JP3267884B2 - Antibacterial and antifouling aluminum or aluminum alloy material and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an aluminum or aluminum alloy (hereinafter referred to as aluminum alloy) material having a photocatalytic film exhibiting antibacterial, antifungal and antifouling properties under light irradiation, and a method for producing the same. More specifically, the present invention relates to a method for forming a photocatalytic film having excellent adhesion to a base material and adhesion of semiconductor fine particles on an aluminum alloy base material having an anodized film formed thereon.

[0002]

2. Description of the Related Art In recent years, nosocomial infections such as MRSA (methicillin-resistant Staphylococcus aureus) have been regarded as a problem. Most hospital-acquired infections are opportunistic infections, in which viruses, bacteria, protozoa, molds, and the like are suddenly activated in a human body with reduced resistance and immunity, and develop. For example, M
Speaking of RSA infection, the germs seem to spread in the hospital mainly through the body of patients and hospital staff, slippers, medical equipment, etc., but the germs attach to dust in the air and cause airborne infection. There is also. Therefore, in order to prevent hospital-acquired infection, it is necessary to sterilize and purify the entire indoor air, and in the past, they have relied on chemical disinfection and air purifiers. However,
In disinfection, the use of chemicals has a problem that the effect on the human body cannot be neglected, and the odor of the chemicals also causes discomfort, and it cannot be performed frequently due to the difficulty of the work. On the other hand, cleaning of the hospital with an air purifier is relatively easy, but since it is based on the principle of removing dust and the like in the air by static electricity, there is a problem that it is difficult to remove bacteria, fungi, and odors associated therewith. Was. In addition, when tobacco tar adheres to the surface of a building member such as a sash or a panel material and becomes dirty, there is a problem that not only the aesthetic appearance is impaired but also bacteria adhere to the portion and easily propagate.

Incidentally, semiconductor fine particles having a photocatalytic action represented by TiO ₂ decompose organic substances by the photocatalytic action, and based on the action, antibacterial, antifungal, antifouling,
It has been known that it has a deodorizing effect, and recently, various materials have been researched and developed utilizing these materials, in which bacteria and molds are difficult to propagate. For example, Japanese Patent Application Laid-Open No. 2-633
No. 3 discloses an antibacterial powder in which an antibacterial metal such as copper or zinc is supported on the surface of titanium oxide particles, and an antibacterial composition is prepared by blending this powder with resin, rubber, glass or the like. In addition, by a known method, in addition to antibacterial treatment of electrical equipment, furniture furniture, interior decoration materials, packaging materials such as food, etc., the above powder can be used as an antibacterial agent for environmental sanitation facilities and equipment. Is taught.

[0004] Japanese Patent Application Laid-Open No. 6-65012 discloses that
Titanium oxide films containing metals such as silver, copper, zinc, and platinum can be used for concrete, glass, plastic, ceramics,
It is disclosed that by coating a substrate made of a material such as a metal, the propagation of various bacteria and fungi on the substrate can be prevented. Further, JP-A-4-307066 discloses that a photocatalyst is attached to the back surface of a panel, a short-wavelength lamp is disposed on the back side of the panel, and the photocatalyst is activated by irradiating the photocatalyst with ultraviolet light from the lamp. There is disclosed a method of refreshing indoor air in which the installed room is deodorized.

[0005]

However, building materials made of aluminum alloy having a complicated shape (hereinafter referred to as aluminum building materials), such as extruded members, contain semiconductor fine particles having photocatalytic action or semiconductor fine particles. Alternatively, in the case of coating a supported paint (hereinafter, collectively referred to as a photocatalyst), there is a problem of the surroundings, and it is difficult to uniformly coat the photocatalyst even on the convex portions and the corner portions. Furthermore, in the usual method of applying a suspension containing semiconductor fine particles to the surface of a substrate, sufficient adhesion cannot be obtained unless the treatment is performed at a temperature exceeding 200 ° C. Also, the method of forming a metal thin film and then oxidizing it to form a predetermined photocatalyst requires a treatment at a temperature exceeding 200 ° C. However, in the case of aluminum alloy,
When exposed to such a high temperature, there is a problem that the strength is significantly reduced.

On the other hand, photocatalysts that cure at a temperature of 200 ° C. or less have been partially put to practical use. Such a photocatalyst film is obtained by dispersing semiconductor fine particles in a low-temperature-curable inorganic polymer such as silicate, but even in such a case, the thermal expansion coefficients of the substrate and the photocatalyst film are different, Cracks occur in the photocatalytic film due to the effect of thermal stress generated at the time of heating and cooling, resulting in poor adhesion to the substrate, and the photocatalytic film peels off when subjected to an impact. Also, even if this photocatalyst is formed on an aluminum alloy ingot that does not itself have corrosion resistance or weather resistance or an aluminum alloy on which an anodic oxide film is formed, cracks are formed in the photocatalyst film as described above. Has occurred,
The photocatalytic film cannot function as a corrosion-resistant film because components that corrode the aluminum alloy or the aluminum alloy forming the anodic oxide film cannot be prevented from directly contacting the base material. Furthermore, the photocatalytic activity of such a photocatalytic film depends on the amount of semiconductor fine particles contained, and the content of the semiconductor fine particles cannot be increased in order to improve properties such as adhesion, so that the photocatalytic activity is low. In some cases, sufficient antibacterial properties or antifouling properties may not be obtained.

