TW460322B - Photo-catalytic oxide-containing composition, process for making a film, and composite of a film with a base material - Google Patents

Abstract

A composition comprising photo-catalytic oxide particles, a solvent-soluble and non-hydrolyzable zirconium compound soluble in a solvent, and the solvent. Preferably, the photo-catalytic oxide particles are titanium oxide particles and have an average particle diameter of 0.005 to 0.3 μpm, and the amount of the zirconium compound is in the range of 3 to 200 parts by weight as ZrO2 based on 100 parts by weight of the oxide particles. A composite composed of a substrate and a film having a photo-catalytic function is made by coating the substrate with the composition and then curing the film coating.

Description

A7 B7 Principle 460322 V. Description of the invention (related to male surname X Xiao system-a composition containing photocatalytic oxides, a very high level of photocatalytic energy in the past two years, and the phenomenon of thickening with time is extremely excellent. The material shows good adhesion when it is cleared at the coating film of the substrate. Technical background The research and development of the photocatalyst effect of oxides such as titanium oxide has become popular in the past ten years. Because it has harmful effects on removal Antifouling of substances, good mechanism for decomposing and purifying those in the air, yellowing compounds, and sterilization, etc., so it is expected to be used in various fields. Photocatalyst (hereinafter referred to as photocatalytic) oxide Particles can be formed in various forms, such as group particles, lysates, and thin films depending on the purpose of use. However, from a practical point of view, it is often easy to form thin films by manipulation. Thinning of photocatalytic oxide particles As a method, for example, a method of forming a photocatalyst oxide thin film on the surface of a broken glass by a sol-gel method (chemical liquid deposition method) is well known. This method of dissolving gels “has a high cost of starting materials and uses a large amount of organic solvents”, so it has safety problems such as working environment. Moreover, since the thin film is a metal oxide, it is necessary to perform the treatment at a high temperature on the glass surface. Treating 'the substrate that can form a photocatalyst film, is limited to heat-resistant materials *, which results in an increase in the use of obstacles. The term "non-hydrolyzable" used in this specification means that a composition containing a titanium compound is used in the step of preparing the composition And it will not be hydrolyzed during the storage of the composition. This paper size applies Chinese National Standard (CNS) A4 specification (2 丨 〇〆297mm) Α ^ —- IT ------. # (Please read the back first Please fill in this page before printing) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs -4- 460322 Α7 ___ Β7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (2) Photocatalyst oxide particles Formula 5 that the adhesive adheres to the substrate. For example, in Japanese Patent Application Laid-Open No. 8-164334, the use of a hydrolyzable product of a hydrolyzable silicon compound as the adhesive film forming property was mentioned. In Japanese Patent Application Laid-Open No. 9-188850, the coating film forming element composed of a siloxane polymer or a silicate, and a coating film composed of a hydrolyzable silane inducer monomer as an adhesive were mentioned. However, since any one of them uses a hydrolyzable silicon compound, hydrolyzation occurs slowly to undergo a polycondensation reaction. As a result, the adhesive force of the composition during storage is reduced and the viscosity is increased, leaving a useful period ( It can shorten the time). Fix the photocatalytic oxide film on the substrate such as glass, plastic, etc., and try to make the photocatalyst exhibit its performance. Perform various treatments as described above. Due to the required characteristics The level is high. So far, no one has found a balance between them and fully satisfied. The purpose of the present invention is to provide a composition containing a photocatalyst oxide, not only to maintain a very high level of photocatalyst oxide photocatalyst performance. 'Furthermore, the workability is extremely small with time-dependent thickening phenomenon. As a thin film forming material, it shows good adhesion when the substrate is coated.着 性。 