric, non-woven fabric, and knitted fabric made of fibrillated composite fibers of polyamide and polyester. Synthetic leather in which a polyurethane resin layer is formed on a base material such as cloth via a polyurethane adhesive can also be used. Further, the photocatalyst-carrying fabric of the present invention can be obtained by treating a processed fabric such as an umbrella, a tent, and a bag.

The fabric carrying the photocatalyst according to the present invention has antibacterial, deodorizing,
It can be used in many applications where an effect such as antifouling is required, for example, interior products such as curtains and wallpapers, daily necessities such as tents, umbrellas, tablecloths, food packaging materials, etc., and also in the agricultural field such as seedling raising sheets.

As the metal carrying the photocatalytic ability shown in the present invention, various metals such as stainless steel, brass, brass, aluminum alloy, titanium alloy and the like can be used as the carrier in addition to simple metals such as aluminum, iron and copper. In addition, depending on the shape and material of the metal used, a photocatalyst carrier may be provided by providing an adhesive layer and a photocatalyst layer according to the present invention on a metal sheet or plate coated with a normal paint, a colored steel plate or a color aluminum sash, or the like. In this case, it is preferable that the adhesive layer and the photocatalyst layer have high light transmittance and are transparent because the color of the base paint is not impaired.

The metal provided with the adhesive layer and the photocatalyst layer can be obtained in any complicated shape such as a plate, a tube, a sphere, a fiber, and a sheet. If the size is 10 microns or more, it can be firmly supported. In addition, depending on uses such as a window frame, furniture, a showcase, and an eyeglass frame which have been completed, the photocatalyst-carrying metal of the present invention can be obtained by treating a processed metal.

The metal supporting the photocatalyst shown in the present invention is a window frame, furniture,
It can be used in many applications requiring antibacterial, deodorizing, and antifouling effects, such as decorative articles, interior panels, exterior panels, fillers for water treatment, strainers, filters, and the like.

The shape of the wood or wood material provided with the adhesive layer and the photocatalyst layer according to the present invention can be any complicated shape such as a plate, a plate, a sphere, and a sheet. Also, the size is
If it is 10 μm or more, it can be firmly supported, and it can be processed into processed wood such as walls, ceiling panels, pillars, furniture, woodwork, etc. And wood materials.

The wood and wood material supporting the photocatalyst according to the present invention can be used in many use situations requiring antibacterial, deodorizing, antifouling and other effects, such as building materials, furniture, woodwork, interior materials and interior materials.

The plastic film provided with the photocatalyst supporting structure according to the present invention is a film in which an adhesive is applied to a surface not supporting a photocatalyst by utilizing its antifouling, antibacterial, and deodorizing functions, thereby enabling automobiles and various transport equipment. Can be attached to the inside of windows of buildings, windows of buildings, frozen / refrigerated showcases, greenhouses, etc. to decompose trace harmful substances in the internal space, prevent contamination of the glass surface and prevent scattering when broken. It is possible to obtain a highly transparent film that is effective for In addition, a thin plastic film on which the photocatalyst-supporting structure according to the present invention is formed can be used 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,
Linear transmission of light with a wavelength of 550nm when formed into a film such as polyimide resin, polystyrene resin, polyvinyl chloride resin, polyvinylidene fluoride resin, fluoroethylene-propylene copolymer resin, or fluoroethylene-ethylene copolymer resin Any highly transparent synthetic resin film or sheet having a ratio of 50% or more can be used. Further, the photocatalyst supporting structure according to the present invention is also 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, so that the underlying wallpaper or a decorative sheet is used. It can be preferably used because the pattern or pattern printed on the surface is not damaged.

The surface of these synthetic resin films or sheets can be subjected to surface treatment to further improve the adhesiveness of the adhesive layer of the photocatalyst supporting structure, and the surface to which the adhesive layer is applied is subjected to corona discharge treatment or UV-ozone treatment. It is also preferable to use a material whose surface is physically oxidized in a trace amount by a method such as a method in which a surface treatment agent such as a silicon-based material is thinly applied to improve the familiarity with the adhesive layer. Further, as shown in the examples, it is possible to form a thin film on the surface or the back surface of these base materials so as to have a heat ray reflection / shielding function or an ultraviolet ray reflection / shielding function. -In addition to being able to be a heat reflection film or an ultraviolet cut film having a deodorizing function, the photocatalyst supporting structure according to the present invention has extremely high durability and photocatalytic activity as shown in the examples. As a result, it is possible to obtain a product with extremely high added value.

As a method for providing the above-mentioned heat ray reflection function,
Conductive metals such as Al, Ag, Cu, Cr, Ni, Ti, stainless steel, aluminum alloys, indium oxide, tin oxide, tin oxide
A method of depositing a conductive metal oxide such as an indium oxide compound on a film surface by a physical method such as sputtering or vacuum deposition, a method of applying a conductive metal oxide solution or a sol solution, drying and applying a plating method, Various methods such as a method of forming a film on a film surface by a CVD method and a method of mixing a material having a heat ray reflection property or a heat ray shielding property in a resin of a base material can be adopted. In addition, as a method of providing an ultraviolet shielding function, a method of applying an ultraviolet absorber or a reflecting agent such as a hindered amine or titanium oxide to the surface of a film to form a film, or adding an ultraviolet absorber to a film base material in advance and mixing. Various methods such as preparatory methods can be adopted, and an appropriate method can be selected according to the purpose of use and structure. When using titanium oxide as an ultraviolet shielding agent or a reflective agent, as described in detail in the present invention, since titanium oxide alone decomposes surrounding organic substances by photocatalysis, the surface of titanium oxide is thinned with water glass or the like. It is desirable to use a coating which has lost photocatalytic activity.

Further, such a material having a heat ray reflection function or a material having an ultraviolet ray shielding function can be added to and mixed with an adhesive layer formed on the back surface of the film to exhibit the effect. For example, "Convertec", March 1996 Materials such as an ultraviolet shielding clear coat agent described in the monthly issue pp95 are of a solvent dispersion type and can be used. As the pressure-sensitive adhesive, an acrylic or silicone-based pressure-sensitive adhesive is usually used, and various ultraviolet ray shielding agents and heat ray shielding agents can be added to the pressure-sensitive adhesive. It is desirable to avoid using a pressure-sensitive adhesive having strong adhesiveness in consideration of contamination due to the residual adhesion of the pressure-sensitive adhesive at the time of replacement. As a method of providing an adhesive and a release film on the photocatalyst-supporting film, for example, a solution-type adhesive is coated on the back surface of the film by gravure printing, and then dried and wound up, and a polypropylene film for release is laminated and wound up The method described above is simple and preferably employed.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic view of a cross section of a photocatalyst supporting structure of the present invention.

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples.

<Evaluation Test Method> 1) Evaluation of Photocatalytic Activity A sample carrying a photocatalyst having a size of 70 mm × 70 mm was placed in a Pyrex glass container having a capacity of 4 L. In this container, a mixed gas of air and aldehyde was added.
pm. UV intensity 2mW / cm ²
Black light (FL 15BL-B manufactured by Matsushita Electric Co., Ltd.)
Was irradiated for 2 hours, the aldehyde gas concentration in the container was measured by gas chromatography, and the photocatalytic activity was evaluated from the decrease. The evaluation criteria were as follows.

Aldehyde gas concentration after irradiation for 2 hours Evaluation 50ppm or less A 50-200ppm B 200-300ppm C 300-450ppm D 450ppm or more E 2) Adhesion evaluation Adhesion is evaluated by the cross-cut tape test specified in JIS K 5400. went. The interval between cuts was 2 mm, and the number of squares was 25. The evaluation score was based on the standard described in JIS K 5400.

3) Immersion test in boiling water Tap water with a conductivity in the range of 170 to 230 μS / cm was placed in a 1000 ml Pyrex glass beaker with a small amount of zeolite, and after heating and boiling, the entire sample cut into 70 mm × 70 mm was submerged. Hang it with a commercially available clip so that it sinks in. After being immersed in boiling water for 15 minutes, it was allowed to cool at room temperature for 4 hours and dried, and then subjected to the adhesion test described in 2), and the evaluation score was obtained according to the standard described in JIS K5400.