[0007] Usually, in order to impart corrosion resistance and weather resistance to aluminum building materials, an acrylic coating film is formed on the anodic oxide film. When a photocatalytic film is formed on the coating film, the coating film itself is decomposed by the photocatalytic action. In order to prevent this, a method of forming a layer that inhibits the photocatalytic action on the coating film and forming a photocatalytic film thereon is conceivable. And the adhesion between the inhibition layer or the inhibition layer and the photocatalyst became a problem, and this was not always a preferable method.

Further, the present inventors have developed a method utilizing electrophoresis as a wet film forming method excellent in throwing power of a photocatalytic film, and have already filed an application. Conditions for obtaining a photocatalyst film with excellent adhesion are narrow.
Further, even if a semiconductor particle such as TiO ₂ is deposited by electrophoresis on a normal electrophoresis method, that is, using a conductive substrate of some kind, for example, a substrate such as iron or stainless steel, the strength of the photocatalytic film can be improved. Alternatively, the adhesion to the substrate is low. This is because a photocatalytic film having poor strength and poor adhesion to a substrate is obtained because only semiconductor fine particles have a small interaction between particles or between particles and a substrate. In order to avoid this, it is necessary to include semiconductor fine particles in the electrophoretic paint. By electrophoresis of the paint, a coating film containing semiconductor fine particles exhibiting photocatalytic action can be obtained on an appropriate substrate. However, usually, the paint itself is an organic substance, and thus is decomposed by the photocatalytic action of the semiconductor fine particles. In addition, the long-term stability is inferior, and the photocatalytic action of the photocatalytic film is low because the content of the semiconductor fine particles cannot be increased.

Accordingly, an object of the present invention is to solve the above-mentioned problems, to provide an excellent photocatalytic action without requiring a special device, to provide excellent adhesion of semiconductor fine particles, and to form an anodic oxide film. An object of the present invention is to provide a method for forming a photocatalytic film that also improves the corrosion resistance of an aluminum alloy substrate.
A more specific object of the present invention is to form an anodic oxide film without lowering the strength of the aluminum alloy substrate, with semiconductor particles being carried with good throwing power even in an aluminum alloy substrate having a complicated shape. A photocatalytic film with improved adhesion of the semiconductor fine particles is formed by a method that also improves the corrosion resistance of the aluminum alloy itself. Further, since the content of the semiconductor fine particles in the photocatalytic film is large, excellent antibacterial and antifungal properties are obtained. An object of the present invention is to provide an aluminum alloy material exhibiting antifouling properties and a method for producing the same.

[0010]

According to the present invention, there is provided, according to the present invention, an adhesion layer of semiconductor fine particles having photocatalytic action on an anodic oxide film formed on a surface of a base material made of an aluminum alloy ; aluminum alloy material characterized by a photocatalyst film made of a non-<br/> machine polymer impregnated between particles of the semiconductor fine particles is formed is provided. In a preferred aspect, there is provided an aluminum alloy material characterized in that an antibacterial metal and / or an antibacterial metal compound is further deposited on the photocatalytic film.

Further, according to the present invention, there is provided a method for producing the above antibacterial aluminum alloy material. One method is to immerse a substrate made of an aluminum alloy having an anodized film in a suspension in which semiconductor particles having a photocatalytic action are dispersed, or to form an anodized film on the semiconductor particle suspension. By coating on the aluminum alloy base material, and then drying, the surface of the anodic oxide film is supported with semiconductor fine particles having a photocatalytic action, and then impregnated with an inorganic polymer, for example, to support the semiconductor fine particles. By dipping the base material in a paint containing an inorganic polymer, and drying and solidifying at a predetermined temperature, a photocatalytic film in which the semiconductor fine particles and the inorganic polymer are mixed is formed on the anodic oxide film. It is characterized by.

As another method, a base made of an aluminum alloy having an anodic oxide film formed thereon is immersed in a suspension in which semiconductor fine particles having a photocatalytic action are dispersed, and the anodic oxide film is formed by electrophoresis. After supporting semiconductor fine particles having a photocatalytic action on the surface and drying, for example, immersing a base material supporting the semiconductor fine particles in a coating material containing an inorganic polymer, and drying and solidifying at a predetermined temperature. By impregnating with an inorganic polymer, a photocatalytic film in which the semiconductor fine particles and the inorganic polymer are mixed is formed on the anodic oxide film.

