WO1998012048A1 - Thin photocatalytic film and articles provided with the same - Google Patents

Abstract

A thin photocatalytic film for use in air flow passages, filtration sections, exterior sections, and sections exposed to light from a built-in illumination machanism in electric appliances employed mainly in a room. It has an enhanced catalytic activity by virtue of addition of various additives. This film can decompose organic matter upon exposure to even a weak light, including one generally obtained in a room, such as the one from a fluorescent lamp, an incandescent lamp, a mercury lamp, or sunlight through a windowpane, and can decompose stains such as nicotine of cigarettes or sebum of, e.g., hands, even when deposited thereon, to offer an antifouling effect. Similarly, in the presence of a very weak light, this film can decompose various substances causative of an offensive odor dispersed in air, such as organic amines and mercaptans, even when deposited thereon, into substances emitting no significant odor or odorless substances, thus offering an deodorant effect of reducing the odor in a room.

Description

 Specification

 Photocatalytic thin film and article provided with the same

 The present invention relates to a photocatalytic thin film in which particles having a photocatalytic function are dispersed in a coating film and an article provided with the photocatalytic thin film, and particularly to an organic polymer material which is a material having low heat resistance, particularly a general-purpose thermoplastic plastic part. The present invention relates to an article in which an oxide photocatalytic thin film is formed in a thin layer on the surface of an object. The present invention also relates to an ultraviolet lamp or an article which does not provide strong ultraviolet rays such as outdoor sunlight and is suitable for use indoors, and which has an oxide photocatalytic thin film on all or a part of the surface.

 For example, air washer, ventilation fan, fan, vacuum cleaner, clothes dryer, dish dryer, dishwasher, garbage disposal, heater, humidifier, dehumidifier, air conditioner, heating cooker, electromagnetic cooker, hair The present invention relates to devices that use an electric blower such as a dryer, a deodorizer, and a kotatsu to create an air flow.

 Various contaminants and microorganisms floating on the air that adhere to the surface of these electrical products are decomposed by the light in the living environment by the photocatalytic function to prevent soiling, deodorization, and antibacterial activity. The present invention relates to a technique for obtaining surface characteristics such as anti-mold, anti-mold, and improvement of wettability, and articles thereof. Background art

Recently, by utilizing the decomposition of organic matter using T i 〇 ₂ photocatalyst, antifouling, deodorizing, material which exhibits an antibacterial effect has attracted attention. This is one using a redox reaction of the semiconductor photocatalyst, such as described in Nyusera mix (1 9 9 6) N o . 2, 5 5, is provided that forms a signature i 0 ₂ thin film on a ceramic style ing. On the other hand, as a film forming method, an oxide thin film is formed on a substrate by a physical method such as sputtering or by a chemical method such as a coating method such as a sol-gel method. The former can form a film at a low temperature using a vacuum device or the like. The latter can be applied to the substrate using a simple device such as a spin coater or a sprayer, and processed at a temperature of usually several hundred ° C to obtain a film. T i 0 _z is a material for antibacterial is effective imaging products anatase ¾, the functional expression that crystallization is valid is broadcast ^ (PiU No. (PTC) WO 9 4 / 1 1 0 9 2, (PTC ) W_〇 5 /] 5 8 1 _6); and V Ding i O _sigma, that have been reported those卨performance of the addition of F e, etc. (W.) oi , A. Ter'miri, MR Hoffmann, J. Phys. Cheiii., 9 «, 13 669-13 679 (1994)).

 The following inventions are known as examples in which the oxide photocatalyst thin film is applied to various devices using the above-mentioned materials and methods.

An air purifier, that is, an apparatus for removing dust and odorous substances from indoor air, is disclosed in Japanese Patent Application Laid-Open Nos. Hei 8-266841, Hei 8-266605, Hei 8-309148. as in, T i 〇 ₂ enclosing the filter and the photocatalyst carrying to principal component, a technique in which a mechanism for irradiating light having a short wavelength by using an ultraviolet lamp of any means thereto.

As an application example to fan the Una by in JP-A-7- three hundred and three thousand eight hundred and nineteen , the T i 0 ₂ on the surface of the metal part key: Technical and baked at about 600 a thin film of photocatalyst to components known Have been.

 Also, in a case of application to a fan as in Japanese Patent Application Laid-Open No. 9-138189 ", a mechanism for irradiating ultraviolet rays with a light emitting diode is known.

As an example of application to ventilation, there is known a configuration in which an ultraviolet lamp is used in combination as disclosed in Japanese Patent Application Laid-Open No. 5-157305 ^. The cleaner Ya garbage The application examples of the processing machine as a deodorizing filter is installed in the ventilation path, as seen in JP-A-7-1 08175, photocatalyst mainly comprising T i 0 ₂ There has been proposed a technology in which the powder is made into a powder form, wrapped in a plastic fiber sheet and heat sealed. Disclosure of the invention

 There are insufficient points for forming an oxide thin film on a substrate having low heat resistance, for example, a plastic part using conventional techniques. The film formed by the sol-gel method has the anti-S, antibacterial tile as a deodorant, which is described in the literature, and has several hundred ° C at least to crystallize titanium oxide. 3 () Heat treatment at 0 ° C or higher is required. Therefore, it is difficult to form a film on a substrate having low heat resistance, such as plastics, particularly general-purpose thermoplastic plastics.

In the light intensity low environment such as indoor, Ding i [) degradation rate of decomposition of _two-body organic matter of, not sufficient, a problem that particularly require a separate light source which is disposed Was also held.

As described above, the devices targeted by the present invention are mainly home appliances used in indoor spaces such as ordinary homes and offices, and these products are mainly made of organic polymer materials (plastics). Used. With the exception of televisions and monitors for personal computers, which are often used for glass parts, plastics account for about 40 to 50% of the weight of general household appliances, and most of the rest are metal. Consisting of Plastics account for nearly 90% by volume. Plastics are widely used for their physical properties, such as light weight, high designability, and low price, but especially thermoplastic thermoplastics have high productivity in molding work. Many are used from.

 The most widely used general-purpose plastics as structural members include polypropylene (PP), acrylic butadiene styrene copolymer (8BS), styrene acryl copolymer (AS), polystyrene (PS), and nylon.

(PA), Polycarbonate (PC), Vinyl Chloride (PVC), Methacryl (PMMA), Polyethylene (PE), Polyacetal (PM), Polyethylene Terephthalate (P), Polybutylene Tele Phthalate

(BT), but none of the materials can withstand deformation in an ij environment exceeding 0.30 ° C.

For example, the heat distortion temperature of AS TM, D-648 (18.6 kg / cm ² ) is around 25 (around TC. Polyphenol containing glass fiber etc. as a special high heat-resistant resin Some such things as lensulfide, polyphenylene oxide, and polyether-termide are very expensive and cannot be used in large quantities in such applications.

 In general, materials with higher heat resistance are more expensive, especially PE, PS, ABS, PP, and FVC, which are used more frequently for exterior parts. These materials average 75% or more of plastic parts. Confuse. Among them, even the ABS with the highest heat resistance has the above-mentioned ASTM heat deformation temperature of 120 C or lower, and at 300 ° C it completely dissolves to become a liquid and undergoes oxidative decomposition.

Further, even when the surface is coated with a paint on an inorganic material such as a metal, a material having a heat resistance exceeding 300 ° C. is limited. Usually, a thermosetting resin is used for the paint. For example, polyester, acrylic, melamine, epoxy, urethane, etc. are typical examples, and baking is performed at a temperature of about 150 ° C. These paints also suffer from problems such as loss of gloss and peeling when exposed to temperatures above 300 ° C. Often occurs.

 As these data show, there was a major problem in heat resistance when using conventional materials to form films by the sol-gel method on general-purpose materials.

 On the other hand, physical methods such as sputtering, CVD, and vacuum deposition, which form a film within a temperature range not exceeding 300 ° C, require large-scale equipment such as vacuum equipment. And production costs are high. In addition, since the film is formed under a high vacuum during the film formation, the composition ratio deviation of the oxide photocatalyst is large, and the photocatalytic performance deteriorates. Further, when an organic material is used as a substrate during film formation, there is a problem that the substrate is reversely sputtered, damaging the substrate, and causing deformation of the substrate. In addition, in a chemical method using a coating method such as a sol-gel method, when a silica sol in which oxide fine particles are dispersed is used, a film formed on a substrate having no heat resistance has a low heat treatment temperature. Sufficient sintering cannot be performed, and the strength and water resistance of the formed oxide film become insufficient.

For the above reasons, in the conventional existing technology, the surface of the organic polymer material are use in general appliances, without causing damage such as deformation or deterioration, the photocatalyst mainly comprising T i 0 ₂ It was practically difficult to form a thin film.

 An object of the present invention is to provide a highly active photocatalytic thin film that can be formed on the surface of a material having poor heat resistance, for example, a plastic or paint, and an article having the antibacterial, antifouling, and deodorizing effects formed from the thin film. It is in.

On the other hand, the device of Ru enhances the organic decomposition effect itself of the photocatalyst mainly comprising T i 〇 _2, etc., no mention is in the invention of the photocatalyst applied technology. That is, devised in material formulation for improving the optical activity of the film containing the T i 0 ₂ is not performed. Therefore, for example, JP-A-8-309148 and JP-A-8-266605, which are conventionally known methods for deodorization, are used. For example, in the case of Japanese Patent Application Laid-Open No. Hei 9-138189, or in a method of decomposing dirt such as oil during cooking In Japanese Unexamined Patent Publication No. 5-157305, the activity of the photocatalyst itself is not sufficient for any of them, so that the decomposition reaction is enhanced by providing a mechanism for irradiating ultraviolet rays and a heating means. These are caused by the fact that the T i 0 body is not sufficiently fast when the light intensity is low. The reason for this is that the light intensity is not sufficient, and no measures have been taken to improve this. An ultraviolet lamp is also used as a means to increase power. As UV lamps, high-pressure mercury lamps and metal halide lamps are usually used, but a power supply and a cooling mechanism are required, leading to an increase in the weight and price of the entire application product. In addition, the lamp had a service life of about 2000 hours, and required periodic replacement work.

In the prior art, T i 0 ₂ to F e, a technique for increasing the decomposition efficiency by the addition of V is in a known hundreds ° has卨performance of perform high temperature treatment and C, the low melting point of heat resistance It is difficult to apply to poor substrate materials.

Another object of the present invention, the photocatalyst film can be deposited at a low temperature, the photolysis efficiency is improved than the decomposition efficiency at T i 0 ₂ alone, conventionally required by the deposit even with a small intensity Ri by the light intensity Is to be able to be decomposed.

In the prior art, in applications such as antibacterial properties, deodorization, and deodorization, the target substance is an organic substance, and since the target substance is a fine particle or a molecular substance, a liquid organic substance or a fine particle organic substance adhered thereto. Was able to be decomposed, but for large-sized fibers and dusts, it took a very long time to decompose even organic substances, or it was extremely difficult to decompose inorganic substances, mainly dust Yes, imperfect in pollution control applications It was something. Since these stains are generally electrically charged and float in the air, if they adhere to the surface of a highly electrically insulating solid, the static electricity is not easily discharged, and the stains remain as they are. turn into. There is also a problem that the light is blocked by the attached inorganic contaminants, so that the photocatalytic surface is not irradiated with sufficient light and the decomposition efficiency of organic substances is reduced.

 Another object of the present invention is to prevent large-sized dust and inorganic-based dirt, which are difficult to decompose and remove in principle with the oxidative decomposition effect of these photocatalysts, from becoming a target member due to electrostatic force. It is to make.

 In order to achieve the above Q, the features of the present invention are electric blowers such as air purifiers, ventilation fans, electric fans, vacuum cleaners, clothes dryers, dish dryers, dishwashers, garbage disposal machines, etc. Among the parts of electrical appliances mainly used indoors that have a mechanism to generate an air flow by being driven, the surface of the air flow path, the filtration mechanism in the air flow path, or the exterior parts exposed to the indoor illumination light Another object of the present invention is to provide a low-temperature curing type highly active oxide photocatalytic thin film.

 The melting point or decomposition temperature of the material of the target component is 300 ° C or less. Particularly, for molded members made of general-purpose thermoplastic plastics, fibrous members, foamed members, and sheet-shaped members, By providing a low-temperature curing type highly active oxide photocatalytic thin film, problems such as contamination, propagation of microorganisms, and generation of offensive odor can be solved.

In the present invention, optimization of the thickness of the thin film of oxide photocatalyst mainly comprising T i 〇 _2, T i 0 ₂ Optimization of the particle size, the addition of low electronegativity suitable ion, the S i 0 ₂ optimization of the mixing ratio of T i 0 ₂ in the case of a binder, the addition of high electron affinity oxide semiconductor, the formulation of the addition of a suitable noble metals, a thin film with improved activity of the reaction of the photocatalytic Is formed on the surface of the air flow path of the above-mentioned electrical product ゃ exterior parts, which has been impossible in the past. It is possible to obtain antifouling, deodorizing, and microbial growth control effects at the level of internal light. In addition, by stacking the films, damage to the organic base, which is susceptible to oxidative decomposition, can be prevented.

At the same time, in the present invention, the specific wavelength required to break the bond between the metal atom of the organometallic compound and the organic S during the process of forming a thin film of an inorganic polymer mainly composed of S i 〇 _z and T i 〇 Incorporating a process that promotes the hydrolysis reaction by irradiating electromagnetic waves containing, the inorganic polymer can be polymerized at a low temperature. The strength of a strong oxide photocatalytic thin film can be obtained at such a low temperature that no deformation, melting, or decomposition occurs on the surface of the plastic.

 Hereinafter, the detailed contents of the low-temperature curing type highly active oxide photocatalytic thin film will be described.

Oxide photocatalyst T i 0. An oxide photocatalytic thin film in which fine particles are dispersed is an element with an electronegativity of less than 1.6 and an ionic radius of less than 0.2 nm and a valence of less than 0.2 nm. The reaction efficiency was improved by adding two or more ions. As the specific elements to be added, Na, Li,, Sr, Mg, Ca, and Zn are particularly effective, and the added amounts of these elements are 0.5 to 20. wt% is preferred. It is most effective to adjust the size of the T i 〇 ₂ fine particles to 5 to 2 O nm.

The T i 0 ₂ particles Oite the oxide photocatalytic thin film dispersed in the S i 〇 _2, Ru preferably der that the weight ratio of T i 〇 ₂ / S i 0 ₂ is 9-5 .

The oxide thin film preferably has a thickness of 100 to 500 nm. The component to be added is, in addition to the above ions, at least an electron affinity The effect is further enhanced when oxide fine particles mainly composed of an oxide semiconductor composed of a metal element having a force of 1.2 or more are dispersed. In particular, those whose elements are composed of Sn, Fe and Cr are preferred. The addition amount is preferably 2 to 50 wt%. Among them, oxide fine particles mainly composed of ATO (antimony-added tin oxide; the weight ratio of antimony is preferably 1% to 0%) are particularly effective. When these semiconductive fine particles are added, the surface resistance value of the film itself is reduced, so that dirt particles, including inorganic dirt that cannot be oxidized and decomposed, are less likely to adhere electrostatically.

Still more effective even if the oxide photocatalytic thin film to a plurality of the laminated structure, the first layer counting Ri by surface Yes dispersed is T i ◦ ₂ particles in S i 0 _2, ¾ prior to its film The oxide fine particles mainly composed of the above oxide semiconductor are dispersed in the second layer counted from the surface. This allows the photocatalyst to function effectively without damaging even surfaces of plastics or the like that are less resistant to oxidation. It is more effective to add at least one of Fe, A1, and Zr to the second layer.

 It is effective to add at least one of Pt :, Rh, Pd, Ag, Cu, and Ni in addition to the above-mentioned ions.

Ding i 0 ₂ has a function as a photocatalyst, having antibacterial due to decomposition of organic matter, deodorant, the effect of the anti-fouling or the like. Its function is attributed to electrons and holes generated when the semiconductor T i 〇 ₂ irradiates light, particularly ultraviolet light. When T i 0 ₂ a semiconductor is irradiated with light having energy higher than bandgap, generates the electronic and hole. Generated electrons and holes to generate ◦ ί I radicals and H radicals by decomposing the water adsorbed on the T i 0 ₂ surface. By reacting this radical with an organic substance, the organic substance can be decomposed. This The photocatalyst decomposes organic substances and the like by the following mechanism, but there are the following two means to further increase the reaction speed. The first is to increase the work of one active point, and the second is to increase the number of active points. Increasing the number of active sites can be achieved by increasing the surface area, that is, by making T i 〇 _z finer. In order to increase the work of the active site, it is necessary to reduce the crystallization of T i i ₂ (anatase) by β and to prevent recombination of electrons and holes. By satisfying the above, the reaction rate can be increased. However, improving the crystallization of Τ 1 [(anatase) and increasing the surface area are contradictory, and it is difficult to achieve both. In other words, increasing the crystallinity leads to an increase in the grain f diameter and a decrease in the surface area. Therefore, there is an optimum range between the direction of improving crystallinity and the direction of increasing surface efficiency. The appropriate region was found to be 5 to 20 rim based on many experimental results of the present invention. Degradation rates in a range of the particle diameter be changing the type of oxide used as the inorganic by-Sunda one has increased when dispersing T i 〇 _z fine particles.

Improving the reaction rate by preventing recombination of electrons and holes can be achieved by increasing the efficiency of electron and hole separation. The T i 0 ₂ surface there are T i defects. This defect becomes a recombination point between the electron and the hole and hinders the reaction. If an ion having an ion radius of about the same as that of Ti is added, it penetrates the Ti defect on the surface, the defect disappears, and the recombination point decreases. Furthermore, since it exists as a positive ion, the electron can be attracted and separated from the hole, and the oxidation reaction of organic matter can be promoted. The present invention has found that an additive having such an effect is effective if the electronegativity is less than 1.6 and the ionic radius is less than 0.2 nm.

Furthermore, the present invention improves the performance by adding other oxide semiconductor particles. I found what I can do. This large oxide semiconductor by Li in the carrier concentration to a small T i 0 ₂ carrier concentration is achieved by injecting the carrier. Therefore, it is necessary to make it easier carrier from the oxide semiconductor to T i 0 ₂ flow. When the electron affinity of the oxide semiconductor is less than or equal to Ti, a Schottky barrier is formed. Therefore, the material to be added has an electron affinity

It must be at least 1.2 eV.

In the present invention, it has also been found that addition of I ″ e, A 丄, and Zr results in loss of the photocatalyst of T i 0 _z . There is a problem that when using a board material mainly composed of an organic substance, the substrate is self-destructed by photocatalysis.

 Therefore, in the present invention, a barrier layer is formed between the substrate and the photocatalyst. By adding Fe, A1, and Zr to the barrier layer, self-destruction can be completely suppressed. Furthermore, because of the high performance of the barrier layer, the thickness can be made sufficiently thin. When conductive fine particles such as AT0 are added and when they are laminated, the performance of the photocatalyst is improved, and the antistatic function is added, so that not only decomposition of organic matter but also dust floating in the air is achieved. It can prevent the adhesion of inorganic substances such as water and provide a higher performance antifouling function. In addition, the present invention has a high activity as described above, and can be decomposed with weaker light illuminance than before, or has an antistatic function, so that the fine particles themselves that become dirty are less likely to adhere due to static electricity. Although it is inexpensive and versatile, a thin film of a highly active photocatalyst having a high film thickness can be formed on the surface of a material that has insufficient heat resistance with conventional film formation methods.

For this purpose, when a solution containing water and a low molecular weight organometallic compound containing titanium and silicon is polymerized into an inorganic polymer, the bond between the metal atom and the organic group of the organometallic compound is broken. By applying a step of irradiating an electromagnetic wave having a specific wavelength necessary for causing the The water splitting reaction is promoted, and a prepolymer of metal oxide is formed in the solution, so that the film formation temperature can be lowered.

 The electromagnetic wave having the specific wavelength is most preferably ultraviolet light. After applying a solution containing a small amount of organic gold compound and water to the surface of the adherend, it is necessary to break the bond between the metal atom and the organic group of the organometallic compound such as ultraviolet light. It is most preferable to irradiate an electromagnetic wave having a specific wavelength and heat and dry at the same time, or to heat and dry the coat after the electromagnetic wave irradiation step.

 In addition, the titanium oxide particles having the photocatalyst W: used in the conventional technology dispersed in the inorganic thin film have a smaller area occupied by titanium oxide than the photocatalyst composed of titanium oxide alone. There was a problem that performance deteriorated. In particular, when film strength is required, a large amount of an inorganic binder is added to increase the strength, but there is a problem that the activity is significantly reduced.

 Therefore, an object of the present invention is to provide an active photocatalyst material even in a configuration in which titanium oxide is dispersed in a binder, and to provide a product using a photocatalyst that functions sufficiently even in a living environment. In particular, use the self-cleaning characteristics of the photocatalyst to reduce product replacement and washing time.

To solve the above problems, the present invention is the AT photocatalyst comprising titanium oxide (), the addition of R u 0 _2. Also, any one of Li, Na, and Mg is added.

 Further, the present invention is a production method for improving the bonding state at the interface between different kinds of semiconductors by directly coating ATO particles on titanium oxide powder. Furthermore, the present method is a coating method in which high-temperature processing is performed as a pretreatment, and a film can be formed at a low temperature of about 120 ° C during coating.

If the electron affinity of the oxide semiconductor is smaller than that of T A Schottky barrier is formed at the particle interface, and the carrier of the added oxide semiconductor cannot be injected into the metal oxide layer ₂ and the effect is not exhibited. On the other hand, when the electron affinity of the oxide semiconductor is smaller than that of T i, a Schottky barrier is not formed at the particle interface of the fine particles, and a quasi-junction is formed. It injected into T i 0 _2, functions effectively. In particular, AT〇 has a slightly lower electron affinity than T i, but there is almost no difference, so the performance is improved. This lambda T 0 is a conductive oxide has high wire carrier rear density, a large amount of carriers AT_〇 are injected into the T i 0 _2, the activity of the photocatalyst countercurrent heat.

