WO2023106194A1 - 複合金属酸化合物分酸液、複合金属酸化合物粉末、複合金属酸化合物膜、及びそれらの製造方法 - Google Patents

複合金属酸化合物分酸液、複合金属酸化合物粉末、複合金属酸化合物膜、及びそれらの製造方法 Download PDF

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WO2023106194A1
WO2023106194A1 PCT/JP2022/044350 JP2022044350W WO2023106194A1 WO 2023106194 A1 WO2023106194 A1 WO 2023106194A1 JP 2022044350 W JP2022044350 W JP 2022044350W WO 2023106194 A1 WO2023106194 A1 WO 2023106194A1
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composite metal
acid compound
metal acid
dispersion
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French (fr)
Japanese (ja)
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隆二 元野
孝文 荒木
周平 原
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Mitsui Kinzoku Co Ltd
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Mitsui Mining and Smelting Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G33/00—Compounds of niobium
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G35/00—Compounds of tantalum
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G39/00—Compounds of molybdenum
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G41/00—Compounds of tungsten
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
    • H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports

Definitions

  • the present invention relates to a composite metal acid compound acid separation liquid, a composite metal acid compound powder, a composite metal acid compound film, and methods for producing them.
  • Titanium oxide (TiO 2 ) having n-type conductivity is one of the materials for forming such a conductive thin film.
  • Patent Document 1 discloses a thermoelectric conversion material obtained by weighing titanium oxide, metal titanium and niobium oxide so as to have a predetermined molar ratio, and mixing the mixture using a dry ball mill.
  • Patent Document 1 when a coating film is formed by kneading a thermoelectric conversion material containing titanium oxide into an acrylic resin, it is difficult to form a uniform coating film. rate was high.
  • the present invention provides a composite metal acid compound acid separation liquid, a composite metal acid compound powder, a composite metal acid compound film, which can easily form a uniform coating film and can form a coating film with excellent conductive performance. and methods of making them.
  • the mixed metal acid compound dispersion of the present invention which has been made to solve the above problems, comprises titanium, Nb, Ta, W, Mo, Si, Zn, Al, Y, La, Ce, Zr, Nd, Sm, and Eu. , Dy, Hf, and a dispersion medium containing one or more elements M selected from the group consisting of a composite metal acid compound dispersion, wherein the particle diameter ( D50) is 100 nm or less.
  • the composite metal acid compound dispersion of the present invention is selected from the group consisting of titanium and Nb, Ta, W, Mo, Si, Zn, Al, Y, La, Ce, Zr, Nd, Sm, Eu, Dy and Hf.
  • a composite of titanium and element M or a mixture of titanium and element M is dispersed in the dispersion medium.
  • the composite or the mixture does not have a crystalline structure and exists as an amorphous structure.
  • the dispersion medium is a polar solvent, and may be any medium as long as the composite or the mixture is uniformly dispersed, such as water, a mixed solvent of water and alcohol, or alcohol.
  • alcohols include methanol, ethanol, propanol, isopropyl alcohol, and mixed solvents thereof, preferably methanol, ethanol, isopropyl alcohol, and mixed solvents thereof.
  • the particle size (D50) measured by particle size distribution measurement using a dynamic light scattering method is 100 nm or less, the dispersibility and solubility in the dispersion medium are improved, which is preferable.
  • the particle diameter (D50) is more preferably 50 nm or less, further preferably 40 nm or less, particularly preferably 30 nm or less, and particularly preferably 25 nm or less.
  • the particle diameter (D50) is preferably greater than 0 nm, more preferably 0.6 nm or more, and even more preferably 1 nm or more.
  • the solution having a particle size (D50) of 100 nm or less as determined by the particle size distribution measurement using the dynamic light scattering method is defined as the "multimetallic acid compound dispersion" of the present invention.
  • the particle diameter (D50) of the composite metal acid compound particles in the composite metal acid compound dispersion of the present invention measured by a particle size distribution measurement using a dynamic light scattering method is 100 nm or less, It is preferably 50 nm or less, further preferably 40 nm or less, particularly preferably 30 nm or less, and particularly preferably 25 nm or less, in terms of improving dispersibility and solubility.
  • the particle diameter (D50) of the composite metal acid compound particles or the like measured by particle size distribution measurement using a dynamic light scattering method is preferably greater than 0 nm, more preferably 0.6 nm or more, and 1 nm or more. It is even more preferable to have Furthermore, all the particles including the composite metal acid compound particles in the composite metal acid compound dispersion of the present invention have a particle diameter (D50) of 10 nm or more and 100 nm or less as measured by a particle size distribution measurement using a dynamic light scattering method. and more preferably 20 nm or more and 50 nm or less.
  • the dynamic light scattering method measures the light scattering intensity from a group of particles moving in Brownian motion by irradiating a solution such as a suspension solution with light such as a laser beam.
  • This is a method for determining the particle size and distribution.
  • the particle size distribution evaluation method uses a zeta potential/particle size/molecular weight measurement system (manufactured by Otsuka Electronics Co., Ltd.: ELSZ-2000ZS), JIS Z 8828: 2019 "Particle size analysis-dynamic light scattering to comply with the law.
  • the solution is filtered with a filter with a pore size of 10 ⁇ m, and ultrasonicated for 3 minutes with an ultrasonic cleaner (manufactured by AS ONE: VS-100III). Take action. Furthermore, the liquid temperature of the solution, which is the mode of measurement, was adjusted to 25°C.
  • the particle diameter (D50) refers to the median diameter (D50), which is the particle diameter indicating the 50% integrated value of the integrated distribution curve.
  • the composite metal acid compound dispersion of the present invention is characterized in that the molar ratio of the element M to the sum of the titanium and the element M is 0.01-0.8. It is preferable that the molar ratio of the element M to the sum of the titanium and the element M is 0.01-0.8 in terms of excellent conductive performance. Furthermore, the molar ratio is more preferably 0.05-0.5.
  • the expression “XY” (where X and Y are arbitrary numbers) means all combinations of “more than/more than X, less than/less than Y” unless otherwise specified.
  • the content of titanium in the composite metal acid compound dispersion of the present invention can be determined by appropriately diluting the composite metal acid compound dispersion with dilute hydrochloric acid as necessary, and performing ICP emission spectrometry (manufactured by Agilent Technologies: AG). -5110), the Ti weight fraction in terms of titanium oxide (TiO 2 ) is measured and calculated. Titanium in the composite metal acid compound of the present invention does not necessarily exist in the form of TiO 2 . It is customary to indicate the content of titanium in terms of TiO2 .
  • the content of the element M in the composite metal acid compound dispersion liquid of the present invention is calculated by measuring the weight fraction of the element M by ICP emission spectrometry.
  • M/(Ti+M) which is the molar ratio of the element M to the sum of the titanium content (Ti) and the element M content (M) calculated by ICP emission spectrometry as described above, is 0.01. -0.8 is preferable, 0.05 to 0.5 is more preferable, 0.2 to 0.5 is even more preferable, and 0.2 to 0.3 is particularly preferable. Titanium and the element M referred to in this specification include their oxides unless otherwise specified.
  • the oxide concentration in the composite metal acid compound dispersion liquid of the present invention is preferably more than 0% by mass and 50% by mass or less.
  • the oxide concentration is the sum of the titanium oxide concentration and the element M oxide concentration.
  • the oxide concentration in the composite metal acid compound dispersion of the present invention is more preferably 1% by mass or more and 20% by mass or less, more preferably 2% by mass or more and 15% by mass or less, and 5% by mass or more and 10% by mass. % or less is particularly preferable.
  • the element M is one or more selected from the group consisting of Nb, Ta, W and Mo.
  • the composite metal acid compound dispersion of the present invention has high transparency and excellent stability when the element M is one or more selected from the group consisting of Nb, Ta, W, and Mo. is preferred.
  • the composite metal acid compound dispersion liquid of the present invention contains a quaternary ammonium compound in the dispersion liquid.
  • the composite metal acid compound dispersion of the present invention contains a quaternary ammonium compound, it functions as a solubilizer and suppresses gelation of the dispersion, which is preferable.
  • quaternary ammonium compounds are highly volatile and easy to remove.
  • the "quaternary ammonium compound" according to the present invention includes those ionized in the composite metal acid compound dispersion of the present invention.
  • a method for producing a titanic acid dispersion in the method for producing a composite metal acid compound dispersion according to the present invention, which will be described later, will be described in detail.
  • the titanic acid dispersion of the present invention is produced. believed to be present in the dispersion.
  • Quaternary ammonium compounds used as solubilizers include, for example, alkylimidazolium, pyridinium, pyrrolidium, tetraalkylammonium and the like.
  • alkylimidazolium include 1-methyl-3-methylimidazolium, 1-ethyl-3-methylimidazolium, 1-propyl-3-methylimidazolium, 1-butyl-3-methylimidazolium.
  • pyridinium and pyrrolidium include N-butyl-pyridinium, N-ethyl-3-methyl-pyridinium, N-butyl-3-methyl-pyridinium, N-hexyl-4-(dimethylamino)-pyridinium, Examples include N-methyl-1-methylpyrrolidinium and N-butyl-1-methylpyrrolidinium.
  • tetraalkylammonium include tetramethylammonium, tetraethylammonium, tetrabutylammonium, and ethyl-dimethyl-propylammonium.
  • anions that form salts with the above cations include OH ⁇ , Cl ⁇ , Br ⁇ , I ⁇ , BF 4 ⁇ , HSO 4 ⁇ and the like.
  • Methods for measuring the concentration of quaternary ammonium compounds present in the dispersion include gas chromatography (GC), liquid chromatography (LC), mass spectrometry (MS), gas chromatography/mass spectrometry (GC-MS), liquid Chromatography-mass spectrometry (LC-MS) and the like may be mentioned, and a method of quantifying N 2 minutes in a gasified sample with a thermal conductivity meter may be used in combination. In addition, it can also be quantified using an ion chromatography method (IC) based on the Kjeldahl method.
  • IC ion chromatography method
  • the method for measuring the concentration of the quaternary ammonium compound present in the solution is preferably liquid chromatography (LC) or liquid chromatography/mass spectrometry (LC-MS), and contains a hardly volatile quaternary ammonium compound.
  • LC liquid chromatography
  • MS liquid chromatography/mass spectrometry
  • the quaternary ammonium compound is more preferably tetramethylammonium hydroxide (TMAH).
  • TMAH tetramethylammonium hydroxide
  • TEAH tetraethylammonium hydroxide
  • TMAH tetramethylammonium hydroxide
  • the composite metal acid compound dispersion of the present invention has a transmittance of 90% or more at a wavelength of 550 nm from the viewpoint of improving the dispersibility and solubility in the dispersion medium.
  • the transmittance is more preferably 95% or more, further preferably 98% or more, and particularly preferably 99% or more.
  • the transmittance of the composite metal acid compound dispersion liquid of the present invention is measured using a spectrophotometer according to the transmittance measurement conditions described later on the composite metal acid compound dispersion liquid of the present invention.
  • the method for producing a composite metal acid compound dispersion of the present invention comprises titanium, Nb, Ta, W, Mo, Si, Zn, Al, Y, La, Ce, Zr, Nd, Sm, Eu, Dy, and Hf.
  • the composite metal acid compound dispersion of the present invention can be produced by mixing and stirring an aqueous titanic acid solution prepared as described below and an element M compound containing an oxide of element M.
  • the element M is one or more selected from the group consisting of Nb, Ta, W and Mo, and the element M compound is preferably an element M oxide dispersion containing an oxide of the element M.
  • a titanium salt solution and aqueous ammonia are mixed to generate a neutralization reaction liquid (hereinafter referred to as a "titanium neutralization step"), and The titanium-containing precipitate is washed (hereinafter referred to as “titanium washing step”), and the washed titanium-containing precipitate, quaternary ammonium salt and water are mixed (hereinafter referred to as “titanium dissolving step”), and titanium A production method for obtaining an acid aqueous solution is mentioned.
