TW406031B - Multi-functional material having photo-catalytic function and production method therefor - Google Patents

Abstract

The multi-functional material according to the present invention is divided into a type in which a photo-catalytic layer having a photo-catalytic function is directly disposed on the surface of a substrate (1) and another in which the photo-catalytic layer (2) is indirectly disposed on the surface of the substrate (1) through a binder layer (6). The mode of binding of photo-catalytic particles constituting the photo-catalytic layer (2) includes binding by surface energy and binding by solid phase sintering. The structure of the photo-catalytic layer (2) includes the structure in which fine particles are packed into gaps between the photo-catalytic particles and mother in which they are not. Further, there is a structure in which metals such as Ag and Pt are fixed to the surfaces of the photo-catalytic particles and another in which they are not.

Description

A7 Ship G3 + Wei-V. Description of the invention (1) The present invention is a multifunctional material with functions such as de-Olympic function, antibacterial function, bactericidal function, antifouling function and its manufacturing method. (Please read the note on the back first (This page) In the past, substances that can cause the adsorption or desorption of oxygen atoms to organic compounds such as malodorous components through irradiation of ultraviolet rays • substances that promote decomposition (oxidation), such as T i 02, ν20β · ζ η 0, W03, etc. In particular, T i 02 particles with an anatase crystal type have a photocatalytic effect of high degree. Therefore, in the past, it has been proposed to form photocatalysts on the surface of wall materials, tiles, glass (mirrors), circulating filter devices or sanitary ware.靥 · The method for forming the above-mentioned photocatalyst 靥 is known to the CVD method, the spray method, the electron beam evaporation method, etc. · The photocatalyst layer formed by T 02 particles and the like is directly formed on the surface of the substrate of plastic, ceramic, resin, etc. However, when using the CVD method, sputtering method, electron beam evaporation method, etc., there must be large-scale equipment, and the product yield is not good, and the manufacturing cost is too high. Also, another method of forming a photocatalyst layer. There are kneaded photocatalyst particles on the binder • Coating on the surface of the substrate by spraying method * or after dip coating by dipping coating method • Method of applying heat treatment (Japanese Patent Application Laid-Open No. 5-201747) · Economy In the case of photocatalyst particles such as T i 0 2 particles by the Shellfish Consumer Cooperative of the Ministry of Intellectual Property Bureau, the photocatalyst particles must be irradiated with ultraviolet rays, and the photocatalyst particles must be in contact with substances that decompose objects such as malodorous gas, as Japanese Unexamined Patent Publication No. 5-2 0 1 7 4 7 discloses that when the photocatalyst particles are kneaded when the binder is applied to the substrate, most of the photocatalyst particles are buried in the binder and may not be exposed to ultraviolet rays. Sometimes, it is impossible to contact with malodorous substances. Also, another method to form a photocatalyst layer is known by Shi Kaiping 5 • 4-This paper size is applicable to Chinese national standards (CNS > A4 specifications (210 X 297 public love)) Printed by the Consumers' Cooperative of the Central Bureau of Standards 406031 B7 V. Invention Method (2) -7 3 9 4. The alkoxide method disclosed in this bulletin. This method applies a titanium alkoxide to a glass substrate and dries it Fired at 100 ° C to form a photocatalyst layer, which is irradiated with ultraviolet rays to form a photocatalyst layer to decompose organic matter in water. The above alkoxide method has the advantage of forming a thin film at a lower temperature, and is used as a substrate for Pyrex glass (pyrex glass). glass) or quartz glass, which is not softened at about 500 ° C, is effective as a raw material, but if a low melting point material such as soda glass is used as a substrate, the temperature at which the film is formed Even if the substrate is softened, the formed photocatalyst film will be buried in the substrate. 'This is because the light cannot reach the photocatalyst layer and cannot function as a photocatalyst, which is its disadvantage. Also,' Kaihei 1 — 2 8 8 3 2 1 The bulletin discloses that ceramic paper sprayed with T i 〇2 sol on fibrous materials, after heat treatment at 400 ~ 700 ° C, sprayed with S η 02 sol, and then heat-treated at 400 ~ 700 ° C. A photocatalyst layer is formed to improve the oxidative decomposition of aldehydes. According to the method disclosed in JP-A-Hei 1 2 8 8 3 2 1, the entire surface of the membrane will be covered with S η 02 having a lower activity than T i 〇2. In addition, cracks tend to occur when the film strength is to be increased. That is, as shown in Fig. 1 (a), when a sol containing T i 〇2 particles 1 〇1 is coated on the surface of the tile 100 and then heat-treated (sintered), as shown in Fig. 1 (b), ) The crack shown 10 2. It is speculated that the reason is that the phase shrinkage (increased density) occurs when the phase is changed to rutile. As shown in Fig. 2 (a) before sintering, the interval between T i 02 grains and 101 is L. After sintering to a rutile type, as shown in Figure 2 (b), the volume will diffuse to the other side. The size of the paper is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) " -5-(Please first (Please read the notes on the back and fill in this page.) __B7__ printed by the Employees' Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs. 5. The interval between the description of the invention (3) is shortened to LiCLiSL. ) 'As a result, cracks occur. On the other hand, JP 4-6 6 0 9 discloses a method that can decompose or improve the quality of the odorous substances contained in ozone in the air in the cabin to purify the ozone in the cabin, and irradiate light to the semiconductor carrying metal Or a solid photocatalyst on a semiconductor of a metal oxide, and at the same time, the air in the compartment to be purified is contacted with the photo bracelet medium, and the photochemical reaction is used to decompose the malodorous substances contained in ozone in the air or improve its quality Ozone purification method inside the car. However, for example, when using a substrate coated with a photocatalyst on the surface of the substrate in sewage or in the environment such as the outer wall, it is easy to attach dirt by the polymers, dust, and fungi contained in the atmosphere or water. Sometimes, there are some kinds of dirt attached to reduce the photocatalyst function. Conventionally, there has been a proposal to reduce the photocatalyst function due to the adhesion of dirt. This bulletin discloses that a photocatalyst layer including a semiconducting semiconductor, an ultraviolet lamp and a heating element disposed opposite to the photocatalyst layer, and a blower, can sequentially heat the entire photocatalyst layer to make the photocatalyst layer or heating element, or the photocatalyst layer and heat generation. The device can be moved by a photocatalyst deodorizing device, and by heating to about 400 ° C, the dirt caused by high molecular and dust can be removed, and the photocatalyst layer can be regenerated. However, the method of regenerating the photocatalyst layer is actually not easy to apply the method to the components used on the equipment installed indoors. Therefore, the fundamental solution should not be to attach dirt to the photocatalyst layer and then remove it. It is important to develop a photocatalyst layer that is not easily stained with dirt, or to develop a photocatalyst function that does not reduce dirt. This paper size is applicable to China National Standard (CNS) A4 (210X297mm) I.-II! I-I -I 1 i —-I --11 ...... II (Please read the back first Please note this page before filling in this page) -6-Printed A7-Coffee Seal · by the Consumers' Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs "7_V. Description of the Invention (4) Also, Special Fair No. 6-7 9 0 6 It has been revealed that a method for removing a bad odor in a home or an office by irradiating light with a strong ultraviolet intensity to a photocatalyst. However, when irradiated with strong ultraviolet light, different odor decomposition rates will be caused by the structure of the photocatalyst. In the above-mentioned prior art, the substrates are all porous. Although sufficient mechanical strength can be obtained by impregnation and other methods, the substrate is glazed tile, and the denser ceramics are not porous, so it cannot be sufficiently obtained. "Mechanical strength" In Ti 02, there are different crystal types such as anatase type, perovskite type and rutile type. In addition, in terms of photoactivity, anatase type is better, and other crystal types are better. The photoactivity is not high. According to a report in the journal "Surface" 1 987, Vol. 25, rutile T i 〇2 can carry uranium, and silver and other metals can increase the photoactivity, but The malodor removal rate, compactness and adhesion are still insufficient. In particular, when silver or silver oxide is used as the additive metal, these are black and are not suitable for magnetic monuments or building materials. "Furthermore, titanium oxide sols produced by hydrothermal or sulfuric acid methods are made of ultrafine particles, so Extremely easy to aggregate. When the agglomerate is applied to the surface of the substrate, uneven gloss and cracks may occur. For this reason, in the past, in order to prevent aggregation, a method of attaching an organic dispersant such as triethanolamine to the surface of the titanium oxide sol has been used. However, a titanium oxide sol obtained by attaching an organic dispersant such as triethanolamine to the surface of this titanium oxide sol is applied to a substrate having low heat resistance such as a resin substrate. When firing and fixing below 300 ° C, the organic dispersant will be firmly fixed to the active part of the titanium oxide sol, and it cannot be fully evaporated and decomposed during the firing process, so the material obtained by this method is not sufficient. The size of the light-touch paper is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) (Please read the precautions on the back and fill in this page) -7-Printed by the Consumers ’Cooperative of the Central Standards Bureau of the Ministry of Economy 〇3ΐ b7__ 5. Description of the invention (5) The medium effect does not have sufficient deodorant or antibacterial properties.

In addition, Japanese Patent Application Laid-Open No. 5-2 5 3 5 4 4 discloses a method of kneading a rutinite-type oxidizing agent on a binder, applying the same to the surface of a substrate, and heat-treating the substrate. This method forms an adhesive layer on the surface of the wall material, floor or ceiling surface of the residential house, and sprays on the surface of the adhesive layer to make a part of the photocatalyst with anatase titanium oxide as the main body. The fine powder is exposed to the adhesive layer and adhered to it, and then heated in a range of 300 ° C to 90 ° C to melt the adhesive layer, and then cooled to fix the adhesive layer. However, in this method, Deodorization can be improved when heat treatment is performed at a temperature of 300 ° C or higher and 900 ° C or lower, but low deodorization characteristics cannot be obtained at a low temperature of 300 ° C or lower. Therefore, it is extremely difficult to add a good photocatalytic activity such as excellent deodorizing properties to substrates such as plastics without heat resistance. It is speculated that the reason for this is that when photocatalyst particles are to be uniformly coated on the substrate, it is necessary to monodisperse the photocatalyst fine particles in the suspension in the preliminary step '. To this end, an organic dispersant is added, and the dispersant is in Below 0 0 ° C, it can not be fully decomposed, gasified, and left to cover the active sites on the photocatalyst particles. Therefore, the present invention aims at providing a photocatalyst layer which can be exposed on the surface of a substrate, which can fully exert the photocatalytic effect, and at the same time can be a material having excellent versatility because the photocatalyst layer is retained on the substrate. In addition, the present invention aims to form a photocatalyst layer which is difficult to peel off on a relatively dense substrate such as glass, tile, metal, plastic, or the like. In addition, the present invention aims at forming a photocatalyst layer on a low-melting-point base material such as, for example, soda glass which is relatively inexpensive and easy to process. This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) (Please read the precautions on the back before filling this page) Order ~ 8-A7 B7 406031 V. Description of the invention (6) In addition, the present invention is based on The purpose is to provide a multifunctional material that does not easily adhere to dirt and can prevent the function from being reduced due to dirt. It has antibacterial or deodorizing properties and excellent mechanical strength. Also, the present invention aims to provide a multifunctional material with excellent peel strength even if it is a photocatalyst layer mainly composed of anatase T i 0 2 as a main body. Furthermore, the present invention aims to improve the rutile type. T i 〇2 is for the purpose of photocatalytic activity of the photocatalyst layer of the main body. In addition, the present invention aims to improve the appearance of the photocatalyst layer mainly by supporting the photocatalyst layer with rutile τ i 〇2 as the main body, and decolorizing the photocatalyst layer at the same time. Furthermore, the present invention aims at providing a multifunctional material with a good photocatalyst function even at a low temperature heat treatment below 300 ° C. The related multifunctional materials of the present invention are those that form a photocatalyst layer directly or through an adhesive layer on the surface of substrates such as ceramic tiles, sanitary ware, glass, ceramics, resin, gold tincture, wood, etc., especially for the photocatalyst layer Photocatalyst particle type, particle size, voids formed between photocatalyst particles, porosity, the relationship between the adhesive layer and photocatalyst layer, particles filled with voids between photocatalyst particles, and metal particles fixed on the surface of photocatalyst particles Taking into account the design, it will not only have the photocatalyst effect of the photocatalyst layer such as deodorization, but also become a multifunctional material with excellent antibacterial or abrasion resistance. Brief description of the drawing: (a) in Figure 1 shows the previous T i 02 sol sintered shape. The paper size applies the Chinese National Standard (CNS) Α4 specification (210X297 mm) ^-(Read the first (Please fill in this page again)

、 1T Printed by the Consumer Cooperative of the Central Procurement Bureau of the Ministry of Economic Affairs B8. 丨 406031 ^ ___ V. Description of the invention (7) State '(b) shows the state after sintering of golden red phosphorus type. Figure 2 (a) shows the previous T 02 State before sintering • (b) shows the state after sintering. (Please read the caution on the back page first) Figure 3 shows the photocatalyst that forms the photocatalyst layer in the multifunctional material with photocatalyst function of the present invention The state where the particles are combined with potential energy is indicated by a pattern. Figure 4 shows the state in which the photocatalyst particles constituting the photocatalyst layer are combined with each other by solid-phase sintering in the multifunctional material. Figure 5 shows the state. Multi-functional materials * The state where the gap formed between the photo-catalyst particles constituting the photo-catalyst layer is filled with small particles. • It is shown in a schematic diagram. Figure 6 shows the surface of the photo-catalyst particles of the multi-functional material with metal particles fixed on it. State * is shown in a schematic diagram. Figure 7 shows the state of gold catalyst particles on the surface of the photocatalyst particles of the multifunctional material shown in Figure 4 (4). The surface of the photocatalyst particles of the material is fixed with gold particles on the surface. * It is shown in a schematic diagram. • Printed by Shelley Consumer Cooperative, Bureau of Intellectual Property, Ministry of Economic Affairs. Figure 9 shows the photocatalyst layer in the multifunctional material. The photocatalyst particles bonded to the substrate to form the photocatalyst book are in a state where they can be combined with each other, and are shown in a model diagram. Figure 10 shows the multifunctional material in which the photocatalyst layer is bonded by an adhesive. The base material, the photocatalyst particles constituting the photocatalyst 为 are combined with each other by solid-phase sintering and are shown in a schematic diagram. Figure 11 shows the photocatalyst of this multifunctional material that is bonded to the base material through an adhesive and a photocatalyst layer. The void formed between the particles is filled with small particles. -10-This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 406031Α7 Β7 5. The state of the invention description (8) is shown in a pattern diagram · Figure 12 shows the state where metal particles are fixed on the surface of the photocatalyst particles of the multifunctional material shown in Figure 9. Figure 13 shows a pattern diagram. Figure 13 shows the surface of the photocatalyst particles of the multifunctional material shown in Figure 10 on the surface. grain The state of the child is shown in a schematic diagram. Figure 14 shows the state where gold particles are fixed on the photocatalyst particles of the multifunctional material shown in Figure 11. Figure 15 shows the photocatalyst function of the present invention. Manufacturing method diagram of multifunctional materials. Figure 16 (a) and (b) are enlarged diagrams of Ti02 particles. Figures (a) to (c) of Figure 17 illustrate the sintering mechanism of Ding 102 particles. Figure 18 shows the test results of the antibacterial test. Figure 19 shows the loading logic when the dry step is inserted before the BLB lamp is irradiated. The comparison result of the test results is shown in Figure 20. Fig. 21 shows the relationship between the amount of Cu supported and the amount of Cu applied. Fig. 21 shows the manufacturing steps of another embodiment. Fig. 22 shows the test result circle of the antibacterial test. Fig. 23 When the drying step K is inserted before the BLB lamp is irradiated • Comparison of the test results of the Cu load with and without the step. The second and fourth circle is the relationship between the Cu load and the Cu coating arrangement. · This paper size applies to the national standard (CNS) A4 specification (210 X 297 male «) (Please read the notes on the back first> ^^ (This page) -------- Order--I--I --- § · Printed by Shelley Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs __406031 B7 V. Description of Invention (9) Picture 2 5 Table * Correlation between the load of Ag and the survival rate of bacteria β Figure 26 is the basic outline conceptual diagram when the cross-sectional direction of the multifunctional material is observed with EPA (electronic microanalyzer). Fig. 27 is a conceptual diagram of the basic outline when the cross-sectional direction of a multifunctional material is observed with an EPA (electronic microanalyzer). Figure 28 shows the correlation between the combination of T i 02 and S η 02 with film strength and photoactivity. Figure 29 shows the correlation between heat treatment temperature and photoactivity. Figure 30 is a diagram illustrating a method for measuring the activity of a photocatalyst film. Figure 31 is a diagram illustrating a method for measuring the activity of a photocatalyst film. Figure 33 is a diagram illustrating a method for measuring the activity of a photocatalyst film. Figure 33 is a graph showing the relationship between the ultraviolet irradiation time and the change in ρ ρ value. Figure 3 4 shows 11 3. Correlation diagram with the variation of ρ Η value. Figures 3 and 5 show the correlation between porosity, deodorization (R3.), And abrasion resistance. Printed by Shelley Consumer Cooperative of the China Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling out this page) Figure 36 shows the relationship between film thickness and deodorization (R3〇). Figure 3 7 It is a graph showing the correlation between film thickness and deodorization (R30) and abrasion resistance. Figure 38 is a graph showing the correlation between the amount of S η 02 added, deodorization (R3.), And abrasion resistance. Figures 3 and 9 show the relationship between the amount of S η 02 and the resistance to staining. The paper size applies the Chinese National Standard (CNS) A4 specification (210 × 297 mm) -12-89. ^ Amendment to the Chinese specification of Patent Application No. 8312001 Page-406031 A7 B7 May 89, Republic of China, 5. Description of the invention (10 series of graphs · 40th graph shows the correlation between the amount of S η 〇2 and the porosity of the surface of the Ti 02 layer · Figure 41 Figure 4 shows the correlation between the amount of Sn02 added and the porosity on the surface of the Ti02 layer. Figure 4-2 shows the relationship between the amount of Sn02 added and the deodorant R30 (L) and peel resistance. Fig. 44 is a graph showing the correlation between the number of coating times and stain resistance. Fig. 4 is a graph showing the correlation between the number of coating times and abrasion resistance. Fig. 4 6 is the number of coating times and T i 02. The correlation diagram of the porosity of the layer surface. Figures 4 and 7 show the state where the thermosetting resin on the photocatalyst particles is decomposed and irradiated with ultraviolet rays, and the photocatalyst particles are exposed to the outside air. Figures 4 and 8 show Fig. 4 is a diagram of another embodiment shown in Fig. 4. Fig. 4 9 shows the same as Fig. 4 and 7 Fig. 50 shows another embodiment of a state where small particles are filled in the spaces between photocatalyst particles. Fig. 51 shows a process diagram for manufacturing multifunctional materials using rutile T i 02. Fig. 5 2 Concentration of Cu solution when dried Cu solution is photo-reduced. The paper size is in accordance with Chinese National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before filling this page) · 1111111 · 11111111 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs -13-, / 406031 A7 88-Β · # Τ Β7 V. Description of the invention (11) Relationship between degree and photoactivity 圔 · Figure 5 3 is a dry Cu solution The relationship between the Cu solution concentration and photoactivity during photoreduction. Figure 54 shows the Cu solution concentration and the malodor removal rate R3 when the gold tincture supported on the rutile T i O 2 film is Cu. Correlation diagrams (reduction of metal ions are carried out after drying the gold tincture salt solution). Figure 5 5 shows when the metal supported on the rutile-type T i 02 thin film using a wall tile as the substrate is Cu. Correlation between the degree of solution collapse and odor removal rate 113. (Reduction of metal ions Execute after drying the metal salt solution). Figure 56 shows the firing temperature of the rutile T i ◦ 2 film and the odor removal rate R3 after fixing Cu. Figures 5 and 7 show Ag and C Correlation between the solution concentration and color difference of u 第 · 58 圔 shows the relationship between the porosity degree and R 30 and abrasion resistance. Figure 5 9 shows the relationship between the loading of copper and the survival rate of bacteria. · Figure 60 shows the relationship between the coating arrangement of copper and copper loading. Figure 61 shows the relationship between the loading of silver and the survival rate of bacteria. · Figure 62 shows the loading of silver. Relationship between color and color difference. Fig. 63 shows the effect of decolorization treatment with KI aqueous solution. Fig. 64 shows the change in P value of KI aqueous solution and removal rate of malignant solution before and after decolorization with KI aqueous solution. R 3. The relationship between the changes in this paper size applies to Chinese National Standard (CNS) A4 specifications (210 X 297 mm) < Jing first read the notes on the back and write this page) Installation · II! I Order ---- 1! · Line Printed by the Cooperative of Intellectual Property of the Ministry of Economic Affairs, Fong Cooperative Co., Ltd. * 06031 Α7 __Β7-_ V. Description of the invention (12) Figure 圆 The 65th circle is a circle with comparative antibacterial effect. (Please read "Cautions on the back side / 4 Write this page> Figures 6 and 6 are graphs showing the abrasion resistance to the weight-to-weight ratio of vaporized tin in thin films. Figure 6 and 7 are the photoactivities of the reset ratio of tin oxide in films. Figure 6 and 8 Figure 6 shows the abrasion resistance of the rubidium oxide reset ratio in the thin film in the comparative example. Figures 6 and 9 show the photoactivity diagrams of the weight ratio of vaporized plutonium in the thin film in the comparative example. Figure 70 shows the support of silver. Correlation between the location of bacteria and the survival rate of circle. [Symbols] ^ '-1: substrate, 2: photocatalyst layer, 3: photocatalyst particles, 4: small particles, 5: electron recovery particles, 6: binder layer The following is a more detailed description of the present invention. According to the drawings, the description is as follows. Figures 3 to 14 show the photocatalyst function related to the present invention. Structure of multifunctional materials • Divided into various types of display • The multifunctional material with photocatalyst function of the present invention belongs to any of the constructors • The multifunctional material shown in Section 3 printed by the shelling consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A photocatalyst layer 2 having a photocatalyst function is directly provided on the surface of the substrate 1. This photocatalyst layer 2 is formed by combining fine photocatalyst particles 3 with surface energy or curved surface potential and the like. The structure is shown in FIG. 4. The functional material is a photocatalyst layer 2 provided with a photocatalyst function directly on the surface of the substrate 1. The photocatalyst layer 2 is a photocatalyst particle 3 formed by solid-phase sintering. The multifunctional material shown in the fifth circle is on the surface of the substrate 1. Directly set photocatalyst layer 2 with photocatalyst function. The paper size of the photocatalyst that constitutes this photocatalyst layer 2 applies the Chinese National Standard (CNS) A4 specification (210 X 297 male «) -15 &Quot; A7… -1 1____ 5. Description of the invention (13) The space formed between the medium particles 3 is filled with particles 4 smaller than the space, and by this small particle 4, the photocatalyst particle 3 The structure is combined with each other. Also, the figure shows the structure in which the internal voids are filled with particles 4. However, the particles 4 may be filled at least in the surface of the photocatalyst particles 3 voids. That is, the mechanical strength of the photocatalyst layer will reach When the internal force is attenuated, the external force of Fuda is still important. Therefore, only the surface of the photocatalyst particles can be filled with fine particles. However, at this time, the internal photocatalyst particles will be combined by potential energy. To obtain sufficient strength, the average particle diameter of the photocatalyst particles is still preferably 0.04 # m. The photocatalyst particles 3 constituting the photocatalyst layer 2 are formed directly on the surface of the multifunctional material-based substrate 1 shown in FIG. 6 as potential energy for each other. Combined, the surface of the photocatalyst particles 3 is more immobilized with silver, copper, or cuprous oxide capturing electron particles 5. The photocatalyst particles 3 constituting the photocatalyst layer 2 are formed directly on the surface of the multifunctional material-based substrate 1 shown in FIG. 7. Solid-state sintering is combined with each other, and silver, platinum and other gold particles 5 are fixed on the surface of the photocatalyst particles 3. The multifunctional material shown in Figure 8 is straight on the surface of the substrate 1. A photocatalyst layer 2 having a photocatalyst function is provided, and the gap formed between the photocatalyst particles 3 constituting the photocatalyst layer 2 is filled with particles 4 smaller than the gap. The photocatalyst particles 3 are combined with each other by the small particles 4 and the photocatalyst particles 3 On the surface, silver, platinum and other metal particles are fixed 5. The 9th chaotic multifunctional material is a photocatalyst layer 2 having a photocatalyst function provided on the surface of the substrate 1 through an adhesive layer 6. The photocatalyst layer 2 is a surface layer portion It is exposed to the outside, while the lower layer is buried in the adhesive layer 6, and the paper size of the surface layer is in accordance with Chinese National Standard (CNS) A4 (210 X 297 mm) ------------ Equipment · 111! 1 Order ----- I-Off (Please read the precautions on the back before filling this page) -16-88.6. (^ ^ 6Q3 | V. Description of the invention (14) Fine photocatalyst particles 3 It can be combined with each other to form a potential. The multifunctional material shown in Fig. 10 is provided with a photocatalyst 靥 2 through the adhesive layer 6 as described above. The photocatalyst layer 2 has photocatalyst particles 3 on the surface layer. Phase sintering is combined to form the multifunctional material shown in Figure 11 by bonding The agent layer 6 is provided with a photocatalyst layer 2 on the base material 1, and a gap formed between the photocatalyst particles 3 constituting the photocatalyst layer 2 is filled with particles 4 smaller than the space, and the photocatalyst particles 3 are combined by the small particles 4. · The multifunctional material in FIG. 12 forms a photocatalyst layer 2 on the surface of the substrate 1 through an adhesive layer 6. The photocatalyst particles 3 constituting the photocatalyst layer 2 are combined with each other at a potential energy, and the photocatalyst particles 3 are on the surface. Electron-capturing particles 5 such as silver, copper, or cuprous oxide are further fixed 5. The multifunctional material shown in FIG. 13 forms a photocatalyst 餍 2 on the surface of the substrate 1 through the adhesive layer 6 to constitute the photocatalyst 靥 2. The medium particles 3 are combined by solid-state sintering with each other. The surface of the photocatalyst particles 3 is further fixed with silver, copper, or cuprous oxide capturing electron particles 5. The multifunctional material of the first to the fourth through the adhesive layer 6, A photocatalyst layer 2 is provided on the substrate 1 * The space formed between the photocatalyst particles 3 constituting the photocatalyst 靥 2 is filled with particles 4 smaller than the space, and the photocatalyst particles 3 are combined with each other by the small particles 4, and the photocatalyst particles The surface of 3 is more solid Gold or silver particles such as silver or platinum 5 · As the base material in any of the above materials 1 It can be any of ceramic tiles, sanitary ware, glass and other ceramics, resins, metals, wood or their composites. Standard (CNS) A4 specification (210 X 297 mm) (Please read the notes on the back first and write this page) Install ----- Order! I-line Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs -17-406031 A7 B7 'Year S :,

