WO2010001818A1 - Tin oxide particles and process for production thereof - Google Patents

Tin oxide particles and process for production thereof Download PDF

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Publication number
WO2010001818A1
WO2010001818A1 PCT/JP2009/061678 JP2009061678W WO2010001818A1 WO 2010001818 A1 WO2010001818 A1 WO 2010001818A1 JP 2009061678 W JP2009061678 W JP 2009061678W WO 2010001818 A1 WO2010001818 A1 WO 2010001818A1
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tin oxide
oxide particles
tin
compound
particles according
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PCT/JP2009/061678
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French (fr)
Japanese (ja)
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憲彦 實藤
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石原産業株式会社
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G19/00—Compounds of tin
    • C01G19/02—Oxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/20—Particle morphology extending in two dimensions, e.g. plate-like
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/42—Magnetic properties

Definitions

  • the present invention relates to tin oxide particles and a method for producing the same.
  • the present invention also relates to a dispersion, a paint, a resin composition and the like containing the tin oxide particles.
  • stannic oxide (SnO 2 ) containing tetravalent tin as a constituent component and stannous oxide (SnO) containing divalent tin as a constituent component are generally known.
  • stannic oxide is a semiconductor and does not exhibit high conductivity by itself, it is also known that high conductivity is obtained by doping different atoms.
  • Stannic oxide is a material excellent in transparency and physical and chemical stability, and is expected to be used for electrical and electronic applications. Specifically, stannic oxide doped with antimony, phosphorus, fluorine, etc. is excellent in conductivity, so it is mixed in plastics, rubber, etc. as a conductive filler and used as a material for conductive plastics. ing.
  • a transparent conductive film is prepared using a paint containing the above conductive filler, a film having extremely low resistance and low haze, and excellent adhesion to the substrate and film strength can be obtained.
  • the transparent conductive film can also be used for transparent electrodes of display devices such as touch panels and liquid crystal displays.
  • a tin oxide thin film is produced on a glass by sputtering using a sintered body of stannic oxide as a target, and transparent conductive oxide coated glass, heat ray reflective glass, low radiation glass, electrothermal glass, etc. are produced. .
  • stannous oxide is dissolved in sulfuric acid or the like and used in a tin plating bath.
  • Stannic oxide is produced by firing a precipitate obtained by reacting a tetravalent tin salt aqueous solution with an alkaline solution.
  • a reaction between a tetravalent tin salt aqueous solution and an alkaline solution is performed in a pH range of 0.5 to 4 to form a tin-containing precipitate, and then calcined in a temperature range of 400 to 1200 ° C. Is described.
  • Patent Document 2 adds a tetravalent tin salt aqueous solution and an alkaline aqueous solution in parallel to neutralize the tin oxide hydrate by maintaining the pH of the neutralization reaction solution at 3 or more.
  • a solution of antimony chloride and an aqueous alkali solution are added in parallel to the product water, and neutralized while maintaining the pH of the neutralization reaction solution at 3 or more, and the surface of the product is antimony oxide. Is prepared and then calcined to produce antimony-doped stannic oxide.
  • stannous oxide for example, in Patent Document 3, an aqueous solution of stannous chloride and an aqueous solution of sodium hydroxide are mixed and reacted, and aged for 2 hours or more in a stationary state at pH 12 to 13.5. Manufacturing.
  • JP 2002-029744 A Japanese Patent No. 3647929 JP-A-1-201022
  • the stannic oxide produced by calcining a precipitate obtained by hydrolysis and neutralization reaction using a tetravalent tin compound as in Patent Documents 1 and 2 has a fine granular shape. These methods cannot produce stannic oxide having a particle shape such as flakes.
  • flat stannous oxide is obtained by a neutralization reaction using a divalent tin compound, but thin flaky stannous oxide is obtained.
  • the stannous oxide is dissolved in sulfuric acid or the like and used in a tin plating bath, and does not describe that stannous oxide is oxidized to produce stannic oxide.
  • the present inventors think that by forming the particle shape of stannic oxide into a flaky shape, a thin tin oxide film can be formed, or a useful material having a high effect such as conductivity can be obtained.
  • the method of producing stannic oxide particles with particle shape was studied. As a result, when a divalent tin compound and an alkali are added so as to maintain the pH in the reactor at 6 or less, and the tin compound is hydrolyzed, thin flaky stannous oxide particles can be obtained.
  • the inventors have found that by burning it, stannic oxide particles maintaining a flaky shape can be obtained.
  • the powder X-ray diffraction profile of the flaky stannous oxide particles and the flaky stannic oxide particles is the peak intensity ratio of the (101) plane to the (110) plane of tin oxide (ratio of peak height). ) was 1.0 or more, and the present invention was completed by finding that the peak intensity ratio was maintained at 1.0 or more even when they were pulverized into irregular shapes.
  • the present invention (1) In powder X-ray diffraction, a tin oxide particle characterized in that the peak intensity ratio of the (101) plane to the (110) plane of tin oxide is 1.0 or more, (2) The tin oxide particles according to (1), wherein the tin oxide has a crystal structure of stannic oxide (SnO 2 ), (3) The tin oxide particles according to (1) or (2), wherein the tin oxide particles have an indefinite shape.
  • Method (20) The method for producing tin oxide particles according to the above (19), characterized by firing after coating with an inorganic compound and / or an organic compound, (21) A dispersion comprising the tin oxide particles according to any one of (1) to (10), (22) A paint containing the tin oxide particles according to any one of (1) to (10), (23) A resin composition comprising the tin oxide particles according to any one of (1) to (10), (24) A tin oxide film, wherein the dispersion according to (21) or the paint according to (22) is applied on a substrate, (25) A conductive material comprising the tin oxide particles according to any one of (1) to (10), (26) A catalyst comprising the tin oxide particles according to any one of (1) to (10), (27) A gas sensor comprising the tin oxide particles according to any one of (1) to (10), and the like.
  • the tin oxide particles of the present invention have a peak intensity ratio of (101) plane to (110) plane of tin oxide of 1.0 or more, and have a unique X-ray profile. Utilizing these characteristics, it is used for conductive materials, catalysts, gas sensors and the like. Further, it has a flaky particle shape and is used for a material for forming a thin tin oxide film, a conductive material, etc. by utilizing the unique particle shape.
  • the method for producing tin oxide particles of the present invention does not require a large-scale apparatus, and uses relatively inexpensive raw materials. Therefore, tin oxide particles having a specific X-ray profile and a specific particle shape are industrially advantageous. This is an advantageous method in which tin oxide particles having the above can be produced relatively easily.
  • FIG. 3 is a diagram showing an X-ray diffraction profile of sample A.
  • FIG. 2 is a scanning electron micrograph showing the particle shape of sample A.
  • FIG. It is a figure which shows the X-ray-diffraction profile of the sample B and the sample Y.
  • 3 is a scanning electron micrograph showing the particle shape of Sample B.
  • FIG. 3 is a scanning electron micrograph showing the particle shape of sample D.
  • FIG. 3 is a scanning electron micrograph showing the particle shape of sample E.
  • FIG. 3 is a scanning electron micrograph showing the particle shape of sample F.
  • FIG. 3 is a scanning electron micrograph showing the particle shape of sample H.
  • FIG. 2 is a scanning electron micrograph showing the particle shape of Sample J.
  • FIG. 2 is a scanning electron micrograph showing the particle shape of a sample L.
  • FIG. 2 is a scanning electron micrograph showing the particle shape of sample N.
  • FIG. 4 is a scanning electron micrograph showing the particle shape of a sample P.
  • 3 is a scanning electron micrograph showing the particle shape of sample R.
  • FIG. 3 is a scanning electron micrograph showing the particle shape of a sample T.
  • FIG. 2 is a scanning electron micrograph showing the particle shape of a sample U.
  • FIG. 4 is a scanning electron micrograph showing the particle shape of sample Y.
  • the peak intensity ratio of the (101) plane to the (110) plane of tin oxide is 1.0 or more.
  • the tin oxide of the present invention may be stannous oxide or stannic oxide, each of which may be contained, and further, stannous hydroxide, stannic hydroxide, etc. May be included.
  • stannous oxides those having a crystal structure of stannous oxide or stannic oxide are preferable, those having a crystal structure of stannic oxide are more preferable, and all of tin oxide is used. Those having a crystal structure of stannic oxide are more preferable.
  • the tin oxide of the present invention has a unique X-ray profile. Specifically, when the crystal structure of stannic oxide is confirmed by powder X-ray diffraction (ray source: Cu-K ⁇ ), The peak height of the (101) plane of stannic oxide that appears at a diffraction angle (2 ⁇ ) of about 33.8 ° is the same as the peak height of the (110) plane that appears at a diffraction angle (2 ⁇ ) of about 26.6 °. Or higher. Further, when the crystal structure of stannous oxide is confirmed by powder X-ray diffraction (ray source: Cu-K ⁇ ), the peak of the (101) plane of stannous oxide appearing at a diffraction angle (2 ⁇ ) of about 29.9 °.
  • the height is equal to or higher than the peak height of the (110) plane appearing at a diffraction angle (2 ⁇ ) of about 33.3 °. That is, in powder X-ray diffraction, the peak intensity ratio expressed by the height of the peak of the (101) plane of tin oxide / the peak height of the (110) plane is 1.0 or more, and 1.1 or more. More preferred is 2 or more. This phenomenon is usually observed in the case of the flaky stannous oxide particles and stannic oxide particles of the present invention, whereas in the case of conventional granular particles, the peak height of the (101) plane is (110 ) Lower than the peak height of the surface.
  • the flaky tin oxide particles of the present invention are considered to be oriented in the (101) plane.
  • the peak intensity ratio gradually decreases, so that it can be understood that the characteristics of the flaky tin oxide particles of the present invention can be specified by the peak intensity ratio. .
  • the peak intensity ratio may be maintained at 1.0 or more even when the shape becomes indefinite including various shapes. Therefore, the particle shape of the tin oxide particles of the present invention is generally a flaky shape, but as long as the peak intensity ratio is satisfied, it is an indefinite shape including various shapes obtained by pulverizing the flaky shape. There may be.
  • the flaky shape refers to a shape having a thickness in the vertical direction that is significantly smaller than that of the thin piece surface in the thin piece having the longest width and the shortest width, preferably the longest width / thickness is 4 or more, more preferably It is about 10 to 1000 and includes shapes generally called thin layer, thin plate, flake, sheet, and nanosheet.
  • the thickness in the direction perpendicular to the flake surface is preferably as thin as 5 ⁇ m or less, more preferably in the range of 0.0005 to 5 ⁇ m, still more preferably in the range of 0.005 to 2 ⁇ m, and still more preferably in the range of 0.01 to 2 ⁇ m.
  • the longest width or the shortest width of the flake surface is preferably in the range of 0.05 to 40 ⁇ m, more preferably in the range of 0.5 to 30 ⁇ m, from the viewpoint of powder characteristics.
  • the flaky shape and its size can be determined by electron microscope observation.
  • the flaky shape and its size can be determined by electron microscope observation.
  • the tin oxide particles may contain an inorganic element other than Sn.
  • an inorganic element for example, for the purpose of imparting conductivity, 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 Al. May be.
  • the amount of substitution can be appropriately set according to the inorganic element.
  • the surface of tin oxide particles can be treated with conventional organic compounds such as surfactants, coupling agents, carboxylic acids, polyols, amines, siloxanes, silica, and alumina. You may coat
  • the surface of tin oxide particles may be coated with a conductive inorganic compound such as tin oxide doped with Sb, P, Nb, W, or the like.
  • a conductive inorganic compound such as tin oxide doped with Sb, P, Nb, W, or the like.
  • the amount of the inorganic compound and / or organic compound and conductive inorganic compound coated on the surface of the tin oxide particles can be appropriately set.
  • the tin oxide particles having a unique X-ray profile of the present invention are obtained by, for example, reacting a tin (II) compound (Sn 2+ ) and an alkali while maintaining the pH at 6 or less, and hydrolyzing the tin (II) compound. can get.
  • a tin (II) compound a divalent tin compound such as tin (II) chloride is used.
  • Water-soluble tin (II) compounds are preferred, and tin (II) chloride is more preferred.
  • the concentration of the tin (II) compound is preferably 0.05 to 150% by weight, more preferably 1.0 to 100% by weight, based on water when used by dissolving in water.
  • alkali hydroxides such as sodium hydroxide, potassium hydroxide and lithium hydroxide
  • alkali carbonates such as sodium carbonate, ammonium compounds such as ammonium carbonate, ammonia and the like
  • Sodium oxide is preferred.
  • the tin (II) compound and the alkali are added while adjusting the pH in the reactor to be 6 or less, preferably 3 to 6, more preferably 3.5 to 5.5. Add while adjusting. In the neutral vicinity where the pH is higher than 6, tin acid hydroxide (Sn 6 O 4 (OH) 4 ) is likely to be formed, and this is not a flaky shape. Moreover, although it may become flat form when pH is 9 or more, this has a thickness larger than 5 micrometers.
  • the method of adding the tin (II) compound and the alkali includes adding the tin (II) compound to the reactor in advance and then adding the alkali, adding the alkali to the reactor in advance and then adding the tin (II) compound,
  • An example is a method in which a tin (II) compound and an alkali are simultaneously added to a reactor.
  • One of these methods or a combination of two or more methods can be used, but it is preferable to add the tin (II) compound and the alkali simultaneously.
  • the temperature of the reactor after the addition is preferably 50 ° C. or higher because hydrolysis of the tin (II) compound can be effectively advanced.
  • the alkali (or tin (II) compound After adding the tin (II) compound (or alkali) and raising the temperature to 50 ° C. or higher, the alkali (or tin (II) compound) may be added. After the temperature is set to 50 ° C. or higher, a tin (II) compound and an alkali may be added simultaneously, and the latter is preferred. A more preferable temperature is about 70 to 105 ° C., and a further preferable temperature is about 85 to 105 ° C.
  • the simultaneous and parallel addition refers to a method in which both of them are separately added to the reactor in small amounts continuously or intermittently. Specifically, it is preferable to add both at the same time over about 10 minutes to 10 hours.
  • the aging temperature is preferably 50 ° C. or higher, more preferably about 70 to 105 ° C., and further preferably about 90 to 105 ° C.
  • the aging time is preferably about 5 minutes to 6 hours.
  • the hydrolysis reaction and aging may be performed in a non-oxidizing atmosphere such as nitrogen gas so that the valence of tin is kept to be bivalent, but can also be performed in ordinary air.
  • the tin (II) compound is hydrolyzed to obtain tin oxide particles having a stannous oxide crystal structure, particularly flaky stannous oxide particles. Thereafter, washing is performed as necessary to remove unnecessary electrolytes present in the aqueous solution. At the time of washing, a pH adjuster is added in order to aggregate the produced hydrolysis product. Examples of the pH adjuster used include inorganic acids such as hydrochloric acid and sulfuric acid, and alkalis such as sodium hydroxide. After washing, if necessary, it is separated into solid and liquid and further dried. A filter such as a filter press or a roll press can be used for solid-liquid separation, and a band heater, batch heater, spray dryer, or the like is used for drying.
  • Drying may be performed in a non-oxidizing atmosphere such as nitrogen gas so that the valence of tin is kept to be bivalent, but drying is also possible in normal air.
  • the drying temperature is preferably in the range of 50 to 120 ° C. Further, after drying, it may be fired as necessary, and a temperature in the range of 120 to 500 ° C. is preferable, and a non-oxidizing atmosphere such as nitrogen, argon, hydrogen or the like is more preferable.
  • impact crushers such as hammer mill and pin mill, grinding crushers such as roller mill, pulverizer and crusher, compression crushers such as roll crusher and jaw crusher
  • dry pulverization may be performed using an airflow pulverizer such as a jet mill.
  • tin oxide particles having a crystal structure of stannous oxide, particularly flaky stannous oxide particles are fired, tin oxide particles having a stannic oxide crystal structure, particularly flaky stannic dioxide, are obtained.
  • Tin particles are obtained, preferably flaky stannic oxide particles in which all of the tin oxide is stannic oxide.
  • the calcination temperature can be set as appropriate, but it may be higher than the temperature at which the flaky stannous oxide particles are oxidized to stannic oxide, and a temperature in the range of 500 ° C. to 1100 ° C. is preferred. More preferably, it is in the range of 600 to 1000 ° C.
  • the firing atmosphere is not particularly limited, but an air (air) atmosphere is preferable.
  • a known heating and firing furnace such as a fluidized furnace, a stationary furnace, a rotary kiln, or a tunnel kiln can be used.
  • a fluxing agent for example, a chlorine compound such as sodium chloride or tin chloride may be added.
  • impact pulverizers such as hammer mills and pin mills, roller pulverizers, milling pulverizers such as pulverizers, compression pulverizers such as roll crushers and jaw crushers, and air currents such as jet mills Dry pulverization may be performed using a pulverizer or the like.
  • the tin (II) compound In order to include the inorganic element in the tin oxide particles, it is preferable to react the tin (II) compound with an alkali and hydrolyze the tin (II) compound in the presence of the inorganic compound, At this time, addition is performed so that the pH in the reactor is maintained at 6 or less.
  • a method of hydrolyzing a tin (II) compound by adding an inorganic compound in advance to a reactor and then adding a tin (II) compound and an alkali; (2) A method in which a tin (II) compound, an alkali and an inorganic compound are added to a reactor to hydrolyze the tin (II) compound.
  • This method includes, for example, a tin (II) compound, an alkali and an inorganic compound. Including a method of adding an inorganic compound in advance to a tin (II) compound solution, a method of adding an inorganic compound to an alkali, and the like. (3) The method of adding an inorganic compound after adding a tin (II) compound and an alkali to a reactor, hydrolyzing a tin (II) compound, etc. are mentioned. Further, as another method, an inorganic compound may be added to the tin oxide slurry, and it is more preferable that the inorganic compound is neutralized and precipitated in the slurry to contain the inorganic element in the tin oxide particles.
  • an inorganic compound may be added and mixed with the tin oxide powder. After the tin oxide particles contain an inorganic element, they may be filtered, washed and dried as necessary.
  • the stannous oxide may be dried in a non-oxidizing atmosphere such as nitrogen gas so that the valence of tin is kept to be divalent, it can be dried even in normal air. The drying of stannic oxide is good in normal air.
  • the drying temperature is preferably in the range of 50 to 120 ° C.
  • it may be fired as necessary, and a part of the tin element can be replaced with an inorganic element by this firing.
  • the firing temperature is preferably in the range of 120 to 1100 ° C.
  • the atmosphere is preferably an air (air) atmosphere, and more preferably a non-oxidizing atmosphere such as nitrogen, argon or hydrogen.
  • impact crushers such as hammer mill and pin mill, grinding crushers such as roller mill, pulverizer and crusher, compression crushers such as roll crusher and jaw crusher
  • dry pulverization may be performed using an airflow pulverizer such as a jet mill.
  • a conventional surface treatment method can be used. Specifically, an inorganic compound or an organic compound is added to the tin oxide slurry for coating. It is more preferable that the inorganic compound or the organic compound is neutralized and precipitated in the slurry and coated. In addition, an inorganic compound or an organic compound may be added to the tin oxide powder and mixed for coating. Further, in order to coat the surface of the tin oxide particles with the conductive inorganic compound, it is preferable to add and coat the compound that becomes the conductive inorganic compound to the slurry of tin oxide, and the compound that becomes the conductive inorganic compound in the slurry.
  • the stannous oxide may be dried in a non-oxidizing atmosphere such as nitrogen gas so that the valence of tin is kept to be divalent, it can be dried even in normal air.
  • the drying of stannic oxide is good in normal air.
  • the drying temperature is preferably in the range of 50 to 120 ° C. Further, after drying, it may be fired as necessary.
  • the firing temperature is preferably in the range of 120 to 1100 ° C.
  • the atmosphere is preferably an air (air) atmosphere, and a non-oxidizing atmosphere such as nitrogen, argon or hydrogen. Is more preferable.
  • impact crushers such as hammer mill and pin mill, grinding crushers such as roller mill, pulverizer and crusher, compression crushers such as roll crusher and jaw crusher
  • dry pulverization may be performed using an airflow pulverizer such as a jet mill.
  • the tin oxide particles can be dispersed in a solvent to obtain a dispersion.
  • a solvent for dispersing the tin oxide particles water, an organic solvent such as alcohol, dimethylformamide (DMF), ketone, or a mixture thereof can be used, and industrially, an aqueous solvent mainly composed of water, or dimethyl It is preferable to use formamide (DMF) or a ketone.
  • the ketone include acetone, 2-butanone, methyl ethyl ketone, and the like.
  • the concentration of the tin oxide particles in the dispersion can be set as appropriate, but is preferably about 0.1 to 10 g / liter, for example.
  • a centrifuge may be used in a timely manner for improving dispersibility.
