KR20000048490A - Thin photocatalytic film and articles provided with the same - Google Patents

Abstract

It is a photocatalyst thin film mainly used for the electric products used in indoor environment, the air flow path, the filtering part, the exterior part or the part illuminated by the built-in lighting equipment. Various additives enhance the catalysis. Generally, it is light that is obtained indoors and decomposes organic matters even by weak light such as fluorescent lamps, incandescent lamps, mercury lamps or sunlight beyond window glass, and decomposes even if contaminants are attached by attachment of cigarettes or sebums such as resin. The antifouling effect is obtained. Similarly, when light causes a variety of odor-causing substances, such as organic amines and mercaptans dispersed in the air, it decomposes and decomposes into low-odorous or non-odorous substances. Obtained.

Description

Photocatalyst thin film and article provided with this {THIN PHOTOCATALYTIC FILM AND ARTICLES PROVIDED WITH THE SAME}

In recent years, materials that exhibit antifouling, deodorization, and antibacterial effects have been attracting attention by utilizing the decomposition of organic substances using TiO ₂ photocatalysts. This uses a redox reaction of a semiconductor photocatalyst as described in New Ceramics (1996) No. 2, 55, and a TiO ₂ thin film formed on a ceramic tile is provided.

On the other hand, as the film forming method, the oxide thin film may be formed by a physical method such as sputtering on a substrate or by a chemical method such as a coating method such as a sol-gel method. The former can be formed at a low temperature by using a vacuum device or the like. The latter can be applied onto a substrate with a simple device such as spincoat or spray and treated at a temperature of several hundred degrees Celsius to obtain a film. It is reported that TiO ₂ , an antibacterial and deodorant material, is effective for anatase type crystals and crystallization is effective for function expression (Patent No. (PTC) WO 94/11092, (PTC) WO 95/15816). In addition, high performance has been reported by adding V, Fe and the like to TiO ₂ (W. Choi, A. Termin, MRHoffmann, J. Phys. Chem., 98, 13669-13679 (1994)).

The following invention is known as an example of applying an oxide photocatalyst thin film to various apparatuses using the above materials and techniques.

For air purifiers, that is, devices intended to remove dust and odorous substances in indoor air, Japanese Patent Application Laid-Open No. 8-266841 or Japanese Patent Application Laid-open No. Hei 8-266605 or Japanese Patent Laid-Open No. 8-309148 imply a filter carrying a photocatalyst mainly composed of TiO _2, as in the JP, and using a means such as a UV lamp in which the technique is installed a mechanism for irradiating light of short wavelength.

Further, a technique of baking the application examples, the photocatalytic thin film as such, the main component TiO ₂ on the surface of the metal parts as those in Japanese Patent Laid-Open No. Hei-7-303819 of the fan at about 600 ℃ known.

In addition, as in Japanese Patent Application Laid-Open No. Hei 9-38189, a mechanism for irradiating ultraviolet rays by installing a light emitting diode is known.

As an application example for a ventilation ship, the structure similar to the use of the ultraviolet lamp like the one of Unexamined-Japanese-Patent No. 5-157305 is known.

In addition, as an example of application as a deodorizing filter installed in the ventilation path of a vacuum cleaner or a food waste treatment machine, a plastic fiber sheet having a photocatalyst mainly composed of TiO ₂ as a powder as shown in Japanese Patent Application Laid-Open No. 7-108175 The same technique as that wrapped and hit seal is proposed.

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photocatalyst thin film in which particles having a photocatalytic function are dispersed in a coating film and an article having the same, in particular in a thin layer on the surface of an organic polymer material, particularly a component made of a general-purpose thermoplastic plastic, having a low heat resistance. An article in which an oxide photocatalyst thin film is formed. Moreover, it is related with the article provided with the oxide photocatalyst thin film in the whole or one part surface suitable for indoor use in which strong ultraviolet rays, such as an ultraviolet lamp and outdoor sunlight, are not obtained.

For example, air cleaner, ventilation line, fan, vacuum cleaner, clothes dryer, dish dryer, dishwasher, food waste processor, heater, humidifier, dehumidifier, air conditioner, heating cooker, electronic cooker, hair dryer, The present invention relates to a device for producing a flow of air using an electric blower such as a deodorizer and a furnace.

Various contaminants and microorganisms suspended in the air attached to the surface of these electrical appliances are decomposed by photocatalytic function by light under living environment to prevent fouling, deodorization, antibacterial and mold. The present invention relates to a technique for obtaining surface characteristics such as wettability improvement, and an article thereof.

BRIEF DESCRIPTION OF THE DRAWINGS The block diagram of the filter type air cleaner main body which concerns on embodiment of this invention,

2 is a perspective view of a filter type air cleaner main body according to an embodiment of the present invention;

3 is a cross-sectional view of an electrostatic precipitating type air purifier main body according to an embodiment of the present invention;

4 is a sectional view of a main body of the ventilation line for a kitchen according to an embodiment of the present invention;

5 is a perspective view of a fan main body according to an embodiment of the present invention;

6 is a perspective view of a cleaner according to an embodiment of the present invention;

7 is a cross-sectional view of the cleaner body according to the embodiment of the present invention;

8 is a sectional view of a main body of a clothes dryer according to an embodiment of the present invention;

9 is a perspective view of a dish dryer main body according to an embodiment of the present invention;

10 is an enlarged cross-sectional view of an exhaust port portion of the dish dryer according to the embodiment of the present invention;

11 is a sectional view of the dish dryer main body according to the embodiment of the present invention;

12 is a perspective view of a dish washer main body according to the embodiment of the present invention;

13 is a cross-sectional view of the dish washer main body according to the embodiment of the present invention;

14 is a cross-sectional view of the dish washer main body according to the embodiment of the present invention;

15 is a perspective view of a food waste processor main body according to an embodiment of the present invention;

16 is a cross-sectional view of the food waste treating body according to the embodiment of the present invention;

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

18 is a cross-sectional view of a low temperature hardening type high active photocatalyst thin film formed on an adherend according to an embodiment of the present invention;

19 is a cross-sectional view of a low temperature hardening type high active photocatalyst thin film formed by laminating two layers on an adherend according to an embodiment of the present invention;

20 shows decomposition test results of organic pigments according to an embodiment of the present invention.

21 is a diagram showing a relationship between an electronegativity and a decomposition rate according to the embodiment of the present invention;

Fig. 22 is a diagram showing the relationship between electronegativity and ion radius according to the embodiment of the present invention;

23 is a view showing the smoke trapping effect of the low temperature hardening type high active photocatalyst thin film according to the embodiment of the present invention;

Fig. 24 is a diagram showing the photolysis effect of the smoke filter according to the embodiment of the present invention;

25 is a diagram showing the ammonia trapping effect of the low-temperature curing type high activity photocatalyst thin film according to the embodiment of the present invention;

Fig. 26 is a diagram showing the photodegradation effect of ammonia gas according to the embodiment of the present invention;

27 is a view showing the photodegradation effect of the smoke-absorbing ABS plate according to the embodiment of the present invention;

28 is a diagram showing the photodegradation effect of salad oil according to the embodiment of the present invention;

29 shows decomposition test results of organic pigments according to the embodiment of the present invention;

30 is a diagram showing the effect of adding a zeolite according to an embodiment of the present invention;

31 is a diagram showing the influence of the ratio of Si and Al according to the embodiment of the present invention;

32 is a view showing the effect of adding an ion exchange zeolite according to an embodiment of the present invention;

33 is a diagram showing the antimicrobial effect of zeolite addition according to an embodiment of the present invention.

34 is a view showing the decomposition test result of the cigarette smoke according to the embodiment of the present invention;

35 is a view showing a decomposition test result of tobacco smoke with respect to the amount of binder added according to the embodiment of the present invention;

36 is a view showing a decomposition test result of tobacco smoke with respect to the amount of silanol introduced according to the embodiment of the present invention;

Fig. 37 is a view showing the decomposition test result of tobacco smoke with respect to the amount of coupling agent addition according to the embodiment of the present invention.

There is an insufficiency in forming oxide thin films on substrates made of low heat resistance, such as plastic, using conventional techniques. Films formed by the sol-gel method include antimicrobial tiles as the antimicrobial and deodorant materials described in the above literature, but heat treatment of several hundred ° C and at least 300 ° C is required to crystallize titanium oxide. Therefore, it is difficult to form a film on a low heat resistance substrate such as plastics, in particular, general-purpose thermoplastics.

In addition, in an environment where light intensity is low, such as indoors, the decomposition rate such as decomposition of organic matter of TiO ₂ itself is not sufficient, and there is a problem that another light source specially installed is required.

The apparatuses of the present invention as described above are mainly made of household telephone products used in indoor spaces such as general homes and offices, but organic polymer materials (plastics) are mainly used for these products. With the exception of monitors of televisions and personal computers, where glass parts are used a lot, about 40 to 50% by weight is made of plastic and most of the rest are made of metals. Plastics account for nearly 90% of the volume. Plastics are widely used because of their light weight, high design, and low price. Among them, thermoplastics are particularly used because of their high mass productivity.

As the most widely used structural members, polypropylene (PP), acrylic butadiene styrene copolymer (ABS), styrene acrylic copolymer (AS), polystyrene (PS), nylon (PA), polycarbonate (PC) , Vinyl chloride (PVC), methacryl (PMMA), polyethylene (PE), polyacetal (POM), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), and the like. It is not able to withstand deformations in more than one environment.

For example, ASTM, D-648 (18.6 kg / cm ² ) has a heat deflection temperature of about 250 ° C. Special high heat-resistance resins such as polyphenylene sulfide, polyphenylene oxide, polyetherimide, etc., which are obtained by winning glass fibers or the like, are very expensive and cannot be used in large quantities for such purposes.

In general, the higher the heat resistance material, the more expensive the price, especially used in exterior parts, PE, PS, ABS, PP, PVC, which averages more than 75% of the plastic parts. Among these, even in ABS having the highest heat resistance, the above ASTM heat deflection temperature is 120 ° C. or lower, and at 300 ° C., it is completely dissolved to form a liquid phase and also undergoes oxidative decomposition.

Moreover, even if the surface which apply | coated the coating material to the surface of inorganic materials, such as metals, it will be limited, The material which has heat resistance exceeding 300 degreeC is limited. Usually, thermosetting resin is used for paint. For example, polyester, acryl, melamine, epoxy, urethane, etc. are typical examples, and it is common to weld at the temperature of about 150 degreeC. These coatings often cause problems such as loss of gloss or peeling when exposed to an environment exceeding 300 ° C.

As these data show, in order to form into a general-purpose material by the sol-gel method by the prior art, there existed a big problem in heat resistance.

On the other hand, in physical methods such as sputtering, CVD, vacuum deposition, and the like, which form a film within a temperature range not exceeding 300 ° C., a large-scale device such as a vacuum device is required and the production cost is high. In addition, since a film is formed under high vacuum during film formation, the composition ratio shift of the oxide photocatalyst is large and the photocatalytic performance deteriorates. In the case of film formation, when an organic material is used as a substrate, there is a problem that reverse sputtering causes damage to the substrate, resulting in deformation of the substrate or the like. In the chemical method by a coating method such as the sol-gel method, when a silica sol in which oxide fine particles are dispersed is used, film formation onto a substrate having no heat resistance cannot be sufficiently sintered because the heat treatment temperature is low. The strength and water resistance of one oxide film are insufficient.

For the above reasons, conventionally known techniques for forming a thin film of a photocatalyst containing TiO ₂ as a main component without damaging deformation or deterioration on the surface of organic polymer materials used in general telephone products It was virtually difficult.

An object of the present invention is to provide a highly active photocatalyst thin film that can be formed on a surface of a material, for example, plastic or paint, which lacks heat resistance, and an article having an antibacterial, antifouling, and deodorizing effect.

On the other hand, in the invention of the photocatalyst applied technology there is no comment on the study to increase the photocatalytic decomposition of the organic material itself effective as the main component such as TiO _2.

In other words, no studies have been made on material blends for improving the photoactivity of a film containing TiO ₂ . Therefore, for example, in the case of Japanese Unexamined Patent Application Publication No. 8-309148, Japanese Unexamined Patent Application Publication No. 8-266605, which is a conventionally known use method for deodorization, or decomposing pollution by evacuation of tobacco, etc. In Japanese Patent Application Laid-Open No. Hei 9-38189 or Japanese Patent Application Laid-Open No. Hei 5-157305, which is an example of application to decomposing contamination such as oil during cooking, neither of them has the activity of the photocatalyst itself. Since it is not enough, the decomposition reaction is increased by providing a mechanism for irradiating ultraviolet rays, heating means, and the like.

These are the biggest reasons that the organic decomposition rate of TiO ₂ itself when light intensity is small is not enough, and since the study to increase this is not done, UV lamp etc. are used together as a means to increase light intensity. As an ultraviolet lamp, a high pressure mercury lamp or a metal halide lamp is usually used, but a mechanism such as a power supply device or a cooling mechanism is required, leading to an increase in weight and price of the entire application. In addition, there was a problem in the practicality, such as the lamp life is about 2000 hours and regular replacement work is required.

In the prior art, although a technique for increasing the decomposition efficiency by adding Fe and V to TiO ₂ is well known, high-temperature treatment at several hundred ° C. has been performed to improve the performance, and application to a substrate material lacking low melting point heat resistance is difficult.

Another object of the present invention is to improve the photodegradation efficiency of the photocatalytic film that can be formed at low temperature than the decomposition efficiency of TiO ₂ alone, so that the deposits can be decomposed at a lower intensity than conventionally required light intensity. There is.

In the prior art, in the use of antimicrobial activity, deodorization, deodorization, etc., since the target substance is an organic substance and the target substance is a fine particle or a molecular form, the adhered liquid organic substance or particulate organic substance could be decomposed, but the size was small. In the case of large fibers and dusts, even if organic matters, decomposition takes a very long time, or decomposition of inorganic matters centered on dirt is very difficult and thus incomplete for the purpose of pollution prevention. Since these contaminants are generally suspended in the air in an electrically charged state, the static electricity is hardly discharged when they are attached to an individual surface having high electrical insulation, and thus remain in the attached state. There is a problem that the light is blocked by the attached inorganic contaminants so that sufficient light is not irradiated on the photocatalyst surface and the decomposition efficiency of organic matters is reduced.

Another object of the present invention is to prevent dusts and inorganic contaminants having large sizes that are difficult to be decomposed and removed in principle by the oxidative decomposition effect of these photocatalysts as members to be subjected to electrostatic forces.

In order to achieve the above object, a feature of the present invention is a mechanism for generating an air flow by driving an electric blower such as an air cleaner, a ventilation line, a fan, a cleaner, a clothes dryer, a dish dryer, a dishwasher, a food waste processor, and the like. Among the components of electrical appliances mainly used indoors, the low temperature hardening type high active oxide photocatalyst thin film is provided on the surface of the air flow passage, the filtration mechanism in the air flow passage, or the exterior parts to which the indoor illumination light is exposed.

The melting point or decomposition temperature of the material of the target part is 300 ° C. or lower, and in particular, a low temperature hardening type high active oxide photocatalyst thin film is formed on a molding member, a fiber member, a foam member, and a sheet member made of a general-purpose thermoplastic. Problems such as contamination, microbial propagation and odor generation are solved.

In the present invention, the film thickness of the oxide photocatalyst thin film mainly composed of TiO ₂ is optimized, the TiO ₂ particle diameter is optimized, the addition of appropriate ions having low electronegativity, and the mixing ratio with TiO ₂ when SiO ₂ is used as the binder. Room light, which has not been possible in the past, by forming a thin film on which the activity of the photocatalytic reaction is improved on the air flow path or the surface of the external parts of the electrical appliance by the addition of an oxide semiconductor having a high electric affinity and the addition of suitable precious metals. Antifouling at the level, deodorization, microbial propagation inhibitory effect will be obtained. In addition, it is possible to prevent damage to the ground of the organic material which is vulnerable to oxidative decomposition by laminating the film.

At the same time, in the present invention, during the process of forming a thin film of an inorganic polymer mainly composed of SiO ₂ or TiO ₂ , an electromagnetic wave containing a specific wavelength necessary for breaking the bond between the metal atom and the organic group of the organometallic compound is irradiated and By adopting the step of promoting the decomposition reaction, the polymerization of the inorganic polymer can be carried out at a low temperature, so it is firm at a low temperature such that deformation, melting, or decomposition does not occur even on the surface of the general-purpose thermoplastic plastic having low heat resistance. The strength of the oxide photocatalyst thin film was obtained.

Hereinafter, the detail of the low temperature hardening type high active oxide photocatalyst thin film is demonstrated.

In the oxide photocatalyst thin film in which TiO ₂ fine particles, which are oxide photocatalysts, are dispersed, an electronegativity is less than 1.6 and an ion radius is less than 0.2 nm, and the reaction efficiency is improved by adding ions having a valence of 2 or less. As a specific addition element, Na, Li, K, Sr, Mg, Ca, Zn are especially effective, and 0.5-20 wt% is preferable as addition amount of these elements. The size of the TiO ₂ fine particles is most effective when adjusted to 5 to 20 nm.

Also in the thin film oxide photocatalyst TiO ₂ fine particles that are dispersed in SiO _2, preferably in a weight ratio of TiO ₂ / SiO ₂ 9 to 5.

It is preferable that the film thickness of the said oxide thin film is 100-500 nm.

If the component to be added is added to the above ions and the oxide fine particles mainly composed of an oxide semiconductor composed of a metal element having at least an electron affinity of 1.2 or more are dispersed, the effect is further increased. In particular, it is suitable that an element consists of Sn, Fe, Cr. As for the addition amount, 2-50 wt% is preferable. Among these, oxide fine particles mainly composed of ATO (antimony-added tin oxide. The weight ratio of antimony is preferably 1% to 10%) are particularly effective. When these semiconductive fine particles are added, the surface resistance value of the film itself is lowered, so that it is difficult to electrostatically adhere to the contamination itself by containing inorganic pollutants which cannot be oxidized.

In addition, the oxide photocatalyst thin film is effective even if it has a plurality of laminated structures. The first layer is counted from the surface, and TiO ₂ fine particles are dispersed in SiO ₂ , and the ions are added to the film, and the second layer is counted from the surface. Oxide fine particles mainly composed of the oxide semiconductor are dispersed. As a result, the photocatalyst functions effectively without damaging the surface of plastics having low durability against oxidation. Moreover, it is more effective if at least 1 sort (s) of Fe, Al, Zr is added to the said 2nd layer.

The additive component is effective to add at least one of Pt, Rh, Pd, Ag, Cu, and Ni in addition to the above ions.

TiO ₂ has a function as a photocatalyst and has functions such as antibacterial, deodorant, and antifouling by decomposition of organic matter. The function is attributable to electrons and holes generated when the semiconductor TiO ₂ is irradiated with light, especially ultraviolet rays. TiO ₂ , a semiconductor, generates electrons and holes when irradiated with light having energy above the band gap. The generated electrons and holes decompose water adsorbed on the TiO ₂ surface to generate H radicals and OH radicals. The OH radicals can decompose the organic material by reacting with the organic material. The photocatalyst decomposes organic matters and the like with such a mechanism, but there are two means to increase the reaction rate. The first is to increase the amount of one active point and the second is to increase the number of active points. In order to increase the number of active sites, it can be achieved by increasing the surface area, that is, making the TiO ₂ fine. In order to increase the amount of the active site, the crystallization of TiO ₂ (anatase) is improved and the recombination of electrons and holes is prevented. By satisfying the above, the reaction rate can be increased. However, improving the crystallization of TiO ₂ (anatase) and increasing the surface area are opposite to each other, making it difficult to achieve compatibility. In other words, improving the crystallinity causes an increase in the particle diameter and lowers the surface area. Therefore, there is an optimum region between the direction of improving the crystallinity and the direction of increasing the surface area. The optimum region was found to be 5-20 nm from most experimental results of the present invention. In the case of dispersing the TiO ₂ fine particles, even if the type of oxide used as the inorganic binder was changed, the decomposition rate increased in the range of the particle diameter.

In order to improve the reaction rate by preventing recombination of electrons and holes, it is achieved by increasing the separation efficiency of electrons and holes. Ti defects exist on the TiO ₂ surface. This defect becomes a recombination point of electrons and holes, which inhibits the reaction. In addition, when ions having an ion radius equal to Ti are added to the Ti defects on the surface, the defects disappear and the recombination point is reduced. In addition, since it is present as a cation, electrons can be attracted and separated from the holes, and the oxidation reaction of the organic material can be promoted. The present invention has found that the conditions of the additive having such an effect are effective in that the electronegativity is smaller than 1.6 and the ion radius is smaller than 0.2 nm.

In addition, it was found that the present invention can be improved in performance by addition of other oxide semiconductor fine particles. This is achieved by injecting a carrier from an oxide semiconductor having a high carrier concentration into TiO ₂ having a low carrier concentration. Therefore, it is necessary to make carrier flow easily from TiO ₂ to oxide semiconductor. When the electron affinity of the oxide semiconductor is Ti or less, a schottky barrier is formed. Therefore, the material to be added needs to have an electron affinity of 1.2 ev or more.

