JPH10249212A - Photocatalyst supporter having odor-preventing/ deodorizing property and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photocatalyst by which excellent odor-preventing/ deodorizing effect is stably exhibited for a long term by carrying the photocatalyst at plenty amount with high adhesion strength on a metallic supporter stable for photocatalytic action and to provide a producing method thereof. SOLUTION: Base material consisting of aluminum alloy formed with an anodic oxide film 1 is immersed into dispersion liquid or a paint solution containing semiconductor particles having photocatalytic action and a cataphoresis method is applied thereto. Or, the base material is immersed into the above-mentioned solution at pressure not higher than the atmospheric pressure. The photocatalyst supporter having odor-preventing/deodorizing property is produced. In the photocatalyst supporter, the semiconductor particles or paint grains 3 containing the semiconductor particles or being carried with them are filled into pores 2 of the anodic oxide film 1 of the base material and carried on the surface thereof.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photocatalyst support having deodorizing and deodorizing properties and a method for producing the same, and more particularly, to a method for producing an anodized film formed on a surface of aluminum or an aluminum alloy as a supporting base material. The present invention relates to a photocatalyst holder having deodorizing and deodorizing properties in which semiconductor fine particles having photocatalytic activity or paint particles containing or supporting semiconductor fine particles are filled and supported in pores and / or on the surface thereof, and a method for producing the same.

[0002]

_2. Description of the Related Art It is known that semiconductor fine particles having a photocatalytic action represented by TiO ₂ have a property of decomposing organic substances by the photocatalytic action. Stain, deodorant and deodorant products have been devised. In particular, regarding deodorization and deodorization, various products have been developed to directly appeal to human sensitivity.
For example, a filter using a TiO ₂ photocatalyst and an air purifier using a photocatalyst are commercially available. As a method for supporting a photocatalyst used for deodorization and deodorization, Japanese Patent Application Laid-Open No. 8-281 is disclosed.
No. 121 describes a method in which TiO ₂ is supported on inorganic fiber paper using a dispersion solution in which TiO ₂ is dispersed in an aqueous silica sol solution, and JP-A-8-266602 discloses a method.
A method is described in which a mixture of an aqueous dispersion of aggregates composed of TiO ₂ and fine fibers and an aqueous dispersion of synthetic resin fibers is formed into a sheet by a wet papermaking method, and TiO ₂ is supported on synthetic fiber paper. Further, as a method of supporting a photocatalyst on a metal-based support, a sputtering method, a sol-gel method, and the like have been devised.

[0003]

When a photocatalyst is used for deodorization and deodorization, the photocatalyst is generally supported on a fibrous support such as paper or cloth, as in the above-mentioned prior art, in view of its adsorptivity. It is considered necessary. However, most of them are made of organic substances, and the fibers themselves are gradually decomposed by the photocatalytic action, so that there is a problem in stability in long-term use. On the other hand, when a photocatalyst is adsorbed and supported on a support made of a metal material or the like that can withstand a photocatalytic action, a sufficient deodorizing / deodorizing effect cannot always be obtained because the surface area is small. In addition, there is a problem that sufficient adhesion between the metal support and the photocatalyst cannot be obtained, and the adsorbed and supported photocatalyst is easily separated. Furthermore, when a photocatalyst is supported on a metal support by a sputtering method or the like, it is difficult to uniformly coat the photocatalyst film on a support having a complicated shape.

Accordingly, an object of the present invention is to solve the above-mentioned problems, to carry a photocatalyst in a sufficient amount and with a high adhesion strength on a metal support which is stable against photocatalysis, and to obtain excellent odor control. -To provide a photocatalyst holder capable of stably exhibiting a deodorizing effect over a long period of time. Further, an object of the present invention is to make it possible to easily produce a photocatalyst holder having the above-described excellent characteristics at a relatively low cost, and to uniformly support the photocatalyst on a support having a complicated shape. An object of the present invention is to provide a method for producing a deodorizing / deodorizing photocatalyst holder.

[0005]