  • the said tin oxide particle can be disperse
  • inorganic binder ((a) polymerizable silicon compound (hydrolyzable silane or hydrolysis product thereof or partial condensate thereof, water glass, colloidal silica, organopolysiloxane, etc.) (B) metal alkoxides, etc.) and (2) organic binders (alkyd resins, acrylic resins, polyester resins, epoxy resins, fluorine resins, modified silicone resins) and the like.
  • the dispersion and the coating material described above are within a range that does not impair the effects of the present invention.
  • Various additives such as fungicides, curing aids, thickeners, fillers and the like may be included as the third component.
  • Dispersants include (1) surfactants ((a) anionic (carboxylates, sulfates, sulfonates, phosphates, etc.), (b) cationics (alkylamine salts, alkylamines) Quaternary ammonium salt, aromatic quaternary ammonium salt, heterocyclic quaternary ammonium salt, etc.), (c) amphoteric (betaine type, amino acid type, alkylamine oxide, nitrogen-containing heterocyclic type, etc.), (d) nonionic type ( Ether type, ether ester type, ester type, nitrogen-containing type, etc.) (2) Silicone dispersant (alkyl modified polysiloxane, polyoxyalkylene modified polysiloxane, etc.), (3) Phosphate dispersant (phosphorus) Acid sodium, sodium pyrophosphate, sodium orthophosphate, sodium metaphosphate, sodium tripolyphosphate, etc.), (4) alkanolamine (Aminomethyl propanol,
  • the flaky tin oxide particles are used as they are.
  • the flaky tin oxide particles solid-liquid separated thereafter may be redispersed in a solvent and used.
  • the dried powder, the fired powder, the powder containing an inorganic element, the surface-coated powder, or the pulverized powder, particularly these flaky stannic oxide particles may be redispersed in a solvent.
  • the redispersion can be performed by using a usual disperser such as a stirrer, a colloid mill, a ball mill, a bead mill, or an ultrasonic wave, and at this time, the third component can be added.
  • a centrifuge may be used in a timely manner for improving dispersibility.
  • Such a dispersion or paint is excellent in long-term storage stability, and a tin oxide film can be obtained by coating a substrate and drying or baking.
  • a method for coating the substrate general methods such as spin coating, spray coating, roller coating, dip coating, flow coating, knife coating, electrostatic coating, bar coating, die coating, brush coating, and a method of dropping droplets are common. The method can be used without limitation. If the film thickness is to be increased, overcoating may be performed. If the solvent is removed from the coated material, a tin oxide film is formed.
  • the film formation is preferably performed at a temperature ranging from room temperature to 800 ° C. The more preferable temperature depends on the boiling point of the solvent. For example, in the case of an aqueous solvent, the temperature is preferably in the range of room temperature to 150 ° C, more preferably in the range of 100 to 150 ° C.
  • tin oxide particles can be mixed with a resin to form a liquid resin composition such as paint or ink as described above, or tin oxide particles can be mixed into a resin to form a plastic molded body, sheet or film. It can also be set as a solid resin composition.
  • a resin the above-mentioned resin binder, biodegradable resin, ultraviolet curable resin, thermosetting resin and the like can be used as appropriate.
  • the amount of tin oxide particles, the amount of other additives, etc. Can be set.
  • the tin oxide particles can be used for various functional material applications. For example, it is also used for conductive fillers, catalysts, catalyst carriers, gas sensors, photocatalysts, infrared shielding agents, ceramic / metal additives, abrasives, and the like. Since the tin oxide particles have a high crystallinity on the (101) plane or have a flaky particle shape, they can be suitably used for conductive fillers, catalysts, catalyst carriers, and gas sensors. As an electrically conductive filler, it can use for an antistatic agent, an electrode material, etc.
  • the catalyst can be used as an oxidation catalyst for acrolein generation by propylene oxidation, a selective reduction catalyst for NO with ammonia, or the like, and the catalyst carrier can be used as a carrier for an oxidation catalyst of methane.
  • the gas sensor is used as a flammable gas detector is used to measure such as CO and H 2 S in the high trace gas detection sensitivity.
  • the tin oxide film can be used for various functional material applications. For example, in addition to being used for transparent materials, conductive films, electrical resistors, electrodes, gas sensors, tin oxide films, etc. are formed on glass substrates to form conductive oxide coated glass, heat ray reflective glass, low radiation glass Used for electrothermal glass.
  • tin oxide particles tin oxide film, etc.
  • the band gap of tin oxide or more It is possible to remove harmful substances, malodorous substances, dirt, and the like by irradiating light with a wavelength having the energy of, and to utilize antifouling and antifogging effects due to the superhydrophilic effect.
  • Example 1 8.63 g of stannous chloride dihydrate (SnCl 2 .2H 2 O reagent) was dissolved in 15.6 g of 35% aqueous hydrochloric acid. The concentration was adjusted by adding 14.8 g of pure water to the solution to obtain a stannous chloride aqueous solution. Next, the above stannous chloride aqueous solution and 5N sodium hydroxide aqueous solution were added simultaneously in 0.5 liters of pure water at 90 ° C. over 30 minutes while maintaining pH 5 ⁇ 0.2. Aged for 10 minutes. Thereafter, the pH was adjusted to 3.0 using a 3N hydrochloric acid aqueous solution, and the mixture was left stirring for 5 minutes to start washing.
  • stannous chloride dihydrate SnCl 2 .2H 2 O reagent
  • sample A flaky tin oxide particles
  • An X-ray diffraction measurement (X-ray diffractometer RINT-1200, manufactured by Rigaku Corporation) of Sample A was performed, and the X-ray diffraction profile thereof is shown in FIG.
  • sample A has an X-ray diffraction profile peculiar to flaky stannous oxide in which the peak intensity ratio of (101) plane to (110) plane of stannous oxide is 1.0 or more. Had.
  • a scanning electron micrograph of Sample A is shown in FIG. From FIG. 2, it was found that the flaky particles had a longest width and a shortest width in the range of 0.05 to 40 ⁇ m and a thickness in the range of 0.005 to 2 ⁇ m. The flaky thickness of each sample was measured from another high-magnification electron micrograph.
  • Example 2 The sample A obtained in Example 1 was baked for 1 hour at a temperature of 900 ° C. in the air to obtain flaky tin oxide particles (sample B) of the present invention.
  • the X-ray diffraction measurement of Sample B was performed, and the X-ray diffraction profile thereof is shown in FIG.
  • the sample B unlike the sample Y obtained in Comparative Example 2 described later, has a flaky shape in which the peak intensity ratio of the (101) plane to the (110) plane is 1.0 or more It had an X-ray diffraction profile unique to stannic oxide.
  • a scanning electron micrograph of Sample B is shown in FIG. From FIG. 4, the flake shape is maintained after firing, and the longest width and the shortest width are each in the range of 0.05 to 40 ⁇ m and the thickness is in the range of 0.005 to 2 ⁇ m. all right.
  • Example 3 17.45 g of stannous chloride dihydrate (SnCl 2 .2H 2 O, manufactured by Wako Pure Chemical Industries, Ltd.) was dissolved in 19.46 g of 35% hydrochloric acid aqueous solution. The concentration was adjusted by adding 18.54 g of pure water to the solution to obtain a stannous chloride aqueous solution. Next, the above stannous chloride aqueous solution and 5N sodium hydroxide aqueous solution were simultaneously added to 0.5 liter of pure water at 90 ° C. over 20 minutes while maintaining pH 4 ⁇ 0.2. Aged for 10 minutes. Thereafter, the pH was adjusted to 3.0 using a 3N hydrochloric acid aqueous solution, and the mixture was left stirring for 5 minutes to start washing.
  • stannous chloride dihydrate SnCl 2 .2H 2 O, manufactured by Wako Pure Chemical Industries, Ltd.
  • sample C flaky tin oxide particles
  • sample C flaky tin oxide particles
  • X-ray diffraction measurement X-ray diffraction specific to flaky stannous oxide in which the peak intensity ratio of (101) plane to (110) plane of stannous oxide was 1.0 or more. Had a profile.
  • Example 4 2.0 g of the sample C obtained in Example 3 was taken in an alumina crucible and baked in the atmosphere at 900 ° C. for 2 hours to obtain flaky tin oxide particles (sample D) of the present invention.
  • a scanning electron micrograph of Sample D is shown in FIG. From FIG. 5, it was found that the longest width and the shortest width were each in the range of 0.05 to 40 ⁇ m and the thickness was in the range of 0.005 to 2 ⁇ m.
  • the peak intensity ratio of (101) plane / (110) plane was 6.2.
  • Example 5 Slowly hand-pulverize 2.0 g of the dried product obtained in Example 3 and 0.4 g of sodium chloride in an agate mortar, take 2.0 g of the mixture in an alumina crucible, and bake at 900 ° C. for 2 hours in the air.
  • the flaky tin oxide powder (sample E) of the present invention was obtained.
  • a scanning electron micrograph of Sample E is shown in FIG. From FIG. 6, it was found that the flaky particles had a longest width of about 0.5 to 6 ⁇ m. The thickness was about 0.08 to 2.0 ⁇ m from a high-magnification electron micrograph.
  • X-ray diffraction measurement was performed, it had an X-ray diffraction profile peculiar to flaky stannic oxide as in Example 2, and the peak intensity ratio of (101) plane / (110) 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 by hand in an agate mortar, and 2.0 g was taken into an alumina crucible, and 900 ° C. in the atmosphere for 2 hours. Firing was performed to obtain a flaky tin oxide powder (sample F) of the present invention.
  • a scanning electron micrograph of Sample F is shown in FIG. From FIG. 7, it was found that they were fine flaky particles having a maximum width of about 0.1 to 0.5 ⁇ m. The thickness was about 0.05 to 1.5 ⁇ m from a high-magnification electron micrograph.
  • X-ray diffraction measurement was performed, it had an X-ray diffraction profile peculiar to flaky stannic oxide as in Example 2, and the peak intensity ratio of (101) plane / (110) plane was 1.0.
  • Example 7 The same procedure as in Example 3 was performed except that 5% aqueous ammonia was used instead of 5N sodium hydroxide as the alkali source used at the time of simultaneous addition in Example 3, and the flaky tin oxide particles ( Sample G) was obtained.
  • Sample G When the sample G was observed with a scanning electron microscope, it was found to be flaky particles having a longest width and a shortest width in the range of 0.05 to 40 ⁇ m and a thickness in the range of 0.005 to 2 ⁇ m.
  • X-ray diffraction measurement was performed, X-ray diffraction specific to flaky stannous oxide in which the peak intensity ratio of (101) plane to (110) plane of stannous oxide was 1.0 or more. Had a profile.
  • Example 8 2.0 g of the sample G obtained in Example 7 was taken in an alumina crucible and baked in the atmosphere at 900 ° C. for 2 hours to obtain flaky tin oxide particles (sample H) of the present invention.
  • a scanning electron micrograph of Sample H is shown in FIG. From FIG. 8, it was found that the flaky particles had a longest width and a shortest width in the range of 0.05 to 40 ⁇ m, and a thickness in the range of 0.005 to 2 ⁇ m.
  • the peak intensity ratio of (101) plane / (110) plane was It was 8.3.
  • Example 9 17.45 g of stannous chloride dihydrate (SnCl 2 .2H 2 O, manufactured by Wako Pure Chemical Industries, Ltd.) was dissolved in 19.46 g of 35% hydrochloric acid aqueous solution. The concentration was adjusted by adding 18.54 g of pure water to the solution to obtain a stannous chloride aqueous solution. Next, 0.14 g of the above stannous chloride aqueous solution and sodium silicate solution (water glass, SiO 2 min; 35 to 38%, reagent, manufactured by Kanto Chemical Co., Inc.) in 0.5 liter of pure water at 90 ° C.
  • a dissolved 5N aqueous sodium hydroxide solution was added simultaneously over 20 minutes while maintaining pH 4 ⁇ 0.2, and after the addition, the solution was aged for 10 minutes. Thereafter, the pH was adjusted to 3.0 using a 3N hydrochloric acid aqueous solution, and the mixture was left stirring for 5 minutes to start washing. When the filtrate specific resistance value reached 15,000 ⁇ cm, washing was stopped, and the obtained cake was left in the atmosphere at 105 ° C. overnight to dry.
  • the dried product was manually pulverized in an agate mortar to obtain flaky tin oxide particles (sample I) of the present invention.
  • Example 10 2.0 g of the sample I obtained in Example 9 was taken in an alumina crucible, fired at 900 ° C. for 2 hours in the atmosphere, and contained silicon of the present invention (0.5 wt% in terms of SiO 2 ).
  • the obtained flaky tin oxide particles (Sample J) were obtained.
  • a scanning electron micrograph of Sample J is shown in FIG. From FIG. 9, it was found that the flaky particles had a longest width and a shortest width in the range of 0.05 to 40 ⁇ m and a thickness in the range of 0.005 to 2 ⁇ m.
  • X-ray diffraction measurement was performed, it had an X-ray diffraction profile peculiar to flaky stannic oxide as in Example 2, and the peak intensity ratio of (101) plane / (110) plane was 5.1.
  • Example 11 flaky tin oxide particles (sample K) of the present invention were obtained in the same manner as in Example 9 except that 0.47 g was used instead of 0.14 g of the sodium silicate solution.
  • the sample K was observed with a scanning electron microscope, it was found to be flaky particles having a longest width and a shortest width in the range of 0.05 to 40 ⁇ m and a thickness in the range of 0.005 to 2 ⁇ m.
  • X-ray diffraction measurement was performed, X-ray diffraction specific to flaky stannous oxide in which the peak intensity ratio of (101) plane to (110) plane of stannous oxide was 1.0 or more. Had a profile.
  • Example 12 2.0 g of the sample K obtained in Example 11 was taken in an alumina crucible and baked at 900 ° C. for 2 hours in the atmosphere to contain silicon of the present invention (1.64% by weight in terms of SiO 2 ).
  • the obtained flaky tin oxide particles (sample L) were obtained.
  • a scanning electron micrograph of Sample L is shown in FIG. From FIG. 10, it was found that the flaky particles had a longest width and a shortest width in the range of 0.05 to 40 ⁇ m, and a thickness in the range of 0.005 to 2 ⁇ m.
  • X-ray diffraction measurement was performed, it had an X-ray diffraction profile peculiar to flaky stannic oxide as in Example 2, and the peak intensity ratio of (101) plane / (110) plane was 6.2.
  • Example 13 flaky tin oxide particles (sample M) of the present invention were obtained in the same manner as in Example 9 except that 0.91 g was used instead of 0.14 g of the sodium silicate solution.
  • the sample M was observed with a scanning electron microscope, it was found to be flaky particles having a longest width and a shortest width in the range of 0.05 to 40 ⁇ m and a thickness in the range of 0.005 to 2 ⁇ m.
  • X-ray diffraction measurement was performed, X-ray diffraction specific to flaky stannous oxide in which the peak intensity ratio of (101) plane to (110) plane of stannous oxide was 1.0 or more. Had a profile.
  • Example 14 2.0 g of the sample M obtained in Example 13 was taken in an alumina crucible, fired at 900 ° C. for 2 hours in the atmosphere, and contained silicon of the present invention (3.2 wt% in terms of SiO 2 ).
  • the obtained flaky tin oxide particles (sample N) were obtained.
  • a scanning electron micrograph of Sample N is shown in FIG. From FIG. 11, it was found that the flaky particles had a longest width and a shortest width in the range of 0.05 to 40 ⁇ m and a thickness in the range of 0.005 to 2 ⁇ m.
  • X-ray diffraction measurement was performed, it had an X-ray diffraction profile peculiar to flaky stannic oxide as in Example 2, and the peak intensity ratio of (101) plane / (110) plane was 2.6.
  • Example 15 the flaky oxidation of the present invention was carried out in the same manner as in Example 9 except that 0.14 g of sodium aluminate (Al 2 O 3 ; 34-39%) was used instead of the sodium silicate solution. Tin particles (sample O) were obtained. When the sample O was observed with a scanning electron microscope, it was found to be flaky particles having a longest width and a shortest width in the range of 0.05 to 40 ⁇ m and a thickness in the range of 0.005 to 2 ⁇ m. Further, when X-ray diffraction measurement was performed, X-ray diffraction specific to flaky stannous oxide in which the peak intensity ratio of (101) plane to (110) plane of stannous oxide was 1.0 or more. Had a profile.
  • Example 16 2.0 g of the sample O obtained in Example 15 was taken in an alumina crucible and baked in the atmosphere at 900 ° C. for 2 hours to obtain aluminum of the present invention (0.5% by weight in terms of Al 2 O 3 ). Flaky tin oxide particles (sample P) were obtained. A scanning electron micrograph of Sample P is shown in FIG. From FIG. 12, it was found that the flaky particles had a longest width and a shortest width in the range of 0.05 to 40 ⁇ m and a thickness in the range of 0.005 to 2 ⁇ m. Moreover, when X-ray diffraction measurement was performed, it had an X-ray diffraction profile peculiar to flaky stannic oxide as in Example 2, and the peak intensity ratio of (101) plane / (110) plane was 10.9.
  • Example 17 17.46 g of stannous chloride dihydrate (SnCl 2 .2H 2 O, manufactured by Wako Pure Chemical Industries) and 0.02 g of antimony chloride (SbCl 3 reagent, manufactured by Nacalai Tesque) 19.46 g of 35% aqueous hydrochloric acid solution Dissolved in. The concentration was adjusted by adding 18.54 g of pure water to the solution to obtain a stannous chloride aqueous solution containing antimony chloride. Next, the above stannous chloride aqueous solution and 5N sodium hydroxide aqueous solution were simultaneously added to 0.5 liter of pure water at 90 ° C. over 20 minutes while maintaining pH 4 ⁇ 0.2. Aged for 10 minutes.
  • sample Q flaky tin oxide particles of the present invention.
  • sample Q was observed with a scanning electron microscope, it was found to be flaky particles having a longest width and a shortest width in the range of 0.05 to 40 ⁇ m, and a thickness in the range of 0.005 to 2 ⁇ m.
  • X-ray diffraction measurement was performed, X-ray diffraction specific to flaky stannous oxide in which the peak intensity ratio of (101) plane to (110) plane of stannous oxide was 1.0 or more. Had a profile.
  • Example 18 2.0 g of the sample Q obtained in Example 17 was taken in an alumina crucible and fired in the atmosphere at 900 ° C. for 2 hours to obtain antimony of the present invention (0.5% by weight in terms of Sb 2 O 5 ).
  • a flaky tin oxide particle doped with (sample R) was obtained.
  • a scanning electron micrograph of Sample R is shown in FIG. From FIG. 13, it was found that the flaky particles had a longest width and a shortest width in the range of 0.05 to 40 ⁇ m and a thickness in the range of 0.005 to 2 ⁇ m.
  • the peak intensity ratio of (101) plane / (110) plane was 1.3.
  • Example 19 Stannous chloride dihydrate (SnCl 2 ⁇ 2H 2 O, manufactured by Wako Pure Chemical Industries, Ltd.) 17.45 g and sodium tungstate (Na 2 WO 4 ⁇ 2H 2 O reagent, manufactured by Wako Pure Chemical Industries, Ltd.) 04 g was dissolved in 19.46 g of 35% aqueous hydrochloric acid. The concentration was adjusted by adding 18.54 g of pure water to this solution to obtain a stannous chloride aqueous solution containing sodium tungstate. Next, the above stannous chloride aqueous solution and 5N sodium hydroxide aqueous solution were simultaneously added to 0.5 liter of pure water at 90 ° C. over 20 minutes while maintaining pH 4 ⁇ 0.2.
  • sample S flaky tin oxide particles of the present invention.
  • sample S was observed with a scanning electron microscope, it was found to be flaky particles having a longest width and a shortest width in the range of 0.05 to 40 ⁇ m and a thickness in the range of 0.005 to 2 ⁇ m.
  • X-ray diffraction measurement was performed, X-ray diffraction specific to flaky stannous oxide in which the peak intensity ratio of (101) plane to (110) plane of stannous oxide was 1.0 or more. Had a profile.
  • Example 20 2.0 g of sample S obtained in Example 19 was taken in an alumina crucible, fired in the atmosphere at 900 ° C. for 2 hours, and doped with tungsten of the present invention (1 wt% in terms of WO 3 ). A tin oxide particle (sample T) was obtained. A scanning electron micrograph of Sample T is shown in FIG. From FIG. 14, it was found that the flaky particles had a longest width and a shortest width in the range of 0.05 to 40 ⁇ m and a thickness in the range of 0.005 to 2 ⁇ m.
  • Example 21 Sample D obtained in Example 4 was pulverized with a centrifugal pulverizer (centrifugal pulverizer ZM-100, manufactured by Lecce), and 10 g of the sample was placed in 1 L of pure water to form a slurry.
