WO2020045164A1 - 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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WO2020045164A1
WO2020045164A1 PCT/JP2019/032433 JP2019032433W WO2020045164A1 WO 2020045164 A1 WO2020045164 A1 WO 2020045164A1 JP 2019032433 W JP2019032433 W JP 2019032433W WO 2020045164 A1 WO2020045164 A1 WO 2020045164A1
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zirconium oxide
water slurry
oxide particles
zirconium
water
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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
    • 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

Definitions

  • 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 particle dispersion utilizes zirconium hydroxide generated by alkali neutralization of a zirconium salt.For example, hydrochloric acid is added at a predetermined concentration to a slurry of zirconium hydroxide.
  • a method of obtaining a dispersion of zirconium oxide particles by heating at a boiling temperature is known (see Patent Document 1).
  • 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.
  • a zirconium salt is neutralized with an alkali in water to obtain a zirconium hydroxide gel, which is once washed, ripened, and ultrasonically oxidized.
  • carboxylic acids such as malic acid, citric acid and tartaric acid
  • a zirconium salt is neutralized with an alkali in water to obtain a zirconium hydroxide gel, which is once washed, ripened, and ultrasonically oxidized.
  • a method of obtaining a dispersion of zirconium oxide particles by performing a 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.
  • Zirconium oxide which has excellent transparency and low viscosity, and in particular, has excellent storage stability over a long period of time in the above-mentioned sense. It has found that it is possible to obtain an aqueous dispersion and organic solvent dispersion of particles, 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.
  • Hydrochloric acid is added to the second water slurry so that the chlorine ion content with respect to the weight of the zirconium oxide particles is 400%.
  • a third water slurry in the range of 0 to 20,000 ppm is obtained.
  • 1 mol part or more of organic acid is added to 1 mol part of zirconium to the third water slurry, and chlorine ion content based on the weight of zirconium oxide particles is added.
  • 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 chlorine ion content based on weight in the range of 1500 to 7000 ppm.
  • a salt of zirconium oxychloride and at least one stabilizing element selected from aluminum, magnesium, titanium and rare earth elements is reacted with a basic substance in water to form zirconium.
  • the first water slurry is filtered, washed with water, and then repulped in water to obtain a second water slurry containing particles of the coprecipitated zirconium and the stabilizing element.
  • An organic acid is added to the slurry in an amount of 1 mol part or more based on 1 mol part of the total amount of zirconium and the stabilizing element, and the chlorine ion content is less than 4000 ppm based on the total weight of zirconium and the stabilizing element in terms of oxide.
  • a third water slurry is obtained, and then hydrochloric acid is added to the third water slurry to obtain a fourth water slurry having a chloride ion content in the range of 4000 to 20,000 ppm based on the total weight of zirconium and the stabilizing element in terms of oxide.
  • a second step of obtaining a fourth water slurry having a chloride ion content based on weight in the range of 4000 to 20,000 ppm A third step of hydrothermally treating the fourth 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 stabilized zirconium oxide particles having a chloride ion content in the range of 1500 to 7000 ppm based on the weight of the stabilized zirconium oxide particles.
  • a method for producing a dispersion A method for producing a dispersion.
  • (stabilized) zirconium oxide particles mean zirconium oxide particles and / or stabilized zirconium oxide particles.
  • both the aqueous dispersion and the organic solvent dispersion of (stabilized) zirconium oxide particles obtained by the method of the present invention may contain fine (stabilized) zirconium oxide particles at a high concentration. It has high transparency and low viscosity, and has a viscosity increase of 20 mPa ⁇ s or less when stored at a temperature of 25 ° C. for 24 months, and is remarkably excellent in long-term storage stability.
  • the viscosity is substantially the same as the viscosity immediately after production, long-term storage stability (Stabilized) aqueous dispersion and organic solvent dispersion of zirconium oxide particles can be obtained.
  • 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 that is, the molar excess during alkali neutralization is usually 1.15 to 1 .5.
  • the molar excess of the basic substance with respect to the acid will be described later.