In recent years, ΛT 0 has attracted attention as a conductive oxide, and ultrafine particles have been commercially available. T i 0 ₂ photocatalyst by adding ultrafine particles AT_〇 more easy simply can be manufactured ATO additive T i 0 ₂ photocatalyst. However, when using this good UNA ultrafine AT 0, AT_〇 particles in contact with T i 0 ₂ fine particles are ultrafine particles AT 0 added is also present, but also particles present in the S i 0 _2, efficient Not. On the other hand, when the production method of the present invention is that firing is added in advance AT_〇 solution Ding i 0 ₂ particles, AT_〇 and T i O, large contact area of the particle, further bonded by firing condition was good heterologous Electron transfer between semiconductors also becomes smooth. The R u 0 ₂ a p-type semiconductor, T i 0 ₂ is an n-type semiconductor, lambda T_〇 to attract absorbed generated electrons and holes caries Chi hall light, recombination of electrons and holes It can be suppressed. Therefore, electrons and holes generated by absorbing light can be effectively used for the catalytic reaction, and the decomposition rate can be further improved.

Also, L i, N a, the addition of M g is the ion radius and near their ionic radii T i, easily penetrate into T i defects T i 0 ₂ surface to增加the stability of the crystal. L i, Na and Mg attract electrons because of their strong ionicity. It is easy to attach and separates electrons and holes generated by absorbing light, which can increase the reaction efficiency.

ィ ン ダ一からなる光触媒である。 さらに、 本発明はし 】 ， N a， M gのうち いずれか一種を添加することを特徴とする光触媒である。 The film forming method of the present invention can be manufactured at about 120 ° C., and can be applied not only to ceramic substrates but also to plastic materials. In normal sol-gel method, 4 0 (or is difficult to apply to plastic products for a temperature of about TC is required, it takes time for 1 Y component than h for the crystallization of T i 〇 _2. Meanwhile since fabrication method of the present invention can be deposited at low temperatures, abundant S material that can be used, can be formed even photocatalyst what kind of _surface:., also 4 possible short-term treatment of several minutes : The production cost can be reduced to a large fcl, and the present invention is obtained by adding RS〇 (RuSrO :,) to a photocatalyst composed of titanium oxide. 0 (S r T i O :,), RS 0,

It is a photocatalyst consisting of a single kind of material. Further, the present invention provides a photocatalyst characterized by adding any one of, Na and Mg.

 The present invention also relates to a production method for improving the state of contact at the interface between different kinds of semiconductors by coating RS0 directly on the semiconductor photocatalyst powder, and furthermore, performing high-temperature treatment as pretreatment. This is a coating method capable of forming a film at a low temperature of about 12 () ° C during coating.

RSO added photocatalyst, by 1 30 and T1s' 〇 contacts, by the e Ichiru of RSO Ding i 0 ₂ photocatalyst is utilized, you on the performance of the photocatalyst. On the other hand, the oxidation activity of the catalyst is due to the redox effect of electrons and holes generated by light absorption. In particular, the formed holes generate hydroxyl radicals and cause strong oxidation. RS◦ is a p-type semiconductor and has a large amount of holes. By RSO and T i 0 ₂ contacts, Hall is injected into the T i (] ₂屮, oxidizing the organic substances in T i 0 ₂ surface can be on improvement of photocatalytic activity. Li, Na, and Mg have ionic radii close to the ionic radius of T i, and easily penetrate T i defects on the surface of T i 〇 ₇ to increase the stability of the crystal. Since Li, Na, and Mg have strong ionicity, they can easily attract electrons, absorb light, separate generated electrons and holes, and increase the reaction efficiency.

RSO addition, there is a method for 1¾ 30 powder Ding 1 0 ₂ powder RS 0 sol technique and titanium oxide emissions powder to be mixed with the then Koti ring firing. The former force is also present RS_〇 particles in contact with the Ti0 ₂ fine ',', also particles present in the S i ◦ ₇ for use in the S i _0? A binder, not efficient. While the latter can be calcined by adding a pre-RS 0 solution T i 〇 ₂ particles,} ^ 8_Rei and Ding 1 〇 ₂ particles larger contact area, further between junction state is also good heterogeneous semiconductor by calcination Electron transfer at the surface becomes smooth. However, to produce RS 7, a temperature of 700 to 850 ° C is required. At temperatures lower than this, RS 0 does not crystallize and does not function as a p-type conductor.

In the case of T i 0 ₂ , the crystal becomes rutile at 600 ° C. or higher. It is the anatase type that exhibits a sufficient function as a photocatalyst. With the rutile type, the performance of the photocatalyst drops rapidly. Therefore, 1 if 3_Rei ^ raising process Ding 1_Rei ₂ after addition, RS 0 is the force T i O _z as a p-type semiconductor phase transition to rutile, lose the function as a photocatalyst. Therefore, Ding i 〇 ₂ similar function as the photocatalyst can be expected ST_〇 using (S r T i 〇 _3), RS 0 added ST 0 photocatalyst is effective. 3 chome 0 has substantially the same bands structure T1s 〇 _2. In addition, the production method is to crystallize by treating at a high temperature of 700 to 850 ° C. Furthermore, RS 0 and ST 0 are both perovskites, and their crystal lattice constants are almost the same because S r-0 is common. Therefore, the manufacturing conditions are very close to those of RS 接合, the bonding state is good, and the activity of the photocatalyst can be improved. W

 16 In addition, conventional photocatalysts require a long time to decompose and remove gases because their decomposition rates are low. When light is not irradiated, it is powerless and works only when light is irradiated. Therefore, the number of bacteria can be reduced by the antibacterial action of bacteria and the like.

 Therefore, it is an object of the present invention to increase the speed of gas removal and to add an antibacterial effect when no light is irradiated.

 In order to solve the above Section 11, the present invention added an adsorbent to a photocatalyst composed of titanium oxide. The added adsorbent is zeolite. The present study is a zeolite obtained by ion-exchanging one of Cu, Ag, Li, Na, and Mg with a photocatalyst consisting of titanium oxide.

 Conventional photocatalysts are composed of a semiconductor photocatalyst material represented by titanium oxide. These materials are characterized in that they can be deoxidized and self-cleaned by a redox reaction of a photocatalyst. In self-cleaning, deterioration of the catalyst may be noticed if stains become noticeable, but antibacterial properties are difficult to judge visually. In spite of the reduced functions, such as film peeling and performance degradation, dangerous germs and other bacteria may proliferate if used unnoticed.

 Therefore, an object of the present invention is to provide a photocatalyst material whose performance can be easily judged visually.

 In order to solve the above problems, the present invention relates to an antibacterial and antifouling material comprising a photocatalyst, wherein deterioration of the function is visually recognized. This is a photocatalyst in which a pigment that absorbs visible light is added to the photocatalyst.

Photocatalysts generally absorb ultraviolet light to produce a catalytic action. In living environments, there is only a small amount of ultraviolet light. Is going. If visible light can be used effectively, a high-performance photocatalyst can be provided in a living environment. As a solar cell, a wet solar cell using titanium oxide using visible light has already been manufactured. This is due to the fact that dyes that absorb visible light are stacked, and electrons excited by absorption of visible light by the dye irradiate the titanium oxide, causing a current to flow. A similar decrease can be expected for photocatalysts. By adding a material that absorbs visible light to titanium oxide, the electrons that absorb visible light and excite it can stimulate the titanium oxide and be used for the redox reaction of the photocatalyst.色素 Sensitive dyes are mostly organic substances and are not only decomposed directly by ultraviolet light, but also easily decomposed by photocatalysis, and because they use visible light effectively, their performance is improved and they are decomposed. Therefore, the present invention focused on a pigment system that is less likely to be degraded by ultraviolet light and conducted a test, and found that the pigment system had a low decomposition rate and further exhibited a sensitizing effect. Despite the fact that pigments are mainly organic substances, they eventually decompose and degrade, but when pigments are added, they gradually decompose in the living environment. By using, it is possible to adjust the disassembly speed at the time of product parts replacement and to make the material replacement time.

The conventional photocatalyst is made of a semiconductor photocatalyst material represented by titanium oxide. These materials are characterized by their antibacterial and self-cleaning properties through the redox reaction of the photocatalyst. Self-cleaning may indicate deterioration of the catalyst if the stain becomes noticeable, but antibacterial properties are difficult to determine visually. In particular, even if functions are deteriorated, such as film peeling and performance degradation, dangerous germs etc. will grow if used unnoticed, which may be a problem. Therefore, the present invention provides a photocatalyst material which can easily determine the performance by visual observation. Therefore, the present invention provides an antibacterial and antifouling material comprising a photocatalyst, wherein deterioration of the function is visually recognized. II. An antifouling material, a photocatalyst made by adding a pigment that absorbs visible light to a photocatalyst made of titanium oxide.

Photocatalysts generally absorb ultraviolet light to produce a catalytic action. Only a small amount of ultraviolet light exists in the living environment, and the photocatalyst performs antibacterial and antifouling by using this minute amount of light. If visible light can be used effectively, a high-performance photocatalyst can be provided under production conditions. As a solar cell, a wet type solar cell using titanium oxide, which has illuminated light, has already been manufactured. This is due to the sensitizing effect in which dyes that absorb visible light are laminated, and the dyes that absorb visible light excite the titanium oxide to excite the titanium oxide, causing a current to flow. A similar decline can be expected for photocatalysts. By adding a material that absorbs visible light to titanium oxide, the electrons that absorb and excite visible light can stimulate the titanium oxide and be used for the redox reaction of the photocatalyst. However, such dyes having a sensitizing effect are mostly organic substances, and are not only decomposed by UV light but also easily decomposed by photocatalysis. Furthermore, since visible light is effectively used, the performance is improved, and it is more easily decomposed, and deteriorates immediately even in a living environment. Therefore, in the present invention, a test was conducted with a focus on a pigment system having little deterioration due to ultraviolet rays, and it was found that the pigment system had a low decomposition rate and also had a sensitizing effect. Since pigments and other raw materials are mainly organic, they eventually decompose and degrade. However, when pigments are added, they are gradually decomposed in the living environment, so if this is used, the decomposition rate can be adjusted at the time of replacement of parts of the product, and the replacement time can be reduced. Becomes Conventionally, a photocatalyst applied to a plastic product is a product obtained by adding an inorganic binder such as a silica force to titanium oxide. Such a photocatalyst in which titanium oxide particles are dispersed in an inorganic binder has a problem that, compared to a photocatalyst composed of only titanium oxide, the performance is reduced by the smaller area occupied by titanium oxide. In particular, when film strength is required, a large amount of an inorganic binder is added to increase the strength, but there is a problem that the activity is significantly reduced. The photocatalyst is excellent in decomposing organic substances, but is ineffective against inorganic dirt. However, stains of inorganic substances by removing the ¾ Re extremely Tsukewaka to _t light catalyzed by the organic contamination on the organic matter, with the dirt of inorganic '? Can extent prevented Ru mower. However, once the inorganic substance adheres, the adhering part does not transmit light and loses the photocatalytic action, so that the organic substance cannot be decomposed, and as a result, the contamination is promoted. To cope with this problem, washing is performed by increasing the hydrophilicity to remove the adhesion of inorganic substances. However, for the photocatalyst material and product to be cleaned, it is necessary to increase the strength by using a large number of binders constituting the photocatalyst, but there is a problem that the photocatalytic action is reduced as described above.

 Accordingly, the present invention provides a photocatalyst material that does not cause film peeling when washing such as water washing does not occur even if a large amount of a binder is added, without causing a decrease in the performance f of the photocatalyst. Inorganic dirt can be easily cleaned, reducing the number of product cleanings and parts replacement.

 According to the present invention, a material having an antibacterial and antifouling action composed of a photocatalyst can be washed with water, can remove inorganic stains, and can be 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. UV curable When using resin, add A], Ti, Si-based coupling agents. When a photocatalyst is coated on a plastic surface, if the seri force is used as a binder, the adhesion to the plastic surface is insufficient. On the other hand, if the material of the organic resin is selected according to the base material, the adhesive strength will be sufficient and the strength will be sufficient for washing. However, organic resins are decomposed by photocatalysis. To prevent this, it is desirable to use an inorganic material, but in this case, the strength is low. Therefore, decomposition can be suppressed by introducing an inorganic functional group to the side chain of the organic resin and bonding the contact portion with the titanium oxide surface by the inorganic system.

 When an organic resin is used, unlike a ceramic material such as silica, the resin can be cured without applying heat. For example, there is a feature that can be achieved by using a room temperature curing resin. However, room-temperature curing systems take about 24 hours, except for instant adhesives. The instant adhesive cures in a short time, but is gradually decomposed by the photocatalyst. UV curing systems are examples of resins that can be cured in a short time and have excellent light resistance.

The UV curing system cures with ultraviolet light, and gradually polymerizes and cures with ultraviolet light irradiated from a fluorescent lamp. However, it is also true that it is gradually decomposed by the photocatalyst. Therefore, by appropriately combining photo-curing and photo-decomposition, light resistance can be improved as a result.

UV curable resin, completely T i 0 catalytic properties of ₂ particle surface resin covered is irretrievably lost. Therefore, addition of couplings agents, can be many Exposure of T i 〇 ₂ surface. In addition, the photocatalyst can maintain a large amount of surface-adsorbed water by adding a force-coupling agent that decomposes the surface-adsorbed water to generate radicals, and can exhibit catalytic performance. BRIEF DESCRIPTION OF THE FIGURES

 FIG. 1 is a configuration diagram of a filtration-type air purifier main body according to an embodiment of the present invention.

 FIG. 2 is a perspective view of a filtration-type air purifier main body according to the embodiment of the present invention.

 FIG. 3 is a cross-sectional view of an electrostatic precipitating air cleaner body according to an embodiment of the present invention.

 FIG. 4 is a pictorial view of the kitchen / jj ventilation fan body according to the embodiment of the present invention.

 FIG. 5 is a perspective view of a fan main body according to the embodiment of the present invention. FIG. 6 is a perspective view of the vacuum cleaner according to the embodiment of the present invention.

 FIG. 7 is a sectional view of the cleaner body according to the embodiment of the present invention. FIG. 8 is a sectional view of the main body of the clothes dryer according to the embodiment of the present invention. FIG. 9 is a perspective view of the tableware dryer main body according to the embodiment of the present invention. FIG. 10 is an enlarged cross-sectional view of an exhaust port portion of the drying machine according to the embodiment of the present invention.

 FIG. 11 is a cross-sectional view of the main body of the dish dryer according to the embodiment of the present invention.

 FIG. 12 is a perspective view of a dishwasher main body according to the embodiment of the present invention.

 FIG. 13 is a sectional view of the dishwasher main body according to the embodiment of the present invention.

 FIG. 14 is a sectional view of the dishwasher main body according to the embodiment of the present invention.

FIG. 15 is a perspective view of a kitchen waste treatment machine main body according to the embodiment of the present invention. You.

 FIG. 16 is a cut-off fi of the kitchen waste treatment machine main body according to the embodiment of the present invention.

The first 7 is a sectional view of the T i 0 ₂ dispersion S i 0 ₂ film formed on the PKT film according to an embodiment of the present invention.

 FIG. 18 is a cross-sectional view of a low-temperature curing type highly active photocatalytic thin film formed on an adherend according to an embodiment of the present invention.

 FIG. 19 is a cross-sectional view of a low-temperature curing type active photocatalytic thin film having two layers formed on the adherend according to the embodiment of the present invention.

 FIG. 0 is a diagram showing a decomposition test result of the organic dye according to the embodiment of the present invention.

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

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

 FIG. 23 is a view showing a smoke-collecting effect of the low-temperature-curing high-activity photocatalytic thin film according to the embodiment of the present invention.

 FIG. 24 is a diagram showing the photodecomposition effect of the smoke deposition filter according to the embodiment of the present invention.

 FIG. 25 is a view showing an ammonia collecting effect of the low-temperature curing type highly active photocatalytic thin film according to the embodiment of the present invention.

 FIG. 26 is a diagram showing the photolysis effect of ammonia gas according to the embodiment of the present invention.

FIG. 27 is a diagram showing the photodecomposition effect of the smoked BS plate according to the embodiment of the present invention. FIG. 28 is a diagram showing the photolytic effect of salad oil according to the embodiment of the present invention.

 FIG. 29 is a diagram showing a decomposition test result of the organic dye according to the embodiment of the present invention.

 FIG. 30 is a graph m showing the effect of adding zeolite according to the embodiment of the present invention.

 FIG. 31 is a diagram showing the influence of the ratio of S i to A] according to the embodiment of the present invention.

 FIG. 32 is a diagram showing the effect of addition of the ion-exchanged zeolite according to the embodiment of the present invention.

 FIG. 33 is a diagram showing the antibacterial effect of adding zeolite according to the embodiment of the present invention.

 FIG. 34 shows the results of a decomposition test of tobacco smoke according to the embodiment of the present invention.

 FIG. 35 is a diagram showing a result of a decomposition test of cigarette smoke with respect to an amount of a binder added according to the embodiment of the present invention.

 FIG. 36 is a diagram showing a result of a decomposition test of cigarette smoke with respect to an introduced amount of silanol according to the embodiment of the present invention.

 FIG. 37 is a diagram showing a result of a decomposition test of tobacco smoke with respect to an added amount of the coupling agent according to the embodiment of the present invention. BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, an example of an embodiment of the present invention will be described with reference to FIGS. 1 to 37. Table 1-Table 1 show the composition of the thin film of low-temperature curing type highly active oxide photocatalyst formed on the surface of various molded products, painted steel sheets, filters, etc. and the effects of the examples. The results are shown in Table 9.

 (Example 1)

 An air purifier, which is a first embodiment of the present invention, will be described with reference to FIGS. 1, 2, and 3. FIG.

 Fig. 1 is a configuration diagram of a filtration-type air purifier main body, and Fig. 2 is a perspective view of the main body. In the air purifier body 1, the condenser motor 7 is fixed to the rear cover〗 '2 with screws 8, the motor driving condenser 11 and the transport switch 9 are set, and the fan 6 is connected to the condenser 5 with the nut 5. Fix to motor 7 and fix rear cover — 1 2 and frame 4 with screws 1 3 | έ) ,, and filter 3 is fixed to panel (intake port) 2 and panel (inlet port) Remove 2 and filter 1 3. The switch knob 10 is fixed to the luck switch 9.

The fan ΰ) rotates due to the driving force of the condenser motor Ί, and creates an air flow. With this air flow, dirty air in the room, including dust, smoke, oil particles, dead bodies of microorganisms and microbes, pollen and foul odors, is sucked through the panel (inlet) 2. The sucked-in dirty air is filtered and cleaned by the filter 3 part, and then discharged from the exhaust port 15 of the grill 14 part. The three parts of the filter have a composite structure to have a function to remove various dirt and odors. The filter 13 is composed of an outer filter 3a, which is a layer covering the outer surface, and an inner filter 13b inside the outer filter 13a (not shown). The basic structure of each filter is a nonwoven fabric layer or a sponge-like porous layer made of polyester, urethane, cellulose, nylon, or electret-treated polyolefin to filter dust. . The inner filter 13b contains, in addition to these basic structures, activated carbon particles and fibers for adsorbing odors, which are mixed, blended, or encapsulated. Still, to neutralize odor in the fiber body 2 Γ) The drug may penetrate or spread on the surface. As the drug, in addition to various kinds of organic acids and flavonoids such as alloids, antibacterial agents for suppressing the growth of microorganisms are also used. In recent years, highly safe chitin and chitosan catechin derivatives have been used. Air volume to be generated is about. 2 to 3 (m ³ // min), the 8-mat room is冇the ability to remove smoke 7 0 ~ ϋ 5% of the tobacco in the operation of the 3 0 min.

In the present embodiment, the outer filter 3a is made of a nonwoven fabric of acryl fibers, and a thin film of a low-temperature-curing type highly active oxide photocatalyst of the sample No. 21 shown in Table 3 described later is formed on the surface of the outer filter 3a. Is formed. § click Lil nonwoven filter scratch, after corona discharge treatment, a thin film of S i 0 ₂ only, i.e. samples N o. 1 2 of the first 1 ¾ is formed as a base layer, after forming the film, sample N o. A low-temperature curable high-active oxide photocatalyst thin film of 21 is formed. The method for forming the film will be described in detail in Example 9 below.After adjusting the predetermined zone and coating the work by various methods, 12 (irradiating with a low-pressure mercury lamp in a TC atmosphere) In the following various examples, films were formed by the same means, and the application method was spraying, dipping, brushing or the like according to the shape of the work.

The outer filter 3a is a component that first filters the dirty air taken in from the panel (inhalation 2) 2. Various foreign substances such as dust, smoke, oil fine particles, microorganisms and dead microorganisms, pollens and foul odors Adheres in large quantities. The panel (inlet) 2 is provided with a number of openings to efficiently suck in air, and the air intake surface of the outer filter 3a is used to open indoor lighting and sunlight from this opening. Light is irradiated. This light oxidizes and decomposes the foreign matter collected on the surface of the outer filter 3a. In particular, tobacco smoke and fine oil particles adhere to the low-temperature curing type highly active oxide photocatalyst on the surface of the filter in a thin film form. And is decomposed efficiently. In addition, various microorganisms such as bacteria and fungi floating in the air are killed or their reproduction is suppressed by the decomposition action of the highly active photocatalyst. Also, by covering the fiber surface of the nonwoven fabric filter with a glassy film, the wettability with smoke particles is improved, and the smoke collection effect is also improved. The exterior parts of the main body of the air purifier 1, panels (inhaler 1) 2, frame 4, operation switch 9, and rear cover 1-2 are injection-molded products of aged plastic plastic Β ΒS It is. A low-temperature-curable, highly active oxide photocatalytic thin film is formed on the outer surface of these components.