  • a centrifugal pulverizer centrifugal pulverizer ZM-100, manufactured by Lecce
  • stannic chloride SnCl 4 .5H 2 O, reagent, manufactured by Wako Pure Chemical Industries, Ltd.
  • antimony chloride SbCl 3 , reagent, manufactured by Nacalai Tesque
  • Example 22 The sample D obtained in Example 4 was baked at 900 ° C. for 2 hours in a nitrogen atmosphere to obtain flaky tin oxide particles (sample V) of the present invention. From the scanning electron micrograph of Sample V, it was found that the longest width and the shortest width were in the range of 0.05 to 40 ⁇ m and the flaky particles had a thickness in the range of 0.005 to 2 ⁇ m. Further, when X-ray diffraction measurement was performed, it had an X-ray diffraction profile peculiar to flaky stannic oxide as in Example 4, and the peak intensity ratio of (101) plane / (110) plane was 6.2.
  • Example 23 The sample V1g obtained in Example 22 was pulverized for 5 minutes with a cracking machine (Ishikawa-type stirring cracker AGA manufactured by Ishikawa Factory Co., Ltd.) to obtain tin oxide particles (sample W). From the scanning electron micrograph of the sample W, it was found that the particles were indefinitely shaped. Further, when X-ray diffraction measurement was performed, it had an X-ray diffraction profile peculiar to stannic oxide, and the peak intensity ratio of (101) plane / (110) plane was 3.1.
  • a cracking machine Ishikawa-type stirring cracker AGA manufactured by Ishikawa Factory Co., Ltd.
  • sample X When the filtrate specific resistance value reached 15,000 ⁇ cm, washing was stopped, and the obtained cake was left in the atmosphere at 105 ° C. overnight to dry.
  • the dried product was manually pulverized in an agate mortar to obtain tin oxide particles (sample X). When the sample X was observed with a scanning electron microscope, it was found to be granular. Further, when X-ray diffraction measurement was performed, it had an amorphous X-ray diffraction profile.
  • Comparative Example 2 2.0 g of the sample X obtained in Comparative Example 1 was taken in an alumina crucible and baked in the atmosphere at 900 ° C. for 2 hours to obtain tin oxide particles (sample Y). A scanning electron micrograph of Sample Y is shown in FIG. From FIG. 16, it was found that this was granular. Further, when X-ray diffraction measurement was performed, it had an X-ray diffraction profile (FIG. 3) peculiar to granular stannic oxide, and the peak intensity ratio of (101) plane / (110) plane was 0. It was 8.
  • Comparative Example 3 The sample Y obtained in Comparative Example 2 was baked at 900 ° C. for 2 hours in a nitrogen atmosphere to obtain tin oxide particles (sample Z). From the scanning electron micrograph of sample Z, it was found that this was granular. Moreover, when X-ray diffraction measurement was performed, it had an X-ray diffraction profile peculiar to granular stannic oxide, and the peak intensity ratio of (101) plane / (110) plane was 0.8. .
  • Table 3 shows the results of measuring the surface resistance values of these coating films with Hirestor UP (manufactured by Dia Instruments). Their film thickness was 19 ⁇ m.
  • the sample U of Example 21 showed a lower surface resistance value than the antimony-added stannic dioxide-coated spherical titanium dioxide, and was found to be usable as a conductive film.
  • the tin oxide particles of the present invention are also used for catalysts, catalyst carriers, gas sensors, photocatalysts, infrared shielding agents, ceramics / metal additives, abrasives, and the like.
  • tin oxide films on which tin oxide particles are formed can be made conductive by forming a tin oxide film on a glass substrate. Used for conductive oxide-coated glass, heat ray reflective glass, low radiation glass, electrothermal glass and the like. It can also be used for various applications such as photocatalytic materials, antireflection materials, and gas barrier materials.

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

酸化スズ粒子及びその製造方法Tin oxide particles and method for producing the same
　本発明は、酸化スズ粒子及びその製造方法に関する。また、その酸化スズ粒子を含有している分散体、塗料、樹脂組成物等に関する。 The present invention relates to tin oxide particles and a method for producing the same. The present invention also relates to a dispersion, a paint, a resin composition and the like containing the tin oxide particles.
　酸化スズとしては、一般に４価のスズを構成成分とする酸化第二スズ（ＳｎＯ２）と２価のスズを構成成分とする酸化第一スズ（ＳｎＯ）が知られている。酸化第二スズは半導体であり、単体では高い導電性を示さないが、異原子をドープすることにより高い導電性を得ることも知られている。酸化第二スズは、透明性、物理的化学的安定性に優れた材料であり、電気・電子的用途に期待される材料である。具体的には、酸化第二スズにアンチモン、リン、フッ素等をドープしたものは、導電性に優れているため、導電性フィラーとしてプラスチックやゴム等に混入され、導電性プラスチックの材料として利用されている。更に、前記の導電性フィラーを配合した塗料を用いて透明導電膜を作製すると、極めて低抵抗かつ低ヘーズで、しかも基体との密着性及び膜強度に優れた膜が得られ、このような膜はＯＡ機器等のディスプレイやＴＶブラウン管の画像表面の帯電防止のために、または電磁界シールドとして用いられている。また透明導電膜は、タッチパネルや液晶ディスプレイ等のディスプレイ装置の透明電極にも利用できる。更に、酸化第二スズの焼結体をターゲットとしてスパッタ法によりガラス上に酸化スズ薄膜を作製し、透明導電性酸化物コートガラス、熱線反射ガラス、低放射ガラス、電熱ガラスなどが製造されている。一方、酸化第一スズは、硫酸等に溶解してスズめっき浴に用いられている。 As tin oxide, stannic oxide (SnO 2 ) containing tetravalent tin as a constituent component and stannous oxide (SnO) containing divalent tin as a constituent component are generally known. Although stannic oxide is a semiconductor and does not exhibit high conductivity by itself, it is also known that high conductivity is obtained by doping different atoms. Stannic oxide is a material excellent in transparency and physical and chemical stability, and is expected to be used for electrical and electronic applications. Specifically, stannic oxide doped with antimony, phosphorus, fluorine, etc. is excellent in conductivity, so it is mixed in plastics, rubber, etc. as a conductive filler and used as a material for conductive plastics. ing. Furthermore, when a transparent conductive film is prepared using a paint containing the above conductive filler, a film having extremely low resistance and low haze, and excellent adhesion to the substrate and film strength can be obtained. Is used for preventing charging of the image surface of a display such as an OA device or a TV CRT, or as an electromagnetic field shield. The transparent conductive film can also be used for transparent electrodes of display devices such as touch panels and liquid crystal displays. Furthermore, a tin oxide thin film is produced on a glass by sputtering using a sintered body of stannic oxide as a target, and transparent conductive oxide coated glass, heat ray reflective glass, low radiation glass, electrothermal glass, etc. are produced. . On the other hand, stannous oxide is dissolved in sulfuric acid or the like and used in a tin plating bath.
　酸化第二スズは、４価のスズ塩水溶液とアルカリ溶液とを反応させた沈殿物を焼成して製造される。例えば特許文献１は、４価のスズ塩水溶液とアルカリ溶液の反応をｐＨが０．５～４の範囲で行い、スズ含有沈殿を生成させ、次いで、４００～１２００℃の温度範囲で焼成することを記載している。また、特許文献２は、４価のスズ塩水溶液とアルカリ水溶液とを水中に並行的に添加し、中和反応液のｐＨを３以上に保持しながら中和して酸化スズの水和物を生成させ、次いで該生成物の水中に塩化アンチモンの溶液とアルカリ水溶液とを並行的に添加し、中和反応液のｐＨを３以上に保持しながら中和して該生成物の表面に酸化アンチモンの水和物を生成させ、しかる後焼成して、アンチモンをドーピングした酸化第二スズを製造する方法を記載している。一方、酸化第一スズについては、例えば特許文献３は、塩化第一スズの水溶液と水酸化ナトリウムの水溶液とを混合して反応させ、ｐＨ１２～１３．５で静置状態で２時間以上熟成して製造することを記載している。 Stannic oxide is produced by firing a precipitate obtained by reacting a tetravalent tin salt aqueous solution with an alkaline solution. For example, in Patent Document 1, a reaction between a tetravalent tin salt aqueous solution and an alkaline solution is performed in a pH range of 0.5 to 4 to form a tin-containing precipitate, and then calcined in a temperature range of 400 to 1200 ° C. Is described. Further, Patent Document 2 adds a tetravalent tin salt aqueous solution and an alkaline aqueous solution in parallel to neutralize the tin oxide hydrate by maintaining the pH of the neutralization reaction solution at 3 or more. Then, a solution of antimony chloride and an aqueous alkali solution are added in parallel to the product water, and neutralized while maintaining the pH of the neutralization reaction solution at 3 or more, and the surface of the product is antimony oxide. Is prepared and then calcined to produce antimony-doped stannic oxide. On the other hand, as for stannous oxide, for example, in Patent Document 3, an aqueous solution of stannous chloride and an aqueous solution of sodium hydroxide are mixed and reacted, and aged for 2 hours or more in a stationary state at pH 12 to 13.5. Manufacturing.
特開２００２－０２９７４４号公報JP 2002-029744 A 特許第３６４７９２９号公報Japanese Patent No. 3647929 特開平１－２０１０２２号公報JP-A-1-201022
　前記の特許文献１、２のように４価のスズ化合物を用い、加水分解、中和反応によって得た沈殿物を焼成して製造した酸化第二スズは、微細な粒状形状を有しており、これらの方法では、薄片状等の粒子形状を有する酸化第二スズは製造できない。一方、特許文献３の方法では、２価のスズ化合物を用いて中和反応によって平板状の酸化第一スズが得られるとしているが、厚みの薄い薄片状の形状の酸化第一スズは得られていない。しかも、その酸化第一スズは硫酸等に溶解してスズめっき浴に用いられるものであって、酸化第一スズを酸化して酸化第二スズを製造することを記載していない。 The stannic oxide produced by calcining a precipitate obtained by hydrolysis and neutralization reaction using a tetravalent tin compound as in Patent Documents 1 and 2 has a fine granular shape. These methods cannot produce stannic oxide having a particle shape such as flakes. On the other hand, in the method of Patent Document 3, flat stannous oxide is obtained by a neutralization reaction using a divalent tin compound, but thin flaky stannous oxide is obtained. Not. Moreover, the stannous oxide is dissolved in sulfuric acid or the like and used in a tin plating bath, and does not describe that stannous oxide is oxidized to produce stannic oxide.
　本発明者らは、酸化第二スズの粒子形状を薄片状にすることにより、薄い酸化スズ膜を形成したり、導電性等の効果の高い有用な材料が得られたりすると考え、薄片状の粒子形状を有する酸化第二スズ粒子を製造する方法を研究した。その結果、２価のスズ化合物とアルカリとを、反応器内のｐＨを６以下に維持するように添加して、スズ化合物を加水分解すると厚みの薄い薄片状酸化第一スズ粒子が得られること、それを焼成することにより薄片状の形状を維持した酸化第二スズ粒子が得られることなどを見出した。また、前記の薄片状酸化第一スズ粒子及び薄片状酸化第二スズ粒子の粉末Ｘ線回折プロファイルは、酸化スズの（１１０）面に対する（１０１）面のピーク強度比（ピークの高さの比）が１．０以上であること、更に、それらを粉砕して不定形状としても前記のピーク強度比は１．０以上に維持されることを見出し、本発明を完成した。 The present inventors think that by forming the particle shape of stannic oxide into a flaky shape, a thin tin oxide film can be formed, or a useful material having a high effect such as conductivity can be obtained. The method of producing stannic oxide particles with particle shape was studied. As a result, when a divalent tin compound and an alkali are added so as to maintain the pH in the reactor at 6 or less, and the tin compound is hydrolyzed, thin flaky stannous oxide particles can be obtained. The inventors have found that by burning it, stannic oxide particles maintaining a flaky shape can be obtained. Further, the powder X-ray diffraction profile of the flaky stannous oxide particles and the flaky stannic oxide particles is the peak intensity ratio of the (101) plane to the (110) plane of tin oxide (ratio of peak height). ) Was 1.0 or more, and the present invention was completed by finding that the peak intensity ratio was maintained at 1.0 or more even when they were pulverized into irregular shapes.
　すなわち、本発明は、
（１）粉末Ｘ線回折において、酸化スズの（１１０）面に対する（１０１）面のピーク強度比が１．０以上であることを特徴とする酸化スズ粒子、
（２）酸化スズが酸化第二スズ（ＳｎＯ２）の結晶構造を有することを特徴とする前記（１）に記載の酸化スズ粒子、
（３）不定形状の粒子形状を有することを特徴とする前記（１）又は（２）に記載の酸化スズ粒子、
（４）薄片状の粒子形状を有することを特徴とする前記（１）又は（２）に記載の酸化スズ粒子、
（５）酸化スズが酸化第一スズ（ＳｎＯ）の結晶構造を有し、しかも、薄片状の粒子形状を有することを特徴とする前記（１）に記載の酸化スズ粒子、
（６）薄片面の厚みが５μｍ以下であることを特徴とする前記（４）又は（５）に記載の酸化スズ粒子、
（７）薄片面の最長幅及び最短幅がそれぞれ０．０５～４０μｍの範囲にあり、厚みが０．００５～２μｍの範囲にあることを特徴とする前記（４）又は（５）に記載の酸化スズ粒子、
（８）スズ以外の無機元素を更に含むことを特徴とする前記（１）～（７）のいずれか一項に記載の酸化スズ粒子、
（９）酸化スズ粒子の表面に無機化合物及び／又は有機化合物を被覆していることを特徴とする前記（１）～（８）のいずれか一項に記載の酸化スズ粒子、
（１０）酸化スズ粒子の表面に導電性無機化合物を被覆していることを特徴とする前記（９）に記載の酸化スズ粒子、
（１１）スズ（ＩＩ）化合物とアルカリとを、反応器内のｐＨを６以下に維持するように添加して、スズ（ＩＩ）化合物を加水分解することを特徴とする酸化スズ粒子の製造方法、
（１２）５０℃以上の温度の水を入れた反応器に、スズ（ＩＩ）化合物とアルカリとを添加することを特徴とする前記（１１）に記載の酸化スズ粒子の製造方法、
（１３）スズ（ＩＩ）化合物とアルカリと無機化合物とを、反応器内のｐＨを６以下に維持するように添加して、スズ（ＩＩ）化合物を加水分解することを特徴とする酸化スズ粒子の製造方法、
（１４）酸化スズが酸化第一スズの結晶構造を有することを特徴とする前記（１１）～（１３）のいずれか一項に記載の酸化スズ粒子の製造方法、
（１５）前記（１１）～（１４）のいずれか一項に記載の方法で得られたスズ（ＩＩ）化合物の加水分解生成物を焼成することを特徴とする酸化スズ粒子の製造方法、
（１６）スズ（ＩＩ）化合物の加水分解生成物と融剤を混合し焼成することを特徴とする前記（１５）に記載の酸化スズ粒子の製造方法、
（１７）酸化スズが酸化第二スズの結晶構造を有することを特徴とする前記（１５）又は（１６）に記載の酸化スズ粒子の製造方法、
（１８）前記（１１）～（１７）のいずれか一項に記載の方法で得られた酸化スズを粉砕することを特徴とする酸化スズ粒子の製造方法、
（１９）前記（１１）～（１８）のいずれか一項に記載の方法で得られた酸化スズ粒子の表面に無機化合物及び／又は有機化合物を被覆することを特徴とする酸化スズ粒子の製造方法、
（２０）無機化合物及び／又は有機化合物を被覆した後に焼成することを特徴とする前記（１９）に記載の酸化スズ粒子の製造方法、
（２１）前記（１）～（１０）のいずれか一項に記載の酸化スズ粒子を含有することを特徴とする分散体、
（２２）前記（１）～（１０）のいずれか一項に記載の酸化スズ粒子を含有することを特徴とする塗料、
（２３）前記（１）～（１０）のいずれか一項に記載の酸化スズ粒子を含有することを特徴とする樹脂組成物、
（２４）基材上に前記（２１）に記載の分散体又は前記（２２）に記載の塗料が塗布されていることを特徴とする酸化スズ膜、
（２５）前記（１）～（１０）のいずれか一項に記載の酸化スズ粒子を含有することを特徴とする導電性材料、
（２６）前記（１）～（１０）のいずれか一項に記載の酸化スズ粒子を含有することを特徴とする触媒、
（２７）前記（１）～（１０）のいずれか一項に記載の酸化スズ粒子を含有することを特徴とするガスセンサー、などである。 That is, the present invention
(1) In powder X-ray diffraction, a tin oxide particle characterized in that the peak intensity ratio of the (101) plane to the (110) plane of tin oxide is 1.0 or more,
(2) The tin oxide particles according to (1), wherein the tin oxide has a crystal structure of stannic oxide (SnO 2 ),
(3) The tin oxide particles according to (1) or (2), wherein the tin oxide particles have an indefinite shape.
(4) The tin oxide particles according to (1) or (2), wherein the tin oxide particles have a flaky particle shape,
(5) The tin oxide particles according to (1) above, wherein the tin oxide has a crystal structure of stannous oxide (SnO) and has a flaky particle shape,
(6) The tin oxide particles according to (4) or (5) above, wherein the thickness of the thin piece surface is 5 μm or less,
(7) The longest width and the shortest width of the thin piece surface are each in the range of 0.05 to 40 μm, and the thickness is in the range of 0.005 to 2 μm, as described in (4) or (5) above Tin oxide particles,
(8) The tin oxide particles according to any one of (1) to (7), further including an inorganic element other than tin,
(9) The tin oxide particles according to any one of (1) to (8) above, wherein the surface of the tin oxide particles is coated with an inorganic compound and / or an organic compound,
(10) The tin oxide particles according to (9), wherein the surface of the tin oxide particles is coated with a conductive inorganic compound,
(11) A method for producing tin oxide particles, comprising adding a tin (II) compound and an alkali so as to maintain the pH in the reactor at 6 or less and hydrolyzing the tin (II) compound. ,
(12) The method for producing tin oxide particles according to (11) above, wherein a tin (II) compound and an alkali are added to a reactor containing water having a temperature of 50 ° C. or higher,
(13) Tin oxide particles characterized by hydrolyzing a tin (II) compound by adding a tin (II) compound, an alkali and an inorganic compound so as to maintain the pH in the reactor at 6 or less Manufacturing method,
(14) The method for producing tin oxide particles according to any one of (11) to (13), wherein the tin oxide has a crystal structure of stannous oxide,
(15) A method for producing tin oxide particles, comprising calcining a hydrolysis product of a tin (II) compound obtained by the method according to any one of (11) to (14),
(16) The method for producing tin oxide particles according to (15), wherein the hydrolysis product of the tin (II) compound and the flux are mixed and fired.
(17) The method for producing tin oxide particles according to (15) or (16) above, wherein the tin oxide has a crystal structure of stannic oxide,
(18) A method for producing tin oxide particles, characterized by pulverizing tin oxide obtained by the method according to any one of (11) to (17),
(19) Production of tin oxide particles, wherein the surface of the tin oxide particles obtained by the method according to any one of (11) to (18) is coated with an inorganic compound and / or an organic compound. Method,
(20) The method for producing tin oxide particles according to the above (19), characterized by firing after coating with an inorganic compound and / or an organic compound,
(21) A dispersion comprising the tin oxide particles according to any one of (1) to (10),
(22) A paint containing the tin oxide particles according to any one of (1) to (10),
(23) A resin composition comprising the tin oxide particles according to any one of (1) to (10),
(24) A tin oxide film, wherein the dispersion according to (21) or the paint according to (22) is applied on a substrate,
(25) A conductive material comprising the tin oxide particles according to any one of (1) to (10),
(26) A catalyst comprising the tin oxide particles according to any one of (1) to (10),
(27) A gas sensor comprising the tin oxide particles according to any one of (1) to (10), and the like.
　本発明の酸化スズ粒子は、粉末Ｘ線回折において、酸化スズの（１１０）面に対する（１０１）面のピーク強度比が１．０以上であり、特異なＸ線プロファイルを有する。その特性を利用して、導電性材料、触媒、ガスセンサー等に用いられる。
　また、薄片状の粒子形状を有し、その特異な粒子形状を利用して、薄い酸化スズ膜を形成する材料や、導電性材料等に用いられる。
　本発明の酸化スズ粒子の製造方法は、大掛かりな装置を要せず、比較的安価な原材料を用いているので、工業的に有利に特異なＸ線プロファイルをもつ酸化スズ粒子や特異な粒子形状を有する酸化スズ粒子を比較的簡単に製造することができる有利な方法である。 In the powder X-ray diffraction, the tin oxide particles of the present invention have a peak intensity ratio of (101) plane to (110) plane of tin oxide of 1.0 or more, and have a unique X-ray profile. Utilizing these characteristics, it is used for conductive materials, catalysts, gas sensors and the like.