According to the present invention, an anodic oxide film having pores is formed on a surface of a substrate made of aluminum or an aluminum alloy, and the anodic oxide film is further provided. The present invention provides a deodorizing and deodorizing photocatalyst holder in which semiconductor fine particles having photocatalytic activity or paint particles containing or supporting semiconductor fine particles are filled and supported in the pores and / or on the surface thereof. Further, according to the present invention, there is also provided a method suitable for producing a photocatalyst holder having the above-mentioned deodorizing and deodorizing properties. In one of the methods, a substrate made of aluminum or an aluminum alloy on which an anodic oxide film is formed is immersed in a dispersion or a coating solution containing semiconductor fine particles having a photocatalytic action under a pressure of less than atmospheric pressure. Characterized in that semiconductor fine particles or paint particles containing or supporting semiconductor fine particles are filled and supported in the pores of and / or on the surface of the anodic oxide film of the material. In another method, semiconductor fine particles having a photocatalytic action are used. A substrate made of aluminum or an aluminum alloy on which an anodic oxide film is formed is immersed in a dispersion liquid or a coating solution containing, and a semiconductor is formed in the pores of the anodic oxide film of the substrate and / or by electrophoresis. It is characterized in that paint particles containing or carrying fine particles or semiconductor fine particles are filled and carried.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION According to the present invention, a porous anodic oxide film is formed on a substrate made of aluminum or an aluminum alloy (hereinafter abbreviated as an aluminum substrate), and a vacuum impregnation method or an electric Semiconductor particles having photocatalytic action such as TiO ₂ by electrophoresis or paint particles containing or carrying semiconductor particles (hereinafter collectively referred to as photocatalysts)
Is adsorbed and carried. The anodic oxide film is an insulating porous film in which pores having a diameter of about 5 to 100 nm are innumerably opened on the surface, and has an extremely large surface area as compared with a normal metal surface. Therefore, by adsorbing and supporting a photocatalyst such as TiO _{2 in} the pores of the anodic oxide film or on the surface thereof, the amount of the photocatalyst supported per unit area is considerably increased, and the photocatalyst film is formed on a flat metal plate. The deodorizing and deodorizing effects are extremely high as compared with those formed with. In addition, since both the anodized film and the aluminum substrate are stable against photocatalysis, they do not decompose by photocatalysis as in conventional synthetic fiber substrates,
Excellent deodorizing and deodorizing effects can be stably exhibited over a long period of time.

Further, since the photocatalyst is adsorbed and carried in the pores of the anodic oxide film, the photocatalyst and the aluminum substrate have high adhesion strength and are excellent in long-term durability. In addition, by controlling the thickness and pore size of the anodic oxide film and the amount of the photocatalyst to be supported, the photocatalysis can be arbitrarily adjusted. Further, since an aluminum substrate having excellent moldability is used as the support base material, and the respective processes of anodic oxidation, vacuum impregnation, and electrophoresis can be performed in a wet manner, photocatalyst holders of various shapes can be formed. That is, after manufacturing the photocatalyst holder according to the present invention, it can be formed into various shapes, and anodized aluminum substrates that have been extruded and processed into a complicated shape in advance to adsorb and support the photocatalyst. Can also. Therefore, the photocatalyst holder of the present invention can be applied to all types of products such as deodorant / deodorant figurines, deodorant / deodorant pen stands, and deodorant / deodorant cases of any shape, structure, and pattern, as well as panel materials. ,
It can be applied to aluminum building materials such as frame materials and frame materials.
It can be used in the form of a deodorizing panel, a deodorant / deodorizing fitting unit, and the like.

As mentioned above, the photocatalyst holder of the present invention
Is in the pores and / or surface of the anodic oxide film on the aluminum substrate
Semiconductor fine particles having a photocatalytic action, for example, TiO.
_Two Exists. Sunlight or fluorescent light
When the light of the lamp is irradiated, TiO _Two Holes (h⁺ ) And
Electronic (e^- ) Is generated and shows photocatalytic action.
The equipment is disassembled. That is, acetaldehyde,
Decomposes offensive odor components such as ammonia and mercaptan
It has a deodorizing and deodorizing effect. Also,
Water is oxidized by the action of the holes to generate OH radicals,
In addition, oxygen in the air is reduced by the action of electrons, and O^2-I
On occurs. These active oxygens have excellent bactericidal action.
As a result, mold and the like hardly occur. Therefore, the present invention
The photocatalyst holder according to
It also shows fungus, fungus and antifouling properties, and has antibacterial, antifungal and antifouling properties.
It can also be used as a form of deodorized products.

Further, when metal ions are present on the surface of semiconductor particles such as TiO ₂ , various metal ions are reduced by the action of electrons generated by light irradiation, and metal ions are contained in pores of the anodic oxide film. Can be precipitated. That is, if an antibacterial metal such as silver or copper or a compound containing an antibacterial metal is deposited, antibacterial and antifungal properties can be maintained even at night when the light of a fluorescent lamp is extinguished. Also,
If a metal such as nickel and tin, which has been conventionally deposited by electrolytic coloring, is deposited, coloring can be performed without using an electrolytic bath or a power supply. Furthermore, if it is a functional material that is ionized in a solution and exerts its function in a reduced state, it becomes possible to deposit the functional material in the pores of the anodic oxide film in the same manner. Functional aluminum products can be manufactured.