In the present invention, it has also been found that the addition of Fe, Al and Zr results in the loss of the photocatalyst of TiO ₂ . In the case of using a substrate material mainly composed of organic substances, there is a problem of self-destruction of the substrate by photocatalytic action.

Therefore, in the present invention, a barrier layer is formed between the substrate and the photocatalyst, but self-destruction can be completely suppressed by adding Fe, Al, and Zr to the barrier layer. Moreover, since it is a high performance barrier layer, it became possible to make film thickness thin enough. When conductive fine particles such as ATO are added or laminated, the photocatalyst performance is improved and an antistatic function is provided to prevent not only organic matter decomposition but also adhesion of inorganic matters such as dust floating in the air. Antifouling function can be provided. In addition, in the present invention, since the above-mentioned activity is high and can be decomposed with a weaker light intensity than the conventional one, or has an antistatic function, the particles having contaminants themselves are hard to adhere to by static electricity. A thin film of an active photocatalyst can be formed on the surface of a material having insufficient heat resistance in the conventional film forming method, which is inexpensive and has high versatility.

To this end, when inorganic polymerized by polymerizing a low molecular weight organometallic compound containing titanium or silicon with water, the specific wavelengths necessary for breaking the bonds between the metal atoms and organic groups of the organometallic compound are polymerized. By introducing a step of irradiating the electromagnetic wave, the hydrolysis reaction of the organometallic compound is promoted, a prepolymer of a metal oxide is formed in the solution, and the film forming temperature can be lowered.

Ultraviolet light is most preferable with the said electromagnetic wave of the said specific wavelength. After applying a solution containing a low molecular weight organometallic compound and water to the surface of the adherend, to irradiate an electromagnetic wave having a specific wavelength necessary to break the bond between the metal atom and the organic group of the organometallic compound, such as ultraviolet light. Most preferably, the coating film is heated to dry at the same time or after the microwave irradiation step.

Further, in the case where the titanium oxide particles having photocatalytic properties used in the prior art are dispersed in the inorganic thin film, there is a problem that the performance decreases as the occupied area of titanium oxide is smaller than that of the photocatalyst composed only of titanium oxide. In particular, when the film strength is required, the inorganic binder is added to increase the strength, but the activity is remarkably lowered.

It is therefore an object of the present invention to provide a product using a photocatalyst which is highly active even in a living environment, even if it is a structure in which titanium oxide is dispersed in a binder. In particular, the self-cleaning characteristics of the photocatalyst reduce the number of parts replacement and cleaning of the product.

In order to achieve the foregoing object, the present invention was added to ATO, RuO ₂ to the photocatalyst made of titanium oxide. In addition, any one of Li, Na, and Mg is added.

Moreover, this invention is a manufacturing method which improves the bonding state of a hetero semiconductor surface by coating ATO particle directly on a titanium oxide powder. In addition, the present invention is a coating method capable of high temperature treatment as a pretreatment, and film formation at a low temperature of about 120 ℃ at the time of coating.

If the electron affinity of the oxide semiconductor is smaller than that of Ti, a Schottky barrier is formed at the particle interface of the fine particles, and the carrier of the added oxide semiconductor cannot be injected into TiO ₂ , and no effect is exhibited. On the other hand, when the electron affinity of the oxide semiconductor is smaller than that of Ti, a schottky barrier is not formed in the particle interface of the fine particles, and the ohmic junction is easily formed, and the carrier of the oxide semiconductor is easily injected into TiO ₂ to function effectively. In particular, although ATO has a slightly smaller electron affinity than Ti, there is almost no difference in performance, and thus an improvement in performance is seen. ATO, which is a conductive oxide, has a high carrier concentration, and a large amount of carriers of ATO are injected into TiO ₂ , thereby improving the activity of the photocatalyst.

In addition, ATO has recently attracted attention as a conductive oxide, and ultrafine particles are commercially available. By the ATO ultrafine particles added to the TiO ₂ photocatalyst it can be produced more simply ATO added TiO ₂ photocatalyst. However, when such ultra-fine particle ATO is used, in addition to ultra-fine particle ATO, some ATO particles contacting TiO ₂ fine particles exist, but some particles present in SiO ₂ are not efficient. On the other hand, in the manufacturing method of the present invention, since the ATO solution is added to the TiO ₂ fine particles before firing, the contact area between the ATO and the TiO ₂ particles is large, and the bonding state is also good by firing, so that electron transfer between the hetero semiconductors is achieved. Also goes smoothly. In addition, RuO ₂ , which is a p-type semiconductor, attracts holes among electrons and holes generated by TiO ₂ and ATO, which are n-type semiconductors, and can suppress recombination of electrons and holes. Therefore, the electrons and holes generated by absorbing light can be effectively used for catalysis, and the decomposition rate can be improved.

In addition, the addition of Li, Na, and Mg causes their ion radius to be close to the ion radius of Ti, which easily invades Ti defects on the TiO ₂ surface and increases the stability of the crystal. In addition, Li, Na, and Mg tend to attract electrons because of their high ionicity, and the reaction efficiency can be increased by separating electrons and holes generated by absorbing light.

The film formation method of the present invention can be produced at about 120 ° C., and can be applied to plastic materials as well as ceramic substrates. In the sol-gel method usually, there is a need for several minutes or hours for the crystallization of an application is difficult, or TiO ₂ to the plastic because it requires a temperature of about 400 ℃. On the other hand, in the production method of the present invention, since the film can be formed at a low temperature, the substrate can be used abundantly and the photocatalyst can be formed on any surface. In addition, a short time treatment such as several minutes can be performed, and a significant reduction in production cost is possible.

In the present invention, RSO (RuSrO ₃ ) is added to a photocatalyst made of titanium oxide. Further, the present invention is a photocatalyst consisting of a STO (SrTiO _3), RSO, binder. Moreover, this invention is a photocatalyst characterized by adding any 1 type of Li, Na, and Mg.

In addition, the present invention is a manufacturing method for improving the bonding state of the interface between different semiconductors by coating RSO directly on the semiconductor photocatalyst powder, and also a coating method capable of forming a film at a low temperature of about 120 ° C. at a high temperature as a pretreatment and coating. to be.

In the RSO-added photocatalyst, the contact of RSO and TiO ₂ causes the performance of the photocatalyst to improve as the TiO ₂ photocatalyst uses holes in the RSO. On the other hand, the oxidation activity of the catalyst is due to the redox action of electrons and holes generated by absorption of light. In particular, the produced holes generate radicals that produce strong oxidation. RSO is a p-type semiconductor and has a large amount of holes. By the RSO and TiO ₂ are in contact the injection hole in the TiO ₂ can be by oxidizing the organic matter such as TiO ₂ on the surface, and enhance the photocatalytic activity.

Li, Na, and Mg have an ion radius close to that of Ti, which easily invades Ti defects on the TiO ₂ surface and increases the stability of the crystal. In addition, Li, Na, and Mg tend to attract electrons because of their high ionicity, and the reaction efficiency can be increased by separating electrons and holes generated by absorbing light.

The addition of RSO includes a method of mixing the RSO powder with the TiO ₂ powder and a method of coating the RSO sol on the titanium oxide powder and baking it. Electronics There is also present in the SiO ₂ particles due to the use of SiO ₂ is also present one RSO particles in contact with the TiO ₂ particles as the binder, is not efficient. On the other hand, the latter can be baked by adding an RSO solution to TiO ₂ fine particles in advance, and the contact area between RSO and TiO ₂ particles is large, and the bonding state is good by firing, so that electron transfer between hetero semiconductors is also smooth. However, in order to manufacture RSO, the temperature of 700-850 degreeC is required, and since RSO does not crystallize at the temperature below this, it does not function as a p-type semiconductor. In the case of TiO ₂ , the crystal becomes rutile at 600 ° C. or higher. It is an anatase type that expresses sufficient function as a photocatalyst. In rutile type, the performance of a photocatalyst falls rapidly. Therefore, when TiO ₂ is subjected to high temperature treatment after the addition of RSO, RSO becomes a p-type semiconductor, but TiO ₂ phase-transforms into a rutile type and loses its function as a photocatalyst. Therefore, the RSO-added STO photocatalyst becomes effective using STO (SrTiO ₃ ) which can expect the same function as TiO ₂ as the photocatalyst. STO has almost the same band structure as TiO ₂ . Moreover, the manufacturing method is crystallized by processing at high temperature, such as 700-850 degreeC. Also, RSO and STO are any crystals or perovskites, and the crystal lattice constants are almost the same because Sr-O is common. Therefore, the fabrication conditions are very close to the RSO and the bonding state is good, and the activity of the photocatalyst can be improved.

In addition, the conventional photocatalyst has a small decomposition rate, and therefore requires time for decomposition and removal of gas. Moreover, when light is not irradiated, it is powerless and acts only at the time of light irradiation. Therefore, although the number of bacteria can be reduced by antibacterial action against bacteria, there is a fear of bacterial propagation if the light irradiation time is long.

Therefore, an object of the present invention is to increase the rate of gas removal and at the same time add an antimicrobial effect during light irradiation.

In order to solve the said subject, this invention added the adsorbent to the photocatalyst which consists of titanium oxide. The added adsorbent is zeolite. Moreover, this invention is the zeolite which ion-exchanged any one of Cu, Ag, Li, Na, and Mg in the photocatalyst which consists of titanium oxide.

The conventional photocatalyst is composed of a semiconductor photocatalyst material represented by titanium oxide. These materials are characterized by being capable of antibacterial and self-cleaning by redox reactions of photocatalysts. Self-cleaning may reveal deterioration of the catalyst when contamination is conspicuous, but antimicrobial properties are difficult to determine visually. In spite of a decrease in function such as peeling of the film and deterioration of performance, when it is used without notice, the growth of dangerous bacteria and the like proceeds, which may cause a problem.

Therefore, the present invention is to provide a photocatalyst material which can be visually judged for performance.

In order to solve the above problems, the present invention is an antibacterial and antifouling material comprising a photocatalyst, characterized in that the antibacterial and antifouling materials comprising a photocatalyst can be visually seen. It is a photocatalyst which added the pigment which absorbs.

Photocatalysts generally absorb ultraviolet light and cause catalysis. In the living environment, only a few ultraviolet rays are present, and photocatalysts perform antibacterial and antifouling by using the trace amount of light. When visible light can be effectively used, a high-performance photocatalyst can be provided in a living environment. In solar cells, wet solar cells using titanium oxide using visible light have already been tested. This is due to the sensitization effect that a dye absorbing visible light is laminated, and electrons excited by the dye absorbing visible light stimulate titanium oxide and current flows. The same reduction can expect the same effect on the photocatalyst. By adding a material that absorbs visible light to titanium oxide, electrons that absorb visible light and excite it can be used for redox reaction of photocatalyst by stimulating titanium oxide. However, the pigment | dye which has such a sensitization effect is many organic substance system, and it decomposes not only directly by an ultraviolet-ray but also by photocatalytic action. In addition, the effective use of visible light also improves performance and makes it easier to decompose and deteriorates even under a living environment. Therefore, in the present invention, a test was focused on a pigment system with little deterioration due to ultraviolet rays. As a result, it was found that the pigment system had a small decomposition rate and a sensitizing effect. Although it is a pigment, since a raw material is a main organic material, any thing decomposes and deteriorates. However, in the case of pigment addition, since it decomposes gradually in a living environment, on the contrary, when the pigment is used, the material can be notified of the replacement time by adjusting the decomposition rate at the time of replacing the product.

Moreover, the conventional photocatalyst consists of the semiconductor photocatalyst material represented by titanium oxide. These materials are characterized by being capable of antibacterial and self-cleaning by redox reactions of photocatalysts. Self-cleaning may reveal deterioration of the catalyst when contamination is conspicuous, but antimicrobial properties are difficult to determine visually. In particular, even if the function is degraded, such as peeling of the film and deterioration of performance, when used without notice, the growth of dangerous bacteria and the like may proceed, which may cause a problem.

Thus, the present invention is to provide a photocatalyst material that can be easily judged performance by eye, the present invention is a photocatalyst, characterized in that the deterioration of the function in the antibacterial, antifouling material consisting of the photocatalyst can be seen visually It is a photocatalyst which added the pigment which absorbs visible light to the photocatalyst which consists of titanium oxide as an antibacterial and antifouling material which consists of.

Photocatalysts generally absorb ultraviolet light and cause catalysis. In the living environment, only a few ultraviolet rays are present, and photocatalysts perform antibacterial and antifouling by using the trace amount of light. When visible light can be effectively used, a high-performance photocatalyst can be provided in a living environment. In solar cells, wet solar cells using titanium oxide using visible light have already been tested. This is due to the sensitization effect that a dye absorbing visible light is laminated, and the dye absorbs visible light and the excited electrons stimulate titanium oxide and current flows. The same reduction can expect the same effect on the photocatalyst. By adding a material that absorbs visible light to titanium oxide, electrons that absorb visible light and excite it can be used for redox reaction of photocatalyst by stimulating titanium oxide. However, the dye having such a sensitizing effect is often organic, and is not only directly decomposed by ultraviolet rays but also decomposed simply by photocatalysis. In addition, the effective use of visible light also improves performance and makes it easier to decompose and deteriorates even under a living environment. Therefore, in the present invention, a test was carried out with a focus on a pigment system with little deterioration due to ultraviolet rays. As a result, it was found that the pigment system had a low decomposition rate and a sensitizing effect. Although it is a pigment, since a raw material is a main organic material, any thing decomposes and deteriorates. However, in the case of pigment addition, since it decomposes gradually in a living environment, on the contrary, when the pigment is used, the material can be notified of the replacement time by adjusting the decomposition rate at the time of replacing the product.

Moreover, the photocatalyst applied to plastic products conventionally adds inorganic binders, such as a silica, to titanium oxide. The photocatalyst in which such titanium oxide particles are dispersed in an inorganic binder has a problem in that performance decreases as the occupied area of titanium oxide is smaller than that of a photocatalyst composed only of titanium oxide. In particular, when the film strength is required, the inorganic binder is added to increase the strength, but the activity is remarkably decreased. In addition, photocatalysts are excellent for decomposing organic matter, but are ineffective against inorganic contamination. However, mineral contamination is extremely attached to organic pollution. Removing organic contamination by photocatalytic action can also prevent the adhesion of inorganic contamination to some extent. However, once the inorganic material is attached, the attached portion does not transmit light and thus loses photocatalytic action, and thus, organic contamination cannot be decomposed, and consequently, contamination is promoted. Therefore, it responds by washing | cleaning by raising hydrophilicity etc. and removing adhesion of an inorganic substance. However, for the photocatalyst material and the product to be cleaned, it is necessary to improve the strength by using a large number of binders constituting the photocatalyst, but there is a problem that the photocatalytic action is lowered as described above.

Therefore, the present invention provides a photocatalyst material which does not cause film peeling when washing with water, without causing degradation of the photocatalyst even when a large amount of binder is added, thereby easily cleaning organic and inorganic contamination. It is possible to reduce the frequency of cleaning and replacement of parts.

According to the present invention, in a material having an antibacterial antifouling effect made of a photocatalyst, water washing is possible, inorganic contamination can be removed, and strength is further strengthened by adding an organic resin.

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

When the photocatalyst is coated on the plastic surface, adhesion with the plastic surface is insufficient when silica is used in the binder. On the other hand, when the organic resin is selected in accordance with the substrate, the adhesive strength is sufficient, resulting in a strength that can withstand cleaning. However, organic resins decompose by photocatalysis. In order to prevent this, it is preferable to use an inorganic material, but in this case, the strength is lowered. Therefore, decomposition can be suppressed by introducing an inorganic functional group into the side chain of the organic resin and joining the contact portion with the titanium oxide surface by the inorganic system.

In the case of using an organic resin, unlike a ceramic material such as silica, it can be cured without applying heat. For example, there are also features that can be achieved by using a room temperature curing resin. However, the room temperature curing system takes about 24 hours in addition to the instant adhesive. The instant adhesive cures in a short time but is slowly decomposed by the photocatalyst. As a resin which can be cured in a short time and is excellent in light resistance, a UV curing system may be mentioned. The UV curing system is cured by ultraviolet rays, and is gradually polymerized and cured by ultraviolet rays emitted from a fluorescent lamp. However, it is also true that the photocatalyst is gradually decomposed. Therefore, by suitably combining photocuring and photolysis, light resistance can be improved as a result.

The UV curable resin completely covers the surface of the TiO ₂ particles with a loss of catalytic properties. Thus, by the addition of a coupling agent of the portion exposed to the surface of TiO ₂ it may be increased. In addition, the photocatalyst decomposes the surface adsorption water to generate radicals, but by adding a coupling agent, a large number of surface adsorption water can be maintained, thereby exhibiting catalytic performance.

Hereinafter, an example of embodiment of this invention is described with reference to FIGS.

Table 1 to Table 9 show the compounding composition of the low temperature hardening type high active oxide photocatalyst thin film formed on the surface of various molded articles, coated steel sheets and filters and the effects of the examples.

(Example 1)

1, 2 and 3 will be described an air cleaner which is a first embodiment of the present invention.

1 is a configuration diagram of a filter type air cleaner main body, and FIG. 2 is a main body perspective view. The air cleaner main body (1) fixes the condenser motor (7) to the rear cover (12) with screws (8), the motor driving condenser (11) and the operation switch (9), and the fan (6) , The nut 5 is fixed to the condenser motor 7, and the rear cover 12 and the frame 4 are fixed with the screws 13. In addition, the filter 3 is fixed to the panel (suction port) 2, and the panel (suction port) 2 is removed to take out the filter 3. The switch knob 10 is fixed to the operation switch 9.

The fan 6 is rotated by the driving force of the condenser motor 7 to produce an air flow. By this airflow, indoor polluted air containing dust, smoke, oil particles, microorganisms or microorganisms, pollen, and odors is sucked from the panel (intake port) 2. The contaminated air sucked in is discharged from the exhaust port 15 of the grill 14 portion after being filtered through the filter 3 portion and cleaned. The filter 3 part has a composite structure in order to have a function for removing various contaminations and odors. The filter 3 consists of the outer filter 3a which is a layer which covers an outer surface, and the inner filter 3b inside the outer filter 3a (illustration omitted). In either filter, a nonwoven fabric layer or a sponge-like porous layer such as polyester, urethane, cellulose, nylon, or electretized polyolefin is used to filter dust. In addition to these basic structures, activated carbon particles and fibers for adsorbing odors are mixed, mixed or enclosed in the inner filter 3b. In addition, a drug for neutralizing odor in the fiber itself may be penetrated or electrodeposited onto the surface. As a medicament, in addition to various organic acids and alkaloids of flavonoids, antibacterial agents for suppressing the growth of microorganisms are also used. Recently, high safety chitin, chitosan, catechin derivatives, and the like are also used. The amount of air to be generated is about 2 to 3 (m ³ / min), and has a capacity of removing 70 to 95% of tobacco smoke in a 30-minute operation in a room of 4 pyeong.

In the present embodiment, the outer filter 3a is made of a nonwoven fabric of acrylic fiber, and the low-temperature-curable high active oxide photocatalyst thin film of Sample No. 21 shown in Table 3 later is formed on this surface. After the corona discharge treatment, the acrylic nonwoven filter was formed of a thin film of SiO ₂ only, that is, sample No. 12 in Table 1 as a base layer, and then a low temperature hardening type high active oxide photocatalyst thin film of sample No. 21 was formed after the film was formed. do. A method of forming a film will be described in detail in Example 9 later, but after curing a predetermined sol and coating the work by various methods, the film is cured while irradiating a low pressure mercury lamp in a 120 ° C atmosphere. In the following examples, films were formed by the same means. The coating method was performed by spraying, dipping, brushing or the like depending on the shape of the work.

The outer filter 3a is a component that filters the contaminated air drawn in from the panel (intake) 2 for the first time, and includes various foreign substances such as dust, smoke, oil particles, microorganisms and microorganisms, pollen, and odors. This is attached in large quantities. A plurality of openings are provided in the panel (suction port) to suck air efficiently, and light such as indoor lighting or sunlight is irradiated to the air intake surface of the outer filter 3a from this opening. By this light, foreign matter collected on the surface of the outer filter 3a is oxidatively decomposed. In particular, cigarette smoke and oil fine particles adhere to the low-temperature hardening type high active oxide photocatalyst on the filter surface in a thin film form, and thus decompose efficiently. In addition, various microorganisms such as bacteria and fungi suspended in the air are suppressed from being killed or propagated by the decomposition of the high activity photocatalyst. In addition, by covering the fiber surface of the nonwoven filter with a glass coating, the wettability with the smoke particles is improved, and the smoke trapping effect is also improved.

The panel (intake port) 2, the frame 4, the operation switch 9 and the rear cover 12, which are exterior parts of the main body of the air cleaner 1, are injection molded articles of thermoplastic ABS. On the outer surface of these parts, a low temperature hardening type high active oxide photocatalyst thin film is formed.