Further, it has a flaky particle shape and is used for a material for forming a thin tin oxide film, a conductive material, etc. by utilizing the unique particle shape.
The method for producing tin oxide particles of the present invention does not require a large-scale apparatus, and uses relatively inexpensive raw materials. Therefore, tin oxide particles having a specific X-ray profile and a specific particle shape are industrially advantageous. This is an advantageous method in which tin oxide particles having the above can be produced relatively easily.
試料ＡのＸ線回折プロファイルを示す図である。3 is a diagram showing an X-ray diffraction profile of sample A. FIG. 試料Ａの粒子形状を示す走査型電子顕微鏡写真である。2 is a scanning electron micrograph showing the particle shape of sample A. FIG. 試料Ｂ及び試料ＹのＸ線回折プロファイルを示す図である。It is a figure which shows the X-ray-diffraction profile of the sample B and the sample Y. 試料Ｂの粒子形状を示す走査型電子顕微鏡写真である。3 is a scanning electron micrograph showing the particle shape of Sample B. FIG. 試料Ｄの粒子形状を示す走査型電子顕微鏡写真である。3 is a scanning electron micrograph showing the particle shape of sample D. FIG. 試料Ｅの粒子形状を示す走査型電子顕微鏡写真である。3 is a scanning electron micrograph showing the particle shape of sample E. FIG. 試料Ｆの粒子形状を示す走査型電子顕微鏡写真である。3 is a scanning electron micrograph showing the particle shape of sample F. FIG. 試料Ｈの粒子形状を示す走査型電子顕微鏡写真である。3 is a scanning electron micrograph showing the particle shape of sample H. FIG. 試料Ｊの粒子形状を示す走査型電子顕微鏡写真である。2 is a scanning electron micrograph showing the particle shape of Sample J. FIG. 試料Ｌの粒子形状を示す走査型電子顕微鏡写真である。2 is a scanning electron micrograph showing the particle shape of a sample L. FIG. 試料Ｎの粒子形状を示す走査型電子顕微鏡写真である。2 is a scanning electron micrograph showing the particle shape of sample N. FIG. 試料Ｐの粒子形状を示す走査型電子顕微鏡写真である。4 is a scanning electron micrograph showing the particle shape of a sample P. 試料Ｒの粒子形状を示す走査型電子顕微鏡写真である。3 is a scanning electron micrograph showing the particle shape of sample R. FIG. 試料Ｔの粒子形状を示す走査型電子顕微鏡写真である。3 is a scanning electron micrograph showing the particle shape of a sample T. FIG. 試料Ｕの粒子形状を示す走査型電子顕微鏡写真である。2 is a scanning electron micrograph showing the particle shape of a sample U. FIG. 試料Ｙの粒子形状を示す走査型電子顕微鏡写真である。4 is a scanning electron micrograph showing the particle shape of sample Y.
　本発明の酸化スズ粒子は粉末Ｘ線回折において、酸化スズの（１１０）面に対する（１０１）面のピーク強度比が１．０以上である。
　本発明の酸化スズは、酸化第一スズであっても、酸化第二スズであってもよく、それらをそれぞれ含んでいてもよく、更には、水酸化第一スズ、水酸化第二スズ等を含んでいてもよい。酸化スズのうち種々の用途に用いられることから、酸化第一スズ又は酸化第二スズの結晶構造を有するものが好ましく、酸化第二スズの結晶構造を有するものがより好ましく、酸化スズの全部が酸化第二スズの結晶構造を有するものが更に好ましい。先に記載のとおり、本発明の酸化スズは特異なＸ線プロファイルを有し、具体的には、酸化第二スズの結晶構造を粉末Ｘ線回折（線源；Ｃｕ－Ｋα）で確認すると、回折角（２θ）３３．８°程度に現れる酸化第二スズの（１０１）面のピークの高さが、回折角（２θ）２６．６°程度に現れる（１１０）面のピークの高さと同じかそれよりも高い。また、酸化第一スズの結晶構造を粉末Ｘ線回折（線源；Ｃｕ－Ｋα）で確認すると、回折角（２θ）２９．９°程度に現れる酸化第一スズの（１０１）面のピークの高さが、回折角（２θ）３３．３°程度に現れる（１１０）面のピークの高さと同じかそれよりも高い。すなわち、粉末Ｘ線回折において、酸化スズの（１０１）面のピークの高さ／（１１０）面のピークの高さで表されるピーク強度比は１．０以上であり、１．１以上がより好ましく、２以上が更に好ましい。
　この現象は本発明の薄片状酸化第一スズ粒子及び酸化第二スズ粒子の場合には通常見られるが、一方、従来の粒状粒子の場合には（１０１）面のピークの高さは（１１０）面のピークの高さよりも低く、したがって、本発明の薄片状酸化スズ粒子は従来の粒状粒子とは異なり、（１０１）面に配向していると考えられる。本発明の薄片状酸化スズ粒子を強度に粉砕して破壊すると、前記のピーク強度比は次第に小さくなることからも、本発明の薄片状酸化スズ粒子の特徴をピーク強度比で特定できることが理解できる。なお、粉砕の程度により、種々の形状を包含する不定形状になっても前記のピーク強度比が１．０以上を維持している場合がある。したがって、本発明の酸化スズ粒子の粒子形状は、一般に薄片状形状であるが、ピーク強度比を満足する限り、その薄片状形状を粉砕して得られるような種々の形状を包含する不定形状であってもよい。 In the powder X-ray diffraction of the tin oxide particles of the present invention, the peak intensity ratio of the (101) plane to the (110) plane of tin oxide is 1.0 or more.
The tin oxide of the present invention may be stannous oxide or stannic oxide, each of which may be contained, and further, stannous hydroxide, stannic hydroxide, etc. May be included. Among tin oxides, those having a crystal structure of stannous oxide or stannic oxide are preferable, those having a crystal structure of stannic oxide are more preferable, and all of tin oxide is used. Those having a crystal structure of stannic oxide are more preferable. As described above, the tin oxide of the present invention has a unique X-ray profile. Specifically, when the crystal structure of stannic oxide is confirmed by powder X-ray diffraction (ray source: Cu-Kα), The peak height of the (101) plane of stannic oxide that appears at a diffraction angle (2θ) of about 33.8 ° is the same as the peak height of the (110) plane that appears at a diffraction angle (2θ) of about 26.6 °. Or higher. Further, when the crystal structure of stannous oxide is confirmed by powder X-ray diffraction (ray source: Cu-Kα), the peak of the (101) plane of stannous oxide appearing at a diffraction angle (2θ) of about 29.9 °. The height is equal to or higher than the peak height of the (110) plane appearing at a diffraction angle (2θ) of about 33.3 °. That is, in powder X-ray diffraction, the peak intensity ratio expressed by the height of the peak of the (101) plane of tin oxide / the peak height of the (110) plane is 1.0 or more, and 1.1 or more. More preferred is 2 or more.
This phenomenon is usually observed in the case of the flaky stannous oxide particles and stannic oxide particles of the present invention, whereas in the case of conventional granular particles, the peak height of the (101) plane is (110 ) Lower than the peak height of the surface. Therefore, unlike the conventional granular particles, the flaky tin oxide particles of the present invention are considered to be oriented in the (101) plane. When the flaky tin oxide particles of the present invention are crushed and broken to a high strength, the peak intensity ratio gradually decreases, so that it can be understood that the characteristics of the flaky tin oxide particles of the present invention can be specified by the peak intensity ratio. . Depending on the degree of pulverization, the peak intensity ratio may be maintained at 1.0 or more even when the shape becomes indefinite including various shapes. Therefore, the particle shape of the tin oxide particles of the present invention is generally a flaky shape, but as long as the peak intensity ratio is satisfied, it is an indefinite shape including various shapes obtained by pulverizing the flaky shape. There may be.
　薄片状形状とは、最長幅及び最短幅を有する薄片において、その薄片面に対し有意に小さい垂直方向の厚みを有する形状をいい、好ましくは、最長幅／厚みが４以上であり、更に好ましく、１０～１０００程度であり、一般に薄層状、薄板状、フレーク状、シート状、ナノシート状と呼ばれる形状を包含する。薄片面に対する垂直方向の厚みは、５μｍ以下の薄いものが好ましく、０．０００５～５μｍの範囲がより好ましく、０．００５～２μｍの範囲が更に好ましく、０．０１～２μｍの範囲が更に好ましい。薄片面の最長幅、あるいは最短幅は、粉体特性の観点からそれぞれ０．０５～４０μｍの範囲が好ましく、０．５～３０μｍの範囲がより好ましい。薄片状形状やその大きさは、電子顕微鏡観察によって求めることができる。薄片状形状やその大きさは、電子顕微鏡観察によって求めることができる。 The flaky shape refers to a shape having a thickness in the vertical direction that is significantly smaller than that of the thin piece surface in the thin piece having the longest width and the shortest width, preferably the longest width / thickness is 4 or more, more preferably It is about 10 to 1000 and includes shapes generally called thin layer, thin plate, flake, sheet, and nanosheet. The thickness in the direction perpendicular to the flake surface is preferably as thin as 5 μm or less, more preferably in the range of 0.0005 to 5 μm, still more preferably in the range of 0.005 to 2 μm, and still more preferably in the range of 0.01 to 2 μm. The longest width or the shortest width of the flake surface is preferably in the range of 0.05 to 40 μm, more preferably in the range of 0.5 to 30 μm, from the viewpoint of powder characteristics. The flaky shape and its size can be determined by electron microscope observation. The flaky shape and its size can be determined by electron microscope observation.
　酸化スズ粒子には、Ｓｎ以外の無機元素が含まれていてもよい。無機元素としては、例えば導電性等を付与する目的で、Ｓｎの一部をＳｂ、Ｐ、Ｎｂ、Ｗ等の無機元素で置換してもよく、また、Ｓｉ、Ａｌ等の無機元素で置換してもよい。その置換量は無機元素に応じて適宜設定することができる。また、酸化スズの粒子表面を、溶媒への分散性、樹脂の親和性等の観点から、従来の界面活性剤、カップリング剤、カルボン酸、ポリオール、アミン、シロキサン等の有機化合物やシリカ、アルミナ等の無機化合物で被覆してもよい。また、Ｓｂ、Ｐ、Ｎｂ、Ｗ等でドープした酸化スズ等の導電性無機化合物を酸化スズの粒子表面に被覆してもよい。酸化スズ粒子の表面に被覆する無機化合物及び／又は有機化合物、導電性無機化合物の量は適宜設定することができる。 The tin oxide particles may contain an inorganic element other than Sn. As an inorganic element, for example, for the purpose of imparting conductivity, 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 Al. May be. The amount of substitution can be appropriately set according to the inorganic element. In addition, from the viewpoint of dispersibility in a solvent, affinity of resin, etc., the surface of tin oxide particles can be treated with conventional organic compounds such as surfactants, coupling agents, carboxylic acids, polyols, amines, siloxanes, silica, and alumina. You may coat | cover with inorganic compounds, such as. Alternatively, the surface of tin oxide particles may be coated with a conductive inorganic compound such as tin oxide doped with Sb, P, Nb, W, or the like. The amount of the inorganic compound and / or organic compound and conductive inorganic compound coated on the surface of the tin oxide particles can be appropriately set.
　本発明の特異なＸ線プロファイルを持つ酸化スズ粒子は、たとえば、スズ（ＩＩ）化合物（Ｓｎ２＋）とアルカリとをｐＨ６以下に維持して反応させ、スズ（ＩＩ）化合物を加水分解することによって得られる。スズ（ＩＩ）化合物としては、塩化スズ（ＩＩ）等の２価のスズ化合物を用いる。水溶性のスズ（ＩＩ）化合物が好ましく、塩化スズ（ＩＩ）がより好ましい。スズ（ＩＩ）化合物の濃度は、水に溶解して用いる場合は水に対して０．０５～１５０重量％が好ましく、より好ましくは１．０～１００重量％である。アルカリとしては、水酸化ナトリウム、水酸化カリウム、水酸化リチウム等の水酸化アルカリ、炭酸ナトリウム等の炭酸アルカリ、炭酸アンモニウム等のアンモニウム化合物、アンモニアなどを用いることができ、そのうち水酸化アルカリ、特に水酸化ナトリウムが好ましい。スズ（ＩＩ）化合物とアルカリとの添加は、反応器内のｐＨが６以下となるように調整しながら添加し、好ましくはｐＨが３～６、更に好ましくは３．５～５．５になるように調整しながら添加する。ｐＨが６よりも高い中性付近では、スズの酸水酸化物（Ｓｎ６Ｏ４（ＯＨ）４）が生成しやすく、これは薄片状の形状ではない。また、ｐＨが９以上では平板状となる場合があるが、このものは厚みが５μｍよりも大きいものである。
　スズ（ＩＩ）化合物とアルカリの添加方法は、反応器にスズ（ＩＩ）化合物を予め添加した後にアルカリを添加したり、反応器にアルカリを予め添加した後にスズ（ＩＩ）化合物を添加したり、反応器にスズ（ＩＩ）化合物とアルカリを同時並行的に添加する方法が挙げられる。それらの一つの方法、あるいは二つ以上の方法を組み合わせることもできるが、スズ（ＩＩ）化合物とアルカリを同時並行的に添加するのが好ましい。添加後の反応器の温度は５０℃以上とすると、スズ（ＩＩ）化合物の加水分解を有効に進めることができるため好ましい。スズ（ＩＩ）化合物（又はアルカリ）を添加し５０℃以上に昇温した後にアルカリ（又はスズ（ＩＩ）化合物）を添加してもよく、予め反応器に水を入れておき、その水の温度を５０℃以上とした後に、スズ（ＩＩ）化合物とアルカリを同時並行的に添加してもよく、後者が好ましい。より好ましい温度は７０～１０５℃程度であり、更に好ましい温度は８５～１０５℃程度である。
　前記の同時並行添加とは、両者のそれぞれを別々に少量ずつ連続的あるいは間欠的に反応器に添加する方法をいう。具体的には両者を１０分～１０時間程度かけて同時に添加するのが好ましい。
　スズ（ＩＩ）化合物とアルカリを添加した後、熟成すると、酸化第一スズの結晶性がより高くなるため好ましい。熟成温度は５０℃以上が好ましく、７０～１０５℃程度がより好ましく、９０～１０５℃程度が更に好ましい。熟成時間は、５分～６時間程度が好ましい。前記の加水分解反応や熟成はスズの価数が２価を保つように窒素ガス等の非酸化性雰囲気で行ってもよいが、通常の大気中でも可能である。 The tin oxide particles having a unique X-ray profile of the present invention are obtained by, for example, reacting a tin (II) compound (Sn 2+ ) and an alkali while maintaining the pH at 6 or less, and hydrolyzing the tin (II) compound. can get. As the tin (II) compound, a divalent tin compound such as tin (II) chloride is used. Water-soluble tin (II) compounds are preferred, and tin (II) chloride is more preferred. The concentration of the tin (II) compound is preferably 0.05 to 150% by weight, more preferably 1.0 to 100% by weight, based on water when used by dissolving in water. As the alkali, alkali hydroxides such as sodium hydroxide, potassium hydroxide and lithium hydroxide, alkali carbonates such as sodium carbonate, ammonium compounds such as ammonium carbonate, ammonia and the like can be used. Sodium oxide is preferred. The tin (II) compound and the alkali are added while adjusting the pH in the reactor to be 6 or less, preferably 3 to 6, more preferably 3.5 to 5.5. Add while adjusting. In the neutral vicinity where the pH is higher than 6, tin acid hydroxide (Sn 6 O 4 (OH) 4 ) is likely to be formed, and this is not a flaky shape. Moreover, although it may become flat form when pH is 9 or more, this has a thickness larger than 5 micrometers.
The method of adding the tin (II) compound and the alkali includes adding the tin (II) compound to the reactor in advance and then adding the alkali, adding the alkali to the reactor in advance and then adding the tin (II) compound, An example is a method in which a tin (II) compound and an alkali are simultaneously added to a reactor. One of these methods or a combination of two or more methods can be used, but it is preferable to add the tin (II) compound and the alkali simultaneously. The temperature of the reactor after the addition is preferably 50 ° C. or higher because hydrolysis of the tin (II) compound can be effectively advanced. After adding the tin (II) compound (or alkali) and raising the temperature to 50 ° C. or higher, the alkali (or tin (II) compound) may be added. After the temperature is set to 50 ° C. or higher, a tin (II) compound and an alkali may be added simultaneously, and the latter is preferred. A more preferable temperature is about 70 to 105 ° C., and a further preferable temperature is about 85 to 105 ° C.
The simultaneous and parallel addition refers to a method in which both of them are separately added to the reactor in small amounts continuously or intermittently. Specifically, it is preferable to add both at the same time over about 10 minutes to 10 hours.
It is preferable to ripen after adding the tin (II) compound and the alkali because the crystallinity of stannous oxide becomes higher. The aging temperature is preferably 50 ° C. or higher, more preferably about 70 to 105 ° C., and further preferably about 90 to 105 ° C. The aging time is preferably about 5 minutes to 6 hours. The hydrolysis reaction and aging may be performed in a non-oxidizing atmosphere such as nitrogen gas so that the valence of tin is kept to be bivalent, but can also be performed in ordinary air.
　前記のようにスズ（ＩＩ）化合物を加水分解して、酸化第一スズの結晶構造を有する酸化スズ粒子、特に薄片状酸化第一スズ粒子が得られる。その後、必要に応じて水溶液中に存在する不要な電解質を除去するため、洗浄する。洗浄に際しては生成した加水分解生成物を凝集させるためにｐＨ調整剤を添加する。用いるｐＨ調整剤としては、塩酸、硫酸等の無機酸や水酸化ナトリウム等のアルカリが挙げられる。洗浄後、必要に応じて、固液分離し、更に乾燥する。固液分離には、フィルタープレス、ロールプレス等の濾過器を用いることができ、また、乾燥にはバンド式ヒーター、バッチ式ヒーター、噴霧乾燥機等が用いられる。乾燥はスズの価数が２価を保つように窒素ガス等の非酸化性雰囲気で行ってもよいが、通常の大気中でも乾燥は可能である。乾燥の温度は５０～１２０℃の範囲が好ましい。更に、乾燥した後、必要に応じて焼成してもよく、１２０～５００℃の範囲の温度が好ましく、窒素、アルゴン、水素等の非酸化雰囲気下がより好ましい。乾燥後あるいは焼成後には、酸化スズ粒子の凝集程度に応じ、ハンマーミル、ピンミル等の衝撃粉砕機、ローラーミル、パルペライザー、解砕機等の摩砕粉砕機、ロールクラッシャー、ジョークラッシャー等の圧縮粉砕機、ジェットミル等の気流粉砕機等を用いて乾式粉砕を行ってもよい。 As described above, the tin (II) compound is hydrolyzed to obtain tin oxide particles having a stannous oxide crystal structure, particularly flaky stannous oxide particles. Thereafter, washing is performed as necessary to remove unnecessary electrolytes present in the aqueous solution. At the time of washing, a pH adjuster is added in order to aggregate the produced hydrolysis product. Examples of the pH adjuster used include inorganic acids such as hydrochloric acid and sulfuric acid, and alkalis such as sodium hydroxide. After washing, if necessary, it is separated into solid and liquid and further dried. A filter such as a filter press or a roll press can be used for solid-liquid separation, and a band heater, batch heater, spray dryer, or the like is used for drying. Drying may be performed in a non-oxidizing atmosphere such as nitrogen gas so that the valence of tin is kept to be bivalent, but drying is also possible in normal air. The drying temperature is preferably in the range of 50 to 120 ° C. Further, after drying, it may be fired as necessary, and a temperature in the range of 120 to 500 ° C. is preferable, and a non-oxidizing atmosphere such as nitrogen, argon, hydrogen or the like is more preferable. After drying or firing, depending on the degree of aggregation of the tin oxide particles, impact crushers such as hammer mill and pin mill, grinding crushers such as roller mill, pulverizer and crusher, compression crushers such as roll crusher and jaw crusher Alternatively, dry pulverization may be performed using an airflow pulverizer such as a jet mill.
