JP2003126699A - Photocatalyst film fixed body - Google Patents

Abstract

PROBLEM TO BE SOLVED: To develop photocatalyst film fixed body capable of strongly fixing titanium oxide exhibiting photocatalytic activity onto a surface of heat-resistant materials such as metal and easily accomplishing strengthening of the catalytic function by forming a porous structure. SOLUTION: The photocatalyst film fixed body is obtained by baking a ceramic film comprising a sintered body of a mixture using at least titanium oxide exhibiting the photocatalytic activity and a MQ resin on a surface of the heat-resistant material.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a titanium oxide-based photocatalyst film-attached body comprising a ceramic film firmly supported by a heat-resistant material.

[0002]

BACKGROUND OF THE INVENTION Conventionally, a photocatalyst having a titanium oxide exhibiting a photocatalytic action attached to the surface of a ceramic has been known. It is widely used for various applications such as antibacterial and antibacterial, antifouling, deodorant and purification by utilizing the catalytic action of titanium oxide such as oxidation, reduction and decomposition under the action of light. However, although titanium oxide can be firmly fixed to the surface of ceramic, it is difficult to firmly fix titanium oxide to the surface of metal. In addition, the conventional photocatalyst has a problem that it is difficult to fully exhibit the photocatalytic function due to its poor specific surface area.

[0003]

DISCLOSURE OF THE INVENTION The present invention provides a photocatalyst film-attached body which can firmly fix titanium oxide exhibiting a photocatalytic effect to the surface of a heat-resistant material such as metal and can easily enhance the photocatalytic function by making it porous. Is the development of.

[0004]

The present invention is a photocatalyst film comprising a heat-resistant surface baked with a ceramic film made of a sintered body of a mixture of at least titanium oxide exhibiting a photocatalytic action and MQ resin. An attachment body is provided.

[0005]

EFFECTS OF THE INVENTION According to the present invention, a mixture using MQ resin is sintered on the surface of a heat-resistant material and baked to obtain a ceramic film in which titanium oxide exhibiting a photocatalytic action is uniformly dispersed. It can be firmly adhered to various heat-resistant materials including, and the ceramic film can be easily made porous, and a photocatalyst film attached body having a large specific surface area that is excellent in photocatalysis action with the above-mentioned uniform dispersibility can be easily formed. Also excellent in sustainability.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The photocatalyst film-attached body according to the present invention comprises:
A ceramic film made of a sintered body of a mixture containing at least titanium oxide and a MQ resin having a photocatalytic action is baked on the surface of a heat-resistant material. Such a photocatalyst film-attached body can be formed, for example, by applying the mixture onto a heat-resistant material and sintering the mixture. That is, by sintering, the MQ resin of the mixture is converted into silica or the like, and becomes a titanium oxide-containing ceramic film that exhibits a photocatalytic action, and in the process of ceramicization, it is baked and firmly fixed on the surface of the heat-resistant material.

As the titanium oxide exhibiting a photocatalytic action, one or more suitable substances exhibiting a photocatalytic action such as oxidation / reduction or decomposition under the action of light can be used. Above all, anatase type titanium oxide can be preferably used from the viewpoint of photocatalytic action and the like. The particle size of the titanium oxide to be used is preferably 50 μm or less, more preferably 30 μm or less, and particularly preferably 0.05 to 20 μm from the viewpoint of uniform dispersibility, but not limited to this.
Further, the content of the titanium oxide in the photocatalyst film-attached body can be appropriately determined, but generally, from the viewpoint of catalytic action, it is 5 to 95% by weight, preferably 10 to 80% by weight, particularly 15% by weight.
˜70% by weight.

As the MQ resin, an appropriate one known as a tackifier of a silicone adhesive can be used. In particular, a monofunctional M unit represented by the general formula: R ₃ SiO— from the viewpoint of the binder function and the formation of ceramics,
Those composed of a polymer with a tetrafunctional Q unit represented by Si (O-) ₄ are preferable. In particular, M which is excellent in shape retention when the titanium oxide is held in a film form as a binder
Q resin is preferred.

In the above general formula of MQ resin, R is, for example, an aliphatic hydrocarbon group such as a methyl group, an ethyl group or a propyl group, an aromatic hydrocarbon group such as a phenyl group, an olefin group such as a vinyl group and the like. Or an appropriate structural unit such as a hydrolyzable group such as a bidoxyl group.

The amount of the MQ resin and the titanium oxide used is 1 to 500 parts by weight, preferably 20 to 200 parts by weight, and particularly 40 to 100 parts by weight of the titanium oxide per 100 parts by weight of the MQ resin. It is preferable from the standpoints of action and adhesion to the heat resistant material.