In this example, a schematic diagram of the thin film of the sample of this acrylic nonwoven fabric filter shown in Table 6 below (shown in Table 6 below) is shown in FIG. Here, the plastic adherend 189 is an acrylic fiber, and the low-temperature-curable high-active oxide photocatalytic thin film is composed of the first surface 1 ^ 19 4 and the second surface layer 192. they become a state of T i 〇 ₂ particles〗 8 7 and lithium 1 9 0 in S i 0 ₂ film 1 8 6 are dispersed in the second layer 1-9 in 2 ¾ face antimony-doped tin oxide fine particles 1 9 3 are dispersed.

 A thin film of a low-temperature curable S-active oxide photocatalyst of No. 86 is formed. In the acrylic nonwoven fabric filter, the first layer is formed after corona discharge treatment, and after this film is formed, the second layer of the low-temperature curing type highly active oxide photocatalyst containing を T0 of sample No. 86 is formed. Two layers are formed.

 These exterior parts are irradiated with light such as indoor lighting or sunlight. Therefore, even if various kinds of foreign substances as described above adhere, they are oxidized and decomposed as in the case of the filter.

Fig. 3 is a cross-sectional view of the electrostatic precipitating air purifier. The whole consists of a front cover 16 and a rear cover 17. An inlet 19 and an exhaust 20 are provided on the front cover 16 and panel 18, and the inlet 19 and In the ventilation path connecting the intake port 19 and the exhaust port 20, there is a pre-filter 21 with a removable S. In the rear, a dust collecting electrode 22 and a discharge electrode 23 are provided facing each other, and further, an ozone removing filter 24 for removing ozone generated from the dust collecting electrode 22 and the discharge electrode 23 is provided. Yes, there is a dust collection unit in which a pre-filter 21, a dust collection electrode 22, a discharge electrode 23, and an ozone removal filter 24 are mounted on a frame 25. Further behind, there is a cushioning material 26, a duct 28 that connects the blower 27 and the dust collection unit, and a blower 27 at the contact portion with the dust collection unit, and the cushioning material 26 is a duct. The duct 28 is attached to the blower 27, and the duct 28 is attached to the blower 27. The purified 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 purifier.

 In this embodiment, the pre-filter 21 is a nylon net, on which a thin film of a low-temperature curing type highly active oxide photocatalyst of the sample No. 21 shown in Table 3 below is formed. ing. After the nylon net is irradiated with ultraviolet rays, a thin film of a low-temperature-curable high-active oxide photocatalyst of Sample No. 21 is formed. A schematic diagram of the thin film on the surface of the nylon net is shown in FIG. Here, the plastic adherend 189 is a Nymouth fiber, and the low-temperature-curable high-active oxide photocatalytic thin film 191 is composed of S 10,

The Ti 0 ₂ fine particles 18 7 and the lithium 19 0 are dispersed in 18 6.

 The rear cover 17 is an injection molded product of ΛBS, and the front cover

16 is plastically processed zinc-plated steel sheet, the outer surface of which is painted with polyester-based baking paint. On the outer surface of the rear cover 17 and the front force bar〗 6, the sample No. W

 28 An oxide photocatalytic thin film is formed.

 (Example 2)

 A ventilation fan according to a second embodiment of the present invention will be described with reference to FIG. 4. FIG. 4 is a cross-sectional view of a structure of a kitchen ventilation fan as viewed from a side. The box-shaped frame 29 has a motor 30 attached thereto, and the motor 30 has blades 31 attached thereto. In addition, a shirt 32 is attached to the outside (exhaust side) of the frame 29, and an orifice 33 is attached to the indoor side (intake side) of the frame 29. A lighting fixture 3 with a fluorescent tube 34 is attached to the _I-. Section inside the tail of the orifice 3 (suction). A filter 36 is attached to the indoor side (intake side) of the orifice 33 and the lighting fixture 35. At the bottom of the filter 36, there is an oil bottle: 37.

Ventilation capacity is common, if the diameter of the blade 3 1 of 2 5 (cm), about 8 0 0 ~ 1 0 0 0 (m 3 Z time).

 The structure in Fig. 4 shows a ventilation fan for kitchen use, but the basic structure is the same for general indoors, toilets, bathrooms, etc., except for the mounting angle and the location of parts. is there.

 As in the case of the above-described air purifier, the structure of the filter 36 can be made into a composite structure according to various uses to provide a deodorizing function and an antibacterial function.

In this embodiment, the filter 36 is a single-layer filter made of a non-woven fabric of acryl fiber, and a thin film of a low-temperature curing type highly active oxide photocatalyst of the sample No. 22 shown in Table 3 is provided on the surface thereof. Is formed. § click Lil nonwoven fabric filter scratch, after corona discharge treatment, a thin film of only S i O _z, sample N o. 1 2 of ie Table 1 is formed as a base layer was made form this film After thinning the sample Ν 2. A film is formed.

 The frame 29 is an injection molded product of PS (high impact styrene resin), and the orifice 33 and the blade 31 are ABS molded products. On the surface of these molded parts, a low-temperature-curable high-active oxide photocatalytic thin film of sample No. 86 was formed in the same manner as in the above-described air cleaner.

 Shirts 32, which are parts facing the outdoors, are made of cold-rolled steel sheet that has been subjected to hot-dip galvanized treatment, and its surface is electrodeposited with an acrylic resin. A low-temperature-curing plastic active oxide photocatalyst thin film of Sample No. 86 was formed.

 The indoor surface of the filter 36 is irradiated with light from indoor lighting, and the opposite surface is irradiated with light emitted from the lighting equipment 35. Light emitted from the lighting equipment 35 is also applied to parts such as the frame 29, the orifice 33, and the blades 31 and the oil pocket 37. The surface of the shutter 8 facing the outside is irradiated with sunlight.

In the case of this embodiment, since the ventilation fan is used in a kitchen, the degree of dirt is very large as compared with a normal ventilation fan. That is, a large amount of edible oil fine particles scattered during cooking adhere to the surface in large amounts. In the case of a ventilation fan for a kitchen, a lighting device 35 is generally provided conventionally. This is a function provided to illuminate the hand at the time of cooking, and can be turned on in synchronization with the operation of the ventilation fan, or can be turned on independently only the lighting function. Since the organic matter decomposition efficiency of the photocatalyst according to the present invention is larger than that of the conventional one, a sufficient decomposition action can be obtained at the level of indoor lighting without the use of additional lighting equipment, especially when the dirt load is small. It may not be sufficient in places with heavy dirt loads, such as kitchens. However, if an ordinary fluorescent or incandescent lighting function is provided as in this embodiment, A sufficient effect can be obtained even in a place where the dirt load is large, such as a toilet or a toilet.

 (Example 3)

 A fan according to a third embodiment of the present invention will be described with reference to FIG. 5. FIG. 5 shows an external perspective view of the structure of the fan. Fan body base

A column 39 is mounted on the column 38, and a slide pipe 40 is slidably inserted on the column 39. The slide pipe 40 supports a head 44 composed of blades 41, guards 42, and a motor 43 upward. The strut 39 is formed so as to be thicker downward in consideration of strength. The blades 4 1 are rotated by the driving force of the electric motor 4 3, and an air flow is created ahead of the main body ¾ tfi. The guard 4 2 serves to prevent a finger or the like from touching the rotating blade 4 1. However, the guard 4 2 is designed to further increase safety by preventing accidents such as a child. The whole may be covered with nets 45 (not shown). A remote control holder 14 4; is attached to the lower part of the column 39, and the remote control 47 is usually stored in the remote control holder 46. Remote controller

When the operation mode is set by the switch operation of 47, the infrared signal is received from the infrared emitting section 48 of the remote controller 47, and the signal is received by the infrared receiving section 49 on the top of the main unit 38. Perform the setting operation.

 In this embodiment, the blade 41 is an injection molded product of ΛS resin. On the surface of the blade 1, a low-temperature-curable high-active oxide photocatalytic thin film of Sample No. 86 is formed in the same manner as in the case of the molded article such as ABS.

Guard 42 is made of a polyester wire baked and coated with a steel wire rod, and the surface thereof is also formed with a low-temperature curing type highly active oxide photocatalytic thin film of sample No. 86. Net 45 is made of nylon fiber, on which a low-temperature-curable high-active oxide photocatalytic thin film of sample No. 86 is formed. I have.

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

 On the surfaces of these transparent parts, a thin film of a low-temperature-curable high-active oxide photocatalyst of Sample No. 86 was formed. After forming a film of a titanate coupling agent on the surface of the target part, the first layer is formed. After forming this film, the sample No. 86 is cured at a low temperature including ΛT0. A second layer of a highly active oxide photocatalyst is formed.

 The surfaces of the blades 41 and guards 4'2, etc., are exactly the same as the blades and frames of the air purifier and ventilation fan described above, and foreign substances floating in the air adhere and become dirty. According to the method, since the low-temperature curing type highly active oxide photocatalyst film is formed, the adhered dirt is oxidized and decomposed at the illuminance level of the indoor illumination light, and the dirt is hardly stained.

 In this embodiment, a mechanism for performing remote control using infrared light is used. On the surface of a transparent component used for a light emitting portion and a light receiving portion of the infrared signal, a low-temperature curing type highly active oxide photocatalytic thin film is provided. The signal transmission is not hindered by the dirt adhering to the component surface.

 In this embodiment, the case of a fan using propeller type blades is used, but a fan using sirocco type blades can obtain the same effect with completely the same configuration.

 (Example 4)

 A vacuum cleaner according to a fourth embodiment of the present invention will be described with reference to FIGS.

Fig. 6 shows a perspective view of the external appearance of the vacuum cleaner, and Fig. 7 shows a cross-sectional view of the ^ You. The vacuum cleaner body 50 has a lower cover 51 covering the lower portion of the synthetic resin molded product, an upper cover 52 covering the upper portion, a lid cover 53, a grill power cover 54, and a handle portion 5. 5 mag, and a pair of large-diameter rear wheels on the left and right sides at the lower rear

5 6 and a small-diameter free wheel 5 7 are arranged in the center of the bottom of the front lower part. At the center of the upper cover 52, a main body switch 58 is provided. The main body switch 58 is composed of a central infrared receiving section 59, a power switch 60 and a cordless button 61. Be composed. The dust collection chamber (; 2 has a suction hose section

Suction consisting of 6 and extension tube ί; 4 and suction port 6 5 ΠHose assembly

6 6 are connected. A handle part 67 is connected to the upper part of the extension pipe part (; 4), and a hand operation part 68 is attached to the hand holding part 67. The hand operation part 68 has an infrared signal. The infrared signal transmitted from the infrared signal transmitting section 69 is transmitted to the infrared light receiving section 59 of the cleaner main body 50, so that the infrared signal can be operated wirelessly. The vacuum cleaner body 50 is provided with a dust collection chamber 62 at the front inside, an electric blower unit 70 and a code reel unit 71 at the rear inside, and furthermore, the ', 11 dynamic blower unit 70 and code A control board 72 is provided above the reel unit 71.

 In addition, a first exhaust ventilation passage 73 that is provided in a direction from the lower end to the upper end of the back of the removing machine 50 is formed in the rear of the electric blower unit 70 so as to be long in the up-down direction. The lower end of 73 further communicates with a second exhaust ventilation path 74 formed below the electric blower section 70. This first exhaust ventilation path

7 3 and the second exhaust ventilation path 74 constitute an exhaust ventilation path 75 (not shown), and the second exhaust ventilation path 7 communicates with the electric blower unit 70. 3 communicates with the exhaust ventilation section 76. In the upper part of the dust collecting chamber 62, paper filter mounting portions 77, 78 are provided.

Attach a thick paper filter (79) to 7 7 and 7 8 and attach the upper part of the dust collection chamber 62. By closing the lid cover 53, the mounting port 80 and the paper filter 79 are set at predetermined positions. The universal wheel 57 is rotatably mounted in a horizontal direction in a recess formed in the front bottom of the lower cover 51. Garbage, dust, mites, and microorganisms sucked from the mounting U80 together with the airflow are collected on a paper filter 79.

 The air flow from which these solids have been removed is passed through a communication port 8 3 provided with an auxiliary filter 8 2 provided on a partition plate 8 1 between the dust collection chamber 6 2 and the electric blower 70. The electric blower unit 70 guides the electric blower unit 70 to cool the electric blower unit 70, and the cooled air flow passes through a second exhaust air passage 74 and a first exhaust air passage 3 to an exhaust filter. The air is exhausted from the exhaust ventilation section 76 provided with 8 4.

 In this embodiment, the upper cover 52 of the cleaner body, the lid cover 53, the grill cover 54, the handle 55, the extension pipe portion 64 of the suction hose assembly 66, the suction portion 65, The handle part 67 is an injection-molded product of ABS resin, and a thin film of a low-temperature-curable high-active oxide photocatalyst of Sample No. 86 is formed on the surface of these molded products. After forming a film of a titanium-based coupling agent on the surface of the target part, the first layer is formed, and after forming this film, low-temperature curing including the sample No. 86 8 A second layer of a high activity oxide photocatalyst is formed.

Since the vacuum cleaner is a highly mobile object as compared with the articles according to the other embodiments, the surface of the exterior component is easily scratched. In other words, the main body of the vacuum cleaner and the suction port often collide with furniture and wall surfaces while traveling on the floor surface, and as a result, scratches are gradually formed, resulting in loss of luster and appearance. Not only does this impair the aesthetics above, but it can also lead to cracks and other damage due to scratches. In order to prevent this, conventional UV-curable acryl trees Although the surface hardness has been ensured by performing a coating process using a fat or the like, according to the present invention, Si used as a binder and a Ti 0 ₂ constituting a low-temperature curing type highly active oxide photocatalytic thin film. 0 harder than ABS hardness of ₂ film, because it has a hardness of about 2 H～4 H in pencil hardness, difficulty Kunar effect scratched when such scratches used for these exterior parts is obtained At the same time, the original effects such as antifouling and suppression of microbial growth can be obtained.

 In particular, the handle part G7 is a part that can be touched with bare hands, and it is easy for bacteria to propagate using nutrients such as attached shores as nutrients, and conventional antibacterial agents such as imidazole and thiazoline are used. Also, inorganic antibacterial agents such as copper-based, illilead-based, and silver-based antibacterial agents have been kneaded into the molding resin to increase the antibacterial effect, but these treatments become unnecessary.

In addition, since the suction port and wheels make sliding or rotating movements, using a vacuum cleaner in a dry environment tends to charge static electricity. Often adheres to the surface. To prevent this, conventionally, various surfactants and hydrophilic polymers such as polyamides and polyethylene glycols have been kneaded into the molding resin to reduce the resistance, but according to the present invention, However, since the resistance value of the low-temperature curing type highly active oxide photocatalytic thin film can be reduced, an effect of preventing adhesion of dust and the like can be obtained even with an ABS resin having a high electric resistance value _; A hand operation unit 68 is attached to the handle unit 67, and a control board on which electronic components are mounted is attached to the back of the hand operation unit 68. If static electricity is charged in the vicinity of the part 68, a malfunction of the control board may be induced, and the antistatic effect according to the present invention is effective not only for adhesion of dust but also for malfunction of the control board. .

Also, an infrared signal transmitter 6 9 provided in the same operation unit 68 is provided. The infrared ray receiving section 59 of the main body 1 of the vacuum cleaner is made of a transparent AS resin molded product as in the case of the fan of the third embodiment described above, but a low-temperature curing type highly active oxide photocatalytic thin film is formed on the surface. Because of the formation, the effect of preventing the obstruction of the transmission and reception of the infrared signal due to dirt is obtained.

 In addition, the exhaust filter 84 attached to the exhaust ventilation section 76 of the main body is made of a nonwoven fabric of acrylic and PP, and the surface of this exhaust filter 84 has been cured at a low temperature of Sample No. 21. A thin film of a highly active oxide photocatalyst is formed. The exhaust ventilation section 76 is provided with a number of openings, and the air discharge surface of the exhaust filter 84 is irradiated with light such as room lighting or sunlight from the openings. Is also cleaned.

 In addition, by making the upper cover 52 that covers the upper part of the main body, the lid cover 53, the grill cover 54, and the hand holding part 55, etc. transparent parts, external light reaches the inside and collects. The antibacterial effect and the deodorizing effect can be obtained by forming the low-temperature curing type highly active oxide photocatalyst thin film according to the present invention on the surface of the filter of the paper filter 79 and the filter of the auxiliary filter 82 inside the dust chamber 62.

 (Example 5)

Referring to FIG. 8, a clothes dryer according to a fifth embodiment of the present invention will be described. FIG. 8 shows a cross-sectional view of the main body of the clothes dryer. 8 5 is an outer frame, 8 6 is an opening / closing lid, 8 7 is a rotating drum, 8 8 is a heat source, 8 9 is an exhaust port, 9 is a two-wing fan, 9 1 is a fan casing, and 9 2 is a motor for power. Reference numeral 93 denotes a belt that transmits the power of the motor 92 to the rotary drum 87, reference numeral 94 denotes a round belt that transmits the power of the motor 92 to the fan 90, and reference numeral 95 denotes a first belt. An airtight filter, reference numeral 96 denotes a second airtight felt, reference numeral 97 denotes a partition plate, reference numeral 98 denotes a circulating duct for guiding the circulating air discharged from the finning 91 to the heat source 88. Reference numeral 9 denotes a printer, and reference numeral 100 denotes a fan casing. An FD beam fixed to the outer frame 85, 101 is a mounting ring for mounting a bearing 002, and the rotating drum 87 is rotatably slidably supported by a bearing 102. I have. The rotating drum 87 rotates together with the two-blade fan 90 when the driving force of the motor 92 is transmitted through the belt 93. By this rotation, at the same time as the clothes are agitated, circulating wind (solid arrow) is generated, and the circulating wind is heated when passing through the heat source 88, enters the rotating drum 87, and causes the moisture of the clothes. Is steamed and dried. Thereafter, circulating air is sent to the heat source 88 through the circulation duct 98 by the double-wing fan 9 (), and is repeatedly heated to repeatedly dry the clothes. Inside the opening / closing lid 86, a luminous qij device 104 with a fluorescent tube 103 is attached. A shock absorbing material 105 for absorbing impact is attached along the inner peripheral surface of the rotating drum 87. The cushioning material 10 δ is made of a foam.

 In this embodiment, the inner surface of the rotating drum 87, which is the part to which the light of the lighting equipment is irradiated, such as the cushioning material 105, the rear filter device E 99, and the inner surface of the opening / closing lid 86. These components are made of ABS or PP resin, and a thin film of a low-temperature-curable high-active oxide photocatalyst having a sample No. 86 is formed on the surface thereof. After forming a film of the silane coupling agent on the surface of the target component, the first layer is formed, and after forming this film, a low-temperature-curable high-active oxide containing AT0 of sample No. 86 is formed. A second layer of photocatalyst is formed.

 The luminaire can be lit at any time during the drying operation or as an independent operation irrespective of the drying operation. It effectively oxidizes and decomposes organic substances and odorous substances contained in the air that comes into contact with it, thereby suppressing the growth of microorganisms and deodorizing.

Because the clothes are rotating during the drying operation, the light can reach evenly and evenly. Therefore, it is more effective to use an operation program that turns on the rotating drum 87 for a certain period of time after the drying operation to clean the inside of the rotating drum 87.

 The outer frame 1 is made of a zinc-plated steel plate, and the outer surface is coated with an epoxy resin powder. On the surface of this painted surface, a low-temperature-curable high-active oxide photocatalytic thin film containing ATo of sample No. 86 was formed.

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

 The effect of the photocatalytic thin film on the outer surfaces of the outer frame 85 and the opening / closing lid 86, which are these exterior components, is similar to the exterior components of Examples 1 to 4 described above. And the like.

 (Example 6)

 A dish dryer according to a sixth embodiment of the present invention will be described with reference to FIGS. 9, 10, and 11. FIG.

 Fig. 9 shows an external perspective view of the dish dryer. FIG. 10 shows an enlarged sectional view of the vicinity of the exhaust port 128. Fig. 11 shows a Si cutaway of the main body.

The inside of the main body 106 is divided into a drying room # 07 and an operation control room 108 by a partition plate 109 vertically. In the operation control room 108, a heating fan unit 114 for sending dry air consisting of a fan motor 110, a blower fan 111, a casing 112, and a heater 113 is provided. A controller 11 is provided between the drying chamber 107 and an intake port 117 provided with an intake filter 116 connected with a duct 115 and the heating unit 114. 8 is provided. An upper basket 119 and a lower basket 120 for storing tableware are arranged above and below the drying chamber 107. The lower cage 120 is mounted on the lower part of the door 122 so that it can be freely tilted. It is arranged on the water pan 124 placed on top of the pipe 125. Similarly, the upper car 1 19 is also installed on the movable rail 1 23. The MJ moving rail 123 is arranged on a roller (not shown) rotatably provided on a side wall of the drying chamber 107 so as to be movable back and forth. By pulling the handle 1 2 6 forward, the lower car 1 20 force from the drying chamber 1 07; by pulling the tip of the car, the upper basket 1 9 can be pulled out. It has become. The exhaust port provided on the panel 127 has a letter shape and is provided with an exhaust filter 122). An opening 130 provided in the main body 10 (the cut-off plate 10) of the main body 10 and the exhaust duct 13 1 are connected to the drying unit 107. Temperature detector 1 Numeral 32 is hardly affected by the outside air temperature. It is located inside the exhaust duct 13 1.