In the present Example, the schematic diagram of the sample shown in Table 6 later, and the thin film of the surface of this acrylic nonwoven fabric filter is shown in FIG. 19 at the surface of these target ABS components. The plastic adherend 189 is here acrylic fiber, and the low temperature hardening type high active oxide photocatalyst thin film is composed of a surface first layer 194 and a surface second layer 192, all of which contain TiO ₂ particles in the SiO ₂ film 186. 187 and lithium 190 are in a dispersed state, and antimony-added tin oxide fine particles 193 are dispersed in the surface second layer 192.

The thin film of the low temperature hardening type high active oxide photocatalyst of No.86 is formed. In the acrylic nonwoven fabric filter, after the corona discharge treatment, a first layer is formed, and after forming the film, a second layer of a low temperature hardening type high active oxide photocatalyst containing ATO of Sample No. 86 is formed.

These exterior parts are irradiated with light such as indoor lighting or sunlight. Therefore, even if various foreign matters as mentioned above adhere, they are oxidized and decomposed similarly to the case of a filter.

3 is a cross-sectional view of the electrostatic precipitating air cleaner. The whole consists of the front cover 16 and the rear cover 17. The pre-filter 16 is provided in the front cover 16 and the panel 18, and the intake port 19 and the exhaust port 20 are installed, and the intake port 19 and the air filter connecting the intake port 19 and the exhaust port 20 are freely detachable. There is 21. At the rear, the dust collecting electrode 22 and the discharge electrode 23 are replaced, and the dust collecting electrode 22 and the ozone removal filter 24 for removing ozone generated from the discharge electrode 23 are provided. And a dust collecting unit in which the pre-filter 21, the dust collecting electrode 22, the discharge electrode 23, and the ozone removing filter 24 are mounted on the frame 25. Furthermore, at the rear, there are a cushioning material 26, a duct 28 for connecting the blower 27 and the dust collecting unit and a blower 27 to the contact portion with the dust collecting unit, and the shock absorbing material 26 is provided in the duct 28, In addition, the duct 28 is installed in the blower 27, there is a blowing unit composed of the same body. The cleaned air is exhausted from the exhaust port 20.

The pre-filter 21 plays the same role as the outer filter 3a in the case of the filtration type air cleaner.

In this embodiment, this prefilter 21 is a net made of nylon, and a thin film of the low temperature hardening type high active oxide photocatalyst of Sample No. 21 shown in Table 3 later is formed on this surface. The net made of nylon forms a thin film of a low temperature hardening type high active oxide photocatalyst of Sample No. 21 after ultraviolet irradiation treatment. The schematic diagram of the thin film of this nylon net surface is shown in FIG. 18 in sectional drawing. Plastic adherend 189, in which nylon fibers, and has low-temperature curing type high activity oxide photocatalyst thin film 191 is a TiO ₂ fine particles (187) and lithium 190 is dispersed in SiO ₂ film 186.

The rear cover 17 is an injection molded product of ABS, and the front cover 16 is a plastic processed galvanized steel sheet, and the outer surface thereof is coated with a polyester coating paint. On the outer surface of these rear cover 17 and front cover 16, the low temperature hardening type high active oxide photocatalyst thin film of sample No. 86 is formed similarly to the above.

(Example 2)

The ventilation line which is 2nd Example of this invention is demonstrated by FIG.

4 is a cross-sectional view showing the structure of the kitchen ventilation line. The box 30 is provided with an electric motor 30, and the motor 30 is provided with a blade 31. Moreover, the shutter 32 is provided in the outdoor side (exhaust side) of the frame 29, and the orifice 33 is provided in the indoor side (intake side) of the frame 29. As shown in FIG. The luminaire 35 with the fluorescent tube 34 is provided above the indoor side (intake side) of the orifice 33. The filter 36 is provided in the indoor side (intake side) of the orifice 33 and the luminaire 35. Below the filter 36 is an oil pocket 37.

Ventilation capacity is about 800 to 1000 (m ³ / hour) when the diameter of the general blade 31 is 25 (cm).

Although the structure of FIG. 4 shows the ventilation line of the specification of a kitchen, the installation angle and the positional relationship of parts are also slightly different in general indoors, a toilet, a bathroom, etc., and the basic structure is the same.

The structure of the filter 36 is the same as that of the above-described air purifier, and can be given a deodorizing function or an antimicrobial function in a complex structure according to various uses.

In this embodiment, the filter 36 is a single layer filter made of a nonwoven fabric of acrylic fiber, and a thin film of the low temperature hardening type high active oxide photocatalyst of Sample No. 22 shown in Table 3 is formed on the surface thereof. After the corona discharge treatment, the acrylic nonwoven filter was formed of a thin film of SiO ₂ only, that is, sample No. 12 in Table 1 as a base layer, and a thin film of a low temperature hardening type high active oxide photocatalyst of sample No. 22 was formed after the film was formed. do.

The frame 29 is an injection molded product of PS (high impact styrol resin), and the orifice 33 and the blade 31 are injection molded products of ABS. On the surface of these molded parts, the low temperature hardening type high active oxide photocatalyst thin film of sample No. 86 is formed similarly to the said air cleaner.

The shutter 32, which is a component facing the outside, is made of a cold rolled steel sheet subjected to hot dip galvanizing, and an acrylic resin is electrodeposited on the surface thereof, and the sample No. The low temperature hardening type high active oxide photocatalyst thin film of 86 is formed.

The surface facing the indoor of the filter 36 is irradiated with light by indoor lighting, and the opposite surface is irradiated with light emitted from the luminaire 35. In addition, light emitted from the luminaire 35 is irradiated to components such as the frame 29, the orifice 33, the blade 31, and the oil pocket 37. Sunlight is irradiated on the surface of the shutter 8 facing the outdoors.

In the case of this embodiment, since it is a ventilation line used for a kitchen, the degree of contamination is very large compared with a normal ventilation line. That is, a large amount of cooking oil fine particles scattered at the time of cooking adheres to the surface. In the case of the ventilation line for a kitchen, the lighting fixture 35 is generally provided. This is a function set for illuminating the surroundings at the time of cooking, and may be turned on in synchronization with the operation of the ventilation line or may illuminate only the illumination function independently. Since the organic decomposition efficiency of the photocatalyst according to the present invention is larger than that of the conventional one, in the case of a normal pollutant load, a sufficient decomposition effect can be obtained at the level of indoor lighting without special lighting equipment, but a pollution load such as a kitchen is In large places, it may be insufficient. However, when the lighting function by a normal fluorescent lamp or an incandescent lamp is provided as in this embodiment, a sufficient effect can be obtained even in a place with a large pollution load such as a kitchen or a bathroom.

(Example 3)

The fan which is 3rd Example of this invention is demonstrated by FIG.

5 shows the structure of a fan by an external perspective view. A strut 39 is provided on the base body 38 of the fan body, and the slide pipe 40 slides freely on the strut 39. The slide pipe 40 supports the head 44 which consists of the blade 41, the guard 42, the electric motor 43, etc. on the upper side. The strut 39 is formed with the diameter thickened downward in consideration of the strength. The blade 41 rotates by the driving force of the electric motor 43, and creates an air flow forward from the back of the main body. The guard 42 serves to prevent the finger or the like from contacting the rotating blade 41, but the entire guard 42 is net 45 (not shown) to further increase safety to prevent accidents such as children. May be covered). The remote control holder 46 is provided in the lower part of the support | pillar 39, and normally, the remote control 47 is accommodated in the remote control holder 46. As shown in FIG. When the operation mode is set by the switch operation of the remote control 47, an infrared signal is sent from the infrared light emitting unit 48 of the remote control 47, and the infrared light receiving unit 49 on the upper surface of the main body 38 is used to transmit a signal. Receive the setting operation.

In this embodiment, the blade 41 is an injection molded article of AS resin. As for the surface of the blade 41, the low temperature hardening type high active oxide photocatalyst thin film of sample No. 86 is formed similarly to the case of molded articles, such as said ABS.

The guard 42 is made of a steel wire coated with polyester welding, and the surface thereof is similarly formed with a low temperature hardening type high active oxide photocatalyst thin film of Sample No. 86. The net 45 is made of nylon fiber, and the surface of the low temperature hardening type high active oxide photocatalyst thin film of Sample No. 86 is formed.

In addition, the infrared light emitting portion 48 of the remote control 47 and the infrared light receiving portion 49 on the upper surface of the main body base 38 are made of AS resin which is a transparent member.

The thin film of the low temperature hardening type high active oxide photocatalyst of sample No. 86 was formed also on the surface of these transparent components. On the surface of the target part, a first layer is formed after forming a film of a titanate coupling agent, and after forming the film, a second layer of a low temperature hardening type high active oxide photocatalyst containing ATO of Sample No. 86 is formed. do.

The surfaces of the blades 41 and the guards 42 and the like are completely the same as those of the blades and frames of the air purifier or the ventilation line, and foreign matter floating in the air adheres to and contaminates. Since the film of the oxide photocatalyst is formed, at the illuminance level of the indoor illumination light, the adhered contamination is oxidatively decomposed and difficult to be contaminated.

In the present embodiment, since the low temperature hardening type high active oxide photocatalyst thin film is formed on the surface of the transparent part used for the remote control mechanism using infrared rays or the light emitting portion and the light receiving portion of the infrared signal, the surface of the component The contamination of the signal does not interfere with signal contact.

In this embodiment, an example of a fan using a propeller blade is used, but the same effect can be obtained with a completely identical configuration even in a fan using a sirocco blade.

(Example 4)

6 and 7, a cleaner according to a fourth embodiment of the present invention will be described.

6 is an external perspective view of the cleaner, and FIG. 7 is a sectional view of the cleaner body. The vacuum cleaner body 50 includes a lower cover 51 of a synthetic resin molded article covering a lower part, an upper cover 52 covering an upper part, a cover cover 53, a grill cover 54, a handle part 55, and the like. A pair of large rear wheels 56 and a small diameter wheel 57 are disposed at the center of the bottom surface of the front lower portion. A main body switch unit 58 is provided at the center of the upper cover 52, and the main body switch unit 58 is composed of an infrared light receiving unit 59 in the center, a power switch 60, and a cord reel button 61. The suction chamber assembly 66 which consists of the suction hose part 63, the extension pipe part 64, and the inlet part 65 is connected to the said dust collecting chamber 62. As shown in FIG. A handle portion 67 is connected to an upper portion of the extension pipe portion 64, and a handle manipulation portion 68 is provided at the handle portion 67. The handle manipulator 68 is provided with an infrared signal transmitting unit 69, and the infrared signal transmitted from the infrared signal transmitting unit 69 is transmitted to the infrared light receiving unit 59 of the cleaner body 50. Because it is operated wirelessly. The vacuum cleaner main body 50 has a dust collecting chamber 62 installed inside the front, and an electric blower unit 70 and a cord reel unit 71 are installed in the rear of the inside of the cleaner body 50, and the electric blower unit 70 and the cord reel unit ( The control board 72 is provided in the upper part of 71).

Further, in the rear of the electric blower unit 70, a first exhaust ventilation path 73 that is vertically elongated, which is provided from the lower end of the rear surface of the cleaner body 50 to the upper end, is formed, and the first exhaust ventilation path ( The lower end of 73 passes through the second exhaust air passage 74 formed at the lower portion of the electric blower 70. An exhaust vent 75 (not shown) is formed by the first exhaust vent 73 and the second exhaust vent 74, and the second exhaust vent 74 is connected to the electric blower unit 70. The first exhaust gas passage 73 is connected to the exhaust gas vent 76 to pass through. Paper filter mounting portions 77 and 78 are provided above the dust collecting chamber 62, and a thick paper of the paper filter 79 is attached to the paper filter mounting portions 77 and 78 to collect the dust collecting chamber 62. By closing the cover cover 53 constituting the upper portion of the mounting hole 80 and the paper filter 79 is set at a predetermined position. The free wheel 57 is freely rotated in the horizontal direction in a recess formed in the front bottom of the lower cover 51. Garbage, dust, mites, and microorganisms sucked with air flow from the installation port 80 are collected in the paper filter 79.

The air flow from which these solids have been removed includes a communication port 83 provided with an auxiliary filter 82 provided in the partition plate 81 between the dust collecting chamber 62 and the electric blower 70. The air flow is guided to the electric blower 70 to cool the electric blower 70, and the cooled air flows through the second exhaust ventilation path 74 and the first exhaust ventilation path 73 to exhaust filter 84. It exhausts from the exhaust vent part 76 provided with.

In the present embodiment, the upper cover 52, the cover cover 53, the grill cover 54 of the cleaner body, the extension pipe portion 64, the intake portion of the handle portion 55 or the suction hose assembly 66 ( 65) The handle portion 67 is an injection molded article of ABS resin, and a thin film of a low temperature hardening type high active oxide photocatalyst of Sample No. 86 is formed on the surface of these molded articles. On the surface of the target part, a first layer is formed after forming a film of a titanate coupling agent, and after forming the film, a second layer of a low temperature hardening type high active oxide photocatalyst containing ATO of Sample No. 86 is formed. do.

Since a vacuum cleaner is a thing with high mobility compared with the article by other Example, the surface of an exterior part is easy to be damaged. In other words, the cleaner body or the intake part repeatedly collides with furniture or a wall surface while driving the floor surface, thereby causing scratches to be gradually formed and losing glossiness such as loss of gloss. In some cases, damage such as cracking may occur. In order to prevent this, the surface hardness has been secured by performing a coating treatment using an ultraviolet curing acrylic resin or the like, but according to the present invention, the hardness of the SiO ₂ film used as the binder or the TiO ₂ constituting the low temperature curing type high active oxide photocatalyst thin film is increased. Since it is harder than ABS and has a hardness of about 2H to 4H as a pencil hardness, when used in these exterior parts, the effect of making scratches such as scratches hard to be obtained, and the original effect of antifouling and microbial propagation inhibition And the like can be obtained.

In particular, since the handle part 67 is a part which contacts with bare hands, it is easy to propagate bacteria by nourishing body fats, such as sweat attached, and the like, and conventionally, antimicrobial agents of organic substances such as imidazole, thiazolin, and copper Inorganic antimicrobial agents such as), zinc, silver, etc. were beaten into the molding resin to obtain an antimicrobial effect, but such treatment is unnecessary.

In addition, since the intake portion and the wheel portion accompany the sliding or rotational movement, when the cleaner is used in a dry environment, it is easy to charge the static electricity, and the fibers and dusts such as the rug and the like are often attached to the surfaces of the parts. In order to prevent this, conventionally, various surfactants, polyamides, polyethylene glycol-based hydrophilic polymers, etc. have been prevented by kneading in the molding resin to lower the surface resistance, but according to the present invention, the resistance value of the low temperature hardening type high active oxide photocatalyst thin film Since it can be reduced, even in the ABS resin molding resin having a high electrical resistance value can be obtained with the effect of preventing the adhesion of dust and the like. The handle part 67 is provided with the handle operation part 68, The control board which mounts electronic components is provided in the back of this handle operation part 68, but static electricity is installed in this handle operation part 68 vicinity. When charged, it may cause a malfunction of the control board, and the antistatic effect according to the present invention is effective in preventing malfunction of the control board as well as attachment of dust.

In addition, the infrared ray transmitting portion 69 and the infrared ray receiving portion 59 of the cleaner main body 1 provided in the handle operating portion 68 are made of transparent AS resin as in the case of the fan of the third embodiment. It is made of a molded article, but since the low temperature hardening type high active oxide photocatalyst thin film is formed on the surface, the effect of preventing the reception and reception of the infrared signal by contamination is obtained.

The exhaust filter 84 provided on the exhaust vent 76 of the main body is made of a blended nonwoven fabric of acryl and PP, but a thin film of a low temperature hardening type high active oxide photocatalyst of Sample No. 21 is formed on the surface of the exhaust filter 84. It is. The exhaust vent part 76 is provided with a number of openings, and since the air discharge surface of the exhaust filter 84 is irradiated with light such as indoor lighting or sunlight from the opening, the surface of the filter is also cleaned.

In addition, by using the upper cover 52, the cover cover 53, the grill cover 54, the handle part 55, and the like as transparent parts, the external light reaches the inside and the dust collecting chamber ( 62) When the low temperature hardening type high active oxide photocatalyst thin film according to the present invention is formed on the filter fiber surface of the paper filter 79 or the auxiliary filter 82, the antibacterial effect or the deodorizing effect may be obtained.

(Example 5)

8, the clothes dryer of the fifth embodiment of the present invention will be described.

8 is a sectional view showing a main body of the clothes dryer. Reference numeral 85 denotes an outer frame, 86 an opening / closing lid, 87 a rotating drum, 88 a heat source, 89 an exhaust port, 90 a double wing fan, 91 a fan casing, 92 a motor, 93 is the motor Belt for transmitting the power of 92 to the rotary drum 87, 94 is a ring belt for transmitting the power of the motor 92 to the two-wing fan 90, 95 is the first hermetic felt, 96 Is a second hermetic felt, 97 is a partition plate, 98 is a circulation duct for guiding the circulating wind discharged from the fan casing 91 to the heat source 88, 99 is a lint filter device, and 100 is the fan casing 91 ) FD beam fixing the outer frame 85, 101 is a mounting ring for installing the bearing 102, the rotation drum 87 is supported by the bearing 102 to rotate freely sliding. The rotary drum 87 is rotated together with the two-wing fan 90 by the driving force of the motor 92 is transmitted through the belt 93. By this rotation, the circulation wind (solid arrow) is generated at the same time as the clothing is stirred, and when the circulation wind passes through the heat source 88, it is heated and enters the rotary drum 87 to evaporate the moisture of the clothing. To dry. Thereafter, the circulating wind is sent to the heat source 88 by passing through the circulation duct 98 by the wing fan 90, and is heated again to repeat drying of the garment. Inside the opening / closing lid 86, a luminaire 104 having a fluorescent tube 103 is provided. Along the inner circumferential surface of the rotating drum 87, a shock absorbing material 105 is attached. The cushioning material 105 consists of a foam of PP.

In the present embodiment, the inner surface of the rotating drum 87, which is a component to which the light of the luminaire is irradiated, the components such as the buffer member 105, the lint filter device 99, the inner surface of the opening and closing lid 86, and the like, are made of ABS or the like. It consists of PP resin, and the thin film of the low temperature hardening type high active oxide photocatalyst of sample No. 86 is formed in the surface. On the surface of the target component, a first layer is formed after forming a film of silane coupling agent, and after forming the film, a second layer of a low temperature hardening type high active oxide photocatalyst containing ATO of Sample No. 86 is formed.

The luminaire can be voluntarily lit as an independent operation during or during the drying operation, and when the light of the fluorescent tube 103 is irradiated, it is contained in the attached organic matter or in contact air on the surface of the part. Because of the effective oxidative decomposition of odorous substances, the effect of inhibiting or deodorizing the growth of microorganisms is obtained.

Since the clothes are rotating during the drying operation, the light does not reach evenly enough. Therefore, it is more effective to use an operation program such as cleaning the inside of the rotating drum 87 by lighting for a predetermined time after the drying operation ends.

In addition, the outer frame 1 is made of a galvanized steel sheet, the outer surface is made of powder coating of epoxy resin. On the surface of this coating surface, the low temperature hardening type high active oxide photocatalyst thin film containing the ATO of sample No.86 is formed.

The outer surface of the opening / closing lid 86 is an injection molded body of PS resin, and a low temperature hardening type high active oxide photocatalyst thin film containing ATO of sample No. 86 is formed on this surface.

The effect of the photocatalyst thin film on the outer surface of the outer frame 85 and the opening / closing lid 86 which are these exterior parts is similar to the case of the exterior parts of Examples 1 to 4 described above. Is obtained.

(Example 6)

9, 10, and 11 illustrate a dish dryer which is a sixth embodiment of the present invention.

9 shows an external perspective view of the dish dryer. 10 shows an enlarged cross-sectional view of the vicinity of the exhaust port 128. 11 shows a main body section view.

The interior of the main body 106 is divided up and down by the partition plate 109 into the drying chamber 107 and the operation control room 108. In the operation control room 108, a heating blower unit 114 for delivering dry air consisting of a fan motor 110, a blower fan 111, a casing 112, and a heater 113 is provided with the drying chamber 107. The controller 118 is disposed between the intake port 117 in which the intake filter 116 connected to the duct 115 and the heating blower unit 114 are arranged. In addition, upper and lower baskets 119 and lower baskets 120 for storing dishes are arranged above and below the drying chamber 107. The lower basket 120 is disposed on the water support plate 124 placed on the movable rail 125 connected to the hinge 122 so that the lower basket 120 can be inclined freely. Similarly, the upper basket 119 is disposed on the movable rail 123. The movable rails 123 and 125 are arranged to be movable back and forth on a roller (not shown) rotatably installed on the side wall of the drying chamber 107, and by pulling the handle 126 of the door 121 directly forward. The lower basket 120 pulls the end of the barrel from the drying chamber 107 so that the upper basket 119 can be pulled out. The exhaust port 128 provided on the panel 127 forms a lattice shape and includes an exhaust filter 129. It is connected to the drying chamber 107 by an opening 130 and an exhaust duct 131 provided in the partition plate 109 of the main body 106. The temperature detector 132 is disposed in the exhaust duct 131 which is hardly affected by the outside air temperature.