Sex. Another object of the present invention is to provide a thin film formed from the photocatalyst-containing oxide composition. Still another object of the present invention is to provide a composite body, which is formed by coating the above-mentioned photocatalyst-containing oxide composition on the surface of a substrate to form a transparent film that is strongly adhered to the substrate and is not easily peeled off from the substrate. Constituted by. (Please read the precautions on the back before filling this page] -Installation-iT_ Silk paper performance depends on Zhongguanjiapi (CNS) A side ^ (2) Gx297 male thin} 460322 Α7 ________ Β7 V. Inventor Group Reviewing the results of various suitable photocatalyst oxide-containing compositions as film-forming materials, it was found that by adding specific compounds, the photocatalyst-oxide-containing composition can not only maintain a very high level of photocatalyst energy, but also with time Good workability with very little viscosifying phenomenon and good adhesion as a film-forming material, so the present invention was completed. In other words, according to the present invention, an oxide particle with photocatalytic energy, solvent solubility and non- A composition comprising a hydrolyzable compound and a solvent. Furthermore, according to the present invention, there is provided a thin film formed from the photocatalyst-containing oxide composition. According to the present invention, the photocatalyst-containing oxide is further formed according to the present invention. The composition is applied on the surface of the substrate to form a composite composed of a film and a substrate. The best form of the invention When the photocatalytic oxide particles used in the present invention are irradiated with a light source having a larger energy than the band gap between the crystalline conductor and the valence electron band, the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs prints organic compounds. The redox reaction shows the catalytic activity of metal oxides. Specific examples of metal oxides that show catalytic activity as mentioned above include rutile titanium oxide, osmium-like titanium oxide, blue crystal oxide, Acid bromide, tin oxide, oxide, iron oxide, etc. belong to the above-mentioned photocatalyst reaction, because the photocatalyst reaction occurs near the surface of the oxide particles, and from the viewpoint of photocatalytic activity, it is based on fine oxide particles. (CNS) Ege (plus χ297 male thin ^ ------ -6-printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 4 6 0 3 2 2. a? —___________ B7 V. Description of the invention (4) '' " However, it is difficult to manufacture if the average particle size is less than 〇〇〇05_. Therefore, the average particle size used is usually in the range of 0.05 ~ 〇3_, and the average particle size is in the range of 0-01 ~ 〇 · 1. β m is ideal. Its specific surface area is preferably in the range of 50 ~ 400 m2. Among them, photocatalytic metal oxides are converted into “Si”, because U particles such as the above are available from Guyi, and are harmless and chemically Stability, most suitable for use. Titanium oxide produced by well-known methods can be used without limitation. When titanium oxide is produced by hydrolytic decomposition, sol containing titanium oxide produced by hydrolytic decomposition can also be used. Also, It is also possible to obtain titanium oxide fine particle powder from this sol and disperse it in a solvent. Other oxidized fine particles may be prepared by a well-known gas phase method. A particularly preferred method for preparing titanium oxide fine particles is The method of hydrolyzing titanium gas or titanium sulfate by hydrolyzing is not only easy to operate, but also low in price. The method of hydrolyzing is not particularly limited, and a method in which a reflux cooler is installed in the hydrolyzing tank and the evaporated gas is condensed and returned to the hydrolyzing tank is ideal. The titanium oxide particles prepared by this method have good transparency and good dispersibility. The blending amount of the photocatalytic oxide in the composition is preferably in a range of 1 to 25% by weight based on the total amount of the aforementioned composition. When it is less than 1% by weight, the photocatalyst energy is insufficient. When it exceeds 25% by weight, not only the dispersion of the oxide particles is reduced and the viscosity is increased, but the composition is unstable, which is not desirable. The lead compounds used in the present invention are those that act as a binder when the photocatalyst-containing oxide composition is used in the coating process of the substrate, which is biased towards the Chinese paper standard (CNS) A4 specification (210X297). ) I- nn I ~ K .....- III # (#Read the notes on the back before filling this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 460322 A7 ____B7 V. Description of Invention (5) Solution Any one of the compounds in water or organic solvents can be used. Α The water-soluble hammer compound 'such as oxychloride, zirconium hydroxy gas, nitrate, sulfonic acid, acetic acid, etc. which form acidic aqueous solution, and carbonic acid. Zirconium compounds, such as cyanide, potassium acid, potassium acid, sodium salt, etc., which form a sensible aqueous solution, are dissolved in organic solvents such as propionate hammer. Among them, water-soluble compounds such as oxochloride, chloridylchloride, nitrate, and ammonium carbonate are preferred because of the operational environment because the composition can be prepared without using an organic solvent. In addition, complex compounds and complex salts of at least one of a hydroxyl group and a carbonic acid group can be used. This high molecular zirconium compound is commercially available (e.g. Magnesium Elekiron