  • the titanium salt solution may be any solution in which titanium is dissolved, such as titanyl sulfate aqueous solution, titanyl chloride aqueous solution, and titanium fluoride aqueous solution.
  • the titanyl sulfate aqueous solution is obtained by dissolving titanyl sulfate in hot water.
  • the titanyl sulfate aqueous solution is preferably prepared so as to contain 8 to 15% by mass of titanium in terms of TiO 2 .
  • a neutralization reaction liquid can be produced by mixing and reacting a titanium salt solution, for example, an aqueous solution of titanyl sulfate and aqueous ammonia.
  • a titanium salt solution for example, an aqueous solution of titanyl sulfate and aqueous ammonia.
  • reverse neutralization in which an aqueous solution of titanyl sulfate is added to aqueous ammonia and reacted.
  • the concentration of ammonia in the aqueous ammonia solution used for reverse neutralization is preferably 10% by mass to 40% by mass.
  • the ammonia concentration is 25% by mass, titanium is less likely to remain undissolved, and titanium or titanium oxide can be completely dissolved in water.
  • the ammonia concentration is 30% by mass or less, it is close to a saturated aqueous solution of ammonia, which is preferable.
  • the ammonia concentration of the aqueous ammonia solution is preferably 5% by mass or more, more preferably 10% by mass or more, even more preferably 15% by mass or more, and particularly preferably 20% by mass.
  • the ammonia concentration is preferably 30% by mass or less, more preferably 35% by mass or less, and even more preferably 40% by mass or less.
  • the amount of titanyl sulfate aqueous solution added to ammonia water is preferably such that the molar ratio of NH 3 /TiO 2 is 1 or more and 200 or less, more preferably 10 or more and 100 or less.
  • the titanyl sulfate aqueous solution added to the ammonia water preferably has a molar ratio of NH 3 /SO 4 2- of 1 or more, and more preferably 5 or more, from the viewpoint of generating a titanic acid compound that dissolves in diluted ammonia water. Preferably, it is more preferably 10 or more.
  • the molar ratio of NH 3 /SO 4 2- is preferably 50 or less, more preferably 40 or less, and even more preferably 30 or less.
  • the time required for adding the titanyl sulfate aqueous solution to the aqueous ammonia is preferably within 1 minute, more preferably within 30 seconds, and even more preferably within 10 seconds. That is, instead of gradually adding the titanyl sulfate aqueous solution over time, for example, it is preferable to add the titanyl sulfate aqueous solution at once, for example, to add it to the ammonia water in the shortest possible time for neutralization reaction.
  • the neutralization reaction can be carried out while maintaining a high pH.
  • Tianium washing process By washing the slurry of the titanium-containing precipitate in the neutralization reaction liquid obtained by reverse neutralization, impurities are removed and the titanium-containing precipitate is obtained.
  • the slurry of the titanium-containing precipitate obtained by reverse neutralization contains, as impurities, unnecessary components other than titanium or titanium oxide hydrates or ions and ammonia, such as sulfate compounds such as ammonium sulfate. is preferably removed.
  • the cleaning method for example, the method of removing sulfate compounds
  • the cleaning method is arbitrary.
  • filtration methods using a membrane such as reverse osmosis filtration using ammonia water or pure water, ultrafiltration, and microfiltration, centrifugation and other known methods can be employed.
  • the titanium cleaning step may be performed at room temperature, and no particular temperature adjustment is required.
  • titanium melting process Tianium melting process
  • a dispersion medium such as water and a quaternary ammonium salt
  • examples of quaternary ammonium salts include tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide (TEAH), tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, methyltripropylammonium hydroxide, water Methyltributylammonium oxide, tetrapentylammonium hydroxide, tetrahexylammonium hydroxide, ethyltrimethylammonium hydroxide, dimethyldiethylammonium hydroxide, benzyltrimethylammonium hydroxide, hexadecyltrimethylammonium hydroxide, or (2-hydroxyethyl) hydroxide ) trimethylammonium and the like.
  • TMAH tetramethylammonium hydroxide
  • TEAH tetraethylammonium hydroxide
  • TMAH tetrae
  • the amount of the quaternary ammonium salt added as described above, if the amount of quaternary ammonium is large, the solubility of titanium or titanic acid in water can be increased.
  • a quaternary ammonium salt containing 0.44 mol or more of quaternary ammonium is preferably mixed with 1 mol of titanium contained in the precipitate.
  • problems such as obstruction of film formation and inhibition of catalytic action may occur. It is preferable to mix a quaternary ammonium salt having 1.0 mol or less of quaternary ammonium per 1 mol of titanium contained in the containing precipitate.
  • titanium neutralization process, titanium washing process, and titanium dissolution process may be performed at room temperature, and there is no particular need to adjust the respective temperatures.
  • each oxide dispersion containing an oxide of Nb, Ta, W, and Mo as the element M will be described below.
  • a method for producing a dispersion containing an oxide of Nb, that is, a niobic acid dispersion will be described below.
  • niobium neutralization step an acidic niobium solution is added to an aqueous ammonia solution to generate a neutralization reaction liquid (hereinafter referred to as a "niobium neutralization step"), and The niobium-containing precipitate is washed (hereinafter referred to as "niobium washing step"), an organic nitrogen compound is added to the washed niobium-containing precipitate (hereinafter referred to as "niobium dissolving step”), and a niobium acid dispersion is obtained. production method to obtain.
  • the acidic niobium solution is an acidic niobium solution containing fluoride ions obtained by solvent extraction of a solution in which niobium is dissolved in an acidic solution containing hydrofluoric acid.
  • the acidic niobium solution containing fluoride ions eg, an aqueous niobium fluoride solution
  • the acidic niobium solution containing fluoride ions is preferably adjusted to contain 1 to 100 g/L of niobium in terms of Nb 2 O 5 by adding water (eg, pure water).
  • water eg, pure water
  • the niobium concentration is 1 g/L or more in terms of Nb 2 O 5
  • the niobium concentration is 100 g/L or less in terms of Nb 2 O 5 , it is preferable because the niobate compound hydrate is easily soluble in water, and the niobate compound hydrate that is more reliably soluble in water is synthesized. To achieve this, it is more preferably 90 g/L or less, even more preferably 80 g/L or less, and particularly preferably 70 g/L or less.
  • the pH of the niobium fluoride aqueous solution is preferably 2 or less, more preferably 1 or less, from the viewpoint of completely dissolving niobium or niobium oxide.
  • Niobium neutralization step In the niobium neutralization step, it is preferable to obtain a precipitate slurry containing niobium by adding an acidic niobium solution containing fluoride ions to aqueous ammonia of a predetermined concentration, that is, by a reverse neutralization method.
  • the ammonia concentration of the ammonia water used for reverse neutralization is preferably 10% by mass to 30% by mass.
  • the ammonia concentration is 10% by mass, niobium is less likely to remain undissolved, and niobium or niobium acid can be completely dissolved in water.
  • the ammonia concentration is 30% by mass or less, it is close to a saturated aqueous solution of ammonia, which is preferable.
  • the ammonia concentration of the aqueous ammonia is preferably 10% by mass or more, more preferably 15% by mass or more, even more preferably 20% by mass or more, and particularly preferably 25% by mass.
  • the ammonia concentration is preferably 30% by mass or less, more preferably 29% by mass or less, and even more preferably 28% by mass or less.
  • the amount of the niobium fluoride aqueous solution added to the aqueous ammonia is preferably such that the molar ratio of NH 3 /Nb 2 O 5 is 95 or more and 500 or less, more preferably 100 or more and 450 or less. More preferably, it is 110 or more and 400 or less.
  • the amount of the niobium fluoride aqueous solution added to the ammonia water is preferably such that the NH 3 /HF molar ratio is 3.0 or more from the viewpoint of generating amines and niobic acid compounds that dissolve in dilute ammonia water. It is more preferably 4.0 or more, and even more preferably 5.0 or more.
  • the NH 3 /HF molar ratio is preferably 100 or less, more preferably 50 or more, and even more preferably 40 or more.
  • the time required for adding the niobium fluoride aqueous solution to the aqueous ammonia is preferably within 1 minute, more preferably within 30 seconds, and even more preferably within 10 seconds. That is, instead of gradually adding the niobium fluoride aqueous solution over time, it is preferable to add the aqueous solution of niobium fluoride at once, for example, to the ammonia water in the shortest possible time for neutralization reaction.
  • the reverse neutralization step since the acidic niobium fluoride aqueous solution is added to the alkaline aqueous ammonia, the neutralization reaction can be carried out while maintaining a high pH.
  • the niobium fluoride aqueous solution and ammonia water can be used at room temperature.
  • niobium cleaning process In the niobium washing step, a fluorine compound such as ammonium fluoride is removed from the niobium-containing precipitate slurry obtained by the reverse neutralization method to produce a niobium-containing precipitate from which the fluorine compound has been removed.
  • Fluorine compounds such as ammonium fluoride are present as impurities in the precipitation slurry containing niobium obtained by the inverse neutralization method, and therefore these are preferably removed.
  • the method for removing the fluorine compound is arbitrary, but for example, a method by filtration using a membrane such as reverse osmosis filtration using ammonia water or pure water, ultrafiltration, or microfiltration, centrifugation, or other known methods. can be adopted.
  • a membrane such as reverse osmosis filtration using ammonia water or pure water, ultrafiltration, or microfiltration, centrifugation, or other known methods.
  • temperature control is not particularly required, and the removal may be carried out at room temperature.
  • the precipitation slurry containing niobium obtained by the reverse neutralization method is decanted using a centrifuge, and washing is repeated until the amount of free fluoride ions is 100 mg / L or less. , a niobium-containing precipitate from which fluoride ions are removed is obtained.
  • the cleaning liquid used for removing fluoride ions is aqueous ammonia.
  • ammonia water of 5.0 mass% or less is preferable, ammonia water of 4.0 mass% or less is more preferable, ammonia water of 3.0 mass% or less is further preferable, and ammonia of 2.5 mass% Water is particularly preferred. If the ammonia water content is 5.0% by mass or less, ammonia and ammonium ions are suitable for fluorine, and an unnecessary increase in cost can be avoided.
  • niobium melting process a niobic acid dispersion is produced by adding an organic nitrogen compound to a niobium-containing precipitate slurry.
  • the niobium-containing precipitate slurry is obtained by diluting the niobium-containing precipitate from which fluoride ions have been removed as described above with pure water or the like to form a slurry.
  • the niobium concentration of the niobium-containing precipitation slurry is obtained by sampling a part of the slurry, drying it at 110° C. for 24 hours, and then calcining it at 1,000° C. for 4 hours to generate Nb 2 O 5 .
  • the weight of Nb 2 O 5 thus produced can be measured and the niobium concentration of the slurry can be calculated from the weight.
  • a niobic acid dispersion is obtained by mixing an organic nitrogen compound with the niobium-containing precipitation slurry from which fluoride ions have been removed.
  • the obtained niobium-containing precipitation slurry is added to the organic nitrogen compound and mixed with pure water so that the final mixture has a niobium concentration of 0.1 to 40% by mass in terms of Nb 2 O 5 . Then, while stirring the mixture, the liquid temperature is maintained at room temperature (25° C.) for 1 hour to obtain a niobic acid dispersion.
  • the organic nitrogen compound mixed with the niobium-containing precipitation slurry is preferably an amine, especially an aliphatic amine, and/or a quaternary ammonium compound.
  • the aliphatic amine is preferably mixed so that the concentration of the aliphatic amine in the niobium-containing precipitation slurry is 40% by mass or less.
  • the aliphatic amine concentration in the niobium-containing precipitation slurry is preferably mixed to 0.1% by mass or more, more preferably 20% by mass or more.
  • the aliphatic amine is more preferably methylamine or dimethylamine, and particularly preferably methylamine.
  • the quaternary ammonium compound is preferably mixed so that the concentration of the quaternary ammonium compound in the niobium-containing precipitation slurry is 40% by mass or less.
  • the concentration of the quaternary ammonium compound in the niobium-containing precipitation slurry is preferably 0.1% by mass or more, more preferably 20% by mass or more.