Hereinafter, the present invention will be described in detail.
As the anodic oxide film of the aluminum substrate to be filled with the photocatalyst, the pore diameter of the anodic oxide film formed by ordinary anodic oxidation treatment is generally 50 nm or less, and it is difficult to fill the photocatalyst. It is necessary to use an aluminum substrate having Various methods are known as a method for forming such an anodized film having a large pore diameter. First, in one method, an aluminum substrate is, for example, sulfuric acid, phosphoric acid, oxalic acid, malonic acid, maleic acid, or the like. Anodizing at a high voltage in an aqueous solution of one or more acids such as mineral acids or organic acids such as an acid, for example, in an electrolytic bath containing 5 to 30% of phosphoric acid and 3 to 40% of oxalic acid; An anodic oxide film having pores larger than a normal pore diameter is formed on the substrate surface. In general, when anodizing is performed at a high voltage of 150 to 220 V DC, an anodic oxide film having a pore diameter of usually 120 nm or more is obtained, and the pores can be filled with the photocatalyst. That is, the voltage of the anodic oxidation treatment is 150 V
If it is less than 220 V, it is not preferable because it is difficult to obtain pores large enough for filling the photocatalyst. On the other hand, if it exceeds 220 V, it adversely affects the physical properties such as the strength of the anodic oxide film.

In another method, an aluminum substrate is first anodized in an aqueous solution of one or more of the above-mentioned mineral acids or organic acids to form a porous anodized film on the surface of the aluminum substrate. Let it. As the electrolysis conditions, an anodic oxide film having a large cell size and a large pore diameter is obtained by high voltage electrolysis of 35 V or more, preferably 50 to 160 V. Then, the film is immersed in an aqueous solution of one or more of phosphoric acid, sulfuric acid, oxalic acid, and sulfamic acid, preferably an aqueous solution of 3 to 10% of phosphoric acid, to perform a process of expanding the pores of the film. By such a method, finally, 50 nm or more, preferably 100 to 1 nm
The porous anodic oxide film suitable for filling the photocatalyst of the present invention is obtained by adjusting the pore size to 000 nm and the pore depth to about 3 to 10 μm. In order to shorten the time required for the process of expanding the pores of the coating, the immersion and the alternating current electrolysis are alternately repeated at short intervals in an aqueous solution containing 3 to 10% of phosphoric acid. The enlargement process can be performed in a relatively short time.

As the semiconductor to be filled in the pores of the anodic oxide film, any semiconductor can be used as long as it has a relatively high mobility of electrons and holes and has a photocatalytic action as described above. For example, TiO ₂ , SrTiO ₃ , Zn
O, CdS, SnO _{2 and the} like can be mentioned, and among them, TiO ₂ is particularly preferable. When using paint particles containing or carrying semiconductor fine particles, the paint is fluorine-based, silicate-based, acrylic-based, polyester-based or polyurethane-based, etc., semiconductor fine particles are uniformly dispersed,
Preferably, the coating material for the building material is not particularly limited as long as it has appropriate strength and adhesion, and can be appropriately selected depending on the application. In addition, among the above-mentioned paints, inorganic paints such as fluorine-based paints and silicate-based paints are more preferable in view of their oxidation resistance.

The particle size of the semiconductor fine particles used or the coating particles containing or carrying the semiconductor fine particles is 1 nm.
It is preferable to adjust the particle diameter to 700 nm, preferably 5 nm to 300 nm. When the semiconductor fine particles are contained or supported in the paint, it is apparent that the semiconductor fine particles are made smaller than the particle diameter of the paint particles. Particle size is 1n
When it is smaller than m, the band gap becomes large due to the quantum size effect, and there is a problem that the photocatalytic performance cannot be obtained unless it is under illumination including short-wavelength light such as a high-pressure mercury lamp. Further, when the particle size is too small, there are problems that handling is difficult and dispersibility is deteriorated. A particle size of 5 nm or more is preferred from the viewpoint of handleability. On the other hand, when the particle size exceeds 700 nm, it becomes difficult to fill the pores of the anodic oxide film on the aluminum substrate.

As a method of filling the fine particles of the semiconductor into the pores of the anodic oxide film on the aluminum substrate, an electrophoresis method in a dispersion of the fine particles of the semiconductor can be suitably used. For example, a polarity is developed on the surface of the semiconductor fine particles (for example,
A surfactant is adsorbed on the particle surface, the pH of the solution is made higher than the isoelectric point of the semiconductor fine particles, and 10 to 30% by weight of the semiconductor fine particles are dispersed in an aqueous solution to prepare an aqueous dispersion bath. In this bath, direct current electrolysis (voltage 30 to 200) was performed using the aluminum substrate on which the anodized film was formed as an anode.
V) Then, an electrophoresis method of filling semiconductor fine particles into the pores of the anodic oxide film can be employed. As an electrophoresis method,
A DC voltage scanning method in which a DC voltage is scanned from a low voltage to a high voltage at a constant boosting rate for a predetermined time, a DC constant voltage method in which electrolysis is performed at a constant voltage for a predetermined time, and the like can be adopted.

