Photocatalyst thin film and article equipped therewith

Description: TECHNICAL FIELD [Detailed description of the invention]

【0001】

[Technical field to which the invention belongs]

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 an organic polymer material having low heat resistance, particularly a general-purpose thermoplastic plastic part. The present invention relates to an article in which an oxide photocatalyst thin film is formed in a thin layer on the surface. The present invention also relates to an ultraviolet lamp and an article in which an oxide photocatalyst thin film is provided on the whole or a part of an article suitable for indoor use, which cannot obtain strong ultraviolet rays such as outdoor sunlight.

【0002】

For example, air washer, ventilation fan, electric fan, vacuum cleaner, clothes dryer, dish dryer, dishwasher, kitchen waste disposer, heater, humidifier, dehumidifier, air conditioner, cooker, electromagnetic cooker, hair dryer , Dehumidifier, electric blower such as kotatsu, to create air flow.

【0003】

Various dirt components and microorganisms floating in the air adhering to the surface of these electrical products are decomposed by the photocatalytic function by light in the living environment, and are antifouling, deodorant, antibacterial, and antifouling. Related to technology for obtaining surface properties such as mold and wettability improvement and its articles.

【0004】

[Conventional technology]

In recent years, TiO₂ Materials that exhibit antifouling, deodorizing, and antibacterial effects by utilizing the decomposition action of organic substances using photocatalysts are attracting attention. This uses the redox reaction of a semiconductor photocatalyst as described in Non-Patent Document 1, and is TiO.₂ A thin film formed in a ceramic style is provided.

【0005】

On the other hand, as a film forming method, the oxide thin film may be formed on a substrate by a physical method such as sputtering or a chemical method such as a coating method such as a sol-gel method. The former can be formed at a low temperature using a vacuum device or the like. The latter can be obtained by applying it on a substrate with a simple device such as spin coating or spraying, and usually treating it at a temperature of several hundred ° C. TiO, a material for antibacterial and deodorant₂ It has been reported that anatase-type crystals are effective and crystallization is effective for functional expression (Patent Documents 1 and 2). Also TiO₂ It has been reported that V, Fe, etc. are added to the product to improve its performance (Non-Patent Document 2).

【0006】

The following inventions are known as examples of applying the oxide photocatalyst thin film to various devices using the above materials and methods.

【0007】

An air purifier, that is, a device for removing dust and malodorous substances in the indoor air, is described in TiO as described in Patent Document 3, Patent Document 4, and Patent Document 5.₂ This is a technique in which a filter carrying a photocatalyst containing the above as a main component is included, and a mechanism for irradiating a short wavelength light by means such as an ultraviolet lamp is provided therein.

【0008】

Further, as an application example to an electric fan, as described in Patent Document 6, TiO on the surface of a metal part.₂ There is known a technique for firing a thin film of a photocatalyst containing the above as a main component at about 600 ° C.

【0009】

Further, even in an application example to a fan as in Patent Document 7, a mechanism for irradiating ultraviolet rays by attaching a light emitting diode is known.

【0010】

As an example of application to a ventilation fan, a configuration in which an ultraviolet lamp as described in Patent Document 8 is used in combination is known.

【0011】

Further, as an application example as a deodorizing filter installed in the ventilation path of a vacuum cleaner or a kitchen waste treatment machine, as seen in Patent Document 9, TiO₂ A technique has been proposed in which a photocatalyst containing the above as a main component is powdered, wrapped in a plastic fiber sheet, and heat-sealed.

【0012】

[Patent Document 1]

No. (PTC) WO 94/11092 [Patent Document 2]

No. (PTC) WO 95/15816 [Patent Document 3]

Japanese Unexamined Patent Publication No. 8-266841 [Patent Document 4]

Japanese Unexamined Patent Publication No. 8-266605 [Patent Document 5]

Japanese Unexamined Patent Publication No. 8-309148 [Patent Document 6]

Japanese Unexamined Patent Publication No. 7-303819 [Patent Document 7]

Japanese Unexamined Patent Publication No. 9-38189 [Patent Document 8]

Japanese Patent Application Laid-Open No. 5-157305 [Patent Document 9]

Japanese Unexamined Patent Publication No. 7-108175 [Non-Patent Document 1]

New Ceramics (1996) No.2,55 [Non-Patent Document 2]

W.Choi, A.Termin, MRHoffmann, J.Phys.Chem., 98,13669-13679 (1994) [0013]

[Problems to be Solved by the Invention]

There are insufficient points for forming an oxide thin film on a base material having low heat resistance, for example, a plastic part, by using the conventional technique. Antibacterial tiles are used as antibacterial and deodorant materials described in the above literature for those formed by the sol-gel method, but heat treatment of several hundred ° C, at least 300 ° C or higher is required to crystallize titanium oxide. Is. Therefore, it is difficult to form a film on a base material having low heat resistance, such as plastics, particularly general-purpose heat-plastic plastics.

【0014】

In addition, in an environment with low light intensity such as indoors, TiO₂ There is also a problem that the decomposition rate of the organic matter itself, such as decomposition, is not sufficient, and in particular, another arranged light source is required.

【0015】

The devices covered by the present invention as described above are mainly home appliances used in indoor spaces such as general homes and offices, but these products are mainly made of organic polymer materials (plastics). It is used. With the exception of monitors for TVs and personal computers, which often use glass parts, about 40 to 50% of the weight ratio of parts for general household appliances is plastic, and most of the rest is made of metals. .. In terms of volume ratio, plastic accounts for nearly 90%. Plastics are widely used because they are easy to reduce in weight, have high design, and are inexpensive. Among them, thermoplastic plastics are often used because of their high mass productivity in molding work. It is used.

【0016】

The most widely used general-purpose plastics as structural members include polypropylene (PP), acrylic butadiene styrene copolymer (ABS), styrene acrylic copolymer (AS), polystyrene (PS), nylon (PA), and polycarbonate (). PC), vinyl chloride (PVC), methacrylic (PMMA), polyethylene (PE), polyacetal (POM), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), etc. It cannot withstand deformation in an environment that exceeds it.

【0017】

For example, ASTM, D-648 (18.6kg / cm)²) The thermal deformation temperature is around 250 ° C. As a special high heat resistant resin, there are some such as polyphenylene sulfide, polyphenylene oxide, and polyetherimide in which glass fiber or the like is kneaded, but they are very expensive and cannot be used in large quantities in the above-mentioned applications.

【0018】

In general, the higher the heat resistance of a material, the higher the price, and PE, PS, ABS, PP, and PVC are often used for exterior parts, etc., which account for 75% or more of plastic parts on average. Even ABS, which has the highest heat resistance, has the above-mentioned ASTM thermal deformation temperature of 120 ° C or less, and at 300 ° C, it completely dissolves and becomes liquid, and oxidative decomposition proceeds.

【0019】

Further, even when the surface of an inorganic material such as a metal coated with a paint is targeted, the 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 and the like are typical examples, and it is common to bake at a temperature of about 150 ° C. When these paints are exposed to an environment exceeding 300 ° C, problems such as loss of luster and peeling often occur.

【0020】

As shown by these data, there is a big problem in heat resistance property for a general-purpose material to form a film by the sol-gel method in the conventional technique.

【0021】

On the other hand, physical methods such as sputtering, CVD, and vacuum deposition, which are methods for forming a film within a temperature range not exceeding 300 ° C, require a large-scale device such as a vacuum device, and the production cost is high. .. Further, since the film is formed under a high vacuum during film formation, the composition ratio deviation of the oxide photocatalyst is large, and the photocatalyst performance deteriorates. Further, when an organic material is used as a substrate at the time of film formation, there is a problem that the substrate is reverse-sputtered and damaged, which causes deformation of the substrate and the like. Further, in the chemical method by the coating method such as the sol-gel method, when the silica sol in which the oxide fine particles are dispersed is used, the film formation on the substrate having no heat resistance is sufficient because the heat treatment temperature is low. Sintering is not possible, and the strength and water resistance of the formed oxide film become insufficient.

【0022】

For the above reasons, in the conventional existing technology, the surface of the organic polymer material used for general electric appliances is not damaged such as deformation and deterioration, and TiO.₂ It was practically difficult to form a thin film of a photocatalyst mainly composed of.

【0023】

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

【0024】

On the other hand, TiO₂ There is no mention in the invention of the above-mentioned photocatalyst application technique about a device for enhancing the organic matter decomposition effect itself of the photocatalyst whose main component is such as.

【0025】

That is, TiO₂ No ingenuity has been made in material formulation to improve the photoactivity of the film containing. Therefore, for example, in the case of JP-A-8-309148 and JP-A-8-266605, which are conventionally known usage methods for the purpose of deodorization, or in the case of decomposing stains caused by tobacco tar or the like. In the case of JP-A-9-38189, which is a law, and in JP-A-5-157305, which is an application example for applications such as decomposing stains such as oil during cooking, all of them are photocatalysts themselves. Since the activity is not sufficient, the decomposition reaction is enhanced by installing a mechanism for irradiating ultraviolet rays and a heating means.

【0026】

These are TiO when the light intensity is low.₂ The biggest reason is that the decomposition rate of organic matter itself is not sufficient, and no measures have been taken to increase this. Therefore, an ultraviolet lamp or the like is also used as a means for increasing the light intensity. As the ultraviolet lamp, a high-pressure mercury lamp or a metal halide lamp is usually used, but a mechanism such as a power supply device and a cooling mechanism is required, which leads to an increase in the weight and price of the entire applied product. In addition, the life of the lamp is about 2000 hours, and there is a problem in practicality such as the need for regular replacement work.

【0027】

In the prior art, TiO₂ Although a technique for adding Fe and V to increase the decomposition efficiency is known, it is difficult to apply it to a substrate material having a low melting point and poor heat resistance due to high performance treatment at several hundred ° C. Is.

【0028】

Another object of the present invention is to improve the photodecomposition efficiency of a photocatalytic film that can be formed at a low temperature.₂The purpose is to improve the decomposition efficiency of a single substance so that the deposits can be decomposed even with an intensity lower than the light intensity conventionally required.

【0029】

Further, in the prior art, in applications such as antibacterial property, deodorization, and deodorization, the target substance is an organic substance, and since the target substance is a fine particle or a molecular form, the attached liquid organic substance or fine particle organic substance is present. Although it was possible to decompose it, it takes a very long time to decompose large-sized fibers and dust even if it is an organic substance, or it is extremely difficult to decompose inorganic substances such as dust, and it is contaminated. It was incomplete in preventive applications. Since these stains are generally suspended in the air in an electrically charged state, when they adhere to the surface of a solid with high electrical insulation, the static electricity is not easily discharged and remains attached. It ends up. There is also a problem that the light is blocked by the adhering inorganic stains, the photocatalyst surface is not sufficiently irradiated with light, and the decomposition efficiency of the organic matter is lowered.

【0030】

Another object of the present invention is to prevent large-sized dust and inorganic stains, which are difficult to decompose and remove in principle by the oxidative decomposition effect of these photocatalysts, from being targeted by electrostatic force. To do.

【0031】

[Means for solving problems]

In order to achieve the above object, the feature of the present invention is to drive an electric blower such as an air purifier, a ventilation fan, an electric fan, a vacuum cleaner, a clothes dryer, a dishwasher, a dishwasher, and a kitchen waste disposer. Among the parts of electrical products mainly used indoors that have a mechanism to generate an air flow, the temperature is low on the surface of the air flow path, the filtration mechanism in the air flow path, or the exterior parts exposed to indoor illumination light. The purpose is to provide a curable highly active oxide photocatalyst thin film.

【0032】

The melting point or decomposition temperature of the material of the target part is 300 ° C or less, and in particular, low-temperature curing type height is used for molding members made of general-purpose thermoplastic plastic, fiber members, foam members, and sheet-like members. By providing the active oxide photocatalyst thin film, problems such as contamination, microbial propagation, and foul odor generation, which have been conventional problems, can be solved.

【0033】

In the present invention, TiO₂ Optimization of thin film thickness of oxide photocatalyst mainly composed of, TiO₂Optimization of particle size, addition of suitable ions with low electronegativity, SiO₂ TiO when using₂ A thin film with improved photocatalytic reaction activity by optimizing the mixing ratio with the above, adding an oxide semiconductor with high electron affinity, adding appropriate noble metals, etc., to the air flow path of the above electric products. And by forming it on the surface of exterior parts, it has become possible to obtain antifouling, deodorizing, and microbial growth suppression effects at the indoor light level, which was not possible in the past. In addition, by stacking the films, it is possible to prevent damage to the organic-based substrate, which is vulnerable to oxidative decomposition.

【0034】

At the same time, in the present invention, SiO₂ And TiO₂ During the process of forming a thin film of an inorganic polymer mainly composed of, a step of irradiating an electromagnetic wave containing a specific wavelength necessary for breaking the bond between a metal atom of an organometallic compound and an organic group to promote a hydrolysis reaction. Since the inorganic polymer can be polymerized at a low temperature by incorporating the above, the surface of a general-purpose thermoplastic plastic having low heat resistance as described above is not deformed, melted, or decomposed. It has become possible to obtain the strength of an oxide photocatalyst thin film that is strong at low temperatures.

【0035】

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

【0036】

Oxide photocatalyst TiO₂ The reaction efficiency is improved by adding ions having an electronegativity of less than 1.6 and an ionic radius of less than 0.2 nm to an oxide photocatalyst thin film in which fine particles are dispersed and having a valence of 2 or less. It is a thing. As specific elements to be added, Na, Li, K, Sr, Mg, Ca and Zn are particularly effective, and the amount of these elements added is preferably 0.5 to 20 wt%. TiO₂ It is most effective to adjust the size of the fine particles to 5 to 20 nm.

【0037】

Also TiO₂ Fine particles are SiO₂ In the oxide photocatalyst thin film dispersed therein, TiO₂ / SiO₂ It is preferable that the weight ratio of is 9 to 5.

【0038】

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

【0039】

The effect is further enhanced when the component to be added is, in addition to the above-mentioned ions, further dispersed oxide fine particles mainly composed of an oxide semiconductor composed of a metal element having at least an electron affinity of 1.2 or more. In particular, those in which the elements are Sn, Fe, and Cr are preferable. 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 10%) are particularly effective. When these semi-conducting fine particles are added, the surface resistance value of the film itself is lowered, so that the stains themselves, including inorganic stains that cannot be oxidatively decomposed, are less likely to be electrostatically adhered.

【0040】

Furthermore, it is also effective to have a plurality of laminated structures of oxide photocatalyst thin films, and the first layer counting from the surface is SiO.₂ Inside TiO₂ The fine particles are dispersed, and the above-mentioned ions are added to the film, and the oxide fine particles mainly composed of the above-mentioned oxide semiconductor are dispersed in the second layer counting from the surface. is there. As a result, the photocatalyst functions effectively without damaging the surface of plastic or the like having low durability against oxidation. Further, it is more effective if at least one of Fe, Al, and Zr is added to the second layer.

【0041】

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

【0042】

TiO₂ Has a function as a photocatalyst, and has antibacterial, deodorant, antifouling, etc. effects by decomposing organic substances. Its function is TiO, which is a semiconductor.₂ Is caused by electrons and holes generated when light is irradiated with light, especially ultraviolet rays. TiO which is a semiconductor₂ Generates electrons and holes when irradiated with light that has more energy than the bandgap. The generated electrons and holes are TiO₂ Water adsorbed on the surface is decomposed to generate H radicals and OH radicals. When this OH radical reacts with the organic substance, the organic substance can be decomposed. The photocatalyst decomposes organic substances and the like by such a mechanism, but there are the following two means for further increasing the reaction rate. The first is to increase the workload of one active site, and the second is to increase the number of active sites. To increase the number of active sites, increase the surface area, that is, TiO₂ Can be achieved by making the particles finer. In addition, in order to increase the workload of active sites, TiO₂It is to improve the crystallization of (anatase) and prevent the recombination of electrons and holes. By satisfying the above, the reaction rate can be increased. But TiO₂Improving the crystallization of (anatase) and increasing the surface area are contradictory, and it is difficult to achieve both. That is, improving the crystallinity causes an increase in the particle size and a decrease in the surface area. Therefore, there is an optimum region between the direction of improving the crystallinity and the direction of increasing the surface area. From the results of many experiments of the present invention, it was found that the optimum region is 5 to 20 nm. TiO₂ Even if the type of oxide used as the inorganic binder was changed when the fine particles were dispersed, the decomposition rate increased within this particle size range.

【0043】

Improving the reaction rate by preventing the recombination of electrons and holes is achieved by increasing the separation efficiency of electrons and holes. TiO₂ There are Ti defects on the surface. This defect becomes the recombination point of the electron and the hole and inhibits the reaction. When an ion having an ionic radius similar to that of Ti is added to this, the Ti defect on the surface is invaded, the defect disappears, and the recombination point decreases. Furthermore, since it exists as a positive ion, it can attract electrons and separate them from holes, and can promote the oxidation reaction of organic substances. The present invention has found that the conditions of the additive having such an effect are that the electronegativity is smaller than 1.6 and the ionic radius is smaller than 0.2 nm.

【0044】

Furthermore, it has been found that the present invention can be improved in performance by adding other oxide semiconductor fine particles. This is TiO with a low carrier concentration₂ It is achieved by injecting carriers from an oxide semiconductor having a large carrier concentration. Therefore, from oxide semiconductors to TiO₂ It is necessary to make it easy for carriers to flow. A Schottky barrier is formed when the electron affinity of the oxide semiconductor is Ti or less. Therefore, the material to be added needs to have an electron affinity of 1.2 ev or more.

【0045】

Further, in the present invention, when Fe, Al, Zr is added, TiO₂ It was also found that the photocatalyst of was lost. When a substrate material mainly composed of organic substances is used, there is a problem that the substrate is self-destructed by photocatalytic action.

【0046】

Therefore, in the present invention, a barrier layer is formed between the substrate and the photocatalyst, and by adding Fe, Al, Zr to this barrier layer, self-destruction can be completely suppressed. Furthermore, because it is a high-performance barrier layer, the film thickness can be made sufficiently thin. When conductive fine particles such as ATO are added or laminated, the performance of the photocatalyst is improved and the antistatic function is added, so that not only the decomposition of organic matter but also dust floating in the air, etc. It is possible to prevent the adhesion of inorganic substances and provide a higher performance antifouling function. Further, in the present invention, the above-mentioned activity is high, the film can be decomposed with a weaker light illuminance than the conventional one, or the antistatic function is provided. Although the thin film of the highly active photocatalyst has high cost and versatility, it is possible to form a film on the surface of a material whose heat resistance is insufficient by the conventional film forming method.

【0047】

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

【0048】

Ultraviolet light is most preferable as the electromagnetic wave having the specific wavelength. After applying a solution containing a low molecular weight organometallic compound and water to the surface of the adherend, a specific wavelength required for breaking the bond between the metal atom and the organic group of the organometallic compound such as ultraviolet light is set. It is most desirable to irradiate the electromagnetic waves to be possessed and heat-dry at the same time, or to heat-dry the coating film after the electromagnetic wave irradiation step.

【0049】

Further, in the case where the photocatalytic titanium oxide particles used in the conventional technique are dispersed in the inorganic thin film, the performance is deteriorated because the occupied area of titanium oxide is smaller than that of the photocatalyst composed only of titanium oxide. There was a problem of doing. In particular, when film strength is required, a large amount of inorganic binder is added to increase the strength, but there is a problem that the activity is significantly reduced.

【0050】

Therefore, an object of the present invention is to provide a highly active photocatalyst material even if 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, the self-cleaning characteristics of the photocatalyst are used to reduce the number of parts replacement and cleaning of the product.

【0051】

In order to solve the above problems, the present invention uses a photocatalyst made of titanium oxide, ATO, RuO.₂Is added. In addition, any one of Li, Na, and Mg is added.