Printed by the Central Standards Bureau of the Ministry of Economic Affairs, Shelley Consumer Cooperative, V. Description of the Invention (15) In addition, the photocatalyst particles 3 are semiconductor particles with a light band gap that can fully exert antibacterial functions and deodorizing functions. . The reason why photocatalyst particles have antibacterial properties is that they may be electrocuted by voltages higher than those specified by the Inca, but it is generally assumed that they have active oxygen generation when they are irradiated with light. To generate active oxygen, one of the conduction bands of the semiconductor must be above the hydrogen generation site when expressed in the optical band mode, and the upper end of the atomic valence electron band is below the oxygen generation potential. Semiconductors that can meet this condition are T i 02, S rTi 03, Y11, 51 (:, Gallium Phosphide * 0 (15, 0 < 156, MO S 3, etc.) The position will move upwards, so if it is 1 ~ 1nm fine particles, Sn02, W03, Fe203, B i20 3, etc. can also generate active oxygen. Among them, it is chemically stable, cheap and highly active fine particles, namely anatase. The type T i 0 2 is the best. In addition, the electron trapping particles refer to the photocatalyst being irradiated with light and generating electrons and positron holes (positive holes), which can trap electrons and prevent recombination of electrons and positron holes. Specifically, it can be silver, copper, platinum, palladium, nickel, cobalt, iron, cuprous oxide, etc. The adhesive layer 6 is made of a thermoplastic material such as glaze, inorganic glass, thermoplastic resin, solder, etc. When the adhesive layer is composed of such thermoplastic materials, a photocatalyst can be applied to the adhesive layer at room temperature by a simple and inexpensive spraying method, etc., and only the heat treatment is needed to firmly make the substrate 1, The combination of the adhesive layer 6 and the photocatalyst layer 2 is beneficial Reduce manufacturing cost. The size of wood paper is applicable to China National Standard (CNS) 8-4 specification (210X297 mm) ---------- ¾ ------ ir ------ A (Please (Please read the notes on the back before filling in this page) -18-Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 406031 V. Invention Description (16) In addition, the present invention relates to multifunctional materials with photocatalyst function, which can be used in thermoplastic materials. The photocatalyst layer formed by laminating or burying a part of the photocatalyst particles on the formed sheet-shaped adhesive layer. The above-mentioned sheet-shaped multifunctional material can be pasted onto existing tiles, bathroom ceramics, building materials, etc., and heated It is also possible to add deodorant, antifouling, antibacterial, and antifungal properties to the existing tiles. The average particle diameter of the photocatalyst particles 3 constituting the photocatalyst layer 2 is to increase its specific surface area and increase its photocatalyst. The activity is preferably 0.3 Wm or less. The thickness of the photocatalyst layer 2 is preferably from 0.1 to 0.9 vm. When 0.1 #m or less, the photocatalyst particles are partially buried in the adhesive layer 6 Inside, the surface of multifunctional materials will generate Part of the fungus stays in this part, reducing its antibacterial properties. Moreover, when it is 0.9 or more, the thickness will become uneven, and it will be difficult to remove dirt when stains are attached to the product. The thickness of the photocatalyst layer is referred to here Refers to the part that includes the upper surface of the photocatalyst film and is buried in the lower glazed layer. Specifically, elemental analysis such as E PMA (electron line analyzer) is applied to obtain the value of the main component elements that constitute the glazed layer. Increase, the distance from the uppermost layer to the outermost surface of a certain part is measured. Also, the effect of changing the thickness of the photocatalyst layer 2 can be obtained, that is, the thickness is 0.2 # m ≧ 0. Below 4 # m, rainbow-colored patterns can be caused by the interference of light on the thick part of the photocatalyst layer, and only when the base color of the substrate on the appearance, the pattern or a combination of the two are formed, can be removed 0. Ivin ~ (please read the precautions on the back before filling this page) except for the part affected by light interference above. This paper size applies to China National Standard (CNS) A4 specification (210X297 mm) __ ^ --- --------_ 5. Description of the invention (π) 0.2iim, or 0.4 # m ~ ljwm of the photocatalyst / thick film thickness section, which can be widely used in this method for tiles, washstands, baths, toilets, fluidizers, conditioning tables, etc. (Please (Read the precautions on the back before filling in this page.) When only photocatalyst particles 3 are combined with each other, you can only rely on the mutual potential energy (adsorption) or sintering between the photocatalyst particles. However, when photocatalyst particles are to be sintered with each other, they must be sintered at a relatively high temperature. On the other hand, when they are adsorbed, the specific surface area of the photocatalyst particles must be increased to a considerable level, and their filling properties need to be improved. Otherwise, they cannot be fully combined. The active point of the particle adsorbs part of the particle, and the method is limited when it is a multifunctional material with sufficient catalytic activity and abrasion resistance. * In addition, in order to strengthen the combination of the photocatalyst particles 3, particles with a larger gap than the photocatalyst particles 3 are used. At the same time, not only can't get sufficient binding force, but also cover-part of the photocatalyst particles exposed on the surface of the multifunctional material, and the part on the surface of the multifunctional material that cannot exert the catalytic activity is formed, so that the fungus stays in that part. Significantly reduces antibacterial properties. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs In addition, the gaps between the photocatalyst particles referred to herein are the necks of the photocatalyst particles 3 and 3 as shown in Fig. 16 (a), as shown in Fig. 16 (b The space between the photocatalyst particles 3 and 3 shown in) is both. Therefore, the particle 4 with a smaller particle size than the photocatalyst particle is referred to as the particle whose diameter is smaller than the neck between the photocatalyst particles and any larger part of the gap between the photocatalyst particles. When the photocatalyst particles are combined with each other, the 16th (b) system is the most effective method. The small particles 4 systems that are filled in the voids of the photocatalyst particles 3 are basically not made of materials, but the ones with the best adsorption power are best. Material with extremely poor capacity The paper size applies the Chinese National Standard (CNS) A4 (210 X 297 mm): -20-Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs __〇31 g_V. Description of the invention (18 ) Can not achieve the purpose of combining photocatalyst particles with each other, and materials with too strong adsorption capacity will cover the surface activity of photocatalyst particles before they are inserted into the gap. From this point of view, the material to be filled in the gaps of the photocatalyst particles is preferably a metal such as tin, titanium, silver, copper, zinc, iron, platinum, cobalt, palladium, nickel, or an oxide thereof. Zeolite, activated carbon, clay, etc., which have been conventionally used as adsorption carriers are not suitable. Of the above metals or oxides, thorium oxide is most suitable for those with moderate adsorption capacity. In addition, metals such as silver and copper or their oxides can not only combine photocatalyst particles with each other, but also have unique antibacterial and deodorizing properties. Therefore, for applications that make use of this function, they also have auxiliary photocatalysts especially when not exposed to light. Function, so very suitable. That is, the small particles 4 filled in the gaps of the photocatalyst particles 3 can also use the metal particles 5 »In addition, the average particle diameter of the particles 4 filled in the gaps of the photocatalyst particles 3 is 4/5 or less on average An average particle diameter of 3 is preferred. The particles 4 embedded in the voids of the photocatalyst particles 3 will not only enter the gaps between the photocatalyst particles but also adhere to the photocatalyst particles if the current manufacturing method is adopted. If the diameter of the particles buried in the voids is greater than 4/5, the photocatalyst particles At the average particle size, the probability of adhering to the surface of the photocatalyst particles is higher than that of the voids embedded in the photocatalyst particles, and the bonding strength between the photocatalyst particles 3 is reduced. In addition, when the particles buried in the gap are larger than the photocatalyst particles, a part of the photocatalyst particles will be covered. The surface of the multifunctional material will generate a part that cannot exhibit the catalytic activity, and the fungus will be retained in this part, especially Significantly reduces antibacterial properties. In addition, the average particle size of the paper filled in the voids of the photocatalyst particles 3 is in accordance with the Chinese National Standard (CNS) A4 (210X297 mm) ~ " ~~ '-21-(Please read the cry on the back first Please fill in this matter 萸) 8a Amendment A7 B7 .4QM31 Printed by Shelley Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of Invention (19) When the diameter is less than 0 1 / im, the specific surface area can be increased to obtain a moderate Adsorption force • So it ’s most suitable. Also • For the total amount of photocatalyst particles 3 and filler particles 4, the amount of particles 4 filled in the voids of the photocatalyst particles 3 is based on a Mohr ratio of 10% to 60. % Is suitable. • Photocatalyst particles do not produce sintering at a temperature range. When the photocatalyst is fixed on the substrate with an adhesive, too few particles are buried in the air. • The photocatalyst particles cannot be firmly fixed. In combination with * on the other hand, if too many particles are buried and emptied, a part on the surface of the multifunctional substrate that cannot exhibit the catalytic activity will be generated, and the bacteria will be retained in this part, which will significantly reduce the antibacterial property. Fan Ye is suitable Medium particle 3 void particle 4 substance, it is best to choose the vapor pressure of the substance which is more than that of the photocatalyst particle * It is most suitable to aggregate the particles filled in the gap of the photocatalyst particle at the neck between the photocatalyst particles. Ground bonding to improve the peeling strength of photocatalyst 靥 Not only filling, but also by sintering method is better. • When the substance with high vapor pressure is selected as the particle 4 embedded in the void, it can be sintered. Auxiliary effects can also reduce the sintering temperature. The above-mentioned substances with vapor pressure include tin oxide, bismuth gas, zinc oxide, etc. However, for safety reasons, tin oxide is suitable. Also, the photocatalyst particles 3 are removed. The layer of the filled particles 4 preferably has a thickness of more than 0.1 / im, and if the thickness of the layer is less than 0.1 / im, the photocatalyst particles (and sometimes due to differences in manufacturing methods are buried Particles) will be partially buried in the adhesive layer 6, and the Chinese paper standard (CNS > A4 specification (210 X 297 mm)) will be applied on the surface of the multifunctional material to the paper size. -22 ·! 1 —-(Please read first Note on the back of this page) i) Printed by the Shellfish Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economy / 7 >). 〇_X 406031 —4... Β · ι-Μ ^ 5. Description of the invention (2〇 ) Into the part that can not exert the catalytic activity, this part will leave fungi in it, which will significantly reduce the antibacterial property. * The thickness of the layer including the particles filled with the voids containing the photocatalyst particles refers to the top surface to the embedment. In terms of the thickness up to the lower part of the adhesive, the thickness after the unevenness is averaged. Fig. 15 illustrates an example of a method for manufacturing a multifunctional material with a photocatalyst function according to the present invention. As shown in FIG. 15 (a), a substrate 1 is prepared. As shown in FIG. 15 (b), an adhesive layer 6 and an adhesive layer 6 are formed on the surface of the substrate 1. The softening temperature is selected to be higher than that of the substrate 1. Made of a material with a low softening temperature • For example, when the substrate 1 is a ceramic tile • Enamel or ceramic, the adhesive layer 6 is a glaze layer or a printed layer is used directly * Then as shown in the figure (c), Photocatalyst layer 2 made of photocatalyst particles such as T i 0 particles is formed on layer 6. At this time, photocatalyst layer 2 is When the adhesive force does not fall off from the adhesive layer 6 at the time, it is placed on it or before the adhesive 餍 6 is formed on the surface of the substrate 1 • The photocatalyst layer 2 is formed as shown by a circle (b >) On the adhesive layer 6 · Place the adhesive layer 6 on the substrate 1 · Then, it is higher than the softening temperature of the adhesive layer by 20 ° C or higher and 3 2 OeC or lower, and is higher than that of the substrate 1 Atmosphere temperature heating treatment with a low softening temperature *, as shown in this (d) or the 9th to 14th circles, a part of the layer below the edge of the adhesive layer in the photocatalyst layer 2 can be immersed in adhesion The adhesive layer solidifies the adhesive layer, and a part of it is buried in the adhesive layer, and it is firmly held in it. • Photocatalyst particles 3 which constitute the surface layer of the photocatalyst layer 2 that is exposed to outside air. Potential energy, intermolecular force, or sintering, such as n I 1 ϋ ϋ I n III · n · ϋ n · I n * 1 1 · 1 · n I (Please read the note on the back 3 '·; (Buy) This paper size applies to China National Standard (CNS) A4 specifications (210 X 297 public love) -23--η; ν ΰ. 4 # 一-一一 一 ~ ^ Β7 V. Description of the invention (21) 1 6 Figure (a) —like One part is combined, the other parts are as shown in Fig. 16 (b) —these are detached, that is, the surface of the photocatalyst particles in the table is essentially outside. Here, the heat treatment temperature is made higher than the adhesive layer 6 The softening temperature is higher than 20 ° C and higher than 3 2 0 ° (: The range below is because it takes a long time to soften the adhesive layer when the temperature is lower than 20 ° C. • The photocatalyst particles 3 cannot be fully maintained. When the temperature is above 3 2 0 eC, the adhesive layer will melt rapidly, the photocatalyst particles will be buried in the adhesive, or the concave and convex surface will occur, and even cracks or pinholes will occur. Therefore, the optimal temperature is 40 ° C. Above 3 0 Ot or less. Also, the specific gravity of the photocatalyst particle 3 is "5 t. When the specific gravity of the adhesive layer 6 is db. 0 to 5 t-5b 彡 3, preferably 0. 5 彡 5t-5b guest 2 0 is better. This is because the photocatalyst particles and the adhesive layer between the Ministry of Economic Affairs and the Intellectual Property Bureau of Shellfish Consumer Cooperatives printed 406031 A7 (please read the precautions on the back first to write this page). The specific gravity difference is too small, the melt adhesion During lamination • The vertical movement speed of the photocatalyst particles in the adhesive layer becomes slower. • The photocatalyst particles are easily peeled after firing. When the specific gravity difference between the photocatalyst particles and the adhesive layer is too large, the vertical movement speed of the photocatalyst particles will be increased. The photocatalyst particles will be almost buried in the adhesive layer. When this happens locally, the bottom will retain bacteria, reducing antibacterial activity. In addition, if another application of this method is to make δ t — Sb> 3. 0, a second adhesive of 彡 彡 5t — 5bS3.0 can be set between the adhesive 靥 and the photocatalyst particles. The landing layer is intended to rescue * Also, when 5 t — 5b < 0 can be pressurized during heat treatment, it has the effect of increasing the specific gravity difference by 5 t — 5b • Therefore, by HI PlΛ, hot extrusion β class, also 0 彡 —5b 彡 3 · 〇 The same effect at -24-This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) Printed by the shellfish consumer cooperation of the Central Standards Bureau of the Ministry of Economic Affairs _____406031 b7 V. Description of the invention (μ) 〇 In addition, the photocatalyst particle voids constituting the exposed portion of the self-adhesive layer 6 are specifically the neck portion of the photocatalyst particle 3 b shown in FIG. 16 (a), or the first 16 The photocatalyst particles 3 shown in FIG. Binding, the particles may fill the voids smaller than the particle size of 4 (S η, like Ti 'An'Cu'Zn'Fe, Pt, CO, Pd, Ni or a metal oxide). In addition, another method for manufacturing the multifunctional material with photocatalyst function of the present invention can form an adhesive layer 6 made of a thermoplastic material on a substrate 1 made of ceramic, resin, or metal, and the adhesive layer 6 A mixture of photocatalyst particles 3 and particles with a small particle size mixed with a sol state or in a light state is formed to form a photocatalyst layer 2, and then the adhesive layer 6 is softened, and a part of the lower part of the photocatalyst layer 2 is buried. The adhesive layer 6 is then cured. This method is extremely simple, because the mixture of the particles 4 embedded in the voids and the photocatalyst particles can be mixed in advance in a sol state or in the state of a precursor to form a photocatalyst layer, so it is convenient to control the photocatalyst particles 3 and the embedded voids. The mixing ratio between particles 4. Another method for manufacturing the multifunctional material with photocatalyst function of the present invention is to coat the thin film adhesive layer 6 made of a thermoplastic material with a mixture of photocatalyst particles 3 and particles 4 with a small particle size in a sol or photoplasma state. The resulting mixture is used to form a photocatalyst layer 2. The sheet-shaped adhesive layer 6 forming the photocatalyst layer is placed on or adhered to a substrate such as ceramic, resin, or metal, and then the adhesive layer is softened and the photocatalyst layer is buried. A part of the lower layer is adhered to the standard of the adhesive paper. China National Standard (CNS) A4 (210X297 mm) I ^ i- I- I -I II n II— 1 ^ 1 HI m -¾, -a ( Please read the notes on the back before filling out this page) -25-Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs of the People's Republic of China 406031A7 B7 — _________ V. Description of Invention (23) The adhesive layer is then cured. In addition, another method for manufacturing a multifunctional material with photocatalyst function according to the present invention can form an adhesive layer 6 made of a thermoplastic material on a substrate 1 made of ceramic, resin, or metal, and then use the adhesive here. A photocatalyst layer 2 made of photocatalyst particles 3 is formed on the layer 6, and then the adhesive layer 6 is softened. A part of the lower part of the photocatalyst layer 2 is buried in the adhesive layer 6, and then cured, and then coated with a small particle size. The solution of the particles is in the photocatalyst layer, and the small particles 4 with a small particle size are fixed to the photocatalyst particles by heat treatment. If the particles embedded in the void are oxides, this method is extremely convenient and easy to implement, and can make a large number of particles embedded in the void when making a more porous photocatalyst layer. The multifunctional material method can form a photocatalyst layer 2 made of photocatalyst particles 3 on a sheet-shaped adhesive layer 6 made of a thermoplastic material, and then place or stick the sheet-shaped adhesive layer 6 formed of a photocatalyst layer on Ceramic, resin or metal, etc., then soften the adhesive layer, bury a part of the photocatalyst layer underneath the adhesive layer, and then solidify, and then apply the solution containing gold rhenium particles 4 to the photocatalyst The layer is fixed to the photocatalyst particles 3 through heat treatment to fix the particles having a small particle size. In addition, another method for manufacturing the multifunctional material with photocatalyst function of the present invention can form an adhesive layer 6 made of a thermoplastic material on a substrate 1 made of ceramic, resin, or metal, and the adhesive layer 6 The photocatalyst layer 2 is formed by forming photocatalyst particles 3, and then the above-mentioned adhesive layer 6 is softened. A part of the photocatalyst layer 2 is buried in the adhesive layer, and then the adhesive paper is cured. CNS) A4 specification (210X297mm) I- — I ......! S—---— 1 ^ 1 1 lie I ·--n * νβ (Please read the precautions on the back before filling this page ) 406031 A7 B7 7.22 Printed by the Consumers ’Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs 5. Description of the invention (24) The coating layer is coated with an ionic solution containing small metal particles 4 on the photocatalyst layer and then irradiated with ultraviolet rays The light reduces metal ions to fix the photocatalyst particles. This method is simple and easy to implement if the particles buried in the void are gold tincture, and gold tincture can be fixed in a very short time (a few minutes). In addition, the lamp used for ultraviolet irradiation may be any one of an ultraviolet lamp, a BLB lamp, a xenon lamp, a mercury lamp, and a fluorescent lamp. * Another method for manufacturing a multifunctional material with a photocatalyst function according to the present invention can be adhered to a sheet made of a thermoplastic material. On the agent layer 6, a photocatalyst layer 2 formed of photocatalyst particles 3 is formed, and the sheet-shaped adhesive layer 6 forming the photocatalyst layer is placed or pasted on a substrate such as ceramic, resin, or metal, and then the adhesion is softened. A part of the photocatalyst layer is buried under the adhesive layer, and then the adhesive layer is cured, and then the photocatalyst layer 2 is coated with an ionic solution containing small gold tincture particles 4 and then irradiated with light including ultraviolet rays to reduce Gold ions to fix photocatalyst particles. In addition, in another method for manufacturing a multifunctional material with photocatalyst function according to the present invention, an adhesive layer 6 made of a thermoplastic material can be formed on a substrate 1 such as ceramic, resin, or metal, and the adhesive layer 6 can be formed on the adhesive layer 6. A photocatalyst layer 2 formed of photocatalyst particles 3 is formed, and an ionic solution containing the above-mentioned small-sized gold tincture particles 4 is coated on the photocatalyst layer 2 and then irradiated with light including ultraviolet rays to reduce metal ions, and the photocatalyst particles 3 are immobilized, and then The adhesive 6 is softened, a part of the lower part of the photocatalyst layer is buried in the adhesive 餍, and then the adhesive layer is cured. In this way, it can be completed in one heating process step (please read the precautions on the back before filling this page). This paper scale 4 uses the ten countries and countries (CNS) A4 size (210X297 mm)- 27 406 (^ 1 Printed by the Consumer Cooperatives of the Central Procurement Bureau of the Ministry of Economic Affairs 5. Production Description (25) Productivity. In addition, another manufacturing method of the multifunctional material with photocatalyst function of the present invention is made of thermoplastic materials. A photocatalyst layer 2 made of photocatalyst particles 3 is formed on the sheet-shaped adhesive layer. An ionic solution of metal particles 4 having a small particle diameter is coated on the photocatalyst layer 2 and then the light including ultraviolet rays is irradiated to reduce metal ions and fixed. The photocatalyst particles 3 are melted, and the thin-film adhesive layer forming the photocatalyst layer 2 is placed on or adhered to a substrate 1 made of ceramic, resin, or metal, and then the adhesive layer 6 is softened to form one of the photocatalyst layers 2 A part of the lower layer is buried in the adhesive layer, and then the adhesive layer is cured. Here, Zn0 can be used as the photocatalyst particles, and the metal particles 4 filled in the spaces of the photocatalyst particles can be silver or silver oxide. A The g or silver oxide particles can not only strengthen the combination of Zn η 0 particles of the photocatalyst, but also enhance the photocatalytic effect of Zn η 0. It also has antibacterial and deodorizing effects. In addition, when Zn η 0 is selected as the photocatalyst, it can solve the problem of silver. The problem of coloring with ions is based on the choice of the base color, pattern or combination of the substrate to improve its decorative effect. In addition, the metal ions that can be filled with the photocatalyst particle voids are formed into insoluble colorless or white salts. It is also possible for the salt solution to be in contact with the photocatalyst layer and then irradiate light such as ultraviolet rays. At this time, it is not necessary to rely on the combination of Z η 0 and A g or A g 0, and it can also solve the problem of the coloration of the particles buried in the gap. The base color, pattern, or a combination of the two can be used to enhance the decorative effect. In addition, T i 02 can also be used as the photocatalyst particles 3 described above, and the heat treatment temperature of the softened adhesive layer 6 is above 80 ° C above 100 °. Below 0 ° C. This paper size applies to China's national standard (CNS> A4 size (210X297 mm) —. 1 1 II II--ml I — 1--I--I------- X »0¾, -'... (Please read the notes on the back before filling this page) -28 ~ Printed by Zhengong Consumer Cooperative, Central Bureau of Standards, Ministry of Economic Affairs_4〇06〇31β7_ V. Description of the invention (26) When the temperature is above 80 ° C, After initial sintering, necks can be formed between T i 02 particles, which can increase the bonding strength between T i 〇2 particles. However, when the temperature is above 1 ο 〇o ° C, the intermediate sintering process is performed. Due to the solid phase of τ i 〇2 The photocatalyst layer shrinks in volume due to sintering, and it is easy to crack. T i 02 is the photocatalyst particle described above, and ag is the particle 4 that fills the gap of the photocatalyst particle. Salt solutions of insoluble colorless or white salts can also be aqueous halides such as KI, KC $, and FeCj? 3. Ag is insoluble with Ag I and AgC $, and is colorless or white salt, so it can be matched with the base color, pattern or combination of the substrate to improve its decorative effect. Before the step of coating the photocatalyst particles on the adhesive layer, if it is desired to have a dispersing step, in this dispersing step, a sol or a precursor of the photocatalyst particles can be dispersed in the solution. The heat treatment temperature of the softened adhesive layer can be gasified at a lower temperature. In the prior art, the insufficient deodorizing property below 320 ° C is because the dispersant adhered to the surface of T i 〇2 particles in the dispersing step is not sufficiently vaporized, and remains without being evaporated, so that T i 〇 2 The particle surface cannot be sufficiently exposed on the uppermost surface of the substrate, which results in the failure to fully exert the photocatalytic function. Further, as the dispersant capable of being vaporized at a low temperature, an organic dispersant having a molecular weight of 10,000 or less, and a phosphoric acid-based dispersant is preferred. Specific examples are given below. I -------- • Install ------ Order ------ \ (Please read the precautions on the back before filling in this page) This paper size applies to China National Standard (CNS) A4 Specifications (210X297mm) -29-Consumption cooperation by employees of the Central Bureau of Standards, Ministry of Economic Affairs, printed A7 ^ G6Q ^ 1 b7 V. Description of the invention (27) Example 1 On the surface of a 1 500 square ceramic tile substrate, 8 # Spraying method to form an adhesive layer made of si 〇2—Αβ2〇3—Na / K20 glass material, after drying, apply a 15% solution of butyl i 〇2 sol aqueous solution by spraying to form a film thickness of 0.8 # The Ti02 layer of m is then heated and fired at a different atmosphere temperature in a rolling kiln to produce a substrate formed by laminating an adhesive layer and a Ti02 layer, and then cooled and solidified as a functional material. 007〜0. 2; / This is called the T i 02 sol aqueous solution means hydrolyzing T i C ί under hydrothermal conditions in a range of 1 0 ~ 2 0 0 ° C in a hot press to obtain a crystallite diameter of 007 ~ 0. 2; / 5% 的 范围 The m anatase d i02 on the left and right, disperse this ore in a sol state by several% to tens% in an acidic aqueous solution such as nitric acid, hydrochloric acid, or an alkaline aqueous solution such as ammonia, and add 0.5% or less to improve dispersibility. Three Organic surface salts of ethylamine and trimethylolamine, isoamyl alcohol, trimethylolpropane, etc. are used as surface treatment agents. In addition, the particle size of T i 02 sol is treated by a painter observed by S EM The crystal grain size is calculated from the integral width of powder X-ray diffraction. In addition, the coating method is a spray coating method, but the same results can be obtained by the dip coating method and the spin coating method. Multifunctional material evaluates antibacterial and abrasion resistance〃 The antimicrobial effect of the antimicrobial agent test on E. coli (Escherichia Coli W3110 strain). The bacterial solution was dripped on the top surface of the multifunctional material which had been sterilized with 70% ethanol in advance. 0.15mj? (l ~ 5xl04CFU), a glass plate (10x10cm) is placed so that it is close to the top surface of the substrate as a sample. Irradiate a white light for 30 minutes (3500 candles). CNS > A4 specification (210X297mm) ---------- installation ------ order ------ M (Please read the notes on the back before filling in this ear) 30 _ A7 ___406031 b7 V. Description of the invention (28)) After wiping the irradiated sample with sterilized gauze and the sample kept under shading conditions The bacterial solution was recovered in 10m {physiological saline, and the bacterial growth rate was 9%, which was used as the evaluation index. The abrasion resistance was evaluated by sliding frictional damage using a plastic wiping rubber, and its appearance was evaluated. Table 1 below The change in antibacterial abrasion resistance caused by changing the sintering temperature when ceramic tiles are used as the substrate and S i 02_ A 5 203-Na / K20 glass is used as a binder. Table 1 Substrate = Magnetic Tick, Binder = S i 02— Α $ 203— Na / ~ K 2 0 Glass Photocatalyst = T i 0 2 Printed by the Consumers ’Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs

No. 1 2 3 4 5 firing temperature (° C) 700 780 880 980 1000 and softening temperature 20 100 200 300 320 difference rc) antibacterial + + + + + + + +---abrasion resistance Δ ○ ◎ ◎ ◎ (Please read the precautions on the back before filling out this page) + + +: Coliform survival rate is below 10% + +: Coliform survival rate is from 10 ¾ to 30% +: Coliform survival rate is from 30% to 70% Paper size is compliant with Chinese National Standard (CNS) A4 (210X297 mm) -31-Printed by the Shellfish Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs 406031 A7 __________ B7 V. Description of the Invention (29)-: The survival rate of coliform % Or more ◎: The wear and tear did not start after 40 times. 0: The damage started after 10-40 slides, and the photocatalyst layer (1 ^ 〇2 film) was peeled. △: The damage started after 5-1Q slides. Film) Peel X: The damage is seen after 5 or less slides, and the photocatalyst layer (Ti〇2 film) is peeled. The specific gravity of S i 〇2-Αί203-Na / κ20 glass used as a binder is 2. 4. The film thickness during coating is 2 0 0 / zm 'Softening temperature is 6 8 0 ° C »Also, T i obtained in Table 1 2 2 N 0 • 1 ~ 3 is anatase type, the specific gravity is 3. 9 N 0. 4. 5 is the rutile type, and the specific gravity is 4. 2 »The firing temperature of NO.1 in Table 1 is only higher than the softening temperature of the binder 2 At 0 ° C, the viscosity of the adhesive cannot be sufficiently reduced, so the anatase T i 02 constituting the bottom layer of the photocatalyst layer cannot be fully embedded in the adhesive layer. Therefore, it only slides 5 to 10 in the abrasion resistance test. Once damaged, it was peeled. In addition, the antibacterial properties are due to the use of anatase with excellent photocatalytic activity and the observation of TG-DTA above 300 ° C. The organic components of Ti 02 sol have almost all decomposed, vaporized, and adhered to the surface of Ti 02 surface. Dispersants such as treatment agents should have been vaporized, and the firing temperature is 7 0 ° C, so a very high processing temperature gives an excellent value of ten + β NO. 3 ~ 5 series firing temperature is 800 ° C or more In terms of durability below 1000 ° C, it can withstand 40 times of back and forth sliding test without changing into extremely excellent ones. The reason is that the surface T i 02 particles form the neck after initial firing. In addition, when treated at 1 100 ° C, 'the paper is cooled and solidified to the Chinese national standard (CNS> A4 specification (210X297 mm)' -32----------- ¾ .-- ----, 玎 ------, Α (Please read the notes on the back before filling out this page) Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs A7 __4JD6Q31 67 _ V. After the description of the invention (30) The T i 〇2 layer on the surface of the multifunctional material was found to have cracked since it was taken out from the rolling mill. This was judged by TMA when measuring the T i 02 test piece. The antibacterial properties of NO. 4, NO. 5 are poor. Two reasons can be guessed. One is that the T i 02 particles have phase-shifted to the rutile type. The other should be that the firing temperature is higher than the softening temperature of the binder. At 300 ° C, the viscosity of the binder becomes too low, and the T i 0 2 particles constituting the photocatalyst layer are buried in the binder layer. The phase transition of the T i 0 2 particles to the rutile type is not For this reason, although the rutile T i 02 is slightly inferior to the anatase T i 02, it still has some photocatalytic activity. For example, directly spray T i 〇2 sol on porous oxygen The aluminum substrate, after being fired at 950 ° C, still has + antibacterial properties after being cooled and solidified. Therefore, it can be seen that the firing temperature is 300 ° C higher than the softening temperature of the binder. The viscosity is too low, and the T i 02 particles constituting the photocatalyst layer are buried in the binder layer, which should be one of the reasons. In addition, τ i and Si (the main component of the adhesive) ), You can see the mixed layer of Ti and Si, and confirm that T i 02 of the photocatalyst particles has been embedded. From the above embodiment 1, that is, at least the photocatalyst is T i 02 and the binder layer is S i 02_Aj? 2 〇3— The following facts can be confirmed when Na / K2〇 glass is used. ① The firing temperature is higher than the softening temperature of the binder by 20 ° c, and the high-temperature conditions exceeding 300 ° C are antibacterial. The abrasion resistance and abrasion resistance are both poor. The reason is that the viscosity of the adhesive at this temperature has been adjusted by the value of the stomach suitable for embedding T i 02 in the adhesive layer. CNS) A4 specification (210X297 mm) '~~ ------ HI ^ imm?---- In 11 < ^ 民 I— II Ϊ.--I-I -i- 丁 In nnn- - .___ ^ (锖 Please read the precautions on the back and fill in this page). A7 --- By_ V. Description of the invention (31) ②① The multifunctional material produced is confirmed to be τ i ο2 particles have been embedded in the adhesive layer ③ When the firing temperature is 800 ° C or more and 1000 ° C or less, after 40 or more sliding tests, the abrasion resistance has not changed, and the abrasion resistance is excellent, and it is estimated that it should be T i 〇2 forms a neck between the particles and is firmly bonded. Example 2 An adhesive layer made of S i 02 — Aj? 203-PbO glass was formed on the surface of a 100x100x5 alumina substrate (96% alumina density) by spraying. After drying, 15% of a Ti02 sol aqueous solution was spray-coated to form a Ti02 layer with a film thickness of 0.8 # m, and then each embodiment in a rolling kiln was heated and fired at different atmospheric temperatures to fire the laminated binder layer. After forming the substrate with Ti 0 2 layer, it cools and solidifies much more functional material. Table 2 below shows the changes in antibacterial properties and abrasion resistance caused by changing the firing temperature by using alumina as the base material and using s i 〇2 — A j? 203 — P b 0 glass as a binder. H— ί I- I tn--n I ii (^ 1 ^ 1 ^^^ 1 \ 9J (Please read the notes on the back before filling out this page)

Centimeter 97 2 4 3 A7 __ ^ 〇6n ^ f_ V. Description of the invention (32) (Table 2) Base material = alumina plate (100x10 0x5), binder = S i 02— Aj? 203— PbO glass Photocatalyst = T i 0 2 N 0. 6 7 8 g 10 Firing temperature (° C) 560 580 740 840 860 and softening temperature 20 40 200 300 320 Difference (° C) Antibacterial + + + + + + + + + + + Abrasion resistance Δ 〇〇 ◎ ◎ S i 〇2 — Α 203_ P b 〇 The softening temperature of the glass used is 5 4 0 ° C, the specific gravity is 3.8, the film at the time of coating Thickness is 1 50. The crystal forms of the obtained T i 〇2 were all anatase type. Printed by the Consumer Cooperative of the Central Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling out this page). In the abrasion resistance test of Table 2, NO. 6 is damaged and peeled off after 10 slidings, but NO · 7 , 8 will not be damaged by sliding more than 10 times, NO. 10 will not be damaged if sliding more than 40 times. NO. 9,10 is not damaged when sliding for more than 40 times. The firing temperature is above 80 ° C, and necks are formed between T i 02 particles, and T i 02 particles are firmly bonded to each other. To. The scale of this paper is applicable to the National Standard for National Standards (CNS) (210 fathers and 297 publications) '_ 35 _ Printed by the Consumer Affairs Cooperative of the Central Government Bureau of the Ministry of Economic Affairs A 7 R7-4060ST-V. Description of the Invention (33) .7, it will be damaged and peeled after sliding less than 10 times. This is because the firing temperature is 20 ° C higher than the softening temperature of the adhesive. The anatase T i 02 particles were not sufficiently embedded in the adhesive layer. In contrast, N 0.7, 8 will not be damaged by sliding more than 10 times. This should be the temperature of the neck, but the difference between the firing temperature and the softening temperature of the adhesive can be adjusted. The viscosity of the adhesive is caused by the value that T i 0 2 can be buried in the adhesive moderately. On the other hand, in the antibacterial test of Table 2, NO. 6 ~ NO. 9 can get good results of ++ or ++, but N0.1 〇 is only +. This is because the firing temperature is 32 ° C higher than the softening temperature of the adhesive, and the viscosity of the adhesive is too low. T i 02 particles constituting the photocatalyst layer are buried in the adhesive layer. Example 3 In S i 02— Aj? 2〇3— B aO glass material was melt-cooled and solidified in the model, and the glass flakes were processed into 1 0 X 1 0 0 X 1 glass flakes, and then sprayed with 1 5% T i 02 sol. 8 / zm 的 Ti02 层。 Aqueous solution (the same as in Example 1). The glass sheet was then placed on an alumina substrate (100x100x5), and the temperature of the atmosphere was changed in each embodiment of the Silicon liquid furnace. After heating and firing, the functional material was cooled and solidified. Table 3 below shows the changes in bacterial resistance and abrasion resistance when the firing temperature of the multifunctional material is changed. This paper size applies to China National Standard (CNS > A4 size (210X297 mm) '-36-I. In!--I-in I- ------ I-1-I -I- I — j --- (Please read the notes on the back before filling this page) _406031 ^ _ V. Description of the invention (34) (Table 3) Substrate = alumina plate (100x100x5), adhesive = S i 02— Aj ? 203-B a 0 sheet photocatalyst = T i 0 2

No. 11 12 13 14 Firing temperature (° C) 640 740 840 940 and softening temperature 20 120 220 320 Poor (.C) Antibacterial resistance + + + + + + + +-Wear resistance X 〇 ◎ ◎ (Please (Please read the notes on the back before filling in this page) Si 02— Α々2〇3—Β a printed here used by the Central Bureau of Specimen and Consumer Products Cooperative of the Ministry of Economic Affairs ◦The softening temperature of glass binder 6 At 20 ° C, the specific gravity is 2.8. The crystalline form of T i 〇2 on the multifunctional material is NO. 1 1 ~ 13, which is anatase type, and NO. 14 is rutile type. In the abrasion resistance test shown in Table 3, no. 1 1 series is damaged after 10 times of sliding, and it is peeled off. No. 12 series is not damaged at least 10 times of sliding. No. 13, 14 is 40 Will not be damaged more than two times, with excellent results. No. 13 and 14 will not be damaged after sliding more than 40 times. The firing temperature is above 80 ° C, and the neck is generated between T i 02 particles. The size of this paper is applicable to China National Standard (CNS) A4. (210X297 mm): '-37-406031 ί: 5. Description of the invention (35) T i 〇2 particles are firmly bonded to each other. It will be damaged if it slides for less than 10 times. The peeling NO. 11 is because the firing temperature is only 20 ° C higher than the softening temperature of the adhesive. It cannot sufficiently reduce the viscosity of the adhesive. T i 02 particles are not fully embedded in the binder. In comparison, NO.12 is not damaged after 10 or more slides. Although this temperature is not up to the temperature of the neck, the difference between the firing temperature and the softening temperature of the adhesive can adjust the adhesive. The viscosity is caused by burying T i 0 2 in the adhesive layer to a moderate value. On the other hand, in the antibacterial test of Table 3, No. 11 to 13 + + or ++ had excellent effects, but Ν Ο · 1 4 was one. This is because T i 02 will become a rutile type. The firing temperature is 3 2 0 ° C higher than the softening temperature of the adhesive. The viscosity of the adhesive is too low. The T i 〇2 particles that make up the photocatalyst layer are buried in the adhesive. Caused by two reasons in the agent. From the above, after coating T i 02 particles in the binder in advance, it is printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling out this page). In the method of multifunctional materials, the same effect can be obtained as in the method of applying a binder on the surface of the substrate and then coating the T i 02 particles with multiple functional materials. Example 4 at 1 0 0 X 1 0 The surface of the substrate made of polyimide resin of 0 X 5 is coated with an acrylic resin binder, and then a 15% Ti02 sol aqueous solution is spray-coated to form a Ti02 layer having a film thickness of 0.8 # m. Then the laminated adhesive is fired in a nickel-chromium heat-resistant alloy furnace at 150 ° C. The paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) _ 38-406031 β77, description (36) The base material of the layer and Ti02 layer is a multifunctional material. Table 4 below shows the effects of antibacterial properties and abrasion resistance when the firing temperature of the above-mentioned multifunctional material is changed. (Table 4) = Polyimide resin, Binder = Acrylic resin photocatalyst = T i 02, firing temperature 1 5 Ot

No. 15 16 Antibacterial and abrasion resistance 〇 + + 〇 The 15% TiO2 sol aqueous solution in Table 4 is prepared by the following method. NO. 15: Directly use the 15% T i 0 2 sol aqueous solution used in Example 1. Printed by the Consumer Cooperative of the Central Bureau of Quasi-Economy Bureau of the Ministry of Economic Affairs. No. 16: Use in a hot press at 1 1 0 ~ 1 50 ° C; After dissolving TiCj? Aqueous solution, adjust the product to pHO with nitric acid. 8 Disperse without using a surface modifier, and then remove the aggregates. Spraying is carried out immediately after removing condensate. Here, the specific gravity of Ti 02 is 3.9, the crystal type is anatase type, (Please read the precautions on the back before filling this page) The specific gravity of acrylic resin is 0.9, which can correspond to glass softness. The viscosity at 4 points is 70 ° C. The paper scale is in accordance with China National Standard (CNS) A4 (210X297mm) -39-Printed by the Shellfish Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs _ 40603 ^ 7__ V. Description of the invention (37) In terms of abrasion resistance, NO 15 > N 0. 16 can be swiped more than 10 times without damage. This is because the difference between the firing temperature and the softening temperature of the adhesive has caused the viscosity of the adhesive to be adjusted to a value where T i 002 can be buried in the adhesive moderately. On the other hand, in the antibacterial test, No. 15 is one, but NO • 16 is ++, which means that anti-bacterial multifunctional materials can be manufactured below 30 ° C. According to DTA — TG, this different antibacterial property is due to the Ti02 sol in NO. 15 which can decompose the component of evaporation at 200 ~ 350 ° C, that is, this phenomenon is not seen in NO. 16, so it can be known whether there is an organic component Covering T i 02 becomes a difference in antibacterial properties. Here, the specific gravity difference between anatase and acrylic resin is 3, and as long as the difference is such a degree, the T i 0 2 particles constituting the photocatalyst layer are not buried in the adhesive layer, and it is confirmed that the particles have a good Antibacterial. Example 5 After forming an adhesive layer on a surface of alumina substrate of 100 X 1 0 0 X 5 with glass materials of different specific gravity by spraying, a 15% butyl 102 sol aqueous solution was spray-dried. .8 / ^ 111 layer of Ding 丨 〇2 layer, and then heated and fired in a roll-shaped Fuzhong 750 ° C atmosphere temperature to laminate the bonded layer and the substrate made of Ti 02, cooled Cured much more functional materials. Table 7K in Table 5 below changes the firing temperature of the above-mentioned multifunctional materials to combat the effects of bacterial resistance and abrasion resistance β This paper uses the Chinese National Standard (CNS) (210X297 mm) ^^ 1- ^ nt m- n ^ i 1 ^ 1 i ^^^^ 1 eJ (Please read the notes on the back before filling out this page) -40-Printed by the Shellfish Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 406031 ^ 5. Description of the invention ( 38) (Table 5) Substrate = alumina plate (100X 100X 5), photocatalyst = T i 0

No. 17 18 1 9 20 Binder-kind Si〇2-Al 2 〇3-P b 〇Si〇2-Al 2 0 3 _ P b ο Cementing agent-specific gravity 5.3 3.8 2.8 2.4 Ti〇2 Specific gravity 3.9 3.9 3.9 3.9 Glass softening temperature 480 540 620 680 (° C) Firing temperature (° c) 750 750 750 750 Antibacterial + + + + + + + + + + + Abrasion resistance X 〇〇〇 In the test, NO.17 ~ NO.20 all got excellent + + + results. The firing temperature is higher than the softening temperature of the adhesive by 30 ° C to 300 ° C. It can be seen that the difference between the firing temperature and the softening temperature of the adhesive can adjust the viscosity of the adhesive to a moderate level. This result was obtained by embedding the value of T i Ο 2 in the binder. In terms of abrasion resistance, NO.17 is damaged if it is slid less than 5 times. However, it is not damaged if it is slid more than 10 times for NO. 18 ~ 20 (please read the precautions on the back before filling this page) This paper size applies to the Chinese National Standard (CNS) A4 (210X297 mm). Printed by Shellfish Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs. 406031 A7 __B7 V. Description of the invention (39) Injury. According to the investigation, the reason is that Ν Ο · 17 is different from others. The specific gravity of the binder is larger than that of T i 02, so the anatase T i 〇2 particles that constitute the lowermost layer of the photocatalyst layer cannot be fully embedded in the adhesive. Caused by the cement layer. Therefore, it is learned that the abrasion resistance of the 'multifunctional material' is also affected by the specific gravity between T i 0 2 and the binder. When the specific gravity of the adhesive is larger than that of T i 0 2, it will also cause poor abrasion resistance. Example 6 An adhesive layer formed of S i 〇2 — A 芡 2〇3_B a 0 glass frit (softening temperature 6 2 0 ° C) was sprayed on the surface of a 150 square ceramic tile substrate. 02 sol and S η 02 sol The stirred aqueous solution is fired at 750 ° C, cooled and solidified with more functional materials. 01 / im ， The crystallite size of the SnO2 particles is 0. 01 / im, and the microcrystalline particle size of the SnO2 particles is adjusted to a pH value of 1 1 by the NH3 aqueous solution. 0. 0 0 3 5 # m »Table 6 shows the antibacterial and anti-friction properties of the multifunctional material produced as described above, when the amount of S π 02 (mole ratio) for the total amount of T i 02 particles and S η 02 is changed. The test results are shown in the table. ^ This paper size applies the Chinese National Standard (CNS) A4 specification (210 X297 mm). ----- ^ (Please read the precautions on the back before filling this page) 42 406031 a7 __ B7 __ V. Description of the invention (40) (Table 6) Substrate = tile, adhesive = S i 02— Aj? 203-Ba0 glass photocatalyst = T i 02, void particles = Sn02 (0 · 0 0 3 5 ^ m) (Please read the precautions on the back before filling this page)

No. 2 1 22 23 24 25 Sn 〇2 (mol%) 0 10 20 60 100 Antibacterial + + + + + + + + + + +-Abrasion resistance Cooperative society printed on abrasion resistance. As the amount of S η 02 increases, the abrasion resistance can be improved. When it is added more than 10%, it will not be damaged or changed if it is swiped 40 times. In the antibacterial test, the range of more than 20% is the same as when it is not added. The range is +++ to 60%. It can be ++, but when the weight is added, the probability of T i 02 particles per unit substrate surface is increased. Large increase, antibacterial properties worsen, at 100% is-. Therefore, the addition amount of S η 02 is in terms of mol ratio, and it can be provided in the range of 10% to 60%, preferably 10% to 20% of the total amount of T i 02 and S 11〇2. Multifunctional material with excellent antibacterial and abrasion resistance. This paper uses China National Standards (CNS) A4 (210X297 mm) -43-Printed by the Shell Consumer Cooperative of the Central Samples Bureau of the Ministry of Economic Affairs 406031 A7 __B7___ V. Description of the invention (41) S η 02 Increased Can improve abrasion resistance according to the following authors. That is, at a high temperature above 600 ° C, S η 02 has a higher vapor pressure than T i 〇2, and the interval between T i 0 2 particles 3 b before sintering is shown in Fig. 17 (a). L. 'But the surface of T i 02 particles 3 with a positive curvature surface has a high vapor pressure' and the surface with a negative curvature ', that is, the surface of the neck where two T 02 particles 3 b meet, has a low vapor pressure. As a result, as shown in Fig. 17 (b), the neck system enters S η 0 2 with a vapor pressure higher than T i 02, so it is condensed as shown in Fig. 17 (c) and sintered by a gasification-condensation mechanism. . Moreover, when sintering is performed by the gasification-condensation mechanism, the interval L 2 of the T i 0 2 particles after sintering is approximately equal to the interval LQ before sintering, so no cracks and the like will occur, as described above. In the composite material in which the T i 02 particle layer is held on the surface of the substrate, when the space between the T i 02 particles exposed on the outermost surface is filled with S η 〇2 particles and fired at 60 ° C or higher, it will not Cracking occurred, and combined with the neck between T i ◦ 2 particles, the abrasion resistance characteristics can be improved. Comparative Example 7 and Example 6—Similarly, S i 〇2 was formed on the surface of a 1 500 square ceramic tile — AJ2203- B a 〇 Binder (softening temperature 6 2 0 ° C) formed by the adhesive layer, sprayed on it mixed T i 02 sol and S η 〇2 sol after stirring the aqueous solution at 750. (: Firing, cooling, and solidification are much more functional materials. This paper size applies to China National Standard (CNS) A4 specifications (210 × 297 mm) (Please read the precautions on the back before filling out this page) -44-406031 B7 V. Description of the invention (42) In addition, the sol concentration of the T i 02 particles is 4 to 6% by weight, and the pH value is adjusted to 1 1 with an aqueous NH 3 solution, and the particle size of the crystallites is the same as that in Example 6. 0 1, S The microcrystalline particle size of the n02 particles is 0.0008 μm, which is larger. The antibacterial property test and abrasion resistance test were performed on the multifunctional material produced as described above. The results compared with Example 6 are shown in Table 7 below. (Table 7 )

Base material = Magnetic tile, Binder = S i 02-A52〇3— B a 0 glass material Photocatalyst = T i 02, void particles = S n02 (0 · 0 0 8 0 m), heat treatment 75 0 ° C

No. 26 27 28 29 30 S η 0 2 (mol%) 0 10 20 60 100 Antibacterial + + + + + + + + + + +-Abrasion resistance 〇〇〇 ◎ ◎ Employee Consumer Cooperative, Central Bureau of Standards, Ministry of Economic Affairs Printing (Please read the precautions on the back before filling this page) As a result, it was found that the effect of Sn02 particles of 0. 008jt / m to improve abrasion resistance is weaker than that of Sn02 particles of 0.035em, which is weaker against T i 〇 When the Mohr ratio of 2 and Sn02 is more than 60%, the sliding can be achieved 40 times without damage, which is the point of change. In the antibacterial test, it is the same as when using the Sn02 particles of 0.035vm, and the range is more than 20%. It can be the same as when it is not added. The paper size applies the Chinese National Standard (CNS) A4 (210X297 mm) -45- Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs. Λ Α7__406031 Β7 V. Description of Invention (43) + + + results, staying at + + up to 60% ^ ^ more when shell ij covers T The probability of i 〇2 particles increased and the antibacterial property deteriorated, and it was-at 100%. Therefore, when 0_ Οίμπι Ti02 particles are used and 0.00 8 ^ m SnO 2 particles are added, it is difficult to provide a multifunctional material with excellent antibacterial properties and excellent abrasion resistance. This is because the larger the particle size is, the smaller the vapor pressure of the S η 02 particles will be. If the remaining S η 2 particles that are not vaporized are 0. 0035iim, they will exist in the gaps between the Ti02 particles to improve the bonding strength. In contrast, compared with the gap between T i 02 particles at time 0.08, the S n02 particles are larger, and the S n02 particles cannot enter the voids. Instead, the probability is higher on the T i 02 particles. From the above, it can be seen that the size of the S η 2 particles that should be buried in the voids of the T i 02 particles is preferably 4/5 or less for the T i 02 particle size. Example 8 An adhesive layer made of Sn 02—A5203—B a 0 glass frit (softening temperature 6 2 0 ° C) was formed on the surface of a 150 square ceramic tile substrate, and Ti was spray-coated on it. 〇2 sol aqueous solution, then fired at 750 ° C, cooled and solidified into a composite material, and then sprayed with S η 〇2 sol aqueous solution after spraying on the heat treatment at 1 10 ° C, more functional materials. At this time, the Ti 02 sol aqueous solution was the same as that used in Example 6, and the Sn 02 sol was 0.035 μm. The antibacterial test and the Mohs' tensile scale for the multifunctional materials made as described above apply the Chinese National Standard (CNS) A4 specification (210X297 mm): (Please read the precautions on the back before filling this page) -46-

Printed by Shelley Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (44) Damage test, the results are shown in Table 8 · (Table 8)

Base material = Magnetic tile, Binder = S i 02—Αί203—Β a 0 Glass material Photocatalyst = T i 〇2, Void particle = S n02 (0 · 0035 / ίπι), Heat treatment 750 eC / 110eC

