Titanium dioxide-based photocatalytic coating substrate, and titanium dioxide-based organic dispersions

Description: TECHNICAL FIELD [Detailed description of the invention]

Photocatalytic coating based on titanium dioxide Organic dispersion based on base material and titanium dioxide The present invention is based on titanium dioxide partially incorporated in the form of particles and is a photocatalyst. With respect to a substrate having a coating with properties. The present invention also presents these substrates. And based on monodisperse titanium dioxide particles that can be used in this method Also related to new organic dispersions. Materials for various uses, such as vehicles (automobiles, etc.) or buildings (gala) S, metal, ceramics, face materials, exterior materials or roofing materials (eg tiles, etc.) Other properties, especially anti-UV, anti-stain (repelling dirt), anti-bacterial, anti-glare (g) Rare is glare, especially excessive brightness that makes the eyes uncomfortable. ), Antistatic or functionalized by imparting properties such as antimicrobial properties It is known to do. This is a transparent glazing (window glass, like a windshield for transportation) Especially in the case of glazing), they have specific properties depending on the intended use By attaching a thin layer intended to be imparted to their surface Attempts have been made to make them functional. Is it a stack of alternating layers with a high index of refraction and layers with a low index of refraction? There is a layer having an optical function such as a so-called anti-glare layer composed of the same. Also, the obi For the anti-static function or the anti-icing type heating function, a conductive thin layer, for example, metal or Can also provide a conductive thin layer based on a doped metal oxide. Heat engine Noh, for example anti-sun rays or low emissivity thermal function, made from silver type metal A thin layer or a thin layer based on a metal oxide or a nitride can be used. To get the "rain repellent" effect, a hydrophobic layer, such as fluorine or organic silane It is possible to provide a layer based on the above. Another property desired today is the chronological performance of appearance and surface properties, especially of the substrate. Stains that gradually build up on the surface, especially those of organic origin, such as finger marks and in the atmosphere Dirt such as existing volatile organics, or even condensation-type stains, they form By successfully removing it when it is formed, the frequency of cleaning is reduced and ( Or) to obtain the performance that can improve the field of view. One solution to these stain problems is, for example, to photocatalyst these stains. Therefore, it consists of adhering a coating for decomposition onto the substrate. This co The components of the coating result in the oxidation of organic substances under the action of radiation of appropriate wavelengths. It initiates a radical reaction. This decomposition generates radicals under the action of light (photocatalytic effect) of any compound Can be caused by. This can be especially about titanium dioxide , It has already been used for the treatment of building substrates, especially glass substrates. Thus, a solution or roller of titanium compound to create photocatalytic properties on the substrate. It is known to use an id-like titanium dioxide dispersion. However, the base material A solution of the titanium compound used for processing or colloidal titanium dioxide It can be seen that the specific characteristics of the dispersion affect the quality of the photocatalytic coating. It was. Also, depending on this specific feature, the quality of adhesion of the coating to the substrate Can be very variable. Finally, if the substrate is a glass substrate, The coating causes a lack of transparency and flau on the glass Things happen. Therefore, one object of the present invention is based on titanium dioxide, which exhibits good photocatalytic properties. Coating that is durable, transparent and industrially manufactured It is an object of the present invention to provide a novel substrate having the above-mentioned coating. For this purpose, the present invention presents titanium dioxide on a portion of at least one surface. A base material provided with a coating having photocatalytic properties based on the above two. At least part of titanium oxide is crystalline and part is mainly anatase (sharp) On the substrate incorporated in the coating in the form of particles crystallized in the form of cones) Related. The present invention is also a method for producing this base material, which is a combination of at least one organometallic compound. Liquid phase pyrolysis from a suspension containing a substance and a dispersion of titanium dioxide particles or so-called zo It consists of attaching a coating by gel gel technology and the particles are the best It also relates to the method described above, which characterizes the particles incorporated during the final coating. Finally, the present invention It has a size in the range of 5 to 70 nm, is monodisperse, and is mainly an anatase crystal. Titanium dioxide particles in shape as well as -Shows latent heat of vaporization lower than the latent heat of vaporization of at least one organic solvent, preferably water. Organic solvent Concerning organic dispersions containing. This dispersion is used in the production of substrates according to the present invention. To. Other advantages of the present invention are more apparent with reference to the following description, examples and drawings. Will be. FIG. 1: Sectional view of a substrate provided with a coating according to the present invention. Figure 2: Sol-gel adhesion technology with so-called coating dip coating Schematic (diagram). Figure 3: Schematic diagram of the so-called cell coating adhesion technology. Figure 4: Schematic diagram of the so-called spray coating adhesion technique. Figure 5: Schematic diagram of the layered coating adhesion technique. Thus, first of all, the present invention is based on titanium dioxide on at least a portion of one side. A base material provided with a coating having photocatalytic properties based on the above. At least part of titanium dioxide is crystalline and part is primarily anatase ( The substrate incorporated into the coating in the form of particles crystallized in the form of anatase) Regarding. Overall, titanium dioxide in the form of particles in the coating or otherwise , Partly anatase or rutile crystalline form or a mixture of anatase and rutile Crystallized in form, preferably at least 25%, especially about 30-80% crystallinity To. This crystallinity is TiO in the coating₂Crystalline TiO relative to the total weight of₂of Represents weight. For the coated titanium dioxide particles, the properties of the crystalline phase are mainly a. It is preferably a natase crystal system. "Mainly" means the dioxide of the coating This means that the proportion of anatase in the titanium particles is greater than 50% by weight. Ko The particles of the coating preferably show an anatase ratio greater than 80%. The crystallinity and properties of the crystalline phase are measured by X-ray diffraction. Crystalline titanium dioxide particles incorporated into the coating range from 5 to 80 nm. Surrounding, preferably in the range of 5 to 70 nm, even more preferably in the range of 10 to 50 nm Shows the average dimensions of. Diameter is transmission electron micros Measured by copy) (TEM). Titanium dioxide particles are incorporated into the coating using a binder. preferable. According to the first embodiment, there is no binder that incorporates the particles into the coating. It is a machine system. This inorganic binder is a particularly amorphous or partially crystalline acid. Form of compound (or mixture of oxides) such as silicon, titanium, tin, zirconium or Amorphous or partially crystalline oxides (or oxides) consisting of aluminum oxides Can be provided in the form of a mixture of). If this binder is a silicon oxide , Can be limited to the role of the matrix with respect to titanium dioxide particles. However However, in the case of amorphous or partially crystalline titanium dioxide, this binder Is itself involved in the photocatalytic action of the particles, which is insignificant when compared to the photocatalytic effect of the particles. It can show some photocatalytic action, albeit to some extent. According to the second embodiment of the present invention, the binder is at least partially present. It can also be of a mechanical system, especially in the form of a polymeric matrix. this Is complementary to the properties of titanium dioxide particles, especially hydrophobic and / or sparse. It can relate to polymers that can be oily. An example of such a matrix is described