TW201404466A - Material coated with photo catalyst, commodity including the same, and method for manufacturing the same - Google Patents

Abstract

A material coated with photo catalyst comprises: an aluminum material; a photo catalyst body layer being formed on a surface of the aluminum material, and including a metallic oxide particle having photo catalyst activity; an interposing layer being formed between the aluminum material and the photo catalyst body layer, and including aluminum and carbon. The material coated with photo catalyst is manufactured by forming the photo catalyst body layer, including a metallic oxide particle having photo catalyst, on the surface of the aluminum material, and by heating the aluminum material in a state that the aluminum material, on which the photo catalyst body layer is formed, placed in a space including hydrocarbon-containing substance.

Description

Photocatalyst-coated material, article, and photocatalyst-coated material manufacturing method

The present invention relates to a material coated with a photocatalyst, an article having a material coated with a photocatalyst, and a method of producing a photocatalyst-coated material.

When a semiconductor is irradiated with light having an energy of a band gap or more, an organic substance such as a resin that contacts the surface of the semiconductor is decomposed by a strong redox action. The industry is promoting the development of the photocatalytic activity of the semiconductor for the decomposition or detoxification of harmful substances contained in the atmosphere, water, etc., the deodorization of living spaces, the prevention of contamination of solid surfaces in living spaces, and the antibacterial of living spaces. Various environmental purification technologies. Examples of the semiconductor photocatalyst used for these purposes include metal oxides such as titanium oxide, zinc oxide, zirconium oxide, and tungsten oxide. Further, when it is actually used for environmental purification, since the surface of the semiconductor is activated, in order to increase the activity of the photocatalyst, the particles of the metal oxide are often immobilized on the surface of the substrate in the form of a film or a layer to increase the photocatalyst. The surface area of the reaction is used.

For example, Japanese Patent Publication No. Hei 6-293519 (hereinafter referred to as Patent Document 1) discloses a method of coating a suspension of titanium oxide particles as a method of immobilizing a particle of titanium oxide which is most commonly used as a semiconductor photocatalyst. The titanium oxide film is produced by being baked on a support and calcined to fix the titanium oxide particles on the support.

Japanese Patent Publication No. Hei 7-316342 (hereinafter referred to as Patent Document 2) discloses a laminated body including a synthetic resin as light. A synthetic resin composition layer obtained by the catalyst titanium oxide particles.

However, in the method described in Patent Document 1, in order to increase the surface area of the photocatalytic reaction, it is necessary to increase the thickness of the titanium oxide film. When the thickness of the titanium oxide film is increased, the adhesion between the titanium oxide particles and the support is lowered. Further, when the baking temperature is increased to promote the fixation of the titanium oxide particles on the support, it is difficult to use a material which is softened at a relatively low temperature like an aluminum material as a material of the support.

In addition, when an organic material such as a synthetic resin is used as a binder in the laminate described in Patent Document 2, and the titanium oxide particles as a photocatalyst are immobilized, the organic binder itself is deteriorated by the photocatalytic action of the titanium oxide particles. . Therefore, there is a problem that the adhesion between the titanium oxide particles is lowered. Further, although it is not described in Patent Document 2, when an organic material such as a synthetic resin is used as a binder and titanium oxide particles as a photocatalyst are fixed to a substrate, titanium oxide particles and the like are present in the same manner as described above. The problem of poor adhesion between substrates.

Accordingly, an object of the present invention is to solve the above problems and to provide a photocatalyst-coated material capable of improving the adhesion between an aluminum material as a substrate and a photo-contact layer, an article having the photocatalyst-coated material, and A method of manufacturing a material coated with a photocatalyst.

The present inventors have conducted intensive studies in order to solve the problems of the prior art, and as a result, have found that a coating material capable of achieving the above object can be obtained by heating an aluminum material having photocatalytic active metal oxide particles under specific conditions. A material coated with photocatalyst. The present invention has been completed based on the findings of the inventors.