  • the quaternary ammonium compound is more preferably tetramethylammonium hydroxide (TMAH) or tetraethylammonium hydroxide (TEAH).
  • niobium neutralization process may be performed at room temperature, and there is no particular need to adjust the respective temperatures.
  • a tantalum salt solution is added to an aqueous amine solution to generate a primary reaction liquid (hereinafter referred to as a “tantalum primary neutralization step"), and the primary reaction liquid is added to aqueous ammonia.
  • a secondary reaction solution is generated (hereinafter referred to as a “tantalum secondary neutralization step”), and tantalum-containing precipitates generated in the secondary reaction solution are washed (hereinafter referred to as a “tantalum washing step”), and washed.
  • a production method of mixing the subsequent tantalum-containing precipitate, amine, and water (hereinafter referred to as a "tantalum dispersion step") to obtain a tantalic acid dispersion can be mentioned.
  • a tantalic acid dispersion liquid by mixing a tantalic acid compound, an amine, and water using a tantalic acid compound to be described later.
  • the tantalum salt solution that is the starting material may be any solution in which tantalum is dissolved.
  • a tantalum fluoride aqueous solution, a tantalum chloride aqueous solution, and the like can be mentioned.
  • the tantalum fluoride aqueous solution is obtained by reacting tantalum, tantalum oxide or tantalum hydroxide with hydrofluoric acid (HF) such as hydrofluoric acid aqueous solution to obtain tantalum fluoride (H 2 TaF 7 ), which is dissolved in water.
  • HF hydrofluoric acid
  • H 2 TaF 7 tantalum fluoride
  • This tantalum fluoride aqueous solution is preferably prepared by adding water (for example, pure water) so as to contain 1 to 100 g/L of tantalum in terms of Ta 2 O 5 .
  • water for example, pure water
  • the tantalum concentration is 1 g/L or more, the tantalum acid compound hydrate is easily soluble in water. is more preferable, and considering productivity, it is more preferably 10 g/L or more, and more preferably 20 g/L or more.
  • the tantalum concentration is 100 g/L or less, the water-soluble tantalate compound hydrate is obtained. is more preferably 80 g/L or less, and more preferably 70 g/L or less.
  • the pH of the tantalum fluoride aqueous solution is preferably 2 or less, more preferably 1 or less.
  • a tantalum chloride aqueous solution can be prepared by dissolving tantalum chloride (TaCl 5 ) in a small amount of methanol and then adding water.
  • Talum primary neutralization step After reacting the tantalum salt solution with the aqueous amine solution (primary neutralization), it is important to carry out a treatment (secondary neutralization) for reacting with aqueous ammonia.
  • tantalum or tantalic acid is added in the subsequent dispersion step. It cannot be suitably dispersed in water, much less an aqueous solution.
  • the tantalum primary neutralization step it is preferable to perform reverse neutralization in which a tantalum salt solution such as a tantalum fluoride aqueous solution is added to the amine aqueous solution and reacted.
  • a tantalum salt solution such as a tantalum fluoride aqueous solution
  • tantalum or tantalic acid cannot be suitably dispersed in water, much less an aqueous solution, in the subsequent dispersion step. It is speculated that the reverse neutralization causes the structure of tantalum or tantalic acid to become more soluble in water.
  • an alkylamine or the like can be preferably exemplified.
  • the alkyl group of the alkylamine preferably has 1 to 6 carbon atoms, preferably 4 or less, more preferably 3 or less, and most preferably 2 or less.
  • alkylamines include methylamine, dimethylamine, trimethylamine, ethylamine, methylethylamine, diethylamine, triethylamine, methyldiethylamine, dimethylethylamine, n-propylamine, di-n-propylamine, tri-n-propylamine, iso -propylamine, diiso-propylamine, triiso-propylamine, n-butylamine, di-n-butylamine, tri-n-butylamine, iso-butylamine, diiso-butylamine, triiso-butylamine and tert-butylamine, n- Pentylamine, n-hexylamine and the like can be mentioned.
  • methylamine, dimethylamine, trimethylamine, ethylamine, methylethylamine, diethylamine, triethylamine, methyldiethylamine and dimethylethylamine are preferable, and among them, methylamine, dimethylamine and trimethylamine are more preferable.
  • the tantalum salt solution to an aqueous amine solution containing an amine in an amount equal to or more than the fluorine contained in the tantalum salt solution, i.e., one or more amines.
  • the tantalum salt solution to an amine aqueous solution containing an amine having a molar ratio of 2 or less to the fluorine contained in the tantalum salt solution, especially 1.8 or less.
  • the tantalum primary neutralization step when a tantalum salt solution such as an aqueous tantalum fluoride solution is added to an aqueous amine solution, it is preferable to carry out a neutralization reaction within 1 minute. That is, instead of gradually adding the tantalum salt solution over time, it is preferable to add the tantalum salt solution all at once, for example, within 1 minute for neutralization reaction. At this time, the addition time of the tantalum salt solution is preferably 1 minute or less, more preferably 30 seconds or less, and more preferably 10 seconds or less.
  • tantalum secondary neutralization step In the tantalum secondary neutralization, it is preferable to add the primary reaction liquid obtained in the tantalum primary neutralization step to aqueous ammonia to obtain the secondary reaction liquid.
  • a precipitate referred to as “tantalum-containing precipitate" is produced in the water.
  • reverse neutralization is carried out by adding the primary reaction liquid obtained in the primary tantalum neutralization step to aqueous ammonia to react. is preferred.
  • the aqueous ammonia solution preferably has an ammonia concentration of 10 to 30% by mass. Among them, it is preferably 15% by mass or more, more preferably 20% by mass or more, and more preferably 25% by mass or more. On the other hand, it is more preferably 29% by mass or less, more preferably 28% by mass or less.
  • the primary reaction liquid is mixed with ammonia in a molar ratio of 7.5 or more to fluorine contained in the primary reaction liquid, especially 8 More preferably, it is added to an aqueous ammonia solution containing ammonia of 0.0 or more, especially 8.5 or more.
  • the primary reaction liquid it is preferable to add the primary reaction liquid to aqueous ammonia containing ammonia in a molar ratio of 10.0 or less to fluorine contained in the primary reaction liquid. It is more preferable to add to the aqueous ammonia containing ammonia at a ratio of 5 or less, more preferably 9.0 or less.
  • the primary reaction solution when the primary reaction solution is added to the aqueous ammonia, it is preferable to carry out the neutralization reaction within 1 minute. That is, instead of adding the primary reaction solution gradually over a period of time, it is preferable to add the primary reaction solution all at once, for example, within 1 minute for neutralization reaction.
  • the addition time of the primary reaction solution is preferably 1 minute or less, more preferably 30 seconds or less, and more preferably 10 seconds or less.
  • the secondary reaction liquid obtained by the secondary neutralization of tantalum, especially the tantalum-containing precipitate contains impurities such as fluorine compounds such as ammonium fluoride, hydrates of tantalum or tantalic acid, ions, and unnecessary substances other than amines. Since the components are present in the water, it is preferable to remove the unwanted components.
  • the cleaning method for example, the method of removing fluorine compounds
  • the cleaning method is arbitrary.
  • filtration methods using a membrane such as reverse osmosis filtration using ammonia water or pure water, ultrafiltration, and microfiltration, centrifugation and other known methods can be employed.
  • tantalum dispersion step Next, a tantalum-containing precipitate obtained by washing in a tantalum washing step, for example, a tantalum-containing precipitate obtained by removing fluorine, is added with a dispersion medium such as water and then treated with an amine and/or a quaternary ammonium compound.
  • a tantalic acid dispersion can be prepared by stirring as necessary to promote the reaction.
  • the type of amine to be added is the same as the amine that can be used in the primary neutralization.
  • the amount of amine added as described above, if the amount of amine is large, the dispersibility or solubility of tantalum or tantalic acid in water can be enhanced. It is preferable to adjust as described above from the viewpoint that there is a possibility of causing problems such as becoming or inhibiting the catalytic action.
  • the quaternary ammonium compound is preferably mixed so that the concentration of the quaternary ammonium compound in the tantalum-containing precipitate is 40% by mass or less.
  • the quaternary ammonium compound concentration in the tantalum-containing precipitate is preferably mixed to 0.1% by mass or more, more preferably 20% by mass or more.
  • the quaternary ammonium compound is more preferably tetramethylammonium hydroxide (TMAH) or tetraethylammonium hydroxide (TEAH).
  • the tantalum primary neutralization process, the tantalum secondary neutralization process, the tantalum washing process, and the tantalum dispersion process may be performed at room temperature, and there is no particular need to forcibly adjust the temperature.
  • tungsten neutralization step As an example of a method for producing a tungstic acid dispersion, an acidic aqueous tungsten solution is added to an aqueous ammonia solution to generate a neutralization reaction solution (hereinafter referred to as a "tungsten neutralization step"), and The tungsten-containing precipitate is washed (hereinafter referred to as "tungsten washing step"), an organic nitrogen compound is added to the tungsten-containing precipitate after washing (hereinafter referred to as "tungsten dissolving step”), and the tungstic acid dispersion is production method to obtain.
  • tungsten washing step an organic nitrogen compound is added to the tungsten-containing precipitate after washing
  • the acidic tungsten aqueous solution refers to a tungsten sulfate aqueous solution obtained by solvent extraction of a solution in which tungsten is dissolved in an acidic aqueous solution containing sulfuric acid.
  • the tungsten sulfate aqueous solution is preferably adjusted to contain 1 to 100 g/L of tungsten in terms of WO3 by adding water (for example, pure water).
  • water for example, pure water
  • the tungsten concentration is 1 g / L or more in terms of WO 3
  • the tungsten concentration is 100 g / L or less in terms of WO3 , it is preferable because it becomes a water-soluble tungstate compound hydrate, and in order to more reliably synthesize a water-soluble tungstate compound hydrate.
  • the pH of the aqueous tungsten sulfate solution is preferably 2 or less, more preferably 1 or less.
  • tungsten neutralization step when a tungsten sulfate aqueous solution is added to an ammonia aqueous solution, in the so-called reverse neutralization method, a tungsten sulfate aqueous solution is added to an ammonia aqueous solution of 10% by mass to 30% by mass, that is, by the reverse neutralization method, It is preferred to obtain a slurry of tungstate compound hydrates, a so-called slurry of tungsten-containing precipitates.
  • the concentration of ammonia in the aqueous ammonia solution used for reverse neutralization is preferably 10% by mass to 30% by mass.
  • the ammonia concentration is 10% by mass, tungsten is less likely to remain undissolved, and tungsten or tungsten oxide can be completely dissolved in water.
  • the ammonia concentration is 30% by mass or less, it is close to a saturated aqueous solution of ammonia, which is preferable.
  • the ammonia concentration of the aqueous ammonia solution is preferably 10% by mass or more, more preferably 15% by mass or more, even more preferably 20% by mass or more, and particularly preferably 25% by mass.
  • the ammonia concentration is preferably 30% by mass or less, more preferably 29% by mass or less, and even more preferably 28% by mass or less.
  • the amount of the tungsten sulfate aqueous solution added to the aqueous ammonia is preferably such that the molar ratio of NH 3 /WO 3 is 0.1 or more and 300 or less, more preferably 5 or more and 200 or less.
  • the aqueous solution of tungsten sulfate added to aqueous ammonia preferably has a molar ratio of NH 3 /SO 4 2- of 3.0 or more, from the viewpoint of producing amines and tungstic compounds that dissolve in dilute aqueous ammonia. 0.0 or more, and more preferably 20.0 or more.
  • the molar ratio of NH 3 /SO 4 2- is preferably 200 or less, more preferably 150 or less, and even more preferably 100 or less.
  • the time required to add the aqueous solution of tungsten sulfate to the aqueous ammonia is preferably within 1 minute, more preferably within 30 seconds, and even more preferably within 10 seconds. That is, instead of gradually adding the aqueous solution of tungsten sulfate over time, it is preferable to add the aqueous solution of tungsten sulfate at once, for example, to the ammonia water in the shortest possible time for neutralization reaction. Further, in reverse neutralization, since an acidic tungsten sulfate aqueous solution is added to alkaline ammonia water, the neutralization reaction can be carried out while maintaining a high pH. The aqueous tungsten sulfate solution and aqueous ammonia can be used at room temperature.
