Photocatalyst body and method of production thereof

Light touch media and its manufacturing method

[Technical Field of Invention]

The present invention relates to a photocatalyst medium with excellent photocatalyst functions, a method of manufacturing the same, and a photocatalyst composition using the same.

[Literature Technology]

If a semiconductor is irradiated with light of a wavelength with energy above its energy band gap, an oxidation-reduction reaction will occur. Such semiconductors are called photocatalyst semiconductors, or just photocatalysts.

The photocatalyst can be used in the form of powder suspended in a solution, and used in the form of being supported on some substrates. From the point of photocatalyst activity, in terms of its surface area, the former is generally more active, but from the practical point of view, in terms of ease of handling, most of the latter have to be used.

In order to support the photocatalyst on the substrate, a method of sintering or supporting the photocatalyst particles on the substrate at a high temperature is adopted. In addition, a method of supporting a photocatalyst on a substrate using a certain fluorine-based polymer as a binder has also been proposed. For example, Japanese Patent Laid-Open No. 4-284851 describes a method of laminating and pressing a mixture of photocatalyst particles and a fluorine-based polymer. Polymer method. In addition, Japanese Patent Application Laid-Open No. 7-171408 describes a method for bonding photocatalyst particles to a substrate through a non-decomposable binder composed of an inorganic system such as monohydrate and an organic system such as a silicone polymer. , And a method for manufacturing a photocatalyst in which a hardly decomposable bonding agent is provided on the substrate as the first layer, and a second layer composed of the hardly decomposable bonding agent and photocatalyst particles is provided on the first layer. In addition, Japanese Patent Laid-Open No. 5-309267 describes the use of a metal oxide formed from a metal oxide sol as a support and immobilization material for photocatalyst powder, and the metal oxide sol system is adopted by the sol-gel method Metal alkoxides, acetylacetonates, carboxylates and other metal organic compounds, or the alcohol solution of the chloride of titanium tetrachloride is hydrolyzed in the presence of an acid or alkali catalyst.

[The problem to be solved by the invention]

Recently, photocatalysts have been used to try to decompose, purify or sterilize harmful substances, malodorous components, oils, etc. produced in the daily life environment. The scope of application of photocatalyst is rapidly expanding. Along with this, a method that enables the photocatalyst particles to be carried on all substrates without impairing the function of the photocatalyst, which can be strong and can be used for a long period of time is sought after. In particular, when titanium oxide sol with excellent photocatalyst function is used as a photocatalyst, the adhesion function to the substrate is weak, so its adhesion improvement is particularly required.

However, the aforementioned conventional technical methods still have the following problems: the adhesion strength is insufficient, and there are few people who can carry it for a long period of time. If the adhesion strength is to be increased so that it can be carried for a long time, the photocatalyst function will decrease on the contrary. When using a matrix composed of organic polymer resin, compared with anatase type, even the so-called rutile type titanium oxide, which has a weak catalyst function, undergoes photocatalytic reaction and reacts with organic polymer resin. The photochemical reaction itself is complementary, and it will degrade and decompose due to long-term use.

In addition, when organic polymer resin is used as the matrix, it can be pre-coated with silica sol, etc. However, the silica sol may cause cracks or voids during the process of agglomeration and drying. The performance of the binder is problem.

[Methods to solve the problem]

In order to solve the above problems, the inventors explored a method that can support the photocatalyst particles on all substrates strongly and for a long period of time without damaging the function of the photocatalyst, using amorphous titanium peroxide sol as a binder. It is found that the photocatalyst particles can be supported on all substrates strongly and for a long period of time without impairing the function of the photocatalyst, and the present invention is finally completed.

That is, the present invention relates to a method for manufacturing a photocatalyst composed of a photocatalyst supported and fixed on a substrate, and a method for manufacturing a photocatalyst using a photocatalyst such as titanium oxide and an amorphous titanium peroxide sol. The substrate is provided with a photocatalyst One layer (does not have the function of photocatalyst prepared by using amorphous titanium peroxide sol), and a second layer (made by using photocatalyst and amorphous titanium peroxide sol) is provided on the first layer of photocatalyst Body manufacturing method, the photocatalyst medium manufactured by this method, and the photocatalyst composition used in the manufacturing.