【0052】

Further, the present invention is a manufacturing method for improving the bonding state of dissimilar semiconductor interfaces by directly coating titanium oxide powder with ATO particles. Further, the present invention is a coating method capable of forming a film at a low temperature of about 120 ° C. at the time of coating by performing a high temperature treatment as a pretreatment.

【0053】

When the electron affinity of the oxide semiconductor is smaller than that of Ti, a Schottky barrier is formed at the particle interface of the fine particles, and the carrier of the added oxide semiconductor is TiO.₂It cannot be injected inside and no effect appears. On the other hand, when the electron affinity of the oxide semiconductor is smaller than that of Ti, a Schottky barrier is not formed at the particle interface of the fine particles, an ohmic contact is formed, and the carrier of the oxide semiconductor is easily TiO.₂ It is injected into and works effectively. In particular, ATO has a slightly smaller electron affinity than Ti, but there is almost no difference, so performance improvement can be seen. This is because ATO, which is a conductive oxide, has a high carrier concentration, and a large amount of carriers of ATO are TiO.₂ Infused into, the activity of the photocatalyst is improved.

【0054】

In recent years, ATO has attracted attention as a conductive oxide, and ultrafine particles are commercially available. TiO₂ Addition of ultrafine particles ATO to the photocatalyst makes it easier to add ATO TiO₂ A photocatalyst can be produced. However, when such ultrafine particle ATO is used, TiO is added when ultrafine particle ATO is added.₂ There are ATO particles that have come into contact with fine particles, but SiO₂ Some particles are present inside, which is not efficient. On the other hand, in the case of the production method of the present invention, TiO₂ ATO and TiO are added to the fine particles in advance and fired.₂ The contact area of the particles is large, the bonding state is good by firing, and the electron transfer between dissimilar semiconductors becomes smooth. RuO is a p-type semiconductor.₂ Is an n-type semiconductor, TiO₂ Since ATO attracts holes among the generated electrons and holes by absorbing light, it is possible to suppress the recombination of electrons and holes. Therefore, the electrons and holes generated by absorbing light can be effectively used for the catalytic reaction, and the decomposition rate can be further improved.

【0055】

In addition, when Li, Na, and Mg are added, their ionic radii are close to the ionic radius of Ti, and TiO₂ It easily penetrates Ti defects on the surface and increases crystal stability. Further, since Li, Na, and Mg have strong ionicity, they can easily attract electrons, and can absorb light to separate the generated electrons and holes to increase the reaction efficiency.

【0056】

The film forming method of the present invention can be produced at about 120 ° C., and can be applied not only to ceramic substrates but also to plastic materials. The usual sol-gel method requires a temperature of about 400 ° C, which makes it difficult to apply to plastic products or TiO.₂ It takes more than 10 minutes to crystallize. On the other hand, since the production method of the present invention can form a film at a low temperature, there are abundant base materials that can be used, and a photocatalyst can be formed on any surface. In addition, it can be processed in a short time of several minutes, and the production cost can be significantly reduced.

【0057】

The present invention uses RSO (RuSrO) as a photocatalyst made of titanium oxide.₃) Is added. Further, the present invention is STO (SrTiO).₃), RSO, and binder. Furthermore, the present invention is a photocatalyst characterized by adding any one of Li, Na and Mg.

【0058】

Further, the present invention is a manufacturing method in which the semiconductor photocatalyst powder is directly coated with RSO to improve the bonding state of the interface between dissimilar semiconductors. Further, a high temperature treatment is performed as a pretreatment, and the temperature is 120 ° C. during coating. This is a coating method that enables film formation at a low temperature.

【0059】

RSO-added photocatalysts are RSO and TiO₂ When they come into contact with each other, the holes in the RSO are TiO.₂ The use of the photocatalyst improves the performance of the photocatalyst. On the other hand, the oxidative activity of the catalyst is due to the redox action of electrons and holes generated by the absorption of light. In particular, the generated holes generate hydroxide radicals and generate a strong oxidizing action. RSO is a p-type semiconductor and has a large number of holes. RSO and TiO₂ By contacting TiO₂ Holes are injected inside, TiO₂ The activity of the photocatalyst can be improved by oxidizing organic substances and the like on the surface.

【0060】

Li, Na, Mg have an ionic radius close to that of Ti, and TiO₂ It easily penetrates Ti defects on the surface and increases crystal stability. Further, since Li, Na, and Mg have strong ionicity, they can easily attract electrons, and can absorb light to separate the generated electrons and holes to increase the reaction efficiency.

【0061】

RSO addition makes RSO powder TiO₂ There is a method of mixing with powder and a method of coating titanium oxide powder with RSO sol and firing. The former is TiO₂ There are RSO particles that have come into contact with fine particles, but SiO₂To be used as a binder₂Some particles are present inside, which is not efficient. On the other hand, the latter is TiO₂ RSO solution can be added to the fine particles in advance and fired, and RSO and TiO₂ The contact area of the particles is large, the bonding state is good by firing, and the electron transfer between dissimilar semiconductors becomes smooth. However, a temperature of 700 to 850 ° C is required to produce RSO, and at a temperature lower than this, RSO does not crystallize and therefore does not function as a p-type semiconductor. TiO₂ In the case of, the crystal becomes rutile type at 600 ° C or higher. It is the anatase type that exhibits sufficient function as a photocatalyst. In the rutile type, the performance of the photocatalyst deteriorates sharply. Therefore, after adding RSO, TiO₂ If RSO is treated at high temperature, RSO becomes a p-type semiconductor, but TiO₂ Phase transitions to the rutile type and loses its function as a photocatalyst. Therefore, TiO as a photocatalyst₂ STO (SrTiO) that can be expected to have similar functions₃) Is used to enable the RSO-added STO photocatalyst. STO is TiO₂ It has almost the same band structure as. In addition, the manufacturing method is to crystallize by treating at a high temperature of 700 to 850 ° C. Furthermore, both RSO and STO are perovskite crystals, and their crystal lattice constants are almost the same because Sr-O is common. Therefore, the production conditions are very close to those of RSO, the bonding state is good, and the activity of the photocatalyst can be improved.

【0062】

Further, since the conventional photocatalyst has a low decomposition rate, it takes time to decompose and remove the gas. In addition, it is powerless when it is not irradiated with light, and it works only when it is irradiated with light. Therefore, the number of bacteria can be reduced by the antibacterial action of bacteria and the like, but there is a risk of bacterial growth if the light non-irradiation time is long.

【0063】

Therefore, an object of the present invention is to increase the speed of gas removal and to add an antibacterial action when not irradiated with light.

【0064】

In order to solve the above problems, the present invention added an adsorbent to a photocatalyst made of titanium oxide. The added adsorbent is zeolite. Further, the present invention is a zeolite in which any one of Cu, Ag, Li, Na and Mg is ion-exchanged with a photocatalyst made of titanium oxide.

【0065】

The conventional photocatalyst is made of a semiconductor photocatalyst material typified by titanium oxide. These materials are characterized by being antibacterial and self-cleaning by the redox reaction of the photocatalyst. Self-cleaning may show deterioration of the catalyst if dirt becomes noticeable, but antibacterial properties are difficult to judge visually. In particular, even if the function is deteriorated such as film peeling and performance deterioration, if it is used without noticing it, dangerous bacteria and the like will propagate, which may cause a problem.

【0066】

Therefore, the present invention is to provide a photocatalytic material whose performance can be easily judged visually.

【0067】

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

【0068】

Photocatalysts generally absorb ultraviolet light to produce a catalytic action. Only a small amount of ultraviolet rays are present in the living environment, and the photocatalyst uses this small amount of light to perform antibacterial and antifouling. If visible light can be used effectively, a high-performance photocatalyst can be provided in a living environment. As for solar cells, wet solar cells using titanium oxide using visible light have already been prototyped. This is due to the sensitizing action of stacking dyes that absorb visible light, and the electrons excited by the dye absorbing visible light stimulate titanium oxide to allow an electric current to flow. Similar reductions can be expected to have similar effects on photocatalysts. By adding a material that absorbs visible light to titanium oxide, the electrons that absorb visible light and are excited can stimulate titanium oxide and be used for the redox reaction of the photocatalyst. However, many of the dyes having such a sensitizing effect are organic substances, and are not only directly decomposed by ultraviolet rays but also easily decomposed by photocatalytic action. Furthermore, the effective use of visible light improves performance, makes it easier to decompose, and deteriorates immediately even in a living environment. Therefore, in the present invention, a test was conducted focusing on a pigment system that is less deteriorated by ultraviolet rays, and it was found that the pigment system has a low decomposition rate and also has a sensitizing effect. Although it is a pigment, the raw material is mainly an organic substance, so it will eventually decompose and deteriorate. However, in the case of pigment addition, it gradually decomposes in the living environment, so if this is used, the decomposition rate can be adjusted at the time of parts replacement of the product, and the material can be made to know the time of replacement.

【0069】

Further, the conventional photocatalyst is made of a semiconductor photocatalyst material typified by titanium oxide. These materials are characterized by being antibacterial and self-cleaning by the redox reaction of the photocatalyst. Self-cleaning may show deterioration of the catalyst if dirt becomes noticeable, but antibacterial properties are difficult to judge visually. In particular, even if the function is deteriorated such as film peeling and performance deterioration, if it is used without noticing it, dangerous bacteria and the like will propagate, which may cause a problem.

【0070】

Therefore, since the present invention provides a photocatalyst material whose performance can be easily visually determined, the present invention is an antibacterial and antifouling material made of a photocatalyst, characterized in that deterioration of function can be visually observed. It is an antifouling material and is a photocatalyst made by adding a pigment that absorbs visible light to a photocatalyst made of titanium oxide.

【0071】

Photocatalysts generally absorb ultraviolet light to produce a catalytic action. Only a small amount of ultraviolet rays are present in the living environment, and the photocatalyst uses this small amount of light to perform antibacterial and antifouling. If visible light can be used effectively, a high-performance photocatalyst can be provided in a living environment. As for solar cells, wet solar cells using titanium oxide using visible light have already been prototyped. This is due to the sensitizing action of stacking dyes that absorb visible light, and the electrons excited by the dye absorbing visible light stimulate titanium oxide to allow an electric current to flow. Similar reductions can be expected to have similar effects on photocatalysts. By adding a material that absorbs visible light to titanium oxide, the electrons that absorb visible light and are excited can stimulate titanium oxide and be used for the redox reaction of the photocatalyst. However, many of the dyes having such a sensitizing effect are organic substances, and are not only directly decomposed by ultraviolet rays but also easily decomposed by photocatalytic action. Furthermore, the effective use of visible light improves performance, makes it easier to decompose, and deteriorates immediately even in a living environment. Therefore, in the present invention, a test was conducted focusing on a pigment system that is less deteriorated by ultraviolet rays, and it was found that the pigment system has a low decomposition rate and also has a sensitizing effect. Although it is a pigment, the raw material is mainly an organic substance, so it will eventually decompose and deteriorate. However, in the case of pigment addition, it gradually decomposes in the living environment, so if this is used, the decomposition rate can be adjusted at the time of parts replacement of the product, and the material can be made to know the time of replacement.

【0072】

Further, conventionally, the photocatalyst applied to plastic products is titanium oxide to which an inorganic binder such as silica is added. Such a photocatalyst in which titanium oxide particles are dispersed in an inorganic binder has a problem that the performance is deteriorated because the occupied area of titanium oxide is smaller than that of a photocatalyst composed of only titanium oxide. In particular, when film strength is required, a large amount of inorganic binder is added to increase the strength, but there is a problem that the activity is significantly reduced. In addition, photocatalysts are excellent in decomposing organic substances, but are ineffective against stains on inorganic substances. However, the dirt of the inorganic substance adheres extremely on the dirt of the organic substance. If the stains on organic substances are removed by photocatalytic action, the adhesion of stains on inorganic substances can be prevented to some extent. However, once the inorganic substance adheres, the attached portion does not transmit light and the photocatalytic action is lost, and the dirt of the organic substance cannot be decomposed, and as a result, the dirt is promoted. Therefore, cleaning is performed by increasing the hydrophilicity to remove the adhesion of inorganic substances. However, with respect to the photocatalytic material and product to be washed, it is necessary to improve the strength by using a large amount of binders constituting the photocatalyst, but there is a problem that the photocatalytic action is lowered as described above.

【0073】

Therefore, the present invention provides a photocatalyst material in which the performance of the photocatalyst does not deteriorate even if a large amount of binder is added, and the film does not peel off when washed with water or the like. Dirt can be easily cleaned, reducing the number of product cleanings and parts replacement.

【0074】

The present invention is a photocatalytic material having an antibacterial and antifouling action, which can be washed with water to remove inorganic stains, and the strength is further increased by adding an organic resin.

【0075】

Further, in the photocatalyst of the present invention, the organic resin used as a binder has a silanol group, or the organic resin has UV curability. When using a UV curable resin, add an Al, Ti, Si-based coupling agent.

【0076】

When the photocatalyst is coated on the plastic surface and silica is used as the 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 becomes sufficient and the strength that can withstand cleaning is generated. However, the organic resin is decomposed by photocatalytic action. In order 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 into the side chain of the organic resin and binding the contact portion with the titanium oxide surface by the inorganic system.

【0077】

Further, when an organic resin is used, unlike a ceramic material such as silica, it 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 things like instant adhesives. The superglue cures in a short time, but is gradually decomposed by the photocatalyst. Examples of the resin that can be cured in a short time and have excellent light resistance include a UV curing system. The UV curing system is cured by ultraviolet rays, and is gradually polymerized and cured by ultraviolet rays irradiated from a fluorescent lamp. However, it is also a fact that it is gradually decomposed by a photocatalyst. Therefore, by appropriately combining photocuring and photodecomposition, light resistance can be improved as a result.

【0078】

UV curable resin is completely TiO₂ The surface of the particles is covered with resin and the catalytic properties are lost. Therefore, by adding a coupling agent, TiO₂ The exposed part of the surface can be increased. Further, the photocatalyst decomposes the surface-adsorbed water to generate radicals, but by adding a coupling agent, a large amount of surface-adsorbed water can be retained and the catalytic performance can be exhibited.

【0079】

BEST MODE FOR CARRYING OUT THE INVENTION

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

【0080】

Tables 1 to 9 show the composition of the thin film of the low-temperature curable highly active oxide photocatalyst formed on the surface of various molded products, painted steel sheets, filters, etc. and the effects of the examples.

【0081】

(Example 1) The air purifier, which is the first embodiment of the present invention, will be described with reference to FIGS. 1, 2 and 3.

【0082】

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 main body 1, the condenser motor 7 is fixed to the rear cover 12 with screws 8, the condenser for driving the motor 11 and the operation switch 9 are fixed, and the fan 6 is fixed to the condenser motor 7 with the nut 5 and is connected to the rear cover 12. The frame 4 is fixed with screws 13. Further, the filter 3 is fixed to the panel (suction port) 2, and the panel (suction port) 2 is removed to take out the filter 3. The switch knob 10 is fixed to the operation switch 9.

【0083】

The driving force of the condenser motor 7 causes the fan 6 to rotate, creating an air flow. This air flow sucks in dirty air in the room containing dust, smoke, oil fine particles, microorganisms, dead microorganisms, pollen, foul odors, etc. from the panel (suction port) 2. The dirty air sucked in is filtered and cleaned by the three parts of the filter, and then discharged from the exhaust port 15 of the 14th part of the grill. The three parts of the filter have a composite structure to have a function to remove various stains and odors. The filter 3 is composed of an outer filter 3a, which is a layer covering the outer surface, and an inner filter 3b inside the outer filter 3a (not shown). The basic structure of each filter is a non-woven fabric layer such as polyester, urethane, cellulose, nylon, or polyolefins that have been electretized, or a sponge-like porous layer for filtering dust. In addition to these basic structures, activated carbon particles and fibers for adsorbing odors are mixed, blended, or sealed in the inner filter 3b. In addition, a chemical for neutralizing the odor may permeate the fiber itself or spread it on the surface. As the drug, in addition to various organic acids and flavonoid alkaloids, antibacterial agents for suppressing the growth of microorganisms are also used. In recent years, highly safe chitin, chitosans, catechin derivatives and the like have also been used. The amount of air generated is about 2 to 3 (m)³/ Minute), and has the ability to remove 70 to 95% of cigarette smoke in a room of 8 tatami mats after 30 minutes of operation.

【0084】

In this example, the outer filter 3a is made of a non-woven fabric of acrylic fiber, and a thin film of the low-temperature curing type highly active oxide photocatalyst of sample No. 21 shown in Table 3 described later is formed on the surface thereof. Acrylic non-woven fabric filter is SiO₂ Only a thin film, that is, sample No. 12 in Table 1 is formed as an underlayer, and after forming this film, a thin film of a low-temperature curable highly active oxide photocatalyst of sample No. 21 is formed. The method of forming the film will be described in detail in Example 9 described later, but after adjusting a predetermined sol and coating the work by various methods, it is cured while irradiating a low-pressure mercury lamp in an atmosphere of 120 ° C. I let you. In the following examples among various examples, a film was formed by the same means. As for the coating method, a method such as spraying, dipping, or brush coating was performed according to the shape of the work.

【0085】

The outer filter 3a is the part that first filters the dirty air taken in from the panel (suction port) 2, and contains various foreign substances such as dust, smoke, oil particles, microorganisms and dead microorganisms, pollen and foul odors. Adheres in large quantities. The panel (suction port) 2 is provided with a large number of openings for efficiently sucking air, and the air suction surface of the outer filter 3a is exposed to light such as indoor lighting and sunlight from these openings. Be irradiated. Foreign matter collected on the surface of the outer filter 3a is oxidatively decomposed by this light. In particular, cigarette smoke and oil fine particles adhere to the low-temperature curable highly active oxide photocatalyst on the surface of the filter in the form of a thin film, so that they are efficiently decomposed. In addition, various microorganisms such as bacteria and molds floating in the air are killed or their reproduction is suppressed by the decomposing action of the highly active photocatalyst. Further, by covering the fiber surface of the non-woven fabric filter with a glassy film, the wettability with smoke particles is improved, and the smoke collecting effect is also improved.

【0086】

In addition, the panel (suction port) 2, frame 4, operation switch 9, and rear cover 12, which are the exterior parts of the main body 1 of this air purifier, are injection-molded products of thermoplastic plastic AS. A low temperature curable highly active oxide photocatalyst thin film is formed on the outer surface of these parts.

【0087】

In this embodiment, on the surface of these target ABS parts, a schematic view of the thin film on the surface of the sample acrylic non-woven fabric filter shown in Table 6 described later is shown in FIG. 19 as a cross-sectional view. The plastic adherend 189 is an acrylic fiber here, and the low-temperature curing type highly active oxide photocatalyst thin film is composed of a surface first layer 194 and a surface second layer 192, both of which are SiO.₂ TiO in membrane 186₂ Fine particles 187 and lithium 190 are dispersed, and antimony-added tin oxide fine particles 193 are dispersed in the surface second layer 192.

【0088】

A thin film of No. 86 low-temperature curing type highly active oxide photocatalyst is formed. In the acrylic non-woven fabric filter, the first layer is formed after the corona discharge treatment, and after this film is formed, the second layer of the low temperature curable highly active oxide photocatalyst containing the ATO of sample No. 86 is formed. ..

【0089】

These exterior parts are irradiated with light such as interior lighting and sunlight. Therefore, even if various foreign substances as described above are attached, they are oxidatively decomposed as in the case of the filter.