The intake port 1] 7 is an injection-molded product made of PP, and the intake filter 1-16 is a net made of Nylon. The table t & i includes the sample No. shown in Table 7 below. A thin film of low-temperature-curable highly active oxide photocatalyst was formed. Nets made of nylon, after ultraviolet irradiation treatment, samples N o. 9 1 of low-temperature curing type high active oxide photocatalyst containing silver in _r intake filter one 1 1 6 surface of the thin film is formed of a chamber Because of the illumination light, attached organic matter and odorous substances in the air taken in are oxidatively decomposed. The low temperature curing type highly active oxide photocatalyst thin film of Sample No. 91 is also formed on the exhaust port 128 and the exhaust filter 122 as well. Exhausted moisture is likely to condense around the intake and exhaust ports and become moist, and mold and bacteria may proliferate.However, if a photocatalyst with high decomposition efficiency according to the present invention is used, indoor light is effective. Proliferation of these microorganisms can be suppressed. In the formulation of Sample No. 91, the silver contained in the composition! ) Particularly suitable because the body has antimicrobial activity. Zeola loaded with silver to enhance antibacterial effect Ceramic particles such as itaperite may be mixed.

 In the drying room 107, a lighting fixture 13 4 with a fluorescent tube 13 8 is attached. The lighting function is turned on when the door 1 2 1 is opened to check the degree of drying of the internal dishes.

It can also be used as a function to clean the interior of 107. That is, the drying room

By forming a photocatalytic thin film on the surface of the internal component 107, an antibacterial and antifouling effect can be obtained in a portion irradiated with light. In this embodiment, the upper basket

1 19, the lower basket i 20 has a structure in which a boride-based powder resin is baked and painted on an iron frame. After the surface of this painted SH is subjected to ultraviolet irradiation, the sample No. A thin film of low-temperature curable high-active oxide photocatalyst containing copper of 92 is formed. These upper and lower baskets are members that come into direct contact with tableware and are required to be clean.However, the effect of the photocatalyst provides antifouling on the surface and the effect of suppressing the growth of microorganisms. Will be kept. Copper, like silver, has its own antibacterial action, so its antibacterial effect is enhanced.

 As in the case of the clothes dryer of Example 5, during the drying operation, the dishes become shadows and the light does not reach evenly enough. It is more effective to use an operation program that cleans the data.

 The door 121 is a force made of a molded article of ABS resin. On this surface, a low-temperature curing type highly active oxide photocatalytic thin film containing ATO of sample No. 86 is formed. The effect of the photocatalytic thin film on the surface of the door 121 is such that sufficient indoor stains and antibacterial effects can be obtained with room light, as in the case of the exterior parts of Examples 1 to 5 described above.

(Example 7) A dishwasher according to a seventh embodiment of the present invention will be described with reference to FIGS. 12, 13 and 14.

 Fig. 12 is a perspective view of the appearance of the dishwasher, and Figs. 13 and 14 are sectional views of the dishwasher.

 The tableware storage tank 1 36 is arranged inside the outer frame 135, and the front opening II is opened and closed. 8 is provided, and a downstream basket 13 9 for storing tableware is arranged on this step 13 8 in a detachable manner. A pump i 4 () is disposed outside the bottom of the tableware storage tank 1 36. This pump 14 () has a pump motor 14 1. A lower arm nozzle 142 that pivots directly below the tableware lower basket 133 is hidden. The upper arm i of the lower arm nozzle 142 is provided with a few small holes 144. The lower basket for storing tableware 139 is provided with a bench lily tube 145 for sending the washing water sent from the pump 140 to the upper nozzle 144. The upper arm nozzle 144 pivots about the center as a fulcrum immediately below the container storage upper basket 146. A plurality of small holes 147 are provided on the upper surface of the upper arm nozzle 144. A heater 148 is arranged at the bottom or back of the tableware storage tank 1:36. A heater cover 14 9 is arranged so as to enclose the heater 14 8. Tableware storage tank 1 36 A water supply solenoid valve 150 is arranged on the outer side surface.Tableware storage tank 1 3 6 An exhaust duct 15 1 is arranged on the upper outer surface and connected to the exhaust port 15 2 A control panel 15 3 is located on the top of the outer surface of the door 13 7. A drain pump 15 4 and a ventilation unit 15 5 are located outside the bottom of the tableware storage tank 1 36. Are located.

During the cleaning operation, water is supplied from the water supply solenoid valve 150, the pump i 40 is driven, and pressurized water is supplied to the lower arm nozzles 14 2 at the same time as the heater. Energize 1 4 8 to raise the water temperature. At the same time as the water spouts from the hole 144, when it is sent to the upper arm nozzle 144 through the bench lily tube 144, the water also spouts from the hole 144. In this way, the upper and lower arm nozzles rotate and evenly spray hot water onto the dishes in the dish storage basket 146 to remove dirt. After the cleaning operation is completed, the drain pump 154 is turned on to discharge the wastewater, and the same operation as above is repeated several times to rinse and remove the internal dirt. When the final rinsing operation is completed, the operation moves to the drying operation. Energize the fan unit 15 and rotate the fan fan 15 6, and the fan duct 丄 57, heater located at the bottom of the tableware storage tank 1 36. Air is supplied to the tableware storage tanks 1 36 through 4 8. At this time, the heater 1 148 is energized ONZOF P 'for a certain period of time, and cool air is turned into hot air. This hot air converts the water droplets and residual water inside and the water droplets attached to the tableware into steam, which is discharged through the exhaust duct 15 1 through the exhaust port 15 2 to the outside.

 In this embodiment, the exhaust port 152 is an ABS resin molded product, and a thin film of a low-temperature curing type highly active oxide photocatalyst containing silver of sample No. 91 is formed similarly to the above-mentioned dish dryer. Have been. Exhausted moisture tends to condense and become moist around the exhaust port, and molds and bacteria may proliferate.However, if a photocatalyst having high decomposition efficiency according to the present invention is used, indoor light can be effectively used. The propagation of microorganisms can be suppressed.

Lighting equipment 159 equipped with a fluorescent tube 158 is installed inside the tableware storage tank 135. The lighting function is turned on when the door 13 7 is opened, and is used not only for the original function of lighting such as checking the degree of washing and drying of the dishes inside, but also for cleaning the inside of the dish storage tank 1 36. Can be used. That is, by forming a photocatalytic thin film on the surface of the internal component of the tableware storage tank 136, an antibacterial and antifouling effect can be obtained in a portion irradiated with light. In this embodiment, the tableware storage upper basket 146 and the tableware storage lower basket 139 have a configuration in which a polyamide powder resin is baked and painted on an iron frame. In the sample, a thin film of a low-temperature curable high-active oxide photocatalyst containing copper of sample No. 92 is formed.

 These upper and lower baskets are members that come into direct contact with tableware and are required to be clean.However, the effects of the photocatalyst can keep the surface clean and prevent the growth of microorganisms. It is.

Other members to which the light of the lighting equipment 159 is irradiated include a tableware storage tank 1336, an upper arm nozzle i44, a triarm nozzle 144, and a knuckle tube 145. The parts used are PP resin injection molded products and SUS plastic deformed products. After corona discharge treatment on the surface of these components, a thin film of S iota 0 ₂ only, i.e. samples N o. 1 2 of Table 1 is formed as an underlying layer, after forming the membrane, Low temperature curing of sample No. 2] ¾ A thin film of highly active oxide photocatalyst is formed.

The formation of a photocatalytic thin film on the components inside the dish storage tank 1 36 and the addition of lighting equipment 1 59 has the effect of improving the drying efficiency as a unique effect of the dishwasher. This _{effect, T i 0 2, S i} 0 2 according to the present invention is a basic material for low-temperature curing type high active oxide photocatalyst thin film is both a good material to water wettability, were removed from the soiled dishes Even if substances that repel water, such as oils and fats, adhere to them, they are decomposed by the light of the lighting equipment 159, so that the effect of always maintaining high water wettability can be obtained.

The washing operation involves raising the water temperature to 60 to 70 ° C during the final rinsing, raising the internal temperature, and then discharging the moisture out of the machine by blowing air. Water droplets remaining inside 36 cause a decrease in drying efficiency. Tableware storage tank 1 3 6, upper arm nozzle 1 4 4, lower Parts such as the nozzles 142 and bench lily tubes 1 and 4 are required to have high water resistance, so they are often made of hydrophobic materials and usually have poor surface wettability. On the surface of a material with poor water wettability, water does not spread in a film-like state and adheres in the form of droplets with a high contact angle. During the cleaning operation, a detergent containing a surfactant is added, so that the surface tension of the cleaning water decreases and the contact angle decreases, resulting in a well-wetted state. Very low in water, and the surface tension of water is very high. Therefore, at the end of the final rinsing, the rinsing water adheres in the form of countless water droplets having a high contact angle to the surface of each component inside the tableware storage vessel 1336.

 These water droplets with a high contact angle have a larger amount of water and do not dry easily as compared with the case of a thin water film. In addition, since the water in the form of water droplets is reduced and dried while maintaining the shape of the water droplets during drying, the surface area is also small, so the drying speed is slower and the drying time is about three times as long. Tableware is often made of glass, ceramics, or wood with good water wettability, and it dries relatively quickly.However, when the dishwasher is finished with water droplets attached, open the door 1 37 and open the upper and lower tableware baskets. Drops fall on tableware due to the vibrations when pulling out the tableware, causing a problem that wet tableware is dried.

 When parts such as tableware storage tank 1 36, upper arm nozzle 144, lower arm nozzle 144, bench lily tube 1 45, etc. are made of PP molded products, the amount of residual water due to attached water droplets at the end of rinsing is In contrast to the case of about 30 g, when the photocatalyst film according to the present invention was formed, the amount of residual water attached was reduced to about 5 g. Further, the low-temperature curing type highly active oxide photocatalytic thin film according to the present invention has a high photoactivity and has an action of decomposing fats and oils attached by the light of the lighting equipment 159, so that the wettability due to the attachment of the fats and oils decreases There is no.

As in the case of the dish dryer of Example 6, the dishes are shaded during the drying operation. Since the light does not reach evenly and evenly, it is more effective to use an operation program that turns on the light for a certain period of time after the drying operation is completed to decontaminate the inside of the tableware storage tank 136.

 Also, the door 1337 is a force made of a molded product of PP resin \ After corona discharge treatment on this surface, a sample No. 12 is formed as an underlayer, and after this film is formed , Sample No. 2], a thin film of a low-temperature curing type highly active oxide photocatalyst is formed.

 The effect of the photocatalytic thin film on the surface of the door 1337 is similar to the case of the exterior parts of Examples 1 to 6 above, in which the indoor light can provide sufficient antifouling and antibacterial effects. is there. In this embodiment, the stationary type dishwasher is described, but the effect of the photocatalytic thin film can be obtained in the same manner in the case of a tabletop type. In the case of the desktop type, '4: Since the internal light is applied to the f-plane of the exterior component, it is effective to form a photocatalytic thin film on the side surfaces and the surface of the outer wall member on the ceiling.

 (Example 8)

 A kitchen waste disposal machine according to an eighth embodiment of the present invention will be described with reference to FIGS. 15 and 16. FIG.

 Fig. 15 shows an external perspective view of the kitchen waste treatment machine, and Fig. 16 shows a cross section of a wooden body.

Inside the frame 160, there is a rotatable agitating blade 161, which is rotatably supported at the center, and a garbage tank 164, which is provided with garbage at the top, is provided with garbage. The medium contains a culture substrate 165. The culture substrate 165 is made by cutting sawdust, rice hulls, rice straw, etc., whose main component is fibrin, which is hardly decomposed by microorganisms such as lignin. Each grain is porous and has voids. It has a complex particle size and large voids are formed between the particles. The rotating shaft 166 is provided with three stirring blades 161, supported by a bearing 1667 provided in the processing tank 16, and the end of the rotating shaft protruding on one side is a drive motor.

The transmission is connected with a transmission gear such as a chain with an appropriate reduction ratio. The inner lid 1 7 1 has an upper panel at the upper opening 1 7 0 of the processing tank 1 6 4

It is installed in the open and close position at 17 2. In addition, ventilation fan 173, intake port 174, and exhaust port 175 are provided near the upper part of processing tank 164, and are generated in processing tank 164 by rotation of ventilation fan 173. The exhausted cracked gas and water are discharged outside the machine through the exhaust port 175. In addition, an appropriate net-like filter is disposed at each of the intake port 174 and the exhaust ports 1-5. Further, an opening / closing lid 1-6 of the intake port 17 is provided, and the intake port 174 is configured to be opened and closed by reciprocating a solenoid 177 mounted on the frame body 60. Further, an operation section 178 for operation is provided on the upper panel 172, and by this operation, the controllers 1.9 are operated, and the kitchen waste disposal machine is operated. After a few months, the culture substrate 165 needs to be replaced because the voids are filled with decomposed substances and the porosity decreases, making it impossible to process garbage. For this reason, a discharge port 180 and a discharge path 18 1 are formed at the bottom of the processing tank 16 4, and the culture body 16 5 that has fallen into the discharge path i 8 1 is ejected to remove the frame 160. Can be taken out of the room.

 The air in the upper space of the culture substrate 1645 of the treatment tank 1664 contains a large amount of substances having high odor intensity, such as trimethylamine-methylmercaptan, ammonia, and hydrogen sulfide, as decomposition gas together with moisture. Due to the strong odor, the conventional kitchen waste disposal machine could not be installed in the kitchen, and when installing it in the veranda of an apartment house, there was a problem of odor leakage to the surrounding area.

Conventional deodorizing mechanism: adsorbents such as activated carbon ゃ, manganese-based thermal decomposition catalyst Various deodorizing mechanisms have been devised, but none of them was sufficient in terms of effect and life.

In this embodiment, exhaust filters 18 2,] 83 are provided in the exhaust ports 1-5, and ultraviolet lamps 18 4 are provided in the gaps. Exhaust filter — 18 2 has zeolite as a main component, and exhaust filter 18 3 has activated carbon as a Byone component. Each of them has a honeycomb structure, and ultraviolet rays emitted from ultraviolet lamps 18 4 are inside the honeycomb. _U The exhaust filters 18 2 and 18 3 have a low-temperature-curing 光 active oxide photocatalytic thin film of sample No. 62 as shown in the table on the inner surface of the honeycomb. Has been established.

The low-temperature curable high-active oxide photocatalyst according to the present invention has a high decomposition efficiency, and in applications where the load of organic substances is relatively small as in Examples 1 to 7 described above, the level of indoor lighting equipment, that is, the wavelength is 25 0-3 5 0 ultraviolet light (nm) is 0. 0 0 1~ 0. 0 1 m W Zcm 2 level illuminance 0 or by mounting a fluorescent lamp and white heat lamps,. 0 1~ 0. 1 m W In the case of a force that could be decomposed by the _c! level illuminance, for example, in the case of a β load of several ppm in ammonia concentration as in the present embodiment, it is necessary to arrange an ultraviolet ray generating 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 large and the ultraviolet intensity is lower than that of the conventional oxide photocatalyst. It is smaller than when used. When the input garbage is most actively decomposed, the above-mentioned odorous substances are generated in the largest amount.

The garbage is most actively decomposed between 1 hour and 8 o'clock after being thrown in. Therefore, turning on the ultraviolet lamp 184 in accordance with this timing can extend the life of the lamp. Exhaust filter 1 8 3 is activated carbon When the odor concentration is low, the activated carbon adsorbs the odor, and the adsorption efficiency gradually decreases as the amount of adsorption increases. Adsorbed malodorous substances can be decomposed and activated carbon can be regenerated.

 The frame 160 is made of painted steel plate, and the outer lid 1 11 is made of an injection-molded product of PP resin. This surface is coated with an organic coating film of chlorinated polyethylene. On the surface of the film, a thin film of a low-temperature curing type highly active oxide photocatalyst of Sample No. 21 was formed.

The effect of the photocatalyst thin film on the surface of the outer frame 160 and the outer lid 171, as in the case of the exterior parts of Examples 1 to 7 described above, has the effect of sufficient antifouling and antibacterial effects with room light. Is obtained. Especially, in the case of a kitchen garbage disposal machine, garbage is handled, so that these exterior parts are often stained with juice dripping from the garbage. When the garbage disposer is placed outdoors, sunlight is irradiated on these exterior parts. Ultraviolet light illuminance wavelength 2 5 0-3 5 0 sunlight (nm) is 0. 1 ~ 5. 0 m W / cm 2 level and a high strength as compared with the room lighting or the like, is dirty juice such garbage Can also be decomposed.

 In the above Examples 1 to 8, a path through which an air flow generated by an electric motor passes through an adherend such as various thermoplastics, a filtering mechanism such as a filter provided in the path, or an indoor Combination and composition of low-temperature curing type highly active oxide photocatalytic thin film formed on the surface of exterior parts exposed to external light such as lighting or the parts provided inside the equipment and exposed to light emitted by lighting equipment. The curing conditions of the film and the characteristics of each composition will be described below with reference to Examples 9 to 16.

(Example 9) To prepare a solution prepared by dispersing T i 〇 ₂ fine particles S i 0 ₂ sol. Using this solution, a film was formed on the PET film, and the PET film shown in Fig. 17 was produced. The procedure is shown below.

First, a description will be given S i 0 ₂ sol preparation method. 5 g of tetraethoxysilane was dissolved in 100 ml of a mixed solution of water, ethanol and propanol (3:27:70), and the mixture was incubated at 40 ° C for 5 hours. The obtained solution was allowed to stand at room temperature for 2 weeks to obtain a SiO ₂ sol.

Then have fabrication method Nitsu solution dispersed with T i 0 ₂ fine particles is described in S i 〇 ₂ sol. T i (fine particles were added to the previously prepared S i 0 ₂ sorbable as T i 0 ₂ / S i O _z = 9 in E distribution ratio. The concentration of the ^ form was 4 wt% and required. weight aqueous added to adjust the subsequent 2 4 hr volume to disperse the T i 0 ₂ particles in S i 0 ₂ sol using Jirukoniaboru of 5ιηιιιφ -. treated with mill, S i 0 ₂ sol in to prepare a solution prepared by dispersing T i 0 ₂ fine particles.

The Ti 0 and Si ₂ sol prepared by dispersing fine particles were coated on PET film 185 and irradiated with a low-pressure mercury lamp (intensity: 15 mW / cm ² ) at 120 ° C. to form a Plasti Kkufirumu with a T i 0 ₂ particles 1 8 7 Ding was dispersed i 〇 ₂ dispersion S i 〇 ₂ film 1 8 8 Coat in S i 0 ₂ film 1 8 6 was treated for 5 minutes with. The thin film obtained on the PET film 185 had good film quality and strength, and the thickness was 300 nm.

The activity of decomposing organic substances by the titanium oxide was evaluated. The activity test was performed by coating a red-violet organic dye on the thin film and irradiating 1 (mWZcni ² ) light at 254 nm. The decomposition rate was determined from the change from the initial transmittance of the dye. FIG. 20 shows the results.

Another with T i 0 ₂ dispersion S i 〇 ₂ film for comparison in the drawing, and no film Si0 ₂ The results for the membrane are also shown. There is no change in the ho Tondo dye amount in Ding i 〇 ₂ dispersion S i O _z film without and S i 〇 ₂ film, T i 0 ₂ dispersion S i 0 ₂ film located 4 5 after 3 0 minutes for % Decomposition was obtained.

Thus, T i 0 having a photocatalytic function, it was possible to prepare a dispersion S i 0 ₂ film with PET off Ilm. The film forming method of the present invention can be manufactured at a temperature of about 12 (TC and can be applied to a plastic material other than a Pyrex glass substrate. Because of the need for temperature, application to plastic products is difficult, and it takes more than 10 minutes to crystallize Ti.On the other hand, the manufacturing method of the present invention enables film formation at low temperatures. As a result, there are plenty of substrates that can be used, photocatalysts can be deposited on any surface ifi, and processing time can be as short as a few minutes, which can significantly reduce production costs.

Next, a cocatalyst was added to improve the performance of the photocatalyst. During S i O _z sol previously prepared by adding various nitrates in a solution prepared by dispersing T i 〇 ₂ particles was deposited on a PET film were carried decomposition reaction of the dye. The results are shown in Table 1.

Table 1

 Effect of additives

 It was found that the photocatalyst added with N a L i, K, Μ g, C a S r, and η η was effective, and F e and A 1 became deactivators.

Figure 21 shows the results of plotting the effect of adding a cocatalyst on electronegativity. The smaller the electronegativity seems to be, the more effective it is. In particular, since Li Na and Mg are effective, it was found that not only the electronegativity but also the ionic radius was important. Figure 22 shows the relationship between 10; qi-negativity, the ion radius, and the effect of addition. Thus, it was found that it is effective to add an ion having an electronegativity of less than 1.6 and an ionic radius of less than 0.2 nm and having a valence of 2 or less. (Example 10)

The S i 0 solution prepared by dispersing the different T i 0 ₂ fine particle Kai ₂ sol was several prepared. _{Incidentally, T i 0 2 / S i} 0 2 ratio is set to 9 in a weight ratio, L i added amount was set to 5 wt%, Example 1 similar operation at T i 0 ₂ dispersion S i 0 ₂ film on the PET film The decomposition rate after 10 minutes was measured using an organic dye.

 Table 2

Decomposition rate T i 0 ₂ dye to particle size

Table 2 shows the conditions and test results of the prepared samples. Ri by these results, the size of the dispersed T i 0 ₂ particles were found to be. 8 to 0 nm is most effective. As described above, the decomposition rate changes depending on the particle size, and when the ratio T i 0 ₂ / S i 0 ₂ is further reduced, the optimum particle size of the T i 〇 ₂ fine particles changes, but in the range of 5 to 20 nm. If so, the decomposition rate was good. Therefore, it was found that the Ti 0 ₂ particle size of the Li added catalyst should be 5 to 20 nm. The above results were the same for Na, K, Mg, Ca, Sr, and Zn other than Li.