According to such a method, a photocatalytic film having excellent throwing power and excellent adhesion of semiconductor fine particles can be formed even on aluminum building materials and aluminum building material components having complicated shapes. Further, since the photocatalyst film is mainly composed of semiconductor fine particles and only the voids between the particles are filled with the inorganic polymer, the content of the semiconductor fine particles is high, and the surface of the formed photocatalytic film is formed. Since a sufficient amount of semiconductor fine particles are exposed, excellent photocatalysis is exhibited. In a preferred embodiment, the pH is equal to or higher than the isoelectric point of the semiconductor fine particles used,
In addition, a semiconductor fine particle suspension adjusted to a value that does not corrode the aluminum alloy base material is used. In still another preferred embodiment, an antibacterial metal and / or an antibacterial metal compound is further deposited on the photocatalytic film formed by the above method.

[0014]

DETAILED DESCRIPTION OF THE INVENTION The formation of a photocatalytic film according to the present invention is as follows.
An anodized film having pores is formed on the surface of an aluminum alloy substrate, and the aluminum alloy substrate is immersed in a solution in which semiconductor particles such as TiO ₂ are suspended, or the semiconductor particles are suspended. The semiconductor fine particles are supported on an anodic oxide film of an aluminum alloy substrate by applying a turbid liquid or by performing an electrophoresis method in a semiconductor fine particle suspension, and thereafter, a paint containing an inorganic polymer This is done by dipping in. Since the method for forming the photocatalytic film is a wet process, even for aluminum building materials having a complicated shape,
Since the photocatalytic film has excellent throwing power and is a treatment at a low temperature, there is no possibility that a problem of deterioration in strength of the aluminum alloy due to heating may occur.

As described above, even when semiconductor particles are deposited on a substrate such as iron or stainless steel by electrophoresis, the strength and adhesion of the photocatalytic film composed of the semiconductor particles are low. Further, even if the suspension in which the semiconductor fine particles are dispersed is applied on the base material, or the base material is immersed in the suspension and dried, the strength and adhesion of the photocatalytic film composed of the semiconductor fine particles can be improved. Sex is low. However, as in the present invention, an aluminum alloy having an anodized film formed thereon is used as a base material, and a material carrying semiconductor fine particles is immersed in a coating material containing an inorganic polymer to form a gap between the semiconductor fine particles. By filling with an inorganic polymer, the inorganic polymer acts as an adhesive between the semiconductor fine particles and between them and the anodic oxide film of the aluminum alloy substrate, and a photocatalytic film having excellent strength and adhesion can be obtained. .

Hereinafter, preferred embodiments of the present invention will be described in detail. As described above, in forming the photocatalytic film according to the present invention, it is necessary to use an aluminum alloy substrate on which an anodized film is formed. The pore diameter of the anodic oxide film formed on the aluminum alloy by ordinary anodic oxidation treatment is
Generally, it is 10 nm to 20 nm. Further, the aluminum alloy is anodized at a high voltage in a mixed acid solution of one or more of a mineral acid or an organic acid such as sulfuric acid, phosphoric acid, oxalic acid, malonic acid, and maleic acid, and the surface of the aluminum alloy is subjected to anodic oxidation. A method of forming an anodic oxide film having pores larger than a normal pore diameter is known. Generally, when anodizing is performed at a high voltage of DC130V to 220V, an anodic oxide film having a pore diameter of 100 nm or more is obtained. .

Here, when the pore diameter is smaller than the particle diameter of the semiconductor fine particles, the semiconductor fine particles are supported on the anodic oxide film, and the photocatalytic film is formed on the anodic oxide film. Also,
When the pore diameter is larger than that of the semiconductor fine particles, the semiconductor fine particles are supported inside the pores and on the anodic oxide film, and a photocatalytic film is formed inside the pores and on the anodic oxide film.
In the present invention, since the photocatalytic film composed of only semiconductor fine particles formed on the anodic oxide film is impregnated with the inorganic polymer, the pore diameter of the anodic oxide film is not particularly limited.

A method of improving the corrosion resistance of the anodic oxide film may be performed with a sealing treatment. However, the sealing treatment is not particularly limited in the production method of the photocatalytic film in the present invention. However, it goes without saying that it is preferable to form a photocatalytic film after performing a sealing treatment in order to improve the corrosion resistance of the aluminum alloy.

As described above, the photocatalytic film formed by the method of the present invention has no problem such as peeling of semiconductor fine particles and exhibits excellent corrosion resistance and weather resistance. Such semiconductor fine particles used for the photocatalytic film are made of semiconductor fine particles having a photocatalytic action, for example, TiO ₂ . When light of sunlight or fluorescent light is irradiated to the semiconductor fine particles, a hole on TiO ₂ surface (h ⁺⁾ and electrons (e ^-) having a photocatalytic action occurs, the decomposition of water and various organic substances row Will be In addition, water is oxidized by the action of the holes and O
H radicals, also by the action of electrons, oxygen in the air is reduced, O ₂ ^- generated radicals. These active oxygens have an excellent bactericidal action, and as a result, mold and the like hardly occur.

