WO2024162472A1 - 金属酸化合物含有液、及びその製造方法 - Google Patents

金属酸化合物含有液、及びその製造方法 Download PDF

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WO2024162472A1
WO2024162472A1 PCT/JP2024/003545 JP2024003545W WO2024162472A1 WO 2024162472 A1 WO2024162472 A1 WO 2024162472A1 JP 2024003545 W JP2024003545 W JP 2024003545W WO 2024162472 A1 WO2024162472 A1 WO 2024162472A1
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acid compound
metal
containing liquid
metal acid
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French (fr)
Japanese (ja)
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賢 松尾
隆二 元野
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

Definitions

  • the present invention relates to a liquid containing a metal acid compound and a method for producing the same.
  • Metal acid compound-containing liquids which are liquids containing oxides of rare metals and semimetal elements such as tantalum (Ta), niobium (Nb), titanium (Ti), molybdenum (Mo), tungsten (W), zirconium (Zr), hafnium (Hf), silicon (Si), and rare earth elements, are materials used in various industrial applications. Many metal acid compound-containing liquids have low dispersibility. Therefore, development of metal acid compound-containing liquids with high dispersibility has been promoted. As one of the metal acid compound-containing liquids with high dispersibility, the applicant of the present application has disclosed a tantalic acid dispersion liquid with high dispersibility in water (Patent Document 1).
  • the tantalum dispersion liquid disclosed in Patent Document 1 is produced by adding a tantalum salt solution to an amine aqueous solution to produce a primary reaction liquid, adding the primary reaction liquid to ammonia water to produce a secondary reaction liquid, washing the tantalum-containing precipitate produced in the secondary reaction liquid, and mixing the washed tantalum-containing precipitate with amine and water.
  • the present invention aims to provide a metal acid compound-containing liquid that has a low environmental impact and is highly dispersible, and a method for producing the same.
  • the metal acid compound-containing liquid of the present invention which has been made to solve the above problems, is a metal acid compound-containing liquid containing a metal and/or metalloid element and a tertiary amine compound, and is characterized in that the particle diameter (D50) of particles in the metal acid compound-containing liquid measured by dynamic light scattering method is 1000 nm or less.
  • the metal acid compound-containing liquid of the present invention is a metal acid compound-containing liquid containing a metal and/or metalloid element and a tertiary amine compound, and the particle diameter (D50) of the particles in the metal acid compound-containing liquid measured by dynamic light scattering method is 1000 nm or less, thereby having a low environmental impact and excellent dispersibility.
  • the metal acid compounds in the metal acid compound-containing liquid of the present invention are presumed to exist in the liquid as polymetal acid polynuclear complex ions in which metal atoms or metalloid atoms and oxygen atoms are multi-stage condensed in the liquid. Furthermore, the metal acid compounds also include those that exist in the liquid as ions in an ionic state with these metal oxides and alkali metals such as lithium.
  • the metal and/or metalloid elements contained in the metal acid compound-containing liquid of the present invention are preferably one or more selected from Ta, Nb, Ti, Zr, Mo, W, Hf, Si, and rare earth elements.
  • the metal acid compound-containing liquid of the present invention contains a tertiary amine compound.
  • the tertiary amine compounds in the metal acid compound-containing liquid of the present invention are presumed to exist in the liquid as ions in an ionic bond with a metal and/or metalloid element.
  • the tertiary amine compound contained in the metal acid compound-containing liquid of the present invention is preferably a tertiary amine compound having 3 to 9 carbon atoms, from the viewpoint of good dispersibility and affinity with solvents such as water. Furthermore, it is more preferable that the tertiary amine compound is one or more selected from the group consisting of trimethylamine, triethylamine, and tri-n-propylamine.
  • Methods for measuring the content of the tertiary amine compound in the metal acid compound-containing liquid of the present invention include gas chromatography (GC), liquid chromatography (LC), mass spectrometry (MS), gas chromatography-mass spectrometry (GC-MS), and liquid chromatography-mass spectrometry (LC-MS). Measurement by liquid chromatography (LC) and liquid chromatography-mass spectrometry (LC-MS) is particularly preferred.
  • the particle diameter D50 of the particles in the metal acid compound-containing liquid of the present invention is 1000 nm or less in particle diameter distribution measurement using dynamic light scattering, this is preferable from the viewpoints of small change over time and therefore stability, as well as the formation of a good coating film with fewer uncovered areas during film formation and ensuring a sufficient coating weight. Furthermore, a smaller particle diameter (D50) of the particles in the metal acid compound-containing liquid is preferable from the viewpoints of small change over time and therefore stability, as well as the formation of a good coating film with fewer uncovered areas during film formation and ensuring a sufficient coating weight.
  • the particle diameter (D50) of the particles in the metal acid compound-containing liquid is preferably 900 nm or less, more preferably 800 nm or less, particularly preferably 700 nm or less, more preferably 600 nm or less, more preferably 500 nm or less, particularly preferably 400 nm or less, more preferably 300 nm or less, more preferably 200 nm or less, particularly preferably 100 nm or less, more preferably 80 nm or less, more preferably 50 nm or less, particularly preferably 30 nm or less, more preferably 20 nm or less, more preferably 10 nm or less, particularly preferably 5 nm or less, and most preferably 3 nm or less.
  • the particle diameter (D50) of the particles in the metal acid compound-containing liquid of the present invention is measured using a dynamic light scattering method, and the liquid in which the particle diameter (D50) of the particles is 1000 nm or less is the "metal acid compound-containing liquid" of the present invention.
  • the dynamic light scattering method is a method in which a solution such as a suspension is irradiated with light such as a laser beam to measure the light scattering intensity from a group of particles undergoing Brownian motion, and the particle size and distribution are obtained from the temporal variation of the intensity.
  • the particle size distribution is evaluated in accordance with JIS Z 8828:2019 "Particle size analysis - dynamic light scattering method” using a zeta potential, particle size, and molecular weight measurement system (ELSZ-2000ZS, manufactured by Otsuka Electronics Co., Ltd.).
  • the solution is filtered through a filter with a pore size of 2 ⁇ m immediately before the measurement, and ultrasonic treatment is performed at 28 kHz for 3 minutes using an ultrasonic cleaner (VS-100III, manufactured by AS ONE Co., Ltd.).
  • the particle size (D50) refers to the median diameter (D50), which is the particle size that shows the 50% cumulative value of the cumulative distribution curve.
  • particle diameter (D50) includes both “initial particle diameter D50” which indicates the particle diameter (D50) of particles in the metal acid compound-containing liquid of the present invention adjusted to a liquid temperature of 25°C immediately after production, and “time-dependent particle diameter D50” which indicates the particle diameter (D50) of particles in the metal acid compound-containing liquid of the present invention after the metal acid compound-containing liquid of the present invention is left to stand for 20 days from the day of production in an incubator set at room temperature of 25°C.
  • the "containing liquid" in this invention is not limited to a solute dispersed or mixed in a solvent in a single molecular state, but also includes an aggregate in which multiple molecules are attracted to each other through intermolecular interactions, such as (1) polymer molecules, (2) solvated molecules, (3) molecular clusters, and (4) colloidal particles dispersed in a solvent.
  • the metal acid compound-containing liquid of the present invention is a metal acid compound-containing liquid containing a metal and/or metalloid element and a tertiary amine compound, and is characterized in that the maximum transmittance of the metal acid compound-containing liquid in the wavelength range of 550 nm to 700 nm is 70% T or more.
  • the metal acid compound-containing liquid of the present invention is a metal acid compound-containing liquid containing a metal and/or metalloid element and a tertiary amine compound, and since the maximum transmittance of the metal acid compound-containing liquid in the wavelength range of 550 nm to 700 nm is 70% T or more, the liquid has a low environmental impact and excellent dispersibility.
  • metal and/or metalloid elements and tertiary amine compounds contained in the metal acid compound-containing liquid of the present invention are as described above, so a detailed explanation is omitted here.
  • the metal acid compound-containing liquid of the present invention preferably has a maximum transmittance of 70%T or more in the wavelength range of 550nm to 700nm, since this provides high dispersion and excellent uniformity of the liquid components. It is more preferable that the maximum transmittance in the wavelength range of 550nm to 700nm is 75%T or more, even more preferable that it is 80%T or more, particularly preferable that it is 85%T or more, more preferably that it is 90%T or more, even more preferably that it is 95%T or more, particularly preferable that it is 98%T or more, even more preferably that it is 99%T or more, and most preferably that it is 100%T or more. Note that if the measured value exceeds 100%T due to measurement error of the spectrophotometer used to measure the transmittance, etc., it is considered to be 100%T.
  • the metal acid compound-containing liquid of the present invention preferably has at least one of the transmittances at wavelengths of 550 nm, 600 nm, 650 nm, and 700 nm of 70% T or more, more preferably 75% T or more, even more preferably 80% T or more, particularly preferably 85% T or more, more preferably 90% T or more, even more preferably 95% T or more, particularly preferably 98% T or more, even more preferably 99% T or more, and most preferably 100% T or more. Note that if the measured value exceeds 100% T due to measurement error of the spectrophotometer used to measure the transmittance, it is considered to be 100% T.
  • the metal acid compound-containing liquid of the present invention preferably has a minimum transmittance in the wavelength range of 550 nm to 700 nm of 70% T or more, more preferably 75% T or more, even more preferably 80% T or more, particularly preferably 85% T or more, more preferably 90% T or more, even more preferably 95% T or more, particularly preferably 98% T or more, even more preferably 99% T or more, and most preferably 100% T or more. Note that if the measured value exceeds 100% T due to measurement error of the spectrophotometer used to measure the transmittance, it is considered to be 100% T.
  • the metal acid compound-containing liquid of the present invention is a liquid in a state in which the maximum transmittance in the wavelength range of 550 nm to 700 nm is 70%T.
  • transmittance includes both “initial transmittance” which indicates the transmittance of the metal acid compound-containing liquid of the present invention adjusted to a liquid temperature of 25°C immediately after production, and “temporal transmittance” which indicates the transmittance of the metal acid compound-containing liquid of the present invention after it has been left to stand for one month from the day the metal acid compound-containing liquid of the present invention was produced in an incubator set at room temperature of 25°C.
  • the transmittance in the wavelength range of 550 nm to 700 nm is measured for the metal acid compound-containing liquid of the present invention using a spectrophotometer in accordance with the following transmittance measurement conditions and in accordance with JIS K 0115, 2004 "General rules for spectrophotometric analysis methods.”
  • the metal acid compound-containing liquid of the present invention is characterized in that the content of the metal and/or metalloid element in the metal acid compound-containing liquid is more than 0 mass% and less than 30% in terms of metal equivalent of the metal and/or metalloid element.
  • the content of the metal and/or metalloid element in the metal acid compound-containing liquid of the present invention is preferably 0.1% by mass or more and 30% by mass or less in terms of the metal and/or metalloid element metal equivalent, in terms of improving the liquid stability of the metal acid compound-containing liquid of the present invention.
  • the content of the metal and/or metalloid element in the metal acid compound-containing liquid is more preferably 0.1% by mass or more and 25% by mass or less, even more preferably 0.15% by mass or more and 20% by mass or less, and particularly preferably 0.15% by mass or more and 15% by mass or less, in terms of the metal and/or metalloid element metal equivalent.
  • the content of metal and/or metalloid elements in the metal acid compound-containing liquid of the present invention is calculated by diluting the liquid appropriately with dilute hydrochloric acid as necessary, and measuring the mass fraction of the metal and/or metalloid elements in metal equivalent using inductively coupled plasma optical emission spectrometry (ICP optical emission spectrometry (AG-5110 manufactured by Agilent Technologies)) in accordance with JIS K0116:2014.
  • ICP optical emission spectrometry AG-5110 manufactured by Agilent Technologies
  • the metallic acid compound-containing liquid of the present invention is characterized in that it contains hydrogen peroxide in addition to the above-mentioned metal and/or metalloid element and tertiary amine compound. Since hydrogen peroxide water is used in the manufacturing method of the metal acid compound-containing liquid of the present invention described below, the metal acid compound-containing liquid of the present invention may contain hydrogen peroxide.
  • the hydrogen peroxide according to the present invention includes hydrogen peroxide that is ionized in the metal acid compound-containing liquid of the present invention.
  • hydrogen peroxide that is ionized in the metal acid compound-containing liquid of the present invention.
  • the addition of hydrogen peroxide in the manufacturing process causes anion species containing a metal element and/or a metalloid element to complex, forming a peroxo complex with excellent solubility stability.
