WO2012127889A1 - 球状の水酸化マグネシウム粒子、及び球状の酸化マグネシウム粒子、並びにそれらの製造方法 - Google Patents

球状の水酸化マグネシウム粒子、及び球状の酸化マグネシウム粒子、並びにそれらの製造方法 Download PDF

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WO2012127889A1
WO2012127889A1 PCT/JP2012/050706 JP2012050706W WO2012127889A1 WO 2012127889 A1 WO2012127889 A1 WO 2012127889A1 JP 2012050706 W JP2012050706 W JP 2012050706W WO 2012127889 A1 WO2012127889 A1 WO 2012127889A1
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magnesium hydroxide
magnesium oxide
particles
magnesium
mass
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PCT/JP2012/050706
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English (en)
French (fr)
Japanese (ja)
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黒田　明
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タテホ化学工業株式会社
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Priority to KR1020137023864A priority Critical patent/KR101859071B1/ko
Priority to CN201280014702.4A priority patent/CN103443028B/zh
Publication of WO2012127889A1 publication Critical patent/WO2012127889A1/ja

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F5/00—Compounds of magnesium
    • C01F5/14—Magnesium hydroxide
    • C01F5/16—Magnesium hydroxide by treating magnesia, e.g. calcined dolomite, with water or solutions of salts not containing magnesium
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F5/00—Compounds of magnesium
    • C01F5/02—Magnesia
    • C01F5/06—Magnesia by thermal decomposition of magnesium compounds
    • C01F5/08—Magnesia by thermal decomposition of magnesium compounds by calcining magnesium hydroxide
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F5/00—Compounds of magnesium
    • C01F5/14—Magnesium hydroxide
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/20—Particle morphology extending in two dimensions, e.g. plate-like
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/30—Particle morphology extending in three dimensions
    • C01P2004/32—Spheres
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/50—Agglomerated particles
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/14—Pore volume
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/16—Pore diameter
    • C01P2006/17—Pore diameter distribution
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/22—Rheological behaviour as dispersion, e.g. viscosity, sedimentation stability