　このようにして得られた酸化第一スズの結晶構造を有する酸化スズ粒子、特に薄片状酸化第一スズ粒子を焼成すると、酸化第二スズの結晶構造を有する酸化スズ粒子、特に薄片状第二酸化スズ粒子が得られ、好ましくは酸化スズの全部が酸化第二スズである薄片状酸化第二スズ粒子が得られる。焼成の温度は適宜設定することができるが、薄片状酸化第一スズ粒子が酸化第二スズに酸化される温度より高い温度であればよく、５００℃～１１００℃の範囲の温度が好ましい。より好ましくは６００～１０００℃の範囲である。焼成温度が前記範囲より高いと、生成する酸化第二スズ粒子間の焼結が進むため好ましくない。また、焼成の雰囲気は特に制限がないが、空気（大気）雰囲気が好ましい。焼成には、流動炉、静置炉、ロータリーキルン、トンネルキルン等の公知の加熱焼成炉を用いることができる。焼成の際には融剤、例えば塩化ナトリウム、塩化スズ等の塩素化合物を添加してもよい。焼成後、焼結の程度に応じ、ハンマーミル、ピンミル等の衝撃粉砕機、ローラーミル、パルペライザー、解砕機等の摩砕粉砕機、ロールクラッシャー、ジョークラッシャー等の圧縮粉砕機、ジェットミル等の気流粉砕機等を用いて乾式粉砕を行ってもよい。 When the thus obtained tin oxide particles having a crystal structure of stannous oxide, particularly flaky stannous oxide particles, are fired, tin oxide particles having a stannic oxide crystal structure, particularly flaky stannic dioxide, are obtained. Tin particles are obtained, preferably flaky stannic oxide particles in which all of the tin oxide is stannic oxide. The calcination temperature can be set as appropriate, but it may be higher than the temperature at which the flaky stannous oxide particles are oxidized to stannic oxide, and a temperature in the range of 500 ° C. to 1100 ° C. is preferred. More preferably, it is in the range of 600 to 1000 ° C. When the firing temperature is higher than the above range, sintering between the produced stannic oxide particles proceeds, which is not preferable. The firing atmosphere is not particularly limited, but an air (air) atmosphere is preferable. For firing, a known heating and firing furnace such as a fluidized furnace, a stationary furnace, a rotary kiln, or a tunnel kiln can be used. In firing, a fluxing agent, for example, a chlorine compound such as sodium chloride or tin chloride may be added. After firing, depending on the degree of sintering, impact pulverizers such as hammer mills and pin mills, roller pulverizers, milling pulverizers such as pulverizers, compression pulverizers such as roll crushers and jaw crushers, and air currents such as jet mills Dry pulverization may be performed using a pulverizer or the like.
　酸化スズ粒子に前記の無機元素を含ませるには、スズ（ＩＩ）化合物とアルカリとを反応させ、スズ（ＩＩ）化合物を加水分解する際に無機化合物を存在させて行うことが好ましく、なお、この時も反応器内のｐＨを６以下に維持するように添加する。具体的には、
（１）反応器に予め無機化合物を含有させた後に、スズ（ＩＩ）化合物とアルカリとを添加して、スズ（ＩＩ）化合物を加水分解する方法、
（２）スズ（ＩＩ）化合物とアルカリと無機化合物とを反応器に添加して、スズ（ＩＩ）化合物を加水分解する方法、この方法は、例えば、スズ（ＩＩ）化合物とアルカリと無機化合物とを別々に添加する方法、スズ（ＩＩ）化合物溶液に無機化合物を予め混合して添加する方法、アルカリに無機化合物を予め混合して添加する方法などを含む。
（３）スズ（ＩＩ）化合物とアルカリとを反応器に添加して、スズ（ＩＩ）化合物を加水分解した後に、無機化合物を添加する方法、などが挙げられる。
　また、別の方法として、酸化スズのスラリーに無機化合物を添加してもよく、スラリー中で無機化合物を中和し析出させて、酸化スズ粒子に無機元素を含ませるのがより好ましい。また、酸化スズの粉末に、無機化合物を添加し混合してもよい。
　酸化スズ粒子に無機元素を含ませた後、必要に応じて、濾過、洗浄し、乾燥してもよい。酸化第一スズの乾燥はスズの価数が２価を保つように窒素ガス等の非酸化性雰囲気で行ってもよいが、通常の大気中でも乾燥は可能である。酸化第二スズの乾燥は通常の大気中でよい。乾燥の温度は５０～１２０℃の範囲が好ましい。更に、乾燥した後、必要に応じて焼成してもよく、この焼成によりスズ元素の一部を無機元素で置換することができる。焼成温度は１２０～１１００℃の範囲が好ましく、雰囲気は空気（大気）雰囲気下が好ましく、窒素、アルゴン、水素等の非酸化雰囲気下がより好ましい。
　乾燥後あるいは焼成後には、酸化スズ粒子の凝集程度に応じ、ハンマーミル、ピンミル等の衝撃粉砕機、ローラーミル、パルペライザー、解砕機等の摩砕粉砕機、ロールクラッシャー、ジョークラッシャー等の圧縮粉砕機、ジェットミル等の気流粉砕機等を用いて乾式粉砕を行ってもよい。 In order to include the inorganic element in the tin oxide particles, it is preferable to react the tin (II) compound with an alkali and hydrolyze the tin (II) compound in the presence of the inorganic compound, At this time, addition is performed so that the pH in the reactor is maintained at 6 or less. In particular,
(1) A method of hydrolyzing a tin (II) compound by adding an inorganic compound in advance to a reactor and then adding a tin (II) compound and an alkali;
(2) A method in which a tin (II) compound, an alkali and an inorganic compound are added to a reactor to hydrolyze the tin (II) compound. This method includes, for example, a tin (II) compound, an alkali and an inorganic compound. Including a method of adding an inorganic compound in advance to a tin (II) compound solution, a method of adding an inorganic compound to an alkali, and the like.
(3) The method of adding an inorganic compound after adding a tin (II) compound and an alkali to a reactor, hydrolyzing a tin (II) compound, etc. are mentioned.
Further, as another method, an inorganic compound may be added to the tin oxide slurry, and it is more preferable that the inorganic compound is neutralized and precipitated in the slurry to contain the inorganic element in the tin oxide particles. Further, an inorganic compound may be added and mixed with the tin oxide powder.
After the tin oxide particles contain an inorganic element, they may be filtered, washed and dried as necessary. Although the stannous oxide may be dried in a non-oxidizing atmosphere such as nitrogen gas so that the valence of tin is kept to be divalent, it can be dried even in normal air. The drying of stannic oxide is good in normal air. The drying temperature is preferably in the range of 50 to 120 ° C. Furthermore, after drying, it may be fired as necessary, and a part of the tin element can be replaced with an inorganic element by this firing. The firing temperature is preferably in the range of 120 to 1100 ° C., and the atmosphere is preferably an air (air) atmosphere, and more preferably a non-oxidizing atmosphere such as nitrogen, argon or hydrogen.
After drying or firing, depending on the degree of aggregation of the tin oxide particles, impact crushers such as hammer mill and pin mill, grinding crushers such as roller mill, pulverizer and crusher, compression crushers such as roll crusher and jaw crusher Alternatively, dry pulverization may be performed using an airflow pulverizer such as a jet mill.
　酸化スズ粒子の表面に無機化合物及び／又は有機化合物を被覆するには、従来の表面処理方法を用いることができ、具体的には酸化スズのスラリーに無機化合物や有機化合物を添加し被覆するのが好ましく、スラリー中で無機化合物や有機化合物を中和し析出させて被覆するのがより好ましい。また、酸化スズの粉末に、無機化合物や有機化合物を添加し混合して被覆させてもよい。
　また、酸化スズ粒子の表面に導電性無機化合物を被覆するには、酸化スズのスラリーに導電性無機化合物となる化合物を添加し被覆するのが好ましく、スラリー中で導電性無機化合物となる化合物を中和あるいは加水分解し析出させて被覆するのがより好ましい。
　酸化スズ粒子の表面に無機化合物及び／又は有機化合物あるいは導電性無機化合物を被覆した後、必要に応じて、濾過、洗浄し、乾燥してもよい。酸化第一スズの乾燥はスズの価数が２価を保つように窒素ガス等の非酸化性雰囲気で行ってもよいが、通常の大気中でも乾燥は可能である。酸化第二スズの乾燥は通常の大気中でよい。乾燥の温度は５０～１２０℃の範囲が好ましい。更に、乾燥した後、必要に応じて焼成してもよく、焼成温度は１２０～１１００℃の範囲が好ましく、雰囲気は空気（大気）雰囲気下が好ましく、窒素、アルゴン、水素等の非酸化雰囲気下がより好ましい。
　乾燥後あるいは焼成後には、酸化スズ粒子の凝集程度に応じ、ハンマーミル、ピンミル等の衝撃粉砕機、ローラーミル、パルペライザー、解砕機等の摩砕粉砕機、ロールクラッシャー、ジョークラッシャー等の圧縮粉砕機、ジェットミル等の気流粉砕機等を用いて乾式粉砕を行ってもよい。 In order to coat the surface of the tin oxide particles with an inorganic compound and / or an organic compound, a conventional surface treatment method can be used. Specifically, an inorganic compound or an organic compound is added to the tin oxide slurry for coating. It is more preferable that the inorganic compound or the organic compound is neutralized and precipitated in the slurry and coated. In addition, an inorganic compound or an organic compound may be added to the tin oxide powder and mixed for coating.
Further, in order to coat the surface of the tin oxide particles with the conductive inorganic compound, it is preferable to add and coat the compound that becomes the conductive inorganic compound to the slurry of tin oxide, and the compound that becomes the conductive inorganic compound in the slurry. It is more preferable to coat by neutralization or hydrolysis and precipitation.
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 necessary. Although the stannous oxide may be dried in a non-oxidizing atmosphere such as nitrogen gas so that the valence of tin is kept to be divalent, it can be dried even in normal air. The drying of stannic oxide is good in normal air. The drying temperature is preferably in the range of 50 to 120 ° C. Further, after drying, it may be fired as necessary. The firing temperature is preferably in the range of 120 to 1100 ° C., the atmosphere is preferably an air (air) atmosphere, and a non-oxidizing atmosphere such as nitrogen, argon or hydrogen. Is more preferable.
After drying or firing, depending on the degree of aggregation of the tin oxide particles, impact crushers such as hammer mill and pin mill, grinding crushers such as roller mill, pulverizer and crusher, compression crushers such as roll crusher and jaw crusher Alternatively, dry pulverization may be performed using an airflow pulverizer such as a jet mill.
　前記の酸化スズ粒子を溶媒に分散させて、分散体とすることができる。酸化スズ粒子を分散する溶媒としては、水又はアルコール、ジメチルホルムアミド（ＤＭＦ）、ケトン等の有機溶媒、あるいはそれらの混合物を用いることができ、工業的には水を主体とする水性溶媒、あるいはジメチルホルムアミド（ＤＭＦ）、ケトンを用いるのが好ましい。ケトンとしてはアセトン、２－ブタノン、メチルエチルケトン等を例示することができる。分散体中の酸化スズ粒子の濃度は適宜設定することができるが、例えば０．１～１０ｇ／リットル程度が好ましい。また、分散性の改良のため、適時遠心分離機などを用いてもよい。
　また、前記の酸化スズ粒子を溶媒に分散させ樹脂バインダーを配合して、塗料とすることができる。樹脂バインダーとして具体的には、（１）無機系バインダー（（ａ）重合性ケイ素化合物（加水分解性シラン又はその加水分解生成物又はその部分縮合物、水ガラス、コロイダルシリカ、オルガノポリシロキサン等）、（ｂ）金属アルコキシド類等）、（２）有機系バインダー（アルキド系樹脂、アクリル系樹脂、ポリエステル系樹脂、エポキシ系樹脂、フッ素系樹脂、変性シリコーン系樹脂）等が挙げられる。
　前記の分散体や塗料には、酸化スズ粒子、溶媒、樹脂バインダー以外にも、本発明の効果を阻害しない範囲で、分散剤、ｐＨ調整剤、消泡剤、乳化剤、着色剤、増量剤、防カビ剤、硬化助剤、増粘剤等の各種添加剤、充填剤等が第三成分として含まれていてもよい。分散剤としては、（１）界面活性剤（（ａ）アニオン系（カルボン酸塩、硫酸エステル塩、スルホン酸塩、リン酸エステル塩等）、（ｂ）カチオン系（アルキルアミン塩、アルキルアミンの４級アンモニウム塩、芳香族４級アンモニウム塩、複素環４級アンモニウム塩等）、（ｃ）両性（ベタイン型、アミノ酸型、アルキルアミンオキシド、含窒素複素環型等）、（ｄ）ノニオン系（エーテル型、エーテルエステル型、エステル型、含窒素型等）等、（２）シリコーン系分散剤（アルキル変性ポリシロキサン、ポリオキシアルキレン変性ポリシロキサン等）、（３）リン酸塩系分散剤（リン酸ナトリウム、ピロリン酸ナトリウム、オルトリン酸ナトリウム、メタリン酸ナトリウム、トリポリリン酸ナトリウム等）、（４）アルカノールアミン類（アミノメチルプロパノール、アミノメチルプロパンジオール等）等が挙げられる。分散体や塗料中の酸化スズ粒子の配合量、その他の添加剤の配合量等は適宜設定することができる。 The tin oxide particles can be dispersed in a solvent to obtain a dispersion. As the solvent for dispersing the tin oxide particles, water, an organic solvent such as alcohol, dimethylformamide (DMF), ketone, or a mixture thereof can be used, and industrially, an aqueous solvent mainly composed of water, or dimethyl It is preferable to use formamide (DMF) or a ketone. Examples of the ketone include acetone, 2-butanone, methyl ethyl ketone, and the like. The concentration of the tin oxide particles in the dispersion can be set as appropriate, but is preferably about 0.1 to 10 g / liter, for example. In addition, a centrifuge may be used in a timely manner for improving dispersibility.
Moreover, the said tin oxide particle can be disperse | distributed to a solvent, a resin binder can be mix | blended, and it can be set as a coating material. Specifically, (1) inorganic binder ((a) polymerizable silicon compound (hydrolyzable silane or hydrolysis product thereof or partial condensate thereof, water glass, colloidal silica, organopolysiloxane, etc.) (B) metal alkoxides, etc.) and (2) organic binders (alkyd resins, acrylic resins, polyester resins, epoxy resins, fluorine resins, modified silicone resins) and the like.
In addition to the tin oxide particles, the solvent, and the resin binder, the dispersion and the coating material described above are within a range that does not impair the effects of the present invention. Various additives such as fungicides, curing aids, thickeners, fillers and the like may be included as the third component. Dispersants include (1) surfactants ((a) anionic (carboxylates, sulfates, sulfonates, phosphates, etc.), (b) cationics (alkylamine salts, alkylamines) Quaternary ammonium salt, aromatic quaternary ammonium salt, heterocyclic quaternary ammonium salt, etc.), (c) amphoteric (betaine type, amino acid type, alkylamine oxide, nitrogen-containing heterocyclic type, etc.), (d) nonionic type ( Ether type, ether ester type, ester type, nitrogen-containing type, etc.) (2) Silicone dispersant (alkyl modified polysiloxane, polyoxyalkylene modified polysiloxane, etc.), (3) Phosphate dispersant (phosphorus) Acid sodium, sodium pyrophosphate, sodium orthophosphate, sodium metaphosphate, sodium tripolyphosphate, etc.), (4) alkanolamine (Aminomethyl propanol, aminomethyl propanediol, etc.) The amount of the tin oxide particles and the like. Dispersion and in the paint, the blending amount of the other additives can be appropriately set.
　前記のスズ（ＩＩ）化合物を加水分解して得た生成物（薄片状酸化第一スズ粒子）は、製造した状態でも薄片状酸化スズ粒子が分散した状態であるため、そのまま薄片状酸化スズ粒子を含む分散体として用いてもよく、あるいは、その後に固液分離した薄片状酸化スズ粒子を溶媒に再分散させて用いてもよい。また、乾燥した粉末、焼成した粉末、無機元素を含ませた粉末、表面被覆処理した粉末あるいは粉砕した粉末、特に薄片状酸化第二スズ粒子のこれらの粉末を溶媒に再分散させてもよい。再分散は、通常の撹拌機、コロイドミル、ボールミル、ビーズミル、超音波等の分散機を用いることができ、その際に、上記の第三成分を添加することができる。また、分散性の改良のため、適時遠心分離機などを用いてもよい。 Since the product (flaky stannous oxide particles) obtained by hydrolyzing the tin (II) compound is in a state in which the flaky tin oxide particles are dispersed even in the produced state, the flaky tin oxide particles are used as they are. Alternatively, the flaky tin oxide particles solid-liquid separated thereafter may be redispersed in a solvent and used. Alternatively, the dried powder, the fired powder, the powder containing an inorganic element, the surface-coated powder, or the pulverized powder, particularly these flaky stannic oxide particles, may be redispersed in a solvent. The redispersion can be performed by using a usual disperser such as a stirrer, a colloid mill, a ball mill, a bead mill, or an ultrasonic wave, and at this time, the third component can be added. In addition, a centrifuge may be used in a timely manner for improving dispersibility.
　このような分散体や塗料は、長期保存安定性に優れており、基材にコートし、乾燥あるいは焼成することにより酸化スズ膜を得ることができる。基材にコートする方法としては、スピンコート、スプレー塗装、ローラーコート、ディップコート、フローコート、ナイフコート、静電塗装、バーコート、ダイコート、ハケ塗り、液滴を滴下する方法等、一般的な方法を制限なく用いることができる。膜厚をより厚くするのであれば、重ね塗りを行ってもよい。コートしたものから溶媒を除去すれば酸化スズ膜が成膜する。成膜は室温～８００℃の範囲の温度で行うのが好ましい。より好ましい温度は、溶媒の沸点によるが、例えば、水性溶媒であれば室温～１５０℃の範囲が好ましく、更に好ましくは１００～１５０℃の範囲である。 Such a dispersion or paint is excellent in long-term storage stability, and a tin oxide film can be obtained by coating a substrate and drying or baking. As a method for coating the substrate, general methods such as spin coating, spray coating, roller coating, dip coating, flow coating, knife coating, electrostatic coating, bar coating, die coating, brush coating, and a method of dropping droplets are common. The method can be used without limitation. If the film thickness is to be increased, overcoating may be performed. If the solvent is removed from the coated material, a tin oxide film is formed. The film formation is preferably performed at a temperature ranging from room temperature to 800 ° C. The more preferable temperature depends on the boiling point of the solvent. For example, in the case of an aqueous solvent, the temperature is preferably in the range of room temperature to 150 ° C, more preferably in the range of 100 to 150 ° C.
　また、酸化スズ粒子は樹脂と混合して、前記のように塗料、インキ等の液状樹脂組成物とすることもでき、あるいは、酸化スズ粒子を樹脂中に混合してプラスチック成形体、シート、フィルム等の固体樹脂組成物とすることもできる。このような樹脂としては前記の樹脂バインダーや生分解性樹脂、紫外線硬化性樹脂、熱硬化性樹脂等を適宜用いることができ、酸化スズ粒子の配合量、その他の添加剤の配合量等は適宜設定することができる。 In addition, tin oxide particles can be mixed with a resin to form a liquid resin composition such as paint or ink as described above, or tin oxide particles can be mixed into a resin to form a plastic molded body, sheet or film. It can also be set as a solid resin composition. As such a resin, the above-mentioned resin binder, biodegradable resin, ultraviolet curable resin, thermosetting resin and the like can be used as appropriate. The amount of tin oxide particles, the amount of other additives, etc. Can be set.
　前記の酸化スズ粒子は種々の機能性材料用途に用いることができる。例えば、導電性フィラー、触媒、触媒担体、ガスセンサー、光触媒、赤外線遮蔽剤、セラミックス・金属の添加剤、研磨材等にも用いられる。酸化スズ粒子は、（１０１）面の結晶性が高い、あるいは、薄片状の粒子形状を有するために、導電性フィラー、触媒、触媒担体、ガスセンサーに好適に用いることができる。導電性フィラーとしては帯電防止剤、電極材料等に用いることができる。触媒としては、プロピレン酸化によるアクロレイン生成の酸化触媒、アンモニアによるＮＯの選択的還元触媒等に用いることができ、触媒担体としてはメタンの酸化触媒用の担体等に用いることができる。また、ガスセンサーとしては、可燃性ガス警報器などとして使用され、ガス検出感度が高く微量のＣＯやＨ２Ｓなどの測定にも用いられる。
　また、酸化スズ膜は種々の機能性材料用途に用いることができる。例えば、透明性材料、導電膜、電気抵抗体、電極、ガスセンサーに使用されるほかに、ガラス基板上に酸化スズ膜等を形成して導電性酸化物コートガラス、熱線反射ガラス、低放射ガラス、電熱ガラスなどに使用される。また、光触媒性材料、反射防止材料、ガスバリヤー性材料等にも用いることができる。これらの用途への使用は従来から用いられている形態、担持状態、配合割合に応じて酸化スズ粒子、酸化スズ膜等を適用すればよく、例えば光触媒として用いる場合は、酸化スズのバンドギャップ以上のエネルギーを有する波長の光を照射して、有害物質、悪臭物質、汚れ等を除去したり、超親水性効果による防汚、防曇作用等を活用したりすることができる。 The tin oxide particles can be used for various functional material applications. For example, it is also used for conductive fillers, catalysts, catalyst carriers, gas sensors, photocatalysts, infrared shielding agents, ceramic / metal additives, abrasives, and the like. Since the tin oxide particles have a high crystallinity on the (101) plane or have a flaky particle shape, they can be suitably used for conductive fillers, catalysts, catalyst carriers, and gas sensors. As an electrically conductive filler, it can use for an antistatic agent, an electrode material, etc. The catalyst can be used as an oxidation catalyst for acrolein generation by propylene oxidation, a selective reduction catalyst for NO with ammonia, or the like, and the catalyst carrier can be used as a carrier for an oxidation catalyst of methane. Further, as the gas sensor is used as a flammable gas detector is used to measure such as CO and H 2 S in the high trace gas detection sensitivity.