No. 31 32 33 34 35 S η 0 8 (molX) 0 10 20 60 100 Antibacterial + + + + + + + + + + +-Wear resistance 〇〇 ◎ ◎ η 〇2 Increases the abrasion resistance * When adding more than 20% Mohr ratio, it will not be damaged or changed after 40 times of sliding. In the antibacterial test, it will be more than 20%. It is the same as the non-additive. It can be +10 up to 60%, but when the weight is increased, it will cover the surface of the substrate T i 0. The probability of particles is greatly increased. 0% is one. · In this test, s η〇2 sol is heat treated at a lower temperature of 110 ° C, so sintering of the gasification-condensation mechanism as in Example 6 does not occur. Only wear resistance It can still be improved, because the particle size is smaller than T i 〇2 particles, that is, s η 〇2 particles that are larger than the surface and have strong adsorption force have been embedded in this paper. The Chinese national standard (CNS) A4 specification is applicable. (210 X 297 mm) I ---------- installation ---- I --- order --------- M (Please read the precautions on the back first, ViS write this page ) 406031 B7 V. Description of the invention (45) τ i 02 T i 02 particles are firmly bound to each other. Example 9 On the surface of a 150 square ceramic tile substrate, an adhesive layer formed of si 〇2-A52〇3-B a 0 frit (softening temperature 6 20 ° C) was formed thereon by spraying method. After coating the Ti 02 sol aqueous solution, it was fired at 750 ° C, cooled and solidified into a composite material, and a copper acetate aqueous solution was coated thereon to be dried and then irradiated with ultraviolet rays to reduce copper ions, while fixing the photocatalyst Layers, much more functional materials. Mercury lamps are used here as illumination lamps. The Cu particles fixed to the photocatalyst layer here have an average size of about 0.004 β m. The antibacterial resistance test and the abrasion resistance test were performed on the multifunctional material produced as described above. The results are shown in Table 9. (Please read the notes on the back before filling out this page) The paper size printed by the Central Standards Bureau of the Ministry of Economic Affairs, Shellfish Consumer Cooperative, is applicable to the Chinese National Standard (CNS) A4 (210X297 mm) -48-4060.S1 B7 V. Description of the invention (46) (Table 9) Substrate = tile, binder = S i 〇2— Aj? 203_B a 0

T 7 II heat light at the physical medium ’ο particle gap empty u

Nly m Jw 4 5 original also light

No. 36 37 38 39 40 Cu amount (raol%) 0 10 20 60 100 Antibacterial + + + + + + + + + + + + + + + Wear resistance 〇〇 ◎ ◎ (Please read first and back Please pay attention to this page and fill in this page again) Printed by the Consumers' Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs said that the abrasion resistance can be improved as the amount of CU increases. Neither will it be damaged nor will it change. In the antibacterial test, the range of more than 20% is the same as when it is not added. + + 'Cu has its antibacterial effect, so the addition of a large amount did not reduce the antibacterial property. However, it is possible that the addition of a small amount of copper is dominated by the photocatalyst effect of the Ti02 particle layer, and the addition of a large amount of copper is the result of the domination of copper. If only copper is expected to function, copper will slowly dissolve in the liquid, and its life will be shorter than those without photocatalyst. In addition, when the amount of copper added is too large, the cost is high, so it is not meaningful to set the amount of copper added too much. From this example, it can be known that not only oxides such as S η 02 can be used. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm): -49-406031 A7 B7 V. Description of the invention (47), for example Metals such as copper can also be used as embedded T particles. 0 2 Particle layer voids printed by Example 1 of the Central Bureau of Standards of the Ministry of Economic Affairs of Shellfish Consumer Cooperatives 1 0 On the surface of a 1 500 square tile substrate, si 〇 2 — Ai? 203 — B a 0 glass (softening temperature 6 2 OeC) Adhesive layer 'Coated with Ti 02 sol aqueous solution by spray coating method, fired at 95 ° C to cool and solidify into a composite material, coated with an aqueous copper acetate solution, and Irradiate light containing ultraviolet rays to reduce copper ions, while fixing the photocatalyst layer, it is a more functional material. At this time, the light was irradiated with a B L B lamp for several minutes. In the τ i 02 series, the anatase phase is transformed into the rutile type during the heat treatment. 4ym。 The film thickness of T i 02 is adjusted to 0.4m when spraying. The multifunctional material produced as described above was subjected to an antibacterial test and an abrasion resistance test. Good results can also be obtained in this temperature range without the abrasion resistance test. With or without the addition of copper, it can be swiped for 40 times without damage and no change. "Antibacterial test is shown in Fig. 18." When not added, T i 〇2 is rutile type, so it is worse +. Antibacterial properties can be improved when copper is added one by one. Moreover, when not only the BLB lamp is irradiated, even when not irradiated, as long as the Cu supporting amount is 0.7 yg / cm2 or more, the antibacterial activity can be +, and the Cu supporting amount is 1.2 / zg / cm2 or more. Sex is + ten +. From the above, it is known that for multifunctional materials that provide antibacterial properties and excellent abrasion resistance, it is still preferable that the Cu load be more than 0 · 7eg / cm2. -、 玎 ------ · " (Please read the notes on the back before filling in this page) This paper size applies to China National Standard (CNS) A4 (210X297 mm) 50 406031 a? _B7_ V. Description of the invention (48) More preferably, it is 1-2 jag / cm 2 or more. As for the copper carrying capacity, before the B L B lamp is irradiated after the copper acetate aqueous solution is applied, the drying step can be significantly increased. This relationship is shown in FIG. 19. This is due to the high concentration of gold ions during photoreduction after drying. In addition, when the optimum amount of copper is applied, the copper carrying capacity can be the highest (Figure 20, Figure 20 is an example of copper acetate with a copper concentration of 1% by weight). According to Figure 20, the coating amount is intended to be 0. When 7 / zg / cm2 or more, it may be 0.2 mg / cm2 ~ 2.7 mg / cm2, or when it is 1.2 / zg / cm2 or more, it may be 0.3 mg / cm2 ~ 2.4 mg / cm2 » Example 1 1 Printed by the Shellfish Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs (please read the precautions on the back before filling this page). On the surface of a 1 500 square tile substrate, si 02 — A $ 2〇3_B a 0 glass (The softening temperature of 680 ° C) is formed on the adhesive layer by spraying the Ti 0 2 sol aqueous solution by spraying method, and then fired at 95 ° C, and then cooled and solidified into a composite material. It is coated with an aqueous solution of silver nitrate, and then irradiated with ultraviolet rays to reduce silver ions. While fixing the photocatalyst layer, it is a multifunctional material. At this time, use a BLB lamp to irradiate for several minutes. During the heat treatment of Ti 02, the anatase phase is transformed into rutile. The film thickness of T i 〇2 is adjusted to 0.4 / ^ m during spraying. The multifunctional material produced as described above was subjected to an antibacterial test and an abrasion resistance test. Those who are not added in the abrasion resistance test can also obtain good results in this temperature range. The paper size is applicable to the Chinese National Standard (CNS) A4 (210X297 mm) '-51-406031 $ Staff Consumer Cooperatives of the Central Bureau of Standards, Ministry of Economic Affairs Imprint V. Description of Invention (49) Good result. With or without the addition of silver, it can be swiped for 40 times without damage and no change. The antibacterial test is shown in Figure 70. When not added, τ i 02 is rutile, so it is inferior. However, when silver is added, it is improved, and not only the BLB lamp is irradiated, but even when not irradiated, the antibacterial property can be increased to + + when the silver load is greater than 0.05 μ2 / cm2. When a g load is 0.1 # g / cm2 or more, the antibacterial property can reach + + +. However, when the silver load is changed from brown to black, the appearance is not good, but when the silver load is less than 1 β g / c m2, it will not be colored. From the above, it can be known that the carrying amount of silver is preferably 0.05 leg / cm2 to 1 g / cm2, preferably 0.5 leg / cm2 to 1 leg / cm2. Example 1 2 An adhesive layer formed of S i 〇2—Aj? 203—B a 0 glass (softening temperature 68 ° C.) was formed on the surface of a 150 square ceramic tile substrate. After spraying Ti 02 sol aqueous solution by spraying method, it is fired at 95 ° C, cooled and solidified into a composite material, and a silver nitrate aqueous solution is applied thereon to be dried and then irradiated with ultraviolet rays to reduce silver ions, while fixing the photocatalyst Layers, multi-functional materials. ”At this time, use a BLB lamp to irradiate for several minutes. ^ Τ i 02 system was transformed into a rutile phase during the heat treatment process. For various multifunctional materials produced as described above, various film thicknesses of T i 02 were changed to perform abrasion resistance test and antibacterial test. ---------- Installation— (Please read the precautions on the back before filling this page) The size of the paper is applicable to China National Standard (CNS) A4 (210X297 mm) _ 52-406031 B7 Ministry of Economic Affairs Printed by the Consumer Standards Cooperative of the Central Bureau of Standards 5. Description of the invention (5 (丨) 1 In the abrasion resistance test »In this test, the range within 2 β m is good 1 1 Good results > After 40 times sliding back and forth Damage > No change 0 1 1 9 in antibacterial test film thickness 0 + 1 for U m or more + 1 »1 I Please 1 I 0 * 2 for 10 m or more + 10 ＋ therefore T i 〇2 The film thickness is based on the first reading 1 I 0 reading 1 1 U m or more, preferably 0 2 β m or more 0 back 1 I 1 Note I Italian gold I Example 1 3 contention 1 I then I at 1 5 0 Square tile substrate surface »shaped S i 0 2 " Wobenzhuang A 2 〇3 — B a 0 glass (softening temperature 6 2 0 ec) adhesive sheet 1 1 layer > coated with T i 0 by spraying method After the 2 sol aqueous solution, it was fired at 1 1750 ° C to cool and solidify into a composite material. Silver nitrate 1 1 was applied on the aqueous solution and dried 9 and then irradiated with ultraviolet rays to reduce silver ions. I was fixed on the photocatalyst layer. Subsequently, it was fired at 9 0 0 ° c 1 0 0 0 ° c to cool and solidify. 1 I functionalized material 0 1 1 I At this time, the irradiation light was irradiated with a BLB lamp for several minutes. 0 and 1 1 T i 0 2 was heat treated. During the project, the anatase phase was transferred to the rutile type, and the silver system that was fixed on the surface was changed to white 1 1 with the heat treatment of the white and black brown machine. Therefore, it can be seen that it changes to silver oxide during firing. The system is dispersedly attached and fixed, so I did not see it after burning /! 70 ％,- Growth of particles 〇1 I Perform antibacterial test and abrasion resistance on the multifunctional material produced as described above 1 1 I test ○ 1 1 In the abrasion resistance test t can be good without adding it in this temperature range 1 1 Good Results With or without the addition of silver, it can slide back and forth for 40 times without being damaged by 1 1 ♦ No change. 1 1 sheet of paper M Ns 6 / f fiQ31_ V. Description of the invention (51) The antibacterial test system is shown in No. 70 圚. When not added, T i 〇2 is rutile, so it is inferior, but when silver is added, the antibacterial property can be improved. (Please read the back first Note on this page) Example 1 4 S 1 〇 2 — Α) 22〇 3 — B a 0 glass frit (softening temperature 6 2 0 ° C) The adhesive layer was coated with a Ti 〇2 knee solution by spray coating, and then fired at 820 ° C, cooled and solidified into a composite material, and an aqueous silver nitrate solution was applied thereon. Dry, and then irradiate with ultraviolet rays to reduce the silver ion to fix the photocatalyst layer, and then apply a 0.1 cc / cm 2 of 0.1 Moore / KI aqueous solution, and irradiate ultraviolet rays for 5 seconds, more functional materials • The carrying capacity of silver is 2 # g / cm »· It is coated with 0.1 lmol / cm2 of 0.1 Moore / 芡 KI aqueous solution, and then irradiated with ultraviolet light for 5 seconds, so it is a dark brown multifunctional The material is decolorized to white. • Better in appearance. • Printed by Example 15 of the Intellectual Property Bureau of the Ministry of Economic Affairs, Shellfish Consumer Cooperative. S 1 〇 2 — A i2a〇a_B a 0 (Softening temperature 6 2 0) The adhesive layer formed by spray coating T i 0 »sol aqueous solution on it, fired at 8 2 0 ° C, cooled and solidified into a multifunctional material. And irradiate light including ultraviolet rays, while continuously dropping the bath water drawn from the public bath in the multifunctional material, and observe the change of the bath water. • The ratio is -54-This paper standard is applicable to national standards (CNS) ) A4 size (210 X 297 mm) Printed by the Shellfish Consumer Cooperative of the temporary Hui Property Bureau of the Ministry of Economic Affairs Δδ. 6. ^ 40603¾ {_B7__ V. Description of the invention (52) For the sake of simplicity, the same device is also dropped and the bath water is dropped on the substrate without the photocatalyst layer. Observed after the 14th day, the bath water was dropped on the multifunctional Compared with the bath water dripped on the substrate without the photocatalyst layer, the turbidity of the material is not particularly different, but there is a difference in the odor of the sludge. The bath water system can smell the sludge odor, and the slime-like slime and organic deposits can also be seen on the substrate. Compared to this, the phenomenon is not seen when the bath water is dripped from the multifunctional material. Tests show that this multifunctional material can be used as paving stones in artificial waterfalls or fountains in water circulation methods such as parks and department stores. From the above description, it can be seen that due to the bonding by the material with a lower softening temperature than the substrate The photocatalyst layer is fixed by the agent layer, so that the photocatalyst particles constituting the surface part of the photocatalyst layer are not buried in the adhesive layer. Therefore, the surface of the photocatalyst particles is substantially exposed to the outside. • And • Part of the particle system that forms the lower layer of the photocatalyst in the photocatalyst particles is partially buried in the adhesive 靥 *, so it can significantly improve the holding power of the photocatalyst ，, and it is difficult to peel off. Figure 21 shows another Illustrating the manufacturing steps of an embodiment • In this embodiment, thermoplastics such as inorganic glass or thermoplastic resin are used as the substrate 1, and a photocatalyst calendar 2 is directly formed on the surface of this thermoplastic substrate 1. That is, as shown in FIG. 21 ( a) as shown * Prepare the thermoplastic substrate 1 and, as shown by the circle (b), form a photocatalyst layer 2 formed of photocatalyst particles such as T i 02 particles on the surface of the thermoplastic substrate 1 and then heat treated as shown in the figure ( c) In the photocatalyst layer 2 shown below, the thermoplastic substrate is selected by the above-mentioned thermoplastic substrate, and the thermoplastic substrate is precipitated, and the thermosetting substrate is solidified and embedded in the thermoplastic paper. The paper is compliant with China National Standard (CNS) A4 Specifications (210 X 297 cm) -55--------------- -------- I I--I I-^ 1 .. (Please read the back first (Notes written on this page) 406031A7 _B7____ 5. Description of the invention (53) It is firmly held in the base material. Also, the photocatalyst particles 3 in the photocatalyst layer 2 constituting the surface layer in contact with the outside air are bound together by mutual adsorption or sintering between potential molecules. The preferred conditions and the like of this embodiment are the same as those of the above-mentioned embodiment ', and are described below in detail. Example 1 6 The surface of a glass substrate made of a glass S i 02—Ai2〇3-Na / K20 glass with a square shape of 1 50 was coated by spraying method at 1 5%.

Ti02 sol aqueous solution to form a Ti02 layer with a film thickness of 0.8em, and then the glass substrate laminated with the Ti02 layer was put into a ceramic film type with excellent film release properties, and then each embodiment was different. Atmospheric temperature is heated and fired in a rolling animal, and then cooled and solidified. 007〜0. The T i 0 2 sol aqueous solution referred to herein refers to hydrolyzing T i C Wen 4 under hydrothermal conditions in a range of 100 to 2 0 0 ° C in a hot press to obtain a crystallite diameter of 007 ~ 0. 2μτη is printed on the left and right anatase Ti02 Printed by the Shellfish Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling this page) Make this ore dispersed in the sol state by several% to tens% in nitric acid, hydrochloric acid, etc Acid. Aqueous solution or ammonium aqueous solution such as ammonia, and in order to improve the dispersibility, the organic acid salts of triethylamine and trimethylamine in the range of 0.5%, isoamyl alcohol, trimethylolpropane, etc. are added as the surface. Treatment agent. The particle size of the T i 02 sol is obtained through the image processing of S EM observation, and the crystal particle size is calculated from the integral width of the X-ray diffraction of the powder. The coating method is a spray coating method, but the same results can be obtained by the dip coating method and the spin coating method. ^ Zhang Zhiyuan uses the Chinese National Standard (CNS) M specifications (210X297) > _ 56 _ A7 __406031 b7_ V. Description of the invention (54) Evaluation of antibacterial and abrasion resistance for all multifunctional materials.

The test of resistance to tadpoles was for bactericidal effect on coliform (Escherichia Coli W3110 strain). Bacterial solution 0.15mJ? (1 ~ 5xl04CFU) was dripped on the top surface of the multifunctional material sterilized with 70% ethanol in advance, and a glass plate (10x10cm) was placed on the top surface of the base material as a sample. After irradiating a white lamp (3500 candles) for 30 minutes, wipe the irradiated sample with the sterilized gauze and the bacterial solution held under the shading condition, and recover it in 10mi physiological saline to determine the bacterial survival rate. As an evaluation index, the abrasion resistance is a sliding abrasion using a plastic wiping rubber, and the appearance is compared for evaluation. The following Table 10 shows the influence of the glass substrate made of S i 02—Aj? 203-Na / K2◦ on the antibacterial and abrasion resistance when the firing temperature is changed. --------- Batch of clothes ----- 1T ------ ^ (Please read the notes on the back before filling out this page) Printed on paper by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs The scale is applicable to China National Standard (CNS) M specification (2ΐ〇χ297mm) 406031 A7 B7 V. Description of the invention (55) (Table 1 0) Substrate = S i 〇2-A and 2〇3—Na / K20 Glass Photocatalyst = T i〇2

No. 1 2 3 4 5 Firing temperature (° C) 700 780 880 980 1000 and softening temperature 20 100 200 300 320 Difference (.C) Antibacterial + + + + + + + +---Abrasion resistance △ 〇 ◎ ◎ + +: Coliform survival rate is 10% or less +: Coliform survival rate is 10% or more and 30¾ or less +: Coliform survival rate is 30% or more and 70% or less-: Coliform life is more than 70% ◎: Printed by Shelley Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs after 40 rounds of wear and tear (please read the precautions on the back before filling this page) 〇: After 10-40 times of sliding, the photocatalyst layer (^ ( ^ Film) peeling △: damage starts after 5-10 slides, the photocatalyst layer (Ti〇2 film) peels X: damage occurs after 5 or less slides, the photocatalyst layer (1 ′ 丨 〇2 film) peels here, The specific gravity of the glass substrate composed of S i 02-AJ2203_Na / K20 is 2.4, and the softening temperature is 680 ° C. Furthermore, T i 0 2 is obtained in Table 10, and N 1 is an anatase type of 1 to 3, with specific gravity. 3.9 This paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) -58-Printed by Zhengong Consumer Cooperative, Central Bureau of Standards, Ministry of Economic Affairs A7 __406031 b7_ V. Description of the invention (56), No. 4,5 series rutile type, the specific gravity is 4.2. The firing temperature of NO.1 in Table 10 is only 20 ° C higher than the softening temperature of the glass substrate. The viscosity of the glass substrate cannot be sufficiently reduced, so the anatase T i 02 constituting the lowermost layer of the photocatalyst layer cannot be fully embedded in the glass substrate. For this reason, it was damaged only by sliding 5 to 10 times in the abrasion resistance test. The antibacterial properties are due to the use of anatase with excellent photocatalytic activity and the observation of TG — DTA above 300 ° C. The organic components of T i 02 sol have almost all decomposed, gasified, and adhered to the surface of T i 02 Dispersants such as surface treatment agents should have been gasified, and the firing temperature was 700 ° C, so a very high processing temperature gives an excellent value of ++. NO. 3 ~ 5 series firing temperature is 800 ° Above C and below 1000 ° C, in terms of durability, they can withstand 40 or more times of back-and-forth sliding tests without changing into extremely excellent ones. The reason is that the surface of T i 02 particles formed on the surface after initial firing. , When processed at 1 100 ° C, after cooling and solidifying, it is taken out from the rolling rich and found on the surface of the multifunctional glass The cracking of the Ti 0 2 layer has occurred. This is judged by the TMA measurement of the T i 0 2 test piece, and it is known that the medium-term sintering that caused significant volume shrinkage of Ding 102 occurred. No. 4, NO. 5 antibacterial properties Both are poor. Two reasons can be guessed. One is that the T i 02 particles have phase-shifted to rutile, and the other is that the firing temperature is 300 ° C higher than the softening temperature of the glass substrate. The viscosity becomes too low, and the T i 02 particles constituting the photocatalyst layer are buried in the glass substrate. The T i 0 2 particle phase transition to the rutile type is not the reason here. Although the rutile T i 〇2 is slightly inferior to the anatase T i 02, it still has some photocatalytic activity. For example, the direct spray coating of T i 〇2 solution paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) n ^ · ^ ϋ— »— ^ 1 — ^ 1 It I 士 ^ 1 ^ 1 t ^ nm V- 丨 (Please read the notes on the back before filling this page) -59-

0β031Α7 _ B7 _ V. Description of the invention (57) The sample adhered to the porous alumina substrate and cooled and solidified after firing at 9 5 OeC still has + antibacterial properties. The softening temperature of the material is 30 Ot, the viscosity of the glass substrate is too low, and the T i 02 particles constituting the photocatalyst 靥 are buried in the glass substrate. This should also be one of the reasons. When T i and S i (the main component of the glass substrate), a mixed layer of T i and S i can be seen, and it is confirmed that T i 0 2 of the photocatalyst particles has been embedded in it. · From Example 1 4 above, ie * at least the photocatalyst is T i 02, the glass substrate is S i 〇2—AJ? 2〇3—Na / K20 composition can confirm the following facts ① firing temperature is 20 ° C higher than the softening temperature of the glass substrate, not more than 3 When producing multifunctional glass at a temperature of 0 ° C, it can produce multifunctional glass with excellent antibacterial and abrasion resistance. The reason is that the viscosity of the glass substrate has been adjusted to be immersed in the glass substrate at this temperature. The value of T i 02 is embedded. ②① The multi-functional glass produced is confirmed to have fgTi 02 particles. Into glass substrates. ③ When the firing temperature is more than 800 ° C and less than 100 eC, after 40 or more sliding tests, the abrasion resistance has not changed, and the abrasion resistance is excellent. * Based on It is presumed that necks should be formed between T i 〇2 particles, so that they can be firmly combined. Example 17 7 This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm)----- III! I Order · I! I ---- (Please read the note on the back first to write this page) Printed by Shelley Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs A7406031 b7 V. Description of Invention (58) S i〇2 at 1 00x1 00x5 — The surface of the glass substrate composed of Αβ2〇3-P b 0 was coated with a 15% Ti02 sol aqueous solution (the same as in Example 16) by spraying to form a Ti〇2 layer with a film thickness of 0.8em. The glass substrate laminated with Ti02 layer is placed in a ceramic film type with excellent release properties. Each example is heated and fired in a rolling animal at a different atmosphere temperature, and then cooled and solidified. Table 1 1 below shows the antibacterial properties when a glass substrate composed of S i 〇2-Aj? 203 — PbO is used and the firing temperature is changed. The impact of the loss of friction. (Table 1 1) Substrate = S i 〇2 — Aj22〇3_PbO Glass Photocatalyst = T i 0 2 --------- Approve clothes-(Please read the precautions on the back before filling this page)

.1T Printed by the Consumer Cooperatives of the Central Procurement Bureau of the Ministry of Economic Affairs

No. 6 7 8 9 10 Firing temperature (° C) 560 580 740 840 860 and softening temperature 20 40 200 300 320 difference rc) antibacterial + + + + + + + + + + + abrasion resistance Δ 〇〇 ◎ ◎ Here S i 02 — AJ? 2 03 — PbO is composed of soft paper of glass substrate size, using China National Standards (CNS) A4 specifications (210X2.97 mm) Employees of the Central Procurement Bureau of the Ministry of Economic Affairs Cooperative printed μ Α7406031β7 V. Description of the invention. (59) The transformation temperature is 5 4 0 aC 'and the specific gravity is 3 · 8. The crystal forms of the obtained T i 〇2 are all anatase. Table 11 In the abrasion resistance test No. 6 is damaged and peeled off after sliding less than 10 times, but NO. 7, 8 will not be damaged after sliding more than 10 times, NO. 9, and NO. 10 It won't be damaged by sliding more than 40 times. NO.9 '10 is not damaged even if it slides more than 40 times. It should be a firing temperature of 80 ° C or more, and a neck is formed between T i 02 particles, and T i 0 2 particles are firmly bonded to each other. To. Ν Ο .6 is damaged and peeled after sliding for less than 10 times. This is because the firing temperature is 20 ° C higher than the softening temperature of the glass substrate. The viscosity of the glass substrate cannot be sufficiently reduced, which constitutes the most photocatalyst layer. The lower layer of anatase T i 02 particles cannot be fully embedded in the glass substrate. In contrast, NR 0, 7, 8 will not be damaged by sliding more than 10 times. This should be the temperature of the neck, but the difference between the firing temperature and the softening temperature of the glass substrate can be adjusted. The viscosity of the glass substrate is due to the value that T i 02 can be embedded in the adhesive moderately. "On the other hand, in the antibacterial test of Table 11, NO. 6 ~ NO. 9 can be obtained as +++ or ++. As a result, NO.10 is only + »This is because the firing temperature is higher than the softening temperature of the glass substrate by 3 2 0 ° C, the viscosity of the glass substrate is too low, and T 02 particles constituting the photocatalyst layer are buried in the glass Caused by the substrate ”Example 1 8 This paper size applies to the Chinese National Standard (CNS) A4 specification (210X297 mm). I order (please read the precautions on the back before filling this page) -62-

B a 0 glass on a 100X 100x5 glass substrate made of Si 02-Aje203-Ba0 composition, coated with a 15% Ti 02 sol aqueous solution (the same as in Example 1) by spraying method to form a film thickness 0.8 # m 的 T i 〇2 餍, and then the glass substrate to which the T i 〇2 layer is bonded is placed in a ceramic mold with excellent film release property, and then each embodiment uses a different atmosphere temperature in silicon carbide Heated hip furnaces are heated and fired and then cooled and solidified much. Functional glass · The following table 12 shows the effect on the antibacterial and abrasion resistance when the firing temperature of the multifunctional glass is changed (Table 12) 02 — AJ? 20 Photocatalyst = T i 0 2

No. 11 12 13 14 Firing temperature (ec) 640 740 840 940 and 20 120 220 320 difference between softening temperature) Antibacterial + + + + + + + +-Wear resistance X ○ ◎ ◎ Here S i 〇 2— AJZ2〇3— B a 0 composition of the softening temperature of the glass substrate is 620 · (:, specific gravity is 2.8 · multifunctional materials on the table above paper standards applicable to the S solid standard (CNS > A4 specifications (210 x 297 public money) ----— — — — — Ill— —. I I --- II ^ 1111111 (Please read the notice on the back WWi # to write this page) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs- 63-Printed by the Central Samples Bureau, Ministry of Economic Affairs, Masonry Consumer Cooperatives _406031 s'_ V. Description of Invention (61)

The crystalline type of Ti02 NO. 11 ~ 13 is anatase type, and NO.1 4 is rutile type. In the abrasion resistance test of Table 12, NO. 11 series was damaged after 5 slips, peeling, N 0. 12 series was not damaged more than 10 times, and NO. 1 3, 1 4 were 40 It will not be damaged more than twice, with excellent results. No.13,14 which will not be damaged after sliding more than 40 times, is caused by the firing temperature of 80 ° C or more, the neck between the T i 02 particles, and the T i 0 2 particles firmly bonded to each other. . It will be damaged if it slides less than 10 times. The peeling NO.11 is because the firing temperature is only 20 ° C higher than the softening temperature of the glass substrate. It cannot sufficiently reduce the viscosity of the glass substrate and form the anatase type of the bottom layer of the photocatalyst layer. T i 02 particles are not fully embedded in the glass substrate. In contrast, N 0. 12 is not damaged after more than 10 slidings. This is because the temperature does not reach the temperature of the neck. However, the difference between the firing temperature and the softening temperature of the glass substrate can already adjust the viscosity of the glass substrate to a value in which the T i 02 is embedded in the glass substrate appropriately. On the other hand, in the antibacterial test of Table 12, NO. 11 ~ 13 series ++ or ++ has excellent effect, but N0..1 4 series one * This series will become rutile type because of T i 02, burn The forming temperature is 320 ° C higher than the softening temperature of the glass substrate, and the viscosity of the glass substrate is too low, which is caused by two reasons that the T i 02 particles constituting the photocatalyst layer are buried in the glass substrate. Example 1 9 This paper ^ standard is free to use Chinese national standard (0?) 8 4 specifications (210 ~ 297 mm ^ ~ _ 64----------- ^ ------ iT- ----- Λ (Please read the notes on the back before filling out this page) Central Labor Department, Ministry of Economic Affairs, Consumer and Industrial Cooperation Du Yinzhuang A7_406031 B7 V. Description of Invention (62) Each embodiment uses a different proportion of 1 ο 〇X 1 〇〇X 5 glass substrate, on the surface of the substrate, a 1 5% T i 02 sol aqueous solution was spray-coated to form a T i 〇2 layer with a film thickness of 0 _ 8 4 m, and then this was The glass substrate laminated with Ti 02 layer is placed in a ceramic film type with excellent release properties. Then, each embodiment is heated and fired in a rolling type at different atmospheric temperatures, and then cooled and solidified. Glass》 The following Table 13 shows the effect of improving the specific gravity of the glass substrate of the above multifunctional materials on antibacterial and abrasion resistance. (Table 1 3) Photocatalyst = T i 0 2 (Please read the precautions on the back before filling this page )

No. 15 16 1 7 18 Type of glass substrate Si〇2-Al 2 0 3 ~ P b 〇SiO〇2-Al 2 0 3-P b 0 Specific gravity of glass substrate 5.3 3. 8 2.8 2.4 T i 0 2 Specific gravity 3. 9 3.9 3.9 3.9 Glass substrate softening 480 540 620 680 Temperature (° c) Firing temperature (° c) 750 750 750 750 Antibacterial + + + + + + + + + + + Abrasion resistance X 〇〇〇〇〇〇〇〇〇〇 This paper size applies to the Chinese National Standard (CNS) A4 (210X297 mm) -65-Printed by the Central Labor Bureau of the Ministry of Economic Affairs, Shellfish Consumer Cooperative, 406031 g. 5. Description of the invention (63) Antibacterial test, NO.15 Excellent results are obtained from ~ 18 + + "The firing temperature is higher than the softening temperature of the glass substrate by 30 ° C or more and 300 ° C or less. It can be seen that the difference between the firing temperature and the softening temperature of the glass substrate, This result can be obtained by adjusting the viscosity of the glass substrate to a value where T i 02 can be buried in the glass substrate moderately. In terms of abrasion resistance, No. 15 series is damaged after sliding less than 5 times, but No. 16 ~ 18 is not damaged by sliding more than 10 times. According to the investigation, the reason should be that No.15 is different from others. The specific gravity of the glass substrate is greater than that of T i 02, so the anatase T i 02 particles that constitute the lowermost layer of the photocatalyst layer cannot be fully embedded in the glass substrate. Because of this, it is known that the abrasion resistance of multifunctional glass substrates is also affected by the specific gravity between τ i 02 and the glass substrate. When the specific gravity of the glass substrate is greater than T i 〇2, it will also cause poor abrasion resistance. Sex. Example 2 0 The surface of a glass substrate made of S i 02-A5203-B a 0 (softening temperature 6 2 0 ° C) of 150 square was sprayed with a mixture of Ti 02 sol and S η 02 sol. The subsequent aqueous solution is fired at 75 ° C, cooled, and solidifies more functional materials. In addition, the concentration of the sol of T i 02 is 4 to 6% by weight, and the pH value is adjusted to 1 with NH3 aqueous solution. The crystallite size of the T i 02 particles is the size of this paper. It is applicable to China National Standard (CNS) A4 (210X297 Mm) 1.1 Binding I ^ (Please read the notes on the back before filling this page) MSL ·

40〒 V. Description of the invention (64) 0. 01 # m, the microcrystalline particle size of the Sn〇2 particles is 0. 0 0 3 5 # m T i Ο * and Sn02 combined SiSnOj * Effect on antibacterial and abrasion resistance when placed (Moore ratio) Photocatalyst = Ti 02, void particles = Sn02 (0 · 0 0 3 5 jti m)

No. 19 20 21 22 23 S η 0 2 (mol X 0 10 20 60 100 Antibacterial + + + + + + + + + + +-Wear resistance ◎ ◎ ◎ ◎ Introduction of wear resistance Increasing the position of S η 02 can improve abrasion resistance * When adding more than 10% • It will not be damaged or changed after sliding 40 times. During the antibacterial test, it is more or less than 20%. The same as the additive * + + + can be + + to 60%, but when the amount is increased, the probability of T i 02 particles covering the surface of the substrate is greatly increased, and the antibacterial property is deteriorated. At 100%, 1. This paper size applies the National Solid State Standard (CNS) A4 specification (21〇X 297 male «) ------ III I --- i — — — — — — — — — — — — — (谙First read the note on the back and write this page> Printed by the Consumer Property Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs and printed by the Ministry of Economic Affairs Printed by the Ministry of Economic Affairs Printed by Shellfish Consumer Cooperatives of the Ministry of Economic Affairs 406031 at B7 V. Invention Description (65) Therefore s In terms of mol ratio, the added amount is 10% or more and 60% or less of the total amount of τ i 0 2 and S 1102, preferably 10% or more and 20% or less. It can provide antibacterial properties and wear resistance. Loss Multifunctional glass. Here the abrasion resistance can be improved with the increase of the amount of S η 02, and its operation can be explained according to the description of Figure 17 above. As described above, the glass substrate is held on the surface of the glass substrate. In a composite material with a T i 02 particle layer, when the gap between the T i 02 particles exposed on the outermost surface is filled with S η 0 2 particles and fired at 60 ° C or higher, cracks do not occur, and T is combined. i 02 The neck between particles can improve the abrasion resistance. Comparative Example 2 1 Same as Example 20, at 150 square Si i 02 — Α $ 203-Β a 0 composition (softening temperature 6 2 0 ° C ) On the surface of the resulting substrate, coating and mixing by spraying method, stirring the aqueous solution of Ti 02 sol and S 1102 sol, and then firing at 750 ° C, cooling and solidifying the multifunctional glass. The concentration of Ti02 sol is 4 ~ 6% by weight. 'The pH value is adjusted to 1 1 with an aqueous ammonia solution, and the crystallite size is the same as in Example 2 0. The sample size is 0.01 #! 11,511〇2. The larger one is 0.08 to m. The antibacterial test and abrasion resistance test on the multifunctional glass made as described above are compared with actual tests. Example 2 The comparison results are shown in Table 15 below. (Please read the precautions on the back before filling this page) This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) -68-Central Ministry of Economic Affairs 橾Printed by the Zhuhai Bureau Shellfisher Consumer Cooperative __406031 b7 V. Description of Invention (66) (Table 1 5)

Base material = S i 〇2— Aj2203— B a 0 Glass Photocatalyst = T i 02, void particles = S n02 (0 · 0080em), heat treatment 750 ° C

No. 24 25 26 27 28 S η 02 (mol% 0 10 20 60 100 antibacterial + + + + + + + + + + +-abrasion resistance 〇〇〇 ◎ ◎ The result is known. 〇〇8 # m The effect of Sn02 particles on improving abrasion resistance is weaker than when using Sn02 particles of 0. 〇35μιη, and the slip ratio can be reached 40 times when the molar ratio of the total amount of T i 02 and S η 02 is 60% or more. It will not be damaged and will change. In the antibacterial test, it is the same as when using Sn02 particles of 0. 0035μιη, and the range is more than 20%. The result can be the same as when not added, and the result is less than 60%. So far, it stays at + +. More often, the probability of T i 02 particles covering the surface of the glass substrate increases, and the antibacterial property deteriorates, which is one at 100%. Therefore, when using 0. Oljum Ti02 particles, add 0 . 008 # m Sn02 particles, it is difficult to provide multifunctional glass with excellent antibacterial properties and abrasion resistance. This is because the larger the particle size, the larger the particle size of the S η 02 particles, this paper uses the Chinese National Standard (CNS) Α4 specification ( 210X297 mm) One 69---------nn in --- nn TIII ....... I WAN (Please read the precautions on the back before (Write this page) The Ministry of Tao ’s Central Standards Bureau, Shellfish Consumer Cooperation Du printed 406031 D / V. Description of the invention (67) The vapor pressure will be smaller, and the remaining S η 0 2 particles that are not gasified will be 0.035 There will be voids between Ti02 particles at #m 'to increase the bonding strength. Compared with that, at 0. 008 // m, compared with the voids between T i 〇2 particles, S η 〇2 particles are larger. S η 〇2 particles can not enter the gap, but will have a higher probability on T i 02 particles. From the above, we can know that the size of Sn 02 particles that should be buried in the voids of T i 0 2 particles The diameter is preferably less than 4/5. Example 2 2 The surface of a glass substrate formed with a composition of 1 50 0 square Sn02—Aj? 2〇3-B a 0 (softening temperature 6 2 0 ° C), and T i 〇2 sol aqueous solution was sprayed on it by spraying method, and then fired at 75 ° C, cooled and solidified into a composite material, and then sprayed with S η 02 sol aqueous solution at 1 1 0 ° C. Heat treatment, many functional materials. At this time τ i 02 sol aqueous solution is the same as in Example 20, and Sn 0 2 sol is 0.035 # m. For the production as above The material can be tested for antibacterial resistance and abrasion resistance. The results are shown in the following table. 6 »This paper size is applicable to China National Standard (CNS) A4 specification (210X297 mm). Packing-(Please read the precautions on the back before filling in (This page)

1T 70

A7D &7; Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs V. Invention Description (68) 406031 (Table 1 6) Substrate = S i 〇2-Αί2〇3— B a 0 Glass Photocatalyst = T i 〇2, empty Excluding particles = Sn02 (0 * 0035 烊 111), heat treatment 750. (: / 110 begging

No. 29 30 31 32 33 S η 0 2ft (mo 1X 0 10 20 60 100 Antibacterial + + + + + + + + + + +-Abrasion resistance 〇〇 ◎ ◎ ◎ Increasing the amount of η 0 * can improve abrasion resistance. When the Mohr ratio is added more than 20%, it will not be damaged or changed after 40 times of sliding. In the antibacterial test, it will be more than 20%. It is the same as the non-additive. It can be + + until 60%, but when the amount is increased, the probability of covering T 102 particles on the surface of the substrate is greatly increased. • Antibacterial deterioration * 1 0 0% The time is one. In this test, because the S η 〇2 sol is heat-treated at a lower temperature of 110 ° C, sintering of the gasification-condensation mechanism as in Example 5 does not occur. However, the abrasion resistance is still good. Increase, this is because the particle diameter of T i 02 particles is smaller, that is, S η 02 particles that are larger than the surface and have strong adsorption force have penetrated into the space between T i 〇 * particles, so that T i 〇 «particles Firmly combined with each other This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) I! I _! Ei! · — —-^ (Please read the notes on the back first to write this page) Α7 4060οί The invention description (69) is caused together. Example 2 3 The surface of the glass substrate formed by the composition of 15 0 square S i 02-A and 203 — B a 0 (softening temperature 6 2 0 ° C), The T i 〇2 sol aqueous solution was spray-coated thereon, and then fired at 750 ° C, and cooled to solidify into a composite material. A copper acetate aqueous solution was coated thereon to be dried, and then irradiated with ultraviolet rays to reduce copper Ion, the photocatalyst layer is fixed on one side, and there are many functional materials. Here, a mercury lamp is used as the illumination lamp. Here, the average Cu particle size fixed to the photocatalyst layer is about 0. 004 μm. The antibacterial test and the abrasion resistance test were performed, and the results are shown in Table 17. (Table 17) Substrate = S i 〇2— 入 艾 2〇3—8 3〇 glass photocatalyst = Ti〇2, void particles = Cu (0.004 # m) 'Heat treatment 7 5 0 t / light reduction I --------- ¾ ------ 1T ------- A (Please read the precautions on the back before (Fill in this page) Printed by the Consumer Cooperatives of the Central Government Bureau of the Ministry of Economic Affairs