In preparing the mixture for forming the photocatalyst film-attached body, if necessary, for example, for the purpose of improving the shape-retaining power of the titanium oxide or improving the flexibility of the coated film, Appropriate polymers having a binder function and the like can be blended. By the way, silicone rubber can be preferably used for improving the shape retention and flexibility. Silicone rubber functions as a binder, and upon sintering, forms a ceramic film component similar to MQ resin.

The silicone rubber is not particularly limited,
An appropriate one can be used. Examples include dimethyl siloxane, diphenyl siloxane, and methyl phenyl siloxane, and various modified silicone rubbers such as phenol modified products, melamine modified products, epoxy modified products, polyester modified products, acrylic modified products, urethane modified products, etc. Can also be used.

The molecular weight of the silicone rubber is not particularly limited, but is 10,000 to 2,000,000, especially 20,000 to 1,500,000, especially 50,000 from the viewpoint of the flexibility imparting property when used as a coating film or the like. ˜1,000,000 is preferable. The use ratio of the silicone rubber can be appropriately determined, but generally 1000 parts by weight or less per 100 parts by weight of MQ resin, from the viewpoint of sintering strength and the like,
In particular, the amount is 3 to 500 parts by weight, particularly 5 to 200 parts by weight.

From the viewpoint of improving the flexibility and strength of the coating film, it is effective to add various organic compounds such as polymers. By the way, examples of the organic compounds include hydrocarbon-based polymers, vinyl-based or styrene-based polymers, acetal-based polymers and butyral-based polymers, acrylic-based polymers and polyester-based polymers, urethane-based polymers and cellulose-based polymers, fibrin-based polymers and Various kinds of wax or wax can be used.
Above all, a cellulosic polymer such as ethyl cellulose can be preferably used from the viewpoint of improving strength.

The amount of the organic compound used is MQ resin 100.
It is generally 1000 parts by weight or less, especially 5 to 500 parts by weight, especially 10 to 200 parts by weight per part by weight from the viewpoint of improving strength, but not limited thereto. It should be noted that such an organic compound decomposes and disappears during the sintering process.

When preparing the mixture for forming the photocatalyst film-attached body, an appropriate inorganic substance other than the titanium oxide may be blended, if necessary. Above all, the needle-shaped crystal filler is preferably used from the viewpoint of increasing the specific surface area by making the obtained ceramic coating porous so as to increase the photocatalytic function.

As the needle-like crystal filler, one or more kinds of alkali titanate fibers such as potassium titanate and those composed of an appropriate inorganic substance that can withstand the sintering temperature such as aluminum borate can be used. Inorganic,
In particular, the amount of the needle-shaped crystal filler blended is 1 to 500 parts by weight per 100 parts by weight of MQ resin, from the viewpoint of making it porous and the like.
Above all, 20 to 00 parts by weight, particularly 40 to 100 parts by weight is preferable.

The mixture for forming the photocatalyst film-attached body is prepared, for example, by using MQ resin and the titanium oxide, and if necessary, one or more kinds of an organic compound such as silicone rubber or ethyl cellulose, and an inorganic material, respectively. ,
It can be carried out by a method such as mixing with a ball mill using an organic solvent or the like, if necessary.

Appropriate ones can be used as the organic solvent. Generally, toluene, xylene, butyl carbitol, ethyl acetate, butyl cellosolve acetate, methyl ethyl ketone, methyl isobutyl ketone, etc. are used. The mixed solution is preferably, but not limited to, prepared so that the solid content concentration is 5 to 85% by weight from the standpoint of spreadability and the like. Upon preparation thereof, appropriate additives such as a dispersant, a plasticizer, and a combustion improver can be added, if necessary.

The photocatalyst film-attached body can be formed by applying a mixture containing at least MQ resin and the titanium oxide to a heat-resistant material and sintering it as described above. Appropriate methods can be adopted for giving. By the way, as an example, there is a method of applying a liquid mixture on the heat-resistant material by an appropriate method such as a coating method or a dipping method.

[0021] Further, the mixture is retained in the form of a sheet, or the mixture is reinforced with a reinforcing base material.
It is also possible to adopt a method in which it is applied on a heat-resistant material via an adhesive layer such as an adhesive layer and sintered as necessary. In that case, organic substances such as the adhesive layer are decomposed and disappear in the process of forming the ceramic film by sintering.