The tin oxide film can be used for various functional material applications. For example, in addition to being used for transparent materials, conductive films, electrical resistors, electrodes, gas sensors, tin oxide films, etc. are formed on glass substrates to form conductive oxide coated glass, heat ray reflective glass, low radiation glass Used for electrothermal glass. It can also be used for photocatalytic materials, antireflection materials, gas barrier materials and the like. For use in these applications, it is only necessary to apply tin oxide particles, tin oxide film, etc. according to the form, loading state, and blending ratio conventionally used. For example, when used as a photocatalyst, the band gap of tin oxide or more It is possible to remove harmful substances, malodorous substances, dirt, and the like by irradiating light with a wavelength having the energy of, and to utilize antifouling and antifogging effects due to the superhydrophilic effect.
　以下、本発明を実施例により説明するが、本発明はそれら実施例に限定されるものではない。 Hereinafter, the present invention will be described by way of examples, but the present invention is not limited to these examples.
　実施例１
　塩化第一スズ２水和物（ＳｎＣｌ２・２Ｈ２Ｏ試薬）８．６３ｇを３５％塩酸水溶液１５．６ｇ中に溶解した。この溶解液に純水を１４．８ｇ添加して濃度調整を行い、塩化第一スズ水溶液を得た。
　次に、９０℃の純水０．５リットル中に上記の塩化第一スズ水溶液と５規定の水酸化ナトリウム水溶液をｐＨ５±０．２を維持しながら３０分かけて同時添加を行い、添加後、１０分間熟成した。その後、３規定の塩酸水溶液を用いてｐＨを３．０とし、５分間撹拌放置して洗浄を開始した。濾液比抵抗値が１０万Ωｃｍとなった時点で洗浄を中止し、得られたケーキを大気中１０５℃で一晩放置して、乾燥した。乾燥物をメノウ乳鉢で手粉砕を行い、本発明の薄片状酸化スズ粒子（試料Ａ）を得た。
　試料ＡのＸ線回折測定（リガク社製　Ｘ線回折装置　RINT-1200）を行い、そのＸ線回折プロファイルを図１に示した。図１に示されるように試料Ａは酸化第一スズの（１１０）面に対する（１０１）面のピーク強度比が１．０以上であるような薄片状酸化第一スズに特有のＸ線回折プロファイルを有していた。試料Ａの走査型電子顕微鏡写真を図２に示した。図２から最長幅及び最短幅がそれぞれ０．０５～４０μｍの範囲にあり、厚みが０．００５～２μｍの範囲にある薄片状粒子であることがわかった。なお、各試料の薄片状の厚みについては別の高倍率の電子顕微鏡写真より測定した。 Example 1
8.63 g of stannous chloride dihydrate (SnCl 2 .2H 2 O reagent) was dissolved in 15.6 g of 35% aqueous hydrochloric acid. The concentration was adjusted by adding 14.8 g of pure water to the solution to obtain a stannous chloride aqueous solution.
Next, the above stannous chloride aqueous solution and 5N sodium hydroxide aqueous solution were added simultaneously in 0.5 liters of pure water at 90 ° C. over 30 minutes while maintaining pH 5 ± 0.2. Aged for 10 minutes. Thereafter, the pH was adjusted to 3.0 using a 3N hydrochloric acid aqueous solution, and the mixture was left stirring for 5 minutes to start washing. When the specific resistance value of the filtrate reached 100,000 Ωcm, washing was stopped, and the resulting cake was left in the atmosphere at 105 ° C. overnight and dried. The dried product was manually pulverized in an agate mortar to obtain flaky tin oxide particles (sample A) of the present invention.
An X-ray diffraction measurement (X-ray diffractometer RINT-1200, manufactured by Rigaku Corporation) of Sample A was performed, and the X-ray diffraction profile thereof is shown in FIG. As shown in FIG. 1, sample A has an X-ray diffraction profile peculiar to flaky stannous oxide in which the peak intensity ratio of (101) plane to (110) plane of stannous oxide is 1.0 or more. Had. A scanning electron micrograph of Sample A is shown in FIG. From FIG. 2, it was found that the flaky particles had a longest width and a shortest width in the range of 0.05 to 40 μm and a thickness in the range of 0.005 to 2 μm. The flaky thickness of each sample was measured from another high-magnification electron micrograph.
　実施例２
　実施例１で得られた試料Ａを、大気中９００℃の温度で１時間焼成して、本発明の薄片状酸化スズ粒子（試料Ｂ）を得た。
　試料ＢのＸ線回折測定を行い、そのＸ線回折プロファイルを図３に示した。図３に示されるように試料Ｂは、後述の比較例２で得られた試料Ｙとは異なり、（１１０）面に対する（１０１）面のピーク強度比が１．０以上であるような薄片状酸化第二スズに特有のＸ線回折プロファイルを有していた。試料Ｂの走査型電子顕微鏡写真を図４に示した。図４より、薄片形状を焼成後も維持しており、最長幅及び最短幅がそれぞれ０．０５～４０μｍの範囲にあり、厚みが０．００５～２μｍの範囲にある薄片状粒子であることがわかった。 Example 2
The sample A obtained in Example 1 was baked for 1 hour at a temperature of 900 ° C. in the air to obtain flaky tin oxide particles (sample B) of the present invention.
The X-ray diffraction measurement of Sample B was performed, and the X-ray diffraction profile thereof is shown in FIG. As shown in FIG. 3, the sample B, unlike the sample Y obtained in Comparative Example 2 described later, has a flaky shape in which the peak intensity ratio of the (101) plane to the (110) plane is 1.0 or more It had an X-ray diffraction profile unique to stannic oxide. A scanning electron micrograph of Sample B is shown in FIG. From FIG. 4, the flake shape is maintained after firing, and 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. all right.
　実施例３
　塩化第一スズ２水和物（ＳｎＣｌ２・２Ｈ２Ｏ、和光純薬工業社製）１７．４５ｇを３５％塩酸水溶液１９．４６ｇ中に溶解した。この溶解液に純水を１８．５４ｇ添加して濃度調整を行い、塩化第一スズ水溶液を得た。
　次に、９０℃の純水０．５リットル中に上記の塩化第一スズ水溶液と５規定の水酸化ナトリウム水溶液をｐＨ４±０．２を維持しながら２０分かけて同時添加を行い、添加後、１０分間熟成した。その後、３規定の塩酸水溶液を用いてｐＨを３．０とし、５分間撹拌放置して洗浄を開始した。濾液比抵抗値が１万５０００Ωｃｍとなった時点で洗浄を中止し、得られたケーキを大気中１０５℃で一晩放置して、乾燥した。乾燥物をメノウ乳鉢で手粉砕を行い、本発明の薄片状酸化スズ粒子（試料Ｃ）を得た。
　試料Ｃを走査型電子顕微鏡で観察したところ、最長幅及び最短幅がそれぞれ０．０５～４０μｍの範囲にあり、厚みが０．００５～２μｍの範囲にある薄片状粒子であることがわかった。また、Ｘ線回折測定を行ったところ、酸化第一スズの（１１０）面に対する（１０１）面のピーク強度比が１．０以上であるような薄片状酸化第一スズに特有のＸ線回折プロファイルを有していた。 Example 3
17.45 g of stannous chloride dihydrate (SnCl 2 .2H 2 O, manufactured by Wako Pure Chemical Industries, Ltd.) was dissolved in 19.46 g of 35% hydrochloric acid aqueous solution. The concentration was adjusted by adding 18.54 g of pure water to the solution to obtain a stannous chloride aqueous solution.
Next, the above stannous chloride aqueous solution and 5N sodium hydroxide aqueous solution were simultaneously added to 0.5 liter of pure water at 90 ° C. over 20 minutes while maintaining pH 4 ± 0.2. Aged for 10 minutes. Thereafter, the pH was adjusted to 3.0 using a 3N hydrochloric acid aqueous solution, and the mixture was left stirring for 5 minutes to start washing. When the filtrate specific resistance value reached 15,000 Ωcm, washing was stopped, and the obtained cake was left in the atmosphere at 105 ° C. overnight to dry. The dried product was manually pulverized in an agate mortar to obtain flaky tin oxide particles (sample C) of the present invention.
When sample C was observed with a scanning electron microscope, it was found to be flaky particles having a longest width and a shortest width in the range of 0.05 to 40 μm and a thickness in the range of 0.005 to 2 μm. Further, when X-ray diffraction measurement was performed, X-ray diffraction specific to flaky stannous oxide in which the peak intensity ratio of (101) plane to (110) plane of stannous oxide was 1.0 or more. Had a profile.
　実施例４
　実施例３で得られた試料Ｃをアルミナルツボに２．０ｇ取り、大気中で９００℃、２時間焼成を行って、本発明の薄片状酸化スズ粒子（試料Ｄ）を得た。
　試料Ｄの走査型電子顕微鏡写真を図５に示した。図５より、最長幅及び最短幅がそれぞれ０．０５～４０μｍの範囲にあり、厚みが０．００５～２μｍの範囲にある薄片状粒子であることがわかった。また、Ｘ線回折測定を行ったところ、実施例２と同様、薄片状酸化第二スズに特有のＸ線回折プロファイルを有しており、（１０１）面／（１１０）面のピーク強度比は６．２であった。 Example 4
2.0 g of the sample C obtained in Example 3 was taken in an alumina crucible and baked in the atmosphere at 900 ° C. for 2 hours to obtain flaky tin oxide particles (sample D) of the present invention.
A scanning electron micrograph of Sample D is shown in FIG. From FIG. 5, it was found that the longest width and the shortest width were each in the range of 0.05 to 40 μm and the thickness was in the range of 0.005 to 2 μm. Moreover, when X-ray diffraction measurement was performed, it had an X-ray diffraction profile peculiar to flaky stannic oxide as in Example 2, and the peak intensity ratio of (101) plane / (110) plane was 6.2.
　実施例５
　実施例３で得られた乾燥物２．０ｇと塩化ナトリウム０．４ｇをメノウ乳鉢でゆっくりと手粉砕を行い、その中からアルミナルツボに２．０ｇ取り、大気中で９００℃、２時間焼成を行い、本発明の薄片状酸化スズ粉末（試料Ｅ）を得た。
　試料Ｅの走査型電子顕微鏡写真を図６に示した。図６より、最長幅が０．５～６μｍ程度の薄片状粒子であることがわかった。厚みは高倍率の電子顕微鏡写真より０．０８～２．０μｍ程度であった。また、Ｘ線回折測定を行ったところ、実施例２と同様、薄片状酸化第二スズに特有のＸ線回折プロファイルを有しており、（１０１）面／（１１０）面のピーク強度比は２．０であった。 Example 5
Slowly hand-pulverize 2.0 g of the dried product obtained in Example 3 and 0.4 g of sodium chloride in an agate mortar, take 2.0 g of the mixture in an alumina crucible, and bake at 900 ° C. for 2 hours in the air. The flaky tin oxide powder (sample E) of the present invention was obtained.
A scanning electron micrograph of Sample E is shown in FIG. From FIG. 6, it was found that the flaky particles had a longest width of about 0.5 to 6 μm. The thickness was about 0.08 to 2.0 μm from a high-magnification electron micrograph. Moreover, when X-ray diffraction measurement was performed, it had an X-ray diffraction profile peculiar to flaky stannic oxide as in Example 2, and the peak intensity ratio of (101) plane / (110) plane was 2.0.
　実施例６
　実施例３で得られた乾燥物２．０ｇと塩化第一スズ０．４ｇをメノウ乳鉢でゆっくりと手粉砕を行い、その中からアルミナルツボに２．０ｇ取り、大気中で９００℃、２時間焼成を行い、本発明の薄片状酸化スズ粉末（試料Ｆ）を得た。
　試料Ｆの走査型電子顕微鏡写真を図７に示した。図７より、最長幅が０．１～０．５μｍ程度の微小薄片状粒子であることがわかった。厚みは高倍率の電子顕微鏡写真より０．０５～１．５μｍ程度であった。また、Ｘ線回折測定を行ったところ、実施例２と同様、薄片状酸化第二スズに特有のＸ線回折プロファイルを有しており、（１０１）面／（１１０）面のピーク強度比は１．０であった。 Example 6
2.0 g of the dried product obtained in Example 3 and 0.4 g of stannous chloride were slowly pulverized by hand in an agate mortar, and 2.0 g was taken into an alumina crucible, and 900 ° C. in the atmosphere for 2 hours. Firing was performed to obtain a flaky tin oxide powder (sample F) of the present invention.
A scanning electron micrograph of Sample F is shown in FIG. From FIG. 7, it was found that they were fine flaky particles having a maximum width of about 0.1 to 0.5 μm. The thickness was about 0.05 to 1.5 μm from a high-magnification electron micrograph. Moreover, when X-ray diffraction measurement was performed, it had an X-ray diffraction profile peculiar to flaky stannic oxide as in Example 2, and the peak intensity ratio of (101) plane / (110) plane was 1.0.
　実施例７
　実施例３において同時添加時使用のアルカリ源を５規定の水酸化ナトリウムの代わりに、５％アンモニア水を使用する以外は実施例３と同様に操作を行い、本発明の薄片状酸化スズ粒子（試料Ｇ）を得た。
　試料Ｇを走査型電子顕微鏡で観察したところ、最長幅及び最短幅がそれぞれ０．０５～４０μｍの範囲にあり、厚みが０．００５～２μｍの範囲にある薄片状粒子であることがわかった。また、Ｘ線回折測定を行ったところ、酸化第一スズの（１１０）面に対する（１０１）面のピーク強度比が１．０以上であるような薄片状酸化第一スズに特有のＸ線回折プロファイルを有していた。 Example 7
The same procedure as in Example 3 was performed except that 5% aqueous ammonia was used instead of 5N sodium hydroxide as the alkali source used at the time of simultaneous addition in Example 3, and the flaky tin oxide particles ( Sample G) was obtained.
When the sample G was observed with a scanning electron microscope, it was found to be flaky particles having a longest width and a shortest width in the range of 0.05 to 40 μm and a thickness in the range of 0.005 to 2 μm. Further, when X-ray diffraction measurement was performed, X-ray diffraction specific to flaky stannous oxide in which the peak intensity ratio of (101) plane to (110) plane of stannous oxide was 1.0 or more. Had a profile.
　実施例８
　実施例７で得られた試料Ｇをアルミナルツボに２．０ｇ取り、大気中で９００℃、２時間焼成を行って、本発明の薄片状酸化スズ粒子（試料Ｈ）を得た。
　試料Ｈの走査型電子顕微鏡写真を図８に示した。図８より、最長幅及び最短幅がそれぞれ０．０５～４０μｍの範囲にあり、厚みが０．００５～２μｍの範囲にある薄片状粒子であることがわかった。また、Ｘ線回折測定を行ったところ、実施例２と同様、薄片状酸化第二スズに特有のＸ線回折プロファイルを有しており、（１０１）面／（１１０）面のピーク強度比は８．３であった。 Example 8
2.0 g of the sample G obtained in Example 7 was taken in an alumina crucible and baked in the atmosphere at 900 ° C. for 2 hours to obtain flaky tin oxide particles (sample H) of the present invention.
A scanning electron micrograph of Sample H is shown in FIG. From FIG. 8, it was found that the flaky particles had a longest width and a shortest width in the range of 0.05 to 40 μm, and a thickness in the range of 0.005 to 2 μm. Moreover, when X-ray diffraction measurement was performed, it had an X-ray diffraction profile peculiar to flaky stannic oxide as in Example 2, and the peak intensity ratio of (101) plane / (110) plane was It was 8.3.
　実施例９
　塩化第一スズ２水和物（ＳｎＣｌ２・２Ｈ２Ｏ、和光純薬工業社製）１７．４５ｇを３５％塩酸水溶液１９．４６ｇ中に溶解した。この溶解液に純水を１８．５４ｇ添加して濃度調整を行い、塩化第一スズ水溶液を得た。
　次に、９０℃の純水０．５リットル中に上記の塩化第一スズ水溶液とケイ酸ナトリウム溶液（水ガラス、ＳｉＯ２分；３５～３８％、試薬、関東化学社製）０．１４ｇを溶解させた５規定の水酸化ナトリウム水溶液をｐＨ４±０．２を維持しながら２０分かけて同時添加を行い、添加後、１０分間熟成した。その後、３規定の塩酸水溶液を用いてｐＨを３．０とし、５分間撹拌放置して洗浄を開始した。濾液比抵抗値が１万５０００Ωｃｍとなった時点で洗浄を中止し、得られたケーキを大気中１０５℃で一晩放置して、乾燥した。乾燥物をメノウ乳鉢で手粉砕を行い、本発明の薄片状酸化スズ粒子（試料Ｉ）を得た。
　試料Ｉを走査型電子顕微鏡で観察したところ、最長幅及び最短幅がそれぞれ０．０５～４０μｍの範囲にあり、厚みが０．００５～２μｍの範囲にある薄片状粒子であることがわかった。また、Ｘ線回折測定を行ったところ、酸化第一スズの（１１０）面に対する（１０１）面のピーク強度比が１．０以上であるような薄片状酸化第一スズに特有のＸ線回折プロファイルを有していた。 Example 9
17.45 g of stannous chloride dihydrate (SnCl 2 .2H 2 O, manufactured by Wako Pure Chemical Industries, Ltd.) was dissolved in 19.46 g of 35% hydrochloric acid aqueous solution. The concentration was adjusted by adding 18.54 g of pure water to the solution to obtain a stannous chloride aqueous solution.
Next, 0.14 g of the above stannous chloride aqueous solution and sodium silicate solution (water glass, SiO 2 min; 35 to 38%, reagent, manufactured by Kanto Chemical Co., Inc.) in 0.5 liter of pure water at 90 ° C. A dissolved 5N aqueous sodium hydroxide solution was added simultaneously over 20 minutes while maintaining pH 4 ± 0.2, and after the addition, the solution was aged for 10 minutes. Thereafter, the pH was adjusted to 3.0 using a 3N hydrochloric acid aqueous solution, and the mixture was left stirring for 5 minutes to start washing. When the filtrate specific resistance value reached 15,000 Ωcm, washing was stopped, and the obtained cake was left in the atmosphere at 105 ° C. overnight to dry. The dried product was manually pulverized in an agate mortar to obtain flaky tin oxide particles (sample I) of the present invention.
When the sample I was observed with a scanning electron microscope, it was found to be flaky particles having a longest width and a shortest width in the range of 0.05 to 40 μm and a thickness in the range of 0.005 to 2 μm. Further, when X-ray diffraction measurement was performed, X-ray diffraction specific to flaky stannous oxide in which the peak intensity ratio of (101) plane to (110) plane of stannous oxide was 1.0 or more. Had a profile.
　実施例１０
　実施例９で得られた試料Ｉをアルミナルツボに２．０ｇ取り、大気中で９００℃、２時間焼成を行って、本発明のケイ素（ＳｉＯ２に換算して０．５重量％）を含有した薄片状酸化スズ粒子（試料Ｊ）を得た。
　試料Ｊの走査型電子顕微鏡写真を図９に示した。図９より、最長幅及び最短幅がそれぞれ０．０５～４０μｍの範囲にあり、厚みが０．００５～２μｍの範囲にある薄片状粒子であることがわかった。また、Ｘ線回折測定を行ったところ、実施例２と同様、薄片状酸化第二スズに特有のＸ線回折プロファイルを有しており、（１０１）面／（１１０）面のピーク強度比は５．１であった。 Example 10
2.0 g of the sample I obtained in Example 9 was taken in an alumina crucible, fired at 900 ° C. for 2 hours in the atmosphere, and contained silicon of the present invention (0.5 wt% in terms of SiO 2 ). The obtained flaky tin oxide particles (Sample J) were obtained.
A scanning electron micrograph of Sample J is shown in FIG. From FIG. 9, it was found that the flaky particles had a longest width and a shortest width in the range of 0.05 to 40 μm and a thickness in the range of 0.005 to 2 μm. Moreover, when X-ray diffraction measurement was performed, it had an X-ray diffraction profile peculiar to flaky stannic oxide as in Example 2, and the peak intensity ratio of (101) plane / (110) plane was 5.1.
