TW201014797A - Tin oxide particles and the method for preparing the same - Google Patents

Abstract

Novel tin oxide particles characterized in that in powder X-ray diffraction, the peak intensity ratio of the (101) plane to the (110) plane of tin oxide is 1.0 or higher. The tin oxide particles have a flake-like shape, and the longest width and shortest width of the face of the flake fall within the range of 0.05 to 40μm and the thickness is preferably 0.005 to 2μm. The tin oxide particles are produced by adding both a tin(II) compound and an alkali into a reactor in such a manner as to keep the pH in the reactor at 6 or below to hydrolyze the tin(II) compound. The obtained hydrolyzate may be further fired, as necessary. The tin oxide particles are useful as conductive material, catalyst, gas sensor, and so on, and can be either used as dispersions, or incorporated into coating materials, resin compositions, and so on.

Description

201014797 6. Description of the Invention: TECHNICAL FIELD OF THE INVENTION The present invention relates to tin oxide particles and a method of manufacturing the same. Further, a dispersion containing the tin oxide particles, a coating material, a resin composition, and the like. [Prior Art] Tin oxide is generally known as tin oxide (Sn02) having tetravalent tin as a constituent component and stannous oxide (Sn0) having divalent tin as a constituent component. Oxide Tin is a semiconductor. Although the monomer does not exhibit high conductivity, it is also known that high conductivity can be obtained by blending heteroatoms. Tin oxide is a material excellent in transparency and physicochemical stability, and is expected to be used for electrical and electronic applications. Specifically, antimony, phosphorus, fluorine, and the like are blended in tin oxide, and since it is excellent in electrical conductivity, it is mixed with plastic, rubber, or the like in the form of a conductive filler, and is used as a material of a conductive plastic. Further, when a transparent conductive film is formed using a coating material containing the above-mentioned conductive filler, a film having extremely low electrical resistance and low haze, φ and excellent adhesion to a substrate and film strength can be obtained. The display surface of the OA machine and the image of the TV Brown tube are charged, so they are used as electromagnetic protection. Further, the transparent conductive film can also be used for a transparent electrode of a display device such as a touch panel or a liquid crystal display. Further, a tin oxide film is formed on the glass by sputtering using a sintered body of tin oxide as a target to produce a transparent conductive oxide-coated glass, a heat-reflecting glass, a low-radiation glass, an electrothermal glass, or the like. On the other hand, stannous oxide is dissolved in sulfuric acid or the like and used in a tin plating bath. The tin oxide is produced by calcining a precipitate of a tetravalent tin salt aqueous solution and an alkaline aqueous solution. For example, Patent Document 1 describes that a reaction between a tetravalent tin salt aqueous solution and an alkaline solution is carried out at a pH of 〇5 to 4 to form a tin-containing precipitate, and secondly, it is calcined at a temperature of 400 to 120 (TC). Further, Patent Document 2 describes that a tetravalent tin salt aqueous solution and an alkaline aqueous solution are added in parallel in water', while maintaining the pH of the neutralization reaction liquid at 3 or more, and neutralizing the hydrate forming tin oxide, followed by In the water of the product, a ruthenium chloride solution and an aqueous solution are added in parallel, and while maintaining the pH of the neutralization reaction liquid at 3 or more, a hydrate of oxidized ruthenium is formed on the surface of the product, and then calcined. A method of producing tin oxide mixed with bismuth. On the other hand, regarding stannous oxide, for example, Patent Document 3 is a mixture of an aqueous solution of cerium chloride and an aqueous solution of sodium hydroxide, and is reacted at a pH of 12 to 13.5'. In the case of the aging, the aging is carried out for 2 hours or more. [PRIOR ART DOCUMENT] [Patent Document 1] JP-A-2002-029744 [Patent Document 2] Patent No. 3647929 [PATENT DOCUMENT 3] -201 022 SUMMARY OF THE INVENTION (Problems to be Solved by the Invention) As in the above-mentioned Patent Documents 1 and 2, a tin oxide compound produced by calcining a precipitate obtained by hydrolysis and neutralization reaction using a tetravalent tin compound is used. In such a method, it is not possible to produce tin oxide having a particle shape such as a flaky shape. On the other hand, in the method of -6-201014797 of Patent Document 3, although a divalent tin compound is used, it is neutralized. In the reaction, a flat-shaped stannous oxide is obtained, but it is not possible to obtain a sheet-like shape of stannous oxide. The stannous oxide is dissolved in sulfuric acid or the like and used in a tin plating bath, and no stannous oxide is described. Oxidation to produce tin oxide. (Means for Solving the Problem) The present inventors have considered that a thin tin oxide film is formed by using a particle shape of tin oxide as a sheet, and a useful material having high effects such as conductivity is obtained, and the material is manufactured. A method of oxidizing tin particles having a flaky particle shape. As a result, it was found that when a divalent tin compound and a base are added, the pH in the reactor is maintained at 6 or less, and tin is added. When the compound is hydrolyzed, flaky cuprous oxide particles having a small thickness are obtained, and the tin oxide particles which maintain the flaky shape are obtained by calcination. f, and the powder X of the flaky oxidized stannous particles and the flaky tin oxide particles are found. In the cross-sectional view of the ray, the peak intensity ratio (peak height ratio) of the (101) plane of the tin oxide (110) plane is 1.0 or more, and even if it is pulverized into an indefinite shape, the above-described peak intensity ratio can be made. The present invention is completed at 1.0 or more. That is, the present invention is (1) a tin oxide particle characterized by a peak of a (1 01 ) plane with respect to a (110) plane of a tin oxide in powder X-ray diffraction. (2) The tin oxide particles according to the above (1), wherein the tin oxide is a crystal structure having tin oxide (Sn02), and the tin oxide particles described in (1) or (2) above, In the case of the above-mentioned (1) or (2), the tin oxide particles according to the above (1) or (2) have a flaky particle shape, and (5) the tin oxide described in the above (1). Particles, among them, The tin is a crystal structure having stannous oxide (SnO), and has a particle shape of a sheet. (6) The tin oxide particles according to (4) or (5) above, wherein the thickness of the sheet surface is (5) The tin oxide particles according to the above (4) or (5), wherein the longest width and the shortest width of the sheet surface are in the range of 〇. 5 to 40 μm, and the thickness is in the range of 0.005 to 2 μm. (8) The tin oxide according to any one of the above (1) to (7)