No. 34 35 36 37 38 cu Amount (mo1%) 0 10 20 60 100 Antibacterial + + + + + + + + + + + + + + + Abrasion resistance 〇〇 ◎ ◎ ^ Chinese Standard (CNS)-Α4 specification (21〇χ 297 public envy-72 406031 A7 B7 V. Description of the invention (70) Wear resistance As mentioned above, with the increase of the amount of c U, wear resistance can be improved. When it is 0% or more, it will not be damaged or changed if it is swiped 40 times. In the antibacterial test, the range of more than 20% is the same as that of the non-additive. Adding a large amount of copper is not controlled by the photocatalytic action of the T i Ο 2 particle layer, but a large amount of copper is dominated by the effect of copper. When copper is expected to work, copper will slowly dissolve in the liquid, and its life will be shorter than those without photocatalyst. In addition, if the amount of copper added is too much, the cost will be higher, so setting too much amount of copper is not necessary. This example shows that it is not only possible to use oxides such as S η 02 such as copper Metals of the same kind can also be used as particles embedded in the voids of the Ti 02 particle layer. Example 2 4 is composed of 150 square Si 〇2-Aj? 2〇3— B a 0 Industrial and consumer cooperatives printed batches of clothing — (Please read the precautions on the back before filling in this page)-The surface of the glass substrate made of softening temperature 6 2 0 ° C, coated with Ti 02 sol aqueous solution by spraying method, It is fired at 95 ° C, cooled and solidified into a composite material, and coated with an aqueous solution of copper acetate, and then irradiated with light including ultraviolet rays, while reducing copper ions, fixing the photocatalyst layer, and multifunctional glass. At this time, use B The LB lamp is irradiated for several minutes. T i 02 is anatase phase transferred to rutile during heat treatment. The film thickness of T i 02 is in accordance with the Chinese standard (CNS) A4 (210X297 mm). -73 Printed by the Central Bureau of Quasi-Ministry of Economic Affairs of the People's Republic of China, 406021 ^ I-__ V. The description of the invention (71) is adjusted to 0.4em when spraying. Abrasion resistance test. In addition, good results can also be obtained in this temperature range. With or without addition of copper, it can not be damaged after 40 slidings and does not change. The antibacterial test is shown in Figure 22. T i when not added 02 is rutile type, so it is inferior to +. Antibacterial activity can be improved when copper is added one by one. When not only the BLB lamp is irradiated, as long as the copper carrying capacity is not less than 0.7 eg / cm2, the antibacterial activity can be + +, Cu supporting capacity is 1.2eg / cm2 or more to make the antibacterial property +++ »From the above, it is known that for multifunctional materials that provide antibacterial properties and excellent abrasion resistance, the Cu supporting capacity is still 0. 7 eg / cm 2 is more preferably, more preferably 1.2 jt / g / cm2 or more. As for the copper carrying capacity, before the B L B lamp is irradiated after the copper acetate aqueous solution is applied, the drying step can be significantly improved. This relationship is shown in Fig. 23. This is due to the higher metal ion concentration during photoreduction after drying. In addition, when the optimum amount of copper is applied, the copper carrying capacity can be the highest (Figure 24 shows an example of copper acetate with a copper concentration of 1% by weight). According to Figure 20, the coating amount is intended to be 0.7 · eg / cm2. In the above case, it may be 0.2 mg / cm2 ~ 2.7 mg / cm2. If it is 1.2 vg / (: 1112 or more, it may be 0.3 1118 / (: 1112 ~ 2.4111 叾 / cm2.) This paper size is applicable China National Standard (CNS) A4 (210X297 mm) I i Binding ^ (Please read the notes on the back before filling this page) _ 74 _ Printed by the Central Barrier Bureau of the Ministry of Economic Affairs, Shellfish Consumer Cooperative, ___4060 "b7_ V. Description of the invention (72) Example 2 5 The surface of a glass substrate formed with a composition of 1 500 square Si 〇2-Ai203-B a 〇 (softening temperature 6 8 0 ° C) was coated with T by spraying method. i 〇2 sol aqueous solution, fired at 95 ° C, cooled and solidified into a composite material 'coated with silver nitrate aqueous solution, and then irradiated with light including ultraviolet rays, while reducing silver ions, fixed photocatalyst layer, to obtain Multifunctional glass. At this time, use a BLB lamp to irradiate for several minutes. T i 02 is anatase phase transferred to gold during heat treatment Stone type. The film thickness of Ti 02 is adjusted to 0.4 vm during spraying. The multifunctional glass produced as described above is subjected to an antibacterial test and abrasion resistance test. Those not added in the abrasion resistance test are also in this temperature range. Good results can be obtained. With or without adding silver, it can be swiped for 40 times without damage and no change. The antibacterial test is shown in Figure 25. When not added, T i 02 is rutile, so it is poor. However, when silver is added, it is improved, and not only the BLB lamp is irradiated, but even when it is not irradiated, the antibacterial property can be increased to +0.5 when the silver load is above 0.05 // g / cm2. The Ag load is 〇. Antibacterial properties can reach + + + when 1 μ g / cm2 or more. However, when the silver carrying capacity changes from brown to black, the appearance is not good, but the silver carrying capacity remains below 1 μ g / cm 2. No coloring "From the above, it can be known that the loading capacity of silver is 0.05 g / cm2 ~ l # g / cm2, preferably 0-1 g / cm2 ~ 1 g / This paper scale applies to China Knead (CNS > Α4 size (210X297 mm) I --------- 1 ------ 1T ------, · ^ (Please read the precautions on the back before filling (This page) Ministry of Economy The Central Bureau of Standards printed 406031 at ___________ for industrial and consumer cooperatives. B7 V. Description of the invention (73) Example 2 6 In 1 50 0 square S i 02-A ^ 203— B aO glass (softening temperature 6 8 0 ° C) The surface of the resulting glass substrate is coated with an aqueous solution of TiO 2 sol by spraying, and then fired at 95 ° C, cooled and solidified into a composite material, and then coated with an aqueous silver nitrate solution, and then irradiated with ultraviolet rays. The light, while reducing silver ions, while fixing the photocatalyst layer, is more functional glass. At this time, a LB lamp was used, and the irradiation was performed for several minutes. In the T i 02 series, the anatase phase was transferred to the rutile type during the heat treatment. For the multi-functional glass made as above, change the film thickness of T i 02 to perform abrasion resistance test, anti-bacterial test. In the abrasion resistance test, it has a good effect within the range of 2 / zm of this test. After 40 times of sliding back and forth, it will not be damaged and cannot be changed. In the antibacterial test, the film thickness is ++ when the film thickness is 0.1 # or more, and ++ when the film thickness is 0.1 or more. Therefore, the thickness of the Ti02 film is preferably 0.1 μm or more, and more preferably 0.2 μm or more. From the above description, it can be seen that fixing the photocatalyst particles to the thermoplastic base material prevents the photocatalyst particles constituting the surface layer portion of the photocatalyst layer from being buried in the thermoplastic base material. Therefore, the photocatalyst particles have a surface that is substantially exposed to the outside. Play photocatalyst effect. In addition, part of the particles constituting the lower layer of the photocatalyst layer among the photocatalyst particles are embedded in the thermoplastic substrate, so the holding power of the photocatalyst layer can be significantly improved, and it is difficult to peel off. Figures 26 and 27 are based on EPMA (the electronic wire microanalyzer's paper scale is applicable to China National Standard (CNS) A4 specifications (210X297 mm)) ---------- i ---- --IT ------ Λ (Please read the notes on the back before filling out this page) Printed by the Consumer Cooperatives of the Central Procurement Bureau of the Ministry of Economic Affairs __40G0S1 _ ^ __ V. Description of the Invention (74)) Observe the multifunctional materials Conceptual drawing of the basic outline in the direction of the cross section. It can be seen from this that, from the surface exposed to the outside air, there is first a region (A region) constituting the component of the photocatalyst layer 2 with a certain concentration, and then the component of the photocatalyst layer gradually decreases. In addition, the components constituting the amorphous layer (binder layer) are absent or present on the surface in a small amount, and the concentration is gradually increased inward. When it reaches a certain film thickness, it becomes a certain concentration (B zone). Here, the A region is defined as a photocatalyst layer, the B region is an amorphous layer, and the middle C region is an intermediate layer. However, Fig. 26 is only a conceptual diagram for the convenience of explanation. In fact, as shown in Fig. 27, the concentration in a certain concentration illustrated in Fig. 26 often changes due to manufacturing process reasons. At this time, as shown in FIG. 27, the minimum concentration values that reach the area corresponding to a certain area (A / area, B > area) are regarded as A / area and (: / area, B-area respectively). The boundary with the area. Here the thickness of the photocatalyst layer refers to the thickness of area A or A /, and the thickness of the intermediate layer refers to the thickness of area C or C >. The thickness of this intermediate layer can be controlled by The speed of the photocatalyst particles moving toward the softened amorphous, and the possible movement time, that is, the thickness can be changed. The speed of movement can control the difference between the specific gravity of the photocatalyst particles and the amorphous layer, the firing speed, the atmospheric pressure, etc. Also, it is possible The moving time can be changed by changing the time that the amorphous material is kept at the softening temperature. The thickness of the intermediate layer can be made to be more than 1/3 of the thickness of the photocatalyst layer to improve its adhesion. The specific examples are described below. Paper size applies to China National Standard (CNS) A4 (210X297 mm) ---------- installation ------ order ------ 4 {Please read the precautions on the back first Fill out this page again) 406031__B7 _ V. Description of the invention (75) Example 2 7 By The spray method is used to form a Si 〇2-Ai? 2 03—N a / K2◦ amorphous layer on a 10 cm square alumina substrate. After drying and firing, the average particle size is coated by the spray method. 0 01 // 1111'102 sol aqueous solution, changing the time to maintain it at 8 50 ° C, and firing to form 0.2em, 0.5 / ^ m, l # m film thickness of Zhiqin type T i 02 film. Then, a copper acetate aqueous solution was spray-coated on this anatase T i 02 film, and then the sample was obtained by light reduction (light source: 20W BLB lamp, distance from the light source to the sample 10 cm, irradiation time 30 seconds). Based on the cross-sectional elemental analysis (T i, S i) of the EPMA sample, the film thickness was measured, and antibacterial properties and abrasion resistance were evaluated.

An antibacterial test was performed on the bactericidal effect of Escherichia Coli W3110 strain. Bacterial solution was dripped on the top surface of the multifunctional material sterilized with 70% ethanol in advance 0.15m and (1 ~ 5x 1 04CFU printed by the Shellfish Consumer Cooperative of the Central Bureau of the Ministry of Economic Affairs (please read the precautions on the back first) Fill in this page) '), place a glass plate (10x10cm) close to the top surface of the substrate as a sample. After irradiating for 30 minutes with a white light (3500 candles), wipe the irradiated sample with the sterilized gauze and the bacterial solution kept under the shading condition, and recover it in 1 Omi? Physiological saline to determine the survival rate of the bacteria. As an evaluation indicator. The evaluation criteria are shown in Table 1 above. The results are shown in Table 18 together with Table 7 and the antibacterial properties are all + + +. The abrasion resistance was also ◎ or ○, both of which had good results, and the samples in which the ratio of the thickness of the intermediate layer to the thickness of the photocatalyst layer was 1/3 or more were ◎. This paper size applies to China National Standard (CNS) A4 (210X297 mm) -78-Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 406031 at ____B7 V. Description of the invention (76) (Table 1 8) Ti〇2 film thickness (Mm) Interlayer thickness (em) Holding time (hours) Interlayer thickness / Ti〇2 Film thickness Antibacterial peel resistance 1 0.42 16 0.42 +++ ◎ 1 0.33 2 0.33 +++ ◎ 1 0.30 1 0.30十 〇0.5 0.17 2 0. 34 ◎ 0.5 0.13 1 0.26 ++ 〇〇0.2 0.08 2 0. 40 +++ ◎ 0.2 0.05 1 0. 25 +++ 〇1 0 0 +++ Δ ----- ---- νΐ 衣 ------ ΐτ ------ (Please read the precautions on the back before filling in this page) This paper uses the Chinese National Standard (CNS) A4 size (210X297 mm) 88. 4 ^ 6031 V. Description of the invention (77) Comparative example 2 8 (Please read the precautions on the back ir # first to write this page) On a 10 cm square alumina substrate, apply the average particle size by spray coating. 0. 0 1 # m T i Ο 2 sol aqueous ammonia dispersion, fired at 8 50 eC to obtain an anatase-type T i 02 film with a thickness of 1 楢, and then apply a copper acetate aqueous solution to this anatase by spraying Mineral type T i 02 film ►Then light reduction (light source: 20W BLB lamp, the distance from the light source to the sample is 10 cm, irradiation for 30 seconds) * Get the sample • Evaluate the antibacterial and abrasion resistance of the obtained sample. Results The antibacterial property is excellent + + +, However, the abrasion resistance is slightly insufficient. △ From the above description, it can be seen that the photocatalyst layer is held on the surface of the substrate by the amorphous layer. The upper part of the photocatalyst layer is exposed to the outside air and the photocatalyst layer particles are in between. Among the multifunctional materials that are combined with each other and have the function of photocatalyst, the amorphous layer and the photocatalyst can have an intermediate layer that can continuously change the bromine content of both components, so as to further improve the photocontact film and the substrate. The adhesion between the two layers can be improved, and the peeling resistance can be improved. The thickness of the intermediate layer can be more than 1/3 of the thickness of the optical layer. The photocatalyst layer 2 is formed by sintering. Fig. 1 (a) is a conventional state diagram of Ti02 particles before sintering. (B) State diagram after sintering. * As shown in Fig. 1 (a). Cloth containing T i 02 particles 3 * to increase film strength And the heat treatment (sintering) is applied, that is, cracking is very easy to occur as shown in Figure 1 (b). It is speculated that the reason should be that the phase transfer to the rutile type will cause the shrinkage of the cross product (raise the density), In addition, TiO 2 particles 101 -80 before sintering-this paper size is applicable to Chinese National Standard (CNS) A4 (210 X 297 mm). Printed by the Bayer Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs. A7___406031 B7 ) The interval is L. After sintering to the rutile type, it will diffuse to the other's volume and shorten the interval between the particles to 1 ^ 1 (1 ^ 1 < 1 ^.). As a result, cracking occurs. Therefore, after sintering, Sn02 is solidified at the neck of the Ti02 particles 3 that can be bonded, and the neck is thickened to strengthen the bonding of Ti02 particles 3 to each other and increase the film strength. In order to form the photocatalyst layer 2 as described above, S η 02 sol is mixed in Ti 02 sol, and after stirring, it is coated on substrate 1 and heat-treated (sintered) at a predetermined temperature. In addition, the T i 〇2 sol concentration is adjusted to about 4 to 6% by weight. 'The NH3 temperature is adjusted to pH 1 1. The average initial particle size of the T i 02 particles is 0.01 / im (10 nm), and the Sn02 sol concentration is 妁. 0035 ^ m。 10% by weight, adjusted to pHll with NH3 solution, the average initial particle size of 51102 particles is 0.035 ^ m. The average initial-phase particle size shown here refers to the crystallite size (initial particles) obtained from the half-value width of the diffraction rays of XRD (X-ray diffraction). Here, the S η 02 system has a higher vapor pressure than T i 〇2, and the interval between the T i 02 particles 3 before sintering is L as shown in FIG. 17 (a). For example, the surface of the titanium oxide particles 3 with a positive curvature has a high vapor pressure, and the surface with a negative curvature, that is, the surface of the neck where two titanium oxide particles 3 meet, has a low vapor pressure. As a result, as shown in Fig. 17 (b), Sn02 with a vapor pressure higher than that of titanium oxide enters in the neck, solidifies as shown in Fig. 17 (c), and is sintered by a gasification-solidification mechanism. Then when sintering by the gasification-solidification mechanism, the paper size after sintering applies the Chinese National Standard (CNS) Α4 specification (210X297 mm) " -81---------- f --- --- 1T ------ A (Please read the precautions on the back before filling out this page) Printing policy of the Central Laboratories Bureau of the Ministry of Economic Affairs, Paiger Consumer Cooperatives ___ 40G € 31 b7 V. Invention Description (79) T i The gap L 2 of the 〇2 particles is the interval l from the sintering. It is about the same, so no cracks and the like will occur. As described above, when the interval of T i 02 particles is not substantially changed before and after sintering, and it has a photoactivity (R3.) Of 50% or more as a photocatalyst coating, it must be as shown in FIG. In terms of 02, the mixing ratio of S η 〇2 is 20 to 70%. The compounding ratio is expressed by the weight ratio of the fixed components contained in the sol. In addition, the evaluation of photoactivity was based on the decomposition of methyl mercaptan, and the removal rate (R3.) After 30 minutes of light irradiation was used as an index. Specifically, put a 150 square tile forming a photocatalyst film in a 1 L glass container, and place it at a distance of 8 cm from the light source (4W BLB lamp), and inject 3 to 5 p pm of methyl mercaptan, After confirming that there is no adsorption in the dark, turn on the fluorescent lamp and measure the concentration change over time by gas chromatography. Here R3〇 = (X〇-X3.) / X〇x 1 0 0% but X0 = Initial concentration [ppm], X3O = Concentration [ppm] after 30 minutes >> The evaluation of the film strength was performed by sliding back and forth abrasion of the plastic wiping rubber to compare the change in appearance. The evaluation criteria ◎, ○, △, and X are as described in Table 1 above. Fig. 29 is a graph showing the correlation between heat treatment temperature and photoactivity. When adding an organic stabilizer to T i 02 sol, although the photoactivity will be reduced, the heat treatment temperature is set to 3 0 0 ~ 8 5 0 ° at this time. C. This series is difficult to generate activity when the heat treatment temperature is below 300 ° C, and the structure of T i 02 will change from anatase type to rutile type when the temperature is above 850 ° C. This paper size applies to China National Standards (CNS) A4 (210 X 297 mm) I- Approval n ^ IIII ^ (Please read the precautions on the back before filling this page) 40B031 Staff Consumption of the Central Standards Bureau of the Ministry of Economic Affairs Cooperative printing 5. Description of the invention (80) From the above description, it can be known that a sol containing titanium oxide particles and a substance having a higher vapor pressure than this titanium oxide is coated on the tile, and sintered at a predetermined temperature, by gas The sintering of a solidification mechanism is used to form a film, so before and after sintering, the interval between the titanium oxide particles is about the same, and cracking is unlikely to occur. In addition, the neck system between the titanium oxide particles is solidified with S η 02 and the like, and the peeling strength of the film can be improved. In particular, if the addition amount of S η 02 (within T i 02) is 2 0 to 70%, both the film strength and the photoactivity can be satisfied, and it is more than 300 ° C above 8 5 0 ° C. Heat treatment in the following range can obtain sufficient photoactivity. As for the method for measuring R 30 by gas chromatography, because the measuring device is expensive, only one sample can be measured by one device, and the efficiency is poor. In addition, it is common practice to increase the photoactivity when gold alloys such as lead are supported on Ti 02. However, when the photocatalyst film of the above structure has metal absorption and gas attached, to what extent is the correct photoactivity? It's hard to judge. In addition, once a tile or the like is applied to a wall surface, the activity of a photocatalyst film formed on the surface cannot be measured by gas chromatography. In addition, instead of using gas chromatography to evaluate the photoactivity method, it may be possible to consider investigating the survival rate of bacteria after killing cells by irradiating light with a photocatalyst. The metal-supported photocatalyst film can kill bacteria only by the antibacterial force of the metal itself, and it is difficult to judge the true photoactivity. For this purpose, the following method for measuring the activity of the photocatalyst film can be applied. The first method is to form T i 〇2 as the main light on the surface of the substrate ------------ I-- (Please read the precautions on the back before filling this page)

• 1T This paper size is applicable to China National Standard (CNS) A4 (210X297mm) _ 83 _

Printed by Shelley Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (81) Catalyst film surface • Drip aqueous solution of osmium osmium such as potassium iodide or potassium vaporized solution, and then irradiate ultraviolet rays to the dripped alkali halide aqueous solution for a predetermined period of time. The difference between the PΗ value of the previous halogenated alkali aqueous solution and the pΗ value after irradiation 'to determine the activity of the photocatalyst film. The second method is to form a photocatalyst film on the surface of the substrate with T i 02 as the main body. Potassium chloride, etc._ Add the P Η indicator 混合 mixed solution to the aqueous solution of plutonium, and then irradiate the dropped mixed liquid with ultraviolet light for a predetermined time, and change the color of the mixed liquid to determine the activity of the photocatalyst film. The third method is on the substrate The photocatalyst film with T 10 2 as the main body formed on the surface is in close contact with the activity measurement film. In this state, the activity measurement film is irradiated with ultraviolet rays for a predetermined time. The activity of the photocatalyst film is judged by the color change of the activity measurement film. 0 is a drawing explaining the first and second activity measurement methods. The surface of this substrate 1 is formed with T i 02 as the main body. Catalyst layer 2 · To test whether this photocatalyst layer 2 is photoactive, drip aqueous alkali solution 30 such as potassium iodide or potassium gasification on the surface of photocatalyst 靥 2, and then drop the lutetium halide aqueous solution 30 · Ultraviolet lamp 40 Ultraviolet irradiation for a predetermined time * Judging the activity of the photocatalyst layer 2 from the difference between the pH value of the halogenated alkali aqueous solution before the irradiation and the pH value after the irradiation. Figure 3 3 shows the correlation between the ultraviolet irradiation time and the amount of change in pH In the figure, the concentration of the halogenated alkali aqueous solution 30 is 0.1 Moore /. The UV lamp 40 uses a BLB fluorescent lamp 20 W, the rejection distance between the photocatalyst layer 2 and the UV lamp 40 is 20 cm, and the irradiation time is 60 minutes. The size of the shovel is in accordance with Chinese standards (CNS> A4 size (210 * 297 mm) --- 111! 11 ··! 1 order · 111! 11. ^^ (Please read the notes on the back first (This page)

Β7 406031 V. Description of the invention (82) Test · ------ Install i I (please read the note on the back first to write this page) From the figure, you can know that * anatase type * gold-carrying type, rutile Any one of the photocatalysts 赝 2 is within 30 minutes of UV irradiation, the pH value of the halogenated alkali aqueous solution 30 is equal to the pH value of the halogenated aqueous solution 酴, which will rise due to the following oxidation reaction. Simultaneous with the reduction reaction, the reduction reaction will be caused by OH- (hydroxy ion). Oxidation reaction: 2I- + 2h + = I2 Reduction reaction: 0 * + 2H20 + 4e- = 40H_ Therefore, it can be improved by ultraviolet irradiation. When the p Η value of the hafnium halide aqueous solution 30 is 0, the photocatalyst layer 2 represents those having photoactivity. The line 34 shows 113. Correlation diagram with the amount of change in pH value • Here, R 30 is the ratio (%) of the gas (methylthiolase, etc.) that is reduced 30 minutes after UV irradiation, from which it can be seen that R 3 0 and pH value There is a proportional relationship between the amount of change. That is, the amount of change in P 无 is an indicator of the presence or absence of photoactivity. • The pH change in the first method printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs is set by a pH meter or a pH test piece. In the second method, the second method is to drop a mixed solution of halogenated residual aqueous solution including pH indicator 3 30 on the surface of the photocatalyst layer 2, and then irradiate the dropped mixed solution with ultraviolet light for a predetermined time to change the color of the mixed solution. Judging the activity of photocatalyst 靥 2 · p Η indicates that the pH value is about 4.5 before ultraviolet light is irradiated to the halogenated alkali aqueous solution 30, and the p 后 after ultraviolet irradiation is 5.5. This paper standard is in accordance with Chinese standards ( CNS) A4 specification (210 X 297 mm) 85 B7 40GG〇i 5. Description of the invention (83) 6. 5 · So methyl red is suitable · Also, the above first method and second method are in the photocatalyst layer 2 Surface drops (please read this note on the back first to write this page) A mixed solution of pH indicator 薬 is added to a halogenated aqueous solution 30 or a halogenated alkaline aqueous solution 30. However, the situation in which the liquid on the substrate drops and spreads on each substrate is different. A certain liquid thickness cannot be ensured. The noodles are different. To solve this problem, there is the method shown in the 31st group. This method is to drip the hafnium halide aqueous solution 30 equal to the surface of the photocatalyst layer 2, and then paste a halogenated test solution 3 on a transparent plate 60 such as a glass plate. 0 * It can keep a certain thickness and prevent drying. Also * Liquid halides such as aqueous halogenated solution 3 are based on the surface of the substrate 1 as the level. * So it is difficult to judge the vertical surface or ceiling surface of the installed wall. The activity of the photocatalyst thin film · To solve this problem, the method shown in Section 3 2 圚 can be used. This method is based on the surface of the photocatalyst 靥 2 formed on the surface of the substrate 1 closely contacting the activity measurement film 70, and in this state, it is irradiated with ultraviolet rays. The activity measurement film 70 can be used to judge the activity of the photocatalyst layer 2 based on the color change of the activity measurement film 70 It can be prepared by adding an aqueous halogenated alkali solution such as potassium iodide or potassium chloride and a mixture of p Η indicator ， to the organic binder, and drying and forming into a thin film. Secondly, examine the porosity of the photocatalyst layer 2 Degree refers to the percentage of pores. • Porosity is 10% to 40%, preferably 10% to 30%. The crystal particle size of the photocatalyst particles is 0. liim or less, preferably this paper. The standard is applicable to China Standard for Domestic Standards (CNS) A4 (210 * 297 public love) _ _ '' Staff Consumer Cooperative Cooperatives Seal of the Central Bureau of Standards of the Ministry of Economic Affairs 40 (^ 031 B7 V. Description of the invention (84) It is better to be less than 0.04 . 1 / zm 可以 可以。 The smaller the crystal size, the effective area per unit volume of the reaction can be increased, so the film thickness of the photocatalyst layer is about 0.1 / zm about. Each photocatalyst particle is solid-phase sintered with each other to form a neck. In order to improve the strength of the layer, the crystallite size will increase to above 0.1 U τη, reducing the effective reaction area per unit volume, so the film thickness is 0. 5vm or more, preferably 0.6em or more ", and particles having a crystal size of O. Olem or less, preferably 0.008 or less, are added between the photocatalyst particles constituting the photocatalyst layer formed on the surface of the substrate. By adding these particles, the gaps between the photocatalyst particles can be buried to improve the particle filling rate and surface smoothness, and thereby improve the film strength to shear stress. "Improving surface smoothness can reduce contamination." The porosity is reduced, but the diameter of the pores buried here is less than 0.01 " m, preferably less than 0. 008vm. The size of the particles is only larger than the size of the gas (number A). So not-affect its deodorant. Basically, the particle size of the crystal grains below 0. Olem, preferably below 0. 008 can be any kind, but in addition to being buried in the gaps of the photocatalyst particles, a part of the particles will cover the surface, so it is best to T i 02, Sn02, ZnO, S rTi 03, Fe203, B i203, W03 and other oxide semiconductors or Ag, Cu, etc. which do not affect the photocatalytic activity are suitable. In addition, basically, the method for adding particles having a crystal grain size of 0.01 # m or less, preferably 0.008em or less, may be any method. For example, hydrothermal treatment is used to generate the ultrafine particles as described above, and then dispersed into a sol with an appropriate dispersion liquid. The paper size applies the Chinese National Standard (CNS) A4 specification (2 丨 0X297 mm) ------ ---- ^ ------ 1T ------- ^ (Please read the notes on the back before filling out this page) 406031 V. Description of the invention (85) (Please read the notes on the back and fill in (This page) Coating on the photocatalyst layer by spraying method 'Low temperature heat treatment to prevent the formation of particles to evaporate the organic dispersant Diluent * Organic ingredients can also be used · In addition, metal particles with a smaller gap than the photocatalyst 靥 formed on the surface of the substrate can also be fixed Improved photocatalytic activity and better deodorant properties. Here, the type of metal particles is anything as long as it can capture electrons. For example, it can be Cu, Ag, P t, etc. The size of gold particles must be It is the average of its average particle size compared to the surface of the photocatalyst layer The smaller the gap diameter is, the average pore diameter of the surface of the photocatalyst layer is measured with an electron microscope when the porosity is between 10% and 40% of the sample. It is approximately equal to the diameter of the photocatalyst particle. Therefore, it is required to be smaller than the diameter of the photocatalyst particle. • It is preferable that the particle size of the photocatalyst is smaller than the starting material. • The starting material for the photocatalyst layer is usually less than 0.05, so it is better to use it below 0.05 # m. The specific examples of porosity are as follows: Example 2 8 The coating arrangement was changed by spraying to apply a crystal grain size of 0. 0 1 iim T i 0 A square ceramic tile substrate was fired at 700 ° C to 900 eC to form a photocatalyst layer. The crystal size of the anatase phosphorous T i 0 2 particles was evaluated based on the obtained samples. -88 on the surface of the layer-This paper Standards are applicable to China National Standard (CNS) A4 specifications (210 X 297 mm). Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs. 406031 at ___B7 _V. Description of the invention (S6) Porosity, deodorant, abrasion resistance, resistance Peelability. R 3 was measured. (L) to evaluate deodorization. R 3. (L) is the removal rate after light irradiation. Specifically, a sample is formed in a 11-liter glass container with a photocatalyst film-forming surface at a distance of 8 cm from the light source (BLB fluorescent lamp 4W). Methyl mercaptan gas was injected into the container at 3 ppm, and the change in concentration when the light was irradiated for 30 minutes was measured. The abrasion resistance was evaluated by using a plastic eraser to slide back and forth and comparing its appearance changes. The evaluation indicators are as described above and as shown below. ◎: Unchanged 40 times back and forth. 0: Scratches after sliding back and forth for more than 10 times and less than 40 times. Photocatalyst layer (T i 0 2 film) peeling. △: Scratches after sliding back and forth for more than 5 times and less than 10 times. Photocatalyst. Layer (T i Ο 2 film) peeling-X: Scratches appear after sliding back and forth 5 times or less. Photocatalyst layer (T i ◦ 2 film) peeling peeling test is performed under stricter conditions than the abrasion resistance test, instead of rubber. Use a silicon (rough) eraser (LION TYPEWRITER ERASER 5 0 2) that can apply high shear force. Specifically, a coarse eraser was used to rub back and forth 20 times with equal force, and the standard sample and the state of the scratch were evaluated by visual comparison. The criteria are as follows. ◎: Completely unchanged 〇: Slight changes can be seen by the light △: Slight changes The dimensions of this paper are in accordance with China National Standard (CNS) A4 (210X297 mm) ~ '-89-(Please read the back (Note ^, please fill in this page again) _ 406031 b7 V. Description of the invention (87) X: —The change results are shown in Figures 35 to 37. FIG. 35 shows the relationship between the porosity and the deodorization and abrasion resistance when the thickness of the photocatalyst film is 0.8. The deodorant property can be improved with the increase of porosity, 10% can be 50%, and 3 ^% can reach more than 80%. In contrast, the abrasion resistance is ◎ 'at 30% and 0 at 40%, and △ or X at higher porosity. Therefore, it can be seen from the above that when a material having both deodorizing properties and abrasion resistance is to be produced, the porosity of the photocatalyst film must be 10% to 40%, preferably 10% to 30%. Figure 36 shows the effect of film thickness on deodorization when the crystal particle size of the photocatalyst particles of the photocatalyst thin film constituting 20 to 30% porosity is changed. When the crystal grain size is 0 · lem, the film thickness has an effect on R30 (L), and the thinner the thickness, the lower the deodorizing property. However, when the thickness is less than 0.04 / zm, the film thickness does not affect it. When the film thickness is 0.1 Mm, it also has excellent deodorizing properties. From the above, it can be seen that the crystal particle size of the photocatalyst particles is only required to be less than 0.1 / zm, and preferably less than or equal to 0.04 vm. Even if the film thickness is about 0.1 lem, good deodorizing properties can be ensured. Printed for Pakcon Consumer Cooperative (please read the notes on the back before filling out this page) Figure 3 7 shows the photocatalyst particle crystal grain size and the film in the bonded state when the photocatalyst film constituting the porosity 20 ~ 30% is changed Effect of thickness on deodorization and peel resistance. If the required mechanical strength value is increased to the level of the peel resistance test, the sample without neck will become △ or X. For 0.4ym, it is still insufficient, and it must grow to about 0.1 l // m. However, if the photocatalyst particles grow to this paper size, the Chinese National Standard (CNS) A4 specification (210X297) will be applied. 406031 A7 _B7 _ V. Description of the invention (88)

When the thickness is about 0. lym, the film thickness will affect the deodorization. The thicker the film, the higher the deodorization. Specifically, a film thickness of R3Q (L) can be 50% or more, and can reach 80% or more at 0.6 / zin. From the above results, it is understood that when the photocatalyst particles sintered with each other are solid-phase, necks are formed between the particles, and when the crystal grain size is increased to 0 · lvm or more, the film strength can be sufficiently improved. At this time, the reaction effective area per unit volume is reduced by increasing the crystal grain size to be greater than or equal to 0 · l # m, so the film thickness must be 0.5 μm or more, and preferably 0.6 μm or more. Example 2 9 On a 15 cm square tile substrate, an ammonia-gel suspension of a sol with a crystalline particle size of 0. 0 1 // 111 and a sol of 02 was spray-coated at 7 5 0 ° C. Fired to form a photocatalyst film. The porosity of the Ti02 thin film at this stage is 45%, and the crystal size of the Ti02 particles is 0.02 ν m. Spray different coatings with different crystal sizes on them.