  • the amount of hydrogen peroxide present in the liquid is quantitatively analyzed by, for example, measuring the absorbance of the liquid at a wavelength of 410 nm using a spectrophotometer (Hitachi, Ltd.: U-2900) to quantify the amount of hydrogen peroxide present in the liquid.
  • the metallic acid compound-containing liquid of the present invention may further contain a resin.
  • the metal acid compound-containing liquid of the present invention is preferably one that contains a resin, since the resin is uniformly compatible with the metal acid compound and acts to adhere to the substrate, thereby improving film-forming properties and adhesion to the substrate.
  • the resins contained in the liquid containing the metal acid compound include polyolefin compounds, polyvinyl compounds, etc.
  • the resin contained in the metal acid compound-containing liquid of the present invention may be an anionic water-soluble resin and/or a nonionic water-soluble resin.
  • the anionic water-soluble resin and/or the nonionic water-soluble resin is uniformly compatible with the above-mentioned metal acid compound and acts to adhere to the substrate, thereby improving the film-forming properties and adhesion to the plastic film substrate.
  • a cationic water-soluble resin is a resin that has a positive charge in the polymer in water with a pH of 7, and has a functional group such as an amino group, an imino group, a tertiary amine group, a quaternary ammonium group, or a hydrazino group.
  • An anionic water-soluble resin is a resin that has a negative charge in the polymer in water with a pH of 7, and has a functional group such as a carboxyl group, a sulfone group, a sulfate ester group, or a phosphate ester group.
  • a nonionic water-soluble resin is a resin that does not fall under the above-mentioned cationic water-soluble resin or anionic water-soluble resin, and has a functional group such as a hydroxyl group, an ether group, or an amide group in the polymer.
  • these resins contain one or more water-soluble homopolymers selected from the group consisting of acrylic polymers, urethane polymers, styrene polymers, olefin polymers, amide polymers, siloxane polymers, epoxy polymers, vinyl chloride polymers, and vinyl acetate polymers, and/or water-soluble copolymers consisting of two or more of these polymers.
  • these resins contain one or more water-soluble homopolymers of acrylic polymers, styrene polymers, and olefin polymers, and/or water-soluble copolymers consisting of two or more of these polymers.
  • the metal acid compound-containing liquid of the present invention may further contain a high-boiling point solvent.
  • the high-boiling point solvent is preferably a solvent having a boiling point of 180°C or higher at 1 atmospheric pressure, and examples of such solvents include polyhydric alcohol solvents and glycol solvents.
  • examples of polyhydric alcohol solvents include glycerin (boiling point: 290°C), 1,6-hexanediol (boiling point: 250°C), 1,7-heptanediol (boiling point: 259°C), etc.
  • examples of glycol-based solvents include ethylene glycol (boiling point: 197.3° C.), propylene glycol (boiling point: 188.2° C.), diethylene glycol (boiling point: 244.3° C.), triethylene glycol (boiling point: 287.4° C.), oligoethylene glycol (boiling point: 287° C.
  • polyethylene glycol (PEG) (boiling point: 460° C. or higher), polyethylene glycol (PEG)-polypropylene glycol (PPG) copolymer (boiling point: 460° C. or higher), diethylene glycol monohexyl ether (boiling point: 260° C.), polyoxyalkylene monoalkyl ether (boiling point: 260° C. or higher), polyoxyethylene sorbitan monolaurate (boiling point: 321° C. or higher), other anionic fluorosurfactants (boiling point: 180° C. or higher), amphoteric fluorosurfactants (boiling point: 180° C.
  • boiling point 180° C. or higher
  • amine oxides 180° C. or higher
  • Glycerin is particularly preferred.
  • the boiling point mentioned above is the boiling point at 1 atmosphere.
  • high boiling point solvents have the characteristic of having a high boiling point, if the boiling point at 1 atmosphere is excessively high, the high boiling point solvent may decompose before boiling, making it impossible to measure the boiling point accurately. In such cases, the boiling point at reduced pressure may be measured and converted to the boiling point at 1 atmosphere using a general-purpose boiling point conversion table.
  • the metal acid compound-containing liquid of the present invention may contain, as unavoidable impurities, components derived from one or more metal and/or semimetal elements, such as Ta, Nb, Ti, Zr, Mo, W, Hf, Si, and rare earth elements, and components other than the components derived from ammonia, tertiary amine compounds, and hydrogen peroxide (referred to as "other components"), to the extent that the action and effect of the liquid are not impaired.
  • components derived from one or more metal and/or semimetal elements such as Ta, Nb, Ti, Zr, Mo, W, Hf, Si, and rare earth elements
  • other components such as ammonia, tertiary amine compounds, and hydrogen peroxide
  • dispersants may be added to the metal acid compound-containing liquid of the present invention as appropriate for the application.
  • the complex metal acid compound-containing liquid of the present invention is characterized by having the metal acid compound-containing liquid of the present invention and at least one element A selected from the group consisting of Li, Na, Ma, Al, K, Ca, V, Mn, Fe, Co, Ni, Cu, Zn, Sn, Sr, and Ba. It is presumed that in the complex metal acid compound-containing liquid of the present invention, the complex metal acid compound of the present invention and element A are present in the form of ions in an ionic bond therebetween.
  • Element A may contain compounds such as Li, Na, Mg, Al, K, Ca, V, Mn, Fe, Co, Ni, Cu, Zn, Sn, Sr, and Ba.
  • examples of compounds include oxides, alkali metal salts of metal acids, alkaline earth metal salts of metal acids, chlorides, metal alkoxides, and polyoxometalates.
  • the content of element A in the composite metal acid compound-containing liquid of the present invention is such that, when the total molar content of each element A in metal conversion is X, the molar ratio X/M of the total molar number (X) of each element A in metal conversion to the total molar number (M) of one or more metal acid compounds selected from the group consisting of Nb, Ta, Ti, Mo, W, Zr, Hf, Si, and rare earth elements in metal conversion is preferably more than 0 to 3.0, and more preferably 0.0002 to 2.0.
  • the molar ratio X/M may be 0.001 to 1.0, 0.005 to 0.8, 0.01 to 0.5, 0.1 to 0.4, or 0.2 to 0.3.
  • the composite metal acid compound-containing liquid of the present invention is a homogeneous liquid, even if these compounds are in a suspended state, improved homogeneity and improved reactivity (reaction rate) are expected. Furthermore, if these compounds dissolve in the composite metal acid compound-containing liquid of the present invention and become a homogeneous liquid, the most reactive state can be achieved.
  • the metal acid compound-containing film of the present invention is characterized by containing metal acid compound particles contained in the metal acid compound-containing liquid of the present invention.
  • the metal acid compound-containing film of the present invention includes a dried film obtained by applying the metal acid compound-containing liquid of the present invention to the surface of a substrate and then drying, for example, vacuum drying, and a fired film obtained by further firing the resulting dried film.
  • the metal acid compound-containing film of the present invention also includes a metal acid compound-containing film having different physical properties such as a crystal structure, which is produced by vacuum drying or firing the metal acid compound-containing liquid of the present invention, and may have an amorphous structure, a single crystal structure, or a polycrystalline structure.
  • the complex metal acid compound-containing film of the present invention is characterized in that it contains complex metal acid compound particles contained in a complex metal acid compound-containing liquid.
  • the composite metal acid compound-containing film of the present invention includes a dried film obtained by applying the composite metal acid compound-containing liquid of the present invention to the surface of a substrate, followed by drying, for example, vacuum drying, and a fired film obtained by further firing the resulting dried film.
  • the composite metal acid compound-containing film of the present invention also includes a metal acid compound-containing film having different physical properties, such as a crystal structure, that is produced by vacuum drying or firing the composite metal acid compound-containing liquid of the present invention, and may have an amorphous structure, a single crystal structure, or a polycrystalline structure.
  • the method for producing a liquid containing a metal acid compound of the present invention is characterized by comprising the steps of neutralizing an acidic metal aqueous solution containing a metal and/or metalloid element with an alkaline aqueous solution to produce a precipitate containing the metal and/or metalloid element, and adding a tertiary amine compound and hydrogen peroxide to the precipitate to produce a liquid containing a metal acid compound.
  • the method for producing the tantalic acid compound-containing liquid which is the metal acid compound-containing liquid of the present invention, is described below.
  • tantalum, tantalum oxide, tantalum hydroxide, or tantalum alkoxide is reacted with hydrofluoric acid (HF) such as hydrofluoric acid solution to form tantalum fluoride (H 2 TaF 7 ), which is then dissolved in water to obtain an acidic metal aqueous solution, that is, an aqueous tantalum fluoride solution.
  • HF hydrofluoric acid
  • tantalum chloride it is possible to omit the step of dissolving in hydrofluoric acid and to produce an acidic tantalum aqueous solution by adding water to tantalum chloride.
  • the tantalum fluoride aqueous solution it is preferable to adjust the tantalum fluoride aqueous solution to contain tantalum at 1 to 100 g/L in terms of Ta 2 O 5 by adding water (e.g., pure water).
  • water e.g., pure water
  • the tantalum content is 1 g/L or more in terms of Ta 2 O 5 , since it is a tantalic acid compound hydrate that is easily soluble in water, and in consideration of productivity, it is more preferable that the tantalum content is 10 g/L or more, and even more preferable that the tantalum content is 20 g/L or more.
  • the tantalum content is 100 g/L or less in terms of Ta 2 O 5 , since it is a tantalic acid compound hydrate that is easily soluble in water, and in order to more reliably synthesize a tantalic acid compound hydrate that is easily soluble in water, it is more preferable that the tantalum content is 90 g/L or less, even more preferable that the tantalum content is 80 g/L or less, and particularly preferable that the tantalum content is 70 g/L or less.
  • the pH of the tantalum fluoride aqueous solution is preferably 2 or less, more preferably 1 or less, from the viewpoint of completely dissolving tantalum or tantalum oxide.
  • the tantalum fluoride aqueous solution is neutralized with an alkaline aqueous solution to obtain a fluorine-containing tantalum hydrate cake.
  • the alkaline aqueous solution used to neutralize the tantalum fluoride aqueous solution is preferably 10% to 30% ammonia water.
  • the ammonia content of the ammonia water used for neutralization is preferably 10% to 30% by mass. If the ammonia content is 10% by mass, tantalum is less likely to remain undissolved, and tantalum or tantalic acid can be completely dissolved in water. On the other hand, if the ammonia content is 30% or less by mass, it is preferable because it is close to a saturated aqueous solution of ammonia.
  • the ammonia content of the ammonia water 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 or more.
  • the ammonia content 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 addition is preferably such that the molar ratio of NH 3 /Ta is 95 or more and 500 or less, more preferably such that the molar ratio of NH 3 /Ta is 100 or more and 450 or less, and even more preferably such that the molar ratio of NH 3 /HF is 3.0 or more, more preferably such that the molar ratio of NH 3 /HF is 4.0 or more, and even more preferably such that the molar ratio of NH 3 /HF is 5.0 or more, from the viewpoint of generating a tantalic acid compound that is soluble in amine or dilute ammonia water.
  • the molar ratio of NH 3 /HF is preferably 100 or less, more preferably such that the molar ratio of NH 3 /HF is 50 or less, and even more preferably such that the molar ratio of NH 3 /HF is 40 or less.
  • the addition time for the above-mentioned neutralization reaction is preferably within 10 minutes, more preferably within 8 minutes, and even more preferably within 5 minutes. In other words, it is preferable to carry out the neutralization reaction in as short a time as possible, for example by adding it all at once, rather than gradually adding it over a period of time.
  • the aqueous tantalum fluoride solution and aqueous ammonia can be used at room temperature.
  • the fluorine-containing tantalum hydrate cake obtained by the above-mentioned neutralization reaction is decanted with dilute ammonia water using a centrifuge, and washing is repeated until the amount of liberated fluoride ions becomes 100 mg/L or less, thereby removing the fluoride ions from the fluorine-containing tantalum hydrate cake and obtaining a tantalum-containing precipitate.
  • the fluorine-containing tantalum hydrate cake obtained by the above-mentioned neutralization reaction contains fluorine compounds such as ammonium fluoride as impurities, so it is preferable to remove these.
  • the tantalum content of the obtained tantalum-containing precipitate is determined by taking a portion of the tantalum-containing precipitate, drying it at 110° C. for 24 hours, and then firing it at 1000° C. for 4 hours to produce Ta 2 O 5.