The amorphous titanium peroxide sol used in the present invention can be produced as follows. Yuru Titanium Hydride TiCl₄To the titanium salt aqueous solution, add alkali metal hydroxide such as ammonia or sodium hydroxide. The produced light blue-white, amorphous titanium hydroxide Ti(OH)₄Also known as orthotitanate H₄TiO₄If the titanium hydroxide is washed and separated, and treated with hydrogen peroxide water, the amorphous titanium peroxide solution of the present invention can be obtained. This amorphous titanium peroxide sol has a pH of 6.0-7.0, a particle diameter of 8-20nm, and its appearance is a yellow transparent liquid, and it is stable when stored at room temperature for a long period of time. In addition, the concentration of the sol is usually adjusted to 1.40-1.60%, and the concentration can be adjusted as needed. When using at a low concentration, it can be diluted with distilled water or the like.

This amorphous titanium peroxide sol is in an amorphous state at room temperature and has not yet crystallized into anatase titanium oxide. It can be made with excellent adhesion and high film-forming properties. Uniform and flat film, and the dry coating film has the property of being insoluble in water.

In addition, if the amorphous titanium peroxide sol is heated above 100°C, it will become anatase-type titanium oxide sol. The amorphous titanium peroxide sol is coated on the substrate and then dried and fixed by heating above 250°C. It becomes anatase titanium oxide.

The photocatalyst that can be used in the present invention can be TiO₂, ZnO, SrTiO₃, CdS, CdO, CaP, InP, In₂O₃, CaAs, BaTiO₃, K₂NbO₃, Fe₂O₃, Ta₂O₅, WO₃, SaO₂, Bi₂O₃, NiO, Cu₂O, SiC, SiO₂, MoS₂, MoS₃, InPb, RuO₂, CeO₂Among them, titanium oxide is preferred. Titanium oxide can be used in the form of particles or powder, or in the form of sol.

Sol-like titanium oxide, that is, titanium oxide sol can be produced by heating amorphous titanium peroxide sol at a temperature above 100°C as described above, but the properties of titanium oxide sol will vary with heating temperature and heating time. For example, the anatase titanium oxide sol produced by treating at 100°C for 6 hours has a pH of 7.5 to 9.5, a particle diameter of 8 to 20 nm, and its appearance is a yellow suspended liquid.

This titanium oxide sol is stable for long-term storage at room temperature, but when mixed with acid or metal aqueous solution, precipitation will occur. The presence of Na ions may sometimes impair the photocatalyst activity or acid resistance. In addition, the sol concentration is usually adjusted to 2.70~2.90%, but the concentration can be adjusted and used as needed.

The above-mentioned titanium oxide sol is preferably used as the photocatalyst, and the commercially available "ST-01- (manufactured by Ishihara Sangyo Co., Ltd.) or "ST-31- (manufactured by Ishihara Sangyo Co., Ltd.) can also be used.

In the present invention, the base system can use inorganic materials such as ceramics and glass, organic materials such as plastic, rubber, wood, and paper, and metal materials such as aluminum and steel. Among these, especially suitable for organic polymer resins such as acrylonitrile resin, vinyl chloride resin, polycarbonate resin, methyl methacrylate resin (acrylic resin), polyester resin, polyurethane resin, etc. The material can exert excellent effects. The size or shape is not limited, and may be honeycomb, fibrous, filter sheet, bead, foam, or these aggregates. Furthermore, if it is a substrate that passes through ultraviolet rays, the inner surface of the substrate can be applied with light-touch media, and it can also be applied to the coated article.

In the present invention, an adhesive that is not decomposed by a photocatalyst means that it is difficult to be described in the aforementioned JP-A No. 7-171408, such as inorganic and fluorine-based polymers such as water glass, colloidal silica, cement, etc. An adhesive decomposed by a photocatalyst composed of organic systems such as silicon-based polymers.