(I) The tin oxide particle according to any one of the above (1) to (8), wherein the surface of the tin oxide particle is coated with an inorganic compound and/or organic The tin oxide particle according to the above (9), wherein the surface of the tin oxide particle is coated with a conductive inorganic compound, and the method for producing (11) a tin oxide particle is characterized in that tin (II) is used. The compound and the base are added to the pH of the reactor to be maintained at 6 or less to hydrolyze the tin (antimony) compound, and (12) the method for producing tin oxide particles according to (11), wherein a temperature of 50 ° C or higher is added. In the water reactor, a tin (π) compound and a base are added, and -8-201014797 (13) is a method for producing tin oxide particles, which is characterized in that a tin (II) compound and a base and an inorganic compound are used in the reactor. The method for producing a tin oxide particle according to any one of the above (1) to (1), wherein the tin oxide is oxidized, wherein the tin oxide is oxidized. Crystal structure of stannous, (15) - oxygen species A method for producing a tin-based particle, which is characterized in that the hydrolyzed product of the tin (II) compound obtained by the method according to any one of the above (11) to (14) is calcined, and (16) as described above (15) And a method for producing a tin oxide particle according to the above (15) or (16), wherein the method for producing a tin oxide particle according to the above (15) or (16) is the method for producing a tin oxide particle according to the above (15) or (16), wherein The tin oxide is a crystal structure having a tin oxide, and (18) a method for producing a tin oxide particle, characterized in that the tin oxide obtained by the method according to any one of the above (11) to (17) is pulverized. (19) A method for producing a tin oxide particle, characterized in that the surface of the tin oxide particle obtained by the method according to any one of the above (11) to (18) is coated with an inorganic compound and/or an organic compound, (20) The method for producing tin oxide particles according to the above (19), wherein the inorganic compound and/or the organic compound are coated and then calcined, and the (21) dispersion is characterized by containing (1) to (1 0) as described above. Tin oxide particles as described in any one of them A coating material containing the tin oxide particles according to any one of the above (1) to (1), and a resin composition of the above (2), characterized in that it is characterized in that The tin oxide particle according to any one of the above (1) to (10), and the tin oxide film of (24), characterized in that the dispersion according to the above (21) is applied onto a substrate or as described above. (22) A coating material according to (22), wherein the conductive material is characterized by containing the tin oxide particles according to any one of the above (1) to (1), and (26) a catalyst. The tin oxide particle according to any one of the above (1) to (10), which is characterized in that the gas sensor according to any one of the above (1) to (10) is contained. Tin particles. (Effect of the Invention) The tin oxide particles of the present invention have a specific X at a peak intensity ratio of (1 〇 1 ) plane to the (1 〇 1 ) plane of the tin oxide (11 〇) plane in powder X-ray diffraction. A ray cutaway view. This property is used for conductive materials, catalysts, gas sensors, and the like. Further, it is used in a particle shape having a flaky shape, and a material of a thin tin oxide film, a conductive material, or the like is formed by using a specific particle shape. The method for producing tin oxide particles of the present invention does not require a bulky device and uses a relatively inexpensive raw material, so that it is relatively simple to manufacture industrially advantageous tin oxide particles having a specific X-ray cross-sectional view and tin oxide having a specific particle shape. An advantageous method of particles. -10-201014797 [Embodiment] The peak intensity ratio of the tin oxide particles of the present invention in the powder X-ray diffraction with respect to the (101) plane of the tin oxide (110) plane is 1.0 or more. The tin oxide of the present invention may be stannous oxide or tin oxide, or may contain each of them, and may contain stannous hydroxide, tin hydroxide or the like. In tin oxide, since it can be used for various purposes, it is preferable to use a crystal structure having stannous oxide or tin oxide 1, and a crystal structure having tin oxide is preferable, and all the tin oxides are crystal structures having tin oxide. It is better. As described in the foregoing, the tin oxide of the present invention has a special X-ray cross-sectional view, specifically, by powder X-ray diffraction (line source; Cu-KoO confirms the crystal structure of tin oxide, at the diffraction angle ( 2Θ) 3 The peak height of the (101) plane of tin oxide appearing at around 3.8° is the same as or higher than the peak height of the (110) plane appearing at a diffraction angle (2Θ) of about 26.6°. Also, if powder X-ray is used The diffraction (line source; Cu-Κα) confirms the crystal structure of stannous oxide, and then the peak height of the (101) plane of the stannous oxide which appears at a diffraction angle (2Θ) of 29.9°, and the diffraction angle (2Θ The peak height of the (110) plane appearing at around 33.3° is the same or higher. That is, the peak of the peak height of the (101) plane of the tin oxide / the peak height of the (110) plane in the powder X-ray diffraction The intensity ratio is 1.0 or more, more preferably 1.1 or more, and 2 or more is more preferable. This phenomenon is generally observed in the case of the flaky cuprous oxide particles and tin oxide particles of the present invention, and on the other hand, in the prior grain In the case of a particle, the peak height of the (101) plane is a ratio (110) plane The peak height is lower -11 - 201014797. Therefore, the flaky tin oxide particles of the present invention are different from the conventional granulated particles, and are considered to be aligned in the (101) plane. If the flaky tin oxide particles of the present invention are strongly pulverized In the case of the above-described peak intensity ratio, the peak intensity ratio is gradually reduced, so that it is understood that the peak intensity ratio can specify the characteristics of the flaky tin oxide particles of the present invention. Further, depending on the degree of pulverization, even if it is an indefinite shape including various shapes, In some cases, the peak intensity ratio of the above-described tin oxide particles may be 1.0 or more. Therefore, the particle shape of the tin oxide particles of the present invention is generally a sheet-like shape, but if the peak intensity ratio is satisfied, the sheet-like shape may be pulverized. The shape of the sheet is defined as the shape having a longest width and the shortest width, and has a shape which is small and has a thickness in the vertical direction with respect to the sheet surface. Preferably, the longest width/thickness is 4 or more. More preferably, it is about 10 to 1 000, and generally contains so-called thin layer, thin plate, sheet, flake, and nano tablets. The shape is preferably as thin as 5 μm or less with respect to the vertical direction of the sheet surface, more preferably in the range of 0.0005 to 5 μm, and preferably in the range of 0.005 to 2 μm, preferably 0.01 to 2 μm. The range is more preferably. The longest width of the sheet surface, or the shortest width, is preferably in the range of 0.05 to 40 μm from the viewpoint of powder characteristics, and more preferably in the range of 0.5 to 30 μm. The shape of the sheet and the size thereof are preferable. The flaky shape and the size thereof can be determined by observation with an electron microscope. The tin oxide particles may contain an inorganic element other than Sn. The inorganic element may be used for the purpose of imparting conductivity, for example. A part of Sn may be substituted with an inorganic element such as Sb, P, Nb or W, or may be substituted with an inorganic element such as Si or A1. The amount of substitution can be appropriately set according to the inorganic element -12- 201014797. Further, from the viewpoints of dispersibility of the solvent, affinity of the resin, etc., the surface of the particles of the tin oxide may be subjected to an organic compound such as a surfactant, a coupling agent, a carboxylic acid, a polyhydric alcohol, an amine, a decane or the like. An inorganic compound such as cerium oxide or aluminum oxide is coated. Further, the surface of the particles of tin oxide may be coated with a conductive inorganic compound such as tin oxide such as Sb, P, Nb or W. The amount of the inorganic compound and/or the organic compound or the conductive inorganic compound to be coated on the surface of the tin oxide particles can be appropriately set. The tin oxide particles having a specific X-ray cross-sectional view of the present invention, for example, can be obtained by reacting a tin (II) compound (Sn2+) with a base at a pH of 6 or less * and hydrolyzing a tin (II) compound. The tin (II) compound can be used as a divalent tin compound such as tin (II) chloride. A water-soluble tin (Π) compound is preferred, and tin (II) chloride is more preferred. The concentration of the tin (II) compound is preferably from 0.05 to 150% by weight, more preferably from 1.0 to 100% by weight, based on the water when it is dissolved in water. As the base, an alkali hydroxide such as sodium hydroxide, potassium hydroxide or lithium hydroxide, an alkali