4) Total light transmittance The total light transmittance at a wavelength of 550 nm of the supported sample was measured with a self-recording spectrophotometer (U-4000 manufactured by Hitachi, Ltd.) using the carrier before supporting the adhesive layer and the photocatalytic layer as a reference.

5) Durability evaluation The supported sample was irradiated with black light using an ultraviolet intensity of 3 mW / cm ^2.
Of light in a constant temperature / humidity bath at a temperature of 40 ° C and a relative humidity of 90% for 500 hours, and then perform the adhesion test described in 2) and follow JIS K540
The evaluation score was obtained according to the criteria described in 0.

6) Accelerated weathering test using a sunshine carbon arc weather meter The accelerated weathering test using a sunshine carbon arc weather meter specified in JIS K5400 was performed using a WEL-SUN-HCH type manufactured by Suga Test Instruments Co., Ltd. The test was performed under the conditions of 500 hours, a black panel temperature of 63 ° C., a cycle of 120 minutes, and a rainfall of 18 minutes. After subjecting three samples to the accelerated weathering test, the presence or absence of blistering, cracking, peeling, and whitening and changes in the surface are visually compared with the original test specimen not subjected to the accelerated weathering test. evaluated.

Evaluation Criteria A: No change was observed in any of the three samples. B: A slight change was observed in one or two samples. C: A slight change was observed in all three samples, or one or two samples. In addition, after the test, the adhesion test described in 2) was performed and the JI
The evaluation score was obtained based on the standard described in SK5400.

7) Antibacterial evaluation test method A sample cut into 5 cm squares is disinfected with 80% ethanol and 150
After it dried sterilized at ° C., to set the bacterial suspension of E. coli which had been adjusted to dropped incubator before 0.2ml sample 10 ⁵ cells / ml of cell concentration by performing dilution and pre-preculture. Irradiated with black light (2 x 15 W, 10 cm distance from light source), illuminated with fluorescent light (2 x 15 W, distance 10 cm from light source), or not irradiated with light , 3
Four samples are set under each kind of light irradiation condition. After a predetermined time (1, 2, 3, 4 hours), the sample is taken out, and the bacterial solution on the sample is wiped off with sterile gauze immersed in sterile physiological saline. Put the wiped sterile gauze in 10 ml of sterile physiological saline and mix well. The supernatant is inoculated on an autoclave-sterilized 95 mmφ Petri dish agar medium, and cultured at 36 ° C. for 24 hours, and the number of E. coli colonies is counted. The same procedure was followed to drop the Escherichia coli bacterial solution and put it into the incubator.The sample was treated in the same manner, and the number of E. coli colonies was counted. Then, the survival rate of each sample at a predetermined time after the irradiation with the fluorescent lamp is calculated. Evaluation criteria were based on the following criteria. Residual rate of E. coli after 4 hours Evaluation 20% or less A 20% to 40% B 40% to 60% C 60% to 80% D 80% or more E 8) Antifouling property ( Evaluation of oil-fat decomposition activity) As an index for evaluating the antifouling function, a commercial salad oil containing linoleic acid as the main component was used to measure how quickly oil-fat components adhering to the surface can be decomposed. The amount of decomposition in was determined. Salad oil 1cm thinly with paper on the surface of the photocatalyst supporting structure cut into 5cm square
^It applied so that it might become 0.1-0.15 mg per ² . The amount of coating was determined by measuring the weight before and after coating with a precision balance. Samples were adjusted to the distance between the sample and black light to ultraviolet intensity at the sample surface is 3 mW / cm ^2, after lighting black light, seeking relationship elapsed time and weight loss, salad oil after predetermined time The amount of decomposition was measured and used as an index of antifouling property.

Salad oil residual ratio after light irradiation for 24 hours Evaluation 10% or less A 30 to 10% B 50 to 30% C 80 to 50% D 80% or more E <Example> The following materials were used as the material of the carrier.

(TA) Primer-treated polyester film (TB) Vinyl chloride film (TC) Soda lime glass plate (TD) Metal aluminum plate (TE) High-density polyethylene net (Thread thickness 0.2 mm, mesh opening 0.6 mm (TF) Polypropylene tube (inner diameter 30 mm, outer diameter 36 mm) The following polysiloxane was used in the adhesive layer.

(PS-1) Silicon tetramethoxide monomer (manufactured by Shin-Etsu Chemical) (PS-2) Polymethoxysiloxane (product name Colocoat trade name methyl silicate 51) (PS-3) Polyethoxysiloxane (product name Colcoat product trade name ethyl silicate 40) Adhesion The following were used as the colloidal silica contained in the layer.

(KS-1) Catalyst Chemicals trade name Cataloid SI-350, particle diameter 7-9nm (KS-2) Nissan Chemical trade name Snowtex ST-XS, particle diameter 4-6nm Resin which introduces polysiloxane or colloidal silica The following solutions were used.

(J-1) Acrylic-silicone resin xylene solution having a silicon content of 3% by weight (J-2) Acrylic-silicon resin xylene solution having a silicon content of 10% by weight (J-3) Acrylic-silicon resin having a silicon content of 20% by weight Silicone resin emulsion aqueous solution (J-4) Acrylic-silicon resin emulsion aqueous solution having a silicon content of 50% by weight (J-5) Polyester-silicon resin xylene solution having a silicon content of 10% (J-6) Acrylic resin xylene solution (J -7) Polyester resin xylene solution (J-8) Epoxy-silicon resin methyl ethyl ketone solution having a silicon content of 3% by weight Polysiloxane or colloidal silica was mixed with the resin solution to adjust the concentration, thereby obtaining a solution for forming an adhesive layer. The adhesive layer was formed by a dipping method when the thickness was 2 μm or less and a shape other than a flat plate, and was formed by a baker applicator when the thickness was 2 μm or more and a flat shape.
In particular, when the shape of the carrier was tubular or net-like, the dipping method was used. The drying of the adhesive layer is performed when the material of the carrier is (TE),
(TF) at 80 ° C, (TB) at 60 ° C, otherwise
Performed at 120 ° C.

 The following were used as the photocatalyst.

(C-1) Titanium oxide fine particles (trade name P-25, manufactured by Nippon Aerosil Co., Ltd., crystal particle diameter 27 nm) (C-2) Titanium oxide sol (acid nitric acid sol, crystal particle diameter)
(C-3) Titanium oxide sol (pH9 weak alkaline sol,
(Crystal particle diameter: 20 nm) The metal oxide gel or metal hydroxide gel supported together with the photocatalyst was obtained by drying the following sol solution.

(Z-1) Silica sol: Catalysis SI, manufactured by Catalyst Kasei
−30, specific surface area after drying at 150 ° C. 180 m ² / g (Z-2) alumina sol: alumina sol manufactured by Nissan Chemical Co., Ltd.
Specific surface area after drying at 200, 150 ° C. 400 m ² / g (Z-3) zirconia sol: hydrolyze zirconium tetrabutoxide (TBZR) manufactured by Nippon Soda in ethanol,
After drying at 150 ° C and then heat-treating at 300-500 ° C, the specific surface area of peptized with dilute nitric acid aqueous solution, and further dried at 150 ° C is 50-80m2 / g (Z-4) niobium oxide sol : Specific surface area of CBMM niobium acid aqueous solution neutralized with 10% ammonia water, dried at 150 ° C and then peptized with dilute nitric acid aqueous solution, and peptized product dried at 150 ° C has a specific surface area of 60m2 / g (Z- 5) Aqueous solution of acrylic silicon resin emulsion containing 20% by weight of silicon (Z-6) Silane coupling agent manufactured by Nippon Unicar
Tri (β-methoxyethoxy) vinylsilane (trade name: A
-172) A titanium oxide photocatalyst was dispersed in the above solution, and a predetermined amount of a surfactant was added to obtain a solution for forming a photocatalyst layer. The photocatalyst layer was formed by a dipping method when the thickness was 2 μm or less or the carrier shape was other than a flat plate, and was formed by a bar coater when the carrier was a flat plate and the thickness was 2 μm or more. The drying of the photocatalyst layer
Performed at the same temperature as the adhesive layer was dried.

Hereinafter, the compositions of Examples and Comparative Examples in which the types, amounts, thicknesses, film forming methods, and the like of the above materials were changed, and the performances of the obtained photocatalyst-supporting structures are collectively described in Tables 1 to 4.

