CN1254365C - Thin photocatalytic film and articles provided with the same - Google Patents

Abstract

This invention relates to photocatalyst films, primarily applied to air channels, filter components, external parts, and parts illuminated by built-in lighting devices in electrical appliances used in indoor environments. Various additives enhance the catalytic effect. Even with very weak light available indoors, such as fluorescent lamps, incandescent bulbs, mercury lamps, or sunlight through windows, it can decompose organic matter and also break down dirt formed from cigarette smoke or hand sebum, achieving a stain-resistant effect. Similarly, with weak light, it can decompose various odor-producing substances such as organic amines or thiols dispersed in the air, breaking them down into low-odor or odorless substances, thus achieving a deodorizing effect that reduces indoor odors.

Description

Photocatalyst thin film and articles having the same

technical field

The present invention relates to a photocatalyst thin film in which particles with photocatalyst function are dispersed in the coating film and an article with the thin film, especially on organic polymer materials with poor heat resistance, especially on the surface of commonly used thermoplastic products An article formed with a thin layered oxide photocatalyst film. In addition, it also relates to an article provided with an oxide photocatalyst thin film on all or part of the surface of an article that cannot receive strong ultraviolet rays such as ultraviolet lamps and outdoor sunlight, and is suitable for indoor use.

For example, it involves air purifiers, ventilation fans, electric fans, vacuum cleaners, clothes dryers, tableware dryers, dishwashers, kitchen waste disposal machines, heaters, humidifiers, dehumidifiers, air conditioners, heating and cooking devices, electromagnetic Stoves, hair dryers, deodorizers, heaters, etc., use electric blowers to circulate air.

It also involves the use of light in the surrounding living environment to decompose various pollution components and microorganisms attached to the surface of the above-mentioned electrical appliances and floating in the air through photocatalysis to obtain antifouling, deodorizing, antibacterial, antifungal, and improved moisture. Technology of surface properties such as wet performance and its articles.

Background technique

In recent years, materials that use the decomposition of organic substances with TiO ₂ photocatalysts to achieve antifouling, deodorizing, and antibacterial effects have attracted much attention. As described in "New Ceramics"("NewCeramics") (1996) No. 2, 55, a material in which a TiO ₂ thin film is formed on a ceramic sheet by utilizing the oxidation-reduction reaction of a semiconductor photocatalyst.

In addition, there is an oxide thin film formed on a substrate by a physical film-forming method such as sputtering and a chemical film-forming method such as a coating method such as a sol-gel method. The former can form a film at a relatively low temperature using a vacuum device or the like. The latter can be coated on the substrate with simple devices such as spin coaters and sprayers, and can generally be processed at a temperature of several hundred degrees to obtain a thin film. _TiO2, which is an antibacterial and deodorizing material, is effective if it is an anatase crystal, and it has been reported that crystallization contributes to the development of functions (Patent No. (PTC) WO94/11092, (PTC) WO 95/15816). In addition, it is also reported that adding V, Fe, etc. to TiO ₂ can improve its performance (W. Chio, A. Termin, MR Hoffmann, J. Phys. Chem., 98, 13669-13679 (1994)).

The present invention can be fully understood by the examples shown below in which oxide photocatalyst thin films are applied to various devices using the above-mentioned materials and methods.

An air cleaner is a device for removing dust and malodorous substances in indoor air, as described in Japanese Patent Laid-Open Publication No. 8-266841, Japanese Patent Laid-Open Publication No. 8-166605 and Japanese Patent Laid-Open Publication No. 8-309148 The filter contains a photocatalyst mainly composed of TiO ₂ inside, and the technology of irradiating short-wavelength light with a device such as an ultraviolet lamp is installed in it.

In addition, as an application example of an electric fan, as described in Japanese Patent Laid-Open Publication No. Hei 7-303819, a technology of firing a photocatalyst thin film mainly composed of TiO ₂ on the surface of a metal member at about 600°C.

In the application example of the fan described in Japanese Patent Laid-Open Publication No. Hei 9-38189, it is known that a light-emitting diode is attached to irradiate ultraviolet rays.

As an example applied to a ventilating fan, a structure using an ultraviolet lamp described in Japanese Patent Laid-Open Publication No. Hei 5-157305 is known.

As an application example of a deodorizing filter installed in the air path of a vacuum cleaner and a kitchen garbage disposer, as proposed in Japanese Patent Laid-Open Publication No. 7-108175, a photocatalyst with _TiO as the main component is made into a powder, and used Plastic fiber sheet wrapped, and then heat-sealed technology.

disclosure of invention

Using the conventional technology, there is a defect in forming an oxide film on a substrate with poor heat resistance, such as a plastic product. When utilizing the sol-gel method to form a film, the antibacterial sheet as an antibacterial and deodorant material described in the above-mentioned literature must be subjected to heat treatment at several hundred degrees, at least 300°C, in order to crystallize titanium oxide. It is very difficult to form a film on a substrate with poor heat resistance, such as a widely used thermoplastic.

In addition, in an environment with weak light intensity such as indoors, the decomposition speed of TiO ₂ itself such as organic matter decomposition is not fast enough, and there is a problem that other light sources must be specially equipped.

The aforementioned devices used as objects of the present invention are mostly household appliances used in general households and offices, and these products are mainly composed of organic polymer materials (plastics). With the exception of televisions and computer monitors, which often use glass parts, about 40 to 50% of the parts by weight in general household appliances are made of plastic, and the rest are almost all made of metal. In terms of volume ratio, plastic accounts for nearly 90%. Plastic is widely used because it is light, has high plasticity, and is cheap. Thermoplastics, in particular, are used in large quantities due to their high throughput in forming operations.

Common plastics that are the most widely used materials of construction include polypropylene (PP), acrylonitrile-butadiene-styrene (ABS), acrylonitrile-styrene (AS), polystyrene ( PS), nylon (PA), polycarbonate (PC), vinyl chloride (PVC), methacrylic acid (PMMA), polyethylene (PE), polyoxymethylene (POM), polyethylene terephthalate ( PET), polybutylene terephthalate (PBT), etc., but any of the above materials will deform in an environment with a temperature higher than 300 °C.

For example, the heat distortion temperature of ASTM and D-648 (18.6kg/cm ² ) is around 250°C. In addition, there are polyparaphenylene sulfide and polybiphenylene sulfide in which glass fibers are melted as special high heat-resistant resins. Ether, polyetherimide, etc., but because of their very high price, it is difficult to use them in large quantities.

Generally, the better the heat resistance, the higher the price, especially PE, PS, ABS, PP, PVC, which are widely used as shell parts, account for more than 75% of all plastic parts on average. Among them, even the aforementioned ASTM heat distortion temperature of ABS with the best heat resistance is below 120°C, and it will completely melt into a liquid state at a temperature of 300°C, and undergo oxidative decomposition.

In addition, even when the paint is applied to the surface of inorganic materials such as metals, materials with a heat resistance of more than 300° C. are limited. Generally, thermosetting resins are used as coatings, representative examples of which are polyester resins, acrylic resins, melamine resins, epoxy resins, polyurethane resins, etc., which can generally be baked at a temperature of 150°C. If these coatings are exposed to an environment with a temperature exceeding 300°C, most of them will lose their luster and peel off.

As described in the above examples, conventional techniques have had serious problems in heat resistance when films are formed on the surface of commonly used materials by the sol-gel method.

On the other hand, the method of forming a film at a temperature not exceeding 300°C includes sputtering (sputtering) method, CVD, vacuum evaporation method and other physical methods. Since a large device such as a vacuum device is required, the production cost is high. . In addition, since the film formation is carried out in a high vacuum state, the composition ratio of the oxide photocatalyst changes greatly, so that the performance of the photocatalyst will deteriorate. Moreover, if an organic material is used as a substrate during film formation, it will cause damage to the sputtered substrate, resulting in deformation of the substrate. In addition, when using a chemical method such as a coating method such as a sol-gel method, if a silica sol in which oxide particles are dispersed is used, when a film is formed on a substrate without heat resistance, the heat treatment temperature is relatively low. Low, so sufficient sintering cannot be performed, and the strength and water resistance of the formed oxide film are unsatisfactory.

From the above reasons, it can be seen that it is actually difficult to form a photocatalyst film with _TiO2 as the main component without causing adverse effects such as deformation or deterioration on the surface of the organic polymer material used in general electrical products using the conventional technology.

The purpose of the present invention is to provide a highly active photocatalyst film that can be formed on the surface of a material with poor heat resistance, such as plastic or paint, and an article that has antibacterial, antifouling, and deodorizing effects.

On the other hand, research has also been conducted on improving the decomposition effect of organic matter itself in a photocatalyst mainly composed of TiO ₂ , which is not mentioned in the invention of the aforementioned photocatalyst application technology.

That is, conventionally, no studies have been conducted on the combined use of materials for improving the photoactivity of TiO ₂ -containing films. Therefore, for example, conventionally known methods for the purpose of deodorization, such as Japanese Patent Publication No. 8-309148, Japanese Patent Publication No. 8-266605, or methods for the purpose of decomposing tar pollution of cigarettes, such as Japanese Patent Publication No. Publication No. 9-38189, the application example of decomposing pollution caused by cooking oil, etc., as in Japanese Patent Laid-Open Publication No. 5-157305, etc., because the activity of any photocatalyst itself is not sufficient, so it is necessary A device for irradiating ultraviolet rays and a heating device are attached to improve the effect of the decomposition reaction.

The biggest reason for the above situation is that when the light intensity is low, the organic matter decomposition rate of TiO ₂ itself is not fast enough. Since there is no research on improving the decomposition rate, the method of using ultraviolet lamps is generally used to increase the light intensity. High-pressure mercury lamps or metal halide lamps can be used as ultraviolet lamps, but power supply units and cooling devices are also required, which increases the weight and price of the entire product. In addition, the life of the lamp is generally about 2000 hours and needs to be replaced regularly, which also brings problems to practical use.

In the prior art, it is known to add Fe and V to _TiO2 to improve the decomposition efficiency, but high-temperature treatment of several hundreds of degrees is required to achieve high performance, so it is difficult to apply to substrates with low melting point and poor heat resistance material.

Another object of the present invention is to make the photodecomposition efficiency of the photocatalyst film formed at low temperature higher than the decomposition efficiency of TiO2 monomer, so that the attached matter can be decomposed with the intensity lower than the light intensity required in the past.

In addition, when the prior art is used for antibacterial, deodorizing or deodorizing purposes, the target object is organic matter. Since the target object is in the form of fine particles or molecules, the attached liquid organic matter or particulate organic matter can be decomposed, but if It is a relatively large fibrous substance or dust, even if it is the same organic matter, it will take a long time to decompose, and it is difficult to decompose the inorganic matter mainly composed of dust, so it cannot be fully antifouling. Since these pollutants generally float in the air in a charged state, once they come into contact with an individual surface with high electrical insulation, it is not easy to discharge static electricity and become completely attached. The light is covered by the attached inorganic pollutants, so that the surface of the photocatalyst cannot receive sufficient light, which causes the problem of lower decomposition efficiency of organic matter.

Another object of the present invention is to prevent relatively large dust or inorganic pollutants that are theoretically difficult to decompose and remove by the oxidative decomposition effect of the above-mentioned photocatalyst from being adsorbed on the target member by electrostatic force.

The feature of the present invention in order to achieve the above object is that there is an electric motor for starting the air purifier, ventilation fan, electric fan, vacuum cleaner, clothes dryer, tableware dryer, dishwasher, kitchen garbage disposer, etc., which are mainly used indoors. A low-temperature curing high-activity oxide photocatalyst film is provided on the surface of the electrical product components of the device that the blower circulates the air, such as the air channel or the filter device in the air channel, or the surface of the housing part of the indoor lighting light.

The melting point or decomposition temperature of the material used as the object is generally below 300°C, especially when the molded parts, fiber parts, foam parts or sheet parts made of commonly used thermoplastics are provided with low-temperature curing high-activity oxides. Photocatalyst thin films can solve problems left over from the past such as pollution, microbial reproduction, and odor generation.

In the present invention, through the optimization of the film thickness of the oxide photocatalyst film based on TiO ₂ , the optimization of the particle size of TiO ₂ , the addition of suitable ions with lower electronegativity, when SiO ₂ is used as the binder The optimization of the mixing ratio with _TiO2 , the addition of oxide semiconductors with high electron affinity, the addition of appropriate noble metals, etc., form the reactivity of photocatalysts in the air passages of the above-mentioned electrical products or on the surface of housing parts. Films with increased lightness can achieve anti-fouling, deodorizing and inhibiting microbial growth effects that were not possible with indoor light levels in the past.

At the same time, in the process of forming the inorganic polymer film mainly composed of _SiO2 and _TiO2 in the present invention, in order to destroy the combination of metal atoms and organic groups of organometallic compounds, it is necessary to irradiate electromagnetic waves containing specific wavelengths to promote As a means of hydrolysis reaction, since the polymerization of inorganic polymers is carried out at low temperatures, at low temperatures where deformation, melting, and decomposition do not occur, even in the above-mentioned thermoplastics that are poor in heat resistance and are widely used The surface of plastic can also form oxide photocatalyst film with certain strength.

Hereinafter, details of the low-temperature curing type highly active oxide photocatalyst thin film will be described.

Adding ions with a valence of 2 or less of an element having an electronegativity of less than 1.6 and an ionic radius of less than 0.2 nm to an oxide photocatalyst thin film in which TiO ₂ fine particles are dispersed as an oxide photocatalyst can improve reaction efficiency. Among the specific elements to be added, the most effective ones are Na, Li, K, Sr, Mg, Ca, and Zn. The addition amount of these elements is preferably 0.5 to 20 wt%. If the size of _TiO2 particles is adjusted to 5 to 20 nm, the most effective efficient.

Also, in the oxide photocatalyst thin film in which TiO ₂ fine particles are dispersed in SiO ₂ , the weight ratio of TiO ₂ /SiO ₂ is preferably 9-5.

The thickness of the oxide thin film is preferably from 100 to 500 nm.

In addition to the above-mentioned ions, the added components can also disperse oxide particles mainly composed of oxide semiconductors composed of metal elements with an electron affinity of at least 1.2, so that the effect will be better. Particularly suitable are semiconductors composed of elements such as Sn, Fe, and Cr. The amount added is preferably from 2 to 50 wt%. Among them, oxide particles mainly composed of ATO (antimony-added tin oxide, preferably 1% to 10% by weight of antimony) are particularly effective. The addition of these semiconducting particles can reduce the surface resistance of the membrane itself, so that pollutants, including inorganic pollutants that are difficult to oxidatively decompose, are difficult to electrostatically adsorb.

In addition, it is also effective to make the oxide photocatalyst film into a multi-layered structure. The first layer from the surface is a film in which _TiO2 particles are dispersed in _SiO2 . The above-mentioned ions are added to the film, and the second layer from the surface is The layer is a thin film in which oxide particles mainly composed of the above-mentioned oxide semiconductor are dispersed, so that it will not have adverse effects on the surface of plastics with poor oxidation durability, and can effectively obtain photocatalytic action. In addition, if Adding at least one element of Fe, Al, and Zn to the above-mentioned second layer will be more effective.

It is also effective to add at least one of Pt, Rh, Pd, Ag, Cu, and Ni in addition to the aforementioned ions.

TiO ₂ has the function of a photocatalyst, and has antibacterial, deodorizing, and antifouling effects by decomposing organic matter. Its function originates from electrons and holes generated after irradiating _TiO2 as a semiconductor with light, especially ultraviolet light. When _TiO2, which is a semiconductor, is irradiated with light having an energy higher than the band gap, electrons and holes are generated. After the generated electrons and holes decompose the moisture adsorbed on the surface of _TiO2 , H radicals and OH radicals are generated. The OH free radical reacts with the organic matter and can decompose the organic matter. Although the above-mentioned structure can make the photocatalyst decompose organic substances, etc., there are the following two methods to greatly increase the reaction speed. First, increase the workload of an active point, and second, increase the number of active points. Increasing the number of active sites means increasing the surface area, ie, by micronizing TiO ₂ . In addition, in order to increase the workload of the active point, the crystallization of TiO ₂ (anatase) can be sufficiently performed to prevent the recombination of electrons and holes. After meeting the above conditions, the reaction rate can be increased. However, sufficient crystallization of TiO ₂ (anatase) and increase in surface area are just opposite, and it is difficult to satisfy both aspects. That is, an increase in crystallinity leads to an increase in particle size, thereby reducing the surface area. Therefore, there is an optimum particle size range between increasing crystallinity and increasing surface area. According to the results of multiple experiments in the present invention, it is found that the optimum particle size range is 5-20 nm. When dispersing _TiO2 fine particles, even if the type of oxide used as the inorganic binder is changed, the decomposition rate can be accelerated as long as the particle size is within the above-mentioned range.

Preventing the recombination of electrons and holes to speed up the reaction can be achieved by improving the separation efficiency of electrons and holes. There are Ti defects on the surface of _TiO2 , which become the recombination points of electrons and holes, hindering the reaction. If ions with an ionic radius close to that of Ti are added, the Ti defects on the surface can be invaded, and the defects can be eliminated, thereby reducing recombination points. Furthermore, since positive ions are present, electrons can be attracted to separate them from holes, thereby promoting the oxidation reaction of organic substances. The present invention finds that the condition of the additive with the above effective effects is that the electronegativity is less than 1.6 and the ionic radius is less than 0.2nm.

In addition, the present inventors have found that high performance can also be achieved by adding other oxide semiconductor fine particles, which can be achieved by injecting carriers from an oxide semiconductor with a high carrier concentration to TiO ₂ with a low carrier concentration. Therefore, the carrier must be able to easily flow from the oxide semiconductor to TiO ₂ . If the electron affinity of the oxide semiconductor is smaller than that of Ti, a Schottky barrier (blocking layer) is formed. Therefore, the electron affinity of the additive material needs to be above 1.2 eV.

In addition, the present invention also found that the photocatalytic action of TiO ₂ was lost by adding Fe, Al, and Zr. When a substrate material mainly composed of organic matter is used, there is a problem that the substrate itself is damaged due to photocatalytic action.

Therefore, in the present invention, although an interlayer is formed between the substrate and the photocatalyst, if Fe, Al, and Zr are added to the interlayer, the above-mentioned self-destruction can be completely suppressed. Furthermore, since the above-mentioned barrier is a high-performance barrier, the film can be very thin. When conductive particles such as ATO are added or stacked, it not only improves the performance of the photocatalyst, but also has the effect of preventing electrification, which not only enables the decomposition of organic matter, but also prevents the adsorption of inorganic matter such as dust floating in the air. Provides higher antifouling properties. In addition, because the above-mentioned activity of the present invention is high, it can be decomposed with a weaker brightness than before, and has an antistatic effect, so the highly active photocatalyst film with the characteristics that the particles that become pollutants themselves are difficult to electrostatically adsorb can be used It is widely used at a low price, and it is possible to form a film on the surface of a material that does not have sufficient heat resistance by using a conventional film forming method.

Therefore, when a solution of a low-molecular-weight organometallic compound containing titanium or silicon and water is subjected to macromolecularization such as inorganic polymerization, in order to break the bond between the metal atom and the organic group of the organometallic compound, it is necessary to use a laser having a specific wavelength. Electromagnetic wave irradiation can accelerate the hydrolysis reaction of the organometallic compound, form a metal oxide prepolymer in the solution, and lower the film formation temperature.

The electromagnetic wave of the specific wavelength is preferably ultraviolet light. After coating a solution containing a low-molecular-weight organometallic compound and water on the surface of the coating, in order to break the bond between the metal atom and the organic group of the organometallic compound, it is preferable to irradiate it with electromagnetic waves having a necessary specific wavelength, such as ultraviolet light. , while heating and drying, or heating and drying the coating film after electromagnetic wave irradiation.

In addition, the photocatalyst formed by dispersing the titanium oxide particles having photocatalytic performance used in the prior art in the inorganic thin film is compared with the photocatalyst composed of only titanium oxide, because the area occupied by titanium oxide is smaller, so the performance poor. Especially when there is a certain requirement for film strength, if a large amount of inorganic binder is added, although the strength is increased, the activity is significantly reduced.

The object of the present invention is to provide a photocatalyst material having high activity by dispersing titanium oxide in a binder, and to provide a product capable of sufficiently exerting a photocatalyst function even in daily life environment. In particular, the use of the self-cleaning properties of photocatalysts can reduce the number of parts replacement and washing of products.

In order to solve the above-mentioned problems, the present invention adds ATO, RuO ₂ , and any of Li, Na, and Mg to a photocatalyst composed of titanium oxide.

In addition, the present invention is a production method of directly coating ATO particles on titanium oxide powder to improve the bonding state at the interface between dissimilar semiconductors. Further speaking, the present invention uses high temperature treatment as pretreatment, and a coating method that can form a film at a low temperature of 120°C during coating.

When the electron affinity of the oxide semiconductor is lower than that of Ti, a Schottky barrier is formed on the particle surface of the fine particles, so that the carrier added with the oxide semiconductor cannot be implanted into TiO ₂ , and the effect cannot be exhibited. In this case, when the electron affinity of the oxide semiconductor is lower than that of Ti, instead of forming a Schottky barrier at the particle interface of the fine particles, a resistive junction is formed, so that the carrier of the oxide semiconductor can be easily implanted. TiO ₂ , thus effectively functioning. In particular, although the electron affinity of ATO is slightly smaller than that of Ti, the difference is basically the same, so performance can be improved. This is because the carrier concentration of ATO as a conductive oxide is high, and a large number of carriers of ATO can be injected into _TiO2 , thereby improving the activity of the photocatalyst.