  • the sulfur content is removed from the tungsten-containing precipitate slurry obtained by the reverse neutralization method to produce a sulfur-free tungsten-containing precipitate.
  • the slurry of the tungsten-containing precipitate obtained by the reverse neutralization method contains, as impurities, sulfate ions remaining unreacted with tungsten or tungsten oxide, and the sulfur content of hydrogen sulfate ions, so these are removed. is preferred.
  • the sulfur removal method is arbitrary, but for example, a method by filtration using a membrane such as reverse osmosis filtration using ammonia water or pure water, ultrafiltration, or microfiltration, centrifugation, or other known methods. can be adopted.
  • temperature control is not particularly required, and the removal may be carried out at room temperature.
  • the tungsten-containing precipitate slurry obtained by the reverse neutralization method is decanted using a centrifuge, and washed until the conductivity of the tungsten-containing precipitate slurry is 500 ⁇ S / cm or less.
  • a tungsten-containing precipitate from which the sulfur content has been removed is obtained.
  • the conductivity was measured by adjusting the liquid temperature of the slurry of the tungsten-containing precipitate to 25 ° C., immersing the measurement part of a conductivity meter (manufactured by AS ONE: ASCON2) in the supernatant liquid of the slurry of the precipitate, and measuring the conductivity. After the value stabilized, the value was read.
  • the cleaning liquid used to remove the sulfur content is aqueous ammonia.
  • ammonia water of 5.0 mass% or less is preferable, ammonia water of 4.0 mass% or less is more preferable, ammonia water of 3.0 mass% or less is further preferable, and ammonia of 2.5 mass% Water is particularly preferred.
  • ammonia water content is 5.0% by mass or less, ammonia and ammonium ions are suitable for the sulfur content, and an unnecessary increase in cost can be avoided.
  • the tungsten-containing precipitate slurry is obtained by diluting the tungsten-containing precipitate, from which the sulfur content has been removed as described above, with pure water or the like to form a slurry.
  • the tungsten concentration of the tungsten-containing precipitation slurry from which the sulfur content was removed a part of the slurry was sampled, dried at 110 ° C. for 24 hours, and then calcined at 1,000 ° C. for 4 hours to remove WO3 . Generate.
  • the weight of the WO 3 thus produced can be measured and the tungsten concentration of the slurry can be calculated from the weight.
  • the tungstic acid solution of the present invention is obtained by mixing an organic nitrogen compound with the tungsten-containing precipitation slurry from which the sulfur content has been removed.
  • the resulting tungsten-containing precipitation slurry is added to the organic nitrogen compound and mixed with pure water so that the final mixture has a tungsten concentration of 0.1 to 40% by mass in terms of WO3 ,
  • a colorless and transparent tungstic acid solution of the present invention is obtained.
  • the organic nitrogen compound mixed with the tungsten-containing precipitation slurry is preferably an aliphatic amine and/or a quaternary ammonium compound.
  • the aliphatic amine is preferably mixed so that the concentration of the aliphatic amine in the tungsten-containing precipitation slurry is 40% by mass or less.
  • the aliphatic amine concentration in the tungsten-containing precipitation slurry is preferably mixed to 0.1% by mass or more, more preferably 20% by mass or more.
  • the aliphatic amine is more preferably methylamine or dimethylamine.
  • the quaternary ammonium compound is preferably mixed so that the concentration of the quaternary ammonium compound in the tungsten-containing precipitation slurry is 40% by mass or less.
  • the concentration of the quaternary ammonium compound in the tungsten-containing precipitation slurry is preferably 0.1% by mass or more, more preferably 20% by mass or more.
  • the quaternary ammonium compound is more preferably tetramethylammonium hydroxide (TMAH).
  • the above-described tungsten neutralization process, tungsten cleaning process, and tungsten melting process may be performed at room temperature, and there is no particular need to adjust the temperature of each.
  • an acidic molybdenum aqueous solution is added to an ammonia aqueous solution to generate a neutralization reaction solution (hereinafter referred to as "molybdenum neutralization step"), and The molybdenum-containing precipitate is washed (hereinafter referred to as "molybdenum washing step"), an organic nitrogen compound is added to the washed molybdenum-containing precipitate (hereinafter referred to as "molybdenum dissolving step”), and the molybdic acid dispersion is production method to obtain.
  • the acidic molybdenum aqueous solution refers to an aqueous molybdenum sulfate solution obtained by solvent extraction of a solution obtained by dissolving molybdenum in an acidic aqueous solution containing sulfuric acid.
  • the molybdenum sulfate aqueous solution is preferably adjusted to contain 1 to 100 g/L of molybdenum in terms of MoO 3 by adding water (for example, pure water).
  • water for example, pure water
  • the molybdenum concentration is 1 g / L or more in terms of MoO 3
  • /L or more is more preferable.
  • the molybdenum concentration is 100 g / L or less in terms of MoO 3 , it is preferable because it becomes a molybdate compound hydrate that is easily soluble in water.
  • the pH of the molybdenum sulfate aqueous solution is preferably 2 or less, more preferably 1 or less, from the viewpoint of completely dissolving molybdenum or molybdenum oxide.
  • molybdenum neutralization step when adding an aqueous molybdenum sulfate solution to an aqueous ammonia solution, in the so-called reverse neutralization method, an aqueous solution of molybdenum sulfate is added to an aqueous ammonia solution of 10% to 30% by weight, that is, by the reverse neutralization method, It is preferred to obtain a slurry of molybdate compound hydrate, a slurry of so-called molybdenum-containing precipitates.
  • the concentration of ammonia in the ammonia aqueous solution used for reverse neutralization is preferably 10% by mass to 30% by mass.
  • concentration of ammonia in the ammonia aqueous solution used for reverse neutralization is preferably 10% by mass to 30% by mass.
  • ammonia concentration is 10% by mass, molybdenum is less likely to remain undissolved, and molybdenum and molybdenum oxide can be completely dissolved in water.
  • ammonia concentration is 30% by mass or less, it is close to a saturated aqueous solution of ammonia, which is preferable.
  • the ammonia concentration of the aqueous ammonia solution is preferably 10% by mass or more, more preferably 15% by mass or more, even more preferably 20% by mass or more, and particularly preferably 25% by mass.
  • the ammonia concentration is preferably 30% by mass or less, more preferably 29% by mass or less, and even more preferably 28% by mass or less.
  • the amount of the molybdenum sulfate aqueous solution added to the aqueous ammonia is preferably such that the molar ratio of NH 3 /MoO 3 is 0.1 or more and 300 or less, more preferably 5 or more and 200 or less.
  • the molybdenum sulfate aqueous solution added to the ammonia water preferably has a NH 3 /SO 4 2- molar ratio of 3.0 or more, from the viewpoint of generating amines and molybdic acid compounds that dissolve in dilute ammonia water. 0.0 or more, and more preferably 20.0 or more.
  • the molar ratio of NH 3 /SO 4 2- is preferably 200 or less, more preferably 150 or less, and even more preferably 100 or less.
  • the time required for adding the molybdenum sulfate aqueous solution to the aqueous ammonia is preferably within 1 minute, more preferably within 30 seconds, and even more preferably within 10 seconds. That is, instead of gradually adding the molybdenum sulfate aqueous solution over time, it is preferable to add the aqueous solution of molybdenum sulfate to the ammonia water in as short a time as possible, for example, to carry out the neutralization reaction. Further, in reverse neutralization, since an acidic molybdenum sulfate aqueous solution is added to alkaline aqueous ammonia, the neutralization reaction can be carried out while maintaining a high pH.
  • molybdenum washing process In the molybdenum washing step, the sulfur content is removed from the molybdenum-containing precipitate slurry obtained by the reverse neutralization method to produce a sulfur-free molybdenum-containing precipitate.
  • the slurry of the molybdenum-containing precipitate obtained by the reverse neutralization method contains, as impurities, sulfuric acid ions remaining unreacted with molybdenum or molybdenum oxide, and the sulfur content of hydrogensulfate ions, so these are removed. is preferred.
  • the sulfur removal method is arbitrary, but for example, a method by filtration using a membrane such as reverse osmosis filtration using ammonia water or pure water, ultrafiltration, or microfiltration, centrifugation, or other known methods. can be adopted.
  • temperature control is not particularly required, and the removal may be carried out at room temperature.
  • the slurry of the molybdenum-containing precipitate obtained by the reverse neutralization method is decanted using a centrifuge, and the slurry of the molybdenum-containing precipitate is washed until the electrical conductivity of the slurry is 500 ⁇ S/cm or less.
  • a molybdenum-containing precipitate from which the sulfur content has been removed is obtained.
  • the conductivity was measured by adjusting the liquid temperature of the slurry of the molybdenum-containing precipitate to 25 ° C., immersing the measurement part of a conductivity meter (manufactured by AS ONE: ASCON2) in the supernatant liquid of the slurry of the precipitate, and measuring the conductivity. After the value stabilized, the value was read.
  • the cleaning liquid used to remove the sulfur content is aqueous ammonia.
  • ammonia water of 5.0 mass% or less is preferable, ammonia water of 4.0 mass% or less is more preferable, ammonia water of 3.0 mass% or less is further preferable, and ammonia of 2.5 mass% Water is particularly preferred.
  • ammonia water content is 5.0% by mass or less, ammonia and ammonium ions are suitable for the sulfur content, and an unnecessary increase in cost can be avoided.
  • molybdenum dissolution process In the molybdenum dissolving step, a molybdenum-containing precipitate is slurried, and an organic nitrogen compound is added to the molybdenum-containing precipitate slurry to produce a molybdic acid dispersion.
  • the molybdenum-containing precipitate slurry is obtained by diluting the molybdenum-containing precipitate from which the sulfur content has been removed as described above with pure water or the like to form a slurry.
  • the molybdenum concentration of the molybdenum-containing precipitation slurry from which the sulfur content was removed was obtained by sampling a part of the slurry, drying it at 110 ° C. for 24 hours, and then calcining it at 1,000 ° C. for 4 hours to remove MoO 3 . Generate.
  • the weight of MoO 3 thus produced can be measured and the molybdenum concentration of the slurry can be calculated from the weight.
  • a molybdic acid dispersion is obtained by mixing an organic nitrogen compound with the molybdenum-containing precipitation slurry from which the sulfur content has been removed.
  • the obtained molybdenum-containing precipitation slurry is added to the organic nitrogen compound and mixed with pure water so that the final mixture has a molybdenum concentration of 0.1 to 40% by mass in terms of MoO3 ,
  • a molybdic acid dispersion is obtained by maintaining the liquid temperature at room temperature (25° C.) for 1 hour while stirring the mixture.
  • the organic nitrogen compound mixed with the molybdenum-containing precipitation slurry is preferably an amine, especially an aliphatic amine, and/or a quaternary ammonium compound.
  • the aliphatic amine is preferably mixed so that the concentration of the aliphatic amine in the molybdenum-containing precipitation slurry is 40% by mass or less. From the same point of view, the concentration of aliphatic amine in the molybdenum-containing precipitation slurry is preferably 0.1% by mass or more, more preferably 20% by mass or more.
  • the aliphatic amine is more preferably methylamine or dimethylamine, and particularly preferably methylamine.
  • the quaternary ammonium compound is preferably mixed so that the concentration of the quaternary ammonium compound in the molybdenum-containing precipitation slurry is 40% by mass or less.
  • the concentration of the quaternary ammonium compound in the molybdenum-containing precipitation slurry is preferably 0.1% by mass or more, more preferably 20% by mass or more.
  • the quaternary ammonium compound is more preferably tetramethylammonium hydroxide (TMAH) or tetraethylammonium hydroxide (TEAH).
  • molybdenum neutralization process molybdenum washing process, and molybdenum dissolving process may be performed at room temperature, and there is no particular need to adjust the respective temperatures.