In Examples 1 to 18 and Comparative Examples 1 to 4, titanium oxide (P) manufactured by Japan Aerosil Co., Ltd.
-25) was used. The results are shown in Table 1.

Comparative Example 1 was a case where the photocatalyst layer was carried without providing the adhesive layer. The photocatalyst layer had no adhesion and was easily peeled off. Degraded by the action, holes and cracks were observed.

In Examples 1-1 and -2, acrylic-silicon resin or polyester-silicon resin was used for the adhesive layer, and the adhesion of the photocatalyst layer was good and the durability was good.

In Examples -3 to -12, when the resin containing polysiloxane was used for the adhesive layer, the catalytic activity was good, and the adhesion and durability were also good. The resin into which the polysiloxane was introduced was an acryl-silicone resin (Examples 3, 4,
5) or polyester-silicone resin (Example-)
Even in the case of 9), the durability was good. Even when the resin into which the polysiloxane was introduced was an acrylic resin (Example-7) or a polyester resin (Example-12), a good product was obtained.

On the other hand, as shown in Comparative Example-2, even when the acrylic-silicon resin containing polysiloxane was used for the adhesive layer, when the content of polysiloxane was 70% by weight,
The photocatalyst layer did not adhere and peeled off.

In Examples -13 to -18, the resin containing colloidal silica was used for the adhesive layer, and the catalytic activity, adhesion and durability were good. In particular, when a resin having a fine particle diameter (KS-2) is used for the colloidal silica and the resin into which the colloidal silica is introduced is an acrylic-silicon resin (Examples 15 and 16), very good results are obtained. Thing was obtained.

On the other hand, when the content of the colloidal silica in the adhesive layer was as large as 50% by weight (Comparative Example-3), the adhesion and durability were rapidly deteriorated.

In Examples -1 to -18, titanium oxide (P-25) manufactured by Nippon Aerosil Co., Ltd. shown in (C-1) was used as a photocatalyst.
Most of the metal oxide sol or metal hydroxide sol complexed to the photocatalyst layer uses silica sol, but all of them are good. In Examples -8 and -9, the results of carrying on a polyethylene net or polypropylene tube were shown, but a product excellent in photocatalytic activity, adhesion and durability was obtained. Even if the content of the silica sol in the photocatalyst layer was reduced to 30% by weight (Example-6), a good product was obtained. However, if the content was reduced to 20% by weight (Comparative Example-4), adhesion and durability were improved. Got worse quickly.

In Example-11, alumina sol was used instead of silica sol, and a good product was obtained as in the case of silica sol.

In Example-17, the thickness of each of the adhesive layer and the photocatalyst layer was set to 0.
The values of 5 μm and 0.1 μm were shown, but the adhesion and durability were good, and the photocatalytic activity showed a high value even though the film thickness was extremely thin.

 The data of Examples -19 to 23 are shown in Table 2.

Example -19 Use of titania sol Instead of fine particle titanium oxide (P-25) manufactured by Nippon Aerosil Co., Ltd., a nitric acid titania sol (titanium oxide content: 12% by weight) was replaced with a silica sol (catalyst SI-
30) was added to the mixture adjusted to pH 1.5, dispersed, and a surfactant was added to obtain a coating solution for a photocatalyst layer. Polymethoxysiloxane (PS-2) was added to the resin solution used in Example-10.
Was added so that the SiO ₂ content in the dried adhesive layer was 35% by weight to prepare a solution for the adhesive layer.

An adhesive layer was applied to a soda-lime glass substrate cut to 7 cm × 7 cm and having a thickness of 1 mm using a baker applicator, and a photocatalytic layer was applied using a bar coater. The drying temperature was the same as in the above example.

The obtained photocatalyst carrier had a very high total light transmittance.

Example -20 Use of silica-alumina sol Example 19 was repeated except that the silica sol used in Example 19 was replaced by a 50:50 mixed sol solution of alumina sol and silica sol manufactured by Nissan Chemical Industries, Ltd. A photocatalyst carrier was produced using exactly the same raw materials and method.

The obtained photocatalyst carrier had high adhesiveness and high catalytic activity.

Example-21 Coating by gravure printing method Using the adhesive layer solution and the photocatalyst solution used in Example-9, a polyester film (Cosmoshine A4100) manufactured by Toyobo Co., Ltd. was dried to a thickness of 3 μm. Gravure printing was performed at a speed of 10 m / min and a temperature of 130 ° C. in the drying zone. A microgravure coater (70 cm width) manufactured by Yasui Seiki Co., Ltd. was used for printing.

The resulting photocatalyst carrier had a very high total light transmittance of 95%.

Example-22 Application by Spray Method Using the adhesive layer solution and the photocatalyst layer solution used in Example-9, a spray gun WIDER88 manufactured by Iwata Coating Machine Industry Co., Ltd. was used on a soda lime glass substrate. Spray applied. Both the adhesive layer and the photocatalyst layer were dried at 120 ° C. for 30 minutes.

The obtained photocatalyst carrier had good adhesiveness and photocatalytic activity.

Example 23 Use of Epoxy-Silicone Resin The same procedure as in Example 12 was repeated, except that the polyester resin xylene solution was replaced by a 3 wt% silicon content epoxy resin methyl ethyl ketone solution. A photocatalyst carrier was prepared.

The obtained photocatalyst carrier had good adhesiveness and photocatalytic activity.

Table 3 shows the compositions and performance test results of Examples 24 to 35 below.

In Examples -24 to -25, an acrylic-silicon resin is used for the adhesive layer, and 50% by weight of fine particles of titanium oxide P-25 (C-1) manufactured by Nippon Aerosil Co., Ltd. are shown in (Z-1) as the photocatalytic layer. This is an example of using a composite obtained by preparing a raw material powder and a sol solution so as to have a composition containing 25% by weight of a silica sol and 25% by weight of an alumina sol shown in (Z-2). It was good, and durability and accelerated weather resistance were also good.

In Examples -26 to -31, a resin containing a polysiloxane was used for the adhesive layer, and in the photocatalyst layer, fine particles of (C-1) titanium oxide were used in Examples -26 to -28. For −31, the titania sol of (C-2) was used, and the type and amount of the sol liquid for forming the gel to be composited were changed.
The catalyst activity was good, and the adhesion, durability, and accelerated weather resistance after the boiling water test were all good. The resin into which the polysiloxane was introduced was an acryl-silicone resin (Example-26,
-27, -28) or epoxy-silicone resin (Examples -29, -30) showed good adhesion, durability, and accelerated weather resistance after the boiling water test. As the resin into which polysiloxane was introduced, an excellent resin was obtained even with an acrylic resin (Example-31).

In Examples -32 and -33, the results were shown in which they were supported on polyethylene nets or polypropylene pipes. However, products having good photocatalytic activity, adhesion and durability were obtained.

In Examples -32 to -35, a resin containing colloidal silica was used for the adhesive layer, and the catalytic activity, adhesion after boiling water test, durability, and accelerated weather resistance were good. In particular,
In the case where a fine particle (KS-2) is used as the colloidal silica and the resin into which the colloidal silica is introduced is an acrylic-silicon resin emulsion (Example-3)
4, 35), very good products were obtained.

In Example-29, the nitric acid-titania sol (titanium oxide content: 12% by weight), the silica sol (catalyst SI-30) manufactured by Catalysis Chemical Co., Ltd., and the alumina sol-200 manufactured by Nissan Chemical Co., Ltd. were adjusted to pH 1.5 and dispersed in the photocatalyst layer. Then, a predetermined amount of a surfactant was added to make a coating solution for the photocatalyst layer, and the thickness of the adhesive layer and the photocatalyst layer was set to 0.5 μm and 0.3 μm, respectively, by a dipping method. Thus, the photocatalytic activity also showed a high value for a small film thickness.

Even if the total content of the silica sol and the alumina sol in the photocatalyst layer was reduced to 30% by weight (Example -30), a good product was obtained.

The samples obtained in Examples -24 to -35, which were subjected to a durability test using a black light under high temperature and high humidity, a boiling water immersion test, and an accelerated weather resistance test using a sunshine carbon arc weather meter, were again subjected to photocatalytic activity. The amount of acetaldehyde photodegraded by the same method as the initial test showed that all samples showed exactly the same decomposition activity as the initial acetaldehyde decomposition, and the initial photocatalytic activity was completely maintained. Was.