(Example 11) L i added amount in Table 3 shows the results of examining the T i O _z ZS i 0 dye decomposition rate when, varying (1 0 minutes after decomposition rate) and membrane strength. The preparation of the solution and the film formation method were performed in the same manner as in Example 1. From these results, it was found that the conditions under which both the decomposition rate and the film strength were effective were that the amount of Li added was 0.5 to 20 wt% and the Ti 0 ₂ ZS i 〇 ₂ was 9 to 5. The third table and i added amount, T i 0, / S i 0 decomposition rate Sample No. amount of dye to ₂ ratio _{(%) Ti0 2 / SiO z} ( weight ratio) after 10 minutes degradation rate film strength

 1 9 0 9 2 5 〇

2 0 1 9 9 0 〇

2 1 5 9 1 0 0 〇

2 2 1 0 9 1 0 0 〇

2 3 2 0 9 1 0 0 〇

2 4 5 〇 9 6 5 X

 2 5 0 8 2 5 〇

2 6 1 8 8 8 〇

 2 7 5 8 1 0 0 〇

 2 8 1 0 8 1 0 0 〇

2 9 2 〇 8 1 0 0 〇

 3 0 5 0 8 6 0 X

 3 1 0 6 2 5 〇

 3 2 1 6 8 6 〇

 3 3 5 6 1 0 0 〇

 3 4 1 0 6 1 0 0 〇

 3 5 2 0 6 1 0 0 〇

 3 6 5 0 6 6 0 X

 3 7 0 4 1 5 〇

 3 8 1 4 1 5 〇

 3 9 5 4 2 0 〇

 4 0 1 0 4 2 0 〇

 1 2 〇 4 2 0 〇

4 2 5 0 4 1 5 〇 The Table 4 shows the results of examining the dye decomposition rate and film quality, varying _{T i 0 2 / S i 0} 2 and the film thickness. The solution preparation and film formation were performed in the same manner as in Example 1, but the film thickness was adjusted by changing the solid content of the solution from 0.5 to 8 wt%.

Results thickness was found to be 1 0 0-5 0 0 if _{nm T i 0 2 / S i} 0 decomposition rate without being affected by ₂ ratio, both film quality is good.

 The above results were the same for Na,, Mg, Ca, Sr, and Zn other than Li.

 Table 4

T i 0 ₂ / S i 〇 ₂ ratio, decomposition rate of dye with respect to film thickness

 (Example 12)

The in Table 5 is an oxide semiconductor other than T i 0 ₂ lambda T_〇,〗 T_〇 examines the dye decomposition rate when adding a Z n 0, F e _z 〇 _3, C r ₂ 〇 ₃ particles Results Indicated. Incidentally, in tests examining the dye decomposition rate, the intensity of the UV lamp (254 nm) was 0. ² m WZ cin 2. In addition, unless otherwise noted, the dye decomposition test after this example was performed under the above conditions. Results AT_〇 a _{F e 2 0 3, C r} 2 〇 ₃ fine particles added is effective, the amount is effective if the addition in either case, in particular〗 0 ~ 2 0 wt% is S also effective there were. Here, the electron affinities of the constituent elements of each oxide are as follows, and it is effective to use an oxide semiconductor with a constituent element having an electron affinity of 1.2 oV or more. I was separated.

 Table

 Decomposition rate of dye for various oxide semiconductor additions

構成元素 T i S n I n Z n F e C r

Constituent elements T i S n I n Z n F e C r

 Electron affinity (eV) 1.25 1.2 0 0.2 1 1.2 3.16 3.54

If the electron affinity of the oxide semiconductor is smaller than that of T i, a Schottky barrier is formed at the particle interface of the fine particles, and the added oxide semiconductor carrier cannot be injected into T i [] ₂ and the effect appears. Absent. On the other hand, when the electron affinity of the oxide semiconductor is smaller than that of T i, a Schottky barrier is not formed at the particle interface of the fine particles, and a homojunction is formed. It injected into T i 0 _7, functions effectively. AT 0, which was particularly effective, has an electron affinity that is a little smaller than T 1 ^ There is almost no difference between them. This is a conductive oxide AT_〇 have high carrier concentration, a large amount of carriers Λ T_〇 is injected into the T i 〇 _2, the activity of the photocatalyst is improved. Furthermore, it was also found that the effect of adding Li is large even when such an oxide semiconductor is added.

In addition, as a method of effectively utilizing the carrier of the oxide semiconductor, not only addition of fine particles but also lamination can be employed. The Table 6 shows the results obtained by laminating a T i 0 ₂ / S i 〇 ₂ film and AT_〇 film. The results show that lamination is effective, and that the performance is further improved by adding i to both. In addition, it was found that it is effective to alternately laminate many times.

 Table 6

 Degradation rate of dye in ATO laminated film

(実施例 1 3 )

(Example 13)

Papermaking create the S i 〇 ₂ solution containing dispersed particle diameter 5 nm T i 〇 _z particulates in the sol, this A g, P t, P d , R h, N i, C u, R u 0 , fine particles were added 2 wt% with respect to T i 0 ₂ respectively. Incidentally, T i 0 ₂ / S i 〇 ₂ ratio was 9 by weight. Fabricated A g, with R u 0 ₂ particles added T i 0 ₂ dispersion S i 〇 ₂ sol, A g in the same manner as in Example 1, P t, P d, R h, N i, C u the R u O _z particles was added T i 0 ₂ dispersion S i O ₂ film was formed on a PET film was examined degradation characteristics of the organic IroHata. Results divide that A g, PL, P d, R h, i, degradation rate by adding C u, R υ 0 ₂ fine particles is large summer as shown in Table 7.

 Table Ί

 Degradation rate of dye to noble metal addition

 (Example 14)

For the Li-added photocatalyst and the Li-free photocatalyst prepared in Example 1, using a fluorescent lamp, sunlight, an incandescent lamp, and a mercury lamp, the cigarette canister and the acetate lamp were used. The degradation characteristics of aldehyde, urea, and E. coli were compared. As a result, as shown in Table 8, the decomposition characteristics of citric acid, acetate urea, urea, and Escherichia coli were higher than those of the Li-free photocatalyst, no matter which lamp was used. It turned out to be 5 times as effective. As described above, it was found that the Li-added catalyst can provide a sufficient effect not only with the ultraviolet lamp but also with the lamp used in the living environment. Similar effects were obtained when Na, K, Mg, Ca, Sr, and Zn other than Li were added.

 Table 8

 Decomposition test results of organic substances using various lamps

 (Decomposition ratio when Li 10 (wt%) is added and when i is not added)

(Example 15)

When the Li-added Ti 0 ₂ dispersed Si ₂ film prepared in Example 1 is directly formed on a PET film, the photocatalytic action causes damage to the base PET film. Therefore, when the coat of the L i added T i 0 ₂ minutes dispersion S i 0 ₂ film produced in Example 9, to prepare a film having one layer of S i 〇 ₂ film between P ET film. Further, a sample or a Li-added Ti 0 ₂ dispersed Si 0 ₂ film to which Al, Fe, and Zr nitrates, which are components that deactivate the photocatalytic action in the Si 0 ₂ film, are added. A sample with Λ Τ Ο added was prepared, Various tests were performed. The results are shown in Table 9.

 Table 9

Dye decomposition test and durability test results of S i O _z laminated film (T i 0 ₂ / S i 0 ₂ = 9, L i (wt%) = 10

結果は L i 添加 T i 〇 ₂分散 S i 〇 ₂膜と P E Tフィルムの間に、 ノ リ ァ層として S i 〇₂ 膜を 1層設けることで長期間使用しても膜剥がれを 防ぐことができた。 さらに、 A 1 , F e , Z r を添加することで光触媒 活性を完全に失活させることができ、 接着強度を維持できることが分か つた。 また、 A Τ 0添加膜では帯電防止効果が加味され埃等の付着も抑 制でき、 有機物の分解だけでなく、 無機物の付着も防ぐことができ、 よ り優れた防汚効果を有したフィルムを作製できた。

Results Between L i added T i 〇 ₂ dispersion S i 〇 ₂ film and PET film, is prevented even film peeling was used for a long time by providing one layer of S i 〇 ₂ film as Roh Li § layer did it. Furthermore, it was found that by adding A 1, Fe, and Zr, the photocatalytic activity could be completely deactivated, and the adhesive strength could be maintained. In addition, the AΤ0-added film has an antistatic effect and can suppress the adhesion of dust and the like, and can prevent not only decomposition of organic substances but also adhesion of inorganic substances, and a film having a more excellent antifouling effect. Could be produced.

 Various articles having a mechanism for generating an air flow by a motor as shown in Examples 1 to 8 using a low-temperature curing type highly active oxide photocatalytic thin film having the composition shown in Examples 9 to 16 described above. The following is a summary of the results of the evaluation of the specific effects of use. First, the effects of applying the low-temperature curing type highly active oxide photocatalyst thin film according to the present invention to a filtration mechanism provided in an air passage will be summarized.

A typical airborne contaminant in a room is tobacco smoke. Tobacco smoke is a suspension of fine particles of tar substances and soots. These fine particles form a film on the filter and accumulate, and the filter gradually turns brown and becomes dirty. Dirt from the smoke of the tobacco was evaluated. The front is a suction side of ventilation fan air volume is 5 (m ³ min), the subject area and fixed copy and paste the polyester fiber nonwoven filter one 1 O cm X 1 O cm. The ventilation fan with the nonwoven fabric was placed in a container having a capacity of 45,000 (cm ³ ) and sealed. A cigarette smoke generator was provided in the container. The cigarette smoke generator has a tube attached to the filter of the lit cigarette, which is connected to a diaphragm pump. When the diaphragm pump is driven at a flow rate of 1,800 (cm ³ , second) and the end of the tube on the tobacco side is depressurized, smoke passing through the tobacco filter is released. Exhausted from the discharge side of the pump and burns one cigarette in about 1.5 minutes When a cigarette smoke generation and ventilation fan are driven in a container with such a configuration, the ventilation fan exhaust is also discharged into the container As a result, the tobacco smoke filled in the container will pass through the non-woven filter part many times. Five cigarettes were continuously burned, the ventilation fan was driven for 10 minutes, the container was opened, and the nonwoven fabric filter was removed to obtain a sample. On the fiber surface of this nonwoven fabric filter, a low-temperature curable high-active oxide photocatalytic thin film according to the present invention is formed. The creation method was the same as that described in Example 9. Force that is targeted to the PET film in Example 9, where, in a solution prepared by adding lithium nitrate solution prepared by dispersing Ding i 0 ₂ particles in S i 〇 ₂ sol屮, surface oxidation by ozone atmosphere After immersing the treated non-woven fabric filter and holding it for 1 minute, pull up the filter and disperse the unnecessary solution by air blow, then use a low-pressure mercury lamp (strength: 15 m (W / cm ² ) while irradiating for 5 minutes to cure the film and form a photocatalytic thin film on the fiber surface.The composition of this film is sample No. 2 in Table 1. The sample prepared in Step 2 was irradiated with fluorescent light to evaluate the degree of decomposition of dirt attached to the sample. The color difference in the soiled state before light irradiation was set to 100%, and cigarettes were used. Sample N o contamination with smoke, the color difference before depositing as merely dispersed Ding i 0 ₂ fine particles to the S i 0 ₂屮in. For comparison of the evaluation of the antifouling effect as 0%. 1 Sample No. 12 was also evaluated by forming a thin film on the surface of one fiber of the filter in the same manner as in the case of a film of S i 〇 ₂ containing no T i ϋ ₂ fine particles.

The results are shown in FIGS. 23 and 24. Fig. 23 shows the degree of contamination of the filter over time when a smoke filter test was performed under the same conditions. This is the result of evaluation. Compared to the accession Lil fibers untreated, T i 0 ₂ and S i 0 _{2 If} the marked with oxide photocatalytic thin vitreous whose components are about 50% discoloration quickly, i.e., about 50% The smoke collection efficiency has been improved. Fig. 24 shows that the filter that has absorbed smoke under the above conditions and illuminated with a fluorescent lamp irradiates the filter that turned brown, and the photocatalyst decomposed the adhering substances, and the discolored filter returned to its original color. This is the result of evaluating the degree of return by color difference measurement over time. The integrated light amount in the figure indicates the integrated value of light with a wavelength of 2 “) 0 to 350 (nm). The sample No. 12 in the figure does not include Ti 0 ₂ It is the case of only S i O _z, little bleaching effect by decomposition is not observed. samples N o. 1 1 and sample N o. 2 a T i O _z is contained the same amount, any effect As can be seen, sample No. 2 is a formulation according to the present invention to which Li N〇 ₃ was added, and it can be seen that the rate of bleaching was greatly improved, especially in the initial stage. In the case of an actual air purifier, ventilation fan, etc., a small amount of dirt adheres and the room light is illuminated at the same time, so the initial decomposition speed is reduced. As the amount of dirt attached increases, light is blocked by dirt, making it difficult to reach the photocatalytic thin film on the fiber surface. In decomposition efficiency drop. Therefore be broken before the dirt is adhered thicker becomes important.

In an actual environment, in order to attach the same amount of dirt to the filter as in this test using the above-mentioned equipment, the above-mentioned ventilation fan was operated between closed 6 tatami mats (approximately 20 m ² ). In this case, 20 tobaccos were burned, which corresponded to the amount of dirt after 120 minutes of operation.

Next, the results obtained by examining the deodorizing effect when the low-temperature curing type highly active oxide photocatalytic thin film according to the present invention is applied to a filtering mechanism provided in a block of an air flow path are summarized. Evaluated for removing ammonia as a representative odorant Was done. Inspection was carried out with the exact same configuration as in the above cigarette case. Instead of a cigarette smoke generator, a certain amount of ammonia gas is injected into the container to adjust the ammonia gas concentration inside the container to 25 (ppm), and then a low-temperature curing type highly active oxide photocatalytic thin film is formed. The ventilation fan to which the nonwoven fabric was attached was driven. First, the results of measuring the adsorption effect of ammonia gas by a vitreous oxide photocatalyst thin film as in the case of smoke collection are shown in Fig. 5. 0 (%) with respect to the above ammonia gas remaining, T i O _a and if S i 0 are marked ₂ of oxide photocatalyst thin glass membrane whose components after 1 more hours It can be seen that the sample was adsorbed and removed to a concentration of 50 (%) or less. The effect of collecting ammonia gas as well as smoke is recognized.

 After the ammonia gas was adsorbed until it was saturated, the incandescent lamp disposed inside the container was turned on so that the light hit the entire surface of the filter. The ammonia gas concentration in the container was measured over time, and the ammonia decomposition effect was evaluated. The results are shown in FIG. 26.

With the filter No. 12 containing no T i 0 ₂ , almost no change in density was observed. No. 11 and No. ₂ containing T i 〇 ₂ show that the ammonia gas concentration was reduced and decomposed with light irradiation, but No. 2 was L i N 0 according to the present invention. decomposition efficiency by ₃ that blended is improved greatly, the sample N o. as compared to 1 1, about three times the decomposition efficiency was obtained.

 The antifouling and deodorizing effects as described above are described as typical examples of applications to air purifiers and ventilation fans. However, it can be said that filters of various types of articles having the same mechanism exert the same effect. Not even.

Next, the results of evaluating the specific effects of the various articles shown in Examples 1 to 8 when used as exterior parts are summarized below. As a sample, Thermoplastic ABS resin for injection molding (Techno Polymer Co., Ltd .: Taflex 451, white colored product) used most frequently for exterior parts was used. A plate-shaped molded product of 5 cm × 5 cm was prepared, and this surface was subjected to corona discharge treatment. On this corona discharge treated surface, a low-temperature curing type highly active oxide photocatalytic thin film having the composition of Sample No. 86 shown in Table 6 in Example 12 was formed. And sample N o. 1 1 in Table 1 as a merely dispersed with T i 〇 ₂ particles in S I_〇 ₂ for comparison, S i 〇 free of T i 〇 ₂ fine particles, only As for the film No. 12, sample No. 12 was similarly evaluated by forming a thin film on the surface of the molded plate. First of all, we evaluated the fouling of cigarette smoke in the same way as above. After the ABS plate in the central portion 5 cm X 5 cm of the arrangement portion of the _r filters one of investigations in exactly the same configuration as the test of the above-mentioned non-woven filter one were fixed by burning 1 0 cigarettes The ventilation fan was driven for 120 minutes, and the white ABS plate was stained brown. The ABS plate was removed, light was irradiated under various conditions in the same manner as in the above, and the removal rate was evaluated by measuring the color difference before and after that. The results are shown in FIG.

As a result, almost the same results as in the case of the filter were obtained, but since the amount of dirt adhering to the filter was less than that of the case of the filter, the same decoloring effect was obtained with less than half the amount of light. The sample N o. 8 6 is Yes formulated as ATO also added ingredients, in addition to L i N 0 _3, sample N o. Compared 1 1, have been obtained yet slightly higher decomposition efficiency.

Next, the results of an evaluation of the antifouling effect when an article is used in an environment that uses a large amount of oil, such as a kitchen, and is contaminated with oils and fats are summarized. About 5 (μm) of salad oil was placed on a 5 cm X 5 cm glass plate on which a low-temperature curing type highly active oxide photocatalytic thin film having the composition of Sample No. 86 shown in Table 6 of Example 12 was formed. m) thinly, irradiate with the light of the ultraviolet lamp, oil weight Changes were measured over time. The results are shown in FIG. As a result, sample N o. 1 in 2 little weight change that does not contain T i 0 ₂ is not permitted. No. 11 and No. ₂ containing T i 0 ₂ are reduced in weight due to the decomposition and volatilization of oil with light irradiation, while N o 2 is L i N〇 ₃ according to the present invention. The decomposition efficiency was greatly improved by the addition of, and the decomposition efficiency was approximately twice as high as that of the sample No. 11.

 In forming the low-temperature curing type highly active oxide photocatalytic thin film according to the present invention, including the case of the series of examples described above, various methods can be used to improve the adhesion to the base material. . As a method using a primer, for example, it is effective to form a photocatalytic film after applying various coupling agents in advance.

 Examples include a silane coupling agent and an organic titanium-based compound.

 Examples of the silane coupling agent include vinyl tris (/ 9 methoxy methoxy) silane, vinyl triethoxy silane, vinyl thymethoxy silane, γ- (methacryloxypropyl) trimethoxy silane, β (3,4) Ethoxyl hexyl) Ethyl trimethoxy silane, γ-glycidoxypip pyridine methoxysilane, γ—Glycidoxypropyl methyljetoxirane, Ν— / 9 (aminoethyl) γ—Aminobutyl propyl trimethoxy Orchid, η-β (aminoethyl) γ-aminopropylmethyldimethoxysilane, γ-aminopropyltriethoxysilane, Ν-phenyl, γ-aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, etc. Can be used.

As the organic titanium-based compound, titanium ester, titanium acetate, and titanium chelate can be used. Tan, Tetra_n—Butoxytitanium, Tetrakis (2-Ethylhexyloxy) Titanium, G i—Propoxy'bis (acetylacetonato) Titanium, Titanium-I-Proboxoxyoctylene glycolet And titanium stearate are effective.

 In addition, a method of oxidizing the surface of an object using various surface modifying means to introduce a hydroxyl group, a carbonyl group, a carboxyl group, or the like, and firmly bonding the low-temperature-curable active oxide photocatalytic thin film according to the present invention is also effective. There is.

 Specifically, there are methods such as ultraviolet irradiation, electron beam irradiation, corona discharge treatment, and ozone atmosphere treatment. In the case of a relatively hydrophilic resin such as a polyamide resin or a polyester resin, a high adhesive force can be obtained without the above-mentioned pretreatment, but a polyolefin resin is not suitable for a crystalline resin. It is effective to perform these pre-processing.

 In the present invention, as described above, it is effective to mix Ag or Cu as an additional component for increasing the activity of the photocatalyst. These can simultaneously lower the electrical insulation of the film itself, obtain an antistatic effect, and also obtain an effect of suppressing the growth of microorganisms. It is known that 8.8 1 ^ 1 has high antibacterial properties, especially high bacterial resistance.When these Ag and Cu are used in combination, microorganisms can reproduce even when not exposed to light. It can be suppressed.

The scope of application to which the present invention is applied is not limited to the devices described above with reference to specific examples. In other words, the principle of the present invention is that the irradiation of an electromagnetic wave of a specific wavelength such as ultraviolet light can promote the polymerization of an inorganic polymer. As a result, even if the surface of a material having low heat resistance such as plastics is used, T a point to form a thin film of the inorganic photocatalysts for the i 0 ₂ as a main component, the lability of the photocatalyst mainly comprising this Ding i 0 ₂ addition of various components Taking advantage of the fact that it can be increased several times, from general-purpose thermoplastic plastics to thermosetting plastics or plastic coated surfaces, photocatalytic functions can be provided. Organic substances can be decomposed on the surface of unprecedented low heat-resistant materials with weak light intensity unlike before. In addition, by adding semiconductors and conductive fine particles that lower the surface resistance of the film, an antistatic effect on the surface of the coating film can be obtained, so that dirt due to static electricity is reduced.