  • the titanium acid dispersion containing the quaternary ammonium compound and the element M oxide dispersion containing the organic nitrogen compound obtained through each of the above-described production steps are compared to the total amount of titanium and element M.
  • a mixture prepared so that the molar ratio M/(Ti+M) is 0.01 to 0.8 is stirred at room temperature (25° C.) for 10 minutes to form the composite metal acid compound dispersion of the present invention.
  • a liquid is obtained.
  • the element M oxide dispersions are niobic acid dispersions, tantalic acid dispersions, tungstic acid dispersions, molybdic acid dispersions, and mixed dispersions thereof.
  • the total addition amount of the organic nitrogen compound containing the quaternary ammonium compound in the titanic acid dispersion and the organic nitrogen compound in the element M oxide dispersion was 0.00 in terms of the molar ratio of the organic nitrogen compound/(Ti+M). It is preferably 44-2.0, more preferably 0.46-1.6, and particularly preferably 0.5-1.3.
  • the organic nitrogen compound in the titanic acid dispersion is preferably an amine or a quaternary ammonium compound.
  • the quaternary ammonium compound in the titanic acid dispersion is tetramethylammonium hydroxide (TMAH) or tetraethylammonium hydroxide (TEAH), it not only has high solubility but also high crystallization suppression and high Tetramethylammonium hydroxide (TMAH) is more preferable because it suppresses solation.
  • the organic nitrogen compound in the element M oxide dispersion is preferably an amine or a quaternary ammonium compound. Further, the organic nitrogen compound in the element M oxide dispersion is more preferably tetramethylammonium hydroxide (TMAH), in accordance with the titanic acid dispersion.
  • the composite metal acid compound film of the present invention is characterized by containing the composite metal acid compound in the composite metal acid compound dispersion liquid described above.
  • the composite metal oxide compound film of the present invention can be used as a conductive film for smartphone displays, touch panels, solar cells, and the like.
  • the composite metal acid compound film of the present invention preferably has a surface resistivity of 20.0 ⁇ / ⁇ from the viewpoint of excellent conductive performance.
  • the surface resistivity is more preferably 10.0 ⁇ / ⁇ or less, further preferably 5.0 ⁇ / ⁇ or less, particularly preferably 1.0 ⁇ / ⁇ or less, and 0.5 ⁇ / ⁇ or less. is more particularly preferable, and 0.1 ⁇ / ⁇ or less is particularly preferable.
  • the surface resistivity is preferably 0 ⁇ / ⁇ or more, more preferably more than 0 ⁇ / ⁇ , and even more preferably 0.0001 ⁇ / ⁇ or more.
  • the surface resistivity is a value measured according to JIS-K6911.
  • the surface resistivity was measured using a resistivity meter (manufactured by Mitsubishi Chemical Corporation: Loresta-GX MCP-T700) by applying a 4-terminal probe to each surface of the sample formed in the form of a coating film. is the surface resistivity of
  • the method for producing a composite metal acid compound film of the present invention includes a coating step of applying the above-described composite metal acid compound dispersion of the present invention to the surface of a base material, and A drying step of drying the metal acid compound dispersion to obtain a coating film, and firing the coating film in the atmosphere at a firing temperature of 600° C. or more and 1,200° C. or less for a firing time of 30 minutes or more and 10 hours or less.
  • a coating film firing step and the fired coating film is fired in a reducing atmosphere at a firing temperature of 600° C. or more and 1,200° C. or less for a firing time of 30 minutes or more and 10 hours or less to form a composite metal acid compound film. and an oxide film reduction step for obtaining the oxide film.
  • the composite metal acid compound dispersion obtained by the above-described method for producing a composite metal acid compound dispersion of the present invention is filtered with a filter having a pore size of 2 ⁇ m, for example, while being filtered with a syringe. Drop it on the surface of the material and apply it by spin coating (1,500 rpm, 30 seconds). Next, the coated area is air-dried with high-pressure air to form a coating film on the surface of the substrate. Then, the base material on which the coating film is formed is placed in a static furnace and fired in the air at a firing temperature of 600 ° C. or higher and 1,200 ° C. or lower for a firing time of 30 minutes or more and 10 hours or less.
  • the composite metal oxide compound film of the present invention can be obtained by firing in a reducing atmosphere (so-called hydrogen reduction) at a firing temperature of 600° C. to 1,200° C. for a firing time of 30 minutes to 10 hours.
  • the baking temperature in the coating film baking step is 900° C. or more and 1,100° C. or less, the baking time is 3 hours or more and 10 hours or less, and the oxide film is More preferably, the firing temperature in the reduction step is 900° C. or higher and 1,100° C. or lower, and the firing time is 3 hours or longer and 10 hours or shorter.
  • the composite metal acid compound film of the present invention is characterized in that the crystal structure of the composite metal acid compound crystal grains in the composite metal acid compound film of the present invention includes the rutile type.
  • the crystal structure of the composite metal acid compound crystal particles in the composite metal acid compound film of the present invention contains the rutile type, it is preferable in terms of excellent conductivity.
  • the anatase ratio which indicates the ratio of the molar ratio of the anatase form to the total molar ratio, is preferably less than 100%, more preferably 80% or less, further preferably 60% or less, and particularly 40% or less. It is preferably 20% or less, more preferably 10% or less, and even more preferably 5% or less. A percent anatase of 0% is most preferred.
  • anatase rate (%) of the composite metal acid compound crystal particles in the composite metal acid compound film of the present invention is determined by X-ray diffraction measurement in accordance with ASTM D 3720-90, and the following formula (1) can be calculated.
  • the XRD peak area (Ir) indicating the rutile crystal structure and the XRD peak area (Ia) indicating the anatase crystal structure in the formula (1) protrude from the baseline in the corresponding diffraction line of the X-ray diffraction spectrum.
  • a known method may be used for calculating the area, such as computer calculation, approximate triangulation, or the like.
  • the weight of the rutile powder (Wr) is the measured value of the weight of the rutile powder
  • the weight of the anatase powder (Wa) is the measured value of the weight of the anatase powder.
  • K is a constant that is calculated by plotting several points of the difference between the actual weight ratio and the X-ray intensity ratio, and corrects this difference.
  • the anatase rate is 100%. Further, when an XRD peak indicating a rutile crystal structure is observed but no XRD peak indicating an anatase crystal structure is observed, the anatase rate is set to 0%.
  • the total ratio of the amorphous and anatase forms which indicates the ratio of the total molar ratio of the amorphous and anatase forms to the total molar ratio, is preferably less than 100%, more preferably 80% or less, and even more preferably 60% or less. , particularly preferably 40% or less, more preferably 20% or less, particularly preferably 10% or less, and even more particularly preferably 5% or less. Most preferably, the combined proportion of the amorphous and anatase forms is 0%.
  • the total ratio of amorphous and anatase forms refers to the change of the amorphous crystal structure to the anatase form by heating a sample taken from the composite metal acid compound film at 400° C. for 3 hours in an air atmosphere. is the anatase rate of the sample. Since the XRD peak indicating the amorphous crystal structure is broadening, it is impossible to calculate a strict intensity ratio, so by heating the sample to change the amorphous to anatase type, A region can be specified. For example, in a composite metal acid compound film with an anatase rate of 40% and an amorphous peak detected, the composite metal acid compound film is heated at 400 ° C. for 3 hours in an air atmosphere, and the composite metal acid compound film heated for 3 hours. If the anatase ratio of is 60%, the total ratio of amorphous and anatase forms in the composite metal acid compound film is set to 60%.
  • the composite metal acid compound powder of the present invention is selected from titanium and Nb, Ta, W, Mo, Si, Zn, Al, Y, La, Ce, Zr, Nd, Sm, Eu, Dy and Hf.
  • the composite metal acid compound powder is represented by the following composition formula (1) and has a particle size distribution using a laser diffraction/scattering method: Cumulative 10% particle size (D10) from the smallest measured particle size is 3 ⁇ m or more, cumulative 50% particle size (D50) is 50 ⁇ m or more, cumulative 50% particle size (D90) is 100 ⁇ m or more, and cumulative particle size The ratio [(D90-D10)/D50] is 4 or less.
  • x represents the total content of the element M. Further, x is a numerical value that satisfies the inequality expressed by 0.05 ⁇ x ⁇ 0.5.
  • the composite metal acid compound powder of the present invention is represented by the above compositional formula (1), where "x" indicates the sum of the contents (moles) of the element M, and is represented by 0.05 ⁇ x ⁇ 0.5. satisfy the inequality. Further, “O” represents an oxygen element, and if the valence of the element M is “a”, the inequality expressed by y ⁇ 2+(a/2 ⁇ 2)x is satisfied.
  • the composite metal acid compound powder of the present invention has a cumulative 10% particle size (D10) from the smaller particle size measured by particle size distribution measurement using a laser diffraction/scattering method of 3 ⁇ m or more, and a cumulative 50% particle size ( D50) is 50 ⁇ m or more, the cumulative 90% particle size (D90) is 100 ⁇ m or more, and the cumulative particle size ratio [(D90 ⁇ D10)/D50] is 4 or less, the particle size is large and the particle size distribution is narrow. is preferred. Also, the cumulative 10% particle diameter (D10) is more preferably 7 ⁇ m or more, and even more preferably 40 ⁇ m or more.
  • the cumulative 50% particle diameter (D50) is more preferably 100 ⁇ m or more, and even more preferably 150 ⁇ m or more.
  • the cumulative 90% particle size (D90) is more preferably 200 ⁇ m or more, and even more preferably 300 ⁇ m or more.
  • the upper limit of the cumulative particle size ratio [(D90-D10) / D50] is preferably 4 or less, more preferably 3 or less, 2.8 or less, 2.5 or less, 2.3 Below, it is more preferably 2 or less, and particularly preferably 1.9 or less, 1.5 or less, or 1.3 or less.
  • the lower limit of the cumulative particle size ratio [(D90-D10)/D50] is theoretically preferable as close to 0 as possible. It is more preferably 0.5 or more, more preferably more than 0, and particularly preferably 0 or more.
  • the laser diffraction/scattering method is performed by a dynamic light scattering method according to JIS Z 8825:2013 using a particle size distribution measuring device (manufactured by Microtrack Bell Co., Ltd.: MT3300EXII). Moreover, filtering is not performed, and the following dispersion processing using ultrasonic waves is performed.
  • the procedure for ultrasonically dispersing the composite metal acid compound crystal particles in the composite metal acid compound powder is as follows. First, as a pretreatment for dispersion treatment by ultrasonic waves, 1 mg of sample powder and 20 mL of pure powder are put into a PP wide-mouthed bottle with a capacity of 50 mL, and the PP wide-mouthed bottle is ultrasonically cleaned (manufactured by AS ONE: VS-100III). set. Next, in a state in which pure water is filled up to 5 cm above the inner floor of the washing machine, ultrasonic dispersion treatment is performed at a frequency of 28 kHz for 60 minutes.
  • the composite metal acid compound powder of the present invention preferably has a dust resistance value of 15.0 ⁇ cm or less because it is less likely to aggregate and has excellent fluidity.
  • the dust resistance value is more preferably 10.0 ⁇ cm or less, further preferably 5.0 ⁇ cm or less, particularly preferably 1.0 ⁇ cm or less, and 0.5 ⁇ cm The following are more particularly preferred.
  • the dust resistance value is preferably 0 ⁇ cm or more, more preferably over 0 ⁇ cm, and even more preferably 0.001 ⁇ cm or more.
  • the dust resistance value is measured using a resistivity meter (manufactured by Mitsubishi Chemical Analytech: MCP-PD51). Specifically, after a powder sample is filled in a cylindrical measurement container to form a powder sample layer, a predetermined load is applied to the top surface of the powder sample layer to compact it to obtain a powder compact. Next, the green compact is compacted under conditions of a temperature of 25° C. and a humidity of 50%, and the thickness and resistance are measured, and the volume resistivity of the green compact is calculated from these values and the inner diameter of the measurement container. This is taken as the dust resistance value.
  • a resistivity meter manufactured by Mitsubishi Chemical Analytech: MCP-PD51.
