WO2020045163A1 - Méthode de production d'une dispersion aqueuse et d'une dispersion de solvant organique de particules d'oxyde de zirconium - Google Patents

Méthode de production d'une dispersion aqueuse et d'une dispersion de solvant organique de particules d'oxyde de zirconium Download PDF

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WO2020045163A1
WO2020045163A1 PCT/JP2019/032431 JP2019032431W WO2020045163A1 WO 2020045163 A1 WO2020045163 A1 WO 2020045163A1 JP 2019032431 W JP2019032431 W JP 2019032431W WO 2020045163 A1 WO2020045163 A1 WO 2020045163A1
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zirconium oxide
oxide particles
dispersion
water
water slurry
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Japanese (ja)
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考則 森田
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堺化学工業株式会社
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G25/00—Compounds of zirconium
    • C01G25/02—Oxides

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  • the present invention relates to a method for producing each of an aqueous dispersion and an organic solvent dispersion of zirconium oxide particles, and more specifically, has a low viscosity and high transparency while containing fine zirconium oxide particles at a high concentration, and has a long term.
  • the present invention relates to a method for producing an aqueous dispersion of zirconium oxide particles and an organic solvent dispersion having excellent storage stability.
  • the zirconium oxide particle dispersion obtained by the method of the present invention is useful for various uses in the optical field, particularly, as a material for an optical composite resin such as an LED sealing resin and an antireflection film.
  • inorganic oxide particle dispersions such as silica, alumina, zinc oxide, tin oxide, zirconia, titania, and the like have been used in various industrial fields, particularly, in the optical field, used to adjust the refractive index. ing.
  • zirconium oxide has a high refractive index, and in recent years, various proposals have been made to use it as a highly functional resin or film which is compounded with a transparent resin or film to improve its refractive index.
  • the refractive index of the sealing resin is increased, so that light emitted from the light emitter can be more efficiently extracted, and the luminance of the LED can be improved. Is known to improve.
  • zirconium oxide is also used for the antireflection film on the display surface of a flat panel display (FPD) such as a liquid crystal display (LCD) and an electroluminescence display (EL).
  • FPD flat panel display
  • LCD liquid crystal display
  • EL electroluminescence display
  • the antireflection film is a laminated film in which a low refractive index layer and a high refractive index layer are laminated, and a composite resin material in which zirconium oxide is dispersed in the high refractive index layer is used.
  • a typical method for obtaining a zirconium oxide dispersion uses zirconium hydroxide generated by alkali neutralization of a zirconium salt.For example, hydrochloric acid is added to a slurry of zirconium hydroxide at a predetermined concentration, A method of obtaining a zirconium oxide dispersion by heating at a boiling temperature is known (see Patent Document 1). However, according to this method, the resulting zirconium oxide has an average particle diameter of 50 nm or more, so that the dispersion liquid does not have sufficient transparency.
  • An aqueous solution containing a zirconium salt is added to an aqueous solution of an alkali metal hydroxide heated to 60 ° C. or higher and neutralized, that is, reverse neutralized, filtered, washed, added with water, stirred, and acidified.
  • an alkali metal hydroxide heated to 60 ° C. or higher and neutralized, that is, reverse neutralized, filtered, washed, added with water, stirred, and acidified.
  • Patent Document 2 There is also known a method of obtaining a zirconia dispersion by heating and stirring at a temperature of 80 to 100 ° C.
  • the zirconium salt is neutralized with an alkali in water to obtain a zirconium hydroxide gel, which is once washed, aged, and then subjected to ultrasonic wave.
  • a method of obtaining a zirconium oxide dispersion by performing hydrothermal treatment again in the presence of the carboxylic acid after sufficient dispersion by irradiation or the like see Patent Document 3).
  • the zirconium salt is reacted with an alkali in water to obtain a slurry of zirconium oxide particles, which is then filtered, washed, and repulped, and the resulting slurry is added to 1 part by mole of zirconium in the slurry.
  • a method for obtaining a highly transparent aqueous dispersion of zirconium oxide particles by washing the resulting aqueous dispersion of zirconium oxide particles after adding 1 mol part or more of an organic acid and performing a hydrothermal treatment at a temperature of 170 ° C. or higher is also proposed. (See Patent Document 4).
  • the zirconium oxide particle dispersion As the use of the zirconium oxide particle dispersion has been expanded and its use has increased, the demand for its long-term storage stability has been increasing. No description is given, and depending on the obtained aqueous dispersion, the long-term storage stability may actually be poor.
  • Stabilizers such as acetic acid, ⁇ -diketone, and salicylic acid are added to an aqueous dispersion of zirconium oxide particles together with an organic solvent, and the mixture is filtered, and water is replaced with an organic solvent.
  • a solvent dispersion has been proposed (see Patent Document 5), it has not been clarified how much stability with time.
  • the dispersion of known zirconium oxide nanoparticles is not sufficient long-term storage stability, to ensure long-term storage stability, or to prevent deterioration Usually, it is stored at a refrigeration temperature or a freezing temperature, and is returned to a normal temperature when used.
  • an object of the present invention is to provide a method for producing an aqueous dispersion of zirconium oxide particles and an organic solvent dispersion, which are particularly excellent in storage stability over a long period of time.
  • the present invention relates to water of zirconium oxide nanoparticles having excellent long-term storage stability regardless of temperature, for example, in an environment without temperature control ranging from about 10 ° C. to about 40 ° C., and thus in an environment at room temperature.
  • An object of the present invention is to provide a method for producing each of a dispersion and an organic solvent dispersion.
  • the inventor of the present invention started from a step of reacting zirconium oxychloride with a basic substance in alkaline water to obtain a first water slurry containing zirconium oxide particles.
  • the second and third water slurries of zirconium oxide particles obtained on the way, and in some cases, the aqueous dispersion
  • the zirconium oxide particles contain a high concentration of fine zirconium oxide particles.
  • it has excellent transparency, low viscosity and, in particular, aqueous dispersion of zirconium oxide particles and organic It has found that it is possible to obtain the medium dispersion, and have reached the present invention.