Examples of the semiconductor fine particles carried on the anodized film, the electron - hole mobility is relatively large, but any semiconductor having a photocatalytic action as described above may be used, for example, TiO ₂ , SrTiO ₃ , Zn
O, CdS, SnO _{2 and the} like. Among them, Ti is particularly preferred from the viewpoint of chemical stability, safety to living bodies, and the like.
O ₂ is preferred. The particle size of the semiconductor fine particles used is 1 nm
It is preferable to adjust the particle size to 1000 nm, preferably 5 nm to 300 nm. When the particle size is smaller than 1 nm, the band gap becomes large due to the quantum size effect, and there is a problem that the photocatalytic action is not exhibited unless illumination is performed including short-wavelength light such as a low-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 is 100
If the thickness exceeds 0 nm, precipitation in the suspension becomes easy,
There is a problem that the electrophoresis cannot be performed quickly.

When the suspension containing the semiconductor fine particles is carried on the aluminum alloy substrate on which the anodic oxide film is formed by dipping or coating, the suspension of the semiconductor fine particles is 0.1 to 10%. 50% by weight, preferably 5
A dispersion in which about 20% by weight of semiconductor fine particles are dispersed in water is used. In order to prevent aggregation and precipitation of the semiconductor particles,
It is necessary to add a peptizer or a dispersant such as an amine compound or a carboxylate described later so that the semiconductor fine particles can be stably dispersed in water. In this method, the amount of the semiconductor particles supported on the substrate depends only on the amount of the semiconductor particles contained in the suspension. Here, when the supporting amount of the semiconductor fine particles is small, the photocatalytic activity of the obtained photocatalyst film becomes small, and when the supporting amount is large, on drying, or
When immersed in an inorganic polymer-containing paint, the photocatalytic film is easily peeled off. From the above, it is preferable to use a suspension containing semiconductor fine particles in which 5 to 20% by weight of semiconductor fine particles are dispersed in water. When the substrate is immersed in the semiconductor fine particle suspension or when the semiconductor fine particle suspension is applied to the substrate, the method is not particularly limited, and may be performed by a method such as ordinary dip coating or spray coating. it can.

On the other hand, when the semiconductor fine particles are supported on the substrate by electrophoresis, the suspension in which the semiconductor fine particles are dispersed is 0.1 to 50% by weight, preferably 0.5 to 10% by weight. Use is made of semiconductor fine particles dispersed in water. In order to prevent aggregation and precipitation of the semiconductor fine particles in the suspension, a deflocculant comprising an organic acid such as lauric acid, stearic acid, and oleic acid, a lower amine, a soda salt such as caustic soda, a surfactant, and the like. And a dispersant must be added so that the semiconductor fine particles are stably dispersed in water. Examples of the peptizer and dispersant include p of suspension described below.
From the viewpoint of H and the like, it is preferable to use lower amines among the above compounds. In the case of the electrophoresis method, the concentration of the semiconductor fine particles increases in the vicinity of the base material, and since the particles aggregate, the content of the semiconductor fine particles in the suspension is reduced as compared with the immersion method or the coating method. It is excellent in the stability of the semiconductor fine particles in the suspension. Further, at the time of electrophoresis, an action of aggregating the semiconductor fine particles occurs, and therefore, a photocatalytic film having a higher content of the semiconductor fine particles is formed than when the substrate is simply immersed in the semiconductor fine particle suspension.

Further, as described above, the charge state of the semiconductor fine particles depends on the pH of the solution, and therefore it is necessary to adjust the pH of the solution. The pH can be adjusted by the type and amount of the deflocculant or dispersant. For example, when TiO ₂ is used as the semiconductor fine particles, the isoelectric point is around neutral. Therefore, when the pH is set to the alkaline side, the semiconductor fine particles take on a negative charge and are electrophoresed on the anode. However, if the pH is too high, the aluminum alloy substrate on which the photocatalytic film is formed will be corroded.
Therefore, the pH of the suspension is between 8 and 13, preferably between 10 and 13.
It is necessary to adjust to 12.

The electrode material used as the cathode in the electrophoresis treatment may be stable to the compounds and pH contained in the suspension, and may be stable to electrochemical reactions occurring at the cathode, for example, generation of hydrogen. And stainless steel, carbon and the like can be used.