　実施例１１
　実施例９において、ケイ酸ナトリウム溶液０．１４ｇに代えて０．４７ｇを用いること以外は実施例９と同様に操作して、本発明の薄片状酸化スズ粒子（試料Ｋ）を得た。
　試料Ｋを走査型電子顕微鏡で観察したところ、最長幅及び最短幅がそれぞれ０．０５～４０μｍの範囲にあり、厚みが０．００５～２μｍの範囲にある薄片状粒子であることがわかった。また、Ｘ線回折測定を行ったところ、酸化第一スズの（１１０）面に対する（１０１）面のピーク強度比が１．０以上であるような薄片状酸化第一スズに特有のＸ線回折プロファイルを有していた。 Example 11
In Example 9, flaky tin oxide particles (sample K) of the present invention were obtained in the same manner as in Example 9 except that 0.47 g was used instead of 0.14 g of the sodium silicate solution.
When the sample K was observed with a scanning electron microscope, it was found to be flaky particles having a longest width and a shortest width in the range of 0.05 to 40 μm and a thickness in the range of 0.005 to 2 μm. Further, when X-ray diffraction measurement was performed, X-ray diffraction specific to flaky stannous oxide in which the peak intensity ratio of (101) plane to (110) plane of stannous oxide was 1.0 or more. Had a profile.
　実施例１２
　実施例１１で得られた試料Ｋをアルミナルツボに２．０ｇ取り、大気中で９００℃、２時間焼成を行って、本発明のケイ素（ＳｉＯ２に換算して１．６４重量％）を含有した薄片状酸化スズ粒子（試料Ｌ）を得た。
　試料Ｌの走査型電子顕微鏡写真を図１０に示した。図１０より、最長幅及び最短幅がそれぞれ０．０５～４０μｍの範囲にあり、厚みが０．００５～２μｍの範囲にある薄片状粒子であることがわかった。また、Ｘ線回折測定を行ったところ、実施例２と同様、薄片状酸化第二スズに特有のＸ線回折プロファイルを有しており、（１０１）面／（１１０）面のピーク強度比は６．２であった。 Example 12
2.0 g of the sample K obtained in Example 11 was taken in an alumina crucible and baked at 900 ° C. for 2 hours in the atmosphere to contain silicon of the present invention (1.64% by weight in terms of SiO 2 ). The obtained flaky tin oxide particles (sample L) were obtained.
A scanning electron micrograph of Sample L is shown in FIG. From FIG. 10, it was found that the flaky particles had a longest width and a shortest width in the range of 0.05 to 40 μm, and a thickness in the range of 0.005 to 2 μm. Moreover, when X-ray diffraction measurement was performed, it had an X-ray diffraction profile peculiar to flaky stannic oxide as in Example 2, and the peak intensity ratio of (101) plane / (110) plane was 6.2.
　実施例１３
　実施例９において、ケイ酸ナトリウム溶液０．１４ｇに代えて０．９１ｇを用いること以外は実施例９と同様に操作して、本発明の薄片状酸化スズ粒子（試料Ｍ）を得た。
　試料Ｍを走査型電子顕微鏡で観察したところ、最長幅及び最短幅がそれぞれ０．０５～４０μｍの範囲にあり、厚みが０．００５～２μｍの範囲にある薄片状粒子であることがわかった。また、Ｘ線回折測定を行ったところ、酸化第一スズの（１１０）面に対する（１０１）面のピーク強度比が１．０以上であるような薄片状酸化第一スズに特有のＸ線回折プロファイルを有していた。 Example 13
In Example 9, flaky tin oxide particles (sample M) of the present invention were obtained in the same manner as in Example 9 except that 0.91 g was used instead of 0.14 g of the sodium silicate solution.
When the sample M was observed with a scanning electron microscope, it was found to be flaky particles having a longest width and a shortest width in the range of 0.05 to 40 μm and a thickness in the range of 0.005 to 2 μm. Further, when X-ray diffraction measurement was performed, X-ray diffraction specific to flaky stannous oxide in which the peak intensity ratio of (101) plane to (110) plane of stannous oxide was 1.0 or more. Had a profile.
　実施例１４
　実施例１３で得られた試料Ｍをアルミナルツボに２．０ｇ取り、大気中で９００℃、２時間焼成を行って、本発明のケイ素（ＳｉＯ２に換算して３．２重量％）を含有した薄片状酸化スズ粒子（試料Ｎ）を得た。
　試料Ｎの走査型電子顕微鏡写真を図１１に示した。図１１より、最長幅及び最短幅がそれぞれ０．０５～４０μｍの範囲にあり、厚みが０．００５～２μｍの範囲にある薄片状粒子であることがわかった。また、Ｘ線回折測定を行ったところ、実施例２と同様、薄片状酸化第二スズに特有のＸ線回折プロファイルを有しており、（１０１）面／（１１０）面のピーク強度比は２．６であった。 Example 14
2.0 g of the sample M obtained in Example 13 was taken in an alumina crucible, fired at 900 ° C. for 2 hours in the atmosphere, and contained silicon of the present invention (3.2 wt% in terms of SiO 2 ). The obtained flaky tin oxide particles (sample N) were obtained.
A scanning electron micrograph of Sample N is shown in FIG. From FIG. 11, it was found that the flaky particles had a longest width and a shortest width in the range of 0.05 to 40 μm and a thickness in the range of 0.005 to 2 μm. Moreover, when X-ray diffraction measurement was performed, it had an X-ray diffraction profile peculiar to flaky stannic oxide as in Example 2, and the peak intensity ratio of (101) plane / (110) plane was 2.6.
　実施例１５
　実施例９において、ケイ酸ナトリウム溶液に代えてアルミン酸ナトリウム（Ａｌ２Ｏ３；３４～３９％）を０．１４ｇ使用する以外は実施例９と同様に操作して、本発明の薄片状酸化スズ粒子（試料Ｏ）を得た。
　試料Ｏを走査型電子顕微鏡で観察したところ、最長幅及び最短幅がそれぞれ０．０５～４０μｍの範囲にあり、厚みが０．００５～２μｍの範囲にある薄片状粒子であることがわかった。また、Ｘ線回折測定を行ったところ、酸化第一スズの（１１０）面に対する（１０１）面のピーク強度比が１．０以上であるような薄片状酸化第一スズに特有のＸ線回折プロファイルを有していた。 Example 15
In Example 9, the flaky oxidation of the present invention was carried out in the same manner as in Example 9 except that 0.14 g of sodium aluminate (Al 2 O 3 ; 34-39%) was used instead of the sodium silicate solution. Tin particles (sample O) were obtained.
When the sample O was observed with a scanning electron microscope, it was found to be flaky particles having a longest width and a shortest width in the range of 0.05 to 40 μm and a thickness in the range of 0.005 to 2 μm. Further, when X-ray diffraction measurement was performed, X-ray diffraction specific to flaky stannous oxide in which the peak intensity ratio of (101) plane to (110) plane of stannous oxide was 1.0 or more. Had a profile.
　実施例１６
　実施例１５で得られた試料Ｏをアルミナルツボに２．０ｇ取り、大気中で９００℃、２時間焼成を行って、本発明のアルミニウム（Ａｌ２Ｏ３に換算して０．５重量％）を含有した薄片状酸化スズ粒子（試料Ｐ）を得た。
　試料Ｐの走査型電子顕微鏡写真を図１２に示した。図１２より、最長幅及び最短幅がそれぞれ０．０５～４０μｍの範囲にあり、厚みが０．００５～２μｍの範囲にある薄片状粒子であることがわかった。また、Ｘ線回折測定を行ったところ、実施例２と同様、薄片状酸化第二スズに特有のＸ線回折プロファイルを有しており、（１０１）面／（１１０）面のピーク強度比は１０．９であった。 Example 16
2.0 g of the sample O obtained in Example 15 was taken in an alumina crucible and baked in the atmosphere at 900 ° C. for 2 hours to obtain aluminum of the present invention (0.5% by weight in terms of Al 2 O 3 ). Flaky tin oxide particles (sample P) were obtained.
A scanning electron micrograph of Sample P is shown in FIG. From FIG. 12, it was found that the flaky particles had a longest width and a shortest width in the range of 0.05 to 40 μm and a thickness in the range of 0.005 to 2 μm. Moreover, when X-ray diffraction measurement was performed, it had an X-ray diffraction profile peculiar to flaky stannic oxide as in Example 2, and the peak intensity ratio of (101) plane / (110) plane was 10.9.
　実施例１７
　塩化第一スズ２水和物（ＳｎＣｌ２・２Ｈ２Ｏ、和光純薬工業社製）１７．４５ｇ及び塩化アンチモン（ＳｂＣｌ３試薬、ナカライテスク社製)０．０２ｇを３５％塩酸水溶液１９．４６ｇ中に溶解した。この溶解液に純水を１８．５４ｇ添加して濃度調整を行い、塩化アンチモンを含む塩化第一スズ水溶液を得た。
　次に、９０℃の純水０．５リットル中に上記の塩化第一スズ水溶液と５規定の水酸化ナトリウム水溶液をｐＨ４±０．２を維持しながら２０分かけて同時添加を行い、添加後、１０分間熟成した。その後、３規定の塩酸水溶液を用いてｐＨを３．０とし、５分間撹拌放置して洗浄を開始した。濾液比抵抗値が１万５０００Ωｃｍとなった時点で洗浄を中止し、得られたケーキを大気中１０５℃で一晩放置して、乾燥した。乾燥物をメノウ乳鉢で手粉砕を行い、本発明の薄片状酸化スズ粒子（試料Ｑ）を得た。
　試料Ｑを走査型電子顕微鏡で観察したところ、最長幅及び最短幅がそれぞれ０．０５～４０μｍの範囲にあり、厚みが０．００５～２μｍの範囲にある薄片状粒子であることがわかった。また、Ｘ線回折測定を行ったところ、酸化第一スズの（１１０）面に対する（１０１）面のピーク強度比が１．０以上であるような薄片状酸化第一スズに特有のＸ線回折プロファイルを有していた。 Example 17
17.46 g of stannous chloride dihydrate (SnCl 2 .2H 2 O, manufactured by Wako Pure Chemical Industries) and 0.02 g of antimony chloride (SbCl 3 reagent, manufactured by Nacalai Tesque) 19.46 g of 35% aqueous hydrochloric acid solution Dissolved in. The concentration was adjusted by adding 18.54 g of pure water to the solution to obtain a stannous chloride aqueous solution containing antimony chloride.
Next, the above stannous chloride aqueous solution and 5N sodium hydroxide aqueous solution were simultaneously added to 0.5 liter of pure water at 90 ° C. over 20 minutes while maintaining pH 4 ± 0.2. Aged for 10 minutes. Thereafter, the pH was adjusted to 3.0 using a 3N hydrochloric acid aqueous solution, and the mixture was left stirring for 5 minutes to start washing. When the filtrate specific resistance value reached 15,000 Ωcm, washing was stopped, and the obtained cake was left in the atmosphere at 105 ° C. overnight to dry. The dried product was manually pulverized in an agate mortar to obtain flaky tin oxide particles (sample Q) of the present invention.
When the sample Q was observed with a scanning electron microscope, it was found to be flaky particles having a longest width and a shortest width in the range of 0.05 to 40 μm, and a thickness in the range of 0.005 to 2 μm. Further, when X-ray diffraction measurement was performed, X-ray diffraction specific to flaky stannous oxide in which the peak intensity ratio of (101) plane to (110) plane of stannous oxide was 1.0 or more. Had a profile.
　実施例１８
　実施例１７で得られた試料Ｑをアルミナルツボに２．０ｇ取り、大気中で９００℃、２時間焼成を行って、本発明のアンチモン（Ｓｂ２Ｏ５に換算して０．５重量％）をドープした薄片状酸化スズ粒子（試料Ｒ）を得た。
　試料Ｒの走査型電子顕微鏡写真を図１３に示した。図１３より、最長幅及び最短幅がそれぞれ０．０５～４０μｍの範囲にあり、厚みが０．００５～２μｍの範囲にある薄片状粒子であることがわかった。また、Ｘ線回折測定を行ったところ、実施例２と同様、薄片状酸化第二スズに特有のＸ線回折プロファイルを有しており、（１０１）面／（１１０）面のピーク強度比は１．３であった。 Example 18
2.0 g of the sample Q obtained in Example 17 was taken in an alumina crucible and fired in the atmosphere at 900 ° C. for 2 hours to obtain antimony of the present invention (0.5% by weight in terms of Sb 2 O 5 ). A flaky tin oxide particle doped with (sample R) was obtained.
A scanning electron micrograph of Sample R is shown in FIG. From FIG. 13, it was found that the flaky particles had a longest width and a shortest width in the range of 0.05 to 40 μm and a thickness in the range of 0.005 to 2 μm. Moreover, when X-ray diffraction measurement was performed, it had an X-ray diffraction profile peculiar to flaky stannic oxide as in Example 2, and the peak intensity ratio of (101) plane / (110) plane was 1.3.
　実施例１９
　塩化第一スズ２水和物（ＳｎＣｌ２・２Ｈ２Ｏ、和光純薬工業社製）１７．４５ｇ及びタングステン酸ナトリウム（Ｎａ２ＷＯ４・２Ｈ２Ｏ試薬、和光純薬工業社製）０．０４ｇを３５％塩酸水溶液１９．４６ｇ中に溶解した。この溶解液に純水を１８．５４ｇ添加して濃度調整を行い、タングステン酸ナトリウムを含む塩化第一スズ水溶液を得た。
　次に、９０℃の純水０．５リットル中に上記の塩化第一スズ水溶液と５規定の水酸化ナトリウム水溶液をｐＨ４±０．２を維持しながら２０分かけて同時添加を行い、添加後、１０分間熟成した。その後、３規定の塩酸水溶液を用いてｐＨを３．０とし、５分間撹拌放置して洗浄を開始した。濾液比抵抗値が１万５０００Ωｃｍとなった時点で洗浄を中止し、得られたケーキを大気中１０５℃で一晩放置して、乾燥した。乾燥物をメノウ乳鉢で手粉砕を行い、本発明の薄片状酸化スズ粒子（試料Ｓ）を得た。
　試料Ｓを走査型電子顕微鏡で観察したところ、最長幅及び最短幅がそれぞれ０．０５～４０μｍの範囲にあり、厚みが０．００５～２μｍの範囲にある薄片状粒子であることがわかった。また、Ｘ線回折測定を行ったところ、酸化第一スズの（１１０）面に対する（１０１）面のピーク強度比が１．０以上であるような薄片状酸化第一スズに特有のＸ線回折プロファイルを有していた。 Example 19
Stannous chloride dihydrate (SnCl 2 · 2H 2 O, manufactured by Wako Pure Chemical Industries, Ltd.) 17.45 g and sodium tungstate (Na 2 WO 4 · 2H 2 O reagent, manufactured by Wako Pure Chemical Industries, Ltd.) 04 g was dissolved in 19.46 g of 35% aqueous hydrochloric acid. The concentration was adjusted by adding 18.54 g of pure water to this solution to obtain a stannous chloride aqueous solution containing sodium tungstate.
Next, the above stannous chloride aqueous solution and 5N sodium hydroxide aqueous solution were simultaneously added to 0.5 liter of pure water at 90 ° C. over 20 minutes while maintaining pH 4 ± 0.2. Aged for 10 minutes. Thereafter, the pH was adjusted to 3.0 using a 3N hydrochloric acid aqueous solution, and the mixture was left stirring for 5 minutes to start washing. When the filtrate specific resistance value reached 15,000 Ωcm, washing was stopped, and the obtained cake was left in the atmosphere at 105 ° C. overnight to dry. The dried product was manually pulverized in an agate mortar to obtain flaky tin oxide particles (sample S) of the present invention.
When the sample S was observed with a scanning electron microscope, it was found to be flaky particles having a longest width and a shortest width in the range of 0.05 to 40 μm and a thickness in the range of 0.005 to 2 μm. Further, when X-ray diffraction measurement was performed, X-ray diffraction specific to flaky stannous oxide in which the peak intensity ratio of (101) plane to (110) plane of stannous oxide was 1.0 or more. Had a profile.
　実施例２０
　実施例１９で得られた試料Ｓをアルミナルツボに２．０ｇ取り、大気中で９００℃、２時間焼成を行って、本発明のタングステン（ＷＯ３に換算して１重量％）をドープした薄片状酸化スズ粒子（試料Ｔ）を得た。
　試料Ｔの走査型電子顕微鏡写真を図１４に示した。図１４より、最長幅及び最短幅がそれぞれ０．０５～４０μｍの範囲にあり、厚みが０．００５～２μｍの範囲にある薄片状粒子であることがわかった。また、前記と同様にＸ線回折測定を行ったところ、実施例２と同様、薄片状酸化第二スズに特有のＸ線回折プロファイルを有しており、（１０１）面／（１１０）面のピーク強度比は３．０であった。 Example 20
2.0 g of sample S obtained in Example 19 was taken in an alumina crucible, fired in the atmosphere at 900 ° C. for 2 hours, and doped with tungsten of the present invention (1 wt% in terms of WO 3 ). A tin oxide particle (sample T) was obtained.
A scanning electron micrograph of Sample T is shown in FIG. From FIG. 14, it was found that the flaky particles had a longest width and a shortest width in the range of 0.05 to 40 μm and a thickness in the range of 0.005 to 2 μm. Further, when X-ray diffraction measurement was performed in the same manner as described above, it had an X-ray diffraction profile peculiar to flaky stannic oxide as in Example 2, and the (101) plane / (110) plane The peak intensity ratio was 3.0.
　実施例２１
　実施例４で得られた試料Ｄを遠心粉砕機（レッチェ社製　遠心粉砕機ZM-100）で粉砕した後、その試料１０ｇを１Ｌの純水中に入れ、スラリー化を行なった。
　このスラリーを９０℃に昇温した後、塩化第二スズ（ＳｎＣｌ４・５Ｈ２Ｏ、試薬、和光純薬工業社製）２．３３ｇと塩化アンチモン（ＳｂＣｌ３、試薬、ナカライテスク社製）０．１４ｇを３規定塩酸水溶液に溶解した溶液と５規定の水酸化ナトリウム水溶液を、一定ｐＨを保ちながら、６０分にわたり同時添加を行った。更に熟成を６０分間行い、その後、脱水・洗浄し、乾燥した。乾燥した粉末をメノウ乳鉢で軽く粉砕した後、アルミナルツボに２．０ｇ仕込み、大気中で６５０℃、６０分間の焼成を行って、本発明のアンチモンドープ酸化スズを被覆した薄片状酸化スズ粒子（試料Ｕ）を得た。
　試料Ｕの走査型電子顕微鏡写真を図１５に示した。図１５より、最長幅及び最短幅がそれぞれ０．０５～４０μｍの範囲にあり、厚みが０．００５～２μｍの範囲にある薄片状粒子であることがわかった。また、前記と同様にＸ線回折測定を行ったところ、実施例２と同様、薄片状酸化第二スズに特有のＸ線回折プロファイルを有しており、（１０１）面／（１１０）面のピーク強度比は３．４であった。 Example 21
Sample D obtained in Example 4 was pulverized with a centrifugal pulverizer (centrifugal pulverizer ZM-100, manufactured by Lecce), and 10 g of the sample was placed in 1 L of pure water to form a slurry.
After this slurry was heated to 90 ° C., stannic chloride (SnCl 4 .5H 2 O, reagent, manufactured by Wako Pure Chemical Industries, Ltd.) 2.33 g and antimony chloride (SbCl 3 , reagent, manufactured by Nacalai Tesque) 0 A solution prepared by dissolving .14 g in a 3N aqueous hydrochloric acid solution and a 5N aqueous sodium hydroxide solution were simultaneously added over 60 minutes while maintaining a constant pH. Further aging was performed for 60 minutes, and then dehydration, washing and drying were performed. After the dried powder was lightly pulverized in an agate mortar, 2.0 g was charged into an alumina crucible, and baked at 650 ° C. for 60 minutes in the atmosphere to give flaky tin oxide particles coated with the antimony-doped tin oxide of the present invention ( Sample U) was obtained.
A scanning electron micrograph of Sample U is shown in FIG. From FIG. 15, it was found that the longest width and the shortest width are in the range of 0.05 to 40 μm, and the flaky particles have a thickness in the range of 0.005 to 2 μm. Further, when X-ray diffraction measurement was performed in the same manner as described above, it had an X-ray diffraction profile peculiar to flaky stannic oxide as in Example 2, and the (101) plane / (110) plane The peak intensity ratio was 3.4.
　実施例２２
　実施例４で得た試料Ｄを窒素雰囲気下９００℃、２時間の焼成を行って、本発明の薄片状酸化スズ粒子（試料Ｖ）を得た。
　試料Ｖの走査型電子顕微鏡写真から、最長幅及び最短幅がそれぞれ０．０５～４０μｍの範囲にあり、厚みが０．００５～２μｍの範囲にある薄片状粒子であることがわかった。また、Ｘ線回折測定を行ったところ、実施例４と同様、薄片状酸化第二スズに特有のＸ線回折プロファイルを有しており、（１０１）面／（１１０）面のピーク強度比は６．２であった。 Example 22
The sample D obtained in Example 4 was baked at 900 ° C. for 2 hours in a nitrogen atmosphere to obtain flaky tin oxide particles (sample V) of the present invention.