  • the following methods for producing an aqueous dispersion of zirconium oxide particles and an organic solvent dispersion are provided. Furthermore, according to the present invention, similarly, there are provided methods for producing an aqueous dispersion and an organic solvent dispersion of stabilized zirconium oxide particles, which are solid solutions containing a stabilizing element.
  • Zirconium oxychloride is reacted with a basic substance in water to obtain a first water slurry containing zirconium oxide particles in a pH range of 8.6 to 9.6.
  • the first step The first water slurry is filtered, washed with water, and repulped in water to obtain a second water slurry containing zirconium oxide particles.
  • the second water slurry contains 1 mol of an organic acid per 1 mol of zirconium.
  • a second water slurry having a chlorine ion content in the range of 5,000 to 20,000 ppm with respect to the weight of the zirconium oxide particles A third step of hydrothermally treating the third water slurry to obtain a zirconium oxide particle aqueous dispersion precursor, and washing the zirconium oxide particle aqueous dispersion precursor by ultrafiltration, with respect to the weight of zirconium oxide.
  • a method for producing an aqueous dispersion of zirconium oxide particles comprising a fourth step of obtaining an aqueous dispersion of zirconium oxide particles having a chloride ion content in the range of 1500 to 7000 ppm.
  • Method for producing aqueous dispersion of stabilized zirconium oxide particles reacting zirconium oxychloride and a salt of at least one stabilizing element selected from aluminum, magnesium, titanium and rare earth elements with a basic substance in water, A first step of obtaining a first water slurry having a pH in the range of 8.6 to 9.6 containing particles of a coprecipitate of zirconium and the stabilizing element; The first water slurry is filtered, washed with water, and repulped in water to obtain a second water slurry containing particles of zirconium and the coprecipitate of the stabilizing element.
  • One mole part or more of an organic acid is added to 1 mole part of the total amount of the stabilizing element, and the chlorine ion content in the range of 5000 to 20,000 ppm with respect to the total weight of zirconium and the oxide of the stabilizing element is added.
  • a second step of obtaining a water slurry of 3 A third step of hydrothermally treating the third water slurry to obtain a stabilized zirconium oxide particle aqueous dispersion precursor which is a solid solution containing the stabilizing element, and the stabilized zirconium oxide particle aqueous dispersion precursor
  • a fourth step of washing by ultrafiltration to obtain an aqueous dispersion of the stabilized zirconium oxide particles having a chlorine ion content in the range of 1500 to 7000 ppm with respect to the weight of the stabilized zirconium oxide particles.
  • a method for producing an aqueous dispersion of zirconium particles A method for producing an aqueous dispersion of zirconium particles.
  • the method of the aqueous dispersion of zirconium oxide particles according to the present invention comprises reacting zirconium oxychloride with a basic substance in water to form a first aqueous slurry containing zirconium oxide particles in a pH range of 8.6 to 9.6. After filtering, washing and washing with water, re-pulp in water again to obtain a second water slurry containing zirconium oxide particles, adding an organic acid to the second water slurry, and adding chlorine ions to the weight of the zirconium oxide particles.
  • a third water slurry having a content in the range of 5,000 to 20,000 ppm is obtained, which is subjected to hydrothermal treatment, washed by ultrafiltration, and has a chlorine ion content in the range of 1500 to 7000 ppm with respect to the weight of the zirconium oxide particles. This is to obtain a certain aqueous dispersion of zirconium oxide particles.
  • an aqueous dispersion of stabilized zirconium oxide particles which is a solid solution containing a stabilizing element, can be obtained.
  • (stabilized) zirconium oxide particles mean zirconium oxide particles and stabilized zirconium oxide particles.
  • the (stabilized) aqueous dispersion of zirconium oxide particles thus obtained has high transparency and low viscosity even if it contains fine zirconium oxide particles at a high concentration, and furthermore has a high temperature. It has a long-term storage stability in which the amount of increase in viscosity when stored at 25 ° C. for 24 months is 20 mPa ⁇ s or less.
  • the viscosity of the aqueous dispersion of zirconium oxide particles is substantially the same as the viscosity immediately after production, and has extremely excellent long-term storage stability (stabilized). A liquid can be obtained.
  • the (stabilized) zirconium oxide particle organic solvent dispersion obtained by substituting water as the dispersion medium of the (stabilized) zirconium oxide particle aqueous dispersion thus obtained in accordance with the present invention also comprises water.
  • the dispersion liquid even if it contains fine zirconium oxide particles at a high concentration, it has high transparency and low viscosity and is excellent in long-term storage stability.
  • First Step In the production of the aqueous dispersion of zirconium oxide particles according to the present invention, as a first step, zirconium oxychloride is reacted with a basic substance in water to obtain a pH of 8.6 to 9.6 containing zirconium oxide particles. Obtain a first water slurry that is in the range.
  • the temperature at which the zirconium oxychloride is reacted with the above basic substance in water is not particularly limited, but is usually in the range of 10 to 50 ° C, preferably 15 to 40 ° C. Range.
  • the molar excess of the basic substance with respect to the acid is usually 1 to 1. It is preferably in the range of 15. The molar excess of the basic substance with respect to the acid will be described later.
  • the neutralization reaction for neutralizing zirconium oxychloride with a basic substance in water by the present inventors, for example, even when the same amount of an aqueous solution of potassium hydroxide is used, strictly, the neutralization reaction is performed by the above-described neutralization reaction. It was found that the pH of the resulting first water slurry was different, resulting in a different chloride ion concentration. In other words, in the first step of neutralizing zirconium oxychloride with a basic substance in water to obtain a first water slurry containing zirconium oxide particles, zirconium oxychloride and a basic acid used for neutralization thereof are used. It has been found that the pH of the first water slurry obtained by the neutralization reaction is more sensitive than the molar ratio of the substances, and the pH changes the chloride ion concentration in the first water slurry.
  • the pH of the first water slurry obtained in the first step that is, the chloride ion concentration affects the chloride ion concentration of the water slurry or dispersion of the zirconium oxide particles obtained in the subsequent step, In turn, it affects its long-term storage stability.