Secondly, there are several methods for the modulation of the composition of the optical touch media of the present invention.

First, a method of uniformly suspending titanium oxide powder in an amorphous titanium peroxide sol can be cited. In order to make it uniformly turbid, it is advantageous to use ultrasonic waves after mechanical stirring.

Next, the aforementioned titanium oxide sol and amorphous titanium peroxide sol are mixed to prepare a mixed sol. The mixing ratio of the two is determined by the part of the product or the use conditions of the machine to which the phototouch media of the present invention is applicable, but in this case, the adhesion, film formation, and corrosion resistance of the phototouch media prepared by the mixed sol to the substrate must be considered Sex and so on. Moreover, it can be roughly divided into three types. People will come in contact with it, or it is highly likely to be visually necessary, such as interior tiles, sanitary pottery, various unit products, food utensils, building interior and exterior materials, and automobile interior materials. People will not touch, but they must be cosmetically visually. For example, lighting fixtures, underpasses, roads, tunnels, civil engineering materials, electrical appliance exterior panels, etc. Usually, people cant touch or see, can use the organic decomposition function produced by photocatalyst function, or the properties of semiconductor metal itself, purification tank, various drainage treatment devices, boilers, shower boxes, air conditioners, oil fume The components inside the machine, or assembled in other machines, etc.

Next, in the above classification , it is preferable that the total amount of the titanium oxide sol and the amorphous titanium peroxide sol is mixed with the mixed sol of the titanium oxide sol at a ratio of 30% by weight or less to form a photocontact medium. This product is sufficient for sterilization or pollution prevention in daily life, residual odor decomposition, and the film surface is very hard, there will be no abrasion caused by cleaning or adhesion of debris, and it is difficult to adhere by contact. Of fingerprints and so on.

In addition, for purification tanks belonging to the above classification , in order to reduce the residual organic matter (BOD) value of the final wastewater treatment water, the photocatalytic media used has high photocatalytic activity is the most important performance. For this reason, the best is , For the total amount of titanium oxide sol and amorphous titanium peroxide sol, the mixed sol of titanium oxide sol is mixed at a ratio of more than 70% by weight to form a photocontact medium. This light touch media has poor cosmetic properties, but the distinction is usually not touched or seen by humans. In addition, the problem of how much residue will adhere can also be solved by regular removal and cleaning.

Furthermore, in the above classification , it is preferable that the total amount of the titanium oxide sol and the amorphous titanium peroxide sol is mixed with the mixed sol of the titanium oxide sol at a ratio of 20 to 80% by weight to form a film. This photocatalyst medium can show the intermediate properties of the first two in terms of hardness, adhesion of impurities, and photocatalyst activity.

For coating or spraying amorphous titanium peroxide sol, mixed sol, etc. on the substrate, a known method such as dipping, spraying, and coating can be used. There are many cases of repeated coating during coating.

After coating or spraying and covering as described above, it can be dried and cured to obtain the photocontact medium of the present invention, but it can also be sintered at about 200-400°C to be cured and supported. In addition, the photocatalyst function of titanium oxide is reduced due to the influence of sodium ions. Therefore, when using organic polymer resins that are easily decomposed by photocatalysts as the matrix, clean the resin with substances containing sodium ions such as sodium hydroxide solution before coating. It is advantageous for the sodium source to exist on the surface.

In addition, when using amorphous titanium peroxide sol as the first layer, if it is heated to 250°C or higher, crystals of anatase-type titanium oxide will be formed to produce a photocatalytic function. Therefore, drying is performed at a lower temperature than this, for example, 80°C or less. Curing. Also, at this time, for the same reason as described above, sodium ions are added to the titanium peroxide sol. Before forming, it is possible to mix photocatalysts and particles composed of spontaneous ultraviolet radiation materials or light-storing ultraviolet radiation materials or particles mixed with these radiation materials.