In performing the electrophoresis treatment, an aluminum alloy substrate 3 having an anodic oxide film formed thereon and a cathode 4 are placed in a container 1 filled with a semiconductor fine particle suspension 2 using an apparatus as shown in FIG. It is set and electrophoresis is performed with a direct current using the aluminum alloy substrate 3 as an anode. As the electrophoresis method, there are a DC voltage scanning method in which a DC voltage is scanned from a low voltage to a high voltage at a constant step-up speed for a predetermined time, and a DC constant voltage method or a constant current method in which electrolysis is performed at a constant voltage or a constant current for a predetermined time. Can be adopted. In either case, the applied voltage must be equal to or higher than the insulation voltage of the insulating layer called the barrier layer at the bottom of the anodic oxide film. This is because a current does not flow unless a voltage higher than the insulation voltage of the barrier layer is applied, and the semiconductor fine particles are not migrated to the anode side. Conversely, if the applied voltage is extremely high, the anodic oxide film itself may be broken down during electrophoresis. From the above, the voltage applied during electrophoresis is 1% less than the insulation voltage of the anodic oxide barrier layer.
A voltage of 0 V to 100 V, preferably 20 V to 60 V is suitable.

In the present invention, an immersion method, a coating method,
Alternatively, it is necessary to support the semiconductor fine particles by electrophoresis and then dry them. Dipping and coating as described above,
Alternatively, the state after the electrophoresis is equivalent to the state in which a suspension of semiconductor fine particles is placed on a substrate, and when the substrate is immersed in an inorganic polymer paint without drying, the semiconductor The fine particles diffuse into the paint, and finally the amount of the semiconductor fine particles contained in the photocatalyst film decreases, and the photocatalytic activity decreases. However, when the solvent is removed by drying, a photocatalytic film having an adhesive property that does not peel off when immersed in the paint is obtained. Here, since the purpose of drying is simply to remove the solvent, the temperature is not particularly limited. However, at a temperature exceeding 200 ° C., drying at about room temperature is sufficient since the strength of the aluminum alloy base material is reduced and there is no need to intentionally heat the aluminum alloy base material.

The inorganic polymer used in the present invention must be a material that can withstand photocatalysis, and from this viewpoint, fluorine-based and silica-based polymers are suitable. Further, when the curing temperature exceeds 200 ° C., the strength of the aluminum alloy substrate is reduced, and even when the curing temperature is less than 200 ° C., cracks may occur in the photocatalytic film due to a difference in thermal expansion coefficient with the substrate. . From this point, the curing temperature is suitably lower than 200 ° C., preferably room temperature to about 100 ° C.

As a solvent for dispersing the inorganic polymer to form a coating, the inorganic polymer used is stably dispersed, and
The solvent is not particularly limited as long as the solvent is scattered (evaporated) during curing and does not remain in the photocatalytic film. With respect to the amount of the inorganic polymer to be contained in the paint, the purpose of the present invention is only to fill the gap between the semiconductor fine particles, and the inorganic polymer does not need to have a high content. If the content is about the same as that of a usual paint, a coating film is formed on the photocatalytic film, and the semiconductor fine particles are covered and obscured. On the other hand, if the content is small, the voids between all the semiconductor fine particles cannot be filled by a single impregnation treatment, and the impregnation treatment must be repeated, which is not preferable from the viewpoint of workability. From the above points, the content of the inorganic polymer is preferably in the range of 5% by weight to 20% by weight.

The semiconductor fine particles 10 as shown in FIG. 2 are formed by the dipping method, the coating method or the electrophoresis method as described above.
Is adsorbed on the anodic oxide film 12 of the aluminum alloy substrate 11. By impregnating this with an inorganic polymer, as shown in FIG. 3, the photocatalyst film 14 in which the inorganic polymer 13 is impregnated in the gaps between the semiconductor fine particles is formed. With such a photocatalyst film, there is no possibility that semiconductor fine particles will be lost, and since the photocatalyst film is formed on the anodic oxide film, the corrosion resistance of the aluminum alloy substrate is also improved. Further, since the amount of the semiconductor fine particles contained in the photocatalyst film is large, an excellent photocatalytic action is exhibited. From the above, the photocatalyst film obtained by the present invention not only has excellent adhesion to the aluminum alloy substrate, excellent corrosion resistance, but also exhibits a high photocatalytic action, thus exhibiting excellent antibacterial, antifungal and antifouling properties. I do. Further, since the photocatalytic film can be formed by a wet method at a temperature of about room temperature, the photocatalytic film is a method for forming a photocatalytic film which is excellent in the coverage of the photocatalytic film, does not cause a reduction in the strength of the aluminum alloy, and is excellent in mass productivity.

The photocatalytic action is exhibited only during light irradiation, but when it is desired to exhibit antibacterial and antifungal properties even in darkness, silver, copper, etc. By depositing an antibacterial metal or an antibacterial metal compound, an antibacterial and antifungal effect is exhibited even in the dark.

As a method for precipitating an antibacterial metal or an antibacterial metal compound, a solution of an appropriate compound containing an antibacterial metal such as silver or copper such as silver nitrate or copper chloride is prepared, and a photocatalytic film is formed in this solution. A method of immersing the formed aluminum alloy base material or applying the solution to a photocatalytic film by spraying or the like, and then irradiating ultraviolet rays with an ultraviolet lamp or a black light can be suitably used. By this ultraviolet irradiation, antibacterial metal ions or antibacterial metal compound ions are reduced by electrons generated by the photocatalytic action of the photocatalytic film, and the antibacterial metal or antibacterial metal compound is deposited on the surface of the photocatalytic film. In this case, the amount of antibacterial metal or antibacterial metal compound deposited is the amount of antibacterial metal ion or antibacterial metal compound ion in the solution, the amount of coating when applied, and the amount of alcohol or EDTA added to the solution. It can be controlled by the concentration of the reducing agent, the intensity of the ultraviolet light, and the irradiation time.