The inlet port 117 is an injection molded product made of PP, and the inlet filter 116 is a net made of nylon, and a thin film of the low temperature hardening type high active oxide photocatalyst of Sample No. 91 shown in Table 7 is formed on the surface thereof. have. After the net made of nylon is subjected to ultraviolet irradiation, a thin film of a low temperature hardening type high active oxide photocatalyst containing silver of Sample No. 91 is formed.

Since the illumination light of the room is irradiated to the surface of the intake filter 116, the attached organic matter or odorous substances in the air to be attracted are oxidatively decomposed. Similarly, the exhaust port 128 and the exhaust filter 129 have a low temperature hardening type high active oxide photocatalyst thin film of Sample No. 91. In the vicinity of the intake and exhaust vents, the discharged moisture is easily condensed by moisture, and mold or bacteria may grow. However, when the photocatalyst having high decomposition efficiency according to the present invention is used, the growth of these microorganisms is effectively performed by room light. Can be suppressed. The composition of Sample No. 91 is particularly suitable because silver contained in the composition has an antibacterial effect. In order to enhance the antibacterial effect, you may mix ceramic particles such as zeolite and apatite supported with silver.

Moreover, the lighting fixture 134 with the fluorescent tube 133 is provided in the drying chamber 107. The lighting function may be utilized as a function for cleaning the inside of the drying room 107 as well as an original function of lighting to turn on when the door 121 is opened to check the degree of drying of the dishes inside. That is, by forming a photocatalyst thin film on the surface of the internal part of the drying chamber 107, the antibacterial and antifouling effect of the part to which light is irradiated is acquired. In this embodiment, the upper basket 119 and the lower basket 120 have a structure in which a polyamide-based powdered resin is welded and coated on an iron frame. A thin film of a low temperature hardening type high active oxide photocatalyst containing 92 copper is formed. These baskets are members that are in direct contact with tableware, so cleanliness is required. However, since the surface antifouling and microbial propagation inhibitory effect are obtained by the effect of the photocatalyst, they are kept clean. Copper has the same antimicrobial effect as silver, so the antimicrobial effect is effective.

As in the case of the clothes dryer of the fifth embodiment, since the dishes are not shadowed enough to reach the light evenly during the drying operation, the operation program such as cleaning the interior of the drying room 107 by lighting for a certain time after the completion of the drying operation is used. More effective.

The door 121 is a molded article of ABS resin, but a low temperature hardening type high active oxide photocatalyst thin film containing ATO of sample No. 86 is formed on this surface. The effect of the photocatalyst thin film on the surface of this door 121 is that effect such as sufficient antifouling, antibacterial, etc. are obtained by room light similarly to the case of the exterior parts of Examples 1 to 5 described above.

(Example 7)

12, 13 and 14, a dish washing machine according to the seventh embodiment of the present invention will be described.

12 is an external perspective view of the dishwasher, and FIGS. 13 and 14 are cross-sectional views of the dishwasher.

The table storage chamber 136 is disposed inside the outer frame 135, and the stepped portion 138 is installed below the side wall of the table storage chamber 136, in which a door 137 for opening and closing the front opening is installed. The lower basket 139 for storing the dish is detachably attached to the stepped portion 138. The pump 140 is disposed outside the bottom of the dish storage chamber 136. This pump 140 has a pump motor 141. The lower arm nozzle 142 which rotates immediately under the lower basket 139 for dish storage is arrange | positioned. On the upper surface of the lower arm nozzle 142, a plurality of small holes 143 are provided. In the lower basket 139 for storing dishes, a venturi tube 145 for sending washing water delivered from the pump 140 to the upper arm nozzle 144 is disposed. The upper arm nozzle 144 is rotated with the center as the support point just below the upper basket 146 for storing dishes. On the upper surface of the upper arm nozzle 144, a plurality of small holes 147 are provided. The heater 148 is disposed at a bottom portion or a rear portion outside the dish storage chamber 136. The heater cover 149 is arrange | positioned so that the heater 148 may be enclosed. A water supply solenoid valve 150 is disposed at an outer surface of the dish storage chamber 136. An exhaust duct 151 is disposed above the outer surface of the dish storage chamber 136, and is connected to the exhaust port 152. The control panel 153 is disposed above the outer surface of the door 137. A drain pump 154 and a blowing unit 155 are disposed outside the bottom of the dish storage chamber 136.

In the washing operation, water is supplied from the water supply solenoid valve 150 to drive the pump 140 to supply pressure water to the lower arm nozzle 142 and energize the heater 148 to raise the water temperature. When water is ejected from the hole 143 and is sent to the upper arm nozzle 144 via the venturi tube 145, the water is also ejected from the hole 147. In this way, the upper and lower arm nozzles rotate and evenly spray hot water onto the dishes in the dish storage container 146 to eliminate contamination. After the cleaning operation is finished, the drain pump 154 is energized to discharge the sewage, and the same operation is repeated several times to rinse and remove the internal contaminants. When the final rinsing operation is finished, the process shifts to the drying operation. The blower fan 156 is rotated by energizing the blower unit 155 to pass through the blower duct 157 and the heater 148 disposed at the bottom of the dish storage chamber 136 and into the dish storage chamber 136. To supply. At this time, the heater 148 turns ON / OFF electricity supply for a predetermined time, and makes cold air warm air. By the warm air, the water droplets inside, the remaining water, and the water droplets attached to the dishes are converted into steam and discharged from the exhaust port 152 through the exhaust duct 151 out of the apparatus.

In this embodiment, the exhaust port 152 is formed of an ABS resin molded product or a thin film of a low temperature hardening type high active oxide photocatalyst containing silver of the same sample No. 91 as the above-described dish dryer. In the vicinity of the exhaust port, the discharged moisture is easily condensed and contaminated with mold or bacteria. However, when the photocatalyst having high decomposition efficiency according to the present invention is used, the propagation of these microorganisms can be effectively suppressed by room light. have.

Inside the dish storage chamber 136, a lighting device 159 having a fluorescent tube 158 is provided. The lighting function may be utilized as a function to clean the inside of the dish storage chamber 136 as well as the original function of lighting to turn on when the door 137 is opened to check the degree of washing and drying of the tableware therein. That is, by forming a photocatalyst thin film on the surface of the internal component of the dish storage chamber 136, the antibacterial and antifouling effect of the part to which light is irradiated is acquired.

In the present embodiment, the upper basket 146 for storing dishes and the lower basket 139 for storing dishes have a structure in which a polyamide-based powdered resin is welded and coated on an iron frame. A thin film of a low temperature hardening type high active oxide photocatalyst containing .92 copper is formed.

Since the upper and lower cylinders are members which come into direct contact with tableware, cleanliness is required. However, since the surface antifouling and microbial propagation inhibitory effect are obtained by the effect of the photocatalyst, they are kept clean.

Examples of the member to which light from the light fixture 159 is irradiated include the dish storage chamber 136, the upper arm nozzle 144, the lower arm nozzle 142, the venturi tube 145, and the like. Use resin injection molded products or SUS plastic modified products. On the surface of these parts, after corona discharge treatment, a thin film of SiO ₂ alone, that is, Sample No. 12 in Table 1 is formed as a base layer, and after forming the film, a thin film of a low temperature hardening type high active oxide photocatalyst of Sample No. 21 is formed. do.

The photocatalyst thin film is formed on the components inside the dish storage chamber 136, and the drying efficiency is improved as a unique effect of the dish washing machine. This effect is achieved even if the water-resistant material such as TiO ₂ , SiO _{2, which} is a basic material of the low temperature-curable high-active oxide photocatalyst thin film according to the present invention, has a good water wettability and a splashing material such as oil or fat removed from dirty dishes. Since it decomposes | disassembles by the light of 159, the effect which always maintains high water wettability is obtained.

In the operation of dish washing, the water temperature is raised to 60 to 70 ° C at the time of the final rinsing, and the moisture is discharged out of the device by the blowing operation, or the water droplets remaining inside the dish storage chamber 136 are dried. This causes a decrease in efficiency. Parts such as the dish storage chamber 136, the upper arm nozzle 144, the lower arm nozzle 142, and the venturi tube 145 often require hydrophobic materials because of high water resistance. Wetting is bad. On the surface of the raw material having poor water wettability, the water does not become wet in a film form and is attached in the form of droplets of high contact angle. In the washing operation, detergent containing surfactant is added, so the surface tension of the washing water is lowered and the contact angle is lowered so that it becomes wet well.However, almost no detergent component is contained in the rinsing water at the time of the final rinsing. high. Therefore, at the end of the final rinsing, the rinsing water is attached to the surface of each part inside the dish storage chamber 136 in a myriad of droplets having a high contact angle.

These water droplets having a high contact angle have a large amount of water as compared to the case of a water film that has been thinly formed into a film and hardly dry. In addition, since the water of the droplet shape is reduced and dried while maintaining the droplet shape at the time of drying, the surface area is also reduced, so that the drying speed becomes slower, and the time required for drying is about three times. Tableware has a lot of wettability of glass, porcelain or wood, and it dries relatively quickly.However, when the dishwasher is finished with water droplets attached to the dishwasher itself, it is vibrated when the door 137 is opened to draw out the upper and lower dish containers. A drop of water drops causes a problem of soaking dry dishes.

When parts such as the dish storage chamber 136, the upper arm nozzle 144, the lower arm nozzle 142, and the venturi tube 145 are made of PP molded products, the residual water amount due to the droplets at the end of rinsing Although silver is about 30 g, when the photocatalyst film by this invention was formed, the amount of adhesion residues was reduced to about 5 g. Moreover, since the low temperature hardening type high active oxide photocatalyst thin film of this invention has a high photoactivity, it has a function which decomposes the fats and oils adhered by the light of the luminaire 159, and there is no fall of water wettability by adhesion of fats and oils.

As in the case of the dish dryer of the sixth embodiment, since the dishes are shadowed and the light does not reach evenly during the drying operation, an operation program such as cleaning the inside of the dish storage chamber 136 by lighting for a predetermined time after the drying operation is used is used. Is more effective.

The door 137 is made of a PP resin molded product, but after the corona discharge treatment, the sample No. 12 is formed as a base layer on the surface, and after forming the film, the low temperature hardening type high active oxide photocatalyst of the sample No. 21 is formed. A thin film of is formed.

The effect of the photocatalyst thin film on the surface of the door 137 is such that the effect of antifouling, antibacterial, etc. sufficient with room light is obtained in the same manner as in the case of the exterior parts of the first to sixth embodiments. In the present embodiment, the installation type dishwasher is described, but the same effect can be obtained for the table type to obtain the effect of the photocatalyst thin film. In the case of the desk type, since the room light is irradiated on the front surface of the exterior part, it is effective to form a photocatalyst thin film on the surface of the outer wall surface member of the side surface or the ceiling part.

(Example 8)

15 and 16, a food waste processor as an eighth embodiment of the present invention will be described.

15 is an external perspective view of the food waste treatment machine, and FIG. 16 is a sectional view of the main body.

Inside the frame 160, a treatment tank 164 having a stirring blade 161 rotatably supported at the center portion and having a living garbage inlet 163 installed thereon is disposed therein, and a culture substrate 165 is contained therein. have. The culture base 165 is a sawdust, rice husk, rice straw, etc., which are mainly composed of fibers that are difficult to be decomposed into microorganisms such as lignin, and each grain is porous and has a particle size. Large pores are also formed between the eggs.

Three stirring blades 161 are installed on the rotating shaft 166, and are supported by a bearing 167 installed in the processing tank 164, and the rotating shaft end portion protruding from one side is transferred to the driving motor 168 and the chain. The means 169 is connected at an appropriate reduction ratio. In the upper opening 170 of the processing chamber 164, the inner cover 171 is freely opened and closed on the upper panel 172. In addition, near the upper portion of the processing chamber 164, a ventilation fan 173, an intake port 174, and an exhaust port 175 are provided, and the decomposition gas generated in the processing chamber 164 by the rotation of the ventilation fan 173 and Water is discharged out of the device through the exhaust port 175. In addition, an appropriate mesh filter is disposed in each of the inlet port 174 and the exhaust port 175.

Moreover, the opening / closing cover 176 of the inlet port 174 is provided to open and close the inlet port 174 by the reciprocating motion of the solenoid 177 provided in the frame body 160. In addition, the upper panel 172 is provided with an operation unit 178 for driving, the controller 179 is operated by this operation to operate the food waste processor.

After several months, the culture substrate 165 is filled with decomposition products and the like, so that the porosity decreases so that it is not possible to process household waste. For this reason, the outlet 180 and the discharge path 181 are formed in the bottom part of the process chamber 164, and it is taken out of the frame body 160 by scraping the culture base material 165 which fell in the discharge path 181. can do.

The upper air gap air of the culture substrate 165 of the treatment chamber 164 contains moisture and a large amount of substances having a high odor intensity such as trimethylamine, methyl mercaptan, ammonia, hydrogen sulfide and the like as decomposition gas. Because of the strong odor, the conventional food waste disposal system cannot be installed in the kitchen, and the leakage of odor to the surrounding households has become a problem even when it is installed in the veranda of the apartment house or the like.

Conventionally, as a deodorizing mechanism, various kinds of deodorizing mechanisms using an adsorption material such as activated carbon or a thermal decomposition catalyst of manganese have been devised, but none of them are sufficient in terms of effects and lifespan.

In this embodiment, exhaust filters 182 and 183 are provided in the exhaust port 175, and the ultraviolet lamp 184 is disposed in the gap. The exhaust filter 182 has a zeolite as a main component, and the exhaust filter 183 has a honeycomb structure, with activated carbon as its main component, and ultraviolet rays emitted from the ultraviolet lamp 184 are irradiated to the inside of the honeycomb. On the inner surface of the honeycomb of the exhaust filters 182 and 183, a low temperature hardening type high active oxide photocatalyst thin film of Sample No. 62 shown in Table 5 is formed.

The low temperature hardening type high active oxide photocatalyst according to the present invention has a high decomposition efficiency, and in applications where the organic load is relatively small as in Examples 1 to 7, the lighting fixture level in the room, that is, the wavelength is 250 to 350 nm. UV light is 0.001 to 0.01mW / cm ^2, the luminance level or degradation in an amount of 0.01 to 0.1mW / cm ² of illumination levels by the mounting of a fluorescent lamp or incandescent possible haeteoteuna of, for example, as in this embodiment can be an ammonia concentration ppm In the case of high load of the level, it is necessary to arrange the ultraviolet generation means.

Ultraviolet lamps such as mercury lamps and metal halide lamps can be used. However, according to the present invention, since the decomposition efficiency is higher than that of the conventional oxide photocatalyst, the deodorizing effect is high, and the ultraviolet intensity is smaller than that of the conventional oxide photocatalyst. do. The most odorous substances are produced in the largest amount when the household waste is actively decomposed.

Since household waste is normally decomposed most 1 hour to 8 hours after the input, the life of the lamp can be kept long by turning on the ultraviolet lamp 184 at this timing. The exhaust filter 183 is based on activated carbon, and when the odor concentration is low, the activated carbon is adsorbed and the adsorption efficiency gradually decreases as the amount of adsorption increases. It is also possible to decompose odorous substances adsorbed and to regenerate activated carbon.

The frame body 160 is made of a coated steel sheet, and the outer cover 171 is made of an injection molded product of PP resin, but an organic coating film of chlorinated polyethylene is coated on this surface, and a sample No. A thin film of a .21 low temperature hardening type high active oxide photocatalyst is formed.

The effect of the photocatalyst thin film on the surface of the outer frame 160 or the outer cover 171 is the same as in the case of the exterior parts of the first to seventh embodiments described above. Is obtained. Especially in the case of the food waste treatment machine, since there are many chances of contaminating these exterior parts by the soup coming out of the household waste, the antifouling effect by the low temperature hardening type high active oxide photocatalyst thin film of this invention is large. When food waste handlers are placed outdoors, sunlight is irradiated on these exterior parts. Ultraviolet light intensity of wavelength 250-350 (nm) of sunlight is 0.1-5.0 mW / cm ² level, high intensity compared with indoor lighting, and can also decompose contaminants such as household garbage soup.

In Examples 1 to 8 described above, an external component to which an external light such as a filtration mechanism such as a filter installed in the path or an interior light, or an indoor light is irradiated, to an adherend such as various thermoplastics, The composition of the low temperature hardening type high active oxide photocatalyst thin film, the curing conditions of the membranes, and the characteristics of each compound composition, which were formed on the surface of the components to which the light emitted from the luminaire, irradiated, were observed. It will be described using.

(Example 9)

A solution in which TiO ₂ fine particles were dispersed in SiO ₂ sol was prepared. This solution was used to form a TiO ₂ film on the PET film to prepare the PET film of FIG. 17. The procedure is shown below.

First, description will be made in the production process of the SiO ₂ sol. 5 g of tetraethoxysilane was dissolved in 100 ml of a water-ethanol-propanol (3:27:70) mixed solution and stirred at 40 ° C. for about 5 hours. The obtained solution was left to stand at room temperature for 2 weeks to obtain SiO ₂ sol.

Next will be described the process of the solution obtained by dispersing TiO ₂ particulates in the SiO ₂ sol. TiO ₂ fine particles were added to TiO ₂ / SiO ₂ = 9 by weight in the SiO ₂ sol prepared above. In addition, the solid content concentration was 4 wt% and adjusted by adding the required amount of water. Thereafter, a 5 hr zirconia ball was used to treat the TiO ₂ fine particles in a SiO ₂ sol in a 24hr ball mill to prepare a solution in which the TiO ₂ fine particles were dispersed in the SiO ₂ sol.

The PET film 185 was coated with dispersed SiO ₂ sol of the prepared TiO ₂ fine particles, and treated for 5 minutes while irradiating a low pressure mercury lamp (strength: 15 mW / cm ² ) at 120 ° C. in the SiO ₂ film 186. A plastic film coated with a TiO ₂ dispersed SiO ₂ film 188 in which TiO ₂ fine particles 187 was dispersed was formed. The thin film obtained on the PET film 185 had both good film quality and strength and a film thickness of 300 nm.

The decomposition activity of the organic substance by this titanium oxide was evaluated. In addition, the activity test was carried out by coating a thin film of organic pigments of red color on the thin film and irradiating 1 (mW / cm ² ) light at 254 nm. The decomposition rate was obtained from the amount of change from the initial dye transmittance. The result was shown in FIG.

In addition to the TiO ₂ dispersion SiO ₂ film adhesion, the figure also shows the results of the film free and SiO ₂ film for comparison. Although there was almost no change in the amount of pigment in the TiO ₂ dispersed SiO ₂ film and the SiO ₂ film, a result of decomposition of 45% was obtained after 30 minutes in the case of the TiO ₂ dispersed SiO ₂ film.

As described above, a PET film with a TiO ₂ dispersed SiO ₂ film having a photocatalyst function could be produced. The film formation method of the present invention can be produced at about 120 ° C., and can be applied to plastic materials in addition to pyrex glass substrates. In the sol-gel method usually, there is a need for several minutes or hours for the crystallization of an application is difficult, or TiO ₂ to the plastic because it requires a temperature of about 400 ℃. On the other hand, in the production method of the present invention, since the film can be formed at a low temperature, the substrate can be used abundantly and the photocatalyst can be formed on any surface. In addition, a short time treatment of several minutes is possible, and a significant reduction in production cost is possible.

Subsequently, a cocatalyst was added to improve the performance of the photocatalyst. First, the addition of nitrate to various film formed on the PET film in dispersing the TiO ₂ fine particles in a prepared SiO ₂ sol solution was subjected to the decomposition reaction of the coloring matter. The results are shown in Table 1.

Effect of Additives Sample No. additive Addition amount (wt%) TiO ₂ / SiO ₂ (weight ratio) Rate of decomposition after 10 min (wt%) One NaNO ₃ 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 was found that photocatalysts containing Na, Li, K, Mg, Ca, Sr, and Zn were effective, and Fe and Al became deactivators.

FIG. 21 shows the results of plotting the effect of adding the cocatalyst on the electronegativity. The smaller the electronegativity seems to be more effective, but in particular Li, Na, Mg is effective because it was found that not only the electronegativity but also the ionic radius. Fig. 22 shows the relationship between electronegativity, ion radius, and addition effect. As described above, it was found that it is effective to add ions having an electronegativity of less than 1.6, an ion radius of less than 0.2 nm, and an valence of 2 or less.

(Example 10)

Several kinds of solutions in which TiO ₂ fine particles having different particle diameters were dispersed in SiO ₂ sol were prepared. In addition, the TiO ₂ / SiO ₂ ratio was 9 by weight, the Li addition amount was 5 wt%, and a TiO ₂ dispersed SiO ₂ film was formed on a PET film in the same manner as in Example 1, using an organic dye for 10 minutes. The subsequent decomposition rate was investigated.