  • the weight of the Ta 2 O 5 thus produced is measured, and the tantalum content of the tantalum-containing precipitate can be calculated from the weight.
  • the cleaning solution used to remove fluoride ions is preferably dilute ammonia water.
  • dilute ammonia water of 1% by mass or more and 35% by mass or less is preferable. With such dilute ammonia water, the ammonia and ammonium ions are suitable for fluorine, and unnecessary increases in costs can be avoided.
  • the method for removing fluorine compounds is arbitrary, but for example, methods using membranes such as reverse osmosis filtration, ultrafiltration, and microfiltration using ammonia water or pure water, centrifugation, and other known methods can be used.
  • membranes such as reverse osmosis filtration, ultrafiltration, and microfiltration using ammonia water or pure water, centrifugation, and other known methods can be used.
  • fluoride ions from the fluorine-containing tantalum hydrate cake, there is no particular need to adjust the temperature, and the process can be carried out at room temperature.
  • a tertiary amine compound and pure water are added to the obtained tantalum-containing precipitate, and the mixture is stirred for 10 minutes to obtain a tantalum-containing mixed liquid.
  • 35% by mass hydrogen peroxide is added to the tantalum-containing mixed liquid, and the mixture is stirred for 30 minutes to obtain a tantalic acid compound-containing liquid.
  • the tertiary amine compound is preferably mixed so that the content of the tertiary amine compound in the tantalum-containing mixed liquid is 30 mass% or less, and more preferably 20 mass% or less. From the same viewpoint, the tertiary amine compound is preferably mixed so that the content of the tertiary amine compound in the tantalum-containing mixed liquid is 0.1 mass% or more, and more preferably 1 mass% or more, and may be 5 mass% or more, or 10 mass% or more. Furthermore, the tertiary amine compound is preferably one or more selected from trimethylamine, triethylamine, and tri-n-propylamine.
  • the hydrogen peroxide content of the hydrogen peroxide solution is preferably 0.5% by mass to 35% by mass.
  • the hydrogen peroxide is preferably added so that the molar ratio of hydrogen peroxide to tantalum, H 2 O 2 /Ta, is 0.6 to 1.5, and more preferably 0.7 to 1.2, since hydrogen peroxide may decompose during mixing.
  • the above-mentioned method for producing a tantalic acid compound-containing liquid preferably includes a step of removing hydrogen peroxide from the obtained tantalic acid compound-containing liquid. If hydrogen peroxide is contained in the tantalic acid compound-containing liquid, the inside of a sealed container may be filled with gas produced by decomposition of the hydrogen peroxide, causing the container to expand or, in the worst case, burst.
  • the method for removing hydrogen peroxide is arbitrary, but examples include stirring under open/reduced pressure conditions and drying under reduced pressure.
  • the method for producing the niobium acid compound-containing liquid which is the metal acid compound-containing liquid of the present invention, is described below. Note that explanations of parts that overlap with the method for producing the tantalic acid compound-containing liquid described above will be omitted.
  • niobium, niobium oxide, or niobium hydroxide is reacted with hydrofluoric acid (HF) such as an aqueous solution of hydrofluoric acid to produce niobium fluoride (H 2 NbF 7 ), which is then dissolved in water to obtain an aqueous solution of niobium fluoride, which is an acidic aqueous solution of metal.
  • hydrofluoric acid such as an aqueous solution of hydrofluoric acid
  • H 2 NbF 7 niobium fluoride
  • the niobium fluoride aqueous solution it is preferable to adjust the niobium fluoride aqueous solution to contain 1 to 100 g/L of niobium in terms of Nb 2 O 5 by adding water (e.g., pure water).
  • water e.g., pure water
  • the niobium content is 1 g/L or more in terms of Nb 2 O 5 , since it is a niobium compound hydrate that is easily soluble in water, and in consideration of productivity, it is more preferable that it is 10 g/L or more, and even more preferable that it is 20 g/L or more.
  • the niobium content is 100 g/L or less in terms of Nb 2 O 5 , since it is a niobium compound hydrate that is easily soluble in water, and in order to synthesize a niobium compound hydrate that is easily soluble in water more reliably, it is more preferable that it is 90 g/L or less, even more preferable that it is 80 g/L or less, and particularly preferable that it is 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.
  • the niobium fluoride aqueous solution is neutralized with an alkaline aqueous solution to obtain a fluorine-containing niobium hydrate cake.
  • the alkaline aqueous solution used to neutralize the niobium fluoride aqueous solution is preferably 10% to 30% by mass ammonia water.
  • the amount of addition is preferably such that the molar ratio of NH 3 /Nb is 95 or more and 500 or less, more preferably such that the molar ratio of NH 3 /Nb is 100 or more and 450 or less, and even more preferably such that the molar ratio of NH 3 /HF is 3.0 or more, more preferably such that the molar ratio of NH 3 /HF is 4.0 or more, and even more preferably such that the molar ratio of NH 3 /HF is 5.0 or more, from the viewpoint of generating a niobic acid compound that dissolves in amine or dilute ammonia water.
  • the molar ratio of NH 3 /HF is preferably 100 or less, more preferably such that the molar ratio of NH 3 /HF is 50 or less, and even more preferably such that the molar ratio of NH 3 /HF is 40 or less.
  • the addition time in the above-mentioned neutralization reaction is preferably within 10 minutes, more preferably within 8 minutes, and even more preferably within 5 minutes.
  • the fluorine-containing niobium hydrate cake obtained by the above-mentioned neutralization reaction is decanted with dilute ammonia water using a centrifuge, and washing is repeated until the amount of liberated fluoride ions becomes 100 mg/L or less, thereby removing the fluoride ions from the fluorine-containing niobium hydrate cake and obtaining a niobium-containing precipitate.
  • the fluorine-containing niobium hydrate cake obtained by the above-mentioned neutralization reaction contains fluorine compounds such as ammonium fluoride as impurities, so it is preferable to remove these.
  • the washing liquid used to remove the fluoride ions is preferably dilute ammonia water.
  • the niobium content of the obtained niobium-containing precipitate is determined by taking a portion of the niobium-containing precipitate, drying it at 110° C. for 24 hours, and then firing it at 1000° C. for 4 hours to produce Nb 2 O 5.
  • the weight of the Nb 2 O 5 thus produced is measured, and the niobium content of the niobium-containing precipitate can be calculated from the weight.
  • niobium-containing precipitate a tertiary amine compound and pure water are added to the obtained niobium-containing precipitate, and the mixture is stirred for 10 minutes to obtain a niobium-containing mixed liquid.
  • 35% by mass of hydrogen peroxide is added to the niobium-containing mixed liquid, and the mixture is stirred for 30 minutes to obtain a niobium acid compound-containing liquid.
  • the tertiary amine compound is preferably mixed so that the content of the tertiary amine compound in the niobium-containing mixed liquid is 0.1% by mass or more and 30% by mass or less.
  • the tertiary amine compound is preferably one or more selected from trimethylamine, triethylamine, and tri-n-propylamine.
  • the hydrogen peroxide content of the hydrogen peroxide solution is preferably 0.5% by mass to 35% by mass.
  • the hydrogen peroxide is preferably added so that the molar ratio of hydrogen peroxide to niobium, H 2 O 2 /Nb, is 0.6 to 1.5, and more preferably 0.7 to 1.2, since hydrogen peroxide may decompose during mixing.
  • the method for producing the titanic acid compound-containing liquid which is the metal acid compound-containing liquid of the present invention, is described below. Note that explanations of parts that overlap with the method for producing the tantalic acid compound-containing liquid described above will be omitted.
  • titanium, titanium oxide, or titanium hydroxide is reacted with hydrofluoric acid (HF) such as hydrofluoric acid solution to form titanium fluoride (H 2 TiF 6 ), which is then dissolved in water to obtain an acidic metal aqueous solution, that is, an aqueous titanium fluoride solution.
  • hydrofluoric acid such as hydrofluoric acid solution
  • titanium fluoride H 2 TiF 6
  • an acidic metal aqueous solution that is, an aqueous titanium fluoride solution.
  • titanium chloride or titanyl sulfate it is possible to omit the step of dissolving in hydrofluoric acid and to produce an acidic titanium aqueous solution by adding water to these.
  • the titanium fluoride aqueous solution it is preferable to adjust the titanium fluoride aqueous solution to contain 1 to 100 g/L of titanium in terms of TiO 2 by adding water (e.g., pure water).
  • water e.g., pure water
  • the titanium content is 1 g/L or more in terms of TiO 2
  • the titanic acid compound hydrate is easily soluble in water, and in consideration of productivity, it is more preferable that it is 10 g/L or more, and even more preferable that it is 20 g/L or more.
  • the titanium content is 100 g/L or less in terms of TiO 2 , it is preferable because the titanic acid compound hydrate is easily soluble in water, and in order to more reliably synthesize a titanic acid compound hydrate that is easily soluble in water, it is more preferable that it is 90 g/L or less, even more preferable that it is 80 g/L or less, and particularly preferable that it is 70 g/L or less.
  • the pH of the titanium fluoride aqueous solution is preferably 2 or less, more preferably 1 or less, from the viewpoint of completely dissolving titanium or titanium oxide.
  • the titanium fluoride aqueous solution is neutralized with an alkaline aqueous solution to obtain a fluorine-containing titanium hydrate cake.
  • the alkaline aqueous solution used to neutralize the titanium fluoride aqueous solution is preferably 10% to 30% ammonia water.
  • the amount of addition is preferably such that the molar ratio of NH 3 /Ti is 95 or more and 500 or less, more preferably such that the molar ratio of NH 3 /Ti is 100 or more and 450 or less, and even more preferably such that the molar ratio of NH 3 /HF is 3.0 or more, more preferably such that the molar ratio of NH 3 /HF is 4.0 or more, and even more preferably such that the molar ratio of NH 3 /HF is 5.0 or more, from the viewpoint of generating a titanic acid compound that dissolves in amine or dilute ammonia water.
  • the molar ratio of NH 3 /HF is preferably 100 or less, more preferably such that the molar ratio of NH 3 /HF is 50 or less, and even more preferably such that the molar ratio of NH 3 /HF is 40 or less.
  • the addition time in the above-mentioned neutralization reaction is preferably within 10 minutes, more preferably within 8 minutes, and even more preferably within 5 minutes.
  • the fluorine-containing titanium hydrate cake obtained by the above-mentioned neutralization reaction is decanted with dilute ammonia water using a centrifuge, and washing is repeated until the amount of liberated fluoride ions becomes 100 mg/L or less, thereby removing the fluoride ions from the fluorine-containing titanium hydrate cake and obtaining a titanium-containing precipitate.
  • the fluorine-containing titanium hydrate cake obtained by the above-mentioned neutralization reaction contains fluorine compounds such as ammonium fluoride as impurities, so it is preferable to remove these.
  • the washing liquid used to remove the fluoride ions is preferably dilute ammonia water.
  • the niobium content of the obtained titanium-containing precipitate is determined by taking a part of the titanium-containing precipitate, drying it at 110° C. for 24 hours, and then calcining it at 1000° C. for 4 hours to produce TiO 2.
  • the weight of the TiO 2 thus produced can be measured, and the titanium content of the titanium-containing precipitate can be calculated from the weight.
  • a tertiary amine compound and pure water are added to the obtained titanium-containing precipitate and stirred for 10 minutes to obtain a titanium-containing mixed liquid.
  • 35% by mass hydrogen peroxide is added to the titanium-containing mixed liquid and stirred for 30 minutes to obtain a titanic acid compound-containing liquid.
  • the tertiary amine compound is preferably mixed so that the content of the tertiary amine compound in the titanium-containing mixed liquid is 0.1% by mass or more and 30% by mass or less.
  • the tertiary amine compound is preferably one or more selected from trimethylamine, triethylamine, and tri-n-propylamine.
  • the hydrogen peroxide content of the hydrogen peroxide solution is preferably 0.5% by mass to 35% by mass.
  • the hydrogen peroxide is preferably added so that the molar ratio of hydrogen peroxide to titanium, H 2 O 2 /Ti, is 0.6 to 1.5, and more preferably 0.7 to 1.2, since hydrogen peroxide may decompose during mixing.
  • the method for producing the zirconium acid compound-containing liquid which is the metal acid compound-containing liquid of the present invention, is described below. Note that explanations of parts that overlap with the method for producing the tantalic acid compound-containing liquid described above will be omitted.