carbonate such as sodium carbonate or the like, an ammonium compound such as ammonium carbonate φ, ammonia or the like can be used, and among them, alkali hydroxide, particularly sodium hydroxide is used. good. The addition of the tin (II) compound and the base is carried out while adjusting the pH in the reactor to 6 or less, preferably adjusted to a pH of 3 to 6, more preferably 3.5 to 5.5. In the vicinity of a pH higher than 6 neutral, a tin acid anhydride (Siu〇4(OH)4) is easily formed, which is not in the form of a flake. Further, when the pH is 9 or more, the plate may be formed into a flat shape. However, the thickness thereof is more than 5 μm. The addition method of the tin (II) compound and the base may be carried out by adding a tin (II) compound to the reactor and then adding a base. A method in which a tin (II) compound is added in advance to the reactor after the addition of a-13-201014797 base, and a tin (II) compound and a base are simultaneously added in a reactor. In either case, it is also possible to combine two or more methods, but it is preferred to add the tin (II) compound and the base in parallel at the same time. If the temperature of the reactor after the addition is 50. (: The above is effective in the hydrolysis of the tin (II) compound. It is also preferable to add a tin (II) compound (or a base) and raise the temperature to 50 ° C or more and then add a ruthenium (or tin (II) compound). After adding water to the reactor in advance, and the temperature of the water is 50° C. or higher, the tin (II) compound may be added in parallel with the base, preferably the latter. The preferred temperature is about 70 to 105 ° C. More preferably, the temperature is about 85 to 1 0 5 ° C. The above-mentioned simultaneous parallel addition refers to a method in which both are added to the reactor in small amounts continuously or intermittently. Specifically, the two are 10 In the case of addition of the tin (II) compound and the base, the addition of the tin (II) compound and the base is preferred because the crystallinity of the stannous oxide is higher, and the aging temperature is preferably 50 ° C or more. Preferably, the temperature is about 105 ° C, preferably about 90 to 105 ° C. The ripening time is preferably from about 5 minutes to about 6 hours. The above hydrolysis reaction and ripening are maintained at a valence of tin valence, in nitrogen, etc. Under non-oxidizing ambient gases, but also in the usual atmosphere The tin (Π) compound is hydrolyzed as described above to obtain tin oxide particles having a crystal structure of stannous oxide, particularly flaky stannous oxide particles. Thereafter, if necessary, in order to remove an unnecessary electrolyte present in the aqueous solution, In the case of washing, a pH adjuster is added to agglomerate the produced hydrolyzate. The pH adjuster used may be a mineral acid such as hydrochloric acid or sulfuric acid, or a base such as sodium hydroxide. After the net, if necessary, solid-liquid separation and further drying. For solid-liquid separation, filters such as filter paper pressurization and drum pressurization can be used, and belt heaters and batch heaters can be used for drying. , spray dryer, etc. Drying is carried out in a non-oxidizing atmosphere such as nitrogen gas in the form of a valence of tin, but it can also be dried in a normal atmosphere. The drying temperature is in the range of 50 to 120 °C. Further, after drying, it can be calcined as needed, », after non-oxygen or calcination of nitrogen, argon, hydrogen, etc., according to the impact pulverizer, roll mill, roller mill, sputum type according to tin oxide particles. Dry pulverization by a pulverizing mill to treat the particles obtained in this manner, in particular, the tin oxide particles φ of the flaky tin oxide crystal structure is preferably set to a temperature at which all of the tin oxide is calcined, and the temperature of the tin oxidation is higher. Preferably, the temperature is preferably from 600 to the above range, and the generated oxidized or calcined ambient gas is preferably a special gas. The smouldering can be used to heat the sinter, such as ballast, and chlorination. It is more preferable to use a chlorine compound such as tin and a temperature in the range of 120 to 500 ° C as a preferred environment gas. The degree of agglomeration after drying, using a grinding mill such as a hammer mill, a needle mill, a pulverizer or the like It is also possible to obtain a compression pulverizer such as a machine, a jet mill, etc. When the tin oxide tin oxide particles having a stannous oxide crystal structure are fired, a flaky tin oxide having oxidized ions, particularly flaky tin oxide particles, and tin oxide is obtained. particle. If the flaky cuprous oxide particles are oxidized, it is in the range of 1 〇〇〇 °c in the range of 500 ° C to 1 1 〇 〇 °C. If the calcination temperature is higher than that between the tin particles, it is not preferable. There is no restriction, but the air (atmospheric) environment uses a flow furnace, a stationary furnace, a rotating crucible, and a tunnel. A flux such as chlorine may also be added during calcination. After calcination, according to the degree of sintering, -15-201014797 is used as a grinding mill, a roller mill, a pulverizer, a pulverizer, a pulverizer, a pulverizer, etc., such as a hammer mill, a needle mill, or the like. The air pulverizer such as a compression pulverizer or a jet mill may be subjected to dry pulverization. In the tin oxide particles, the above-mentioned inorganic element is contained, and the tin (bismuth) compound is reacted with a base. When the tin (II) compound is hydrolyzed, the presence of the inorganic compound is preferably carried out, and at this time, the pH in the reactor is maintained. Add below 6. Specifically, (1) a method in which a tin (U) compound and a base are added to a reactor, a tin (Π) compound is added to the reactor, and (2) a tin (II) is added to the reactor. a compound and a base and an inorganic compound, a method of hydrolyzing a tin (II) compound, which comprises, for example, a method of separately adding a tin (II) compound and a base and an inorganic compound, and premixing and adding an inorganic substance to the tin (II) compound solution. A method of a compound, a method of adding an inorganic compound in advance to a base, or the like. (3) A method in which a tin (II) compound and a base are added to a reactor, and a tin (II) compound is hydrolyzed, and an inorganic compound is added. Further, in another method, an inorganic compound may be added to the slurry of tin oxide, and the inorganic compound may be neutralized and precipitated in the slurry, and the inorganic element is preferably contained in the tin oxide particles. Further, a mixed inorganic compound may be added to the powder of tin oxide. After the inorganic oxide element is contained in the tin oxide particles, it may be filtered, washed, and dried as needed. The drying of the stannous oxide is carried out in a non-oxidizing atmosphere such as nitrogen gas at a valence of valence of tin, but it may be dried in a normal atmosphere. The drying of tin oxide can also be carried out in the usual atmosphere. Drying -16- 201014797 The temperature is preferably in the range of 50 to 120 °C. Further, after drying, calcination may be carried out as needed, and by this calcination, a part of the tin element may be substituted with an inorganic element. The calcination temperature is preferably in the range of 1 20 to 1 1 〇〇 ° C, and the ambient gas is preferably air (atmospheric) ambient gas, preferably in a non-oxidizing atmosphere such as nitrogen, helium or hydrogen. After drying or after calcination, according to the degree of agglomeration of the tin oxide particles, a grinding mill, a roller mill, a pulverizer, a pulverizer or the like, a pulverizer, a drum pulverizer, and a smashing type are used. Dry pulverization may be carried out by a jet mill such as a compression pulverizer or a jet mill. When the surface of the tin oxide particles is coated with the inorganic compound and/or the organic compound, the surface treatment method may be used. Specifically, it is preferable to add the inorganic compound and the organic compound to the slurry of the tin oxide, and the inorganic compound is added to the slurry. It is more preferable to neutralize and coat the organic compound. Further, it is also possible to add a mixed coating inorganic compound and an organic compound to the powder