In addition, ATO has attracted attention as a conductive oxide in recent years, and its ultrafine particles are commercially available. Adding ultrafine particle ATO to TiO ₂ photocatalyst can prepare TiO ₂ photocatalyst with ATO more conveniently. However, when the above-mentioned ultrafine ATO is used, the addition of the ultrafine ATO brings the ATO particles into contact with the TiO ₂ fine particles, but particles are also present in the SiO ₂ , which is ineffective. On the other hand, in the preparation method of the present invention, since the ATO solution is pre-added to the _TiO2 particles for firing, the contact area between ATO and _TiO2 particles is relatively large, and the different semiconductors can be bonded in a good joint state by firing. The electron transfer becomes smooth. In addition, since the p-type semiconductor RuO ₂ can attract the electrons and holes in the holes generated by the light absorption of the n-type semiconductor TiO ₂ and ATO, the recombination of electrons and holes is suppressed. Therefore, the electrons and holes generated by light absorption can be effectively used in catalytic reactions to further improve the decomposition efficiency.

In addition, since the ionic radius of the added Li, Na, and Mg is close to that of Ti, it is easy to enter the Ti defects on the surface of TiO ₂ , thus increasing the stability of the crystal. Moreover, since Li, Na, and Mg have strong ionicity and are easy to attract electrons, electrons and holes generated by light absorption can be separated, thereby improving reaction efficiency.

The film forming method of the present invention can be carried out at about 120°C, and can be used not only on ceramic substrates, but also on plastic materials. Since the general sol-gel method requires a temperature of about 400°C, it is difficult to be used in plastic products, and the crystallization of TiO ₂ also takes more than 10 minutes. However, the manufacturing method of the present invention can form a film at a low temperature, so many substrates can be used, and a photocatalyst film can be formed on any surface. Moreover, the processing time is very short, just a few minutes, which can significantly reduce production costs.

The present invention is formed by adding RSO (RuSrO ₃ ) to a photocatalyst formed of titanium oxide. Specifically, the present invention is a photocatalyst composed of STO (SrTiO ₃ ), RSO and a binder. Furthermore, the present invention is a photocatalyst characterized by adding any metal among Li, Na, and Mg.

The present invention is a method of directly coating RSO on semiconductor photocatalyst powder to improve the state of interfacial bonding between different semiconductors. Specifically, the pretreatment is high temperature treatment, and the coating is formed at a low temperature of about 120°C during coating. method.

When RSO and TiO ₂ are in contact, the TiO ₂ photocatalyst utilizes the pores of RSO to improve the performance of the photocatalyst added with RSO. In addition, the oxidation activity of the catalyst originates from the redox effect of electrons and holes generated by light absorption, especially the generated holes generate OH radicals, which have a strong oxidation effect. RSO is a p-type semiconductor with a large number of holes. The contact between RSO and _TiO2 brings holes into _TiO2 , which can oxidize the organic matter on the surface of _TiO2 , thereby improving the photocatalytic activity.

The ionic radius of Li, Na, and Mg is close to that of Ti, so it is easy to enter the Ti defects on the surface of TiO ₂ , thus increasing the stability of the crystal. Moreover, since Li, Na, and Mg have strong ionicity and are easy to attract electrons, electrons and holes generated by light absorption can be separated, thereby improving reaction efficiency.

The method of adding RSO includes the method of mixing RSO powder into TiO ₂ powder, and the method of coating and firing RSO sol on titanium oxide powder. Although the former RSO particles are also in contact with TiO ₂ fine particles, there are also particles present as a bond. In the _SiO2 used as the agent, this is ineffective. The latter can be fired by adding RSO solution to the _TiO2 particles in advance, so that the contact area between RSO and _TiO2 particles will increase, and the dissimilar particles with good bonding state can be made by firing. Electron transfer between semiconductors becomes smooth. However, the preparation of RSO requires a temperature of 700-850°C. If the temperature is lower than the above-mentioned temperature, RSO cannot be crystallized, so that it does not have the function of a p-type semiconductor. When the temperature is above 600°C, the crystallization of _TiO2 can be rutile. The anatase type fully exhibits the photocatalytic effect, and the photocatalytic effect of the rutile type drops sharply. Therefore, if the TiO ₂ is subjected to high temperature treatment after adding RSO, the RSO is transformed into a p-type semiconductor, and the TiO ₂ is phase-transferred to the rutile type. , This will lose the role of photocatalyst. Therefore, it is expected to use STO (SrTiO ₃ ) which has the same function as TiO ₂ photocatalyst, so that the STO photocatalyst with RSO added is effective. STO and _TiO2 have basically the same light band (band) structure. In addition, its preparation method requires high temperature treatment at 700-850°C to crystallize it. The crystallization of RSO and STO is perovskite type, and its lattice constant It is common and almost the same as Sr-O. Therefore, the preparation conditions are also very close to RSO, and the junction state is also good, which improves the photocatalytic activity.

In addition, since the decomposition speed of conventional photocatalysts is relatively slow, it takes a certain amount of time to decompose and remove the gas. In addition, it does not work when there is no light, and it only works when light is used. Therefore, although the number of bacteria and the like can be reduced by using the antibacterial effect, if there is no light for a long time, bacteria may multiply.

Therefore, the object of the present invention is to increase the antibacterial effect of the dark time while accelerating the gas removal rate.

In order to solve the above problems, the present invention adds an adsorbent to the photocatalyst composed of titanium oxide, and the added adsorbent is zeolite. Specifically, the present invention is a zeolite obtained by ion-exchanging any metal element among Cu, Ag, Li, Na, and Mg in a photocatalyst composed of titanium oxide.

Conventional photocatalysts are composed of semiconductor photocatalyst materials represented by titanium oxide. The characteristics of these materials are that they can perform antibacterial and self-cleaning by utilizing the oxidation-reduction reaction of photocatalysts. If the pollution is serious, self-cleaning may degrade the catalyst, while antibacterial Sex is difficult to judge visually. In particular, there is a risk of promoting the growth of bacteria, etc., if the product is used carelessly regardless of functional deterioration such as film peeling or performance deterioration.

Therefore, the present invention provides a photocatalyst material whose performance can be easily judged visually.

In order to solve the above-mentioned problems, the present invention provides an antibacterial and antifouling material composed of a photocatalyst whose performance deterioration can be judged visually. That is, a photocatalyst in which a pigment that absorbs visible light is added to a photocatalyst composed of titanium oxide.

Photocatalysts generally produce catalytic effects after absorbing ultraviolet rays. Only a small amount of ultraviolet rays exist in the daily life environment. Photocatalysts use these weak lights for antibacterial and antifouling. If visible light can be effectively utilized, high-performance photocatalysts can be provided in everyday environments. In the field of solar cells, wet solar cells using titanium oxide that can utilize visible light have been developed. This type of battery utilizes the layering of pigments that can absorb visible light, and the electrons excited by the pigments absorbing visible light stimulate titanium oxide to flow current. The same reduction can also achieve the same effect in photocatalysts. Add materials capable of absorbing visible light to titanium oxide, and the electrons excited by absorbing visible light will stimulate titanium oxide, which is beneficial to the redox reaction of photocatalysts. However, most of the pigments with the above-mentioned light-enhancing effect are organic substances, which are not only directly decomposed by ultraviolet rays, but also easily decomposed by photocatalytic action. Furthermore, due to the effective use of visible light, the performance has been improved, making it easier to disassemble, which also degrades quickly in everyday environments. Therefore, the present invention conducted intensive research on pigments that are not affected by ultraviolet rays, and found pigments that decompose slowly and have a luster-enhancing effect. Since the raw materials of pigments are mainly organic matter, they will decompose and deteriorate. However, after pigments are added, they will slowly decompose in the daily environment. If this characteristic is used to adjust the decomposition rate to match the replacement cycle of product parts, it will be possible to know whether product parts need to be updated from the color of the material.

In addition, conventional photocatalysts are composed of semiconductor photocatalyst materials typified by titanium oxide. These materials are characterized by antibacterial and self-cleaning properties using photocatalyst redox reactions. If the pollution is serious, self-cleaning may degrade the catalyst, and the antibacterial property is difficult to judge visually. In particular, in the case of functional deterioration such as film peeling or performance deterioration, there may be a problem of promoting the growth of dangerous bacteria and the like if used carelessly.

Therefore, the present invention provides a photocatalyst material whose performance can be easily judged visually. The present invention is an antibacterial and antifouling material composed of a photocatalyst whose performance deterioration can be judged visually. That is, a photocatalyst in which a pigment that absorbs visible light is added to a photocatalyst composed of titanium oxide.

Photocatalysts generally produce catalytic effects after absorbing ultraviolet rays. The ultraviolet rays in the daily environment are very weak, and photocatalysts use these weak rays for antibacterial and antifouling. If visible light can be effectively utilized, high-performance photocatalysts can be provided in everyday environments. In the field of solar cells, wet solar cells using titanium oxide that can utilize visible light have been developed. This type of battery utilizes the layering of pigments that can absorb visible light, and the electrons generated by the pigment absorbing visible light stimulate titanium oxide to flow current. The same reduction can also achieve the same effect in photocatalysts. Add materials capable of absorbing visible light to titanium oxide, and the electrons excited by absorbing visible light will stimulate titanium oxide, which is beneficial to the redox reaction of photocatalysts. However, most of the pigments with the above-mentioned light-enhancing effect are organic substances, which are not only directly decomposed by ultraviolet rays, but also easily decomposed by photocatalytic action. Furthermore, due to the effective use of visible light, the performance has been improved, making it easier to disassemble, which also degrades quickly in everyday environments. Therefore, the present invention carried out in-depth research on pigments that are not affected by ultraviolet rays, and found pigments that decompose slowly and have a brightening effect. Since the raw materials of pigments are mainly organic matter, they will decompose and deteriorate. However, after pigments are added, they will slowly decompose in the daily environment. If this characteristic is used to adjust the decomposition rate to match the replacement cycle of product parts, it will be possible to know whether product parts need to be updated from the color of the material.

Conventionally, photocatalysts used for plastic products are those in which an inorganic binder such as silica is added to titanium oxide. These photocatalysts in which titanium oxide particles are dispersed in an inorganic binder have a problem that the area occupied by titanium oxide is smaller than those of photocatalysts composed only of titanium oxide, resulting in inferior performance. Especially when film strength is required, since a large amount of inorganic binder is added, the strength is increased, but the activity is significantly reduced. Moreover, although photocatalysts are beneficial to the decomposition of organic matter, they are powerless to inorganic pollutants. However, inorganic pollutants will definitely adhere to organic pollutants. If organic pollutants are removed by photocatalysis, the adhesion of inorganic pollutants can be prevented to a certain extent. However, once the inorganic pollutants are attached, light cannot pass through the attached parts, so the photocatalyst will lose its function and cannot decompose the organic pollutants, resulting in more serious pollution. Therefore, it is possible to adopt a countermeasure of improving hydrophilicity and washing to remove adhering inorganic substances. However, for photocatalyst materials and products that need to be washed, it is necessary to use a large amount of binders constituting the photocatalyst to increase the strength, but this will weaken the photocatalyst effect.

Therefore, the present invention provides a photocatalyst material in which photocatalyst performance does not deteriorate even when a large amount of binder is added, and film peeling does not occur during washing such as washing with water. In this way, not only organic pollutants can be simply removed, but also inorganic pollutants can be washed, reducing the number of product washings and parts replacement.

The material composed of photocatalyst and having antibacterial and antifouling effects of the present invention can remove inorganic pollutants by washing with water, and can also increase strength by adding organic resin.

In addition, the organic resin used as a binder in the photocatalyst of the present invention has a silanol group or UV curability. When using UV curable resin, Al, Ti, Si type coupling agent is added.

When the photocatalyst is coated on the plastic surface, if silica is used as a binder, the adhesion to the plastic surface is not sufficient. And choose an organic resin that can be used with the substrate, the adhesion is quite good, and it is washable. However, organic resins are decomposed by photocatalysis. In order to prevent this, it is preferable to use inorganic materials, but the strength will be reduced. Therefore, the decomposition can be suppressed by introducing an inorganic functional group into the side chain of the organic resin, and using the inorganic group to bring the titanium oxide surface into contact with the organic resin.

Also, unlike ceramic materials such as silica, organic resins cure even without heating. For example, the above characteristics occur when using a room temperature curing resin. However, room temperature curing resins generally require 24 hours of action to cure, except for instant adhesives. Instant adhesives are cured in a short time, but are slowly decomposed by the action of photocatalysts. For example, UV curable resin is a resin that can be cured in a short time and has good light resistance. UV curable resins are cured by ultraviolet radiation, and gradually polymerized and cured after being irradiated with ultraviolet light from fluorescent lamps. However, it is also slowly cured by the influence of photocatalysts. Therefore, a proper combination of photocuring and photolysis can improve light resistance.

If the UV curable resin completely covers the _TiO2 particle surface, the catalyst will lose its activity. Therefore, by adding a coupling agent, the exposed portion of the TiO ₂ surface can be increased. In addition, the photocatalyst decomposes the moisture adsorbed on the surface to generate free radicals, but due to the addition of a coupling agent, it can store a large amount of moisture adsorbed on the surface, so that the catalytic effect can be manifested.

A brief description of the attached drawings

Fig. 1 is a structural view of the main body of the filter-type air cleaner in the implementation state of the present invention.

Fig. 2 is a side view of the main body of the filter-type air cleaner in the implementation state of the present invention.

Fig. 3 is a cross-sectional view of the main body of the electrostatic precipitator air cleaner in the implementation state of the present invention.

Fig. 4 is a cross-sectional view of the main body of the kitchen ventilation fan in the implementation state of the present invention.

Fig. 5 is a side view of the main body of the electric fan in the implementation state of the present invention.

Fig. 6 is a side view of the vacuum cleaner in the implementation state of the present invention.

Fig. 7 is a cross-sectional view of the main body of the vacuum cleaner in the implementation state of the present invention.

Fig. 8 is a cross-sectional view of the main body of the clothes dryer in the implementation state of the present invention.

Fig. 9 is a side view of the main body of the dish dryer in the implementation state of the present invention.

Fig. 10 is an enlarged sectional view of an exhaust port portion of the dish dryer in an embodiment of the present invention.

Fig. 11 is a sectional view of the main body of the dish dryer in the implementation state of the present invention.

Fig. 12 is a side view of the main body of the dishwasher in the implementation state of the present invention.

Fig. 13 is a sectional view of the main body of the dishwasher in the implementation state of the present invention.

Fig. 14 is a sectional view of the main body of the dishwasher in the implementation state of the present invention.

Fig. 15 is a side view of the main body of the kitchen garbage disposer in the implementation state of the present invention.

Fig. 16 is a sectional view of the main body of the kitchen garbage disposer in the implementation state of the present invention.

17 is a cross-sectional view of a TiO ₂ -dispersed SiO ₂ film formed on a PET film in an embodiment of the present invention.

Fig. 18 is a cross-sectional view of a low-temperature-curable highly active photocatalyst thin film formed on a coating in an embodiment of the present invention.

19 is a cross-sectional view of a two-layer laminated low-temperature curing type highly active photocatalyst thin film formed on a coating in an embodiment of the present invention.

Fig. 20 shows the results of a decomposition test of an organic dye in the practice state of the present invention.

Fig. 21 shows the relationship between electronegativity and decomposition rate in the embodiment of the present invention.

Fig. 22 shows the relationship between electronegativity and ionic radius in the embodiment of the present invention.

Fig. 23 shows the smoke trapping effect of the low-temperature curing type highly active photocatalyst film in the embodiment of the present invention.

Fig. 24 shows the photodecomposition effect of the smoke-adsorbed filter in the embodiment of the present invention.

Fig. 25 shows the ammonia gas trapping effect of the low-temperature curing type highly active photocatalyst thin film in the embodiment of the present invention.

Fig. 26 shows the photodecomposition effect of ammonia gas in the embodiment of the present invention.

Fig. 27 shows the photodecomposition effect of the smoke-adsorbed ABS board in the embodiment of the present invention.

Fig. 28 shows the effect of photolysis of salad oil in the embodiment of the present invention.

Fig. 29 shows the results of a decomposition test of an organic dye in an embodiment of the present invention.

Fig. 30 shows the effect of adding zeolite in the practice state of the present invention.

Fig. 31 shows the effect of the ratio of Si and Al in the embodiment of the present invention.

Fig. 32 shows the effect of adding ion-exchanged zeolite in the practice state of the present invention.

Fig. 33 shows the antibacterial effect after adding zeolite in the embodiment of the present invention.

Fig. 34 shows the results of a decomposition test of cigarette smoke in the practice state of the present invention.

Fig. 35 shows the results of a decomposition test of cigarette smoke corresponding to the amount of binder added in the embodiment of the present invention.

Fig. 36 shows the results of a decomposition test of cigarette smoke corresponding to the introduced amount of silanol in the embodiment of the present invention.

Fig. 37 shows the results of a decomposition test of cigarette smoke corresponding to the amount of coupler added in the embodiment of the present invention.

The best state to implement the invention

Hereinafter, an embodiment of the present invention will be described with reference to FIGS. 1 to 37 .

Tables 1 to 9 show the composition and embodiment effects of the low-temperature curing high-activity oxide photocatalyst film formed on the surfaces of various molded products, coated steel sheets, and filters.

(Example 1)

An air cleaner as Embodiment 1 of the present invention will be described with reference to FIG. 1 , FIG. 2 and FIG. 3 .

Fig. 1 is a structural diagram of a filter-type air cleaner main body, and Fig. 2 is a side view of the main body. The composition of the main body 1 of the air cleaner is as follows: the capacitive motor 7 is fixed on the rear cover 12 with screws 8, and then the capacitor 11 and the operation switch 9 for driving the motor are fixed, and the fan 6 is fixed on the capacitive motor 7 through the nut 5. On, back cover 12 and frame 4 are fixed with screw 13. In addition, the filter 3 is fixed on the sizing template (suction port) 2, and the filter 3 can be drawn out by removing the template (suction port) 2. On-off button 10 is fixed on the operation switch 9.

The driving force of the capacitive motor 7 is used to operate the fan 6 to circulate air. Indoor air polluted by dust, smog, oil particles, microorganisms and microorganism residues, pollen and stench, etc. is sucked into the template (suction port) 2 through air circulation. The inhaled polluted air is partially filtered and purified by the filter 3, and then discharged from the exhaust port 15 of the grille 14. Part 3 of the filter is a composite structure with functions of removing various pollutions and odors. The filter 3 is composed of an outer filter 3a covering the outer surface and an inner filter 3b (not shown) inside the outer filter 3a. In order to filter dust, the basic structure of any filter is to use a nonwoven fabric layer or a sponge-like porous layer such as polyester, polyurethane, cellulose fiber, nylon, or electret-treated polyolefin. In addition to having the above-mentioned basic structure, the inner filter 3b also mixes, blends or seals activated carbon particles and fibrous substances in order to adsorb odor. In addition, sometimes in order to neutralize the peculiar smell of the fiber itself, some drugs are also soaked or spread on the surface. In addition to various organic acids or flavonoid alkaloids, etc., the drugs used may also be used in combination with antibacterial agents to inhibit the growth of microorganisms. In recent years, chitin, chitosan, and catechin derivatives, which are relatively safe, have also been used. The air volume generated is about 2-3 (m ³ /min), and 70-95% of cigarette smoke can be removed by running in a room with 8 seats for 30 minutes.

In this embodiment, the outer filter 3a is made of a non-woven fabric of polyacrylonitrile fibers, and the low-temperature curing type highly active oxide photocatalyst film of sample No. 21 shown in Table 3 below is formed on its surface. After the polyacrylonitrile nonwoven fabric filter is treated by corona discharge, a thin film containing only _SiO2 is formed on it, that is, the bottom layer represented by sample No.12 in Table 1. After the film is formed, sample No. 21 low-temperature curing highly active oxide photocatalyst film. The film formation method will be described in detail in Example 9 described later. In short, it is to prepare a specified sol, coat the product with various methods, and then irradiate it with a low-pressure mercury lamp in an atmosphere of 120°C to cure it. . The practical examples in the following examples are also formed by the same method. The coating method can be carried out by various methods such as spraying, dipping, and brushing according to the shape of the product.

The outer filter 3a is the first part to filter the polluted air inhaled by the template (suction port) 2, on which a large amount of dust, smog, oil particles, microorganisms and microorganism residues, pollen and malodorous foreign matter are adsorbed. In order to efficiently suck air, a plurality of openings are provided on the template (suction port) 2, and the air suction surface of the outer filter 3a is irradiated with light such as indoor lighting and sunlight from the openings. Utilize these light rays to oxidize and decompose the foreign matter trapped on the surface of the outer filter 3a, especially smoke and oil particles, because they are adsorbed on the low-temperature curing high-activity oxide photocatalyst on the filter surface in a thin film, so they can be effectively absorbed break down. Various microorganisms such as bacteria and molds floating in the air are killed or their reproduction is inhibited by the decomposition of highly active photocatalysts. In addition, if the fiber surface of the non-woven fabric filter is covered with a glassy film, it can improve its wetting performance with smoke particles, which can increase the smoke trapping effect.

In addition, the external components of the main body 1 of the air cleaner, such as the template (suction port) 2, the frame 4, the operation switch 9 and the rear cover 12, are injection molded products of thermoplastic ABS. A low-temperature curing type highly active oxide photocatalyst film was formed on the outer side of these parts.

Fig. 19 shows a simulated cross-sectional view of a thin film formed on the surface of the ABS member of this example on the surface of a sample polyacrylonitrile nonwoven fabric filter shown in Table 6 described later. The plastic covering body 189 in the figure is polyacrylonitrile fiber; the low-temperature curing type highly active oxide photocatalyst film is composed of the first layer 194 of the surface and the second layer 192 of the surface, all of which are dispersed TiO _particles in the SiO film ₁₈₆ 187 and lithium 190, tin oxide particles 193 to which antimony is added are dispersed in the second surface layer 192.

A No.86 low-temperature curing type highly active oxide photocatalyst film was formed. The polyacrylonitrile non-woven fabric filter was treated with corona discharge to form the first layer, and after forming the film, the second layer of the low-temperature curing type highly active oxide photocatalyst containing ATO of sample No. 86 was formed.