  • a method of adding an aqueous solution of a basic substance to an aqueous solution of a zirconium oxychloride salt for example, a method of adding an aqueous solution of zirconium oxychloride to an aqueous solution of a basic substance
  • the zirconium chloride aqueous solution and the basic substance aqueous solution may be added in advance to a so-called filling solution placed in a precipitation reactor at the same time, but any method may be used.
  • a simultaneous neutralization method in which the mixture is simultaneously added to a so-called filling solution placed in a reaction vessel 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, is difficult to stir, and has a chlorine ion content of the obtained zirconium oxide particles.
  • the concentration of zirconium oxide particles in the first water slurry is preferably in the range of 1 to 10% by weight.
  • the second step is to filter and wash the first water slurry obtained in the first step, repulp it in water, and to prepare a second water slurry containing the zirconium oxide particles.
  • An organic acid and hydrochloric acid are added to the second water slurry to obtain a water slurry (fourth water slurry) containing zirconium oxide particles having a chloride ion content in the range of 4000 to 20,000 ppm based on the weight of the zirconium oxide particles. This is the step of obtaining.
  • the order of adding the organic acid and hydrochloric acid may be the following method (a) of adding the organic acid first, or the following method (b) of adding hydrochloric acid first.
  • the method (a) is as follows.
  • (A) The first water slurry is filtered and washed, and then repulped in water to obtain a second water slurry containing the zirconium oxide particles.
  • the second water slurry contains 1 mol part of zirconium.
  • 1 mol part or more of an organic acid is added to obtain a third water slurry having a chlorine ion content of less than 4000 ppm based on the weight of the zirconium oxide particles, and then hydrochloric acid is added to the third water slurry to obtain a zirconium oxide particle.
  • Method (b) is as follows.
  • (B) The first water slurry is filtered and washed, and then repulped in water to obtain a second water slurry containing the zirconium oxide particles. Hydrochloric acid is added to the second water slurry, and zirconium oxide is added. A chlorine water content based on the weight of the particles is in the range of 4,000 to 20,000 ppm).
  • a third water slurry is obtained, and then the organic acid is added to the third water slurry in an amount of 1 mol part or more per 1 mol part of zirconium. And obtaining a fourth water slurry having a chlorine ion content in the range of 4000 to 20,000 ppm based on the weight of the zirconium oxide particles.
  • the method (a) When the method (a) is used, 1 mol part or more of organic acid is added to 1 mol part of zirconium to the second water slurry, and the chlorine ion content with respect to the weight of the zirconium oxide particles is 3000 ppm or less. It is preferable to obtain a water slurry of No. 3 and particularly preferable to obtain a third water slurry of 2000 ppm or less.
  • the first step when the zirconium oxychloride and the basic substance are reacted in water to obtain a first water slurry containing zirconium oxide particles, a large amount of the basic substance is used with respect to the zirconium oxychloride.
  • the pH at the time of the reaction is higher than the above range, the obtained zirconium oxide particles occlude the internal substance in a large amount, and in the second step, the basic substance cannot be completely removed.
  • the hydrochloric acid added in the third step is consumed for neutralization in the hydrothermal treatment in the fourth step, and as a result, an aqueous dispersion of zirconium oxide particles having a target chlorine ion content cannot be obtained.
  • the first step when the first water slurry containing zirconium oxide particles is obtained by reacting zirconium oxychloride and the above-mentioned basic substance in water, the amount of the above-mentioned basic substance with respect to zirconium oxychloride is reduced.
  • the pH at the time of the above reaction is lower than the above range, it is difficult to control the content of chloride ions that the obtained zirconium oxide particles occlude inside, and as a result, the chlorine ion content of The dispersion is large, and an aqueous dispersion of zirconium oxide particles having a stable chlorine ion content cannot be obtained.
  • the second water slurry has an electric conductivity of 500 ⁇ S / cm or less. Is preferred.
  • 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.
  • an organic acid and hydrochloric acid are added to the second water slurry to form a water slurry containing zirconium oxide particles having a chloride ion content with respect to the weight of the zirconium oxide particles in a predetermined range.
  • the hydrochloric acid also functions as a deflocculant
  • the organic acid is also a deflocculant like hydrochloric acid (chloride ion)
  • the zirconium oxide particles in the obtained third water slurry are obtained.