  • zirconium, zirconium oxide, or titanium hydroxide is reacted with hydrofluoric acid (HF) such as hydrofluoric acid solution to produce zirconium fluoride (H 2 ZrF 6 ), which is then dissolved in water to obtain an acidic metal aqueous solution, that is, an aqueous zirconium fluoride solution.
  • HF hydrofluoric acid
  • zirconium fluoride H 2 ZrF 6
  • an acidic metal aqueous solution that is, an aqueous zirconium fluoride solution.
  • zirconium chloride or zirconium sulfate it is possible to omit the step of dissolving in hydrofluoric acid and add water to these to produce an acidic titanium aqueous solution.
  • the zirconium fluoride aqueous solution it is preferable to adjust the zirconium fluoride aqueous solution to contain 1 to 100 g/L of zirconium in terms of ZrO2 by adding water (e.g., pure water).
  • water e.g., pure water
  • the zirconium content is 1 g/L or more in terms of ZrO2
  • the zirconium content is 100 g/L or less in terms of ZrO2 , it is preferable because the zirconium oxide hydrate is easily soluble in water, and in order to more reliably synthesize the zirconium oxide hydrate that is easily soluble in water, it is more preferable that it is 90 g/L or less, even more preferable that it is 80 g/L or less, and particularly preferable that it is 70 g/L or less.
  • the pH of the zirconium fluoride aqueous solution is preferably 2 or less, more preferably 1 or less, from the viewpoint of completely dissolving zirconium or zirconium oxide.
  • the zirconium fluoride aqueous solution is neutralized with an alkaline aqueous solution to obtain a fluorine-containing zirconium hydrate cake.
  • the alkaline aqueous solution used to neutralize the zirconium fluoride aqueous solution is preferably 10% to 30% ammonia water.
  • the amount of addition is preferably such that the molar ratio of NH 3 /Zr is 95 or more and 500 or less, more preferably such that the molar ratio is 100 or more and 450 or less, and even more preferably such that the molar ratio is 110 or more and 400 or less.
  • the amount of addition is preferably such that the molar ratio of NH 3 /HF is 3.0 or more, more preferably such that the molar ratio is 4.0 or more, and even more preferably such that the molar ratio is 5.0 or more.
  • the molar ratio of NH 3 /HF is preferably 100 or less, more preferably such that the molar ratio is 50 or less, and even more preferably such that the molar ratio is 40 or less.
  • the addition time in the above-mentioned neutralization reaction is preferably within 10 minutes, more preferably within 8 minutes, and even more preferably within 5 minutes.
  • the fluorine-containing zirconium hydrate cake obtained by the above-mentioned neutralization reaction is decanted with dilute ammonia water using a centrifuge, and washing is repeated until the amount of liberated fluoride ions becomes 100 mg/L or less, thereby removing the fluoride ions from the fluorine-containing zirconium hydrate cake and obtaining a zirconium-containing precipitate.
  • the fluorine-containing zirconium hydrate cake obtained by the above-mentioned neutralization reaction contains fluorine compounds such as ammonium fluoride as impurities, so it is preferable to remove these.
  • the washing liquid used to remove the fluoride ions is preferably dilute ammonia water.
  • the zirconium content of the obtained zirconium-containing precipitate is determined by taking a portion of the zirconium-containing precipitate, drying it at 110° C. for 24 hours, and then calcining it at 1000° C. for 4 hours to produce ZrO 2.
  • the weight of the ZrO 2 thus produced is measured, and the zirconium content of the zirconium-containing precipitate can be calculated from the weight.
  • a tertiary amine compound and pure water are added to the obtained zirconium-containing precipitate and stirred for 10 minutes to obtain a zirconium-containing mixed liquid.
  • 35% by mass hydrogen peroxide is added to the zirconium-containing mixed liquid and stirred for 30 minutes to obtain a zirconium oxide compound-containing liquid.
  • the tertiary amine compound is preferably mixed so that the content of the tertiary amine compound in the zirconium-containing mixed liquid is 0.1% by mass or more and 30% by mass or less.
  • the tertiary amine compound is preferably one or more selected from trimethylamine, triethylamine, and tri-n-propylamine.
  • the hydrogen peroxide content of the hydrogen peroxide solution is preferably 0.5% by mass to 35% by mass.
  • the hydrogen peroxide is preferably added so that the molar ratio H 2 O 2 /Zr between hydrogen peroxide and zirconium is 0.6 to 1.5, and more preferably 0.7 to 1.2, since hydrogen peroxide may decompose during mixing.
  • the method for producing the silicon acid compound-containing liquid which is the metal acid compound-containing liquid of the present invention, is described below. Note that explanations of parts that overlap with the method for producing the tantalic acid compound-containing liquid described above will be omitted.
  • silicon or silicon oxide is reacted with hydrofluoric acid (HF) such as an aqueous solution of hydrofluoric acid to produce silicon fluoride (H 2 SiF 6 ), which is then dissolved in water to obtain an aqueous solution of silicon fluoride, which is an acidic metal solution.
  • HF hydrofluoric acid
  • the silicon fluoride aqueous solution it is preferable to adjust the silicon fluoride aqueous solution to contain 1 to 100 g/L of silicon in terms of SiO 2 by adding water (e.g., pure water).
  • water e.g., pure water
  • the silicon content is 1 g/L or more in terms of SiO 2 , it is preferable because it becomes a silicic acid compound hydrate that is easily soluble in water, and in terms of productivity, it is more preferable that it is 10 g/L or more, and even more preferable that it is 20 g/L or more.
  • the silicon content is 100 g/L or less in terms of SiO 2 , it is preferable because it becomes a silicic acid compound hydrate that is easily soluble in water, and in order to synthesize a silicic acid compound hydrate that is more reliably soluble in water, it is more preferable that it is 90 g/L or less, even more preferable that it is 80 g/L or less, and particularly preferable that it is 70 g/L or less.
  • the pH of the silicon fluoride aqueous solution is preferably 2 or less, more preferably 1 or less, from the viewpoint of completely dissolving silicon or silicon oxide.
  • the silicon fluoride aqueous solution is neutralized with an alkaline aqueous solution to obtain a fluorine-containing silicon hydrate cake.
  • the alkaline aqueous solution used to neutralize the silicon fluoride aqueous solution is preferably 10% to 30% ammonia water.
  • the amount of addition is preferably such that the molar ratio of NH 3 /Si is 95 or more and 500 or less, more preferably such that the molar ratio is 100 or more and 450 or less, and even more preferably such that the molar ratio is 110 or more and 400 or less.
  • the amount of addition is preferably such that the molar ratio of NH 3 /HF is 3.0 or more, more preferably such that the molar ratio is 4.0 or more, and even more preferably such that the molar ratio is 5.0 or more.
  • the molar ratio of NH 3 /HF is preferably 100 or less, more preferably such that the molar ratio is 50 or less, and even more preferably such that the molar ratio is 40 or less.
  • the addition time in the above-mentioned neutralization reaction is preferably within 10 minutes, more preferably within 8 minutes, and even more preferably within 5 minutes.
  • the fluorine-containing silicon hydrate cake obtained by the above-mentioned neutralization reaction is decanted with dilute ammonia water using a centrifuge, and washing is repeated until the amount of liberated fluoride ions is 100 mg/L or less, thereby removing the fluoride ions from the fluorine-containing silicon hydrate cake and obtaining a silicon-containing precipitate.
  • the fluorine-containing silicon hydrate cake obtained by the above-mentioned neutralization reaction contains fluorine compounds such as ammonium fluoride as impurities, so it is preferable to remove these.
  • the washing liquid used to remove the fluoride ions is preferably dilute ammonia water.
  • the silicon content of the obtained silicon-containing precipitate is determined by taking a portion of the silicon-containing precipitate, drying it at 110 ° C for 24 hours, and then calcining it at 1000 ° C for 4 hours to produce SiO 2.
  • the weight of the SiO 2 thus produced is measured, and the silicon content of the silicon-containing precipitate can be calculated from the weight.
  • a tertiary amine compound and pure water are added to the obtained silicon-containing precipitate and stirred for 10 minutes to obtain a silicon-containing mixed liquid.
  • 35% by mass hydrogen peroxide is added to the silicon-containing mixed liquid and stirred for 30 minutes to obtain a silicon acid compound-containing liquid.
  • the tertiary amine compound is preferably mixed so that the content of the tertiary amine compound in the silicon-containing mixed liquid is 0.1% by mass or more and 30% by mass or less.
  • the tertiary amine compound is preferably one or more selected from trimethylamine, triethylamine, and tri-n-propylamine.
  • the hydrogen peroxide content of the hydrogen peroxide solution is preferably 0.5% by mass to 35% by mass.
  • the hydrogen peroxide is preferably added so that the molar ratio of hydrogen peroxide to silicon, H 2 O 2 /Si, is 0.6 to 1.5, and more preferably 0.7 to 1.2, since hydrogen peroxide may decompose during mixing.
  • the method for producing the silicon oxide compound-containing liquid is not limited to the above-mentioned method, but may be produced by the following method.
  • Another example of a method for producing a silicon oxide compound-containing liquid may include a mixing step of adding an acidic aqueous solution to a raw material containing silicon, stirring the mixture at 15°C or higher and 50°C or lower to obtain a mixture containing a precursor of a silicon compound, and a stirring step of adding a solution containing an organic nitrogen compound to the mixture, stirring the mixture at 15°C or higher and 50°C or lower to produce a silicon compound-containing liquid.
  • an acidic aqueous solution is added to the raw material containing silicon, and the mixture is stirred at 15°C to 50°C to obtain a mixture containing a precursor of the silicon compound.
  • Silicon-containing raw materials include tetraethoxysilane (TEOS), tetramethoxysilane (TMOS), sodium silicate, etc. It is preferable that the silicon-containing raw material contains at least one of tetraethoxysilane and sodium silicate.
  • the acidic aqueous solution examples include acetic acid, hydrochloric acid, sulfuric acid, and phosphoric acid. It is preferable that the acidic aqueous solution contains at least one of acetic acid, hydrochloric acid, and phosphoric acid.
  • the acetic acid content is preferably 0.001% by mass to 3.0% by mass.
  • the silicon-containing raw material is TEOS
  • the acetic acid content is 0.001% by mass or more, the silanol ester group Si-O-CH 2 -OH 3 in TEOS can be efficiently hydrolyzed to form a Si-OH structure.
  • the acetic acid content is 3.0% by mass or less, the acetic acid content in the silicon acid compound-containing liquid, which is the final product, can be reduced, which is preferable.
  • the acetic acid content is preferably 0.001% by mass or more, more preferably 0.005% by mass or more, and even more preferably 0.01% by mass or more.
  • the acetic acid content is preferably 3.0% by mass or less, more preferably 2.5% by mass or less, even more preferably 2.0% by mass or less, particularly preferably 1.5% by mass or less, more particularly preferably 1.0% by mass or less, even more particularly preferably 0.5% by mass or less, even more particularly preferably 0.1% by mass or less, even more particularly preferably 0.05% by mass or less, even more particularly preferably 0.04% by mass or less, even more particularly preferably 0.03% by mass or less, and even more particularly preferably 0.02% by mass or less.
  • the acetic acid content described in this specification is the content when added to the silicon-containing raw material in the mixing step, unless otherwise specified.
  • the acetic acid content in the silicon acid compound-containing liquid is preferably 0.02% by mass to 10% by mass.
  • the acetic acid content is more preferably 0.05% by mass or more, even more preferably 0.1% by mass or more, particularly preferably 0.15% by mass or more, and even more particularly preferably 0.2% by mass or more.
  • the acetic acid content is more preferably 5% by mass or less, even more preferably 3% by mass or less, particularly preferably 1% by mass or less, and especially preferably 0.5% by mass or less.
  • the amount of acetic acid added to the silicon-containing raw material is preferably such that the molar ratio of CH 3 COOH/Si is 0.01 or more and 0.3 or less, more preferably 0.02 or more and 0.25 or less, and even more preferably 0.03 or more and 0.2 or less.
  • the time for adding acetic acid to the silicon-containing raw material is preferably 5 minutes or less, more preferably 3 minutes or less, and even more preferably 1 minute or less.
  • the content of acetic acid in the silicon oxide compound-containing liquid is preferably such that the molar ratio of CH 3 COOH/Si is 0.01 or more and 0.3 or less, more preferably 0.02 or more and 0.25 or less, and even more preferably 0.03 or more and 0.2 or less.