These external parts are irradiated by light such as indoor lighting and sunlight, so even if the above-mentioned various foreign substances are adsorbed, they can be oxidized and decomposed in the same way as the filter.

Fig. 3 is a sectional view of the electrostatic precipitating air cleaner. The whole is composed of a front cover 16 and a rear cover 17 . A suction port 19 and an exhaust port 20 are provided on the front cover 16 and the template 18 , and a detachable pre-filter 21 is arranged in the air intake port 19 and the air passage connecting the suction port 19 and the exhaust port 20 . Dust collecting electrode 22 and discharge electrode 23 are relatively arranged at the rear, and the deozone filter 24 for removing the ozone generated by dust collecting electrode 22 and discharge electrode 23 is also set, prefilter 21, dust collecting electrode 22, discharge electrode 23, The deozone filter 24 is packed into the frame 25 together to form a dust collection unit. The buffer material 26 contacting with the dust collection unit, the ventilation duct 28 and the ventilation duct 27 connecting the blower fan 27 and the dust collection unit are arranged at the back, the cushion material 26 is installed on the ventilation duct 28, and the ventilation duct 28 is installed on the ventilation duct 27, The three are connected together to form an air supply unit. The purified air is exhausted from the exhaust port 20 .

The above-mentioned pre-filter 21 plays the same role as the outer filter 3a of the filter-type air cleaner.

In this embodiment, the pre-filter 21 is a net made of nylon, and the low-temperature curing type highly active oxide photocatalyst film of sample No. 21 shown in Table 3 described later is formed on the surface. After the nylon mesh was irradiated with ultraviolet rays, the low-temperature curing high-activity oxide photocatalyst film of sample No. 21 was formed on it. The simulated sectional view of the nylon mesh surface film is shown in FIG. 18 . The plastic coating 189 is nylon fiber, and the low-temperature curing type highly active oxide photocatalyst thin film 191 is in a state in which TiO ₂ fine particles 187 and lithium 190 are dispersed in the SiO ₂ film 186 .

The back cover 17 is an ABS injection molded product, and the front cover 16 is made of a plasticized galvanized steel plate, and the outer surface is coated with a polyester baking varnish. In the same manner as above, No. 86 low-temperature curing type highly active oxide photocatalyst thin film was formed on the outer surfaces of the rear cover 17 and the front cover 16 .

(Example 2)

A ventilating fan according to Embodiment 2 of the present invention will be described with reference to FIG. 4 .

Fig. 4 is a side sectional view of a kitchen ventilation fan. A motor 30 is mounted on the box-shaped frame 29 and an impeller 31 is mounted on the motor 30 . An awning 32 is installed on the outdoor side (exhaust side) of the frame 29, and a flow measuring hole 33 is provided on the indoor side (suction side) of the frame 29. An illuminating device 35 with a fluorescent tube 34 is provided above the indoor side (suction side) of the flow measuring hole 33 . A filter 36 is arranged on the indoor side (suction side) of the flow measuring hole 33 and the lighting device 35, and an oil accumulation bag 37 is arranged at the bottom of the filter 36.

Generally, if the diameter of the impeller 31 is 25 cm, the ventilation capacity is about 800 to 1000 (m ³ /time).

The structure of the kitchen ventilating fan shown in Fig. 4 is slightly different in the installation angle and component positions of the general indoor, toilet and bathroom ventilating fans, but the basic structure is the same.

The structure of the filter 36 is the same as that of the aforementioned air cleaner, and it is a composite structure suitable for various purposes, and has a deodorizing function and an antibacterial function.

The filter 36 of this embodiment is a single-layer filter made of polyacrylonitrile fiber nonwoven fabric, and the low-temperature curing type highly active oxide photocatalyst film of sample No. 22 shown in Table 3 is formed on its surface. After the polyacrylonitrile non-woven fabric is treated by corona discharge, a thin film containing only _SiO2 is first formed, that is, the bottom layer represented by sample No. 12 shown in Table 1. After the film is formed, the film of sample No. 22 is formed Low temperature curing type highly active oxide photocatalyst film.

The frame 29 is an injection molded product of PS (polystyrene resin), and the flow measuring hole 33 and the impeller 31 are injection molded products of ABS. On the surface of these molded parts, a low-temperature curing type highly active oxide photocatalyst film of sample No. 86, which is the same as that of the aforementioned air cleaner, was formed.

In addition, the parts on the outdoor side, such as the awning 32, are made of hot-dip galvanized cold-rolled steel plate, and the surface is electroplated with acrylic resin, and the surface is also formed with the same low-temperature curing type of sample No. 86 as above. Highly active oxide photocatalyst thin film.

The surface of the filter 36 facing the room is irradiated with the indoor lighting light, and the reverse surface is irradiated with the light from the lighting device 35 . In addition, components such as the frame 29 , the flow measuring hole 33 , the impeller 31 and the oil storage bag 37 are also irradiated by the light emitted by the illuminating device 35 . The surface of the awning 8 that is outside is irradiated by sunlight.

The present embodiment is a ventilating fan for kitchen, so, compared with general ventilating fans, its degree of pollution increases greatly. That is, a large amount of edible oil particles scattered during cooking adhered to the surface. Ventilation fans for kitchens have always been equipped with lighting devices 35, which are designed for easy operation during cooking. They can be used simultaneously when the ventilation fans are working, or they can be used for lighting alone. Since the organic matter decomposition efficiency of the photocatalyst of the present invention is higher than before, if it is an occasion with less pollution, there is no need to install lighting devices in particular, and sufficient decomposition effects can be obtained as long as the indoor lighting level is used. However, places with serious pollution such as kitchens Satisfactory results cannot be obtained. However, if general fluorescent lamps or incandescent bulbs are used in combination as shown in this embodiment, sufficient effects can be obtained even in heavily polluted places such as kitchens and toilets.

(Example 3)

Referring to Fig. 5, an electric fan as Embodiment 3 of the present invention will be described.

Fig. 5 is a side view of the appearance of the electric fan structure. A support column 39 is installed on the base 38 of the electric fan main body, and a sliding pipe 40 that can freely expand and contract is inserted in the support column 39 . The slide tube 40 supports a head 44 made up of an impeller 41 , a guard 42 , a motor 43 and the like located thereon. Considering the problem of strength, the diameter of the support column 39 becomes larger as it goes down. The impeller 41 is driven by the driving force of the motor 43 to generate air flow from the back of the main body to the front. The effect of guard 42 is to prevent finger from contacting with rotating impeller 41, in order to prevent accidents such as children, whole guard 42 is covered with net 45 (not shown in the figure), will be safer like this. A remote control seat 46 is installed on the support column 39 bottoms, and the general remote control device 47 is packed in the remote control seat 46 . The operation mode can be set by using the switch operation of the remote control device 47, that is, an infrared signal is emitted from the infrared light emitting part 48 of the remote control device 47, and then the signal is received by the infrared light receiving part 49 on the main body base 38, so that the setting operation is performed .

In this embodiment, the impeller 41 is an injection-molded product of AS resin, and the surface of the impeller 41 is formed with the same sample No. 86 low-temperature curing type high-activity oxide photocatalyst film as the molded product such as the aforementioned ABS.

The protective device 42 is made of a steel wire material coated with polyester-based baking varnish, and the same low-temperature-curing high-activity oxide photocatalyst film of sample No. 86 is formed on its surface. The net 45 is made of nylon fibers, and the low-temperature-curable high-activity oxide photocatalyst film of sample No. 86 is also formed on its surface.

In addition, the infrared light emitting part 48 of the remote control device 47 and the infrared light receiving part 49 on the upper surface of the main body base 38 are transparent members made of AS resin.

On the surface of these transparent parts, the low-temperature curing type highly active oxide photocatalyst film of sample No. 86 was also formed. A titanate-based coupling agent thin film is formed as the first layer on the surface of the target member, and after the film is formed, a low-temperature curing type highly active oxide photocatalyst thin film of Sample No. 86 is formed as the second layer.

The surfaces of the impeller 41 and the protective device 42 are the same as the impeller and frame of the aforementioned air purifier and ventilation fan, and are polluted due to adsorption of foreign matter floating in the air, but due to the formation of the low-temperature curing type highly active oxide photocatalyst of the present invention Therefore, with the brightness level of indoor lighting, the adsorbed pollutants can be oxidized and decomposed, which has the effect of being difficult to pollute.

In addition, the present embodiment is equipped with a remote operation device utilizing infrared rays. Since a low-temperature curing type high-activity oxide photocatalyst film is formed on the surface of the transparent components used in these infrared signal transmitting and receiving parts, it will not be caused by the adhesion of the component surface. Contaminants can affect signal reception.

This embodiment is an example of an electric fan using a helical impeller, and if it is an electric fan using a multi-bladed impeller, the same effect can be obtained with the same configuration.

(Example 4)

Referring to Fig. 6 and Fig. 7, a vacuum cleaner as a fourth embodiment of the present invention will be described.

Fig. 6 is a side view of the appearance of the vacuum cleaner, and Fig. 7 is a sectional view of the main body of the vacuum cleaner.

The main body 50 of the vacuum cleaner is composed of a synthetic resin molded product lower cover 51 covering the lower part, an upper cover 52 covering the upper part, a middle cover 53, a grille cover 54 and a handle part 55. Rear wheel 56 is provided with the less freely rotatable wheel 57 of diameter at the bottom center of front lower part. A main body switch part 58 is arranged in the center of the upper cover 52 , and the main body switch part 58 is composed of an infrared light receiving part 59 located in the center, a power switch 60 and a signal bobbin button 61 . The dust collection chamber 62 is connected to a suction pipe assembly 66 composed of a suction pipe part 63 , an extension pipe part 64 , and a suction port part 65 . The upper part of the extension pipe part 64 is connected with a handle part 67 on which a manual operation part 68 is installed. An infrared signal emitting part 69 is installed on the manual operation part 68, and the infrared signal transmitted by the infrared signal emitting part 69 is transmitted to the infrared receiving part 59 of the vacuum cleaner main body 50 for wireless operation. A dust collection chamber 62 is arranged in front of the main body 50 of the vacuum cleaner, an electric blower 70 and a signal bobbin part 71 are arranged side by side at the rear inside, and a control board 72 is also arranged on the top of the electric blower 70 and the signal bobbin part 71 .

In addition, at the rear of the electric blower part 70, a first exhaust ventilation channel 73 is formed along the up-down direction from the back lower end of the vacuum cleaner main body 50 to the upper end, and the lower end of the first exhaust ventilation channel 73 is formed at the bottom of the electric blower part 70. The second exhaust ventilation channel 74 of the above-mentioned first exhaust ventilation channel 73 and the second exhaust ventilation channel 74 form an exhaust ventilation channel 75 (not shown in the figure), so that the second exhaust ventilation channel 74 is connected with the electric motor The blower part 70 is connected, and the first exhaust air passage 73 is connected with the exhaust air passage 76 . The upper part of the dust collection chamber 62 is provided with paper filter installation parts 77 and 78, the thick paper of the paper filter 79 is housed on the paper filter installation parts 77 and 78, and the middle cover 53 constituting the upper part of the dust collection chamber 62 is closed, The mounting port 80 and the paper filter 79 can be fixed at predetermined positions. The freely rotatable wheels 57 are mounted in a recess formed at the front bottom of the lower cover 51 so as to be able to rotate freely and horizontally. Garbage, dust, ticks, microorganisms, etc. sucked from the installation port 80 with the air flow are collected in the paper filter 79 .

Then, the air flow that has removed the above-mentioned solids is introduced into the electric blower 70 through the partition plate 81 that is arranged between the dust collecting chamber 62 and the electric blower 70, and is provided with the communication port 83 of the auxiliary filter 82, and the electric blower 70 is cooled. Afterwards, the cooled air flows through the second exhaust ventilation passage 74 and the first exhaust ventilation passage 73 , and is discharged from the exhaust ventilation section 76 provided with the exhaust filter 84 .

In this embodiment, the upper cover 52, the middle cover 53, the grille cover 54, the handle part 55, the extension tube part 64 of the suction pipe assembly 66, the suction port part 65 and the handle part 67 on the main body of the vacuum cleaner are all ABS injection molding. Products, the low-temperature curing type highly active oxide photocatalyst film of sample No.86 was formed on the surface of these molded products. A titanate-based coupling agent thin film is formed as the first layer on the surface of the target part. After forming this film, a low-temperature curing type highly active oxide photocatalyst thin film containing ATO of Sample No. 86 is formed to form the second layer.

Compared with the articles of other embodiments, the surface of the outer part of the vacuum cleaner is easily damaged due to its high mobility. That is, the main body and the suction port of the vacuum cleaner often rub and collide with furniture or walls when running on the ground, which will not only gradually form scratches and lose luster, affect the appearance, but may also cause damage. In order to prevent the occurrence of the above situation, in the past, UV-curable acrylic resin or the like was applied to ensure surface hardness, but the TiO ₂ constituting the low-temperature-curable high-activity oxide photocatalyst film of the present invention and SiO ₂ used as a binder The hardness of the film is greater than that of ABS, and its hardness reaches the level of pencil hardness 2H to 4H. Therefore, when used for exterior parts, it can not only obtain the effect of making it difficult to form scratches, but also obtain its own antifouling and inhibit microbial reproduction. and other effects.

In particular, the handle part 67 is a part that is directly in contact with the hand, and the body fat such as sweat absorbed on it is used as a nutrient component, which easily causes bacteria to multiply. In the past, imidazoles, thiazolines, etc. were mixed into the molding resin. Organic antibacterial agent or copper, zinc, silver inorganic antibacterial agent, to obtain antibacterial effect, but the present invention just does not need to carry out these treatments.

In addition, since the suction port and the wheels can slide or rotate, static electricity is likely to be generated when the vacuum cleaner is used in a dry environment, and a large amount of fibers or dust such as carpets are adsorbed on the surface of the above-mentioned parts. In order to prevent the occurrence of the above situation, in the past, various surfactants or polyamides, polyethylene glycols and other hydrophilic polymers were mixed into the molding resin to reduce the surface resistance to achieve the goal. The present invention The low-temperature curable high-activity oxide photocatalyst film has a small resistance value, and can obtain the effect of preventing dust, etc. from adhering even with ABS molding resins with a high resistance value. A manual operation part 68 is set on the aforementioned handle part 67, and a control substrate carrying electronic components is installed on the back side of the manual operation part 68. If static electricity is generated near the manual operation part 68, it will also induce a wrong operation of the control substrate. The anti-static effect can not only prevent the adsorption of dust, etc., but also prevent the wrong operation of the control board.

In addition, the infrared signal emitting part 69 arranged on the manual operation part 68 and the infrared light receiving part 59 of the vacuum cleaner main body 1 are the same as the electric fan of the aforementioned embodiment 3, all of which are made of transparent AS resin. The cured highly active oxide photocatalyst thin film can prevent the influence of pollution on the transmission and reception of infrared signals.

Also, the exhaust filter 84 provided on the exhaust ventilation part 76 of the main body is made of a blended non-woven fabric of polyacrylonitrile and PP, and the surface of the exhaust filter 84 is formed on the surface of the exhaust filter 84. photocatalyst thin film. The exhaust ventilating part 76 is provided with a plurality of openings, and since the air discharge surface of the exhaust filter 84 is irradiated by light such as indoor lighting and sunlight from the openings, the filter surface is also purified.

In addition, parts such as the upper cover 52 covering the upper part of the main body, the middle cover 53, the grille cover 54 and the handle part 55 are all transparent, so that external light can irradiate the inside. 79 and the filter fiber surface of the auxiliary filter 82 form the low-temperature curing type highly active oxide photocatalyst film of the present invention, and antibacterial and deodorizing effects can also be obtained.

(Example 5)

Referring to Fig. 8, a clothes dryer as a fifth embodiment of the present invention will be described.

Fig. 8 is a sectional view of the main body of the clothes dryer. 85 is an external frame, 86 is a switch cover, 87 is a rotating drum, 88 is a heat source, 89 is an exhaust port, 90 is a double-wing fan, 91 is a fan cover, 92 is a motor that forms power, and 93 is the power transmission of the motor 92 The conveyor belt to the rotary drum 87, 94 is the circular conveyor belt that transmits the power of the motor 92 to the double-wing fan 90, 95 is the first sealing felt, 96 is the second sealing felt, 97 is a partition, 98 is the fan cover 91 The exhausted circulating air guides the circulating air channel of the heat source 88, 99 is a cloth filter device, 100 is the FD shaft that fixes the fan cover 91 on the outer frame 85, 101 is the installation ring (bearing sleeve) for installing the bearing 102, and the rotating drum 87 is supported by bearing 102 and can rotate freely. The rotary drum 87 rotates together with the two-wing fan 90 by the driving force generated by the motor 92 transmitted by the conveyor belt 93 . While stirring the clothes by rotation, a circulating air (indicated by solid arrows) is generated, which is heated when passing through the heat source 88, and then enters the rotating drum 87 to evaporate the moisture in the clothes and make them dry. Then, utilize the double-blade fan 90 to make the circulating air reach the heat source 88 through the inside of the circulating air duct 98, and reheat to make the clothes dry repeatedly. Along the inner peripheral surface of the rotary drum 87, a shock-absorbing material 105 is attached. The cushioning material is PP foam

In the present embodiment, as the internal part of rotating drum 87 is the part that is subjected to the light irradiation of illuminating device, as parts such as buffer material 105, cloth system filter device 99, the inner surface of switch cover 86 are all made of ABS or PP resin, The low-temperature curing type highly active oxide photocatalyst film of sample No.86 was formed on their surfaces. An organic silane coupling agent film was formed as the first layer on the surface of the target member, and after forming this film, a low-temperature curing type highly active oxide photocatalyst film containing ATO of sample No. 86 was formed as the second layer.

The lighting device can be used in the drying process, or it can be used independently with the drying operation. If it is irradiated with the light of the fluorescent lamp 103, it can effectively oxidize and decompose the organic matter attached to the surface of the above-mentioned parts and the organic matter contained in the contacted air. Malodorous substances, which can effectively inhibit the reproduction of microorganisms and deodorize.

Because the clothes are rotating during the drying process, light cannot reach every place. It is more effective if the lighting device is opened for a period of time to purify the inside of the rotary drum 87 after drying.

In addition, the outer frame 1 is made of galvanized steel sheet, and the outer side thereof is coated with epoxy resin powder paint. A low-temperature curing type highly active oxide photocatalyst film containing ATO of sample No. 86 was formed on the surface of the coating film.

The outside of the switch cover 86 is an injection-molded product of PS resin, and a low-temperature curing type highly active oxide photocatalyst film containing ATO of sample No. 86 is also formed on the surface.

The above-mentioned external components, such as the photocatalyst film on the outside of the external frame 85 and the switch cover 86, have the same functions as the external components of the aforementioned embodiments 1-4, and sufficient antifouling and antibacterial effects can be obtained by using indoor light.

(Example 6)

Referring to FIG. 9 , FIG. 10 and FIG. 11 , a tableware dryer as Embodiment 6 of the present invention will be described.

Fig. 9 is a side view of the appearance of the tableware dryer. FIG. 10 is an enlarged cross-sectional view near the exhaust port 128 . Fig. 11 is a sectional view of the main body.

The inside of the main body 106 is divided into upper and lower parts of a drying chamber 107 and an operation control chamber 108 by a partition 109 . The operation control room 108 is provided with the heating and blowing unit 114 which is composed of fan motor 110, blower fan 111, cover 112 and heater 113 for sending out dry air. A controller 118 is provided between the air intake 117 of the air intake filter 116 and the heating and blowing unit 114 . In the drying chamber 107, tableware is collected, and an upper basket 119 and a lower basket 120 are arranged on its upper part. The lower basket 120 is arranged on a container 124 for receiving water on a movable rod 125 connected with a hinge 122 , and can be freely inclined toward the bottom of the door 121 . Likewise, a layup basket 119 is also provided on the movable bar 123 . The movable rods 123, 125 are installed on a freely rotatable drum (not shown) arranged on the side wall of the drying chamber 107, and can move forward and backward. When the handle 126 of the door 121 is pulled by hand, the lower basket 120 leaves the drying chamber 107, and because the front end of the basket is pulled, the lower basket 120 and the upper basket 119 all move to the outside from the drying chamber 107. The exhaust port 128 provided in the template 127 has a lattice shape and includes an exhaust filter 129 . The opening portion 130 of the partition 109 provided on the main body 106 is connected to the drying chamber 107 through an exhaust air passage 131 . In order to protect the temperature detector 132 from the influence of external temperature, it is arranged inside the exhaust air duct 131 .

The suction port 117 is an injection-molded product of PP, and the suction filter 116 is a mesh made of nylon, and a low-temperature curing type highly active oxide photocatalyst film of sample No. 91 shown in Table 7 below is formed on the surface. . After the nylon mesh was irradiated with ultraviolet rays, the silver-containing low-temperature curing type high-activity oxide photocatalyst film of Sample No. 91 was formed.

Since the surface of the air intake filter 116 is irradiated by indoor lighting light, the adsorbed organic matter and the malodorous substances in the absorbed air can be oxidized and decomposed. The low-temperature curing type highly active oxide photocatalyst film of sample No. 91 was also formed on the exhaust port 128 and the exhaust filter 129 in the same manner. Since the discharged moisture condenses around the suction and exhaust ports, it is easy to cause a wet state and cause mold and bacteria to multiply. However, using the photocatalyst with high decomposition efficiency of the present invention can effectively suppress the above-mentioned problems with indoor light. Microbial reproduction. In the composition of sample No. 91, silver contained in the composition itself has an antibacterial effect, so the effect is better. In order to enhance the antibacterial effect, ceramic particles such as silver-loaded zeolite or apatite may also be mixed.