of tin oxide. In addition, it is preferable to coat a conductive inorganic compound on the surface of the tin oxide particles, and to add a compound which is a conductive inorganic compound to the slurry of tin oxide, and to neutralize or water the compound which becomes a conductive inorganic compound in the slurry. Parsing out the coverage is better. After coating the surface of the tin oxide particles with an inorganic compound and/or an organic compound or a conductive inorganic compound, it may be filtered, washed, and dried as needed. The drying of the stannous oxide is carried out in a non-oxidizing atmosphere such as nitrogen gas in the same manner as the valence of tin, but it can also be dried in a normal atmosphere. The drying of tin oxide can also be carried out in the usual atmosphere. The drying temperature is preferably in the range of 50 -17 - 201014797 ~ 120 °C. Further, after drying, calcination may be carried out as needed, and the calcination temperature is preferably in the range of 120 to 1100 ° C, and the ambient gas is preferably air (atmospheric) ambient gas, and non-oxidizing environment such as nitrogen, argon or hydrogen. It is better under gas. After drying or after calcination, according to the degree of agglomeration of the tin oxide particles, a grinding mill, a roller mill, a pulverizer, a pulverizer, or the like, a pulverizer, a drum pulverizer, or the like is used. Dry pulverization may be carried out by a jet mill such as a crusher or a jet mill such as a pulverizer. The above tin oxide particles are dispersed in a solvent to form a dispersion. As the solvent in which the tin oxide particles are dispersed, an organic solvent such as ice or alcohol, dimethylformamide (DMF), ketone or the like, or a mixture thereof, industrially using water as a main solvent or dimethyl group can be used. Indoleamine (DMF) and ketone are preferred. The ketone may, for example, be acetone, 2-butanone or methyl ethyl ketone. The concentration of the tin oxide particles in the dispersion can be appropriately set, and is preferably, for example, about 0.1 to 10 g/l. Further, in order to improve the dispersibility, a centrifuge or the like may be used as appropriate. Further, the above tin oxide particles are dispersed in a solvent and a resin binder is blended to prepare a coating material. Specific examples of the resin binder include (1) an inorganic binder (a) a polymerizable hydrazine compound (hydrolyzable decane or a hydrolyzate thereof or a partial condensate thereof, water glass, colloidal cerium oxide, or organic condensate) (2) an organic binder (alkyd resin, acrylic resin, polyester resin, epoxy resin, fluorine resin, modified polyfluorene) Oxygen resin). In addition to the tin oxide particles, the solvent, and the resin binder, the dispersion and the coating material may contain a dispersing agent, a pH adjusting agent, an antifoaming agent, and the like, in the range of not inhibiting the effects of the present invention. As the third component, various additives such as an emulsifier, a coloring agent, an extender, an antifungal agent, a hardening aid, and a tackifier, and a sputum-filling agent are used. Examples of the dispersant include (1) a surfactant ((a) an anion (carboxylate, sulfate, sulfonate, phosphate, etc.), (b) a cationic (alkylamine, alkylamine) a quaternary ammonium salt, an aromatic quaternary ammonium salt, a heterocyclic quaternary ammonium salt, etc.), (c) an amphoteric (betaine type, amino acid type, alkylamine oxide, nitrogen-containing heterocyclic type, etc.), d) non-p ion system (ether type, ether ester type, ester type, nitrogen type, etc.), (2) polyfluorene-based dispersant (alkyl modified polyoxane, polyoxyalkylene modified Polyoxane, etc., (3) phosphate dispersant (sodium phosphate, sodium pyrophosphate, sodium orthophosphate, sodium metaphosphate, sodium tripolyphosphate, etc.), (4) alkanolamines (amine methyl propyl acrylate) The amount of the tin oxide particles in the dispersion and the coating material, the amount of the other additives, and the like can be appropriately set, and the product obtained by hydrolyzing the tin (II) compound (flaky oxygen φ) can be appropriately set. The stannous particles are in a state of being dispersed in the form of flaky tin oxide particles, so they are directly used as flaky tin oxide. The dispersion of the particles may be used, or the flaky tin oxide particles separated by solid-liquid separation may be redispersed in a solvent, and the dried powder, the calcined powder, the powder containing the inorganic element, and the surface coating may be used. The treated powder or the pulverized powder, in particular, the powder of the flaky tin oxide particles may be redispersed in a solvent. The redispersing may be carried out using a conventional disperser, a colloid mill, a ball mill, a bead mill, an ultrasonic wave or the like. In addition, the above-mentioned third component may be added. Further, in order to improve the dispersibility, a centrifuge or the like may be used as appropriate. -19- 201014797 Such dispersions and coatings are excellent in long-term storage stability, coated on a substrate, and dried. Or calcination can obtain a tin oxide film. The method of coating on a substrate is spin coating, spray coating, roller coating, dip coating, flow coating, knife coating, electrostatic coating, rod coating, A general method such as coating, brushing, or dropping a droplet can be used without limitation. If the film thickness is thicker, it can be repeatedly applied. If the solvent is removed from the coating, oxygen is formed. The film is preferably formed at a temperature ranging from room temperature to 800 ° C. The temperature is preferably based on the boiling point of the solvent, for example, in the range of room temperature to 150 ° C, more preferably in the case of an aqueous solvent. Further, the tin oxide particles are mixed with a resin, and the liquid resin composition such as a coating material or an ink may be used as described above, or the tin oxide particles may be mixed in the resin to form a plastic molded body or sheet. A solid resin composition such as a film may be used. The above-mentioned resin binder, biodegradable resin, ultraviolet curable resin, thermosetting resin, etc. may be suitably used for such a resin, and the blending amount of tin oxide particles and other additives may be used. The amount of the above tin oxide particles can be used for various functional materials. For example, it can also be used for conductive additives, catalysts, catalyst carriers, gas sensors, photocatalysts, infrared shielding agents, ceramics. , metal additives, honing materials, etc. Since the tin oxide particles have high crystallinity on the (1 01 ) plane or have a flake-like particle shape, they are suitably used for a conductive filler, a catalyst, a catalyst carrier, and a gas sensor. The conductive filler can be used for an antistatic agent, an electrode material, and the like. As the catalyst, an oxidizing catalyst for oxidizing acrolein with propylene, a selective catalyst for reducing NO with ammonia, and the like can be used as a carrier for an oxidation catalyst for methane. Also, the gas sensor can be used -20-

201014797 As a flammable gas alarm, etc., and gas detection induction is used for the measurement of trace amounts of CO and H2S. Further, the tin oxide film can be used for various functional materials in addition to a transparent material, a conductive film, a resistor, and a device, and a glass of a tin oxide film oxide on a glass substrate, a heat reflecting glass, and a low emission can be used. Glass and so on. It can also be used for photocatalytic materials, anti-reflective materials, and. For the use of these applications, when a tin oxide particle or a tin oxide film is used as a photocatalyst according to the shape and blending ratio used previously, it is possible to remove harmful substances, malodorous substances, dirt, and the like by irradiating a band gap of tin oxide. In order to use anti-fouling and anti-fog effects. [Examples] Hereinafter, the present invention will be described based on examples, but the present invention is limited thereto. Example 1 Stannous chloride 2 hydrate (SnCl 2 · 2H20 was dissolved in 15.6 g of a 35% hydrochloric acid aqueous solution. The concentration was adjusted by dissolving 14.8 g to obtain a solution of stannous chloride followed by pure water at 90 ° C. 0.5 liter of the above solution and 5 equivalents of sodium hydroxide aqueous solution are added for 30 minutes while being added, and after being added, the aging is 10 degrees high, and it can also be used. For example, an electrode, a gas sensation, etc., and a conductive glass are coated. The isothermal and supported state of the electrothermal glass gas barrier material, for example, the wavelength of light used for the amount of super-hydrophilic effect is not recognized by these practical drugs. 