Ltd., detailed in the company's Data Sheet 150, Sep. 1985). The wrong compound may be used alone or in combination of two or more kinds. In the case of using water-dispersed photocatalyst oxide sol, in order to avoid the phenomenon of pH oscillation, when the non-dispersed photocatalyst oxide sol is acidic, it is preferable to use a zirconium compound showing acidity, and the water-dispersed photocatalyst oxide sol is alkaline. In this case, it is preferable to use a zirconium compound exhibiting basicity. It is also possible to use an acidic sol by adding an alkali, or by adding an acid to the basic sol and mixing it with a compound. The compounding amount of the hafnium compound with respect to the photocatalytic oxide particles is preferably a weight ratio of 3 to 100 parts by weight based on the weight ratio of the zirconium compound converted to the photocatalytic oxide particles. When the lead compound is less than 3 parts by weight, the bonding force of the thin film formed on the substrate to the substrate is weakened. When the binding compound is relative to the photocatalytic oxide particles-(Please read the precautions on the back before filling this page)

460322 A7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (6) When the amount is increased, its photocatalyst can be reduced, and once it exceeds 200 parts by weight, its photocatalyst can be greatly reduced. In the case of photocatalytic oxide particle-based titanium oxide ', the degree of change in contact angle can be controlled by changing the ratio of the wrong compound and titanium oxide and using ultraviolet irradiation. From the above, the more preferable blending amount is in the range of 5 to 60 parts by weight. In the present invention, a solvent-based water and / or an organic solvent used for preparing a photocatalyst-containing oxide composition is prepared. Among organic solvents, those which are hydrophilic are preferred. The hydrophilic organic solvents are, for example, monovalent alcohols such as methanol, ethanol, and propanol; butanol; polyvalent alcohols such as ethylene glycol, diethylene glycol, and glycerol; and ketones such as acetone and methyl ethyl fluorenone. Category, esters such as ethyl acetate, butyl acetate, and solvent-soluble weaving agents such as ethyl weaving agent. These types may be used alone or in combination of two or more types, and it is appropriate to decide which one is considered in consideration of the stability of the composition, the type of the substrate, the drying conditions during film formation, and the economy. The composition of the present invention is mainly composed of oxide particles having photocatalytic energy, a solvent-soluble and non-hydrolyzable zirconium compound, and a solvent, and it may contain various additives. For example, in order to improve the film-forming property of the composition, dispersants such as glycerin, polyvinyl alcohol, methyl cellulose, and polyethylene glycol 4 may be contained, and dispersants such as polyacrylic acid and polymethacrylic acid may be contained. If necessary, the bacteria on the surface are sterilized in the dark, and metal particles such as silver and copper can also be added. In order to improve the photocatalytic property, it is also possible to add platinum group metals such as palladium and platinum. Additives of this type are used in the amount of about 10 to ΙΟΟΟΟρρηι = the composition of the present invention. The above-mentioned photocatalytic oxide particles, solvent-soluble and non-hydrolyzable hydrazone compounds and solvents are added to the paper as needed. Applicable standards ^^ (CNS) from the secret (21 () > < 297)-(Please read the precautions on the back before filling in this page}

* ST comprehensive-In n ^ — ^^ 1 Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs X 297 mm) 460322 A7 _____ _B7___ V. Description of the invention ΓΤ" * -—— The various additives are prepared by stirring It can be stored intact and has good storage stability. The composition of the present invention can be applied to various materials and substrates composed of formed bodies to form a surface of the substrate with a photocatalytic oxide film. Glass, plastic, ceramics, Metal, wood, paper, concrete, etc. can be used as the object of the substrate with almost no restrictions. Among them, glass is particularly suitable. Electric lamps and lighting fixtures are also suitable as substrates. In such cases, the composition is an internal agent. It is appropriate to mix water and organic solvents.