The Sn02 sol was dried at 110 ° C to obtain a sample. The obtained samples were evaluated for deodorization and abrasion resistance. Printed by the Shellfish Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling in this page) The results are shown in Figure 38, changing the crystal particle size of the S η 〇2 sol from 0.00 3 54m to 〇. 〇l / zm, no change in deodorization, and good results were obtained. In contrast, when adding 30% by weight or more, the crystal particle size of S η 02 sol is different, and the effect of abrasion resistance is different β, that is, when adding particles below 0.08, it can be improved to ◎ or 〇, But 0. 0 1 / zm does not have an added effect. It can be known that the crystal size between the photocatalyst particles is 0.01. This paper size is applicable to China National Standard (CNS) A4 (210X297 mm) — a 91 _

Ⅴ, invention said Meng) "® The following is preferably 0. 0 0 8 #m particles can improve abrasion resistance. Example 3 0 The amount of addition is changed, the particle size of the crystal by spraying method 〇1 jam T i 〇2sol suspension of ammonia gel type is coated on a 15 cm square tile substrate, fired at 850 eC to form a photocatalyst film with a film thickness of 0.2 # m. Then, acetic acid is applied by spraying. The copper aqueous solution was applied to the photocatalyst film, and then photoreduced (the light source was a 20W BLB lamp, the distance from the light source to the sample was 10 cm, and the irradiation time was 10 seconds) to obtain the sample. • The copper carried at this time: Department 2 # g / cm2, its particle size coefficient is nm ~ 10 nm. The crystalline particle size of the photocatalyst particles is 0.1 # ιη. The samples obtained were evaluated for their resistance to abrasion and abrasion. Results R30 (L) was 8 9% * Abrasion resistance Compared with Figure 36, R30 (L) can be significantly improved from 18% to 89% due to copper loading. • Printed by Shelley Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs. By forming a photocatalyst film with a porosity of 10% to 40% on the surface of the substrate, preferably 10% to 30%, it can provide both Materials for anti-Olympic properties and abrasion resistance · Second, the description of the embodiment of the particles filled by the photocatalyst layer is smaller than the voids. • The voids in this example refer to the gaps between the particles and the neck. In terms of both concave parts. In addition, photocatalyst slurries are usually more sensitive * The film strength is not easy to stain, but the temperature for forming the photocatalyst layer must be increased for this purpose. The paper size of 92 substrates is applicable to China. CNS A4 specification (210 X 297 mm) 406031 A7 Printed by the Central Government Bureau of the Ministry of Economic Affairs, Shellfish Consumer Cooperatives, printed B7 V. Description of the invention (90) The material is limited, and the subsequent works according to the present invention are here In the method of filling particles with voids, the porosity 光 of the photocatalyst layer in which particles are added in front of the voids can be 10% or more. In addition, the film with a porosity of 10% or more has excellent deodorizing properties, so it is only necessary to appropriately adjust its filling amount. It can provide a multifunctional material with excellent antifouling and deodorizing properties. The particles with smaller voids filled in the voids are preferably made of inorganic crystalline materials, and more preferably those with photocatalytic activity. i 0 2, Sn02, Z η 0 > S r T i 03, Fe203, B i2 03, WO 3 oxide semiconductors are preferred. The size of the particles smaller than the voids is basically larger than the pore diameter of the generated The average value can be small, considering the reduction of voids and the reduction of particles attached to the surface of particles with a photocatalyst function to improve surface smoothness, and reduce surface defects, making it less prone to staining, improving film strength, etc., specifically 0.01 Below #m, preferably small particles below 0.008em are preferred. However, the Ti02 film is an anatase type. When heat-treated at a temperature below 85 ° C to fix it on the substrate, the average porosity is about the same as the particle diameter of T i 02 when observed with an electron microscope. 2 particle diameter is sufficient. The starting material of the Ti02 thin film with photocatalytic activity is usually a raw material of less than 0.05 / im, so it is preferably less than 0.05 #m. Here, if the porosity of the surface of the layer having the photocatalytic function of the filled particles in the void is 20% or less, it is difficult to be stained. Moreover, the maximum width of the opening is preferably 0.04 # m or less. The porosity here refers to the porosity of the surface of the substrate. The maximum width of the openings refers to the phase of the particles with photocatalytic function that constitute the surface of the substrate (please read the precautions on the back before filling this page). Paper size applies to China National Standard (CNS) A4 (210X297 mm) Printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs 406031 _ ^ __ V. Description of the invention (91) The maximum value of the gap between two adjacent particles ( Mean + 3 X standard deviation). In addition, if the used filler particles are in front of the void, the porosity of the layer with photocatalyst function is about 10%, the porosity will be reduced to less than 10%, and the porosity system buried here will crystallize. Particles with a particle size of less than 0.1 Ole can be larger than the size (number A) of the gas, so it does not affect the deodorization, and can maintain the same as the T i 02 film with a porosity of 10% or more. Its deodorant properties. In addition, when the crystalline photocatalyst particles are mainly used as the layer having the photocatalyst function, there is no scale, and the solid adhered form attached to the glass becomes dirt. Even if it is attached, it is easier to wipe and remove. It is also less likely to grow algae when used in flowing water. The crystalline photocatalyst particles herein refer to the photocatalyst particles peeled from the material when the powder X-rays are diffracted from the material under the conditions of 50 KV-3 0 0 mA. In the case of T i 0 2 particles, the photocatalyst particles which are crystallized to an extent of 20 = 25.3 ° in the anatase system and 20 = 27.4 ° in the rutile type). The method for filling the particles with the above-mentioned voids can be formed by applying a metal alkoxide, an organic metal salt sulfate, or the like, and then drying and heat-treating. For example, a process using a metal alkoxide is a method in which a solution of a mixed metal alkoxide in an appropriate diluent and a salt is applied on the outermost surface of the photocatalyst layer and then dried and heat-treated. Suitable diluents here are alcohols, alcohols such as propanol'methanol, etc., but are not limited thereto. It is best not to include water. Metal alkoxides hydrolyze suddenly when they contain water, which can cause cracking. Also 'added hydrochloric acid is used to prevent the size of this paper from applying Chinese National Standard (CNS) A4 specifications (210X297 mm) " ~ -94-(Please read the precautions on the back before filling out this page> 406031 A7 ____B7 _ 5. Description of the invention (92) Prevent cracking during drying or heat treatment. The method of coating metal alkoxide is usually by the pouring method, but it is not limited to this. The pouring system is best performed in dry air. In general air When coating in (atmosphere), it will be hydrolyzed due to the moisture in the air and it is difficult to control the film thickness. It can be applied once or several times. It can be determined by the fillability of the photocatalyst layer before coating. After being placed in dry air for several minutes, the particles in the photocatalyst layer can be filled with particles to form a film. Here, if the layer before filling the filled particles and the filled particles are made of the same material, the thermal expansion coefficient In the same way, it can be formed into a film with excellent mechanical strength. In addition, specific examples will be given to further explain the use of titanium alkoxide. The surface of the photocatalyst layer is coated with titanium alkoxide, and dried and heat treated. During the process, the coating amount of titanium alkoxide at one time is from 10 / zg / cm2 to 1 〇0 μg / cm2 when converted to T i 02. If the coating amount is too small, the number of coatings must be increased. , The efficiency is not good, on the contrary, when the amount of coating is too large, one coating will become too thick film, and cracks will occur when drying or heat treatment. Read the notes on the reverse side and fill in this page) In the above dry heat treatment process, the heat treatment temperature is set to 400 ° C to 800 ° C. When the temperature is below 400 ° C, the amorphous Ti 02 cannot be crystallized into anatase T i When the temperature is higher than 02, 0 0 ° C, the grain growth is suddenly promoted, and the photoactivity is reduced. Also, the amount of hydrochloric acid to the titanium alkoxide in the coating liquid is set to 1% to 10% by weight. When 1% by weight or less It does not have sufficient anti-cracking effect. When the content is more than 10% by weight, the hydrochloric acid is usually a 3 6% aqueous solution. Too much water content promotes hydrolysis and cracking. When the amount of hydrochloric acid is large, it is best to dilute the paper again. GM China National Standard (CNS) A4 (210X297 mm) -95-88. ie Λ 丘-4〇e〇si £ Α7 Β7 Printed by the Cooperative of Intellectual Property of the Ministry of Economic Affairs, Cooperative Co., Ltd. 5. Description of the invention (93) There are many agents. • Diluent can inhibit hydrolysis. Its ratio is hydrochloric acid (remove water): Diluent = 1: 100 ~ 1: About 1000 is appropriate · In addition • Form a layer with photocatalyst function * Fill the voids generated on the surface of the layer with smaller particles than voids, and then fix at least one kind of copper, silver, zinc, iron, cobalt, nickel on this layer, Gold palladium and platinum in palladium and platinum are composed of the above-mentioned metals, which are estimated to have a relatively high adsorption portion of the photocatalyst functional layer. There will be no adhesion of alkali metals, calcium, etc. in the dust component, which will eventually be lost. Photocatalyst activity • As a result, the antibacterial effect of photocatalysts will not be affected. # It can also prevent the adhesion of fungi. • In addition, * as the above-mentioned gold tincture, when using silver, copper, and zinc * these metals have antibacterial properties * and are more effective Prevents the adhesion of fungi. In addition, the electron capture effect of the gold tincture can further improve the photoactivity of the photocatalyst layer. The size of the fixed metal * is so large that it can occupy the adsorption portion of the photocatalyst layer in advance. Must be available It is advisable to maintain a low level of tritium activity. • From this point of view, it is advisable to use a few nm to 1 Onm. The method of fixing the above-mentioned metal employment can be using the Kyohara method, heat treatment method, sputtering method, CVD method, etc., among which The photoreduction method eliminates the need for large-scale equipment, is simpler and can be firmly fixed. So it is more suitable. When the photoreduction method is used, it contains at least one type of silver. Copper, zinc, iron, cobalt, nickel, palladium, and platinum. Aqueous solution of gold and ions irradiated with ultraviolet rays. Light containing at least one kind of silver * mesh. Zinc. Iron, cobalt, nickel, palladium, and platinum. The aqueous solution of gold ions can be copper acetate * silver nitrate * copper carbonate, rhenium sulfate. · Gas cuprous gas, cuprous gas, platinum chloride, palladium gas, nickel chloride, zinc nitrate, cobalt gaseous, ferrous chloride, ferric chloride, etc. — — — — — — — — — — — — — · 1111111 ^ · 1111111 (Please read the note on the back first " this page) This paper size is applicable to China S Standard (CNS) A4 (210 X 297) %) -96-Printed by the Consumers Cooperatives of the Central Government Bureau of the Ministry of Economic Affairs 406031 A7 ___B7 ._ five described (94) substantially invention is made by any method can be used, but to a spray coating method or the dip coating will be relatively simple. From the viewpoint of using a small amount of solution, it can be applied uniformly, and the film thickness is easy to control, and it can be applied freely when it is not intended to be applied to the back surface. As long as the light containing ultraviolet rays can be irradiated with ultraviolet rays, it can be any one of ultraviolet lamps, LB lamps, xenon lamps, mercury lamps, and fluorescent lamps. The method of irradiating the light containing ultraviolet rays is preferably to arrange the sample so that it can irradiate the irradiation surface vertically. This can improve the irradiation efficiency. The irradiation time is preferably about 10 seconds to 10 minutes. When the irradiation time is too short, the above-mentioned species of gold can not fully adhere to the highly adsorbed part of the photocatalyst layer, and alkali metals and calcium in the dust component will be attached to cause the loss of photocatalytic activity. When the time is too long, the metal species will be excessively attached. , The light cannot reach the photocatalyst layer sufficiently, reducing the photocatalytic activity. The distance between the sample and the light source is preferably 1 cm ~ 30 cm. When the distance is too close, the entire sample cannot be uniformly irradiated, and the metal species are unevenly attached. When the distance is too far, the illuminance of the irradiated light will be inversely proportional to the distance doubled. It is difficult to attach metal species firmly. The following specific examples illustrate that the voids generated by the photocatalyst layer are filled with particles smaller than the voids. Example 3 1 On a 15 cm square ceramic tile substrate, an ammonia-gel suspension of a butyl sol of 10 1 / ^ 111 with a crystal grain size of 0.0 1 / ^ 111 was spray-coated, and fired at 750 ° C. To form a photocatalyst film. The porosity of the Ti 02 film at this stage is 45%, and the crystal grain size of T i ◦ 2 particles is 0. 0 2 // m. This paper is coated with different crystal grain sizes by spraying method. Applicable to China National Standard (CNS) A4 specification (210X297 mm) " -97-(Please read the precautions on the back before filling this page) Printed by A7 __406031 b7 _ of the Consumer Cooperatives of the Central Bureau of the Ministry of Economic Affairs of the Ministry of Economic Affairs V. Description of Invention (95)

The Sn02 sol was dried at 110 ° C to obtain a sample. The obtained samples were evaluated for deodorization, abrasion resistance, and resistance to staining. The evaluation of the deodorant property was determined by measuring R 3. (L) to be evaluated. The abrasion resistance was evaluated by using a plastic eraser to slide back and forth and comparing its appearance changes. The evaluation indicators are as described above and as shown below. ◎: Unchanged 40 times back and forth. 0: Scratches after sliding back and forth more than 10 times and less than 40 times, the photocatalyst layer (T i 0 2 film) is peeled off. (T i ◦ 2 film) Peel X: Scratches appear after sliding back and forth 5 times or less. The evaluation of the photocatalyst layer (T i 0 2 film) is not easy to be stained. After drying, wipe the ink with ethanol to evaluate the contamination degree, and evaluate according to the following standards. ◎: Can be completely wiped off without leaving traces. ○: Slightly traces left: Gray-black traces are slightly left. X: Black traces are left. The results are shown in Figs. 39 to 46. Figs. 3 to 9 are graphs showing the relationship between the amount of S η 02 added and the resistance to staining. Here, the amount of S η 02 added is represented by the weight ratio of S η 02 to the total weight of the amounts of T i 〇 2 and S η 02. Adding more than 30% S η 02 can significantly improve the resistance to staining. There are three reasons for this. The first paper size is the National Standards of China (CNS) Α4 specification (21 × 297 mm): ---------- installation ------ order ---- --Λ (Please read the notes on the back before filling this page) 40603

A7 B7 Printed by the Shellfish Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (T6 Γ can reduce porosity to less than 20% by adding more than 30% S η 〇2 (Figure 40), the second series The pores with large pore age are reduced due to the addition of SnO2. Figure 41 shows the maximum width of the pores with S added to Sn02. When 30% or more of SnO2 is added, the pore width is reduced to a small pore width of 0.04μιη. Third factor Adding S η 02 to improve the surface roughness, which affects its non-stainability. Figure 4 2 shows the deodorizing properties and abrasion resistance of S η 02. For the anti-Olympic properties, S η The crystallite size of 02 sol changed from 0. 0035 # m to 0.01 # m. There was almost no change, showing excellent results. Also, when the amount of S η 02 was below 50% R 3. It has a good result of more than 80%. When comparing the relationship between the addition of S η 02 and porosity in Figure 39, it can be seen that S η 〇2 when the addition amount is 40% to 50% * Porosity is 10% The following * good deodorization. This situation is very different from the relationship between porosity and deodorization when no interstitial particles are added (Figure 35). The reason is presumed to be Downward, ie * At this time, the porosity can be reduced to less than 10%. However, compared with the 4th one, there are about 0. 02 # ιη of pores left behind. Also, the crystal size of the particles buried in the voids is also 0. 0035 # m. It is larger than the size (number A) of the gas, and the gas channel is not closed under the condition that the particles do not grow. In terms of abrasion resistance, the SnO 2 addition is set to 3 0. When it is above%, the effect is different due to the difference in the crystal size of the S η 〇2 sol. That is, when adding particles below 0.08 Am, it can be improved to ◎ or 〇, but this paper size applies the Chinese national standard (CNS ) A4 specification (210 X 297 mm) ------------ Γ ------ II Order-! I (Please read the note on the back first to write this page) 4060S1 A7 ____B7___ 5 、 Explanation of the invention (97) 0. 0 1 // The addition effect will not be seen when it is m. ^ The following facts are learned from the above experiments. (Please read the precautions on the back before filling this page) (1) Form T on the substrate For i 02 film, when particles smaller than the void (S η 02 sol) are added to the voids formed on the surface of the film, the stain resistance is improved. (2) For the total weight of Ti〇2 and Sn〇2i, When the amount of Sn02 added is 30% by weight or more, it is not easy to stain and improve wear resistance. (3) For the total weight of 1'102 and 31102, the amount of Sn02 added is 50% by weight or less 04 / zm 以下 不 不 沾 staining when the porosity is below 20% and the widest width of the pores is below 0.04 / zm. Example 3 2 Printed by the Consumers' Cooperative of the Central Bureau of Standards and Assistance of the Ministry of Economic Affairs-The side of the urinal that is not exposed to light is set to form an anatase-type D02 film, and the field test is performed for 2 weeks. Compared with those that do not form an anatase T i 02 film. As a result, they will turn yellow due to attached fungi and urine scale. However, ordinary toilets are not easy to remove dirt with a brush. However, toilets with an anatase-type T i 0 2 film formed on the side can be used to remove yellow urine scales. Since this side is not exposed to light, it can be seen that it is not due to the photocatalyst effect of the anatase T i 02 film, but because the surface is formed with a crystalline anatase T i 02 film that does not easily adhere to dirt. Available results. This paper size is applicable to China National Standards (CNS) A4 Washing (210X297 mm) -100-Printed by Shellfish Consumer Cooperatives, Central Standards Bureau, Ministry of Economic Affairs 406031 at ______ B7___ V. Description of Invention (98) Example 3 3 On the surface of a 15 cm square tile, a si 02-A i? 203-N a / K2〇 glass material was coated, and then sprayed on the surface, with a crystal size of 0.01 Ti02 sol, an ammonia-gel suspension, It was fired at 75 ° C. to obtain three kinds of thin films of 0 2 / zm, 0.4 # m, and 0.8 with a film thickness of m. The porosity of the Ti02 thin film at this stage is 45%, and the crystal size of the Ti02 particles is 0_02em. Then, a dry coating was used as a carrier coating method on the cooled sample using a patch coating method. A mixture of titanium tetraethoxide, 36% hydrochloric acid, and ethanol was mixed and dried. The coating amount is 40 to 50 // g / cm2 in terms of Ti02. It was then fired at 500 ° C for 10 minutes. This titanium alkoxide coating step is repeated 1 to 5 times. The obtained samples were evaluated for deodorant properties, antibacterial properties, abrasion resistance, and stain resistance. The antibacterial system was tested using E. coli (Eschericia coli W3110 strain). On the top surface of the multifunctional material sterilized with 70% ethanol in advance, 0.15m ^ (1 ~ 50,000 CFU) of bacterial solution was dropped, and placed on a glass plate (100 X 1 00), which was closely attached to the top layer of the substrate. Surface "as the sample" After irradiating white light (3500 candlelight) for 30 minutes, wipe the bacterial solution on the irradiated sample with sterilized gauze, and recover it in 10mj? Physiological saline to determine the survival rate of the bacteria and evaluate it. Standards ++, ++, +, all are the same as above. Under the above conditions, the deodorizing property is R 3. (L) is 80% or more, and the antibacterial property is +++. This paper size applies to 11 Chinese standards (CNS) A4 scale (210X297 mm) ^ '-101-(Please read the precautions on the back before filling out this page) 406031 A7 _ B7 _ V. Description of the invention (99) Not easy The stain resistance (Fig. 44) and abrasion resistance (Fig. 45) are related to the number of times the titanium alkoxide is applied and T i ◦ 2 film thickness. The more times the titanium alkoxide is applied, the more it will improve its resistance to staining and abrasion. In addition, the thinner the film thickness of T i 02 is, the less the number of times of titanium alkoxide coating can be used to improve its stain resistance and abrasion resistance. The reason is presumably that the porosity of the surface of the Ti02 layer can be reduced by the titanium alkoxide coating as one of the reasons. Fig. 46 shows the relationship between the porosity of the Ti02 layer surface, the number of times of titanium alkoxide coating, and the thickness of the Ti02 film. The surface porosity of the Ti 〇2 layer is reduced as the number of titanium alkoxide coatings increases, and the thinner the T i 〇2 film, the more the porosity is reduced under the same number of titanium alkoxide coatings. This relationship Corresponds to the relationship between the number of times of titanium alkoxide coating and the thickness of T i 0 2 and the resistance to staining and abrasion resistance. In particular, the stain resistance is the same as in Example 31, and the porosity is 20% or less. -Example 3 4 Printed by the Shellfish Consumer Cooperative of the Central Bureau of Standards and Quarantine of the Ministry of Economic Affairs (please read the precautions on the back before filling out this page). Coat the surface of a 15 cm square tile with S i 02_ Aj? 2o3 — N a / K20 frit, followed by spraying on the surface, an ammonia-gel suspension of crystalline size 0.01 / zm 1'102 sol, fired at 750 ° C for 2 hours. 〇2 # m。 The porosity of the Ti02 film at this stage is 45%, and the crystal size of the Ti02 particles is 0. 〇2 # m. Then, a mixture of titanium tetraethoxide, 36% hydrochloric acid, and ethanol was mixed with the dry air as a carrier by the pouring method on the cooled sample with dry air as a carrier, and the coating amount was dried. It is 40 ~ 50 # g / cm2 in terms of T i 0 2. It was then fired at 500 ° C for 10 minutes. This paper was scaled to the Chinese National Standard (CNS) A4 (210X297 mm) -102-Printed by the Shelley Consumers Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 406031 _______________________ ζΑ l 5. Description of the invention (lfl0) • Repeat this titanium enzymatic coating step three times, and then apply 1 reset% silver nitrate aqueous solution on the sample. • Light reduction (light source system 2 OW B LB lamp * distance from the light source to the sample) 10 cm, irradiation time 30 seconds) Sample obtained • The amount of silver carried on the surface of the sample is 0. c m58 * The particle size of silver is about 4 On m on average. Measure the antibacterial property and long-term use of the obtained sample. Antibacterial properties after the long-term use: The antibacterial properties after long-term use were tested as follows. First, the surface of the obtained sample was thoroughly washed with acetic acid and so on. Water, immerse the sample in it for one month. • After removing the sample, wash it with ethanol, and then sterilize the top surface of the multifunctional material with 70% ethanol. Then place 0. 15mJ? (L ~ 50000CFU) of coliform liquid. In glass plate ( 1 0 0 X 1 0 0) * Adhere to the top surface of the substrate as the sample. • After irradiating the white light (3 500 candles for 30 minutes), wipe the bacterial solution on the irradiated sample with sterilized gauze. Recovered from physiological saline solution (10 m) 2, and determined the survival rate of bacteria * The evaluation index is the same as the antibacterial test of Example 3. For comparison, the test of Example 3 3 was also tested. Results • Initial antibacterial In terms of properties • The sample produced in this example is also + + + like the sample produced in Example 3 3 • However, after one month, the antibacterial properties of the two are different • That is, the sample produced in Example 3 3 is antibacterial Reduced to +, and the sample produced in this example still maintains the initial +++. • This may be due to the adhesion of silver on the highly adsorbed part of the T i 〇 »layer surface. Due to the location · The paper size applies to the Chinese National Standard (CNS) A4 specification (210 X 297 g) — — — — — --- IIIII-— — — I —-- I I ---- I < Please (Please read the note on the back first and write this page) Printed by Shellfish Consumer Cooperative, Central Bureau of Standards, Ministry of Economic Affairs 406031_b7 _Five Description of the invention (101) From the above description, it is known that 'a layer having a photocatalyst function is formed on the surface of a substrate, and the voids generated on the surface of the layer are filled with particles smaller than the voids. Therefore, compared with conventional photocatalyst films, The amount of voids and the size of the voids become smaller, and the smoothness of the surface is better. It can maintain good deodorization, improve film strength under antibacterial properties, and it is difficult to attach polymers, dust, and fungi constituting dirt components. Next, an example of the use of soda glass with a lower melting point as a substrate will be described. That is, when a photocatalyst film is to be formed on the surface of a low-melting-point substrate, at the temperature at which the photocatalyst film is formed, the substrate begins to soften, and the formed photocatalyst film is buried in the substrate, so light cannot reach the photocatalyst layer. , Can not play the photocatalyst function and other defects. For this reason, in this case, the photocatalyst particles are fixed by coating a layer such as S i 0 with a higher melting point than the substrate. Examples will be specifically described below. Example 3 5 Before the titanium oxide was coated on the soda glass, a silica coating was applied on the surface of the soda glass. On the surface of a 10 cm square soda glass, apply silicon dioxide as follows. Tetraethoxysilane, 3 6% hydrochloric acid, pure water, and ethanol were mixed in a weight ratio of 6: 2: 6: 86. It will become hot at this time, so let it stand for 1 hour. It is then cast on soda glass. Next, a coating liquid is prepared. The coating solution was prepared by mixing titanium tetraethoxide and ethyl alcohol in a 1: 9 (weight ratio) solution, and adding 10% by weight of 3% 6% hydrochloric acid to titanium tetraethoxide. The amount of 3 6% hydrochloric acid added here is the size of this paper. Applicable to China National Standard (CNS) A4 (210X297 mm)-104-(Please read the precautions on the back before filling this page) 406031 A7 B7 Central Ministry of Economic Affairs Printed by the Zhuhai Bureau Shellfish Consumer Cooperatives 5. Description of the Invention (102) For titanium tetraethoxide, it is 1% to 30% by weight, preferably 5% to 20% by weight. When an appropriate amount of hydrochloric acid is added, cracking during post-drying 'firing can be prevented. That is, when the amount of hydrochloric acid is too small, cracking cannot be sufficiently prevented. When the amount of hydrochloric acid is too large, the hydrolysis of the hydrochloric acid reagent increases, which accelerates the hydrolysis of titanium tetraethoxide, making it difficult to obtain a homogeneous coating film. Next, 'the solution was cast on the surface of the soda glass substrate in dry air. The dry air referred to here is not completely air-free, but refers to those with less water than ordinary air. At this time, when coated in ordinary air without drying treatment, titanium tetraethoxide will be hydrolyzed by the moisture in the air. When the amount of coating film is too large at one time, it is easy to dry and burn it in subsequent projects. When cracked. It is also difficult to control the amount of coating film when accelerating hydrolysis. To prevent cracking, the amount of titanium oxide supported at a time is preferably 1000 M g / cm 2 or less. The amount of titanium oxide carried at this time was 45 / zg / cm ^, and then dried in a dry air for 1 to 10 minutes to form a titanium oxide film. In this step, titanium oxide can be formed according to the following principles. Here, the starting material is titanium tetraethoxide, which is one of the titanium alkoxides (it is also possible to form titanium oxide by using other titanium alkoxides). The main reason is that the titanium tetraethoxide will cause hydrolysis reaction with water in dry air during the coating process to form titanium hydroxide compound. In addition, dehydration condensation reaction occurs during drying, and irregular titanium oxide is formed on the substrate. The titanium oxide particles produced at this time are those with high purity of about 3 to 1 5 nm. For this reason, compared with titanium oxide obtained by other manufacturing methods, this titanium oxide can be sintered at low temperature β at 300 ° C ~ 500 ° C. The composite material obtained by the above-mentioned method is a much more functional material. Repeat as needed from the coating of titanium tetraethanolate to firing (please read the precautions on the back before filling this page) This paper size is applicable to China National Standard (CNS) A4 (210X297 mm) -105- 406031 A7 B7 5. In the step (103) of the invention description, a thick titanium oxide is obtained. The thus-obtained sample was evaluated for its anti-odor properties and bacteria characteristics. Results are shown in Table 19. Abrasion resistance, resistance (please read the notes on the back before filling out this page) Printed by the Central Consumers ’Association of the Ministry of Economic Affairs, printed on paper sizes, using the Chinese National Standard (CNS) A4 (210X297 mm) -mR -106 Printed by the Consumer Cooperatives of the Central Bureau of Procurement, Ministry of Economic Affairs 406031 V. Description of Invention (104) (Table 1 9) Firing Temperature (.0 Abrasion Resistance R3 (L) r3 (d) Antibacterial (L) Antibacterial (D) 300 ◎ 0% 0% —-400 ◎ 60¾ 0¾ +-500 ◎ 60¾ 3f〇 + One (Please read the precautions on the back before filling in this purchase)

'1T This paper size applies to China National Standards (CNS > Α4 size (210X297mm) ~ 6. φ · 40G〇J! 4-. A7 _ B7 5. Description of the invention (105) The deodorant property is placed on the sample The initial concentration of methyl mercaptan was adjusted to 2 ppm in a cylindrical container with a diameter of 26 cm x 21 cm. * Irradiated with a 4W BLB fluorescent lamp at 8 cm from the light source. The methyl mercaptan removal rate (R 3. )), And the rate of removal of methyl mercaptan (R 30 (D)) for 30 minutes after being exposed to light. The antibacterial properties are tested using coliform (Escherichia coli W3110 strain). The top material of the functional material was dripped with 0.15mJ2 bacterial solution (1 ~ 50000CFU), placed on a glass plate (1 0 Ox 1 00), and held close to the top surface of the substrate as a sample. Irradiated white light (5200 Candle light) After 30 minutes, wipe the irradiated sample with the sterilized gauze and keep the bacterial solution of the sample kept under the shading condition * recovered in 1 〇ιηί physiological saline * to find the survival rate of the bacteria. +, ++, +, the same series as above · Excellent sliding test at 3 0 ° C firing temperature As a result, R30 (L) is 0%. This may be caused by the uncrystallized anatase from anatase. In the synthesis experiment, the anatase temperature can be confirmed by X-ray at 4 0 eC. The test also has a good result of ◎, and R30 (L) can also be improved to about 60%. Also, the antibacterial property can also be +. Also, the sliding test result of ◎ can also be obtained at 500 ° C. However, R 30 (L) can also be raised to about 60%. Also, at the temperature of 550 eC when the temperature is raised. China National Standard (CNS) A4 Specification (210x297 mm) _ ----------- i.Packing—— (谙 Read the notes on the back first and write this page> i- »· --line Printed by mir. A7 B7 406031, Shelley Consumer Cooperative of the Intellectual Property Bureau of Economic Village, V. Description of Invention (108) Example 3 6 In order to improve the photocatalyst characteristics of the sample obtained in Example 3 5 of the Fund, it supports metal particles and photocatalyst Reduction reaction simultaneously with oxidation reaction • Without reduction reaction, the electrons are not consumed and the particles are charged and the oxidation reaction cannot proceed. Example 1 The reason why R3〇 (L) is only 60% may be because of this. To prevent this from happening, carry metal particles on titanium oxide particles and remove electrons to prevent electrification. Gold particles can be carried as follows: Apply gold salt solution to photocatalyst, and irradiate it for 20 minutes from 20W BLB fluorescent lamp for 20 minutes. Metal salt solution is 1% reset ethanol solution of copper acetate when carrying copper, and 1% by weight of silver nitrate when silver is used. Ethanol / water = 1/1 mixed solution • Washed after irradiation • and dried • The use of an ethanol-containing solution instead of an aqueous solution of gold tincture here is because the metal salt aqueous solution has good wettability to the sample. Deodorant properties • Abrasion resistance properties * Antibacterial properties • Results are shown in Table 20 • Also • The firing temperature sample was obtained using only 500 eC · -------- 11 --- ^ i — II ----- --- 11-< Please read the note on the back first to write this page) Printed by Shelley Consumer Cooperatives, Bureau of Intellectual Property, Ministry of Economic Affairs, Paper size Applicable to Chinese National Standard (CNS) A4 (210 x 297 mm) A7 406031 B7 V. Description of the invention (107) (Table 20) Firing temperature (. 〇Abrasion resistance R3〇 (L) R30 (D) Antibacterial property (L) Antibacterial property (D) 500 ◎ 98¾ 98¾ +++ ++ (Please read the precautions on the back before filling out this page) Central Bureau of Standards, Ministry of Economic Affairs The paper size printed by the employee consumer cooperative is applicable to the Chinese National Standard (CNS) A4 (210X297 mm) -110-406031 A7 __B7 _ V. Description of the invention (108) The sliding test shows good results. In addition, R30 (L) was significantly increased to 98%. Antibacterial properties are also + + +. Comparative Example 3 7 In Examples 3 and 5, the same conditions were applied except that no silicon dioxide was applied. That is, titanium oxide was coated on a 10 cm square soda glass. The results are shown in Table 21. (Please read the notes on the back before filling out this page)

, 1T Printed by the Central Standards Bureau of the Ministry of Economic Affairs, Consumer Cooperatives. The paper size is applicable to the Chinese National Standard (CNS) A4 (210X297). -111-406031 V. Description of the invention (109) A7 B7 (Table 2 1) Burned Temperature (.0 Abrasion resistance R30 (L) R3〇 (D) Antibacterial (L) Antibacterial (D) 300 ◎ 0¾ 0¾--400 ◎ 0¾ 0¾--500 ◎ 0% 0%-_ (please first Read the notes on the back and fill out this page)

、 1T The printed paper of the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs shall be printed in accordance with the Chinese National Standard (CNS) A4 (210X297 mm) -112-Printed by the Central Government Bureau of the Ministry of Economic Affairs of the Bayer Consumer Cooperative 406031 at B7 Description of the invention (110) From Table 21, 300, 0, 400. <: 500. 0 all obtained good results in the sliding test, and R30 (L) was 0% even after the titanium tetraethoxide coating film was repeatedly applied 10 times to the firing step. The antibacterial properties are all the same. Why R3Q (L) is not good at 300 ° C, it is possible that the titanium oxide is still unable to crystallize from amorphous titanium oxide to anatase. As for 400 ° C, at 50 ° C, it should have crystallized from amorphous titanium oxide to anatase. R30 (L) cannot be explained for the above reasons. The reason is that the soda glass of the substrate is softened, so the titanium oxide film is buried in the glass. From the above description, it can be seen that even if it is a base material with a relatively low melting point, a high melting point layer can be interposed between the photocatalyst layers, and it can be produced as a multifunctional material with deodorant and antibacterial properties. Next, a preferred embodiment in which a photocatalytic effect is imparted to a plastic surface having poor heat resistance will be described. Basically, the material of the substrate is not limited to plastics with poor heat resistance, but can also be ceramics, ceramics, metals, glass, or composites of these materials. The shape of the substrate can be any shape, and it can be a ball. , Cylindrical objects, cylindrical objects, tiles, wall materials, floor plates and other plate-shaped objects, can also be sanitary ceramics, vanity, bath, sink, toilet seat and other complex shapes. The surface of the substrate may be porous or dense. The type of binder may also be thermoplastic materials such as inorganic glassy, thermoplastic resin, solder, and thermosetting materials such as fluororesin, siloxane resin, and sand resin. However, it must be irradiated with ultraviolet rays in the post-process. The paper size is applicable to China National Standard (CNS) A4 specification (210X297 mm) -----------, installed— (Please read the note on the back first Fill in this page for the item >