In addition, a lighting device 134 with a fluorescent lamp 133 is also installed inside the drying chamber 107. The function of the lighting device is not only to illuminate when the door 121 is opened, to confirm the dryness of the inner tableware (this is the original function of the lighting), but also to The function of purifying the interior of the drying chamber 107 . That is, by forming a photocatalyst thin film on the surface of the internal parts of the drying chamber 107, antibacterial and antifouling effects are produced on the part irradiated with light. In this embodiment, the upper basket 119 and the lower basket 120 are formed by drying and coating polyamide powder resin on the iron frame. low-temperature curing highly active oxide photocatalyst film. The upper and lower baskets are parts that are in direct contact with the tableware, so it is very important to keep them clean. The use of photocatalysts can prevent surface pollution and inhibit the reproduction of microorganisms, so that the purpose of cleaning can be achieved. Copper, like silver, is also a metal that has antibacterial effect by itself, so it can improve the antibacterial effect.

The same as the clothes dryer in Embodiment 5, the tableware will have shadows during the drying process, so that the light cannot shine on every place. If the lighting device is turned on for a period of time after the drying is completed, the inside of the drying chamber 107 is purified. This will work better.

The door 121 is a molded product of ABS resin, and a low-temperature curing type highly active oxide photocatalyst film containing ATO of sample No. 86 is formed on the surface thereof. The effect of the photocatalyst thin film on the surface of the door 121 is the same as that of the external parts of the foregoing embodiments 1-5, and sufficient antifouling and antibacterial effects can be obtained by using indoor light.

(Example 7)

Referring to Fig. 12, Fig. 13 and Fig. 14, a dishwasher as a seventh embodiment of the present invention will be described.

Fig. 12 is a side view of the appearance of the dishwasher. 13 and 4 are sectional views of the dishwasher.

A cutlery collection tank 136 is provided inside the outer frame 135, and a section 138 is provided at a side wall lower portion of the cutlery collection tank 136 on which a door 137 for opening and closing its front opening portion is provided. The lower basket 139 for tableware collection which can be freely attached and detached is provided on the section 138 . A pump 140 is provided outside the bottom of the cutlery collection tank 136 , and the pump 140 is equipped with a pump motor 141 . A rotatable lower nozzle 142 is arranged vertically below the lower basket 139 for tableware collection, and a plurality of holes 143 are arranged on the lower nozzle 142 . The lower basket 139 for tableware collection is provided with a venturi tube 145 for sending clean water from the pump 140 to the upper spout 144 . The upper spout 144 rotates on its center vertically below the upper basket 146 for tableware collection. A plurality of holes 147 are arranged on the upper nozzle 144 . A heater 148 is arranged on the outer bottom or back of the cutlery collecting tank 136 . A heater cover 149 is also provided to cover the heater 148 . The water supply solenoid valve 150 is provided on the outer surface of the tableware collection tank 136 . An exhaust ventilation channel 151 is arranged on the outer top of the tableware collecting tank 136, and it is connected with the exhaust port 152. A control template 153 is arranged on the upper part of the outer side of the door 137 . A drainage pump 154 and an air blowing unit 155 are arranged outside the bottom of the cutlery collection tank 136 .

When washing, the water supply electromagnetic valve 150 is used to start the pump 140, and when the pressed water is supplied to the lower nozzle 142, the heater 148 is turned on to increase the water temperature. While the water is ejected from the hole 143, it is delivered to the upper nozzle 144 through the Venturi tube 145, so that the water is also ejected from the hole 147, so that the warm water can be sprayed to the tableware collection basket without omission while turning the upper and lower nozzles. 146 on the tableware, wash away the dirt. After washing, connect the drain pump 154 to discharge the sewage, then repeat the above operation several times to flush the internal dirt, so that it can be thoroughly cleaned. Dry after rinsing. Connect the air supply unit 155 to make the air supply fan 156 run, and send the wind to the tableware collection tank 136 through the air supply channel 157 and the heater 148 arranged at the bottom of the tableware collection tank 136 . At this time, the heater 148 is intermittently energized for a certain period of time to convert the cold wind into warm wind, and use the warm wind to convert the internal water droplets, residual moisture, and water droplets attached to the tableware into water vapor, which passes through the exhaust channel 151. Exhausted from the exhaust port 152.

In this embodiment, the exhaust port 152 is a molded product of ABS resin, and the silver-containing low-temperature curing type highly active oxide photocatalyst film of sample No. 91 is formed in the same manner as the above-mentioned tableware dryer. Since the exhausted moisture condenses around the exhaust port, it is easy to form a wet state, which leads to the growth of mold and bacteria, but if the photocatalyst with high decomposition efficiency of the present invention is used, it can Effectively inhibit the reproduction of the above-mentioned microorganisms.

A lighting device 159 with a fluorescent lamp 158 is provided inside the cutlery collecting tank 136 . The effect of the lighting device is not only to illuminate when the door 137 is opened to confirm the cleaning and dryness of the inner tableware (this is the original function of the lighting), but also to purify the inside of the tableware collection tank 136 . That is, by forming a photocatalyst thin film on the surface of the inner parts of the tableware collecting tank 136, an antibacterial or antifouling effect is produced on the part irradiated by light.

In this embodiment, the upper basket 146 for tableware collection and the lower basket 139 for tableware collection are formed by baking-coating polyamide powder resin on an iron frame, and the surface of the coating film is formed with the sample No.92 containing Copper low-temperature curing highly active oxide photocatalyst film.

Since the upper and lower baskets are parts that are in direct contact with the tableware, it is very important to keep them clean. The use of photocatalysts can prevent surface pollution and inhibit the reproduction of microorganisms, so that the purpose of cleaning can be achieved.

Other parts that are irradiated by light from the lighting device 159 include the tableware collection tank 136, the upper nozzle 144, the lower nozzle 142, the venturi 145, etc., and these parts are injection molded products of PP resin or plastically deformed products of SUS. After corona discharge treatment on the surface of these parts, a thin film containing only SiO2 is formed, that is, the bottom layer represented by sample No. oxide photocatalyst film.

A photocatalyst thin film is formed on the internal parts of the tableware collecting tank 136, and the unique effect of the dishwasher with the lighting device 159 is to improve the drying efficiency. Both TiO ₂ and SiO ₂ , the base materials of the low-temperature-curable highly active oxide photocatalyst film of the present invention, are materials with good water wettability. The light of the device 159 is decomposed, so it is possible to always maintain high water wettability.

In the process of washing dishes, the temperature of the water in the final rinsing operation rises to 60-70°C. After the internal temperature rises, although the moisture is discharged to the outside of the machine through the air supply, the drying efficiency of the moisture remaining in the dish collecting tank 136 but decreased. Due to the higher water resistance requirements to parts such as the tableware collecting tank 136, the upper nozzle 144, the lower nozzle 142 and the Venturi tube 145, hydrophobic materials are mostly used, and the water wettability of the general surface is relatively poor. On the surface of a material with poor water wettability, water does not exist in a film-like wet state, but adheres in the form of water droplets with a large contact angle. Since detergents containing surfactants are used during washing, the surface tension of the washing water decreases, the contact angle decreases, and it turns into a state of good wetting. However, there is almost no detergent in the water in the final rinse, so Water has a very high surface tension. Therefore, when the final rinsing operation ends, countless water droplets with relatively large contact angles adhere to the surface of each component inside the tableware collection tank 136 .

These water droplets with a large contact angle have a larger amount of water than a water film that develops into a thin film, and are less likely to dry. Moreover, the droplet-shaped water shrinks and dries in a droplet-like shape during drying, and since the surface area becomes smaller, the drying speed is slower, and the time required for drying is about three times. The tableware is mostly made of glass, ceramics or wood with good water wettability, which can be dried relatively quickly. However, if the dishwasher itself ends the washing operation with water droplets attached, when the door 137 is opened, the upper and lower tableware collection baskets will be taken out. The vibration generated during the operation will cause water to drip on the tableware, which will cause the undesired situation that the dried tableware will be wet again.

When parts such as the tableware collection tank 136, the upper nozzle 144, the lower nozzle 142, and the Venturi pipe 145 are PP molded products, the residual water amount of the attached water droplets is about 30g when the flushing ends, and when forming the photocatalyst film of the present invention, the attached The amount of residual water will be reduced to about 5g. In addition, due to the high photoactivity of the low-temperature curing type high-activity oxide photocatalyst film of the present invention, the light of the illuminating device 159 can decompose the attached oily substances, so the water will not be reduced due to the adhesion of oily substances. Wetting properties.

Same as the tableware dryer in Embodiment 6, the tableware will have shadows during the drying process, so that the light cannot shine on every place. If the lighting device is turned on for a certain period of time after the drying is completed, the inside of the tableware collection tank 136 can be illuminated. Purify for better results.

The door 137 is a molded product of PP resin. After corona discharge treatment, the bottom layer of sample No.12 is first formed. After the film is formed, the low-temperature curing high-activity oxide light of sample No.21 is formed. catalyst film.

The effect of the photocatalyst thin film on the surface of the door 137 is the same as that of the external parts of the aforementioned embodiments 1 to 6, and sufficient antifouling and antibacterial effects can be obtained by using indoor light. In this example, a built-in dishwasher was described, but the same effect of the photocatalyst film can also be obtained in a table-top dishwasher. If the dishwasher is table-top, it is effective to form a photocatalyst film on the surface of the outer wall member on the side or top because the light in the room is irradiated in front of the outer wall member.

(Embodiment 8)

Referring to Fig. 15 and Fig. 16, a description will be given of a kitchen waste disposer as Embodiment 8 of the present invention.

Fig. 15 is a side view of the appearance of the kitchen garbage disposer, and Fig. 16 is a sectional view of the main body.

The center of the frame 160 has a freely rotatable agitating wing 161, and a treatment tank 164 equipped with a waste input port 163 is provided on its upper part, and a culture substrate 165 is inserted therein. The culture substrate 165 is a material formed by cutting sawdust, rice husk, and straw, which are mainly composed of cellulose that is difficult for microorganisms such as lignin to decompose. There are also large gaps between the grains.

Three stirring blades 161 are housed on the rotating shaft 166, supported by bearings 167 arranged in the treatment tank 164, and one side protruding rotating shaft end is connected with the motor 168 by transmission means 169 such as chains with appropriate reduction ratio. The upper opening 170 of the treatment tank 164 is provided with an inner cover 171 which can freely open and close the upper mold plate 172 . In addition, a ventilating fan 173, an air inlet 174 and an exhaust port 175 are also provided near the upper part of the treatment tank 164, and the gas and moisture decomposed in the treatment tank 164 are discharged from the exhaust port 175 by the rotation of the ventilating fan 173. In addition, filters with meshes of appropriate size are respectively provided on the air intake port 174 and the exhaust port 175 .

In addition, a switch cover 176 for the suction port 174 is also provided, which opens or closes the suction port 174 by the reciprocating motion of the electromagnetic coil 177 provided on the frame 160 . In addition, the upper template 172 is provided with an operation part 178 for controlling the operation, and the operation part controls the operation of the controller 179 to make the kitchen garbage disposer operate.

After a few months, the culture substrate 165 is filled with decomposed substances and the porosity of the culture substrate 165 is reduced, and the waste cannot be processed any more, so it needs to be replaced. To this end, a discharge port 180 and a discharge channel 181 are provided at the bottom of the treatment tank 164 , and the culture substrate 165 entering the discharge channel 181 can be discharged from the frame 160 .

In addition to moisture, the air in the gap at the top of the culture substrate 165 of the treatment tank 164 also contains a large amount of decomposition gas, such as very smelly gases such as trimethylamine, methyl mercaptan, ammonia, and hydrogen sulfide. Because the odor is very strong, in the past, the kitchen garbage disposer was not placed in the kitchen, but placed on the balcony of the residential area, but even so, the odor will still permeate.

Conventional deodorization methods use adsorbent materials such as activated carbon or manganese-based thermal decomposition catalysts, etc., but these are not ideal because they are not effective or have a short lifespan.

In this embodiment, exhaust filters 182 and 183 are provided at the exhaust port 175, and an ultraviolet lamp 184 is provided in the gap between them. Exhaust filter 182 is mainly composed of zeolite, and exhaust filter 183 is mainly composed of activated carbon, so they all have a honeycomb structure, and the ultraviolet rays emitted by the ultraviolet lamp 184 can irradiate the inside of the honeycomb structure. The low-temperature curing type highly active oxide photocatalyst film of sample No. 62 shown in Table 5 was formed on the inner surface of the honeycomb structure of the exhaust filters 182 and 183 .

The decomposition efficiency of the low-temperature curing type highly active oxide photocatalyst thin film of the present invention is higher, and in the application that organic load is less like aforementioned embodiment 1～7, utilize indoor lighting device level, promptly wavelength is 250～350 (nm) Ultraviolet light with a brightness of 0.001-0.01mW/cm ² , or fluorescent lamps and incandescent lamps with a brightness of 0.01-0.1mW/cm ² can decompose organic matter, but as shown in this example, if the concentration of ammonia gas is several ppm In the case of such a high load, it is necessary to install an ultraviolet emitting device.

Generally, ultraviolet lamps such as mercury lamps or metal halide lamps can be used, but the decomposition efficiency of the present invention is higher than that of the previous oxide photocatalysts, so the deodorizing effect is better, and the requirements for the intensity of ultraviolet rays are also higher than those using the previous oxide photocatalysts. The situation is low. When the input garbage is most actively decomposed, that is when the above-mentioned malodorous substances are produced the most.

Since the decomposition of rubbish is generally most active during the period of 1 hour to 8 hours after being put in, the service life of the lamp can be extended if the UV lamp 184 is turned on in a timely manner. Exhaust filter 183 is mainly composed of activated carbon. When the odor concentration is small, the odor can be adsorbed in the above-mentioned activated carbon, but with the increase of the adsorption amount, the adsorption efficiency will gradually decrease. Therefore, regular irradiation of ultraviolet rays will make the adsorption Decomposes the malodorous substances and regenerates the activated carbon.

In addition, the frame 160 is made of painted steel plate, and the outer cover 171 is an injection molded product of PP resin, and its surface is coated with a vinyl chloride organic coating film. photocatalyst thin film.

The effect of the photocatalyst film on the surface of the outer frame 160 and the outer cover 171 is the same as that of the outer parts of the aforementioned embodiments 1-7, that is, sufficient antifouling and antibacterial effects can be obtained by using indoor light. Especially when garbage is processed by a kitchen garbage disposer, the sewage generated by the garbage often pollutes external parts, so the antifouling effect of the low-temperature curing type highly active oxide photocatalyst film of the present invention is better. When the kitchen garbage disposer is placed outdoors, the external parts are irradiated by sunlight, and the ultraviolet light with a wavelength of 250-350 (nm) has a brightness of 0.1-5.0mW/cm ² , which is stronger than indoor lighting and can also Sewage from decomposing garbage.

Covering bodies such as various thermoplastics formed in the above-mentioned Examples 1 to 8, passages for the air flow generated by the motor, filtering devices such as filters provided in the passages, and external parts that are irradiated with external light such as indoor lighting devices , The ratio of the low-temperature curing high-activity oxide photocatalyst film installed on the surface of the component irradiated by the light of the lighting device inside the device, as well as the curing conditions of the film and the characteristics of each ratio composition, etc., will be implemented in the following Examples 9 to 16 will be described.

(Example 9)

A solution in which _TiO2 microparticles were dispersed in _SiO2 sol was prepared. This solution was used to form a _TiO2 film on a PET film to produce the PET film of Figure 17. The following is the operation process.

First, the preparation method of SiO ₂ sol will be described. Dissolve 5g of tetraethoxysilane in a mixed solution of 100ml of water-ethanol-propanol (3:27:70), stir at 40°C for about 5 hours, and then place the resulting solution at room temperature for 2 weeks to become SiO ₂ sol.

Next, a method for preparing a solution in which TiO ₂ fine particles are dispersed in SiO ₂ sol will be described. First, TiO 2 fine particles were added to the obtained SiO ₂ sol at a weight ratio of TiO ₂ /SiO ₂ =9, and then a necessary amount of water was added to _adjust the solid content concentration to 4 wt%. Next, in order to disperse the TiO ₂ fine particles in the SiO ₂ sol, ?5mm zirconia balls were passed through a ball mill for 24 hours, thus preparing a solution in which the TiO ₂ fine particles were dispersed in the SiO ₂ sol.

Then, on the PET film 185, the SiO ₂ sol dispersed with TiO ₂ particles prepared above was coated, and irradiated with a low-pressure mercury lamp (intensity: 15 mW/cm ² ) at 120° C. for 5 minutes to form a SiO ₂ film 186 coated on the PET film 185. A plastic film of a SiO ₂ film 188 in which TiO _{2 particles are dispersed in TiO 2 particles} 187 . The film quality and strength of the thin film formed on the PET film 185 were good, and its film thickness was 300 nm.

The organic matter decomposition activity of titanium oxide was evaluated. In the activity test, a magenta-based organic pigment was coated on a film, and then irradiated at 254 nm with a light intensity of 1 (mW/cm ² ). The decomposition rate can be obtained from the amount of change in the initial dye transmittance. Figure 20 shows the above test results.

In the figure, in addition to the _TiO2 dispersed _SiO2 film, the results of no film and _SiO2 film are shown for comparison. In the case of the SiO ₂ film without TiO ₂ dispersion and the SiO ₂ film, there was almost no change in the amount of the pigment, and in the case of the SiO ₂ film with TiO ₂ dispersed, about 45% of it was decomposed after 30 minutes.

In this way, a PET film coated with a SiO ₂ film in which TiO ₂ having a photocatalytic action is dispersed can be produced. The film-forming method of the present invention can be performed at about 120°C, and can be used for plastic materials other than borosilicate glass substrates. Because the general sol-gel method needs a temperature of about 400°C, it is difficult to be used in plastic products, and the crystallization of _TiO2 also needs more than 10 minutes, but the preparation method of the present invention can form a film at a low temperature, Therefore, there are many substrates that can be used, and photocatalyst films can be formed on the surface of any material. In addition, the film formation time is as short as a few minutes, so the production cost can be greatly reduced.

Then, in order to improve the photocatalyst performance, an auxiliary catalyst can be added. That is, various nitrates were added to the solution in which TiO ₂ fine particles were dispersed in the SiO ₂ sol prepared above, and then a film was formed on a PET film, and the decomposition reaction of the pigment was carried out. The results are shown in Table 1.

The addition effect of table 1 additive Sample No. Additives Amount added (wt%) TiO ₂ /SiO ₂ (weight ratio) Decomposition rate after 10 minutes (wt%) 1 _NaNO3 5 9 70 2 LiNO ₃ 5 9 100 3 Mg(NO ₃ ) ₂ 5 9 50 4 Ca(NO ₃ ) ₂ 5 9 40 5 Sr(NO ₃ ) ₂ 5 9 30 6 Ba(NO ₃ ) ₂ 5 9 20 7 Al(NO ₃ ) ₃ 5 9 0 8 Fe(NO ₃ ) ₃ 5 9 0 9 Zn(NO ₃ ) ₄ 5 9 35 10 Zr(NO ₃ ) ₄ 5 9 5 11 - - 9 25 12 - - 0(SiO ₂ ) 0

It can be seen from Table 1 that the photocatalysts added with Na, Li, K, Mg, Ca, Sr, and Zn are effective, while Fe and Al are deactivators.

Fig. 21 is a graph showing the effect of electronegativity and the addition of a co-catalyst. It can be seen from the figure that the smaller the electronegativity, the better the effect, especially when Li, Na, and Mg are added. It can be seen that in addition to electronegativity, the ionic radius is also very important. Figure 22 shows the relationship between electronegativity, ionic radius and the effect of addition. It can be seen from the figure that if the electronegativity of the element is less than 1.6 and the ionic radius is less than 0.2nm, adding ions whose valence number is below 2 will be effective .

(Example 10)

Several solutions of _TiO2 particles with different particle sizes dispersed in _SiO2 sol were prepared. The weight ratio of TiO ₂ /SiO ₂ is 9, and Li addition is 5wt%. Operate in the same way as in Example 1, form a SiO ₂ film dispersed with TiO ₂ on the PET film, and then use an organic pigment to detect the decomposition rate after 10 minutes .

Table 2 Pigment decomposition rate corresponding to _TiO2 particle size Sample No. Li addition amount (wt%) TiO ₂ /SiO ₂ (weight ratio) TiO ₂ particle size (nm) Decomposition rate after 10 minutes (wt%) 13 5 9 2 40 14 5 9 5 86 15 5 9 8 94 16 5 9 10 100 17 5 9 20 100 18 5 9 30 65

Table 2 shows various conditions and test results of the prepared samples. From the above results, it can be seen that the dispersed _TiO2 particles are most effective when the particle size is 8-10 nm. The decomposition rate also varies with different particle sizes. If the ratio of TiO ₂ /SiO ₂ becomes smaller, the optimum particle size of TiO ₂ particles will also change. The range is 5-20nm, and the decomposition rate at this time is ideal. Therefore, it is best when the radius of the TiO ₂ particles to which the Li catalyst is added is 5-20 nm. In addition to Li, Na, K, Mg, Ca, Sr, and Zn can also obtain the same results.

(Example 11)

Table 3 shows the state of the pigment decomposition rate (decomposition rate after 10 minutes) and film strength when the amount of Li added, TiO ₂ /SiO ₂ changes. The preparation method of the solution and the method of film formation are the same as in Example 1. From these results, it can be seen that the effective conditions for both the decomposition rate and the film strength are 0.5 to 20 wt % of Li addition and 9 to 5 TiO ₂ /SiO ₂ .