 In the present invention, the light applied to the surface of the component on which the photocatalytic film is formed is the power of a fluorescent lamp, an incandescent lamp, a mercury lamp, sunlight, or the like; Absent. In other words, the effect can be obtained even if the light is transmitted through a component made of a transparent material such as a transparent plastic or glass. For example, panel 2 and frame 4 in the air purifier shown in Figs. 1 to 3 | Front cover 1 (;, panel 18; frame 29 in the ventilation fan in Fig. 4; Figs. 6 to 7 Upper cover 52, lid cover 53, grill cover に お け る) 4, suction port 65, exhaust ventilation section 76, and opening / closing lid 86, ring for the clothes dryer shown in FIG. Door filter 9 9, Door 1 2 1, Exhaust 8 1 2 8, Inlet 1 1 7, Dishwasher door in FIGS. 12 to 14 in the dish dryer of FIGS. 9 to 11 13 7 、 Exhaust port 15 2 、 Parts such as inner lid 71, intake port 1 74, exhaust port 1 75, etc. A part to be supported or placed around it. The force ',' made of a molded article of heat-transformed thermoplastic plastic. In addition, light is introduced into the interior, and it can develop curing such as decomposition of dirt, deodorization, and antibacterial activity.

Examples of transparent plastic include 、 Ρ Μ Λ, AS, PC, Λ BS, Particularly preferred are PVC and poly (4-methylpentene) -i (TPX). Further, these transparent plastic materials may be colored by mixing a pigment or a dye. However, when colored, yellow or red-green colored is not preferred because it absorbs short wavelength light and reduces the decomposition effect. A preferred color tone is blue or black (smoke).

 As a result of intensive studies, the present inventors clarified the relationship between the color of the transparent component and the decomposition efficiency of the photocatalyst. About the color of the transparent material discussed below

Specified by Hunter, Lab method as shown in JIS-II-8730. In other words, it is represented by an L value that represents the degree of achromatic black and white (lightness), an a value that represents the degree of red and green, and a b value that represents the degree of blue and yellow.

 The larger the L value, the better. With regard to coloring, transparent yellow parts absorb more short-wavelength light required for the decomposition reaction in the photocatalyst than other colors, and reduce textual efficiency. That is, in the Lab method, the smaller the b value, the better. Further, it is preferable that the value a is in a range from a fixed value to a fixed value.

Figure 29 shows the results of evaluating the relationship between these colors and the separation efficiency. Using a plate made of PMMA resin and colored with various pigments under the same conditions as the test in Fig. 24, five cigarettes were burned and attached to the filter. The decolorization and decomposition rate of the smoke stain was measured. The photocatalyst material used is the sample No. 2 in Table 1, and the PMMA resin is a 2.0 mm (mm) thick steel plate made by coloring Acrypet MD of Mitsubishi Rayon Co., Ltd. in each color. Used. This is a resin to which an ultraviolet absorber is added, and absorbs ultraviolet light near 360 (nm). The decomposition rate in Fig. 29 is 2 It shows the decolorization rate obtained from the change in color difference after irradiating a filter with 40-watt fluorescent light at a distance of (m) for 20 hours to a dirty filter. Each chromatographic plate of the sample was placed on a soiled filter, illuminated by passing through a fluorescent lamp, and the decomposition rate was calculated based on the degree of decolorization. In a standard actual smoking environment, if a decomposition rate of 40 (%) or more is obtained in the test under these conditions, the product can withstand continuous use without accumulation of smoke stains.

 From this test result, if the L value is +5 () or more, and the a value is -2 () or more and +20 or less, and the b value is +20 or less, 40 ( %) It was found that the following decomposition rate could be obtained.

 This test complies with JI S-Z-8730 (color difference display method). The measuring instrument used was Z 1001 DP manufactured by H-Hon Denshoku Kogyo Co., Ltd., in accordance with JI S-Z-8722. It is. As a measurement sample, the transmitted light of a 2.0 (mm) thick plate was measured.

 By installing the member having the above-described action according to the present invention in a portion where air flows in various devices, the attached organic matter can be effectively decomposed, so that an air flow is generated. Or, any device having a structure that filters the air flow can be applied to any product.

For example, it can be applied to oil heaters, gas fan heaters, electric heaters, and kotatsu as heating appliances. It can be similarly applied to air conditioners, dehumidifiers, and cool air fans. It can also be applied to heating and ultrasonic humidifiers. It can also be applied to heating utensils such as ovens and electromagnetic cookers. It can also be used for hair dryers. Further, it can also be used for devices having a cooling fan. That is, various kinds of computers such as a personal computer, a processor, and the like, displays of such computer equipment such as a cathode ray tube, and a copy machine. —Equipment using an electrophotographic mechanism, such as the one beam printer, the liquid crystal projector, the cooling fan attached to the equipment such as the slide projector, and the cooling wind using the cooling fan of these equipment. The low-temperature curing type highly active oxide photocatalyst thin film similar to the present invention can be provided also on the intake and exhaust ports used for ventilation of the air, and on a part of the filter attached to the intake and exhaust ports, and the same effect can be obtained. it can.

 (Example 16)

The procedure for manufacturing a filter with a photocatalyst having the composition shown in Table 1 and a Ti0 ₂ photocatalyst with the addition of Λ0 or Ru 0, -A Τ0 is shown below.

Τ〇 Τ〇 Solution was prepared as follows. And dissolve the S n C Mr. propanol Lumpur, was prepared 1 0 wt% S N_〇 _z solution. Also, to prepare 4 w L% S b ₂ 〇 ₅ made by dissolving Lee Sopurobokishia Nchimon propanol. Then these two solutions was equivalent mixing molar ratio of 1 to the S n () _7: 1 2-amino ethanol was added, followed by the addition of 4 moles of water with respect to S N_〇 _z , 5 wL% ATO solution was prepared. R u 0 ₂ - ATO solution the AT 0 solution by dissolving ruthenium § cetyl § cetearyl over Bok _{0.0 5 wt% R u 0 2} - was 5 wt% AT 0 solution.

Next, AT 0 and R u 0 ₂ - shows a AT_〇 added T i 0 ₂ powder method of producing.

AT 0 added and R u 0 ₂ - cases AT_〇 added also added to the solution to prepare a predetermined amount of T i 0 ₂ powder (anatase) above, after 2 hours agitated at 6 0 ° C, - Dan after the dried powder 2 5 0 ° C in an evaporating dish, 3 hours treatment with sense with 5 5 0 ° C, AT_〇 and R u 0 ₂ - the amount of different T i 〇 ₂ powder aT 0 Produced.

Next, add 0 and 1 1-10 ₂ _AT and add Ti i _z photocatalytic Ing liquid manufacturing procedure and AT 0 added and R u 0 ₂ - shows a AT_〇 added T 〖0 ₂ method for producing the photocatalyst filter scratch.

Hatcho 0-added and 1-reach ₂ — Λ Τ Ο-added Ti 0 ₂ Photocatalyst coating solution was prepared by adding a predetermined amount of the previously prepared powder into a 4 wt% S 1 _Oz sol and adding zirconia balls. The mixture was milled for 20 hours to prepare a coating solution. A filter made of acrylic fiber is immersed in the coating liquid prepared in this way, and the excess coating liquid is removed by air blowing. The composition of each photocatalyst was as shown in Table 10 below.

 The film forming method of the present invention can be manufactured at about 120 ° C., and can be applied to plastic materials other than Pyrex glass substrates. The ordinary Zosol gel method requires a temperature of about 40 CTC, which makes it difficult to apply it to plastic products, and requires more than 10 minutes to crystallize T i 0,. On the other hand, since the film formation method of the present invention can form a film at a low temperature, a variety of substrates can be used, and a photocatalyst can be formed on any surface. In addition, the processing can be performed in a short time of several minutes, and the production cost can be significantly reduced. As a photocatalyst filter, it can be applied to an air washer or the like. In this case, it is possible to remove malodorous components, bacteria, cigarette smoke, and the like that are present in the air. In particular, since ordinary filters are adsorbed and removed by an adsorbent, the effect is lost after saturation absorption and replacement is required. On the other hand, filters with photocatalysts absorb adsorbed odor components, bacteria, cigarette smoke, etc. Since it can be removed by photocatalysis, the number of filter replacements can be reduced.

A photocatalyst filter having the composition shown in Table 10 was attached to an air washer and operated in a room full of tobacco smoke, and the filter absorbed the tobacco smoke to discolor. Take out this discolored filter and irradiate it with fluorescent light The color change was measured to determine the decomposability of the adsorbed tobacco smoke. The decomposition rate was calculated from the amount of discoloration measured by a colorimeter.

Table 10 shows the decomposition rate 5 hours after irradiation with a fluorescent lamp. The decomposition rate of 添加 Λ 0 added catalyst is larger than that of Ο Τ Ο non-added catalyst. Further, Ru0 ₂ one AT 0 added is further summer decomposition rate is large, it can be seen that R U_〇 _z, AT O added pressure is effective.

AT 0 added photocatalyst, by A Ding 〇 and T i 0 ₂ contacts, by the i element of the AT 0 Ding i 〇 ₂ photocatalyst is utilized to improve the performance of the photocatalyst. If the electron affinity of the oxide semiconductor is smaller than that of T j, 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 T i () ₂ and the effect appears. Absent. On the other hand, when the electron affinity of the oxide semiconductor is smaller than that of T i, a Schottky barrier is not formed at the particle interface of the fine particles, and an ohmic junction is formed. _It is injected during ₂ and works effectively. In particular, ATO has an electron affinity that is slightly smaller than T i ί, and there is almost no difference between them. This 0 A T is a conductive oxide has high wire carrier rear density, a large amount of carriers AT 0 is injected into the T i 〇 _2, the activity of the photocatalyst is improved. In recent years, AT0 has attracted attention as a conductive oxide, and ultrafine particles (particle size of 200 angstrom or less, particularly preferably from 20 angstrom to 100 angstrom or less are commercially available) are commercially available. T i 〇 ₂ photocatalyst by adding ultrafine particles AT O easier ATO additive pressurized T i 0 ₂ photocatalyst can be manufactured. However by using such ultrafine particles ΛΤ Ο, 5 w L% AT_〇 added T i 0 ₂ to prepare a photocatalyst with filter was subjected to the same test, the decomposition rate after 5 hours was 35% Less than 42% of the photocatalyst of the present invention. Ultra fine particles Ti 0 ₂ with ATO addition ATO particles in contact with the fine particles also exist in the force ^ S i 0, and there are particles in the force, which is not efficient. Meanwhile, since the ¾ bright field is to be fired by adding roughness or dimethyl AT 0 solution T i 〇 ₂ particles, AT 0 and T i 〇 ₂ large contact surface product is particles, Li joined state by the calcined And the electron transfer between different kinds of semiconductors becomes smooth. Further a p-type conductor R U_〇 _z is, T i 0 ₂ is an _n-type semiconductor, to attract Hall of ¾ child and holes lambda TO has generated absorbs light, the recombination of electrons and holes Can be suppressed. Therefore, 12 atoms and holes generated by absorbing light can be effectively used for the catalytic reaction, and the decomposition rate can be further improved. Due to the above effects, the decomposition performance of the photocatalyst was improved in the present invention.

 (Example 1)

 The performance of the photocatalyst can be further improved by adding not only ATO but also other additives.

Table 11 shows the composition of the catalyst obtained by adding L1, Na, and Mg to the photocatalyst prepared in Example 16 and the results of the cigarette smoke decomposition test. The results show that the decomposition rate is improved regardless of whether Li, Na, or Mg is added, and that a higher performance filter can be manufactured. L i, N a, and M g have an ion radius close to the ion radius of T i, and easily penetrate T i defects on the surface of T i O ₂ to increase the stability of the crystal. Since i, Na, and Mg have strong ionicity, they can easily attract electrons, absorb light, separate electrons and holes, and increase the reaction efficiency.

 (Example 18)

Comparison of the decomposition characteristics of acetate aldehyde, urine, ammonia, and Escherichia coli using the fluorescent lamp, sunlight, incandescent lamp, and mercury lamp for the Li-added photocatalyst and the Li-free photocatalyst prepared in Example 16 did. As a result, L i one R u〇 _z Regardless of the type of lamp used, the decomposition catalyst for acetoaldehyde, urea, ammonia, and Escherichia coli was found to be three to five times as effective as the non-added photocatalyst. Thus L i one R U_〇 ₂ ATO additive catalyst was divide that sufficient effect can be obtained in lamp used under life i boundary. Similar effects were obtained when ^^ and Mg were added except for Si.

 As described above, it is possible to form a photocatalyst on any material surface by a simple method and low-temperature film formation, to provide a highly active photocatalyst that is effective in the living environment, and to use a material with excellent anti- and antifouling effects. Therefore, the number of parts exchange and the number of cleanings of various applied products can be reduced.

 Table 10

SiO, (WL%) TiO, (wt%) AT0 (wt%) RuO z (wt%) 5 hours after the decomposition rate (%)

 1 0 9 0 0 3 0

 1 0 8 8 2 3 6

 1 0 8 5 5 4 2

 1 0 8 0 1 0 3 8

 1 0 7 0 2 0 3 1

 1 0 8 7.9 8 2 0.02 4 8

 1 0 84.9 5 5 0.05 4 9

 1 0 7 9.9 1 0 0.1 4 3

 1 0 6 9.8 20 0.2 3 8

1 0 3 7.5 50 0.5 2 8 SS / 6 iz Australia L

轹

(Example 19)

The procedure for fabricating the filter with an RS-added T i 0 _? Photocatalyst shown in Table 12 is shown below.

 The RS0 solution was prepared as follows. Ruthenium acetyl acetate was dissolved in propanol to prepare a 2 moi% Ru 0, solution. Also,

5 r (N 0) ₂ was then dissolved in propanol to prepare a 2 mol% S r 0 solution of these two solutions was equivalent mixing molar ratio of 1 with respect to R u O _z:

1 2-amino Noetano one Honoré added followed by the addition of 4 moles of water with respect to R u 0 _2, to produce a 1 moi% RS 0 solution.

Next, a 1 0 added T1s 〇 ₂ powder method of producing. The previously prepared solution

After stirring at 60 ° C. for 1 hour, the powder was once dried at 250 ° C. in an evaporating dish to obtain a powder, and then treated at 850 ° C. for 5 hours to prepare an RS 0 powder.

Next, 3_Rei added Ding 〖〇 shows photocatalytic Koti packaging liquid manufacturing procedure and RS 0 added T i 0 ₂ method for producing the photocatalyst filter.

1 ^ 3_Rei added Ding 1 〇 ₂ photocatalyst Koti ring solution both RS previously prepared 0 powder and Ding i 〇 ₂ 4 (ANATA one zero) powder w L% S i 0, a predetermined amount added in the sol Then, milling was performed for 20 hours using zirconia balls to prepare a coating solution. A filter made of acrylic fiber is immersed in the coating solution prepared in this way, and the excess coating solution is removed by air blowing, and treated at 120 ° C for 5 minutes to remove the filter with a photocatalyst. Was prepared. The composition of each photocatalyst is as shown in Table 12.

The film formation method of the present invention can be manufactured at about 120 ° C., and can be applied to plastic materials other than Pyrex glass substrates. The ordinary sol-gel method required a temperature of about 400 ° C, which made it difficult to apply to plastic products.It took more than 10 minutes to crystallize T i 0, It is. On the other hand, according to the manufacturing method of the present invention, since the film formation is a “J-function” at a low temperature, the usable substrate is abundant, and the photocatalyst can be formed on any surface. As a photocatalyst filter, it can be applied to an air washer, etc. In this case, removal of odorous components, bacteria, tobacco smoke, etc. existing in the air. In particular, a filter with a photocatalyst loses its effect after saturated adsorption and needs to be replaced, because a normal filter is an adsorbent for removing and absorbing water. Fine ffl, tobacco smoke, etc. can be removed by the photocatalyst Sakugawa, so the number of filter replacements can be reduced.If a photocatalyst filter with the composition shown in Table 12 is installed in an air washing machine, this smoke will be removed. Operates in a full room Tobacco smoke was adsorbed to the filter 1 and the color was changed.The discolored filter was taken out, the color change was measured by irradiating a fluorescent lamp, and the decomposability of the adsorbed tobacco smoke was examined. The rate was calculated from the amount of discoloration measured by a colorimeter.

 Table 12 shows the decomposition rate 5 hours after irradiation with a fluorescent lamp. The decomposition rate of the R S0 -added catalyst was higher than that of the R S0 -free catalyst, indicating that the addition of R S0 was effective.

RSO added photocatalyst, by 1¾ 3 0 and T1s 0 ₂ contacts, by a hole in the RSC) is T i 0 ₂ photocatalyst utilized, you increase the performance of the photocatalyst. The oxidation activity of the photocatalyst is due to the oxidation-reduction of electrons and holes generated by light absorption. In particular, the generated holes generate hydroxyl radicals and cause a strong oxidizing action. RS 0 is a p-type semiconductor and has a large number of holes. By RSO and T i 0 ₂ contacts, holes are injected into the Ding i 〇 _2, oxidizing the organic substances in T i 〇 ₂ surface, the activity of the photocatalyst is improved. The performance of the photocatalyst can be further improved not only by adding RS〇 but also by adding other additives.

Table 13 shows the composition of the photocatalyst prepared in Example 19 to which, Na and Mg were added, and the results of the cigarette smoke decomposition test. The results show that the decomposition rate is improved regardless of whether Li, Na, or Mg is added, and that a higher-performance filter can be manufactured. L i, N a, and M g have an ion radius close to the ion radius of T 1 and easily enter T i 0, the T i defect in table fii, and increase the stability of the product. Also, i, _^λ:; M g may easily attract electrons for strong ionic, electrons and holes generated by absorption of light is separated to increase the anti応効rate.

 Table 12

S i 0 _z (wt%) T i 0 ₂ (wt%) RS 0 (wt%) Decomposition rate (%) after 5 hours

 1 0 9 0 0 3 0

 1 0 8 8 2 3 8

 1 0 8 5 5 4 8

 1 0 8 0 1 0 4 6

 1 0 7 0 2 0 3 5

1 0 4 0 5 0 2 7 ―

 挲 ε I ^

 8 L

f ££ 0IL6d £ / lDd OAS. (Example 20)

Comparison of the decomposition characteristics of acetate aldehyde, urine, ammonia, and Escherichia coli using the fluorescent lamp, sunlight, incandescent lamp, and mercury lamp for the Li-added photocatalyst and the Li-free photocatalyst prepared in Example 19 did. Consequently L i - be used Ru_〇 ₂ one RS_〇 added photocatalyst any lamp, § Se Toarudehi de, urea, ammonia, decomposition characteristics of E. coli, it is 3-5 times the effect of the additive-free photocatalyst I understood that. Thus, it has been found that the Li-Ru0-RSO-added catalyst can provide a sufficient effect for a lamp used in a living environment. Similar effects were obtained when & and Mg other than 1 were added.

 (Example 21)

In the method of mixing the RS_〇 powder as in Example 1 9 T i 0 ₂ powder, the force also RS 0 particles in contact with T i 〇 ₂ particles present; uses S i 0 ₂ as Vine da one since also the particles present in S i 0 _2, efficient at an unsupported. On the other hand, if the RS 0 solution can be added to the T i 0 ₂ fine particles beforehand and fired, the contact area between the RS 0 and the T i 〇 ₂ particles will be large, the bonding state will be good by firing, and the electrons between heterogeneous semiconductors will be improved. Movement becomes smooth. However, the production of RS〇 requires a temperature of 700-850 ° C, and at temperatures below this, RS〇 does not crystallize and does not function as a p-type semiconductor. For T i 〇 _2, the crystal becomes rutile at 6 0 0 ° C or higher. It is the anatase type that expresses a sufficient function as a photocatalyst. With the rutile type, the performance of the photocatalyst drops rapidly. Therefore, if the high temperature processing T i 0 ₂ after RSO addition, RS 0 is the force to be a p-type semiconductor, T i 0 ₂ is a phase transition to a rutile type, lose the function as a photocatalyst. Use Therefore, as a photocatalyst T i 0 ₂ similar function can be expected ST 0 a (S r T i 〇 ₃₎ Therefore, RSO-added ST photocatalyst becomes effective. STO has a band structure similar to that of TOι Ο _ζ . In addition, the manufacturing method is to crystallize by processing at a high temperature of 700 to 85 CTC. Furthermore, both RSO and STO are perovskites, and their crystal lattice constants are almost the same because Sr-0 is common. Therefore, the manufacturing conditions are very close to RS0, and the bonding state can be improved. The following shows the method for preparing RS-doped S-Cho powder.

ST0 powder was produced as follows. The Lee Seo propoxy titanium Natick Bok dissolved in pro Pano Ichiru to prepare a 2 mol% T i ◦ ₂ solution, followed by Ding i (molar ratio relative to input L: 1 of S r (N_〇 _{3) 2} was added , T i 0 ₂ molar ratio to 1: 1 2-amino Noetano one Sole added followed by the addition of 4 moles of water with respect to T 1 〇 _2, to prepare a 1 mol% ST 0 solution .

 Next, this solution was stirred at 60 ° C for 2 hours, then dried at 250 ° C in an evaporating dish to form a powder, and then treated at 850 ° C for 5 hours to prepare an STO powder. . The method for preparing the R S0 -added ST0 powder is as follows.

 A predetermined amount of ST0 powder was added to the RS0 solution prepared in Example 19, and the mixture was stirred at 60 for 2 hours, then dried at 250 "C once in an evaporating dish to obtain a powder. For 5 hours to produce RS〇-added ST〇 powder

 Next, a procedure for preparing an R S〇 -added STO photocatalytic coating solution and a method for preparing an R S〇 -added STO photocatalyst filter will be described.

S_〇 added STO photocatalyst co one tee packaging solution, adding a predetermined amount of RS_〇 added ST_〇 powder prepared above in 4 w L% S i 〇 ₂ sol and 2 0 hours milling with Jirukoniabo Le Thus, a coating solution was prepared. A filter made of acrylic fiber is immersed in the coating solution prepared in this way, and the excess coating solution is removed by air blowing, and the temperature is set at 120 ° C for 5 minutes. After the treatment, a filter with a photocatalyst was produced. The prepared RS〇-added ST〇 photocatalyst is composed of ST〇 powder that has been sintered and grown at high temperature, and thus has a slightly poorer adhesion to the acrylic fiber than the TiO-based one, but looks beautiful. The composition of each photocatalyst is as shown in Table 14.