、 1T -113-40GQ31 A7 _____B7 5. Description of the invention (111) Therefore, it is still appropriate to use light-resistant materials. Again, only 3 0 0. (: For heat treatment at the following temperature, because the case is extremely useful, thermoplastic materials are materials that can be softened below 300 ° C, and thermosetting materials are preferably materials that can be hardened below 300 ° C. The material-based thermoplastic materials that can satisfy this condition are boric acid-based glass, solder, acrylic resin, etc., and the thermosetting materials are fluorine-containing resin, siloxane resin, silicone resin, etc. Coating these adhesives The method of layering on the substrate, when using thermoplastic materials, spraying method, roll coating method, dip coating method, etc. can be used. Any method can be used. It can also be other methods. Moreover, the binder components may not be prepared. The binder composition is the same when forming materials. For example, when the binder is made of inorganic glass, the coating can be a suspension of inorganic glassy composition such as granular, frit, block, powder, etc. It can also be a mixed form containing a salt constituting a metal component. When the binder is a resin, a resin solution of that composition can also be used, or it can be other.-Coat the photocatalyst particles on the binder layer and dry it. Coated Bonding layer to evaporate moisture, etc. At this time, the drying method can be placed at room temperature, or it can be heated with the substrate, etc. Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs {Please read the note on the back first Please fill in this page again) Before coating the photocatalyst particles on the adhesive layer, you can also use a softer temperature than the substrate on which the adhesive is applied, and the adhesive layer can be changed to the adhesive when the product is completed It can be heat treated at a softening temperature. When the photocatalyst particles are formed on the binder layer by this method, the binder layer can be made smoother, and a small amount of the photocatalyst particles can be used to fully exert the effect. The method of using a thermosetting material, mixing a binder and a hardening agent to coat the substrate, may be, for example, adding a diluent to a thermosetting resin, and then adding this paper to the standard of China National Standards (CNS) Λ4 ( 210X297 mm) -114-406031 A7 ____B7 ._ 5. Description of the invention (112) Add a hardener, and apply the resulting mixture to the surface of the substrate. The viscosity for thickening is preferably more than 105 poise and less than 105 poise. The photocatalyst particles can be recoated with a high viscosity of more than 105 poises, and the photocatalyst particles can be buried so as not to be completely buried in the adhesive layer. When the photocatalyst is less than 105 poises, A part of at least the lowermost layer of the particle layer is buried in the lower layer of the binder. The method of coating the photocatalyst particles on the surface of the adhesive layer basically can be a method of applying a suitably treated starting material on the surface of the adhesive layer. The starting material is preferably a sol suspension of a photocatalyst-constituting substance, and other photocatalysts may be used to form a suspension of fine particles. In order to obtain a uniform coating film, a surface treatment agent such as a dispersant must be added in any method so that the photocatalyst composition in the suspension liquid does not aggregate. When applying to the adhesive layer, a spraying method, a roll coating method, a dip coating method, or the like may be used, and any method may be used, and other methods may also be used. The printed policy of the Central Government Bureau of the Ministry of Economic Affairs, Shellfish Consumer Cooperative (please read the precautions on the back before filling this page) The thickness of the photocatalyst layer embedded in the adhesive layer, in terms of the strength of the bond between it and the substrate, The thickness of the photocatalyst layer is preferably more than 1/4. The thickness of the photocatalyst layer can be obtained by analyzing the constituents of the photocatalyst particles in the cross-section direction, such as E PMA. The amount of the constituent elements of the photocatalyst particles is about a certain upper layer, and the amount of the constituent elements of the photocatalyst particles gradually The buried portion is formed between the depth from which the depth is reduced to the amount of the component elements constituting the binder. The surface treatment agent attached to the photocatalyst is mainly composed of the ingredients used in the sol as a starting material for dispersing the photocatalyst particles. Specifically, the Chinese paper standard (CNS) A4 size (210 X 297 mm) can be used for this paper size. -115-406031 ___ B7 ___ 5. Description of the invention (113) Isopentyl alcohol, trimethylolpropane , Triethanolamine, trimethylolamine, silicone resin, alkyl chlorosilane, etc. Those who contain light with a wavelength of 1. 7m w / cm2 or more and 390nm or less as the light source can be a LB fluorescent lamp, an ultraviolet lamp, a germicidal lamp, a xenon lamp, a mercury lamp, and the like. The reason why light with a wavelength of 1. 7 m W / cm 2 or more and 390 nm or less is necessary is that dispersant components such as silicone resins have a certain degree of photo-corrosion resistance, so it must be unable to decompose to such a degree of ultraviolet intensity. At this time, the shorter the wavelength of the ultraviolet rays, the faster the dispersant can be decomposed. However, depending on the type of the binder, the binder may be decomposed and it is also harmful to the human body. Therefore, it is inferred from this point to be more than 250nm. When the illuminance is about 3 m W / cm2, the decomposition speed can be increased due to the increase in illuminance. However, increasing the illuminance will not increase the decomposition speed relatively, so it is only necessary to use 3 m W / cm 2 or less. The above steps are shown schematically in Figures 4 to 7. The lower layer of the substrate 1 having a part of the photocatalyst layer 2 interposed therebetween is buried in the adhesive layer 6. Printed by the Consumers' Cooperatives of the Central Bureau of Standards, Ministry of Economic Affairs (please read the precautions on the back before filling this page) 6 a is a layer formed by surface treatment agents that hinder photocatalytic activity. UV is a light beam with a wavelength of 1. 7 m / (; 1112 to 39〇11111). Next, a layer composed mainly of photocatalyst particles 3 and thermosetting resin 6 is formed on the surface of the substrate, and ultraviolet rays are similarly irradiated to Those who expose the photocatalyst layer will be explained (refer to Figures 4 to 8). This method also uses thermosetting resin to firmly fix the photocatalyst particles 3 on the substrate, and contains 1. 7m W / cm2 or more 39 by irradiation. The paper size of light with a wavelength below ηιτι applies to the Chinese National Standard (CNS) A4 (210X297 mm) -116-406031 at B7____ 5. Description of the invention (114) Light, photocatalyst is generated on the light irradiated part of the surface of the photocatalyst particles The reaction, the surface treatment agent and the thermosetting resin in the direction of the light source are preferentially decomposed * gasified, and the photocatalyst particles are exposed to the outside air, and the full photocatalytic activity can be obtained. In addition, the formation is mainly caused by the photocatalyst particles and the thermosetting resin. The method of layer formation can be, for example, sequentially adding a thermosetting resin, a diluent, a hardening agent to a sufficiently dispersed photocatalyst sol suspension, and applying the obtained mixed solution to The surface of the substrate is formed by heat treatment. Here, the sol in the photocatalyst sol suspension has a crystal grain size of 0. 0 5 μm or less, more preferably 0.001 μm or less. The smaller the photocatalyst activity is, the better the sol system in the photocatalyst sol suspension is as monodisperse as possible. The better the dispersibility, the more uniform coating film can be obtained. The thermosetting resin system used here is the best It is suitable for white light or general fluorescent light with horizontal light resistance. This resin is more resistant to use when used. Therefore, siloxane resin and fluorine-containing resin are the best. Printed by Industrial and Consumer Cooperatives (Please read the precautions on the back before filling this page) Thinner can reduce the viscosity of the mixed solution of photocatalyst sol and thermosetting resin, making the mixed solution easier to apply on the surface of the substrate. Adder. Therefore, the diluent used is basically a solvent that can achieve this purpose. For example, water, ethanol, propanol, etc. can be used. The coating method of the mixed liquid can be the above spraying method, dip coating method, roller Any of the methods of the "spin coating method" may be used, and other methods may also be used. Heat treatment usually uses electric furnace, gas furnace, vacuum furnace, pressure furnace, etc., but it is not limited to this. (CNS) A4 secret (21〇 × 297 male thin) ~ '-117-406031 V. Description of the invention (115) The main surface of the substrate can be formed with a thermosetting resin or a photocurable resin layer (intermediate layer C). A layer made of photocatalyst particles and thermosetting resin (refer to Figure 49). In this method, even if there is unevenness on the substrate, the heat can be placed between the substrate and the photocatalyst. The curable resin layer or the photocurable resin layer forms a smooth surface before coating the photocatalyst layer, and is easily formed into a uniform photocatalyst layer. In addition, the thermosetting resin layer or the photocurable resin layer disposed between the substrate and the photocatalyst layer can be sufficiently combined with the substrate, so that even if the surface of the substrate has unevenness, the photocatalyst can be formed thinly. The layer formed by particles and thermosetting resin can simultaneously concentrate photocatalyst particles near the surface of the substrate, and can further shorten the time for subsequent processes to irradiate light with a wavelength of less than 1. 7 m W / cm2 and less than 3 0 0 nm. In addition, since the photocatalyst particles and the thermosetting resin are formed on the upper layer, after the process and after use, it is enough to be decomposed, and the ultraviolet rays with the strength of vaporization will not reach the thermosetting resin layer or the photocurable resin disposed in the middle. Layer, so you can choose the thermosetting resin in this part. For example, you can choose a cheap epoxy resin with low cost, and you can also choose a colored resin for decorative effects. Printed by the Central Standards Bureau of the Ministry of Economic Affairs, Shellfish Consumer Cooperative (please read the precautions on the back, and then fill out this page). Here, the method of forming a thermosetting resin layer placed between the substrate and the photocatalyst layer can be cured by heat A diluent is added to the resin, followed by a hardener, and the resulting mixed solution is coated on the surface of the substrate. When the photocatalyst layer is a photocurable resin, it may be irradiated with ultraviolet light instead of heat treatment. Here, the diluent can reduce the viscosity of the mixed liquid and make it easier to add the mixed liquid to the surface of the substrate. Therefore, the diluent used is basically as long as it can achieve the paper size of this table, using the Chinese National Standard (CNS) A4 specification (210X297 mm): — ~~ -118-406031 a? ___ _B7 _ V. Description of the invention ( 116). For example, water, ethanol, propanol and the like can be used. Moreover, as shown in FIG. 50 (a) (b), the voids formed in the photocatalyst layer exposed on the surface of the substrate according to the method described above can be filled with particles smaller than the voids (void particles: 4). Abrasion resistance is more ideal. The size of particles smaller than the void may be substantially smaller than the average value of the generated porosity or unevenness. The amount of particles smaller than the void is such that the porosity added to the surface can be less than 20%. Therefore, it is not easy to stain. Specific examples are given below. Example 3 8 Consumption cooperation printed by employees of the Central Bureau of Standards and Quarantine of the Ministry of Economic Affairs (please read the precautions on the back before filling in this page) On the surface of a 10 cm square alumina substrate, coated on the average particle size. 〇1 Mm titanium oxide sol (those treated with an amine-based dispersant) Sequentially add 10% by weight of a siloxane resin, a diluent, and a hardening agent to the mixed solution obtained by firing at 150 ° C for comparison Sample. This sample was irradiated with various light sources for a predetermined period of time to obtain a sample, and the deodorant characteristic R 3 when the obtained sample was irradiated with light was evaluated. (L). The deodorizing property R30 (L) when it is irradiated here means that the sample surface is placed 8 cm away from the light source (BLB fluorescent lamp 4W) in a 11 liter glass container, and the initial concentration is injected with methyl mercaptan gas. It is 3 p pm and the rate of change in concentration after 30 minutes of light exposure. The results are shown in Table 2-2. This paper size is applicable to China National Standard (CNS) A4 (210X297 mm) -119-406031 ay ____ B7 V. Description of the invention (117) (Table 2 2) Light source ultraviolet intensity (W / cm2) Exposure time (say) R 3 〇 (L) (%) No irradiation—-30 BLB 0.3 7 32 BLB 1. 69 5 52 UV lamp 2. 0 3 74 UV lamp 2.0 1 82 I -------- install ---- -Order (please read the precautions on the back before filling this page) Printed by the Central Laboratories of the Ministry of Economic Affairs, Consumer Work Cooperatives, UV deodorization characteristics can reach more than 50% when the UV intensity is 1.69m W / cm2 or more. At 2 m W / cm 2 or more, the deodorizing property R30 (L) can be a good effect of 70% or more. Good results are obtained when the ultraviolet intensity is 1.69m W / cm2 or more. The photocatalyst reaction occurs on the light-irradiated part of the surface of the photocatalyst particles. The surface treatment agent and the thermosetting resin in the direction of the light source are preferentially decomposed. Gasification, exposing the photocatalyst particles to the outside air, can obtain full photocatalytic activity. Example 3 9 A 10 cm square alumina substrate surface coated with a solution of a diluent and a hardener added to a siloxane resin, dried at room temperature for about 6 hours, and then coated at an average particle diameter of 0. 0 1 // ΙΠ Titanium oxide sol (with amine-based dispersant _ f Chinese paper standard (CNS) A4 size (210X297 mm) is used for this paper size) 406031 A7 B7 _ V. Description of the invention (118) (Please read the back first For the matters needing attention, please fill in this page again) Disperse treatment person) Add 10% by weight of siloxane resin, diluent, and hardener to the mixed solution obtained by firing at 150 ° C for comparison sample = this sample Specimens were irradiated for a predetermined period of time to obtain samples, and the deodorant characteristics R3Q (L) of the obtained samples when light was irradiated were evaluated. The results are shown in Table 2-3. (Table 2 3) UV intensity of light source (W / cm2) Irradiation time (say) R 3〇 (L) (¾) No irradiation-one 34 BLB 0. 3 7 38 BLB 1.69 5 61 UV lamp 2.0 3 82 UV lamp 3.0 1 84 The results of printing by the Shellfish Consumer Cooperative of the Central Sample Bureau of the Ministry of Economic Affairs show that the deodorization characteristics can reach more than 50% when the UV intensity is 1.69m W / cm2 or more, and the deodorization characteristics can be R3 (L) when the 2m W / cm2 or more It is a good effect of more than 70%. Good results can be obtained when the ultraviolet intensity is above 1.69m W / cm2, because the photocatalyst reaction is generated on the light-irradiated part of the surface of the photocatalyst particles, so that it can be preferentially decomposed. The gasification cannot be gasified by heat treatment. The surface treatment agent attached to the light-irradiated surface on the surface of the photocatalyst particles, as a result, the size of the paper can be adapted to the Chinese National Standard (CNS) A4 specification (210X297 mm) ~ -121-A7 B7 406031_ V. Description of the invention (119) Caused by the exposure of the media particles to the outside air (please read the precautions on the back before filling this page) Example 4 0 Add a thinner and harden the surface of a 10 cm square alumina substrate to a siloxane resin The solution of the agent was dried at room temperature for about 6 hours, and then coated on an average particle size of 0.1 OlMin titanium oxide sol (those treated with an amine dispersant) and sequentially added 10% by weight of a siloxane resin and a diluent. 2ym 约。, The mixture obtained by the hardener, fired at 1 50 ° C "at this stage, the average particle void size of the surface of the material is 0.1 ~ 0. 2ym about. It irradiates light with an ultraviolet intensity of 2 m W / cm2 (ultraviolet lamp). After printing for 3 days, it is confirmed that R3O (L) can be 80% or more after printing by the Central Standards Bureau of the Ministry of Economic Affairs. The sol is 70% by weight and has an average particle size of 0.035vm. The osmium oxide sol is dried at 110 ° C to obtain a sample. This sample also has a ruler 3. (L) is a good result of 81%. In addition, when using a plastic eraser to perform a sliding-dynamic friction test, the sample without the addition of thorium oxide was scratched less than 5 times, and the titanium oxide was peeled off. The sample with the thorium oxide added did not change at least 10 times. From the above, it can be seen that when the voids formed on the surface of the material are filled with hafnium oxide particles having a smaller size than the voids, it is confirmed that the abrasion resistance can be improved. From the above description, it can be seen that even when a layer having a photocatalytic effect is formed at a low temperature of 300 ° C or lower, a material having good photocatalytic activity can be provided. Next, the explanation is the same as the purpose of irradiating UV to expose, but different methods can also provide a method of multifunctional materials that can be fired at a low temperature below 300 ° C and also have sufficient photocatalytic effect. This paper size is applicable to China National Standard (CNS) A4 (210X297 mm) 122 406031 A7 B7 ___ V. Description of the invention (120) (Please read the precautions on the back before filling this page) This method uses water and heat Method, sulfuric acid method, etc., before adding a good treatment agent such as a dispersant, a surfactant, or the like to the titanium oxide sol, the metal fine particles are fixed on the surface of the titanium oxide sol. Here, the metal fine particles refer to metal fine particles that can capture electrons when titanium oxide is irradiated with light to generate electrons and positive holes when carrying titanium oxide. Specifically, silver, copper, platinum, palladium, nickel, iron, cobalt, etc. 》 The method of fixing metal particles on the surface of titanium oxide sol is the simplest method. The titanium oxide sol used here is preferably produced by a hydrothermal method or a sulfuric acid method, but is not limited thereto. The sulfuric acid method referred to herein is a method for synthesizing titanium oxide according to the following steps. First, ilmenite is reacted with sulfuric acid, so that titanium, iron and the like become soluble water-based sulfates. Water extraction is used to produce titanium and iron sulfate solutions as the main components. Second, insoluble suspended matter such as Si 02 is removed. It is then cooled to 10 ～ 15 ° C printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs to precipitate iron sulfate and separate and remove it. Secondly, the titanyl sulfate in the solution is hydrolyzed to form hydrous titanium oxide. Using a pressure device such as a hot press, hydrothermally treat the obtained hydrous titanium oxide in high-temperature and high-pressure water (usually at a saturated steam pressure of 110 ° C to 200 ° C) to make it crystallize to obtain a titanium oxide sol. In addition, hydrothermal method refers to the use of pressure devices such as autoclaves to hydrothermally treat titanium tetrachloride, titanium sulfate, etc. in high temperature and high pressure water (usually under saturated steam pressure of 110 ° C to 200 ° C). Source, a method of obtaining titanium oxide sol by hydrolysis. The method of fixing metal particles on the surface of titanium oxide sol by photoreduction method, specifically as shown below. First, the titanium oxide sol suspension prepared by hydrothermal method or sulfuric acid method is used as the acid paper. The Chinese national standard (CNS) ) A4 specification (210X297mm) — '— -123-A7 B7 ^ (/ G031 V. Description of the invention (121) (Please read the precautions on the back before filling this page) Properties or alkaline. Titanium oxide The point system is pH 6.5, which is easy to agglomerate when it is neutral. In addition, it is suitable to use ammonia when it is adjusted to be alkaline. Because alkali metals such as sodium and potassium are easily attached to titanium oxide, if these metals first occupy titanium oxide The active site will reduce the photocatalytic activity, and at the same time, it will prevent silver, copper, platinum, palladium, nickel, iron, cobalt, etc. from attaching to the active site of titanium oxide. Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs. It is about the same metal salt solution as the titanium oxide sol suspension. It is mixed with the titanium oxide agglomerate suspension and irradiated with ultraviolet rays to fix the metal. If necessary, it can also precipitate excess metal. The term "metal salt solution" used herein refers to a salt and a solvent of a metal containing a titanium oxide supported on the titanium oxide, which is irradiated with light to generate electrons and a metal that can trap electrons, and more specifically refers to a metal salt solution and a solvent. Solution containing salts and solvents of silver, copper, platinum, palladium, nickel, iron, cobalt, etc. Salts containing silver, copper, platinum, palladium, nickel, iron, cobalt, etc. can be silver nitrate, copper acetate, copper carbonate, sulfuric acid Copper, cuprous chloride, copper chloride, platinum chloride, palladium chloride, nickel chloride, cobalt-chloride 'ferrous chloride', ferric chloride, etc. In addition, the solvent can be water, ethanol, propanol, etc. 'However, it is better to use the same kind of titanium oxide sol suspension as possible. Β If necessary, add ρ Η adjuster to the solvent. The agent used to adjust the acidity can be nitric acid, sulfuric acid, hydrochloric acid, etc., which can be used when adjusted to alkaline. Ammonia. You must pay attention to the following points when irradiating light containing ultraviolet rays. First, the light source is only required to irradiate light containing ultraviolet rays. Specifically, it can be an ultraviolet lamp, a BLB lamp, a xenon lamp, a mercury lamp, a fluorescent lamp, etc. Basically , The method of irradiating light containing ultraviolet rays is not set However, it is better to irradiate from the top of the container. The ultraviolet rays will not be absorbed by the container. The distance between the second light source and the container is about several cm to several 10 cm. When the sample is too close (cns) A4 ^ (210x297 / ^) A --- 8B. A7 B7 406031 V. Description of the invention (122) (Please read the note on the back to write this page) The liquid on the liquid will dry out due to the heat from the light source. • Too far Illumination will be reduced * The irradiation time will vary depending on the illuminance of the light source * For a few seconds to several ten seconds, the gold tin can be firmly adhered to the photocatalyst particles. Secondly, a coating is formed on the surface of the substrate. The thin film made of titanium oxide sol is formed into a multifunctional material with a photocatalyst function. The heat treatment is usually hydrothermal treatment using an electric furnace or gas rich in the atmosphere or using a hot press. But it is not limited to this. The average particle diameter of the titanium oxide particles in the obtained titanium oxide film is preferably 1 or less. Larger particles will reduce the catalyst activity due to a decrease in specific surface area. Printed by the Shellfish Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs * By sticking When the agent is formed on the surface of the base material by applying the sol applied in the first item of 圔 Lifan 圔 to apply heat treatment to produce a material with a photocatalytic effect and an intermediary adhesive, it can further improve the close contact with the base material. • The specific method varies depending on whether the adhesive is a thermoplastic adhesive or a thermosetting adhesive. • One embodiment is shown below, but as long as it is configured as described above, other methods may be used. The thermoplastic adhesive referred to here may be specifically acrylic glass, inorganic glass such as glaze, solder, etc., and the thermosetting adhesive may be fluorine-containing resin, epoxy resin, siloxane resin, etc. When using a thermoplastic binder, follow the steps below to make a material with photocatalyst function. • First, apply a thermoplastic adhesive on the surface of the substrate. • Second, apply a titanium oxide sol with metal particles on it. • Heat treated. • Here. The heat treatment is lower than the heat-resistant temperature of the base material and the softening point of the thermoplastic adhesive -125-This paper size applies to Chinese national standards (CNS > A4 specifications (210 X 297 mm) 406031 A7 B7 5 、 Explanation of invention (123) * (Please read the precautions on the back before filling this page) High temperature implementation. When the heat treatment is performed at this temperature, a part of the lower layer of the titanium oxide layer supporting the metal particles is buried in the adhesive layer, thereby firmly bonding the substrate and the titanium oxide film supporting the metal particles. When a thermosetting adhesive is used, a material having a photocatalytic effect can be produced by the following steps. First, a thermosetting adhesive is applied to a base material, and a diluent and a mixed liquid prepared by the hardener are sequentially added, and then hardened by a method such as heat treatment. Next, a titanium oxide sol on which metal particles are carried is coated with a thermal hardener resin, a diluent, and a mixture of hardeners, and the mixture is hardened by a heat treatment method. A photo-curable adhesive can be used in place of the thermo-curable adhesive. As described above, the Central Standards Bureau of the Ministry of Economic Affairs, Shellfish Consumer Cooperative, printed the titanium oxide sol produced by the hydrothermal method or the sulfuric acid method as described above. Before adding surfactants such as dispersants and surfactants, fix silver and copper. When platinum, palladium, nickel, iron, cobalt and other metal particles are dissolved on the surface of the gel, the active part of the titanium oxide sol can be covered with metal particles such as silver, copper, platinum, palladium, nickel, iron, and cobalt in advance. Therefore, even if surface treatment agents such as dispersants and surfactants are added in post-engineering, they will not lose their activity due to such substances adsorbing on the active part of the titanium oxide sol. Therefore, the photocatalyst sol can be stably dispersed by the action of surface treating agents such as dispersants, surfactants, etc., and a uniform film can be formed on the surface of the substrate. At the same time, dispersion can be prevented even if it is fired at a low temperature below 300 ° C. Surface treatment agents such as surfactants and surfactants are attached to the active sites of the photocatalyst particle layer formed on the surface of the substrate to reduce the photocatalytic effect. At the same time, silver 'copper' platinum, palladium, nickel 'iron, etc. Electron-capture effect of gold particles such as cobalt The paper size is applicable to China National Standard (CNS) A4 (210X297 mm) 1 ~ -126-406031 A7 B7 V. Description of the invention (124) The effect is to improve the photocatalytic activity. The following specific examples are given below (please read the precautions on the back before filling this page). Example 4 1 In a hot press, add water in a cold bath to a hydrothermal treatment at 140 ° C titanium tetrachloride. The obtained liquid was an anatase titanium oxide sol. 8。 Dispersion of the anatase titanium oxide sol in nitric acid, the pΗ value of this dispersion is 0.8. To this dispersion, an aqueous solution of 3 to 5% by weight copper sulfate was added to adjust the pH to about 0.8, and the container was irradiated with ultraviolet rays from above the container. At this time, the light source is a 4W BLB lamp, and the distance is about 10 cm for 15 minutes. A dispersant formed by adding an organic acetate to this solution was used to stabilize the sol, and the deodorant characteristic R 3 of the obtained sample when irradiated with light was measured. (L) and antibacterial properties. The deodorant property R3Q (L) during light irradiation is in a 11-liter glass-container, the sample surface is arranged 8cm away from the light source (BLB fluorescent lamp 4W), and methyl mercaptan gas is injected so that the initial concentration is 3 p pm. Change rate of concentration after 30 minutes of light. Printed by the Shellfish Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs. The antibacterial properties were tested using E. coli (Escherichia coli W 3 110 strain). 0.15mj? Bacteria solution (10,000 ~ 50000CFU) was dripped on the top surface of the multifunctional material sterilized with 70% ethanol in advance, and it was placed on a glass plate (100X 1 〇0), which was close to the substrate The uppermost surface is used as the sample. ”After irradiating white light (5200 candle light) for 30 minutes, wipe the irradiated sample and the bacterial solution of the sample kept under the shading condition with sterilized gauze, and recover it on this paper. For the scale, the Chinese National Standard (CNS) A4 (210X297 mm) 40G031 A7 B7 V. Description of the invention (125) Γ 0 m physiological saline, to obtain the survival rate of bacteria, as an evaluation index, + + +, ++ ， + ， — System is the same as the above-mentioned result. R3O (L) system is 8 5%, and the antibacterial system ++ has excellent results. Comparative Example 4 2 An anatase-type titanium oxide sol was obtained by adding liquid in a cold bath to hydrothermal treatment of titanium tetrachloride at 140 ° C in an autoclave. 8。 Dispersion of the anatase titanium oxide sol in nitric acid, the pΗ value of this dispersion is 0.8. To this solution is added a dispersant made of an organic acetate to stabilize the sol. The sol was coated on a 15 cm square ceramic tile substrate and heat treated at 150 ° C to obtain a sample. The obtained sample was measured for its deodorizing property R30 (L) and antibacterial property when irradiated with light. Results R3O (L) was 5%, and the antibacterial activity was one. The results were not good. Example 4 3 An anatase titanium oxide sol was obtained by adding a liquid obtained by adding water in a cold bath to a titanium tetrachloride hydrothermally treated at 140 ° C in a hot press. 8。 The obtained anatase titanium oxide sol was dispersed in nitric acid, and the pH value of this dispersion was 0.8. To this dispersion, an aqueous solution of 3 to 5% by weight copper sulfate was added to adjust the pH to about 0.8, and the container was irradiated with ultraviolet rays from above the container. At this time, the light source is a 4W BLB lamp, and the distance is about 10 cm for 15 minutes. Add a dispersant made of organic acetate to this solution, stabilize the sol, and then coat the surface of 10 cm square alumina substrate. This paper is suitable for China National Standard (CNS) A4 (210X297 mm) " -128----------- install ------- order ------ quan (please read the notes on the back before filling this page) Printed by a consumer cooperative 406031 A / B7 V. Description of the invention (126) A diluent of propanol and hardener is added to the siloxane resin in advance to make a mixed solution, and the material is dried at 10 ° C Then, apply the mixed solution prepared by adding the amount of 20% by weight of siloxane resin, propanol, and hardener to the sol prepared according to the method described above, and sinter at 150 ° C to obtain a sample. The obtained sample had a deodorizing property R 3 upon light irradiation. (L). Results R30 (L) was 80%, and excellent results were obtained. Consumption cooperation between employees of the Central Bureau of Standards, Ministry of Economic Affairs, Du printed comparative example 4 4 An anatase and an anatase-type titanium oxide sol were obtained from a liquid obtained from water in a hydrothermal bath at 140 ° C in an autoclave. In nitric acid, 0.8 »was added to this solution. Secondly, add the propanol-liquid of the diluent in a 10 cm square alumoxane resin, and add the amount of titanium oxide to the sol made at 100 ° C to dry the material. The deodorant characteristic (L) of the mixed liquid obtained from the propanol and the hardener during the light irradiation of the obtained sample was 22%, and its effect was inconspicuous. From the above, it can be known that the surface of silver, copper, platinum, palladium, nickel, and iron-titanium sol can be fixed by adding a dispersant and interfacial activity by hydrothermal method or thiotitanium sol. It can also be based on 300 ° C. Materials, such as plastic materials,