【0090】

FIG. 3 shows a cross-sectional view of an electrostatic precipitator type air purifier. The whole is composed of a front cover 16 and a rear cover 17. The front cover 16 and the panel 18 are provided with the intake port 19 and the exhaust port 20, and the intake port 19 and the removable pre-filter 21 are provided in the ventilation path connecting the intake port 19 and the exhaust port 20. At the rear, the dust collection electrode 22 and the discharge electrode 23 are provided facing each other, and further, there is a dust collection electrode 22 and an ozone removal filter 24 for removing ozone generated from the discharge electrode 23. There is a dust collection unit in which a dust collection electrode 22, a discharge electrode 23, and an ozone removal filter 24 are mounted on a frame body 25. Further behind, there is a cushioning material 26 at the contact part with the dust collecting unit, a duct 28 connecting the blower 27 and the dust collecting unit, and a blower 27. The cushioning material 26 is attached to the duct 28, and the duct 28 is a blower 27. There is a blower unit that is attached to and is composed of the same body. The purified air is exhausted from the exhaust port 20.

【0091】

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

【0092】

In this embodiment, the pre-filter 21 is a nylon net, and a thin film of the low-temperature curing type highly active oxide photocatalyst of sample No. 21 shown in Table 3 described later is formed on the surface thereof. In the nylon net, a thin film of the low-temperature curing type highly active oxide photocatalyst of sample No. 21 is formed after the ultraviolet irradiation treatment. A schematic view of the thin film on the surface of the nylon net is shown in FIG. 18 in a cross-sectional view. The plastic adherend 189 is a nylon fiber here, and the low temperature curable highly active oxide photocatalyst thin film 191 is SiO₂ TiO in membrane 186₂ Fine particles 187 and lithium 190 are dispersed.

【0093】

The rear cover 17 is an ABS injection-molded product, the front cover 16 is a galvanized steel plate plastically processed, and the outer surface is painted with a polyester-based baking paint. On the outer surfaces of the rear cover 17 and the front cover 16, the low-temperature curing type highly active oxide photocatalyst thin film of sample No. 86 is formed in the same manner as described above.

【0094】

(Example 2) The ventilation fan, which is the second embodiment of the present invention, will be described with reference to FIG.

【0095】

FIG. 4 shows a cross-sectional view of the structure of the kitchen ventilation fan as viewed from the side. The electric motor 30 is attached to the box-shaped frame 29, and the blades 31 are attached to the electric motor 30. A shutter 32 is attached to the outdoor side (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 35 with a fluorescent tube 34 is attached to the upper part of the orifice 33 on the indoor side (intake side). A filter 36 is attached to the indoor side (intake side) of the orifice 33 and the luminaire 35. There is an oil pocket 37 at the bottom of the filter 36.

【0096】

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

【0097】

The structure shown in Fig. 4 shows a kitchen-specific ventilation fan, but the basic structure is the same for general indoor use, toilet use, bathroom use, etc., except for the mounting angle and the positional relationship of the parts.

【0098】

As in the case of the air purifier described above, 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.

【0099】

In this embodiment, the filter 36 is a single-layer filter made of a non-woven fabric of acrylic fibers, and a thin film of the low-temperature curing type highly active oxide photocatalyst of Sample No. 22 shown in Table 3 is formed on the surface thereof. Acrylic non-woven fabric filter is SiO₂ Only a thin film, that is, sample No. 12 in Table 1 is formed as an underlayer, and after this film is formed, a thin film of a low-temperature curable highly active oxide photocatalyst of sample No. 22 is formed.

【0100】

The frame 29 is an injection-molded product of PS (high-impact styrene resin), and the orifice 33 and the blade 31 are injection-molded products of ABS. Similar to the air purifier described above, a low-temperature curable high-activity oxide photocatalyst thin film of sample No. 86 is formed on the surface of these molded parts.

【0101】

The shutter 32, which is a component facing the outside, is made of cold-rolled steel sheet that has been subjected to molten galvanized treatment, and the surface is electrodeposited with acrylic resin, and the surface of the shutter 32 is similarly sample No. 86. A low-temperature curing type highly active oxide photocatalyst thin film is formed.

【0102】

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 fixture 35. In addition, parts such as the frame 29, the orifice 33, the blades 31, and the oil pocket 37 are also irradiated with the light emitted from the luminaire 35. The surface of the shutter 8 facing the outdoors is irradiated with sunlight.

【0103】

In the case of this embodiment, since it is a ventilation fan used in the kitchen, the degree of dirtiness is very large as compared with a normal ventilation fan. That is, a large amount of fine particles of cooking oil scattered during cooking adhere to the surface in a large amount. In the case of a ventilation fan for a kitchen, a lighting fixture 35 is generally provided. This is a function provided for illuminating the hand during cooking, and it can be turned on in synchronization with the operation of the ventilation fan, or only the lighting function can be turned on independently. Since the organic matter decomposition efficiency of the photocatalyst according to the present invention is higher than that of the conventional one, in the case of a normal low dirt load, a sufficient decomposition action can be obtained at the level of indoor lighting without installing a lighting fixture in particular. It may be insufficient in the case of a place with a large dirt load such as. However, if a lighting function using a normal fluorescent lamp or an incandescent lamp is provided as in this embodiment, a sufficient effect can be obtained even in a place with a large dirt load such as a kitchen or a toilet.

【0104】

(Example 3) The electric fan, which is the third embodiment of the present invention, will be described with reference to FIG.

【0105】

FIG. 5 shows the structure of the electric fan by an external perspective view. A support column 39 is mounted on the base portion 38 of the fan body, and a slide pipe 40 is slidably inserted on the support column 39. The slide pipe 40 supports the head 44 composed of blades 41, guards 42, electric motor 43, etc. above. The support column 39 is formed by increasing its diameter downward in consideration of strength. The blade 41 is rotated by the driving force of the electric motor 43 to create an air flow in front of the back surface of the main body. The guard 42 plays a role of preventing fingers and the like from coming into contact with the rotating blade 41, but in order to prevent accidents such as children and to further improve safety, the entire guard 42 is net 45 (not shown). It may be covered with. A remote control holder 46 is attached to the lower part of the support column 39, and normally the remote control 47 is stored in the remote control holder 46. When the operation mode is set by operating the switch of the remote controller 47, an infrared signal is transmitted from the infrared emitting unit 48 of the remote controller 47, and the signal is received by the infrared receiving unit 49 on the upper surface of the base 38 of the main body to perform the setting operation.

【0106】

In this embodiment, the blade 41 is an injection molded product of AS resin. On the surface of the blade 41, a low-temperature curing type highly active oxide photocatalyst thin film of sample No. 86 is formed as in the case of a molded product such as ABS.

【0107】

The guard 42 is made of a steel wire having a polyester-based baking finish, and a low-temperature curing high-activity oxide photocatalyst thin film of sample No. 86 is also formed on the surface thereof. The net 45 is made of nylon fiber, and a low-temperature curable highly active oxide photocatalyst thin film of sample No. 86 is formed on the surface thereof.

【0108】

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

【0109】

A thin film of the low-temperature curing type highly active oxide photocatalyst of Sample No. 86 is also formed on the surface of these transparent parts. After forming a film of a titanate-based coupling agent on the surface of the target part, the first layer is formed, and after forming this film, a low-temperature curable highly active oxide containing ATO of sample No. 86 A second layer of photocatalyst is formed.

【0110】

The surfaces of the blades 41 and guards 42 are exactly the same as the blades and frames of the air purifier and ventilation fan described above, and foreign matter floating in the air adheres to them and becomes dirty. Since the film of the type highly active oxide photocatalyst is formed, the attached dirt is oxidatively decomposed at the illuminance level of the indoor illumination light, which has the effect of making it difficult to get dirty.

【0111】

Further, in this embodiment, a mechanism for remote control using infrared rays is used, but a low-temperature curing type highly active oxide photocatalyst thin film is formed on the surfaces of transparent parts used for the light emitting part and the light receiving part of the infrared signal. Therefore, the signal communication is not hindered by the dirt adhering to the surface of the component.

【0112】

In this embodiment, an example of a fan using propeller type blades is used, but the same effect can be obtained with a fan using sirocco type blades with exactly the same configuration.

【0113】

(Example 4) A vacuum cleaner, which is a fourth embodiment of the present invention, will be described with reference to FIGS. 6 and 7.

【0114】

FIG. 6 shows an external perspective view of the vacuum cleaner, and FIG. 7 shows a cross-sectional view of the vacuum cleaner body. The vacuum cleaner body 50 is composed of a lower cover 51 of a synthetic resin molded product that covers the lower part, an upper cover 52 that covers the upper part, a lid cover 53, a grill cover 54, a handle portion 55, and the like. The large-diameter rear wheel 56 and the small-diameter universal wheel 57 are arranged in the center of the bottom surface of the lower front part. A main body switch portion 58 is provided in the central portion of the upper cover 52, and the main body switch portion 58 is composed of an infrared light receiving portion 59 in the center, a power switch 60, and a cord reel button 61. A mouthpiece hose assembly 66 including a suction hose portion 63, an extension pipe portion 64, and a mouthpiece portion 65 is connected to the dust collection chamber 62. A handle portion 67 is connected to the upper portion of the extension pipe portion 64, and a hand operation portion 68 is attached to the handle portion 67. The hand operation unit 68 is provided with an infrared signal transmitting unit 69, and the infrared signal transmitted from the infrared signal transmitting unit 69 is transmitted to the infrared receiving unit 59 of the vacuum cleaner main body 50, so that it is wireless. Be manipulated. The vacuum cleaner main body 50 is provided with a dust collecting chamber 62 in front of the inside, an electric blower part 70 and a cord reel part 71 are attached to the inner rear, and a control board 72 is further above the electric blower part 70 and the cord reel part 71. It is provided.

【0115】

Further, behind the electric blower unit 70, a first exhaust ventilation passage 73 that is long in the vertical direction and is provided from the lower end to the upper end of the back surface of the vacuum cleaner main body 50 is formed, and the lower end of the first exhaust ventilation passage 73 is formed. Further, it communicates with the second exhaust ventilation passage 74 formed in the lower part of the electric blower unit 70. The first exhaust ventilation passage 73 and the second exhaust ventilation passage 74 form an exhaust ventilation passage 75 (not shown), and the second exhaust ventilation passage 74 is communicated with the electric blower unit 70 to form the first exhaust. The ventilation path 73 is communicated with the exhaust ventilation section 76. Paper filter mounting portions 77,78 are provided on the upper part of the dust collecting chamber 62, and the thick paper of the paper filter 79 is attached to the paper filter mounting portions 77,78, and the lid cover 53 constituting the upper part of the dust collecting chamber 62 is attached. By closing, the mounting port 80 and the paper filter 79 are set in place. The free wheel 57 is horizontally rotatably attached to a recess formed in the front bottom of the lower cover 51. Dust, dust, mites, and microorganisms sucked in with the air flow from the attachment port 80 are collected by the paper filter 79.

【0116】

Then, the air flow from which these solid substances have been removed is sent to the electric blower unit 70 via a communication port 83 provided with an auxiliary filter 82 provided in the partition plate 81 between the dust collection chamber 62 and the electric blower 70. It is guided to cool the electric blower unit 70, and the cooled air flow is exhausted from the exhaust ventilation unit 76 provided with the exhaust filter 84 through the second exhaust ventilation passage 74 and the first exhaust ventilation passage 73. Will be done.

【0117】

In this embodiment, the upper cover 52, lid cover 53, grill cover 54, handle portion 55 of the vacuum cleaner body, extension pipe portion 64, mouthpiece portion 65, and handle portion 67 of the mouthpiece hose assembly 66 are injection-molded with ABS resin. It is a product, and a thin film of the low-temperature curing type highly active oxide photocatalyst of sample No. 86 is formed on the surface of these molded products. After forming a film of a titanate-based coupling agent on the surface of the target part, the first layer is formed, and after forming this film, a low-temperature curable highly active oxide containing ATO of sample No. 86 A second layer of photocatalyst is formed.

【0118】

Since the vacuum cleaner is a highly mobile object as compared with the articles according to the other embodiments, the surface of the exterior parts is easily scratched. That is, the vacuum cleaner body and the mouthpiece often collide with furniture and walls while traveling on the floor, which gradually forms scratches and loses its luster. Not only is it damaged, but it may also be damaged, such as cracks, triggered by scratches. In order to prevent this, conventional coating treatment with an ultraviolet curable acrylic resin or the like has been performed to secure the surface hardness. However, according to the present invention, TiO constituting a low temperature curable highly active oxide photocatalyst thin film is formed.₂And SiO used as a binder₂ The hardness of the film is harder than ABS, and the pencil hardness is about 2H to 4H. Therefore, when used for these exterior parts, the effect of preventing scratches and other scratches can be obtained, and at the same time, the original hardness is obtained. It is possible to obtain effects such as antifouling and suppression of microbial growth.

【0119】

In particular, the handle portion 67 is a part that can be touched with bare hands, and bacteria can easily grow by using body fats such as attached sweat as nutrients. Conventionally, organic antibacterial agents such as imidazole and thiazolin, copper, etc. An inorganic antibacterial agent such as zinc or silver was kneaded into the molding resin to obtain an antibacterial effect, but these treatments are unnecessary.

【0120】

In addition, since the mouthpiece and wheels are subject to sliding or rotational movement, static electricity is likely to be charged when using a vacuum cleaner in a dry environment, and fibers such as carpets and dust adhere to the surface of the above parts. I often do it. In order to prevent this, various surfactants and hydrophilic polymers such as polyamide and polyethylene glycol have been kneaded into the molding resin to reduce the surface resistance. However, according to the present invention, this has been prevented. Since the resistance value of the low-temperature curing type highly active oxide photocatalyst thin film can be lowered, the effect of preventing the adhesion of dust and the like can also be obtained even with ABS molding resins having a high electric resistance value. A hand operation unit 68 is attached to the handle portion 67, and a control board on which electronic components are mounted is attached to the back surface of the hand operation unit 68. Static electricity is generated in the vicinity of the hand operation unit 68. When charged, the control board may malfunction, and the antistatic effect according to the present invention can prevent not only the adhesion of dust but also the malfunction of the control board.

【0121】

Further, the infrared signal transmitting unit 69 provided in the hand operating unit 68 and the infrared receiving unit 59 of the vacuum cleaner main body 1 are molded of transparent AS resin as in the case of the electric fan of the third embodiment described above. Although it is made of a product, since a low-temperature curing type highly active oxide photocatalyst thin film is formed on the surface, it is possible to obtain an effect of preventing the reception and transmission of infrared signals from being hindered by dirt.

【0122】

Furthermore, the exhaust filter 84 attached to the exhaust ventilation part 76 of the main body is made of a blended non-woven fabric of acrylic and PP, and the surface of this exhaust filter 84 is the low-temperature curing type highly active oxide photocatalyst of sample No. 21. A thin film is formed. The exhaust ventilation portion 76 is provided with a large number of openings, and the air discharge surface of the exhaust filter 84 is irradiated with light such as indoor lighting and sunlight from these openings, so that the surface of the filter is also cleaned. Will be done.

【0123】

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, the handle portion 55, and other parts transparent, the outside light reaches the inside and the paper inside the dust collection chamber 62. When the low-temperature curable highly active oxide photocatalytic thin film according to the present invention is formed on the filter fiber surface of the filter 79 or the auxiliary filter 82, an antibacterial effect and a deodorizing effect can be obtained.

【0124】

(Example 5) The clothes dryer according to the fifth embodiment of the present invention will be described with reference to FIG.

【0125】

FIG. 8 shows a cross-sectional view of the main body of the clothes dryer. 85 is the outer frame, 86 is the opening / closing lid, 87 is the rotating drum, 88 is the heat source, 89 is the exhaust port, 90 is the double-wing fan, 91 is the fan casing, 92 is the motor that is the power, 93 is the power of the motor 92. Belt that transmits to the rotating drum 87, 94 is a round belt that transmits the power of the motor 92 to the double-wing fan 90, 95 is the first airtight felt, 96 is the second airtight felt, 97 is the partition plate, 98 is. A circulation duct that guides the circulating air discharged from the fan casing 91 to the heat source 88, 99 is a lint filter device, 100 is an FD beam that fixes the fan casing 91 to the outer frame 85, and 101 is a mounting ring for attaching a bearing 102. The rotary drum 87 is rotatably slidably supported by the bearing 102. The rotating drum 87 rotates together with the double-wing fan 90 by transmitting the driving force of the motor 92 via the belt 93. By this rotation, the clothes are agitated, and at the same time, a circulating air (a solid line is lost) is generated, and when the circulating air passes through 88 parts of the heat source, it is heated and enters the rotating drum 87 to remove the moisture of the clothes. Evaporate and dry. After that, the double-wing fan 90 passes through the circulation duct 98, and the circulating air is sent to the heat source 88, which is heated again and the clothes are repeatedly dried. A lighting fixture 104 with a fluorescent tube 103 is attached to the inside of the opening / closing lid 86. A cushioning material 105 that absorbs impact is attached along the inner peripheral surface of the rotating drum 87. The cushioning material 105 is made of a foam of PP.

【0126】

In this embodiment, the inner surface parts of the rotating drum 87, such as the cushioning material 105, the lint filter device 99, and the inner surface of the opening / closing lid 86, which are the parts to be irradiated with the light of the lighting equipment, are made of ABS or PP resin. A thin film of the low-temperature curing type highly active oxide photocatalyst of Sample No. 86 is formed on their surfaces. After forming a film of silane coupling agent on the surface of the target part, the first layer is formed, and after forming this film, the low-temperature curable highly active oxide photocatalyst containing ATO of sample No. 86 The second layer is formed.

【0127】

The luminaire can be arbitrarily lit during the drying operation or as an independent operation regardless of the drying operation, and when the light of the fluorescent tube 103 is irradiated, the attached organic matter or contact with the above-mentioned component surface. Since the malodorous substance contained in the air is effectively oxidatively decomposed, the effect of suppressing the growth of microorganisms and deodorizing can be obtained.

【0128】

Since the clothes are rotating during the drying operation, the light does not reach evenly enough, so it is more effective to use an operation program that lights up for a certain period of time after the drying operation to clean the inside of the rotating drum 87. is there.

【0129】

The outer frame 1 is made of galvanized steel plate, and the outer surface is powder-coated with epoxy resin. A low-temperature curable highly active oxide photocatalyst thin film containing ATO of sample No. 86 is formed on the surface of this painted surface.

【0130】

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

【0131】

The effects of the photocatalytic thin film on the outer surfaces of the outer frame 85 and the opening / closing lid 86, which are the exterior parts, are the same as in the case of the exterior parts of Examples 1 to 4 described above, and the effects such as sufficient antifouling and antibacterial effects by indoor light are obtained. Is obtained.

【0132】

(Example 6) The dishwasher according to the sixth embodiment of the present invention will be described with reference to FIGS. 9, 10 and 11.

【0133】

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

【0134】

The inside of the main body 106 is divided into a drying chamber 107 and an operation control chamber 108 by a partition plate 109. In the operation control chamber 108, a heating blower unit 114 for sending out dry air including a fan motor 110, a blower fan 111, a casing 112, and a heater 113 is connected to the drying chamber 107 by a duct 115. A controller 118 is arranged between the intake port 117 in which the filter 116 is arranged and the heating / blowing unit 114. In addition, an upper basket 119 and a lower basket 120 for storing tableware are arranged above and below the drying chamber 107. The lower car 120 is arranged below the door 121 on a water pan 124 resting on a movable rail 125 connected to a hinge 122 so that it can be tilted freely. Similarly, the upper car 119 is also arranged on the movable rail 123. The movable rails 123 and 125 are arranged so as to be movable back and forth on a roller (not shown) rotatably provided on the side wall of the drying chamber 107, and the handle 126 of the door 121 is pulled toward the front. The lower car 120 pulls the tip of the car from the drying chamber 107 so that the upper car 119 can be pulled out to the outside. The exhaust port 128 provided on the panel 127 forms a grid pattern and includes an exhaust filter 129. The opening 130 provided in the partition plate 109 of the main body 106 and the exhaust duct 131 are connected to the drying chamber 107. The temperature detector 132 is arranged in the exhaust duct 131 which is not easily affected by the outside air temperature.