When paint particles containing or carrying semiconductor fine particles are used, if the paint particles undergo electrophoresis, the photocatalyst can be filled in the pores of the anodic oxide film in the same manner as described above. Further, a method of immersing an aluminum substrate having an anodized film formed therein in a coating material is also possible. Furthermore, if the photocatalyst cannot be filled in the pores of the anodic oxide film even when immersed in a paint under normal atmospheric pressure, an aluminum substrate with the anodic oxide film formed is placed in an appropriate vacuum vessel, After evacuation of the inside, a method of introducing a paint, and dipping the aluminum substrate on which the anodic oxide film is formed in the paint in vacuum or under reduced pressure can be adopted.

By the above method, as shown in FIG. 1, an aluminum substrate having the photocatalyst 3 filled in the pores 2 of the anodic oxide film 1 is obtained. As shown in FIG. 1, the photocatalyst is filled up to the upper end of the anodic oxide film, which is an embodiment for the purpose of antibacterial, antifungal and antifouling properties in addition to deodorizing and deodorizing effects.
That is, as shown in FIG. 2, in a case where the photocatalyst 3 is filled only in the lower part of the pores 2 of the anodic oxide film 1, bacteria, mold, and dirt are diffused through the pores of the anodic oxide film to the photocatalyst surface. Otherwise, antibacterial, antifungal, and antifouling properties cannot be exhibited, so in order to express the above properties favorably, a photocatalyst is filled up to the upper end of the anodic oxide film, and the antibacterial, antifungal, and antifouling properties are improved on the surface of the aluminum substrate. It is desirable to be able to express. Further, as shown in FIG. 3, an embodiment in which the unevenness of the anodic oxide film 1 is coated with the photocatalyst 3 is also possible. In this case, the photocatalyst that is not filled in the pores 2 is easy to peel off, but the area covered with the photocatalyst is larger than that in FIGS. 1 and 2, and the pores of the anodic oxide film are gas molecules. This is the most suitable mode for deodorization and deodorization because it allows easy access. The antibacterial, antifungal and antifouling properties are intermediate between those shown in FIGS.

[0017] Furthermore, after the photocatalyst is filled, an antibacterial metal such as silver or copper or a compound containing an antibacterial metal is precipitated by the photocatalytic action, so that the antibacterial and antifungal effect is obtained even in the dark as described above. Can be expressed. The method of precipitating the antibacterial metal or the compound containing the antibacterial metal is a solution of an appropriate compound containing an antibacterial metal such as silver or copper such as silver nitrate or copper sulfate, or an appropriate reduction such as ethanol or EDTA. A solution to which an agent has been added is prepared. One method is to immerse an aluminum substrate filled with a photocatalyst in the pores of the anodic oxide film in the solution and irradiate the solution with ultraviolet rays using an ultraviolet lamp, a black light, or the like. The antimicrobial metal ion or antimicrobial metal compound ion is reduced by the electrons generated by this, and the antimicrobial metal or a compound containing the antimicrobial metal is deposited on the photocatalyst surface. In this case, the amount of the antibacterial metal or the compound containing the antibacterial metal deposited is controlled by the amount of the antibacterial metal ion in the solution, that is, the concentration of the prepared solution, the concentration of the reducing agent, and the irradiation time of ultraviolet rays. As another method, there is a method in which the solution is applied by spraying or the like to the surface of an aluminum substrate filled with a photocatalyst in pores of an anodized film, and then irradiated with ultraviolet rays. In this method, the amount of antibacterial metal ions in the aqueous solution,
In other words, the amount of the antibacterial metal or the compound containing the antibacterial metal can be controlled by the concentration of the prepared solution, the concentration of the reducing agent, and the amount of application. Also, in any method, if the surface of the photocatalyst is completely covered with the antibacterial metal or the compound containing the antibacterial metal, the photocatalytic action cannot be exhibited, so that it is necessary to control the deposition amount to such an extent that the surface is not covered. There is.

In the case of depositing an antibacterial metal or a compound containing an antibacterial metal, as shown in FIG. The compound 4 containing a metal can be deposited on the surface of the aluminum substrate. Alternatively, as shown in FIG. 5, the photocatalyst 3 is filled only in the pores 2 of the anodic oxide film 1 and the antibacterial property is contained in the pores of the anodic oxide film. Compound 4 containing metal or antibacterial metal
Can also be precipitated. Further, as shown in FIG. 6, after coating the unevenness of the anodic oxide film 1 with the photocatalyst 3, the antibacterial metal or the compound 4 containing the antibacterial metal can be deposited on the photocatalyst surface. In the case of FIG. 4, the antibacterial and antifungal effects are high, but since the antibacterial metal or the compound containing the antibacterial metal is deposited on the surface, the effect of the antibacterial metal or the compound containing the antibacterial metal is sustained, such as exfoliation. May be inferior in sex. In the case of FIG. 5, the antibacterial and antifungal effect is lower than that of FIG. 4, but the antibacterial metal or the compound containing the antibacterial metal is in the pores of the anodic oxide film. It is difficult, and the durability of the effect is improved as compared with the case of FIG. In the case of FIG. 6, since the antibacterial metal or the compound containing the antibacterial metal is precipitated from the surface into the pores of the anodic oxide film, the antibacterial metal or the compound containing the antibacterial metal deposited on the surface is peeled off. However, since the antibacterial metal or the compound containing the antibacterial metal in the pores is difficult to peel off, the persistence of the effect is shown in FIG.
Is equivalent to Which aspect is adopted depends on
An appropriate mode may be selected from the antibacterial and antifungal effects and the life thereof.