Surface treatment and hardening of the substrate formed by the four-type oxidation of this dispersed salt were performed, and then coated as a titanium sol of 2015 0 R η n C titanium chloride. The liquid p Η dispersant and surface coating pre-agent were prepared and the cloth was calcined according to the above weight% silicon ° C to obtain L). The value of cold dispersing is determined by qualitative dissolution. First, the sand is used as the mixing method. Before surface treatment agents such as oxidizing agents produced by the R 3 0 acid method, metal particles such as cobalt are sintered at low temperature to oxidize materials that do not have heat resistance and photocatalytic activity. (Please read the precautions on the back before filling this page) This paper size is applicable to China National Standard (CNS) A4 size (210X297 mm) 129 A7 B7 406031 V. Description of the invention (127) The above examples mainly describe anatase The ore type T i 0 2 will be described below with respect to the rutile type τ i 〇2. (Please read the precautions on the back before filling out this page.) Figure 51 is a flow chart showing the steps of using rutile T i 0 2 to manufacture multifunctional materials. In the present invention, a rutile T i 02 film is first formed on the surface of a substrate such as a tile. The method for forming a rutile Ti02 film can be Ti02 sol titanium alkoxide, titanium sulfate, titanium chloride solution as a raw material, coated on a substrate, and then subjected to heat treatment and the like. When using T i 〇2 sol, since the isoelectric point of T i 〇2 is about pH 6.5, which is about neutral, it is extremely easy to uniformly coat the substrate with an aqueous solution dispersed in acid or alkali. When the substrate is made of metal, it is preferable to use an alkali dispersion from the viewpoint of corrosion resistance. The acid may be sulfuric acid, hydrochloric acid, acetic acid, phosphoric acid, organic acid, and the like. Alkali can be ammonia and hydroxides containing alkali metals, but ammonia is the best in terms of not generating metal contaminants after heat treatment. In addition, an organic acid, a phosphoric acid-based dispersant, a surface treating agent, and a surfactant may be further added to these dispersions. In addition, when the particle size is small, organic sintering can be generated at a low temperature, and a photocatalyst film with excellent peeling can be obtained at a low temperature, so the average particle size of the Ti0 2 sol is less than 0.05 / zm. The printing of the Central Standards Bureau Shellfish Consumer Cooperative is preferably below 0. Olem. The coating method for the substrate is to spray the above raw materials, dip coating, roll coating, spin coating, CVD, electron beam evaporation, ammonium sputtering and other methods without special equipment, and it is more suitable to obtain a coating film cheaply. It is heat-treated by firing in the air using an electric furnace or gas stove or using a heat press. On the other hand, prepare at least one kind of copper, silver, iron, cobalt, platinum, nickel, and palladium. The paper size is applicable to China National Standard (CNS) A4 (210X297 mm) Α Α7 406031 _Βτ _._ 5. Description of the invention (128) , A solution of cuprous oxide (a solution containing metal ions) is coated on the rutile T i 02 film. When coating the metal salt solution, it is advisable to use a method in which the metal salt solution does not penetrate to the back of the substrate. The solution in the metal salt solution may use water, ethanol, etc. When using water, it is also effective to add alcohols and unsaturated hydrocarbons as gasification oxidants. When used as an ethanol solution, ether, acetone, and methanol are more suitable than other solvents because they do not cause rust on the metal substrate. They have a fast drying speed and are harmless. Then, in order to improve the carrying efficiency of the above-mentioned metal salt aqueous solution, it is dried at room temperature to about 100 ° C, and irradiated with light having a wavelength below 390 nm to the metal salt to reduce the osmium ions. The rutile T i 02 The film precipitates and solidifies the metal. Here, the lamps used for irradiation are ultraviolet lamps, B L B (Black Light Blu) lamps, gas lamps, mercury lamps, egg light lamps, and the like. In this case, in order to improve the irradiation efficiency, it is preferable that the light can be irradiated onto the surface vertically. Β-Specific embodiments are described below. Example 4 5 Printed by the Central Laboratories of the Ministry of Economic Affairs, Shellfish Consumer Cooperative (please read the precautions on the back before filling this page). Spray the ammonia particle dispersion with an average particle size of 0.01 # m Ti02sol at 1 0 cm square alumina substrate on 900. (： Temperature firing to form a rutile T i 02 film. Then, this rutile T i 〇2 film was coated with an aqueous copper acetate solution by spraying, and then light-reduced (light source system 2 WBLB lamp 'sample The distance from the light source is 10 cin, and the exposure time is 10 seconds.) The sample is obtained. The light activity A (L) of the obtained sample is evaluated. This standard is applicable to the Chinese national standard (€ can) 8 4 specifications (210 father 297 mm) ) -131-406031 A7 B7 V. Description of the invention (129) (Please read the notes on the back before filling out this page) Photoactive A (L) is based on the gas concentration as the Y coordinate and the reaction time as the X coordinate. The absolute value of the inclination when the curve approximates a straight line. That is, when X t is the concentration for t hours, X t = X 0. 1 0 _A (... ......... On the thin layer of photocatalyst irradiated with ultraviolet light, observe the reduction of the decomposition gas concentration after t hours to obtain. In this experiment, the decomposition gas system uses methyl sulfuric acid with a malodorous component, and the sample is placed in the initial concentration of methyl mercaptan. Adjusted to 2 p pm in diameter 2 6 cmx 2 1 cm high cylindrical container, 8 cm from light source When the 4W BLB fluorescent lamp is irradiated, it is obtained from the change of methyl mercaptan concentration in time. The obtained results are shown in Fig. 52 and Fig. 53. Fig. 52 and Fig. 53 show the copper concentration and light. The correlation diagram of the activity A (L), where Fig. 52 is the result of spraying copper acetate aqueous solution after drying and photoreduction after drying, and Fig. 53 is the result of photoreducing the copper acetate aqueous solution without drying after spraying. The Central Standards Bureau Shellfish Consumer Cooperative printed the 53rd figure after spraying, when the copper acetate in the state of light reduction without drying was reduced, even if the copper concentration in the solution was increased to 0.1% by weight to 0.1% by weight ， A (L) is still about 3X10 _5, no change, has become saturated. In contrast, Figure 5 2 after spraying copper acetate aqueous solution after drying and photoreduction, 0. 001% by weight is 2x10-5 The value is about the same as that of non-drying people, but it can be significant when it is increased to 0.1% by weight. This paper size is applicable to China National Standard (CNS) A4 (210 X297 mm): -132-^ 06031 a? __B7 _ 5. The description of the invention (130) is increased to an A (L) value of about 1 X 10-2. Example 4 6. Example 4 5—When a rutile T i 02 film is formed on a floor tile and a wall tile, and copper is fixed to the rutile T i 02 film by photoreduction (coated with copper acetate aqueous solution and dried) Investigate the relationship between the concentration of the metal component in the solution and the odor removal rate R3. The results are shown in Figure 54 and Figure 55. From this figure, it can be seen that the photoreduction treatment after drying, if the concentration of gold tincture in the solution can reach a certain level To a certain extent, the malodor component can be removed even when the substrate is a tile. Example 4 7 Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs (please read the precautions on the back before filling out this page). Spray the ammonia particle size with an average particle size of 0. 〇l # m Ti02sol at 1 5 A square ceramic tile substrate is fired and formed at various temperatures to form a rutile T i 〇2 film. Next, a copper acetate aqueous solution was coated on this rutile T i 0 2 film by a spraying method, and then light-reduced (the light source system is a 20W BLB lamp 'the sample is 10 cm away from the light source and irradiated for 10 seconds)' Get the sample. The deodorant characteristic r3 of the obtained sample was evaluated. . The results obtained are shown in Figure 5-6. 9 0 〇. The R3D value under 〇 (porosity 10%) is better than those without rutile of Umbrella genus β. When the temperature is increased to 1 0 0 0 C (porosity 3%), no gold is supported. The sample was R 3. A sharp decrease in value 'was also observed in the sample to which copper was added. As described above, there are two reasons why the deodorizing property of '100 ° C is lower than that of 900 ° C. The first is the photocatalyst gold red paper that can be in contact with the decomposition gas when reducing porosity. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm): -133-Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 406031 | 8d at-^ --- V. Description of the invention (131) The surface area of the stone-shaped τ i 〇2 film is reduced, and the deodorization characteristics of the unsupported metal sample may be lowered for this reason. Another reason is that as the porosity decreases, Photoreduction method analysis of the existence of gold particles can also be reduced. • Caused by the increase in the average free path during the movement of the electrons. • The relationship between the concentration of silver and copper in the solution and the color difference during the coating film is shown in Figures 5 and 7. This figure shows that * compared to silver * the color difference and brightness change of copper are small, and the coloring is not obvious. Also, the difference in coloring is when the copper system is analyzed by ESCA (electron beam spectrometry for chemical analysis), etc. • You can check out Oi / im Ti02 sol ammonia dispersion at 1 5 cm Square ceramic tile substrate at various temperatures Sintered to form a rutile T i 0 2 film. Then, a rutile T i 0 2 film was coated with an aqueous silver nitrate solution by spraying, and then light-reduced (light source is a 20W BLB lamp, and the sample distance from the light source is 10 cm distance, irradiation for 10 seconds) * Obtained samples • Evaluated the rutile-type T i 〇2 film of the obtained samples, the porosity, deodorization characteristics R30, and abrasion resistance * The results are shown in Section 5 8 蹰 Porosity is 1 0 It has good deodorization performance when it is more than 40%, and its wear resistance is more than 0 when it is less than 40%. The wear resistance is evaluated by sliding friction using a plastic eraser, and the external changes are evaluated and evaluated. · This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) — — — — — — — — — — — — ^ -------- ^-— — 1 —-- -^ (Please read the note on the back WWi # first to write this page) -134-Printed by the Consumers' Cooperative of the Central Government Bureau of the Ministry of Economic Affairs 406031 at Β7 V. Description of the invention (132) ◎: Swipe back and forth 40 times without starting Variety. ：: There are scratches when sliding between 10 times and 40 times, and the titanium oxide film peels. (Triangle | delta): There are flaws after sliding 5 to 10 times, and a titanium oxide film peels. X: There are scars after sliding 5 times or less, and the titanium oxide film peels. Example 4 9 An ammonia dispersion having an average particle size of 0.01 / zm Ti02 sol was spray-coated on a 10 cm square alumina substrate having a glaze layer formed in advance at 8 50 ° C to 100 °. 〇. (: Sintered at a temperature to form a rutile T 丨 〇2 film. Then, a silver nitrate aqueous solution was coated on this rutile T i 02 film by spraying method, and then light-reduced (light source system 2 0W BLB lamp 'sample distance The light source was at a distance of 10 cm and was irradiated for 10 seconds) to obtain a sample. 'Evaluate the obtained sample for antibacterial resistance, abrasion resistance, peel resistance, pollution resistance,' acid resistance, rub resistance, and silver coloration. Antibacterial properties Using coliform (Escherichia coli W3110 strain) test. 0.15m ^ of bacterial solution (1 ~ 50,000 CFU) was dripped on the top surface of the multifunctional material sterilized with 70% ethanol in advance, and placed on a glass plate (100 × 10). 〇), close to the top surface of the substrate as the sample. Irradiate a white light (5200 candle) for 30 minutes ， Recovered from 10 mp physiological saline solution, and obtained the survival rate of bacteria as the evaluation index, ++, ++, ++, + — are in accordance with the above-mentioned paper standards applicable to the Chinese National Standard (CNS) A4 specification (2丨 〇 > < 297 gong) ----------- install-(Please read the notes on the back before filling this page) * 1Τ 135 A7 B7 406031 V. Description of the invention (133) Sample · (Please first (Read the notes on the reverse side and write this page) Peel resistance test is a test that makes the abrasion resistance test conditions more severe. Instead of plastic erasers, use a mixed yarn eraser (LION TYPEWRITER ERASER 502) that can apply large shear forces. · Specifically, the surface of the sample was rubbed with a sand-rubber eraser with equal force for 20 times, and the state of the flaw was visually compared with the standard sample. The evaluation criteria are as follows. · Printed by the Industrial and Commercial Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. 〇: Slight changes can be seen under different light X: Changes at a glance · Pollution resistance test is related to the test that is not easily stained · Evaluation method is based on 0.5% methylene blue aqueous solution in the sample The surface is stained. After washing, it is washed with water, and the presence or absence of stains is visually observed. The evaluation criteria are as follows: The stains can be completely removed.... Although no stains are visible, traces remain. Δ: Light stains are left. X: Obvious Fouling on the ground. Acid-resistant system is immersed in 10% HCP aqueous solution for 120 hours, and then visually observe whether the rutile T i 0 2 film layer on which silver is carried on the surface of the substrate changes. The evaluation criteria are as follows. Changes 〇: Slight discoloration Δ: Slight discoloration X: Significant discoloration · This paper size applies to 0 Chinese standards (CNS> A4 specifications (210 X 297 mm) 136 406031 A7 B7 _ V. Description of the invention (134) Alkali resistance After immersion in a 5% Na 2 O aqueous solution for 120 hours, visually observe whether the rutile T i 02 thin film layer holding silver on the surface of the substrate has changed, and the evaluation criteria are as follows: :: No change at all. : Slightly discolored △: Slightly discolored X: Significantly changed. The silver colorability was evaluated by comparing visually with a sample without adding silver. The evaluation criteria are as follows: 未: Not colored 〇: Slightly colored △: Slightly colored X: Slightly colored The seven items evaluated above the brown part are shown in Table 2 4. Table 5 shows the effect of film thickness and firing temperature on antibacterial properties. ---------- ^ ----- -1T ------ ^ (Please read the notes on the back before filling this page) The paper size printed by the Employees' Cooperative of the Central Bureau of the Ministry of Economic Affairs of the People's Republic of China is suitable for China National Standards (CNS) A4 (210X297 mm) -137-406031 A7 B7 V. Description of the invention (135) (Table 24) Thickness of photocatalyst Relationship with various characteristics Printed film thickness (" m) of consumer cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs Antibacterial α) Wear resistance Peel resistance Pollution resistance Acid and alkali resistance Agi Color 0.1 +++ ◎ ◎ ◎ ◎ ◎ ◎ 0.2 H + ◎ ◎ ◎ ◎ ◎ ◎ 0.3 +++ ◎ ◎ ◎ ◎ ◎ ◎ 0.4 +44 ◎ ◎ ◎ ◎ ◎ ◎ 0.5 +++ ◎ 〇〇〇〇〇〇0.6 +44 ◎ 〇〇〇〇〇〇0.7 +++ ◎ 〇〇〇〇〇〇〇0.8 +++ ◎ 〇〇〇〇〇〇〇〇〇 ＋＋＋ ◎ 〇〇〇〇〇〇1.0 +++ ◎ XX 〇〇〇 / frnrtlLL. Bg layer (0.4) Δ (please first Read the notes on the reverse side and fill in this page again) This paper is again applicable to China National Standard (CNS) A4 (210X297 mm) -138-Printed by A7 B7, Shellfish Consumer Cooperative, Central Standards Bureau, Ministry of Economic Affairs 136) (Table 2 5) Film thickness and sintering temperature Influence of bacterial properties temperature film thickness 880 ° C 900 ° C 920 ° C 940 ° C 960 ° C 980 ° C 0.1 1 +++ ++ ++ 0 2 # m +++ ++ 0.3 m +++ +++ +++ ++ 0.4 ^ m +++ +++ +++ 0. 5 ^ m +++ +++ +++ ++ 0 · 6 # m +++ +++ +++ 0.7 ^ m +++ +++ +++ +++ 0.8 ^ m +++ +++ +++ 0.9 ^ m +++ +++ +++ 1. O ^ m + ++ Gutter (please read the precautions on the back before writing this page) This paper ship applies the side standard (CNS) M outline) _ m _ 406031 A7 B7 Staff consumption cooperation of the Central Bureau of Standards of the Ministry of Economic Affairs V. Description of the invention (〖37〉 In terms of antibacterial properties, when the film thickness of the photocatalyst film produced in this embodiment is in the range of 0.1 to 1 / zm, the good results of + + + can be obtained as long as the firing temperature is appropriate. . However, as shown in Table 24, the film thickness is reduced to 0. The samples sintered at 980 ° C at a high temperature below are + +. The antibacterial properties tend to be slightly lower. This may be caused by the partial immersion of the photocatalyst film into the glaze layer due to the softening of the glaze layer. In addition, silver itself has antibacterial power, but the tendency of the antibacterial property to depend on the firing temperature indicates that the antibacterial power of the composite material produced by the method of the present case is related to the properties of the rutile T i 〇2 film other than the antibacterial effect of silver. Even the result (such as the above-mentioned silver is only carried by the holder after firing). L'z / zm 的 可以 可以 ， Almost all samples of the photocatalyst film are sunk into the glaze layer due to the softening of the glaze layer, but in this embodiment, the firing temperature is an appropriate temperature, at least 0.1 / zm or more can be It was confirmed that the photocatalyst film was kept on the uppermost surface layer of the sleeve layer. In terms of abrasion resistance, the film thickness of the photocatalyst film produced in this example is in the range of 0 · 1 Mm to 1 / zm, and good results are obtained. Compared with the same manufacturing method for comparison, the sample without glaze was Δ, and excellent results were obtained. This is due to the presence of the glaze layer, so a part of the lower layer of the photocatalyst film is buried in the glaze layer due to the softening of the glaze during firing. In contrast, in the peel resistance test, the ratio of 0.1 / zm to 0.4em is ◎, 0.4, and the ratio of am above 0 to 9jtim is 〇 ′ 1 is X, and the film thickness of the photocatalyst film can be seen. There is a tendency to deteriorate when increasing. This is because the thickness of the film is buried in the glaze layer. The thickness ratio is increased, so that it is easy to peel off. In the abrasion resistance test, it is assumed that normal people are resistant to peeling (please read the precautions on the back before filling this page). Sheet The Zhang scale is applicable to the Chinese National Standard (CNS) A4 (21 × 297 mm) -140-400031 s; _ V. Description of the invention (138) The deterioration of the test is caused by the difference in the shear force. In terms of pollution resistance, the thickness of the photocatalyst film is 0.1 m ~ (Please read the precautions on the back before filling in this page) 0 · 4 / zm is ◎, 0.4ym ~ 0 · 9em is 0, 1 / / m is X. The thicker the visible light catalyst film, the worse the pollution resistance. In terms of acid resistance, 0.1 // 111 ~ 1; ^ 111 film thickness of the photocatalyst film produced in this embodiment shows excellent results. Make 0.4 // m ~ 1 is 111 when it is 111, and 0.1 is "111 ~ 0.4 when it is 111 or less, it is ©. It can be seen that a thin film has better results. In terms of alkali resistance, this embodiment produced 0 .1 ~ 1 The thickness of the photocatalyst thin film system shows excellent results. When it is 0.4 ~ lAim, it is 〇, 〇 · Ιμπι ~ 0.4; when it is less than αιη, it can be seen that the thin film has better results. 》 About the coloring property of silver is 0.1; czm ~ 0.4em film thickness of the photocatalyst thin film is ©, 0.4em ~ 0 · 9 is 0, 1 is X, the thickness of the visible light catalyst film increases, there is The tendency is getting worse. This tendency is consistent with the pollution resistance. The seal of the staff consumer cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs shows that the thickness of the photocatalyst film is 0.1 μm ~ 0.9 // m. Ιμιη ~ 0.4 jum is preferred. In addition, when the photocatalyst film is fixed to the substrate through the glaze layer, the abrasion resistance can be improved. In addition, the appearance decoration is also affected by the thickness of the film, that is, 〇. At β m ~ 0.4, the rainbow-colored stripe pattern can be generated by the interference effect of visible light and photocatalyst film, which is unique and unique. Impressions. On the contrary, below 0.2em or below 0.4 # m and below 0.9jc / m, this paper size will not apply the Chinese National Standard (CNS) A4 specification (210X297 mm > -141-Central Standard of the Ministry of Economic Affairs) A7 printed by the Bureau Cooperative Consumer Cooperative _____B7 V. Description of the invention (139) The above-mentioned rainbow-colored stripe pattern can be directly applied to the color of the substrate or the color, pattern or combination of the glaze composition. Example 5 0 An ammonia dispersion having an average particle diameter of 0 · 01 / zm Ti〇2 sol was spray-coated on a 15 cm square tile substrate at 90 °. (: Temperature-firing forming to 0 · 8 // m-thick rutile butadiene 〇2 thin film. Then, the surface of this tile was spray coated with a copper acetate aqueous solution (solution concentration of 0.2% by weight, 0.5% by weight, 1% by weight) by spray coating method. Then, after light reduction (light source is a 20W BLB lamp, the sample is 10 cm away from the light source and irradiated for 30 seconds), the sample is obtained. The antibacterial property of the obtained sample is evaluated, and the copper load is recovered by the residual aqueous solution after irradiation. Calculated from the difference between the initial amount of copper and the amount of copper recovered. Figures 5 and 9 show the amount of copper supported. Correlation between the bacterial survival rate during light (L) and dark (D). The following facts can be seen from the drawing "First, antibacterial properties can be improved by carrying copper, and second, when light (L) is darker (D) ) It is possible to improve the antibacterial property with a small amount of copper. This light (L) is caused by the photocatalytic function of the rutile T i 02 film which restores the photoactivity by supporting copper. +/- 1 2 / Z g / cm2 or more can be ++, and can be increased to ++ when 0.3 # g / cm2 or more is added. It is well known that copper itself also has an antibacterial effect, so increasing the copper load in the dark can also increase the antibacterial property. At this time, it is ++ when carrying 0 · 7 // g / cm2 or more, and it can be increased to ++ when carrying 1.2 A g / cm2 or more. The paper size is applicable to China Standards (CNS) A4 (210X297). ^) ^ -142-I -------- Kunyi ------, 1T ------ " (Please read the precautions on the back before filling this page) A7 B7 ^ 06031 V. Description of the invention (140) • Therefore, when evaluated at the + + level, it is 0. 12) tig / cm2 ～ 0. 7iig / cm2, at the + + + level, it is 0. 3 卩 g / cm * ~ 1. 2 Under the copper load of # g / cm2, the good antibacterial property under light irradiation (L) is due to the special effect obtained by combining copper and rutile T i 02 film. "Because of the existence of rutile T i 02 film Can reduce the amount of copper loading • Can reduce the amount of copper loading, especially for the use of this composite material in the environment where there is water • The use of copper in the environment where the water will dissolve, such as used in a washstand or sanitary Spherical surfaces in ceramics can also reduce the amount of dissolution. For copper *, the same effect can be obtained even when it is in the form of cuprous oxide. copper, Part of the photorecovery effect can also be observed by C u 2 + C U +, which can be imagined. On the other hand, the amount of supported net is 0.7jtig / cm2 or more, preferably 1. 2 # g Above 60 cm / cm2, good antibacterial properties can be obtained regardless of the presence or absence of light exposure. Also, Fig. 60 shows the relationship between the copper coating arrangement and copper placement when the copper concentration in the solution is 1% reset. From this figure, it can be seen that purely increasing the copper coating amount will not increase the copper load holding capacity. When the copper load capacity is to be 0.7 # g / cm2 or more, it must be 0.2mg / cm2 ~ 2.7mg / cm *, if it is 1.2 # g / cma or more, it is better to be 0.3mg / cm2 ~ 2.4mg / cm2. This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 public love> III — I --- I ------ IIIH — ^ «— — — — 11-- (Please read the notes on the back first, fill out this page) Printed by Shelley Consumer Cooperative, Bureau of Intellectual Property, Ministry of Economic Affairs 406031 A7 B7 V. Description of the invention (141) Example 5 1 The average particle diameter of 0 · 01 // m Ti〇2 sol was spray coated (please read the precautions on the back before filling this page). 5 cm square tile substrate, 9 〇〇。 0 temperature firing to form a 0 · thick rutile Ti0 2 film. Then the surface of this tile was spray coated with a silver nitrate aqueous solution (solution concentration of 0.2% by weight, 〇). 5% by weight, 1% by weight), and then light-reduced (light source is a 200 WBLB lamp, the distance between the sample and the light; the distance of the source is 10 cm, and the irradiation is 30 seconds) to obtain the sample. The antibacterial properties of the obtained samples were evaluated, and the amount of silver supported was calculated from the difference between the initial silver amount and the recovered silver amount after recovering the residual aqueous solution after irradiation. Figure 61 shows the relationship between the silver load and the survival rate of bacteria at light time (L) and dark time (d). The following facts are known from the drawing. First of all, copper and silver are different. There is an overlap between the curve of the bacterial survival rate at the time of light irradiation (L) and the time of dark (D). This does not mean that silver and copper have different results. It just means that silver has higher antibacterial power than copper, and it can produce an effect with a small amount of load. Therefore, it is necessary to support light (L) and dark (D). The difference between the quantities is included in the experimental error range. The cooperation between the staff of the Bureau of the Ministry of Economic Affairs and the rate increase of the staff. From the figure, it can be seen that 'the carrying capacity of silver is 0. 005 from g / c m2 or more', preferably 0 lvg / cm2 or more, regardless of the presence or absence of light On the other hand, Figure 62 shows the relationship between the color difference between the amount of silver supported and the sample that does not support silver. 'When the amount of silver supported is 1 β g / cm2 or more, the color difference will be Suddenly the difference becomes 2 or more. Usually when the color difference is 2 or more, the difference in color can be clearly seen. It will change from brown to black when silver is attached. The appearance of this paper applies the Chinese National Standard (CNS) A4 specification (210X297 mm) 406031 A7 B7 _ V. Description of the invention (142) (Please read the precautions on the back before filling in this (P.) It is indecent and unsuitable. Therefore, it is best to control the color difference to be less than 2. For this reason, the silver load is preferably less than 1 V g / cm 2. The color difference is measured with a spectrophotometer (manufactured by Tokyo Denshoku Co., Ltd.). Moreover, in the above-mentioned embodiments, in order to prevent the active part of the photocatalyst from being covered by a surface treatment agent or a polymer substance or dust to reduce its activity or restore its activity, it has been disclosed that silver, copper, platinum, palladium, gold, nickel , Iron, cobalt, zinc and other gold tincture particles cover the active part of the microparticles with photocatalytic activity, but when these metals are non-ferrous metals coated in large amounts, their original colors will adhere to the surface of the substrate, destroying the substrate color, pattern And other design concerns. Therefore, the decoloring method designed to maintain the high photocatalytic activity without damaging the color and pattern of the substrate will be described below. Basically, it consists of two steps: the step of immobilizing metal microparticles on photocatalytically active particles, and reacting the above metal particles with an aqueous solution or gas to form a colorless or white salt at least on the surface of the metal microparticles to produce a metal containing Method for catalyst of microparticles "The order of the above two steps can be arbitrarily printed by the Shellfish Consumer Cooperative of the Central Sample Bureau of the Ministry of Economic Affairs. That is, after fixing the non-ferrous metal fine particles to the particles having photocatalytic activity, the above-mentioned metal fine particles are reacted with an aqueous solution or a gas to form a colorless or white salt at least on the surface of the gold tincture fine particles, or the non-ferrous metal fine particles are allowed to react with an aqueous solution or a gas. At least the colorless or white salt is formed on the surface of the metal fine particles, and then it is fixed to the particles having photocatalytic activity. It is also possible to mix the particles having photocatalytic activity with colored metal fine particles and then fix them on the substrate. At this time, for example, a step of sequentially mixing particles with photocatalytic activity and non-ferrous metal particles is applied, and the above-mentioned mixing is applied on this paper. The size of the paper is applicable to China National Standard (CNS) A4 (210X297 mm) -145-406031;] V. Invention Explanation (143) The step of liquid-to-substrate, the step of firing to fix the mixture to the substrate, and the step of reacting with the gas to form a colorless or white salt at least on the surface of the metal particles. In addition, the step of firing to fix the above mixture to the substrate and reacting with the gas to form a colorless or white salt at least on the surface of the metal particles can be performed simultaneously. "Colored metal particles refer to silver, copper, platinum, palladium, gold In terms of metal particles, nickel, iron, cobalt, and zinc have a small tendency to be reduced easily. When a colorless or white salt is formed by the reaction of an aqueous solution, or when a catalyst containing metal fine particles is used in a liquid, the colorless or white salt formed is preferably insoluble or insoluble. When the catalyst containing metal fine particles is used in the substrate, the particles having photocatalytic activity can be fixed to the substrate in advance, and then the catalyst containing metal fine particles can be made, or the catalyst containing metal fine particles can be made and then fixed. On the substrate. Printed by the Consumer Cooperatives of the Central Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling this page). Pre-fix the particles with photocatalytic activity on the substrate, and then make the catalyst containing metal particles in order. The step of forming a particle layer having photocatalytic activity on a substrate, the step of fixing non-ferrous metal particles on it, and the step of forming a colorless or white salt to cover the non-ferrous metal particles. The step of forming a colorless or white salt to cover any non-ferrous metal particles can be, for example, contacting gold tincture particles with a solvent that can react with the above-mentioned non-ferrous metal particles to form at least a colorless or white salt on the surface of the metal particles. Standard (CNS) A4 specification (210X297 mm) '-146-406031 at _____B7__ V. Description of the invention (144) Liquid method, or contacting metal particles with the above-mentioned non-ferrous metal particles, at least can be formed on the surface of metal particles Colorless or white salt reaction gas method. Among the salts of the above-mentioned colored metal fine particles, those which are colorless or white are preferably insoluble or insoluble salts. These can easily form at least a salt on the surface of metal fine particles under the reaction of an aqueous solution, and can be used stably in an environment surrounded by water. The non-ferrous metal fine particles are white or colorless, and may be, for example, silver chloride, silver bromide, silver iodide, silver oxalate, silver thiosulfate, silver cyanide, silver thiocyanate, cuprous chloride, bromide. Cuprous, cuprous cyanide, cuprous thiocyanide, cuprous oxide, zinc phosphate, zinc oxalate, zinc cyanide, palladium cyanide, zinc sulfide, zinc carbonate, ferrous carbonate, zinc oxide, etc. A solution which can form the above salts, for example, potassium chloride solution, sodium chloride solution, ammonium chloride solution, ferric chloride solution, etc. when silver chloride is used, and potassium iodide solution, iodide-sodium solution, iodine when silver iodide is used Iron solution, hydrogen peroxide water, ozone water, etc., but it is not limited to this, as long as the soluble salt solution containing the anion of each salt can be widely used. " (Please read the notes on the back and fill in this page again.) In addition, the reaction gas that can form the above salts can be widely used as long as it is a gas containing an anion element of each salt. For example, when the salt is an oxide such as zinc oxide or cuprous oxide, it can be heated in the air, oxygen, or water vapor, or reacted with an oxidant such as O3 to oxidize the surface of metal particles to form an oxide layer. Specific examples are given below. This paper size is applicable to China National Standards (CNS) Λ4 specification (210X297 mm) ~~ -147-406031 A7 ________B7 _ V. Description of the invention (145) Example 5 2 On the surface of a 15 cm square tile base material After coating a titanium oxide sol having an average particle diameter of 0.01 # m, it was heat-treated at 900 ° C to form a rutile titanium oxide film. The sample stopped at this stage is used as the comparison sample 1. Thereafter, a silver nitrate aqueous solution was applied by a spray method, and the LB lamp was irradiated for 10 minutes to fix silver on a rutile titanium oxide film. At this time, the silver carrying capacity was 1_ 2 # g / cm 2 and was brown. The sample up to this stage is the comparison sample 2. Then, on the comparative sample 2, a 0.1 mol potassium iodide aqueous solution was applied at a ratio of 0.1 cc / cm2 to make it react, and as a result, the surface of the sample became yellow-white and finally white. This should be caused by the formation of a silver iodide layer. This sample was referred to as Implementation Sample 1. The color difference, light activity, deodorizing properties, and antibacterial properties of these samples were evaluated. The color difference was measured using a spectrophotometer (manufactured by Tokyo Denshoku Co., Ltd.). In this case, the standard sample is comparative sample 1. The results are shown in Figure 63. Results The color difference of the comparison sample 2 is 3 _ 5, compared with that, it is printed on the consumer cooperative of the Central Quasi Bureau of the Ministry of Economic Affairs of Potassium Iodide (please read the precautions on the back before filling this page). The color difference is reduced to 1 to reduce its coloration. The photoactivity was evaluated by Δρ Η test. The results of photoactivity and deodorization characteristics are shown in Figure 64. When comparative samples 1 and 2 were compared, the comparative sample 2 was restored to photoactivity due to the support of silver. Δρ Η 'R3〇 (L ) Have good results. When the test sample 1 and the comparison sample 2 are compared, Δρ Η and ruler 3 are compared. (L) are numerical values of the same degree. It is learned that the decolorized paper is suitable for China's National Standards (CNS) Ya 4 4 (210X297 mm) ~ ~ -148-406031 at ______B7 _ V. Description of the invention (146) Sex has not changed, maintaining good characteristics. (Please read the note on the back. Please fill in this page before filling in this page.) And 'Antibacterial properties are tested using coliform (Escherichia coli W3 110 strain)'. The top surface of the multifunctional material sterilized with 70% ethanol was dripped to the top surface of 0.15mj. ? Bacteria liquid (2x104CFU), placed on a glass plate (100x100), close to the top surface of the substrate as a sample. After irradiating with white light (3500 candle light) for 30 minutes, wipe the bacterial solution of the irradiated sample (L) and the sample (D) kept under the shading condition with sterilized gauze, and recover them in 10 mp physiological saline. Number of bacteria. The antibacterial results are shown in Figs. Comparative sample 1 did not carry silver, so no antibacterial effect was seen in the dark (D). In contrast, Sample 1 was subjected to a decolorization treatment, and the surface of silver changed to a compound, but in the dark (D), it still had an antibacterial effect. In addition, under the light (L), you can see a stronger antibacterial effect, not only the antibacterial effect of silver, but also the effect of rutile titanium oxide thin-film restoration of photocatalytic activity. Example 5 3 The Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs printed on a 15 cm square sanitary pottery forming body, coated with glaze, fired at 1100 ~ 1200 ° C, and coated with an average particle size of 0.01. The anatase titanium oxide sol was fired at 900 ~ 100 ° C, and the rutile titanium oxide film was fixed on the base body of the sanitary ceramic forming body. Then, an aqueous silver nitrate solution was applied thereon, and silver was deposited on the titanium oxide film by irradiating ultraviolet rays. An aqueous solution of ferric chloride is coated thereon, and it can be decolorized when irradiated with ultraviolet rays. The color difference is reduced from 3 to 0.3. In addition, the antibacterial light is irradiated with light on this paper. The size of the paper is applicable to the Chinese National Standard (CNS) A4 (210X297 mm) ~ -149-406031 at _____B7 __ V. Description of the invention (147) When it is dark, it will contact the sample 3 0 Minutes, it was confirmed that τκ, which was less than 10% of the original number of bacteria, had an excellent effect. Example 5 4 After coating glaze on a 15 cm square sanitary pottery shaped body, it was fired at 1100 to 1200 ° C and coated with an average particle diameter of 0.01 / 1m of anatase titanium oxide sol. It was fired at 900 ~ 1000 ° C, and the rutile titanium oxide film was fixed on the sanitary ware forming green body substrate. Then, an aqueous silver nitrate solution was applied thereon, and silver was deposited on the titanium oxide film by irradiating ultraviolet rays. The sample was placed in a desiccator (ozone concentration 10 p pm) with an ozone generator for about 2 hours to decolorize it. It was confirmed that only less than 10% of the original bacterial count showed excellent results. Example 5 5 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling this page). After coating glaze on a 15 cm square sanitary pottery shaped body, apply it from 1 100 to 1200. ° C firing, coating and dispersing an anatase titanium oxide sol having an average particle size of 0.01 Olwm in a nitric acid aqueous solution and a mixed solution of silver nitrate aqueous solution, and then firing, and fixing the titanium oxide film on a sanitary ceramic forming base substrate. At this time, it will be brown when fired below 700 ° C, but it will be discolored when fired above 700 ° C. It can be seen that the silver surface reacts with the components in the atmosphere. In addition, it was fired at 850 ° C to fix the Ryzenite type titanium oxide film on the substrate of the sanitary ceramic forming body, and the antibacterial properties of the obtained sample were measured. The light was in contact with the sample for 3 hours in the dark, and it was confirmed. Only less than 10% of the original bacterial count showed excellent results. The scale of this paper applies the Chinese National Standard (CNS) Λ4 specification (210X297 mm) -150-A7 B7 406031 V. Description of the invention (148) Example 5 6 (Please read the precautions on the back before filling this page) on 1 5 cm square sanitary pottery shaped body coated with glaze, fired at 1100 ~ 1200 ° C, coated with anatase titanium oxide sol with an average particle size of 0.01, at 9 0 ~ 1 0 0 0 Bake at ° C, fix rutile titanium oxide film on the base material of sanitary ceramics, and then apply silver nitrate aqueous solution on it, and then irradiate ultraviolet rays to precipitate silver on the oxide film. Then, hydrogen peroxide water was applied thereon to decolorize it. In addition, when the antibacterial system was exposed to light, it was in contact with the sample for 3 hours in the dark, and it was confirmed that only 10% or less of the original bacterial count showed excellent results. Next, the rutile-type T i 0 2 particles and hafnium oxide are mixed to improve the compactness and adhesion of the photocatalyst film, and to increase the activity. The method for forming the photocatalyst film is any of the following two methods. One is a method in which T i 02 sol and hafnium oxide sol are mixed on the surface of the substrate and fired. Printed by the Central Bureau of the Ministry of Economic Affairs, Shellfish Consumer Cooperative, mixed T i 02 sol and osmium oxide sol were carried out in alkaline aqueous solution. Electrochemically speaking, when both can be sufficiently dispersed, it is alkaline. The alkaline aqueous solution can be ammonia, hydroxides containing test metals or alkaline earth metals, but considering that it will not generate metal pollutants after heat treatment, ammonia is the best. In addition, organic or phosphoric acid-based dispersants, surface treatment agents, and surfactants may be further added to these dispersions. The coating method may be a method of spraying, spraying, dip coating, roll coating, spin coating, CVD, electron beam evaporation, sputtering, and the like to make the coating film into the above-mentioned mixed solution, and any of them may be used, and other methods may also be used. However, the size of the paper used for spraying and dipping is applicable to the Chinese National Standard (CNS) A4 (210X297 mm) -151-B7 406031 V. Description of the invention (149) The coating roller system need not be CVD, electron beam evaporation, sputtering Special equipment is required for plating, and it is advantageous that a coating film can be formed inexpensively. (Please read the precautions on the back before filling in this page) After coating, the film can be dried before firing. It is better to dry at room temperature ~ 10 o ° c. The firing temperature is performed at a temperature sufficient to produce rutile under these conditions. This temperature is above 830 ° C under the coexistence of ytterbium oxide at normal pressure. It is not necessary to form a solid solution of Ti02 and hafnium oxide. To form a solid body of τ i 0 2 and hafnium oxide must be kept at high temperature for a long time, and the production efficiency is not good. Another method is a method in which a rutile-type Ti02 thin film is formed, and a hafnium oxide sol is added thereon and fired. Printed by the Consumers' Cooperative of the China Standards Bureau of the Ministry of Economic Affairs. This method is firstly coated with a titanium-containing starting material on the substrate. The starting materials here can be Ti02 sol, titanium alkoxide, titanium sulfate, titanium chloride solution, and the like. When using T i 〇2 sol, since the isoelectric point of T i 〇2 is pH 6.5, which is too about neutral, it is extremely easy to uniformly coat the substrate with an aqueous solution dispersed in acid or alkali. When the substrate is made of a metal, an alkali dispersion is preferred from the viewpoint of corrosion resistance. For ceramics, tiles, ceramics, etc., either acid or alkali dispersions can be used. The acid may be nitric acid, sulfuric acid, hydrochloric acid, acetic acid, phosphoric acid, organic acid, and the like. It can be ammonia, alkali metal hydroxide, but ammonia is the best β in view of the fact that gold rhenium pollutants will not be formed after heat treatment. In addition, organic acids and phosphoric acid can be added to these dispersions. Dispersant 'surface treatment agent, surfactant. Also, the average particle size of the T i 〇2 sol of the starting material is 0.05 to m or less, preferably 0.01 to m or less. In addition, when the particle size is small, initial sintering can be generated at low temperature. The paper size is applicable to the Chinese National Standard (CNS) M specification (21〇 > < 297 mm-152-152 406031 _____B7 _ V. Description of the invention (150) Photocatalyst film with excellent peel strength can also be produced at low temperature. The coating method for the substrate may be spraying, dipping, roller Coating, spin coating, CVD, electron beam evaporation, sputtering and other methods to make it a coating film, any of them can be, and other methods, but spraying, dip coating, and roller coating are not necessary such as CVD, Electron beam evaporation and sputtering require special equipment, and it is advantageous to be able to form a coating film at low cost. After coating, the film can be dried before firing. It is advisable to dry at room temperature to 100 ° C. Then, the coated composite material is fired. Firing is performed at the temperature at which rutile is formed, and it is usually more than 900 ° C under normal pressure. Thereafter, it is coated on the cooled and solidified composite material, which can be used as a starting material of tin source, and fired. As a starting material for tin sources, hafnium oxide sol and the like are used. It is advisable to use an alkaline aqueous solution for the rubidium oxide sol. Electrochemically speaking, the rubidium sol is stable when it is alkaline. The alkaline aqueous solution may be ammonia, a hydroxide containing an alkali metal or an alkaline earth metal. However, it is considered that ammonia is the best solution after the heat treatment does not cause the formation of metal pollutants. In addition, organic or phosphoric acid-based dispersants, surface treatment agents, and surfactants may be added to these dispersions. Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling this page). The coating method for the substrate can be spray coating, dip coating, roll coating, spin coating, CVD, electron beam. Any method to make it a coating film by evaporation, sputtering, etc. Any of them can be used, but other methods are also available, but spraying, dipping, and roller coating are not necessary such as CVD, electron beam evaporation, and sputtering requires special equipment. 'It is advantageous that the coating film can be formed inexpensively. After coating, the film can be dried before firing. Drying is preferably performed at room temperature to about 100 ° C. The firing temperature is the temperature at which organic added components can be evaporated from osmium oxide, and it is more than 300 ° C under normal pressure. It is not necessary to form a solid solution of T i 02 and thorium oxide. The paper size is applicable to the Chinese National Standard (CNS) A4 (210X297 mm) -153-406031 A7 ________B7 _ 5. The description of the invention (151). To form a solid body of T i 〇2 and hafnium oxide must be maintained at 1¾ ° C for a long time 'production efficiency is not good. In addition, a thin film made of a mixture of rutile T i 〇2 and thorium oxide having a crystal grain size of less than 0.01 μm can be formed on the surface of the substrate, and at least one of copper, silver, uranium, iron, and cobalt can be fixed on the thin film. Metals such as nickel, palladium, and copper oxide "These metals have the function of capturing electrons, which can increase the photocatalytic activity of a thin film made of a mixture of rutile T i 〇2 and crystal grains below 0.01. In particular, copper and silver have antibacterial power by themselves and can have antibacterial properties even when they are not illuminated, so they can also have a certain degree of antibacterial power when they are not illuminated in the dark. The method of fixing at least one type of copper 'silver, platinum, iron, cobalt, nickel, palladium, and cuprous oxide in cuprous oxide may be by coating at least one metal salt aqueous solution of these metals' and then using a photoreduction method or Heat treatment method fixed method. Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling out this page) The metal salt solution is basically as long as the metal species is dissolved in the cation. Specifically, it can be copper acetate, silver nitrate, copper carbonate, copper sulfate 'cuprous chloride, copper chloride, platinum chloride, palladium chloride, nickel chloride, cobalt chloride, ferrous chloride, and ferric chloride. The method of coating the metal salt solution includes spraying method or dip coating method, but it can be applied in a small amount, can be uniformly coated, the coating film is easy to control, and it does not want to adhere to the back. You can do whatever you want. Spraying method is the most suitable . In the photoreduction method, at least one kind of copper, silver, and platinum I is fixed on a thin film formed by a mixture of rutile-type Ti02 and osmium oxide having a crystal grain size of less than 0 Olem. The paper is again applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) '-154-406031 A7 ___B7 _ 5. Description of the invention (152), iron, cobalt, thallium, palladium, metal in cuprous oxide. The light source for irradiating light containing ultraviolet rays is only required to irradiate light containing ultraviolet rays. Specifically, it may be any one of ultraviolet lamps, BL lamps, xenon lamps, mercury lamps, and fluorescent lamps. For the method of irradiating light containing ultraviolet rays, it is better to arrange a sample so that the irradiation surface can receive light vertically. In this way, the best irradiation efficiency can be obtained. The distance between the sample and the light source is preferably 1 cm ~ 30 cm. When the distance is too close, the sample surface cannot be irradiated with uniform illuminance. The adhesion of the above metal species is prone to unevenness. When the distance is too far, the illuminance of the emitted light becomes inversely proportional to the distance square, and it is difficult to firmly attach the metal. . Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs (please read the precautions on the back before filling this page). In the heat treatment method, heating is performed after the metal has a temperature sufficient to fix it. Its temperature is preferably above 100 ° C. However, the metal will be oxidized when treated at a high temperature above 800 ° C. At this time, the metal is preferably a metal that is oxidized without losing the electron capture effect, or does not lose its antibacterial properties. It is limited to silver and copper. Silver and copper can be produced by high-temperature firing without losing the electron capture effect or antibacterial property. That is, a method in which T i 02 sol and osmium oxide sol are mixed in advance, coated on the surface of a substrate, and then coated with a metal salt aqueous solution, followed by firing. This method can be completed in one firing process, which can improve production efficiency and reduce manufacturing costs. The following is a specific example. Example 5 7 Suspension A was prepared by adding 4 to 6% by weight of a crystal grain size of 0.01 ml # m T i 0 2 sol in an aqueous ammonia solution adjusted to P Η 1 1. Add 10% by weight of crystal grains in another container. 〇〇〇35 / zm osmium oxide paper size of this paper applies Chinese National Standard (CNS) A4 specifications (210X297 mm): '-155-406031 A7 B7__ 5. Description of the invention ( 153) (Please read the precautions on the back before filling this page) The sol was made into suspension B in an ammonia solution adjusted to ρ Η 1 1. The suspension A and the suspension B were mixed at a predetermined ratio, and then spray-coated on the surface of a 15 cm square tile base material, dried, and fired at 850 ° C for 2 hours to obtain a sample. The T i 02 crystal type in the obtained sample was a rutile type. The lattice constant of T i Ο 2 was measured by powder X-ray diffraction. As a result, no solid solution of thorium oxide was found in the T i 02 lattice. "The photoactivity and abrasion resistance of the obtained sample were evaluated." The photoactivity is in the sample. The potassium iodide aqueous solution was dripped on the surface, and then the dropped potassium iodide aqueous solution was irradiated with ultraviolet rays for 30 minutes. The difference between the p Η value of the potassium iodide aqueous solution before the irradiation and the ρ Η value of the potassium iodide aqueous solution after the irradiation was evaluated. That is, according to this method, if the photoactivity on the surface of the sample is high, the redox reaction shown below can be sufficiently performed, so the ρ Η value after irradiation will be higher than the ρ Η value before irradiation. Oxidation reaction: 2I- + 2h + = I2 Reduction reaction .. 〇2 + 2H20 + 4 e_ = 40H- Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs. The abrasion resistance is caused by sliding friction of a plastic eraser to compare the changes in appearance. The evaluation indexes ◎, ○, △, and X are as described above. Figure 66 shows the effect of the weight ratio of hafnium oxide in the film on abrasion resistance. The presence or absence of hafnium oxide showed good abrasion resistance, and the results were ◎ or 〇. Due to the high temperature treatment at 850 ° C, sintering occurs and the particles in the film are firmly bonded to each other. In particular, it is ◎ when tin oxide is 30% or more. This is due to the T i 〇2 sol (crystal size 0.01 em) of the starting materials and the oxide sol (this paper size applies to China. National Standard (CNS) A4 size (210 X 297 mm) 406031) V. Description of the invention (154) The particle size ratio between the crystal grain diameters of 0. 0 0 3 5 # m) is 2 or more, so the hafnium oxide particles of fine particles can be buried in the voids of T i 0 2 particles to improve the filling property and make the film More dense. Figures 6 and 7 show the effect of the weight ratio of hafnium oxide in the film on the photoactivity. For comparison, the Δρ Η of copper-bearing sample (R3. 60%) in rutile T i 02 with good antibacterial and deodorizing properties is also shown here, and it has excellent antibacterial properties. ΔρΗ of the anatase-type T i Ο 2 sample (R 3: 97%) of the anatase type and deodorizing property. The ΔρΗ of the rutile-type T i 02 added with thoria is not as good as that of anatase-type T i 02, but it is still more than 10%, 80%, and more preferably 20% by weight. At 70% or less, the Λρ Η of the copper-carrying sample in the rutile T i 02 is larger, and it is known that it has good photoactivity. It can be seen that the photocatalytic activity cannot be improved when adding thorium oxide with an average particle size of greater than 0/1 // printed by the Shellfish Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling this page). It is still insufficient to move the position of the conductive belt upward due to the micronization of thorium oxide. The thorium oxide particles do not have a band pitch sufficient to generate active oxygen. In addition, if the amount is not more than 10%, sufficient photoactivity cannot be generated because the amount of hafnium oxide particles is insufficient. On the other hand, when the effect is reduced above 80%, the possibility of the existence of ytterbium oxide adjacent to each other in the photocatalyst layer is high, and the grains grow to an average particle diameter of 0.1 or more during heat treatment. Comparative Example 5 8 Suspension A was prepared by adding 4 to 6% by weight of a crystal grain size of 0.01 / m T i 0 2 in an aqueous ammonia solution adjusted to pH 1 1. Another paper size is applicable to China National Standard (CNS) A4 (210X297 mm) -157-406031 at Β7 V. Description of the invention (155) Add 10% by weight crystal grain in the container 0. 0 1 // m Pyrene oxide sol (please read the precautions on the back before filling in this page). Prepare suspension B in an ammonia solution adjusted to P Η 1 1. The suspension A and the suspension B were mixed at a predetermined ratio, and then spray-coated on the surface of a 15 square ceramic tile substrate, dried, and fired at 850 ° C for 2 hours to obtain a sample. The T i 02 crystal type in the obtained sample was a rutile type. Furthermore, the lattice constant of T i 0 2 was measured by powder X-ray diffraction. As a result, no solid solution of thorium oxide was found in the T i 〇 2 lattice. The light activity and abrasion resistance of this sample were evaluated. Fig. 68 shows the influence of the weight ratio of hafnium oxide in the film on the abrasion resistance. The presence or absence of hafnium oxide showed good abrasion resistance, and the result was 0. Due to the high temperature treatment at 850 ° C, sintering occurs and the particles in the film are firmly bonded to each other. However, even if the amount of hafnium oxide is increased, the abrasion resistance cannot be improved. This is because the particle size ratio between the T i 〇2 sol (crystal particle size 0, 01; am) and the hafnium oxide sol (crystal particle size 0.0 1 // m) of the starting material is approximately equal. Figure 6-9 shows the effect of the weight ratio of thorium oxide in the film on the photoactivity. For comparison, the Λρ Η of the copper-bearing sample in the rutile type T i 02 with good antibacterial and deodorant properties is shown here together with the anatase type with excellent antibacterial and deodorant properties. △ pH of T i 02 sample. The rutile-type Ti i 〇2Λρ added with thorium oxide is far less than ΛρΗ of the anatase-type T i 02 sample, and it is far less than the rutile-type Ti 〇2 sample carrying copper ΛρΗ. Example 5 9 This paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) -158-A7 B7 406031 I-V. Description of the invention (156) (Please read the precautions on the back before filling this page) Add 4 to 6% by weight of the crystal grain size. Olym T i 0 2 sol was prepared as a suspension a in an aqueous ammonia solution adjusted to pH 1 1. In addition, 10% by weight of a crystal grain size of 0.05% was added to a container; ammonium oxide sol was prepared as suspension b in an ammonia aqueous solution adjusted to ρ Η 11 1. The suspension A and the suspension B were mixed at a predetermined ratio, and then spray-coated on the surface of a 15 cm square tile base material, and dried at 850. (: Burned for 2 hours to obtain a composite material. The τ i 〇2 crystal type in the obtained composite material is a rutile type, and the weight ratio of hafnium oxide in the film is 60%. T i is measured by powder X-ray diffraction. The lattice constant of 2 is the number. As a result, there is no solid solution of hafnium oxide in the τ i 〇2 lattice. The composite material is coated with a 5% by weight copper acetate aqueous solution by spraying method, and then dried and light reduced (light source It is a 20W BLB lamp, the distance from the light source to the sample is 0cm, and the sample is irradiated for 1 minute). The deodorant characteristics of the obtained sample are evaluated. The employee consumer cooperative of the Central Standards Bureau of the Ministry of Economic Affairs printed this R3q system to obtain it according to the following test. Decomposed gas The sample was placed in methyl mercaptan using an initial concentration of methyl mercaptan adjusted to 2 p pm in a cylindrical container with a diameter of 2 cm and a height of 2 cm, and a 4W BLB fluorescent lamp was irradiated at a distance of 8 cm from the light source. After 30 minutes of irradiation, the reduction rate of methyl mercaptan concentration was calculated as the deodorizing property R30 (L) ° under light irradiation, and the deodorizing property R30 (D) in the dark was based on methylsulfide when 30 minutes of no light was passed. Calculate and calculate the alcohol concentration reduction rate. The results are shown in Table 2 6. For the sake of comparison, the samples prepared in Example 5 7 and Comparative Example 5 8 (the weight ratio of hafnium oxide was 60%) were also tested together. From Table 26, it can be seen that the effect shown below can be obtained by adding copper. This paper size Applicable to China National Standard (CNS) A4 specification (210X297 mm) -159-A7 B7 406031 V. Description of invention (157) (Table 2 6) Sample R 3 〇 (L) R 3 〇 (D) Example 5 7 82 0 Example 5 9 97 92 Comparative Example 5 8 32 0 (Sn02i weight ratio is 60%) From Table 26, it can be seen that compared with the sample of Example 5 R30 (L) slightly increased, this may be Due to the electron capture effect of copper. Compared with the samples of Examples 5 7 and Comparative Examples 5 and 8, R3Q (L) can be significantly improved. This increase in dark activity should be caused by the catalyst effect of copper. From the above It can be seen from the description that among the materials forming the photocatalyst film on the surface of the substrate, the T i 〇2 component of the photocatalyst film can be made into a rutile-type firing temperature treatment, which can make it have sufficient density and T i 02 film strength. At this time, in addition to the rutile T i 02, there is a crystalline oxide with a particle size of 0. Ol ^ m or less. Photocatalytic activity of media film. In addition, when fixing at least one kind of copper, silver 'platinum' iron, cobalt, nickel, palladium on the photocatalyst film, the photo-touch can be enhanced by electron capture. (CNS) A4 specification (210X297 mm) ---------- ^ ------ 1T ------ ^ (Please read the notes on the back before filling this page) Ministry of Economy Printed by the Central Bureau of quasi- Bureau of Shellfish Consumer Cooperatives -160 — A7 B7 1060 ^ 1 5. Description of the invention (158) Media activity. As mentioned above, the present invention relates to a multifunctional photocatalyst which has antibacterial, antifouling, cellular, odorous, or decomposable harmful substances such as NOx. It is extremely suitable as wall material, tile, glass, Mirror 'circulation filtering device, such as water-circulating artificial waterfall or stone used for paving in the fountain, or sanitary ceramics such as toilet and vanity. MR S A and other bacteria-infected hospital equipment for preventing infections, residential equipment, anti-critical equipment, and anti-virus equipment are used. (Please read the notes on the back before filling in this education.) Pack,? Τ-Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs This paper size applies to the Chinese National Standard (CNS) A4 (210X297 mm) 161

Claims (1)