  • the concentration of chloride ions in the water slurry obtained in each step and, in some cases, the precursor giving the aqueous dispersion, more precisely, zirconium oxide By optimally controlling the chloride ion content with respect to the weight of the particles and finally setting the chloride ion content within a predetermined range, the intended zirconium oxide particle dispersion, particularly, has excellent long-term storage stability.
  • An aqueous dispersion of zirconium oxide particles and an organic solvent dispersion can be obtained.
  • a method of adding an aqueous solution of a basic substance to an aqueous solution of zirconium oxychloride for example, a method of adding an aqueous solution of zirconium oxychloride to an aqueous solution of a basic substance, a method of adding an aqueous solution of zirconium oxychloride to an aqueous solution of a basic substance, A zirconium aqueous solution and a basic substance aqueous solution may be added simultaneously to a so-called filling liquid placed in a precipitation reactor in advance, and any method may be used.
  • the zirconium oxychloride aqueous solution and the basic substance are added to the filling liquid.
  • a simultaneous neutralization method of adding simultaneously is preferable.
  • an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide, ammonia, or the like is preferably used, but is not limited thereto.
  • the basic substance is usually used as an aqueous solution.
  • the concentration of the aqueous zirconium oxychloride solution is preferably 2.4 mol / L or less, and the concentration of the basic substance aqueous solution is preferably 10 mol / L or less.
  • a first water slurry having a zirconium oxide particle concentration of usually 1 to 20% by weight is thus obtained.
  • concentration of zirconium oxide particles in the first water slurry exceeds 20% by weight, such a first water slurry has a high viscosity and is difficult to stir, so that in the second step, washing in the second step is difficult.
  • the concentration of zirconium oxide particles in the first water slurry is preferably in the range of 1 to 10% by weight.
  • the first water slurry obtained in the first step is filtered, washed with water, repulped in water, and contains zirconium oxide particles, as described above.
  • a third water slurry having a content in the range of 5000 to 20000 ppm, preferably 6000 to 12000 ppm is obtained.
  • the first step when a first water slurry containing zirconium oxide particles is obtained by neutralizing zirconium oxychloride and the basic substance in water to obtain a first water slurry, the amount of the basic substance relative to zirconium oxychloride is large.
  • the pH at the time of the reaction exceeds 9.6
  • the first water slurry is filtered, washed with water, repulped to water again, and the second water slurry is washed.
  • the third water having a chlorine ion content in the range of 5,000 to 20,000 ppm based on the weight of the zirconium oxide particles is obtained. No slurry can be obtained.
  • the finally obtained aqueous dispersion of zirconium oxide particles has a low chlorine content relative to the zirconium oxide particles, and is inferior in the intended long-term storage stability.
  • the zirconium oxychloride and the basic substance are subjected to a neutralization reaction in water to obtain a first water slurry containing zirconium oxide particles
  • the amount of the basic substance to zirconium oxychloride used is small.
  • the pH is lower than 8.6
  • the aqueous dispersion of zirconium oxide particles finally obtained is excellent in long-term storage stability, but the molar excess of alkali to acid during the neutralization reaction is 1 Since the reaction is performed under smaller conditions, unreacted zirconium oxychloride will remain in the reaction mixture after the neutralization reaction.
  • Zirconium oxychloride is a strongly acidic substance and is highly corrosive to metals, and if it remains in the reaction mixture, may corrode the associated reaction equipment.
  • the coating apparatus may be corroded.
  • the first water slurry is filtered and washed in the second step, and then repulped in water to obtain a second water slurry.
  • the second water slurry is 500 ⁇ S / cm or less. It preferably has electrical conductivity.
  • the obtained first water slurry is filtered and washed, and the obtained cake is repulped in water to form a second water slurry.
  • Stirring with a stirrer may be used as a water slurry, but if necessary, in addition to wet media dispersion such as a bead mill, ultrasonic irradiation, using means such as a high-pressure homogenizer, the above cake may be repulped in water. Good.
  • the organic acid added to the second water slurry in the second step is a deflocculant, and is a so-called acid dissolving method in which the zirconium oxide particles in the obtained third water slurry are dispersed by repulsively charging each other. Used to glue.
  • organic acid preferably, a carboxylic acid or a hydroxycarboxylic acid is used.
  • organic acids include, for example, formic acid, acetic acid, monocarboxylic acids such as propionic acid, oxalic acid, malonic acid, succinic acid, fumaric acid, dicarboxylic acids such as maleic acid and higher polybasic acids Acids, lactic acid, malic acid, tartaric acid, citric acid, salts of hydroxycarboxylic acids such as gluconic acid and the like can be mentioned.
  • these organic acids are generally used in an amount of 1 mol part or more based on 1 mol part of zirconium in the third water slurry to be subjected to hydrothermal treatment. It is used in the range of mole parts, most preferably in the range of 1-3 mole parts.
  • the amount of the organic acid is less than 1 mol part per 1 mol part of zirconium in the third water slurry, not only the obtained aqueous dispersion of zirconium oxide particles is insufficient in transparency but also the viscosity May also be higher.
  • the amount of the organic acid exceeds 5 parts by mol with respect to 1 part by mol of zirconium in the third water slurry, there is no particular effect corresponding thereto and it is not economical.
  • the third water slurry containing the organic acid is subjected to hydrothermal treatment at a temperature of 170 ° C. or higher to obtain a zirconium oxide particle aqueous dispersion precursor.
  • the organic acid is a deflocculant
  • the third water slurry is subjected to hydrothermal treatment under severe conditions in the presence of the deflocculant. Peptized more effectively.
  • the zirconium oxide particle concentration of the third water slurry subjected to the hydrothermal treatment is usually in the range of 1 to 20% by weight, and preferably in the range of 1 to 10% by weight.
  • the concentration of zirconium oxide particles in the third water slurry is preferably in the range of 1 to 10% by weight.
  • the temperature of the hydrothermal treatment is usually 170 ° C. or higher, preferably a temperature of 170 ° C. to 230 ° C.
  • the obtained aqueous dispersion of zirconium oxide particles not only does not have sufficient transparency, but also contains sedimenting coarse aggregated particles and has a high viscosity. Sometimes.