in European Patent Publication No. 675087. Epoxide-containing alkoxysilane, which can be hydrolyzed Epoxide-free silane, colloidal silica, catalyst and at least one water Reported as a hybrid obtained from a solution containing a resolvable alkylsilane fluoride The matrix is described. This fluorinated alkylsilane has the following general formula: CF₃-(CF₂)_n-(CH₂)_m-SiX₃(Here, n is 0-12, m is 2-5, and X is a hydrolyzable functional group. Is) belongs to. The epoxide-containing alkylsilane has the following formula:<img file="JPH11512336A_D0001.tif" />(Where p has a value of 0 or 1 and r has a value of 0, 1 or 2 and s is an integer in the range 1-6 M is an alkyl group having a hydrogen atom or 1 to 4 carbon atoms. M'and M'' are alkyl groups with 1 to 3 carbon atoms) belongs to. Epoxide-free silanes have the following general formula:<img file="JPH11512336A_D0002.tif" />(Here, N and N'are organic groups bonded to a silicon atom by a Si-C bond. , Contains a group capable of reacting with the hydrolyzed silane present in the composition Is not Q and Q'are hydrolyzable functional groups) belongs to. Also, oleophobic and / or hydrophobic grafted onto coatings according to the invention. Gender layers, eg, U.S. Pat. Nos. 5,368,892 and 5,389427. Layers based on fluorinated organic silanes described in and European Patent Publication No. 692 A layer based on the perfluolalkylsilane described in No. 463, in particular the following equation: CF₃-(CF₂)_n-(CH₂)_m-SiX₃(Where n is 0-12, m is 2 ~ 5, X is a hydrolyzable functional group) You can also choose to put a layer based on perfluolalkylsilane. Due to the incorporation of titanium dioxide particles, the coating is 1.40 ~ 2 It can exhibit a refractive index in the range of .35, preferably in the range of 1.6 to 2.3. This is because the titanium dioxide particles are porous and have a lower refraction than the massive titanium dioxide. Due to the fact that it shows a rate. Therefore, the resulting coating is lumpy It exhibits a low index of refraction compared to the index of refraction of the titanium dioxide-based coating. The optical advantage of obtaining a low index of refraction is in the case of glass-based substrates. Is very important to. Layers with massive titanium dioxide with a high index of refraction are carriers It causes an increase in light reflection of glass and a decrease in light transmission. By the way, for some High light, especially in the field of transparent flat glass to be installed in vehicles (automobiles, etc.) It is imperative to have a transmission level (75% minimum for windshields) Light transmission is required). To amplify the photocatalytic action of titanium dioxide particles in a coating according to the present invention In addition, the particles achieve better shielding of UV light or have an absorption band in the visible region. Catalysts and additives that can be moved towards, as well as titanium dioxide It can be loaded with metals that can increase the number of electron carriers in particular. Wear. Many aspects are possible to amplify this photocatalytic action. According to the first aspect, at least some of the titanium dioxide particles in the coating In the crystal lattice of iron, copper, ruthenium, cerium, molybdenum, bismuth, ta Metal ions selected from enthal, niobium, cobalt, nickel or vanadium Can be included. The weight of these ions relative to the weight of the titanium dioxide particles The quantity ratio is generally in the range of 0.01 to 10%. According to the second aspect, at least a part of the titanium dioxide particles are iron, copper, luteni. Umm, cerium, molybdenum, bismuth, tantalum, niobium, cobalt, nicke Choose from le, vanadium, tungsten, tin, zirconium, cadmium or zinc It can be at least partially coated with a layer of oxide or salt of the metal of choice. The weight ratio of these metals to the weight of titanium dioxide particles is 0.01-20% It is generally a range. According to the third aspect, at least a part of the titanium dioxide particles are platinum, silver or b. It can be at least partially coated with a layer of metal selected from dium. two The weight ratio of these metals to the weight of titanium oxide particles ranges from 0.01 to 5%. Can be. According to the fourth aspect, in addition to the titanium dioxide particles, the coating according to the present invention is added. Choose from cadmium, tin, tungsten, zinc, cerium or zirconium Additive particles based on the compound of the metal to be made are included. These particles are common It has a colloidal size in the range of 5 to 100 nm. Titanium dioxide particles The weight ratio of these particles to the weight of the particles should be in the range of 0.01 to 20%. It is common. These additive particles are CeO₂, SnO₂, WO₃, ZnO, ZrO₂Or Cd Se_xS_y(Here, x and y are in the range 0 to 1 and x + y is 1.) It can consist of such metal oxides or sulfides. The thickness of the coating of the substrate according to the present invention is variable. This thickness is generally Range from 5nm to 1μ, preferably range from 5nm to 100nm, even more preferred Is in the range of 5 to 80 nm, actually in the range of 10 to 80 nm, for example 20 to 50 n Can be in the range of m. In fact, this thickness can depend on various parameters To. This thickness is due to the intended use of the substrate and the titanium dioxide particles in the coating. It can depend on the dimensions. The coating is also smoother on smoother surfaces. You can also select non-surfaces. In fact, if the photocatalytically active region If it can be made wider, it is advantageous to have a certain degree of roughness. However, exaggeration By the way, this can be disadvantageous by promoting the adhesion of dirt. The coating is based on titanium dioxide particles embedded in the binder In some cases, the particles or the microcrystals that make up the particles "go out" on the surface of this binder. The adhesion method and coating thickness can be selected so as to "come". Substrate according to the present invention can be varied in terms of properties. Any type of building Building materials (metal, concrete, etc.) and glass, ceramic or glass ceramics A base material based on a cook can be used. Titanium dioxide-based coaty between the coating and substrate according to the invention One or more different thins that have different or complementary functions from the function of the Layers can be attached. It has antistatic, thermal or optical functions in particular A barrier to the migration (surface migration) of certain components derived from the layer or substrate Layers to form, such as alkali metals (especially Natriu if the substrate is made of glass) Can relate to layers that form a barrier against mion). High refractive index The invention is provided with alternating "anti-glare" layers of thin layers and thin layers with a low index of refraction. The idea is to have the coating be the last layer of that stack it can. In this case, the coating is preferably having a relatively low index of refraction of 10. This is a silicon oxide type inorganic matrix with a coating of titanium dioxide. Places in which titanium is embedded or in which it is composed of a mixed oxide of titanium and silicon. It is true. Antistatic function and / or thermal function (heating by providing a current line, low spokes) Layers with radiation, anti-sun rays, etc.) are especially metal-type conductive materials such as silver, Alternatively, tin-doped indium oxide (ITO) or fluorine-type halogen is added. Tin oxide (SnO)₂: F) or indium-doped zinc oxide (Z) nO: In), fluorine-doped zinc oxide (ZnO: F), aluminum Zinc oxide (ZnO: Al) or tin-doped zinc oxide (Zn) Based on a doped metal oxide type conductive material such as O: Sn) You can choose from. Such layers are powder pyrolyzed from dibutyl tin difluoride DBTF or European. By liquid phase or gas phase pyrolysis as described in Patent Publication No. 648196. Can be obtained. In the gas phase, monobutyltin chloride and fluoride precursor Mixture (optionally H₂Specially (combined with O-type "mild" oxidizer) Can be used for. The layer with antistatic function has a surface resistance value of 20 to 1000 Ω / scare. Is preferable. The layer can be equipped with current lines to give the layer polarity. This controlled polarization has a size of a girder of mm that can adhere on the coating. It is possible to control the adhesion of dry dust that sticks due to strikes, especially electrostatic action. To do. This dust is expelled by suddenly reversing the polarization of the layer. To reduce the reflection of light and / or to make the reflected color of the substrate even more neutral. Can select a thin layer having an optical function. In this case, this thin layer It has a refractive index intermediate between the refractive index of the coating and the refractive