【0135】

The intake port 117 is an injection-molded product made of PP, and the intake filter 116 is a nylon net, and the surface of the intake filter 116 is a low-temperature curing type highly active oxide photocatalyst of sample No. 91 shown in Table 7 described later. Thin film is formed. After the nylon net is irradiated with ultraviolet rays, a thin film of a low-temperature curable highly active oxide photocatalyst containing silver of sample No. 91 is formed.

【0136】

Since the surface of the intake filter 116 is irradiated with indoor illumination light, the attached organic substances and malodorous substances in the air taken in are oxidatively decomposed. Similarly, the low-temperature curing type highly active oxide photocatalyst thin film of sample No. 91 is formed in the exhaust port 128 and the exhaust filter 129. Moisture discharged from the intake and exhaust ports tends to condense and become moist, and mold and bacteria may grow. However, if a photocatalyst with high decomposition efficiency according to the present invention is used, it is effective with indoor light. The growth of these microorganisms can be suppressed. The formulation of Sample No. 91 is particularly suitable because the silver itself contained in the composition has an antibacterial effect. In order to enhance the antibacterial effect, ceramic particles such as zeolite or apatite carrying silver may be mixed.

【0137】

A lighting fixture 134 with a fluorescent tube 133 is attached to the inside of the drying chamber 107. The lighting function is lit when the door 121 is opened, and can be used not only as the original function of lighting such as checking the degree of drying of the tableware inside, but also as a function of cleaning the inside of the drying chamber 107. That is, by forming a photocatalyst thin film on the surface of the internal parts of the drying chamber 107, antibacterial and antifouling effects of the portion irradiated with light can be obtained. In this embodiment, the upper basket 119 and the lower basket 120 have a structure in which a polyamide-based powder resin is baked and coated on an iron frame, and the surface of the coated surface is subjected to ultraviolet irradiation treatment and then sample No. 92. A thin film of a low-temperature curable highly active oxide photocatalyst containing copper is formed. These upper and lower baskets are members that come into direct contact with tableware and are required to be clean, but they are kept clean because the effect of the photocatalyst provides antifouling on the surface and the effect of suppressing the growth of microorganisms. Is done. Like silver, copper has its own antibacterial effect, so it has the effect of enhancing the antibacterial effect.

【0138】

As in the case of the clothes dryer of Example 5, the tableware becomes a shadow during the drying operation and the light does not reach sufficiently evenly. Therefore, after the drying operation is completed, the tableware is lit for a certain period of time to clean the inside of the drying chamber 107. It is even more effective to use an operation program that does.

【0139】

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

【0140】

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

【0141】

FIG. 12 shows an external perspective view of the dishwasher, and FIGS. 13 and 14 show a cross-sectional view of the dishwasher.

【0142】

A tableware storage tank 136 is arranged inside the outer frame 135, and a step portion 138 is provided at the lower part of the side wall of the tableware storage tank 136 provided with a door 137 for opening and closing the front opening of the tableware storage tank 136. The lower basket 139 is detachably arranged. The pump 140 is located on the outside of the bottom of the tableware storage tank 136. This pump 140 has a pump motor 141. A lower arm nozzle 142 that rotates directly under the tableware storage lower basket 139 is arranged. A plurality of small holes 143 are provided on the upper surface of the lower arm nozzle 142. In the lower basket 139 for storing tableware, a Venturi pipe 145 that sends the washing water sent from the pump 140 to the upper arm nozzle 144 is arranged. The upper arm nozzle 144 rotates with the center as a fulcrum directly below the upper basket 146 for storing tableware. A plurality of small holes 147 are provided on the upper surface of the upper arm nozzle 144. A heater 148 is arranged on the bottom or back of the tableware storage tank 136. The heater cover 149 is arranged so as to wrap the heater 148. A water supply solenoid valve 150 is arranged on the outer surface of the tableware storage tank 136. An exhaust duct 151 is arranged on the upper part of the outer surface of the tableware storage tank 136 and is connected to the exhaust port 152. The control panel 153 is located on the upper part of the outer surface of the door 137. A drainage pump 154 and a blower unit 155 are arranged on the outside of the bottom of the tableware storage tank 136.

【0143】

During the cleaning operation, water is supplied from the water supply solenoid valve 150, the pump 140 is driven, pressure water is supplied to the lower arm nozzle 142, and at the same time, the heater 148 is energized to raise the water temperature. At the same time that water is ejected from the hole 143, when it is sent to the upper arm nozzle 144 via the Venturi tube 145, water is also ejected from the hole 147. In this way, the upper and lower arm nozzles rotate to evenly spray hot water onto the dishes in the tableware storage basket 146 to remove dirt. After the cleaning operation is completed, the drainage pump 154 is energized to discharge sewage, and then the same operation as above is repeated several times to rinse and remove the internal dirt. When the final rinsing operation is completed, the drying operation is started. The blower unit 155 is energized, the blower fan 156 is rotated, and the air is supplied into the tableware storage tank 136 through the blower duct 157 and the heater 148 arranged at the bottom of the tableware storage tank 136. At this time, the heater 148 turns on / off the energization for a certain period of time to turn the cold air into warm air. This warm air converts the water droplets and residual water inside and the water droplets adhering to the tableware into steam, passes through the exhaust duct 151, and is discharged to the outside of the machine through the exhaust port 152.

【0144】

In this embodiment, the exhaust port 152 is an ABS resin molded product, but a thin film of a low-temperature curing type highly active oxide photocatalyst containing silver of sample No. 91 is formed like the above-mentioned dishwasher. Moisture discharged from the exhaust port tends to condense and become moist, and mold and bacteria may grow. However, if a photocatalyst with high decomposition efficiency according to the present invention is used, these can be effectively used in room light. It is possible to suppress the growth of microorganisms.

【0145】

A lighting fixture 159 equipped with a fluorescent tube 158 is attached to the inside of the tableware storage tank 136. The lighting function is lit when the door 137 is opened, and can be used not only as the original function of lighting such as washing the dishes inside and checking the degree of dryness, but also as a function of cleaning the inside of the tableware storage tank 136. That is, by forming a photocatalyst thin film on the surface of the internal parts of the tableware storage tank 136, antibacterial and antifouling effects of the portion irradiated with light can be obtained.

【0146】

In this embodiment, the upper basket for storing tableware 146 and the lower basket for storing tableware 139 have a structure in which a polyamide-based powder resin is baked and painted on an iron frame, and sample No. 92 is formed on the surface of this painted surface. A thin film of a low-temperature curable high-activity oxide photocatalyst containing copper is formed.

【0147】

These upper and lower baskets are members that come into direct contact with tableware and are required to be clean, but they are kept clean because the effect of the photocatalyst provides antifouling on the surface and the effect of suppressing the growth of microorganisms. Is done.

【0148】

Other members that are irradiated with light from the lighting fixture 159 include tableware storage tank 136, upper arm nozzle 144, lower arm nozzle 142, venturi tube 145, etc. These parts are PP resin injection molded products and SUS plastic deformed products. Is used. After corona discharge treatment on the surface of these parts, SiO₂ Only a thin film, that is, sample No. 12 in Table 1 is formed as an underlayer, and after forming this film, a thin film of a low-temperature curable highly active oxide photocatalyst of sample No. 21 is formed.

【0149】

By forming a photocatalytic thin film on the parts inside the tableware storage tank 136 and attaching the lighting fixture 159, there is an effect of improving the drying efficiency as an effect peculiar to the dishwasher. This effect is achieved by TiO, which is the basic material of the low-temperature curing type highly active oxide photocatalytic thin film according to the present invention.₂ , SiO₂ Is a material with good water wettability, and at the same time, even if a substance that repels water such as oils and fats removed from dirty tableware adheres, it is decomposed by the light of the lighting equipment 159, so it is always highly wet. By obtaining the effect of keeping.

【0150】

The operation of washing dishes is to raise the water temperature to 60 to 70 ° C at the final rinse, raise the internal temperature, and then expel moisture to the outside of the machine by blowing air, but it remains inside the dish storage tank 136. Water droplets cause a decrease in drying efficiency. Since parts such as the tableware storage tank 136, the upper arm nozzle 144, the lower arm nozzle 142, and the Venturi tube 145 are required to have high water resistance, hydrophobic materials are often used, and the surface is usually poorly wetted. 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 water droplets with a high contact angle. Since a detergent containing a surfactant is added during the washing operation, the surface tension of the washing water decreases, the contact angle becomes low, and the water becomes well wet. It is almost absent and the surface tension of water is very high. Therefore, at the end of the final rinse, the rinse water adheres to the surface of each component inside the tableware storage tank 136 in the form of innumerable water droplets having a high contact angle.

【0151】

These high contact angle water droplets have a large amount of water and do not dry easily as compared with the case of a thin film-like water film. In addition, since water droplets are shrunk and dried while maintaining the shape of water droplets during drying, the surface area is also reduced, so that the drying speed is further slowed down and the time required for drying is about three times longer. Most of the tableware is made of glass, ceramics, or wood, which has good water wettability, and it dries relatively quickly. However, when the dishwasher itself is finished with water droplets on it, open the door 137 and open the upper and lower tableware storage baskets. Water droplets fall on the tableware due to the vibration when pulling out, causing a problem that the dried tableware gets wet.

【0152】

When parts such as the tableware storage tank 136, the upper arm nozzle 144, the lower arm nozzle 142, and the venturi tube 145 are made of PP molded products, the amount of residual water due to the adhering water droplets at the end of rinsing is about 30 g. When the photocatalyst film according to the present invention was formed, the amount of residual water adhered was reduced to about 5 g. Further, since the low-temperature curing type highly active oxide photocatalyst thin film according to the present invention has high photoactivity and has an action of decomposing oils and fats attached by the light of the lighting equipment 159, the water wettability is not deteriorated by the adhesion of the oils and fats.

【0153】

As in the case of the dishwasher of Example 6, the dishes are shadowed during the drying operation and the light does not reach sufficiently evenly. Therefore, after the drying operation is completed, the tableware is lit for a certain period of time to clean the inside of the tableware storage tank 136. It is even more effective to use an operation program that makes it more effective.

【0154】

In addition, the door 137 is made of a molded product of PP resin, and sample No. 12 is formed as an underlayer on this surface after corona discharge treatment, and after this film is formed, sample No. 21 A thin film of a low-temperature curing type highly active oxide photocatalyst is formed.

【0155】

The effect of the photocatalytic thin film on the surface of the door 137 is that sufficient antifouling and antibacterial effects can be obtained with indoor light, as in the case of the exterior parts of Examples 1 to 6 described above. In this embodiment, the stationary dishwasher has been described, but the effect of the photocatalytic thin film can be obtained in exactly the same manner for the tabletop type. In the case of the desktop type, since the room light is irradiated to the front surface of the exterior parts, it is effective to form a photocatalyst thin film on the surface of the outer wall surface member of the side surface or the ceiling portion.

【0156】

(Example 8) The kitchen waste processing machine according to the eighth embodiment of the present invention will be described with reference to FIGS. 15 and 16.

【0157】

FIG. 15 shows an external perspective view of the kitchen waste processing machine, and FIG. 16 shows a cross-sectional view of the main body. Inside the frame 160, a processing tank 164 having a stirring blade 161 rotatably supported in the center and a kitchen waste input port 163 at the top is arranged, and a culture base material 165 is contained therein. There is. The culture medium 165 is mainly composed of fiber elements that are not easily decomposed by microorganisms such as lignin, and is made by cutting sawdust, rice husks, rice straw, etc., and each grain is porous and has voids. The particle size is complicated, and large voids are formed between the grains.

【0158】

Three stirring blades 161 are installed on the rotating shaft 166 and are supported by bearings 167 provided in the processing tank 164, and the end of the rotating shaft protruding from one side is appropriately decelerated by a drive motor 168 and a transmission means 169 such as a chain. They are connected by a ratio. An inner lid 171 is installed on the upper panel 172 so as to be openable and closable in the upper opening 170 of the treatment tank 164. Further, a ventilation fan 173, an intake port 174, and an exhaust port 175 are provided near the upper part of the treatment tank 164, and the decomposition gas and moisture generated in the treatment tank 164 are passed through the exhaust port 175 by the rotation of the ventilation fan 173. Exhaust to the outside. Further, appropriate mesh-like filters are arranged at the intake port 174 and the exhaust port 175, respectively.

【0159】

Further, an opening / closing lid 176 of the intake port 174 is provided, and the intake port 174 is opened / closed by the reciprocating movement of the solenoid 177 attached to the frame body 160. Further, the upper panel 172 is provided with an operation unit 178 for operation, and the controller 179 is operated by this operation to operate the kitchen waste processor.

【0160】

After several months, the culture base material 165 needs to be replaced because the voids are filled with decomposition products and the porosity is reduced and the kitchen waste cannot be treated. Therefore, a discharge port 180 and a discharge path 181 are configured at the bottom of the treatment tank 164, and the culture base material 165 that has fallen into the discharge path 181 can be taken out of the frame body 160 by an operation of scraping it out.

【0161】

The air in the upper void of the culture medium 165 of the treatment tank 164 contains a large amount of substances having a high malodor intensity such as trimethylamine, methyl mercaptan, ammonia, and hydrogen sulfide as decomposition gas as well as humidity. Due to this strong odor, the conventional kitchen waste disposer cannot be installed in the kitchen, and even when it is installed in the balcony of an apartment house, leakage of the odor to the surrounding households has been a problem.

【0162】

Conventionally, various deodorizing mechanisms have been devised using an adsorbent such as activated carbon or a manganese-based pyrolysis catalyst, but none of them is sufficient in terms of effect and life.

【0163】

In this embodiment, the exhaust filters 182 and 183 are provided in the exhaust port 175 portion, and the ultraviolet lamp 184 is arranged in the gap between them. The exhaust filter 182 is mainly composed of zeolite, and the exhaust filter 183 is mainly composed of activated carbon, both of which have a honeycomb structure, and the ultraviolet rays emitted from the ultraviolet lamp 184 are radiated to the inner part of the honeycomb. .. The low-temperature curable high-activity oxide photocatalyst thin film of sample No. 62 shown in Table 5 is formed on the inner surface of the honeycombs of the exhaust filters 182 and 183.

【0164】

The low-temperature curing type highly active oxide photocatalyst according to the present invention has high decomposition efficiency, and in applications such as Examples 1 to 7 described above in which the load on organic substances is relatively small, the indoor lighting equipment level, that is, the wavelength is 250 to 350. Ultraviolet light of (nm) is 0.001 ~ 0.01mW / cm² 0.01 ~ 0.1mW / cm depending on the level of illuminance or the installation of fluorescent or incandescent lamps² Decomposition was possible with a level of illuminance, but in the case of a high load with an ammonia concentration of several ppm, for example, as in this example, it is necessary to arrange an ultraviolet generating means.

【0165】

An ultraviolet lamp such as a mercury lamp or a metal halide lamp can be used, but 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 also uses the conventional oxide photocatalyst. It can be smaller than the case where it is used. When the input garbage is decomposed most actively, the above-mentioned odorous substance is generated in the largest amount.

【0166】

Since the decomposition of kitchen waste is usually most active between 1 hour and 8 hours after being put in, the life of the lamp can be maintained for a long time by turning on the ultraviolet lamp 184 at this timing. The exhaust filter 183 is based on activated carbon, and when the odor concentration is low, the odor is adsorbed on this activated carbon, and the adsorption efficiency gradually decreases as the amount of adsorption increases. Then, the adsorbed malodorous substance can be decomposed and the activated carbon can be regenerated.

【0167】

The frame 160 is made of painted steel plate, and the outer lid 171 is made of injection molded product of PP resin. An organic coating film of chlorinated polyethylene is applied to this surface, and a sample is applied to the surface of this coating film. A thin film of No. 21 low-temperature curing type highly active oxide photocatalyst is formed.

【0168】

The effects of the photocatalytic thin film on the surfaces of the outer frame 160 and the outer lid 171 are the same as in the case of the exterior parts of Examples 1 to 7 described above, in which sufficient antifouling and antibacterial effects can be obtained with indoor light. Is. In particular, in the case of a kitchen waste treatment machine, since kitchen waste is handled, there are many chances that these exterior parts are soiled by the juice dripping from the kitchen waste, so that the low-temperature curing type highly active oxide photocatalyst thin film of the present invention has a great antifouling effect. When the kitchen waste disposer is placed outdoors, sunlight is applied to these exterior parts. Ultraviolet light illuminance with a wavelength of 250 to 350 (nm) of sunlight is 0.1 to 5.0 mW / cm² Compared to the level and indoor lighting, the strength is high, and dirt such as the juice of kitchen waste can be decomposed.

【0169】

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

【0170】

(Example 9) SiO₂ TiO in the sol₂ A solution in which fine particles were dispersed was prepared. TiO on PET film using this solution₂ A film was formed to prepare the PET film shown in FIG. The procedure is shown below.

【0171】

First, SiO₂ A method for producing a sol will be described. 5 g of tetraethoxysilane was dissolved in 100 ml of a mixed solution of water-ethanol-propanol (3:27:70), and the mixture was stirred at 40 ° C. for about 5 hours. The resulting solution was left at room temperature for 2 weeks to SiO₂ It was made into a sol.

【0172】

Next, SiO₂ TiO in the sol₂ A method for preparing a solution in which fine particles are dispersed will be described. Made first and SiO₂ TiO in the sol₂ Fine particles TiO by weight₂/ SiO₂Added as = 9. The solid content concentration was 4 wt%, and the required amount of water was added for adjustment. Then, using a 5 mmφ zirconia ball, SiO₂ TiO in the sol₂ Treated with a 24hr ball mill to disperse fine particles, SiO₂ TiO in the sol₂A solution in which fine particles were dispersed was prepared.

【0173】

Made on PET film 185 and TiO₂ SiO in which fine particles are dispersed₂ Coated with sol, low pressure mercury lamp at 120 ° C (strength: 15mW / cm)²) And treat for 5 minutes while irradiating SiO₂ TiO in membrane 186₂ TiO in which fine particles 187 are dispersed₂ Distributed SiO₂ A plastic film coated with film 188 was formed. The thin film obtained on the PET film 185 had good film quality and strength, and the film thickness was 300 nm.

【0174】

The decomposition activity of organic matter by this titanium oxide was evaluated. In the activity test, a thin film was coated with a reddish purple organic dye and 1 (mW / cm) at 254 nm.²) Was irradiated. The decomposition rate was determined from the amount of change from the initial dye transmittance. The results are shown in Fig. 20.

【0175】

TiO for comparison in the figure₂ Distributed SiO₂ In addition to with a film, without a film and SiO₂ Membrane results are also shown. TiO₂ Distributed SiO₂ No membrane and SiO₂ There is almost no change in the amount of dye in the film, but TiO₂ Distributed SiO₂ The result was that 45% decomposition was obtained after 30 minutes in the case of the presence of a membrane.

【0176】

In this way, TiO having a photocatalytic function₂ Distributed SiO₂ A PET film with a film could be produced. The film forming method of the present invention can be produced at about 120 ° C., and can be applied to plastic materials other than Pyrex (registered trademark) glass substrates. The usual sol-gel method requires a temperature of about 400 ° C, which makes it difficult to apply to plastic products or TiO.₂ It takes more than 10 minutes to crystallize. On the other hand, since the production method of the present invention can form a film at a low temperature, there are abundant base materials that can be used, and a photocatalyst can be formed on any surface. In addition, it can be processed in a short time of several minutes, and the production cost can be significantly reduced.