The compositions and performance test results of the following Examples 36 to 53 are shown in Table 4,
The results are shown in Table 5.

Comparative Example-5 is a case where the photocatalyst layer was carried without providing the adhesive layer. The photocatalyst layer did not have any adhesiveness and was easily peeled off. Degraded by the action, holes and cracks were observed with a stereoscopic microscope.

In Examples -36 to -37, an acrylic-silicon resin was used for the adhesive layer, 40 to 50% by weight of fine particles of titanium oxide P-25 manufactured by Nippon Aerosil Co., Ltd. were used as the photocatalyst layer, and the silica sol shown in (Z-1) was 40%. Wt.%, Acrylic silicone resin emulsion 10 ~ 20 wt.% The composition is prepared by preparing a raw material powder and a sol solution so as to have a composition of 10 ~ 20% by weight. The properties and accelerated weather resistance were also good.

In Examples -38 to -42, an acrylic-silicon resin containing polysiloxane was used for the adhesive layer, and the same photocatalyst powder as in Example -36 was used for the photocatalyst layer to form a composite gel. The type and amount of the sol were changed and used, and the catalyst activity was good, and the adhesion, durability, and accelerated weather resistance after the boiling water test were all good. Acrylic-silicone resin containing 3% silicon content (Examples -38 and 39) or acrylic-silicon resin containing 10% silicon content (Examples -40, 41 and 4)
In each of 2), adhesion, durability and accelerated weather resistance after the boiling water test were good.

In Examples -44 and -45, the results were shown in which the carrier was supported on a polyethylene net or a polypropylene tube, but a product excellent in photocatalytic activity, adhesion and durability was obtained.

As the resin into which polysiloxane was introduced, a good epoxy-silicone resin (Examples 43 and 46), a polyester resin (Example 44), and an acrylic resin (Example 47) were also obtained.

On the other hand, as shown in Comparative Example-6, even if an acrylic-silicon resin containing polysiloxane was used for the adhesive layer, if the polysiloxane content was 70% by weight,
The photocatalyst layer did not adhere and peeled off.

In Examples -48 to -53, a resin containing colloidal silica was used for the adhesive layer, and the catalytic activity, adhesion after boiling water test, durability, and accelerated weather resistance were good. In particular,
In the case where a resin having a fine particle diameter (KS-2) is used as the colloidal silica, and the resin into which the colloidal silica is introduced is an acrylic-silicon emulsion resin (Example-50,
~ 53), very good products were obtained.

On the other hand, when the content of the colloidal silica in the adhesive layer was as large as 50% by weight (Comparative Example-7), the adhesiveness and durability were rapidly deteriorated.

In Examples -44 to -47, instead of the fine particle titanium oxide (P-25) manufactured by Nippon Aerosil Co., Ltd. for the photocatalyst layer, a nitric acid titania sol (titanium oxide content: 12% by weight) and a silica sol manufactured by Catalysis Chemical Co., Ltd. -30) and Nissan Chemical's alumina sol-200 or Nippon Soda's zirconia sol
It was adjusted to H1.5 and dispersed, a predetermined amount of surfactant was added to make a coating solution for the photocatalyst layer, and the adhesive layer and the photocatalyst layer were provided by the bar coating method, but the adhesion and durability were good. Thus, the photocatalytic activity also showed a high value for a small film thickness.

Even if the total content of the acryl-silicone resin emulsion and the silane coupling agent in the photocatalyst layer was reduced to 20% by weight (Example-47), a good product was obtained. Example -8), even when an acrylic-silicone emulsion resin was added, the adhesion and durability were sharply reduced.

The samples obtained in Examples -36 to -53, which were subjected to a durability test using black light under high temperature and high humidity, a boiling water immersion test, and an accelerated weather resistance test using a sunshine carbon arc weather meter, were again subjected to photocatalytic activity. Was examined by the amount of photodegradation of acetaldehyde by the same method as in the initial stage, and all samples showed exactly the same value as the initial amount of acetaldehyde decomposition, indicating that the initial photocatalytic activity was completely maintained. .

Example-54 A sample of the titanium oxide photocatalyst structure was prepared by the same method as that used in Example 42, and the antibacterial property was evaluated using the sample.

As a result, in a dark place where no light was irradiated, the survival rate of E. coli was 92% after 1 hour, 91% after 2 hours, and 91% after 3 hours. Irradiated, the survival rate after 1 hour was 52% and after 2 hours was 29%
% After 3 hours. In addition, the viability of Escherichia coli was 76% after 1 hour, 54% after 2 hours, and 22% after 3 hours even when irradiated with fluorescent light. Higher antibacterial properties were shown.

The following silicon compounds were used for the coating solution of the photocatalyst.

(S-1) 5% by weight ethanol solution of tetraethoxysilane (Wako Pure Chemicals reagent grade) (S-2) 5% by weight ethanol solution of tetramethoxysilane (Shin-Etsu Chemical) (S-3) Methyltriethoxysilane (S-4) Tri (β-methoxyethoxy) vinylsilane (manufactured by Nippon Unicar: trade name: A-172) 5% by weight ethanol solution (Z-1) ) To (Z-3), the titanium oxide photocatalyst powder or the sol solution in the sol solution and the silicon compound solution is adjusted to an appropriate range of pH 1.5 to 9 depending on the type of raw materials and additives used. The mixture was dispersed in water or a mixed solvent of water and ethanol as a solvent, and a predetermined amount of a surfactant was added to obtain a coating solution for forming a photocatalyst layer. Table 6 summarizes the content of the components contained in the coating solution of the obtained photocatalyst layer, the viscosity immediately after preparation of the coating solution and 90 days after sealing, and the sedimentation state of the particles.

Examples -55 to -57 show that titanium oxide powder (P-
25) Example of using 90
The stability of the photocatalyst coating liquid after a lapse of days has become very good.

In Examples -58 to -60, a nitric acid-titania sol was used as a photocatalyst, and in Examples -59 and -60, silica sol and alumina sol were used in combination as a metal oxide sol to be complexed, and methyltriethoxysilane was used as a silicon compound. Used. This makes it possible to significantly improve the boiling water resistance of the coated product formed using this coating solution, particularly the boiling water resistance in tap water. In Examples -61 and -62, tetramethoxysilane was used as the silicon compound, and the effect of maintaining the stability of the liquid could be obtained even with a small amount of addition.

In Example-63, powdery titanium oxide (P
-25) and nitric acid-titania sol are used in combination. As the metal oxide sol to be complexed, silica sol and zirconia sol are used in combination, and tetramethoxysilane is added so that the stability of the coating solution and the sedimentation of the particles are good. Could be something.

In Examples -64 to -66, coating liquids were prepared by changing the type of the silicon compound, and all of them were stable coating liquids with a predetermined addition amount.

On the other hand, in Comparative Examples -9 to -13, since no silicon compound was added, the viscosity of the coating solution was extremely increased after 90 days, and the sedimentation of particles always occurred. When used as a liquid, it was difficult to control the film formation conditions, and it was not possible to obtain a photocatalyst-coated product of a constant quality.

<Examples 67 to 71> Using the photocatalyst coating solutions prepared in Examples -55 to -59, photocatalyst-coated products were prepared using the following carriers.
The following materials were used as the material of the carrier.

(SA) Primer-treated polyester film (SB) Soda-lime glass plate (SC) Metal aluminum plate (SD) High-density polyethylene mesh (thickness 0.2 mm, mesh opening 0.6 mm) (SE) Polypropylene tube ( When the thickness of the adhesive layer is less than 2 microns or the carrier shape is other than flat, use the dipping method. When the carrier is flat and the thickness is more than 2 microns, use a baker applicator. Formed. Drying of the adhesive layer depends on the material of the carrier, (S
D) and (SE) were performed at 80 ° C, and the others were performed at 120 ° C.
The photocatalyst layer was formed by dipping when the thickness was 2 μm or less or the carrier shape was other than a flat plate, and was formed by a bar coater when the carrier was a flat plate and the thickness was 2 μm or more. The drying of the photocatalyst layer was performed at the same temperature as the drying of the adhesive layer. Hereinafter, the types and amounts of the above materials, the thickness of the coating film,
Tables 7 and 8 collectively describe the performances of the photocatalyst supporting structures of Examples and Comparative Examples in which the film forming method and the like were changed.