index of the substrate and a suitable optical thickness. Preferably, Al₂O₃, SnO₂, In₂O₃Or silicon oxycarbide or It can consist of an oxynitride type oxide or a mixture of oxides. In order to obtain the maximum attenuation of the reflected color, this thin layer has two types sandwiching this thin layer. Refraction close to the square root of the product of the squares of the index of refraction of the material (ie the substrate and its coating) It is preferable to show the rate. Similarly, approximately λ / 4 (where λ is in the visible region) Approximate average wavelength, especially wavelengths of about 500-550 nm) optical thickness ( That is, it is advantageous to select (the product of the geometric thickness and the refractive index). Titanium dioxide-based coating constitutes the last layer of anti-glare layer stack It is preferable to form. Thin layers that have a barrier function against alkali metals include silicon oxides, nitrides, and o. Xynitride or oxycarbide, fluorine-containing aluminum oxide Al₂O₃: F or It can be selected based on aluminum nitride. When the base material is made of glass There is a transfer of sodium ions into the titanium dioxide-based coating. This thin layer is useful because it can adversely affect its photocatalytic properties under certain conditions. It was proved to be. All of these optional thin layers are cathode sputtered in a known manner. Type vacuum technology or other pyrolysis type technology, such as solid phase, liquid phase or It can be attached by vapor phase pyrolysis. Each of the above layers has a number of functions Can be combined, but by stacking those layers Wear. Such layers are as described in European Patent Publication No. 518755, Ethylene and SiH diluted in nitrogen₄From a mixture with and to CVD (Chemical Vapor Deposition) Therefore, it can be obtained. Quite surprisingly, the substrates according to the invention are like visible and / or ultraviolet light. As soon as it is exposed to suitable radiation, it actually exhibits two properties instead of one. Due to the presence of photocatalytic titanium dioxide, this substrate removes organic stains. Decomposes by the dical oxidation process and promotes their gradual disappearance .. Substrates according to the present invention have also been noted, especially if the binder is inorganic. It can also show an outer surface that is hydrophilic and / or lipophilic, which is insignificant. It brings two benefits that are not nonexistent. First, hydrophilicity is the coating water Allows complete wetting by. In fact, condensation-shaped droplets that obstruct the field of vision adhere Instead, a completely transparent continuous thin film of water is observed to form on the surface of the substrate. .. This anti-condensation effect makes the contact angle with water less than 5 ° after exposure to light. It can be controlled by setting. Along with hydrophilicity, substrates according to the invention can also be lipophilic, which is organic. Allows wetting of system stains, in this case organic stains, as well as with water, On the substrate in the form of a continuous film that is less noticeable than the highly localized "spots" Has a tendency to adhere. Thus, the effect of "repelling organic stains" is obtained, and this Works in two steps. That is, the dirt diffuses as soon as it adheres to the substrate. So already barely noticeable at that stage, and then initiated by photocatalysis It gradually disappears due to radical decomposition. The present invention is a monolith unit or a double transparent plate glass or a laminated type multiple unit. "Anti-staining" incorporating the above-mentioned base material, regardless of whether it is flat, flat or curved. And / or (or) "anti-condensation" transparent flat glass. This transparent plate glass is used in the construction industry, for example, in the production of double transparent plate glass. Uses for (outer surface and / or inner surface, i.e. surface 1 and / or surface 4 You can place a ting). This is the transparent plate glass of the roof Cleaning is not easy or very frequently, such as in airport clear glass. This is a great advantage for transparent glass sheets that require. Also, the field of view The same is true for vehicle windows, which is an essential safety standard. Squeeze And this coating can be applied to car windshields, side windows or Can be attached to windows, especially windows facing the interior of the room .. In this case, this coating prevents the formation of condensation and / or (or) finger marks, Nico Chin or organic matter (plastic in guest room interiors, especially dashboard plus Volatile plasticizer type released by tics; sometimes "foggin" It can remove traces of) type of dirt (referred to by the term "g)". Many other uses are possible, especially aquariums, store windows, greenhouses, indoors Furniture or street furniture glass, or mirrors, TV screens young Alternatively, it can be used for electrically controlled variable absorbent glass. Another advantageous use of the coating according to the present invention is to tie this coating to the next tie. Consists of combining with electrically controlled variable absorption transparent glazing: electricity Chromium transparent plate glass, liquid crystal transparent plate glass (with optional two-color dye), suspension Transparent plate glass containing a particle system, viologen transparent plate glass, etc. All of these Type of transparent glass plate generally has an "active" component placed between multiple transparent substrates. In this case, on the outer surface of at least one of these substrates It is advantageous to place the ting. Especially in the case of electrochromium transparent plate glass, when it is in a colored state, Its absorption results in some surface heating, which is based on titanium dioxide. It is possible to actually promote the photocatalytic decomposition of the carbonaceous material adhering to the ting. For more details on the structure of electrochromium transparent glass, see Europe It would be advantageous to refer to Patent Publication No. 575207. This European patent publication Describes an electrochromium laminated double transparent glass plate, based on titanium dioxide. The coating to be applied can be preferably arranged on the surface 1. Another subject of the present invention lies in the various methods of making the substrate. According to the first method of the present invention, the method for producing a base material is at least one organometallic. Coating by liquid phase pyrolysis from a dispersion containing the compound and titanium dioxide particles The titanium dioxide particles form the final coating. It shows the characteristics of the particles incorporated in it. Pyrolysis adhesion technology is a float glass strike when using a glass substrate. It is advantageous because it allows the coating to be continuously applied directly on the device. To. According to the second method, the method for producing the base material is based on at least one organometallic compound. From dispersions containing titanium dioxide particles, dip coating, cell coating, Sol-gel with layered coating or spray coating type adhesion method The titanium dioxide particles consist of attaching a coating by technology. It shows the characteristics of the particles incorporated in the final coating. The principle of so-called sol-gel technology using the adhesion method by dip coating is It becomes clear from Fig. 2. This is a suitable component of coating (3) the substrate (1) Immersed in a liquid dispersion (4) containing the mixture, and then using the motor means (5). It consists of pulling the substrate (1) out of it at a controlled rate. Pull-out speed With proper selection, the thickness of the solution remaining on both sides of the substrate and the actual adhesion It is possible to adjust the thickness of the coated coating after heat treatment. become. This treatment involves evaporating the solvent, decomposing organometallic compounds and oxides. At the same time, it aims to decompose the mechanical strength of the coating. is there. The cell coating technology is revealed in Figure 3. It consists of: Ma Instead, two substantially parallel planes (6) and (7) and two seals (8) and ( Form a narrow cavity defined in 9). These faces (6) and ( At least one of 7) consists of the surface of the substrate (1) to be treated. The cavite A controlled embodiment of the solution filled with a dispersion containing an organometallic compound and particles. So, for example, a peristaltic pump (10) is used to form a wet meniscus (new moon shape). In this way (ie, due to surface tension, the part of the liquid surface near the cavity wall surface is the central part. Take out (at a speed that makes it higher than). Of the substrate (1) when the solution was