The photocatalyst-coated material according to the present invention comprises: an aluminum material, a photo-contact dielectric layer comprising photocatalytic active metal oxide particles formed on the surface of the aluminum material, and an aluminum layer formed between the aluminum material and the photo-contact dielectric layer Intermediary layer with carbon.

Further, in the photocatalyst-coated material of the present invention, the thickness of the photocontact medium layer is preferably 1 nm or more and 10 μm or less.

Further, in the photocatalyst-coated material of the present invention, the interposer preferably contains carbides of crystallized aluminum.

The article based on the present invention is provided with a photocatalyst-coated material having the above characteristics.

The photocatalyst-coated material manufacturing method according to the present invention comprises: a photo-contacting dielectric layer forming step of forming a photo-contacting dielectric layer containing photocatalytic active metal oxide particles on the surface of the aluminum material; and the aluminum layer on which the photo-contacting dielectric layer is to be formed The heating step of heating is carried out in a state in which the material is contained in a space containing a hydrocarbon-containing substance.

In the method for producing a photocatalyst-coated material of the present invention, the heating step is preferably carried out at a temperature of 450 ° C or more and less than 660 ° C.

According to the present invention, the adhesion between the aluminum material as the substrate and the photocontact medium layer can be improved.

(aluminum)

The photocatalyst-coated material of the present invention is provided with an aluminum material as a photo-contacting dielectric layer. The substrate. The aluminum material as the substrate is not particularly limited. In an embodiment of the present invention, a foil or a plate of pure aluminum or aluminum alloy can be used as the aluminum material. Such an aluminum material preferably has an aluminum purity of 98% by mass or more based on the value measured by the method described in "JIS H 2111". The aluminum material used in the present invention also includes: lead (Pb), bismuth (Si), iron (Fe), copper (Cu), manganese (Mn), magnesium (Mg), chromium (Cr) added to the extent necessary. ), at least one of zinc (Zn), titanium (Ti), vanadium (V), gallium (Ga), nickel (Ni), and boron (B) as an alloy of its composition, or inevitable The content of the impurity element is limited to aluminum. The thickness of the aluminum material is not particularly limited. In general, it is preferably 5 μm or more and 200 μm or less in the case of a foil, and is preferably 0.2 mm or more in the case of a sheet.

The above aluminum material can be produced by a known method. For example, a melt of aluminum or an aluminum alloy having the above-described predetermined composition is prepared, and the ingot obtained by casting the melt is appropriately homogenized. Thereafter, the ingot is subjected to hot rolling and cold rolling, whereby an aluminum material as a substrate can be obtained. Further, the intermediate annealing treatment may be performed at a temperature of 150 ° C or higher and 400 ° C or lower in the middle of the cold rolling step.

Alternatively, the aluminum material may be suitably pretreated prior to the step of forming the photocontact media layer.

(photo-touch layer)

In the photocatalyst-coated material of the present invention, a photo-contact dielectric layer containing photocatalytic active metal oxide particles is formed on the surface of the aluminum material as the substrate. The metal oxide particles having photocatalytic activity contained in the photocontacting medium layer are not particularly limited. In one embodiment of the present invention, examples of the metal oxide particles include particles of titanium oxide, zinc oxide, zirconium oxide, tungsten oxide, and the like, and it is particularly preferable to use anatase-type titanium oxide particles.

Metal oxide particles having photocatalytic activity contained in the photocontacting medium layer The shape and size are not particularly limited, and the size (particle diameter) of the dispersed particles is preferably 0.01 nm or more and 10 μm or less, and more preferably 1 nm or more and 150 nm or less in order to increase the photocatalytic activity. In addition, the particle size was selected from any of the photographs obtained by cross-sectional observation by a scanning transmission electron microscope (STEM: Scanning Transmission Electron Microscopy), and the particle diameter was calculated and obtained by the average value.