  • the hydrochloric acid content is preferably 0.001% to 3.0% by mass. If the hydrochloric acid content is 0.001% by mass or more, sodium chloride can be efficiently produced from sodium silicate when the silicon-containing raw material is sodium silicate. On the other hand, if the hydrochloric acid content is 3.0% by mass or less, this is preferable because chlorine is less likely to remain in the final product, the silicon oxide compound-containing liquid. From this perspective, the hydrochloric acid content is preferably 0.001% by mass or more, more preferably 0.005% by mass or more, and even more preferably 0.01% by mass or more.
  • the hydrochloric acid content is preferably 3.0% by mass or less, more preferably 2.5% by mass or less, even more preferably 2.0% by mass or less, particularly preferably 1.5% by mass or less, more particularly preferably 1.0% by mass or less, even more particularly preferably 0.5% by mass or less, even more particularly preferably 0.1% by mass or less, even more particularly preferably 0.05% by mass or less, even more particularly preferably 0.04% by mass or less, even more particularly preferably 0.03% by mass or less, and even more particularly preferably 0.02% by mass or less.
  • the hydrochloric acid content described in this specification is the content when added to the silicon-containing raw material in the mixing step, unless otherwise specified, and is the value converted by the weight of HCl in a 0.5N hydrochloric acid aqueous solution.
  • the hydrochloric acid content in the silicon oxide compound-containing liquid is preferably 0.02% by mass to 10% by mass.
  • the hydrochloric acid content is more preferably 0.05% by mass or more, even more preferably 0.1% by mass or more, particularly preferably 0.15% by mass or more, and even more particularly preferably 0.2% by mass or more.
  • the hydrochloric acid content is more preferably 5% by mass or less, even more preferably 3% by mass or less, particularly preferably 1% by mass or less, and especially preferably 0.5% by mass or less.
  • the amount of hydrochloric acid added to the silicon-containing raw material is preferably such that the molar ratio of HCl/Si is 0.5 or more and 1.5 or less, more preferably 0.55 or more and 1.3 or less, and even more preferably 0.6 or more and 1.1 or less.
  • the time for adding hydrochloric acid to the silicon-containing raw material is preferably 10 minutes or less, more preferably 5 minutes or less, and even more preferably 3 minutes or less.
  • the content of hydrochloric acid in the silicon oxide compound-containing liquid is preferably such that the molar ratio of HCl/Si is 0.5 or more and 1.5 or less, more preferably 0.55 or more and 1.3 or less, and even more preferably 0.6 or more and 1.1 or less.
  • the liquid temperature of the mixed liquid during stirring is preferably 15° C. to 50° C., more preferably 20° C. to 45° C., and even more preferably 25° C. to 40° C. If the liquid temperature of the mixed liquid exceeds 50° C., the water in the mixed liquid evaporates too much, and Si-OH groups in the mixed liquid undergo dehydration condensation to partially form SiO 2 fine particles, which may not dissolve when a solution containing an organic nitrogen compound is added during the stirring step.
  • the stirring time varies depending on the type of raw material containing silicon, the amount of acidic aqueous solution added, the decompression conditions, etc.
  • the stirring time is preferably from 30 minutes to 24 hours, more preferably from 1 hour to 15 hours, and even more preferably from 2 hours to 12 hours.
  • the stirring time is preferably from 10 minutes to 10 hours, more preferably from 30 minutes to 7 hours, and even more preferably from 1 hour to 5 hours.
  • the resulting mixture containing the precursor of the silicon compound is advanced to the next stirring step.
  • the resulting mixture containing the precursor of the silicon compound requires the following treatment as a pretreatment before proceeding to the next stirring step.
  • some of the Na in the sodium silicate reacts with some of the Cl in the hydrochloric acid, and the generated NaCl is contained in the precursor of the silicon compound, so it is advisable to remove NaCl from the precursor of the silicon compound.
  • the method for removing the NaCl is to first put the mixture containing the precursor of the silicon compound into a centrifuge tube and collect the precipitated transparent gel by centrifuging (4500 rpm, 10 minutes). Next, water is added to the collected transparent gel, which is then put into a centrifuge tube and centrifuged (4500 rpm, 20 minutes) multiple times with the water replaced, thereby removing NaCl from the precursor of the silicon compound.
  • a solution containing an organic nitrogen compound is added to the mixture containing the precursor of the silicon compound, and the mixture is stirred at 15°C or higher and 50°C or lower to produce a silicon oxide compound-containing liquid.
  • examples of the organic nitrogen compound include primary amines, secondary amines, tertiary amines, and quaternary ammonium salts.
  • the organic nitrogen compound preferably contains at least one of primary amines, secondary amines, and quaternary ammonium salts, and specific examples include methylamine, ethylamine, dimethylamine, diethylamine, and tetramethylammonium hydroxide. Note that a solution containing an organic acid, rather than an organic nitrogen compound, may be added to the mixture containing the silicon compound precursor.
  • the amount of the organic nitrogen compound added to the mixture containing the precursor of the silicon compound is preferably such that the amine/Si molar ratio is 0.5 or more and 15 or less, more preferably 1 or more and 10 or less, and even more preferably 1.5 or more and 5 or less.
  • the amount of the organic nitrogen compound added to the mixture containing the precursor of the silicon compound is preferably such that the amine/Si molar ratio is 1.7 or more, more preferably 1.3 or more, and even more preferably 1.3 or more.
  • the amine/Si molar ratio is preferably 1.5 or less, more preferably 1.2 or less, and even more preferably 1 or less.
  • the time for adding the organic nitrogen compound to the mixture containing the silicon compound precursor is preferably within 60 minutes, more preferably within 30 minutes, and even more preferably within 10 minutes.
  • the liquid temperature during stirring is preferably 15°C to 50°C, more preferably 20°C to 45°C, and even more preferably 25°C to 40°C.
  • the organic nitrogen compound etc. will evaporate, making it difficult for the silicon compound precursor to dissolve, and increasing the possibility that the silicon compound precursor will remain.
  • the stirring time is preferably from 10 minutes to 24 hours, more preferably from 30 minutes to 20 hours, and even more preferably from 1 hour to 15 hours.
  • a solution containing an organic nitrogen compound can be added to a mixed solution containing a silicon compound precursor, and stirred at 15°C to 50°C to produce a silicon oxide compound-containing liquid.
  • the silicon compound precursor contains many Si-OH structures, which makes it easier to dissolve in silicon acid.
  • molybdenum or molybdenum oxide is reacted with hydrofluoric acid (HF) such as an aqueous solution of hydrofluoric acid to form molybdenum fluoride (H 2 MoF 6 ), which is then dissolved in water to obtain an aqueous solution of molybdenum fluoride, which is an acidic metal solution.
  • HF hydrofluoric acid
  • H 2 MoF 6 molybdenum fluoride
  • the molybdenum fluoride aqueous solution it is preferable to adjust the molybdenum fluoride aqueous solution to contain 1 to 100 g/L of molybdenum in terms of MoO 3 by adding water (e.g., pure water).
  • water e.g., pure water
  • the molybdenum content is 1 g/L or more in terms of MoO 3
  • the molybdenum content is 100 g/L or less in terms of MoO 3 , it is preferable because the molybdenum acid compound hydrate is easily soluble in water, and in order to more reliably synthesize the molybdenum acid compound hydrate that is easily soluble in water, it is more preferable that it is 90 g/L or less, even more preferable that it is 80 g/L or less, and particularly preferable that it is 70 g/L or less.
  • the pH of the molybdenum fluoride aqueous solution is preferably 2 or less, more preferably 1 or less, from the viewpoint of completely dissolving molybdenum or molybdenum oxide.
  • the molybdenum fluoride aqueous solution is neutralized with an alkaline aqueous solution to obtain a fluorine-containing molybdenum hydrate cake.
  • the alkaline aqueous solution used to neutralize the molybdenum fluoride aqueous solution is preferably 10% to 30% ammonia water.
  • the amount of addition is preferably such that the molar ratio of NH 3 /Mo is 95 or more and 500 or less, more preferably such that the molar ratio is 100 or more and 450 or less, and even more preferably such that the molar ratio is 110 or more and 400 or less.
  • the amount of addition is preferably such that the molar ratio of NH 3 /HF is 3.0 or more, more preferably such that the molar ratio is 4.0 or more, and even more preferably such that the molar ratio is 5.0 or more.
  • the molar ratio of NH 3 /HF is preferably 100 or less, more preferably such that the molar ratio is 50 or less, and even more preferably such that the molar ratio is 40 or less.
  • the addition time in the above-mentioned neutralization reaction is preferably within 10 minutes, more preferably within 8 minutes, and even more preferably within 5 minutes.
  • the fluorine-containing molybdenum hydrate cake obtained by the above-mentioned neutralization reaction is decanted with dilute ammonia water using a centrifuge, and washing is repeated until the amount of liberated fluoride ions becomes 100 mg/L or less, thereby removing the fluoride ions from the fluorine-containing molybdenum hydrate cake and obtaining a molybdenum-containing precipitate.
  • the fluorine-containing molybdenum hydrate cake obtained by the above-mentioned neutralization reaction contains fluorine compounds such as ammonium fluoride as impurities, so it is preferable to remove these.
  • the washing liquid used to remove the fluoride ions is preferably dilute ammonia water.
  • the molybdenum content of the obtained molybdenum-containing precipitate is determined by taking a portion of the molybdenum-containing precipitate, drying it at 110° C. for 24 hours, and then calcining it at 1000° C. for 4 hours to produce MoO 3.
  • the weight of the MoO 3 thus produced can be measured, and the molybdenum content of the molybdenum-containing precipitate can be calculated from the weight.
  • a tertiary amine compound and pure water are added to the obtained molybdenum-containing precipitate and stirred for 10 minutes to obtain a molybdenum-containing mixed liquid.
  • 35% by mass hydrogen peroxide is added to the molybdenum-containing mixed liquid and stirred for 30 minutes to obtain a molybdenum acid compound-containing liquid.
  • the tertiary amine compound is preferably mixed so that the content of the tertiary amine compound in the molybdenum-containing mixed liquid is 0.1% by mass or more and 30% by mass or less.
  • the tertiary amine compound is preferably one or more selected from trimethylamine, triethylamine, and tri-n-propylamine.
  • the hydrogen peroxide content of the hydrogen peroxide solution is preferably 0.5% by mass to 35% by mass.
  • the hydrogen peroxide is preferably added so that the molar ratio of hydrogen peroxide to molybdenum, H 2 O 2 /Mo, is 0.6 to 1.5, and more preferably 0.7 to 1.2, since hydrogen peroxide may decompose during mixing.
  • the method for producing the tungsten acid compound-containing liquid which is the metal acid compound-containing liquid of the present invention, is described below. Note that explanations of parts that overlap with the method for producing the tantalic acid compound-containing liquid described above will be omitted.
  • tungsten or tungsten oxide is reacted with hydrofluoric acid (HF) such as an aqueous solution of hydrofluoric acid to form tungsten fluoride (H 2 MoF 6 ), which is then dissolved in water to obtain an aqueous tungsten fluoride solution, which is an acidic metal solution.
  • HF hydrofluoric acid
  • H 2 MoF 6 tungsten fluoride
  • the tungsten fluoride aqueous solution is preferably adjusted to contain 1 to 100 g/L of tungsten in terms of WO 3 by adding water (e.g., pure water).
  • water e.g., pure water
  • the tungsten content is 1 g/L or more in terms of WO 3
  • the tungsten content is 100 g/L or less in terms of WO 3 , it is preferable because the tungsten acid compound hydrate is easily soluble in water, and in order to more reliably synthesize the tungsten acid compound hydrate that is easily soluble in water, it is more preferable that it is 90 g/L or less, even more preferable that it is 80 g/L or less, and particularly preferable that it is 70 g/L or less.
  • the pH of the tungsten fluoride aqueous solution is preferably 2 or less, and more preferably 1 or less, from the viewpoint of completely dissolving tungsten or tungsten oxide.
  • the tungsten fluoride aqueous solution is neutralized with an alkaline aqueous solution to obtain a fluorine-containing tungsten hydrate cake.
  • the alkaline aqueous solution used to neutralize the tungsten fluoride aqueous solution is preferably 10% to 30% ammonia water.
  • the amount of addition is preferably such that the molar ratio of NH 3 /W is 95 or more and 500 or less, more preferably such that the molar ratio of NH 3 /W is 100 or more and 450 or less, and even more preferably such that the molar ratio of NH 3 /HF is 3.0 or more, more preferably such that the molar ratio of NH 3 /HF is 4.0 or more, and even more preferably such that the molar ratio of NH 3 /HF is 5.0 or more, from the viewpoint of generating a tungstic acid compound that dissolves in amine or dilute ammonia water.