Degradation Rate of Pigment to TiO ₂ Particle Diameter Sample No. Li addition amount (wt%) TiO ₂ / SiO ₂ (weight ratio) TiO ₂ particle size (nm) Rate of decomposition after 10 min (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

The conditions and test results of the samples prepared in Table 2 are shown. From these results, the size of the dispersed TiO ₂ particles was found to be from 8 to 10nm is most effective. In this way, the decomposition rate was changed according to the particle diameter, and when the TiO ₂ / SiO ₂ ratio was reduced, the optimum particle diameter of the TiO ₂ fine particles was changed, but the decomposition rate was good in the range of 5 to 20 nm. Therefore, it was found that the TiO ₂ particle diameter of the Li addition catalyst was good if it was 5 to 20 nm. Moreover, the above result was the same also about Na, K, Mg, Ca, Sr, Zn other than Li.

(Example 11)

Table 3 shows the results obtained by examining the dye decomposition rate (degradation rate after 10 minutes) and the film strength when the Li addition amount, TiO ₂ / SiO ₂ is changed. In addition, the solution preparation and the film-forming method were performed similarly to Example 1. From these results, it was found that the conditions under which both the decomposition rate and the film strength were effective were Li added in an amount of 0.5 to 20 wt% and TiO ₂ / SiO ₂ was 9 to 5.

Decomposition Rate of Pigment to Li Addition and TiO ₂ / SiO ₂ Ratio Sample No. Li addition amount (wt%) TiO ₂ / SiO ₂ (weight ratio) Degradation rate after 10 minutes Membrane strength 19 0 9 25 ○ 20 One 9 90 ○ 21 5 9 100 ○ 22 10 9 100 ○ 23 20 9 100 ○ 24 50 9 65 × 25 0 8 25 ○ 26 One 8 88 ○ 27 5 8 100 ○ 28 10 8 100 ○ 29 20 8 100 ○ 30 50 8 60 × 31 0 6 25 ○ 32 One 6 86 ○ 33 5 6 100 ○ 34 10 6 100 ○ 35 20 6 100 ○ 36 50 6 60 × 37 0 4 15 ○ 38 One 4 15 ○ 39 5 4 20 ○ 40 10 4 20 ○ 41 20 4 20 ○ 42 50 4 15 ○

Table 4 shows the results obtained by examining the pigmentation rate and film quality when the TiO ₂ / SiO ₂ and the film thickness were changed. In addition, the preparation and film formation method of the solution was carried out in the same manner as in Example 1, the film thickness was adjusted by changing the solid concentration of the solution to 0.5 to 8wt%.

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

The above result was the same also about Na, K, Mg, Ca, Sr, Zn other than Li.

TiO ₂ / SiO ₂ Ratio, Degradation Rate of Pigment to Film Thickness Sample No. Li addition amount (wt%) TiO ₂ / SiO ₂ (weight ratio) Film thickness (nm) Degradation rate after 10 minutes (wt%) Membrane 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 results of examining the dye decomposition rate when ATO, ITO, ZnO, Fe ₂ O ₃ , Cr ₂ O ₃ fine particles which are oxide semiconductors other than TiO ₂ were added. In addition, the intensity | strength of the ultraviolet lamp (254 nm) was 0.2 mW / cm <^2> in the test which irradiates a dye decomposition rate. In addition, unless otherwise indicated, the pigment | dye decomposition test after this Example was performed on the said conditions. As a result, the addition of ATO, Fe ₂ O ₃ , Cr ₂ O ₃ fine particles is effective, the addition amount is effective in any case, especially 10 to 20wt% was the most effective. Here, the electron affinity of each oxide member element is as follows, and it turned out that it is effective to use the oxide semiconductor using the member element which has an electron affinity of 1.2 eV or more.

Degradation Rate of Pigment with Various Oxide Semiconductor Additions Sample No. Li addition amount (wt%) TiO ₂ / SiO ₂ (weight ratio) Oxide addition amount (wt%) Degradation 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 Fe ₂ O ₃ (1.0) 66 75 10 9 Fe ₂ O ₃ (5.0) 68 76 10 9 Fe ₂ O ₃ (10.0) 70 77 10 9 Fe ₂ O ₃ (20.0) 71 78 10 9 Fe 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

Member 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 smaller than that of Ti, a Schottky barrier is formed at the particle interface of the fine particles, and the carrier of the added oxide semiconductor cannot be injected into TiO ₂ , so that no effect occurs. On the other hand, when the electron affinity of the oxide semiconductor is smaller than that of Ti, a schottky barrier is not formed at the particle interface of the fine particles, which is an ohmic junction, and the carrier of the oxide semiconductor is easily injected into TiO ₂ to function effectively. ATO, which was particularly effective, had a slightly smaller electron affinity than Ti, but showed an improvement in performance since there was little difference. ATO, which is a conductive oxide, has a high carrier concentration, and a large amount of carriers of ATO are injected into TiO ₂ to improve photocatalytic activity. In addition, it was also found that the addition effect of Li is great even when such an oxide semiconductor is added.

Moreover, as a method of effectively using the carrier which an oxide semiconductor has, it is possible not only to add a fine particle but also to laminate. Table 6 shows the result of laminating a TiO ₂ / SiO ₂ film and an ATO film. As a result, it was found that lamination is effective, and the performance is further improved by adding Li to both sides. Moreover, it turned out that it is effective also to laminate | stack several times alternately.

Pigment Degradation Rate of ATO Laminated Film Sample No. First layer Li addition amount (wt%) Second layer Li addition amount (wt%) Decomposition 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 fine particles having a particle diameter of 5 nm was dispersed in a SiO ₂ sol was prepared, and ₂ wt% of Ag, Pt, Pd, Rh, Ni, Cu, and RuO ₂ fine particles were added to TiO ₂ , respectively. In addition, TiO ₂ / SiO ₂ ratio was set to 9 by weight. The TiO ₂ dispersed SiO ₂ film containing Ag, Pt, Pd, Rh, Ni, Cu, RuO ₂ fine particles was added in the same manner as in Example 1 using the prepared Ag, RuO ₂ fine particle added TiO ₂ dispersed SiO ₂ sol, and PET film. It formed in the phase and investigated the decomposition characteristic of organic pigment. As shown in Table 7, the decomposition rate was increased by the addition of Ag, Pt, Pd, Rh, Ni, Cu, and RuO ₂ fine particles.

Degradation Rate of Pigments for Addition of Precious Metals Sample No. Li addition amount (wt%) TiO ₂ / SiO ₂ (weight ratio) Precious metal addition amount (wt%) Decomposition 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)

For the Li-added photocatalyst prepared in Example 1 and the Li-free photocatalyst, the degradation characteristics of the cigarette stand, acetaldehyde, urea, and E. coli were compared using a fluorescent lamp, sunlight, incandescent lamp, and mercury lamp. As a result, as shown in Table 8, it was found that the Li-added photocatalyst had three to five times more effective decomposing characteristics of cigarette stand, acetaldehyde, urea, and E. coli than Li-free photocatalyst, regardless of which lamp was used. As described above, it was found that the Li-added catalyst can obtain a sufficient effect not only from the ultraviolet lamp but also from the lamp used in the living environment. Moreover, the same effect at the time of adding Na, K, Mg, Ca, Sr, Zn other than Li was acquired.

Decomposition test results of organic matter by various lamps (decomposition ratio of adding Li 10 (wt%) / no Li) Tobacco Acetaldehyde Element Escherichia coli Pigment (Acld Red) Fluorescent lamp 3 3 3 3 3 sunlight 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)

When the Li-added TiO ₂ dispersed SiO ₂ film produced in Example 1 forms directly on a PET film, damage is caused to the PET film of the substrate by photocatalytic action. So, to prepare a film is installed first layer SiO ₂ film is provided between the PET film to coat the TiO ₂ dispersion was added Li SiO ₂ film produced in Example 9. In addition, prepare a sample the addition of ATO in the SiO _2, Al, Fe, was added to each of nitrates of Zr sample or Li addition of TiO ₂ dispersed SiO ₂ film which is a component for deactivating the photocatalytic action in the film, performing the various tests It was. The results are shown in Table 9.

Pigmentation test and durability test results of SiO ₂ laminate (TiO ₂ / SiO ₂ = 9, Li (wt%) = 10) Sample No. ATO (wt%) SiO ₂ (wt%) Element added (wt%) Decomposition after 20 minutes (wt%) Peeling after 10 days (Tape test result) With dust 96 0 radish radish 65 U (×) U 97 20 radish radish 82 U (×) radish 98 0 U radish 65 (×) U 99 0 U Al (5) 65 No (○) U 100 0 U Fe (5) 66 No (○) U 101 0 U Zr (5) 65 No (○) U 102 20 U Al (5) 83 No (○) radish 103 20 U Fe (5) 82 No (○) radish 104 20 U Fe (5) 82 No (○) radish

The result was that film peeling could be prevented even when used for a long time by providing one layer of the SiO ₂ film as a barrier layer between the Li-added TiO ₂ dispersed SiO ₂ film and the PET film. In addition, it was found that by adding Al, Fe, and Zr, the photocatalytic activity can be completely deactivated and the adhesive strength can be maintained. In addition, in the ATO-added film, the antistatic effect is added, and adhesion of dust and the like can be suppressed, and not only the decomposition of organic matter but also the adhesion of inorganic matter can be prevented, and thus a film having more excellent antifouling effect can be produced.

Specific effects when the low temperature hardening type high active oxide photocatalyst thin film of the composition shown in Examples 9 to 16 is used for various articles having a mechanism for generating air flow by an electric motor as shown in Examples 1 to 8 The evaluation results are summarized below. First, the effect of the case where the low temperature hardening type high active oxide photocatalyst thin film of this invention was applied to the filter mechanism provided in the air flow path is summarized.

Typical air pollutants in the room are tobacco smoke. Tobacco smoke is rich in tar and soot particles. These particles form a film on the filter and accumulate, and the filter is gradually colored brown and contaminated. The contamination by this cigarette smoke was evaluated. On the front side of the suction side of the ventilation line having a blowing amount of 5 (m ³ / min), a 10 cm × 10 cm polyester fiber nonwoven filter was attached and fixed. A ventilation line with this nonwoven fabric was installed and sealed in a 45,000 cm ³ container. In this container, a cigarette smoke generator was juxtaposed. This tobacco smoke generator is provided with a tube on the filter side of the ignited cigarette, and this tube is connected to a diaphragm pump. When the diaphragm pump is driven at a flow rate of 1,800 cm ³ / sec, and the tube end on the tobacco side is depressurized, the smoke passing through the filter of the cigarette is exhausted from the discharge side of the pump, and one cigarette is burned for about 1.5 minutes. . When the tobacco smoke generating device and the ventilation line are driven in the container having such a configuration, since the exhaust of the ventilation line is also discharged into the container, the cigarette smoke filled in the container passes through the nonwoven filter portion many times. Five cigarettes were burned continuously, the ventilation line was driven for 10 minutes, the container was opened, and the nonwoven filter was removed to make a sample. The low temperature hardening type high active oxide photocatalyst thin film by this invention is formed in the fiber surface of this nonwoven fabric filter. The manufacturing method was produced by the method described in Example 9. In Example 9, the PET film is applied, but in this solution, lithium nitrate is added to a solution in which TiO ₂ fine particles are dispersed in a SiO ₂ sol, and the nonwoven filter subjected to surface oxidation treatment by an ozone atmosphere is immersed for 1 minute. After holding, the filter was pulled up and the unnecessary solution was scattered by air blow, followed by curing for 5 minutes while irradiating a low pressure mercury lamp (strength: 15 mW / cm ² ) at 120 ° C. to form a photocatalyst thin film on the fiber surface. . The composition of this film is sample No. 2 in Table 1.

Thus, the decomposition degree of the attached contaminant was evaluated by irradiating the sample manufactured by the light of fluorescent lamp. Evaluation was carried out using a color difference meter (Nihon Denki Kyosha: Z-1001DP) to change the color of the nonwoven fabric filter. The antifouling effect was evaluated by setting the color difference in the contaminated state before light irradiation to 100% and the color difference before adhering the contaminants caused by tobacco smoke to 0%. For comparison, only the TiO ₂ fine particles were dispersed in SiO ₂ , and the sample No. 11 and only the SiO ₂ film containing no TiO ₂ fine particles were formed. A thin film was formed on the filter fiber surface in the same manner. Evaluated.

This result is shown in FIG. 23 and FIG. Fig. 23 shows the results of evaluating the filter contamination state with color difference over time when the filter passes through the smoke under the above conditions. Compared to the untreated acrylic fiber, when the glassy oxide photocatalyst thin film containing TiO ₂ or SiO ₂ is attached, the color change is about 50% faster, that is, the collection efficiency of the smoke is increased by about 50%. FIG. 24 is a time-dependent measurement of color difference in which the adsorbed smoke under the above conditions is irradiated with brown light to fluorescent filters to decompose deposits by a photocatalyst, and the color of the discolored filter is returned to its original color tone. The result is evaluated. The accumulated light amount in the figure represents an integrated value irradiated with light having a wavelength of 250 to 350 nm. Sample No. 12 in the figure is a case where only SiO ₂ does not contain TiO ₂ , and decolorization effect due to decomposition is hardly recognized. The same amount of TiO ₂ was contained in sample No. 11 and sample No. ₂ , and the effect was recognized, but sample No. 2 was a prescription according to the present invention with LiNO ₃ added, and it was found that the speed of discoloration was greatly improved. . Especially in the initial stage, the decomposition efficiency more than twice that of LiNO _{3 addition} is obtained. In the case of an actual air cleaner, a ventilation line, etc., since a small amount of contaminants are attached and the room light is illuminated, the speed of initial decomposition becomes important. As the adhesion amount of the contaminants increases, light is blocked by the contaminants, making it difficult to reach the photocatalyst thin film on the fiber surface, thereby degrading the decomposition efficiency. Because of this, it is important to decompose the contaminants before they become thick.

In an actual environment, in order to attach the same level of contaminants to the filter as in this test using the above apparatus, 20 cigarettes are burned when the ventilation line is operated in a closed three-ply space (about 20 m ² ). This was equivalent to the amount of contaminants after 120 minutes of operation.

Next, the result of having examined the deodorizing effect when the low temperature hardening type high active oxide photocatalyst thin film of this invention is applied to the filter apparatus provided in the air flow path is put together. As a representative malodorous substance, evaluation was carried out for the removal of ammonia. The examination was conducted in the same configuration as that of the cigarette. Instead of the cigarette smoke generator, a certain amount of ammonia gas was injected into the container and the ammonia gas concentration in the container was adjusted to 25 (ppm), and then a ventilation line provided with a nonwoven fabric having a low temperature hardening type high active oxide photocatalyst thin film was driven. . First, the result of measuring the adsorption effect of the ammonia gas by the glassy oxide photocatalyst thin film similarly to the case of smoke collection is shown in FIG. In the untreated acrylic fiber, 90% (%) or more of ammonia gas remains even after 1 hour, and 50% (%) after 1 hour when a glassy oxide photocatalyst thin film containing TiO ₂ or SiO ₂ is attached. It can be seen that adsorption is removed to the following concentration. The effect of collecting ammonia gas as well as smoke is recognized.

After adsorb | sucking until this ammonia gas was saturated, the incandescent bulb arrange | positioned inside the container was turned on, and light was made to contact a filter surface. The ammonia decomposition effect was evaluated by measuring the ammonia gas concentration in a container with time. This result is shown in FIG.

In the filter of Sample No. 12 containing no TiO ₂ , almost no change in concentration was recognized. No. 11 and No. ₂ containing TiO ₂ showed that the ammonia gas concentration decreased and decomposed by light irradiation. However, No. 2 significantly improved the decomposition efficiency by mixing LiNO _{3 according} to the present invention. Approximately three times the decomposition efficiency was obtained as compared with No. 11.

The antifouling and deodorizing effect described above is described as a representative example of an application example for an air cleaner or a ventilation line, but of course, the same effect can be achieved with filters of various articles having the same mechanism.

Next, the result of having evaluated the specific effect at the time of using for the exterior parts of various articles as shown in Examples 1-8 is put together below. As the sample, a thermoplastic ABS resin (technopolymer company: Turplex 451, white colored product) for injection molding, most often used for exterior parts, was used. A plate-shaped molded article of 5 cm x 5 cm was produced, and this surface was subjected to corona discharge treatment. On this corona discharge treatment surface, the low temperature hardening type high active oxide photocatalyst thin film of the sample No. 86 composition shown in Table 6 in Example 12 was formed. Compared to a thin film on the mold plate surface similarly to the sample No.12 as the SiO ₂ TiO ₂ in the table as the only sikyeoteul dispersing the fine particles in the sample 1 and No.11, SiO ₂ membrane only containing no TiO ₂ particles for the case Formed and evaluated. First, the contaminants caused by tobacco smoke were evaluated as described above. The examination was carried out in the exact same configuration as the test of the nonwoven fabric filter described above. After fixing a 5 cm x 5 cm ABS plate in the center of the filter arrangement part and burning 10 cigarettes, the white ABS plate was contaminated brown by driving a ventilation line for 120 minutes. The ABS plate was removed, and light was removed under the same conditions as before, and the removal rate was evaluated by color difference measurement before and after. This result is shown in FIG.

As a result, almost the same results as in the case of the filter were obtained, but since the attached contaminants themselves were smaller than in the case of the filter, the same decolorization effect was obtained with less than half the amount of light. In addition, sample No. 86 was added to LiNO ₃ and ATO was also blended as an additive component, and a slightly higher decomposition efficiency was obtained compared to sample No. 11.

Next, the result of evaluating the antifouling effect when the article is used in an environment using a lot of oil components such as a kitchen and contaminated by fat or oil is summarized. Salad oil was applied thinly to a thickness of about 5 (μm) on a glass plate of 5 cm x 5 cm in which a low-temperature-curable high active oxide photocatalyst thin film of the composition of Sample No. 86 shown in Table 12 was formed. Light was irradiated and the weight change of oil was measured over time. This result is shown in FIG. As a result, almost no change in weight was found in Sample No. 12 containing no TiO ₂ . No. 11 and No. ₂ containing TiO ₂ were deteriorated in weight due to decomposition and volatilization of oil by light irradiation, but No. 2 greatly improved the decomposition efficiency by blending LiNO _{3 according} to the present invention. Compared to No. 11, about two times the decomposition efficiency was obtained.

When forming the low temperature hardening type high active oxide photocatalyst thin film by this invention including the case of a series of Examples above, various methods can be used in order to improve adhesiveness with a base material. As a method of using a primer, it is effective if a photocatalyst film is formed after apply | coating various coupling agents beforehand, for example.

As an example, a silane coupling agent and an organotitanium type compound are mentioned.

Examples of the silane coupling agent include vinyltris (βmethoxyethoxy) silane, vinyltriethoxysilane, vinyltmethoxymethoxysilane, γ- (methacryloxypropyl) trimethoxysilane, and β- (3,4-epoxy Cyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, n -beta-(aminoethyl) -γ-aminopropylmethyldimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, and the like. Can be used.

As the organotitanium compound, titanium esters, titanium acylates and titanium chelates can be used, and in particular, tetra-i-propoxytitanium, tetra-n-butoxytitanium, tetrakis (2-ethylhexyldioxy) titanium, Di-i-propoxy bis (acetylacetonato) titanium, titanium-i-propoxy octylene glycolate, titanium stearate, etc. are effective.

In addition, the method of oxidizing the surface of the object using various surface modification means to introduce a hydroxyl group, a carbonyl group, a carboxyl group and the like to firmly bond the low temperature hardening type high active oxide photocatalyst thin film according to the present invention is also effective.

Specific examples include ultraviolet irradiation, electron beam irradiation, corona discharge treatment, ozone atmosphere treatment, and the like. In the case of relatively hydrophilic resins such as polyamide resins and polyester resins, high adhesion can be obtained without the above pretreatment, but it is effective to perform these pretreatments for polyolefin resins and high crystalline resins.

In the present invention, as an additive component for enhancing the activity of the photocatalyst, the effect of mixing Ag and Cu is as described above. At the same time, they lower the electrical insulation of the membrane itself, obtain an antistatic effect, and furthermore, an effect of suppressing microbial propagation. It is known that ions of Ag and Cu have high antibacterial properties, in particular, bacterial resistance. When these Ag and Cu are used in combination, the growth of microorganisms can be suppressed even when no light is reached.

The application range made into the object of this invention is not limited to the apparatus demonstrated by giving the above specific example. That is, the principle of the present invention can promote the polymerization of inorganic polymers by irradiating electromagnetic waves of a specific wavelength such as ultraviolet rays, and as a result, the photocatalyst having TiO ₂ as a main component even on surfaces of materials having low heat resistance such as plastics Photocatalyst is formed on the surface coated with thermosetting plastics or plastic materials from thermoplastic general purpose plastics, taking advantage of the fact that an inorganic thin film is formed and the reaction activity of the TiO ₂ photocatalyst is increased by adding various components. By using this principle, the organic material is decomposed to a weak light intensity which is not conventionally present on the surface of a low heat resistant material which is not conventionally used. Moreover, since the antistatic effect of the surface of a coating film is acquired by adding a semiconductor and conductor fine particles, such as lowering the surface resistance value of a film | membrane itself, the adhesion of the dirt by static electricity is reduced.