Table 3 Corresponding to the amount of Li added, the pigment decomposition rate of TiO ₂ /SiO ₂ Sample No. Li addition amount (wt%) TiO ₂ /SiO ₂ (weight ratio) Decomposition rate after 10 minutes Membrane strength 19 0 9 25 ○ 20 1 9 90 ○ twenty one 5 9 100 ○ twenty two 10 9 100 ○ twenty three 20 9 100 ○ twenty four 50 9 65 x 25 0 8 25 ○ 26 1 8 88 ○ 27 5 8 100 ○ 28 10 8 100 ○ 29 20 8 100 ○ 30 50 8 60 x 31 0 6 25 ○ 32 1 6 86 ○ 33 5 6 100 ○ 34 10 6 100 ○ 35 20 6 100 ○ 36 50 6 60 x 37 0 4 15 ○ 38 1 4 15 ○ 39 5 4 20 ○ 40 10 4 20 ○ 41 20 4 20 ○ 42 50 4 15 ○

Table 4 shows the pigment decomposition rate and film quality when TiO ₂ /SiO ₂ and film thickness were changed. The preparation of the solution and the method of forming the film are the same as in Example 1, and the film thickness is adjusted within the limit of the concentration of solid components in the solution within the range of 0.5-8 wt%.

As a result, when the film thickness is 100 to 500 nm, the decomposition rate and film quality are not affected by the TiO ₂ /SiO ₂ ratio, which is good.

In addition to Li, Na, K, Mg, Ca, Sr, and Zn can also obtain the same results as above.

Table 4 Pigment decomposition rate corresponding to TiO ₂ /SiO ₂ ratio and film thickness Sample No. Li addition amount (wt%) TiO ₂ /SiO ₂ (weight ratio) Film thickness (nm) Decomposition rate after 10 minutes (wt%) membranous 43 10 9 50 80 good 44 10 9 100 92 good 45 10 9 300 100 good 46 10 9 500 100 good 47 10 9 600 100 bad 48 10 8 50 60 good 49 10 8 100 74 good 50 10 8 300 100 good 51 10 8 500 100 good 52 10 8 600 100 bad 53 10 6 50 20 good 54 10 6 100 35 good 55 10 6 300 100 good 56 10 6 500 100 good 57 10 6 600 100 good

(Example 12)

Table 5 shows the measurement results of pigment decomposition rates when oxide semiconductors other than TiO ₂ , such as ATO, ITO, ZnO, Fe ₂ O ₃ , and Cr ₂ O ₃ fine particles, were added. When performing the test for measuring the pigment decomposition rate, the intensity of the ultraviolet lamp (254 nm) was 0.2 mW/cm ² . In addition, unless otherwise specified, the pigment decomposition test after this example was also carried out under the above-mentioned conditions. As a result, it is effective to add fine particles of ATO, Fe ₂ O ₃ , and Cr ₂ O ₃ , and the addition amount is not limited, but 10 to 20 wt % is most effective. The electron affinity of each oxide constituent element is as follows, and an oxide semiconductor using a constituent element having an electron affinity of 1.2 eV or more is effective.

Table 5 Pigment decomposition rates corresponding to various oxide semiconductor additions Sample No. Li addition amount (wt%) TiO ₂ /SiO ₂ (weight ratio) Addition amount of oxide (wt%) Decomposition rate after 10 minutes (wt%) 58 10 9 - 65 59 10 9 ATO(1.0) 68 60 10 9 ATO(5.0) 72 61 10 9 ATO(10.0) 80 62 10 9 ATO(20.0) 82 63 10 9 ATO(50.0) 73 64 10 9 ITO(1.0) 55 65 10 9 ITO(5.0) 50 66 10 9 ITO(10.0) 42 67 10 9 ITO(20.0) 38 68 10 9 ITO(50.0) 33 69 10 9 ZnO(1.0) 62 70 10 9 ZnO(5.0) 56 71 10 9 ZnO(10.0) 48 72 10 9 ZnO(20.0) 42 73 10 9 ZnO(50.0) 35 74 10 9 _Fe2O3 ( _1.0 ) 66 75 10 9 _Fe2O3 ( _5.0 ) 68 76 10 9 _Fe2O3 ( _10.0 ) 70 77 10 9 _Fe2O3 ( _20.0 ) 71 78 10 9 Cr ₂ O ₃ (50.0) 72 79 10 9 Cr ₂ O ₃ (1.0) 65 80 10 9 Cr ₂ O ₃ (5.0) 67 81 10 9 Cr ₂ O ₃ (10.0) 69 82 10 9 Cr ₂ O ₃ (20.0) 73 83 10 9 Cr ₂ O ₃ (50.0) 48

Elements Ti Sn In Zn Fe Cr

Electron affinity (eV) 1.25 1.2 0.2 -1.2 3.16 3.54

When the electron affinity of the oxide semiconductor is lower than that of Ti, a Schottky barrier is formed on the particle surface of the fine particles, so that the carrier added with the oxide semiconductor cannot be implanted into TiO ₂ , and the effect cannot be exhibited. In this case, when the electron affinity of the oxide semiconductor is lower than that of Ti, the Schottky barrier is not formed at the particle interface of the particle, but a resistive junction is formed, so that the carrier of the oxide semiconductor can be easily implanted into TiO ₂ , thus effectively functioning. Particularly effective is ATO, whose electron affinity is slightly smaller than that of TiO ₂ , but which has almost no difference in action and can exhibit improved performance. This is because the carrier concentration of ATO as a conductive oxide is high, and a large number of carriers of ATO can be injected into _TiO2 , thereby improving the activity of the photocatalyst. Furthermore, when the above-mentioned oxide semiconductor is added, the effect of adding Li will also increase.

In addition, as a method of effectively utilizing a carrier having an oxide semiconductor, in addition to adding fine particles, a stacking method may also be employed. Table 6 shows the test results when the TiO ₂ /SiO ₂ film and the ATO film were laminated. The results proved that stacking works. Moreover, if Li is added to both of the above-mentioned films, the performance can be further improved. In addition, multiple alternate laminations are also effective.

Table 6 Decomposition rate of ATO laminated film Sample No. Tier 1 Li addition amount (wt%) layer 2 Li addition amount (wt%) Decomposition rate after 20 minutes (wt%) 84 TiO ₂ /SiO ₂ =9 0 ATO 0 45 85 TiO ₂ /SiO ₂ =9 5 ATO 5 70 86 TiO ₂ /SiO ₂ =9 10 ATO 5 75 87 TiO ₂ /SiO ₂ =9 20 ATO 5 73

(Example 13)

A solution in which TiO ₂ microparticles with a particle diameter of 5 nm were dispersed in SiO ₂ sol was prepared, and 2 wt % of Ag, Pt, Pd, Rh, Ni, Cu, and RuO ₂ microparticles were added thereto corresponding to TiO ₂ . The weight ratio of TiO ₂ /SiO ₂ was 9. Using the SiO sol dispersed with TiO ₂ prepared above and adding Ag and _{RuO 2} particles, operate in the same manner as in Example 1 to form Ag, Pt, Pd, Rh, Ni, Cu, RuO ₂ particles on the PET film. The SiO ₂ films dispersed with TiO ₂ were used to measure the decomposition characteristics of organic pigments. The results are shown in Table 7. By adding Ag, Pt, Pd, Rh, Ni, Cu, and RuO ₂ fine particles, the decomposition rate was greatly improved.

Table 7 corresponds to the pigment decomposition rate of adding precious metals Sample No. Li addition amount (wt%) TiO ₂ /SiO ₂ (weight ratio) Amount of precious metal added (wt%) Decomposition rate after 20 minutes (wt%) 88 10 9 Pt(0.5) 74 89 10 9 Rh(0.5) 72 90 10 9 Pd(0.5) 75 91 10 9 Ag(0.5) 78 92 10 9 Cu(0.5) 76 93 10 9 Ni(0.5) 68 94 10 9 Ru(0.5) 75 95 10 9 -(0) 65

(Example 14)

Irradiate with fluorescent lamps, sunlight, incandescent lamps, and mercury lamps, and compare the decomposition effects of the photocatalysts prepared in Example 1 with Li added and those without Li added on cigarette smoke, acetaldehyde, urea, and coliform bacteria. The results are shown in Table 8. The photocatalyst to which Li was added was 3 to 5 times more effective in decomposing cigarette smoke, acetaldehyde, urea, and coliform bacteria than the photocatalyst to which Li was not added, no matter which lighting tool was used. The catalyst to which Li is added can obtain a sufficient effect not only under the irradiation of an ultraviolet lamp, but also by using a lamp in daily life environment. In addition, addition of Na, K, Mg, Ca, Sr, and Zn in addition to Li can also obtain the same effect.

Table 8

    Test results of decomposition of organic matter by various lamps

(Decomposition rate ratio when 10 wt% Li is added/when Li is not added) cigarette smoke Acetaldehyde urea coliform bacteria Pigment (AcId Red) fluorescent light 3 3 3 3 3 sunshine 5 5 5 5 5 black light 5 5 5 5 5 incandescent lamp 3 3 3 3 3 mercury lamp 4 4 4 4 4

(Example 15)

If the Li-added TiO ₂ -dispersed SiO ₂ film prepared in Example 1 was directly formed on the PET film, the photocatalytic action would affect the PET film as the substrate. Therefore, when coating the Li-added TiO ₂ -dispersed SiO ₂ film prepared in Example 9, an additional SiO ₂ film was provided between it and the PET film. In addition, a sample was prepared in which a component that can deactivate the photocatalyst was added to the SiO ₂ film, such as Al, Fe, Zr nitrate, or ATO was added to the SiO ₂ film dispersed with Li and TiO ₂ Samples for various tests. The results are shown in Table 9.

Table 9

Pigment decomposition test and durability test results of SiO ₂ laminated film

(TiO ₂ /SiO ₂ =9, Li(wt%)=10) Sample No. ATO (wt%) SiO ₂ (wt%) Added elements (wt%) Decomposition rate after 20 minutes (wt%) Peeling condition after 10 days (result of test with adhesive tape) Dust attached 96 0 none none 65 Yes (×) have 97 20 none none 82 Yes (×) none 98 0 have none 65 None (×) have 99 0 have Al(5) 65 None (○) have 100 0 have Fe(5) 66 None (○) have 101 0 have Zr(5) 65 None (○) have 102 20 have Al(5) 83 None (○) none 103 20 have Fe(5) 82 None (○) none 104 20 have Fe(5) 82 None (○) none

As a result of the test, if a layer of SiO 2 film was placed between the SiO ₂ film in which Li was added and TiO ₂ dispersed and the PET film, peeling of the film _could be prevented even after long-term use. Moreover, the addition of Al, Fe, and Zr can completely deactivate the photocatalyst, so that the adhesive strength can be effectively maintained. In addition, the film added with ATO can increase the anti-static effect, and can inhibit the adsorption of dust, etc., so that it can not only decompose organic matter, but also prevent the adhesion of inorganic matter, so as to obtain a film with better antifouling effect.

The low-temperature curing type highly active oxide photocatalyst thin film formed according to the proportion shown in the foregoing embodiments 9 to 16 is applied to the various articles with the use of the motor to generate the air flow device shown in the embodiments 1 to 8, and its specific effect The evaluation results are summarized below. First, the effect of the low-temperature-curable highly active oxide photocatalyst thin film of the present invention when used in a filter device installed in an air passage is summarized.

A typical pollutant in indoor air is cigarette smoke. Cigarette smoke is floating tar-like substances and soot particles. These particles form a film and accumulate on the filter, and the filter is gradually polluted and colored into a brown color. The pollution from cigarette smoke is assessed below. Paste the polyester fiber non-woven fabric film that area is 10cm * 10cm on the front of the ventilating fan suction side of 5 (m ³ /min) in air volume, and fix. The ventilating fan on which the nonwoven fabric was pasted was placed in a container with a capacity of 45,000 (cm ³ ) and sealed. Simultaneously, a cigarette smoke generating device is placed in the container. In this cigarette smoke generator, a tube is attached to the filter side of the lit cigarette, and the tube is connected to a diaphragm pump. The diaphragm pump is driven with an air volume of 1,800 (cm ³ /sec), and if the pressure at the cigarette side nozzle drops, the cigarette smoke that has passed through the filter will be discharged from the outlet of the pump. It takes about 1.5 minutes to light a cigarette. If the smoke generating device and the ventilating fan in the container constituted as above are operated, the gas discharged from the ventilating fan is also discharged into the same container, so the cigarette smoke filling the container will pass through the nonwoven filter part many times. After lighting 5 cigarettes continuously and operating the ventilation fan for 10 minutes, the container was opened, and the nonwoven fabric was taken out as a sample. The fiber surface of the nonwoven fabric filter forms the low-temperature curing type highly active oxide photocatalyst film of the present invention. The preparation method is as described in Example 9. In embodiment 9, the PET film is used as the object, and in this embodiment, lithium nitrate is added to the solution in which _TiO particles are dispersed in the SiO _sol , and then the non-woven fabric filter that has been subjected to surface oxidation treatment in the ozone atmosphere is soaked. In it, the filter was taken out after 1 minute, and the unnecessary solution was evaporated by blowing air, and then irradiated with a low-pressure mercury lamp (intensity: 15mW/cm ² ) at 120°C for 5 minutes to cure the film and form light on the surface of the fiber. catalyst film. The composition of this film was Sample No. 2 in Table 1.

The above-prepared samples were irradiated with light from a fluorescent lamp to evaluate the degree of decomposition of the adsorbed pollutants, and the color change of the nonwoven fabric filter was evaluated with a color difference meter (Nippon Denshoku Kogyo Co., Ltd.: Z-1001DP). Taking the color difference of the pollution state before illumination as 100%, and the color difference before no pollutants are adsorbed as 0%, the antifouling effect of the pollution caused by cigarette smoke was evaluated. As a comparison, the film in which only TiO ₂ particles were dispersed in SiO ₂ was used as sample No. 11, and the film containing only SiO ₂ particles without TiO ₂ was used as sample No. 12, and a thin film was formed on the surface of the filter fiber in the same way. Evaluate.

The results are shown in Figures 23 and 24. Fig. 23 shows the results of evaluating the degree of contamination of the filter based on the color difference over time when the smoke filter passing test was performed under the same conditions. Compared with untreated polyacrylonitrile fibers, in the case of attaching a glassy oxide photocatalyst film containing TiO ₂ and SiO ₂ components, about 50% of them changed color quickly, that is, the smoke collection efficiency was improved. About 50%. Fig. 24 is a photo of a filter that has absorbed smoke under the above conditions and turned brown under the above-mentioned conditions by irradiating light from a fluorescent lamp, decomposing the attached matter using a photocatalyst, and evaluating the change of the color of the filter that has changed back to its original color by measuring the color difference over time. degree. The cumulative light quantity in the figure is represented by the cumulative value when irradiated with light having a wavelength of 250 to 350 nm. Sample No.12 in the figure is a film containing only SiO ₂ without TiO ₂ , which has almost no decomposition and decolorization effect. Sample No. 11 and Sample No. 2 contain the same amount of TiO ₂ , although both are effective, but Sample No. 2 is the formula of the present invention with LiNO ₃ added, and its decolorization speed is greatly improved. Especially in the initial stage, its decomposition efficiency was more than 2 times that of the membrane without _LiNO3 added. When it is actually used in an air purifier or ventilation fan, etc., the initial decomposition speed is important because a small amount of pollution is attached and it is irradiated by indoor light. As the amount of pollutants attached increases, the light is blocked by the pollutants and cannot reach the photocatalyst film of the fiber film, so the decomposition efficiency decreases. Therefore, it is very important to decompose pollutants before they accumulate thickly.

In order to make the filter adhere to the same level of pollution as in this test using the above-mentioned device in the actual living environment, the above-mentioned ventilation fan was used in an airtight 6 seats (about 20m ² ), and then 20 cigarettes were lit, and the ventilation fan was operated for 120 Minutes later the amount of contamination is the same as in this test.

The following are the evaluation results of the deodorizing effect when the low-temperature curing type highly active oxide photocatalyst thin film of the present invention is used in a filter device installed in an air passage. The effect of removing ammonia gas, which is a representative malodorous substance, was evaluated. The study was carried out with the same composition as the above-mentioned cigarette smoke, but a certain amount of ammonia gas was introduced into the container to replace the cigarette smoke generating device, and after adjusting the concentration of ammonia gas in the container to 25 (ppm), the low-temperature solidification was formed in the container. The ventilation fan of the nonwoven fabric of the highly active oxide photocatalyst film is activated. First, the initial adsorption effect of ammonia gas on the same glassy oxide photocatalyst thin film used for smog trapping was measured, and the results are shown in FIG. 25 . When using untreated polyacrylonitrile fibers, more than 90 (%) of ammonia gas remains after 1 hour, and when using glassy oxide photocatalyst films containing _TiO2 and _SiO2 , ammonia gas is destroyed after 1 hour More than 50 (%) is removed by adsorption, which proves that the photocatalyst film can not only trap smog, but also adsorb ammonia.

After the ammonia gas is saturated and adsorbed, the incandescent light bulb placed inside the container is turned on, so that the light shines on the surface of the filter. Measure the ammonia gas concentration in the container over time to evaluate the decomposition effect of ammonia gas. The result is shown in FIG. 26 .

When using the filter of sample No. 12 that does not contain TiO ₂ , there is little change in the concentration. However, when using sample No.2 containing TiO ₂ , the concentration of ammonia gas decreased with the irradiation of light, which indicated that it had been decomposed. No.2 is the formulation of the present invention mixed with LiNO ₃ , which greatly improves the decomposition efficiency. Compared with sample No.11, its decomposition efficiency is about 3 times.

The above-mentioned antifouling and deodorizing effects are explained by using examples of air cleaners and ventilating fans. Of course, the same effects can be exhibited on filters of various other items with the same structure.

Next, specific effects when used in the exterior parts of various articles shown in Examples 1 to 8 were evaluated, and the results are summarized as follows. As a sample, it is preferable to use thermoplastic ABS plastic for injection molding (Technopolima Corporation: Taflex 451, white colored product) used for exterior parts. A plate-like molded article of 5 cm x 5 cm was produced, and the surface thereof was subjected to corona discharge treatment. A low-temperature curing type highly active oxide photocatalyst thin film having the composition of Sample No. 86 shown in Table 6 of Example 12 was formed on the corona discharge-treated surface. For comparison, the film of sample No. 11 in which only TiO ₂ particles were dispersed in SiO ₂ in Table 1 and the film of sample No. 12 in which only SiO ₂ was contained without TiO ₂ particles were formed on the surface of the formed plate, to evaluate. First, the initial cigarette smoke pollution was evaluated in the same manner as above. Examination was conducted with the same configuration as the aforementioned nonwoven fabric filter test. A 5 cm x 5 cm ABS plate was fixed in the center where the filter portion was installed, and after 10 cigarettes were lit, the ventilation fan was operated for 120 minutes, and the white ABS was stained brown. This ABS plate was taken out, it was irradiated with the light of various conditions similar to the above, and the removal rate was evaluated by measuring the color difference before and after. The result is shown in FIG. 27 .

As a result, almost the same result as the filter is obtained, but since the attached dirt itself is less than the case of using the filter, the same degree of decolorization effect can be obtained with half the amount of light. In addition, in sample No.86, in addition to LiNO ₃ , ATO components were also added, and compared with sample No.11, a more ideal decomposition efficiency could be obtained.

The following are the results of an evaluation of the antifouling effect on articles used in an environment with a lot of oily fume, such as a kitchen, on stains caused by oils and fats. Formed on the 5cm * 5cm glass plate of the 5cm * 5cm glass plate of the sample No.86 shown in the table 6 of embodiment 12, the low-temperature curing type highly active oxide photocatalyst film is coated with a thin layer of salad oil with a thickness of about 5 (μm). The time-dependent change of the oil weight was measured under ultraviolet light irradiation, and the results are shown in FIG. 28 . As a result, sample No. 12, which did not contain TiO ₂ , had almost no change in weight. And containing TiO ₂ sample No.11 and No.2 along with light irradiation, grease is decomposed volatilization, so weight reduces to some extent, but No.2 is owing to have used the formula that has mixed _LiNO of the present invention, so its The decomposition efficiency has been greatly improved, and compared with sample No.11, its decomposition efficiency is about 2 times.

Including the above series of embodiments, when forming the low-temperature curing type highly active oxide photocatalyst film of the present invention, in order to improve the adhesion between the film and the underlying material, various methods can be used. As a method of using a primer, various coupling agents can be applied in advance, and then a photocatalyst film can be formed.

The following are examples of silane coupling agents and organotitanium compounds.

Silane coupling agents include vinyl tris (β methoxyethoxy) silane, vinyl triethoxy silane, vinyl trimethoxy silane, γ-(methacryloxypropyl) trimethoxy silane, β (3,4 Epoxycyclohexyl)ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, N- β(aminoethyl)γ-aminopropyltrimethoxysilane, n-β(aminoethyl)γ-aminopropylmethyldimethoxysilane, γ-aminopropyltriethoxysilane, N-benzene Base-γ-aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, etc.

The organic titanium compound can use titanium ester, titanium acylate, titanium chelate, especially effective is tetraisopropoxytitanium, tetra-n-butoxytitanium, tetrakis (2-ethylhexyloxy)titanium, diisopropoxytitanium, Propoxy bis(acetylacetonate)titanium, isopropoxycaprylyl titanate, titanium stearate, and the like.

In addition, it is also effective to use various surface modification means to oxidize the surface of the object to introduce groups such as hydroxyl, carbonyl, and carboxyl, so that the low-temperature curing type high-activity oxide photocatalyst film of the present invention can be firmly combined. .

Specifically, there are methods such as ultraviolet irradiation, electron beam irradiation, corona discharge treatment, and treatment in an ozone atmosphere. When using hydrophilic resins such as polyamide resins and polyester resins, ideal adhesion can be obtained without the above pretreatment, while for polyolefin resins and highly crystalline resins, the above pretreatment It is effective.

In the present invention, it is effective to mix both Ag and Cu as the additive component for enhancing the photocatalytic activity as described above. This can not only reduce the electrical insulation of the membrane itself, prevent electrification, but also obtain the effect of inhibiting the reproduction of microorganisms. It is well known that Ag and Cu ions have antibacterial properties, especially strong resistance to bacteria. When Ag and Cu are used together, they can inhibit the reproduction of microorganisms even if they are not irradiated with light.