 A photocatalyst filter having the composition shown in Table 14 was attached to an air washer and operated in a room full of tobacco smoke, and the filter absorbed the tobacco smoke and discolored. The discolored filter was taken out and irradiated with a fluorescent light to measure the color change, and the decomposability of the adsorbed tobacco smoke was examined. The decomposition rate was calculated from the amount of discoloration measured with a colorimeter.

Table 14 shows the decomposition rate 5 hours after irradiation with a fluorescent lamp. RS 0 added ST0 catalyst decomposition rate than the RSO added T i 〇 ₂ catalysts are greatly summer, it can be seen that RS0 added S Ding 0 is valid.

 The performance of the photocatalyst can be further improved not only by adding R S0 but also by adding other additives.

 Table 14 shows the composition of the catalyst prepared by adding Na and Mg to the prepared R S0 -added STO photocatalyst and the results of the cigarette smoke decomposition test. The results show that the decomposition rate is improved when any of Li, Na and Mg is added, and a more efficient filter can be produced. Li, Na, and Mg have ionic radii close to the ionic radius of Ti, and easily penetrate Ti defects on the ST0 surface to increase the stability of the crystal. Since Li, Na and Mg have strong ionicity, they can easily attract electrons and absorb light to separate generated electrons and holes, thereby increasing the reaction efficiency.

The STO photocatalyst filter with the addition of RS 0 has slightly poor adhesion as described above. Therefore, by mixing a good T i 〇 ₂ system adhesion were prepared Koti ring photocatalytic filter foremost accession Lil fibers. Composition and tobacco smoke The degradability is 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, the p-type semiconductor RS 0 injects holes into the STO, or ST〇 absorbs light and attracts the holes out of the holes formed by the absorption of light. Coupling can be suppressed. Therefore, electrons and holes generated by absorbing light can be effectively used for the catalytic reaction, and the decomposition rate can be further improved. According to the effects described above, the decomposition performance of the photocatalyst could be improved in the present invention.

In this way, it is possible to form a photocatalyst on any material surface at a low temperature with a simple method, to provide a highly active photocatalyst that is effective in the living environment, and to have excellent antibacterial and antifouling effects. Therefore, the number of parts replacement and cleaning of various applied products can be reduced.

_{Si0 2 (wt%) STO (} wt%) RSO (wt%) Li (N0 3) (wt%) Na (N0 3) (wt%) ¾ (N0 3) 2 (wt%) 5 hours after the decomposition rate ( %)

1 0 85 0 5 43

 1 0 80 5 5 58

 1 0 7 5 1 0 5 68

 1 0 65 20 5 66

 1 0 35 50 5 4 δ

 1 0 85 0 5 40 m

1 0 80 5 o 56

 1 0 7 5 1 0 δ 6 δ

 1 0 65 20 5 63

 1 0 35 50 5 42

 1 0 85 0 O 40

 1 0 80 5 5 56

 1 0 75 1 0 5 64

 1 0 65 20 5 6 2

1 0 35 50 o 4 1

o o o O O o O O o o O O O O o o

CO-00 00 CO 00 00 CO 00 00 an o O cn cn o

CO i cn

 o cn o O O o CJi O O cn O cn cn n

 p (y) "(/) \ o ((/ soiwt Tio000t RSSTw LiN o¾o

Ol Oi Oi D CO cn CO

 CO CD 00 00 o 00 CO o

^ '2 i m

8

££ 0IL6d £ ILDd (Example 22)

S i 0 were produced T i 〇 ₂ particles and Zeorai Bok solution was dispersed with (aluminum silicate) min ₂ sol. The solution to form a T i 0 ₂ film on § s Lil fiber was used to prepare a photocatalyst with filter. The procedure is described below.

First, the method for preparing the S i [] ₂ sol will be described [nj]. Dissolve 5 g of tetraethoxysilane in a mixed solution of 丄 100 ml of water-ethanol-propanol (3:27:70) at 540 oC for 5 o'clock. did. The obtained solution was left at room temperature for 2 weeks to obtain a Si ₂ sol.

Next, T i 0 ₂ particles and Zeorai method of producing soluble solution obtained by dispersing Bok described S i 0 ₂ sol. Was added to the S丄0 ₂ sol prepared above the T i 0 ₂ fine particles as _{T i 0 2 / S i 0} 2 = 9 by weight, a predetermined amount of ZSM - 5 (Synthesis Zeorai DOO, hereinafter the same.) Was added. The solid content was adjusted to 4 wt.% And adjusted by adding necessary amount of water. Then 5 mm was treated with 2 4 hr baud mill to disperse the T i 0 ₂ particles and ZSM 5 in S i 0 Bull with Jirukonia balls φ, S i 0, T i in the sol A solution in which O ₂ fine particles and ZSM-5 were dispersed was prepared.

The § click Lil fibers were produced in the ZSM 5 added T i 0 ₂ fine particle dispersion S i 0 ₂ sol co one Bok to, T i O was treated 5 min at 1 2 0 ° C in S i 0 ₂ film _z particulates and Z SM- 5 was formed T i O _z dispersion S i 0 ₂ film filter one who co Bok the dispersed. The composition of the produced photocatalyst was S 0 ₂ = 8 wt%, T 0 ₂ = 72 wt%, and Z SM-5 = 20 wt%.

As a photocatalytic filter, it can be applied to an air washer or the like. In this case, it is possible to remove malodorous components, bacteria, cigarette smoke, and the like that are present in the air. In particular, saturated filters are used because ordinary filters use an adsorbent to remove them. The effect is lost after wearing, and the filter needs to be replaced.On the other hand, filters with photocatalysts can remove adsorbed odor components, bacteria, tobacco smoke, etc. by photocatalysis, so the number of filter replacements should be reduced. Can be. The photocatalyst filter prepared above was sealed in a glass container, and gas aldehyde, which is a gas component, was injected at 400 ppm, and the inside of the container was circulated with a fan to irradiate a fluorescent lamp to examine the photocatalytic performance. The gas was analyzed by connecting an infrared detector and circulating the gas, and the gas was always measured. The measurement results are shown in FIG. In the absence of zeolite, the acetate aldehyde starts at the beginning; S decreases sharply and then gradually decreases. When the gas is injected, it returns to the initial value, and when this operation is repeated, Adsorption and decomposition reactions reach equilibrium. This indicates that the acetate was first adsorbed on T i し₂ and rapidly decreased, and then gradually decomposed by the action of the photocatalyst. Next, when the gas is injected, the acetate aldehyde is adsorbed on the vacant adsorption site decomposed by the photocatalyst, rapidly decreasing, and then gradually decomposed. On the other hand, when zeolite is added, the guided gas almost disappears from the atmosphere due to the effect of zeolite as an adsorbent. Next, the adsorbed gas is gradually decomposed by the action of a photocatalyst. Therefore, by adding zeolite and taking into account the adsorption effect, the gas in the air can be quickly adsorbed and removed, and then the photocatalyst is decomposed and the air can always be kept clean.

 (Example 23)

In order to investigate the effect of the Ziolite Si: A1 ratio, three types of Si: A1 = 80:20, 50:20, and 30:20 were added and the difference was examined. Was. As shown in Fig. 31, the results showed that the larger the S i ratio, the better the performance. Zeolite with a large Si ratio has a large surface area, so it not only has a large amount of adsorption, but also has a large amount of adsorbed water and provides surface adsorbed water necessary for photocatalysts This is because it can be done.

 (Example 24)

Next, we examined the performance when Cu, Ag, Li, Na, and Mg ions were introduced into the zeolite by ion exchange. As shown in Fig. 32, the results show that Cu and Ag ion exchange did not change much before and after ion exchange (compared with Fig. 30). On the other hand, the performance of the Li, Na, Mg ion exchange was improved. This is because strongly ionic elements such as Na, Li, and Mg generate a positively charged space in the zeolite, and Ti 0 ₂ absorbs the light to generate electrons. This is because they attract, separate electrons and holes, suppress recombination, and increase the reaction efficiency.

 For the addition of Cu, Λg ion exchange zeolite, an antibacterial test was performed using Owaki 菡. The results are shown in FIG. Escherichia coli proliferates during periods of no zeolites or light exposure. When zeolite was added, the E. coli sterilization rate during light irradiation was similar, but the number of E. coli decreased slightly without light irradiation. The Cu, Ag ion exchange zeolite improved the sterilization rate of Escherichia coli during light irradiation, and the sterilization rate during non-light irradiation was much better than the others.

 As described above, the addition of zeolite improves the antibacterial properties of the dark reaction, and if Cu and Ag ions are exchanged, the performance is improved both during light irradiation and during the dark reaction. The agent could be prepared.

 In this way, photocatalysts can be formed on any material surface, providing highly active photocatalysts that are effective in the living environment, and efficiently removing gas components in the air by adsorption effects and decomposition reactions.

 (Example 25)

S i 0 ₂ T in the sol i 0 ₂ fine particles and the solution created in which a blue pigment is dispersed Made. Using this solution, a Ti film was formed on the acrylic fiber to prepare a filter with a photocatalyst. The procedure was as follows.

First, the theory ¾ for the S i 〇 ₂ sol of production method. 5 g of tetraethoxysilane was dissolved in 100 m 2 of a mixed solution of water, ethanol and propanol (3:27:70) and stirred at 40 ° C. for about 5 hours. The obtained solution was allowed to stand at room temperature for 2 weeks to obtain a SiO ₂ sol.

Then S i 0, it will be described T i 0 ₂ particles and method of producing a solution containing a dispersed靑色pigment in the sol. Was added and in S i 〇 sol previously prepared a T i 〇 ₂ fine particles in heavy i¾ ratio Ding _{i O z / S ί Ο ζ} = 9, predetermined逛of CU monounsaturated Taroshianin (blue pigment) Was added. The concentration of form components was 4 w 1.% and adjusted by adding necessary amount of water. Then 5 ^ to have JTJ the Jirukoniaboru was treated with 2 4 hr baud mill to disperse the T i O _z particles to S i 0 ₂ sol, S i 0 ₂ T i 0 in the sol, dispersing fine particles A solution was prepared.

T i () fine particle dispersion prepared on the acrylic fiber is coated. The S i O _z sol is coated, and the mixture is treated with 12 (TC for 5 minutes to disperse the Ti 〇 _z fine particles in the S i O ₂ film. A filter 1 coated with a Ti _iz dispersion Sio ₂ film was formed, and the composition of the produced photocatalyst is shown in Table 16.

 As a photocatalyst filter, it can be applied to an air washer or the like. In this case, it is possible to remove malodorous components, bacteria, cigarette smoke, and the like that are present in the air. In particular, ordinary filters are absorbed and removed by an adsorbent, so the effect is lost after saturated adsorption and the filter needs to be replaced. On the other hand, a filter with a photocatalyst removes adsorbed malodor components, bacteria, cigarette smoke, etc. Since it can be removed by photocatalysis, the number of filter replacements can be reduced.

A photocatalyst filter with the composition shown in Table 16 was attached to the air washer, It was operated in a room full of cigarette smoke, and the filter absorbed the cigarette smoke and discolored it. The discolored filter was taken out and irradiated with fluorescent light to measure the change in color, and the decomposability of the adsorbed tobacco smoke was examined. The decomposition rate was calculated from the amount of discoloration measured by a colorimeter.

 Fig. 34 shows the results of the decomposition test. The results showed that the decomposition performance was improved by adding the blue pigment.

Table 16 shows the results of evaluating the film strength and light resistance other than the decomposition performance _: each evaluation was performed as follows.

 In the strength test, the produced filter was repeatedly bent and pulled to evaluate whether the powder fell. If the powder did not fall due to bending and pulling, repeated bending and pulling were performed, and then air was blown at ZmZsec to check whether the powder peeled off. The evaluation was rated as X when peeled by bending or pulling, rated as △ when peeled by blowing air when not peeled, and rated as 〇 when peeled in any case.

 The light fastness was measured by irradiating the fabricated filter with a low-pressure mercury lamp (254 nm, 3 mW cm ') and measuring the time when the change in color reached 20% or more.

 The evaluation results showed that the addition of a pigment reduced the film strength, and that the film easily peeled off at 20 wt% or more. It can be easily peeled off, but if there is no bending or pulling operation, it will not be peeled off.

As for the light fastness, it was found that the larger the amount of the pigment added, the greater the deterioration. Although pigments are excellent in light resistance, they contain organic groups and are gradually decomposed by photocatalysts. However, since this evaluation condition is quite accelerated, the condition usually used is the light of a fluorescent lamp, and the 35 hours in Table 16 is equivalent to 3 to 5 years under the fluorescent lamp. As described above, the pigment-added catalyst is inferior in film strength and light resistance, but since the filter catalyst is colored, the performance of the filter can be seen, so that it is easy to judge when to replace the filter. .

 To increase the adhesion strength to the filter, addition of an organic resin is also effective. Table 17 shows the composition and various evaluation results when the acrylic resin was added to the solution prepared above. The film strength was dramatically improved by the addition of resin. In addition, there was no change in luminescence, but the performance was satisfactory under fluorescent lighting, and the decomposability of tobacco was good.

 As described above, it was found that an excellent filter can be manufactured by adding a pigment and, if necessary, a resin.

The first 6 Table pigment _{(%) T i 0 2 (} wt%) S i 0 2 (t.%) Film strength lightfastness

 0 9 0 1 0 な し No change

1 0 8 1 9 Δ5 0

2 0 7 2 8 X 4 0

5 0 4 5 5 X 3 5

Resin (m%) Pigment _{(wt%) Ti0 2 (wt} %) Si0 2 (wt%) film strength lightfastness washing test 5 hours after the decomposition rate (%)

0 30 6 3 7 X 3 5 1 4 3

 皲

1 0 27 5 6.7 6.3 Δ3 5 5 4 5

 2 0 24 5 0.4 5.6 〇 3 5 1 0 or more 4 2

5 0 1 5 3 1.5 3.5 〇 35 1 0 or more 3 9

(Example 26)

 The degradation characteristics of acetate aldehyde, urine, ammonia, and Escherichia coli were compared between the pigment-added photocatalyst and the pigment-free photocatalyst prepared in Example 25 using a fluorescent lamp, sunlight, a heating lamp, and a mercury lamp. . As a result, it was found that the decomposition characteristics of acetate, urea, ammonia, and Escherichia coli were 3 to 5 times as effective as those of the pigment-free photocatalyst, regardless of the lamp used. As described above, it was found that the pigment-added catalyst was able to obtain a sufficient effect not only with an ultraviolet lamp, but also with a lamp used in a living environment. In addition, the same results were obtained when red, green, green, etc. other than blue were added.

 As described above, a photocatalyst can be formed on any material surface, a highly active photocatalyst effective in a living environment can be provided, and the photocatalyst can be easily replaced.

 (Example 27)

To prepare a solution prepared by adding T i 0 ₂ particles and accession Lil resin S i 0 ₂ sol屮. The solution T i 0 ₂ film is formed on the Accession lil fiber was used to prepare a photocatalyst with filter. The procedure is shown below.

First, a description will be given S i 0 ₂ sol preparation method. 5 g of tetraethoxysilane was dissolved in 100 ml of a mixed solution of water, ethanol and propanol (3:27:70) and stirred at 40 "C for about 5 hours. The solution was left at room temperature for 2 weeks to obtain S i 0, sol.

Next, T i 0 ₂ particles and solvent solution method of producing the addition of § click lil resin described S i 0 ₂ sol. S i 0 ₂ T i 〇 in the sol Ding i 0 ₂ particles in a weight ratio previously prepared, was added as S i 〇 ₂ = 9, was added a predetermined amount of § click Li Le resin. The solid content was 4% w / 1%, and the required amount of water was added. Adjusted. Then S i 〇 using Jirukoniaboru of 5 inm, was treated with 2 4 hr ball mill to disperse the T i 〇 ₂ fine particles in sol屮to disperse T i 0 ₂ particles in S i 0 ₂ sol A solution was prepared.

The T i 0 ₂ fine particle dispersion S i 〇 ₂ sol prepared in accession Lil fiber cord one Bok to, T 〖0 ₂ particles are dispersed in 1 2 0 ° S i 0 ₂ film was treated for 5 minutes with C A filter was formed by coating the obtained T i 〇 _ζ dispersed S i O ₂ film. Table 18 shows the composition of the prepared photocatalyst.

 As a photocatalyst filter, it can be applied to an air washer or the like. In this case, it is possible to remove malodorous components, bacteria, cigarette smoke, etc., which are present in the air blister. In particular, since ordinary filters are absorbed and removed by an adsorbent, the effect is lost after saturated adsorption and must be replaced. On the other hand, filters with photocatalysts absorb adsorbed odor components, bacteria, cigarette smoke, etc. Can be removed by photocatalysis, so that the number of filter replacements can be reduced.

 A photocatalyst filter having the composition shown in Table 18 was attached to an air purifier and operated in a room full of tobacco smoke, and the filter absorbed the tobacco smoke and discolored. The discolored filter was taken out and irradiated with fluorescent light to measure the change in color, and the decomposability of the adsorbed tobacco smoke was examined. The decomposition rate was calculated from the amount of discoloration measured by a colorimeter.

Figure 35 shows the results of the decomposition test. When using S i 0 ₂ a (Circa) as a by-Nda, performance as a photocatalyst beat low when the amount of the binder increases. On the other hand, in the case of the acrylic resin, it was found that the performance of the photocatalyst hardly changed even if the amount of the binder was large.

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

In the strength test, bending and pulling of the prepared filter were repeated. It was evaluated whether the powder fell. If the powder did not fall off due to bending and pulling, repeated bending and pulling were performed, and it was checked whether the powder was peeled off by spraying with 2 mZ sec. The evaluation was evaluated as X when peeled by bending or pulling, rated as △ when peeled by blowing air when not peeled, and rated as 〇 when peeled in any case.

The light fastness was measured by irradiating the fabricated filter with a low-pressure mercury lamp (254 nm, 10 mW / cm ² ) and examining the time when the amount of color change was 20% or more. In the water washing test, the filter was repeatedly washed with water, and the number of times until the catalyst was peeled was evaluated.

 The evaluation results showed that the addition of an acrylic resin improved the film strength, and that the film did not peel off at 5 wt% or more. Regarding the light resistance, it was found that the larger the amount of the acrylic resin added, the greater the deterioration. The acrylic resin contains an organic group and is gradually decomposed by a photocatalyst. However, since this evaluation condition is quite accelerating, the condition usually used is the light of a fluorescent lamp, and 5 hours in Table 18 is equivalent to 3 to 5 years with a fluorescent lamp.

 In the water washing test, it was found that if the resin addition amount was 10 wt% or less h, the resin was sufficiently washed and used repeatedly.

 As described above, sufficient strength could be obtained by adding the organic resin. In addition, the performance of the catalyst was the same as when no resin was added, and a washable photocatalyst filter was manufactured.

As described above, the catalyst containing an acrylic resin has poor light resistance, but has excellent film strength, and can wash the filter catalyst. Until now, photocatalysts had only been effective for self-cleaning of organic and other contaminants and had no effect on inorganic contaminants such as dust.However, cleaning can remove inorganic contaminants and extend the life of the filter. Can be longer.

 (Example 28)

 The degradation characteristics of acetate aldehyde, urea, ammonia, and Escherichia coli were measured for the photocatalyst with acryl resin and the photocatalyst without acryl resin, prepared in Example 27, using a fluorescent lamp, sunlight, a white lamp, and a mercury lamp. Compared. As a result, it was found that the decomposition characteristics of acetate, urea, ammonia, and Escherichia coli were as effective as those of the photocatalyst without acrylic resin, regardless of the lamp used. Thus, it was found that the acrylic resin-added catalyst can provide a sufficient effect not only with an ultraviolet lamp but also with a lamp used in a living environment.

 (Example 29)

 In recent years, silanol-modified acrylic resins in which silanol groups have been introduced into the side chains of acrylic resins have been developed for acryl resins in order to improve their chemical properties. To the solution prepared in Example 27 from this silanol-modified acrylic resin, an acrylic resin having a different amount of silanol group introduced was added to prepare a filter. Fig. 36 shows the evaluation results of the filter for decomposition of cigarette smoke and light resistance. The decomposition characteristics of tobacco smoke did not change significantly with the amount of silanol groups introduced (the amount of silanol introduced in the figure), indicating that the performance did not deteriorate. On the other hand, it was found that the light resistance can be improved by increasing the amount of introduced silanol groups.

 From the above, it was found that by using a silanol-modified acrylic resin, light resistance was improved and an excellent photocatalytic filter could be produced.

 (Example 30)

When an organic resin is used, unlike a ceramic material such as silica, it can be cured without applying heat. For example, use a room temperature curing resin This can be achieved. However, room-temperature curing systems take about 24 hours, except for instant adhesives. Instant adhesives are hardened in a short time, and are gradually decomposed by photocatalysts. UV-curable resins can be cured in a short time and have excellent light resistance. The UV curing system cures with ultraviolet rays, and gradually polymerizes and cures with ultraviolet rays emitted from a fluorescent lamp. However, it is also true that it is gradually decomposed by the photocatalyst. Therefore, by appropriately combining photocuring and photodecomposition, light resistance can be improved as a result.

A solution was prepared by adding a UV curable resin to Ti 0 _? Fine particles. This solution was used to form a T i 0 ₂ film on Atta Lil fibers, to produce a photocatalyst with filter. The procedure is shown below.