  • the method for producing a composite metal acid compound powder of the present invention includes a drying step of vacuum-drying the above-described composite metal acid compound dispersion to obtain a dry powder, and firing the dry powder in the atmosphere at a temperature of 600 ° C. or higher.
  • the composite metal acid compound dispersion obtained by the above-described method for producing a composite metal acid compound dispersion of the present invention is placed in a stationary furnace and vacuum-dried at a heating temperature of about 80° C. for 7 hours.
  • a heating temperature of about 80° C. for 7 hours By removing the moisture in the composite metal acid compound dispersion of the present invention, an intermediate product of the composite metal acid compound powder containing the composite metal acid compound crystal particles contained in the composite metal acid compound dispersion of the present invention is obtained. (hereinafter referred to as "dry powder") is obtained.
  • the obtained dry powder is placed in a stationary furnace and fired in the atmosphere at a firing temperature of 600 ° C. or higher and 1,200 ° C. or lower for a firing time of 30 minutes or more and 10 hours or less, and then reduced.
  • the composite metal acid compound powder of the present invention is obtained by firing in an atmosphere (so-called hydrogen reduction) at a firing temperature of 600° C. or higher and 1,200° C. or lower for a firing time of 30 minutes or longer and 10 hours or shorter.
  • the obtained dry powder is fired in the atmosphere at a firing temperature of 600 ° C. or higher and 1,200 ° C. or lower for a firing time of 30 minutes or more and 10 hours or less, and then in a reducing atmosphere (so-called hydrogen reduction). is 600° C.
  • the firing temperature in the firing step is 900° C. to 1,100° C.
  • the firing time is 3 hours to 10 hours
  • the firing temperature in the reduction step is 900° C. to 1,100° C.
  • the firing time is 3.
  • the time is 10 hours or more, the time is sufficient for the growth of the composite metal acid compound crystal grains, and unnecessary costs can be suppressed, which is more preferable.
  • a powder obtained by pulverizing the fired product may be used as the composite metal acid compound powder.
  • the under-sieves fine particle side
  • the sieve top coarse particle side
  • a sieve when classifying using a sieve, it is preferable to use a sieve with an opening of 150 ⁇ m to 1,000 ⁇ m. When it is 150 ⁇ m to 1,000 ⁇ m, the proportion on the sieve does not become too large and re-pulverization is not repeated, and the composite metal acid compound powder which requires re-pulverization is not classified under the sieve.
  • the composite metal acid compound powder of the present invention thus obtained is mixed with water or an organic solvent as a dispersion medium, and wet pulverized using media such as beads to obtain a composite metal acid compound powder dispersion.
  • organic solvents used as dispersion media include alcohols, esters, ketones, aromatic hydrocarbons, aliphatic hydrocarbons, ethers, and mixed solvents thereof.
  • a binder such as a resin component may be added in order to improve the film-forming properties of the composite metal acid compound film of the present invention using the composite metal acid compound powder dispersion.
  • Resin components used as binders include, for example, acrylic resins, polyurethanes, epoxy resins, polystyrene, polycarbonates, glycol-based resins, cellulose-based resins, mixed resins thereof, and copolymer resins.
  • a composite metal acid compound film of the present invention is characterized by containing the composite metal acid compound powder of the present invention described above.
  • the composite metal acid compound film of the present invention may be formed from the composite metal acid compound powder of the present invention produced from the composite metal acid compound dispersion of the present invention described above.
  • the composite metal oxide compound film of the present invention can be used as a conductive film for smartphone displays, touch panels, solar cells, and the like.
  • the composite metal acid compound powder of the present invention is characterized in that the crystal structure of the composite metal acid compound crystal grains in the composite metal acid compound powder of the present invention includes the rutile type.
  • the crystal structure of the composite metal acid compound crystal particles in the composite metal acid compound powder of the present invention contains the rutile type, it is preferable from the viewpoint of excellent conductivity.
  • the crystal structure of the composite metal acid compound crystal particles in the composite metal acid compound powder of the present invention is an X-ray diffraction pattern obtained by X-ray diffraction measurement performed according to the following powder X-ray diffraction measurement conditions.
  • Powder X-ray diffraction measurement conditions ⁇ Diffraction device: MiniFlex2 (manufactured by Rigaku Corporation) ⁇ X-ray tube: Cu ⁇ Tube voltage/tube current: 30 kV, 15 mA ⁇ Slit: DS-SS; 1.25 degrees, RS; 0.3 mm ⁇ Monochromator graphite ⁇ Measurement interval: 0.01 degree ⁇ Counting method: constant counting method ⁇ X-ray analysis software: PDXL2 Version 2.9.1.0
  • anatase rate (%) of the composite metal acid compound crystal particles in the composite metal acid compound film of the present invention is calculated by the above formula (1) after performing X-ray diffraction measurement in accordance with ASTM D 3720-90. can do.
  • the crystal structure of the composite metal acid compound crystal particles in the composite metal acid compound film formed from the above-described composite metal acid compound powder of the present invention includes the rutile type. Characterized by When the crystal structure of the composite metal acid compound crystal particles in the composite metal acid compound film formed from the composite metal acid compound powder of the present invention contains the rutile type, it is preferable in terms of excellent conductivity.
  • the crystal structure of the composite metal acid compound crystal particles in the composite metal acid compound film formed from the composite metal acid compound powder of the present invention is determined by X-ray diffraction measurement performed under the above-described thin film X-ray diffraction measurement conditions.
  • anatase rate (%) of the composite metal acid compound crystal particles in the composite metal acid compound film formed from the composite metal acid compound powder of the present invention is measured by X-ray diffraction in accordance with ASTM D 3720-90. and can be calculated by the above formula (1).
  • the composite metal acid compound dispersion liquid, the composite metal acid compound film, and the composite metal acid compound powder of the present invention described above are not composited with the element M or the oxide of the element M, and the residual titanium or titanic acid, such as M- O + TiO 2 and additives such as Si, Zr, Zn, Al, Y, V, La (La, Ce, Nd, Eu, Gd, Dy, Yb), Hf, etc., within the range that does not inhibit their effects. It may contain oxide powder.
  • the content of the above-described additive is preferably less than 0.5% by mass, more preferably less than 0.1% by mass, when the composite metal acid compound of the present invention is taken as 100% by mass. It is more preferably less than 0.01% by mass.
  • the composite metal acid compound dispersion liquid, the composite metal acid compound film, and the composite metal acid compound powder of the present invention contain components derived from titanium or titanic acid, elements M to elements M, to the extent that their effects are not impaired.
  • a component derived from the oxide and a component other than the component derived from the dispersion medium (referred to as “other components”) may be contained.
  • Other components include, for example, Si, Zr, Zn, Al, Y, V, La-based (La, Ce, Nd, Eu, Gd, Dy, Yb), Hf, and the like. However, it is not limited to these.
  • the content of the above-mentioned other components is preferably less than 5% by mass, more preferably less than 4% by mass, and less than 3% by mass, based on 100% by mass of the composite metal acid compound of the present invention. It is even more preferable to have The composite metal acid compound dispersion liquid, the composite metal acid compound film, and the composite metal acid compound powder of the present invention are not intended and are assumed to contain unavoidable impurities.
  • the total content of inevitable impurities is preferably less than 1% by mass, more preferably less than 0.1% by mass, and more preferably less than 0.01% by mass when the composite metal acid compound of the present invention is 100% by mass. % is more preferred.
  • the antistatic film of the present invention is characterized by having the composite metal oxide compound film of the present invention described above.
  • the antistatic film of the present invention has, for example, a laminate structure comprising a substrate film and the composite metal acid compound film of the present invention formed on the substrate film.
  • the material of the base film is not particularly limited, but various resins and the like can be used, and can be appropriately selected according to the application.
  • the composite metal acid compound of the present invention is a mixture of titanium oxide particles and oxide particles of element M, or a mixture of partially composite metal acid compound particles and single metal acid compound particles. It also includes mixtures.
  • the composite metal acid compound dispersion of the present invention has high dispersibility and is easy to form a uniform coating film. Also, the composite metal acid compound film of the present invention formed from the composite metal acid compound dispersion of the present invention and the composite metal acid compound powder of the present invention have excellent conductive properties.
  • the composite metal acid compound dispersion liquid, the composite metal acid compound powder, and the composite metal acid compound film according to Examples 1 to 12, the titanate dispersion liquid, the titanium oxide powder, and the titanium oxide film according to Comparative Example 1, and the comparative example 2 is a list of physical property values and measurement results of titanic acid mixed powder and titanic acid mixed film according to No. 2.
  • FIG. 1 The composite metal acid compound dispersion liquid, the composite metal acid compound powder, and the composite metal acid compound film according to Examples 1 to 12, the titanate dispersion liquid, the titanium oxide powder, and the titanium oxide film according to Comparative Example 1, and the comparative example 2 is a list of physical property values and measurement results of titanic acid mixed powder and titanic acid mixed film according to No. 2.
  • Example 1 The composite metal acid compound dispersion according to Example 1 was obtained by mixing a titanic acid dispersion and a niobic acid dispersion prepared as described later, and stirring the resulting mixture at room temperature (25° C.) for 10 minutes. was taken.
  • a titanic acid dispersion was obtained, for example, by the steps described below.
  • titanyl sulfate manufactured by Tayka, TiO 2 concentration 33.3% by mass, sulfuric acid concentration 51.1% by mass
  • TiO 2 concentration 33.3% by mass, sulfuric acid concentration 51.1% by mass 33.3 g
  • TiO 2 concentration 33.3% by mass, sulfuric acid concentration 51.1% by mass 33.3 g
  • An aqueous titanyl sulfate solution titanium concentration (converted to TiO2 ) of 11% by mass, sulfuric acid of 17% by mass, pH of 1 or less) was obtained.
  • This titanyl sulfate aqueous solution was added to 2,200 g of 25% by mass ammonia water (18.9 mol of ammonia per 1 mol of sulfuric acid in the titanyl sulfate aqueous solution) over a period of less than 1 minute. After that, the mixture was stirred for 15 minutes to obtain a neutralization reaction liquid (pH 12).
  • This neutralization reaction liquid was a slurry of a titanium-containing substance, in other words a slurry of a titanium-containing precipitate.
  • This neutralization reaction liquid was decanted using a centrifuge and washed until the sulfuric acid content of the supernatant became 100 mg/L or less to obtain a titanium-containing precipitate from which sulfuric acid was removed. At this time, ammonia water was used as a cleaning liquid.
  • TiO 2 concentration contained in the titanium-containing precipitate was calculated from the mass.
  • the TiO2 concentration was 11.0 wt%.
  • TMAH concentration 50% by mass
  • a titanic acid aqueous solution was obtained by shaking for 24 hours with a shaker.
  • the niobic acid dispersion was obtained, for example, by the steps described below.
  • reaction liquid was a slurry of niobate compound hydrate, in other words, a slurry of niobium-containing precipitates.
  • this reaction liquid was decanted using a centrifuge and washed until the amount of liberated fluoride ions became 100 mg/L or less to obtain a niobium-containing precipitate from which the fluoride ions were removed. At this time, ammonia water was used as a cleaning liquid.
  • the niobium-containing precipitate from which the fluoride ions were removed was diluted with pure water to obtain a slurry. A portion of this slurry was dried at 110° C. for 24 hours and then calcined at 1,000° C. for 4 hours to produce Nb 2 O 5 , and the concentration of Nb 2 O 5 contained in the slurry was calculated from its weight.
  • the particle size (D50) of the resulting niobium-containing precipitate slurry was less than 1 nm as determined by particle size distribution measurement using a dynamic light scattering method.
  • the niobium-containing precipitate slurry diluted with pure water is mixed with 40% by mass of methylamine and pure water so that the final mixture has a niobium concentration of 5% by mass in terms of Nb 2 O 5 , and this While stirring the mixture, the liquid temperature was kept at room temperature (25° C.) for 1 hour to obtain a niobic acid dispersion.