The application range of the present invention is not limited to the devices described in the specific examples above. That is, the principle of the present invention is to promote the polymerization of inorganic polymers by irradiation of electromagnetic waves of specific wavelengths such as ultraviolet _rays . Inorganic thin film of photocatalyst composed of various components; by adding various components, the reactivity of the photocatalyst mainly composed of _TiO2 is increased several times, so that the surface of the coating film of thermoplastic, thermosetting plastic or plastic material used in large quantities has photocatalytic effect . Utilizing this principle, organic matter is decomposed on the surface of materials with poor heat resistance that cannot be used conventionally with a light intensity that is weaker than conventional ones. In addition, by adding semiconductor or conductive particles that can reduce the surface resistance of the film itself, the effect of preventing the surface of the coating film from being charged can be obtained, and the dirt adsorbed by static electricity can be reduced.

In the present invention, the light irradiated on the surface of the member on which the photocatalyst thin film is formed includes light from fluorescent lamps, incandescent bulbs, mercury lamps, sunlight, etc., and these lights do not necessarily have to be directly irradiated. That is, it is effective as long as the irradiated light can pass through a member made of a transparent material such as transparent plastic or glass. For example, template 2, frame 4, front cover 16, template 18 in the air cleaner of Figures 1 to 3; frame 29 in the ventilation fan of Figure 4; upper cover 52, Middle cover 53, grille cover 54, suction inlet part 65, exhaust ventilation part 76; switch cover 86 and cloth filter device 99 in the clothes dryer of Fig. 8; tableware dryer of Fig. 9 to Fig. 11 The door 121, the exhaust port 128, and the suction port 117; the door 137, the exhaust port 152 in the dishwasher in Figures 12 to 14; the inner cover 71, There are air filter materials on the suction port 174, exhaust port 175 and other parts, and the parts arranged around them are thermoplastic moldings. Since these parts are transparent, light can shine into them and decompose the dirt inside. , deodorization and sterilization.

The most ideal transparent plastics are PMMA, AS, PC, ABS, PVC, poly-4-methylpentene-1 (TPX) and the like.

In addition, the above-mentioned transparent plastic materials can also be colored by mixing pigments and dyes. However, when coloring, yellow, red, or green absorb short-wavelength light and reduce the decomposition effect, so it is not good. For coloring, blue or black (smoky gray) is preferable.

The inventors of the present invention clarified the relationship between the color of the transparent member and the decomposition efficiency of the photocatalyst as a result of earnest research. The color of the transparent member discussed below is defined in accordance with the Hunter, Lab method shown in JIS-Z-8730. That is, the L value represents the degree of black and white without color (brightness); the a value represents the degree of red and green; the b value represents the degree of blue and yellow.

The larger the L value, the better. In terms of color, compared with other colors, yellow-based transparent parts will absorb a large amount of short-wavelength light useful for the decomposition reaction of photocatalysts, reducing the decomposition rate, that is, the smaller the b value in the Lab method, the better, and the a value Preferably within a certain range.

The results of evaluating the relationship between the above color and decomposition efficiency are shown in FIG. 29 . Using the PMMA resin as the primer and color-coated plates colored by various dyes, under the same conditions as the test in Figure 24, 5 cigarettes were lit to measure the decolorization and decomposition rate of the cigarette smoke attached to the filter. The photocatalyst material used is sample No.2 in Table 1, the PMMA resin is Acrypet MD produced by Mitsubishi Viscose Co., Ltd., and the thickness of the color-coated plate is 2.0 (mm). This resin is a resin added with an ultraviolet absorber, which absorbs ultraviolet rays around 360 (nm). The decomposition rate in Fig. 29 is based on the decolorization rate calculated from the change in color difference after irradiating the polluted filter with a 40-watt fluorescent lamp for 20 hours at a distance of 2 (m). Place each color-painted plate as a sample on the contaminated filter, and after irradiating with a fluorescent lamp, calculate the decomposition rate according to the degree of decolorization. In a standard actual smoking environment, if a decomposition rate of 40 (%) or more can be obtained by using this condition test, the accumulation of pollution such as smoke can be suppressed and continuous use can be achieved.

As a result of the test, under the condition that the L value is +50 or more, the a value is in the range of -20 to +20, and the b value is +20 or less, a decomposition rate of 40 (%) or more can be obtained.

This test was performed in accordance with JIS-Z-8730 (color difference expression method), and the measuring instrument used was Z1001DP manufactured by Nippon Denshoku Kogyo Co., Ltd. based on JIS-Z-8722. The measurement sample is the transmitted light of a 2.0 (mm) thick plate.

Arranging the components with the above functions in the air circulation parts of various devices can effectively decompose the attached organic matter, so it can be conveniently applied to any device with a structure that allows air circulation or can filter air flow.

For example, it can be used in heating devices such as oil heaters, gas heaters or electric heaters and stoves. It can also be used in air conditioners, dehumidifiers or cooling fans. Additionally, it can be used in heated or ultrasonic humidifiers. Also suitable for heating cooking appliances such as stoves or induction hobs, as well as hair dryers. It can also be used in devices equipped with cooling fans. That is, various computers such as personal computers and word processors, computer monitors such as Braun tubes, copiers, laser printers, and other devices using electrophotography. It can be installed on the cooling fan part attached to the liquid crystal projector or slide projector, etc., the suction port and exhaust port part of the cooling air passage using the above-mentioned cooling fan, and the filter part installed on the above-mentioned suction and exhaust port part. The same low-temperature curing type highly active oxide photocatalyst film as the present invention can obtain the same effect.

(Example 16)

The production process of a filter with a photocatalyst having the composition shown in Table 10, that is, a filter with a TiO ₂ photocatalyst doped with ATO or RuO ₂ -ATO is as follows.

The preparation method of ATO solution is as follows. Dissolve _SnCl4 in propanol to prepare a 10wt% _SnO2 solution. Separately, antimony isopropoxide was dissolved in propanol to prepare a 4 wt % Sb ₂ O ₅ solution. Then, after mixing the two solutions in equivalent, 2-aminoethanol was added at a molar ratio of 1:1 corresponding to SnO ₂ , and then 4 times molar water was added corresponding to SnO ₂ to prepare a 5wt% ATO solution. Then, ruthenium acetoacetate was dissolved in the above-mentioned ATO solution to prepare a 0.05wt% RuO ₂ -5wt% ATO solution.

Next, a method for producing TiO ₂ powder to which ATO and RuO ₂ -ATO are added will be described. Regardless of whether ATO or RuO ₂ -ATO is added, TiO ₂ powder is added to the solution prepared above, stirred at 60°C for 2 hours, and dried in an evaporating dish at 250°C to obtain a powder , and then treated at 550° C. for 3 hours to prepare TiO ₂ powders with different addition amounts of ATO and RuO ₂ -ATO.

Next, the preparation steps of ATO-added and RuO ₂ -ATO-added TiO ₂ photocatalyst coating solutions, and the preparation steps of ATO-added and RuO ₂ -ATO-added TiO ₂ photocatalyst filters will be described.

Whether it is to prepare the TiO ₂ photocatalyst coating solution with ATO added or RuO ₂ -ATO added, a specified amount of the above-prepared powder is added to 4wt% SiO ₂ sol, and then ground with zirconia balls for 20 hours , to prepare the coating solution. A filter made of polyacrylonitrile fibers was dipped in the above-mentioned coating solution, air was blown thereon, the residual coating solution was removed, and the filter was treated at 120° C. for 5 minutes to obtain a photocatalyst-attached filter. The composition of each photocatalyst is shown in Table 10.

The film forming method of the present invention can be carried out at about 120°C, and can be applied to plastic materials other than borosilicate glass substrates. Since the general sol-gel method requires a temperature of about 400°C, it is difficult to be used in plastic products, and the crystallization of TiO ₂ also takes more than 10 minutes. However, the manufacturing method of the present invention can form a film at a low temperature, so many substrates can be used, and a photocatalyst film can be formed on any surface. Moreover, the processing time is very short, just a few minutes, which can significantly reduce production costs.

Photocatalyst filters can be used in air purifiers, etc., and can remove malodorous components, bacteria, and cigarette smoke that exist in the air. In particular, a general filter will lose its function when the adsorption and removal of the adsorbent reaches saturation and must be replaced. In contrast, the filter with a photocatalyst absorbs odorous components, bacteria, and cigarette smoke, etc., through the action of the photocatalyst. removed, so the number of filter replacements can be reduced.

In a room full of cigarette smoke, an air purifier with a photocatalyst filter having the composition shown in Table 10 was activated, and the filter was discolored due to adsorption of cigarette smoke. The discolored filter was taken out, irradiated with a fluorescent lamp, the color change was measured, and the decomposing property of the adsorbed cigarette smoke was tested. In addition, the resolution ratio was calculated from the measured discoloration amount using a color meter.

Table 10 shows the decomposition rate after fluorescent lamp irradiation for 5 hours. The decomposition rate of the catalyst added with ATO was higher than that of the catalyst without ATO added. In addition, the decomposition rate further increases after adding RuO ₂ -ATO. This proves that addition of RuO ₂ and ATO is effective.

In the photocatalyst added with ATO, ATO is in contact with TiO ₂ , and the TiO ₂ photocatalyst utilizes the electrons of ATO to improve the performance of the photocatalyst.

When the electron affinity of the oxide semiconductor is lower than that of Ti, a Schottky barrier is formed on the particle surface of the fine particles, so that the carrier to which the oxide semiconductor is added cannot be implanted into TiO ₂ , and the effect cannot be exhibited. In this case, when the electron affinity of the oxide semiconductor is lower than that of Ti, instead of forming a Schottky barrier at the particle interface of the fine particles, a resistive junction is formed, so that the carrier of the oxide semiconductor can be easily implanted. TiO ₂ , thus effectively functioning. In particular, although the electron affinity of ATO is slightly smaller than that of Ti, since the difference between them is insignificant, an improvement in performance can be exhibited. This is because the carrier concentration of ATO as a conductive oxide is high, and a large amount of ATO carrier can be injected into _TiO2 , thereby improving the activity of the photocatalyst. In addition, ATO has attracted much attention as a conductive oxide in recent years, and its ultrafine particles (with a particle size of 200 angstroms or less, preferably in the range of 20 to 100 angstroms) are commercially available. Adding ultrafine ATO to TiO ₂ photocatalyst can prepare TiO ₂ photocatalyst with ATO more conveniently. But, use above-mentioned ultraparticulate ATO, make the filter that has added the _TiO2 photocatalyst of 5wt% ATO, when carrying out similar test, the decomposition rate after 5 hours is 35%, compared with 42% of the photocatalyst of the present invention. Small. Although the addition of ultrafine ATO also makes ATO particles contact with TiO ₂ particles, there are still particles in SiO ₂ , which is ineffective. On the other hand, in the preparation method of the present invention, since the ATO solution is added to the particles in advance for firing, the contact area between ATO and _TiO2 particles is relatively large, and the electrons between different semiconductors in a good junction state can be obtained by firing. The transfer went smoothly. In addition, since the p-type semiconductor RuO ₂ can attract the electrons and holes in the holes generated by the light absorption of the n-type semiconductor TiO ₂ and ATO, the recombination of electrons and holes is suppressed. Therefore, the electrons and holes generated by light absorption can be effectively used for catalytic reactions, further improving the decomposition rate. It can be seen from the above effects that the present invention further improves the decomposition performance of the photocatalyst.

(Example 17)

In addition to adding ATO, other additives can be added to further improve the performance of the photocatalyst.

Table 11 shows the composition of the catalyst in which Li, Na, and Mg were added to the photocatalyst prepared in Example 16 and its decomposition test results on cigarette smoke. As a result, adding any one of Li, Na, and Mg can improve the decomposition rate, and a filter with better performance can be produced. Since the ionic radius of Li, Na, and Mg is similar to that of Ti, it is easy to enter the Ti defect on the surface of TiO ₂ , thereby increasing the stability of the crystal. In addition, since Li, Na, and Mg have strong ionic properties, electrons are easily attracted, and electrons generated by light absorption are separated from holes, thereby improving reaction efficiency.

(Example 18)

The photocatalyst added with Li and the photocatalyst without Li added in Example 16 were irradiated with fluorescent lamp, sunlight, incandescent lamp, and mercury lamp, and their decomposition effects on acetaldehyde, urea, ammonia, and coliform bacteria were compared. As a result, regardless of which light was used, the photocatalyst added with Li-RuO ₂ -ATO had 3 to 5 times the effect of decomposing acetaldehyde, urea, ammonia, and coliform bacteria than that of no catalyst added. This proves that the photocatalyst to which Li-RuO ₂ -ATO is added can obtain a sufficient effect by utilizing the light in the daily environment. In addition, the same effect can be obtained by adding Na and Mg to the photocatalyst other than Li.

As mentioned above, using a simple method, it is possible to form a film at a lower temperature and form a photocatalyst on the surface of any material, providing a highly active photocatalyst that is effective in daily life environments. Since it is a material with good decontamination effect, it is possible to reduce the frequency of replacement and cleaning of various product parts using this photocatalyst.

Table 10 SiO ₂ (wt%) TiO ₂ (wt%) ATO (wt%) RuO ₂ (wt%) Decomposition rate after 5 hours (%) 10 90 0 30 10 88 2 36 10 85 5 42 10 80 10 38 10 70 20 31 10 87.98 2 0.02 48 10 84.95 5 0.05 49 10 79.9 10 0.1 43 10 69.8 20 0.2 38 10 37.5 50 0.5 28

Table 11 SiO ₂ (wt%) TiO ₂ (wt%) ATO (wt%) RuO ₂ (wt%) Li(NO ₃ ) ₂ (wt%) Na(NO ₃ ) ₂ (wt%) Mg(NO ₃ ) ₂ (wt%) Decomposition rate after 5 hours (%) 10 85 0 5 35 10 83 2 5 42 10 80 5 5 53 10 75 10 5 52 10 65 20 5 36 10 84 0 1 5 42 10 82 2 1 5 56 10 79 5 1 5 59 10 74 10 1 5 58 10 64 20 1 5 46 10 34 50 1 5 34 10 85 0 5 33 10 83 2 5 40 10 80 5 5 51 10 75 10 5 49 10 65 20 5 34 10 84 0 1 5 40 10 82 2 1 5 52 10 79 5 1 5 56 10 74 10 1 5 57 10 64 20 1 5 48 10 34 50 1 5 38 10 85 0 5 32 10 83 2 5 40 10 80 5 5 50 10 75 10 5 50 10 65 20 5 33 10 84 0 1 5 39 10 82 2 1 5 48 10 79 5 1 5 47 10 74 10 1 5 47 10 64 20 1 5 42 10 34 50 1 5 39

(Example 19)

The fabrication procedure of the filter with RSO-added TiO ₂ photocatalyst shown in Table 12 is as follows.

The RSO solution was prepared as follows. Dissolve ruthenium acetoacetate in propanol to prepare a ₂ mol% RuO solution. Separately, Sr(NO ₃ ) ₂ was dissolved in propanol to prepare a 2 mol% SrO solution. Then, these two solutions were mixed equivalently, 2-aminoethanol was added at a molar ratio of 1:1 corresponding to RuO ₂ , and water was added 4 times molar corresponding to RuO ₂ to prepare a 1 mol% RSO solution.

The following is the method to prepare _TiO2 powder with added RSO. The above-prepared solution was stirred at 60°C for 2 hours, then dried at 250°C with an evaporating dish to obtain powder, and then treated at 850°C for 5 hours to obtain RSO powder.

The following is the preparation method of the TiO ₂ photocatalyst coating solution with RSO added and the TiO ₂ photocatalyst filter with RSO added.

The method of preparing the _TiO2 photocatalyst coating solution with RSO added is to add a specified amount of RSO powder or _TiO2 powder (anatase type) prepared above in 4wt% _SiO2 sol, and then grind it with zirconia pellets After 20 hours, the coating solution was obtained, and the filter made of polyacrylonitrile fiber was immersed in the above coating solution, and after blowing air, the remaining coating solution was removed, and the filter was treated at 120°C for 5 minutes to obtain a photocatalyst-attached filter. filter. The composition of each photocatalyst is shown in Table 12.

The film forming method of the present invention can be carried out at about 120°C, and can be applied to plastic materials other than borosilicate glass substrates. Since the general sol-gel method requires a temperature of about 400°C, it is difficult to be used in plastic products, and the crystallization of TiO ₂ also takes more than 10 minutes. However, the manufacturing method of the present invention can form a film at a low temperature, so many substrates can be used, and a photocatalyst film can be formed on any surface. Moreover, the processing time is very short, just a few minutes, which can significantly reduce production costs.

Photocatalyst filters can be used in air purifiers, etc., and can remove malodorous components, bacteria, and cigarette smoke that exist in the air. In particular, ordinary filters will lose their function when the adsorption and removal of the adsorbent reaches saturation and need to be replaced, but the odorous components, bacteria, and cigarette smoke adsorbed by the filter with photocatalyst are removed by photocatalyst action, so , can reduce the frequency of filter replacement.

In a room full of cigarette smoke, an air purifier with a photocatalyst filter having the composition shown in Table 12 was activated, and the filter was discolored due to adsorption of cigarette smoke. The discolored filter was taken out, irradiated with a fluorescent lamp, the color change was measured, and the decomposing property of the adsorbed cigarette smoke was tested. In addition, the resolution ratio was calculated from the measured discoloration amount using a color meter.

Table 12 shows the decomposition rate after fluorescent lamp irradiation for 5 hours. The decomposition rate of the catalyst added with RSO was greater than that of the catalyst without RSO added. This proves that adding RSO works.

In the photocatalyst with RSO added, RSO is in contact with TiO ₂ , and the TiO ₂ photocatalyst utilizes the pores of RSO to improve the performance of the photocatalyst. The oxidation activity of the photocatalyst causes a redox reaction of electrons and holes generated by light absorption. In particular, the generated holes generate OH radicals, which have a strong oxidation effect. RSO is a p-type semiconductor with a large number of holes. By contacting RSO with _TiO2 , holes are injected into _TiO2 to oxidize organic matter on the surface of _TiO2 , thereby improving the activity of photocatalysts.

In addition to adding RSO, other additives can also improve the performance of photocatalysts.

Table 13 shows the composition of the catalyst in which Li, Na, and Mg were added to the photocatalyst prepared in Example 19 and its decomposition test results on cigarette smoke. As a result, adding any one of Li, Na, and Mg can improve the decomposition rate, and a filter with better performance can be produced. Since the ionic radius of Li, Na, and Mg is similar to that of Ti, it is easy to enter the Ti defect on the surface of TiO ₂ , thereby increasing the stability of the crystal. In addition, since Li, Na, and Mg have strong ionic properties, electrons are easily attracted, and electrons generated by light absorption are separated from holes, thereby improving reaction efficiency.

Table 12 SiO ₂ (wt%) TiO ₂ (wt%) RSO(wt%) Decomposition rate after 5 hours (%) 10 90 0 30 10 88 2 38 10 85 5 48 10 80 10 46 10 70 20 35 10 40 50 27

Table 13 SiO ₂ (wt%) TiO ₂ (wt%) RSO(wt%) Li(NO ₃ ) ₂ (wt%) Na(NO ₃ ) ₂ (wt%) Mg(NO ₃ ) ₂ (wt%) Decomposition rate after 5 hours (%) 10 85 0 5 40 10 83 2 5 46 10 80 5 5 58 10 75 10 5 57 10 65 20 5 41 10 85 0 5 38 10 83 2 5 44 10 80 5 5 56 10 75 10 5 55 10 65 20 5 42 10 85 0 5 38 10 83 2 5 43 10 80 5 5 56 10 75 10 5 54 10 65 20 5 5 39

(Example 20)

The photocatalyst with Li added and the photocatalyst without Li added in Example 19 were irradiated with fluorescent lamp, sunlight, incandescent lamp, and mercury lamp, and their decomposition effects on acetaldehyde, urea, ammonia, and coliform bacteria were compared. As a result, regardless of which light was used, the photocatalyst added with Li-RuO ₂ -RSO had 3 to 5 times the effect of decomposing acetaldehyde, urea, ammonia, and coliform bacteria than no catalyst added. This proves that the photocatalyst to which Li-RuO ₂ -RSO is added can obtain a sufficient effect by utilizing the light in the daily environment. In addition, the same effects can be obtained by adding Na and Mg to photocatalysts other than Li.

(Example 21)

In the method of mixing RSO powder with TiO ₂ powder in Example 19, although TiO ₂ fine particles were in contact with RSO particles, particles were also present in SiO ₂ used as a binder, which was ineffective. In addition, if RSO solution is added to TiO ₂ particles before firing, the contact area between RSO and TiO ₂ particles will increase, and the electron transfer between dissimilar semiconductors with good joint state can be smoothed by firing. However, a temperature of 700 to 850° C. is required to prepare RSO. If the temperature is lower than the above temperature, RSO cannot be crystallized and thus does not function as a p-type semiconductor. When the temperature is above 600°C, the crystallization of TiO ₂ is rutile type, and when the photocatalytic effect is fully exhibited, it is anatase type, and the photocatalytic effect is poor when it is rutile type. Therefore, if the TiO ₂ is treated at a high temperature after adding RSO, although the RSO is converted into a p-type semiconductor, the TiO ₂ undergoes a phase transition into a rutile type, thus losing the role of a photocatalyst. Therefore, STO (SrTiO ₃ ), which has the same effect as TiO ₂ photocatalyst, is generally used, so that the STO photocatalyst added with RSO is effective. STO and _TiO2 have almost the same frequency band (band). In addition, this preparation method requires high-temperature treatment at 700-850°C to crystallize it. The crystals of RSO and STO are both perovskite-type, and their lattice constants are almost the same as those of Sr-O. Therefore, the preparation conditions are also very close to those of RSO, and the bonding state is also good. The following is the preparation method of STO powder with RSO added.