Further, conventionally, a metal such as nickel, tin, or copper is deposited in the pores of the anodic oxide film by electrolytic coloring to color the aluminum substrate. Not only the antibacterial metal or the compound containing the antibacterial metal, but also the metal that has been deposited by electrolytic coloring is in the pores of the anodic oxide film in the same manner as the deposition of the aforementioned antibacterial metal or the compound containing the antibacterial metal. Can be deposited,
Thereby, products colored in various colors can be manufactured.
In this case, the control of the amount of the deposited metal, that is, the control of the color tone, can be carried out in the same manner as the above-mentioned method of controlling the deposited amount of the antibacterial metal or the compound containing the antibacterial metal. As for coloring, a method of applying a solution containing metal ions by a suitable method such as a spray method on the surface of an aluminum substrate filled with a photocatalyst in the pores of the anodic oxide film as described above, and then irradiating with ultraviolet rays. adopt. For example, as shown in FIG. 7, a solution containing metal ions and a suitable reducing agent is sprayed by a sprayer 7 while an aluminum substrate 6 is transported by a transport device 5 such as a conveyor, and then an ultraviolet ray is irradiated by an ultraviolet irradiation device 8. Is a continuous production process, unlike the conventional batch type using an electrolytic bath, which not only improves productivity, but also increases the huge electrolytic bath and power supply required for electrolytic coloring. Is completely unnecessary.

When the above-described photocatalytic action is used for coloring the aluminum substrate, the filling of the photocatalyst 3 into the pores 2 of the anodic oxide film 1 is preferably performed as shown in FIG. If the photocatalyst is in a filled state as shown in FIG. 2, the coloring metal 9 precipitates in the pores 2 of the anodic oxide film 1 as shown in FIG.
The same adhesive strength as metal deposited by conventional electrolytic coloring can be secured. Also, using photocatalysis only for coloring,
Thereafter, when the antibacterial, antifungal, and antifouling properties due to the photocatalytic action are unnecessary, the sealing (semi-sealing) of the anodic oxide film 1 is further performed as shown in FIG. ) Treatment to improve corrosion resistance and durability. Even if such a sealing treatment is performed, it exhibits deodorizing and deodorizing properties if the inside of the pores is in communication with the atmosphere.

In the filled state as shown in FIG. 8, deodorizing and deodorizing properties and antibacterial, antifungal and antifouling properties are exhibited by the photocatalytic action.
As shown in (2), after depositing the coloring metal 9, the photocatalyst 3 is filled again to the upper end of the anodic oxide film. In particular, if the semiconductor used for the photocatalyst is TiO ₂ , since the TiO ₂ is almost transparent, the color tone of the coloring metal deposited at the lower portion does not change, and various colors can be selected depending on the coloring metal. On top of that, it shows sufficient deodorant and deodorant properties, and antibacterial, antifungal and antifouling properties. In addition, when an organic paint is deposited in the pores of the anodic oxide film and then a photocatalyst is formed, the organic paint itself is decomposed due to the photocatalysis and causes a fading phenomenon. It is stable, and can exhibit good deodorant / deodorant properties, antibacterial / antifungal / antifouling properties while maintaining the color tone over a long period of time.

[0022]

EXAMPLES Hereinafter, the effects of the present invention will be described more specifically with reference to examples, but it is needless to say that the present invention is not limited to the following examples.

Example 1 Anodization was performed by applying a direct current of 200 V to an aluminum substrate as an anode in an electrolytic bath containing 20% of phosphoric acid and 5% of oxalic acid at 30 ° C., and the hole diameter was about 250 nm and the depth of the holes was about 250 nm. About 5μ
An anodic oxide film having m pores was produced. Then
A silicate in which 10% by weight of a fine powder of TiO ₂ (average particle size: 10 nm) as a photocatalyst was mixed and dispersed uniformly was diluted 10 times with ethanol to prepare a photocatalyst-carrying coating material, and 1 atm (sample 1) or 0 atm. The aluminum substrate on which the anodized film was formed was immersed in a paint under a pressure of 0.2 atm (sample 2), and was gently lifted.
The silicate was allowed to react for a period of one minute and coated with a silica coating supporting the photocatalyst. For comparison, a photocatalyst was prepared in the same manner as the sample under the condition of 1 atm (Comparative Example 1) or 0.2 atm (Comparative Example 2) using an aluminum substrate on which no anodized film was formed. The supported silica coating was coated.