  • a mixture prepared by mixing the titanic acid dispersion and the niobic acid dispersion so that the molar ratio Nb/(Ti+Nb) is 0.05 was stirred at room temperature (25° C.) for 10 minutes, and then the mixture was was placed in a stationary furnace to obtain a composite metal acid compound dispersion according to Example 1.
  • the oxide concentration of the composite metal acid compound dispersion according to Example 1 was 10% by mass. The oxide concentration was calculated from each oxide concentration of the titanic acid dispersion and the niobic acid dispersion before mixing.
  • the composite metal acid compound powder according to Example 1 was obtained as follows.
  • the composite metal acid compound dispersion according to Example 1 was placed in a stationary furnace and vacuum-dried at a heating temperature of about 80° C. for 7 hours to obtain A dry powder was obtained by evaporating the water from the Then, the dry powder is placed in a stationary furnace, fired in the atmosphere at a firing temperature of 900 ° C. for 3 hours, and then hydrogen-reduced at a firing temperature of 1,000 ° C. for 1 hour. Thus, a composite metal acid compound powder according to Example 1 was obtained.
  • the composite metal oxide compound film according to Example 1 was obtained as follows.
  • the composite metal acid compound dispersion liquid according to Example 1 was dropped onto a 15 mm x 15 mm glass substrate using a syringe, and applied by spin coating (1,500 rpm, 30 seconds). Then, the applied portion was air-dried with high-pressure air to form a coating film on the glass substrate. The coating film is placed in a stationary furnace, baked in the atmosphere at a baking temperature of 900 ° C. for 3 hours, and then hydrogen-reduced at a baking temperature of 1,000 ° C. for 1 hour. , a composite metal oxide compound film according to Example 1 was obtained. Moreover, the crystal structure of the composite metal acid compound according to Example 1 was rutile type, and the anatase rate was 0%.
  • Example 2 The composite metal acid compound dispersion according to Example 2 was prepared so that the molar ratio Nb/(Ti+Nb) was 0.5 when the titanic acid dispersion and the niobic acid dispersion were mixed.
  • a composite metal acid compound dispersion according to Example 2 was obtained in the same manner as in Example 1. Further, the composite metal acid compound powder and the composite metal acid compound film according to Example 2 were prepared in the same manner as in Example 1 except that they were produced from the composite metal acid compound dispersion liquid according to Example 2. A composite metal acid compound powder and a composite metal acid compound film according to No. were obtained.
  • the oxide concentration of the composite metal acid compound dispersion liquid according to Example 2 was calculated in the same manner as in Example 1 and was 10% by mass.
  • the crystal structure of the composite metal acid compound according to Example 2 was rutile type, and the anatase rate was 0%.
  • Example 3 The composite metal acid compound dispersion according to Example 3 was prepared so that the molar ratio Nb/(Ti+Nb) was 0.3 when the titanic acid dispersion and the niobic acid dispersion were mixed. In the same manner as in Example 1, a composite metal acid compound dispersion according to Example 3 was obtained. Further, the composite metal acid compound powder and the composite metal acid compound film according to Example 3 were prepared in the same manner as in Example 1 except that they were produced from the composite metal acid compound dispersion liquid according to Example 3. A composite metal acid compound powder and a composite metal acid compound film according to No. were obtained. The oxide concentration of the composite metal acid compound dispersion liquid according to Example 3 was calculated in the same manner as in Example 1 and was 10% by mass. The crystal structure of the composite metal acid compound according to Example 3 was rutile type, and the anatase ratio was 0%.
  • Example 4 The composite metal acid compound dispersion according to Example 4 was prepared so that the molar ratio Nb/(Ti+Nb) was 0.01 when the titanic acid dispersion and the niobic acid dispersion were mixed. A composite metal acid compound dispersion according to Example 4 was obtained in the same manner as in Example 1. Further, the composite metal acid compound powder and the composite metal acid compound film according to Example 4 were prepared in the same manner as in Example 1 except that they were produced from the composite metal acid compound dispersion liquid according to Example 4. A composite metal acid compound powder and a composite metal acid compound film according to No. were obtained. The oxide concentration of the composite metal acid compound dispersion liquid according to Example 4 was calculated in the same manner as in Example 1 and was 10% by mass. Moreover, the crystal structure of the composite metal acid compound according to Example 4 was of rutile type, and the anatase ratio was 0%.
  • Example 5 The composite metal acid compound dispersion according to Example 5 was prepared so that the molar ratio Nb/(Ti+Nb) was 0.8 when the titanic acid dispersion and the niobic acid dispersion were mixed.
  • a composite metal acid compound dispersion according to Example 5 was obtained in the same manner as in Example 1.
  • the composite metal acid compound powder and the composite metal acid compound film according to Example 5 were prepared in the same manner as in Example 1 except that they were produced from the composite metal acid compound dispersion liquid according to Example 5.
  • a composite metal acid compound powder and a composite metal acid compound film according to No. were obtained.
  • the oxide concentration of the composite metal acid compound dispersion liquid according to Example 5 was calculated in the same manner as in Example 1 and was 10% by mass.
  • the crystal structure of the composite metal acid compound according to Example 5 was rutile type, and the anatase ratio was 0%.
  • Example 6 The composite metal acid compound dispersion according to Example 6 was obtained by mixing a titanic acid dispersion and a tantalic acid dispersion prepared as described later, and stirring the resulting mixture at room temperature (25° C.) for 10 minutes. was taken.
  • a titanic acid dispersion was obtained in the same manner as in Example 1.
  • the tantalic acid dispersion was obtained, for example, by the steps described below.
  • tantalum hydroxide manufactured by Mitsui Kinzoku Mining Co., Ltd. (Ta 2 O 5 concentration 66% by mass) was dissolved in 120 g of a 55% by mass hydrofluoric acid aqueous solution, and 849 mL of ion-exchanged water was added to obtain a tantalum fluoride aqueous solution ( Ta 2 O 5 concentration of 9.1 mass %) was obtained.
  • This tantalum fluoride aqueous solution was added to 100 mL of 50% by weight dimethylamine over a period of less than 1 minute. After that, the mixture was stirred for 15 minutes to obtain a primary reaction liquid (pH 11). This primary reaction liquid was added to 460 mL of ammonia water (NH 3 concentration: 25% by mass) over a period of less than 1 minute to obtain a secondary reaction liquid (pH 12).
  • This secondary reaction liquid was a slurry of tantalum compound hydrate, in other words, a slurry of tantalum-containing precipitates.
  • this secondary reaction solution was decanted using a centrifuge and washed until the amount of free fluorine in the supernatant became 100 mg/L or less to obtain a tantalum-containing precipitate from which fluorine had been removed. At this time, ammonia water was used as a cleaning liquid.
  • Ta 2 O 5 concentration was 38 mass %.
  • the mixed solution prepared so that the molar ratio Ta/(Ti+Ta) is 0.05 is stirred at room temperature (25° C.) for 1 hour, The mixture was placed in a stationary furnace to obtain a composite metal acid compound dispersion according to Example 6.
  • the oxide concentration of the composite metal acid compound dispersion according to Example 6 was 10% by mass. The oxide concentration was calculated from each oxide concentration of the titanic acid dispersion and the tantalic acid dispersion before mixing.
  • the composite metal acid compound powder and the composite metal acid compound film according to Example 6 were prepared in the same manner as in Example 1 except that they were produced from the composite metal acid compound dispersion liquid according to Example 6. A composite metal acid compound powder and a composite metal acid compound film were obtained.
  • the crystal structure of the composite metal acid compound according to Example 6 was rutile type, and the anatase rate was 0%.
  • Example 7 The composite metal acid compound dispersion according to Example 7 was prepared so that the molar ratio Ta/(Ti+Ta) was 0.2 when the titanic acid dispersion and the tantalic acid dispersion were mixed. A composite metal acid compound dispersion according to Example 7 was obtained in the same manner as in Example 6. Further, the composite metal acid compound powder and the composite metal acid compound film according to Example 7 were prepared in the same manner as in Example 1 except that they were produced from the composite metal acid compound dispersion liquid according to Example 7. A composite metal acid compound powder and a composite metal acid compound film were obtained. The oxide concentration of the composite metal acid compound dispersion liquid according to Example 7 was calculated in the same manner as in Example 6 and was 10% by mass. Moreover, the crystal structure of the composite metal acid compound according to Example 7 was of rutile type, and the anatase rate was 0%.
  • Example 8 The composite metal acid compound dispersion according to Example 8 was obtained by mixing a titanic acid dispersion and a molybdic acid dispersion prepared as described later, and stirring the resulting mixture at room temperature (25° C.) for 10 minutes. was taken.
  • a titanic acid dispersion was obtained in the same manner as in Example 1.
  • the molybdic acid dispersion was obtained, for example, by the steps described below.
  • this reaction liquid was decanted using a centrifuge and washed until the conductivity became 500 ⁇ S/cm or less to obtain a molybdenum-containing precipitate from which sulfur was removed. At this time, ammonia water was used as a cleaning liquid.
  • the molybdenum-containing precipitation slurry diluted with pure water from which the sulfur content has been removed is diluted with 25% by mass of tetramethylammonium hydroxide (TMAH) so that the molybdenum concentration of the final mixture is 10% by mass in terms of MoO3 .
  • TMAH tetramethylammonium hydroxide
  • An aqueous solution and pure water were mixed, and the mixture was kept at room temperature (25° C.) for 1 hour while stirring to obtain a molybdic acid dispersion.
  • the mixed solution prepared so that the molar ratio Mo/(Ti+Mo) is 0.05 is stirred at room temperature (25° C.) for 10 minutes, The mixed solution was placed in a stationary furnace to obtain a composite metal acid compound dispersion solution according to Example 8.
  • the oxide concentration of the composite metal acid compound dispersion according to Example 8 was 5% by mass. The oxide concentration was calculated from each oxide concentration of the titanic acid dispersion and the molybdic acid dispersion before mixing.
  • the composite metal acid compound powder and the composite metal acid compound film according to Example 8 were prepared in the same manner as in Example 1 except that they were produced from the composite metal acid compound dispersion liquid according to Example 8. A composite metal acid compound powder and a composite metal acid compound film were obtained.
  • the crystal structure of the composite metal acid compound according to Example 8 was rutile type, and the anatase rate was 0%.
  • Example 9 The composite metal acid compound dispersion according to Example 9 was prepared so that the molar ratio Mo/(Ti+Mo) was 0.2 when the titanic acid dispersion and the molybdic acid dispersion were mixed.
  • a composite metal acid compound dispersion according to Example 9 was obtained in the same manner as in Example 8.
  • the composite metal acid compound powder and the composite metal acid compound film according to Example 9 were prepared in the same manner as in Example 1 except that they were produced from the composite metal acid compound dispersion liquid according to Example 9.
  • a composite metal acid compound powder and a composite metal acid compound film were obtained.
  • the oxide concentration of the composite metal acid compound dispersion liquid according to Example 9 was calculated in the same manner as in Example 8 and was 2% by mass.
  • the crystal structure of the composite metal acid compound according to Example 9 was rutile type, and the anatase rate was 0%.
  • Example 10 The composite metal acid compound dispersion according to Example 10 was obtained by mixing a titanic acid dispersion and a tungstic acid dispersion prepared as described below and stirring the resulting mixture at room temperature (25°C) for 10 minutes. was taken.
  • a titanic acid dispersion was obtained in the same manner as in Example 1.
  • the tungstic acid dispersion was obtained, for example, by the steps described below.
  • this reaction liquid was decanted using a centrifuge and washed until the conductivity became 500 ⁇ S/cm or less to obtain a tungsten-containing precipitate from which sulfur was removed. At this time, ammonia water was used as a cleaning liquid.
  • the sulfur-removed tungsten-containing precipitation slurry diluted with pure water is mixed with 2% by mass of methylamine and pure water so that the final mixture has a tungsten concentration of 10% by mass in terms of WO3 .
  • the mixture was stirred and kept at room temperature (25° C.) for 1 hour to obtain a tungstic acid dispersion according to Example 10.
  • the mixed solution prepared so that the molar ratio W/(Ti+W) is 0.05 is stirred at room temperature (25° C.) for 10 minutes, The mixture was placed in a stationary furnace to obtain a composite metal acid compound dispersion according to Example 10.