The above-mentioned reinforcing form may be formed by an appropriate system such as a system in which a sheet-shaped mixture is provided on a reinforcing substrate or a system in which a reinforcing substrate is impregnated with the mixture. The reinforcing base material may be formed of a material that disappears during sintering, such as a polymer made of polyester, polyimide, fluororesin, polyamide, or the like, or may disappear even if sintered such as glass, ceramic, or metal. It may be formed of a material that does not. Therefore, as the reinforcing substrate, a resin coating layer or film, fiber or cloth,
Appropriate materials such as non-woven materials, perforated materials such as metal foils and nets or non-porous materials can be used.

In developing the liquid mixture by a coating method or the like, a method such as a doctor blade method or a gravure roll coater method, which is excellent in layer thickness controllability, is preferable. It is preferable to perform a sufficient defoaming treatment such as by using an antifoaming agent together so that no bubbles remain in the spreading layer. The thickness of the mixture layer to be formed is appropriately determined, but is generally 1 μm to 5 mm, preferably 5 μm to 1 mm, particularly 10 to 200 μm.

As the heat material for baking the ceramic coating in the sintering treatment, for example, iron, steel, various metals typified by nickel, aluminum, etc., and appropriate materials made of glass or ceramics can be used. . However, a metal-based heat-resistant material such as copper whose surface is oxidatively deteriorated during the sintering process and a uniform sintered film is difficult to obtain is not preferable. The heat-resistant material may have various forms such as a granular form, a rod form, a sheet form, a plate form, and a container form, and the form thereof is not particularly limited.

The mixture layer may have a porous form, if necessary, for the purpose of smooth vaporization of decomposition gas generated during sintering. By the way, when the ceramic adhesive film is temporarily adhered via an organic adhesive layer and sintered, the formed ceramic film may swell with decomposition gas, and it is possible to prevent it by forming a mixture layer such as a porous sheet form. it can. Porous formation is also effective for increasing the specific surface area.

The porous mixture layer is formed by, for example, a method of forming a large number of fine holes by a punching method or the like in a mixture layer in the form of a sheet, a woven fabric or a non-woven fabric, or a large number of fine holes in a reinforcing base material. It can be performed by an appropriate method such as a method using a metal foil or a net.

If necessary, an adhesive layer may be provided on the mixture layer in a sheet form or a reinforcing form for the purpose of temporarily adhering it to a heat resistant material before sintering. An appropriate adhesive can be used to form the adhesive layer. Above all, the adhesive layer is preferable from the viewpoint of easy adhesion workability. To form the adhesive layer, for example, a suitable adhesive such as a rubber-based or acrylic-based, silicone-based or vinyl alkyl ether-based, polyvinyl alcohol-based or polyvinylpyrrolidone-based, polyacrylamide-based or cellulose-based adhesive can be used. There is no limit.

A water-soluble pressure-sensitive adhesive layer may be provided for the purpose of temporary attachment to a heat-resistant material that is wet like porcelain before unglazed, or a heat-resistant material that easily causes dew condensation on the surface. For the formation of the adhesive layer, for example, a water-soluble polymer such as methoxyethyl acrylate-based polymer, vinyl alcohol-based polymer, vinylpyrrolidone-based polymer, acrylamide-based polymer, acrylic acid copolymer, vinyl methyl ether-based polymer, or cellulose-based polymer. An appropriate adhesive substance such as an adhesive containing a hydrophilic polymer or a hydrophilic polymer may be used.

The adhesive layer such as the pressure-sensitive adhesive layer is formed by applying the adhesive to the mixture layer in the form of a sheet by a suitable coating method such as a doctor blade method or a gravure roll coater method, or a separator according to the method. It can be performed by an appropriate method such as a method of transferring the adhesive layer provided on the mixture layer to the mixture layer. The adhesive layer may be provided in a scattered state for the purpose of smooth volatilization of decomposed gas when the mixture layer is sintered. The adhesive layer in the form of dots can be formed by a coating method such as a rotary screen method.

The thickness of the adhesive layer can be determined according to the type of heat-resistant material and the purpose of use. Generally, the thickness is 1 to 500 μm, especially 5 to 200 μm. The adhesive layer is preferably covered with a separator or the like to prevent contamination or the like until it is temporarily attached to the heat resistant material.

The mixture layer can be satisfactorily temporarily attached to the curved surface portion of the heat-resistant material or the like through an adhesive layer or the like, if necessary. For the temporary attachment, an automatic adhesion method by a robot or the like can be adopted. Further, the mixture layer can be used in an appropriate form such as a sheet form or a punching form.

The sintering treatment of the mixture layer applied to the heat resistant material is
The heating can be performed under appropriate heating conditions depending on the heat resistance of the heat-resistant material. Generally below 1000 ° C, especially 200-80
The heating temperature is 0 ° C., particularly 300 to 600 ° C. While the organic reinforcing base material, adhesive layer, etc. disappeared due to the heat treatment,
The MQ resin forming the mixture layer and the silicone rubber as required are sintered to form a ceramic, which is then baked on a heat-resistant material as a ceramic film containing the titanium oxide dispersed therein to form a photocatalyst film-attached body.