In the present invention, the light irradiated onto the surface of the part on which the photocatalytic film is formed is not necessarily directly exposed to light such as fluorescent lamps, incandescent lamps, mercury lamps, sunlight, or the like. That is, even if it is set as the structure which irradiates the light which permeate | transmitted the component which consists of transparent plastics and glass which are transparent materials, an effect is acquired. For example, the panel 2, the frame 4, the front cover 16, the panel 18, the frame 29 in the ventilation line of FIG. 4 in the air cleaner of FIGS. The upper cover 52, the cover cover 53, the grill cover 54, the intake part 65, the exhaust vent 76 of the cleaner of FIGS. 6 to 7, and the opening / closing lid of the clothes dryer of FIG. 86, lint filter device 99, door 121 in the dish dryer of FIGS. 9 to 11, exhaust port 128, inlet port 117, dishwasher door 137 of FIGS. 12 to 14, exhaust port Parts 152, the inner lid 71, the intake port 174, the exhaust port 175, etc. in the food waste processor of Figs. 15 to 16 are parts that support or are arranged around the air filtration member. It is made of a thermoplastic body, but by using these parts as transparent molded products, light is introduced into the inside to cure contaminants, deodorize, and antibacterial. It is capable of expressing.

As an example of a transparent plastic, PMMA, AS, PC, ABS, PVC, poly-4-methylpentene-1 (TPX), etc. are especially suitable.

Moreover, you may knead | dye and color a pigment and dye to these transparent plastic materials. However, in the case of coloring, the coloring of yellow or red-green type is not preferable because it absorbs short wavelength light and thus degrades the decomposition effect. When coloring, a preferable color tone is blue system or black system (smoke).

As a result of earnestly examining the present inventors, the relationship between the color of a transparent component and the decomposition efficiency of a photocatalyst was made clear. The color of the transparent member discussed below is defined by the Hunter and Lab methods as shown in JIS-Z-8730. That is, it expresses by L value which shows the achromatic degree (brightness) of achromatic color, a value which shows the degree of red and green, and b value which shows the degree of blue and yellow.

L value is so preferable that it is large. Regarding the coloring, the yellowish transparent component has a large absorption of short wavelength light required for the decomposition reaction in the photocatalyst, and thus lowers the efficiency of the sentence. In other words, the smaller the b value in the Lab method, the better. Moreover, it is preferable to make it into the range which is a fixed value or more and a fixed value or less about a value.

The result of having evaluated the relationship between these colors and decomposition efficiency is shown in FIG. Using a color plate colored with various pigments based on PMMA resin, five cigarette powders were burned under the same conditions as in the test of FIG. 24, and the decolorization decomposition rate of the contaminants of tobacco smoke adhered to the filter was measured. The photocatalyst material used was sample No. 2 in Table 1, and the PMMA resin used the color plate of thickness 2.0 (mm) which colored Acripet MD of Mitsubishi Rayon Co., Ltd. in each color. This is a resin to which an ultraviolet absorber is added and absorbs ultraviolet rays in the vicinity of 360 nm. The decomposition rate in FIG. 29 shows the discoloration rate calculated | required from the color difference change after irradiating the filter which contaminated the light of 40-watt fluorescent lamp at the distance of 2 (m) for 20 hours. Each color plate of the sample was placed on a contaminated filter and irradiated through a fluorescent lamp to calculate the decomposition rate to a degree of decolorization. In a standard actual smoking environment, if a decomposition rate of 40 (%) or more is obtained in the test under this condition, the contaminants due to smoke do not accumulate and endure continuous use.

From the test results, it was found that in the case where the L value was +50 or more, the a value was -20 or more and +20 or less, and the b value was +20 or less, a decomposition rate of 40 (%) or more was obtained.

This test is based on JIS-Z-8730 (color difference display method), The measuring instrument used is Z1001DP by the Nippon Denshi Bridge Co., Ltd. product according to JIS-Z-8722. The measurement sample measured the transmitted light of the plate of 2.0 (mm) thickness.

By providing the member having the action as described above according to the present invention at the site where air of various devices flows, the attached organic matter can be effectively decomposed, so that the air flow is generated or the air flow is filtered. As long as the device has a structure such as, it can be easily applied to any product.

As an example, it can apply to a petroleum fan heater, a gas fan heater, electric heaters, a furnace, etc. as a heating mechanism. The same applies to an air conditioner, a dehumidifier, or a cold air balloon. Moreover, it is applicable also to a humidifier of a heating type or an ultrasonic type. The present invention can also be applied to heating cookers such as ovens and electric cookers. Can also be used for hair dryers. Moreover, it can also be used for apparatuses provided with a cooling fan. In other words, various computers such as personal computers and word processors, displays of those computer devices such as CRTs, devices using electrophotographic apparatuses such as copiers and laser beam printers, and devices such as liquid crystal projectors and slide projectors are provided. The same low temperature hardening type high active oxide photocatalyst thin film as the present invention can be provided in the cooling fan portion, the intake port or the exhaust port portion used for ventilation of the cooling wind using the cooling fan of these devices, and the filter portion provided in the intake and exhaust port portions. The effect can be obtained.

(Example 16)

Table 10 ATO added photocatalyst filter of the compositions shown in or RuO ₂ -ATO added TiO ₂ shows a production procedure of the photocatalyst filter attached to or less.

ATO solution was prepared as follows. SnCl ₄ was dissolved in propanol to prepare a 10 wt% SnO ₂ solution. In addition, isopropoxythione was dissolved in propanol to prepare a 4 wt% Sb ₂ O ₅ solution. Next, these two kinds of solutions were mixed in an appropriate amount, ₂ -aminoethanol in a molar ratio of 1: 1 to SnO ₂ was added, and then 4 times molar water to SnO ₂ was added to prepare a 5 wt% ATO solution. The RuO ₂ -ATO solution was dissolved in ruthenium acetylacetate in the ATO solution to make 0.05wt% RuO ₂ -5wt% ATO solution.

Next, it shows the preparation of ATO and RuO ₂ -ATO addition of TiO ₂ powder. In either ATO addition or RuO ₂ -ATO addition, a predetermined amount of TiO ₂ powder (anatase) was added to the previously prepared solution, stirred at 60 ° C. for 2 hours, and then dried at 250 ° C. in an evaporation plate once. To a powder, and then treated at 550 ° C. for 3 hours to prepare TiO ₂ powder having different amounts of ATO and RuO ₂ -ATO.

Then shows the ATO was added and RuO ₂ -ATO added TiO ₂ photocatalyst coating method of fabricating the manufacturing procedures and ATO added RuO ₂ and TiO ₂ was added -ATO photocatalytic filter.

Both ATO and RuO ₂ -ATO-added TiO ₂ photocatalyst coating liquids were all added with a predetermined amount of powder prepared in 4 wt% SiO ₂ sol, and milled for 20 hours using zirconia balls to prepare a coating liquid. The coating liquid thus prepared was immersed in a filter made of acrylic fiber, air blown to remove excess coating liquid, and then treated at 120 ° C. for 5 minutes to produce a photocatalyst filter. The composition of each photocatalyst is as showing in Table 10.

The film formation method of the present invention can be produced at about 120 ° C., and can be applied to plastic materials in addition to pyrex glass substrates. In the sol-gel method usually, there is a need for several minutes or hours for the crystallization of an application is difficult, or TiO ₂ to the plastic because it requires a temperature of about 400 ℃. On the other hand, since the production method of the present invention can form a film at a low temperature, the substrate can be used abundantly, and a photocatalyst can be formed on any surface. In addition, since a short time treatment of several minutes is possible, a significant reduction in production cost is possible.

The photocatalyst filter is applicable to an air cleaner or the like. In this case, it is possible to remove odor components and bacteria, tobacco smoke, etc. present in the air. In particular, since the conventional filter is the adsorption removal by the adsorbent, the effect is lost after saturation adsorption and needs to be replaced. The photocatalyst filter can remove the adsorbed odor components, bacteria, tobacco smoke, etc. by photocatalysis. As a result, the number of filter changes can be reduced.

The photocatalyst filter of the composition shown in Table 10 was installed in the air cleaner, and it operated in the room filled with tobacco smoke, and it adsorb | sucked and discolored the tobacco smoke to the filter. This discolored filter was taken out, the fluorescent lamp was irradiated, the color change was measured, and the degradability of the adsorbed tobacco smoke was examined. In addition, the decomposition rate was computed from the discoloration amount measured with the colorimeter.

Table 10 shows the decomposition rate after 5 hours of fluorescent lamp irradiation. The decomposition rate of the ATO-added catalyst is increasing with respect to the ATO-free catalyst. Further, it is understood that the addition rate of RuO ₂ -ATO is further increased, and that the addition of RuO ₂ and ATO is effective.

In the ATO-added photocatalyst, the performance of the photocatalyst is improved as the TiO ₂ photocatalyst uses electrons of ATO by contacting ATO with TiO ₂ .

When the electron affinity of the oxide semiconductor is smaller than that of Ti, a Schottky barrier is formed at the particle interface of the fine particles so that the carrier of the added oxide semiconductor cannot be injected into the TiO ₂ , so that no effect occurs. On the other hand, when the electron affinity of the oxide semiconductor is smaller than that of Ti, a schottky barrier is not formed in the particle interface of the fine particles and is ohmic-bonded, so that the carrier of the oxide semiconductor is easily injected into TiO ₂ to function effectively. In particular, ATO has a slightly smaller electron affinity than Ti but shows little difference in performance. ATO, which is a conductive oxide, has a high carrier concentration, and a large amount of carriers of ATO are injected into TiO ₂ to improve the activity of the photocatalyst. In recent years, ATO has attracted attention as a conductive oxide, and ultrafine particles (particle size of 200 kPa or less, particularly 20 kPa to 100 kPa or less) are commercially available. By the ATO ultrafine particles added to the TiO ₂ photocatalyst it can be produced more simply ATO added TiO ₂ photocatalyst. However, 5 wt% ATO-added TiO ₂ photocatalyst filter was prepared using the ultra-fine ATO, and the same test was conducted. The decomposition rate after 5 hours was 35%, which is less than 42% of the photocatalyst of the present invention. In the ultrafine ATO addition, some ATO particles are in contact with the TiO ₂ fine particles, but some are present in SiO ₂ and are not efficient. On the other hand, in the present invention, since the ATO solution is added to the TiO ₂ fine particles before firing, the contact area between the ATO and the TiO ₂ particles is large, and the bonding state is also good by firing, so that the electron transfer between the hetero semiconductors is smooth. Done. In addition, since RuO ₂ , which is a p-type semiconductor, attracts holes among electrons and holes generated by TiO ₂ and ATO that are n-type semiconductors absorb light, the recombination of electrons and holes can be suppressed. Therefore, the electrons and holes generated by absorbing light can be effectively used for catalysis, and the decomposition rate can be improved. By the above effects, in the present invention, the decomposition performance of the photocatalyst could be improved.

(Example 17)

The performance of the photocatalyst can be further improved by adding ATO as well as other additives.

Table 11 shows the composition of the catalyst to which Li, Na, and Mg were added to the photocatalyst produced in Example 16 and the decomposition test results of tobacco smoke. The results show that even when any one of Li, Na, and Mg is added, the decomposition rate is improved, and a higher performance filter can be produced. Li, Na, and Mg have an ion radius close to that of Ti, and easily invade Ti defects on the TiO ₂ surface to increase the stability of the crystal. In addition, Li, Na, and Mg tend to attract electrons because of their high ionicity, and the reaction efficiency can be increased by separating electrons and holes generated by absorbing light.

(Example 18)

For the Li-added photocatalyst prepared in Example 16 and the Li-free photocatalyst, decomposition characteristics of acetaldehyde, urea, ammonia, and E. coli were compared using fluorescent lamps, sunlight, incandescent lamps, and mercury lamps. As a result, it can be seen that the Li-RuO ₂ -ATO-added photocatalyst had three to five times the effect of acetaldehyde, urea, ammonia, and E. coli on the decomposition properties of either photocatalyst. In this way, it was found that the Li-RuO ₂ -ATO addition catalyst had a sufficient effect with a lamp used in a living environment. Moreover, the same effect was acquired also when Na and Mg other than Li were added.

As described above, it is possible to form a low temperature film by using a simple method, to form photocatalysts on all material surfaces, to provide a highly active photocatalyst effective in a living environment, and to have excellent antibacterial and antifouling effects. Can be made fewer times.

SiO ₂ (wt%) TiO ₂ (wt%) ATO (wt%) RuO ₂ (wt%) % Degradation 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

SiO ₂ (wt%) TiO ₂ (wt%) ATO (wt%) RuO ₂ (wt%) Li (NO ₃ ) (wt%) Na (NO ₃ ) (wt%) Mg (NO ₃ ) ₂ (wt%) % Degradation 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 One 5 42 10 82 2 One 5 56 10 79 5 One 5 59 10 74 10 One 5 58 10 64 20 One 5 46 10 34 50 One 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 One 5 40 10 82 2 One 5 52 10 79 5 One 5 56 10 74 10 One 5 57 10 64 20 One 5 48 10 34 50 One 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 One 5 39 10 82 2 One 5 48 10 79 5 One 5 47 10 74 10 One 5 47 10 64 20 One 5 42 10 34 50 One 5 39

(Example 19)

RSO addition of TiO ₂ as shown in Table 12 shows a production order of the photocatalyst filter attached to or less.

The RSO solution was prepared as follows. Rothenium acetylacetate was dissolved in propanol to prepare a ₂ mol% RuO ₂ solution. In addition, Sr (NO ₃ ) ₂ was dissolved in propanol to prepare a 2 mol% SrO solution. Then it was mixed and an appropriate amount of the two kinds of solution, a molar ratio of 1 with respect to the RuO _2: was added to 2-amino-ethanol in 1, followed by addition of 4 moles per mole of water with respect to the RuO _2, to thereby prepare a solution of 1mol% RSO.

Next, it shows the preparation of RSO added TiO ₂ powder. The solution prepared above was stirred at 60 ° C. for 2 hours, once dried at 250 ° C. in an evaporating dish to a powder, and then treated at 850 ° C. for 5 hours to prepare RSO powder.

Then, RSO added TiO ₂ illustrates a fabrication method of a photocatalyst coating liquid prepared order, and RSO added TiO ₂ photocatalyst filter.

In the RSO-added TiO ₂ photocatalyst coating solution, a predetermined amount was added to the RSO powder and TiO ₂ (anatase) powder prepared in advance in a 4 wt% SiO ₂ sol, and milled for 20 hours using a zirconia ball to prepare a coating solution. The coating liquid thus prepared was immersed in a filter made of acrylic fiber, air blown to remove excess coating liquid, and treated at 120 ° C. for 5 minutes to produce a photocatalyst filter. The composition of each photocatalyst is as shown in Table 12.

The film formation method of the present invention can be produced at about 120 ° C., and can be applied to plastic materials in addition to pyrex glass substrates. In the sol-gel method usually, there is a need for several minutes or hours for the crystallization of an application is difficult, or TiO ₂ to the plastic because it requires a temperature of about 400 ℃. On the other hand, since the production method of the present invention can form a film at a low temperature, the substrate can be used abundantly, and a photocatalyst can be formed on any surface. In addition, since a short time treatment of several minutes is possible, a significant reduction in production cost is possible.

As a photocatalyst filter, it is applicable to an air cleaner etc. In this case, it is possible to remove odor components and bacteria, tobacco smoke, etc. present in the air. In particular, since the conventional filter is the adsorption removal by the adsorbent, the effect is lost after saturation adsorption and needs to be replaced. The photocatalyst filter can remove the adsorbed odor components, bacteria, tobacco smoke, etc. by photocatalysis. As a result, the number of filter changes can be reduced.

The photocatalyst filter of the composition shown in Table 12 was installed in an air cleaner, and operated in a room filled with tobacco smoke, thereby adsorbing and discoloring tobacco smoke on the filter. This discolored filter was taken out, the fluorescent lamp was irradiated, the color change was measured, and the degradability of the adsorbed tobacco smoke was examined. In addition, the decomposition rate was computed from the discoloration amount measured with the colorimeter.

Table 12 shows the decomposition rate after 5 hours of fluorescent lamp irradiation. The decomposition rate of the RSO addition catalyst is increased with respect to the RSO additive-free catalyst, indicating that RSO addition is effective.

The RSO added photocatalyst, and improve the performance of the photocatalyst according to the TiO ₂ photocatalyst utilizing the hole of RSO by the RSO and TiO ₂ in contact. The oxidation activity of one photocatalyst is due to the redox action of electrons and holes generated by absorption of light. In particular, the generated holes generate hydroxyl radicals, resulting in strong oxidation. RSO is a p-type semiconductor and has a large number of holes. By the RSO and TiO ₂ contacts the hole is injected into the TiO _2, by oxidizing the organic matter such as TiO ₂ on the surface was improved in the photocatalytic activity.

The performance of the photocatalyst can be further improved by adding RSO as well as other additives.

Table 13 shows the composition of the catalyst to which Li, Na, and Mg were added to the photocatalyst produced in Example 19, and the decomposition test results of tobacco smoke. The results show that even when any one of Li, Na, and Mg is added, the decomposition rate is improved, and a higher performance filter can be produced. Li, Na, and Mg have an ion radius close to that of Ti, which easily invades Ti defects on the TiO ₂ surface, thereby increasing the stability of the crystal. In addition, Li, Na, and Mg tend to attract electrons because of their high ionicity, and the reaction efficiency can be increased by separating electrons and holes generated by absorbing light.

SiO ₂ (wt%) TiO ₂ (wt%) RSO (wt%) % Degradation 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

SiO ₂ (wt%) TiO ₂ (wt%) RSO (wt%) Li (NO ₃ ) (wt%) Na (NO ₃ ) (wt%) Mg (NO ₃ ) ₂ (wt%) % Degradation 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 39

(Example 20)

For the Li-added photocatalyst prepared in Example 19 and the Li-free photocatalyst, the decomposition characteristics of acetaldehyde, urea, ammonia, and E. coli were compared using fluorescent lamps, sunlight, incandescent lamps, and mercury lamps. As a result, it was found that the Li-RuO ₂ -RSO-added photocatalyst was 3 to 5 times more effective in decomposing characteristics of acetaldehyde, urea, ammonia, and E. coli than either lamp. As described above, it was found that the Li-RuO ₂ -RSO-added catalyst had a sufficient effect with a lamp used in a living environment. Moreover, the same effect at the time of adding Na and Mg other than Li was acquired.

(Example 21)

Embodiment the RSO method of mixing the powder in the TiO ₂ powder as in Example 19, one also exists a RSO particles in contact with the TiO ₂ fine particles, due to the use of SiO ₂ as a binder, it is also the particles present in the SiO _2, is not efficient. On the other hand, if the RSO solution can be calcined by adding the RSO solution to the TiO ₂ fine particles in advance, the contact area between the RSO and the TiO ₂ particles is large, and the bonding state is good by firing, so that electron transfer between the hetero semiconductors is smooth. However, in order to manufacture RSO, the temperature of 700-850 degreeC is required, and since RSO does not crystallize at the temperature below this, it does not function as a p-type semiconductor. In the case of TiO ₂ , the crystal becomes rutile at 600 ° C. or higher. It is an anatase type that expresses sufficient function as a photocatalyst. In the rutile type, the performance of the photocatalyst decreases rapidly. Therefore, when TiO ₂ is subjected to high temperature treatment after the addition of RSO, RSO becomes a p-type semiconductor, but TiO ₂ phase-transforms into a rutile type and loses its function as a photocatalyst. Therefore, the RSO-added STO photocatalyst becomes effective using STO (SrTiO ₃ ) which can expect the same function as TiO ₂ as a photocatalyst. STO has almost the same band structure as TiO ₂ . Moreover, the manufacturing method is crystallized by processing at high temperature of 700-850 degreeC. RSO and STO are either crystals or perovskite, and the crystal lattice constants are almost the same because Sr-O is common. Therefore, the fabrication conditions are also very close to the RSO and the bonding state can be good. The manufacturing method of RSO addition STO powder is shown below.

STO powder was prepared as follows. Isopropoxide City other dissolved carbonate in propanol to prepare a 2mol% TiO ₂ solution, followed by a molar ratio of 1 with respect to the TiO _2: 2: 1, a molar ratio of 1 with respect to the addition of Sr (NO ₃₎ of the first _2, and TiO ₂ Aminoethanol was added followed by 4 times molar water relative to TiO ₂ to prepare a 1 mol% STO solution.

Next, after stirring this solution at 60 degreeC for 2 hours, it dried once at 250 degreeC on the evaporating plate, it was made into powder, and it processed at 850 degreeC for 5 hours, and manufactured the STO powder.

The manufacturing method of RSO addition STO powder is shown below.

To the RSO solution prepared in Example 19, a predetermined amount of STO powder was added and stirred at 60 ° C. for 2 hours, once dried at 250 ° C. in an evaporation dish to a powder, and then treated at 850 ° C. for 5 hours, followed by RSO addition STO. Powder was prepared.

Next, the manufacturing procedure of RSO addition STO photocatalyst coating liquid and the manufacturing method of an RSO addition STO photocatalyst filter are shown.