The photo-contacting medium layer is formed by, for example, coating a metal oxide particle having photocatalytic activity in a solution by using a stirrer or the like, and a metal oxide precursor having photocatalytic activity in the solution. A coating liquid obtained by subjecting a substance to hydrolysis or hydrothermal treatment to be pelletized, or a coating liquid in which the above two coating liquids are mixed is applied onto the surface of an aluminum material as a substrate.

The thickness of the photo-contacting medium layer may be 1 nm or more and 10 μm or less, and particularly preferably 2 μm or less, from the viewpoint of ensuring the adhesion between the substrate and the photo-contact layer.

The adhesion between the aluminum material and the photo-contact layer is ensured by the presence of an interposer containing aluminum and carbon, which will be described later. However, as a method for further improving the adhesion, a method may be mentioned as follows: when the photo-contact layer is formed, the coating is performed. A metal oxide precursor substance (such as an aqueous solution of peroxotitanic acid) or an organic binder such as a resin is added to the liquid. For example, a metal oxide particle having photocatalytic activity is dispersed in a solution of a metal oxide precursor material (sol) to a gel by a reaction of hydrolysis and polycondensation of an organic compound or a metal salt of a metal alkoxide. In the solution, the coating liquid prepared thereby is applied onto the surface of the aluminum material. Alternatively, the coating liquid obtained by emulsifying the metal oxide particles in a solution may contain a carbon-containing component as an organic binder such as a resin, and the coating liquid prepared thereby may be applied onto the surface of the aluminum material.

(intermediary layer)

In the photocatalyst-coated material of the present invention, an interposer comprising aluminum and carbon is formed between the aluminum material as the substrate and the photocontactor layer. The interposer is obtained by heating an aluminum material having a photo-contact layer formed on the surface in an environment containing a hydrocarbon-containing substance.

Since the interposer does not cover the surface of the photocatalyst-active metal oxide particles contained in the photo-contact layer, it does not affect the photocatalytic activity, and serves to improve the adhesion between the aluminum material as the substrate and the photo-contact layer.

As described above, when the photo-contact layer is formed, a metal oxide precursor substance or a binder is added to the coating liquid, whereby the adhesion between the aluminum material and the photo-contact layer can be further improved. In this case, there is a possibility that the metal oxide precursor substance or the binder (carbonaceous component) added to the coating liquid coats the surface of the metal oxide particles having photocatalytic activity, resulting in a decrease in photocatalytic activity. However, in the photocatalyst-coated material of the present invention, the adhesion between the aluminum material and the photo-contact layer can be ensured by the interposer layer containing aluminum and carbon itself, and therefore added to the coating liquid in order to further improve the adhesion. The amount of metal oxide precursor material or binder is small, and the effect on photocatalytic activity can be minimized. Further, in this case, the metal oxide precursor substance or the carbon-containing component is present between the aluminum material as the substrate and the photo-contact layer by the addition of the metal oxide precursor substance or the binder, thereby further improving The adhesion between the aluminum material and the photo-contact layer is not limited to this, and the adhesion between the metal oxide particles can be improved by being present between the metal oxide particles contained in the photo-contact layer.

Further, the interposer preferably comprises a carbide of crystallized aluminum.

(items with photocatalytic function)

By applying the photocatalyst-coated material of the present invention to various articles, it can be constructed An item with a photocatalytic function. The article having a photocatalytic function is not particularly limited, and examples thereof include decomposition or detoxification of harmful substances contained in the atmosphere, water, and the like, deodorization of a living space, prevention of contamination of a solid surface in a living space, and living space. Antibacterial and other environmentally cleansing items. Specifically, examples of the article include a building material such as a wallpaper, a baffle, a curtain, and a grill, an industrial/household electrochemical product such as an air cleaner, an air conditioner, and a refrigerator, and a wing material such as a heat exchanger.