  • acid deflocculation in which the particles are dispersed by repulsively charging each other.
  • 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 hydrochloric acid is not particularly limited, but a hydrochloric acid having a concentration of 40% or less is preferable.
  • the fourth water slurry containing the organic acid thus obtained and having a chlorine ion content in the range of 4000 to 20,000 ppm based on the weight of the zirconium oxide particles is prepared in the third step.
  • a hydrothermal treatment is performed at a temperature of 170 ° C. or higher to obtain a precursor of an aqueous dispersion of zirconium oxide particles.
  • the organic acid is a deflocculant
  • the fourth water slurry is treated under the harsh conditions of hydrothermal treatment in the presence of the deflocculant.
  • the particles are peptized more effectively.
  • the zirconium oxide particle concentration of the fourth 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.
  • concentration of zirconium oxide particles in the fourth water slurry exceeds 20% by weight, the viscosity of the water slurry is high, which causes difficulty in hydrothermal treatment.
  • concentration of zirconium oxide particles in the fourth 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 thus obtained aqueous dispersion precursor of zirconium oxide particles is washed by ultrafiltration as a fourth step, and the chlorine ion content with respect to the weight of the zirconium oxide particles is reduced.
  • 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 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 with respect to the acid is usually 1.15 to 1.5. Is preferably within the range. The molar excess of the basic substance 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
  • An organic acid is added to the slurry in an amount of 1 mol part or more based on 1 mol part of the total amount of zirconium and the stabilizing element, and the chlorine ion content is less than 4000 ppm based on the total weight of zirconium and the stabilizing element in terms of oxide.
  • a third water slurry is obtained, and then hydrochloric acid is added to the third water slurry to obtain a fourth water slurry having a chloride ion content in the range of 4000 to 20,000 ppm based on the total weight of zirconium and the stabilizing element in terms of oxide.
  • a second water slurry is obtained, and hydrochloric acid is added to the second water slurry to form a third water having a chloride ion content in the range of 4000 to 20,000 ppm based on the total weight of zirconium and the stabilizing element in terms of oxide.
  • a slurry is obtained, and then 1 mol part or more of an organic acid is added to 1 mol part of the total amount of zirconium and the stabilizing element to the third water slurry, and the total amount of zirconium and the stabilizing element in terms of oxide is added.
  • a fourth water slurry having a chloride ion content in the range of 4000 to 20,000 ppm by weight is obtained.
  • the fourth water slurry is subjected to hydrothermal treatment to obtain a stabilized aqueous dispersion of zirconium oxide particles.
  • the precursor is subjected to an ultrafiltration treatment so that the chloride ion content with respect to the weight of the stabilized zirconium oxide particles is in the range of 1500 to 7000 ppm, preferably 2000 to 5000 ppm, and the zirconium oxide particle concentration is reduced.
  • an aqueous dispersion of stabilized zirconium oxide particles in the range of 1 to 30% by weight is obtained.
  • the aqueous dispersion of stabilized zirconium oxide particles obtained by the method of the present invention has the same properties as the above-mentioned aqueous dispersion of zirconium oxide particles.
  • the total light transmittance is 70% or more.
  • D50 having 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, compared to the viscosity at a temperature of 25 ° C. immediately after production, the increase in viscosity at a temperature of 25 ° C. after 24 months of production is 20 mPa ⁇ s or less, preferably Is 10 mPa ⁇ s or less.
  • the aqueous dispersion of the (stabilized) zirconium oxide particles according to the present invention is not affected by the ambient temperature, in particular, not at a refrigeration or freezing temperature of 10 ° C. or lower, but at an ambient temperature. Even after storage for a long period of 40 months or more, an aqueous dispersion of stabilized zirconium oxide particles whose viscosity does not substantially change compared to immediately after production can be obtained.
  • the organic solvent is used as a dispersion medium, and the (stabilized) zirconium oxide is dispersed.
  • An organic solvent dispersion of (stabilized) zirconium oxide particles having a chloride ion content based on the weight of the particles in the range of 1500 to 7000 ppm, preferably 2000 to 5000 ppm can be obtained.