  • the time of the hydrothermal treatment is usually 1 hour or more, preferably 3 hours or more.
  • the temperature of the hydrothermal treatment is shorter than 1 hour, not only the obtained aqueous dispersion of zirconium oxide particles does not have sufficient transparency, but also coarse sedimentable aggregated particles are generated, and the desired transparent An aqueous dispersion of zirconium oxide particles having high properties cannot be obtained.
  • the time of the hydrothermal treatment may be lengthened, an effect corresponding to the time is not particularly obtained, so that usually 10 hours or less is sufficient.
  • the zirconium oxide particle aqueous dispersion precursor thus obtained is washed by ultrafiltration, and the chlorine ion content based on the weight of the zirconium oxide particles is determined.
  • the chloride ion concentration with respect to the weight of the zirconium oxide particles is less than 1500 ppm, the storage stability of the aqueous dispersion becomes poor.
  • the chloride ion concentration with respect to the weight of the zirconium oxide particles exceeds 7000 ppm, there is a risk of corrosion of the manufacturing equipment.
  • the aqueous dispersion of zirconium oxide particles thus obtained can be concentrated, if necessary.
  • This concentration can be achieved by means such as evaporation concentration using a rotary evaporator or concentration using ultrafiltration using an ultrafiltration membrane.
  • the concentration means is not particularly limited, but is preferably concentrated by ultrafiltration using an ultrafiltration membrane.
  • the aqueous dispersion of zirconium oxide particles obtained by the above-mentioned hydrothermal treatment can be washed while being concentrated using an ultrafiltration membrane. That is, the aqueous dispersion of zirconium oxide particles is concentrated by ultrafiltration, and the obtained concentrate is diluted with water by adding water, washed, and the obtained water slurry is again ultrafiltered, and thus, The aqueous dispersion is subjected to ultrafiltration, and by repeating the concentration and dilution, the aqueous dispersion of zirconium oxide particles obtained by the hydrothermal treatment is concentrated and washed, and the remaining by-product salts are repeatedly removed with water. Thus, the aqueous dispersion of zirconium oxide particles can be concentrated to obtain an aqueous dispersion having an increased zirconium oxide concentration.
  • an aqueous dispersion of zirconium oxide particles having a zirconium oxide particle concentration of 10 to 50% by weight, having low viscosity and high transparency, and having excellent long-term storage stability is thus obtained. Obtainable.
  • the upper limit of the zirconium oxide particle concentration of the aqueous dispersion of zirconium oxide particles is usually 50% by weight, and preferably 40% by weight. This is because an aqueous dispersion having a zirconium oxide particle concentration exceeding 50% by weight has a high viscosity and eventually loses fluidity and gels.
  • the aqueous dispersion of zirconium oxide particles obtained by the method of the present invention has a total light transmittance of 70% or more when the zirconium oxide particle concentration is 30% by weight.
  • the D50 having a particle size of 50% by volume on the basis is in the range of 1 to 20 nm, preferably 1 to 10 nm, and the viscosity at the temperature of 25 ° C. immediately after production is 20 mPa ⁇ s or less, preferably 10 mPa ⁇ s or less, and the increase in viscosity at a temperature of 25 ° C. after 24 months of production is 20 mPa ⁇ s or less, preferably 10 mPa ⁇ s, compared to the viscosity at a temperature of 25 ° C. immediately after production. -It is s or less.
  • an aqueous dispersion of zirconium oxide particles whose viscosity does not substantially change after storage for a long period of 40 months or more at room temperature in comparison with immediately after production. Can be obtained.
  • the method of the present invention in order to obtain a stabilized aqueous dispersion of zirconium oxide particles, in the method for producing an aqueous dispersion of zirconium oxide particles described above, instead of the aqueous solution of zirconium oxychloride, zirconium oxychloride and the above stabilizing element are used.
  • the same treatment may be performed using an aqueous solution containing a salt of the above.
  • the concentration of the salt of the stabilizing element in the aqueous solution is preferably 0.5 mol / L or less.
  • the stabilizing element is preferably at least one selected from aluminum, magnesium, titanium and rare earth elements.
  • the salt of the stabilizing element is not particularly limited, but usually, a water-soluble salt such as chloride or nitrate is preferably used.
  • a water-soluble salt such as chloride or nitrate
  • the stabilizing element is aluminum, aluminum chloride is preferably used, and when the stabilizing element is yttrium, yttrium chloride is preferably used.
  • the stabilizing element is generally used in a range of 1 to 20 mol% based on the zirconium element.
  • the molar excess of the basic substance (alkali) with respect to the acid is usually from 1 to 1. It is preferably in the range of 15. The molar excess of the basic substance (alkali) with respect to the acid will be described later.
  • an aqueous dispersion of zirconium oxide particles which is a solid solution containing the stabilizing element
  • zirconium oxychloride and a salt of the stabilizing element are reacted with a basic substance in water.
  • a first water slurry having a pH in the range of 8.6 to 9.6 containing particles of the coprecipitate of zirconium and the stabilizing element was obtained.
  • the first water slurry was filtered and washed with water.
  • the mixture is repulped in water to obtain a second water slurry, and 1 mol part or more of the same organic acid as described above is added to 1 mol part of the total amount of zirconium and the above stabilizing element.
  • a third water slurry having a chloride ion content in the range of 5,000 to 20,000 ppm, preferably 6,000 to 12,000 ppm, based on the total weight of zirconium and the above stabilizing element in terms of oxide.
  • the third water slurry is subjected to hydrothermal treatment to obtain a precursor of an aqueous dispersion of stabilized zirconium oxide particles, which is a solid solution containing the stabilizing element.
  • the dispersion precursor is washed by ultrafiltration, and the aqueous dispersion of the stabilized zirconium oxide particles has a chlorine ion content based on the weight of the stabilized zirconium oxide particles in the range of 1500 to 7000 ppm, preferably 2000 to 4000 ppm. Get.
  • the stabilized aqueous dispersion of zirconium oxide particles obtained by the method of the present invention also has the same properties as the above-described aqueous dispersion of zirconium oxide particles.