【0177】

Next, in order to improve the performance of the photocatalyst, a co-catalyst was added. SiO produced earlier₂TiO in the sol₂ Various abrasive salts were added to a solution in which fine particles were dispersed to form a film on a PET film, and a dye decomposition reaction was carried out. The results are shown in Table 1.

【0178】

[table 1]

<img file="JP2003305371A_D0001.tif" />【0179】

It was found that photocatalysts containing Na, Li, K, Mg, Ca, Sr, and Zn are effective, and Fe and Al are inactivating agents.

【0180】

Figure 21 shows the results of plotting the effect of adding a co-catalyst on electronegativity. The smaller the electronegativity, the more effective it is, but since Li, Na, and Mg are particularly effective, it was found that not only the electronegativity but also the ionic radius is important.

【0181】

FIG. 22 shows the relationship between electronegativity, ionic radius and addition effect. As described above, 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.

【0182】

(Example 10) SiO₂ TiO with different particle sizes in the sol₂ Several kinds of solutions in which fine particles were dispersed were prepared. In addition, TiO₂ / SiO₂ The ratio was 9 by weight, the amount of Li added was 5 wt%, and TiO was performed in the same manner as in Example 1.₂ Distributed SiO₂ A film was formed on a PET film, and the decomposition rate after 10 minutes was examined using an organic dye.

【0183】

[Table 2]

<img file="JP2003305371A_D0002.tif" />【0184】

Table 2 shows each condition and test results of the prepared sample. From these results, dispersed TiO₂ It was found that the most effective particle size is 8 to 10 nm. In this way, the decomposition rate changes depending on the particle size, and TiO₂ / SiO₂ When the ratio is reduced, TiO₂ Although the optimum particle size of the fine particles changed, the decomposition rate was good in the range of 5 to 20 nm. Therefore, the Li-added catalyst TiO₂ It was found that the particle size should be 5 to 20 nm. The above results were also the same for Na, K, Mg, Ca, Sr, and Zn other than Li.

【0185】

(Example 11) Table 3 shows the amount of Li added and TiO.₂ / SiO₂ The results of examining the dye decomposition rate (decomposition rate after 10 minutes) and the film strength when the above was changed are shown. The preparation of the solution and the film forming method were carried out in the same manner as in Example 1. From these results, the conditions under which both the decomposition rate and the film strength are effective are that the amount of Li added is 0.5 to 20 wt% and TiO.₂ / SiO₂ Was found to be 9-5.

【0186】

[Table 3]

<img file="JP2003305371A_D0003.tif" />【0187】

Table 4 shows TiO₂ / SiO₂ And the results of investigating the dye decomposition rate and the film quality when the film thickness was changed are shown. The preparation of the solution and the film forming method were carried out in the same manner as in Example 1, but the film thickness was adjusted by changing the solid content concentration of the solution from 0.5 to 8 wt%.

【0188】

The result is TiO if the film thickness is 100 to 500 nm.₂ / SiO₂ It was found that both the decomposition rate and the film quality were good without being affected by the ratio.

【0189】

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

【0190】

[Table 4]

<img file="JP2003305371A_D0004.tif" />【0191】

(Example 12) Table 5 shows TiO₂ Oxide semiconductors other than ATO, ITO, ZnO, Fe₂O₃, Cr₂O₃The results of examining the pigment decomposition rate when fine particles were added are shown. In the test to examine the pigment decomposition rate, the intensity of the ultraviolet lamp (254 nm) was 0.2 mW / cm.² And said. Unless otherwise specified, the pigment decomposition test after this example was carried out under the above conditions. The result is ATO, Fe₂O₃, Cr₂O₃The addition of fine particles was effective, and the amount of addition was effective if added in any case, and 10 to 20 wt% was the most effective. Here, the electron affinity of the constituent elements of each oxide is as follows, and it was found that it is effective to use an oxide semiconductor using a constituent element having an electron affinity of 1.2 eV or more.

【0192】

[Table 5]

<img file="JP2003305371A_D0005.tif" />【0193】

Constituent elements Ti Sn In Zn Fe Cr Electron affinity (eV) 1.25 1.2 0.2 -1.2 3.16 3.54 When the electron affinity of the oxide semiconductor is smaller than that of Ti, a Schottky barrier is formed at the particle interface of the fine particles, and the carrier of the added oxide semiconductor is TiO.₂It cannot be injected inside and no effect appears. On the other hand, when the electron affinity of the oxide semiconductor is smaller than that of Ti, a Schottky barrier is not formed at the particle interface of the fine particles, an ohmic contact is formed, and the carrier of the oxide semiconductor is easily TiO.₂ It is injected into and works effectively. ATO, which was particularly effective, had a slightly smaller electron affinity than Ti, but there was almost no difference, so performance was improved. This is because ATO, which is a conductive oxide, has a high carrier concentration, and a large amount of carriers of ATO are TiO.₂ Injected into, the activity of the photocatalyst improved. Furthermore, it was also found that the effect of adding Li is large even when such an oxide semiconductor is added.

【0194】

Further, as a method of effectively utilizing the carriers of the oxide semiconductor, not only the addition of fine particles but also the lamination is possible. Table 6 shows TiO₂ / SiO₂ The results when the film and the ATO film are laminated are shown. The results showed that it was effective to stack them, and that the performance was further improved by adding Li to both. It was also found that it is also effective to stack them alternately many times.

【0195】

[Table 6]

<img file="JP2003305371A_D0006.tif" />【0196】

(Example 13) SiO₂ TiO with a particle size of 5 nm in the sol₂ Prepare a solution in which fine particles are dispersed, and add Ag, Pt, Pd, Rh, Ni, Cu, RuO to this solution.₂Each fine particle is TiO₂2 wt% was added. In addition, TiO₂ / SiO₂ The ratio was 9 by weight. Made Ag, RuO₂ Fine particle addition TiO₂ Distributed SiO₂ Using the sol, Ag, Pt, Pd, Rh, Ni, Cu, RuO in the same operation as in Example 1.₂ TiO with fine particles added₂ Distributed SiO₂ A film was formed on the PET film and the decomposition characteristics of the organic dye were investigated.

【0197】

The results are Ag, Pt, Pd, RhNi, Cu, RuO as shown in Table 7.₂ It was found that the decomposition rate was increased by the addition of fine particles.

【0198】

[Table 7]

<img file="JP2003305371A_D0007.tif" />【0199】

(Example 14) Regarding the Li-added photocatalyst and the Li-free photocatalyst prepared in Example 1, the decomposition characteristics of tobacco tar, acetaldehyde, urea, and Escherichia coli were compared using a fluorescent lamp, sunlight, an incandescent lamp, and a mercury lamp. .. As a result, as shown in Table 8, the Li-added photocatalyst is 3 to 5 times more effective than the Li-free photocatalyst in the decomposition characteristics of tobacco, acetaldehyde, urea, and Escherichia coli regardless of which lamp is used. I found out. As described above, it was found that the Li-added catalyst is effective not only in the ultraviolet lamp but also in the lamp used in the living environment. Moreover, the same effect was obtained when Na, K, Mg, Ca, Sr, Zn other than Li was added.

【0200】

[Table 8]

<img file="JP2003305371A_D0008.tif" />【0201】

(Example 15) Li-added TiO prepared in Example 1₂ Distributed SiO₂ When the film is formed directly on the PET film, the PET film of the base material is damaged by the photocatalytic action. Therefore, the Li-added TiO prepared in Example 9₂ Distributed SiO₂ When coating the film, SiO between it and the PET film₂ A film having one layer of a film was prepared. In addition, SiO₂ Samples containing Al, Fe, and Zr nitrates, which are components that inactivate photocatalytic action in the film, or Li-added TiO₂ Distributed SiO₂ Samples with ATO added to the membrane were prepared and various tests were performed. The results are shown in Table 9.

【0202】

[Table 9]

<img file="JP2003305371A_D0009.tif" />【0203】

The result is Li-added TiO₂ Distributed SiO₂ SiO as a barrier layer between the membrane and the PET film₂ By providing one layer of film, it was possible to prevent the film from peeling off even after long-term use.

【0204】

Furthermore, it was found that the photocatalytic activity can be completely inactivated by adding Al, Fe, and Zr, and the adhesive strength can be maintained. In addition, the ATO-added film has an antistatic effect and can suppress the adhesion of dust and the like, and can prevent not only the decomposition of organic substances but also the adhesion of inorganic substances, so that a film having a better antifouling effect can be produced. ..

【0205】

The low-temperature curing type highly active oxide photocatalyst thin film having the compounding composition shown in Examples 9 to 16 described above is applied to various articles having a mechanism for generating an air flow by an electric motor as shown in Examples 1 to 8. The results of evaluating the specific effects of using the product are summarized below. First, the effects of applying the low-temperature curable highly active oxide photocatalyst thin film according to the present invention to a filtration mechanism provided in an air flow path will be summarized.

【0206】

A typical air pollutant in a room is cigarette smoke. Cigarette smoke is a floating form of fine particles of tar substances and soot, and these fine particles form a film on the filter and accumulate, and the filter gradually turns brown and becomes dirty. The smoke pollution of this cigarette was evaluated. Blower volume is 5 (m³A polyester fiber non-woven fabric filter with a target area of 10 cm x 10 cm was attached to the front surface, which is the suction side of the ventilation fan (/ min), and fixed. This non-woven ventilation fan has a capacity of 45,000 (cm)³) Was installed in a container and sealed. A cigarette smoke generator was placed side by side in this container. The cigarette smoke generator has a tube attached to the filter side of the ignited cigarette, and this tube is connected to the diaphragm pump. This diaphragm pump is 1,800 (cm)³When the tube end on the cigarette side is depressurized by driving with an air volume of (/ sec), the smoke that has passed through the cigarette filter is exhausted from the discharge side of the pump, and one cigarette is burned in about 1.5 minutes. When the cigarette smoke generator and the ventilation fan are driven in a container having such a configuration, the exhaust of the ventilation fan is also discharged into the container, so that the cigarette smoke filled in the container passes through the non-woven fabric filter part many times. Will be done. Five cigarettes were burned continuously, the ventilation fan was driven for 10 minutes, the container was opened, and the non-woven fabric filter was removed to prepare a sample. A low-temperature curable highly active oxide photocatalyst thin film according to the present invention is formed on the fiber surface of this non-woven fabric filter. The creation method was created by the method described in Example 9. In Example 9, a PET film is targeted, but here, SiO is used.₂ TiO in the sol₂ A non-woven fabric filter that has been subjected to surface oxidation treatment in an ozone atmosphere is immersed in a solution in which lithium nitrate is added to a solution in which fine particles are dispersed, held for 1 minute, then the filter is pulled up, and unnecessary solution is scattered by air blowing. Low pressure mercury lamp at 120 ° C (strength: 15mW / cm)²) Was treated 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.

【0207】

The sample thus prepared was irradiated with the light of a fluorescent lamp to evaluate the degree of decomposition of the dirt adhering to the sample. The evaluation was performed by using a color difference meter (Nippon Denshoku Kogyo Co., Ltd .: Z-1001DP) to change the color of the non-woven fabric filter. The antifouling effect was evaluated with the color difference in the dirty state before light irradiation as 100% and the color difference before adhering the dirt caused by cigarette smoke as 0%. SiO for comparison₂ Inside TiO₂ Sample No. 11 and TiO as only fine particles dispersed₂ SiO that does not contain fine particles₂ In the case of only a film, sample No. 12 was also evaluated by forming a thin film on the surface of the filter fiber in the same manner.

【0208】

The results are shown in FIGS. 23 and 24. FIG. 23 shows the results of evaluating the degree of dirt on the filter by color difference over time when the smoke filter passing test was performed under the same conditions. TiO compared to untreated acrylic fiber₂ And SiO₂ When a vitreous oxide photocatalyst thin film containing the above is attached, the discoloration is about 50% faster, that is, the smoke collection efficiency is improved by about 50%. Figure 24 shows the degree to which smoke is adsorbed under the above conditions and the filter that has turned brown is irradiated with the light of a fluorescent lamp, the deposits are decomposed by the photocatalyst, and the color of the discolored filter returns to the original color tone. It is the result of evaluation by the time-lapse measurement of. The integrated light amount in the figure represents the integrated value irradiated with light having a wavelength of 250 to 350 (nm). Sample No. 12 in the figure is TiO₂ Does not contain SiO₂ This is only the case, and almost no decolorization effect due to decomposition is observed. Sample No. 11 and Sample No. 2 are TiO₂ Is contained in the same amount, and all are effective, but sample No. 2 is LiNO.₃ It can be seen that the decolorization speed was greatly improved by the formulation according to the present invention to which the above was added. Especially in the early days, LiNO₃ Higher decomposition efficiency is obtained, which is more than twice that of the case without additives. In the case of an actual air purifier or ventilation fan, the initial decomposition speed is important because a small amount of dirt adheres and the room light is illuminated at the same time. As the amount of dirt adhered increases, the light is blocked by the dirt and becomes difficult to reach the photocatalytic thin film on the fiber surface, so that the decomposition efficiency also decreases. For this reason, it is important to decompose the dirt before it adheres thickly.

【0209】

In an actual environment, in order to attach the same level of dirt to the filter as in this test using the above equipment, a closed 6 tatami mat room (about 20 m)²) When the above ventilation fan was operated, 20 cigarettes were burned, which was equivalent to the amount of dirt after 120 minutes of operation.

【0210】

Next, the results of examining the deodorizing effect when the low-temperature curing type highly active oxide photocatalyst thin film according to the present invention is applied to a filtration mechanism provided in an air flow path are summarized. As a typical malodorous substance, the action of removing ammonia was evaluated. The study was conducted with exactly the same configuration as in the case of the above-mentioned cigarette. Instead of a cigarette smoke generator, a certain amount of ammonia gas is injected into the container, the ammonia gas concentration inside the container is adjusted to 25 (ppm), and then a low-temperature curing type highly active oxide photocatalyst thin film is formed. The ventilation fan with the non-woven fabric attached was driven. First, Fig. 25 shows the results of measuring the adsorption effect of ammonia gas by the vitreous oxide photocatalyst thin film as in the case of smoke collection. With untreated acrylic fiber, 90 (%) or more of ammonia gas remains even after 1 hour, whereas TiO₂ And SiO₂ In the case of a vitreous oxide photocatalyst thin film containing the above, it can be seen that it was adsorbed and removed to a concentration of 50 (%) or less after 1 hour. Not only smoke but also ammonia gas collection effect is recognized.

【0211】

After adsorbing this ammonia gas until it was saturated, an incandescent light bulb arranged inside the container was turned on so that the filter surface was exposed to light. The ammonia gas concentration in the container was measured over time to evaluate the ammonia decomposition effect. The result is shown in FIG.

【0212】

TiO₂ Almost no change in concentration was observed with the sample No. 12 filter that did not contain. TiO₂ It can be seen that the ammonia gas concentration of No. 11 and No. 2 including the above decreased with light irradiation and was decomposed, but No. 2 was LiNO according to the present invention.₃ Decomposition efficiency by containing a combination of large break is good, as compared to the sample No.11, about three times the decomposition efficiency was obtained.

【0213】

The antifouling and deodorizing effects described above have been described as typical examples of application to air purifiers and ventilation fans, but it goes without saying that filters of various articles having the same mechanism exert exactly the same effects. Nor.

【0214】

Next, the results of evaluating the specific effects of various articles as shown in Examples 1 to 8 when used for exterior parts are summarized below. As a sample, a heat-plastic ABS resin for injection molding (Technopolymer Co., Ltd .: Taflex 451; white colored product), which is most often used for exterior parts, was used. A 5 cm × 5 cm plate-shaped molded product was prepared, and the surface was subjected to corona discharge treatment. On this corona discharge-treated surface, a low-temperature curing type highly active oxide photocatalyst thin film having the composition of sample No. 86 shown in Table 6 in Example 12 was formed. SiO for comparison₂ Inside TiO₂ Sample No. 11 in Table 1 and TiO as only dispersed fine particles₂ SiO that does not contain fine particles₂ In the case of a single film, sample No. 12 was also evaluated by forming a thin film on the surface of the molded plate in the same manner. First of all, the pollution caused by cigarette smoke was evaluated in the same manner as described above. The study was carried out with exactly the same configuration as the above-mentioned non-woven fabric filter test. A 5 cm x 5 cm ABS plate was fixed in the center of the part where the filter was placed, and after burning 10 cigarettes, the ventilation fan was driven for 120 minutes to contaminate the white ABS plate brown. The ABS plate was removed, irradiated with light under various conditions as before, and the removal rate was evaluated by measuring the color difference before and after that. The result is shown in FIG.

【0215】

As a result, almost the same result as in the case of the filter was obtained, but since the amount of dirt to be attached was less than that in the case of the filter, the same decolorization effect was obtained with less than half the amount of light. Sample No.86 is LiNO₃ In addition to this, ATO is also blended as an additive component, and a slightly higher decomposition efficiency is obtained as compared with Sample No.11.

【0216】

Next, the results of evaluation of the antifouling effect when the article is used in an environment that uses a lot of oil such as a kitchen and is contaminated with oil and fat are summarized. A thin coating of salad oil to a thickness of about 5 (μm) was applied to a 5 cm × 5 cm glass plate on which a low-temperature curable highly active oxide photocatalyst thin film was formed having the composition of sample No. 86 shown in Table 6 of Example 12. Then, the oil was irradiated with the light of an ultraviolet lamp, and the change in the weight of the oil was measured over time. The result is shown in FIG. As a result, TiO₂ Almost no change in weight was observed in sample No. 12 containing no. TiO₂ No. 11 and No. 2 including No. 2 lose weight because the oil decomposes and volatilizes with light irradiation, but No. 2 is LiNO according to the present invention.₃ The decomposition efficiency was greatly improved by blending the above, and the decomposition efficiency was about twice as high as that of sample No.11.

【0217】

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

【0218】

Examples include silane coupling agents and organic titanium compounds.

【0219】

Examples of silane coupling agents include vinyltris (β-methoxyethoxy) silane, vinyltriethoxysilane, vinyltotimethoxysilane, γ- (methacryloxypropyl) trimethoxysilane, β (3,4 epoxycyclohexyl) ethyltrimethoxysilane. , γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, n-β (aminoethyl) γ-aminopropylmethyldimethoxy Silane, γ-aminopropyltrinitoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane and the like can be used.

【0220】

As the organic titanium-based compound, titanium ester, titanium acylate, and titanium chelates can be used, and in particular, tetra-i-propoxytitanium, tetra-n-butoxytitanium, tetrakis (2-ethylhexilioxy) titanium, and di. -i-propoxybis (acetylacetonato) titanium, titanium-i-propoxyoctylene glycolate, titanium stearate, etc. are effective.

【0221】

Further, it is also effective to oxidize the surface of the object by using various surface modification means to introduce a hydroxyl group, a carbonyl group, a carboxyl group, etc. to firmly bond the low temperature curable highly active oxide photocatalytic thin film according to the present invention. There is.

【0222】

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

【0223】

In the present invention, as described above, it is effective to mix Ag and Cu as an additive component for enhancing the activity of the photocatalyst. At the same time, these can lower the electrical insulating property of the film itself, obtain an antistatic effect, and further obtain an effect of suppressing the growth of microorganisms. It is known that Ag and Cu ions have high antibacterial properties, especially bacterial resistance, and when these Ag and Cu are used in combination, the growth of microorganisms can be suppressed even when they are not exposed to light.