  • 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.
  • 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 (stabilized) aqueous dispersion of zirconium oxide particles and the organic solvent dispersion obtained by the method of the present invention may be further subjected to wet media dispersion such as a bead mill, ultrasonic irradiation, high pressure Dispersion treatment using a homogenizer or the like may be performed.
  • the total light transmittance is 70%. %
  • the particle size distribution measured by a dynamic light scattering method has a particle diameter D50 of 50% by volume on a volume basis in the range of 1 to 20 nm, preferably 1 to 10 nm.
  • the viscosity at 20 ° C. 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 greater than the viscosity at a temperature of 25 ° C. immediately after the production. It is 20 mPa ⁇ s or less, preferably 10 mPa ⁇ s or less.
  • both the aqueous dispersion and the organic solvent dispersion of the (stabilized) zirconium oxide particles obtained after storage for a long period of 40 months or more at room temperature are maintained.
  • the viscosity is substantially unchanged compared to immediately after production.
  • aqueous dispersion and an organic solvent dispersion of zirconium oxide nanoparticles having excellent properties can be obtained.
  • 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 (molecular weight cut off 13000) to produce an organic solvent dispersion.
  • Ultrafiltration when replacing water as a dispersion medium of an aqueous dispersion with an organic solvent was performed using "Microza” manufactured by Asahi Kasei Chemicals Corporation, Model ACP-1010D (molecular weight cut off 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 distribution analyzer (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 is poured into a precipitation reactor in which 1500 L of a 0.9 mol / L potassium hydroxide aqueous solution has been previously poured, and the zirconium oxychloride and yttrium chloride are coprecipitated by a so-called reverse neutralization reaction.
  • a first water slurry containing particles of the coprecipitate of zirconium and yttrium was obtained.
  • the pH of the obtained first water slurry was 10.
  • 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 and a chlorine ion concentration of 8 ppm was obtained.
  • the chlorine ion content based on the total weight of zirconium and yttrium oxide calculated based on the chloride ion concentration was 110 ppm.
  • the fourth water slurry was subjected to hydrothermal treatment at 190 ° C. for 3 hours to obtain a transparent aqueous dispersion precursor of stabilized zirconium oxide particles.
  • the transparent dispersion precursor of the stabilized zirconium oxide particles is washed and concentrated with an ultrafiltration membrane, and the stabilized zirconium oxide particles have a concentration of 30.8% by weight and a concentration of 840 ppm of chloride ions.
  • An aqueous dispersion (I-1) was obtained.
  • the chloride ion content based on the weight of the stabilized zirconium oxide particles calculated based on the chloride ion concentration was 2,730 ppm.
  • the methanol was replaced with methanol to obtain a stabilized zirconium oxide particle methanol dispersion (II-1) having a stabilized zirconium oxide particle concentration of 30.8% by weight and a chlorine ion concentration of 810 ppm.
  • the amount of methanol used for dilution was 90 L.
  • the chlorine ion content based on the weight of the stabilized zirconium oxide particles calculated based on the chloride ion concentration was 2630 ppm.
  • Example 2 (Production of stabilized aqueous dispersion of zirconium oxide particles (I-2)) 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 resulting first water slurry was 10.2.
  • Second step The first water slurry is filtered, washed until the washing filtrate has an electric conductivity of 10 ⁇ S / cm or less, repulped 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 3 ppm.
  • the chloride ion content based on the total weight of zirconium and yttrium oxides calculated based on the chloride ion concentration was 40 ppm.
  • the fourth water slurry was subjected to hydrothermal treatment at 190 ° C. for 3 hours to obtain a transparent aqueous dispersion precursor of stabilized zirconium oxide particles.
  • the transparent dispersion precursor of the stabilized zirconium oxide particles is washed and concentrated by an ultrafiltration membrane, and the stabilized zirconium oxide particles have a concentration of 30.4% by weight and a chlorine ion concentration of 1010 ppm.
  • An aqueous dispersion (I-2) was obtained.
  • the chloride ion content based on the weight of the stabilized zirconium oxide particles calculated based on the chloride ion concentration was 3320 ppm.