taken out A film of solution remains on the surface. Then at least the film on the substrate is dried And the cavity is maintained for the time required to cure by heat treatment. Immersion The advantage of this technology over the arting is that it does not rely on the masking system in particular. Even if only one of the two surfaces of the base material (1) is processed, both surfaces are systematically processed. It is possible not to. The spray coating technique is described in detail in FIG. This is an organometallic Dispersion (4) containing compounds and particles in the form of mist with respect to substrate (1) under static conditions Consists of spraying with. The layered coating technique is illustrated in FIG. It consists of: First, Hold by vacuum suction on support (11) made of stainless steel and Teflon Pass the base material (1) over the tank (12). Organic gold in this tank (12) A cylinder grooved in this solution containing a dispersion containing a genus compound and particles. Allow the body (14) to be at least partially immersed. Then the tank (1 The combination of 2) and the tubular body (14) is moved along the entire length of the base material (1). Melting The mask (13) prevents excessively rapid evaporation of the solvent from the liquid (4). This technology For more information on, see the teachings of WO94-01598, International Application Publication No. You can refer to the indications. According to this second method, the substrate is solution on one or both of these surfaces. After coating with, the organometallic compound is thermally decomposed. The above two methods are organometallic compounds and preformed and crystallized dioxide. A dispersion based on titanium particles was used. Organometallic compounds have a metal atom M of titanium, silicon, tin, zirconium, and alumini. It is a compound that can be selected from um and the like. This is the general formula M (OR)₄{Here, M is selected from, for example, titanium, silicon, tin, zirconium or aluminum. Represents the metal of choice R is alkyl, cycloalkyl, aryl, alkylaryl or allie Lualkyl, alkenyl or alkynyl group, acetylacetone group Is one of its derivatives (methyl acetoacetate, ethyl acetoacetate, titanium acetyla Setonate, etc.), amino group or one of its derivatives (titanium triethanolamine) Min, titanium diethanolamine, etc.) or glycolate (titanium tetraoctile) Glicolate) etc.} Can be related to organometallic compounds. Titanate or silicate type compounds are preferred. Organometallic compound Tetraisopropoxytitanium is particularly favorable as an organometallic compound. Suitable. Preferred organometallic titanium compounds are titanium chelates and / or titanium. It is an alkoxide type. These are French Patent No. 231097 It is of the type described in No. 7 and European Patent Publication No. 465309. be able to. Thus, the organometallic titanium compound is of formula R._nTi (OR')_p(Here, p is in the range of 1 to 4, n is equal to 4-p, R is C₁~ C₁₈Alkyl group R'is methyl, ethyl or isobutyl type C₁~ C₄Alkyl group) Can be selected from the compounds of. .. A preferred organometallic silicon compound is of formula R._nSi (OR')_p(Here, p is in the range of 1 to 4, n is equal to 4-p, R is C₁~ C₁₈Alkyl group R'is methyl, ethyl or isobutyl type C₁~ C₄Alkyl group) Can be selected from the compounds of. Preferred compounds are tetramethyl orthosilicate (TMOS), tetra orthosilicate. Ethyl (TEOS) and (CH₃)₂Si (OC₂H₅)₂Is. Of course, a mixture of these compounds can also be used. The particles themselves are doped with dimensions, crystallinity and optionally metal compounds. The above-mentioned features are shown with respect to. The dispersion is a metal oxide (MO) of an organometallic compound._x) By weight vs. particles And TiO contributed by organometallic compounds₂Metal oxides (MO_x) As table It generally contains organometallic compounds in an amount in the range of 5 to 90% by weight. It is preferable to include organometallic compounds in an amount in the range of 15-80% on the same basis. It is even better to include organometallic compounds in amounts in the range of 20-75% on the same basis. Good. If the organometallic compound is based on titanium, the coating will adhere Titanium dioxide and dispersion derived from decomposition of organometallic compounds after heat treatment Can contain both titanium dioxide derived from titanium dioxide particles of One acts as an inorganic binder for the latter, so to speak. The particles are highly reactive at photocatalytic concentrations and are titanium-based organic. Probably concludes the crystallization of titanium dioxide produced by thermal decomposition from metal compounds Promote by acting as a crystallized seed crystal. Thus, during the final coating There are two different sources of titanium dioxide. It is preferable to use monodisperse titanium dioxide particles to obtain a clear coating. I'm sorry. Monodispersity refers to a variance index of at most 0.5, preferably at most 0.3. It shall mean a particle. This variance index is based on the following general formula:<img file="JPH11512336A_D0003.tif" />(Here, φ₈₄84% of the particles are φ₈₄Grains that will have a diameter smaller than the value It is a child diameter φ₁₆16% of the particles are φ₁₆At a particle diameter that will have a diameter smaller than the value Yes, φ₅₀Is the average diameter of the particles) Given by. In addition, regardless of the intended adhesion technique, at least two rather than a single process The coating can be applied in a continuous process, which is preferred. this Diacid throughout the coating thickness if a relatively thick coating is selected It seems to promote the crystallization of titanium oxide. Similarly, there are few types of annealing coating after applying the coating. It can and is preferably subjected to at least one heat treatment. This annealing type heat treatment is sol-gel or sol-gel, especially according to the second method described above. When the coating is applied by the layered coating type technology, Required to decompose organometallic compounds into carbon dioxide after coating the material Su. In contrast, the coating is applied by a pyrolysis technique according to the first method described above. When the organometallic compound is allowed to come into contact with the base material, the organometallic compound is immediately formed. This annealing type heat treatment is not essential because it decomposes. However, Similar to the second method, in the first method as well, after the titanium dioxide is formed and after adhesion. The heat treatment improves crystallinity and adhesiveness. In addition, select the appropriate processing temperature This allows for even better control over crystallinity and crystal properties. And become possible. This annealing is generally a substrate in the oven at a temperature of about 500-550 ° C. Consists of introducing for a period that can range from 1 minute to 3 hours. For both methods, very specifically the coating is relatively long and (or) ) Raw from glass under the action of heating if it must be subjected to high temperature heat treatment The transfer of an excessively large amount of alkali metal into the coating is photocatalytic activity. It can be harmful to the alkali metal between the substrate and the coating. It may be useful to provide a barrier layer against it. Relatively thin coatin If you choose, especially if the coating shows a thickness less than 20 nm , The same can be said. The particles exhibit the desired characteristics of the substrate, especially with respect to size and crystallinity. As long as the liquid phase is aqueous or organic, any type of dioxide A titanium dispersion can be used. However, the organic phase is preferred. Finally, the present invention It has a size in the range of 5 to 70 nm, is monodisperse, and is mainly an anatase crystal. Titanium dioxide particles in shape as well as -Shows latent heat of vaporization lower than the latent heat of vaporization of at least one organic solvent, preferably water. Organic solvent It also relates to organic dispersions containing. The concept of monodispersity is the same as described above. The titanium dioxide particles are the particles of the substrate coating according to the present invention described above. It exhibits the same dimensions and crystallinity characteristics as those of the above. Therefore, the titanium dioxide particles of the dispersion are generally preferred in the range of 5-80 nm. Or show dimensions in the range of 5 to 70 nm, even more preferably in the range of 10 to 50 nm Su. This dimension is measured by TEM. Furthermore, the properties of the crystal phase of these titanium dioxide particles are mainly anatase formation. It is preferably in crystal form. "Mainly" is a dispersion according to the present invention, tita