  • the D50 having a particle diameter of 50% by volume on a volume basis is in the range of 1 to 20 nm, preferably 1 to 10 nm, and the viscosity at the temperature of 25 ° C. immediately after production is 20 mPa ⁇ s or less, preferably Is 10 mPa ⁇ s or less, and the increase in viscosity at a temperature of 25 ° C. after 24 months of production is 20 mPa ⁇ s or less, preferably 10 mPa ⁇ s, compared to the viscosity at a temperature of 25 ° C. immediately after production. s or less.
  • the stabilized zirconium oxide particles have substantially the same viscosity even after being stored for a long period of 40 months or more in a room temperature environment as compared to immediately after production. A dispersion can be obtained.
  • the aqueous dispersion of zirconium oxide particles and the aqueous dispersion of stabilized zirconium oxide particles obtained as described above are further, if necessary, further, wet media dispersion such as a bead mill, ultrasonic irradiation, and high pressure. Dispersion treatment using a homogenizer or the like may be performed.
  • an aqueous dispersion of (stabilized) zirconium oxide particles is obtained through the first to fourth steps as described above. Therefore, according to the present invention, following the fourth step, as a fifth step, water as a dispersion medium of the aqueous dispersion of the (stabilized) zirconium oxide particles is replaced with an organic solvent, whereby the organic solvent is removed.
  • a solvent as a dispersion medium obtain a (stabilized) zirconium oxide particle organic solvent dispersion having a chlorine ion content in the range of 1500 to 7000 ppm, preferably 2000 to 4000 ppm based on the weight of the (stabilized) zirconium oxide particles. Can be.
  • the organic solvent is not particularly limited, but is preferably a water-miscible organic solvent.
  • a water-miscible organic solvent is not particularly limited. Examples thereof include aliphatic alcohols such as methanol, ethanol and 2-propanol, aliphatic carboxylic esters such as ethyl acetate and methyl formate, and acetone.
  • Methyl ethyl ketone aliphatic ketones such as methyl isobutyl ketone, polyhydric alcohols such as ethylene glycol and glycerin, and a mixture of two or more thereof, particularly preferably methanol, methyl ethyl ketone, methyl isobutyl ketone or Is a mixture of
  • the aqueous dispersion in order to replace water as a dispersion medium in an aqueous dispersion of (stabilized) zirconium oxide particles with an organic solvent, the aqueous dispersion is treated with a rotary evaporator to remove water, and then newly. An organic solvent is added, or the aqueous dispersion is subjected to ultrafiltration to remove water as a dispersion medium to obtain a slurry. The slurry is diluted with an organic solvent, and ultrafiltrated again. By repeating filtration and dilution, water, which is the initial dispersion medium, is replaced with an organic solvent, and a (stabilized) zirconium oxide particle organic solvent dispersion in which the dispersion medium is the organic solvent can be obtained.
  • (stabilized) zirconium oxide particles are obtained by replacing water as a dispersion medium in an aqueous dispersion of (stabilized) zirconium oxide particles with a water-miscible organic solvent and using the water-miscible organic solvent as a dispersion medium. After obtaining the organic solvent dispersion, the water-miscible organic solvent is further replaced with another organic solvent, and a new (stabilized) zirconium oxide particle organic solvent dispersion using the other organic solvent as a dispersion medium is formed. You can also get.
  • the (stabilized) zirconium oxide particle organic solvent dispersion thus obtained is further subjected to a wet media dispersion such as a bead mill, ultrasonic irradiation, a high pressure homogenizer or the like, if necessary. May be performed.
  • a wet media dispersion such as a bead mill, ultrasonic irradiation, a high pressure homogenizer or the like, if necessary. May be performed.
  • Such a (stabilized) zirconium oxide particle organic solvent dispersion obtained according to the present invention also has the same properties as the (stabilized) zirconium oxide particle aqueous dispersion described above, and has a low viscosity and high transparency. It has excellent long-term storage stability.
  • the total light transmittance is 70% or more.
  • D50 which is a particle diameter of 50% by volume on a volume basis is in a range of 1 to 20 nm, preferably 1 to 10 nm, and a viscosity at a temperature of 25 ° C. immediately after production. Is 20 mPa ⁇ s or less, preferably 10 mPa ⁇ s or less, and the viscosity at a temperature of 25 ° C. 7 days after production is also 20 mPa ⁇ s or less, preferably 10 mPa ⁇ s or less. Is the same.
  • the long-term storage stability that the increase in viscosity at a temperature of 25 ° C. 24 months after production is 20 mPa ⁇ s or less, preferably 10 mPa ⁇ s or less, compared to the viscosity at a temperature of 25 ° C. immediately after production. Having.
  • the viscosity is substantially unchanged (stabilized) zirconium oxide even after storage for a long period of 40 months or more in a room temperature environment as compared to immediately after production.
  • a particle organic solvent dispersion can be obtained.
  • the long-term storage stability can be improved.
  • the aqueous dispersion of the zirconium oxide particles and the organic solvent dispersion according to the present invention may be stored at a refrigerated temperature and then returned to room temperature during use, or may be stored in a frozen state, and then stored during use. Even after thawing to room temperature, there is no change or deterioration in its physical properties and stability.
  • the ultrafiltration in the fourth step was performed using "Microza” manufactured by Asahi Kasei Chemicals Corporation, Model ACV-3010D (fraction molecular weight 13000), and the ultrafiltration in the fifth step was performed. Filtration was performed using Asahi Kasei Chemicals Corporation "Microza", model ACP-1010D (fraction molecular weight 13000).
  • the particle size distribution, viscosity and total light transmittance of the (stabilized) zirconium oxide particle dispersion, and the chloride ion concentration of the (stabilized) zirconium oxide particle aqueous slurry or dispersion were as follows: Was measured as follows.
  • Particle Size Distribution D50, D90 and Dmax were measured using a dynamic light scattering particle size / particle size distribution measuring device (UPA-UT manufactured by Nikkiso Co., Ltd.).
  • D50, D90 and Dmax are numerical values on a volume basis.