【0224】

The scope of application covered by the present invention is not limited to the apparatus described above with specific examples. That is, the principle of the present invention is that the polymerization of an inorganic polymer can be promoted by irradiating an electromagnetic wave having a specific wavelength such as ultraviolet rays, and as a result, even on the surface of a material having low heat resistance such as plastics, TiO₂ The point of forming an inorganic thin film of a photocatalyst whose main component is₂ Taking advantage of the fact that the reaction activity of the photocatalyst containing the main component is increased several times by adding various components, from general-purpose thermosetting plastics to thermosetting plastics or surfaces coated with plastic materials. It has a photocatalytic function, and by utilizing this principle, it decomposes organic substances with a weak light intensity that has never existed on the surface of a low heat-resistant material that has never existed before. Further, by adding semiconductors and conductor fine particles that lower the surface resistance value of the film itself, an antistatic effect on the surface of the coating film can be obtained, so that dirt adhesion due to static electricity is reduced.

【0225】

In the present invention, the light irradiated to the surface of the component on which the photocatalyst film is formed is the light of a fluorescent lamp, an incandescent lamp, a mercury lamp, sunlight, or the like, but these lights do not necessarily have to be directly emitted. That is, the effect can be obtained even in a configuration in which light transmitted through a component made of transparent plastic or glass, which is a transparent material, is irradiated. For example, panel 2 and frame 4, front cover 16, panel 18 in the air purifier in FIGS. 1 to 3, frame 29 in the ventilation fan in FIG. 4, top cover 52 in the vacuum cleaner in FIGS. 6 and 7, lid. Cover 53, Grill cover 54, Suction port 65, Exhaust ventilation section 76, Opening and closing lid 86 in the clothes dryer shown in Fig. 8, Lint filter device 99, Door 121 in the dishwasher shown in FIGS. 9 to 11, Exhaust port 128, Parts such as the inner lid 71, the intake port 174, and the exhaust port 175 in the intake port 117, the dishwasher door 137 in FIGS. 12 to 14, the exhaust port 152, and the kitchen waste disposer in FIGS. 15 to 16 are air filtering members. It is a part that is supported or placed around it, and is made of a molded body of heat-bonded plastic plastic. By making these parts a transparent molded product, light is introduced into the inside and dirt is decomposed. It is capable of internally developing hardening such as deodorization and antibacterial.

【0226】

As an example of the transparent plastic, PMMA, AS, PC, ABS, PVC, poly 4 methylpentene-1 (TPX) and the like are particularly suitable.

【0227】

Further, these transparent plastic materials may be colored by mixing pigments and dyes. However, in the case of coloring, yellow or red-green coloring is not preferable because it absorbs light having a short wavelength and reduces the decomposition effect. When coloring, the preferred color tone is bluish or black (smoke).

【0228】

As a result of diligent studies, the present inventors have clarified the relationship between the color of transparent parts and the decomposition efficiency of photocatalysts. The color of the transparent member to be discussed below is regulated by the Hunter, Lab method as shown in JIS-Z-8730. That is, it is expressed by an L value representing the degree (brightness) of black and white, which is an achromatic color, an a value representing the degree of red and green, and a b value representing the degree of blue and yellow.

【0229】

The larger the L value, the more preferable. Regarding coloring, the yellowish transparent parts absorb more short-wavelength light required for the decomposition reaction in the photocatalyst than other colors, which lowers the literary efficiency. That is, in the Lab method, the smaller the b value, the more preferable. Further, it is preferable that the a value is in the range of a certain value or more and a certain value or less.

【0230】

Figure 29 shows the results of evaluating the relationship between these colors and resolution efficiency. Using a color plate colored with various pigments based on PMMA resin, 5 cigarettes were burned under the same conditions as in the test shown in FIG. 24 to decolorize and decompose cigarette smoke stains attached to the filter. The rate was measured. The photocatalyst material used was sample No. 2 in Table 1, and the PMMA resin used was a color plate with a thickness of 2.0 (mm) in which Mitsubishi Rayon's acrylic pet MD was colored in each color. This is a resin to which an ultraviolet absorber is added, and absorbs ultraviolet rays in the vicinity of 360 (nm). The decomposition rate in FIG. 29 represents the decolorization rate obtained from the change in color difference after irradiating a filter polluted with the light of a 40 watt fluorescent lamp at a distance of 2 (m) for 20 hours. Each color plate of the sample was placed on a dirty filter, and after irradiating with a fluorescent lamp, 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, it can withstand continuous use without accumulation of smoke stains.

【0231】

From this test result, if the L value is +50 or more, the a value is -20 or more and +20 or less, and the b value is +20 or less, a decomposition rate of 40 (%) or more is obtained. I found that I could do it.

【0232】

This test complies with JIS-Z-8730 (color difference display method), and the measuring instrument used is Z1001DP manufactured by Nippon Denshoku Kogyo Co., Ltd., which conforms to JIS-Z-8722. As the measurement sample, the transmitted light of a 2.0 (mm) thick plate was measured.

【0233】

By installing the member having the above-mentioned action according to the present invention in the air-flowing portion of various devices, the adhering organic matter can be effectively decomposed, so that an air flow can be generated or the air flow can be generated. Alternatively, any device having a structure for filtering the air flow can be easily applied.

【0234】

As an example, it can be applied to oil fan heaters, gas fan heaters, electric heaters, kotatsu, etc. as heating appliances. It can also be applied to air conditioners, dehumidifiers, and cold air fans. It can also be applied to heating type and ultrasonic type humidifiers. It can also be applied to cooking utensils such as ovens and electromagnetic cookers. It can also be used as a hair dryer. It can also be used for devices equipped with a cooling fan. That is, for various computers such as personal computers and word processors, displays for those computer devices such as brown tubes, devices using electrophotographic mechanisms such as copiers and laser beam printers, and devices such as liquid crystal projectors and slide projectors. The low temperature similar to that of the present invention is also applied to the incidental cooling fan part, the intake port and exhaust port part used for ventilation of the cooling air using the cooling fan of these devices, and the filter part attached to those intake and exhaust port parts. A curable highly active oxide photocatalyst thin film can be provided, and the same effect can be obtained.

【0235】

(Example 16) Addition of ATO or RuO, which is a photocatalytic filter having the composition shown in Table 10.₂ -ATO added TiO₂ The procedure for manufacturing a filter with a photocatalyst is shown below.

【0236】

The ATO solution was prepared as follows. SnCl₄ Is dissolved in propanol and 10wt% SnO₂ The solution was prepared. In addition, isopropoxyantimony was dissolved in propanol to 4wt% Sb.₂O₅The solution was prepared. Next, these two solutions are mixed in equivalent amounts and SnO₂ 2-Aminoethanol having a molar ratio of 1: 1 was added to SnO2, and then 4 times the molar amount of water was added to SnO2 to prepare a 5 wt% ATO solution. RuO₂ -ATO solution is 0.05wt% RuO by dissolving ruthenium acetyl acetate in the above ATO solution.₂ A -5 wt% ATO solution was used.

【0237】

Next, ATO and RuO₂ -ATO added TiO₂ The method for producing the powder is shown. ATO addition and RuO₂ -ATO addition A predetermined amount of TiO in both cases₂ Add the powder (anatase) to the previously prepared solution, stir at 60 ° C for 2 hours, dry in an evaporating dish at 250 ° C to make a powder, and then treat at 550 ° C for 3 hours to achieve ATO. And RuO₂ -TiO with different amounts of ATO added₂ A powder was prepared.

【0238】

Next, add ATO and RuO₂ -ATO added TiO₂ Photocatalyst coating liquid preparation procedure, ATO addition and RuO₂ -ATO added TiO₂ The manufacturing method of the photocatalytic filter is shown.

【0239】

ATO addition and RuO₂ -ATO added TiO₂ The photocatalyst coating liquid is 4 wt% SiO made from the powder prepared earlier.₂ A predetermined amount was added to the sol and milled with zirconia balls for 20 hours to prepare a coating liquid. A filter made of acrylic fiber was immersed in the coating liquid prepared in this manner, excess coating liquid was removed by air blowing, and treatment was performed at 120 ° C. for 5 minutes to prepare a filter with a photocatalyst. The composition of each photocatalyst is as shown in Table 10.

【0240】

The film forming method of the present invention can be produced at about 120 ° C., and can be applied to plastic materials other than Pyrex (registered trademark) glass substrates. The usual sol-gel method requires a temperature of about 400 ° C, which makes it difficult to apply to plastic products or TiO.₂ It takes more than 10 minutes to crystallize. On the other hand, since the production method of the present invention can form a film at a low temperature, there are abundant base materials that can be used, and a photocatalyst can be formed on any surface. In addition, it can be processed in a short time of several minutes, and the production cost can be significantly reduced.

【0241】

As a photocatalytic filter, it can be applied to an air cleaner or the like. In this case, it is possible to remove malodorous components, bacteria, cigarette smoke, etc. existing in the air. In particular, since a normal filter is adsorbed and removed by an adsorbent, its effect is lost after saturated adsorption and it is necessary to replace it, whereas a filter with a photocatalyst acts as a photocatalyst on adsorbed malodorous components, bacteria, cigarette smoke, etc. Therefore, the number of filter replacements can be reduced.

【0242】

A photocatalytic filter having the composition shown in Table 10 was attached to an air purifier and operated in a room filled with cigarette smoke, and the filter was adsorbed with cigarette smoke to discolor. The discolored filter was taken out, irradiated with a fluorescent lamp, the color change was measured, and the decomposability of the adsorbed cigarette smoke was examined. The decomposition rate was calculated from the amount of discoloration measured by a colorimeter.

【0243】

Table 10 shows the decomposition rate after 5 hours of fluorescent lamp irradiation. The decomposition rate of the ATO-added catalyst is higher than that of the ATO-free catalyst. Also, RuO₂ -ATO addition has a higher decomposition rate, RuO₂ It can be seen that the addition of ATO is effective.

【0244】

ATO-added photocatalysts are ATO and TiO₂ When they come into contact with each other, the ATO electrons are TiO.₂ The use of the photocatalyst improves the performance of the photocatalyst.

【0245】

When the electron affinity of the oxide semiconductor is smaller than that of Ti, a Schottky barrier is formed at the particle interface of the fine particles, and the carrier of the added oxide semiconductor is TiO.₂It cannot be injected inside and no effect appears. On the other hand, when the electron affinity of the oxide semiconductor is smaller than that of Ti, a Schottky barrier is not formed at the particle interface of the fine particles, an ohmic contact is formed, and the carrier of the oxide semiconductor is easily TiO.₂ It is injected into and works effectively. In particular, ATO has a slightly smaller electron affinity than Ti, but there is almost no difference, so performance improvement can be seen. This is because ATO, which is a conductive oxide, has a high carrier concentration, and a large amount of carriers of ATO are TiO.₂ Injected into, the activity of the photocatalyst improved. In recent years, ATO has attracted attention as a conductive oxide, and ultrafine particles (particle size of 200 angstroms or less, particularly preferably 20 angstroms to 100 angstroms or less) are commercially available. TiO₂ Addition of ultrafine particles ATO to the photocatalyst makes it easier to add ATO TiO₂ A photocatalyst can be produced. However, using such ultrafine particle ATO, 5wt% ATO added TiO₂When a filter with a photocatalyst was prepared and the same test was conducted, the decomposition rate after 5 hours was 35%, which was smaller than 42% of the photocatalyst of the present invention. TiO with the addition of ultrafine particles ATO₂There are ATO particles that have come into contact with fine particles, but SiO₂Some particles are present inside, which is not efficient. On the other hand, in the case of the present invention, TiO₂ ATO and TiO are added to the fine particles in advance and fired.₂ The contact area of the particles is large, the bonding state is good by firing, and the electron transfer between dissimilar semiconductors becomes smooth. RuO is a p-type semiconductor.₂ Is an n-type semiconductor, TiO₂ Since ATO attracts holes among the generated electrons and holes by absorbing light, it is possible to suppress the recombination of electrons and holes. Therefore, the electrons 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 could be improved in the present invention.

【0246】

(Example 17) The performance of the photocatalyst can be further improved not only by adding ATO but also by adding other additives.

【0247】

Table 11 shows the composition of the catalyst in which Li, Na, and Mg were further added to the photocatalyst prepared in Example 16 and the results of the decomposition test of cigarette smoke. The results show that the decomposition rate is improved and a higher performance filter can be produced when any of Li, Na, and Mg is added. Li, Na, Mg have an ionic radius close to that of Ti, and TiO₂It easily penetrates Ti defects on the surface and increases crystal stability. Further, since Li, Na, and Mg have strong ionicity, they can easily attract electrons, and can absorb light to separate the generated electrons and holes to increase the reaction efficiency.

【0248】

(Example 18) Regarding the Li-added photocatalyst and the Li-free photocatalyst prepared in Example 16, the decomposition characteristics of acetaldehyde, urea, ammonia, and Escherichia coli were compared using a fluorescent lamp, sunlight, an incandescent lamp, and a mercury lamp. As a result Li-RuO₂ -It was found that the ATO-added photocatalyst was 3 to 5 times more effective than the non-additive photocatalyst in the decomposition characteristics of acetaldehyde, urea, ammonia, and Escherichia coli regardless of which lamp was used. Like this Li-RuO₂ -It was found that the ATO-added catalyst is sufficiently effective for lamps used in a living environment. Moreover, the same effect was obtained when Na and Mg other than Li were added.

【0249】

As described above, it is a material with excellent antibacterial and antifouling effects, which enables low-temperature film formation by a simple method, can form a photocatalyst on the surface of any material, provides a highly active photocatalyst effective in a living environment, and has excellent antibacterial and antifouling effects. Therefore, the number of parts replacement and cleaning of various applied products can be reduced.

【0250】

[Table 10]

<img file="JP2003305371A_D0010.tif" />【0251】

[Table 11]

<img file="JP2003305371A_D0011.tif" />【0252】

(Example 19) RSO-added TiO shown in Table 12₂ The procedure for manufacturing a filter with a photocatalyst is shown below.

【0253】

The RSO solution was prepared as follows. Ruthenium acetylacetate dissolved in propanol to 2 mol% RuO₂ The solution was prepared. Also, Sr (NO)₃)₂ Was dissolved in propanol to prepare a 2 mol% SrO solution. Next, these two solutions are mixed in equivalent amounts and RuO₂ 2-Aminoethanol with a molar ratio of 1: 1 was added to RuO.₂ A 1 mol% RSO solution was prepared by adding 4 times the molar amount of water.

【0254】

Next, RSO-added TiO₂ The method for producing the powder is shown. The previously prepared solution was stirred at 60 ° C. for 2 hours, dried in an evaporating dish at 250 ° C. to form a powder, and then treated at 850 ° C. for 5 hours to prepare an RSO powder.

【0255】

Next, RSO-added TiO₂Photocatalytic coating liquid manufacturing procedure and RSO-added TiO₂The manufacturing method of the photocatalytic filter is shown.

【0256】

RSO added TiO₂ The photocatalytic coating liquid is the RSO powder and TiO prepared earlier.₂ (Anatase) powder 4wt% SiO₂ A predetermined amount was added to the sol and milled with zirconia balls for 20 hours to prepare a coating liquid. A filter made of acrylic fiber was immersed in the coating liquid prepared in this manner, excess coating liquid was removed by air blowing, and treatment was performed at 120 ° C. for 5 minutes to prepare a filter with a photocatalyst. The composition of each photocatalyst is as shown in Table 12.

【0257】

The film forming method of the present invention can be produced at about 120 ° C., and can be applied to plastic materials other than Pyrex (registered trademark) glass substrates. The usual sol-gel method requires a temperature of about 400 ° C, which makes it difficult to apply to plastic products or TiO.₂ It takes more than 10 minutes to crystallize. On the other hand, since the production method of the present invention can form a film at a low temperature, there are abundant base materials that can be used, and a photocatalyst can be formed on any surface. In addition, it can be processed in a short time of several minutes, and the production cost can be significantly reduced.

【0258】

As a photocatalytic filter, it can be applied to an air cleaner or the like. In this case, it is possible to remove malodorous components, bacteria, cigarette smoke, etc. existing in the air. In particular, since a normal filter is adsorbed and removed by an adsorbent, its effect is lost after saturated adsorption and it is necessary to replace it, whereas a filter with a photocatalyst acts as a photocatalyst on adsorbed malodorous components, bacteria, cigarette smoke, etc. Therefore, the number of filter replacements can be reduced.

【0259】

A photocatalytic filter having the composition shown in Table 12 was attached to an air purifier and operated in a room filled with cigarette smoke, and the filter was adsorbed with cigarette smoke to discolor. The discolored filter was taken out, irradiated with a fluorescent lamp, the color change was measured, and the decomposability of the adsorbed cigarette smoke was examined. The decomposition rate was calculated from the amount of discoloration measured by a colorimeter.

【0260】

Table 12 shows the decomposition rate after 5 hours of fluorescent lamp irradiation. The decomposition rate of the RSO-added catalyst is higher than that of the RSO-free catalyst, indicating that RSO addition is effective.

【0261】

RSO-added photocatalysts are RSO and TiO₂ When they come into contact with each other, the holes in the RSO are TiO.₂ The use of the photocatalyst improves the performance of the photocatalyst. The oxidative activity of the monophotocatalyst is due to the redox action of electrons and holes generated by the absorption of light. In particular, the generated holes generate hydroxide radicals and generate a strong oxidizing action. RSO is a p-type semiconductor and has a large number of holes. RSO and TiO₂ By contacting TiO₂ Holes are injected inside, TiO₂ The activity of the photocatalyst was improved by oxidizing organic substances and the like on the surface.

【0262】

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

【0263】

Table 13 shows the composition of the catalyst in which Li, Na, and Mg were further added to the photocatalyst prepared in Example 19 and the results of the decomposition test of cigarette smoke. The results show that the decomposition rate is improved and a higher performance filter can be produced when any of Li, Na, and Mg is added. Li, Na, Mg have an ionic radius close to that of Ti, and TiO₂It easily penetrates Ti defects on the surface and increases crystal stability. Further, since Li, Na, and Mg have strong ionicity, they can easily attract electrons, and can absorb light to separate the generated electrons and holes to increase the reaction efficiency.

【0264】

[Table 12]

<img file="JP2003305371A_D0012.tif" />【0265】

[Table 13]

<img file="JP2003305371A_D0013.tif" />【0266】

(Example 20) Regarding the Li-added photocatalyst and the Li-free photocatalyst prepared in Example 19, the decomposition characteristics of acetaldehyde, urea, ammonia, and Escherichia coli were compared using a fluorescent lamp, sunlight, an incandescent lamp, and a mercury lamp. As a result Li-RuO₂ It was found that the decomposition characteristics of acetaldehyde, urea, ammonia, and Escherichia coli of the RSO-added photocatalyst were 3 to 5 times more effective than those of the non-additive photocatalyst, regardless of which lamp was used. Like this Li-RuO₂ -It was found that the RSO-added catalyst is sufficiently effective for lamps used in a living environment. Moreover, the same effect was obtained when Na and Mg other than Li were added.

【0267】

(Example 21) RSO powder as in Example 19 is TiO₂ In the method of mixing with powder, TiO₂There are RSO particles that have come into contact with fine particles, but SiO₂ To be used as a binder₂ Some particles are present inside, which is not efficient. On the other hand, TiO₂ If the RSO solution can be added to the fine particles in advance and fired, then RSO and TiO₂ The contact area of the particles is large, the bonding state is good by firing, and the electron transfer between dissimilar semiconductors becomes smooth. However, a temperature of 700 to 850 ° C is required to produce RSO, and at a temperature lower than this, RSO does not crystallize and therefore does not function as a p-type semiconductor. TiO₂ In the case of, the crystal becomes rutile type at 600 ° C or higher. It is the anatase type that exhibits sufficient function as a photocatalyst. In the rutile type, the performance of the photocatalyst deteriorates sharply. Therefore, after adding RSO, TiO₂ If RSO is treated at high temperature, RSO becomes a p-type semiconductor, but TiO₂ Phase transitions to the rutile type and loses its function as a photocatalyst. Therefore, TiO as a photocatalyst₂ STO (SrTiO) that can be expected to have similar functions₃) Is used to enable the RSO-added STO photocatalyst. STO is TiO₂ It has almost the same band structure as. In addition, the manufacturing method is to crystallize by treating at a high temperature of 700 to 850 ° C. Furthermore, both RSO and STO crystals are perovskite, and their crystal lattice constants are almost the same because Sr-O is common. Therefore, the fabrication conditions are very close to RSO, and the bonding state can be good. The method for producing RSO-added STO powder is shown below.