dioxide. This means that the proportion of anatase in the particles is greater than 50% by weight. Used It is preferable that the particles of the dispersed dispersion show an anatase ratio of more than 80%. For the liquid phase, the organic solvent shows a lower latent heat of vaporization than the latent heat of vaporization of water. Is preferable. Latent heat of vaporization vaporizes 1 g of liquid at the boiling temperature of the liquid. It is understood to mean the number of heat required for. Latent heat of vaporization of water at boiling temperature is 5 It is 40 cal / g ("Handbook of Chemistry and Physics" 75th edition). Such organic solvents include alcohols (ethanol, isopropanol, etc.), especially grease. Select from esters such as Cole (ethylene glycol) and ethyl acetate, etc. can do. The concentration of titanium dioxide in the dispersion according to the present invention is 1 g / liter to 300 g / You can choose from a range of liters. These organic dispersions are at most 10 depending on the type of method used to make them. By weight%, preferably at most 5% by weight, even more preferably at most 1% by weight Can contain water in proportion. Monodisperse particles of the dispersion are generally pyrolysis of titanium salts or acids. In contrast to the conversion method, so-called solution or wet pathway manufacturing methods {pyrolysis of titanium salts ( Obtained from thermolysis), thermal hydrolysis or sedimentation}. These are, for example, European Chita dioxide obtained by the method described in Pappa Patent Publication No. 0335773 Can be particles. In particular, at least one titanium compound A is selected from the following (i) to (iv). Shows dimensions of up to 5 nm in the presence of at least one compound B of choice Anatase A production method consisting of hydrolysis in the presence of titanium dioxide seed crystals. At that time, the seed crystal is TiO existing in this seed crystal.₂/ This seed crystal TiO that was present in the hydrolysis medium before introduction₂Titanium weight expressed as It is possible to use the above-mentioned manufacturing method in which the amount ratio is about 0.01% to 3%. Wear: (i) One carboxyl group and few hydroxyl and / or amine groups At least 2 Or -At least two carboxyl groups and hydroxyl and / or amine groups At least one Acid, which indicates (ii) The following equation:<img file="JPH11512336A_D0004.tif" />(Here, n and m are integers in the range 1-6, p is an integer in the range 0-5 R1, R2 and R3 may be the same or different, hydroxyl, a Represents mino, alalkyl, aryl or alkyl group or hydrogen) Organic Phosphoric Acid, (iii) Compounds capable of releasing sulfate ions in acidic media, (iv) The salt of the acid. Therefore, the method for producing this particle involves several steps, first the titanium compound A. , A step of producing a starting solution containing the above-mentioned compound B and titanium dioxide seed crystals. This starting solution is expected to be hydrolyzed and is preferably completely aqueous. I. Another solvent, such as alcohol, can be added at will, but in this case This is because the titanium compound A and the compound B used are substantially soluble in this mixture. The condition is that there is. Titanium compound A is generally a halide, an oxyhalide, or a titanium. Tanalkoxides, sulfates and, more specifically, synthetic sulfates are used. Synthetic sulfate is ion exchange from a very pure titanium chloride solution or sulfuric acid and titanium. Meaning a titanyl sulfate solution produced by reaction with tan alkoxide And. This production is a titanium halide or oxyhalide type titanium compound. It is carried out using objects. Titanium halogen used more specifically in the present invention The isomers or oxyhalides are titanium fluorides, chlorides, bromides and iodides. Oxyfluoride, oxychloride, oxybromide and oxyiodide, respectively). According to a particularly preferred embodiment, the titanium compound is titanium oxychloride Ti. OCl₂Is. The amount of titanium compound A present in the solution to be hydrolyzed is not critical I. The starting solution additionally contains at least one of the above-mentioned compounds B. Of the present invention Non-limiting examples of compound B falling within the range include, among other things, the following compounds: Can: -Hydroxypolycarboxylic acids, especially hydroxydi- or hydroxytricarboxylic acids Acids such as citric acid, maleic acid and tartaric acid, -(Polyhydroxy) monocarboxylic acids, such as glucoheptanic acid and gluconic acid , -Poly (hydroxycarboxylic) acid, such as tartaric acid, Dicarboxyamino acids and their corresponding amides such as aspartic acid, aspartic acid Paragin and glutamic acid, Hydroxylated or non-hydroxylated monocarboxyamino acids, such as lysine , Serine and threonine, Aminotri (methylenephosphonate), ethylenediaminotetra (methyleneho) Sfate), triethylene tetraaminohexa (methylenephosphonate), te Traethylene pentaaminohepta (methylenephosphonate) or pentaethylene Hexaaminoocta (methylenephosphonate), Methylene diphosphonate, 1,1-ethylene diphosphonate, 1,2-ethyle Diphosphonate, 1,1-propylene diphosphonate, 1,3-propylene diphosphonate Phosphonate, 1,6-hexamethylenediphosphonate, 2,4-dihydroxy Pentamethylene-2,4-diphosphonate, 2,5-dihydroxyhexamethyle 2,5-diphosphonate, 2,3-dihydroxybutylene-2,3-diphos Honate, 1-hydroxybenzyl-1,1-diphosphonate, 1-aminoethi Len-1,1-diphosphonate, hydroxymethylene diphosphonate, 1-hydride Loxyethylene-1,1-diphosphonate, 1-hydroxypropylene-1,1 -Diphosphonate, 1-hydroxybutylene-1,1-diphosphonate or 1- Hydroxyhexamethylene-1,1-diphosphonate. As mentioned above, all salts of the above acids can also be used as compound B. In particular, these salts are alkali metal salts, more specifically sodium salts, or ammo. It is one of the nium salts. In addition, these compounds are made from sulfuric acid, ammonium sulfate, potassium, etc. You can also choose. The compound B is preferably a compound having an aliphatic type hydrocarbon moiety. Good. In this case, the length of the hydrocarbon main chain preferably does not exceed 15 carbon atoms. It is even more preferable that the number of carbon atoms does not exceed 10. The amount of compound B is not critical. Molar concentration of compound B relative to titanium compound A Is generally in the range of 0.2 to 10%, preferably in the range of 1 to 5%. Good. Finally, the starting solution contains titanium dioxide seed crystals used in certain embodiments. Thus, the titanium dioxide seed crystals used in the present invention are, first of all, X. Dimensions smaller than 8 nm, measured by linear diffraction, must be indicated. 3 ~ It is preferable to use titanium dioxide seed crystals showing dimensions in the 5 nm range. Next, the titanium dioxide present in the seed crystal is hydrolyzed before introducing this seed crystal. Titanium present in the medium (ie, titanium contributed by titanium compound A) TiO₂The weight ratio expressed as is in the range of 0.01 to 3%. This ratio is It is preferably in the range of 0.05 to 1.5%. Seed crystal proportions are related to particle size Therefore, these two conditions (dimensions and weight ratios) regarding the seed crystal are set in the above-mentioned method. Accurately adjust the final dimensions of titanium dioxide particles when combined with And become possible. Thus, we obtain particles whose dimensions vary in the range of 5-100 nm. Will be possible. To result in the formation of anatase-type titanium dioxide precipitates, anatase-type titanium dioxide Titanium dioxide seed crystals are used. In general, these seed crystals are small in size, so Rather, it exists in the form of anatase with low crystallinity. Seed crystals are generally titanium dioxide It is provided in the form of an aqueous suspension consisting of These are generally to the base of the titanium salt It can be obtained in a known manner by the neutralization method according to the above. Subsequent steps include heating this starting solution in any method known to those of skill in the art, generally heating. By doing so, it consists of hydrolyzing. In the latter case, temperatures above 70 ° C It is preferable to carry out hydrolysis in. Also, first than the boiling temperature of the medium Operate at low temperature and then keep the hydrolysis medium in a stable period at boiling temperature You can also do it. After hydrolysis, the obtained solid titanium dioxide particles precipitated from the mother liquor Recovered by separation, then aqueous solution to obtain titanium dioxide dispersion Redisperse in the medium. This liquid medium is basic even if it is acidic. It may be. An acidic solution, such as an aqueous nitric acid or hydrochloric acid solution, is preferred. Then, in order to obtain an organic dispersion of these titanium dioxide particles, aqueous