  • Viscosity The viscosity was measured with a tuning fork vibration type SV viscometer (SV-1A, manufactured by A & D Corp.
  • Example 1 (Production of Stabilized Aqueous Dispersion of Zirconium Oxide Particles (I-1))
  • the mixed aqueous solution of zirconium oxychloride and yttrium chloride and the aqueous potassium hydroxide solution are simultaneously poured into a precipitation reactor filled with 820 liters of pure water in advance, and the zirconium oxychloride and yttrium chloride are co-precipitated by simultaneous neutralization.
  • a first water slurry containing particles of the coprecipitate of yttrium.
  • the pH of the obtained first water slurry was 9.3.
  • Second step The first water slurry is filtered, washed until the electric conductivity of the water washing filtrate is 10 ⁇ S / cm or less, and repulped again in pure water to remove the particles of the coprecipitate of zirconium and yttrium.
  • a second water slurry was obtained.
  • 42 kg of acetic acid (1.3 mol parts per 1 mol part of the total amount of zirconium and yttrium in the second water slurry) is added to the second water slurry, and the solid content is an oxide of zirconium and yttrium.
  • 600 L of a third water slurry having a converted total weight of 7.5% by weight was obtained.
  • the third water slurry had a chlorine ion concentration of 400 ppm.
  • the chlorine content based on the total weight of zirconium and yttrium oxide calculated based on the chloride ion concentration was 5,330 ppm.
  • the third aqueous slurry was subjected to hydrothermal treatment at 190 ° C. for 3 hours to obtain a transparent aqueous dispersion precursor of stabilized zirconium oxide particles, which is a solid solution containing yttrium.
  • the transparent aqueous dispersion precursor of the stabilized zirconium oxide particles is washed and concentrated by an ultrafiltration membrane, and the stabilized oxidation having a stabilized zirconium oxide particle concentration of 30.0% by weight and a chloride ion concentration of 560 ppm is performed.
  • An aqueous dispersion of zirconium particles (I-1) was obtained.
  • the chlorine content based on the weight of the stabilized zirconium oxide particles calculated based on the chloride ion concentration was 1870 ppm.
  • the chlorine content based on the weight of the stabilized zirconium oxide particles calculated based on the chloride ion concentration was 1,820 ppm.
  • Example 2 In the first step of Example 1, the same procedure as in Example 1 was carried out except that a first aqueous slurry having a pH shown in Table 1 was obtained using an aqueous solution of potassium hydroxide having a concentration shown in Table 1. Aqueous dispersions of zirconium oxide particles (I-2) to (I-6) were obtained, and further, methanol dispersions of stabilized zirconium oxide particles (II-2) to (II-6) were obtained using the dispersions. .
  • Example 7 (Production of aqueous dispersion of zirconium oxide particles (I-7)) First Step 900 L of a 0.6 mol / L zirconium oxychloride aqueous solution and 680 L of a 1.6 mol / L potassium hydroxide aqueous solution were prepared. The zirconium oxychloride aqueous solution and the potassium hydroxide aqueous solution are simultaneously poured into a precipitation reactor filled with 820 L of pure water in advance, and the zirconium oxychloride is precipitated by simultaneous neutralization, so that the first water slurry containing zirconium oxide particles is formed. I got The pH of the obtained first water slurry was 8.7.
  • Second step The first water slurry is filtered, washed until the electric conductivity of the water washing filtrate becomes 10 ⁇ S / cm or less, then repulped to pure water again, and the second water containing the zirconium oxide particles is removed. A slurry was obtained. 42 kg of acetic acid (1.4 mol parts per 1 mol part of zirconium in the second water slurry) is added to the second water slurry, and the solid content is 7.5 wt% in terms of zirconium oxide. % Of a third water slurry was obtained.
  • the chlorine ion concentration of the third water slurry was 950 ppm. Therefore, in the third water slurry, the chlorine content based on the weight of the zirconium oxide particles calculated based on the chloride ion concentration was 12,670 ppm.
  • the third water slurry was subjected to hydrothermal treatment at 190 ° C. for 3 hours to obtain a transparent aqueous dispersion precursor of zirconium oxide particles.
  • the precursor of the transparent aqueous dispersion of zirconium oxide particles is washed and concentrated with an ultrafiltration membrane, and the aqueous dispersion of zirconium oxide particles (I) having a zirconium oxide particle concentration of 31.2% by weight and a chlorine ion concentration of 1320 ppm (I -7) was obtained.
  • the chlorine content based on the weight of zirconium oxide particles calculated based on the chlorine concentration was 4080 ppm.
  • Example 8 and 9 In the first step of Example 1, the same procedure as in Example 1 was carried out except that a first aqueous slurry having a pH shown in Table 1 was obtained using an aqueous solution of potassium hydroxide having a concentration shown in Table 1. Aqueous dispersions of zirconium oxide particles (I-8) to (I-9) were obtained, and further, stabilized methanol dispersions of zirconium oxide particles (II-8) to (II-9) were obtained.
  • the viscosity of the thus-obtained methanol dispersions of stabilized zirconium oxide particles (II-8 to II-9) was 4 mPa ⁇ s when stored at a temperature of 25 ° C for 28 months.
  • Example 10 In the first step of Example 7, oxidation was performed in the same manner as in Example 7 except that a first water slurry having a pH shown in Table 1 was obtained using a potassium hydroxide aqueous solution having a concentration shown in Table 1. An aqueous dispersion of zirconium particles (I-10) was obtained.
  • the aqueous dispersion of the zirconium oxide particles (I-10) thus obtained was sealed at a temperature of 25 ° C., and when stored for 50 months, the viscosity of the aqueous dispersion was 7 mPa ⁇ s at a temperature of 25 ° C. there were.
  • a methanol dispersion of zirconium oxide particles (II-10) was obtained using the above aqueous dispersion (I-10).
  • the viscosity was 2 mPa ⁇ s at a temperature of 25 ° C.