Film thickness measurement and surface roughness measurement: Samples 1 to
The film thickness and surface roughness of the photocatalytic film on the anodic oxide films of Comparative Example 1 and Comparative Examples 1 and 2 were measured with a stylus contact type film thickness meter. Table 1 shows the results.

[Table 1]

Evaluation of antifouling property 1: Salad oil was uniformly applied to the surfaces of Samples 1 and 2 and Comparative Examples 1 and ² so as to have a concentration of 0.1 mg / cm ² , and irradiated with ultraviolet rays using a 100 W ultraviolet lamp. The time until the salad oil was completely decomposed was measured. Table 2 shows the results.

[Table 2]

Evaluation of adhesion: Samples 1 and 2 and Comparative Example 1
-2 Scotch tape test (JIS)
H8602, the adhesion test of the coating film using the cellophane adhesive tape described in 5.8) and JIS H
A scratch test was performed according to the method specified in 8504. Table 3 shows the results.

[Table 3]

Antifouling evaluation 2: After the photocatalyst films on the substrate surfaces of samples 1 and 2 were completely peeled off using # 1200 sandpaper, salad oil was completely removed in the same manner as in the above antifouling evaluation 1. The time until decomposition was measured. Table 4 shows the results.
Shown in

[Table 4]

As can be seen from Table 1, the thicknesses of the photocatalyst films of Samples 1 and 2 and Comparative Examples 1 and 2 were almost the same, but the surface roughness was the same for Sample 1 and Comparative Examples 1 and 2. It was big compared to. On the other hand, in Table 2, the time required for decomposing the salad oil of Sample 1 and Comparative Examples 1 and 2 was almost the same, but the time required for Sample 2 was slightly longer. These results indicate that the photocatalyst film of Sample 2 was not only filled in the pores of the anodic oxide film, but also coated the entire unevenness of the anodic oxide film (the embodiment shown in FIG. 3). . In this case, the surface of the photocatalyst film becomes rougher than that of the sample 1 in order to reflect the unevenness of the anodic oxide film.
Further, at atmospheric pressure, the photocatalyst could not enter the pores of the anodic oxide film, and therefore, a flat photocatalytic film was formed on the substrate surface. The surface roughness was equivalent to that of Nos. 1 and 2. Further, in the antifouling evaluation 1, in Sample 2, the surface coverage of the photocatalyst was small, and the viscosity of the salad oil was high and it was difficult to enter the pores of the anodic oxide film. Recognize.

As shown in Table 3, no peeling of the film was observed in Samples 1 and 2. This indicates that when a photocatalytic film was formed on the anodized film, the adhesion of the film was improved by the anchor effect of the anodized film regardless of whether the coating pressure was under atmospheric pressure or under reduced pressure. ing. The peeling of the film was observed in Comparative Examples 1 and 2, indicating that the adhesion of the film did not depend on the coating pressure when a substrate having no anodized film was used. Further, as can be seen from Table 4, the sample 1 could not decompose the salad oil at all, but the sample 2 did not decompose the salad oil.
Although the required time was longer than the results shown in (1), the salad oil was decomposed and exhibited antifouling properties. In sample 1, the photocatalytic film was present only on the surface, and the entire surface was peeled off, so that the antifouling property was lost. The presence of the photocatalyst film filled therein indicates that the antifouling property is not lost, and the durability of the photocatalytic film and the durability of the photocatalytic action are much better in sample 2 than in sample 1. You can see that it is. From the above, the photocatalyst enters into the pores of the anodic oxide film by coating with a paint containing semiconductor fine particles under the condition of not necessarily a high vacuum of 0.2 atm. Since the pores of the anodic oxide film were filled, it was confirmed that the anodic oxide film did not fall off and adhered very strongly.

Gas decomposition test: Samples 1-2 and Comparative Examples 1
In order to confirm the organic gas decomposability of the aluminum plate 2 and the untreated aluminum plate, a sample of 4 cm ² was placed in a 0.5-liter closed container, and a concentration of 1 was added to each container.
Acetaldehyde was injected so as to be 00 ppm.
Thereafter, the sample was irradiated with ultraviolet light having an intensity of 1 mW / cm ² using a black light. The gas composition in each container 60 minutes after the start of irradiation was measured by gas chromatography, and the concentration of acetaldehyde after the reaction was measured. Table 5 shows the results.