titanium dioxide is used. Any ready-made titanium dioxide particles can be suspended from the tongue dispersion in the organic phase. The method of knowledge can be used. Thus, the aqueous dispersion of titanium dioxide particles was brought into contact with the desired organic solvent and then By heating with water and removing water by distillation, an organic dispersion can be obtained. Wear. Such a method indicates that the selected organic solvent has a boiling temperature higher than the boiling temperature of water. And it can be used only when it is soluble in water. This is, for example, ethylene In the case of glycol. In addition, a hydrophobic chain is graft-bonded to the surface of titanium dioxide particles suspended in water. Then mix with a water-immiscible organic solvent to transfer the titanium dioxide particles into the organic phase. It is also possible to obtain an organic dispersion. Titanium dioxide particles obtained from so-called solution or wet pathway manufacturing methods, especially the above Titanium dioxide granules obtained by hydrolysis at a temperature of about 100 ° C from The offspring are lower than the titanium dioxide particles obtained by another method due to their porosity. It was observed to show a refractive index. As mentioned above, this property is based on these particles. The above, especially when used to produce coatings on materials, especially on glass-based substrates. The coatings obtained, such as, also show a low index of refraction, which is of great interest. The liquid phase of the dispersion according to the present invention is titanium, silicon, tin, zirconium or alumini. Contains at least one organometallic compound based on metal M selected from um Is advantageous. Preferred compounds correspond to the above-mentioned organometallic compounds. .. If the liquid phase of the dispersion according to the invention also contains an organometallic compound, then this compound , Mixing a solution of an organometallic compound with a dispersion in the organic phase of titanium dioxide particles It is common to add by. In addition, the organic metal used in this mixing Additives such as auxiliary solvents, surfactants or stabilizers are added, depending on the nature of the compound. You can also do it. Also, the mixture is agitated by ultrasonic waves. Can also be improved. The solution of the organometallic compound added to the organic dispersion based on titanium dioxide particles is , Generally a solution in the organic phase, this organic phase is ethanol, isopro It can be selected from panol, ethyl acetate and the like. It is also possible to add organometallic compounds to the titanium dioxide dispersion in pure form. To. These organometallic compounds are diethanolamine (DEA), acetylacetone. Derivatives (eg ethyl acetoacetate), glycols, etc. It can be standardized and it is advantageous to do so. The dispersion is TiO contributed by particles and organometallic compounds.₂Metal oxides (MO_x) For the weight of the organometallic compound as a metal oxide (MO)_x)When It is generally included in the range of 5 to 90% by weight, and 15 to 80%. Heavy The amount is preferably in the range of%, preferably in the range of 20-75% by weight. Is practical. As mentioned above, highlight the photocatalytic action of titanium dioxide-based coatings. In order to reach this titanium dioxide catalyst, better absorption of UV light as described above. Additions that can form or move the absorption band towards the visible region Agents or titanium dioxide can be doped to increase the number of electron carriers in particular. Metals can be added. According to the first aspect, the binding to at least a part of the titanium dioxide particles of the dispersion Iron, copper, ruthenium, molybdenum, bismuth, tantalum, niobium, co in the crystal lattice It contains metal ions selected from baltic, nickel or vanadium. these The ratio of the weight of metal ions to the weight of titanium dioxide is in the range of 0.01 to 10%. Can be These dispersions are metal ions during the production of titanium dioxide particles. It can be obtained by introducing the salt of. Thus, European patent publication Diacid by thermal hydrolysis of titanium compound as described in No. 0335773 When obtaining titanium dioxide particles, ions were introduced into the crystal lattice of titanium dioxide. Therefore, metal ions can be added to the thermal hydrolysis medium. According to the second aspect, at least a part of the titanium dioxide particles of the dispersion is iron, copper, Ruthenium, cerium, molybdenum, bismuth, tantalum, niobium, cobalt, Nickel, vanadium, tungsten, tin, zirconium, cadmium or zinc At least partially coated with a layer of metal salt or oxide selected from. The weight-to-titanium dioxide weight ratio of these metals ranges from 0.01 to 20%. Can be These dispersions are made of titanium dioxide particles before being placed in an organic medium. It can be obtained by precipitating a metal salt on top. Therefore, wet route manufacturing When the titanium dioxide particles are still in the aqueous medium after the method, the metal salt is in this aqueous phase. Introduced into and precipitated to coat the titanium dioxide particles at least partially. According to the third aspect, at least a part of the titanium dioxide particles of the dispersion is platinum, silver. Alternatively, it is at least partially coated with a layer of metal selected from rhodium. these The ratio of the weight of the metal to the weight of titanium dioxide can be in the range of 0.01-5%. Wear. These dispersions are metal salts on the titanium dioxide particles before being placed in the organic medium. Can be obtained by reducing. For example, after the wet route manufacturing method When the titanium particles are still in the aqueous medium, a metal salt is introduced into this aqueous phase for reduction. The titanium dioxide particles are then at least partially coated. According to the fourth aspect, in addition to the titanium dioxide particles, cerium and cado are added to the dispersion. Metal compounds selected from Mium, Tin, Tungsten, Zinc or Zirconium Additives in the form of particles based on. These particles are generally 5-100 It has colloidal dimensions in the nm range. Their proportion in the dispersion is 0.1 ~ It can be in the range of 20% by weight. As mentioned above, this metal compound is Ce O₂, SnO₂, WO₃, ZnO, ZrO₂Or CdSe_xS_y(Where x and y are Metal oxides or sulfides in the range 0 to 1 and x + y is 1) Can be The latter particles are aqueous titanium dioxide particles obtained from a wet route. To simply mix with the dispersion and then transfer all particles in the aqueous phase into the organic phase Therefore, it can be introduced. Dispersions according to the invention may exhibit these four forms of character individually or simultaneously. it can. Finally, the present invention relates to the above-mentioned organic dispersion in the method for producing a base material according to the present invention. Regarding use. Other advantageous features and details of the present invention can be found in the non-limiting examples below. It becomes clear. As shown very schematically in Figure 1, all of the following examples are essentially diacids. Titanium-based so-called "anti-staining" coating (3) attached to substrate (1) Regarding clothes. Example Example 1: Making an organic dispersion of titanium dioxide particles Diacid in the presence of seed crystals according to the teachings of European Patent Publication No. 0335773 Prepare an aqueous dispersion of titanium oxide particles. Hydrolysis Continuously add the following to 394.7 g of 1.9 mol / kg titanium oxychloride solution Added. 