  • the molar ratio of NH 3 /HF is preferably 100 or less, more preferably such that the molar ratio of NH 3 /HF is 50 or less, and even more preferably such that the molar ratio of NH 3 /HF is 40 or less.
  • the addition time in the above-mentioned neutralization reaction is preferably within 10 minutes, more preferably within 8 minutes, and even more preferably within 5 minutes.
  • the fluorine-containing tungsten hydrate cake obtained by the above-mentioned neutralization reaction is decanted with dilute ammonia water using a centrifuge, and washing is repeated until the amount of liberated fluoride ions is 100 mg/L or less, thereby removing the fluoride ions from the fluorine-containing tungsten hydrate cake and obtaining a tungsten-containing precipitate.
  • the fluorine-containing tungsten hydrate cake obtained by the above-mentioned neutralization reaction contains fluorine compounds such as ammonium fluoride as impurities, so it is preferable to remove these.
  • the washing liquid used to remove the fluoride ions is preferably dilute ammonia water.
  • the tungsten content of the obtained tungsten-containing precipitate is determined by taking a portion of the tungsten-containing precipitate, drying it at 110° C. for 24 hours, and then calcining it at 1000° C. for 4 hours to produce WO3 .
  • the weight of the WO3 produced in this manner can be measured, and the tungsten content of the tungsten-containing precipitate can be calculated from the weight.
  • tungsten-containing precipitate a tertiary amine compound and pure water are added to the obtained tungsten-containing precipitate and stirred for 10 minutes to obtain a tungsten-containing mixed liquid.
  • 35% by mass hydrogen peroxide is added to the tungsten-containing mixed liquid and stirred for 30 minutes to obtain a tungsten acid compound-containing liquid.
  • the tertiary amine compound is preferably mixed so that the content of the tertiary amine compound in the tungsten-containing mixed liquid is 0.1% by mass or more and 30% by mass or less.
  • the tertiary amine compound is preferably one or more selected from trimethylamine, triethylamine, and tri-n-propylamine.
  • the hydrogen peroxide content of the hydrogen peroxide solution is preferably 0.5% by mass to 35% by mass.
  • the hydrogen peroxide is preferably added so that the molar ratio H 2 O 2 /W of hydrogen peroxide to tungsten is 0.6 to 1.5, and more preferably 0.7 to 1.2, since hydrogen peroxide may decompose during mixing.
  • the method for producing the hafnium acid compound-containing liquid which is the metal acid compound-containing liquid of the present invention, is described below. Note that explanations of parts that overlap with the method for producing the tantalic acid compound-containing liquid described above will be omitted.
  • hafnium or hafnium oxide is reacted with hydrofluoric acid (HF), such as an aqueous solution of hydrofluoric acid, to produce hafnium fluoride (H 2 HfF 6 ), which is then dissolved in water to obtain an aqueous solution of hafnium fluoride, which is an acidic metal solution.
  • HF hydrofluoric acid
  • the hafnium fluoride aqueous solution it is preferable to adjust the hafnium fluoride aqueous solution to contain 1 to 100 g/L of hafnium in terms of HfO 2 by adding water (e.g., pure water).
  • water e.g., pure water
  • the hafnium content is 1 g/L or more in terms of HfO 2
  • the hafnium content is 100 g/L or less in terms of HfO 2 , it is preferable because the hafnium oxide hydrate is easily soluble in water, and in order to more reliably synthesize the hafnium oxide hydrate that is easily soluble in water, it is more preferable to have a hafnium content of 90 g/L or less, even more preferable to have a hafnium content of 80 g/L or less, and particularly preferable to have a hafnium content of 70 g/L or less.
  • the pH of the hafnium fluoride aqueous solution is preferably 2 or less, and more preferably 1 or less, from the viewpoint of completely dissolving hafnium or hafnium oxide.
  • the hafnium fluoride aqueous solution is neutralized with an alkaline aqueous solution to obtain a fluorine-containing hafnium hydrate cake.
  • the alkaline aqueous solution used to neutralize the hafnium fluoride aqueous solution is preferably 10% to 30% ammonia water.
  • the amount of addition is preferably such that the molar ratio of NH 3 /Hf is 95 or more and 500 or less, more preferably such that the molar ratio is 100 or more and 450 or less, and even more preferably such that the molar ratio is 110 or more and 400 or less.
  • the amount of addition is preferably such that the molar ratio of NH 3 /HF is 3.0 or more, more preferably such that the molar ratio is 4.0 or more, and even more preferably such that the molar ratio is 5.0 or more.
  • the molar ratio of NH 3 /HF is preferably 100 or less, more preferably such that the molar ratio is 50 or less, and even more preferably such that the molar ratio is 40 or less.
  • the addition time in the above-mentioned neutralization reaction is preferably within 10 minutes, more preferably within 8 minutes, and even more preferably within 5 minutes.
  • the fluorine-containing hafnium hydrate cake obtained by the above-mentioned neutralization reaction is decanted with dilute ammonia water using a centrifuge, and washing is repeated until the amount of liberated fluoride ions is 100 mg/L or less, thereby removing the fluoride ions from the fluorine-containing hafnium hydrate cake and obtaining a hafnium-containing precipitate.
  • the fluorine-containing hafnium hydrate cake obtained by the above-mentioned neutralization reaction contains fluorine compounds such as ammonium fluoride as impurities, so it is preferable to remove these.
  • the washing liquid used to remove the fluoride ions is preferably dilute ammonia water.
  • the hafnium content of the obtained hafnium-containing precipitate is determined by taking a portion of the hafnium-containing precipitate, drying it at 110° C. for 24 hours, and then calcining it at 1000° C. for 4 hours to produce HfO 2.
  • the weight of the HfO 2 thus produced is measured, and the hafnium content of the hafnium-containing precipitate can be calculated from the weight.
  • hafnium-containing precipitate a tertiary amine compound and pure water are added to the obtained hafnium-containing precipitate and stirred for 10 minutes to obtain a hafnium-containing mixed liquid.
  • 35% by mass hydrogen peroxide is added to the hafnium-containing mixed liquid and stirred for 30 minutes to obtain a hafnium acid compound-containing liquid.
  • the tertiary amine compound is preferably mixed so that the content of the tertiary amine compound in the hafnium-containing mixed solution is 0.1% by mass or more and 30% by mass or less.
  • the tertiary amine compound is preferably one or more selected from trimethylamine, triethylamine, and tri-n-propylamine.
  • the hydrogen peroxide content of the hydrogen peroxide solution is preferably 0.5% by mass to 35% by mass.
  • the hydrogen peroxide is preferably added so that the molar ratio of hydrogen peroxide to hafnium, H 2 O 2 /Hf, is 0.6 to 1.5, and more preferably 0.7 to 1.2, since hydrogen peroxide may decompose during mixing.
  • the method for producing the rare earth element acid compound-containing liquid which is the metal acid compound-containing liquid of the present invention, is described below. Note that explanations of parts that overlap with the above-mentioned method for producing the tantalic acid compound-containing liquid will be omitted.
  • a rare earth element or a rare earth oxide is reacted with hydrofluoric acid (HF), such as an aqueous solution of hydrofluoric acid, to produce a rare earth fluoride, which is then dissolved in water to obtain an aqueous solution of rare earth fluoride, which is an acidic metal solution.
  • HF hydrofluoric acid
  • the rare earth fluoride aqueous solution it is preferable to adjust the rare earth fluoride aqueous solution to contain 1 to 100 g/L of rare earth element in terms of rare earth oxide by adding water (e.g., pure water).
  • water e.g., pure water
  • the rare earth element content is 1 g/L or more in terms of rare earth oxide, since it will become a rare earth element acid compound hydrate that is easily soluble in water, and from the viewpoint of productivity, it is more preferable that it is 10 g/L or more, and even more preferable that it is 20 g/L or more.
  • the rare earth element content is 100 g/L or less in terms of rare earth element oxide, since it will become a rare earth element acid compound hydrate that is easily soluble in water, and in order to synthesize a rare earth element acid compound hydrate that is easily soluble in water more reliably, it is more preferable that it is 90 g/L or less, even more preferable that it is 80 g/L or less, and particularly preferable that it is 70 g/L or less.
  • the pH of the rare earth fluoride aqueous solution is preferably 2 or less, and more preferably 1 or less, from the viewpoint of completely dissolving the rare earth element or rare earth element oxide.
  • the aqueous solution of rare earth fluoride is neutralized with an aqueous alkaline solution to obtain a fluorine-containing rare earth hydrate cake.
  • the aqueous alkaline solution used to neutralize the aqueous solution of rare earth fluoride is preferably 10% to 30% ammonia water.
  • the amount of addition is preferably such that the molar ratio of NH 3 /rare earth element is 95 or more and 500 or less, more preferably such that the molar ratio is 100 or more and 450 or less, and even more preferably such that the molar ratio is 110 or more and 400 or less.
  • the amount of addition is preferably such that the molar ratio of NH 3 /HF is 3.0 or more, more preferably such that the molar ratio is 4.0 or more, and even more preferably such that the molar ratio is 5.0 or more.
  • the molar ratio of NH 3 /HF is preferably 100 or less, more preferably such that the molar ratio is 50 or less, and even more preferably such that the molar ratio is 40 or less.
  • the addition time in the above-mentioned neutralization reaction is preferably within 10 minutes, more preferably within 8 minutes, and even more preferably within 5 minutes.
  • the fluorine-containing rare earth element hydrate cake obtained by the above-mentioned neutralization reaction is decanted with dilute ammonia water using a centrifuge, and washing is repeated until the amount of liberated fluoride ions becomes 100 mg/L or less, thereby removing the fluoride ions from the fluorine-containing rare earth element hydrate cake and obtaining a rare earth element-containing precipitate.
  • the fluorine-containing rare earth element hydrate cake obtained by the above-mentioned neutralization reaction contains fluorine compounds such as ammonium fluoride as impurities, so it is preferable to remove these.
  • the washing liquid used to remove the fluoride ions is preferably dilute ammonia water.
  • the rare earth element content of the rare earth element-containing precipitate obtained is determined by taking a portion of the rare earth element-containing precipitate, drying it at 110°C for 24 hours, and then calcining it at 1000°C for 4 hours to produce rare earth element oxide.
  • the weight of the rare earth element oxide thus produced can be measured, and the rare earth element content of the rare earth element-containing precipitate can be calculated from that weight.
  • a tertiary amine compound and pure water are added to the obtained rare earth element-containing precipitate, and the mixture is stirred for 10 minutes to obtain a rare earth element-containing mixed liquid.
  • 35% by mass hydrogen peroxide is added to the rare earth element-containing mixed liquid, and the mixture is stirred for 30 minutes to obtain a rare earth element acid compound-containing liquid.
  • the tertiary amine compound is preferably mixed so that the content of the tertiary amine compound in the rare earth element-containing mixed liquid is 0.1% by mass or more and 30% by mass or less.
  • the tertiary amine compound is preferably one or more selected from trimethylamine, triethylamine, and tri-n-propylamine.
  • the hydrogen peroxide content of the hydrogen peroxide solution is preferably 0.5% by mass to 35% by mass.
  • the hydrogen peroxide is preferably added so that the molar ratio H 2 O 2 /Hf between hydrogen peroxide and rare earth elements is 0.6 to 1.5, and more preferably 0.7 to 1.2, since hydrogen peroxide may decompose during mixing.
  • the method for producing a metal acid compound-containing film of the present invention includes the steps of applying the metal acid compound-containing liquid of the present invention to a substrate, and drying and/or firing the liquid.
  • the metal acid compound-containing liquid of the present invention used in the method for producing a metal acid compound-containing film of the present invention may be one produced by the method for producing a metal acid compound-containing liquid of the present invention described above.
  • a method for producing the metal acid compound-containing dry film of the present invention which is one of the metal acid compound-containing films of the present invention, includes a coating step in which the metal acid compound-containing liquid of the present invention is applied to the surface of a substrate, and a film drying step in which the metal acid compound-containing liquid applied to the surface of the substrate is dried to obtain a dry film.
  • the metal acid compound-containing liquid obtained by the above-mentioned method for producing a metal acid compound-containing liquid of the present invention is dropped onto the surface of the substrate using a syringe while filtering, for example, with a filter having a pore size of 2 ⁇ m, as necessary, and then applied by spin coating (700 rpm, 10 seconds, then 1500 rpm, 15 seconds).