【0268】

The STO powder was prepared as follows. Isopropoxytitanate is dissolved in propanol and 2 mol% TiO₂Make a solution, then TiO₂ Sr (NO) with a molar ratio of 1: 1 to₃)₂And TiO₂ 2-Aminoethanol with a molar ratio of 1: 1 was added, and then TiO₂ A 1 mol% STO solution was prepared by adding 4 times the moles of water.

【0269】

Next, this solution was stirred at 60 ° C. for 2 hours, 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.

【0270】

The method for producing RSO-added STO powder is shown below.

【0271】

A predetermined amount of STO powder was added to the RSO solution prepared in Example 19, stirred at 60 ° C for 2 hours, dried at 250 ° C in an evaporating dish to form a powder, and then treated at 850 ° C for 5 hours. To prepare an RSO-added STO powder.

【0272】

Next, the procedure for preparing the RSO-added STO photocatalyst coating liquid and the method for preparing the RSO-added STO photocatalyst filter are shown.

【0273】

The RSO-added STO photocatalyst coating liquid is 4 wt% SiO made from the previously prepared RSO-added STO powder.₂ A predetermined amount was added to the sol and milled with zirconia balls for 20 hours to prepare a coating liquid. A filter made of acrylic fiber was immersed in the coating liquid prepared in this manner, excess coating liquid was removed by air blowing, and treatment was performed at 120 ° C. for 5 minutes to prepare a filter with a photocatalyst. The prepared RSO-added STO photocatalyst consists of STO powder sintered and grown at high temperature, so it is slightly TiO.₂ Adhesion with acrylic fiber was poor compared to the system, but the appearance was beautiful. The composition of each photocatalyst is as shown in Table 14.

【0274】

A photocatalytic filter having the composition shown in Table 14 was attached to an air purifier and operated in a room filled with cigarette smoke, and the filter was adsorbed with cigarette smoke to discolor. The discolored filter was taken out, irradiated with a fluorescent lamp, the color change was measured, and the decomposability of the adsorbed cigarette smoke was examined. The decomposition rate was calculated from the amount of discoloration measured by a colorimeter.

【0275】

Table 14 shows the decomposition rate after 5 hours of fluorescent lamp irradiation. RSO-added STO catalyst is RSO-added TiO₂ The decomposition rate is higher than that of the catalyst, indicating that RSO-added STO is effective.

【0276】

Further, the performance of the photocatalyst can be further improved not only by adding RSO but also by adding other additives.

【0277】

Table 14 shows the composition of the prepared RSO-added STO photocatalyst with Li, Na, and Mg added, and the results of the tobacco smoke decomposition test. The results show that the decomposition rate is improved and a higher performance filter can be produced when any of Li, Na, and Mg is added. Li, Na, and Mg have ionic radii close to those of Ti and easily penetrate Ti defects on the STO surface, increasing crystal stability. Further, since Li, Na, and Mg have strong ionicity, they can easily attract electrons, and can absorb light to separate the generated electrons and holes to increase the reaction efficiency.

【0278】

The RSO-added STO photocatalytic filter has slightly poor adhesion as described above. Therefore, TiO with good adhesion₂ The systems were mixed and coated on acrylic fibers to prepare a photocatalytic filter. The composition and the degradability of tobacco smoke are shown in Table 15. As a result, good results were obtained for both adhesion and decomposition of cigarette smoke, and a high-performance photocatalyst could be produced.

【0279】

As described above, RSO, which is a p-type semiconductor, injects holes into the STO or attracts holes among the electrons and holes generated by the STO absorbing light, thus suppressing the recombination of electrons and holes. Can be done. Therefore, the electrons 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 could be improved in the present invention.

【0280】

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

【0281】

[Table 14]

<img file="JP2003305371A_D0014.tif" />【0282】

[Table 15]

<img file="JP2003305371A_D0015.tif" />【0283】

(Example 22) SiO₂ TiO in the sol₂ A solution in which fine particles and zeolite (aluminum silicate) were dispersed was prepared. TiO on acrylic fibers using this solution₂ A film was formed to prepare a filter with a photocatalyst. The procedure is shown below.

【0284】

First, SiO₂ A method for producing a sol will be described. 5 g of tetraethoxysilane was dissolved in 100 ml of a mixed solution of water-ethanol-propanol (3:27:70), and the mixture was stirred at 40 ° C. for about 5 hours. The resulting solution was left at room temperature for 2 weeks to SiO₂ It was made into a sol.

【0285】

Next, SiO₂ TiO in the sol₂ A method for preparing a solution in which fine particles and zeolite are dispersed will be described. SiO produced earlier₂ TiO in the sol₂ Fine particles TiO by weight₂ / SiO₂ It was added as = 9, and a predetermined amount of ZSM-5 (synthetic zeolite, the same applies hereinafter) was added. The solid content concentration was 4 wt%, and the required amount of water was added for adjustment. Then, using a 5 mmφ zirconia ball, SiO₂TiO in the sol₂Treated with a 24hr ball mill to disperse fine particles and ZSM-5, SiO₂TiO in the sol₂ A solution in which fine particles and ZSM-5 were dispersed was prepared.

【0286】

ZSM-5 added TiO made into acrylic fiber₂ Fine particle dispersion SiO₂ Coat the sol and treat at 120 ° C for 5 minutes to SiO₂ TiO in the membrane₂ TiO in which fine particles and ZSM-5 are dispersed₂ Distributed SiO₂ A film-coated filter was formed. The composition of the produced photocatalyst is SiO₂ = 8wt%, TiO₂ = 72wt%, ZSM-5 = 20wt%.

【0287】

As a photocatalytic filter, it can be applied to an air cleaner or the like. In this case, it is possible to remove malodorous components, bacteria, cigarette smoke, etc. existing in the air. In particular, since a normal filter is absorbed and removed by an adsorbent, its effect is lost after saturation adsorption and it is necessary to replace it, whereas a filter with a photocatalyst acts as a photocatalyst on adsorbed malodorous components, bacteria, cigarette smoke, etc. Since the filter can be removed, the number of filter replacements can be reduced.

【0288】

The photocatalyst filter prepared earlier was sealed in a glass container, 400 ppm of acetaldehyde, which is a gas component, was injected, and the inside of the container was circulated by a fan and irradiated with a fluorescent lamp to examine the photocatalyst performance. In addition, the analysis of gas was always measured by connecting an infrared detector and circulating it. The measurement results are shown in Fig. 30. When zeolite is not added, acetaldehyde decreases sharply at first and then gradually decreases, but when gas is injected, it returns to the initial value, and when such an operation is repeated, the adsorption and decomposition reactions reach equilibrium. This is acetaldehyde first TiO₂ It is shown that it is adsorbed on the surface and rapidly decreases, and then gradually decomposed by the action of the photocatalyst. Next, when the gas is injected, acetaldehyde is adsorbed on the vacant adsorption sites that are decomposed by the photocatalyst, rapidly decreases, and then gradually decomposed. On the other hand, when zeolite is added, the introduced gas almost disappears from the atmosphere due to the effect of zeolite as an adsorbent. The adsorbed gas is then gradually decomposed by photocatalytic action. Therefore, by adding zeolite and adding the adsorption effect, the gas in the air can be rapidly adsorbed and removed, and then the photocatalyst can be decomposed to keep the air clean at all times.

【0289】

(Example 23) In order to investigate the influence of the Si: Al ratio of zeolite, three kinds of Si: Al = 80: 20, 50: 20, 30:20 were added and the difference was investigated. As shown in Fig. 31, the results showed that the higher the Si ratio, the higher the performance. This is because zeolite having a large Si ratio not only has a large amount of adsorption because it has a large surface area, but also has a large amount of adsorbed water and can provide surface-adsorbed water required for a photocatalyst.

【0290】

(Example 24) Next, the performance when Cu, Ag, Li, Na, and Mg ions were introduced into zeolite by ion exchange was investigated. As shown in Fig. 32, the results show that Cu and Ag ion exchange does not change much before and after ion exchange (compared to Fig. 30). On the other hand, the performance of Li, Na, Mg ion exchange was improved. This is because highly ionic elements such as Na, Li, and Mg create a + charged space in zeolite, and TiO.₂ Absorbs light and attracts the generated electrons, separates the electrons and holes, suppresses recombination, and increases the reaction efficiency.

【0291】

For the addition of Cu and Ag ion-exchanged zeolites, an antibacterial property test was conducted using Escherichia coli. The results are shown in Figure 33. Escherichia coli is growing while it is not irradiated with zeolite or light. When zeolite was added, the sterilization rate of E. coli at the time of light irradiation was the same, but the number of E. coli was slightly reduced without light irradiation. Cu, Ag ion-exchanged zeolite improved the sterilization rate of one Escherichia coli during light irradiation, and the sterilization rate during non-light irradiation was also significantly better than the others.

【0292】

As described above, the addition of zeolite improves the antibacterial properties of the dark reaction, and further the exchange of Cu and Ag ions results in improved performance both during light irradiation and during the dark reaction, producing an excellent antibacterial agent. I was able to.

【0293】

In this way, a photocatalyst can be formed on the surface of any material, a highly active photocatalyst effective in a living environment is provided, and gas components in the air are efficiently removed by an adsorption effect and a decomposition reaction.

【0294】

(Example 25) SiO₂ TiO in the sol₂ A solution in which fine particles and a blue pigment were dispersed was prepared. TiO on acrylic fibers using this solution₂ A film was formed to prepare a filter with a photocatalyst. The procedure is shown below.

【0295】

First, SiO₂ A method for producing a sol will be described. 5 g of tetraethoxysilane was dissolved in 100 ml of a mixed solution of water-ethanol-propanol (3:27:70), and the mixture was stirred at 40 ° C. for about 5 hours. The resulting solution was left at room temperature for 2 weeks to SiO₂ It was made into a sol.

【0296】

Next, SiO₂ TiO in the sol₂ A method for preparing a solution in which fine particles and a blue pigment are dispersed will be described. SiO produced earlier₂ TiO in the sol₂ Fine particles TiO by weight₂ / SiO₂ It was added as = 9, and a predetermined amount of Cu-phthalocyanine (blue pigment) was added. The solid content concentration was 4 wt%, and the required amount of water was added for adjustment. Then, using a 5 mmφ zirconia ball, SiO₂ TiO in the sol₂ Treated with a 24hr ball mill to disperse fine particles, SiO₂ TiO in the sol₂ A solution in which fine particles were dispersed was prepared.

【0297】

TiO made of acrylic fiber₂Fine particle dispersion SiO₂Coat the sol and treat at 120 ° C for 5 minutes to SiO₂TiO in the membrane₂TiO in which fine particles are dispersed₂Distributed SiO₂A film-coated filter was formed. The composition of the prepared photocatalyst is shown in Table 16.

【0298】

As a photocatalytic filter, it can be applied to an air cleaner or the like. In this case, it is possible to remove malodorous components, bacteria, cigarette smoke, etc. existing in the air. In particular, since a normal filter is absorbed and removed by an adsorbent, its effect is lost after saturation adsorption and it is necessary to replace it, whereas a filter with a photocatalyst acts as a photocatalyst on adsorbed malodorous components, bacteria, cigarette smoke, etc. Therefore, the number of filter replacements can be reduced.

【0299】

A photocatalytic filter having the composition shown in Table 16 was attached to an air purifier and operated in a room filled with cigarette smoke, and the filter was adsorbed with cigarette smoke to discolor. The discolored filter was taken out, irradiated with a fluorescent lamp, the color change was measured, and the decomposability of the adsorbed cigarette smoke was examined. The decomposition rate was calculated from the amount of discoloration measured by a colorimeter.

【0300】

Figure 34 shows the results of the decomposition test. As a result, it was found that the decomposition performance was improved by adding the blue pigment.

【0301】

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

【0302】

In the strength test, the prepared filter was repeatedly bent and pulled to evaluate whether the powder would fall off. If the powder did not fall due to bending and pulling, after repeating bending and pulling, it was investigated whether it could be peeled off by blowing air at 2 m / sec. The evaluation was X when it was peeled off by bending or pulling, Δ when it was peeled off by blowing air when it was not peeled off, and when it was not peeled off in either case.

【0303】

Light resistance is a low pressure mercury lamp (254nm, 3mW / cm) on the manufactured filter.²) Was irradiated, and the time when the amount of change in color became 20% or more was investigated.

【0304】

As for the evaluation result, the strength of the film decreased when the pigment was added, and the film was easily peeled off at 20 wt% or more. It can be easily peeled off, but if there is no operation such as bending or pulling, it will not peel off, so it can be used under conditions that do not cause movement after installation.

【0305】

Regarding the light resistance, it was found that the larger the amount of pigment added, the greater the deterioration. Although the pigment has excellent light resistance, it contains an organic group and is gradually decomposed by a photocatalyst. However, since this evaluation condition is considerably accelerated, the condition normally used is the light of a fluorescent lamp, and 35 hours in Table 16 corresponds to 3 to 5 years under a fluorescent lamp.

【0306】

As described above, the pigment-added catalyst is inferior in film strength and light resistance, but since the filter catalyst itself is colored, the performance of the filter can be seen immediately and the time to replace the filter can be easily determined.

【0307】

The addition of an organic resin is the most effective for increasing the adhesion strength to the filter. Table 17 shows the composition and various evaluation results when the acrylic resin was added to the previously prepared solution. The film strength was dramatically improved by adding the resin. In addition, although there was no change in light resistance, the performance was sufficient under fluorescent lighting, and the degradability of cigarettes was also good.

【0308】

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

【0309】

[Table 16]

<img file="JP2003305371A_D0016.tif" />【0310】

[Table 17]

<img file="JP2003305371A_D0017.tif" />【0311】

(Example 26) Regarding the pigment-added photocatalyst and the pigment-free photocatalyst prepared in Example 25, the decomposition characteristics of acetaldehyde, urea, ammonia, and Escherichia coli were compared using a fluorescent lamp, sunlight, an incandescent lamp, and a mercury lamp. As a result, it was found that the decomposition characteristics of acetaldehyde, urea, ammonia, and Escherichia coli of the Li-added photocatalyst were 3 to 5 times more effective than those of the pigment-free photocatalyst, regardless of which lamp was used. As described above, it was found that the pigment-added catalyst is effective not only in the ultraviolet lamp but also in the lamp used in the living environment. In addition, the above results showed the same effect even when red, yellow, green, etc. other than blue were added.

【0312】

In this way, a photocatalyst can be formed on the surface of any material, a highly active photocatalyst effective in a living environment can be provided, and the time for replacing the photocatalyst can be facilitated.

【0313】

(Example 27) SiO₂ TiO in the sol₂ A solution to which fine particles and acrylic resin were added was prepared. TiO on acrylic fibers using this solution₂ A film was formed to prepare a filter with a photocatalyst. The procedure is shown below.

【0314】

First, SiO₂ A method for producing a sol will be described. 5 g of tetraethoxysilane was dissolved in 100 ml of a mixed solution of water-ethanol-propanol (3:27:70), and the mixture was stirred at 40 ° C. for about 5 hours. The resulting solution was left at room temperature for 2 weeks to SiO₂ It was made into a sol.

【0315】

Next, SiO₂ TiO in the sol₂ A method for preparing a solution to which fine particles and acrylic resin are added will be described. SiO produced earlier₂ TiO in the sol₂ Fine particles TiO by weight₂ / SiO₂ It was added as = 9, and a predetermined amount of acrylic resin was added. The solid content concentration was 4 wt%, and the required amount of water was added for adjustment. Then, using a 5 mmφ zirconia ball, SiO₂ TiO in the sol₂ Treated with a 24hr ball mill to disperse fine particles, SiO₂ TiO in the sol₂ A solution in which fine particles were dispersed was prepared.

【0316】

TiO made of acrylic fiber₂Fine particle dispersion SiO₂Coat the sol and treat at 120 ° C for 5 minutes to SiO₂TiO in the membrane₂TiO in which fine particles are dispersed₂Distributed SiO₂A film-coated filter was formed. The composition of the prepared photocatalyst is shown in Table 18.

【0317】

As a photocatalytic filter, it can be applied to an air cleaner or the like. In this case, it is possible to remove malodorous components, bacteria, cigarette smoke, etc. existing in the air. In particular, since a normal filter is absorbed and removed by an adsorbent, its effect is lost after saturation adsorption and it is necessary to replace it, whereas a filter with a photocatalyst acts as a photocatalyst on adsorbed malodorous components, bacteria, cigarette smoke, etc. Therefore, the number of filter replacements can be reduced.

【0318】

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

【0319】

Figure 35 shows the results of the decomposition test. SiO₂ When (silka) was used as a binder, the performance as a photocatalyst deteriorated as the amount of the binder increased. On the other hand, in the case of acrylic resin, it was found that there was almost no change in the performance of the photocatalyst even if the amount of binder was increased.

【0320】

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

【0321】

In the strength test, the prepared filter was repeatedly bent and pulled to evaluate whether the powder would fall off. If the powder did not fall due to bending and pulling, after repeating bending and pulling, it was investigated whether it could be peeled off by blowing air at 2 m / sec. The evaluation was X when it was peeled off by bending or pulling, Δ when it was peeled off by blowing air when it was not peeled off, and when it was not peeled off in either case.

【0322】

Light resistance is a low pressure mercury lamp (254nm, 10mW / cm) on the manufactured filter.²) Was irradiated, and the time when the amount of change in color became 20% or more was investigated.

【0323】

In the water washing test, the filter was repeatedly washed with water, and the number of times until the catalyst was peeled off was examined and evaluated.

【0324】

The evaluation results showed that the addition of acrylic resin improved the film strength, and the film did not peel off at 5 wt% or more.

【0325】

Regarding the light resistance, it was found that the larger the amount of acrylic resin added, the greater the deterioration. Acrylic resin contains organic groups and is gradually decomposed by a photocatalyst. However, since this evaluation condition is considerably accelerated, the condition normally used is the light of a fluorescent lamp, and 5 hours in Table 18 corresponds to 3 to 5 years under a fluorescent lamp.

【0326】

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

【0327】

As described above, sufficient strength could be obtained by adding the organic resin. Moreover, the performance of the catalyst was the same as that without the addition of the resin even if the resin was added, and a washable photocatalyst filter could be produced.

【0328】

As described above, the acrylic resin-added catalyst is inferior in light resistance, but has excellent film strength, and can clean the filter catalyst. Until now, the photocatalyst had no effect on the stains on inorganic substances such as dust only by self-cleaning the stains on organic substances, but the cleaning can also remove the stains on the inorganic substances and prolong the life of the filter.

【0329】

(Example 28) Regarding the acrylic resin-added photocatalyst and the acrylic resin-free photocatalyst produced in Example 27, the decomposition characteristics of acetaldehyde, urea, ammonia, and Escherichia coli were compared using a fluorescent lamp, sunlight, an incandescent lamp, and a mercury lamp. .. As a result, it was found that the Li-added photocatalyst had the same effect as the acrylic resin-free photocatalyst in the decomposition characteristics of acetaldehyde, urea, ammonia, and Escherichia coli regardless of which lamp was used. As described above, it was found that the acrylic resin-added catalyst is effective not only in the ultraviolet lamp but also in the lamp used in the living environment.