In the RSO-added STO photocatalyst coating solution, a predetermined amount of the RSO-added STO powder prepared above was added to 4 wt% SiO ₂ sol, and milled for 20 hours using a zirconia ball to prepare a coating solution. The filter made of acrylic fiber was immersed in the coating solution prepared as described above, air blow was removed to remove the excess coating solution, and then treated at 120 ° C. for 5 minutes to produce a photocatalyst filter. Produced RSO added STO photocatalyst is, since the powder comprises a STO grown particles to sintering at a high temperature, adhesion to the acrylic fiber Ill = fated creature compared to some TiO ₂ based appearance was beautiful. The composition of each photocatalyst is as shown in Table 14.

The photocatalyst filter of the composition shown in Table 14 was installed in an air cleaner and operated in a room filled with tobacco smoke to adsorb the tobacco smoke to the filter and discolor. This discolored filter was taken out, the fluorescent lamp was irradiated, the color change was measured, and the degradability of the adsorbed tobacco smoke was examined. In addition, the decomposition rate was computed from the discoloration amount measured with the colorimeter.

Table 14 shows the decomposition rate after 5 hours of fluorescent lamp irradiation. RSO-added STO catalysts have a higher decomposition rate than RSO-added TiO ₂ catalysts, indicating that RSO-added STO is effective.

In addition, the performance of the photocatalyst can be further improved by adding RSO as well as other additives.

Table 14 shows the composition of the catalyst in which Li, Na, and Mg were added to the prepared RSO-added STO photocatalyst and the decomposition test results of tobacco smoke. The results show that even when any one of Li, Na, and Mg is added, the decomposition rate is improved, and a higher performance filter can be produced. Li, Na, and Mg have an ion radius close to that of Ti, and easily invade Ti defects on the surface of the STO, thereby increasing the stability of the crystal. In addition, Li, Na, and Mg tend to attract electrons because of their high ionicity, and the reaction efficiency can be increased by separating electrons and holes generated by absorbing light.

As described above, the RSO-added STO photocatalyst filter is slightly poor in adhesion. Thus, the TiO ₂ system having good adhesion was mixed and coated on acrylic fiber to prepare a photocatalyst filter. The composition and degradability of tobacco smoke are shown in Table 15. As a result, good results were obtained in both adhesion and decomposition of tobacco smoke, and a high performance photocatalyst could be produced.

As described above, RSO, which is a p-type semiconductor, can inject holes into STO or attract holes among electrons and holes generated by STO absorbing light, and therefore can suppress recombination of electrons and holes. Therefore, the electrons and holes generated by absorbing light can be effectively used for catalysis, and the decomposition rate can be improved. By the above effects, in the present invention, the decomposition performance of the photocatalyst could be improved.

In this way, it is possible to form a low temperature film by using a simple method, to form a photocatalyst on all material surfaces, to provide a highly active photocatalyst effective in a living environment, and to provide excellent antibacterial and antifouling effects. And cleaning frequency can be reduced.

SiO ₂ (wt%) STO (wt%) RSO (wt%) Li (NO ₃ ) (wt%) Na (NO ₃ ) (wt%) Mg (NO ₃ ) ₂ (wt%) % Degradation 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

SiO ₂ (wt%) TiO ₂ (wt%) RSO / STO (wt%) Li (NO ₃ ) (wt%) Na (NO ₃ ) (wt%) Mg (NO ₃ ) ₂ (wt%) % Degradation 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 fine particles and zeolite (aluminum silicate) were dispersed in SiO ₂ sol was prepared. This solution was used to form a TiO ₂ film on acrylic fibers to produce a photocatalyst attachment filter. The procedure is shown below.

First, description will be made in the production process of the SiO ₂ sol. 5 g of tetraethoxysilane was dissolved in 100 ml of a water-ethanol-propanol (3:27:70) mixed solution and stirred at 40 ° C. for about 5 hours. The obtained solution was left to stand at room temperature for 2 weeks to obtain SiO ₂ sol.

The following describes the preparation of a solution obtained by dispersing TiO ₂ fine particles and the zeolite in the SiO ₂ sol. TiO ₂ fine particles were added in a weight ratio of TiO ₂ / SiO ₂ = 9 in the SiO ₂ sol prepared above, and a predetermined amount of ZSM-5 (synthetic zeolite, hereinafter identical) was added. In addition, the solid content concentration was 4 wt% and adjusted by adding the required amount of water. Then prepare a solution obtained by dispersing TiO ₂ fine particles and the ZSM-5 in the mill process 24 time to, and SiO ₂ sol in order to disperse the TiO ₂ fine particles and the ZSM-5 in the SiO ₂ sol using zirconia balls of 5mmø.

A filter coated with a TiO ₂ dispersed SiO ₂ film containing TiO ₂ particles and ZSM-5 dispersed in a SiO ₂ film was coated with a ZSM-5-added TiO ₂ fine particle dispersed SiO ₂ sol made of acrylic fiber and treated at 120 ° C. for 5 minutes. Formed. The composition of the prepared photocatalyst was SiO ₂ = 8wt%, TiO ₂ = 72wt%, ZSM-5 = 20wt%.

The photocatalyst filter is applicable to an air cleaner. In this case, it is possible to remove odor components and bacteria, tobacco smoke, etc. present in the air. In particular, since a conventional filter is absorbed and removed by an adsorbent, the effect is lost after saturation adsorption and needs to be replaced. However, the photocatalyst filter removes adsorbed odor components, bacteria and tobacco smoke by photocatalytic action. As a result, the number of filter changes can be reduced.

The photocatalyst filter prepared above was enclosed in a glass container, 400 ppm of acetaldehyde as a gas component was put in, and the photocatalyst performance was investigated by circulating the inside of the container with a fan and irradiating a fluorescent lamp. In addition, the gas was always measured by circulating by connecting an infrared detector. The measurement result is shown in FIG. In the case of no zeolite addition, the acetaldehyde decreases rapidly at first and then gradually decreases, but returns to the initial value when gas is injected, and the adsorption and decomposition reaction reaches equilibrium after such an operation is repeated. This indicates that acetaldehyde is first adsorbed to TiO ₂ and rapidly decreases, and then gradually decomposes due to the action of a photocatalyst. Subsequently, when the gas is injected, it is decomposed by the photocatalyst, the acetaldehyde is rapidly adsorbed to the empty adsorption site, and then rapidly decomposed. In contrast, in the zeolite addition, the introduced gas is almost extinguished in the atmosphere due to the effect of the zeolite as an adsorbent. The adsorbed gas is then gradually decomposed by photocatalysis. Therefore, by adding a zeolite to add an adsorption effect, the gas in the air can be quickly adsorbed and removed, and then the photocatalyst is decomposed, so that the air in the air can be kept clean at all times.

(Example 23)

In order to investigate the influence of the Si: Al ratio of the zeolite, three kinds of Si: Al = 80: 20, 50:20 and 30:20 were added to investigate the difference. As shown in FIG. 31, the larger the Si ratio, the higher the performance. This is because zeolites having a large Si ratio not only have a large adsorption amount due to their large surface area, but also provide a surface adsorption water necessary for a photocatalyst due to a large amount of adsorption water.

(Example 24)

Next, the performance when the Cu, Ag, Li, Na, and Mg ions were introduced into the zeolite by ion exchange was examined. As a result, as shown in FIG. 32, Cu and Ag ion exchange are not so changed before and after ion exchange (compared with FIG. 30). On the other hand, Li, Na, Mg ion exchange was shown to improve the performance. This is because ionic elements such as Na, Li, and Mg have a space charged with + in zeolite, attract electrons generated by TiO ₂ absorbing light, separate electrons and holes, and suppress recombination. This is because the reaction efficiency is increased.

About addition of Cu and Ag ion exchange zeolite, the antibacterial test using E. coli was performed. The results are shown in FIG. Escherichia coli propagates while not being zeolite or light irradiated. When zeolite was added, the E. coli sterilization rate at the time of light irradiation was the same, but the number of E. coli was slightly decreased without light irradiation. Cu and Ag ion-exchange zeolites improved the sterilization rate of E. coli at the time of light irradiation, and the sterilization rate while not irradiating light also had much better results than others.

As mentioned above, by adding zeolite, the antimicrobial activity of the dark reaction was improved, and when Cu and Ag ion exchange were performed, the performance was improved both during light irradiation and during the dark reaction, thereby producing an excellent antimicrobial agent.

In this way, photocatalysts can be formed on the surface of all materials, providing a highly active photocatalyst effective in a living environment, and efficiently removing gaseous components in the air by adsorption effects and decomposition reactions.

(Example 25)

A solution in which TiO ₂ fine particles and a blue pigment were dispersed in SiO ₂ sol was prepared. This solution was used to form a TiO ₂ film on acrylic fibers to produce a photocatalyst attachment filter. The procedure is shown below.

First, description will be made in the production process of the SiO ₂ sol. 5 g of tetraethoxysilane was dissolved in 100 ml of a water-ethanol-propanol (3:27:70) mixed solution and stirred at 40 ° C. for about 5 hours. The obtained solution was left to stand at room temperature for 2 weeks to obtain SiO ₂ sol.

Next will be described the process of the solution obtained by dispersing TiO ₂ fine particles, and a blue pigment in the SiO ₂ sol. TiO ₂ fine particles were added in a weight ratio of TiO ₂ / SiO ₂ = 9 in the SiO ₂ sol prepared above, and a predetermined amount of Cu-phthalocyanine (blue pigment) was added. In addition, solid content concentration was adjusted to 4 wt% by adding required amount of water. Thereafter, a 5 mm zirconia ball was used to treat the TiO ₂ fine particles in a SiO ₂ sol for 24 hours to disperse the TiO ₂ fine particles, thereby preparing a solution in which the TiO ₂ fine particles were dispersed in the SiO ₂ sol.

To form a TiO ₂ fine particle dispersion sol of SiO ₂ coating and treated for 5 minutes to 120 ℃ TiO ₂ fine particles are dispersed in the TiO ₂ dispersed SiO ₂ SiO ₂ film filter coating film made of the acrylic fiber. The composition of the produced photocatalyst is shown in Table 16.

The photocatalyst filter is applicable to an air cleaner. In this case, it is possible to remove odor components and bacteria, tobacco smoke, etc. present in the air. In particular, since the conventional filter is absorbed and removed by the adsorbent, the effect is lost after saturation adsorption and needs to be replaced. However, the photocatalyst filter can remove adsorbed odor components, bacteria and tobacco smoke by photocatalytic action. As a result, the number of filter changes can be reduced.

The photocatalyst filter of the composition shown in Table 16 was installed in the air cleaner, it operated in the room filled with tobacco smoke, and the tobacco smoke adsorb | sucked on the filter and discolored. This discolored filter was taken out, the fluorescent lamp was irradiated, the color change was measured, and the degradability of the adsorbed tobacco smoke was examined. In addition, the decomposition rate was computed from the discoloration amount measured with the colorimeter.

34 shows the decomposition test results. The results show that the decomposition performance is improved by adding blue pigment.

Table 16 shows the results of evaluation of film strength and light resistance other than the decomposition performance. In addition, each evaluation was performed as follows.

The strength test evaluated the fall of the powder by repeatedly bending and pulling the produced filter. In addition, when the powder did not fall due to the bending and pulling, it was examined whether the air was peeled off with 2 m / sec after repeated bending and pulling. Evaluation was made into x when peeling by peeling and tension, and made into (triangle | delta) the thing which extruded by exhaling air and peeling when it did not peel, and (circle) in any case.

The light resistance was irradiated with the low pressure mercury lamp (254 nm, 3 mW / cm <^2> ) to the produced filter, and the time to which the amount of change of color became 20% or more was investigated.

The evaluation resulted in that when a pigment is added with respect to a film | membrane intensity | strength, intensity | strength falls, and a film | membrane peels easily at 20 wt% or more. It can be used as long as peeling is simple but there is no peeling, tension, or the like, and there is no peeling.

As for the light resistance, it was found that the greater the amount of pigment added, the greater the deterioration. Although pigments are excellent in light resistance, they contain organic groups and are gradually decomposed by a photocatalyst. However, since this evaluation condition is considerably accelerated, the conditions normally used are light of fluorescent lamps, and 35 hours in Table 16 correspond to 3 to 5 years under fluorescent lamps.

As described above, the pigment addition catalyst is inferior in film strength and light resistance, but since the filter catalyst itself is colored, the performance of the filter can be immediately known in appearance, and the replacement time of the filter can be easily determined.

In order to strengthen the adhesive strength to the filter, the addition of organic resin is most effective. Table 17 shows the composition and various evaluation results when the acrylic resin was added to the solution prepared above. The addition of resin significantly improved the film strength. In addition, there was no change in the light resistance, but sufficient performance under a fluorescent lamp, and the decomposability of the cigarette was also a good result.

As mentioned above, it turned out that the outstanding filter can be manufactured by adding a pigment and adding resin as needed.

Pigment (wt%) TiO ₂ (wt%) SiO ₂ (wt%) Membrane strength Light resistance 0 90 10 ○ No change 10 81 9 △ 50 20 72 8 × 40 50 45 5 × 35

Resin (wt%) Pigment (wt%) TiO ₂ (wt%) SiO ₂ (wt%) Membrane strength Light resistance Flush test % Degradation after 5 hours 0 30 63 7 × 35 One 43 10 27 56.7 6.3 △ 35 5 45 20 24 50.4 5.6 ○ 35 over 10 42 50 15 31.5 3.5 ○ 35 over 10 39

(Example 26)

For the pigment-added photocatalyst and the pigment-free photocatalyst prepared in Example 25, the decomposition characteristics of acetaldehyde, urea, ammonia and Escherichia coli were compared using fluorescent lamps, sunlight, incandescent lamps and mercury lamps. As a result, it was found that the Li-added photocatalyst had three to five times the effect of acetaldehyde, urea, ammonia, and E. coli on the decomposition characteristics of the pigment-free photocatalyst. In this way, it was found that the pigment addition catalyst can obtain a sufficient effect from not only an ultraviolet lamp but also a lamp used in a living environment. Moreover, even if the above result added red, yellow, green, etc. other than blue, the same effect was acquired.

In this way, photocatalysts can be formed on all material surfaces, provide a highly active photocatalyst effective in a living environment, and it is easy to know when to replace the photocatalyst.

(Example 27)

A solution in which TiO ₂ fine particles and acrylic resin were added to SiO ₂ sol was prepared. This solution was used to form a TiO ₂ film on acrylic fibers to produce a photocatalyst attachment filter. The procedure is shown below.

First, description will be made in the production process of the SiO ₂ sol. 5 g of tetraethoxysilane was dissolved in 100 ml of a water-ethanol-propanol (3:27:70) mixed solution and stirred at 40 ° C. for about 5 hours. The obtained solution was left to stand at room temperature for 2 weeks to obtain SiO ₂ sol.

Next will be described the process of the solution was added to the TiO ₂ fine particles and the acrylic resin in the SiO ₂ sol. TiO ₂ fine particles were added in a weight ratio of TiO ₂ / SiO ₂ = 9 in the SiO ₂ sol prepared above, and a predetermined amount of acrylic resin was added. In addition, the solid content concentration was 4 wt% and adjusted by adding the required amount of water. Thereafter, a 5 mm zirconia ball was used to treat the TiO ₂ fine particles in a SiO ₂ sol for 24 hours to disperse the TiO ₂ fine particles, thereby preparing a solution in which the TiO ₂ fine particles were dispersed in the SiO ₂ sol.

And to coat the TiO ₂ particulate dispersed SiO ₂ sol made of acrylic fiber for 5 minutes to 120 ℃ to form the TiO ₂ dispersed SiO ₂ coat film filter which TiO ₂ fine particles are dispersed in a SiO ₂ film. The composition of the produced photocatalyst is shown in Table 18.

The photocatalyst filter is applicable to an air cleaner. In this case, it is possible to remove odor components and bacteria, tobacco smoke, etc. present in the air. In particular, since a conventional filter is absorbed and removed by an adsorbent, the effect is lost after saturation adsorption and needs to be replaced. However, the photocatalyst filter removes adsorbed odor components, bacteria and tobacco smoke by photocatalytic action. As a result, the number of filter changes can be reduced.

The photocatalyst filter of the composition shown in Table 18 was installed in the air cleaner, it operated in the room filled with tobacco smoke, and it adsorb | sucked and discolored the tobacco smoke to the filter. This discolored filter was taken out, the fluorescent lamp was irradiated, the color change was measured, and the degradability of the adsorbed tobacco smoke was examined. In addition, the decomposition rate was computed from the discoloration amount measured with the colorimeter.

35 shows the decomposition test results. When SiO ₂ (silica) was used as the binder, the higher the binder amount, the lower the performance as a photocatalyst. On the other hand, in the case of acrylic resin, even if the amount of binder increased, it turned out that there is little change in the performance of a photocatalyst.

Table 18 shows the results of evaluation of the film strength, light resistance, and the water washing test in addition to the decomposition performance. In addition, each evaluation was performed as follows.

The strength test evaluated whether the powder fell by repeatedly bending and pulling the produced filter. In addition, when the powder did not fall due to the bending and pulling, it was examined whether the air was peeled off with 2 m / sec after repeated bending and pulling. Evaluation was made into x, when peeling by peeling and tension, and made into (triangle | delta) and what peeled off by blowing air, and peeling off when it did not peel.

The light resistance was investigated by applying a low pressure mercury lamp (254 nm, 10 mW / cm ² ) to the fabricated filter, and the time when the amount of color change was 20% or more.

The water washing test was evaluated by examining the number of times until the catalyst was peeled off by repeatedly washing the filter with water.

The evaluation result was that when the acrylic resin was added with respect to the film strength, the strength was improved, and the film did not peel off at 5 wt% or more.

As for the light resistance, it was found that the greater the amount of acrylic resin added, the greater the deterioration. Acrylic resins contain organic groups and are gradually decomposed by a photocatalyst. However, since these evaluation conditions are considerably accelerated, the conditions normally used are light of fluorescent lamps, and 5 hours in Table 18 correspond to 3 to 5 years under fluorescent lamps.

As for the water washing test, it was found that if the amount of the resin added was 10 wt% or more, it was sufficiently washed with water and used repeatedly.

As described above, sufficient strength could be obtained by adding the organic resin. Moreover, the performance of the catalyst was equivalent to no addition even if the resin was added, so that a photocatalytic filter that could be washed was produced.

Thus, the acrylic resin addition catalyst is inferior in light resistance but excellent in film strength, and can wash | clean a filter catalyst. Until now, photocatalysts have not been effective for inorganic contaminants such as dust only by self-cleaning contaminants such as organic matters. However, cleaning can remove inorganic contaminants and extend the life of the filter.

(Example 28)

Decomposition characteristics of acetaldehyde, urea, ammonia, and E. coli were compared with the acrylic resin-added photocatalyst prepared in Example 27 and the acrylic resin-free photocatalyst using fluorescent lamp, sunlight, incandescent lamp, and mercury lamp. As a result, it was found that the Li-added photocatalyst had the same effect as that of acrylaldehyde, urea, ammonia, and E. coli in acrylaldehyde-free photocatalyst. As described above, it was found that the acrylic resin addition catalyst can obtain a sufficient effect not only from the ultraviolet lamp but also from the lamp used in the living environment.

(Example 29)

Recently, in the acrylic resin, a silanol-modified acrylic resin having a silanol group introduced into the side chain of the acrylic resin has been developed in order to improve chemical properties. The silanol-modified acrylic resin was added to the solution prepared in Example 27 to add an acrylic resin having a different amount of silanol group introduced thereto to prepare a filter. 36 shows the results of evaluating the decomposition characteristics and the light resistance of the tobacco smoke of the manufactured filter. The decomposition characteristics of tobacco smoke did not change significantly depending on the amount of silanol group introduced (silanol introduced in the drawing), and it was found that the performance did not deteriorate. On the other hand, it turned out that light resistance can be improved by increasing the introduction amount of a silanol group.

For these reasons, it was found that the use of the silanol-modified acrylic resin improves the light resistance and makes it possible to produce an excellent photocatalyst filter.

(Example 30)

In the case of using an organic resin, unlike a ceramic material such as silica, it can be cured without applying heat. For example, it can achieve by using room temperature hardening resin. However, the room temperature curing system takes about 24 hours in addition to the instant adhesive. The instant adhesive cures in a short time, but is gradually decomposed by a photocatalyst. A UV hardening system is mentioned as resin which can harden | cure in a short time and is excellent in light resistance. A UV curing system hardens | cures by an ultraviolet-ray, and it superpose | polymerizes and hardens | cures slowly by the ultraviolet-ray irradiated from a fluorescent lamp. However, it is also true that the photocatalyst is gradually decomposed. Therefore, by suitably combining photocuring and photolysis, light resistance can be improved as a result.

A solution in which TiO ₂ fine particles were added UV curable resin was prepared. This solution was used to form a TiO ₂ film on acrylic fibers to produce a photocatalyst attachment filter. The procedure is shown below.