Spontaneous ultraviolet radiation material (self-type luminous ceramics) is a material that consumes internal energy and emits light by itself. It uses the radiation attenuation of radium or iron to emit ultraviolet light. In addition, the current situation is to use crushed particles obtained by re-pulverizing refined rock powder containing such ingredients after being solidified.

The light-storing ultraviolet radiation material (light-storing luminescent ceramics) is a material that can take in external energy and release this part while emitting light. It has an ultraviolet region in the light. Commercially available are "Luminoba" (trade name, Nemoto Special Chemical Co., Ltd.), "Kipras" (trade name,<img file="TW460321B_D0002.tif" /><img file="TW460321B_D0003.tif" />Co., Ltd.) and so on. These materials are made of high-purity alumina, strontium carbonate, strontium aluminate containing europium and dysprosium (SrAl₂O₄) Is the main ingredient. The maximum point of the absorption spectrum is 360 nm, and the particle size is 20 μm~50 μm. However, the crushed state before crushing can also be used as crushed particles in the original state.

In addition, in these commercially available products, if moisture is absorbed, the performance may be greatly reduced. In this case, it can be pre-sealed in glass or transparent organic polymer resin such as PC, or it can be mixed in the matrix. Or stick to the surface of the substrate for use.

Particles formed by mixing such spontaneous luminescent ceramics or light-storing luminescent ceramic particles or fine particles of these ceramics (hereinafter referred to as mixed particles) are mixed with the photocatalyst to prepare the photocatalyst, even if the ultraviolet radiation on the photocatalyst is interrupted, The photocatalyst semiconductor of the photocatalyst is excited by the ultraviolet ray emitted from the spontaneous luminescent ceramic particles or the ultraviolet ray emitted from the energy accumulated at the time when the particles of the light-storing luminescent ceramic particles are consumed, and the photocatalyst function is continued. In addition, the particles of spontaneous luminescent ceramics or light-storing luminescent ceramics usually emit green, blue or orange visible light, so they can be used for decoration or guidance in the dark.

Photocatalyst semiconductors can change the ultraviolet wavelength (absorption band) necessary for the catalyst function by adjusting its composition (adding inorganic pigments or metals) or adjusting the heat treatment in the manufacturing process, that is, the excitation wavelength. For example, if in TiO₂Add a small amount of CrO₃, The absorption band will shift on the long wavelength side. In this way, the side of the photocatalyst can meet the emission spectrum characteristics of the spontaneous ultraviolet radiation material or the light-storing ultraviolet radiation material, and the photocatalyst semiconductor that meets the supplied ultraviolet wavelength can be selected.

In addition, on the contrary, the emission spectrum characteristics of the spontaneous ultraviolet radiation material or the light-storing ultraviolet radiation material can also be matched with the excitation wavelength of the photocatalyst semiconductor. For example, the excitation wavelength of titanium oxide is 180 nm~400 nm, but there is no commercially available product for the light-storing ultraviolet radiation material that meets this requirement.

Commercially available long-lasting light-storing ceramics include the "N Luminous-" of Fundamental Special Chemical Co., Ltd., and the afterglow time is more than 1000 minutes. This is the addition of alumina to the main raw material of strontium carbonate or calcium carbonate. Add europium or dysprosium, add lanthanum, cerium, samarium, samarium, sinter, po, ytterbium, erbium, thion, ytterbium, ytterbium, manganese, tin, bismuth and boric acid as a flux and heat at 1300°C Treatment to produce long-term afterglow light-storing ceramics. In this hybrid manufacturing method, a blue light-emitting body with a peak of 440 nm is produced even at the shortest wavelength.

In order to form the excitation wavelength of titanium oxide, that is, the emission wavelength below 400 nm, an addition is added to make the aforementioned "N luminous-have an absorption wavelength with 360 nm as the peak, which is close to the emission wavelength with 440 nm as the peak." Metal elements, or when minerals such as strontium, potassium, borax, etc. have the original phosphorescent wavelength of about 450 nm and do not produce luminescent wavelengths below 440 nm, they will not emit phosphorescent light, which is more than strontium. It is possible to develop light-storing ultraviolet radiation materials by refining and processing mineral elements with shorter wavelengths and non-coloring emission wavelengths below 400 nm.