8.63 g of solution is added with pure water, stannous chloride water ρΗ5±0 · 2 — minutes and minutes. Thereafter, -21 - 201014797 was adjusted to pH 3.0 with 3 equivalents of aqueous hydrochloric acid, and the mixture was stirred for 5 minutes to start washing. The washing was stopped when the filtrate had a specific resistance of 10,000 Ωcm, and the obtained cake was placed in the atmosphere at 105 r overnight and dried. The dried product was hand-pulverized in an agate mortar to obtain the flaky tin oxide particles of the present invention (sample A). X-ray diffraction measurement (X-ray diffraction apparatus RINT-1200 manufactured by Rigaku Corporation) of Sample A was carried out, and this X-ray diffraction cross-sectional view is shown in Fig. 1. As shown in Fig. 1, sample A is an X-ray diffraction cross-sectional view peculiar to flaky tin oxide having a peak intensity ratio of 1.0 or more with respect to the (101) plane of the stannous oxide (11 Å) plane. A scanning electron micrograph of sample A is shown in Fig. 2. Fig. 2 shows that the longest width and the shortest width are in the range of 0.05 to 40 μm, and the thickness is in the range of 〇.〇〇5 to 20111. Further, the thickness of each sheet was measured by an individual high-magnification electron microscope photograph. Example 2 Sample A obtained in Example 1 was calcined at a temperature of 90 ° C for 1 hour in the atmosphere to obtain flaky tin oxide particles of the present invention (sample B). The x-ray diffraction measurement of sample B was carried out. The X-ray diffraction cross-sectional view is shown in Fig. 3. As shown in Fig. 3, the sample B is different from the sample Y obtained in the comparative example 2 described later. The peak intensity ratio of the (101) plane with respect to the (110) plane is 1. 〇 or more of the flaky tin oxide. A ray diffraction cross-sectional view. The scanning electron micrograph of sample B is shown in Fig. 4. It can be seen from Fig. 4 that the shape of the sheet is maintained after the smoke is burned. The longest width and the shortest width are respectively -22 - 201014797, and the thickness is 0.005 to 2 μm. Range of flaky particles. Example 3

17.45 g of stannous chloride 2 hydrate (SnCl 2 · 2Η20, manufactured by Wako Pure Chemical Industries, Ltd.) was dissolved in 19.46 g of a 35 % aqueous hydrochloric acid solution. To the solution, 18.54 g of pure water was added to adjust the concentration to obtain an aqueous solution of stannous chloride. Next, the above-mentioned stannous chloride aqueous solution and 5 equivalents of sodium hydroxide aqueous solution were simultaneously added at a pH of 4 ± 0.2 at 0.5 liter of pure water at 90 ° C for 20 minutes while being added thereto. After the addition, the mixture was aged for 10 minutes. Thereafter, the pH was 3.0 using 3 equivalents of an aqueous hydrochloric acid solution, and the mixture was stirred for 5 minutes to start washing. When the filtrate had a specific resistance of 15,000 Ωcm, the washing was stopped, and the obtained cake was placed in the atmosphere at 1 〇 5 t for one night and dried. The dried product was hand-pulverized in an agate mortar to obtain the flaky tin oxide particles of the present invention (sample C). When the sample C was observed by a scanning electron microscope, it was found that the longest width and the shortest width were in the range of 〇. 5 to 40 μm, and the flaky particles having a thickness in the range of 0.005 to 2 μm. Further, in the X-ray diffraction measurement, an X-ray diffraction cross-sectional view peculiar to the flaky stannous oxide having a peak intensity ratio of 1.0 or more with respect to the (101) plane of the stannous oxide (110) plane is obtained. (Example 4) 2.0 g of the sample C obtained in Example 3 was placed in an aluminum crucible, and calcined at 900 °C for 2 hours in a gas of -23 - 201014797 to obtain flaky tin oxide particles of the present invention (sample D). The scanning electron micrograph of the sample D is shown in Fig. 5» from Fig. 5, the flaky particles having the range of the longest width and the shortest width of 0.05 to 40 μm and the thickness of 0.005 to 2 μm are known. Further, when X-ray diffraction measurement is performed, in the same manner as in the second embodiment, the X-ray diffraction cross-section unique to the flaky tin oxide is used, and the peak intensity ratio of the (101) plane/(110) plane is 6.2. 2.0 g of the dried product obtained in Example 3 and 0.4 g of sodium chloride were slowly pulverized in an agate mortar, and 2.0 g of the aluminum mash was taken out and placed in an aluminum crucible, and calcined at 900 ° C for 2 hours in the atmosphere. Flaky tin oxide particles (sample E). A scanning electron microscope photograph of sample E is shown in Fig. 6. As is apparent from Fig. 6, the flaky particles having a longest width of about 0.5 to 6 μm are obtained. The electron micrograph of the high magnification has a thickness of about 0.08 to 2.0 μm. Further, in the X-ray diffraction measurement, in the same manner as in the second embodiment, the X-ray diffraction cross-section characteristic of the flaky tin oxide was used, and the peak intensity ratio of the (1 0 1 ) plane/(1 1 0) plane was 2.0. Example 6 2.0 g of the dried product obtained in Example 3 and 0.4 g of stannous chloride were slowly pulverized in an agate mortar, and 2.0 g of the aluminum bismuth-24-201014797 was taken out and 900° in the atmosphere. C was calcined for 2 hours to obtain tin oxide particles of the present invention (sample F). A scanning electron microscope photograph of sample F is shown in Fig. 7. It is known that the longest width is about 0.1 to 0.5 μm. The electron micrograph of the rate is about 0.05 to 1.5 μm. Further, in the X-ray diffraction measurement, in the same manner as in the second embodiment, the X-ray diffraction cross-sectional view of the flaky tin oxide is present, and the (1 0 1 ) plane/(1 1 0) plane wave is applied to the embodiment 7 in the embodiment 3. The flaky tin oxide particles of the present invention (sample G) sample G was obtained by a scanning electron microscope, except that the alkali source 5% ammonia water used in the simultaneous addition was used instead of 5 equivalents of sodium hydroxide. When observed, it was found that the longest width and the shortest width were in the range of 0.05 to 40 μm, and the thickness was 0.005 to the range of the flaky particles. Further, in the X-ray diffraction measurement, an X-ray diffraction cross-section unique to the flaky stannous oxide having a peak intensity ratio of j or more on the (101) plane of the stannous oxide (110) plane is obtained. (Example 8) 2.0 g of the sample G obtained in Example 7 was placed in an aluminum crucible, and calcined at 900 °C for 2 hours in the gas to obtain flaky oxygen particles (sample Η) of the present invention. A scanning electron microscope photograph of the sample is shown in Fig. 8. From the picture sheet 7, the peak intensity can be high, and the same intensity and 2 μιη can be used. The phase of the longest width and the shortest width are 0.05 to 40 μm, respectively. The thickness is 0.005~ Flaky particles in the range of 2 μηι. Further, in the X-ray diffraction measurement, in the same manner as in the second embodiment, the X-ray diffraction cross-section characteristic of the flaky tin oxide is used, and the peak intensity ratio of the (1 〇1) plane/(1 1 〇) plane is 8 · 3 Example 9 17.45 g of stannous chloride 2 hydrate (SnCl 2 · 2Η20 and Wako Pure Chemical Industries, Ltd.) was dissolved in 19.46 g of a 35 % aqueous hydrochloric acid solution. To the solution, 18.54 g of pure water was added to adjust the concentration to obtain an aqueous solution of stannous chloride. Next, the above aqueous solution of arsenic chloride and the dissolved sodium citrate solution (water glass, SiO 2 portion; 35 to 38%, reagent, manufactured by Kanto Chemical Co., Ltd.) were 0.14 g in a pure water 〇 5 ° C at 90 ° C. Five equivalents of aqueous sodium hydroxide solution was added while maintaining pH 4±0.2 for 20 minutes, and after the addition, the mixture was aged for 1 minute. Thereafter, the pH was 3.0 using 3 equivalents of an aqueous hydrochloric acid solution, and the mixture was stirred for 5 minutes to start washing. When the filtrate had a specific resistance of 105,000 Qcm, the washing was stopped, and the obtained cake was placed in the atmosphere at 105 ° C overnight, and dried. The dried product was hand-pulverized in an agate mortar to obtain the flaky tin oxide particles of the present invention (Sample I). When the sample I was observed by a scanning electron microscope, it was found that the longest width and the shortest width were in the range of 0.05 to 40 μm, and the thickness was in the range of 0.005 to 2 μm. Further, in the case of performing X-ray diffraction measurement, the X-ray diffraction profile specific to the flaky stannous oxide having a peak intensity ratio of 1.0 -26 to 201014797 or more with respect to the (101) plane of the stannous oxide (110) plane is obtained. . Example 1 〇- 2.0 g of the sample I obtained in Example 9 was placed in an aluminum crucible, and calcined at 900 ° C for 2 hours in a large atmosphere to obtain a hydrazine containing the present invention (converted to 3 丨〇 2 as 0.5). 