Add a specified amount of Tio, fine particles and any of S1, i1, Ti-based coupling agents in toluene, stir at 40 ° C for 2 hours, and then add a specified amount to UV curable resin did. The solid concentration was 4 wt%, and the required amount was adjusted by adding toluene. Then treated with 2 4 hr ball mill to disperse the Ding i 0 ₂ particles in solution using a Jirukoniaboru of 5 mm 0, to prepare a solution prepared by dispersing T 1 0 ₂ particles in a UV curable 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 prepared photocatalyst is shown in Table 19.

 Table 18

TiO, (wt¾) SiO _? (Wt%) film Light resistance Washed fiber 5 hours later ^ ^ (%)

0 90 1 0 Δ No change 1 30

2 88.2 9.8 Δ No change 1 32

5 85.5 9.5 〇 5 h 5 3 1

1 0 8 1 9 〇 3h 1 0 33

20 72 8 〇 2 h 1 0 or more 3 1

50 4 5 〇 2 h 1 0 or more 28 Table 19

Fig. 37 shows the results of examining the decomposition characteristics (decomposition rate after 5 hours) of tobacco smoke with respect to the addition of the coupling agent: ¾. It can be seen that the addition of the coupling agent improves the photocatalytic properties. With the IJV cured resin alone, the resin completely covers the Ti 0 _? _ Particle surface and loses catalytic properties. The addition of couplings in g agent, it is possible to increase the exposed portion of the T i 〇 ₇ surface. In addition, the photocatalyst decomposes the surface adsorbed water to generate radicals. However, by adding a cupping agent, a large amount of the surface adsorbed water can be retained, and the catalyst performance can be exhibited.

Table 19 shows the test results other than the catalyst performance. The water washing test enables water washing with ¹ V curable resin at 10 wt% or more. No deterioration in light resistance was observed even after irradiation for 10 hours without any problem.

 As described above, by using a UV curable resin, a photocatalytic filter having excellent light fastness, which can be coated at room temperature in a short time, was produced.

 In this way, a photocatalyst can be formed on any material surface in a short time at low temperature, providing a highly active photocatalyst that is effective in the living environment, can be washed with water, can remove inorganic dirt, and can replace and clean various application products. Reduce the number.

 (Example 31)

It was prepared and the dispersed solution - T i 〇 ₂ fine completion to S i 0 ₂ sol. this The solution T i O _z layer is formed on the PKT film was used to prepare a PE Ding film. The procedure is shown below.

First, a description will be given S i 0 ₂ sol preparation method. 5 g of tetraethoxysilane was dissolved in 1 () () m 2 of a mixed solution of water, ethanol and prononol (3:27:70) and stirred at 4 CTC for about 5 hours. The obtained solution was allowed to stand at room temperature for 2 weeks to obtain a SiO ₂ sol.

Then have fabrication method Nitsu solution dispersed with T i 0 ₂ fine particles described S i 0 ₂ sol. To the previously prepared S i 0, sol, D i O _z fine particles f were added at a weight ratio of T 丄 0 ₂ / S i 0 _{7. As} 9 _u Further, phosphoric acid, boric acid and L i, Mg, K, and Ca nitrates were each added in prescribed amounts, the solid content concentration was adjusted to 4 wt%, and the required amount of water was added to adjust. Then with 5 of zirconyl two Aboru, in order to disperse the Ding i 0 ₂ particles in S i 0 ₂ sol屮, was treated with 2 4 hr ball mill, T i O _z fine completion to S i 0 ₂ sol屮- A solution in which was dispersed was prepared.

The Ti 0 _z fine particles / -dispersed Si i sol prepared on PET film was coated and treated at 120 ° C for 5 minutes while irradiating with a low-pressure mercury lamp (intensity: 15 mWZcm ² ). Te, to form S i 0 ₂ film T i 0 ₂ plastic film particles are the T i 〇 ₂ dispersion S i 〇 ₂ film dispersed co one and Bok in. The thin film obtained on the PET film had good film quality and strength, and the thickness was 300 nm.

The prepared membrane was rubbed with an eraser with a load of 1 kg, and a strength test was performed. As a result, the film without B and P additions: Γ) The force that caused film peeling at 0 times ⁵ : and the film with B and P additions did not stick even at 100 times. From this, it was found that the film strength was improved by adding B and P.

Next, the decomposition activity of organic substances was evaluated. In addition, the activity test showed that An organic dye was coated and irradiated with light of 0.2 mWZcm ² at a wavelength of 254 nm. The decomposition rate was determined from the amount of change from the initial dye transmittance. Table 20 shows the results. The hollow column in the table indicates that the element was not added.

 Table 20

When B and P are not added The photocatalyst with Li added decomposes by 65% after 10 minutes. When B and P are added, the decomposition rate is improved. Thus, it was found that the performance of the photocatalyst could be further improved by adding B and P. In addition, the effect of additives was the largest for K, followed by C a, M g, and L i. Photocatalysts generate electrons and holes generated by absorbing light, decomposing water, Generates and decomposes organic matter. Therefore, organic matter cannot be decomposed unless water is present on the surface of the photocatalyst. When B and P were not added, water adsorbed on the TiO _z SiO ₂ surface was decomposed. B and P have large water absorption, and more water exists on the catalyst surface by adding BP. Such an increase in surface adsorbed water can improve the decomposability of organic substances.

 Next, conductive particles 液 C0 were added to the previously prepared coating solution, and a film was formed on a PET film in the same manner, and the degradability of the dye was evaluated. The results are shown in Table 21.

 2 1

When ATO was not added, the decomposition rate after 10 minutes was 81%, and when the force was added, the decomposition rate was improved. In particular, the addition of 1 O w L% has the greatest effect, and the decomposition rate reaches 90%. Thus, it was found that the performance can be improved by further adding ΛT 更 に. The surface resistance of the prepared ATO-added film is as low as 10.sup.9 ohms, and the anti-static effect is taken into consideration, so that not only organic substances but also inorganic substances can be prevented from adhering. The same effect was obtained not only for K (potassium) but also for Li (lithium), Ca (calcium), and Mg (magnesium). Industrial applicability

 In the present invention, a mechanism for generating an air flow by an electric motor, such as an air purifier, a ventilation fan, a fan, a vacuum cleaner, a clothes dryer, a dish dryer, a dishwasher, and a garbage disposal machine, is mainly used for indoor use. The low-temperature curing type highly active oxide photocatalytic thin film was provided on the air flow path, the filtration part, the exterior part, and the part illuminated by the built-in lighting mechanism of electrical products used in the environment. The following effects can be obtained.

 According to the present invention, roughly three effects can be obtained.

First, N a in the thin film of oxide photocatalyst such as 0 ₂ or the like conventionally known T i In the present invention, including L i, etc., electronegativity is less than one. 6 ions ^ diameter The addition of ions that are smaller than 0.2 nm and have a valence of 2 or less increased the effect of decomposing organic substances. In addition, metal oxide semiconductors with an electric affinity of 1.2 or more, including antimony-doped tin oxide, and metals of Ag, Cu, i, Pd, Rh, and Pt The addition of the fine particles together further increased the decomposition efficiency. As a result, there is obtained an effect that a mechanism for generating short-wavelength light, such as an ultraviolet lamp, which is required in the conventional oxide photocatalyst, becomes unnecessary. In other words, light that is generally obtained indoors can decompose organic substances even with weak light such as fluorescent lamps, incandescent lamps, mercury lamps, and sunlight through window glass, and it can also be used to remove tobacco and oils such as hand oils. Even if dirt due to the adhered substance adheres, it is decomposed and an antifouling effect is obtained. Similarly, if weak light is used and various odor-causing substances such as organic amines-mercaptans disperse in the air, they are decomposed and decomposed into low-odor or odorless substances. The deodorizing effect of reducing the odor of the water is obtained. Similarly, if various microorganisms such as bacteria, fungi, pollen, etc. drift in the air due to weak light, these microorganisms are killed by the action of decomposing organic substances. As the surface of the member on which the oxide catalyst thin film is formed is kept clean, the effect of reducing the amount of microorganisms floating in the indoor air using these products can be obtained. . Conventionally, these air-filtering parts, such as filters and nets, are often treated as replacement parts. If dirt accumulates or becomes clogged, the parts can be removed and cleaned, or new parts can be removed. However, according to the present invention, the adhered dirt is decomposed, so that the life span up to the end can be extended and the frequency of replacement can be reduced.

 Examples of the specific effects of each application are shown below. The outer frame, frame, case, etc. of the purifier, changer, blower, vacuum cleaner, clothes dryer, dish dryer, dishwasher, garbage disposal machine, etc. Since all exterior components are illuminated with indoor lighting or sunlight, they can be kept in a clean state that is resistant to dirt and hard to propagate microorganisms. If certain air flow path components and components such as filters and nets in the air flow path are installed so that they can be illuminated with indoor lighting and sunlight, not only antifouling and antibacterial but also indoor deodorizing effects can be obtained. Can also be obtained.

 Regarding the antifouling effect, air cleaners, ventilation fans, electric fans, and vacuum cleaners may be remotely operated by providing an infrared receiver on the main unit and an infrared transmitter on the remote controller. This also has the effect of preventing a problem that dirt adheres to the receiving / transmitting portion of the device and hinders transmission / reception of signals.

In general, when the load of dirt is large enough that the intensity of light obtained indoors is not enough to decompose it, or when it is desired to use it for members where indoor light does not sufficiently hit, it is effective to install lighting means such as fluorescent lamps and electric bulbs. Is obtained. If this is still insufficient, a high decomposition effect can be obtained by installing a UV generator such as a mercury lamp or metal halide lamp. In such a case, the present invention According to the above, since the decomposition efficiency is higher than before, the lighting time of the lamps can be shortened, and the output of the lamps can be reduced, so that the power consumption can be saved, the life of the lamps will be prolonged, and the frequency of replacement will be increased. This has the effect of requiring less. For example, decomposition of a large amount of malodorous substances generated from a kitchen waste disposal machine, a large amount of edible oil attached like a kitchen ventilation fan, a dishwasher, a dish dryer, a clothes dryer, etc. When the effect of cleaning the inside of the closed tank / drum is required, it is effective to use light generating means of various wavelengths as described above in combination.

Secondly, in the present invention, as described above, a metal oxide semiconductor having an electric affinity of 1.2 or more, including antimony-added tin oxide in a photocatalytic thin film, or Ag, Cu, Ni, P d, R h, since the addition of fine metal particles I ³ t, the surface resistance of the film itself can be kept low. As an effect of this, it is possible to suppress the phenomenon that large-sized dust and fibers that take time to disassemble, or minerals such as soil that cannot be decomposed, are attached by static electricity. By this action, it is possible to suppress a phenomenon that insoluble stains accumulate on the surface and light does not reach the photocatalytic thin film surface.

 This antistatic effect is effective not only in preventing dirt due to adhesion of dust and the like, but also in preventing malfunction of electronic circuits due to electrostatic charging. In particular, it is highly effective for articles that tend to be triboelectrically charged during use, such as sweepers.

 Specific examples of effects in each application are shown below. Outer parts of the outer frame, frame, and case of air purifiers, ventilation fans, fans, vacuum cleaners, clothes dryers, dish dryers, dishwashers, and kitchen waste treatment machines are particularly effective because they tend to adhere to dust and dirt. is there.

Third, in the present invention, when forming a photocatalytic thin film having the above effects, the photocatalytic thin film is prepared from a solution containing a low molecular weight organometallic compound and water, By irradiating electromagnetic waves of a required specific wavelength, including ultraviolet light, etc. to break the bond between the group atom and the organic group, the reaction for forming a film is promoted.Thus, a thin film is formed at a lower temperature than before. You can now. For this reason, the surface of general-purpose plastics, including ABS, PS, PP, polyester, etc. used for electrical products as described above, and organic paints applied to steel plates, is exposed to heat by the base material. It is now possible to form oxide photocatalyst thin films without causing defects such as softening, deformation, bubble generation, cracking, embrittlement, reduced strength, and reduced toughness.

 The following are examples of specific effects in each application. 'Air purifier, Ventilation 13, Fan, Vacuum cleaner, Clothes dryer, Dish dryer, Dishwasher, Garbage disposer, Synthetic resin molding or coating usually used for exterior parts such as frames, frames and cases Although the steel sheets thus manufactured cannot withstand a high temperature of 300 ° C. or higher, which is the conventional temperature for forming a thin film of an oxide photocatalyst mainly composed of Ti 0, etc., according to the present invention, The film can be easily formed without causing undue damage to the surface of the component.

Similarly, the air flow path parts attached to the above-mentioned articles and the parts of the air flow path such as fans, blades, filters, and nets are made of materials that can withstand heat treatment at 300 ° C or more. Although it was extremely difficult to construct, the present invention has made it possible to easily form the above oxide photocatalytic thin film. Another advantage is that the oxide photocatalyst thin film according to the present invention can form a hard film at a low temperature, and can be used as a substitute for a hard coat such as an acrylic resin which has been conventionally applied to the surface of a plastic molded product. There is also an effect. As a result, the gloss of the molded article can be increased as in the case of the conventional hard coat, the surface can be prevented from being damaged, and an effect of suppressing the growth of microorganisms, an antifouling effect, and an antistatic effect can be obtained. In addition, in the case of application to a class of filters composed of nonwoven fabric, woven fabric, sponge, etc., since the oxide photocatalytic thin film formed on the fiber surface is vitreous, the surface has good adsorbability and wettability. This has the effect of improving odor collection and smoke particle collection efficiency. Although S i 0 ₂ alone trapping efficiency thin film be formed on the same principle is improved, but attached to odor and smoke particles decreases coated Then collecting effect fiber surface, in the present invention this Since the vitreous film itself has photocatalytic properties, the fiber surface is always fjMed, and the ground surface is continuously exposed with a low absorptivity, so that the effect is maintained.

 Furthermore, in the case of a dishwasher, the contact angle of water droplets adhering inside can be reduced by utilizing the antifouling effect of the photocatalyst. This can reduce the total amount of residual water, which has the effect of increasing the drying efficiency of dishes. Various effects can be applied to applications where dew may not be useful if this effect is used.

Claims

Range of claims | ¾1  1. A photocatalytic thin film in which particles having a photocatalytic effect are dispersed in a coat,  Foreword d A photocatalytic thin film characterized in that the coating film contains an organic resin having an inorganic functional group bonded to a side chain.  2. A photocatalytic thin film in which particles having a photocatalytic effect are dispersed in a coating film,  The coating film contains an element having an electronegativity of less than 1.6 and an ionic radius of less than 0.2 nm and a metal element having a valence of 2 or more. Photocatalytic thin film.  3. A photocatalytic thin film in which particles having a photocatalytic effect are dispersed in a coating film,  A photocatalytic thin film, wherein the coating further contains at least one of P, B, K, and Ca.  4. A photocatalytic thin film in which particles having a photocatalytic effect are dispersed in a coating film,  A photocatalytic thin film, characterized in that oxide semiconductor particles comprising a gold bending element having an electron affinity of 1.2 or more are dispersed in the coating film.  5. The photocatalytic thin film according to claim 4, wherein  A photocatalytic thin film, wherein a layer in which the oxide semiconductor particles are dispersed is provided separately from a layer in which the titanium oxide particles are dispersed.  6. The photocatalytic thin film according to any one of claims 1 to 5, Wherein in the coating, conductive fine particles are dispersed, photocatalytic film, wherein the surface resistance of the coating film is less than 1 0 ³ Ω / mouth. 7. In the photocatalytic thin film according to any one of claims 1 to 4,  A photocatalytic thin film, wherein the coating film contains silicon oxide.  8. An article, characterized in that the photocatalytic thin film according to any one of claims 1 to 7 is provided on a substrate surface.  9. An article, comprising a non-aluminum layer between the oxide photocatalyst thin film according to claim 8 and a substrate surface of the article.  10. Al, Zr, and Al, wherein the barrier layer according to claim 9 includes at least one metal element selected from a valence element having a valence of more than 3 or a transition metal. An article characterized by being a metal oxide film containing at least one metal element selected from Fe.  11. An article, wherein the substrate according to any one of claims 8 to 10 is made of an organic polymer compound having a decomposition start temperature of 300 ° C or lower.  1 2. a base material mainly composed of an organic polymer compound;  A barrier layer made of an inorganic substance, provided on the surface of the equipment;  An article comprising an oxide catalyst layer provided on the surface of the barrier layer and catalyzing a decomposition reaction of an organic substance.  1 3. The air flow generated by driving the electric blower takes in the air in the room from the intake port, passes through the filter provided in the ventilation path, and causes dust, oil particles, and smoke floating in the air. , Pollen, various microorganisms, or foul-smelling substances, etc., are collected and purified, and then discharged through an exhaust port. The photocatalyst thin film according to any one of claims 1 to 4 is attached to the surface of a component that is exposed to indoor illumination light or sunlight from outside of the components. An air purifier characterized in that a film is formed.  1 4. The air flow generated by driving the electric blower causes the air taken in from the indoor intake port to be mixed with floating dust, oil particles, smoke, pollen, various microorganisms, or malodorous substances. In a ventilation fan that discharges outside from the outside exhaust Π,  The photocatalyst thin film described in any of the above-mentioned requirements (1) to (4) is formed on the surface of components that are exposed to indoor illumination light or sunlight from outside as a component part block A ventilation fan equipped with a low-temperature curing type highly active oxide photocatalytic thin film characterized by the following features.  1 B. In a fan that generates airflow by rotating blades with an electric motor,  A photocatalytic thin film according to any one of claims 1 to 4 is formed on a surface of a component that comes into contact with indoor illumination light or sunlight from outside. A fan characterized by the following.  16. The suction port communicates with the dust collection chamber, and the pressure in the dust collection chamber is reduced by an electric blower to collect dirt and dust introduced from the suction port into the dust collection chamber. A vacuum cleaner that discharges air from an exhaust port after filtering the dirt and dust;  A vacuum cleaner, wherein the photocatalytic thin film according to any one of claims 1 to 4 is formed on a surface of a part that is exposed to indoor illumination light or sunlight from outside. 1 7. Air taken from outside by an electric blower is heated by a heater for heating and sent into a drying drum containing clothes containing moisture, and the clothes are heated to evaporate the moisture. Exhaust air from the exhaust port, or by condensing moisture with a heat exchanger to remove moisture. After drying the clothes dryer,  A clothes dryer, wherein the photocatalytic thin film according to any one of claims 1 to 4 is formed on a surface of a part that comes into contact with indoor illumination light or sunlight from outside.  1 8. The air taken in from the outside by an electric blower is heated by a heater for heating and sent into the drying room containing the wet dishes, and the dishes are heated to evaporate the attached moisture. In a dish dryer that discharges through the exhaust port together with this moisture-containing air,  A dish dryer, wherein the photocatalytic thin film according to any one of claims 1 to 4 is formed on a surface of a part that is exposed to indoor illumination light or sunlight from outside.  1 9. In the washing tank containing dirty dishes, water is heated and pressurized by a washing pump, and after washing the dishes by spraying from a rotatable arm nozzle provided in the washing tank, A rinsing operation is performed, and thereafter, the outside air is sucked in by an electric blower, and is heated by a cool air or a heating heater to replace the high humidity internal air after the rinsing operation. In a dishwasher that evaporates and dries the moisture remaining inside,  A dishwasher, characterized in that the photocatalytic thin film according to any one of claims 1 to 4 is formed on a surface of a part that is exposed to indoor illumination light or sunlight from outside.  20. Raw garbage is put into a treatment tank in which a culture substrate containing microorganisms is installed, and the garbage is stirred with the culture substrate using a stirrer to decompose the garbage by the metabolic action of microorganisms. At the same time, in a kitchen waste treatment machine that discharges the water generated during decomposition with air using an electric blower, The surface of components that come in contact with indoor lighting or sunlight from outside A kitchen waste treatment machine, wherein the photocatalytic thin film according to any one of Items 1 to 4 is formed.  21. In any one of claims 13 to 20,  An article characterized in that a light source is provided at a position where light is applied to the surface of the photocatalytic thin film.  2 2. In claim 21,  The article wherein the light source is an ultraviolet lamp. 28. In any one of claims 13 to 20,  An article characterized in that a transparent member is used in at least a part of a housing that covers the surface of the photocatalytic thin film so that external light is irradiated on the surface of the photocatalytic thin film. 2 4. In Claim 23,  The transparent member has a threshold value of 50 or more according to the color difference display method of the transmitted light having a thickness of 2 mm, an a value of −20 or more and 20 or less, and a b value of 20 or less. Articles characterized by the following.  25. In the photocatalytic thin film and any one of claims 13 to 20,  An article characterized in that a transparent member is used at least in part of a housing covering the surface of the photocatalytic thin film so that the surface of the photocatalytic thin film is irradiated with external light. 26. In claim 23,  The transparent member has an L value of 50 or more according to a color difference display method for transmitted light having a thickness of 2 iMi, an a value of −20 or more and 20 or less, and a b value of 20 or less. Articles characterized by the following. 2 7. In photocatalyst comprising titanium oxide, at least _{ATO, R u 0 2, STO} (S r T i 0 3), a photocatalyst characterized by including Mukoto any one of RSO and binder. 28. The photocatalyst according to claim 27, wherein any one of Li, Na, and Mg is added.  2 9. Photocatalyst characterized by adding an adsorbent to a photocatalyst consisting of titanium oxide.  30. In the photocatalyst consisting of titanium oxide, Cu, Ag, Li, Na, A photocatalyst characterized by containing zeolite obtained by ion exchange of any of Mg.  3 1. A photocatalyst characterized by adding a pigment that absorbs visible light to a photocatalyst composed of titanium oxide.  3 2. A photocatalyst comprising titanium oxide, which contains an organic resin.  3 3. The photocatalyst according to claim 32, further comprising an A1, Ti, Si-based coupling agent.