(Manufacturing method of material coated with photocatalyst)

The method for producing a photocatalyst-coated material of the present invention comprises: a photo-contacting dielectric layer forming step of forming a photo-contacting dielectric layer containing photocatalytic active metal oxide particles on a surface of an aluminum material; and thereafter forming an aluminum layer on which the photo-contacting dielectric layer is to be formed The heating step of heating is carried out in a state in which the material is contained in a space containing a hydrocarbon-containing substance.

Further, in the photo-contact layer formation step, as described above, by adding a metal oxide precursor substance or a binder to the coating liquid, the metal oxide particles and the metal oxide having photocatalytic activity are formed together. After the precursor material or the photo-contact layer containing the carbon component is heated in a state in which the aluminum material in which the photo-contact layer is formed is placed in a space containing the hydrocarbon-containing substance, the aluminum material and the photo-contact layer can be further improved. Adhesion.

<Light touch media layer forming step>

In the method for producing a photocatalyst-coated material of the present invention, first, a photo-contact dielectric layer containing photocatalytic active metal oxide particles is formed on the surface of an aluminum material. The method of forming the photocontact layer on the surface of the aluminum material as the substrate is not particularly limited. For example, if a metal oxide particle having photocatalytic activity is used in a solution by using a stirrer or the like a coating liquid obtained by emulsification, a coating liquid obtained by hydrolyzing or hydrothermally treating a metal oxide precursor material having photocatalytic activity in a solution, or a mixture of the above two coatings The liquid coating liquid can be applied to the surface of the aluminum material. The method of coating is not particularly limited, and a spin coating method, a bar coating method, a shower coating method, or a dip coating method is suitably employed. The aluminum material having the photocontacting medium layer formed on the surface by coating is dried as needed. The thickness of the photocontacting medium layer can be controlled by the number of coatings, the composition and concentration of the coating liquid. The thickness of the photo-contacting layer formed by the coating is not particularly limited, and the adhesion between the substrate and the photo-contact layer is preferably 1 nm or more and 10 μm or less, and particularly preferably 2 μm or less.

Further, as described above, when a photo-contact layer is formed, a metal oxide precursor substance (such as an aqueous solution of peroxotitanic acid) or an organic binder such as a resin may be added to the coating liquid. In this case, the mass ratio of the binder in the photo-contacting layer is not particularly limited, and the solid content of the coating liquid is usually 100 parts by mass, preferably the binder is 90 parts by mass or less, more preferably It is 10 parts by mass or less.

The organic binder is not particularly limited. Examples of the organic binder include a carboxyl group-modified polyolefin resin, a vinyl acetate resin, a vinyl chloride resin, a vinyl chloride-vinyl acetate copolymer resin, a vinyl alcohol resin, a vinyl fluoride resin, an acrylic resin, and a polyester. A binder of a synthetic resin such as a resin, a urethane resin, an epoxy resin, a urea resin, a phenol resin, an acrylonitrile resin, a nitrocellulose resin, a paraffin wax or a polyethylene wax, and further, a wax, a tar, a glue, Adhesives such as lacquer, turpentine, beeswax and other natural resins. In the heating step after the step of forming the photo-contacting medium layer, it is more preferable to use, for example, a binder which is not completely volatilized by heating in a hydrocarbon atmosphere at a temperature of 450 ° C or more and less than 660 ° C for 1 hour or more and 100 hours or less. . If the binder is completely volatilized in the heating step in the hydrocarbon environment, it is used as a base compared with the case where a resin which is not completely volatilized is used as a binder. The adhesion between the aluminum material and the photo-contact layer is reduced.

The solvent to be used together with the organic binder is not particularly limited. The solvent is preferably a solvating agent of the binder (a solvent in which the binder is easily dissolved). Examples of the solvent include a ketone solvent such as acetone, methyl ethyl ketone or methyl isobutyl ketone, an ester solvent such as ethyl acetate, an aromatic solvent such as toluene or xylene, n-pentane or n-hexane. An aliphatic solvent such as n-heptane or n-octane; an alicyclic solvent such as cyclohexane, methylcyclohexane or cyclopentane; an alcohol solvent such as methanol, ethanol or isopropanol; A glycol solvent such as propylene glycol, a glycol ether solvent such as propylene glycol monomethyl ether or dipropylene glycol monomethyl ether, or the like.