L Version-Amendment 6. Application for Patent No. 8311001 Patent Application 4〇e〇3i Chinese Patent Application Amendment < Please read the precautions on the back before filling in this page > Revised in March, 1989_ 1. A multifunctional material with photocatalyst function * It is characterized by directly setting a photocatalyst layer with photocatalyst function on the surface of the substrate. The surface layer of the photocatalyst layer is taken out from the outside, and at the same time, the fine τ i 02 of the surface layer is combined with each other based on the adsorption position, and the average particle diameter of the T i 02 is 0.3 # m or less · 2. For example, the multifunctional material of the first patent application, in which the gap formed between at least T i 02 constituting the outermost layer is filled with particles smaller than the gap. 3. As in the second scope of the patent application Multifunctional materials * Among them, those on which the electron-trapping particles are fixed on the surface of Ti02 or the small particles filled by the gap. 4. The multifunctional material as described in the second item of the patent application, where T of the photocatalyst layer is formed i 02 is an anatase T i 02. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. 5. If the multifunctional material of the patent application scope item 1 is applied, in which the electron capture particles are fixed on the surface of T i 02 · 6. As many as the patent application scope area item 5 Functional materials, wherein the porosity of the surface layer portion of the photocatalyst layer is 10% to 40%, and particles with a particle size of 0.1 #m or less 〇〇〇35 / zm or more are contained in the pores. 7. Such as The multi-functional material with the scope of patent application No. 5 in which the particles filled in the gap formed between Ti0 2 have a particle size of less than 0.01 jam. The paper size is applicable to Chinese national standards (CNS > A4 specifications ( 210 X 297 mm) Μ0808 406031 6. Scope of patent application (please read the precautions of your noodles before filling out this page) 8. Multi-functional materials such as patent application No. 5 • where the substrate is made of glaze Inorganic glass, thermoplastic resin, solder and other thermoplastic materials are formed into a thin sheet · 9 · Multifunctional materials such as the scope of the first patent application, where the photocatalyst is provided in the adhesive layer provided on the surface of the substrate 餍To bury the aforementioned photocatalyst layer · 1 0 · If the multifunctional material of item 9 of the scope of patent application, in which the gap formed between Ti 02 constituting the outermost surface portion is filled with particles smaller than the gap · 1 1. As of patent application scope 1 The multifunctional material of item 0, wherein the surface of the τ i 02 or the surface of the small particles filled in the void is fixed with electron capture particles * 1 2. The multifunctional material of item 11 of the patent application, wherein the photocatalyst layer It is made of rutile-type Ti 02 thin film, and the electron-trapping particles are at least one kind of copper, silver, and cuprous oxide. 1 3. Such as the multifunctional material of the scope of patent application No. 9, where T i 0 2 is fixed on the surface Those who have electron-trapping particles · Printed by the Industrial and Commercial Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 14. If the multifunctional material of the patent application No. 13 is used, the photocatalyst layer is made of rutile T i 02 film, and the electron @ 得The particle system is at least one kind of copper, silver, and cuprous oxide. 15. The multifunctional material according to item 3, 5, 11, or 13 of the patent application scope, wherein the electron trapping particle system is at least one kind of copper, silver, and cuprous oxide. 1 6.If applying for Fan Xi's multi-functional materials according to item 12 or 14 This paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 * 297 mm> Zhen 08 406031) 6. Scope of patent application, of which at least one kind of copper, silver, The particle size of cuprous oxide is smaller than the gap of T i〇2. (Please read the precautions on the front surface before filling out this page.) 17. If the multifunctional material of the patent application No. 12 or 14 'is fixed in the The material of the T i 02 film is at least one kind of copper or cuprous oxide, and the amount of the substance fixed by the T i 02 film per unit surface is 0. 12 # g / cm2 ～ 1 · 2 // g / cm2 · 18 · For example, if the multifunctional material of the patent application No. 12 or 14 is used, the substance fixed to the Ti 02 film is at least one kind of copper or cuprous oxide, and the fixed amount of the substance fixed to the Ti 02 film per unit area is 0. 7 # g / cm 2 ～ 1.2 Aig / cm2 * 19. Multifunctional material such as patent application No. 12 or 14, in which gold 靥 is silver fixed to the T i 02 film, per unit face 稹Ti 02 film fixed silver set 〇5 〇5 # g / cm2 ～ 1 仁 g / cm1 · 2 0. Multifunctional material such as the patent application No. 9 The surface porosity of the photocatalyst layer is 1 096 ~ 4 0%. • Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 2. For example, the multifunctional material of the 9th scope of the patent application, where the photocatalyst layer surface layer The porosity of the part is 1 0 ~ 2 0% · 2 2. As the multifunctional material of the patent application No. 9, the particle system constituting the photocatalyst layer is 0. 008 # m〜0.1 # mSIZE This paper size Applicable Chinese national standards < CNS) A4 specification (210 * 297 mm) 1 3. The multifunctional material according to item 9 of the patent application park, wherein the adhesive layer formed on the surface of the substrate is an amorphous layer. The crystalline adhesive layer and the photocatalyst layer have a continuous change in the concentration of the components of the two sides in between 406031 6. Intermediate layer in the scope of patent application · 2 4. The multifunctional material such as the ninth patent application, wherein the substrate is It is made of glass containing alkali gold tincture, and the adhesive layer formed on the surface of the glass base # containing alkali metal is made of silicon material. A multifunctional material, in which the photocatalyst layer is formed using titanium alkoxide as a starting material, and the softening point of the low melting point substrate is higher than the crystallization temperature of the titanium alkoxide, and the softening of the intermediate rhenium The point is the same as or higher than the crystallization temperature of the alkoxide. 26. For example, the multifunctional material of the 9th scope of the patent application, wherein the adhesive layer is made of glaze, inorganic glass, thermoplastic resin * solder and other thermoplastic materials Authors · 27. If applying for a patent 9 of the multifunctional material, wherein the specific gravity of the T i 02 is t, the specific gravity of the adhesive layer is < 5b is 0 彡 < 5t-5bS3.0. 28. For example, the multifunctional material for the first item of the patent application park, where the multifunctional material is used as a tile for water-circulating artificial waterfalls or water-jet paving, stone · 2 9 · — many kinds of photocatalyst function A functional material is characterized in that a photocatalyst with photocatalyst function is directly provided on the surface of the substrate. This photocatalyst layer has its surface layer portion exposed to the outside, and this surface layer portion T i 02 is combined by solid phase sintering, and T i The average particle size of 〇2 is 0.3 # m or less. 30. If the multifunctional material of the 29th scope of the patent application, the paper size applies to the Chinese National Standard (CNS > A4 specifications) < 210 * 297 mm) Please read it first. Fill in the notes of Sj and then fill in the page I. I order the Intellectual Property Bureau of the Ministry of Economic Affairs and the Fifth Cooperative Press-4-A8 B8 C8 D8 4CSQ31 6. Scope of Patent Application Electron-trapping particles are fixed on the surface of T i 02 · 31. Multifunctional materials such as the 30th patent application group, where the substrate is made of thermoplastic materials such as glaze, inorganic glass, thermoplastic resin, solder, etc. 32. The multifunctional material according to item 29 of the patent application park, wherein in the photocatalyst layer provided on the surface of the substrate, the photocatalyst is arranged to bury the lower part of the aforementioned photocatalyst book. 3 3. The multifunctional material of the patent application No. 32, in which the electron capture particles are more fixed on the surface of Ti 02. 34. The multifunctional material of the patent application No. 33, wherein the photocatalyst layer is made of rutile T i 02 thin film, the electron-trapping particles are at least one kind of copper, silver, cuprous oxide. 35. Such as the multifunctional material of the patent application No. 34, wherein the at least one kind of copper, silver, and The particle size of copper is The gap between T i 0 2 in the T i 0 2 film is small. 36. For example, the multifunctional material of item 34 of the patent application, wherein the substance fixed to the T i 02 film is at least one copper or cuprous oxide per unit. The amount of immobilization of the material fixed on the surface of Ti02 film is 0.12Aig / cm 2 ～ 1.2Aig / cm2 · 37. Such as the multifunctional material of the patent application No. 34, which is fixed to the Ti 02 film The substance is at least one kind of copper or cuprous oxide, and the immobilization amount of the substance per unit surface of T i02 film is 0.7 jtig / cm2 ~ l. 2 β g / cm 2 · 38 Item of multifunctional materials, in which the paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 * 297 male fluorescent) (please read the unintentional matters on the arm surface before filling out this page). II--III Order I- ----- Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs and printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs and printed M 406031 _______ 6. The scope of the patent application is fixed to the metal silver of the T i 02 film, per unit face T i 〇2 The amount of silver fixed by the film is 0.05 g / cm2 to 1 g / cm2 〇39. The multifunctional material with the scope of patent application No. 30 or 33, among which T i 02 constituting the photocatalyst layer is a rutile type Ti 02 · 40. If the multifunctional material with the scope of patent application No. 30 or 33 is applied, The porosity of the surface layer of the photocatalyst layer is 10% to 40%, and particles with a particle diameter of 0.0035 to 0.1 and less than m are held in the pores. 4 1. Such as the application of the nitrile patent No. 30 or 3 3 The multifunctional material according to item 1, wherein the particles filled in the gap formed between T i 0 2 are those having a particle size of less than 0 1 · 4 2. As many as item 30 or 33 of the patent application scope Functional materials, wherein the electron-trapping particles are at least one kind of copper, silver, and cuprous oxide. 43. The multifunctional material according to item 32 of the patent application, wherein the porosity of the surface layer of the photocatalyst layer is 10 ~ 2 0% · 4 4. The multifunctional material according to item 32 of the patent application park, wherein the porosity of the surface layer portion of the photocatalyst layer is 10% ~ 4 0% · 4 5. The multifunctional material of item, wherein the adhesive layer formed on the surface of the substrate is an amorphous layer, and the amorphous adhesive layer and the photocatalyst layer are formed between There is an intermediate 餍 that continuously changes the concentration of both components. 46. The multifunctional material according to item 32 of the patent application, wherein the substrate is formed of a glass containing an alkali metal component and a glass containing the alkali metal rhenium component The bonding agent formed on the surface of the substrate is made of silicon. The paper size applies to the Chinese national standard (CNS > A4 specification (210 * 297 mm). I n I Βϋ 1 n ϋ ϋ 1. · It ϋ 1 awf I y (Please read the precautions on the back before filling out this page) Seal of the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs of the People's Republic of China 406031 VI. Application for a patent 47. For example, if you apply for a multifunctional material of the 46th national patent, the photocatalyst layer is Titanium alkoxide is formed as a starting material, and the softening viscosity of the above-mentioned low-melting substrate is higher than the crystallization temperature of the titanium fermentate, and the softening point of the intermediate _ is equal to the crystallization of the alkoxide. Temperature or higher than 48. For example, the multifunctional material of the 32nd application range, wherein the adhesive layer is made of thermoplastic materials such as glaze, inorganic glass, thermoplastic resin, solder and the like. 49. If you apply for The range of the 32 multi-functional material, wherein the specific gravity of the T i 02 5 t, the specific gravity of the adhesive layer is 5b, based San 0 (the 5 T- < 5b 螽 3. 0 · 50. Such as the multifunctional material of the scope of application of the patent No. 29, wherein the particle size of the photocatalyst layer is 0. 1 # m ~ 0. The particle size of the photocatalyst layer is 0. 5μπι ~ 0. 9μιη and a neck is formed between the particles constituting the photocatalyst layer. 5 1. As a multifunctional material of the patent application No. 29, the Ti 02 anatase type oxidation combined with solid phase sintering The interval between titanium particles and titanium oxide particles is approximately the same before and after sintering, and the neck between the titanium oxide particles is solidified and its vapor pressure is higher than that of titanium oxide. 52. Such as the multifunctional material of the 29th patent application park, Among them, the multifunctional material is a tile used for artificial waterfalls or water spraying paving in water circulation mode. Stone * 5 3 · A multifunctional material with photocatalyst function, which is characterized in that the photocatalyst function is directly installed on the surface of the substrate. The photocatalyst layer, the photocatalyst layer is the surface layer of the photocatalyst layer, and the paper size constituting the surface layer portion is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 public love)----II-- — — — · 1111111 ^ * — — — — — — — (锖 Read the unintentional matter on the back before filling in this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 406031 § VI. The scope of patent application T i 02 The voids are filled with particles smaller than the voids, and the average particle size of the Ti02 is less than 0.3jum. 54. For example, the multifunctional material in the 53rd aspect of the patent application, where 'is on the surface or gap of T i 〇2 The surface of the filled small particles is fixed with electron-trapping particles. 55. For example, the multifunctional material of the 54th scope of the patent application, where the photocatalyst layer T i 02 is anatase Ti 02 · 5 6. The multifunctional material of item 54 of the patent group *, wherein the electron-trapping particles are at least one kind of copper, silver, and cuprous oxide. 57. The multifunctional material of item 53 in the scope of patent application, which is provided on the surface of the substrate In the adhesive layer, a photocatalyst layer is provided to bury the lower layer of the aforementioned photocatalyst layer. 58. For example, the multifunctional material of the 57th patent application, wherein the surface of T i 02 or the surface of the small particles filled in the air system is solid Those who have electron-trapping particles · 59. Such as the multifunctional material of the 58th top of the patent application range, wherein the electron-trapping particles are at least one kind of copper, silver * cuprous oxide · 60. Such as the scope of the patent application No. 58 Multifunctional material, in which the photocatalyst layer is made of rutile-type Ti 02 thin film, and the electron-g obtained particles are at least one kind of copper, silver, and cuprous oxide. 6 1. Multifunctional materials, where the thickness of the rutile Ti02 film is 0.1 l # m to 0.9 μm. 62. For multifunctional materials with the scope of patent application No. 60, the paper size applies to the Chinese National Standard (CNS ) A4 size (210 X 297 male t) ---- 111 ---- installed! —Order! 4 (Please read the notes on the back before filling in this page) -8-I ο 4 A8B8C8D8 VI. Patent application scope The particle size of the at least one type of copper, silver, and cuprous oxide is smaller than the pore size of Ti〇2 film * (Please read the notes on the mouth first, and then fill out this page) 63. If you apply for the multifunctional material of item 60 in the patent application, the material fixed to the Ti 02 film is at least one copper or cuprous oxide '毎Unit surface 稹 T 02 film fixation system of the substance 〇 12 # g / cm2 ～ 1.2 # g / cm2 · 64. For example, the multifunctional material of the 60th scope of the patent application, which is fixed to the The material of T i 02 film is at least one kind of copper or cuprous oxide per unit surface. T i 0 2 The fixed amount of the substance fixed by the film is 0.7 from g / cm2 to 1. 2itzg / cm2. 65. If applied The multifunctional material of the 60th item of the patent, in which the metal-based silver fixed to the Ti 02 thin film is 稹 T i 〇2 per unit surface of the silver-fixed silver fixed system of 0. 0 5 g / cm2 to 1 inch g / cm2 〇6 6. The multifunctional material according to item 57 of the patent application, wherein the photocatalyst 餍 Ti 02 anatase 构成Type T i 02. 67. For example, if you apply for the multifunctional material of item 57 of the patent, in which the employee's cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs prints the porosity of the optical media table, the porosity is 10% ~ 20%. 68. If you apply The multifunctional material of the 57th aspect of the patent, wherein the porosity of the surface layer portion of the photocatalyst layer is 10% to 40%. 69. The multifunctional material of the 57th aspect of the patent application, wherein the substrate surface The adhesive layer is an amorphous layer. Here, the amorphous adhesive layer and the photocatalyst layer have an intermediate M between them that continuously changes the concentration of the components of both sides. · This paper size applies to the Chinese National Standard (CNS) A4 specification ( 210 * 297 public love) A8B8C8D8 406031 VI. Application for patent scope 70. The multifunctional material of item 57 such as patent application, where the substrate is made of glass containing rhenium and gold osmium, which contains the alkali metal The adhesive layer formed on the surface of the glass substrate of the composition is made of silicon. 71. For example, the multifunctional material of item 70 of the patent application, wherein the photocatalyst layer is formed using titanium alkoxide as a starting material. In addition, the above-mentioned low melting point substrate The softening viscosity is higher than the crystallization temperature of the titanium ferment salt. Also, the softening point of the intermediate layer is equal to or higher than the crystallization temperature of the alcohol toilet. 72. Such as the multifunctional material of the 57th patent application Among them, the adhesive layer is made of thermoplastic materials such as glaze, inorganic glass, thermoplastic resin, solder, etc. and is sheet-like * 7 3. Such as the multifunctional material of the scope of patent application No. 57, where the T The proportion of i 02 is < 5 t, the specific gravity of the adhesive layer is < 5b, the system is 0S5t-5bS3. 0. 74. Such as the application of the scope of the 53rd aspect of the multifunctional material, wherein the particles constituting the photocatalyst layer is 0. 008 # m ~ 0. l # m 的 particle size · 75. The multifunctional material according to item 53 of the patent application, wherein the porosity of the surface layer portion of the photocatalyst layer is 10% ~ 4 0%. A particle size of 0 0035 // m to 0 is contained in the pores. / im 的 particles ^ 76. Such as the multifunctional material of the patent application circle item 53, wherein the particles filled in the gap formed between T i 0 2 is a particle size of 0. 0 1 μιη or less. 77. For example, the application of the patent No. 53 of the multifunctional material 'where the substrate is made of thermoplastic materials such as glaze, inorganic glass, thermoplastic resin, solder, etc. The paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 111 — 11 — 111 · * — — — — — — — 1111111 (Please read the notes on the back before filling out this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs -10-A8B8C8D8 406031 Formed into a thin sheet · 7 8. Multifunctional as the scope of the patent application No. 53 Materials, in which the particles filled in the gap formed between T i 02 have an average particle diameter of 4/5 or less of the average particle diameter of τ i〇a. 79. The multifunctional material according to item 78 of the patent application, wherein The particle filled in the gap of T i 〇2 is based on the total of τ i 02 and the filled particles. The Mohr ratio is 10% to 60%. Functional materials, in which the vapor pressure of the substance constituting the particles filled in the gap of T i 02 is higher than the vapor pressure of the substance constituting T i 〇2, and the particle system filled in the gap of T i 02 is condensed at T i 〇2 Between the neck · 81. The multifunctional material according to the scope of patent application No. 80, wherein the particles filled in the void of T i 〇2 are tin oxide. 82. The multifunctionality like the scope of patent application No. 78 Material * The particle filled in the gap of T i 02 contains at least one kind of silver, silver oxide, copper * cuprous oxide · 83. The multifunctional material as claimed in the scope of patent application No. 78, wherein the T i 0 2 The particles filled in the voids are tin oxide. 84. Such as the multifunctional material of the patent application No. 83, where The Ti 02 is a rutile Ti 02, and the crystalline size of the tin oxide particles filled in the voids of Ti 02 is less than or equal to Oliim * 8 5. As a multifunctional material in the scope of the patent application No. 83, The T i 02 is a rutile T i 02, and the crystalline particle size of the tin oxide particles filled in the voids of T i 〇2 is less than 0.01 # m. The photocatalyst layer is in accordance with the Chinese National Standard (CNS) on the paper scale. A4 specification (210 X 297 male *) ----------· II II III order · 1111! ·;; ^ ': < Please read the 1T side first >! Matters needing attention before filling out this page) Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs-II-Printed by the Consumers’ Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 5 Get 406031___m____ VI. Patent Application There is at least one kind of copper, silver, cuprous oxide in the scope. 86. If the multifunctional material of the scope of application for the patent No. 83, the reset ratio of the vaporized tin is more than 10%, less than 80%. 87. For example, the multifunctional material with the scope of patent application No. 78, in which the particles filled in the gap of T i 02 have photocatalytic activity. 88. The multifunctional material with the scope of patent application No. 53, where the multifunctional material is As a water circulation method of artificial waterfalls or tiles for water spraying paving, stone · 8 9. —A method for manufacturing a multifunctional material with a photocatalyst function, which is specifically coated with metal after forming a photocatalyst layer on the surface of a substrate An alkoxide or an organometallic salt is on the surface of the photocatalyst layer, and is then dried, heat-treated, and a gap is formed between Ti〇2, filled with particles having a particle size of 0.035j ^ m to 0.1 #m. 9 0. Photocatalyst A method for manufacturing a multifunctional material capable of forming a photocatalyst layer on the surface of a substrate, and coating a metal alkoxide or an organometallic salt on the surface of the photocatalyst layer, followed by drying, heat treatment, and forming a gap between T i 02 Fill particles smaller than the gap, and then apply an aqueous solution containing at least one kind of metal ions of copper, silver, and cuprous oxide, and irradiate light containing ultraviolet rays to precipitate fixed gold ions. 91. A photocatalyst A method for manufacturing a functional material, which is characterized in that a photocatalyst made of T i 0 2 is formed on a glass substrate, and then the glass substrate is softened, and a portion of the photocatalyst layer is buried under the glass substrate and then cured. 9 2 .If the patent application Fanyuan Item 91 is used for the manufacture of multifunctional materials, the paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 * 297 mm) — — — — — — — — — — — · II! Order II! I — I! 4 (Please read the precautions on the back before filling this page) -12-A8B8C8D8 406031 VI. Application for patents (please read the precautions on the back before filling out this page) Method, which is coated with τ i 〇 2 In the thinking of the substrate of Pomar [previously provided with a dispersing step as a preliminary step], in this dispersing step, the sol or precursor that should be T i 02 is dispersed in the solution. The dispersant used can only be used in 0035〜 0. The component vaporized at a temperature lower than the heat treatment temperature of the softened glass substrate. · 9 3. — A method for manufacturing a multifunctional material with a photocatalyst function, the gap of Ti〇2 is filled with a particle size of 0.035 ~ 0. L, Ti02 is combined with each other to produce a multifunctional material with a photocatalyst function, which is characterized by mixing Ding 102 with the particle size of sol or precursor or suspension in the state of 〇〇〇〇35μιη ~ 0. L #m 的 particles become a mixture, apply this mixture on a glass substrate to form a photocatalyst layer, and then soften the above glass substrate * make a part of the lower layer of the photocatalyst layer buried in the glass substrate, and then cure. 94. One with light L # m 的 金属 particles, Ti02 are combined with each other The method for manufacturing a multifunctional material with a photocatalyst function is characterized in that a photocatalyst layer made of T i 02 is formed on a glass substrate, and then the above-mentioned glass substrate is softened, and a part of the photocatalyst layer is buried in glass. 0035 # m〜0. Ιμιη The substrate, followed by curing the glass substrate, is then coated with a solution containing the above-mentioned particle size of 0. 0035 jam ~ 0. ljtzm in the photocatalyst layer, and heat-treated to fix the particle size of 0. 0035 # m ~ 0. Ιμιη靥 金 靥 particles in Ti02 · 9 5 manufacturing methods of multifunctional materials with photocatalyst function, the voids of Ti02 are filled with particles with a particle size of 0. 0035μιη to 0. Ιμιη, and Ti〇2 is combined with each other to produce a photocatalyst This paper size is applicable to Chinese National Standard (CNS) A4 specification (210 X 297 male «) -13-A8 B8 C8 D8 406031 VI. The method of multifunctional material with media function in the scope of patent application is characterized by glass substrate shape The photocatalyst layer formed by T i 0 2 then softens the above-mentioned glass substrate, so that a part of the lower portion of the photocatalyst layer is buried in the glass substrate, and then the glass substrate is cured. The photocatalyst layer is then coated with the above particle size 0. 0 0 3 5 # m ~ 0. l # m of ionic solution of metal particles · Then irradiate with ultraviolet rays to reduce the gold ion ions. · Fixed to Ti02 · 9 6. If the application for the patent 圔 多功能 9 5 multifunctional 7jag / cm2 〜l〇 # g / cm2e A method for manufacturing a material, in which a solution containing metal particle ions filled in the voids of T i 02, at least one of the species of gold tin is copper, and the copper carrying capacity is 0.7jag / cm2 ~ l〇 # g / cm2e 97. The method for manufacturing a multifunctional material according to item 95 of the scope of the patent application, wherein the solution containing gold ions particles filled in the voids of T i 02, at least one of the metal species of which is silver, is supported by silver. The amount is 0.05 夂 g / cm2 ~ 1 / zg / cm2 · 9 8. The method for manufacturing a multifunctional material such as the patent application item 95, wherein the light containing ultraviolet rays is irradiated to reduce the gold osmium particles to be fixed to Before T i 02, the photocatalyst coated with the ion solution containing the metal particles is dried. 9 9 . The method for manufacturing a multifunctional material according to item 98 of the patent application, wherein the solution containing the ions of the metal particles is ethanol * 1 0 0. The manufacturing method, in order to form a photocatalyst on a glass substrate, spray the sol or precursor or suspension of T i 02 * At this time, the temperature of the glass substrate is 20. 〇 ~ 8 0 eC · This paper size is in accordance with Chinese National Standard (CNS > A4 size (210 X 297 mm) — — — — — — — — — — — I _! — 丨 ·! | * ^ ( Please read "Precautions for Your Face before filling out this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs -14-A8B8C8D8 4060S1 VI. Application for patent scope 1 0 1. —A method for manufacturing multifunctional materials with photocatalyst function The gap of Ti〇2 is filled with metal particles with a particle size of 0.035jtim ~ 0.1 ljum, and Ti02 is combined with each other to produce a multifunctional material with a photocatalyst function. It is characterized by the formation of T i on a glass substrate The photocatalyst layer formed by 〇2 is coated with an ion solution containing metal particles having a particle size of 0.03 to 5 to 0.1 m in this photocatalyst layer, and then irradiated with light containing ultraviolet rays to reduce metal ions and fixed to the photocatalyst layer. T i 02, re-soften the glass base material to embed a part of the photocatalyst layer underneath the glass base material · and then cure the glass base material · 102. — A method for manufacturing a multifunctional material with photocatalyst function, its special removal For forming glass * The adhesive layer made of glaze tincture is on the surface of the substrate, and then the photocatalyst layer made of T i 02 is formed on this adhesive layer, and then the adhesive layer is softened so that a part of the lower part of the photocatalyst layer is buried in the adhesive. Bonding agent layer, solidified · 103 kinds of multi-functional materials with photocatalyst manufacturing method, which are specially formed on glass and glaze to form a thin layer of adhesive layer made of Ti 02 photocatalyst layer, placed or Paste this sheet-like adhesive layer on the surface of the I substrate, then soften the adhesive layer, so that a part of the photocatalyst layer is embedded in the adhesive layer, and then cured. 1 0 4. —A kind of photocatalyst A method for manufacturing a multifunctional material is characterized in that an adhesive layer is formed on the surface of a substrate, and a photocatalyst layer is formed thereon so that a part of the lower layer of the adhesive layer is buried therein, and the irradiation contains 1.7m W / cm2 or more Surface treatment agents that preferentially decompose and vaporize photocatalysts on surfaces with wavelengths below 390nm make this paper standard applicable to China National Standard (CNS) A4 (210 X 297 mm) — — — — — — — — — — — * IIII! I order i II — II Yin (Please read the notes on the back before filling in this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs -15-A8 B8 C8 D8 4060S1 VI. The scope of patent application Ti〇2 outgas to the outside world · 1 0 5. The manufacturing method of the multifunctional material according to item 104 of the patent application • wherein the adhesive layer is made of glass fiber with a softening temperature below 300 ° C and glaze 薬 Coating the adhesive After the bonding agent layer is coated on the substrate, T i 02 is coated thereon, and then heat-treated at a temperature lower than the softening temperature of the substrate and higher than the softening temperature of the adhesive layer to soften the adhesive and make the photocatalyst layer A part of the lower layer is buried in the adhesive layer to form a photocatalyst layer. 106. A method for manufacturing a multifunctional material such as the patent application No. 104, wherein the adhesive is made of a thermosetting material. So that the above-mentioned adhesive layer is mixed with the hardener and coated on the substrate * and then coated with T i 02 after heat treatment or leaving to thicken, so that a part of the lower layer of the photocatalyst layer is buried in the adhesive layer, After that, it is heat-treated to harden it.的 制造 方法 * Wherein a void is formed on a multifunctional material having a photocatalyst function, and the void is filled with particles having a particle diameter of 0.035 ~ 0.1 μm. 1 0 8. —A method for producing a multifunctional material with a photocatalyst function It is characterized in that after forming a layer mainly composed of T i 0 2 and a thermosetting resin on the surface of the substrate, it is irradiated with light containing a wavelength of 1. 7 m W / cm 2 or more and 390 nm or less to preferentially decompose and vaporize T i 0 2 The above-mentioned ingeniously hardening resin exposes Ti 02 to the outside air · 10 9. A method for manufacturing a multifunctional material such as the patent application No. 108, wherein the Ti 02 and the thermosetting resin are The thermosetting resin in the layer is at least one of silicone resin and fluororesin. The paper size is applicable to the national standard of China (CNS) A4 (210 * 297mm *). — — — — — — — — — — — · 1111111 — — — — — — — — — (Please read the notes on the back before filling out this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs -16-A8 B8 6. Scope of Patent Application 1 1 0 .—A kind of photocatalyst Manufacturers of functional materials (Please read the notes on the mouth surface before filling in this page> • .. method, which is characterized in that the surface of the substrate is formed by a thermosetting resin layer or a photocuring resin to form mainly T i After forming a plutonium with a thermosetting resin, it is irradiated with light containing a wavelength of 7 m W / cm2 and less than 390 nm to preferentially decompose and vaporize the thermosetting resin on Ti 02, exposing Ti02 to outside air. 1 1 1. A method for manufacturing a multifunctional material having a photocatalyst function, which is filled with particles having a particle diameter of 0.005 to 0.1 / im in a gap of T i 0 2 which is combined with each other to produce a multifunction having a photocatalyst function. The material method is characterized in that an adhesive layer made of glass * glaze is formed on the surface of the substrate, and then the adhesive layer is coated with sol or precursor or suspension in a state of mixing T i 02 and A mixture of the above-mentioned small-sized particles to form a photocatalyst layer, and then soften the adhesive layer so that a part of the photocatalyst layer is buried in the adhesive layer, and then cured. 1 1 2 — Photocatalyst Functional multifunctional material manufacturing method, system In the method of combining the voids of T i 02 which are combined with each other, a particle size of 0035 # m ~ 0.ljum, in a method for manufacturing a multifunctional material with the function of printing media of the employee's cooperative of the Intellectual Property Bureau of the Ministry of Economy and Trade, its Specially, a mixture of T i 02 and particles having a small particle size as described above is coated on a thin-layer adhesive layer made of glass or glaze to form a photocatalyst layer. Place or stick the sheet-shaped adhesive layer forming the photocatalyst layer on the surface of the substrate, and then soften the adhesive layer so that a part of the photocatalyst layer is embedded in the adhesive layer, and then cured. 1 13. —Manufacture of a kind of multifunctional material with photocatalyst function. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) -17-A8B8C8D8 Printed by the Consumers ’Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs 6. Scope of patent application The method is based on the method of filling the voids of the butadiene 102 bonded to each other with a particle diameter of 0.035 # m ~ 0.l # m to produce a multifunctional material with a photocatalyst function. Form The adhesive layer made of glass and glaze is then formed on this adhesive layer to form a photocatalyst layer made of T i 02. Then, the above adhesive layer is softened so that a part of the photocatalyst is buried in the adhesive layer. 0035 * Then cure the adhesive layer, and then coat the photocatalyst layer with a solution containing the above-mentioned particle size of 0. 0 0 3 5 // m ~ 0. l # m, after heat treatment to fix the above-mentioned particle size of 0. 0035 ~ 0 · lium particles in Ti02 · 1 1 4. A method for manufacturing a multifunctional material with a photocatalyst function, which is filled with 0. 0035 ~ 0. L # mSIZE 的Particles, in the method for manufacturing a multifunctional material with photocatalyst function, it is characterized in that a photocatalyst layer made of photocatalyst particles is formed on a sheet-shaped adhesive layer made of glass and glaze, and then the sheet-shaped adhesive of the photocatalyst layer is formed The bonding agent layer is placed or pasted on the surface of the substrate, and then the above-mentioned adhesive layer is softened so that a part of the photocatalyst layer is embedded in the adhesive layer, and then the adhesive layer is cured, and then the photocatalyst layer is coated with 0035 # m〜0. 1 / im 的 粒 的 溶液。 After heat treatment To fix the above-mentioned particle size of 0.035 ~ 0. L # m to T i 0 2 · 1 1 5. — A method for manufacturing a multifunctional material with photocatalyst function, which is in the gap of T i 02 which is combined with each other Filled with particles with a particle size of 0035 ~ 0. L # m to produce a multifunctional material with a photocatalyst function, which is characterized in that glass is formed on the surface of the substrate. The paper size is applicable to Chinese National Standard (CNS) A4 specifications. (210 X 297 mm) — — — — — — — — — — — 1111111 «— — — — — — I — ^ (Please read the notes on the back before filling out this page) -18-Ministry of Economy Wisdom A8 B8 printed by the Consumer Cooperative of the Property Bureau-^ mou ------- 6. Scope of patent application, adhesive 餍 made by glaze, and then T i 〇2 photocatalyst formed on this adhesive layer Layer * Then soften the adhesive layer so that a part of the lower part of the photocatalyst layer is buried in the adhesive layer, and then the adhesive layer is cured, and then the photocatalyst layer is coated with the above particle diameter of 0,035 / im ~ 〇 l # m ion solution of gold osmium particles, and then irradiate with ultraviolet light to reduce gold ions It is fixed to T i ◦ 2 · 1 16. The method of making multifunctional materials such as the item 115 of the scope of patent application, wherein it will form with the gold ions that can be filled in the gap of T i 02 The insoluble and colorless or white salt salt solution is contacted with the photocatalyst, and then irradiated with ultraviolet rays. 1 1 7. The method for manufacturing a multifunctional material according to item 1 16 of the patent application scope, wherein the T i 〇2 The gold 靥 particles filled in the space are silver, and between the metal ion and the metal ions, a solution containing KI, KCj ?, F e C)? 3, which is an insoluble, colorless or white salt, is used. · 1 1.. — A method for manufacturing a multifunctional material with a photocatalyst function * The voids of T i 0 2 that are combined with each other are filled with particles having a particle diameter of 0035 # m ~ 0.l # m to produce In the method of a multifunctional material with a photocatalyst function, the method is specifically to form a photocatalyst layer made of T i 02 on a sheet-shaped adhesive layer made of glass or glaze. Then, this is used to form a sheet-shaped adhesive layer made of photocatalyst. Carry or stick on the surface of the substrate, and then soften the adhesive 0 035 # m〜0. Liim 的 金属 particle 的 铁。 I bury a part of the lower part of the photocatalyst layer into the adhesive layer, and then cure the adhesive layer, and then coat the photocatalyst drawer with the above-mentioned particle size of 0. 035 # m ~ 0. Liim of metal particles The size of the paper is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 g) — — II-— — — — — — 1111111 — — — — — — — I (Please read the notes on the back before filling (This page) -19-Printed A8 406031 by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 1 VI. The patent application liquid 'is then irradiated with ultraviolet light to reduce the gold ion to fix it to the photocatalyst particles 1 1 9. A method for manufacturing a multifunctional material with a photocatalyst function, which is a method of manufacturing a multifunctional material with a photocatalyst function in a gap of T i 〇2 that is bonded to each other and filled with particles having a particle diameter of 0.035μιη ~ 〇 · l # m. It is characterized in that an adhesive layer made of glass and glaze is formed on the surface of the substrate, and a photocatalyst made of T i 02 is formed on the adhesive layer. Small metal particles containing the above-mentioned particle size are ionized. The solution is applied on Photocatalyst layer, and then irradiate with ultraviolet rays to reduce Au particles and fix to T i 02, then soften the adhesive layer so that a part of the photocatalyst layer is buried in the adhesive layer, and then cured. 1 2 0 A method for manufacturing a multifunctional material with a photocatalyst function, in which the voids of T i 02 that are combined with each other are filled with a particle diameter of 0035 # m ~ 0.1. From the particles of m to produce a multifunctional material with a photocatalyst function The method is characterized in that a photocatalyst layer made of T i 02 is formed on a thin film adhesive layer made of glass and glaze. The ionic solution containing metal particles having a small particle size is coated on the photocatalyst layer, and then the photocatalyst layer is irradiated. Ultraviolet light reduces gold ions to fix T i 02, and then the thin adhesive layer forming the photocatalyst layer is placed or pasted on the surface of the substrate, and then the above adhesive layer is softened to make a part of the photocatalyst layer The lower layer is embedded with an adhesive layer, and the adhesive layer is solidified. 1 2 1 A method for manufacturing a multifunctional material with a photocatalyst function, which is characterized in that an adhesive bond is formed on the surface of the substrate, and then a surface paper is formed. Scale Use Chinese National Standard (CNS) A4 specification (210 * 297 mm) — — — — — — — — — I · IIII — II order · IIIIIII > (Please read the notes on the mouth first and then fill out this page ) -20-A8B8C8D8 406031 6. The scope of the patent application can be exposed from the adhesive layer. After the lower part can be buried in the photocatalyst layer of the adhesive layer, the surface of this photocatalyst layer is coated with gold alkoxide or organic metal salt. Then, the space formed between T i 0 2 by dry heat treatment is filled with particles with a particle diameter of 0.0 0 35 ~ 0.1 卩 111 · 1 2. — A method for manufacturing a multifunctional material with photocatalyst function, which is characterized in An adhesive layer is formed on the surface of the material, and the surface layer portion can be exposed from the adhesive layer. After the lower layer portion can be buried in the photocatalyst layer of the adhesive layer, the surface of the photocatalyst layer is coated with gold fermented salt or organic metal. Salt, followed by drying heat treatment to form a gap between T i 02, filled with particles of 0. 0 0 3 5 ~ 0. 1 # m, and then coated with metal ions containing at least one copper, silver, cuprous oxide Aqueous solution, reduced by light to precipitate fixed metal particle. 1 2 3. — A method for manufacturing a multifunctional material with a photocatalyst function, which is: a method for forming a photocatalyst layer on a glass substrate containing sickle metal to manufacture a multifunctional material, characterized in that it contains: A silicon layer is formed on top; a titanium alkoxide is coated on the aforementioned silicon layer: dried to obtain amorphous titanium dioxide: those who crystallize amorphous titanium dioxide by heating. 124. Multifunctional material with photocatalytic function, such as the scope of application for patent 123 The manufacturing method, wherein the coating amount of the titanium ferment salt coated on the surface of the photocatalyst layer is converted into T i 02 as 1 0 # g / cm2 ～ 100 “g / cm2 · 1 2 5. 23 The method for manufacturing a multifunctional material with photocatalyst function according to item 3, wherein the heat treatment temperature of the titanium alkoxide coated on the surface of the photocatalyst layer is 4 0 ° C ~ 8 0 0eC. · This paper size is applicable to Chinese national standards (CNS ) A4 size (210 X 297 mm) — — — — — — — — — — I. · IIII _ (Please read the “Notes on the back before filling this page”) Printed by the Consumer Property Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs -twenty one -A8B8C8D8 VI. Application scope of patent 1 26. For the manufacturing method of the multifunctional material of the patent application No. 1 23, in which the titanium alkoxide in the coating solution coated on the surface of the photocatalyst layer is hydrochloric acid, Set to 1% by weight% ~ 10% by weight * 12 7 .—A method for manufacturing a multifunctional material with photocatalyst function, which is characterized by mixing a sol of titanium oxide with a sol having a higher vapor pressure than titanium oxide, and coating After disposing the mixed sol on a substrate, it is sintered at a phase transition temperature lower than the temperature of rutile. 1 2 8. —A method for manufacturing a multifunctional material with a photocatalyst function * It is characterized by: on the surface of the substrate Steps for fixing Ti 02 and non-ferrous metal particles; the step of reacting the above metal particles with a solution or gas to form a colorless or white salt at least on the surface of the metal particles A method for manufacturing a multifunctional material according to item 1, wherein the halogenated salt solution of the liquid system reacting with the above-mentioned metal particles, hydrogen peroxide water, ozone water, 1 3 0. Such as the scope of the application for the patent No. 1 2 8 The manufacturing method of the multifunctional material, wherein the gas system oxygen reacting with the above-mentioned gold rhenium particles, ozone ， 1 3 1. The manufacturing method of the multi-functional material such as the patent application country No. 1 28 * Among which reacts with the above-mentioned gold rhenium particles Liquid or gas system oxidant · 1 2 2 manufacturing methods of multifunctional materials with photocatalyst function, which is characterized by forming a rutile T i 02 film on the substrate surface, and then coating at least one kind of nickel, palladium on the film, Aqueous solution of platinum metal salt or the size of this paper applies Chinese national standard (CNS> A4 size (210x297 feet) (please read the precautions on the back before filling this page) --- IIII 丨 order · I !! _ ^ Ministry of Economy Printed by the Intellectual Property Bureau's Consumer Cooperatives -22-A8B8C8D8 406031 VI. Patent application scope of metal salt in ethanol solution, and then irradiate with ultraviolet light to reduce metal ions, to fix gold tincture on rutile T i 02 film · 1 3 3. The method for manufacturing a multifunctional material according to item 132 of the scope of patent application, wherein the gold ions irradiated with a light source containing ultraviolet rays are reduced to make the coated metal After drying the aqueous solution or ethanol solution of the ruthenium salt, perform 134. The method for manufacturing a multifunctional material such as the 134th patent application scope, wherein the rutile T i 0 2 thin film is through a binder L # m 〜0. 9 # in · 1 The layer is formed on the surface of the substrate. 135. A method for manufacturing a multifunctional material, such as the patent application No. 132, wherein the thickness of the rutile T i 02 film is 0. l # m ~ 0. 9 # in · 1 36. — A method for manufacturing a multifunctional material with a photocatalyst function, which is characterized in that a rutile T i 02 film is formed on the substrate surface, and a copper salt aqueous solution is coated on the film, followed by irradiation with ultraviolet light 1.2 # g / cm2 ~ 10 // g / cm2 copper-gold tincture was fixed on rutile T i 0 2 film by reducing copper ions. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. A method for manufacturing a multifunctional material with a photocatalyst function is characterized in that a rutile T i 02 film is formed on the surface of a substrate, and a silver salt aqueous solution is coated on the film, followed by irradiation with ultraviolet light to reduce silver ions. Fixed 0. 1 # g / cm2 ～ 1 # g / cm2 silver metal to gold red Stone-type T i 0 2 film · 138 · A method for manufacturing a multifunctional material such as the scope of application for patents No. 102, 115 or 119, which can soften the heat of the adhesive bond. Specification (210 * 297 public love) -23-5 CAC A8B8C8D8 VI. Application scope of patent application The processing temperature is 800 eC ~ l 00〇ec · 139. If the patent application scope is i02, 115 or 119 multifunctional material The manufacturing method, wherein the binder is selected from those whose softening temperature is lower than the softening temperature of the substrate, in a range higher than the softening temperature of the binder by 20 eC, 3 2 0 1 and lower than the softening temperature of the substrate Heat treatment at low air temperature · 140. A method for manufacturing a multifunctional material such as patent application No. 102, 103 or 119, which includes the step of applying T i 02 on the adhesive layer Preparatory dispersing step • In this dispersing step, the dispersant that can become T i 02 sol, precursor or suspension in solution is used only in the softer binder 用 lower heat treatment temperature Components that can be gasified at temperature · 141. Rushen The patentable scope of 1〇2 115 or as many as a method for producing a functional material, wherein the specific gravity of the T i 02 < 5 t, the specific gravity of the adhesive layer is < 5b, it is 0 tδ t — 5b 彡 3. 0 1 4 2. For example, the method for manufacturing a multifunctional material with photocatalyst function in item 119 of the patent application scope, wherein the photocatalyst particles are Z nO, and The gold contact particles filled in the voids of T i 02 are silver or silver oxide. * This paper size applies to Chinese national standards (CNS> A4 size (210 X 297 male cage). Read first. Remarks on the back, then I install this page IIII order Printed by the Employees' Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs-24-