The thickness of the thin film formed on the surface of the substrate is in the range of 0 05 to m. When it is thinner than 0.05 // m, the photocatalyst energy is insufficient, and because the photocatalyst reaction occurs near the surface, it is easy to peel off when the film thickness exceeds 111 ′, and it is very unsatisfactory from the economic aspect. D. The substrate of the composition of the present invention The surface coating method can be, for example, a well-known method such as a spin coating method, a doctor blade (continuous flow) coating method, a dip coating method, a spray coating method, a roll coating method, or a brush coating method. In order to prevent the deterioration of the oxide particle substrate, it is not necessary to form a middle layer by applying a silicon dioxide or a fluororesin as a primer coating treatment beforehand in order to prevent degradation of the oxide particle substrate. After the coating process, the coating film is hardened. Hardening method, such as room temperature, heat treatment, etc. The hardening temperature is 20 ~ 200fl (: Among them, the range of 20 ~ 150 C is ideal. The hardening time is based on the solvent. Generally, it is about 10 minutes at 100 C. Heat-resistant substrate In this case, it is also possible to sinter the photocatalyst oxide particles by heat treatment in 2000 ~ 400 C. This paper size applies the Chinese National Standard (CNS) A4ii ^ S- (210 I: Isa ---- --Order ------ Μ-(Please read the notes on the back before filling out this page) -10- — ____ £ 7_ — ____ £ 7_ Printed by the Employee Consumption Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 46 0 322 A7 5 8. Description of the invention (8) The following is a detailed description based on the examples, but the present invention is not limited to the examples. Modification of the wood body pier rolled # 涫 employed by adding titanium tetrachloride (purity 99_9%) to water A solution of titanium tetrachloride with a concentration of 0.25 (moL) mol / liter (2% by weight of oxan). At this time, avoid the temperature of the aqueous solution rising above 50 ° C and perform ice-cooling treatment with a cooling device. Then, 'the 1 A liter of aqueous solution was charged into a reaction layer provided with a reflux cooler and heated to a temperature near the boiling point (104 ° C). It was kept for 60 minutes to produce a hydrolytic decomposition reaction to prepare a water-dispersed oxidized colloidal sol. After decantation and concentration treatment, an electrical dialysis device G3 manufactured by Asahi Kasei Industrial Co., Ltd. was used to obtain a concentration of 25% by weight and ρΗ5 · 5 water dispersion Titanium oxide sol. When one part of the titanium oxide sol was taken out and the particle size of the titanium oxide was examined with an electrophoretic scattered light spectrophotometer, the parallel particle diameter was 0.05 " m 'and the specific surface area was 122 m2 / g. The following coating liquid (composition): ㈣ Example 1 The above acidic water-dispersed titanium oxide sol was added with hydrochloric acid to obtain 20% by weight, concentration, and ρΗ4 of titanium oxide. Then, an acetic acid aqueous solution was added (converted to 22% by weight of Zr02). ) 6 g and 28 g of pure water were prepared into 20 g of the sol to prepare a coating film solution. As a result, the weight ratio of Zr02 / Ti02 in the coating film solution was 33%. Example 2 The above acidic water-dispersed titanium oxide sol was added with water to obtain 20 % Weight concentration, ρΗ5 · 5 of titanium halide. Then add 10 g of acetic acid aqueous solution (contains 22% by weight of Zr02) and 24 g of pure water to prepare a coating film solution. As a result, Zr02 / Ti02 (Heavy Ratio) is 55%. This paper size is applicable to China National Standard (CNS) Α4 specification (2 [0X297 public 嫠) I; ------------- ^ -------, 1τ ---- -# '(Please read the precautions on the back before filling this page) -11-460322 A7 I —____ B7 V. Description of the invention (9)' Lonely ice example 3 (Please read the precautions on the back before