[0032]

EXAMPLES Hereinafter, the effects of the present invention will be specifically described with reference to examples and comparative examples. However, it goes without saying that the present invention is not limited to the following examples.

Anodizing treatment was performed in an electrolytic bath of sulfuric acid 10% by weight at 30 ° C. using an aluminum alloy (A1050) as an anode under the conditions of a DC voltage of 14 V and a current density of 1 A / dm ² , and a pore diameter of about 10 nm and a film thickness of about 10 nm. An anodized film of 10 μm was formed. Also, 5% by weight of a fine powder of anatase type TiO ₂ as a photocatalyst, 50 nm in average particle diameter, was mixed with 5% by weight of monoethanolamine as a deflocculant and uniformly dispersed, and the pH was adjusted with carboxylic acid. 11 by adding
The TiO ₂ sol adjusted to have produced. Further, tetraethyl silicate was added to ethanol so as to be 10% by weight in terms of SiO ₂ weight after curing, and a small amount of hydrochloric acid was further added to prepare a silicate solution.

Example 1 A substrate on which an anodic oxide film was formed was immersed in the above-mentioned TiO ₂ sol, pulled up at a speed of 50 cm / min, and dried at room temperature for 12 hours to obtain a photocatalytic film consisting of only semiconductor fine particles having a thickness of 1 μm. Was. Thereafter, the aluminum alloy substrate on which the photocatalyst film was formed was immersed in the silicate solution, allowed to stand for 10 minutes, pulled up at a speed of 5 cm / min, and dried at 80 ° C. for 2 hours to produce a photocatalyst film.

Example 2 An anodized film-formed substrate was immersed in the above-mentioned TiO ₂ sol as an anode, and a stainless steel plate having an area 5 times as large as the anode was immersed in a sol and subjected to electrophoresis at a voltage of 74 V for 2 minutes.
Adsorb TiO ₂ particles on the anodic oxide film,
It was left to dry for a period of time to obtain a photocatalyst film composed of only semiconductor fine particles having a thickness of 1 μm. Thereafter, the aluminum alloy substrate on which the photocatalytic film was formed was immersed in the silicate solution,
After leaving still for 0 minutes, it is pulled up at a speed of 5 cm / min,
It dried at 2 degreeC for 2 hours, and produced the photocatalyst film.

Comparative Example 1 An anodic oxide film-formed substrate was immersed in the above-mentioned TiO ₂ sol, pulled up at a rate of 50 cm / min, and dried at room temperature for 12 hours to obtain a photocatalytic film consisting of only semiconductor fine particles having a thickness of 1 μm. Was.

Comparative Example 2 A substrate having an anodic oxide film formed thereon as an anode and a stainless steel plate having an area five times that of the anode as a cathode were immersed in the TiO ₂ sol, and subjected to electrophoresis at a voltage of 74 V for 2 minutes.
Adsorb TiO ₂ particles on the anodic oxide film,
It was left to dry for a period of time to obtain a photocatalyst film composed of only semiconductor fine particles having a thickness of 1 μm.

COMPARATIVE EXAMPLE 3 Aluminum alloy (A1) in an electrolytic bath of sulfuric acid 10% by weight at 30 ° C.
050) as an anode, a DC voltage of 14 V and a current density of 1 A /
Anodizing is performed under the conditions of dm ² , and the pore diameter is about 10 n.
An anodic oxide film having a thickness of about 10 μm was formed.

Evaluation of adhesion: On the test pieces prepared in the above Examples 1 and 2 and Comparative Examples 1 to 3, lines each reaching 11 anodized films vertically and horizontally were drawn at intervals of 1 mm using a blade of a cutter knife. Create 100 cross grids and use JIS Z
An adhesion test was carried out using a cellophane adhesive tape specified in 1522.

Hardness evaluation: 5.9 of JIS H8602
It carried out by the pencil scratch resistance test described in the section.

Evaluation of corrosion resistance: JIS H 8681 3.
The test was carried out according to the Cass test described in item 1 and the test time was 24 hours.

Table 1 shows the evaluation results. Table 1
In the results, the test pieces for which no peeling was observed in the results of the adhesion test are marked with ○, and the test pieces for which peeling was observed are marked with x. The hardness indicates the corresponding pencil hardness. The results of the corrosion resistance evaluation were based on the rating numbers specified in the attached drawings of JIS H8602.