  • Example 3 (Production of stabilized aqueous dispersion of zirconium oxide particles (I-3)) Second Step To 60 L of the third water slurry obtained in Example 2, 85 g of 35% hydrochloric acid was added to obtain a fourth water slurry having a chloride ion concentration of 480 ppm. In the fourth water slurry, the chloride ion content based on the total weight of zirconium and yttrium oxide calculated based on the chloride ion concentration was 6420 ppm.
  • the fourth water slurry was subjected to hydrothermal treatment at 190 ° C. for 3 hours to obtain a transparent aqueous dispersion precursor of stabilized zirconium oxide particles.
  • the transparent dispersion precursor of the stabilized zirconium oxide particles is washed and concentrated with an ultrafiltration membrane, and the stabilized zirconium oxide particles having a stabilized zirconium oxide concentration of 30.4% by weight and a chloride ion concentration of 670 ppm are obtained.
  • the chlorine ion content based on the weight of the stabilized zirconium oxide particles calculated based on the chloride ion concentration was 22,10 ppm.
  • Example 4 (Production of stabilized aqueous dispersion of zirconium oxide particles (I-4)) Second Step To 60 L of the third water slurry obtained in Example 2, 65 g of 35% hydrochloric acid was added to obtain a fourth water slurry having a chlorine ion concentration of 380 ppm. In the fourth water slurry, the chloride ion content based on the total weight of zirconium and yttrium oxide calculated based on the chloride ion concentration was 5080 ppm.
  • the fourth water slurry was subjected to hydrothermal treatment at 190 ° C. for 3 hours to obtain a transparent aqueous dispersion precursor of stabilized zirconium oxide particles.
  • the transparent dispersion precursor of the stabilized zirconium oxide particles is washed and concentrated with an ultrafiltration membrane, and the stabilized zirconium oxide particles having a stabilized zirconium oxide concentration of 30.0% by weight and a chloride ion concentration of 530 ppm are obtained.
  • An aqueous dispersion (I-4) was obtained.
  • the chloride ion content based on the weight of the stabilized zirconium oxide particles calculated based on the chloride ion concentration was 1770 ppm.
  • Comparative Example 1 (Production of Stabilized Aqueous Dispersion of Zirconium Oxide Particles (I-5) as Comparative Example) Second Step To 60 L of the third water slurry obtained in Example 2, 25 g of 35% hydrochloric acid was added to obtain a fourth water slurry having a chloride ion concentration of 140 ppm. In the fourth water slurry, the chlorine ion content based on the total weight of zirconium and yttrium oxide calculated based on the chloride ion concentration was 1,830 ppm.
  • the fourth water slurry was subjected to hydrothermal treatment at 190 ° C. for 3 hours to obtain a transparent aqueous dispersion precursor of stabilized zirconium oxide particles.
  • the transparent dispersion precursor of the stabilized zirconium oxide particles is washed and concentrated with an ultrafiltration membrane, and the stabilized zirconium oxide particles having a concentration of 30.0% by weight of stabilized zirconium oxide and a concentration of 190 ppm of chloride ion are provided.
  • the chloride ion content based on the weight of the stabilized zirconium oxide particles calculated based on the chloride ion concentration was 640 ppm.
  • Comparative Example 2 (Production of Stabilized Aqueous Dispersion of Zirconium Oxide Particles (I-6) as Comparative Example) Third Step The third water slurry obtained in Example 2 was subjected to hydrothermal treatment at 190 ° C. for 3 hours to obtain a transparent aqueous dispersion precursor of stabilized zirconium oxide particles.
  • the transparent dispersion precursor of the stabilized zirconium oxide particles is washed and concentrated by an ultrafiltration membrane, and the stabilized zirconium oxide particles have a concentration of 30.7% by weight and a chlorine ion concentration of 3 ppm.
  • aqueous dispersion I-6
  • the chlorine ion content based on the weight of the stabilized zirconium oxide particles calculated based on the chloride ion concentration was 10 ppm.
  • Example 5 (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 1.9 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 10.
  • 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 6 ppm.