3% by weight of flaky tin oxide particles (sample J). A scanning electron microscope photograph of sample J is shown in Fig. 9. As can be seen from Fig. 9, the longest width and the shortest width are flaky particles having a range of 〇. 5 to 40 μm and a thickness of 0.005 to 2 μm. Further, in the X-ray diffraction measurement, in the same manner as in the second embodiment, the X-ray diffraction cross-section characteristic of the flaky tin oxide is used, and the peak intensity ratio of the (1 〇1) plane/(1 1 〇) plane is 5.1 〇. Example 11 In the same manner as in Example 9, except that 0.47 g of a sodium citrate solution was used instead of φ 〇. 14 g, the flaky tin oxide particles of the present invention (sample Κ) were obtained. When the sample was observed by a scanning electron microscope, it was found that the longest width and the shortest width were in the range of 〇. 5 to 40 μm, and the flaky particles having a thickness in the range of 0.005 to 2 μm. Further, in the X-ray diffraction measurement, an X-ray diffraction cross-sectional view peculiar to the flaky stannous oxide having a peak intensity ratio of 1.0 or more with respect to the (101) plane of the stannous oxide (110) plane is obtained. Example 1 2 -27- 201014797 The sample κ 2.0 g obtained in Example 11 was placed in aluminum crucible' and was subjected to 90 (TC calcination for 2 hours in the atmosphere to obtain hydrazine containing the present invention (in terms of SiO 2 of 1.64% by weight) The flaky tin oxide particles (sample L) The scanning electron microscope photograph of the sample L is shown in Fig. 10. As can be seen from Fig. 10, the longest width and the shortest width are respectively in the range of 〇. 5 to 40 μm, and the thickness is 0.005 to 2 In the case of X-ray diffraction measurement, in the same manner as in Example 2, the X-ray diffraction cross section unique to the flaky tin oxide is used, and the peak intensity ratio of the (101) plane/(110) plane is 6.2. Example 1 3 In the same manner as in Example 9, except that 0.91 g of sodium citrate solution was used instead of 0.14 g, the flaky tin oxide particles of the present invention (sample Μ) were obtained. When observed by an electron microscope, it is known that the longest width and the shortest width are in the range of 〜·〇5 to 40 μm, and the thickness is 0.005 to 2 μηη in the range of 0.005 to 2 μηη. Further, when X-ray diffraction is measured, it has a relative oxidation degree. An X-ray diffraction cross-sectional view peculiar to the flaky stannous oxide having a peak intensity ratio of the (101) plane of the tin (110) plane of 1.0 or more. Example 1 4 The sample of the sample obtained in Example 13 was placed in an aluminum crucible. And calcined at 900 °C for 2 hours in the atmosphere to obtain flaky tin oxide particles (sample N) containing ruthenium (converted from -28 to 201014797 to SiO2 of 3.2% by weight). The electron micrograph is shown in Fig. 11. It can be seen from Fig. 11 that the longest width and the shortest width are in the range of 0.05 to 40 μm, and the thickness is in the range of 0.005 to 2 μm, and the X-ray diffraction measurement is performed. Example 2, X-ray diffraction cross-section characteristic of flaky tin oxide, the peak intensity ratio of the (1 〇 1 ) plane / ( 1 1 0 ) plane is Example 15 in Example 9, except that 0.14 g is used. Sodium aluminate (Α12〇3: 34 ～3 9 %) was used in the same manner as in Example 9 except that sodium citrate solution was used to obtain the flaky tin oxide particles of the present invention (sample Ο). When the sample was observed by a scanning electron microscope It can be seen that the longest width and the shortest width are 0.05~ a flaky particle having a thickness of 0.005 to 2 μm φ in the range of 40 μm, and a sheet having a peak intensity ratio of 10 or more with respect to the (101) plane of the (110) plane of the stannous oxide (110) surface when subjected to X-ray diffraction measurement. X-ray diffraction cross-section characteristic of stannous oxide. Example 1 6 The sample Ο obtained in Example 15 was placed in an aluminum crucible and calcined at 900 ° C for 2 hours in the atmosphere to obtain the inscription of the present invention. The flaky tin oxide particles (sample p) converted to Ah 〇 3 (0.5% by weight) -29- 201014797 A scanning electron microscope photograph of sample P is shown in Fig. 12 . As is apparent from Fig. 12, the longest width and the shortest width are each in the range of 0.05 to 40 μm, and the thickness is in the range of 0.005 to 2 μm. Further, in the X-ray diffraction measurement, in the same manner as in the second embodiment, the X-ray diffraction cross-section characteristic of the flaky tin oxide is used, and the peak intensity ratio of the (1 〇1) plane/(1 1 0) plane is 10.9 °. Example 1 7 17.45 g of stannous chloride 2 hydrate (SnCl 2 · 2Η20, manufactured by Wako Pure Chemical Industries, Ltd.) and 0.02 g of lanthanum chloride (SbCl3 reagent, manufactured by Nacarai Tesk Co., Ltd.) were dissolved in 19.46 g of a 35 % aqueous hydrochloric acid solution. . To the solution, 18.54 g of pure water was added to adjust the concentration to obtain an aqueous solution of stannous chloride containing ruthenium chloride. Next, the above-mentioned stannous chloride aqueous solution and 5 equivalents of sodium hydroxide aqueous solution were simultaneously added at a temperature of 0.5 liter of pure water at 90 ° C for 5 minutes while maintaining the pH 4 ± 0.2, and the mixture was aged for 10 minutes. Thereafter, a pH of 3.0 was made using 3 equivalents of an aqueous hydrochloric acid solution, and the mixture was stirred for 5 minutes to start washing. The washing was stopped when the filtrate had a specific resistance of 15,000 Qcm, and the resulting cake was allowed to stand at 105 ° C overnight in the atmosphere and dried. The dried product was hand-pulverized in an agate mortar to obtain the flaky tin oxide particles of the present invention (sample Q). When the sample Q was observed by a scanning electron microscope, it was found that the longest width and the shortest width were in the range of 〇. 5 to 40 μm, and the flaky particles having a thickness in the range of 0.005 to 2 μm. Further, in the X-ray diffraction measurement, the X-ray diffraction cross-section unique to the flaky stannous oxide having a peak intensity ratio of 1.0 or more to the (101) plane of the stannous oxide (110) plane is -30-201014797. . Example 1 8 2.0 g of the sample Q obtained in Example 17 was placed in an aluminum crucible, and 90 (TC was calcined in the air for 2 hours to obtain a flake of the mixed crucible of the present invention (converted to 0.5% by weight of Sb205). Tin oxide particles (sample R) ° Scanning electron micrograph of sample R is shown in Fig. 13. As can be seen from Fig. 13, the longest width and the shortest width are in the range of 〇. 5 to 40 μηι, and the thickness is in the range of 0.005 to 2 μηη. In the X-ray diffraction measurement, in the same manner as in the second embodiment, the X-ray diffraction cross section unique to the flaky tin oxide is used, and the peak intensity ratio of the (101) plane/(110) plane is φ. 1 9 Dissolve 17.4 g of stannous chloride dihydrate (SnCl2 · 2Η20, manufactured by Wako Pure Chemical