[0043]

[Table 1] As is clear from Table 1, only the test pieces of Example 1 and Example 2 show excellent results in all evaluation items.
The test pieces of Comparative Examples 1 and 2 were inferior in adhesion, hardness, and corrosion resistance because the photocatalyst film formed on the substrate was composed of only TiO ₂ particles and there were voids between the particles.

Comparative Example 4 An anatase type Ti as a photocatalyst was added to the silicate solution.
50% by weight of a fine powder of O ₂ (average particle diameter: 20 nm) was mixed at a solid content ratio of 50% by weight, uniformly dispersed, and applied to a glass substrate.
The photocatalyst film having a film thickness of 1 μm was formed by holding at 2 ° C. for 2 hours.

Evaluation of photocatalytic activity: Examples 1 and 2
A salad oil was applied on each of the samples prepared in Comparative Examples 3 and 4 so that the applied amount was 0.1 mg / cm ^2, and the black light was applied so that the ultraviolet intensity on the substrate was 1 mW / cm ^2. And the change in weight was measured while irradiating with ultraviolet rays. FIG. 4 shows the results.

From FIG. 4, it was confirmed that the salad oil was gradually decomposed by irradiating ultraviolet rays in the samples of Example 1, Example 2, and Comparative Example 4. This is Ti
The salad oil was decomposed by the action of holes or the like generated by the incidence of ultraviolet light on O ₂ , and the photocatalytic activity was confirmed in each sample. In addition, it can be seen that the photocatalyst film according to the present invention has higher photocatalytic activity than the conventional photocatalytic film supported on an inorganic polymer as in Comparative Example 4. Further, it was confirmed that the sample of Example 2 had higher photocatalytic activity than the sample of Example 1. This is due to the fact that the TiO ₂ particles contained in the photocatalytic film are larger when the electrophoresis method is used.

Example 3 A substrate having a photocatalyst film prepared in Example 1 was immersed in a 0.05 mol / l aqueous solution of silver nitrate, and irradiated with ultraviolet light from a 100 W ultraviolet lamp to apply 4 μg /
cm ² of silver was deposited.

Example 4 The substrate having the photocatalyst film prepared in Example 2 was immersed in a 0.05 mol / l aqueous solution of silver nitrate, and irradiated with ultraviolet light from an ultraviolet lamp of 100 W to give 4 μg /
cm ² of silver was deposited.

Comparative Example 5 An antibacterial agent having silver supported on zeolite was added to an acrylic paint at 1% by weight, and a 10 µm antibacterial paint was applied on the anodic oxide film-formed substrate prepared in Comparative Example 3 using this paint. gave.

Antibacterial test: 150 μl of distilled water in which 2 × 10 ⁴ Escherichia coli were dispersed was dropped on each of the samples prepared in Examples 1 to 4 and Comparative Examples 3 to 5, and a temperature of 2
The reaction was carried out under a condition of 5 ° C. and a humidity of 70% while irradiating ultraviolet rays with a black light so that the ultraviolet intensity on the substrate was 1 mW / cm ² , or in a dark state for a predetermined time. The bacterial solution after the reaction was collected with a sterile gauze, dispersed in 10 ml of physiological saline, and 100 μl
Was collected, inoculated on an agar medium, cultured at 36 ° C. for 24 hours, and the number of surviving bacteria after the reaction was calculated from the number of generated colonies. FIG. 5 shows the result at the time of light irradiation, and FIG. 6 shows the result at the time of darkness.

FIG. 5 shows that the antibacterial effect was confirmed in the samples of Examples 1 and 2, and the effect was superior to the antibacterial coating of Comparative Example 5. Even in the same samples of Example 1 and Example 2, the antibacterial effect is not recognized in the dark state of FIG. 6, and thus the antibacterial property is due to the photocatalytic action. The difference in the antibacterial effect between Example 1, Example 2, and Comparative Example 4 is due to the difference in photocatalytic activity. In FIG. 5, the samples of Example 3 and Example 4 show the most excellent antibacterial effect. In addition, these samples show a better antibacterial effect under light irradiation than the dark state in FIG. 6, but this is due to the synergistic effect of the silver deposited on the surface of the sample and the photocatalytic action. It is due to the action. From FIG. 6, the samples of Example 3 and Example 4 show better antibacterial effects than the sample of Comparative Example 5 even in the dark state. This is because the amount of silver present on the sample surface is larger in Examples 3 and 4 than in the case where the antibacterial agent is kneaded into the paint as in Comparative Example 5.

[0052]

As described above, according to the present invention, an anodic oxide film is formed on the surface of a base material made of an aluminum alloy, and semiconductor fine particles having a photocatalytic action are immersed, coated, and coated on the substrate.
Alternatively, after being supported by electrophoresis and dried,
By impregnating with an inorganic polymer, a photocatalytic film composed of a mixture of semiconductor fine particles and an inorganic polymer is formed on the anodic oxide film. Since this is a wet process, it is possible to form a photocatalyst film with good flexibility even on an aluminum alloy substrate having a complicated shape, and since the photocatalyst film can be formed at a low temperature, the strength of the aluminum alloy substrate may be reduced. This is a method for forming a photocatalytic film that is not only mass-produced but also rich. This photocatalytic film has a high content of semiconductor fine particles and exhibits excellent photocatalytic activity. In addition, the photocatalytic film has excellent adhesion to the substrate because the inorganic polymer functions as an adhesive between the semiconductor fine particles and between them and the anodic oxide film of the aluminum alloy substrate.