filling this page) The acidic water-dispersed titanium oxide sol was added with nitric acid to obtain a titanium oxide concentration of 20% by weight 'PH 3.5. Next, 8 g of an aqueous zirconium acetate solution (containing 20% by weight in terms of ZrO2) and 27 g of pure water were added to 20 g of the sol to prepare a coating liquid. As a result, the Zr02 / Ti02 (weight ratio) of the coating liquid was 55%. Practical Example 4 The acidic water-dispersed titanium oxide sol was added with water and ethanol to obtain a titanium oxide with a concentration of 10% by weight and ρΗ5.5. Next, 8 g of an aqueous hydroxyzirconium zirconium solution (contained as 20% by weight in terms of ZrO2) and 10 g of pure water were added to 40 g of the sol to prepare a coating film solution. As a result, Zr02 / Ti02 (weight ratio) in the coating liquid became 50%. The ratio of water to ethanol is 25:75 (weight ratio). Example 5 Printed by the Industrial and Commercial Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, instead of the acidic water-dispersed titanium oxide sol in the example, a commercially available anatase-type titanium oxide particle (titanium oxide specific surface area 270m2 / g) was used and the concentration was prepared. A 30% by weight, acidic, water-dispersed titanium oxide sol having a pH of 1.5 was added to a solution of 13.3g of the titanium oxide sol with 9g of hydroxyl zirconium hydroxide aqueous solution (containing 20% by weight in terms of Zr02) and 20g of ethanol to prepare a coating film solution. As a result, Zr02 / Ti02 (weight ratio) in the coating liquid became 45%. The ratio of water to ethanol was 10:90 (weight ratio). Example 6 The above acidic water-dispersed titanium oxide sol was added with ammonia and methanol to obtain a basic water-dispersed sol having a titanium oxide concentration of 20% by weight and a pH of 9. Then, 8,5 g of zirconium acetate, an ammonia solution (containing 20% by weight in terms of Zr02) and 10 g of methanol were added to 20 g of the sol to prepare a coating film solution. As a result, the Zr02 in the coating liquid / the paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) -12- 460322 A7 __________ B7 V. Description of the invention (10) The weight ratio of Τι〇2 becomes 42.5% . The ratio of water to methanol was 15:85 (weight ratio). (谙 Please read the precautions on the back before filling this page) Solid silk will add the above acidic water-dispersed titanium oxide sol to hydrochloric acid and methanol to 20% by weight and ρΗ4 titanium oxide. ZrO2 contains 20% by weight of 4g and 10g of methanol in 20g of this sol to prepare a coating film solution. As a result, Zr02 / Ti02 (weight ratio) in the coating liquid became 20%. The ratio of water to methanol was 25:75 by weight. Comparative Example 1. A 20% by weight titanium oxide solution in water-dispersed titanium oxide sol having ρ η 2 was added to 5 g of tetraethoxysilane, 10 g of ethanol, and 20 g of isopropanol to prepare a coating film solution. As a result, Si02 / Ti02 (weight) in the coating liquid was 35%. Comparative Example 2 20 g of a titanium oxide sol having a concentration of 20% by weight of titanium oxide and a water dispersion of pH 4 were added with 5.2 g of tetramethoxysilane, 10 g of methanol, and 20 g of pure water to prepare a coating liquid. As a result, Si02 / Ti02 (weight ratio) in the 'coating liquid was 50%. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. 20 g of titanium oxide in water with a concentration of 20% by weight and 20 g of titanium trisol dispersed in water were added to prepare a coating liquid. The coating liquids of the examples and comparative examples were respectively coated on a 76 × 26 mm soda glass, and kept in a vertical state for 10 minutes to flow down and remove the excess coating liquid. The coating film was completely cured by holding it in a dryer set at 150 ° C for 10 minutes. With regard to the titanium oxide film thus prepared, according to the following measurement method, the paper size is in accordance with the Chinese National Standard (CNS) A4 specification (2! OX297 