  • Example 11 (Production of stabilized aqueous dispersion of zirconium oxide particles (I-11)) First Step 900 L of a mixed aqueous solution of 0.6 mol / L zirconium oxychloride and 0.03 mol / L yttrium chloride and 680 L of a 1.9 mol / L potassium hydroxide aqueous solution were prepared. The mixed aqueous solution of zirconium oxychloride and yttrium chloride and the aqueous potassium hydroxide solution are simultaneously poured into a precipitation reactor filled with 820 liters of pure water in advance, and the zirconium oxychloride and yttrium chloride are co-precipitated by simultaneous neutralization. And a first water slurry containing particles of the coprecipitate of yttrium. The pH of the obtained first water slurry was 9.3.
  • Second step The first water slurry is filtered, washed until the washing filtrate has an electric conductivity of 10 ⁇ S / cm or less, repulped in pure water, and contains particles of the coprecipitated zirconium and yttrium.
  • a second water slurry was obtained. 42 kg of acetic acid (1.3 mol parts per 1 mol part of the total amount of zirconium and yttrium in the second water slurry) is added to the second water slurry, and the solid content is an oxide of zirconium and yttrium. 600 L of a third water slurry having a converted total weight of 7.5% by weight was obtained.
  • the third water slurry had a chlorine ion concentration of 510 ppm.
  • the chloride ion content based on the total weight of zirconium and yttrium oxide calculated based on the chloride ion concentration was 6,800 ppm.
  • the third aqueous slurry was subjected to hydrothermal treatment at 190 ° C. for 3 hours to obtain a transparent aqueous dispersion precursor of stabilized zirconium oxide particles, which is a solid solution containing yttrium.
  • the transparent aqueous dispersion precursor of the stabilized zirconium oxide particles is washed and concentrated with an ultrafiltration membrane to stabilize the stabilized zirconium oxide particles at a concentration of 30.5% by weight and a chloride ion at a concentration of 710 ppm.
  • An aqueous dispersion of zirconium oxide particles (I-11) was obtained.
  • the chloride ion content based on the weight of the stabilized zirconium oxide particles calculated based on the chloride ion concentration was 2330 ppm.
  • Example 12 (Production of stabilized aqueous dispersion of zirconium oxide particles (I-12)) First Step 900 L of a mixed aqueous solution of 0.6 mol / L zirconium oxychloride and 0.03 mol / L yttrium chloride and 680 L of a 1.9 mol / L potassium hydroxide aqueous solution were prepared. The mixed aqueous solution of zirconium oxychloride and yttrium chloride and the aqueous potassium hydroxide solution are simultaneously poured into a precipitation reactor filled with 820 liters of pure water in advance, and the zirconium oxychloride and yttrium chloride are co-precipitated by simultaneous neutralization. And a first water slurry containing particles of the coprecipitate of yttrium. The pH of the obtained first water slurry was 9.2.
  • Second step The first water slurry is filtered, washed until the washing filtrate has an electric conductivity of 10 ⁇ S / cm or less, repulped again in pure water, and particles of the coprecipitated zirconium and yttrium particles.
  • 42 kg of acetic acid (1.3 mol parts per 1 mol part of the total amount of zirconium and yttrium in the second water slurry) is added to the second water slurry, and the solid content is an oxide of zirconium and yttrium.
  • 600 L of a third water slurry having a converted total weight of 7.5% by weight was obtained.
  • the chlorine ion concentration of the third water slurry was 660 ppm.
  • the chloride ion content based on the weight of the stabilized zirconium oxide particles calculated based on the chloride ion concentration was 8,800 ppm.
  • the third water slurry was subjected to a hydrothermal treatment at 190 ° C. for 3 hours to obtain a transparent aqueous dispersion of stabilized zirconium oxide particles.
  • the precursor of the transparent aqueous dispersion of the stabilized zirconium oxide particles is washed and concentrated by an ultrafiltration membrane, and the stabilized zirconium oxide particle concentration is 30.0% by weight and the chlorine ion concentration is 920 ppm.
  • An aqueous dispersion of zirconium particles (I-12) was obtained.
  • the chlorine ion content based on the weight of the stabilized zirconium oxide particles calculated based on the chloride ion concentration was 3070 ppm.
  • Comparative Example 1 (Production of stabilized aqueous dispersion of zirconium oxide particles (IA)) First Step 900 L of a mixed aqueous solution of 0.6 mol / L zirconium oxychloride and 0.03 mol / L yttrium chloride and 680 L of a 1.9 mol / L potassium hydroxide aqueous solution were prepared. The mixed aqueous solution of zirconium oxychloride and yttrium chloride and the aqueous potassium hydroxide solution are simultaneously poured into a precipitation reactor filled with 820 liters of pure water in advance, and the zirconium oxychloride and yttrium chloride are co-precipitated by simultaneous neutralization. And a first water slurry containing particles of the coprecipitate of yttrium. The pH of the obtained first water slurry was 9.7.
  • Second step The first water slurry is filtered, washed until the washing filtrate has an electric conductivity of 10 ⁇ S / cm or less, repulped again in pure water, and particles of the coprecipitated zirconium and yttrium particles.
  • 42 kg of acetic acid (1.3 mol parts per 1 mol part of the total amount of zirconium and yttrium in the second water slurry) is added to the second water slurry, and the solid content is an oxide of zirconium and yttrium.
  • 600 L of a third water slurry having a converted total weight of 7.5% by weight was obtained.
  • the third water slurry had a chloride ion concentration of 140 ppm.
  • the chlorine ion content based on the total weight of zirconium and yttrium oxide calculated based on the chlorine concentration was 1870 ppm.
  • the third water slurry was subjected to a hydrothermal treatment at 190 ° C. for 3 hours to obtain a transparent aqueous dispersion precursor of stabilized zirconium oxide particles.
  • the transparent aqueous dispersion precursor of the stabilized zirconium oxide particles is washed and concentrated with an ultrafiltration membrane, and the stabilized oxidation having a stabilized zirconium oxide particle concentration of 30.4% by weight and a chlorine ion concentration of 190 ppm is performed.
  • An aqueous dispersion of zirconium particles (IA) was obtained.