[Table 5]

From Table 5, it was found that Sample 2 had the lowest concentration of acetaldehyde, and the other samples had almost the same values. That is, it is understood that Sample 2 decomposed the largest amount of acetaldehyde. In addition, in the case of a simple aluminum plate, it can be seen that acetaldehyde was not decomposed at all. As shown in Table 5, the reason for the difference in the acetaldehyde concentration was due to the difference in the loading state of the photocatalyst on each sample. That is, only the sample 2 is filled with the photocatalyst into the pores of the anodic oxide film, whereas the other samples have a flat photocatalytic film formed on the surface. In sample 2, since the photocatalyst was filled in the pores of the anodic oxide film, the surface area was increased and the amount of the photocatalyst carried per unit area was increased. The reactivity in the phase is increased.

Example 2 Samples 1 and 2 of Example 1 and the sample of Comparative Example 1 were used in
The sample was immersed in 0.5 liter of a 01 mol / liter silver nitrate aqueous solution, and irradiated with ultraviolet rays from a 100 W ultraviolet lamp to deposit 0.1 mg / cm ² of silver on the samples of Samples 1 and 2 and Comparative Example 1.

Adhesion test: Scotch tape test and scratch test were performed on the obtained samples 1 and 2 and the sample of Comparative Example 1 in the same manner as in Example 1 above. Table 6 shows the results.

[Table 6]

Antifungal test 1: Samples 1 and 2 and Comparative Example 1 were tested on the surface of Samples 1 and 2 and Comparative Example 1 based on the antifungal test of general industrial products described in JIS Z 2911-5. To a spore suspension at a temperature of 28 ° C and a humidity of 95
% For 28 days, and the state of mold generation was observed. Further, in order to observe the difference in the antifungal property depending on the presence or absence of light irradiation, a fungicide test was performed for each sample when irradiating light with a 20 W fluorescent lamp and when no light was irradiated. Table 7 shows the results. Table 7 shows the mold coverage of the mold surface.

[Table 7]

Antifungal test 2: The photocatalyst films of Samples 1 and 2 were
After completely exfoliating with 1200 sandpaper, a fungicide test was carried out in the same manner as the fungicide test 1 described above.
Table 8 shows the results. Table 8 shows the mold coverage of the mold surface.

[Table 8]

The sample on which silver was deposited was light brown, indicating that the aluminum substrate could be colored with various metals by photocatalysis. Moreover, as can be seen from Table 6 and Table 3 in the case of Example 1, the adhesion of silver was affected by the adhesion between the photocatalyst film to which the silver was adhered and the aluminum substrate. In No. 2, the photocatalyst and the substrate are separated, and even if the adhesion between the silver and the photocatalyst is strong, the photocatalyst cannot be actually used after being separated from the substrate together with the photocatalyst. In the case of Samples 1 and 2, peeling of the photocatalyst film was not observed, and peeling of silver was not observed. These indicate that, as shown in Table 3, the adhesion of the photocatalyst film was improved by the anchor effect of the anodic oxide film, and that the adhesion between the photocatalyst film and silver was sufficient.

As is clear from Table 7, only when the sample 2 was not irradiated with light, the growth area of the mold was slightly larger than that of the other samples. This is because, in the other samples, silver was precipitated only on the surface of the sample, whereas in sample 2, silver penetrated into the pores of the anodic oxide film and the surface coverage was reduced, so that the mold coverage was reduced. The effect was reduced. However, it is unlikely that such a difference in antifungal property causes a problem in actual use. In addition, when light irradiation is performed, silver antibacterial
Since both the antifungal effect and the antibacterial and antifungal effects of the photocatalyst were exhibited, no mold growth was observed at all. When the surface of the base material was polished with sandpaper and the photocatalyst film adhering to the surface was completely peeled off, the color tone of the aluminum substrate itself was returned in Sample 1, but in Sample 2, the surface of the anodic oxide film was exposed. It remained light brown. Further, as shown in Table 8, the antifungal effect of Sample 2 was maintained, and the photocatalyst and silver were filled in the pores of the anodic oxide film, so that the durability of Antifungal effect of Sample 2 was maintained. It can be seen that the endurance is much better than Sample 1. From these results,
A sample in which a photocatalyst was filled in the pores of the anodized film and silver was deposited in the pores by using the photocatalytic action of the photocatalyst was free from problems such as peeling and falling off of silver. Time,
It was confirmed that a sufficient antifungal effect was exhibited during light irradiation.

[0038]