  • the oxide concentration of the composite metal acid compound dispersion according to Example 10 was 5% by mass. The oxide concentration was calculated from each oxide concentration of the titanic acid dispersion and the tungstic acid dispersion before mixing.
  • the composite metal acid compound powder and the composite metal acid compound film according to Example 10 were prepared in the same manner as in Example 1, except that they were produced from the composite metal acid compound dispersion liquid according to Example 10. A composite metal acid compound powder and a composite metal acid compound film were obtained. Moreover, the crystal structure of the composite metal acid compound according to Example 10 was of rutile type, and the anatase rate was 0%.
  • Example 11 The composite metal acid compound dispersion according to Example 11 was prepared so that the molar ratio W/(Ti+W) was 0.2 when the titanic acid dispersion and the tungstic acid dispersion were mixed. A composite metal acid compound dispersion according to Example 11 was obtained in the same manner as in Example 10. Further, the composite metal acid compound powder and the composite metal acid compound film according to Example 11 were prepared in the same manner as in Example 1, except that they were produced from the composite metal acid compound dispersion liquid according to Example 11. A composite metal acid compound powder and a composite metal acid compound film were obtained. The oxide concentration of the composite metal acid compound dispersion liquid according to Example 11 was calculated in the same manner as in Example 10 and was 2% by mass. Moreover, the crystal structure of the composite metal acid compound according to Example 11 was of rutile type, and the anatase rate was 0%.
  • Example 12 The composite metal acid compound dispersion according to Example 12 was obtained by mixing a titanic acid dispersion, a niobic acid dispersion, a tantalic acid dispersion, a molybdic acid dispersion, and a tungstic acid dispersion prepared as described later. The resulting mixture was stirred at room temperature (25° C.) for 10 minutes.
  • a titanic acid dispersion and a niobic acid dispersion were obtained in the same manner as in Example 1.
  • a tantalic acid dispersion was obtained in the same manner as in Example 6.
  • a molybdic acid dispersion was obtained in the same manner as in Example 8.
  • a tungstic acid dispersion was obtained in the same manner as in Example 10.
  • the molar ratio M/(Ti+M) is 0.1 (total 0.4), specifically, Nb / (Ti + Nb), Ta / (Ti + Ta), Mo / (Ti + Mo), W / (Ti + W) are each 0.1 (total 0.4)
  • the mixed solution prepared to have the following conditions at room temperature (25° C.) for 10 minutes the mixed solution was placed in a stationary furnace to obtain a composite metal acid compound dispersion according to Example 12.
  • the composite metal acid compound powder and the composite metal acid compound film according to Example 12 were prepared in the same manner as in Example 1, except that they were produced from the composite metal acid compound dispersion liquid according to Example 12. A composite metal acid compound powder and a composite metal acid compound film were obtained.
  • the oxide concentration of the composite metal acid compound dispersion according to Example 12 was 10% by mass.
  • the crystal structure of the composite metal acid compound according to Example 12 was rutile type, and the anatase ratio was 0%.
  • Comparative Example 1 does not mix with the dispersion liquid of the oxide of the element M, and contains only the titanic acid dispersion liquid. Further, the titanate powder and the titanate film according to Comparative Example 1 were prepared in the same manner as in Example 1, except that the titanate powder and the titanate film according to Comparative Example 1 were produced from the titanate dispersion according to Comparative Example 1. and a titanium oxide film was obtained. The oxide concentration of the titanic acid dispersion according to Comparative Example 1 was 10% by mass. The crystal structure of the composite metal acid compound according to Comparative Example 1 was of rutile type, and the anatase rate was 0%.
  • Comparative Example 2 is a titanic acid mixed powder comprising titanium oxide and niobium oxide.
  • the crystal structure of the composite metal acid compound according to Comparative Example 2 was rutile type, and the anatase ratio was 0%.
  • the titanic acid mixed powder according to Comparative Example 2 has low dispersibility in a dispersion medium, and cannot be formed into a film using a titanic acid mixed aqueous dispersion dispersed in pure water, and the surface resistivity is measured. I could't. Therefore, the titanic acid mixed film according to Comparative Example 2 was prepared by dissolving the titanic acid-containing mixed resin obtained by kneading the titanic acid mixed powder according to Comparative Example 2 into 8.5% by mass acrylic resin using a syringe. It was dropped onto the substrate and applied by spin coating (1,500 rpm, 30 seconds) to form a coating film on the glass substrate. The coating film was placed in a stationary furnace and fired in the atmosphere at a firing temperature of 100° C. for 1 hour to obtain a titanic acid mixed film according to Comparative Example 2.
  • FIG. 1 shows the physical properties measured by the measuring method described later and the test results.
  • Transmittance measurement conditions ⁇ Measurement device: Ultraviolet-visible-near-infrared spectrophotometer UH4150 type (manufactured by Hitachi High-Tech Science Co., Ltd.) ⁇ Measurement mode: wavelength scan ⁇ Data mode: %T (transmission) ⁇ Measurement wavelength range: 200 to 2,600 nm ⁇ Scan speed: 600 nm/min ⁇ Sampling interval: 2 nm
  • the transmittance at a wavelength of 500 nm was calculated from the transmittance obtained by measurement.
  • ⁇ Dynamic light scattering method> The particle size distribution of the composite metal acid compound dispersions according to Examples 1 to 12 and the titanic acid dispersion according to Comparative Example 1 was evaluated using a zeta potential/particle size/molecular weight measurement system (manufactured by Otsuka Electronics Co., Ltd.: ELSZ-2000ZS ) using dynamic light scattering method according to JIS Z 8828:2019. In addition, it was filtered through a filter with a pore size of 2 ⁇ m, and the above-mentioned dispersion treatment using ultrasonic waves was performed.
  • the particle diameter (D50) refers to the median diameter (D50), which is the particle diameter indicating the 50% integrated value of the integrated distribution curve.
  • the “initial particle size (nm)” in FIG. 1 is the particle size (D50) of the composite metal acid compound in the composite metal acid compound dispersion liquid according to Examples 1 to 11, which was adjusted to a liquid temperature of 25° C. immediately after being produced. is the particle size (D50) of the titanium oxide in the titanic acid dispersion according to Comparative Example 1.
  • the “particle size over time (nm)” in FIG. It is the particle size (D50) of the compound, and the particle size (D50) of the titanium oxide in the titanic acid dispersion according to Comparative Example 1.
  • Comparative Example 2 is a mixed powder, it is not measured.
  • ⁇ Temporal stability test> The composite metal acid compound dispersions according to Examples 1 to 12 and the titanic acid dispersion according to Comparative Example 1 were allowed to stand in a thermostat set at room temperature of 25° C. for one month, and then the particle size over time was measured. The presence or absence of a significant increase in particle size was confirmed by comparing with the particle size, and the presence or absence of precipitates was visually observed. If the particle size over time is 10 times or less than the initial particle size, it is assumed that no significant increase in particle size was observed, and it is evaluated as having stability over time as " ⁇ (GOOD)", and the particle size over time is compared to the initial particle size.
  • ⁇ GOOD
  • the particle size (D50) of the composite metal acid compound over time in the composite metal acid compound dispersions according to Examples 1 to 12 after standing for one month, and the titanate dispersion according to Comparative Example 1 was measured using the dynamic light scattering method described above.
  • D10 ( ⁇ m) in FIG. 1 is the cumulative 10% particle size (D10) from the smaller particle size.
  • D50 ( ⁇ m) in FIG. 1 is the cumulative 50% particle size (D50) from the smaller particle size.
  • D90 ( ⁇ m) in FIG. 1 is the cumulative 90% particle size (D90) from the smaller particle size.
  • (D90-D10)/D50” in FIG. 1 is the ratio of these cumulative particle sizes.
  • D50 (with US) / D50 (without US) is 1 ⁇ 0.5, the powder has excellent fluidity, the resistance when forming a coating film is small, and a film with a uniform film thickness is formed. It is preferable because it is easy to use.
  • “D50 (with US)/D50 (without US)” is more preferably 1 ⁇ 0.3, still more preferably 1 ⁇ 0.2, and particularly preferably 1 ⁇ 0.1.
  • ⁇ Powder resistance value> The powder resistance values of the composite metal acid compound powders according to Examples 1 to 12, the titanium oxide powder according to Comparative Example 1, and the titanic acid mixed powder according to Comparative Example 2 (hereinafter referred to as "powder samples") are It was measured using a resistivity meter (manufactured by Mitsubishi Chemical Analytic Tech: MCP-PD51). Specifically, a cylindrical measurement container with an inner diameter of 20 mm is filled with 5 g of a powder sample to form a powder sample layer, and then a load of 4 kN is applied to the upper surface of the powder sample layer to compact it. got a body The compact is compacted under conditions of a temperature of 25 ° C. and a humidity of 50% (while a load of 4 kN is applied), and the thickness and resistance are measured. The volume resistivity of the body was calculated and taken as the dust resistance value.
  • the surface resistivities of the composite metal acid compound films according to Examples 1 to 12, the titanium oxide film according to Comparative Example 1, and the titanic acid mixed film according to Comparative Example 2 are values measured according to JIS-K6911. is.
  • the surface resistivities of the composite metal acid compound films according to Examples 1 to 12 and the titanium oxide film according to Comparative Example 1 were measured using a resistivity meter (manufactured by Mitsubishi Chemical Corporation: Loresta-GX MCP-T700). , and Comparative Example 2, a four-terminal probe was applied to each surface, and the surface resistivity of each surface was measured.
  • the surface resistivity of the titanic acid mixed film according to Comparative Example 2 was obtained by baking the titanic acid-containing mixed resin in which the titanic acid mixed powder according to Comparative Example 2 was kneaded into 8.5% by mass acrylic resin. , and the film formation conditions are different from those of the composite metal oxide film according to Examples 1 to 11 and the titanium oxide film according to Comparative Example 1.
  • the composite metal acid compound dispersions according to Examples 1 to 12 had excellent solution stability during long-term storage when the molar ratio M/(Ti+M) was 0.01-0.8.
  • the composite metal acid compound dispersions according to Examples 1 to 12 had excellent stability when their pH was 12 or higher.
  • the composite metal acid compound powders according to Examples 1 to 12 had a cumulative 10% particle size (D10) of 3 ⁇ m or more from the smaller particle size as determined by particle size distribution measurement using a laser diffraction/scattering method, and cumulative 50% particles. Since the diameter (D50) is 50 ⁇ m or more, the cumulative 90% particle size (D90) is 100 ⁇ m or more, and the cumulative particle size ratio [(D90 ⁇ D10)/D50] is 4 or less, the particle size is large and the particle size distribution The sintered powder was narrow.
  • the particle size ratio "D50 (with US)/D50 (without US)" before and after dispersion treatment using ultrasonic waves is within the range of 1 ⁇ 0.5. Therefore, the fluidity of the powder is excellent, the resistance when forming a coating film is small, and a film having a uniform thickness can be easily formed.
  • the composite metal acid compound powders according to Examples 1 to 12 had a compaction resistance of 15.0 ⁇ cm or less, and thus were less likely to agglomerate and had excellent fluidity.
  • the composite metal acid compound films according to Examples 1 to 12 had a surface resistivity of 20 ⁇ / ⁇ or less, and were excellent in conductive performance.
  • the composite metal acid compound dispersion liquid according to the present invention can easily form a uniform coating film and can form a coating film having excellent conductive performance.
  • the composite metal oxide compound dispersion film thus obtained is suitable for a wide range of applications such as smartphone displays, touch panels, and solar cells.
  • the composite metal acid compound dispersion liquid according to the present invention is excellent in conductive performance, it is possible to exhibit the same conductive performance even with a smaller amount of the composite metal acid compound than in the conventional art. As a result, it is possible to reduce the amount of the product itself and the associated waste, and to reduce the energy costs during the production and disposal at the time of disposal. In this way, it leads to sustainable management and efficient utilization of natural resources, as well as achieving decarbonization (carbon neutrality).

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