When the photocatalyst semiconductor is only pre-loaded on the surface of the unit particles, after the unit particles are mixed with particles of spontaneous luminescent ceramics or phosphorescent ceramics or mixed with particles to form a molded product, it may be carried on the entire surface. The former type is that the photocatalyst semiconductor does not adhere to the surface of particles of spontaneous luminescent ceramics or light-storing luminescent ceramics or mixes the particles, and the amount of ultraviolet rays radiated from these particles increases. In addition, in the case of the light-storing type luminescent ceramic particles, ultraviolet rays from the outside can be efficiently absorbed.

During the manufacturing process of the photocatalyst, sometimes a photocatalyst function is added to assist the addition of metals (Pt, Ag, Rh, RuO, Nb, Cu, Sn, NiO, etc.). These are well known as those that promote the supplementary photocatalyst reaction.

[Example]

Hereinafter, reference examples and examples are disclosed to explain the present invention more specifically, but the scope of the present invention is not limited to these examples.

Reference example 1 (manufacturing of amorphous titanium peroxide sol)

Titanium tetrachloride TiCl₄50% solution (Sumitomo<img file="TW460321B_D0004.tif" />Co., Ltd.) diluted 70 times with distilled water, and ammonium hydroxide NH₄The 25% OH solution (Takasugi Pharmaceutical Co., Ltd.) is diluted 10 times with distilled water and mixed to a volume ratio of 7:1 for neutralization reaction. After the neutralization reaction, the pH is adjusted to 6.5~6.8, and after a short period of time, the supernatant is removed. Add residual Ti(OH)₄About 4 times the amount of gel in distilled water, fully stir and set aside. Check with silver nitrate, wash repeatedly until no chloride ions in the clear liquid are detected, and finally discard the supernatant and leave only the gel. Depending on the situation, it can be dehydrated by centrifugal separation. Here is the pale white Ti(OH)₄ Add 210 ml of 35% hydrogen peroxide water to 3600 ml twice every 30 minutes. If stirred overnight at 50°C, about 2500 ml of yellow transparent amorphous titanium peroxide sol can be obtained.

In addition, in the above process, if heat generation is not suppressed, substances that are insoluble in water such as ortho-titanic acid may be precipitated. Therefore, it is preferable to suppress heat generation in all the processes.

Reference example 2 (manufacturing of titanium oxide sol from amorphous titanium peroxide sol)

If the above-mentioned amorphous titanium peroxide sol is heated at 100°C, anatase-type titanium oxide will be produced after about 3 hours, and if it is heated for about 6 hours, anatase-type titanium oxide sol can be obtained. If heated at 100°C for 8 hours, it will have light yellow or suspended fluorescence. If concentrated, yellow and opaque products can be obtained. If heated at 100°C for 16 hours, very light yellow ones can be obtained, but these are better than the above 100 When heated at °C for 6 hours, the dry adhesion slightly decreased.

This titanium oxide sol has lower viscosity than amorphous titanium peroxide, so it is concentrated to 2.5% by weight for easy impregnation.

Example 1

The organic substance decomposition test using the mixing ratio of the amorphous titanium peroxide sol and the titanium oxide sol was performed as follows. On the substrate, use a 150x220 mm vertical and horizontal and 4 mm thick halloy stone makeup board (Co., Ltd.<img file="TW460321B_D0005.tif" /><img file="TW460321B_D0006.tif" />system). The substrate was sprayed with mixed sols of various mixing ratios with a thickness of about 2 μm to be coated, dried from room temperature to 70°C, and sintered at about 400°C for 30 minutes to obtain five types of photocatalysts supporting the photocatalyst on the substrate. Put the test light touch media into the test container, and then pour water into the container until the depth of the coloring solution of the decomposed organic matter reaches 1 cm. This coloring solution is an aqueous dispersion of mono-azo red (red liquid) of pollucite red PM-R (<img file="TW460321B_D0007.tif" />Co., Ltd.) diluted to 30 times. Then, in order to prevent the coloring solution in the container from evaporating, the container is covered with lead-tin glass (shading wavelength below 300). 5 cm above the test container, from the substrate At 95cm, set up 2 ultraviolet emitters (20w blue fluorescent tubes) with a distance of 13cm to irradiate various light touch media, and the time when the color of the coloring solution disappears is regarded as the end of the decomposition of organic matter. The result is as follows.