First prepare the STO powder. Isopropoxy titanate was dissolved in propanol to prepare a 2 mol% TiO ₂ solution. Then, corresponding to TiO ₂ , Sr(NO ₃ ) ₂ and 2-aminoethanol were sequentially added at a molar ratio of 1:1, and then 4 times molar water was added to prepare a 1 mol% STO solution.

The solution prepared above was stirred at 60° C. for 2 hours, then dried at 250° C. with an evaporating dish to obtain powder, and then treated at 850° C. for 5 hours to obtain STO powder.

The following is the method for preparing STO powder with added RSO.

Add a specified amount of STO powder to the RSO solution prepared in Example 19, stir at 60°C for 2 hours, then dry it with an evaporating dish at 250°C to obtain a powder, and then treat it at 850°C for 5 hours to obtain the RSO STO powder.

The following are the methods for preparing the RSO-added STO photocatalyst coating solution and the RSO-added STO photocatalyst filter.

The method of preparing the STO photocatalyst coating solution with added RSO is to add a specified amount of the above-mentioned STO powder with RSO added to 4wt% _SiO2 sol, and then grind it with zirconia pellets for 20 hours to obtain a coating solution . A filter made of polyacrylonitrile fibers was dipped in the above-mentioned coating solution, air was blown thereon, the residual coating solution was removed, and the filter was treated at 120° C. for 5 minutes to obtain a photocatalyst-attached filter. Since the above-mentioned STO photocatalyst with RSO added is composed of STO powder sintered and granulated at high temperature, compared with some _TiO2 -based photocatalysts, although the adhesion to polyacrylonitrile fibers is poor, the appearance is better. The composition of each photocatalyst is shown in Table 14.

In a room full of cigarette smoke, an air purifier with a photocatalyst filter having the composition shown in Table 14 was activated, and the filter was discolored due to adsorption of cigarette smoke. The discolored filter was taken out, irradiated with a fluorescent lamp, the color change was measured, and the decomposing property of the adsorbed cigarette smoke was tested. In addition, the resolution ratio was calculated from the measured discoloration amount using a color meter.

Table 14 shows the decomposition rate after fluorescent lamp irradiation for 5 hours. The decomposition rate of the STO catalyst added with RSO is greater than that of the _TiO2 catalyst added with RSO. This proves that STO with RSO added works.

In addition to adding RSO, other additives can also improve the performance of photocatalysts.

Table 14 shows the composition of the catalyst in which Li, Na, and Mg were added to the STO photocatalyst added with RSO and the results of its decomposition test on cigarette smoke. As a result, adding any one of Li, Na, and Mg can improve the decomposition rate, and a filter with better performance can be produced. Since the ionic radius of Li, Na, and Mg is similar to that of Ti, it is easy to enter the Ti defect on the surface of STO, thereby increasing the stability of the crystal. In addition, since Li, Na, and Mg have strong ionic properties, electrons are easily attracted, and electrons generated by light absorption are separated from holes, thereby improving reaction efficiency.

As mentioned before, the adhesion of STO photocatalyst filter with RSO added is poor, it is mixed with _TiO2 photocatalyst with good adhesion, and then coated on polyacrylonitrile fiber to make photocatalyst filter device. Its composition and its decomposability to smog are shown in Table 15. As a result, good adhesiveness can be obtained, and the decomposability to smog is also good, and a high-performance photocatalyst can be obtained.

As described above, since RSO, which is a p-type semiconductor, can inject holes into STO or attract electrons and holes among holes generated by light absorption of STO, recombination of electrons and holes is suppressed. Therefore, the electrons and holes generated by light absorption can be effectively used for catalytic reactions, further improving the decomposition rate. It can be seen from the above effects that the present invention further improves the decomposition performance of the photocatalyst.

As mentioned above, using a simple method, it is possible to form a film at a relatively low temperature and form a photocatalyst on the surface of any material, providing a highly active photocatalyst that is effective in daily life environments. Since it is an antibacterial, antifouling A material with good effect, therefore, it is possible to reduce the frequency of replacement and cleaning of various product parts using the photocatalyst.

Table 14 SiO ₂ (wt%) TiO ₂ (wt%) RSO(wt%) Li(NO ₃ ) ₂ (wt%) Na(NO ₃ ) ₂ (wt%) Mg(NO ₃ ) ² (wt%) Decomposition rate after 5 hours (%) 10 85 0 5 43 10 80 5 5 58 10 75 10 5 68 10 65 20 5 66 10 35 50 5 45 10 85 0 5 40 10 80 5 5 56 10 75 10 5 65 10 65 20 5 63 10 35 50 5 42 10 85 0 5 40 10 80 5 5 56 10 75 10 5 64 10 65 20 5 62 10 35 50 5 41

Table 15 SiO ₂ (wt%) TiO ₂ (wt%) RSO/STO(wt%) Li(NO ₃ ) ₂ (wt%) Na(NO ₃ ) ₂ (wt%) Mg(NO ³ ) ² (wt%) Decomposition rate after 5 hours (%) 10 85 0 5 40 10 80 5 5 52 10 75 10 5 65 10 65 20 5 63 10 35 50 5 45 10 85 0 5 38 10 80 5 5 50 10 75 10 5 61 10 65 20 5 58 10 35 50 5 44 10 85 0 5 38 10 80 5 5 49 10 75 10 5 61 10 65 20 5 60 10 35 50 5 43

(Example 22)

A solution in which TiO ₂ microparticles and zeolite (aluminosilicate) were dispersed in SiO ₂ sol was prepared. Using this solution, a _TiO2 film was formed on polyacrylonitrile fibers to fabricate a photocatalyst-attached filter. The order of making is as follows.

First, the preparation method of SiO ₂ sol will be described. Dissolve 5g of tetraethoxysilane in a mixed solution of 100ml of water-ethanol-propanol (3:27:70), stir at 40°C for about 5 hours, and then place the resulting solution at room temperature for 2 weeks to become SiO ₂ sol.

Next, a method for preparing a solution in which TiO ₂ fine particles and zeolite are dispersed in SiO ₂ sol will be described. First, TiO ₂ microparticles are added to the obtained SiO ₂ sol at a weight ratio of TiO ₂ /SiO ₂ =9, then a predetermined amount of ZSM-5 (synthetic zeolite, the same below) is added, and water is added to make the concentration of the solid content is 4wt%. Next, in order to disperse the TiO ₂ particles and ZSM-5 in the SiO ₂ sol, use 5mm zirconia pellets to pass through a ball mill for 24 hours, thus making the TiO ₂ particles and ZSM-5 dispersed in the SiO ₂ sol The solution.

Coating SiO 2 sol with ZSM-5 dispersed with TiO ₂ particles on the polyacrylonitrile fiber, treated at 120°C for 5 minutes to form a SiO ₂ film coated with TiO ₂ particles and ZSM-5 dispersed in the SiO ₂ film. Filter of _SiO2 membrane dispersed with _TiO2 microparticles. The composition of the prepared photocatalyst is SiO ₂ =8wt%, TiO2=72wt%, ZSM-5=20wt%.

Photocatalyst filters can be used in air purifiers, etc., and can remove malodorous components, bacteria, and cigarette smoke that exist in the air. In particular, ordinary filters will lose their function when the adsorption and removal of the adsorbent reaches saturation and need to be replaced, but the odorous components, bacteria, and cigarette smoke adsorbed by the filter with photocatalyst are removed by photocatalyst action, so , can reduce the frequency of filter replacement.

The above-prepared photocatalyst filter was sealed in a glass container, 400 ppm of acetaldehyde was introduced as a gas component, circulated in the container by a fan, and irradiated with a fluorescent lamp to measure its photocatalytic performance. In addition, the continuously circulating gas is often analyzed with an infrared detector, and the measurement results are shown in FIG. 30 . When no zeolite is added, the acetaldehyde decreases sharply at the beginning, then decreases slowly, and then returns to the initial value after introducing gas. This repeated operation to achieve the equilibrium of adsorption and decomposition reactions. This indicates that acetaldehyde is rapidly reduced by the adsorption of _TiO2 at the initial stage, and then slowly decomposed under the action of photocatalyst. Then, if the gas is introduced again, the acetaldehyde is adsorbed on the adsorption point vacated by the decomposition of the photocatalyst, and it decreases sharply at first, and then decomposes slowly. On the other hand, when zeolite is added, the introduced gas basically disappears from the mist due to the adsorbent effect of zeolite. The adsorbed gas is then slowly decomposed by photocatalysis. Therefore, adding zeolite can increase the adsorption effect, quickly absorb and remove the gas in the air, and then decompose it through photocatalysis, so that the air can always be kept fresh.

(Example 23)

In order to study the influence of the Si:Al ratio in zeolite, zeolite was added according to the three ratios of Si:Al=80:20, 50:20, and 30:20, and the difference was measured. The results are shown in Figure 31, that is, Si The larger the content, the better the performance. The zeolite with more Si content has a larger surface area, so it not only has a larger adsorption capacity, but also has a larger water absorption capacity, which can provide the necessary surface adsorption water for the photocatalyst.

(Example 24)

Next study the performance of ion exchange into Cu, Ag, Li, Na, Mg ions in zeolite, the results are shown in Figure 32, that is, with Cu, Ag for ion exchange, before and after ion exchange (compared with Figure 30) almost There is no change, while ion exchange with Li, Na, Mg can improve the performance. This is because Na, Li, and Mg are elements with strong ionicity, and a positively charged space is generated in the zeolite, which can attract the electrons generated by _TiO2 light absorption, separate the electrons from the holes, and inhibit their recombination, thereby The reason is that the reaction efficiency is greatly improved.

An antibacterial test using coliform bacteria was performed using Cu and Ag-added ion-exchange zeolite. The results are shown in Figure 33, that is, when there is no zeolite and no light, coliform bacteria multiply, and when zeolite is added and light is provided, the sterilization rate of coliform bacteria remains unchanged, but the number of coliform bacteria decreases when there is no light. The ion-exchanged zeolite containing Cu and Ag, and the sterilizing rate of coliform bacteria was improved when it was illuminated, and the sterilizing rate when it was not illuminated was better than the other cases mentioned above.

As mentioned above, the addition of zeolite can improve the antibacterial properties of dark reaction. If the addition of Cu and Ag ion-exchanged zeolite, the performance can be improved during light and dark reaction, making good antibacterial agent.

In this way, a highly active photocatalyst that can be formed on the surface of any material and is effective in daily life environments is provided, and can effectively remove gas components in the air through adsorption effects and decomposition reactions.

(Example 25)

A solution in which _TiO2 microparticles and blue pigment were dispersed in _SiO2 sol was prepared. Use this solution to form a _TiO2 film on polyacrylonitrile fibers to make a filter with photocatalyst attached, the operation procedure is as follows.

First, the preparation method of SiO ₂ sol will be described. Dissolve 5g of tetraethoxysilane in a mixed solution of 100ml of water-ethanol-propanol (3:27:70), stir at 40°C for about 5 hours, and then place the resulting solution at room temperature for 2 weeks to become SiO ₂ sol.

Next, a method for preparing a solution in which TiO ₂ fine particles and a blue pigment are dispersed in SiO ₂ sol will be described. First, TiO ₂ fine particles were added to the obtained SiO ₂ sol at a weight ratio of TiO ₂ /SiO ₂ =9, and then a predetermined amount of Cu-phthalocyanine dye (blue pigment) was added. A necessary amount of water was added to adjust the concentration of the solid content to 4 wt%. To disperse the TiO ₂ particles in the SiO ₂ sol, 5mm zirconia pellets were passed through a ball mill for 24 hours, thus preparing a solution in which the TiO ₂ particles were dispersed in the SiO ₂ sol.

Then, the SiO ₂ sol dispersed with TiO ₂ particles prepared above was coated on the polyacrylonitrile fiber, and treated at 120° C. for 5 minutes to form a TiO 2 sol dispersed with TiO ₂ particles dispersed in the SiO ₂ film _. Particulate _SiO2 membrane filter. The composition of the prepared photocatalyst is shown in Table 16.

Photocatalyst filters can be applied to air purifiers, etc., and can remove malodorous components, bacteria, and cigarette smoke that exist in the air. In particular, ordinary filters will lose their function when the adsorption and removal of the adsorbent reaches saturation and need to be replaced, but the odorous components, bacteria, and cigarette smoke adsorbed by the filter with photocatalyst are removed by photocatalyst action, so , can reduce the frequency of filter replacement.

In a room full of cigarette smoke, an air purifier with a photocatalyst filter having the composition shown in Table 16 was activated, and the filter was discolored due to adsorption of cigarette smoke. The discolored filter was taken out, irradiated with a fluorescent lamp, the color change was measured, and the decomposition property of the adsorbed cigarette smoke was tested. In addition, the resolution ratio was calculated from the measured discoloration amount using a color meter.

The results of the decomposition test are shown in Figure 34. As a result, the addition of blue pigments resulted in improved decomposition performance.

In Table 16, the evaluation results of film strength and light resistance are shown in addition to the decomposition properties. Each evaluation step is shown below.

The strength test is repeated bending and stretching to evaluate whether the powder falls from the filter. If no powder falls after bending and stretching, repeat the above operation, blow air at a speed of 2 m/s, and observe the peeling condition. The case where peeling due to bending and stretching was marked as X, the case where there was no peeling in the above cases but peeled by air blowing was marked as △, and the case where there was no peeling in any case was marked as ◯.

The filter prepared above was irradiated with a low-pressure mercury lamp (254nm, 3mW/cm ² ), and the time until the amount of color change was 20% or more was measured to measure the light resistance.

As a result of the evaluation, with regard to the film strength, if the pigment is added, the film strength decreases, and the pigment content is more than 20% by weight, and the film is easily peeled off. Easy to peel means that it will not peel off unless it is bent or stretched, and it can be used without moving after installation.

With regard to light resistance, the more the amount of pigment added, the worse the light resistance. Although pigments are good for light resistance, photocatalysts can slowly decompose them because they contain organic groups. The evaluation conditions of this test have been strengthened, and the light of fluorescent lamps is generally used, but the 35 hours in Table 16 is equivalent to 3 to 5 years under fluorescent lamps.

The above test results show that the film strength and light resistance of the catalyst added with pigments are both worse. However, if the filter catalyst itself is colored, the change in filter performance can be visually observed quickly, so that it is easy to judge when the filter needs to be replaced.

In order to increase the adhesive strength of the filter, the most effective method is to add organic resin. Table 17 shows the composition and various evaluation results when an acrylic resin was added to the solution prepared above. By adding resin, the film strength can be dramatically improved. In addition, there is no change in light resistance, and its function can be fully exhibited under fluorescent lamps, and the decomposition performance of cigarette smoke is also good.

As mentioned above, it can be seen that the addition of pigments and, if necessary, resins can produce filters with good performance.

Table 16 Pigment (wt%) TiO ₂ (wt%) SiO ₂ (wt%) Membrane strength Lightfastness 0 90 10 ○ no change 10 81 9 △ 50 20 72 8 x 40 50 45 5 x 35

Table 17 Resin (wt%) Pigment (wt%) TiO ₂ (wt%) SiO ₂ (wt%) Membrane strength Lightfastness Washing test Decomposition rate after 5 hours (%) 0 30 63 7 x 35 1 43 10 27 56.7 6.3 △ 35 5 45 20 twenty four 50.4 5.6 ○ 35 10 or more 42 50 15 31.5 3.5 ○ 35 10 or more 39

(Example 26)

Irradiate with fluorescent lamps, sunlight, incandescent lamps, and mercury lamps, and compare the decomposition effects of the photocatalysts prepared in Example 25 with and without pigments on acetaldehyde, urea, ammonia, and coliform bacteria. As a result, regardless of which lamp was used, the photocatalyst to which Li was added had a decomposition rate of acetaldehyde, urea, ammonia, and coliform bacteria that were 3 to 5 times that of the photocatalyst to which no dye was added. Not only ultraviolet lamps but also lamps used in daily life environment can obtain sufficient effect by irradiating the above-mentioned catalyst with added pigment. In addition to blue dyes, red, yellow, and green dyes can also be added to achieve the same effect.

In this way, a highly active photocatalyst that can be formed on the surface of any material and is effective in daily life environments is provided, and it is possible to easily determine when the photocatalyst needs to be replaced.

(Example 27)

A solution in which TiO ₂ microparticles and acrylic resin were added to SiO ₂ sol was prepared. Use this solution to form a _TiO2 film on polyacrylonitrile fibers to make a filter with photocatalyst attached, the operation procedure is as follows.

First, the preparation method of SiO ₂ sol will be described. Dissolve 5g of tetraethoxysilane in a mixed solution of 100ml of water-ethanol-propanol (3:27:70), stir at 40°C for 5 hours, and then place the resulting solution at room temperature for 2 weeks to make it SiO ₂ Sol.

Next, a method for preparing a solution in which TiO ₂ fine particles and acrylic resin are added to SiO ₂ sol will be described. First, TiO ₂ fine particles were added to the obtained SiO ₂ sol at a weight ratio of TiO ₂ /SiO ₂ =9, and then a predetermined amount of acrylic resin was added. After adding the necessary amount of water to adjust the concentration of solid components to 4wt%, in order to disperse the _TiO2 particles in the _SiO2 sol, use 5mm zirconia balls to pass through the ball mill for 24 hours, so that the _SiO2 sol solution with _TiO2 particles dispersed in it.

Then, the SiO ₂ sol dispersed with TiO ₂ particles prepared above was coated on the polyacrylonitrile fiber, and treated at 120° C. for 5 minutes to form a TiO 2 sol dispersed with TiO ₂ particles dispersed in the SiO ₂ film _. Particulate _SiO2 membrane filter. The composition of the prepared photocatalyst is shown in Table 18.

Photocatalyst filters can be applied to air purifiers, etc., and can remove malodorous components, bacteria, and cigarette smoke that exist in the air. In particular, ordinary filters will lose their function when the adsorption and removal of the adsorbent reaches saturation and need to be replaced, but the odorous components, bacteria, and cigarette smoke adsorbed by the filter with photocatalyst are removed by photocatalyst action, so , can reduce the frequency of filter replacement.

In a room full of cigarette smoke, an air purifier with a photocatalyst filter having the composition shown in Table 18 was activated, and the filter was discolored due to adsorption of cigarette smoke. The discolored filter was taken out, irradiated with a fluorescent lamp, the color change was measured, and the decomposing property of the adsorbed cigarette smoke was tested. In addition, the resolution ratio was calculated from the measured discoloration amount using a color meter.

The results of the decomposition test are shown in FIG. 35 . When using _SiO2 (silicon dioxide) as a binder, if there is much binder quantity, photocatalyst performance will fall. When an acrylic resin is used as a binder, even if the amount of the binder is too large, the photocatalyst performance hardly changes.

Table 18 shows the evaluation results of the film strength, light resistance and water washing tests in addition to the decomposition properties. Each evaluation step is as follows.

The strength test is to repeatedly bend and stretch the manufactured filter to evaluate whether the powder falls off. If no powder falls after bending and stretching, repeat the bending and stretching, blow air at a speed of 2 m/sec, and observe the peeling condition. The case where peeling due to bending and stretching was marked as ×, the case where there was no peeling in the above cases but peeled by air blowing was marked as △, and the case where there was no peeling in any case was marked as ◯.

The detection of light resistance is to irradiate the prepared filter with a low-pressure mercury lamp (254nm, 3mW/cm ² ), and measure the time when the color change is above 20%.

In the water washing test, the filter is repeatedly washed with water until the catalyst peels off, and the number of times of washing when this phenomenon occurs is measured.

As a result of the evaluation, the strength of the film can be enhanced by adding the acrylic resin, and the peeling of the film can be prevented when the content is above 5 wt%.

The greater the amount of acrylic resin added, the worse the light resistance, because the acrylic resin contains organic groups, which can be decomposed slowly by photocatalyst action. The evaluation conditions of this test have been strengthened, and the light of fluorescent lamps is generally used. The 35 hours in Table 16 is equivalent to 3 to 5 years under fluorescent lamps.

If the added amount of resin is more than 10 wt %, water washing can be sufficiently performed, so that it can be used repeatedly.

As described above, sufficient strength can be obtained by adding an organic resin. The performance of the catalyst does not change whether or not the resin is added, and a photocatalyst filter that can be washed can be produced.

The catalyst to which the above acrylic resin was added was inferior in light resistance, but had good membrane strength, and the filter catalyst was washable. So far, photocatalysts can only clean organic pollutants, but are ineffective against inorganic pollutants such as dust. Cleaning can remove inorganic substances, which can prolong the service life of filters.

(Example 28)

Irradiate with fluorescent lamps, sunlight, incandescent lamps, and mercury lamps, and compare the photocatalysts prepared in Example 27 with the addition of acrylic resins and the photocatalysts without acrylic resins on the decomposition effects of acetaldehyde, urea, ammonia, and coliform bacteria. As a result, regardless of which lamp was used, the decomposition rate of acetaldehyde, urea, ammonia, and coliform bacteria in the Li-added photocatalyst was the same as that of the photocatalyst without acrylic resin. Not only ultraviolet lamps but also lamps used in daily life environments can obtain sufficient effects by irradiating the above-mentioned acrylic resin-added catalyst.

(Example 29)

In recent years, in order to improve the chemical properties of acrylic resins, silanol-modified acrylic resins in which silanol groups have been introduced into the side chains of acrylic resins have been developed. To the solution prepared in Example 27, acrylic resins having different amounts of silanol introduced were added to prepare filters. Fig. 36 shows the evaluation results of the above-prepared filters on the decomposition characteristics of cigarette smoke and light resistance. The decomposition properties against cigarette smoke did not change significantly depending on the amount of silanol groups introduced (the amount of silanol introduced in the figure), and the performance did not deteriorate. When the amount of silanol introduced is large, the light resistance improves.

As mentioned above, the use of silanol-modified acrylic resin can improve light resistance and produce a photocatalyst filter with good performance.