  • spin coating 700 rpm, 10 seconds, then 1500 rpm, 15 seconds.
  • a metal acid compound-containing dry film is formed on the surface of the substrate by drying at 110° C. for 30 minutes.
  • the method for producing the metal acid compound-containing fired film of the present invention includes a coating step of coating the metal acid compound-containing liquid of the present invention onto the surface of a substrate, a film drying step of drying the metal acid compound-containing liquid coated onto the surface of the substrate to obtain a dried film, and a film firing step of firing the dried film in air at a firing temperature of 300°C to 1,200°C for a firing time of 1 hour to 12 hours to obtain a fired film.
  • the liquid containing the metal acid compound of the present invention is applied to the surface of a substrate, and the substrate is dried to form a dry film containing the metal acid compound of the present invention.
  • the substrate is then placed in a static furnace and baked in air at a baking temperature of 300°C to 1,200°C for a baking time of 1 hour to 12 hours, thereby forming a baked film containing the metal acid compound of the present invention on the surface of the substrate.
  • the method for producing a complex metal acid compound-containing liquid of the present invention is characterized by comprising the steps of neutralizing an acidic metal aqueous solution containing a metal and/or metalloid element with an alkaline aqueous solution to produce a precipitate containing the metal and/or metalloid element, adding a tertiary amine compound and hydrogen peroxide to the precipitate to produce a metal acid compound-containing liquid, and mixing the metal acid compound-containing liquid with at least one element A selected from the group consisting of Li, Na, Ma, Al, K, Ca, V, Mn, Fe, Co, Ni, Cu, Zn, Sn, Sr, and Ba to produce a complex metal acid compound-containing liquid.
  • the metal acid compound-containing liquid of the present invention produced by the above-mentioned method for producing a metal acid compound-containing liquid of the present invention is mixed with at least one element A selected from the group consisting of Li, Na, Ma, Al, K, Ca, V, Mn, Fe, Co, Ni, Cu, Zn, Sn, Sr, and Ba, and the liquid temperature is maintained at an appropriate temperature for a predetermined time while stirring, thereby obtaining the complex metal acid compound-containing liquid of the present invention.
  • element A may be in various forms such as an oxide, hydroxide, metal complex, or salt made of a polyoxometalate or peroxo complex.
  • the method for producing a double metal acid compound-containing film of the present invention includes the steps of applying the double metal acid compound-containing liquid of the present invention to a substrate, and drying and/or firing the same.
  • the complex metal acid compound-containing liquid of the present invention used in the method for producing a complex metal acid compound-containing film of the present invention may be one produced by the method for producing a complex metal acid compound-containing liquid of the present invention described above.
  • the method for producing the complex metal acid compound-containing dry film of the present invention which is the same as the method for producing the metal acid compound-containing dry film of the present invention, includes a coating step of coating the complex metal acid compound-containing liquid of the present invention onto the surface of a substrate, and a film drying step of drying the complex metal acid compound-containing liquid applied onto the surface of the substrate to obtain a dry film.
  • the method for producing the complex metal acid compound-containing fired film of the present invention includes, like the method for producing the metal acid compound-containing fired film of the present invention, a coating step of coating the complex metal acid compound-containing liquid of the present invention onto the surface of a substrate, a film drying step of drying the complex metal acid compound-containing liquid coated onto the surface of the substrate to obtain a dried film, and a film firing step of firing the dried film in the atmosphere at a firing temperature of 300°C to 1,200°C for a firing time of 1 hour to 12 hours to obtain a fired film.
  • X to Y (X and Y are any numbers) is used, unless otherwise specified, it includes the meaning of “X or more and Y or less”, as well as “preferably greater than X” or “preferably smaller than Y”. Furthermore, when “X or more” (X is any number) or “Y or less” (Y is any number), it also includes the meaning of "preferably greater than X” or "preferably less than Y”.
  • the metal acid compound-containing liquid of the present invention and its manufacturing method have a low environmental impact and excellent dispersibility.
  • 1 is a table listing the physical property values and measurement results of metal acid compound-containing liquids according to Examples 1 to 8 of the present invention and Comparative Examples 1 to 9.
  • 1 is a table listing the physical property values and measurement results of metal acid compound-containing liquids according to Examples 9 and 10 of the present invention and Comparative Examples 10 to 12.
  • the metal acid compound-containing liquid according to the embodiment of the present invention will be further described below with reference to the following examples.
  • the metal acid compound-containing liquid according to Examples 1 to 8 and Comparative Examples 1 to 9 is a tantalic acid compound-containing liquid.
  • the metal acid compound-containing liquid according to Examples 9 and 10 and Comparative Examples 10 to 12 is a niobic acid compound-containing liquid.
  • the following examples do not limit the present invention.
  • Example 1 100 g of tantalum hydroxide (Ta 2 O 5 concentration 99.9 mass %) manufactured by Mitsui Mining & Smelting Co., Ltd. was dissolved in 100 g of 55 mass % hydrofluoric acid aqueous solution, and 100 mL of ion-exchanged water was added to obtain an aqueous tantalum fluoride solution (Ta 2 O 5 concentration 33.3 mass %).
  • aqueous tantalum fluoride solution 1000 mL of aqueous ammonia ( NH3 concentration: 25% by mass) was added to obtain a fluorine-containing tantalum hydrate cake.
  • this fluorine-containing tantalum hydrate cake was decanted using a centrifuge with dilute ammonia water and washed until the amount of liberated fluoride ions was 100 mg/L or less, to obtain a tantalum-containing precipitate from which the fluoride ions had been removed.
  • ammonia water was used as the washing liquid.
  • the tantalum content of the obtained tantalum-containing precipitate was determined by taking a portion of the tantalum-containing precipitate, drying it at 110° C. for 24 hours, and then firing it at 1000° C. for 4 hours to produce Ta 2 O 5.
  • the weight of the Ta 2 O 5 thus produced was measured, and the Ta 2 O 5 (tantalum oxide, oxide equivalent) content of the tantalum-containing precipitate calculated from the weight was 50 mass %.
  • the Ta (tantalum, metal equivalent) content of the tantalum-containing precipitate was calculated to be 40.9 mass %.
  • tantalum-containing precipitate 50g of 10% by mass triethylamine and 317g of pure water were added to the obtained tantalum-containing precipitate, and the mixture was stirred for 10 minutes to obtain a tantalum-containing mixed solution.
  • 83g of 35% by mass hydrogen peroxide was added to the tantalum-containing mixed solution so that the final tantalum content was 5% by mass in terms of oxide ( Ta2O5 ), 4.1% by mass in terms of metal (Ta), and the final hydrogen peroxide content was 6.8% by mass, and the mixture was stirred for 30 minutes to obtain a tantalic acid compound-containing solution according to Example 1. No precipitate or sediment was observed in the tantalic acid compound-containing solution according to Example 1.
  • the pH of the tantalic acid compound-containing solution according to Example 1 was 11.0.
  • Example 2 In Example 2, the same manufacturing method as in Example 1 was carried out, except that 35 mass% hydrogen peroxide was added to the tantalum-containing mixed solution so that the final tantalum content was 7.5 mass% in terms of oxide ( Ta2O5 ) and 6.1 mass% in terms of metal (Ta), to obtain a tantalic acid compound-containing solution according to Example 2. No precipitate or sediment was observed in the tantalic acid compound-containing solution according to Example 2. The pH of the tantalic acid compound-containing solution according to Example 2 was 11.1.
  • Example 3 In Example 3, the same manufacturing method as in Example 1 was carried out except that 15 mass % of triethylamine was added to the tantalum-containing precipitate, to obtain a tantalic acid compound-containing liquid according to Example 3. No precipitate or sediment was observed in the tantalic acid compound-containing liquid according to Example 3. The pH of the tantalic acid compound-containing liquid according to Example 3 was 11.3.
  • Example 4 In Example 4, the same manufacturing method as in Example 1 was carried out except that 5 mass % of triethylamine was added to the tantalum-containing precipitate, to obtain a tantalic acid compound-containing liquid according to Example 4. No precipitate or sediment was observed in the tantalic acid compound-containing liquid according to Example 4. The pH of the tantalic acid compound-containing liquid according to Example 4 was 10.9.
  • Example 5 In Example 5, the same manufacturing method as in Example 1 was carried out, except that 15 mass% triethylamine was added to the tantalum-containing precipitate, and 35 mass% hydrogen peroxide was added to the tantalum-containing mixed solution so that the final hydrogen peroxide content was 13.4 mass%, to obtain a tantalic acid compound-containing solution according to Example 5. No precipitate or sediment was observed in the tantalic acid compound-containing solution according to Example 5. The pH of the tantalic acid compound-containing solution according to Example 5 was 10.7.
  • Example 6 In Example 6, the same manufacturing method as in Example 1 was carried out, except that 15 mass% triethylamine was added to the tantalum-containing precipitate, and 35 mass% hydrogen peroxide was added to the tantalum-containing mixed solution so that the final hydrogen peroxide content was 5 mass%, to obtain a tantalic acid compound-containing solution according to Example 6. No precipitate or sediment was observed in the tantalic acid compound-containing solution according to Example 6. The pH of the tantalic acid compound-containing solution according to Example 6 was 10.7.
  • Example 7 In Example 7, the same manufacturing method as in Example 1 was carried out except that 15 mass% trimethylamine was added to the tantalum-containing precipitate, to obtain a tantalic acid compound-containing liquid according to Example 7. No precipitate or sediment was observed in the tantalic acid compound-containing liquid according to Example 7. The pH of the tantalic acid compound-containing liquid according to Example 7 was 11.0.
  • Example 8 In Example 8, the same production method as in Example 1 was carried out except that 10 mass% trimethylamine was added to the tantalum-containing precipitate, to obtain a tantalic acid compound-containing liquid according to Example 8. No precipitate or sediment was observed in the tantalic acid compound-containing liquid according to Example 8. The pH of the tantalic acid compound-containing liquid according to Example 8 was 10.6.
  • Comparative Example 1 In Comparative Example 1, a manufacturing method similar to that of Example 1 was carried out, except that 10 mass% of methylamine was added to the tantalum-containing precipitate, to obtain a tantalic acid compound-containing liquid according to Comparative Example 1. A white precipitate was observed in the tantalic acid compound-containing liquid according to Comparative Example 1. The pH of the tantalic acid compound-containing liquid according to Comparative Example 1 was 10.5.
  • Comparative Example 2 In Comparative Example 2, the same production method as in Example 1 was carried out except that 10 mass% dimethylamine was added to the tantalum-containing precipitate, to obtain a tantalic acid compound-containing liquid according to Comparative Example 2. A white precipitate was observed in the tantalic acid compound-containing liquid according to Comparative Example 2. The pH of the tantalic acid compound-containing liquid according to Comparative Example 2 was 10.2.
  • Comparative Example 3 In Comparative Example 3, the same manufacturing method as in Example 1 was carried out except that 10 mass % TMAH was added to the tantalum-containing precipitate, to obtain a tantalic acid compound-containing solution according to Comparative Example 3. A white precipitate was observed in the tantalic acid compound-containing solution according to Comparative Example 3. The pH of the tantalic acid compound-containing solution according to Comparative Example 3 was 10.1.
  • Comparative Example 4 In Comparative Example 4, the same production method as in Example 1 was carried out except that 5 mass% of methylamine was added to the tantalum-containing precipitate, to obtain a tantalic acid compound-containing solution according to Comparative Example 4. A white precipitate was observed in the tantalic acid compound-containing solution according to Comparative Example 4. The pH of the tantalic acid compound-containing solution according to Comparative Example 4 was 10.3.
  • Comparative Example 5 In Comparative Example 5, the same production method as in Example 1 was carried out except that 5 mass% dimethylamine was added to the tantalum-containing precipitate, to obtain a tantalic acid compound-containing liquid according to Comparative Example 5. A white precipitate was observed in the tantalic acid compound-containing liquid according to Comparative Example 5. The pH of the tantalic acid compound-containing liquid according to Comparative Example 5 was 10.3.
  • Comparative Example 6 In Comparative Example 6, the same production method as in Example 1 was carried out except that 5 mass % TMAH was added to the tantalum-containing precipitate, to obtain a tantalic acid compound-containing solution according to Comparative Example 6. A white precipitate was observed in the tantalic acid compound-containing solution according to Comparative Example 6. The pH of the tantalic acid compound-containing solution according to Comparative Example 3 was 10.5.