<heating step>

In the method for producing a photocatalyst-coated material of the present invention, after the step of forming the photo-contact layer, the aluminum material on which the photo-contact layer is formed is placed in a space containing the hydrocarbon-containing substance and heated. The type of the hydrocarbon-containing substance is not particularly limited. Examples of the type of the hydrocarbon-containing substance include paraffin-based hydrocarbons such as methane, ethane, propane, n-butane, isobutane, and pentane, and olefin-based hydrocarbons such as ethylene, propylene, butene, and butadiene, and acetylene. An acetylene hydrocarbon or the like, or a derivative of such a hydrocarbon. Among these hydrocarbons, a paraffinic hydrocarbon such as methane, ethane or propane is preferred because it is in a gaseous state in the step of heating the aluminum material having the photocontact layer formed thereon. More preferably, it is any one of methane, ethane and propane. The most preferred hydrocarbon is methane.

Further, the hydrocarbon-containing substance may be used in any state such as a liquid or a gas. The hydrocarbon-containing substance may be present in a space in which the aluminum material having the photo-contact layer formed on the surface thereof is present, and may be introduced into the space of the aluminum material on the surface of which the photo-contact layer is formed by any method. For example, when the hydrocarbon-containing substance is in a gaseous state (methane, ethane, propane, etc.), the hydrocarbon-containing substance may be separately filled in the sealed space in which the heating step is performed, or may be one with an inert gas. It may be filled or may be filled together with a reducing gas such as hydrogen. Further, when the hydrocarbon-containing substance is a liquid, the hydrocarbon-containing substance may be separately filled in the sealed space in a vaporized manner, or may be filled together with an inert gas, or may be a reducing gas such as hydrogen. And filled.

In the heating step, the pressure of the heating environment is not particularly limited, and may be normal pressure, reduced pressure or pressurized. Further, the adjustment of the pressure may be performed at any time during the period of maintaining a fixed heating temperature, heating up to a fixed heating temperature, or starting from a fixed heating temperature.

The mass ratio of the hydrocarbon-containing substance to be introduced into the space of the aluminum material on which the photo-contact layer is formed is not particularly limited, and is usually preferably 0.1 part by mass or more and 50 parts by mass based on 100 parts by mass of the aluminum material. The amount is preferably 0.5 parts by mass or more and 30 parts by mass or less or less.

In the heating step, the heating temperature may be appropriately set depending on the composition of the aluminum material to be heated, and the like, and is usually preferably 450 ° C or more and less than 660 ° C, more preferably 530 ° C or more and 620 ° C or less. By setting the heating temperature to 450 ° C or higher, the carbide containing the crystallized aluminum can be contained in the interposer containing aluminum and carbon. However, in the manufacturing method of the present invention, it is not excluded to heat the aluminum material having the photocontacting medium layer formed on the surface at a temperature less than 450 ° C, as long as it is heated at a temperature of at least more than 300 ° C to form a photocontacting medium layer. Aluminum can be used.

The heating time is also dependent on the heating temperature and the like, and is generally 1 hour or more and 100 hours or less.

When the heating temperature is 400 ° C or higher, it is preferred to set the oxygen concentration in the heating environment to 1.0% by volume or less. If the heating temperature is 400 ° C or higher and the oxygen concentration in the heating environment exceeds 1.0% by volume, the thermal oxidation film on the surface of the aluminum material is enlarged and hindered. It contains the formation of an intercalation layer of aluminum and carbon, and the adhesion is lowered.