When using 100% titanium oxide sol on the substrate, the color will disappear after 72 hours from the start of the test. The decomposition ability of organic substances, which is the opposite of the excellent photocatalyst function, will result in a lot of decomposition residues. In addition, the color of the amorphous titanium peroxide sol 100% will disappear within 150 hours, and the decomposition energy of organic substances, that is, the photocatalyst function, is worse than that of the above-mentioned titanium oxide sol 100%, but its adhesion, film formation and corrosion resistance It is excellent in terms of properties and cosmetic properties. In addition, if the mixing ratio of the amorphous titanium peroxide sol and the titanium oxide sol is 1:3 at 78 hours, the mixing ratio of 1:1 at 102 hours, and the mixing ratio of 3:1 at 120 hours, the color will disappear respectively. Moreover, from the above experiments, it can be seen that the photocatalyst function is inversely proportional to adhesion, film-forming properties, corrosion resistance, and cosmetic properties. From these facts, it is known that according to the present invention, it can be used in various applications (applicable parts of the product, use conditions) by changing the mixing ratio.

Example 2

Acrylic resin board and methacrylic resin board are used as the substrate. Dip these resin boards in a 2% sodium hydroxide solution at 80°C for 30 minutes, wash them with water, and then dry them. Dip coating the titanium peroxide sol made in Reference Example I on this resin plate with 0.5% surfactant added 3-4 times as the first layer. The drying system was carried out at 70°C for 10 minutes.

The second layer is dip-coated with the same blending ratio of the 5 types of amorphous titanium peroxide sol and titanium oxide sol as in Example 1 for 3-4 times. In terms of drying and curing, the acrylic resin board is held at 120°C for 3 minutes, and the methacrylic resin After the temperature of the grease board dryer rises to 119°C, it ends. The photocatalyst function is the same as the result of Example 1, but the first layer is particularly excellent in adhesion to the resin plate and the hard decomposition of the resin plate caused by the photocatalyst.

Example 3

Use a commercially available tile with high water absorption as a substrate. First, wash it with a neutral detergent, and after drying, use one that is coated with a surfactant. The photocatalyst composition is based on the weight ratio of 50 parts of the titanium peroxide sol (pH 6.4) prepared in Reference Example 1, 1 part of titanium oxide powder "ST-01- (manufactured by Ishihara Sangyo Co., Ltd.) is added, and it is mechanically stirred for about 15 parts. Minutes later, stir with ultrasonic waves to prevent the formation of particles. Impregnate at a speed of 0.3~0.5cm per second, and dry overnight at 30°C. Then, it is fired at 400°C for 30 minutes to produce a light touch medium. This touch medium It is firmly adhered to the surface of the tiles during the long period of time.

In addition, the above-mentioned tiles were coated with distilled water in which titanium oxide powder was dispersed, and it was found that they could not be adhered well.

Example 4

Coat the glass bead suspension with a spray gun several times on the lead and tin-containing glass surface that has been degreased and treated with surfactant. After drying at 40°C, it was fired at 700°C for 30 minutes. The glass beads fixed on the lead-containing and tin-containing glass were coated with the photocatalyst composition used in Example 3, and after drying, they were fired at 400°C for 30 minutes to produce a photocatalyst. The light touch media can be firmly adhered to a glass bead fixed on lead and tin glass for a long period of time.