Industries, Ltd.) and 0.04 g of sodium tungstate (Na2W04 · 2Η20 reagent, manufactured by Wako Pure Chemical Industries, Ltd.) in 35% hydrochloric acid aqueous solution. In 19.46 g, 18.54 g of pure water was added to the solution to adjust the concentration to obtain an aqueous solution of stannous chloride containing sodium tungstate. Next, the above-mentioned chloride was added to 0.5 liter of pure water at 90 °C. Aqueous tin solution and 5 equivalents of aqueous sodium hydroxide solution While maintaining pH 4 ± 0.2 - while adding for 20 minutes, add it, and then aging for 1 〇 minutes. Thereafter, -31 - 201014797 using 3 equivalents of aqueous hydrochloric acid to make the pH 3.0', and stirring for 5 minutes to start washing. When the filtrate has a specific resistance of 10,000 SOOOQcm, the washing is stopped, and the obtained cake is placed in the atmosphere at 1 〇 5 ° C overnight, and dried. The dried product t is hand-pulverized in an agate mortar to obtain a sheet of the present invention. The tin oxide particles (sample S). When the sample S was observed by a scanning electron microscope, it was found that the longest width and the shortest width were in the range of 0.05 to 40 μm, and the thickness was in the range of 0.005 to 2 μπι. In the ray diffraction measurement, an X-ray diffraction cross-sectional view peculiar to the flaky stannous oxide having a peak intensity ratio of 1.0 or more with respect to the (101) plane of the stannous oxide (110) plane is used. Example 20 Example 19 2.0 g of the obtained sample S was placed in an aluminum crucible and calcined at 900 ° C for 2 hours in the atmosphere to obtain flaky tin oxide particles (sample T) of the blended tungsten of the present invention (in terms of W03: 1% by weight). Sample T scan The electron micrograph is shown in Fig. 14. As can be seen from Fig. 14, the longest width and the shortest width are in the range of 0.05 to 40 μm, and the thickness is in the range of 0.005 to 2 μm, and the X-ray diffraction measurement is performed simultaneously. Example 2 'X-ray diffraction cross-section characteristic of flaky tin oxide, the peak intensity ratio of the (101) plane / (110) plane was 3.0 〇 Example 2 1 The sample D obtained in Example 4 was centrifuged ( After the pulverization of the centrifugal mill (ZM-100) of Rich Corporation-32-201014797, 10 g of this sample was placed in 1 liter of pure water to carry out slurry formation. After the temperature of the slurry was raised at 90 ° C, 2.33 g of tin chloride (SnCl4 · 5H20, reagent, manufactured by Wako Pure Chemical Industries, Ltd.) and 0.14 g of lanthanum chloride (SbCl3, reagent, manufactured by Nacari Tesk Co., Ltd.) were dissolved. A solution of 3 equivalents of aqueous hydrochloric acid solution and 5 equivalents of aqueous sodium hydroxide solution were added while maintaining a constant pH for 60 minutes. Further, it was aged for 60 minutes, after which it was dehydrated, washed, and dried. After the dried powder was lightly pulverized with an agate mortar, 2.0 g of aluminum crucible was placed and calcined at 650 ° C for 60 minutes in the atmosphere. The ruthenium-doped tin oxide-doped tin oxide particles (sample U) of the present invention were obtained. A scanning electron microscope photograph of the sample U is shown in Fig. 15. As can be seen from Fig. 15, the longest width and the shortest width are each in the range of 0.05 to 40 μm, and the thickness is in the range of 0.005 to 2 μm. Further, in the X-ray diffraction measurement as described above, in the same manner as in the second embodiment, the X-ray diffraction cross-section characteristic of the flaky tin oxide is obtained, and the peak intensity ratio of the (1 〇 1 ) plane / (1 1 0 ) plane is 3.4. . Example 22 The sample D obtained in Example 4 was calcined at 9 ° C for 2 hours under a nitrogen atmosphere to obtain a scanning electron micrograph of the flaky tin oxide particle (sample ν ) of the present invention 0 sample V. The longest width and the shortest width are respectively 〇·〇5~40μπι, and the thickness is 0.005~2μπι-33- 201014797. Further, in the case of the x-ray diffraction measurement, in the same manner as in the fourth embodiment, the X-ray diffraction cross-section characteristic of the flaky tin oxide was used, and the peak intensity ratio of the (1 01 ) plane/(1 10) plane was 6.2. Example 23 A sample of the sample V obtained in Example 22 was pulverized by a Likai machine (Ishikawa-type stirring Likai machine AGA manufactured by Ishikawa Kogyo Co., Ltd.) for 5 minutes to obtain tin oxide particles (sample W). From the scanning electron micrograph of the sample W, it was found to be an amorphous particle. Further, in the X-ray diffraction measurement, there is an X-ray diffraction cross-section unique to tin oxide, and the peak intensity ratio of the (1 0 1 ) plane/(1 1 0 ) plane is 3.1. Comparative Example 1 27.12 g of tin chloride pentahydrate (SnCl2 · 5H20, manufactured by Wako Pure Chemical Industries, Ltd.) was dissolved in 19.46 g of a 35% hydrochloric acid aqueous solution. To the solution, 18.54 g of pure water was added for concentration adjustment to obtain a stannous chloride aqueous solution. Next, the above-mentioned aqueous solution of tin chloride and 5 parts of sodium hydroxide aqueous solution were added while maintaining the pH of 4±0.2 for 20 minutes in 0.5 liter of pure water at 90 ° C, and after the addition, the mixture was aged for 10 minutes. Thereafter, a pH of 3.0 was made using a 3 equivalent aqueous hydrochloric acid solution, and the mixture was stirred for 5 minutes to start washing. The washing was stopped when the specific gravity of the filtrate was 15,000 Qcm, and the obtained cake was placed in the atmosphere at 1 〇 5 ° C overnight, and dried. The dried product was hand-pulverized with -34· 201014797 agate mortar to obtain tin oxide particles (sample χ). When the sample X was observed by a scanning electron microscope, it was found to be granular. Further, in the X-ray diffraction measurement, an X-ray diffraction cross-sectional view having an amorphous state is performed. Comparative Example 2 A sample X 2.0 of the sample obtained in Comparative Example 1 was placed in an aluminum crucible, and 900 in an atmosphere. (: calcination for 2 hours, obtaining tin oxide particles (sample Y) 扫描 Scanning electron micrograph of sample Y is shown in Fig. 16» It can be seen from Fig. 16 that it is granular. In addition, when performing X-ray diffraction measurement, it has particles. The X-ray diffraction cross section (Fig. 3) characteristic of the tin oxide, the peak intensity ratio of the (1 0 1) plane / (11 〇) plane is 〇. 8. Comparative Example 3 The sample Y obtained in Comparative Example 2 was nitrogen. After calcination at 900 ° C for 2 hours under ambient gas, tin oxide particles (sample Z) were obtained. Scanning electron micrographs of sample Z were found to be granular, and when subjected to X-ray diffraction measurement, there was granular tin oxide. The unique X-ray diffraction cross-sectional view shows that the peak intensity ratio of the (1 〇1) plane/(110) plane is 0.8. The above samples d, r, t, and u are respectively taken out to 1.0 g of 'clamped copper electrodes, at 100 kg. The powder volume resistance 値( Ωοιη ) was measured under a pressure of /cm 2 (using a multimeter -35-201014797 3457A manufactured by Hewlet Packard Co., Ltd., calculated according to the following formula 1), and is shown in Table 1. Formula 1: Powder volume Resistance 値 (ncm) = {volume resistance 値 (measured 値; Ω) 面积 area of the sample Cm2)}/thickness (cm) The sample R of the blended crucible, the sample T blended with tungsten, and the sample U coated with tin oxide doped with antimony, the volume resistivity of the powder is lower than that of the sample D, and it can be known that it can be used as the conductivity. [Table 1]_Volume resistance 値(Ωαη) Example 4 D 24.5x106 Example 18 R 335 Example 20 T 1.03χ103 Example 21 U 13 The above-mentioned samples V, w, and z were respectively 5.0 g. The aluminum cup was placed in a constant temperature drier at 80 ° C for 4 weeks. Thereafter, the powder volume resistance 値 (Qcm ) was measured by the above method and shown in Table 2. The sample V of Example 22 was When the tin oxide was calcined in a non-oxidizing atmosphere, the sample W of Example 23 was a sample in which the sample V was pulverized, but both of them were low in powder volume resistance, and it was found that the sample can be used as a conductive filler. The sample V