The samples obtained in Examples -67 to -71, which were subjected to a durability test using black light under high temperature and high humidity, a boiling water immersion test, and an accelerated weather resistance test using a sunshine carbon arc weather meter, were again subjected to photocatalytic activity. Was examined by the amount of photodegradation of acetaldehyde by the same method as in the initial stage, and all samples showed exactly the same value as the initial amount of acetaldehyde decomposition, indicating that the initial photocatalytic activity was completely maintained. .

Example-72 A sample of the titanium oxide photocatalyst structure was prepared by the same method as that used in Example 67, and the sample was used to evaluate the antibacterial property by the above method. As a result, in a dark place where no light was irradiated, the survival rate of E. coli was 92% after 1 hour, 91% after 2 hours, and 91% after 3 hours. Is 1
Survival after 52 hours, 29% after 2 hours, 11 after 3 hours
%Met. In addition, the viability of Escherichia coli was 76% after 1 hour, 54% after 2 hours, and 22% after 3 hours even when irradiated with fluorescent light. Higher antibacterial properties were shown.

Example 73 Adhesive Processed Film Acrylic-silicone resin having a silicon content of 3% by weight was added to 25
Xylene-isopropanol containing 50% by weight (50/50)
The solution was mixed with 30% by weight of polysiloxane [methyl silicate 51 manufactured by Colcoat Co., Ltd.] based on the acrylic-silicon resin and 5% by weight of a curing agent (silane coupling agent) based on the acrylic-silicon resin. The obtained adhesive layer solution is mixed with a methyl ethyl ketone solvent to obtain a solid content of 10% by weight.
It was diluted to become.

The diluted solution was applied to a polyester film (Cosmo Shine 50 μm) A4100 manufactured by Toyobo Co., Ltd. using a microgravure coater (70 cm width) manufactured by Yasui Seiki Co., Ltd. Drying zone temperature 1
3 Next, as a photocatalytic layer, a nitric acid titania sol having a titanium oxide content of 20% by weight was dispersed in the polyester film having the adhesive layer formed thereon in a nitric acid silica sol having a silicon oxide content of 20% in the presence of a surfactant. And then diluted with ion-exchanged water-ethanol (50/50) to obtain a solid content of 1
Gravure printing was performed in the same manner as the adhesive layer using a solution prepared as a coating solution of the photocatalyst layer of 0% by weight to obtain a polyester film having a photocatalyst layer having a dry film thickness of 1 μm.

Next, a commercially available acrylic pressure-sensitive adhesive was similarly applied to the surface of the polyester film having the photocatalyst supporting structure, which was not coated with the photocatalyst, by a gravure printing method, and a heat ray shielding coating agent STS-500 manufactured by Sumitomo Osaka Cement Co., Ltd. Was added and mixed so that the solid content was 5%. When this adhesive-coated film is dried and wound up in a drying zone of a gravure printing machine, a polypropylene film (Pyren film-OT20 μm) P-2161 manufactured by Toyobo Co., Ltd.
Was laminated and wound up to obtain an adhesively-processed sticking film.

This film can be used as an adhesive film to be applied to automotive window glass, general household window glass, medical facility window glass, etc.
It could also be used as a shatterproof film in the event of glass breakage.