  • the chlorine content based on the total weight of zirconium and yttrium calculated on the basis of the chloride ion concentration was 630 ppm. (Production of methanol dispersion of zirconium oxide fine particles (II-A))
  • the chlorine ion content based on the weight of the stabilized zirconium oxide particles calculated based on the chloride ion concentration was 720 ppm.
  • the methanol dispersion of the stabilized zirconium oxide particles thus obtained gelled 7 days after the production and lost its fluidity.
  • Methanol was removed from the methanol dispersions of zirconium oxide particles obtained in Examples 7 and 10, and dried.
  • the resulting zirconium oxide fine particles were observed with a TEM (transmission electron microscope). Was about 5 nm.
  • the methanol is removed from the stabilized zirconium oxide particle methanol dispersion, which is the solid solution containing yttrium, obtained in Examples 1 to 6, 8, 9, 11, 12 and Comparative Example 1, dried, and thus obtained.
  • Table 1 shows the molar excess of alkali to acid when the (mixed) aqueous solution of zirconium oxychloride (and yttrium chloride) (acid) in the above Examples and Comparative Examples was neutralized with potassium hydroxide (alkali).
  • the molar excess is represented by the ratio of the molar amount of the alkali used in the neutralization reaction / the molar amount of the acid used.
  • K represents the molar amount of potassium hydroxide used
  • Z represents the molar amount of zirconium oxychloride used
  • Y represents the molar amount of yttrium chloride used.
  • the concentration of the aqueous potassium hydroxide solution used in the first step, the pH of the first water slurry obtained in the first step, the second water obtained in the second step Table 1 shows the chloride ion concentration of the slurry and the chloride ion content (Cl / ZrO 2 ) calculated based on the chloride ion concentration.
  • the conversion in terms of oxides of zirconium and yttrium is shown. Is the chlorine ion content relative to the total weight of
  • the concentration, particle size distribution, total light transmittance, and chloride ion concentration of the methanol dispersion of the zirconium oxide particles obtained in Examples 1 to 10 and Comparative Example 1 were calculated based on the chloride ion concentration (stabilization).
  • Table 3 shows the evaluation results of the chlorine ion content (Cl / ZrO 2 ), the water content, the viscosity at 25 ° C. immediately after the production, the viscosity seven days after the production, and the long-term storage stability with respect to the zirconium oxide particles.
  • the aqueous dispersion of (stabilized) zirconium oxide particles obtained according to the method of the present invention has high transparency and low viscosity even if it contains fine zirconium oxide particles at a high concentration.
  • the amount of increase in viscosity when stored at a temperature of 25 ° C. for 24 months is 20 mPa ⁇ s or less, and the storage stability is remarkably excellent for long-term storage.
  • the viscosity at 25 ° C. is substantially the same as immediately after production, and is extremely excellent in long-term storage stability.
  • an organic solvent dispersion obtained by substituting water as a dispersion medium of the aqueous dispersion of (stabilized) zirconium oxide particles obtained according to the method of the present invention with an organic solvent is also shown in Examples 1 to 10.
  • a viscosity increase amount is 20 mPa. -S or less, and extremely excellent in long-term storage stability.
  • its viscosity at 25 ° C. is substantially the same as immediately after production, and is extremely excellent in long-term storage stability.

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Abstract

La présente invention concerne une méthode de production d'une dispersion aqueuse de particules d'oxyde de zirconium, la méthode comprenant : une première étape consistant à faire réagir de l'oxychlorure de zirconium avec une substance basique dans de l'eau pour obtenir une première suspension aqueuse contenant des particules d'oxyde de zirconium et ayant un pH de 8,6 à 9,6 ; une seconde étape dans laquelle la première suspension d'eau est filtrée, lavée, puis reréduite en pâte dans de l'eau pour obtenir une seconde suspension aqueuse, et 1 partie en mole ou plus d'un acide organique est ajoutée à la seconde suspension aqueuse par rapport à 1 partie en mole de zirconium pour obtenir une troisième suspension aqueuse ayant une teneur en ions chlore de 5 000 à 20 000 ppm par rapport au poids de particules de zirconium ; une troisième étape de traitement hydrothermique de la troisième suspension aqueuse pour obtenir un précurseur d'une dispersion aqueuse de particules d'oxyde de zirconium ; et une quatrième étape dans laquelle le précurseur d'une dispersion aqueuse de particules d'oxyde de zirconium est lavé par ultrafiltration pour obtenir une dispersion aqueuse de particules d'oxyde de zirconium ayant une teneur en ions chlore de 1 500 à 7 000 ppm par rapport au poids des particules d'oxyde de zirconium. La dispersion aqueuse de particules d'oxyde de zirconium ainsi obtenue présente une excellente transparence et une faible viscosité même lorsqu'elle contient une concentration élevée de particules d'oxyde de zirconium, et présente en particulier une excellente stabilité de stockage à long terme quelle que soit la température ambiante.
PCT/JP2019/032431 2018-08-27 2019-08-20 Méthode de production d'une dispersion aqueuse et d'une dispersion de solvant organique de particules d'oxyde de zirconium WO2020045163A1 (fr)

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JP2004010449A (ja) * 2002-06-10 2004-01-15 Hosokawa Micron Corp ジルコニアゾルの製造方法及びジルコニア微粉末の製造方法
JP2006143535A (ja) * 2004-11-19 2006-06-08 Catalysts & Chem Ind Co Ltd ジルコニアゾルの製造方法およびジルコニアゾル
WO2016035689A1 (fr) * 2014-09-05 2016-03-10 堺化学工業株式会社 Dispersion de solvant organique de particules d'oxyde de zirconium et son procédé de production

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004010449A (ja) * 2002-06-10 2004-01-15 Hosokawa Micron Corp ジルコニアゾルの製造方法及びジルコニア微粉末の製造方法
JP2006143535A (ja) * 2004-11-19 2006-06-08 Catalysts & Chem Ind Co Ltd ジルコニアゾルの製造方法およびジルコニアゾル
WO2016035689A1 (fr) * 2014-09-05 2016-03-10 堺化学工業株式会社 Dispersion de solvant organique de particules d'oxyde de zirconium et son procédé de production

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