As described above, the deodorizing and deodorizing photocatalyst support of the present invention forms an anodic oxide film on the surface of an aluminum substrate, and furthermore, forms the anodic oxide film on the surface of the porous anodic oxide film having a large surface area. Is filled with semiconductor particles having photocatalytic activity or paint particles containing or carrying semiconductor particles, so the amount of photocatalyst carried per unit area is considerably large, and a photocatalytic film is formed on a flat metal plate Shows superior deodorant and deodorant properties, antibacterial, antifungal, and antifouling properties as compared to those that have been treated. In addition, since both the anodized film and the aluminum substrate are stable against photocatalysis, they do not decompose by photocatalysis as in the case of conventional synthetic fiber base materials, and provide excellent deodorizing and deodorizing effects over a long period of time. It can be exhibited stably. Further, since the photocatalyst is adsorbed and carried in the pores of the anodic oxide film, the adhesion strength between the photocatalyst film and the aluminum substrate is high and the long-term durability is excellent. In addition, by controlling the thickness and pore size of the anodic oxide film and the amount of the photocatalyst to be supported, the photocatalysis can be arbitrarily adjusted. Furthermore, while using an aluminum substrate excellent in moldability as a support base material,
Since the anodization, vacuum impregnation, and electrophoresis can all be performed in a wet manner, photocatalyst holders of various shapes can be formed. Therefore, the photocatalyst holder of the present invention has an arbitrary shape,
It can be advantageously used as a deodorizing / deodorizing product having a structure or pattern, or as a deodorizing / deodorizing / antibacterial / antifungal / antifouling panel, a building material such as a fitting unit. Further, since various metals used for electrolytic coloring of the aluminum substrate can be deposited in the pores of the anodic oxide film, the deodorizing and deodorizing aluminum building material can be colored by a method having higher productivity than the electrolytic coloring method. Furthermore, it is possible to deposit various functional substances besides the antibacterial metal or the compound containing the antibacterial metal or the coloring metal in the fine pores of the anodic oxide film by utilizing the photocatalytic action. We can provide various functional aluminum products with excellent performance.

[Brief description of the drawings]

FIG. 1 is a partial schematic cross-sectional view of a photocatalyst holder in which pores of an anodized film of an aluminum substrate are completely filled with a photocatalyst according to the present invention.

FIG. 2 is a partial schematic cross-sectional view of a photocatalyst holder in which pores of an anodic oxide film on an aluminum substrate are partially filled with a photocatalyst according to the present invention.

FIG. 3 is a partial schematic cross-sectional view of a photocatalyst holder in which the entire unevenness of the anodic oxide film on the aluminum substrate is coated with a photocatalyst according to the present invention.

FIG. 4 is a partial schematic cross-sectional view showing a state where an antibacterial metal or a compound containing an antibacterial metal is deposited on the photocatalyst holder in the state shown in FIG.

FIG. 5 is a partial schematic cross-sectional view showing a state where an antibacterial metal or a compound containing an antibacterial metal is deposited on the photocatalyst holder in the state shown in FIG. 2;

FIG. 6 is a partial schematic cross-sectional view showing a state where an antibacterial metal or a compound containing an antibacterial metal is deposited on the photocatalyst holder in the state shown in FIG.

FIG. 7 is a schematic explanatory view showing an example of a manufacturing process for depositing a metal by photocatalysis.

FIG. 8 is a partial schematic cross-sectional view showing a state where a coloring metal is deposited on the photocatalyst holder in the state shown in FIG. 2;

9 is a partial schematic cross-sectional view showing a state where the photocatalyst holding body shown in FIG. 8 has been subjected to sealing processing.

FIG. 10 is a partial schematic cross-sectional view showing a state in which pores of an anodic oxide film of the photocatalyst holder shown in FIG. 8 are further filled with a photocatalyst.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Anodized film 2 Micropore 3 Photocatalyst 4 Antibacterial metal or compound containing antibacterial metal 5 Transport device 6 Aluminum substrate 7 Sprayer 8 Ultraviolet irradiation device 9 Metal for coloring

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Kazuhito Hashimoto 2073-2, Iijimacho, Sakae-ku, Yokohama-shi, Kanagawa Prefecture New City Hongodai D Bldg. 213 (72) Inventor Nobuyuki Nakata 1300 Horikiri, Kurobe-shi, Toyama Prefecture (72) Inventor Arai Toshio 841 Fujiki, Toyama City, Toyama Prefecture

Claims (3)

[Claims] An anodic oxide film is formed on the surface of a substrate made of aluminum or an aluminum alloy, and further contains semiconductor fine particles or semiconductor fine particles having a photocatalytic action in the pores of the anodic oxide film and / or on the surface thereof. A photocatalyst holder having deodorizing and deodorizing properties, in which the carried paint particles are filled and carried. 2. A substrate made of aluminum or an aluminum alloy on which an anodic oxide film is formed is immersed in a dispersion or a coating solution containing semiconductor fine particles having a photocatalytic action under a pressure lower than the atmospheric pressure. A method for producing a photocatalyst holder having deodorization and deodorization properties, wherein semiconductor fine particles or paint particles containing or supporting semiconductor fine particles are filled and supported in and / or on the pores of an anodized film. 3. A substrate made of aluminum or an aluminum alloy on which an anodized film is formed is immersed in a dispersion or a coating solution containing semiconductor fine particles having a photocatalytic action,
A deodorizing / deodorizing photocatalyst characterized by filling and supporting semiconductor fine particles or paint particles containing or supporting semiconductor fine particles in and / or on the surface of the anodic oxide film of the base material by electrophoresis. A method for manufacturing a holder.