  • the chlorine ion content based on the weight of the zirconium oxide particles calculated based on the chloride ion concentration was 90 ppm.
  • the fourth water slurry was subjected to a 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 having a zirconium oxide particle concentration of 30.2% by weight and a chloride ion concentration of 1440 ppm ( I-7) was obtained.
  • the chloride ion content based on the weight of the zirconium oxide particles calculated based on the chloride ion concentration was 4790 ppm.
  • a methanol dispersion (II-7) of zirconium oxide particles having a concentration of zirconium oxide particles of 30.3% by weight and a chloride ion concentration of 1400 ppm was obtained.
  • the amount of methanol used for dilution was 90 L.
  • the chlorine ion content based on the weight of the zirconium oxide particles calculated based on the chloride ion concentration was 4610 ppm.
  • the methanol was removed from the methanol dispersion of the zirconium oxide particles obtained in Example 5, dried, and the zirconium oxide fine particles thus obtained were observed with a TEM (transmission electron microscope).
  • the primary particle size was about 5 nm.
  • the methanol is removed from the stabilized zirconium oxide particle methanol dispersion, which is a solid solution containing yttrium, obtained in Examples 1 to 4 and Comparative Examples 1 and 2, and dried.
  • the obtained stabilized zirconium oxide particle powder is obtained.
  • the average primary particle diameter of the stabilized zirconium oxide particles was about 3 nm.
  • 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.
  • E K / (2Z + 3Y) (3)
  • 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.
  • Example 1 shows 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, and the pH of the third slurry obtained in the second step Ion concentration of the water slurry and the chlorine ion content (Cl / ZrO 2 ) calculated based on the chlorine ion concentration, the fourth water slurry obtained in the second step (Examples 1 to 5 and Comparative Example 1)
  • Table 1 shows the chloride ion concentration (Cl / ZrO 2 ) calculated based on the chloride ion concentration and the chloride ion concentration.
  • the chlorine ion content in Examples 1 to 4 and Comparative Examples 1 and 2 is the chlorine ion content with respect to the total weight of zirconium and yttrium as oxides. It is a chloride ion content with respect to weight.
  • the (stabilized) zirconium oxide calculated based on the concentration of the methanol dispersion of the zirconium oxide particles obtained in Examples 1 and 5, the particle size distribution, the total light transmittance, and the chloride ion concentration, as well as the chloride ion concentration.
  • Table 3 shows the results of evaluation of chloride ion content (Cl / ZrO 2 ), water content, viscosity at 25 ° C. immediately after production, viscosity after 7 days from production, and long-term storage stability with respect to the 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 is extremely excellent in long-term storage stability.
  • 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 replacing water as a dispersion medium of the (stabilized) aqueous dispersion of zirconium oxide particles obtained according to the method of the present invention with an organic solvent is also an aqueous dispersion as shown in Table 3.
  • Table 3 an organic solvent dispersion obtained by replacing water as a dispersion medium of the (stabilized) aqueous dispersion of zirconium oxide particles obtained according to the method of the present invention with an organic solvent is also an aqueous dispersion as shown in Table 3.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)

Abstract

La présente invention concerne une méthode de production d'une dispersion aqueuse de particules d'oxyde de zirconium, la méthode comprenant : une étape consistant à faire réagir de l'oxychlorure de zirconium avec une substance basique pour obtenir une première suspension aqueuse contenant des particules d'oxyde de zirconium ; une étape dans laquelle la première suspension aqueuse est lavée pour obtenir une seconde suspension aqueuse, 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 inférieure à 4 000 ppm par rapport au poids de particules de zirconium, puis de l'acide chlorhydrique est ajouté à la troisième suspension aqueuse pour obtenir une quatrième suspension aqueuse ayant une teneur en ions chlore de 4 000 à 20 000 ppm par rapport au poids de particules d'oxyde de zirconium ; une étape de traitement hydrothermique de la quatrième 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 de 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 fines d'oxyde de zirconium, et en particulier, présente une excellente stabilité de stockage à long terme quelle que soit la température ambiante.
PCT/JP2019/032433 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 WO2020045164A1 (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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