(Example 30)

Unlike ceramic materials such as silica, organic resins can be cured without heating. For example, the use of room temperature curing resin can achieve the purpose. However, room temperature curing resins require about 24 hours for all but instant adhesives. Instant adhesives cure in a short time, but decompose slowly due to the action of photocatalysts. Resins that can be cured in a short time and have good light resistance include UV-curable resins. UV-curable resins are resins that are cured by ultraviolet rays, and can be slowly polymerized and cured by ultraviolet rays emitted by fluorescent lamps. However, in reality, it is gradually decomposed by photocatalytic action. Therefore, light resistance can be improved by appropriately combining photocuring and photolysis.

A TiO _{microparticle} -dispersed solution to which UV-curable resin was added was prepared. Using this solution, a _TiO2 film was formed on polyacrylonitrile fibers to fabricate a photocatalyst-attached filter. The operation steps are as follows.

Add a predetermined amount of TiO ₂ fine particles and any one of Si, Al, and Ti-based coupling agents to toluene, stir at 40°C for 2 hours, and then add this to a predetermined amount of UV-curable resin. A necessary amount of toluene was added to adjust the solid content concentration to 4 wt%. Next, in order to disperse the TiO ₂ fine particles, the zirconia pellets of 5 mm were passed through a ball mill for 24 hours to prepare a solution in which the TiO ₂ fine particles were dispersed in the UV curable resin.

The above-prepared solution was coated on the polyacrylonitrile fiber and irradiated with ultraviolet light from a low-pressure mercury lamp for 15 seconds at room temperature to form a photocatalyst-coated filter. The composition of the prepared photocatalyst is shown in Table 19.

Table 18 Resin (wt%) TiO ₂ (wt%) SiO ₂ (wt%) Membrane strength Lightfastness Washing test Decomposition rate after 5 hours (%) 0 90 10 △ no change 1 30 2 88.2 9.8 △ no change 1 32 5 85.5 9.5 ○ 5 hours 5 31 10 81 9 ○ 3 hours 10 33 20 72 8 ○ 2 hours 10 or more 31 50 45 5 ○ 2 hours 10 or more 28

Table 19 TiO ₂ (wt%) UV curable resin (wt%) Coupler (wt%) Washing test Lightfastness 90 0 10 1 no change 85 5 10 5 meta change 80 10 10 10 or more no change 70 20 10 10 or more no change

Fig. 37 shows the decomposition characteristics (decomposition rate after 5 hours) of cigarette smoke according to the amount of coupling agent added. Adding a coupling agent can improve the photocatalytic properties. If only UV curable resin is included, the resin will completely cover the surface of _TiO2 particles and the catalytic properties will disappear. After adding the coupling agent, the exposed portion of the _TiO2 surface can be increased. Moreover, the photocatalyst will decompose the moisture adsorbed on the surface to generate free radicals. After adding the coupling agent, it can better preserve the moisture adsorbed on the surface and make the catalyst show its function.

Table 19 shows the test results other than catalyst performance. As a result of the water washing test, the UV curable resin can be washed with water when the content of the UV curable resin is more than 10 wt%. There was no problem with light resistance, and no deterioration occurred even after 10 hours of irradiation.

As described above, the use of UV curable resin enables room temperature coating in a short period of time to obtain a photocatalyst filter with good light resistance.

In this way, a highly active photocatalyst that is effective in daily life can be formed on the surface of any material in a short time at low temperature, and inorganic pollutants can be removed by washing with water, which can reduce the number of parts replacement and cleaning of various application products.

(Example 31)

A solution in which _TiO2 microparticles were dispersed in _SiO2 sol was prepared. Use this solution to form a _TiO2 film on a PET film to make a PET film, and the operating procedure is as follows.

First, the preparation method of SiO ₂ sol will be described. Dissolve 5g of tetraethoxysilane in a mixed solution of 100ml of water-ethanol-propanol (3:27:70), stir at 40°C for 5 hours, and then place the resulting solution at room temperature for 2 weeks to make it SiO ₂ Sol.

Next, a method for preparing a solution in which TiO ₂ fine particles are dispersed in SiO ₂ sol will be described. First, TiO ₂ microparticles are added to the obtained SiO ₂ sol at a weight ratio of TiO ₂ /SiO ₂ =9, and then, predetermined amounts of phosphoric acid, boric acid, and Li, Mg, K, and Ca nitrates are respectively added. A necessary amount of water was added to adjust the solid content concentration to 4 wt%. Next, in order to disperse the TiO ₂ particles in the SiO ₂ sol, 5 mm zirconia balls were passed through a ball mill for 24 hours to prepare a solution in which the TiO ₂ particles were dispersed in the SiO ₂ sol.

Coat the above-mentioned SiO ₂ sol dispersed with TiO ₂ particles on the PET film, and irradiate it with a low-pressure mercury lamp (intensity: 15mW/cm2) at 120°C for 5 minutes to form a layer coated with TiO ₂ dispersed in SiO ₂ Plastic film of SiO ₂ film of microparticles dispersed with TiO ₂ particles. The film quality and strength of the film obtained on the PET film are good, and the film thickness is 300nm.

A load of 1 kg was applied to the film prepared above, and the surface of the film was wiped with an eraser to perform a strength test. As a result, the film without adding B and P wrinkled after wiping 50 times, while the film added with B and P was still intact after wiping 100 times. This proves that adding B and P can improve the film strength.

Then, the decomposition activity of the organic matter was evaluated. Coating red-purple organic pigments on the film, irradiating with light with a wavelength of 254nm and an intensity of 0.2mW/cm ² for activity test. The decomposition rate can be obtained from the change amount of the initial dye transmittance. The results are shown in Table 20. An empty column in the table indicates that the element was not added.

Table 20 TiO ₂ /SiO ₂ B (wt%) P (wt%) Li (wt%) Ca(wt%) K (wt%) Mg(wt%) Decomposition rate after 10 minutes 9 5 10 70 9 5 10 68 9 3 3 10 70 9 5 10 75 9 5 10 73 9 3 3 10 75 9 5 10 80 9 5 10 78 9 3 3 10 81 9 5 10 73 9 5 10 71 9 3 3 10 72 9 10 65

The decomposition rate of the photocatalyst to which Li was added without adding B and P was 65% after 10 minutes, but the decomposition rate of the photocatalyst to which B and P were added increased. This shows that adding B and P can further improve the performance of the photocatalyst. In addition, the effects of the additives are in the order of K>Ca>Mg>Li.

The photocatalyst absorbs light to generate electrons and holes to decompose water to generate free radicals, and then decomposes organic matter. Therefore, if there is no moisture on the surface of the photocatalyst, the organic matter cannot be decomposed. The photocatalyst without adding B and P will decompose the moisture adsorbed on the surface of TiO ₂ and SiO ₂ . B and P have higher water absorption, and adding B and P can make more water exist on the surface of the catalyst. Therefore, increasing the water adsorbed on the surface can improve the decomposition performance of organic matter.

Then, ATO as conductive particles was added to the above-prepared coating liquid, and a film was formed on a PET film in the same way, and its decomposing property to the pigment was evaluated. The results are shown in Table 21.

Table 21 TiO ₂ /SiO ₂ Bwt% Pwt% Kwt% ATOwt% Decomposition rate after 10 minutes 9 3 3 10 0 81 9 3 3 10 5 85 9 3 3 10 10 90 9 3 3 10 20 88

The decomposition rate of the photocatalyst without ATO was 81% after 10 minutes, while that of the photocatalyst with ATO was improved. Especially when the content is 10wt%, the decomposition rate can reach up to 90%, which shows that adding ATO can further improve the performance. In addition, the surface resistance of the prepared ATO-added film is lower than 10 ⁹ Ω/cm ² , which means that it has an anti-static effect, which can prevent not only organic matter but also inorganic matter from being adsorbed.

In addition to K (potassium), Li (lithium), Ca (calcium), and Mg (magnesium) can be added to obtain the same ATO addition effect.

Possibility of industrial use

Electrical appliances that use electric motors to generate air flow built in air cleaners, ventilation fans, electric fans, vacuum cleaners, clothes dryers, tableware dryers, dishwashers, kitchen waste disposal machines, etc., and are mainly used in indoor environments The low-temperature curing type highly active oxide photocatalyst film of the present invention is provided in the air passage, filter part, exterior part, and part irradiated by the built-in lighting device, so the following effects can be obtained.

The effects obtained by the present invention can be roughly classified into the following three categories.

The 1st, the present invention has added Na, Li etc. electronegativity is less than 1.6, ion radius is less than the ion of the valence of the element of 0.2nm below 2 in oxide photocatalyst film such as known in the past _TiO2 , makes the decomposition effect of organic matter has seen an increase. In addition, metal oxide semiconductors with an electron affinity of 1.2 or more, including antimony-added tin oxide, or metal particles such as Ag, Cu, Ni, Pd, Rh, and Pt, are used in combination to further improve the decomposition efficiency. In this way, good results can be obtained without requiring a short-wavelength light generator such as an ultraviolet lamp, which is necessary for conventional oxide photocatalysts. That is, organic matter can be decomposed by using the light available in general indoors, such as fluorescent lamps, incandescent bulbs, mercury lamps, sunlight that can pass through glass windows, etc., and can also decompose attachments such as cigarette smoke and sebum on hands The anti-fouling effect can be obtained by removing the generated dirt. Similarly, weak light can be used to decompose odor-producing substances such as organic amines or mercaptans dispersed in the air, and decompose them into low-odor or odorless substances. Therefore, the deodorizing effect of reducing indoor odor can be obtained. In addition, the weak light can also decompose various microorganisms such as bacteria, mold and pollen floating in the air, so as to kill these microorganisms or inhibit their reproduction. At the same time, it can also effectively reduce the amount of microorganisms floating in the indoor air where the above-mentioned electrical appliances are used. In the past, air-filtering parts such as filters or meshes needed to be replaced frequently. If dirt accumulated on them or the holes were clogged, they needed to be removed and cleaned, or replaced with new parts. However, this invention can decompose the attached dirt, so it can be extended to The service life of the degree of hole clogging, which reduces the frequency of replacement.

Examples of specific effects of each use are as follows. Because the outer parts such as air purifiers, ventilation fans, electric fans, vacuum cleaners, clothes dryers, tableware dryers, dishwashers, and kitchen waste disposal machines are exposed to indoor lighting or sunlight , Therefore, dirt is difficult to form, microorganisms are difficult to reproduce, and a clean state can be maintained. In addition, if the air circulation parts attached to the above-mentioned electrical appliances or the filters and meshes in the air passages are also irradiated by indoor lighting devices or sunlight, not only antifouling and antibacterial effects can be obtained, but also indoor deodorizing effects can be obtained. .

The main body of the air purifier, ventilation fan, electric fan, and vacuum cleaner is equipped with an infrared receiving part, and an infrared emitting part is installed in the remote control part for remote control. If the above infrared receiving and emitting part is polluted, the signal receiving and emitting will be affected , the present invention has the effect of preventing such pollution.

Generally, when the pollution load that is difficult to decompose completely by indoor light intensity is large, or when it is used for parts that are not sufficiently illuminated by indoor light, the same effect can be obtained if lighting devices such as fluorescent lamps or light bulbs are attached. If this still doesn't work, UV light generating devices such as mercury lamps or metal halides can be used in combination, so that better decomposition effects can be obtained. In this case, since the decomposition rate of the present invention is higher than that of the past, the irradiation time of the lamp can be shortened, or the output power of the lamp can be reduced. Therefore, while saving power consumption, the service life of the lamp can also be extended. And reduce the number of replacements, which is more economical.

For example, it is necessary to decompose a large amount of malodorous substances generated by kitchen garbage disposals, or to decompose a large amount of cooking oil attached to kitchen ventilation fans, or to clean the inside of closed tanks or drums of dishwashers, dish dryers, clothes dryers, etc. In this case, it is effective if the above-mentioned light generating devices of various wavelengths are used in combination.

Second, since metal oxide semiconductors or metal particles such as Ag, Cu, Ni, Pd, Rh, and Pt having an electron affinity of 1.2 or more, including antimony-added tin oxide, are added to the photocatalyst film of the present invention, Therefore, the surface resistance value of the membrane itself is reduced, so that the phenomenon of static electricity adsorption of large dust, fibers, and undecomposable soil and other minerals that decompose for a long time can be suppressed, thereby preventing difficult-to-decompose dirt. Accumulation on the surface prevents light from reaching the photocatalyst thin film.

The anti-static effect not only prevents dust from attracting, but also prevents short circuits caused by static electricity. This is especially effective for items such as vacuum cleaners that tend to be triboelectrically charged when in use.

Examples of specific effects for each use are as follows. Air cleaners, ventilation fans, electric fans, vacuum cleaners, clothes dryers, tableware dryers, dishwashers, and kitchen waste disposal machines are particularly effective because they absorb dust easily.

Third, in the present invention, when forming the photocatalyst thin film with the above-mentioned effects, a solution containing a low-molecular-weight organometallic compound and water is prepared, and in order to break the bond between the metal atom and the organic group, electromagnetic waves of a specific wavelength such as ultraviolet rays are used. Irradiation accelerates the film formation reaction, so thin films can be formed at lower temperatures than conventional ones. Therefore, the above-mentioned oxide photocatalyst film can be formed on the surface of the organic coating coated on the commonly used plastics and steel plates used for the aforementioned electrical products, including ABS, PS, PP, polyester, etc., and the primer of the film will not be affected by Heat will cause softening, deformation, bubbles, cracks, embrittlement, strength reduction, toughness reduction and other adverse conditions.

Examples of specific effects for each use are as follows. Synthetic resin moldings or painted steel sheets commonly used in outer parts such as air purifiers, ventilation fans, electric fans, vacuum cleaners, clothes dryers, tableware dryers, dishwashers, kitchen garbage disposals, frames, boxes, etc. It can withstand the formation temperature of the conventional _TiO2- based oxide photocatalyst thin film, that is, a high temperature of 300°C or higher, but the present invention can easily form a film without causing thermal damage to the surface material of the above-mentioned parts.

In addition, the constituent materials of the air circulation parts attached to the above-mentioned articles or the fans, impellers, filters, meshes and other parts in the air passages are also difficult to withstand high temperatures above 300°C, but the above-mentioned oxides can be easily formed by using the present invention. Photocatalyst film.

In addition, since the oxide photocatalyst thin film of the present invention can form a hard film at a low temperature, it can replace a hard coat such as acrylic resin coated on the surface of a conventional plastic molded article. In this way, it can increase the gloss of molded products, prevent surface damage, and at the same time inhibit the growth of microorganisms, and obtain antifouling and antistatic effects, just like the conventional hard coating.

When applied to filters formed of non-woven fabrics, fabrics, sponges, etc., since the oxide photocatalyst film formed on the fiber surface is glassy, the surface adsorption and wettability are good. Therefore, the odor trapping rate and the smoke trapping rate can be improved. Even if a film containing only _SiO2 is formed, the trapping effect can be improved by the same principle. If the attached odor and smog cover the fiber surface, the trapping effect will be weakened, but in the present invention, because the glassy film itself It has photocatalytic properties, so it can keep the surface of the fiber always clean, and because the bottom layer with high adsorption continues to be exposed, it can maintain the effect better.

In addition, when applied to dishwashers, the antifouling effect of photocatalysts can reduce the contact angle of water droplets attached to the inside, which can reduce the total amount of residual water and improve the drying efficiency of tableware. Utilizing this effect, it can be applied to various applications that are troubled by condensation.

Claims (32)

What is claimed is: 1. A photocatalyst thin film, which is a coating film in which particles having a photocatalytic effect are dispersed, characterized in that the coating film contains an organic resin with an inorganic functional group bonded to its side chain. 2. The photocatalyst thin film according to claim 1, characterized in that said coating film contains metal elements with an electronegativity less than 1.6, an ionic radius less than 0.2 nm, and a valence of 2 or less. 3. The photocatalyst film according to claim 1, wherein said coating film further contains at least one of P, B, K, and Ca. 4. The photocatalyst thin film according to claim 1, wherein oxide semiconductor particles composed of a metal element having an electron affinity of 1.2 or higher are dispersed in the coating film. 5. A photocatalyst thin film, wherein, in the photocatalyst thin film according to claim 4, the layer in which the oxide semiconductor particles are dispersed and the layer in which the titanium oxide particles are dispersed are respectively provided. 6. A photocatalyst thin film, characterized in that conductive particles are dispersed in the photocatalyst thin film according to claim 1, and the surface resistance of the coating film is 10 ⁹ Ω/cm ² or less. 7. A photocatalyst thin film, characterized in that the photocatalyst thin film according to claim 1 contains silicon oxide. 8. An article characterized in that the photocatalyst thin film according to claim 1 is provided on the surface of a substrate. 9. An article characterized by having an interlayer between the oxide photocatalyst thin film according to claim 8 and the surface of said article substrate. 10. An article, characterized in that the interlayer according to claim 9 is a metal oxide film containing a metal element with a valence greater than 3, or at least one metal element selected from Al, Zr, Fe and transition metal elements. 11. An article characterized in that the substrate according to claim 8 is composed of an organic polymer compound having a decomposition initiation temperature of 300°C or lower. 12. An article characterized in that the photocatalyst thin film according to claim 2 is provided on the surface of a substrate. 13. An article characterized in that the photocatalyst thin film according to claim 3 is provided on the surface of a substrate. 14. An article characterized in that the photocatalyst thin film according to claim 4 is provided on the surface of a substrate. 15. An article, characterized in that it consists of a substrate mainly composed of an organic polymer compound, an interlayer formed of inorganic substances arranged on the surface of the substrate, and the interlayer according to claim 1 arranged on the surface of the interlayer. photocatalyst thin film. 16. An article comprising the photocatalyst thin film according to claim 1 on a surface of a base material in contact with light. 17. An article, as claimed in claim 16, wherein a light source is provided at the light irradiation portion on the surface of the photocatalyst film. 18. An article, as claimed in claim 17, wherein said light source is an ultraviolet lamp. 19. An article, as set forth in claim 16, wherein a transparent material is used for at least a part of the frame covering the surface of the photocatalyst thin film in order to irradiate external light onto the surface of the photocatalyst thin film. 20. An article, characterized in that in claim 19, the light is transmitted through a transparent material with a thickness of 2 mm, and the L value measured by the color difference expression method is below 50, the a value is between -20 and 20, and the b value is between Below 20. 21. An article characterized in that, in claim 16, the photocatalyst film is made of a transparent material for at least a part of the frame covering the surface of the photocatalyst film to allow external light to irradiate the surface of the photocatalyst film. 22. An air purifier, which uses the action of an electric blower to generate airflow, sucks in indoor air through the suction port, passes through the filter set in the ventilation channel, and captures dust, oil fume particles, smoke, pollen and various other substances floating in the air. A variety of microorganisms or malodorous substances, etc., are discharged through the exhaust port after purification. It is characterized in that, among the components, the photocatalyst film according to claim 1 is formed on the surface of the component that is in contact with indoor lighting or sunlight from the outside. 23. A ventilation fan equipped with a low-temperature curing type highly active oxide photocatalyst film, which uses the action of an electric blower to generate airflow, and combines the air sucked into the air inlet on the indoor side with the dust, soot particles, smoke, pollen and All kinds of microorganisms or malodorous substances are discharged to the outside from the outdoor side exhaust port, and it is characterized in that, among the constituent parts, the light described in claim 1 is formed on the surface of the parts that are in contact with indoor lighting light or outdoor sunlight. catalyst film. 24. An electric fan, which uses a motor to run the impeller to generate airflow, characterized in that among the components, the photocatalyst film according to claim 1 is formed on the surface of the component that is in contact with indoor lighting or sunlight from the outside . 25. A vacuum cleaner, the suction port is connected to the dust collection chamber, the air pressure in the dust collection chamber is reduced by an electric blower, and the garbage or dust inhaled from the suction port is collected into the dust collection chamber, and after filtering the above garbage or dust, The air is exhausted from the exhaust port, and the photocatalyst film according to claim 1 is formed on the surface of the component that is in contact with indoor lighting light or outdoor sunlight. 26. A clothes dryer, which uses an electric blower to inhale air from the outside, heats it with a heater, and sends it into a drying drum that collects clothes containing moisture, and reheats to evaporate the water in the clothes, and the air containing water Discharge from the exhaust port or use a heat exchanger to condense moisture, remove the moisture, and discharge from the exhaust port. It is characterized in that, among the constituent parts, right is formed on the surface of the component that is in contact with indoor lighting or outdoor sunlight. The photocatalyst film described in claim 1. 27. A tableware dryer, which uses an electric blower to inhale air from the outside, heats it with a heater, and sends it into a drying room where wet tableware is collected, and then heats to evaporate the water attached to the tableware, so that it can be mixed with the water-containing The air is exhausted together from the exhaust port, and the photocatalyst thin film according to claim 1 is formed on the surface of the components that come into contact with indoor illumination light or outdoor sunlight. 28. A dishwasher, in the washing tank where the dirty tableware is collected, the water is heated while being pressurized by the washing pump, so that the water is sprayed from the freely rotatable nozzle installed in the washing tank, and the tableware is washed After washing, use the electric blower to inhale the outside air, so that the cold air or the warm air heated by the heater is replaced with the high-humidity internal air after washing, so that the water remaining in the tableware or the sink is evaporated and dried. It is characterized in that , Among the components, the photocatalyst film according to claim 1 is formed on the surface of the component that is in contact with indoor illumination light or sunlight from the outside. 29. A kitchen garbage disposer, which puts garbage into a treatment tank containing microbial culture substrates, stirs the culture substrates and garbage with a stirring device, and decomposes the garbage through microbial metabolism; uses an electric blower to decompose The moisture generated during the process is discharged together with the air, and it is characterized in that, among the components, the photocatalyst film according to claim 1 is formed on the surface of the component that is in contact with the indoor lighting light or the sunlight from the outside. 30. The photocatalyst thin film according to claim 1, which contains either ATO or a binder. 31. The photocatalyst thin film according to claim 30, wherein any of Li, Na, and Mg is added. 32. The photocatalyst thin film according to claim 1, wherein a pigment that absorbs visible light is added.

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