Example 74 Plate Glass Acrylic-silicon resin having a silicon content of 3% by weight was cut into soda lime glass having a thickness of 1 mm cut into a size of 5 cm × 5 cm.
Xylene-isopropanol containing 25% by weight (50/5
0) A solution obtained by mixing a polysiloxane (methyl silicate 51 manufactured by Colcoat Co., Ltd.) in an amount of 30% by weight with respect to the acrylic-silicone resin was applied to the solution using a No. 7 bar coater, and then 100 ° C.
For 60 minutes to form an adhesive layer. After cooling at room temperature, a nitric acid titania sol having a titanium oxide content of 20% by weight was dispersed in a nitric acid acidic silica sol having a silicon oxide content of 20% in the presence of a surfactant to form a photocatalytic layer coating solution.
Using this solution, it was applied to the surface of the adhesive layer with the same bar coater as No. 7, and dried at 100 ° C. for 60 minutes to obtain a photocatalyst-supporting glass. (Sample.1) Example 75 Glass Fiber Paper The adhesive layer solution used in Example 74 was diluted with a xylene-isopropanol (50/50) solution to a solid content of 5% by weight. This diluted solution was added to E-vest Co., Ltd. E-
Glass-fiber paper SAS-030 (basis weight 30 g / m2) was dipped, pulled up and allowed to stand, and then dried at 100 ° C. for 120 minutes to form an adhesive layer on the surface of the glass-fiber paper. Next, the glass fiber paper having the adhesive layer formed thereon is immersed in a solution obtained by diluting the coating solution for the photocatalyst layer used in Example 74 to 10% by weight with ion-exchanged water, pulled up, and similarly dried at 100 ° C. for 120 minutes As a result, a photocatalyst-supporting glass fiber paper was obtained. (Sample.2) Example 76 Eyeglass Lens Nikon Corporation Eyeglass Lens PC Pointer Coat TC
(+) 1.00S0.00 65mmΦ, xylene-isopropanol (50/50) solution containing 10% by weight of acrylic-silicone resin with 3% by weight of silicon, acrylic polysiloxane (Methylsilicate 51, manufactured by Colcoat Co., Ltd.) Using a solution prepared by mixing 20% by weight with respect to the silicone resin, forming an adhesive layer by the same dipping method as in Example 75;
It was dried at 100 ° C. for 20 minutes. After cooling at room temperature, a nitric acid-titania sol having a titanium oxide content of 5% was dispersed in a nitric acid-acid silica sol having a silicon oxide content of 5% in the presence of a surfactant to form a photocatalytic layer coating solution. Using this solution, a photocatalyst layer was applied to the surface of the adhesive layer by the same dipping method and dried at 100 ° C. for 20 minutes to obtain a photocatalyst-coated eyeglass lens. (Sample.3) Example 77 Polyvinyl chloride wallpaper 1mm thick SG5 manufactured by Sangetsu Co., Ltd. cut into 5cm x 5cm
328 Polyvinyl chloride wallpaper, xylene-isopropanol (50/50) solution containing 25% by weight of an acrylic-silicon resin having a silicon content of 3% by weight, and polysiloxane (methyl silicate 51 manufactured by Colcoat Co., Ltd.) on the acrylic-silicon resin. A solution obtained by mixing 30% by weight with respect to No. 7 was applied with a bar coater No. 7 and dried at 100 ° C. for 20 minutes to form an adhesive layer. After cooling at room temperature, titanium oxide content 20% by weight as photocatalyst layer
Was dispersed in a nitric acid silica sol having a silicon oxide content of 20% in the presence of a surfactant to obtain a coating solution for the photocatalytic layer. Using this solution, No. 7
Apply to the surface of the above adhesive layer with a bar coater.
After drying for minutes, a photocatalyst-carrying wallpaper was obtained. (Sample.4) Example 78 Polyester film The adhesive layer solution used in Example 77 was diluted with a xylene-isopropanol (50/50) solution to a solid content of 25% by weight. This diluted solution is applied to a polyester film (Cosmoshine) A4100 manufactured by Toyobo Co., Ltd. with a microgravure coater (70 cm width) manufactured by Yasui Seiki Co., Ltd. Gravure printing at a temperature of 130 ° C. Next, the polyester film on which the adhesive layer was formed was similarly subjected to gravure printing using the coating solution for the photocatalyst layer used in Example 77 to obtain a polyester film on which a photocatalytic layer having a dry film thickness of 3 μm was formed. Was. (Sample.5) Example 79 PC display protection filter Acrylic-silicon resin with 20% by weight of silicon
A solution obtained by mixing 30% by weight of polysiloxane (methyl silicate 51 manufactured by Colcoat Co., Ltd.) with an acrylic-silicone resin in a xylene solution containing 20% by weight, and diluting with an isopropanol solution to a solid content of 20% by weight. Then, a VDT filter E-filterIII manufactured by Toray Industries, Inc. was immersed, pulled up, and dried at 100 ° C. for 20 minutes to form an adhesive layer. Next, the VDT protection filter having the adhesive layer formed thereon was prepared in Example 7
The coating solution for the photocatalyst layer used in 7 was immersed in a solution diluted to a solid content of 10% by weight with ion-exchanged water, pulled up, and dried similarly at 100 ° C. for 20 minutes to obtain a photocatalyst-coated VDT filter. (Sample.6) Example 80 Phone Case The adhesive layer solution used in Example 77 was diluted with a xylene-isopropanol (50/50) solution to a solid content of 20% by weight. This diluted solution was sprayed with a spray gun WIDER88 manufactured by Iwata Coating Machine Industry Co., Ltd. and manufactured by Hitachi, Ltd.
It was spray painted on the case of the IT-1 type telephone. 2 at 100 ° C
After drying for 0 minutes, the solution of the photocatalyst layer used in Example 1 was spray-coated similarly using a solution diluted to a solid content of 8% by weight with ion-exchanged water. 2 at 100 ° C
After drying for a minute, a telephone case carrying a photocatalyst was obtained.
(Sample.7) Example 81 Eyeglass Lens Nikon Corp. Eyeglass Lens NL70HCCTc (+) 1.00S0.
A polysiloxane (methyl silicate 51, manufactured by Colcoat Co., Ltd.) was added to an acrylic-silicone resin in a xylene-isopropanol (50/50) solution containing 10% by weight of an acrylic-silicone resin having a silicon content of 3% by weight. An adhesive layer was formed by the same dipping method as in Example 79 using a solution prepared by mixing 20% by weight with respect to 100%.
For 20 minutes. After cooling at room temperature, a nitric acid titania sol having a titanium oxide content of 15% was dispersed in a nitric acid acidic silica sol having a silicon oxide content of 15% in the presence of a surfactant to form a photocatalytic layer coating solution. Using this solution, a photocatalyst layer was applied to the surface of the adhesive layer by the same dipping method and dried at 100 ° C. for 20 minutes to obtain a photocatalyst-coated eyeglass lens. (Sample.8) Example 82 Curtain A curtain cloth hospia (for schools and hospitals) manufactured by Kawashima Textile Co., Ltd. was cut into 7 cm × 7 cm, and an epoxy-silicon resin having a silicon content of 3% by weight was converted to 15% by weight of xylene / isopropanol ( A 50/50) solution was impregnated with a solution in which a polysiloxane (methyl silicate 51 manufactured by Colcoat Co., Ltd.) was mixed at 20% by weight with respect to the acrylic-silicone resin, pulled up, and pulled up.
Dry at 120 ° C. for 120 minutes. After cooling at room temperature, a titania sol made of ammonia alkali having a titanium oxide content of 10% by weight as a photocatalyst layer was placed in a silica sol having a silicon oxide content of 10% by weight,
Into the photocatalyst layer dispersed in the presence of a surfactant, the curtain material on which the adhesive layer was formed was impregnated and pulled up.
After drying at 120 ° C. for 120 minutes, a photocatalyst-carrying curtain fabric was obtained.
(Sample.9) Example 83 Nonwoven fabric Cotton nonwoven fabric manufactured by Nisshinbo Co., Ltd. (trade name: Olkos)
Unbleached product (weight per unit area: 50 g / m ² ) is cut into 7 cm x 7 cm, and an acrylic-silicon resin with a silicon content of 3 wt% is added to a 25 wt% xylene / isopropanol (50/50) solution in a polysiloxane (Colcoat Co., Ltd.). ) Methyl silicate 51)
Was spray-coated by using a spray gun WIDER88 type manufactured by Iwata Coating Machine Industry Co., Ltd. After drying at 100 ° C for 30 minutes,
The same solution was applied using the photocatalyst layer solution used in Example 82, and dried at 100 ° C. for 30 minutes, surgical gown, table cloth,
A photocatalyst-supporting cotton nonwoven fabric suitable for toilet seat covers, shoji paper, seedling raising sheets, food packaging materials, and the like was obtained. (Sample.10) Example 84 Printed polyester fabric for umbrella An adhesive layer and a photocatalytic layer were applied in the same manner as in Example 83, using a printed polyester fabric used for a commercially available umbrella. The printed polyester fabric supporting the photocatalyst layer had almost no change in the pattern and texture of the fabric. (Sample.11) Example 85 Wallpaper (woven cloth) An adhesive layer and a photocatalytic layer were applied in the same manner as in Example 83, using a plain textile wallpaper SG6758 manufactured by Sangetsu Corporation. The woven wallpaper supporting the photocatalyst layer was a good carrier that hardly impaired the texture of the fabric. (Sample.1
2) Example 86 Aluminum sash A 7 cm x 7 cm aluminum sash plate was cut into a xylene-isopropanol (50/50) solution containing 25% by weight of an acrylic-silicon resin having a silicon content of 3% by weight, and a polysiloxane (colcoat). (Methyl silicate 51 manufactured by)
Was coated with a No. 7 bar coater and dried at 100 ° C. for 60 minutes to form an adhesive layer. After cooling at room temperature, a nitric acid titania sol having a titanium oxide content of 20% by weight was dispersed in a nitric acid acidic silica sol having a silicon oxide content of 20% in the presence of a surfactant to form a photocatalytic layer coating solution. This solution was applied to the surface of the adhesive layer using a bar coater of No. 7 and dried at 130 ° C. for 10 minutes to obtain an aluminum plate supporting a photocatalyst. (Sample 13) Example 87 Stainless Steel Plate The adhesive layer solution used in Example 86 was diluted with a xylene-isopropanol (50/50) solution to a solid content of 5% by weight. A sample obtained by cutting a SUS316 stainless steel plate (0.2 mm thick) into 7 cm x 7 cm into this diluted solution is immersed, pulled up, allowed to stand, and dried at 120 ° C for 20 minutes to form an adhesive layer on the surface of the stainless plate. Was. Next, the stainless steel plate having the adhesive layer formed thereon was immersed in a solution prepared by diluting the photocatalyst layer coating solution used in Example 86 to 10% by weight with ion-exchanged water, pulled up, and similarly dried at 120 ° C. for 20 minutes. Thus, a stainless steel plate supporting a photocatalyst was obtained. (Sample.14) Example 88 Tinplate Acrylic-silicon resin with a silicon content of 20% by weight
A polysiloxane (methyl silicate 51, manufactured by Colcoat Co., Ltd.) was mixed at 30% by weight with respect to the acrylic-silicone resin in a xylene solution containing 20% by weight, and diluted with an isopropanol solution to a solid content of 20% by weight. ,
Immerse a 0.1 mm thick tin plate cut into 7 cm x 7 cm,
It was pulled up and dried at 100 ° C. for 60 minutes to form an adhesive layer. Next, the tin plate on which the adhesive layer was formed was immersed in a solution prepared by diluting the photocatalyst layer coating solution used in Example 86 to 10% by weight with ion-exchanged water, pulled up, and similarly dried at 100 ° C. for 60 minutes. Thus, a tin plate supporting a photocatalyst was obtained. (Sample.15) Example 89 Blind Tachikawa Blind Industry Co., Ltd. blind "Silky Curtain" (slat width 15 mm type) T-12 (white) 800 mm wide and 700 mm high slats were removed, and the silicon content was 3% by weight. 25% by weight of acrylic-silicone resin
Xylene-isopropanol (50/50) solution containing polysiloxane (methyl silicate manufactured by Colcoat Co., Ltd.)
51) was mixed with an acrylic-silicone resin at 30% by weight, and sprayed with a sprayer WIDER8 manufactured by Iwata Coating Machine Industry Co., Ltd.
It was spray-applied with an 8 type. After drying at 120 ° C. for 20 minutes, Example 86
The solution of the photocatalyst layer used in 1 was spray-coated in the same manner using a solution diluted with ion-exchanged water to a solid content of 8% by weight. After drying at 120 ° C. for 20 minutes, a blind supporting the photocatalyst was obtained. (Sample.16) Example 90 Printed plywood Neowood (2.5 mm thick) printed plywood cut to 7 cm x 7 cm contains 25% by weight of an acrylic-silicon resin having a silicon content of 3% by weight. Xylene
A solution in which 30% by weight of folisiloxane (Colcoat Co., Ltd., methyl silicate 51) was mixed with an iso-propanol (50/50) solution based on acrylic-silicone resin was applied with a No. 7 bar coater and dried at 100 ° C. for 30 minutes. To form an adhesive layer.
After cooling at room temperature, a nitric acid titania sol having a titanium oxide content of 20% by weight was dispersed in a nitric acid acidic silica sol having a silicon oxide content of 20% in the presence of a surfactant to form a photocatalytic layer coating solution. Using this solution, N
o.Apply to the surface of the adhesive layer with a bar coater at 7
After drying for 30 minutes, a catalyst-supported printed plywood was obtained. (Sa
mple. 17) Example 91 Synthetic Wood The adhesive layer solution used in Example 90 was diluted with a xylene-isopropanol (50/50) solution to a solid content of 5% by weight. Eslon Neo-Lumbar FFU-50 manufactured by Sekisui Chemical Co., Ltd. is cut into 7cm x 7cm x 7cm wood, immersed in the diluted solution, pulled up, allowed to stand, dried at 100 ° C for 120 minutes, and adhered to the surface of synthetic wood. A layer was formed. Next, the synthetic wood having the adhesive layer formed thereon was immersed in a solution prepared by diluting the photocatalyst layer coating solution used in Example 90 to 10% by weight with ion-exchanged water, pulled up, and similarly dried at 100 ° C. for 120 minutes. Thus, a synthetic wood supporting photocatalyst was obtained. (Sample.18) Example 92 Wooden Door Daiken Kogyo Co., Ltd. Indoor Wooden Door Engraved Door Model 38 RC0202
-Cut IR6 (oak pattern) into a size of 7cm x 7cm, and add polysiloxane (manufactured by Colcoat Co., Ltd.) to a xylene-isopropanol (50/50) solution containing 10% by weight of an acrylic-silicon resin having a silicon content of 3% by weight. Using a solution prepared by mixing 20% by weight of methyl silicate 51) with respect to the acrylic-silicon resin, an adhesive layer was formed by the same dipping method as in Example 91, and dried at 100 ° C. for 20 minutes. After cooling at room temperature, a nitric acid titania sol having a titanium oxide content of 5% was dispersed in a nitric acid silica sol having a silicon oxide content of 5% in the presence of a surfactant to form a photocatalytic layer coating solution. Using this solution, a photocatalyst layer was applied to the surface of the adhesive layer by the same dipping method, and dried at 100 ° C. for 20 minutes to obtain a photocatalyst-coated wooden door material. (Sample.19) <Evaluation of photocatalytic activity> Using samples of Samples 1 to 19,
The photocatalytic activity was evaluated, and the results shown in Table 9 were obtained.