A predetermined amount of TiO ₂ fine particles and any one of Si, Al, and Ti-based coupling agents were added to toluene, stirred at 40 ° C. for 2 hours, and then added to a predetermined amount of UV curable resin. In addition, the solid content concentration was 4 wt% and adjusted by adding the required amount of toluene. After 24 hours to mill treatment using zirconia balls of the ball to 5mmø dispersing the TiO ₂ fine particles in the solution, to prepare a solution obtained by dispersing TiO ₂ particulates in the UV cured resin.

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

Resin (wt%) TiO ₂ (wt%) SiO ₂ (wt%) Membrane strength Light resistance Flush test % Degradation after 5 hours 0 90 10 △ No change One 30 2 88.2 9.8 △ No change One 32 5 85.5 9.5 ○ 5h 5 31 10 81 9 ○ 3h 10 33 20 72 8 ○ 2h over 10 31 50 45 5 ○ 2h over 10 28

TiO ₂ (wt%) UV Curing Resin (wt%) Coupling (wt%) Flush test Light resistance 90 0 10 One No change 85 5 10 5 No change 80 10 10 over 10 No change 70 20 10 over 10 No change

FIG. 37 shows the results of investigating the decomposition characteristics (decomposition ratio after 5 hours) of tobacco smoke to the amount of the coupling agent added. By addition of a coupling agent, it turns out that a photocatalyst characteristic improves. With UV-curable resins alone, the surface of the TiO ₂ particles completely covers the resin, resulting in loss of catalytic properties. By the addition of a coupling agent may be increased an exposed portion of the surface of TiO _2. In addition, the photocatalyst decomposes the surface adsorption water to generate radicals, but by adding a coupling agent, the surface adsorption water can be kept large, and the catalytic performance can be expressed.

Table 19 shows the test results other than the catalytic performance. In the water washing test, washing with 10 wt% or more of UV curable resin becomes possible. The light resistance did not show any deterioration even after 10 hours of irradiation without any problem.

By using UV curable resin as mentioned above, room temperature coating was possible in a short time, and the photocatalyst filter excellent in light resistance was able to be manufactured.

In this way, photocatalysts can be formed on the surface of all materials in low temperature and short time, and high active photocatalysts can be washed under water in order to effectively clean the environment. Therefore, contaminants of inorganic materials can be removed. Do it less.

(Example 31)

A solution in which TiO ₂ fine particles were dispersed in SiO ₂ sol was prepared. This solution was used to form a TiO ₂ film on the PET film to produce a PET film. The procedure is shown below.

First, description will be made in the production process of the SiO ₂ sol. 5 g of tetraethoxysilane was dissolved in 100 ml of a water-ethanol-propanol (3:27:70) mixed solution and stirred at 40 ° C. for about 5 hours. The obtained solution was left to stand at room temperature for 2 weeks to obtain SiO ₂ sol.

Next will be described the process of the solution obtained by dispersing TiO ₂ particulates in the SiO ₂ sol. TiO ₂ fine particles were added in a weight ratio of TiO ₂ / SiO ₂ to 9 in the SiO ₂ sol prepared above. In addition, a predetermined amount of phosphoric acid, boric acid, and nitrates of Li, Mg, K, and Ca were respectively added, and the solid content concentration was adjusted to 4 wt% by adding water of a required amount. Then using zirconium balls of 5mmø, for 24 hours to a ball mill treatment in order to disperse the fine particles in the TiO ₂ SiO ₂ sol, it was prepared in a solution obtained by dispersing TiO ₂ particulates in the SiO ₂ sol.

To coat the TiO ₂ particulate dispersed SiO ₂ sol prepared on a PET film to 120 ℃ low-pressure mercury lamp (intensity: 15mW / cm ²⁾ and while investigating for 5 minutes, TiO ₂ fine particles are dispersed by TiO ₂ dispersed in a SiO ₂ film A plastic film coated with a SiO ₂ film was formed. The thin film obtained on the PET film had both good film quality and strength and a film thickness of 300 nm.

The strength of the produced membrane was rubbed by rubbing the surface of the membrane using an eraser with a weight of 1 kg. As a result, the B- and P-free films exhibited peeling at 50 times, but the B and P-added films did not have any scratches even at 100 times. For this reason, it turned out that film strength improves by addition of B and P.

Next, the degradation activity of organic matter was evaluated. In addition, the activity test was carried out by coating the thin film with a reddish organic dye and irradiating with light having a wavelength of 254 nm and 0.2 mW / cm ² . The decomposition rate was calculated from the amount of change from the transmittance of the initial dye. Table 20 shows the result. Blanks in the table indicate that the element is not added.

TiO ₂ / SiO ₂ B (wt%) P (wt%) Li (wt%) Ca (wt%) K (wt%) Mg (wt%) Degradation rate after 10 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

In the case of no B or P addition, the Li-added photocatalyst decomposed 65% after 10 minutes, but the decomposition rate was improved when B and P were added thereto. As described above, it was found that the photocatalyst can be further improved by the addition of B and P. Moreover, the effect of an additive was K largest, and became order of Ca, Mg, and Li.

In the photocatalyst, electrons and holes generated by absorbing light decompose water to generate radicals to decompose organic matter. Therefore, organic matter cannot be decomposed unless water is present on the surface of the photocatalyst. In the case of no B or P addition, water adsorbed on TiO ₂ and SiO ₂ surfaces is decomposed. B and P have high water absorption, so that more water is present on the catalyst surface by adding B and P. As the surface adsorption water increases, the degradability of the organic material may be improved.

Next, ATO which is electroconductive particle was added to the coating liquid prepared previously, and it formed into a film on PET film similarly, and evaluated the degradability of a pigment | dye. The results are shown in Table 21.

TiO ₂ / SiO ₂ Bwt% Pwt% Kwt% ATOwt% Degradation 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

In the case of no addition of ATO, the decomposition rate after 10 minutes was 81%, but when ATO was added, the decomposition rate was improved. In particular, the addition of 10wt% has the greatest effect and the decomposition rate reaches 90%. In this way, it was found that the high performance can be achieved by further adding ATO. In addition, the surface resistance of the prepared ATO-added film is lowered to 10 9 square ohms / square band, and it has an antistatic effect, and can prevent adhesion of not only organic matter but also inorganic matter.

In addition, this ATO addition effect was the same result not only with K (potassium) but also Li (lithium), Ca (calcium), and Mg (magnesium).

In the present invention, electric appliances mainly used in an indoor environment incorporating a mechanism for generating air flow by an electric motor, such as an air cleaner, a ventilation line, a fan, a vacuum cleaner, a clothes dryer, a dish dryer, a dishwasher, and a food waste processor. Since the low temperature hardening type highly active oxide photocatalyst thin film was installed in the air flow path, the filtration part, the exterior part, or the part illuminated by the built-in luminaire, the following effects can be obtained.

According to the present invention, three effects are broadly obtained.

First, in the present invention, an ion having an electronegativity of less than 1.6 and an ion radius of less than 0.2 nm, including Na and Li, in a thin film of an oxide photocatalyst such as TiO ₂ , which is known in the art, has an valence of 2 or less. As a result, the organic substance decomposition effect was increased. Further, in addition to this, when the metal oxide semiconductor having an affinity of 1.2 or higher or containing metal fine particles of Ag, Cu, Ni, Pd, Rh, Pt together with antimony-added tin oxide or the like is added, the decomposition efficiency is further increased. Thereby, the effect that the mechanism which produces | generates short wavelength light, such as an ultraviolet lamp required by the conventional oxide photocatalyst, becomes unnecessary. That is, the light generally obtained indoors, even if the light is not weak, such as fluorescent lamps, incandescent lamps, mercury lamps, or sunlight beyond the window glass, decomposes the organic matter and attaches to sediments, such as cigarettes, resins, etc. Even if contaminants adhere to the product, it is decomposed to obtain an antifouling effect. Similarly, when light causes a variety of odor-causing substances such as organic amines and mercaptans dispersed in the air, they are decomposed and decomposed into low odor or non-odorous substances. Obtained. Similarly, when microorganisms such as bacteria, fungi, and pollen that float in the air are attached to each other with weak light, the surface of the member on which the thin film of the oxide catalyst is formed is suppressed by the organic decomposition of these microorganisms. While being kept clean, the effect of reducing the amount of microorganisms suspended in the air of the room using these products is obtained. Conventionally, parts that filter such air, such as filters and nets, are often handled as replacement parts, and when contaminants accumulate or are loaded, it is necessary to take out parts, wash them, or replace them with new ones. According to the present invention, since the contaminants are decomposed, the lifespan until loading can be extended, thereby reducing the frequency of exchange.

Examples of specific effects in each use are shown below. Air purifier, ventilation line, fan, vacuum cleaner, clothes dryer, dish dryer, dish washer, food waste processor's outer frame, frame, and exterior parts of case are all irradiated with indoor lighting or sunlight, which makes it difficult to get dirty. It is possible to maintain a clean state that is difficult to breed. In addition, if the indoor lighting or sunlight is irradiated to the air flow path parts attached to these items, the filter, the net, etc. in the air flow path, the same effect can be obtained not only for antifouling, antibacterial, but also indoor deodorization effect. have.

In terms of the antifouling effect, air cleaners, ventilation lines, fans, and vacuum cleaners may be equipped with an infrared light receiving unit in the main body and an infrared light emitting unit in the remote controller to perform remote operation. However, contaminants may be attached to the infrared light receiving unit. There is also an effect to prevent problems that interfere with the reception and reception of the signal.

In general, when the load of contaminants is large enough that the decomposition is not sufficient due to the intensity of light obtained indoors, or when the member is intended to be used in a member that does not sufficiently receive light in the room, the effect of installing lighting means such as a fluorescent lamp or a light bulb is obtained. Lose. In addition, when it is not enough, high decomposition effect is acquired by providing ultraviolet generating means, such as a mercury lamp and a metal halide lamp. In such a case, according to the present invention, since the decomposition efficiency is higher than before, the lighting time of the lamps can be shortened, or the output of the lamps can be shortened, thereby saving power consumption and extending the life of the lamps. There is an effect that the frequency is at least.

For example, disintegration of a large number of odorous substances generated from food waste disposers, or when cooking oil is attached in a large amount such as a kitchen ventilation line, or in a closed chamber or drum such as a dish washer, dish dryer, or clothes dryer. In the case of necessity, the use of light generating means having various wavelengths as described above is effective.

Secondly, in the present invention, a metal oxide semiconductor having an affinity of 1.2 or more or an Ag, Cu, Ni, Pd, Rh, Pt containing antimony-added tin oxide or the like is added to the photocatalyst thin film as described above. Its surface resistance is suppressed low. With this effect, it is possible to suppress a phenomenon in which minerals such as large dust and fibers, which cannot take time to decompose, or soil that cannot be decomposed by static electricity are attached. By this action, it is possible to suppress the phenomenon that hardly degradable contaminants are deposited on the surface and light does not reach the surface of the photocatalyst thin film.

This antistatic effect is effective in preventing not only contamination by adhesion of dust and the like but also malfunction of an electronic circuit due to electrostatic charging. In particular, it is effective for articles which are easy to frictionally charge during use such as a cleaner.

The specific effect example in each use is shown below. Air purifiers, ventilation lines, fans, cleaners, clothes dryers, dish dryers, dishwashers, food waste disposers, and outer frames, frames, and case exterior parts are particularly effective because dirt is easily attached.

Third, in the present invention, when forming a photocatalyst thin film having the above effects, it is made from a solution containing a low molecular weight organometallic compound and water, and breaks the bond between the metal atom and the organic group. Since the reaction for film formation is promoted by irradiating electromagnetic waves of required specific wavelengths including the like, a thin film can be formed at a lower temperature than conventionally. Therefore, the base material is softened by heat to the surface of general-purpose plastics or organic paints coated on steel sheets containing ABS, PS, PP, polyester, etc. used in the electrical appliances as described above. The oxide photocatalyst thin film can be formed without causing problems such as deformation, bubble generation, crack generation, embrittlement, strength drop, and toughness drop.

Examples of specific effects in each use are shown below. Molded articles made of synthetic resin or coated steel sheets, which are commonly used for outer frames, frames, and case parts of air cleaners, ventilation vessels, fans, cleaners, clothes dryers, dish dryers, dishwashers, and food waste treatment machines, of TiO _2, etc., but the did not withstand the high temperatures of more than 300 ℃ thin film formation temperature of the oxide photocatalyst as the main component, it is possible to form easily a film according to the present invention, without giving a thermal damage on the basis of these component surfaces.

In addition, the air flow path parts attached to the above articles or the fan, blades, filters, and net parts in the air flow paths are similarly very difficult to be formed of a material that withstands heat treatment of 300 ° C. or higher. The oxide photocatalyst thin film can be formed.

As another effect, since the oxide photocatalyst thin film according to the present invention can form a hard film at low temperature, there is also an effect of replacing a hard coat such as an acrylic resin that has been conventionally painted on the surface of a plastic molded article. Accordingly, as in the conventional hard coat, the gloss of the molded article can be increased, and surface scratches can be prevented, and microbial propagation suppression, antifouling effect, and antistatic effect can be obtained.

Moreover, in the case of the application to the filter which consists of a nonwoven fabric, a woven fabric, a sponge, etc., since the oxide photocatalyst thin film formed in the fiber surface is glassy, the surface adsorption property and wettability are improved. For this reason, there exists an effect which improves the collection efficiency of an odor collection and smoke particle. Even if a thin film of SiO ₂ alone is formed, the collection efficiency is improved by the same principle, but when the odor or smoke particles adhere to the fiber surface, the collection effect is reduced, but in the present invention, since the glassy film itself has a photocatalytic property, The effect persists, as the fiber surface is always cleansed and the substrate surface with high adsorption remains exposed.

Furthermore, in the case of the dishwasher, the contact angle of the water droplet adhered inside can be reduced by utilizing the antifouling effect of the photocatalyst. Accordingly, since the total amount of residual water can be reduced, there is an effect of increasing the drying efficiency of the tableware. By using this effect, it is possible to apply various applications to applications such as difficult when dew forms.

Claims (33)

A photocatalyst thin film in which particles having a photocatalytic action are dispersed in a coating film, The photocatalyst thin film of the said coating film containing the organic resin which the inorganic functional group couple | bonded with the side chain. A photocatalyst thin film in which particles having a photocatalytic action are dispersed in a coating film, A photocatalyst thin film comprising an element having a valence of 2 or less as an element having an electronegativity of less than 1.6 and an ion radius of less than 0.2 nm in the coating film. A photocatalyst thin film in which particles having a photocatalytic action are dispersed in a coating film, At least 1 type of P, B, K, and Ca is further contained in the said coating film, The photocatalyst thin film characterized by the above-mentioned. A photocatalyst thin film in which particles having a photocatalytic action are dispersed in a coating film, An oxide semiconductor particle composed of a metal element having an electron affinity of 1.2 or more is dispersed in the coating film. The method of claim 4, wherein The layer in which the oxide semiconductor particles are dispersed is provided separately from the layer in which the titanium oxide particles are dispersed. The method according to any one of claims 1 to 5, Electroconductive fine particles are disperse | distributed in the said coating film, and the surface resistance value of the said coating film is 10 ⁹ ohms / square or less, The photocatalyst thin film characterized by the above-mentioned. According to any one of claims 1 to 4, Silicon catalyst is contained in the said coating film, The photocatalyst thin film characterized by the above-mentioned. The article provided with the photocatalyst thin film in any one of Claims 1-7 on the surface of a base material. An article having a barrier layer between an oxide photocatalyst thin film according to claim 8 and a substrate surface of the article. The metal oxide containing at least one metal element selected from Al, Zr and Fe, wherein the barrier layer according to claim 9 contains a metal element having a valence greater than 3 or at least one metal element selected from transition metals. An article characterized by being a membrane. An article according to any one of claims 8 to 10, wherein the substrate comprises an organic polymer compound having a decomposition start temperature of 300 ° C or lower. Base material mainly composed of organic polymer compound, A barrier layer made of an inorganic material provided on the surface of the base material; An article comprising an oxide catalyst layer catalyzed by a decomposition reaction of an organic substance provided on a surface of said barrier layer. The air flow generated by driving the electric blower receives air from the intake port and passes the filter installed in the ventilation path to remove dust, oil particles, smoke, pollen, various microorganisms or odorous substances suspended in the air. In the air purifier which is collected and cleaned and discharged from the exhaust port, An air cleaner according to any one of claims 1 to 4, wherein the photocatalyst thin film according to any one of claims 1 to 4 is formed on a surface of a component that is exposed to indoor illumination light or sunlight from outside. Due to the air flow generated by driving the electric blower, the air received from the intake port on the inside is discharged to the outside from the exhaust port on the outside with floating dust, oil particles, smoke, pollen, various microorganisms or odorous substances. In the ventilation line, Among the components, the photocatalyst thin film according to any one of claims 1 to 4 is formed on a surface of a component that is exposed to indoor illumination light or sunlight from the outside. Ventilation line, characterized in that provided. In a fan that rotates the blades by an electric motor to generate air flow, The fan according to any one of claims 1 to 4, wherein the photocatalyst thin film according to any one of claims 1 to 4 is formed on a surface of the component that is exposed to indoor illumination light or sunlight from the outside. The pressure in the dust chamber is reduced by an electric blower through the suction port and the dust collecting chamber, so that the dust or dust received from the suction port is collected into the dust chamber, and the dust or dust is filtered, and then the air is discharged from the exhaust port. In the vacuum cleaner to discharge, A vacuum cleaner comprising: the photocatalyst thin film according to any one of claims 1 to 4 is formed on a surface of a component that is exposed to indoor illumination light or sunlight from outside. In a drying drum containing clothes containing moisture, the air received from the outside by the electric blower is heated using a heater for heating and then sent to heat the clothes to evaporate moisture, and the air containing this moisture is discharged from the exhaust port. In the clothes dryer which discharges moisture from the exhaust port after removing moisture by condensing moisture by discharge or heat exchanger, A clothes drying machine according to any one of claims 1 to 4, wherein the photocatalyst thin film according to any one of claims 1 to 4 is formed on a surface of a component that is exposed to indoor illumination light or sunlight from outside. In a drying chamber in which wet dishes are stored, air received from the outside by an electric blower is heated after using a heater for heating to heat the dishes and evaporate the attached moisture, and together with the air containing the moisture, In the dish dryer to discharge, A photocatalyst thin film according to any one of claims 1 to 4, wherein the photocatalyst thin film is formed on a surface of a component that is exposed to indoor illumination light or sunlight from outside. In the cleaning chamber containing the contaminated tableware, the water is heated and pressurized by the cleaning pump, sprayed from the arm nozzle of the rotating material installed in the cleaning chamber to wash the dishes, followed by a rinsing operation. In the dishwasher which sucks the outside air and warms with a cold air or a heating heater to replace the high humidity internal air after the rinsing operation to evaporate and dry the dishes or moisture remaining in the cleaning chamber, A dishwasher according to any one of claims 1 to 4, wherein the photocatalyst thin film according to any one of claims 1 to 4 is formed on a surface of a component that is exposed to indoor illumination light or sunlight from outside. The living waste is put into a processing chamber in which a culture material containing microorganisms is installed, and stirred using a stirring device together with the culture material to decompose the household waste by metabolism of microorganisms and at the same time, water generated during decomposition. In the food waste processor for discharging air together with the air using an electric blower, The food waste treating machine according to any one of claims 1 to 4, wherein the photocatalyst thin film according to any one of claims 1 to 4 is formed on a surface of a component that is exposed to indoor illumination light or sunlight from outside. The method according to any one of claims 13 to 20, An article comprising a light source at a position where light is irradiated onto the surface of the photocatalyst thin film. The method of claim 21, And the light source is an ultraviolet lamp. The method according to any one of claims 13 to 20, An article characterized in that a transparent member is used for at least a part of the box body covering the surface of the photocatalyst thin film so that external light is irradiated onto the surface of the photocatalyst thin film. The method of claim 23, The transparent member has an L value of 50 or more, a value of -20 or more and 20 or less, and b value of 20 or less by color difference display method of 2mm thickness transmitted light. The photocatalyst thin film and the method according to any one of claims 13 to 20, An article characterized in that a transparent member is used for at least a portion of the box body covering the surface of the photocatalyst thin film so that external light is irradiated onto the surface of the photocatalyst thin film. The method of claim 23, The transparent member has an L value of 50 or more, a value of -20 or more and 20 or less, and b value of 20 or less by color difference display method of 2mm thickness transmitted light. In the photocatalyst which consists of titanium oxide, A photocatalyst comprising at least one of ATO, RuO ₂ , STO (SrTiO ₃ ), RSO, and a binder. The method of claim 27, A photocatalyst characterized by adding any one of Li, Na, and Mg. An adsorbent is added to a photocatalyst made of titanium oxide. In the photocatalyst which consists of titanium oxide, A photocatalyst comprising a zeolite obtained by ion-exchanging any one of Cu, Ag, Li, Na, and Mg. A photocatalyst characterized by adding a pigment that absorbs visible light to a photocatalyst made of titanium oxide. In the photocatalyst which consists of titanium oxide, A photocatalyst comprising an organic resin. The method of claim 32, A photocatalyst further comprising Al, Ti, and a Si-based coupling agent.