mm) -13-460322 A7 B7 Printed by the Employees' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs System V. Description of the invention (u) Measure the changes in transparency, photocatalyst energy, adhesion, adhesion, pencil hardness, viscosity increase (stability of viscosity over time) and water contact angle. The results are shown in Table 1. The coating films of Examples and Comparative Examples stored at room temperature for 30 days were treated in the same manner, and the obtained titanium oxide films were subjected to the same various evaluations. The results are shown in Table 2. The transparency is measured using (with) a Hess meter (based on JIS K6718) manufactured by Tokyo Denshoku Technology Co., Ltd. and evaluated in the following three stages. A: Hess ratio less than 2.0% B: Hess ratio 2.0 % Or more and less than 5.0% C: Photocatalyst with a Hessian rate of 5% or more can coat a few drops of red ink on a substrate, and use a black light (365nm) to irradiate with an ultraviolet intensity of 2.1mW / cm2 for 30 minutes. The degree of discoloration of red ink was judged at three stages. A: Significant fading B: Partially fading part C: Not fading Adhesion to the substrate was evaluated using a swab test or alcohol test. In other words, the soda-lime glass substrate moistened with water or alcohol was wiped back and forth 10 times with a squeegee (manufactured by Kresia), then dried and then wiped back and forth 10 times with a squeegee. The state of the membrane. A: There are no scratches on the coating film B: There are some scratches on the coating film (please read the precautions on the back before filling this page) Loading-& This paper size applies to China National Standard (CNS) A4 specifications (210X297 mm) -14- 460322 Α7 Β7 V. Description of the invention (u) c: The adhesion test of the coating film with peeling is a checkerboard tape method in accordance with JIS K5400. The treatment was performed under a cutting injury interval of 1 mm and a number of checkers. The time-dependent viscosity stability of the coating solution is determined by using a Cannon Vance Viscometer (according to JIS K2283) to measure the dynamic viscosity of the coating agent after it is prepared and when it is left at room temperature for 30 days. To determine the viscosity. A: The viscosity increase rate is less than 5%. B: The viscosity increase rate is less than 50%. C: Gelation or separation cannot be measured. The change in water contact angle before and after external irradiation is measured according to the following procedure. In other words, the film was irradiated with black light for 1 hour with ultraviolet light (manufactured by Toshiba, 20W, and ultraviolet intensity of 2.0 mW / cm2). Then, the contact angle meter CA-D manufactured by Kyowa Interface Science Co., Ltd. was used to measure the contact angle of water before and after irradiation. The measurement environment is at 25 ° C and 70RT%. The pen hardness is measured using a ship pen hardness s-type test (JIS K5400). J11 n I— I n -¾Nong-I! V: ， 1τ · ~~ ϊ ~ I. Record-(Please read the precautions on the back before filling out this page) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs Rule one wave paper i quasi standard bidder I centimeter A7 460322 B7 V. Description of invention (13)

The evaluation of the day of preparation is to implement the W-tf-J persimmon [Nα Adhesive Binder / Tl02 ratio f will be like a frog owl 备 rn S island Ν: * Poor < Can be closely attached ^ A 附 杂 A Fragmentation of pencil 4H Privilege rate A 50 before the shot, 10 Cases of stealing 1 ZO, 33% AA, you ρ ZrO) 55% AAAA 5H A 55 24 Be careful of stealing ZrO, 40% AAAA 4H A 45 16 ―Implement Na ZrO, 50% AAAA 5H A 51 20 Implementation: ZrO, 45% BAAA 3H A 43 18: Implementation of ZrO, 43% BAAB 3H B 40 15 Implementation of W. ZrO, 20% AAAA 3H A 42 4 F ： L · Jib'll SiO, 35% ABBC 2H C 68 6 t SiO2 tank, 50% ACAA 3H C 75 8 钲 0% AACCBA 40 7 * ~ 2 Official temperature 30 days in Baolong commentary. Jie Wu Implementation repair 0 thiiίίο l_J Adhesive Qi 丨 Claw 〇2 比 ίψ- ^ bh) _Μ_ .. Fine pm Intestines