INDUSTRIAL APPLICABILITY As described above, the photocatalyst-supporting structure of the present invention has high photocatalytic activity and is highly durable.
For the purpose of antibacterial, deodorization, antifouling, etc., wood and wood materials are used in a wide range of application fields such as various building materials such as lenses, various window glasses, adhesive films, decorative sheets, wallpapers, curtains, blinds and interior products, and interior products. Can be applied.

──────────────────────────────────────────────────の Continued on the front page (31) Priority claim number Japanese Patent Application No. 7-349336 (32) Priority date December 20, 1995 (December 20, 1995) (33) Priority claim country Japan (JP) (31) Priority claim number Japanese Patent Application No. 7-349337 (32) Priority date December 20, 1995 (December 20, 1995) (33) Priority claim country Japan (JP) (31) Priority claim number Japanese Patent Application No. 7-349338 (32) Priority date December 20, 1995 (December 20, 1995) (33) Priority claiming country Japan (JP) (31) Priority claim number Japanese Patent Application No. 7-353742 ( 32) Priority date December 28, 1995 (December 28, 1995) (33) Priority claiming country Japan (JP) (31) Priority claim number Japanese Patent Application No. 8-34350 (32) Priority date 1996 January 29 (1996. 1.29) (33) Priority claiming country Japan (JP) (31) Priority claim number Japanese Patent Application No. 8-52469 (32) Priority date February 15, 1996 (1996. 2.15) (33) Excellent Japan (JP) (31) Priority claim number Japanese Patent Application No. 8-63673 (32) Priority date February 26, 1996 (Feb. 26, 1996) (33) Priority claim country Japan (JP) (31) Priority claim number Japanese Patent Application No. 8-150115 (32) Priority date May 21, 1996 (May 21, 1996) (33) Priority claim country Japan (JP) Application for accelerated examination (72 ) Inventor Shigemichi Miyama 345 Takada, Odawara-shi, Kanagawa Japan Soda Co., Ltd. Odawara Research Laboratories (56) References JP-A-6-296874 (JP, A) JP-A-63-5301 (JP, A) 6-315614 (JP, A) JP-A-7-171408 (JP, A) WO 96/14932 (WO, A1) (58) Fields investigated (Int. Cl. ⁷ , DB name) B01J 21/00- 38/74 B01D 53 / 86,53 / 94 B05D 5/00

Claims (56)