<oxidation step>

In the heating step, the metal oxide particles contained in the photo-contact layer are reduced according to the type thereof to reduce the photocatalytic activity of the photo-contact layer, and therefore, the aluminum material having the photo-contact layer formed on the surface after the heating step may be used. An oxidation step such as an oxidative heating step for heating in an oxidizing atmosphere, an anodizing step for anodizing, or the like is performed. Thereby, the photocatalytic activity of the photocontacting medium layer can be restored.

Further, since the environment containing the hydrocarbon-containing substance is a reducing environment, the natural oxide film formed on the surface of the aluminum material is reduced in the heating step to completely disappear, or the thickness of the natural oxide film is reduced as compared with that before the heating step. The situation. In this case, the portion where the natural oxide film disappears or the portion where the thickness of the natural oxide film is reduced is in contact with the moisture of the use environment, and the aluminum material is corroded. However, in the case where the oxidation step is carried out after the heating step, the oxidation of the portion of the surface of the aluminum material caused by the reduction is promoted. Therefore, the photocatalyst-coated material of the present invention is in a state in which an aluminum oxide film is formed on the surface of the aluminum material as the substrate before being placed in the use environment, thereby suppressing moisture or the like from the contact environment. The metal corrosion caused by the deterioration prevents the quality of the material coated with the photocatalyst from deteriorating over time.

Further, in the oxidative heating step, the oxidizing atmosphere may be filled with oxygen alone in the space of the aluminum material on which the photo-contact layer is formed, and may be filled with oxygen alone or with non-reducing gas. Filled together. The oxidizing atmosphere preferably contains a space of 2% by volume or more and 50% by volume or less of oxygen. The heating temperature is usually preferably 200 ° C or more and 660 ° C or less. The heating time is also dependent on the heating temperature and the like, and is generally preferably 10 seconds or more and 50 hours or less.

The anodic oxidation step is not particularly limited. For example, it may be carried out by applying a voltage of 1000 V or less to an aluminum material having a photocontact layer formed on the surface thereof in a solution such as phosphoric acid or sulfuric acid.

[Examples]

According to the following Examples 1 to 5 and Comparative Examples 1 to 3, samples of the photocatalyst-coated material were produced.

(Example 1)

An aluminum foil having a thickness of 50 μm and a purity of 99.3% by mass was immersed in an aqueous solution in which 1% by mass of anatase-type titanium oxide particles (photocatalyst-active metal oxide particles) having an average particle diameter of 6 nm was dispersed, thereby using aluminum foil. On both sides, a photo-contact dielectric layer having a thickness of 0.1 μm on a single side was formed.

Thereafter, the aluminum foil having the photocontact medium layer formed thereon was held in a methane gas atmosphere at a temperature of 610 ° C for 12 hours, thereby preparing a sample coated with the photocatalyst.

(Example 2)

The sample prepared in the above Example 1 was further kept at a temperature of 600 ° C for 12 hours in the air to prepare a sample coated with a photocatalyst.

(Comparative Example 1)

In the above-mentioned Embodiment 1, an aluminum foil having a photo-contact layer formed on the surface thereof by immersing the aluminum foil in an aqueous solution was kept at 610 ° C for 12 hours in the air, thereby preparing a sample coated with the photocatalyst. .

(Example 3)

Ti(n-OC ₃ H ₇ ) ₄ : 1 molar and C ₃ H ₇ OH were added dropwise to a mixture of H ₂ O ₂ : 1.5 moles and H ₂ O: 10 moles over 1 hour while stirring. A mixture of 1 moles, a solution containing a water-soluble titanium complex as a metal oxide precursor substance which was subjected to stabilization treatment by performing a misalignment.

The above solution was added to a container made of stainless steel, and bead milled for 2 hours using zirconia beads having a diameter of 0.3 mm, whereby anatase-type titanium oxide particles having an average particle diameter of 130 nm (photocatalyst-active metal oxide) were used. The particles are dispersed in the above solution to prepare a coating liquid. In the coating liquid obtained, the mass ratio of the water-soluble titanium complex (metal oxide precursor substance) in the total solid mass is 1% by mass, and the titanium oxide particles (metal oxide particles having photocatalytic activity) The mass ratio was 99% by mass.