Compilation · 脔 Fen leaves W inch:. Hot kite; before the irradiation, mm cautious Add ZrO, 33% AAAA 4H A 52 11 Do it for you ZrO, 55% AAAA 5H A 53 20 ZiO, 40% AAAA 4H A 48 14 ZrO, 50% AAAA 5H A 53 18 ZrO, 45% BAAA 3H A 40 16 Music Performance Jfi ZrO, 43% BAAB 3H B 41 12 Tube Show 丨 [7 ZiCh 20% AAAA 3H A 38 5 SiO? 35% CCCC 7B C 66 5 ι: Κ_ · 々ι | 7 SiO, 50% CCCC 7B C 69 6 hhp ^ n M 0% AA cc BA 3S 6 Packing # -(Please read the notes on the back before filling in this page) Utilization possibilities in the printing industry of the 8th Industrial Cooperative Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs According to the present invention, it is possible to obtain a photocatalyst with a very high level of maintenance, increasing over time. A photocatalyst-containing oxide composition having very few workability characteristics and having good workability characteristics. The film after the substrate is completely hardened by the coating treatment of the composition is not only transparent but strongly and tightly bonded to the substrate 'after a long time, it is strongly bonded to the substrate and exhibits its photocatalytic energy. The film formed by the photocatalyst-containing oxide composition of the present invention is applicable to the Chinese National Standard (CNS) A4 specification (210 > < 297 mm) on this paper. -16- 460322 5. Description of the invention (14) Irradiation by ultraviolet rays And the activity ,, m 4 · and ... members show its specific catalyst effect. Therefore, it has a good function of removing harmful substances temporarily & sampling pollution effect 'to decompose and purify ammonia and sulfur compounds in the atmosphere, and sterilization of field fungi.

For this reason, the sentence; f Ren steep I porcelain, metal, glass, plastic, paper, wood, fiber, concrete and other substrates made of the above-mentioned film complex: the body is expected to be used in various fields . Specific examples of such complexes are: Fan-speed road lighting (anti-fouling), transparent sound-proof walls (anti-fouling) for highways, sound-proof walls for off-duty (off-function), fluorescent lamps (due to the Deodorization and antifouling to prevent the reduction of illumination), fluorescent lamps (antifouling), mirrors, goggles 'lens' window glass (hydrophilic, antifog), road advertising, advertising signs, barriers, Support (anti-fouling), magnetic monument (anti-activity, antibacterial), building materials, exterior wall materials, window glass and other building exterior materials and structures (anti-fouling), wallpaper, window frame (anti-fouling), oscilloscope, Plasma display indicators (anti-fouling, anti-fog), plastics (anti-fouling) of liquid crystal display panels, metal bodies such as automobile bodies, trams, airplanes, ships, and their exterior materials (anti-fouling), Fiber products (antifouling) are all included. ----- ： ----- ^ ---- ^-I '玎 ------ ^ Department (please read and read the notes on the back before filling in this 1) Employees of the Intellectual Property Bureau of the Ministry of Economic Affairs Printed by Consumer Cooperatives -17- This paper size is applicable to China National Standard (CNS) A4 (21〇 × 297)

Claims (1)

Sixth, the scope of the patent application 6. ^ 6 0 3¾ 1.-A kind of composition 'comprising oxidized particles with a photocatalytic activity, a solvent can be Kling! ± and a non-hydrolyzable europium compound, and a solvent, wherein the amount of cone compounds It is converted into Z2Ό2, and it is in a range of 3 to 2000 parts by weight based on the weight of the titanium oxide having photocatalytic activity. 2. The composition according to item [Scope of the patent application], wherein the average particle diameter of the titanium oxide particles having photocatalytic activity is in the range of from 0.005 to 0.3. 3 ' The composition of item 1 or item 2 in the scope of patent application, wherein the solvent is at least one solvent selected from the group consisting of water and a hydrophilic organic solvent. 