(57) [Claims] 1. A structure carrying a photocatalyst having a structure in which an adhesive layer is provided between a photocatalyst layer and a carrier, wherein the adhesive layer comprises a silicon-modified resin having a silicon content of 2 to 60% by weight;
A resin containing 5 to 40% by weight of colloidal silica, or formula (1) SiCln ₁ (OH) n ₂ R ¹ n ₃ (OR ² ) n ₄ formula (1) wherein R ¹ is an amino group, A carboxyl group, or a chlorine atom)
R ² represents an alkyl group having 1 to 8 carbon atoms which is substituted with an alkyl group or an alkoxy group having 1 to 8 carbon atoms, n ¹ is 0
Represents an integer from to 2, and n ⁴ is an integer from 2 to 4, and
n ¹ + n ² + n ³ + n ⁴ = 4. A photocatalyst containing 3 to 60% by weight of a polysiloxane which is a polycondensation reaction product of the compound represented by the formula (1), wherein the photocatalyst layer contains 25 to 95% of a metal oxide gel or a metal hydroxide gel. A photocatalyst supporting structure, which is a particle composite. 2. The method according to claim 1, wherein the silicone-modified resin of the adhesive layer is an acrylic resin.
The photocatalyst-carrying structure according to claim 1, which is a silicone resin. 3. The adhesive layer is a resin containing polysiloxane, wherein the polysiloxane is a hydrolyzate of a silicon alkoxide having at least one C1 to C5 alkoxy group or a product formed from the hydrolyzate. The photocatalyst-carrying structure according to claim 1, wherein: 4. The photocatalyst supporting structure according to claim 1, wherein the adhesive layer is a silicon-modified resin containing polysiloxane. 5. The photocatalyst supporting structure according to claim 1, wherein the adhesive layer is a resin containing colloidal silica, and the particle size of the colloidal silica is 10 nm or less. 6. The photocatalyst supporting structure according to claim 1, wherein the adhesive layer is a silicon-modified resin containing colloidal silica. 7. A porous metal oxide gel or metal hydroxide gel wherein the metal oxide gel or metal hydroxide gel in the photocatalyst layer has a specific surface area after drying at 150 ° C. of 100 m ² / g or more. And is composed of an oxide gel or a hydroxide gel of one or more metals selected from silicon, aluminum, titanium, zirconium, magnesium, niobium, tantalum, tungsten, and tin. The photocatalyst-carrying structure according to any one of claims 1 to 6, wherein 8. The photocatalyst layer is a photocatalyst complex comprising an oxide gel or a hydroxide gel of two or more metals and a photocatalyst, and is dissolved in boiling water having a conductivity of 200 μS / cm at 20 ° C.
The photocatalyst-supporting structure according to any one of claims 1 to 7, wherein the adhesion by a cross-cut tape method specified in JIS K5400 after immersion for 6 minutes is 6 or more. 9. A photocatalyst layer comprising aluminum, titanium,
Porous oxide or hydroxide gel consisting of silicon and one or more metals selected from zirconium and niobium and having a specific surface area of 50 m ² / g or more after drying at 150 ° C. And a photocatalyst composite comprising a photocatalyst. 10. The photocatalyst layer is composed of 10 to 50% by weight of a silicon-modified resin or a silane compound, 15 to 85% by weight of a metal oxide or hydroxide gel as a solid, and 5 to 75% by weight of a photocatalyst. A photocatalyst complex, comprising 20
The adhesiveness according to the grid tape method specified in JISK5400 after immersion in boiling water having a conductivity of 200 μS / cm at 150 ° C. for 15 minutes is 6 or more. A photocatalyst-supporting structure according to any one of the above. 11. The photocatalyst supporting structure according to claim 10, wherein the silicon-modified resin or the silane compound contained in the photocatalyst layer is an acryl-silicon resin, an epoxy-silicon resin, or a silane coupling agent. body. 12. The photocatalyst supporting structure according to claim 1, wherein the thickness of the adhesive layer is 0.1 μm or more. 13. The photocatalyst supporting structure according to claim 1, wherein the thickness of the photocatalyst layer is 0.1 μm or more. 14. The photocatalyst-carrying structure according to claim 1, wherein the total light transmittance of light having a total wavelength of 550 nm of the adhesive layer and the photocatalyst layer is 70% or more. 15. The photocatalyst supporting structure has an ultraviolet intensity of 3 mW / cm.
^The adhesiveness according to the JIS K5400 grid tape method is 6 points or more after irradiating the light of ² black light for 500 hours at a temperature of 40 ° C. and a relative humidity of 90%. 15. The photocatalyst-supporting structure according to any one of 1 to 14. 16. A structure in which an adhesive layer is provided between a photocatalyst layer and glass, wherein the adhesive layer and the photocatalyst layer are those described in any one of claims 1 to 15. Glass carrying a photocatalyst characterized by: 17. The glass carrying a photocatalyst according to claim 16, wherein the shape of the carrier is plate-like, tubular, spherical or fibrous. 18. An interior product using the glass carrying the photocatalyst according to claim 16 at least in part. 19. Glasses using glass carrying the photocatalyst according to claim 16. Description: 20. A glass lens using glass carrying the photocatalyst according to claim 16 or 17. 21. A structure in which an adhesive layer is provided between a photocatalyst layer and a plastic molded body, wherein the adhesive layer and the photocatalyst layer are those described in any one of claims 1 to 15. A plastic molded article carrying a photocatalyst, characterized in that: 22. The plastic molded article carrying a photocatalyst according to claim 21, wherein the molded article is in the form of a plate, a tube, a sphere, a fiber, or a film. 23. A building material using at least a part of the plastic molded article carrying the photocatalyst according to claim 21. 24. An interior product using at least a part of the plastic molded article carrying the photocatalyst according to claim 21. 25. An electric device using at least a part of the plastic molded body carrying the photocatalyst according to claim 21. 26. Furniture using at least a part of the plastic molded article carrying the photocatalyst according to claim 21. 27. A toy using at least a part of the plastic molded article carrying the photocatalyst according to claim 21. 28. A pressure-sensitive adhesive film obtained by applying a pressure-sensitive adhesive to the back surface of the plastic film carrying the photocatalyst according to claim 21. 29. A structure having an adhesive layer provided between a photocatalyst layer and a carrier, wherein the adhesive layer and the photocatalyst layer are formed as described in claim 1
15. A photocatalyst-supporting fabric, characterized by using one described in any one of (15) to (15). 30. Furniture using at least a part of the fabric supporting the photocatalyst according to claim 29. 31. Household goods using at least a part of the cloth supporting the photocatalyst according to claim 29. 32. An interior product using at least a part of the fabric supporting the photocatalyst according to claim 29. 33. A toy using at least a part of the fabric carrying the photocatalyst according to claim 29. 34. A structure having an adhesive layer provided between a photocatalyst layer and a metal, wherein the adhesive layer and the photocatalyst layer are formed as described in claim 1 or 13 or
15. A metal supporting a photocatalyst, wherein the metal described in any one of 15 above is used. 35. The metal supporting a photocatalyst according to claim 34, wherein the shape of the carrier is plate-like, tubular, spherical, fibrous, or sheet-like. 36. A building material using at least a part of the metal carrying the photocatalyst according to claim 34 or 35. 37. An interior product using at least a part of the metal carrying the photocatalyst according to claim 34 or 35. 38. A sash using a metal carrying the photocatalyst according to claim 34 or 35. 39. A blind using the metal carrying the photocatalyst according to claim 34 or 35. 40. A structure in which an adhesive layer is provided between a photocatalyst layer and wood, wherein the adhesive layer and the photocatalyst layer are made of any one of claims 1 to 13 or 15. Wood carrying a photocatalyst, characterized in that: 41. A structure in which an adhesive layer is provided between a photocatalyst layer and a woody material, wherein the adhesive layer and the photocatalyst layer are provided.
Or a wood material carrying a photocatalyst, characterized by being one comprising: 42. The wood carrying a photocatalyst according to claim 40, wherein the carrier has a plate shape, a column shape, a spherical shape or a sheet shape. 43. The wood material supporting a photocatalyst according to claim 41, wherein the carrier has a plate shape, a column shape, a spherical shape or a sheet shape. 44. An interior material using at least a part of the wood carrying the photocatalyst according to claim 40 or 42 and the woody material carrying the photocatalyst according to claim 41 or 43. 45. An interior product using at least a part of the wood carrying the photocatalyst according to claim 40 or 42 and the woody material carrying the photocatalyst according to claim 41 or 43. 46. A woodwork using the wood carrying the photocatalyst according to claim 40 or 42 and the woody material carrying the photocatalyst according to claim 41 or 43. 47. Furniture made of wood carrying the photocatalyst according to claim 40 or 42 and wood material carrying the photocatalyst according to claim 41 or 43. 48. A silicon compound of 0.001 to 5% by weight, a metal oxide and / or hydroxide sol of 0.1 to 30% by weight as a solid content, and a photocatalyst powder and / or sol of 0.1 to 30% of a solid content of a sol. A photocatalyst coating solution characterized by containing by weight. 49. A silicon compound represented by the following general formula (2): SiR ³ n ₅ (OR ⁴ ) 4-n ₅ formula (2) wherein R ³ is an amino group, a chlorine atom, or a carboxyl group. R ⁴ represents an alkyl group having 1 to 8 carbon atoms or an alkyl group having 1 to 8 carbon atoms substituted with an alkoxy group, and n ₅ Represents any number of 0, 1, 2, and 3. 50. The photocatalyst coating liquid according to claim 48, wherein the photocatalyst coating liquid is one or more of alkoxysilanes represented by the formula (1) or a hydrolysis product thereof. 50. The metal oxide and / or hydroxide sol is selected from the group consisting of silicon, aluminum, titanium, zirconium, niobium, tantalum, magnesium, tungsten and tin. 49. The photocatalyst coating solution according to claim 48, wherein the sol is a hydroxide sol having a specific surface area after drying at 150 ° C. of 50 m ² / g or more. 51. The silicon compound is one or more selected from the group consisting of tetramethoxyxylan, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane and hydrolysis products thereof. 49. The photocatalyst coating liquid according to claim 48, wherein 52. A coating agent for producing a photocatalyst supporting structure having an adhesive layer provided between a photocatalyst layer and a carrier, wherein (1) a silicon content as a coating solution of the adhesive layer applied on the carrier. 2-60% by weight of silicone modified resin,
A coating solution comprising a solution containing 1 to 50% by weight as a resin solid content of a resin containing 3 to 60% by weight of polysiloxane or a resin containing 5 to 40% by weight of colloidal silica;
(2) As a coating solution for the photocatalyst layer applied on the adhesive layer,
0.001 to 5% by weight of a silicon compound, 0.1 to 30% by weight of a metal oxide and / or hydroxide sol as a solid, and 0.1 to 30% by weight of a photocatalyst powder and / or a sol. A photocatalyst coating agent comprising two kinds of coating liquids of a liquid. 53. A resin contained in a coating solution of an adhesive layer, wherein the resin is a resin containing a polysiloxane, and the polysiloxane is a hydrolyzate of an alkoxysilane having an alkoxy group having 1 to 5 carbon atoms, or 53. The photocatalytic coating agent according to claim 52, which is produced from a decomposition product. 54. The method according to claim 52, wherein the resin contained in the coating solution for the adhesive layer is a resin containing colloidal silica, and the particle size of the colloidal silica is 10 nanometers or less. Photocatalyst coating agent. 55. The photocatalyst coating agent according to claim 52, wherein the resin contained in the coating solution for the adhesive layer is a silicon-modified resin containing polysiloxane. 56. The photocatalyst coating agent according to claim 52, wherein the resin contained in the coating solution for the adhesive layer is a silicon-modified resin containing colloidal silica.