  • Comparative Example 7 In Comparative Example 7, the same production method as in Example 1 was carried out except that 15 mass% of methylamine was added to the tantalum-containing precipitate, to obtain a tantalic acid compound-containing solution according to Comparative Example 7. A white precipitate was observed in the tantalic acid compound-containing solution according to Comparative Example 7. The pH of the tantalic acid compound-containing solution according to Comparative Example 7 was 10.3.
  • Comparative Example 8 In Comparative Example 8, the same production method as in Example 1 was carried out except that 15 mass% dimethylamine was added to the tantalum-containing precipitate, to obtain a tantalic acid compound-containing liquid according to Comparative Example 8. A white precipitate was observed in the tantalic acid compound-containing liquid according to Comparative Example 8. The pH of the tantalic acid compound-containing liquid according to Comparative Example 8 was 10.4.
  • Comparative Example 9 In Comparative Example 9, the same production method as in Example 1 was carried out except that 15 mass % TMAH was added to the tantalum-containing precipitate, to obtain a tantalic acid compound-containing solution according to Comparative Example 9. A white precipitate was observed in the tantalic acid compound-containing solution according to Comparative Example 9. The pH of the tantalic acid compound-containing solution according to Comparative Example 9 was 10.7.
  • Example 9 100 g of niobium hydroxide (Nb 2 O 5 concentration 99.9 mass %) manufactured by Mitsui Mining & Smelting Co., Ltd. was dissolved in 100 g of 55 mass % hydrofluoric acid aqueous solution, and 100 mL of ion-exchanged water was added to obtain a niobium fluoride aqueous solution (Nb 2 O 5 concentration 33.3 mass %).
  • this fluorine-containing niobium hydrate cake was decanted using a centrifuge with dilute ammonia water and washed until the amount of liberated fluoride ions was 100 mg/L or less, to obtain a niobium-containing precipitate from which the fluoride ions had been removed.
  • ammonia water was used as the washing liquid.
  • the niobium content of the obtained niobium-containing precipitate was determined by taking a part of the tantalum-containing precipitate, drying it at 110° C. for 24 hours, and then firing it at 1000° C. for 4 hours to produce Ta 2 O 5.
  • the weight of the Nb 2 O 5 thus produced was measured, and the Nb 2 O 5 (niobium oxide, oxide equivalent) content of the niobium-containing precipitate calculated from the weight was 50 mass %.
  • the Nb (niobium, metal equivalent) content of the niobium-containing precipitate was calculated to be 35 mass %.
  • Example 10 In Example 10, the same manufacturing method as in Example 9 was carried out except that 10 mass% trimethylamine was added to the niobium-containing precipitate, to obtain a niobic acid compound-containing liquid according to Example 10. No precipitate or sediment was observed in the niobic acid compound-containing liquid according to Example 10. The pH of the niobic acid compound-containing liquid according to Example 10 was 10.7.
  • Comparative Example 10 In Comparative Example 10, the same manufacturing method as in Example 9 was carried out except that 10 mass% methylamine was added to the niobium-containing precipitate, to obtain a niobic acid compound-containing liquid according to Comparative Example 10. A white precipitate was observed in the niobic acid compound-containing liquid according to Comparative Example 10. The pH of the niobic acid compound-containing liquid according to Comparative Example 10 was 10.3.
  • Comparative Example 11 In Comparative Example 11, the same manufacturing method as in Example 9 was carried out except that 10 mass% dimethylamine was added to the niobium-containing precipitate, to obtain a niobic acid compound-containing liquid according to Comparative Example 11. A white precipitate was observed in the niobic acid compound-containing liquid according to Comparative Example 11. The pH of the niobic acid compound-containing liquid according to Comparative Example 11 was 10.2.
  • Comparative Example 12 In Comparative Example 12, the same manufacturing method as in Example 9 was carried out except that 10 mass% TMAH was added to the niobium-containing precipitate, to obtain a niobic acid compound-containing liquid according to Comparative Example 12. A white precipitate was observed in the niobic acid compound-containing liquid according to Comparative Example 12. The pH of the niobic acid compound-containing liquid according to Comparative Example 12 was 10.1.
  • the sample was appropriately diluted with dilute hydrochloric acid, and the following weight fractions were measured in accordance with JIS K0116:2014 using ICP optical emission spectrometry (AG-5110 manufactured by Agilent Technologies): Ta weight fraction calculated as Ta2O5 , Nb weight fraction calculated as Nb2O5 , Ti weight fraction calculated as TiO2 , Mo weight fraction calculated as MoO3 , W weight fraction calculated as WO3 , Zr weight fraction calculated as ZrO2 , Hf weight fraction calculated as HfO2 , Si weight fraction calculated as SiO2 , or rare earth element weight fraction calculated as rare earth element metal.
  • ICP optical emission spectrometry AG-5110 manufactured by Agilent Technologies
  • the particle size distribution was evaluated using a zeta potential, particle size, and molecular weight measurement system (ELSZ-2000, manufactured by Otsuka Electronics Co., Ltd.) in accordance with JIS Z 8828:2019 "Particle size analysis - dynamic light scattering method".
  • ELSZ-2000 zeta potential, particle size, and molecular weight measurement system
  • JIS Z 8828:2019 Particle size analysis - dynamic light scattering method.
  • the solution was filtered with a filter having a pore size of 2 ⁇ m, and ultrasonic treatment was performed at 28 kHz for 3 minutes using an ultrasonic cleaner (VS-100III, manufactured by AS ONE Corporation).
  • the particle size (D50) refers to the median size (D50), which is the particle size showing the 50% integrated value of the integrated distribution curve.
  • the initial particle diameter (D50) of particles in the metal acid compound-containing liquid obtained in Examples 1 to 10 and Comparative Examples 1 to 12, and the particle diameter over time (D50) of particles in the metal acid compound-containing liquid after being left to stand for 20 days in an incubator set at room temperature of 25°C were calculated. Note that the above-mentioned filtering was performed when measuring the "initial particle diameter D50 (nm)", but not when measuring the "over time particle diameter D50 (nm)", and only ultrasonic treatment was performed. Note that for the metal acid compound-containing liquids of Comparative Examples 1 to 12, measurements of the "initial particle diameter D50 (nm)" and “over time particle diameter D50 (nm)” were not performed due to the deposition of precipitates.
  • Figs. 1 and 2 refers to the transmittance of the metal acid compound-containing liquid whose liquid temperature was adjusted to 25°C immediately after production.
  • the "tempered transmittance" in Figs. 1 and 2 refers to the transmittance of the metal acid compound-containing liquid after being left to stand for one month in an incubator set at room temperature of 25°C. Note that the metal acid compound-containing liquids according to Comparative Examples 1 to 12 were not measured for the "initial transmittance" and "tempered transmittance” because precipitates were deposited.
  • ⁇ Film uniformity test> The appearance of the coating film formed on the surface of the glass substrate, which is a substitute for the current collector plate, was evaluated by observing it with an optical microscope.
  • the metal acid compound-containing liquid obtained in Examples 1 to 10 and Comparative Examples 1 to 12 was dropped onto a 50 mm x 50 mm glass substrate that had been degreased and washed with acetone and then dried using a syringe while being filtered with a filter having a pore size of 2 ⁇ m, and was applied by spin coating (1,500 rpm, 15 seconds). The applied portion was then naturally dried to form a coating film on the glass substrate.
  • the glass substrate was observed with an optical microscope (magnification: 40 times) in a central 15 mm x 15 mm range of the formed coating film, and a substrate in which no bubbles, coating unevenness, or cracks were observed was evaluated as having excellent film uniformity and was evaluated as " ⁇ (GOOD)", and a substrate in which even one bubble, coating unevenness, or crack was observed was evaluated as not having excellent film uniformity and was evaluated as " ⁇ (BAD)".
  • ⁇ optical microscope
  • the metal acid compound-containing liquids of Examples 1 to 10 contained a metal and/or metalloid element and a tertiary amine compound, and when the content of the metal and/or metalloid element in the metal acid compound-containing liquid was 0.1 mass% or more and less than 30% in terms of metal equivalent of the metal and/or metalloid element, and the particle diameter (D50) of the particles in the metal acid compound-containing liquid was 1000 nm or less as measured by dynamic light scattering, the liquid had high dispersibility and excellent liquid stability.
  • the metal acid compound-containing liquids of Examples 1 to 10 contained a metal and/or metalloid element and a tertiary amine compound, and when the content of the metal and/or metalloid element in the metal acid compound-containing liquid was 0.1% by mass or more and less than 30% in terms of the metal and/or metalloid element in terms of the metal, and when the maximum transmittance of the metal acid compound-containing liquid in the wavelength range of 550 nm to 700 nm was 70%T or more, the liquid had high dispersibility and excellent liquid stability.
  • the metal acid compound-containing liquids according to Examples 1 to 10 had high dispersibility and excellent liquid stability when the metal and/or metalloid elements contained in the metal acid compound-containing liquid were one or more selected from Ta, Nb, Ti, Zr, Mo, W, Hf, Si, and rare earth elements.
  • the metal acid compound-containing liquid according to Examples 1 to 10 had a reduced environmental impact when the tertiary amine compound contained in the metal acid compound-containing liquid was one or more selected from trimethylamine, triethylamine, and tri-n-propylamine.
  • inventions disclosed in this specification include, in addition to the configurations of each invention or embodiment, to the extent applicable, those that are specified by changing these partial configurations to other configurations disclosed in this specification, those that are specified by adding other configurations disclosed in this specification to these configurations, or those that are specified as higher-level concepts by deleting these partial configurations to the extent that partial effects are obtained.
  • the metal acid compound-containing liquid and its manufacturing method according to the present invention are suitable for forming a uniform metal acid compound coating film on the surface of a substrate, etc., because they have a low environmental impact and high dispersibility.
  • the metal acid compound-containing liquid and its manufacturing method according to the present invention have excellent storage stability and can reduce the rate of defective products caused by precipitation due to changes over time, making it possible to reduce waste and energy costs for waste disposal.
  • the use of amines can be reduced, making it possible to reduce the environmental impact. Reducing waste can reduce the rate of defective products, leading to the sustainable management and efficient benefits of natural resources, as well as the achievement of decarbonization (carbon neutrality).

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JPS573717A (en) * 1980-06-03 1982-01-09 Mitsui Mining & Smelting Co Ltd Precipitation of tantalum or niobium compound
JP2006182714A (ja) * 2004-12-28 2006-07-13 Tohoku Univ 有機タンタル水溶液および乳酸タンタルペルオキシ化合物結晶の製造方法
JP2008044833A (ja) * 2006-07-13 2008-02-28 Hc Starck Gmbh ナノサイズないしマイクロサイズの粒子を製造するための水熱法
JP2018127392A (ja) * 2017-02-10 2018-08-16 多木化学株式会社 ニオブ酸オルガノゾルおよびその製造方法
WO2022018980A1 (ja) * 2020-07-22 2022-01-27 三井金属鉱業株式会社 タンタル酸分散液及びタンタル酸化合物
JP2022033912A (ja) * 2020-02-14 2022-03-02 三井金属鉱業株式会社 ニオブ酸水溶液
WO2023171020A1 (ja) * 2022-03-11 2023-09-14 三井金属鉱業株式会社 タンタル酸化合物分散液およびその製造方法

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JP5008839B2 (ja) * 2005-06-24 2012-08-22 花王株式会社 強誘電体及びその製造方法、並びに、それを用いた強誘電体デバイス

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS573717A (en) * 1980-06-03 1982-01-09 Mitsui Mining & Smelting Co Ltd Precipitation of tantalum or niobium compound
JP2006182714A (ja) * 2004-12-28 2006-07-13 Tohoku Univ 有機タンタル水溶液および乳酸タンタルペルオキシ化合物結晶の製造方法
JP2008044833A (ja) * 2006-07-13 2008-02-28 Hc Starck Gmbh ナノサイズないしマイクロサイズの粒子を製造するための水熱法
JP2018127392A (ja) * 2017-02-10 2018-08-16 多木化学株式会社 ニオブ酸オルガノゾルおよびその製造方法
JP2022033912A (ja) * 2020-02-14 2022-03-02 三井金属鉱業株式会社 ニオブ酸水溶液
WO2022018980A1 (ja) * 2020-07-22 2022-01-27 三井金属鉱業株式会社 タンタル酸分散液及びタンタル酸化合物
WO2023171020A1 (ja) * 2022-03-11 2023-09-14 三井金属鉱業株式会社 タンタル酸化合物分散液およびその製造方法

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