The coating liquid was applied onto the surface of an aluminum foil having a thickness of 50 μm and a purity of 99.3% by mass by a bar coating method, and then dried in air at a temperature of 120 ° C for 3 minutes to be dried. The thickness of the obtained photo-contacting medium layer is about 0.5 μm.

The aluminum material on which the photocontacting medium layer was formed was held in a methane gas atmosphere at a temperature of 610 ° C for 12 hours, thereby preparing a sample coated with a photocatalyst.

(Example 4)

The sample prepared in the above Example 3 was further kept at 610 ° C for 12 hours in the air to prepare a sample coated with a photocatalyst.

(Comparative Example 2)

In the above embodiment 3, light is formed on the surface by coating the surface of the aluminum foil. The aluminum foil of the contact medium layer was kept at 610 ° C for 12 hours in the air, thereby preparing a sample coated with the photocatalyst.

(Example 5)

A polyvinyl alcohol-based resin was added as a binder to a container made of stainless steel, and bead milled for 2 hours using zirconia beads having a diameter of 0.3 mm to thereby obtain anatase-type titanium oxide particles having an average particle diameter of 16 nm (having The photocatalytic active metal oxide particles are dispersed in the above resin to prepare a coating liquid. In the obtained coating liquid, the mass ratio of the resin (adhesive: carbonaceous component) in the total solid mass is 25% by mass, and the mass ratio of the titanium oxide particles (metal oxide particles having photocatalytic activity) is 75 mass%. %.

The coating liquid was applied onto the surface of an aluminum foil having a thickness of 30 μm and a purity of 99.3% by mass by a bar coating method, and then dried in air at a temperature of 200 ° C for 1 minute to dry. The thickness of the obtained photo-contacting medium layer was about 2.5 μm.

The aluminum material on which the photocontacting medium layer was formed was held in a methane gas atmosphere at a temperature of 610 ° C for 16 hours, thereby preparing a sample coated with a photocatalyst.

(Comparative Example 3)

In the above embodiment 5, the aluminum foil having the photocontact layer formed on the surface thereof was coated in the air at a temperature of 610 ° C for 16 hours by coating the surface of the aluminum foil, thereby preparing a sample coated with the photocatalyst. .

With respect to the photocatalyst-coated materials of Examples 1 to 5 and Comparative Examples 1 to 3 obtained above, the adhesion between the photo-contact dielectric layer and the aluminum material was evaluated by a peel test using a tensile tester using an adhesive tape. And proceed. A sample having a photocatalyst-coated material having a width of 10 mm and a length of 100 mm will have a width of 18 mm and a length of 120 mm. Next, the adhesive tape (manufactured by Sekisui Chemical Co., Ltd., trade name "Cellophane Tape") was pressed against the surface of the photo-contacting medium layer and cut into a width of 10 mm. Thereafter, the peel strength [N/cm] required for peeling was measured by a tensile tester using an adhesive tape at a peeling angle of 90° and a peeling speed of 200 mm/min. The value of the peel strength is a value which is stable after the start of the measurement. For each sample, the peel strength was measured at three places, and the adhesion was evaluated by the average value. The average value of the peel strength measured for each sample is shown in Table 1.

As is apparent from Table 1, the photocatalyst-coated material obtained in Examples 1 and 2 of the present invention was obtained in Examples 3 and 4 as compared with the photocatalyst-coated material obtained in Comparative Example 1. The photocatalyst-coated material obtained in Example 5 was compared with the photocatalyst-coated material obtained in Comparative Example 3, as compared with the photocatalyst-coated material obtained in Comparative Example 2. , showing a high degree of closeness. Further, each sample of the photocatalyst-coated material obtained in Examples 1 to 5 was observed by a scanning electron microscope, and as a result, it was confirmed that a carbide containing crystallized aluminum was formed between the aluminum material and the photocontact medium layer. Intermediary layer.