Further, when an antibacterial metal and / or an antibacterial metal compound is deposited on the photocatalytic film, an excellent antibacterial and antifungal effect is exhibited even in the absence of light irradiation. It exhibits further excellent antibacterial, antifungal and antifouling properties due to a synergistic effect of the antibacterial metal and / or antibacterial metal compound. Therefore, the aluminum alloy material on which the photocatalytic film provided by the present invention is formed is an antibacterial, antifungal, and antifouling material having excellent self-cleaning properties, and various sashes, building materials such as panel materials, and the like. It can be used advantageously in the field.

[Brief description of the drawings]

FIG. 1 is a schematic configuration diagram of an electrophoresis apparatus for performing a method of the present invention.

FIG. 2 is a schematic enlarged cross-sectional view of an aluminum alloy substrate having semiconductor fine particles supported on an anodic oxide film according to the present invention.

FIG. 3 is a schematic enlarged cross-sectional view of an aluminum alloy substrate impregnated with an inorganic polymer after supporting semiconductor fine particles on an anodic oxide film.

FIG. 4 is a graph showing a change in weight of a sample coated with salad oil in a photocatalytic activity test accompanying irradiation with ultraviolet light.

FIG. 5 is a graph showing the change over time in the survival rate of E. coli when a sample is irradiated with ultraviolet light in an antibacterial test.

FIG. 6 is a graph showing the change over time in the survival rate of Escherichia coli when a sample is dark in an antibacterial test.

[Explanation of symbols]

 Reference Signs List 1 container 2 suspension of semiconductor fine particles 3 aluminum alloy substrate on which anodic oxide film is formed (anode) 4 cathode 10 semiconductor particles 11 aluminum alloy substrate 12 anodic oxide film 13 inorganic polymer 14 photocatalytic film

──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Kazuhito Hashimoto 2073-2, Iijimacho, Sakae-ku, Yokohama-shi, Kanagawa Prefecture New City Hongodai D-Bridge 213 (72) Inventor Nobuyuki Nakata 1300 Horikiri, Kurobe-shi, Toyama Prefecture (72) Inventor Arai Toshio 841 Fujiki, Toyama City, Toyama Prefecture (56) References JP-A-8-224289 (JP, A) JP-A-8-296060 (JP, A) JP-A-8-302498 (JP, A) (58) Field (Int.Cl. ⁷ , DB name) C25D 11/18 A61N 2/16 B01J 35/02 E04F 13/12 E06B 1/00

Claims (7)

(57) [Claims] 1. An adhesion layer of photocatalytic semiconductor fine particles on an anodic oxide film formed on a substrate surface made of aluminum or an aluminum alloy , and particles of the semiconductor fine particles.
Aluminum or aluminum alloy material, characterized in that the photocatalyst film made of an inorganic polymer impregnated is formed between. 2. The aluminum or aluminum alloy material according to claim 1, wherein an antibacterial metal and / or an antibacterial metal compound is further deposited on the photocatalytic film. 3. The aluminum or aluminum alloy material according to claim 1, wherein the inorganic polymer is a silica-based or fluorine-based polymer material. 4. A substrate made of aluminum or an aluminum alloy having an anodized film formed thereon is immersed in a suspension in which semiconductor fine particles having a photocatalytic action are dispersed, or the semiconductor fine particle suspension is placed on the base material. A semiconductor fine particle having a photocatalytic action is supported on the surface of the anodic oxide film by coating and then drying, and then a mixture of the semiconductor fine particles and the inorganic polymer is formed on the anodic oxide film by impregnation with an inorganic polymer. A method for producing an antibacterial and antifouling aluminum or aluminum alloy material, comprising forming a photocatalyst film comprising: 5. A substrate made of aluminum or an aluminum alloy on which an anodic oxide film is formed is immersed in a suspension in which semiconductor fine particles having a photocatalytic effect are dispersed, and the surface of the anodic oxide film is subjected to photocatalytic action by electrophoresis. An antibacterial property characterized by forming a photocatalytic film composed of a mixture of semiconductor fine particles and an inorganic polymer on the anodic oxide film by supporting semiconductor particles having, drying and then impregnating the inorganic polymer. -A method for producing an antifouling aluminum or aluminum alloy material. 6. The method according to claim 4, wherein an antibacterial metal and / or an antibacterial metal compound is further deposited on the photocatalytic film. 7. The method according to claim 4, wherein a silica-based or fluorine-based polymer material is used as the inorganic polymer.