36% hydrochloric acid 42.02g Citric acid 4.73g Purified water 547.1g Anatase seed crystal showing dimensions in the range of 5 to 6 nm 11.36 g (TiO₂0.2% by weight) Bring this mixture to a boiling point and keep it at that temperature for 3 hours. Particle recovery and redispersion The solution is then filtered and the resulting particles are watered until the chloride is completely removed. Wash with. This particle is then pH 1.5 (HNO)₃Toned by adding In section), redisperse with a solid content of 20% by weight. An aqueous dispersion containing particles with a diameter of 45 nm was obtained as measured by TEM. Was done. Analysis by X-ray diffraction shows that the particles are exclusively in the form of 80% by weight anatase. It has been shown to be based on titanium dioxide. The particles obtained were porous. Dispersion in organic media 100 parts by weight of this dispersion is mixed with 100 parts of ethylene glycol. This mixture Distillation performed under reduced pressure (100 millibars) of water by heating the object to 80 ° C. Then heat to 120 ° C to remove the bound water. A dispersion of titanium dioxide particles in ethylene glycol is obtained. Solid content Was 20% by weight. Particle dimensions measured in ethylene glycol by TEM Was 45 nm. The residual water content was 0.7% by weight with respect to titanium dioxide. Example 2: Production of an organic dispersion of niobium-doped titanium dioxide particles NbCl in hydrolysis medium₅Nb / TiO₂In an amount that makes the molar ratio of Example 1 was repeated, except that it was added. Examples 3-7: Adhesion of the dispersions of Examples 1 and 2 by thermal decomposition Substrate (1) is transparent silica-soda lime 6 mm thick, 50 cm long and 50 cm wide. It is made from glass. A thin layer (2) is optionally provided between the coating (3) and the substrate (1). The following examples 3 to 7 relate to the coating (3) attached by the liquid phase pyrolysis technique. To. Adhesion is exactly at the exit of the float bath chamber the float glass streak Perform continuously using suitable distribution nozzles arranged transversely above the tap. be able to. In this case, adhesion was carried out in a discontinuous manner. To the predetermined dimensions in advance The cut substrate (1) is first heated in an oven to a temperature of 400-650 ° C. Then, pass it at a constant speed in front of a mobile nozzle that injects a suitable solution. Example 3 In this example, the optional layer (2) is not provided. Coating (3) Adhesion using an organic dispersion (A), including: Two kinds of organometallic titanium compounds and two kinds of solvents in the following ratios: Titanium diisopropoxydiacetylacetonate 20% by weight Titanium tetraoctylene glycolate 20% by weight Ethyl acetate 40% by weight Isopropanol 20% by weight Prescriptions included in; An organic dispersion of titanium dioxide particles according to Example 1, which is diluted and exhibits the following characteristics: Weight content of particles 10% Particle size 45nm measured by TEM Microcrystal size 5nm Crystal phase 80% or more anatase -Liquid phase ethylene glycol. The formulation and organic dispersion are derived from the particles in the adhered coating. Titanium dioxide content (organometallic compounds in dispersion A are completely decomposed into oxides TiO obtained from particles when assumed to be₂Weight / during coating Titanium dioxide particles in dispersion A so that the total weight of the oxides) is 25% by weight. The relative ratio should be such that the content is adjusted. When the substrate (1) reaches the desired temperature in the oven, i.e. about 500 ° C, bring it to room temperature. Pass the substrate (1) in front of a nozzle that injects the specified mixture with compressed air. Su. Here, a titanium dioxide layer having a thickness of about 90 nm is obtained. This thickness is noz Adjusted by the rate of travel of the substrate (1) and / or the temperature of the substrate in front of the Is done. This layer is partially crystallized in the form of anatase. This coating disperses with titanium dioxide derived from the decomposition of organometallic compounds Contains both titanium dioxide derived from the body's titanium dioxide, the first one is As it remains, it acts as an inorganic binder for the second one. This layer is excellent It showed mechanical strength. The refractive index was 2.3. Example 4 An electrostatic and / or low radiation layer and / or a layer that weakens the color, especially the reflected color. Fluorine-doped tin oxide SnO for the purpose of forming₂: Thin layer made from F (2) Example 3 is repeated except that the substrate (1) contains the above. This layer is obtained by powder pyrolysis from dibutyl tin difluoride DBTF. .. This layer is also described, for example, in European Patent Publication No. 0648196. It can also be obtained in a known manner by such liquid phase or vapor phase thermal decomposition. Smell A mixture of monobutyltin chloride and a fluorinated precursor (optionally H)₂O type (Combined with a "mild" oxidant) can be used in particular. This thin layer has a thickness of 73 nm, a refractive index of 1.9 and a surface resistance of 50 Ω / scare. Is shown. Treat this substrate as in Example 3 and apply a 12 mm strip of air. As a double transparent glass plate sandwiched between them, the coating (3) should be on surface 1. Assembled (the other substrate has the same properties and dimensions as substrate (1), However, uncoated) has a reflected color purity value of 3.6% (gold). Color region) and 1.1% transmittance. The substrate of Example 3 has a reflected color purity value (gold region) of 26% when assembled in the same manner. And shows a transmittance of 6.8%. SnO₂: F Underlayer has a positive effect on the color of the substrate, both transmissive and reflective In the direction of its color, brought about by the presence of the titanium dioxide coating (3) It significantly "neutralizes" the color and exhibits a relatively high index of refraction. In addition, this lower layer TiO₂Reduces the diffusion of alkali metals into the photocatalytic layer. Therefore, photocatalytic activity Is improved. Blurring is 1 despite the presence of large amounts of particles in the coating % Yo It is also extremely low. Blurring is diffraction against the total light transmittance of the substrate at 560 nm It is defined by the ratio of light transmittance. Example 5 It constitutes a barrier to the diffusion of alkali metals and / or a layer that weakens light reflection. A thin layer (2) based on silicon oxycarbide was contained in the base material (1) for the purpose of making it. Except for, repeat Example 3. This layer is in nitrogen as described in European Patent Publication No. 0518755. Diluted in ethylene and SiH₄Obtained by CVD from a mixture with. this The layer is an alkali metal (Na) derived from the substrate (1).⁺, K⁺) And alkaline earth gold Genus (Ca²⁺) Is especially effective in preventing the tendency of) to diffuse towards the coating (3) It is effective. This thin layer exhibits a thickness of 50 nm and a refractive index of 1.75. SnO₂As with: F, the index of refraction (1.52) and coaty of the base material (1) This layer is also transparent, as it has a index of refraction between the index of refraction (2.3) of the index (3). Weakens the color intensity of the substrate in both hyper and reflection, and the light reflection value of the substrate R_LOverall Can also be reduced to. Furthermore, the lower layer based on silicon oxycarbide is effective against the diffusion of alkali metals. It constitutes a barrier and thus significantly improves the photocatalytic activity of the coating. Example 6 Except for the coating (3) being attached using dispersion B containing the following: And repeat Example 3: -Silicone diluted in ethanol at a rate of 0.1 mol per liter of ethanol Element Tetraoxide Si (OEt)₄Prescription based on; -Organic dispersion of titanium dioxide particles of Example 1. This formulation and organic dispersion contain titanium dioxide in the adhered coating. Predominant {TiO derived from particles assuming complete decomposition₂Weight / (Particle TiO₂Weight + Si (OEt)₄SiO obtained by decomposition of₂of The content of titanium dioxide particles in the dispersion B is adjusted so that (weight)} is 80% by weight. Make the relative ratio so that it is knotted. When the base material (1) reaches the desired temperature in the oven, that is, about 200 ° C., the base material (1) is said to be the base material. Pass (1) in front of the nozzle that injects the dispersion B with compressed air at room temperature. Thus, they are bonded to each other derived from the dispersion and are produced from the decomposition of the organometallic compound. Ji SiO₂Ti O that binds to the substrate by₂A mixed layer of This coaty The anatase has a thickness of about 50 nm and is crystallized in the form of 65% anatase. This layer is TiO₂High specific surface area (> 250 m) increased by particles²High photocatalytic activity is exhibited by / g). In addition, SiO₂The binder is the base material Acts as a barrier to alkali metals, which is particularly effective at the interface with particles To do. Finally, SiO₂Due to its presence and its high porosity, the index of refraction is massive TiO₂Significantly lower than that of the layer. This index of refraction is lower than 1.6. Therefore, this base material Light reflection value R_LDecreases. Example 7 Dispersion B containing 0.1% niobium-doped titanium dioxide particles according to Example 2. Except for, Example 6 is repeated. This layer showed even higher photocatalytic activity. Example 8: Adhesion of the dispersion of Example 1 by immersion coating This example is an adhesion method by dip coating according to the principle clarified from Fig. 2. The so-called sol-gel technique is used. This is a solution containing the dispersion (4 ) Immerse the substrate (1) in it, and then use the motor