The photocatalyst film-attached body according to the present invention is required to have a photocatalytic action based on the titanium oxide in, for example, ceramics, glass products, ceramic products, metal products, enamel products, containers, building materials, electric / electronic devices, and the like. It can be preferably used for forming products for various applications.
Therefore, the heat resistant material may have any shape such as a flat plate shape and a curved surface shape such as a container.

[0034]

EXAMPLES Example 1 130 parts of MQ resin (parts by weight, the same applies hereinafter) and a molecular weight of 3
30 parts of 0,000 silicone rubber (all manufactured by Shin-Etsu Chemical Co., Ltd.), 50 parts of potassium titanate consisting of needle crystals (Otsuka Chemical Co., Ltd.), 30 parts of photoactive titanium oxide (Sakai Chemical Co., Ltd.),
60 parts of ethyl cellulose (manufactured by Hercules) is homogeneously mixed with toluene, and the dispersion is applied onto a polyester film having a thickness of 75 μm by a doctor blade method and dried to form a mixture layer having a thickness of 60 μm in a sheet form. Obtained.

On the other hand, a toluene solution containing 100 parts of polybutyl acrylate having a molecular weight of 1,000,000 was coated by a doctor blade method on a separator made of 70 μm-thick glassine paper treated with a silicone-based release agent, and dried to a thickness. After forming an adhesive layer having a thickness of 20 μm, adhering it to the mixture layer surface to separate the polyester film and the separator, and adhering to the aluminum alloy plate via the adhesive layer,
It was heated at 500 ° C. for 30 minutes and sintered to obtain a photocatalyst film-attached body having a porous ceramic film seized.

Example 2 A photocatalyst film-attached article having a porous ceramic film seized was obtained in the same manner as in Example 1 except that aluminum borate composed of needle crystals was used in place of potassium titanate.

Example 3 A dispersion according to Example 1 obtained by homogeneously mixing MQ resin, silicone rubber, potassium titanate, photoactive titanium oxide and ethyl cellulose was applied to a predetermined portion of an aluminum alloy plate. After drying, dry at 500 ℃ for 30
It was heated and sintered for a minute to obtain a photocatalyst film-attached body having a porous ceramic film burned thereon.

Comparative Example 1 A photocatalyst-coated article was obtained in the same manner as in Example 1 except that rutile type titanium oxide was used instead of photoactive titanium oxide.

Comparative Example 2 An attempt was made to form a photocatalyst film-attached body according to Example 1 except that a mixture containing no MQ resin was used. However, the attached photoactive titanium oxide fell off by rubbing by hand, and the target product could not be obtained.

Evaluation Test The photocatalyst film-attached bodies obtained in Examples and Comparative Examples were placed in a smoking room exposed to sunlight and left for 3 months, and the state of contamination before and after the observation was observed. The results are shown in the table below. Example 1 Example 2 Example 3 Comparison Comparative Example Before standing White White White White White After standing White White White White Yellowing

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C03C 17/25 C03C 17/25 A (72) Inventor Makoto Kai 1-2-1 Shimohozumi, Ibaraki City, Osaka Prefecture issue date TEPCO Engineering Co., Ltd. in the F-term (reference) 4F100 AA21A AB01B AD00A AD00B AG00B AR00B AR00H BA02 BA10A BA10B CA23A DJ01A EJ48A GB07 GB48 JA11A JA11H JJ03B JL08A 4G059 AA01 AB11 AC22 EA04 EB06 4G069 AA03 AA08 BA04A BA04B BA21C BA22C BA48A BB06B BB20B BC03B BC16B BC50B BD03B BE05C BE32C CD10 DA06 EA03X EA03Y EA08 EC22X EC22Y FA03 FA04 FB23 FB36 FC05

Claims (5)

[Claims] 1. A photocatalyst film-attached article, comprising a ceramic film made of a sintered body of a mixture of at least titanium oxide exhibiting a photocatalytic action and MQ resin, which is baked on the surface of a heat-resistant material. 2. The photocatalyst film-attached article according to claim 1, wherein the ceramic film contains a needle-shaped crystal filler. 3. The photocatalyst film-attached article according to claim 1, wherein the mixture before forming the ceramic film contains silicone rubber and ethyl cellulose. 4. The heat resistant material according to any one of claims 1 to 3,
Photocatalyst film-attached body made of glass or other ceramics. 5. The photocatalyst film-attached body according to claim 1, wherein the ceramic film is a porous body.