and W of 23 were lower than the initial powder volume resistance 4 after 4 weeks, and it was found that the change in volume resistance due to heating was low. The reason was considered to be tin oxide (1) 0 1) The reason why the peak intensity ratio of the face/(110) plane is 1.0 or more, the higher the peak intensity ratio is, the larger the volume is. -36- 201014797 [Table 2] Sample volume ΡΙ Ω (Ωαη) Volume resistance ratio (値 after 4 weeks/initial 値) After the first 4 weeks Example 22 V 61.5 189 3.1 Example 23 W 85.2 1226 14.4 Comparative Example 3 Ζ 5.26 2849 542 The sample u obtained in Example 21 and the comparative sample ET-500W (manufactured by Ishihara Sangyo Co., Ltd., added with bismuth tin dioxide-coated spherical titanium dioxide) were divided into 20 g, Aery die A -165 (manufactured by Dainippon Ink Chemical Industry Co., Ltd.) 30.6 g, toluene/n-butanol mixed solvent (toluene·n-butanol=1··1 by weight) 26.4 g and glass beads 50.0 g were placed in 140 ml of Meyer The mayonnaise bottle was shaken for 20 minutes with a paint conditioning tank (manufactured by R_ed-Devil). Next, 15 g of the resin composition was taken out from the vial bottle, and 14.5 g of Acrydic A-165 (manufactured by Dainippon Ink Chemical Industry Co., Ltd.) and a toluene/n-butanol mixed solvent (toluene: n-butanol = 1) were added thereto. : 1 weight φ ratio) 4.6 g, and then shaken for 3 minutes with a paint conditioning tank (manufactured by Red-Devil Co., Ltd.). Next, these resin compositions were placed on a concealing force test paper, coated with a -3 mill coater, and naturally dried overnight at room temperature. The surface resistance of these coating films is shown in Table 3 as a result of measurement by High Rester UP (manufactured by Dia Instrument Co., Ltd.). These film thicknesses are 1 9 μm. The sample U of Example 21 showed a lower surface resistance 相比 than the bismuth-doped tin dioxide-coated spherical titanium oxide, and it was found that it can be used as a conductive film of -37-201014797. [Table 3] Sample surface resistance 値 (Ω/Sq) Example 21 U 3.6xl06 Comparative sample ET-500W Over-Range (industrial availability) The tin oxide particles of the present invention are in addition to the conductive filler It can be used for catalysts, catalyst carriers, gas sensors, photocatalysts, infrared shielding agents, ceramics, metal additives, honing materials, and the like. Further, the tin oxide film in which the tin oxide particles are formed may be used to form a tin oxide film on a glass substrate in addition to a conductive film, a resistor, an electrode, a catalyst, a catalyst carrier, a gas sensor, or a transparent material. Conductive oxide coated glass, hot wire reflective glass, low emission glass, electrothermal glass, and the like. Further, it can be used in various applications such as photocatalytic materials, antireflection materials, and gas barrier materials. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a view showing a X-ray diffraction cross-sectional view of a sample A. Fig. 2 is a scanning electron microscope photograph showing the particle shape of the sample A. Fig. 3 is a view showing a X-ray diffraction cross-sectional view of the sample B and the sample Y. Fig. 4 is a scanning electron microscope photograph showing the particle shape of the sample crucible. -38 - 201014797 Fig. 5 is a scanning electron microscope photograph showing the particle shape of the sample D. Fig. 6 is a scanning electron microscope photograph showing the particle shape of the sample E. Fig. 7 is a scanning electron microscope photograph showing the particle shape of the sample F. Fig. 8 is a scanning electron microscope photograph showing the particle shape of the sample 图. Fig. 9 is a scanning electron microscope photograph showing the particle shape of the sample J. Fig. 10 is a scanning electron micrograph showing the particle shape of the sample L. Fig. 11 is a scanning electron micrograph showing the particle shape of the sample crucible. Fig. 12 is a scanning electron micrograph showing the particle shape of the sample crucible. Fig. 13 is a scanning electron micrograph showing the particle shape of the sample R. Fig. 14 is a scanning electron micrograph showing the particle shape of the sample crucible. Fig. 15 is a scanning electron micrograph showing the particle shape of the sample U. Fig. 16 is a scanning electron micrograph showing the particle shape of the sample crucible. -39-

Claims (1)

201014797 VII. Patent application: 1·- kinds of tin oxide particles, characterized in that in the powder X-ray diffraction, the peak intensity ratio of the (ιοί) plane relative to the tin oxide (110) surface is 1. 〇 or more. 2. The tin oxide particles according to claim 1, wherein the tin oxide is a crystal structure having tin oxide (Sn02). 3. The tin oxide particles according to claim 1 or 2, wherein 'the shape of the particles having an indefinite shape" 4. The tin oxide particles according to claim 1 or 2, wherein the particles have a flaky shape . 5. The tin oxide particles according to claim 1, wherein the tin oxide is a crystal structure having stannous oxide (SnO) and has a flake-like particle shape. 6. The tin oxide particle according to claim 4 or 5, wherein the thickness of the sheet surface is 5 μηι or less. 7. The tin oxide particles according to claim 4 or 5, wherein the longest width and the shortest width of the sheet surface are in the range of 0.05 to 4 μm, and the thickness is in the range of 0·005 to 2 μm. 8. The tin oxide particles according to any one of claims 1 to 7, which further contain an inorganic element other than tin. 9. The tin oxide particles 'where' of any one of the above-mentioned items of the invention are coated with an inorganic compound and/or an organic compound on the surface of the tin oxide particles. 10. The tin oxide particle of claim 9, wherein the surface of the tin oxide particle is coated with a conductive inorganic compound at -40 to 201014797. A method for producing tin oxide particles, characterized in that a tin (II) compound and a base are added at a pH of 6 or less in a reactor to hydrolyze a tin (II) compound. 12. A method of producing tin oxide particles according to claim 11 wherein a tin (II) compound and a base are added to a reactor in which water at a temperature of 50 ° C or higher is added. A method for producing tin oxide particles, characterized in that a tin (II) compound and a base and an inorganic compound are added at a pH of 6 or less in a reactor to hydrolyze a tin (II) compound. The method for producing tin oxide particles according to any one of claims 11 to 13, wherein the tin oxide is a crystal structure having stannous oxide, and the method for producing tin oxide particles is characterized in that The hydrolyzed product of the tin (II) compound obtained by the method of any one of claims 1 to 14 is calcined. 16. The method for producing tin oxide particles according to claim 15, wherein the hydrolyzed product of the tin (II) compound is mixed with a flux to be calcined. A method of producing tin oxide particles according to the fifteenth or sixteenth aspect of the patent application, wherein the tin oxide is a crystal structure having tin oxide. A method for producing a tin oxide particle, which comprises pulverizing tin oxide obtained by the method according to any one of claims 1 to 17. A method for producing a tin oxide particle, characterized in that the surface of the tin oxide particle obtained by the method according to any one of claims 1 to 18 is coated with an inorganic compound and/or an organic compound. . 20. The method for producing tin oxide particles according to claim 19, wherein the inorganic compound and/or the organic compound are coated and then calcined. A dispersion comprising the tin oxide particles according to any one of the claims i to ̄. 22. A coating comprising a tin oxide particle as claimed in any one of claims 1 to 10. A resin composition comprising the tin oxide particles according to any one of claims 1 to 10. A tin oxide film characterized in that a dispersion of a coating according to claim 21 or a coating material of a coating of claim 22 is coated on a substrate, characterized in that The tin oxide particles according to any one of claims 1 to 10 of the patent application. A catalyst comprising a tin oxide particle according to any one of claims 1 to 10. The gas sensor of the invention is characterized in that it contains the tin oxide particles according to any one of claims 1 to 10. -42-