【0330】

(Example 29) In recent years, in acrylic resins, silanol-modified acrylic resins in which silanol groups are introduced into the side chains of acrylic resins have been developed in order to improve chemical properties. A filter was prepared by adding acrylic resins having different silanol groups introduced to the solution prepared in Example 27 with this silanol-modified acrylic resin. FIG. 36 shows the results of evaluating the decomposition characteristics and light resistance of cigarette smoke of the prepared filter. It was found that the decomposition characteristics of cigarette smoke did not change significantly depending on the amount of silanol groups introduced (the amount of silanol introduced in the figure), and the performance did not deteriorate. On the other hand, it was found that the light resistance can be improved by increasing the amount of silanol groups introduced.

【0331】

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

【0332】

(Example 30) When an organic resin is used, it can be cured without applying heat, unlike a ceramic material such as silica. For example, it can be achieved by using a room temperature curing resin. However, room temperature curing systems take about 24 hours, except for those such as instant adhesives. The superglue cures in a short time, but is gradually decomposed by the photocatalyst. Examples of the resin that can be cured in a short time and have excellent light resistance include a UV curing system. The UV curing system is cured by ultraviolet rays, and is gradually polymerized and cured by ultraviolet rays irradiated from a fluorescent lamp. However, it is also a fact that it is gradually decomposed by a photocatalyst. Therefore, by appropriately combining photocuring and photodecomposition, light resistance can be improved as a result.

【0333】

TiO₂ A solution was prepared by adding UV curable resin to the fine particles. TiO on acrylic fibers using this solution₂ A film was formed to prepare a filter with a photocatalyst. The procedure is shown below.

【0334】

A predetermined amount of TiO in toluene₂ The fine particles and any of Si, Al, and Ti coupling agents were added, stirred at 40 ° C. for 2 hours, and then added to a predetermined amount of UV curable resin. The solid content concentration was set to 4 wt%, and the required amount of toluene was added for adjustment. Then TiO in solution using 5 mm ψ zirconia balls₂ Treated with a 24hr ball mill to disperse fine particles and TiO in UV curable resin₂ A solution in which fine particles were dispersed was prepared.

【0335】

Acrylic fibers were coated with the prepared solution and irradiated with ultraviolet rays 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.

【0336】

[Table 18]

<img file="JP2003305371A_D0018.tif" />【0337】

[Table 19]

<img file="JP2003305371A_D0019.tif" />【0338】

FIG. 37 shows the results of examining the decomposition characteristics of cigarette smoke (decomposition rate after 5 hours) with respect to the amount of the coupling agent added. It can be seen that the addition of the coupling agent improves the photocatalytic properties. UV curable resin alone is completely TiO₂ The surface of the particles is covered with resin and the catalytic properties are lost. By adding a coupling agent, TiO₂ The exposed part of the surface can be increased. Further, the photocatalyst decomposes the surface-adsorbed water to generate radicals, but by adding a coupling agent, a large amount of surface-adsorbed water can be retained and the catalytic performance can be exhibited.

【0339】

Table 19 shows the test results other than the catalytic performance. In the water washing test, it is possible to wash with UV curable resin 10 wt% or more. There is no problem with the light resistance, and no deterioration is observed even after irradiation for 10 hours.

【0340】

By using the UV curable resin as described above, a photocatalytic filter capable of coating at room temperature in a short time and having excellent light resistance could be produced.

【0341】

In this way, a photocatalyst can be formed on the surface of any material in a short time at low temperature, a highly active photocatalyst that is effective in a living environment can be provided, it can be washed with water, and inorganic stains can be removed. Reduce the number of times.

【0342】

(Example 31) SiO₂ TiO in the sol₂ A solution in which fine particles were dispersed was prepared. TiO on PET film using this solution₂ A film was formed to prepare a PET film. The procedure is shown below.

【0343】

First, SiO₂ A method for producing a sol will be described. 5 g of tetraethoxysilane was dissolved in 100 ml of a mixed solution of water-ethanol-propanol (3:27:70), and the mixture was stirred at 40 ° C. for about 5 hours. The resulting solution was left at room temperature for 2 weeks to SiO₂ It was made into a sol.

【0344】

Next, SiO₂ TiO in the sol₂ A method for preparing a solution in which fine particles are dispersed will be described. SiO produced earlier₂ In the sol, TiO₂ Fine particles TiO by weight₂ / SiO₂ Was added as 9. Further, phosphoric acid, boric acid and nitrates of Li, Mg, K and Ca were added in predetermined amounts to adjust the solid content concentration to 4 wt%, and the required amount of water was added to adjust. Then, using a 5 mmφ zirconia ball, SiO₂TiO in the sol₂Treated with a 24hr ball mill to disperse the fine particles, SiO₂ TiO in the sol₂ A solution in which fine particles were dispersed was prepared.

【0345】

TiO made on PET film₂ Fine particle dispersion SiO₂ Coated with sol, at 120 ° C, low pressure mercury lamp (strength: 15mW / cm)²) For 5 minutes while irradiating, SiO₂ TiO in the membrane₂ TiO in which fine particles are dispersed₂ Distributed SiO₂ A film-coated plastic film was formed. The thin film obtained on the PET film had good film quality and strength, and the film thickness was 300 nm.

【0346】

The prepared film was subjected to a strength test by rubbing the surface of the film with an eraser under a weight of 1 kg. As a result, the film without B and P was peeled off after 50 times, but the film with B and P was not damaged even after 100 times. From this, it was found that the film strength was improved by adding B and P.

【0347】

Next, the decomposition activity of organic matter was evaluated. In the activity test, a thin film was coated with a reddish purple organic dye and 0.2 mW / cm at a wavelength of 254 nm.²It was carried out by irradiating the light of. The decomposition rate was determined from the amount of change from the initial dye transmittance. The results are shown in Table 20. The hollow column in the table indicates that the element is not added.

【0348】

[Table 20]

<img file="JP2003305371A_D0020.tif" />【0349】

When B and P are not added, the photocatalyst with Li added decomposes 65% after 10 minutes, but when B and P are added to this, the decomposition rate is improved. In this way, it was found that the photocatalyst can be further improved in performance by adding B and P. In addition, the effect of the additive was the largest in K, followed by Ca, Mg, and Li in that order.

【0350】

In the photocatalyst, electrons and holes generated by absorbing light decompose water to generate radicals and decompose organic substances. Therefore, the organic matter cannot be decomposed unless water is present on the surface of the photocatalyst. TiO when B and P are not added₂ , SiO₂ It decomposes the water adsorbed on the surface. B and P have high water absorption, and more water is present on the catalyst surface by adding B and P. Such an increase in surface adsorbed water can improve the decomposability of organic substances.

【0351】

Next, ATO, which is a conductive particle, was added to the coating liquid prepared above, and a film was formed on the PET film in the same manner, and the degradability of the dye was evaluated. The results are shown in Table 21.

【0352】

[Table 21]

<img file="JP2003305371A_D0021.tif" />【0353】

The decomposition rate after 10 minutes was 81% when ATO was not added, but the decomposition rate was improved when ATO was added. In particular, the one added with 10 wt% has the greatest effect and the decomposition rate reaches 90%. In this way, it was found that the performance can be improved by further adding ATO. In addition, the surface resistance of the prepared ATO-added film is as low as 10 9 ohms / , and the antistatic effect is also taken into consideration, so that not only organic substances but also inorganic substances can be prevented from adhering.

【0354】

Furthermore, this ATO addition effect was similar not only for K (potassium) but also for Li (lithium), Ca (calcium), and Mg (magnesium).

【0355】

[Effect of the invention]

In the present invention, mainly in an indoor environment, a mechanism for generating an air flow by an electric motor, such as an air purifier, a ventilation fan, an electric fan, a vacuum cleaner, a clothes dryer, a dish dryer, a dishwasher, and a kitchen waste disposer, is built in. A low-temperature curing type highly active oxide photocatalyst thin film was provided in the air flow path, filtration part, exterior part, and part illuminated by the built-in lighting mechanism of the electrical products used, so it is as follows. The effect can be obtained.

【0356】

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

【0357】

First, the conventionally known TiO in the present invention.₂ An element having an electronegativity of less than 1.6 and an ionic radius of less than 0.2 nm, which contains Na, Li, etc. in a thin film of an oxide photocatalyst such as As a result, the effect of decomposing organic substances was enhanced. Furthermore, in addition to this, it contains antimony-added tin oxide, etc., and has an electron affinity of 1.2. When the above metal oxide semiconductors or the metal fine particles of Ag, Cu, Ni, Pd, Rh, and Pt were added in combination, the decomposition efficiency was further enhanced. This has the effect of eliminating the need for a mechanism for generating short-wavelength light, such as an ultraviolet lamp, which is required in conventional oxide photocatalysts. That is, as light that is generally obtained indoors, organic substances are decomposed even with non-weak light such as fluorescent lamps, incandescent lamps, mercury lamps, and sunlight through window glass, and sebum such as cigarettes and hand oils are used. Even if dirt from the deposits adheres, it decomposes and an antifouling effect can be obtained. Similarly, when various malodor-causing substances such as organic amines and mercaptans dispersed in the air adhere with weak light, they are decomposed and decomposed into low-odor or odorless substances. A deodorizing effect that reduces odor can be obtained. Similarly, when various microorganisms such as bacteria, molds, and pollen floating in the air adhere to each other with weak light, these microorganisms are killed or their reproduction is suppressed by the organic matter decomposition action, so that the thin film of the oxide catalyst is used. At the same time that the surface of the member formed with these products is kept clean, the effect of reducing the amount of microorganisms suspended in the air in the room where these products are used can be obtained. Conventionally, these parts that filter air, such as filters and nets, are often treated as replacement parts, and when dirt accumulates or becomes clogged, the parts are taken out and cleaned, or replaced with new ones. However, according to the present invention, since the adhered dirt is decomposed, the life until clogging can be extended, and the replacement frequency can be reduced.

【0358】

Examples of specific effects in each application are shown below. Interior lighting and sunlight are applied to the outer frames and frames of air purifiers, ventilation fans, electric fans, vacuum cleaners, clothes dryers, dish dryers, dishwashers, kitchen waste disposers, and exterior parts of cases. Therefore, it becomes possible to maintain a clean state in which it is hard to get dirty and it is hard for microorganisms to grow. In addition, if the air flow path parts attached to these articles and the parts such as filters and nets in the air flow path are installed so as to be irradiated with indoor lighting and sunlight, the same antifouling can be achieved. Not only antibacterial but also indoor deodorizing effect can be obtained.

【0359】

Regarding the antifouling effect, air purifiers, ventilation fans, electric fans, and vacuum cleaners may be operated remotely by providing an infrared receiver in the main body and an infrared transmitter in the remote controller. It also has the effect of preventing problems such as dirt adhering to the transmitting portion and hindering the reception and transmission of signals.

【0360】

Generally, when the load of dirt is so large that the intensity of light obtained indoors does not allow sufficient decomposition, or when it is desired to use it for members that are not sufficiently exposed to indoor light, it is effective to attach lighting means such as fluorescent lamps and light bulbs. Is obtained. If it is still insufficient, a high decomposition effect can be obtained by installing an ultraviolet generating means such as a mercury lamp or a metal halide lamp. In such a case, according to the present invention, since the disassembly 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 and the life of the lamps can be shortened. It also has the effect of reducing the frequency of replacement.

【0361】

For example, when a large amount of malodorous substances generated from a kitchen waste disposer are decomposed, a large amount of cooking oil adheres like a kitchen ventilation fan, or when a large amount of cooking oil adheres, such as a dishwasher, a dish dryer, or a clothes dryer. When a cleaning effect inside a closed tank or drum is required, it is effective to use light generating means of various wavelengths as described above in combination.

【0362】

Secondly, in the present invention, as described above, an oxide semiconductor of a metal having an electrical affinity of 1.2 or more, which contains antimony-added tin oxide in the photocatalytic thin film, or metal fine particles of Ag, Cu, Ni, Pd, Rh, Pt. Is added, so that the surface resistance value of the film itself can be suppressed to a low level. As this effect, it becomes possible to suppress the phenomenon that large-sized dust and fibers that take a long time to decompose, or minerals such as soil that cannot be decomposed adhere due to static electricity. By this action, it is possible to suppress the phenomenon that persistent stains are accumulated on the surface and the light does not reach the photocatalyst thin film surface.

【0363】

This antistatic effect is effective not only in preventing stains 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 such as vacuum cleaners that are easily triboelectrically charged during use.

【0364】

Specific examples of effects in each application are shown below. Air purifiers, ventilation fans, electric fans, vacuum cleaners, clothes dryers, dish dryers, dishwashers, outer frames and frames of kitchen waste disposers, and exterior parts of cases are particularly effective because dust easily adheres to them. ..

【0365】

Thirdly, in the present invention, when forming a photocatalytic thin film having the above effects, it is prepared from a solution containing a low molecular weight organometallic compound and water, and the bond between the metal atom and the organic group is broken. Therefore, by irradiating an electromagnetic wave having a required specific wavelength including ultraviolet light or the like, the reaction for forming a film is promoted, so that a thin film can be formed at a lower temperature than before. 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 to be coated on steel plates is softened by heat as a base material. It has become possible to form the oxide photocatalyst thin film without causing problems such as deformation, bubble generation, crack generation, embrittlement, strength decrease, and toughness decrease.

【0366】

Examples of specific effects in each application are shown below. Air purifier, ventilation fan, electric fan, vacuum cleaner, clothes dryer, dish dryer, dishwasher, kitchen waste treatment machine outer frame and frame, synthetic resin molded body or painted steel plate usually used for exterior parts of cases Kind is conventional TiO₂ Although it could not withstand a high temperature of 300 ° C or higher, which is the thin film formation temperature of the oxide photocatalyst mainly composed of the above, according to the present invention, it is easy without causing thermal damage to the substrate on the surface of these parts. It becomes possible to form a film on the surface.

【0367】

In addition, the air flow path parts attached to the above articles and the fan, blade, filter, and net parts in the air flow path are also made of a material that can withstand heat treatment of 300 ° C or higher. Although it was extremely difficult, the present invention has made it possible to easily form the oxide photocatalyst thin film.

【0368】

As another effect, since the oxide photocatalyst thin film according to the present invention can form a hard film at a low temperature, it is an effect that can replace a hard coat such as an acrylic resin that has been conventionally coated on the surface of a plastic molded product. There is also. As a result, the gloss of the molded product can be increased as in the case of the conventional hard coat, the surface can be prevented from being scratched, and the effect of suppressing the growth of microorganisms, the antifouling effect, and the antistatic effect can be obtained.

【0369】

Further, in the case of application to filters made of non-woven fabric, woven fabric, sponge, etc., since the oxide photocatalyst thin film formed on the fiber surface is glassy, the surface adsorptivity and wettability are improved. Therefore, there is an effect of improving the efficiency of collecting odors and smoke particles. SiO₂ Even if a single thin film is formed, the collection efficiency is improved by the same principle, but when the odor or smoke particles adhere to the fiber surface, the collection effect is reduced. In the present invention, the glassy film itself Because of its photocatalytic nature, the fiber surface is constantly cleaned and the highly adsorptive substrate continues to be exposed, thus sustaining the effect.

【0370】

Furthermore, in the case of a dishwasher, the contact angle of water droplets adhering to the inside can be reduced by utilizing the antifouling effect of the photocatalyst. As a result, the total amount of residual water can be reduced, which has the effect of increasing the drying efficiency of tableware. Utilizing this effect, it can be applied to various applications where dew is a problem.

[Simple explanation of drawings]

[Figure 1]

It is a block diagram of the filtration type air purifier main body which concerns on embodiment of this invention.

[Figure 2]

It is a perspective view of the filter type air purifier main body which concerns on embodiment of this invention.

[Fig. 3]

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

[Fig. 4]

It is sectional drawing of the ventilation fan main body for kitchen which concerns on embodiment of this invention.

[Fig. 5]

It is a perspective view of the fan main body which concerns on embodiment of this invention.

[Fig. 6]

It is a perspective view of the vacuum cleaner which concerns on embodiment of this invention.

[Fig. 7]

It is sectional drawing of the vacuum cleaner main body which concerns on embodiment of this invention.

[Fig. 8]

It is sectional drawing of the main body of the clothes dryer which concerns on embodiment of this invention.

[Fig. 9]

It is a perspective view of the dishwasher main body which concerns on embodiment of this invention.

[Fig. 10]

It is an enlarged sectional view of the exhaust port part of the dishwasher which concerns on embodiment of this invention.

[Fig. 11]

It is sectional drawing of the dishwasher main body which concerns on embodiment of this invention.

[Fig. 12]

It is a perspective view of the dishwasher main body which concerns on embodiment of this invention.

[Fig. 13]

It is sectional drawing of the dishwasher main body which concerns on embodiment of this invention.

[Fig. 14]

It is sectional drawing of the dishwasher main body which concerns on embodiment of this invention.

[Fig. 15]

It is a perspective view of the kitchen waste processing machine main body which concerns on embodiment of this invention.

[Fig. 16]

It is sectional drawing of the kitchen waste processing machine main body which concerns on embodiment of this invention.

[Fig. 17]

TiO formed on the PET film according to the embodiment of the present invention₂ Distributed SiO₂It is sectional drawing of the membrane.

[Fig. 18]

It is sectional drawing of the low temperature curing type highly active photocatalyst thin film formed on the adherend which concerns on embodiment of this invention.

[Fig. 19]

It is sectional drawing of the low temperature curing type highly active photocatalyst thin film formed by laminating two layers on the adherend which concerns on embodiment of this invention.

[Fig. 20]

It is a figure which shows the decomposition test result of the organic dye which concerns on embodiment of this invention.

[Fig. 21]

It is a figure which shows the relationship between the electronegativity and the decomposition rate which concerns on embodiment of this invention.

[Fig. 22]

It is a figure which shows the relationship between electronegativity and ionic radius which concerns on embodiment of this invention.

[Fig. 23]

It is a figure which shows the smoke collecting effect of the low temperature curing type highly active photocatalyst thin film which concerns on embodiment of this invention.

[Fig. 24]

It is a figure which shows the photodecomposition effect of the smoke adhesion filter which concerns on embodiment of this invention.

[Fig. 25]

It is a figure which shows the ammonia collecting effect of the low temperature curing type highly active photocatalyst thin film which concerns on embodiment of this invention.

[Fig. 26]

It is a figure which shows the photodecomposition effect of ammonia gas which concerns on embodiment of this invention.

[Fig. 27]

It is a figure which shows the photodecomposition effect of the smoke adhering ABS plate which concerns on embodiment of this invention.

[Fig. 28]

It is a figure which shows the photodecomposition effect of the salad oil which concerns on embodiment of this invention.

[Fig. 29]

It is a figure which shows the decomposition test result of the organic dye which concerns on embodiment of this invention.

[Fig. 30]

It is a figure which shows the addition effect of the zeolite which concerns on embodiment of this invention.

[Fig. 31]

It is a figure which shows the influence of the ratio of Si and Al which concerns on embodiment of this invention.

[Fig. 32]

It is a figure which shows the addition effect of the ion exchange zeolite which concerns on embodiment of this invention.

[Fig. 33]

It is a figure which shows the antibacterial effect of zeolite addition which concerns on embodiment of this invention.

[Fig. 34]

It is a figure which shows the decomposition test result of the cigarette smoke which concerns on embodiment of this invention.

[Fig. 35]

It is a figure which shows the decomposition test result of the cigarette smoke with respect to the binder addition amount which concerns on embodiment of this invention.

[Fig. 36]

It is a figure which shows the decomposition test result of the cigarette smoke with respect to the silanol introduction amount which concerns on embodiment of this invention.

[Fig. 37]

It is a figure which shows the decomposition test result of the cigarette smoke with respect to the addition amount of the coupling agent which concerns on embodiment of this invention.