means (5) to control the speed. It consists of pulling out the base material (1) by degree, and the pulling speed is selected appropriately. Therefore, it becomes possible to adjust the thickness of the dispersion remaining on the surfaces of the two surfaces of the base material. Cote attached to evaporate the solvent and decompose the precursor of the metal oxide It is possible to adjust the thickness of the coating after heat treatment of the ing. Coating (3) is applied using dispersions A or B as defined in Examples 3, 6 or 7. Let me wear it. We also use organic dispersion C, which includes: Titanium tetrab stabilized with a 1: 1 molar ratio of diethanolamine DEA Toxide Ti (O-Bu)₄Based on and tetra per liter of ethanol Formulation diluted in ethanol at a rate of 0.2 mol of butoxide; -A dispersion of titanium dioxide particles according to Example 1 that exhibits the following characteristics: Weight content of particles 10% Particle size 45nm measured by TEM Microcrystal size 5nm Crystal phase 80% or more anatase -Liquid phase ethylene glycol. The formulation and organic dispersion are derived from the particles in the adhered coating. Titanium dioxide content (organometallic compounds in dispersion C are completely decomposed into oxides TiO obtained from particles when assumed to be₂Weight / during coating Titanium dioxide particles in dispersion C so that the total weight of the oxides) is 80% by weight. The relative ratio should be such that the content is adjusted. Dispersions A and B of a base material (1) containing a thin layer (2) based on silicon oxycarbide. Alternatively, after dipping and coating in C, the temperature of the base material (1) is gradually increased. Heat at 550 ° C for 3 hours. Titanium dioxide well crystallized in the form of anatase in three cases The arting (3) was obtained on each side. Anatase crystallinity is heat It was comparable to the example using the debonding technique, but the size of the crystallites was during heat treatment. It got bigger because of the longer interval. This results in good photocatalytic activity Su. This coating had a refractive index of at most 1.8. Example 9: Adhesion of the dispersion of Example 1 by cell coating This example uses a technique called cell coating. The principle is clear from Fig. 3. It will be easy. It consists of: First, two substantially parallel planes (6) and (7) and a narrow cavity separated by two seals (8) and (9) To form. Here at least one of these surfaces (6) and (7) is processed It is composed of the surface of the base material (1) to be used. Next, the dispersion (4) is placed in the cavity. In a controlled manner, a wet meniscus is formed, for example using a peristaltic pump (10). The dispersion (4) is filled in such a manner. Dispersion as the solution is removed The film of (4) is left on the surface of the substrate. The cavity is then maintained for at least the time required for drying. Previous example Heat treatment results in curing of the film on the substrate, as in. Coating (3) is applied using solutions A, B or C described in Examples 3, 6 and 8. Be worn. Disperses A and B or a base material (1) containing a thin layer (2) based on silicon oxycarbide. Is dip-coated in C and then subjected to the same heat treatment as in Example 8. In three cases, a coating (3) comparable to the coating in Example 8 is obtained. However, in this case only one surface of each substrate was treated. Example 10: Adjustment of the properties of the resulting substrate Wetting test 1 This involves attaching a layer of organic silane on the substrate to be evaluated and irradiating it with UVA radiation. It consists of decomposing the layer by photocatalytic action. Organic silane is wet By measuring the contact angle between the substrate and water during irradiation, the properties of the graft layer are changed. The state of decomposition is shown. The rate of disappearance of this layer is related to the photocatalytic activity of the substrate. The organic silanes to be grafted are trichlorsilane and octadecyltrichlorcila. (OTS). Grafting is performed by dip coating. The test equipment consists of a rotary carrier that orbits around 1 to 6 low pressure UVA lamps. Rotate the test piece to be evaluated so that the surface to be evaluated is on the UVA radiation side. Place it on the carrier. Depending on their position and the number of lamps switched on, respectively Test piece is 0.5W / m²~ 50W / m²Receive UVA radiation that changes in the range of .. The time between each contact angle measurement depends on the photocatalytic activity of the test piece under concern 2 It changes in the range of 0 minutes to 3 hours. The measurement is performed using a goniometer. Before irradiation, the glass specimen shows an angle of about 100 °. Angle less than 20 ° At the time, it is considered that the layer was destroyed after irradiation. For each test piece, the average disappearance rate of the layer given at nm / hour, i.e. The thickness of the applied organic silane layer should be less than 20 ° to achieve the final level. Characterized by the quotient divided by the irradiation time that allows. Isobutane test 2: This is the decomposition of isobutane gas in contact with glass treated according to the present invention. Consists of controlling. Introduce an amount of isobutane equal to 20% of the total volume of the test glass and reactor to the reactor Enter. The test equipment is 1 to 6 low pressure UVs with maximum radiation in the 300 to 400 nm range. It consists of a rotating carrier that orbits around the A lamp. Contains a glass test piece to be evaluated Rotate the reactor so that the glass surface to be evaluated is on the UVA radiation side. Put it on the table. Depending on their position and the number of lamps switched on, each Glass is 30W / m²Receives UVA radiation in the range up to. Irradiation is continued for 8 to 22 hours. Then, using gas chromatography, O₂By monitoring the amount of Examine the progress of photolysis of isobutane. This progression is O₂Using the disappearance rate constant of Mol / hour / cm²It is represented by. Palmitic acid test 3: This attaches a layer of palmitic acid on the substrate to be evaluated, which is photocatalytic. Consists of irradiating with UVA radiation so that it is decomposed by. 8 g / liter of palmitic acid in chloroform on a glass test piece to be tested Spray the solution. Glass 30 cm²The amount of palmitic acid attached to the hit It is 1.5 mg. This glass test piece is then placed in the range of 300-400 nm. Introduce into a leak-free reactor surrounded by six UV lamps that emit large radiation. like this 10 W / m on the test glass test piece irradiated with²Power up. Irradiation up to 40 Continue time. The glass test piece is then removed from the reactor. Palmitic acid remaining on the glass test piece To analyze the acid, the glass specimen is washed with a solution of the acid in chloroform. Next The resulting solution was analyzed by liquid chromatography for residual palmitic acid. Analyze the acid. In this way, the time (minutes) for completely decomposing 1.5 mg of palmitic acid is given. available. Also, by reducing the blurring of the glass caused by the layer of palmitic acid. It is also possible to visually observe the decomposition of palmitic acid. Anti-condensation test 4: This is the photocatalytic action on wetting and the structure of the coating (of the hydroxyl groups Percentage, porosity, roughness) consists of observing the results. If the surface is photoreactive If there is, the fine carbonaceous dirt adhering to the coating is continuously destroyed, and the surface The surface becomes hydrophilic and therefore anti-condensation. Also, the first coated base material By storing in cold conditions and then rapidly reheating, or simply Blow on the substrate purely to see if condensation appears, and if condensation appears, this Perform a quantitative evaluation by measuring the time required for the condensation to disappear You can also do it. Contact angle test 5: This is the contact angle of a drop of water on the surface of the coating (3) and the DOP (lid) The surface of the coating by measuring the contact angle of one drop of docusate) To evaluate the hydrophilicity and lipophilicity of the glass in comparison with that on the surface of bare glass. Consists of. For measurement, the base material is exposed to the surrounding atmosphere in a dark place under daylight and left for 1 week. Then, it is carried out after being exposed to UVA irradiation for 20 minutes. Photocatalyst test results<img file="JPH11512336A_D0005.tif" /> Results of Test 4: No condensation appeared on all substrates of Examples 3-9. Results of Test 5: For all substrates in Examples 3-9, the contact angles with water and DOP It was less than 5 ° after exposure to UVA radiation for 20 minutes.