(Comparative Example 4)

In the above embodiment 5, light is formed on the surface by coating the surface of the aluminum foil. The aluminum foil of the touch media layer directly serves as a sample of the material coated with the photocatalyst. That is, in Comparative Example 4, a sample coated with a photocatalyst-coated material was produced in the same manner as in Example 5 except that it was kept at a temperature of 610 ° C for 16 hours in a methane gas atmosphere in Example 5.

For the photocatalyst-coated materials obtained in Examples 2, 4, and 5 and Comparative Example 4, a weather resistance tester by ultraviolet irradiation (EYE Super UV Tester manufactured by Iwasaki Electric Co., Ltd., type: SUV-) was used. W151) Perform a deterioration test. Specifically, the materials coated with the photocatalysts of Examples 2, 4, and 5 and Comparative Example 4 were placed on the weather resistance tester, and the materials coated with the photocatalyst were irradiated with ultraviolet rays under the following conditions.

Ultraviolet irradiation conditions: The photocatalyst-coated material was irradiated with ultraviolet rays for 90 hours at an illuminance of 100 W/m ² at a temperature of 60 ° C and a humidity of 50%.

The adhesion between the photocontactor layer and the aluminum material was evaluated for the material coated with the photocatalyst before the ultraviolet ray was irradiated in the above deterioration test and the photocatalyst coated with the ultraviolet ray. The evaluation of the adhesion was carried out by the same method as the above-described peeling test using a tensile tester.

From Table 2, in Examples 2, 4, and 5 of the present invention, no change in adhesion (peel strength) was observed between the irradiation of the ultraviolet rays and the irradiation of the ultraviolet rays in the deterioration test. On the other hand, in Comparative Example 4, it was found that the adhesion after the ultraviolet ray was irradiated in the deterioration test was significantly lower than that before the irradiation of the ultraviolet ray. From these results, it is known that if you want to make it as in Comparative Example 4 When an organic-based material is used as a binder to immobilize a photo-contact layer containing metal oxide particles having photocatalytic activity on an aluminum material as a substrate, the binder itself is deteriorated by the photocatalytic action of the photo-contact layer, and the photo-contact layer is The adhesion between the aluminum materials is reduced. On the other hand, it is found that when the photocontactor layer is fixed on the surface of the aluminum material by the method of the present invention as in the examples 2, 4, and 5, the adhesion after the ultraviolet ray is irradiated in the deterioration test is not higher than that before the ultraviolet ray irradiation. decline.

The embodiments and examples disclosed above are to be considered as illustrative and not restrictive. The scope of the present invention is intended to embrace all such modifications and modifications and

(industrial availability)

According to the present invention, the adhesion between the aluminum material as the substrate and the photocontact medium layer can be improved, and therefore, the photocatalyst-coated material of the present invention can be used for various environmental purifications by applying it to various articles.

Claims (6)

A photocatalyst-coated material comprising: an aluminum material; a photo-contact dielectric layer comprising photocatalytic active metal oxide particles formed on the surface of the aluminum material; and an aluminum layer formed between the aluminum material and the photo-contact dielectric layer Intermediary layer with carbon. The photocatalyst-coated material according to the first aspect of the invention, wherein the photo-contact layer has a thickness of 1 nm or more and 10 μm or less. The photocatalyst-coated material of claim 1, wherein the interposer comprises a crystallized aluminum carbide. An article having a photocatalyst-coated material of claim 1 of the patent application. A method for producing a photocatalyst-coated material, comprising: a photo-contacting medium layer forming step of forming a photo-contacting dielectric layer containing photocatalytic active metal oxide particles on a surface of an aluminum material; and the aluminum material to be formed with the photo-contacting dielectric layer A heating step of performing heating in a state containing a hydrocarbon-containing substance. The method for producing a photocatalyst-coated material according to claim 5, wherein the heating step is performed at a temperature of 450 ° C or more and less than 660 ° C.