Example 5

In the amorphous titanium peroxide sol, 25% by weight relative to the titanium peroxide in the sol is mixed with a light-storing ultraviolet radiation material.<img file="TW460321B_D0008.tif" />" (Trade name Co., Ltd.<img file="TW460321B_D0009.tif" />), stir it, spray it on the halloysite cosmetic board as the substrate, dry it at room temperature, and burn it at 400°C for 30 minutes. After cooling, the titanium oxide sol whose excitation wavelength is modulated to the emission wavelength of the above-mentioned radiant material is sprayed into It is 1 μm thick, and after drying, it is fired at 40°C for 30 minutes. This photocatalyst medium will continue to act as a photocatalyst by using the ultraviolet rays emitted by the ultraviolet radiation material even if the irradiation of the ultraviolet rays on the photocatalyst medium is interrupted.

Example 6

Put 150 grams of glass beads (manufactured by Toshiba Barotini Co., Ltd.: GB602) into a 120 mm × 80 mm mold and fired at a temperature of 720°C for 30 minutes to prepare a rice bubble candy snack-like matrix. Next, 200ml of 0.85% by weight (titanium conversion) solution of amorphous titanium peroxide sol prepared in Reference Example 1 was mixed with tungsten trioxide WO as a photocatalyst₃(Tokyo Tungsten Co., Ltd.: FI-WO₃) To make the molar ratio of titanium to tungsten 1:4, and then apply it to the glass bead substrate by dipping. As a result, the adhesion amount of the mixture in a water-containing state is 15 g/150 g . The mixture was dried at 100°C for 30 minutes. Then, it was fired at 300°C for 30 minutes to prepare a light touch medium. The photocatalyst has excellent performance in the decomposition energy of the photocatalyst, and can be firmly adhered to the glass bead substrate for a long time. In addition, in addition to using ZnO, SrTiO3, CdS, and InPb as photocatalysts, the photocatalyst was prepared by the above modulation method. These light touch media and TiO₂As a photocatalyst, it can also be firmly adhered to the glass bead substrate for a long period of time.

Example 7

Carry out the same steps as in Example 6, but in the amorphous titanium peroxide sol Medium-mix anatase TiO₂(Manufactured by Ishihara Techno Co., Ltd.: ST-01) and the above-mentioned tungsten trioxide WO₃As a photocatalyst, the mixing ratio of these metal atoms is 1:1:1, and the same photocontact medium as in Example 6 is prepared. The photocontact medium can be firmly adhered to the glass bead substrate for a long period of time.

Example 8

Add the phototouch media obtained in Example 6 and Example 7 into the test container, and then pour water into the container until the depth of the coloring solution of the decomposed organic substance reaches 1 cm. This coloring solution is a 30-fold dilution of pollucite red PM-R (manufactured by Sumitomo Color Co., Ltd.), an aqueous dispersion of monoazo red (red liquid). Then, in order to prevent the coloring solution in the container from evaporating, the container is covered with lead and tin glass (shading wavelength below 300nm). Place two ultraviolet emitters (20w blue fluorescent tubes) at a distance of 13cm apart from the substrate 5cm above the test container and irradiate various photo-contact media. The time when the color of the coloring solution disappears is regarded as the end of the decomposition of the organic matter. . The results are shown in Table 1. In addition, with 100% amorphous titanium peroxide sol as a control group, no change was observed within 150 hours. It can be seen from Table 1 that these photocatalyst media have good photocatalyst decomposition energy.<tables><img file="TW460321B_D0010.tif" /></tables>

[Effects of Invention]

According to the present invention, it is possible to provide a method for manufacturing a photocatalyst medium that can be supported and fixed on a substrate without reducing the function of a photocatalyst with a photocatalyst and can be used for a long time. In addition, when using titanium oxide and amorphous titanium peroxide sol, by changing the mixing ratio, it can be applied to products for various purposes. Furthermore, by pre-mixing the photocatalyst and particles composed of spontaneous ultraviolet radiation materials or light-storing ultraviolet radiation materials or particles mixed with these radiation materials, the photocatalyst function can be uninterruptedly displayed outdoors without ultraviolet radiation.