4. A method for manufacturing a thin film, comprising coating the surface of a substrate with a composition as described in any one of claims 1-3, and then curing the thin film formed on the substrate. 5. The method according to item 4 of the patent application, wherein the thickness of the cured film is in the range of 0.05 / zm ~ 2 / zm. A composite of a film and a substrate, which is manufactured by the following steps: coating the substrate with a composition as described in any one of the patent application scopes Nos. 1-3 to form a film, and then curing the substrate The film formed on the material I. The thickness of the cured film is in the range of 0.05 # ^ ~ 2 # 111 'and the substrate is selected from the group consisting of ceramic, metal, glass, plastic , Paper, wood, concrete, electric lights or lighting fixtures. This paper size applies to China National Standard (CNS) A4 (210 X 297 mm)-.. 1--j-!! _ ^^ ---- l · III --- fi I 11 ^. (Please Read the notes on the back before filling this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 18-: ... V »Application for 9 issues —-* ----— " '公 1 ，，） 、 丨Case No. s! H Category Bc Is ^ Ub,] X〇 The above sheds will be filled by this Office) A4 C4 460322 g Patent Specification No. 87119897 Patent Application Chinese English Name Nationality Amendment One Amendment Date: Q0 MiSfS Oxide Grade Product, Method of Making Thin Film and Thin Film with Omori Masahiro Hidenaka Hidenaka Tetsuko Noriko Utani Nobuo Okubo, Residence and Residence 103- 1-57-13201 [-2 51- 2-lssil 5 Although Machi 105 105 East District Real 5-East Taiwan Tsuno Nishi Takao District Izuta City Green 1City Kiichi City Shibara Habarahara City Prefecture Qianshi City County Chuan County Counties and counties Qin Nai tt- 秦 4- # 十 十 国 & Guo Guoguo Benben Book name (name) Japanese business. Showa Denko Co., Ltd. Ministry of Economic Affairs of the Ministry of Economic Affairs 4 · ^ ^: Industrial and consumer cooperatives printed the national version of the three books' Applicant's residence, residence (office) Representative's name is Shiba Gate, Minato-ku, Tokyo Metropolitan City 丨 Chome No. 13 畨 9 No. 9 Otsukamitsu paper standard (CNS standard) (CNS ) A4 specifications (2iOX297 public envy > Sixth, the scope of the patent application 6. ^ 6 0 3¾ 1.-A kind of composition 'comprising oxidized particles with a photocatalytic activity, a solvent can be Kling! ± and a non-hydrolyzable europium compound, and a solvent, wherein the amount of cone compounds It is converted into Z2Ό2, and it is in a range of 3 to 2000 parts by weight based on the weight of the titanium oxide having photocatalytic activity. 2. The composition according to item [Scope of the patent application], wherein the average particle diameter of the titanium oxide particles having photocatalytic activity is in the range of from 0.005 to 0.3. 3 ' The composition of item 1 or item 2 in the scope of patent application, wherein the solvent is at least one solvent selected from the group consisting of water and a hydrophilic organic solvent. 4. A method for manufacturing a thin film, comprising coating the surface of a substrate with a composition as described in any one of claims 1-3, and then curing the thin film formed on the substrate. 5. The method according to item 4 of the patent application, wherein the thickness of the cured film is in the range of 0.05 / zm ~ 2 / zm. A composite of a film and a substrate, which is manufactured by the following steps: coating the substrate with a composition as described in any one of the patent application scopes Nos. 1-3 to form a film, and then curing the substrate The film formed on the material I. The thickness of the cured film is in the range of 0.05 # ^ ~ 2 # 111 'and the substrate is selected from the group consisting of ceramic, metal, glass, plastic , Paper, wood, concrete, electric lights or lighting fixtures. This paper size applies to China National Standard (CNS) A4 (210 X 297 mm)-.. 1--j-!! _ ^^ ---- l · III --- fi I 11 ^. (Please (Please read the notes on the back before filling out this page) Printed by the Employees' Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 18-