From the scanning electron micrograph of Sample V, it was found that the longest width and the shortest width were in the range of 0.05 to 40 μm and the flaky particles had a thickness in the range of 0.005 to 2 μm. Further, when X-ray diffraction measurement was performed, it had an X-ray diffraction profile peculiar to flaky stannic oxide as in Example 4, and the peak intensity ratio of (101) plane / (110) plane was 6.2.
　実施例２３
　実施例２２で得た試料Ｖ１ｇをらいかい機（石川工場社製石川式撹拌らいかい機AGA）で５分間粉砕して、酸化スズ粒子（試料Ｗ）を得た。
　試料Ｗの走査型電子顕微鏡写真から、不定形状の粒子であることがわかった。また、Ｘ線回折測定を行ったところ、酸化第二スズに特有のＸ線回折プロファイルを有しており、（１０１）面／（１１０）面のピーク強度比は３．１であった。 Example 23
The sample V1g obtained in Example 22 was pulverized for 5 minutes with a cracking machine (Ishikawa-type stirring cracker AGA manufactured by Ishikawa Factory Co., Ltd.) to obtain tin oxide particles (sample W).
From the scanning electron micrograph of the sample W, it was found that the particles were indefinitely shaped. Further, when X-ray diffraction measurement was performed, it had an X-ray diffraction profile peculiar to stannic oxide, and the peak intensity ratio of (101) plane / (110) plane was 3.1.
　比較例１
　塩化第二スズ５水和物（ＳｎＣｌ４・５Ｈ２Ｏ、和光純薬工業社製）２７．１２ｇを３５％塩酸水溶液１９．４６ｇ中に溶解した。この溶解液に純水を１８．５４ｇ添加して濃度調整を行い、塩化第二スズ水溶液を得た。
　次に、９０℃の純水０．５リットル中に上記の塩化第二スズ水溶液と５規定の水酸化ナトリウム水溶液をｐＨ４±０．２を維持しながら２０分かけて同時添加を行い、添加後、１０分間熟成した。その後、３規定の塩酸水溶液を用いてｐＨを３．０とし、５分間撹拌放置して洗浄を開始した。濾液比抵抗値が１万５０００Ωｃｍとなった時点で洗浄を中止し、得られたケーキを大気中１０５℃で一晩放置して、乾燥した。乾燥物をメノウ乳鉢で手粉砕を行い、酸化スズ粒子（試料Ｘ）を得た。
　試料Ｘを走査型電子顕微鏡で観察したところ、粒状であることがわかった。また、Ｘ線回折測定を行ったところ、アモルファス状態のＸ線回折プロファイルを有していた。 Comparative Example 1
Stannic pentahydrate (SnCl 4 · 5H 2 O, manufactured by Wako Pure Chemical Industries, Ltd.) chloride was dissolved 27.12g in 35% hydrochloric acid aqueous solution 19.46 g. The concentration was adjusted by adding 18.54 g of pure water to this solution to obtain an aqueous stannic chloride solution.
Next, the above stannic chloride aqueous solution and 5N aqueous sodium hydroxide solution were simultaneously added to 0.5 liter of pure water at 90 ° C. over 20 minutes while maintaining pH 4 ± 0.2. Aged for 10 minutes. Thereafter, the pH was adjusted to 3.0 using a 3N hydrochloric acid aqueous solution, and the mixture was left stirring for 5 minutes to start washing. When the filtrate specific resistance value reached 15,000 Ωcm, washing was stopped, and the obtained cake was left in the atmosphere at 105 ° C. overnight to dry. The dried product was manually pulverized in an agate mortar to obtain tin oxide particles (sample X).
When the sample X was observed with a scanning electron microscope, it was found to be granular. Further, when X-ray diffraction measurement was performed, it had an amorphous X-ray diffraction profile.
　比較例２
　比較例１で得られた試料Ｘをアルミナルツボに２．０ｇ取り、大気中で９００℃、２時間焼成を行って、酸化スズ粒子（試料Ｙ）を得た。
　試料Ｙの走査型電子顕微鏡写真を図１６に示した。図１６より、これが粒状であることがわかった。また、Ｘ線回折測定を行ったところ、粒状の酸化第二スズに特有のＸ線回折プロファイル（図３）を有しており、（１０１）面／（１１０）面のピーク強度比は０．８であった。 Comparative Example 2
2.0 g of the sample X obtained in Comparative Example 1 was taken in an alumina crucible and baked in the atmosphere at 900 ° C. for 2 hours to obtain tin oxide particles (sample Y).
A scanning electron micrograph of Sample Y is shown in FIG. From FIG. 16, it was found that this was granular. Further, when X-ray diffraction measurement was performed, it had an X-ray diffraction profile (FIG. 3) peculiar to granular stannic oxide, and the peak intensity ratio of (101) plane / (110) plane was 0. It was 8.
　比較例３
　比較例２で得た試料Ｙを窒素雰囲気下９００℃、２時間の焼成を行って、酸化スズ粒子（試料Ｚ）を得た。
　試料Ｚの走査型電子顕微鏡写真から、これが粒状であることがわかった。また、Ｘ線回折測定を行ったところ、粒状の酸化第二スズに特有のＸ線回折プロファイルを有しており、（１０１）面／（１１０）面のピーク強度比は０．８であった。 Comparative Example 3
The sample Y obtained in Comparative Example 2 was baked at 900 ° C. for 2 hours in a nitrogen atmosphere to obtain tin oxide particles (sample Z).
From the scanning electron micrograph of sample Z, it was found that this was granular. Moreover, when X-ray diffraction measurement was performed, it had an X-ray diffraction profile peculiar to granular stannic oxide, and the peak intensity ratio of (101) plane / (110) plane was 0.8. .
　前記の試料Ｄ、Ｒ、Ｔ、Ｕをそれぞれ１．０ｇ取り、銅電極に挟み込み、１００ｋｇ／ｃｍ２の圧力下、その粉体体積抵抗値（Ωｃｍ）の測定を行い（ヒューレットパッカード社製　multimeter 3457Aを使用し、下記式１により算出）、表１に示した。
式１：粉体体積抵抗値（Ωｃｍ）＝{体積抵抗値（測定値；Ω）×試料の面積（ｃｍ２）}／厚み（ｃｍ）
　アンチモンをドープした試料Ｒ、タングステンをドープした試料Ｔ、アンチモンドープ酸化スズで被覆した試料Ｕはいずれも粉体体積抵抗が試料Ｄよりも低くなり、導電性フィラーとして使用できることがわかった。 1.0 g of each of the above samples D, R, T, and U was taken and sandwiched between copper electrodes, and the volume resistivity (Ωcm) of the powder was measured under a pressure of 100 kg / cm 2 (multimeter 3457A manufactured by Hewlett-Packard Company) And calculated by the following formula 1).
Formula 1: Powder Volume Resistance Value (Ωcm) = {Volume Resistance Value (Measured Value; Ω) × Sample Area (cm 2 )} / Thickness (cm)
The sample R doped with antimony, the sample T doped with tungsten, and the sample U coated with antimony-doped tin oxide all had lower powder volume resistance than the sample D, and were found to be usable as conductive fillers.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　前記の試料Ｖ、Ｗ、Ｚのそれぞれ５．０ｇをアルミカップに入れ、８０℃の恒温乾燥機の中で４週間保管した。その後、上記の方法で粉体体積抵抗値（Ωｃｍ）の測定を行い、表２に示した。
　実施例２２の試料Ｖは、酸化第二スズを非酸化性雰囲気下で焼成したものであり、実施例２３の試料Ｗは試料Ｖを粉砕したものであるが、このようなものでも粉体体積抵抗値が低く、導電性フィラーとして使用できることがわかった。
　また、実施例２２、２３の試料Ｖ、Ｗは、初期の粉体体積抵抗値に対する４週間後の比率が低く、加温による体積抵抗の経時変化が低いことがわかった。この原因は、酸化第二スズの（１０１）面／（１１０）面のピーク強度比が１．０以上であることが原因と考えられ、ピーク強度比が高いほど体積抵抗比が低くなっていることがわかった。 5.0 g of each of the above samples V, W, and Z was put in an aluminum cup and stored in a constant temperature dryer at 80 ° C. for 4 weeks. Thereafter, the powder volume resistance value (Ωcm) was measured by the above method, and the results are shown in Table 2.
Sample V of Example 22 is obtained by firing stannic oxide in a non-oxidizing atmosphere, and Sample W of Example 23 is obtained by pulverizing Sample V. It was found that the resistance value was low and it could be used as a conductive filler.
In addition, it was found that Samples V and W of Examples 22 and 23 had a low ratio after 4 weeks with respect to the initial powder volume resistance value, and the change with time in volume resistance due to heating was low. This is considered to be because the peak intensity ratio of (101) plane / (110) plane of stannic oxide is 1.0 or more, and the volume resistance ratio is lower as the peak intensity ratio is higher. I understood it.
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　実施例２１で得た試料Ｕと比較試料ＥＴ－５００Ｗ（石原産業社製、アンチモン添加二酸化第二スズ被覆球状二酸化チタン)のそれぞれを２０ｇ、アクリディックＡ－１６５（大日本インキ化学工業社製）３０．６ｇ、トルエン／ｎ－ブタノール混合溶媒（トルエン：ｎ－ブタノール＝１：１重量比）２６．４ｇ及びガラスビーズ５０．０ｇを１４０ｍｌのマヨネーズ瓶にいれ、ペイントコンディショナー(Red-Devil社製)で２０分間の振盪を行った。
　次に、このマヨネーズ瓶から１５ｇの樹脂組成物を取り出し、この中に、アクリディックＡ－１６５（大日本インキ化学工業社製）１４．５ｇ及びトルエン／ｎ－ブタノール混合溶媒（トルエン：ｎ－ブタノール＝１：１重量比）４．６ｇを加え、更にペイントコンディショナー(Red-Devil社製)で３分間の振盪を行った。
　その後、隠ぺい力試験紙上にこれらの樹脂組成物を載せ、３ミルのアプリケーターを用いて塗布を行い、一晩室温にて自然乾燥を行った。
　これらの塗膜の表面抵抗値をハイレスターＵＰ（ダイヤインスツルメント社製)で測定した結果を表３に示す。これらの膜厚は１９μｍであった。
　実施例２１の試料Ｕは、アンチモン添加二酸化第二スズ被覆球状二酸化チタンに比べて、より低い表面抵抗値を示し、導電膜として使用できることがわかった。 20 g each of the sample U obtained in Example 21 and the comparative sample ET-500W (Ishihara Sangyo Co., Ltd., antimony-added stannic dioxide-coated spherical titanium dioxide), Acridic A-165 (Dainippon Ink Chemical Co., Ltd.) 30.6 g, 26.4 g of toluene / n-butanol mixed solvent (toluene: n-butanol = 1: 1 weight ratio) and 50.0 g of glass beads were put into a 140 ml mayonnaise bottle, and paint conditioner (manufactured by Red-Devil) And shaken for 20 minutes.
Next, 15 g of the resin composition was taken out from the mayonnaise bottle, and 14.5 g of Acrydic A-165 (manufactured by Dainippon Ink and Chemicals, Inc.) and a toluene / n-butanol mixed solvent (toluene: n-butanol) (= 1: 1 weight ratio) 4.6 g was added, and the mixture was further shaken with a paint conditioner (manufactured by Red-Devil) for 3 minutes.
Thereafter, these resin compositions were placed on a hiding power test paper, applied using a 3 mil applicator, and air-dried overnight at room temperature.
Table 3 shows the results of measuring the surface resistance values of these coating films with Hirestor UP (manufactured by Dia Instruments). Their film thickness was 19 μm.
The sample U of Example 21 showed a lower surface resistance value than the antimony-added stannic dioxide-coated spherical titanium dioxide, and was found to be usable as a conductive film.
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
　本発明の酸化スズ粒子は、導電性フィラーのほかに、触媒、触媒担体、ガスセンサー、光触媒、赤外線遮蔽剤、セラミックス・金属の添加剤、研磨材等にも用いられる。
　また、酸化スズ粒子を成膜した酸化スズ膜は、導電膜、電気抵抗体、電極、触媒、触媒担体、ガスセンサー、透明性材料のほかに、ガラス基板上に酸化スズ膜を形成して導電性酸化物コートガラス、熱線反射ガラス、低放射ガラス、電熱ガラスなどに使用される。また、光触媒性材料、反射防止材料、ガスバリヤー性材料等の種々の用途にも用いることができる。 In addition to the conductive filler, the tin oxide particles of the present invention are also used for catalysts, catalyst carriers, gas sensors, photocatalysts, infrared shielding agents, ceramics / metal additives, abrasives, and the like.
In addition to conductive films, electrical resistors, electrodes, catalysts, catalyst carriers, gas sensors, and transparent materials, tin oxide films on which tin oxide particles are formed can be made conductive by forming a tin oxide film on a glass substrate. Used for conductive oxide-coated glass, heat ray reflective glass, low radiation glass, electrothermal glass and the like. It can also be used for various applications such as photocatalytic materials, antireflection materials, and gas barrier materials.

Claims (27)

  1. 　粉末Ｘ線回折において、酸化スズの（１１０）面に対する（１０１）面のピーク強度比が１．０以上であることを特徴とする酸化スズ粒子。 Tin oxide particles, wherein the peak intensity ratio of the (101) plane to the (110) plane of tin oxide is 1.0 or more in powder X-ray diffraction.
  2. 　酸化スズが酸化第二スズ（ＳｎＯ２）の結晶構造を有することを特徴とする請求項１に記載の酸化スズ粒子。 The tin oxide particles according to claim 1, wherein the tin oxide has a crystal structure of stannic oxide (SnO 2 ).
  3. 　不定形状の粒子形状を有することを特徴とする請求項１又は２に記載の酸化スズ粒子。 The tin oxide particles according to claim 1, wherein the tin oxide particles have an indefinite shape.
  4. 　薄片状の粒子形状を有することを特徴とする請求項１又は２に記載の酸化スズ粒子。 The tin oxide particles according to claim 1, wherein the tin oxide particles have a flaky particle shape.
  5. 　酸化スズが酸化第一スズ（ＳｎＯ）の結晶構造を有し、しかも、薄片状の粒子形状を有することを特徴とする請求項１に記載の酸化スズ粒子。 The tin oxide particles according to claim 1, wherein the tin oxide has a crystal structure of stannous oxide (SnO) and has a flaky particle shape.
  6. 　薄片面の厚みが５μｍ以下であることを特徴とする請求項４又は５に記載の酸化スズ粒子。 The tin oxide particles according to claim 4 or 5, wherein the thickness of the thin piece surface is 5 µm or less.
  7. 　薄片面の最長幅及び最短幅がそれぞれ０．０５～４０μｍの範囲にあり、厚みが０．００５～２μｍの範囲にあることを特徴とする請求項４又は５に記載の酸化スズ粒子。 6. The tin oxide particles according to claim 4 or 5, wherein the longest width and the shortest width of the thin piece surface are each in the range of 0.05 to 40 μm and the thickness is in the range of 0.005 to 2 μm.
  8. 　スズ以外の無機元素を更に含むことを特徴とする請求項１～７のいずれか一項に記載の酸化スズ粒子。 The tin oxide particles according to any one of claims 1 to 7, further comprising an inorganic element other than tin.
  9. 　酸化スズ粒子の表面に無機化合物及び／又は有機化合物を被覆していることを特徴とする請求項１～８のいずれか一項に記載の酸化スズ粒子。 The tin oxide particles according to any one of claims 1 to 8, wherein the surface of the tin oxide particles is coated with an inorganic compound and / or an organic compound.
  10. 　酸化スズ粒子の表面に導電性無機化合物を被覆していることを特徴とする請求項９に記載の酸化スズ粒子。 The tin oxide particles according to claim 9, wherein the surface of the tin oxide particles is coated with a conductive inorganic compound.
  11. 　スズ（ＩＩ）化合物とアルカリとを、反応器内のｐＨを６以下に維持するように添加して、スズ（ＩＩ）化合物を加水分解することを特徴とする酸化スズ粒子の製造方法。 A method for producing tin oxide particles, wherein a tin (II) compound and an alkali are added so as to maintain the pH in the reactor at 6 or less to hydrolyze the tin (II) compound.
  12. 　５０℃以上の温度の水を入れた反応器に、スズ（ＩＩ）化合物とアルカリとを添加することを特徴とする請求項１１に記載の酸化スズ粒子の製造方法。 The method for producing tin oxide particles according to claim 11, wherein a tin (II) compound and an alkali are added to a reactor containing water having a temperature of 50 ° C or higher.
  13. 　スズ（ＩＩ）化合物とアルカリと無機化合物とを、反応器内のｐＨを６以下に維持するように添加して、スズ（ＩＩ）化合物を加水分解することを特徴とする酸化スズ粒子の製造方法。 A method for producing tin oxide particles, comprising adding a tin (II) compound, an alkali, and an inorganic compound so as to maintain the pH in the reactor at 6 or less, and hydrolyzing the tin (II) compound. .
  14. 　酸化スズが酸化第一スズの結晶構造を有することを特徴とする請求項１１～１３のいずれか一項に記載の酸化スズ粒子の製造方法。 The method for producing tin oxide particles according to any one of claims 11 to 13, wherein the tin oxide has a crystal structure of stannous oxide.
  15. 　請求項１１～１４のいずれか一項に記載の方法で得られたスズ（ＩＩ）化合物の加水分解生成物を焼成することを特徴とする酸化スズ粒子の製造方法。 A method for producing tin oxide particles, comprising calcining a hydrolysis product of a tin (II) compound obtained by the method according to any one of claims 11 to 14.
  16. 　スズ（ＩＩ）化合物の加水分解生成物と融剤を混合し焼成することを特徴とする請求項１５に記載の酸化スズ粒子の製造方法。 The method for producing tin oxide particles according to claim 15, wherein a hydrolysis product of the tin (II) compound and a flux are mixed and fired.
  17. 　酸化スズが酸化第二スズの結晶構造を有することを特徴とする請求項１５又は１６に記載の酸化スズ粒子の製造方法。 The method for producing tin oxide particles according to claim 15 or 16, wherein the tin oxide has a crystal structure of stannic oxide.
  18. 　請求項１１～１７のいずれか一項に記載の方法で得られた酸化スズを粉砕することを特徴とする酸化スズ粒子の製造方法。 A method for producing tin oxide particles, comprising pulverizing tin oxide obtained by the method according to any one of claims 11 to 17.
  19. 　請求項１１～１８のいずれか一項に記載の方法で得られた酸化スズ粒子の表面に無機化合物及び／又は有機化合物を被覆することを特徴とする酸化スズ粒子の製造方法。 A method for producing tin oxide particles, wherein the surface of the tin oxide particles obtained by the method according to any one of claims 11 to 18 is coated with an inorganic compound and / or an organic compound.
  20. 　無機化合物及び／又は有機化合物を被覆した後に焼成することを特徴とする請求項１９に記載の酸化スズ粒子の製造方法。 The method for producing tin oxide particles according to claim 19, wherein the firing is carried out after coating with an inorganic compound and / or an organic compound.
  21. 　請求項１～１０のいずれか一項に記載の酸化スズ粒子を含有することを特徴とする分散体。 A dispersion comprising the tin oxide particles according to any one of claims 1 to 10.
  22. 　請求項１～１０のいずれか一項に記載の酸化スズ粒子を含有することを特徴とする塗料。 A paint comprising the tin oxide particles according to any one of claims 1 to 10.
  23. 　請求項１～１０のいずれか一項に記載の酸化スズ粒子を含有することを特徴とする樹脂組成物。 A resin composition comprising the tin oxide particles according to any one of claims 1 to 10.
  24. 　基材上に請求項２１に記載の分散体又は請求項２２に記載の塗料が塗布されていることを特徴とする酸化スズ膜。 A tin oxide film, wherein the dispersion according to claim 21 or the paint according to claim 22 is applied on a substrate.
  25. 　請求項１～１０のいずれか一項に記載の酸化スズ粒子を含有することを特徴とする導電性材料。 A conductive material comprising the tin oxide particles according to any one of claims 1 to 10.
  26. 　請求項１～１０のいずれか一項に記載の酸化スズ粒子を含有することを特徴とする触媒。 A catalyst comprising the tin oxide particles according to any one of claims 1 to 10.
  27. 　請求項１～１０のいずれか一項に記載の酸化スズ粒子を含有することを特徴とするガスセンサー。 A gas sensor comprising the tin oxide particles according to any one of claims 1 to 10.
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