Definitions

  • the present invention relates to spherical magnesium hydroxide particles, spherical magnesium oxide particles, and methods for producing them.
  • Magnesium hydroxide particles and magnesium oxide particles are used in various fields. Applications of magnesium hydroxide particles include inkjet paper coating agents, flame retardants, heat storage materials, catalysts and electronic materials. Magnesium oxide particles applications include optical materials, inkjet paper coating agents, catalysts and electronics. Materials and the like.
  • magnesium hydroxide particles are used for coating agents, flame retardants, heat storage materials, catalysts, and electronic materials for inkjet paper, the following is desired.
  • the aggregate structure has a positive charge that is easy to adsorb on the pigment ink having a high affinity with many OH groups and many negative charges in the dye ink, and the dye can easily penetrate between particles.
  • magnesium hydroxide particles having In addition, in the flame retardant, the heat storage material, and the catalyst, magnesium hydroxide particles having an aggregate structure exhibiting excellent dispersibility and high reactivity are demanded. Further, in electronic materials, small magnesium hydroxide particles having excellent dispersibility are required.
  • magnesium oxide particles are used in applications such as optical materials, inkjet paper coating agents, catalysts, and electronic materials, the following are desired.
  • optical materials there is a demand for magnesium oxide particles having an aggregate structure that is excellent in dispersibility and easily diffuses light.
  • magnesium oxide particles having an aggregate structure that has excellent dispersibility and high reactivity are required.
  • small magnesium oxide particles having excellent dispersibility are required for electronic materials.
  • Patent Document 1 discloses that the ion concentration ratio of sulfate ion [(SO 4 ) 2 ⁇ ] / magnesium ion [(Mg) 2+ ] is in the range of 0.3 to 2.0.
  • Spherical magnesium hydroxide particles having a structure in which leaflets in different directions are joined and / or crossed are described.
  • the method described in Patent Document 1 cannot stably form spherical magnesium hydroxide, and plate-like and columnar magnesium hydroxide are mixed, and such magnesium hydroxide particles are dispersed in a resin or the like. There was a problem that the sex was not enough.
  • An object of the present invention is to solve the above-described problems and provide spherical magnesium hydroxide particles and magnesium oxide particles having excellent dispersibility with respect to resins and the like, and methods for producing them.
  • the present inventors have added divalent and trivalent metal element chlorides, divalent and trivalent metals to a dispersion containing one or more compounds selected from the group consisting of Zn, Zr, Hf, and Ti.
  • a reaction liquid obtained by adding one or more compounds selected from the group consisting of nitrates of valent metal elements (excluding Zn, Zr, Hf, and Ti compounds), and further adding an organic acid; It has been found that spherical magnesium hydroxide particles having excellent dispersibility can be obtained by mixing with magnesium oxide particles and causing a hydration reaction under high shear. Further, the present inventors have found that spherical magnesium oxide particles can be obtained by firing the magnesium hydroxide particles of the present invention at 500 ° C. to 1400 ° C. in an air atmosphere.
  • the present invention has a spherical shape in which flaky primary particles are aggregated, and has a mode volume of 1.4 ml / mg or more and a mode diameter of 0.4 ⁇ m or more in a pore distribution.
  • the present invention relates to the magnesium hydroxide particles described above, wherein the 50% particle diameter (D 50 ) of volume accumulation by laser diffraction scattering type particle size distribution measurement is 0.5 to 20 ⁇ m.
  • the present invention relates to the magnesium hydroxide particles described above, wherein the oil absorption is 30 ml / 100 g or more.
  • the present invention further includes 0.01 to 4.0% by mass of one or more metal elements selected from the group consisting of Zn, Zr, Hf, and Ti in terms of oxides, and further includes divalent and trivalent elements. Including one to one or more metal elements selected from the group consisting of metal elements (excluding Zn, Zr, Hf, and Ti) in 0.01 to 5.0% by mass in terms of metal elements It relates to magnesium hydroxide particles.
  • the present invention relates to magnesium oxide particles having a spherical shape in which scaly primary particles are aggregated, having a mode volume of 1.4 ml / mg or more and a mode diameter of 0.4 ⁇ m or more in a pore distribution.
  • the present invention relates to the magnesium oxide particles described above, wherein the 50% cumulative particle diameter (D 50 ) measured by laser diffraction / scattering particle size distribution measurement is 0.5 to 20 ⁇ m.
  • the present invention relates to the magnesium oxide particles described above having an oil absorption of 30 ml / 100 g or more.
  • the present invention further includes one or more metal elements selected from the group consisting of Zn, Zr, Hf, and Ti in an amount of 0.01 to 4.0% by mass in terms of oxides, and further includes divalent and trivalent elements. Including one or more additional metal elements selected from the group consisting of metal elements (excluding Zn, Zr, Hf, and Ti) in an amount of 0.01 to 5.0% by mass in terms of metal elements, It relates to the described magnesium oxide particles.
  • the present invention is a method for producing magnesium hydroxide particles, (A) In a dispersion containing one or more compounds selected from the group consisting of Zn, Zr, Hf, and Ti, divalent and trivalent metal element chlorides, and divalent and trivalent metals Adding one or more compounds selected from the group consisting of elemental nitrates (excluding Zn, Zr, Hf, and Ti compounds), and further adding an organic acid to obtain a reaction solution; (B) mixing the reaction liquid in step (a) and magnesium oxide particles having an average particle size of 0.1 to 30 ⁇ m to obtain a mixed liquid; (here, One or more compounds selected from the group consisting of compounds of Zn, Zr, Hf, and Ti are 0.1 to 5.0% by mass in terms of oxides with respect to the magnesium oxide particles, One or more compounds selected from the group consisting of chlorides of divalent and trivalent metal elements, and nitrates of divalent and trivalent metal elements are in the form of 0.
  • step (C) mixing the mixed solution of step (b) at a temperature of 50 to 100 ° C. using a stirrer having a peripheral speed of 7 to 20 m / s, (D) a step of stirring for a long time at a temperature of 30 to 100 ° C. to obtain a magnesium hydroxide slurry; And (e) relates to a method for producing magnesium hydroxide particles, comprising the step of filtering, washing and drying the magnesium hydroxide slurry in step (d) to obtain magnesium hydroxide particles.
  • the present invention relates to the method for producing magnesium hydroxide particles as described above, wherein the concentration of magnesium oxide in the mixed solution in step (b) is 20 to 200 g / L.
  • the present invention is a method for producing magnesium oxide particles, and the magnesium hydroxide particles described above or the magnesium hydroxide particles obtained by the method described above are calcined at 500 to 1400 ° C. in an air atmosphere.
  • the present invention relates to a method for producing magnesium oxide particles, including a step.
  • the magnesium hydroxide particles and magnesium oxide particles of the present invention have high dispersibility and are useful in various fields. Moreover, according to the manufacturing method of this invention, a magnesium hydroxide particle and a magnesium oxide particle can be manufactured easily.
  • the magnesium hydroxide particles of the present invention have a spherical shape in which flaky primary particles are aggregated, the mode volume of pore distribution is 1.4 ml / mg or more, and the mode diameter is 0.4 ⁇ m or more.
  • the shape of the primary particles is scaly
  • the thickness of the scale (short axis) is, for example, 0.01 to 0.1 ⁇ m
  • the ratio of the maximum length of the scale to the thickness (aspect ratio) is, for example, 10 to 1000.
  • Spherical particles in which primary particles are agglomerated have uniform pores on the particle surface and adsorb liquid and gas molecules compared to hexagonal plate-like magnesium hydroxide particles obtained by conventional manufacturing methods.
  • the mode volume of pore distribution of the magnesium hydroxide particles of the present invention is preferably 1.4 to 10 ml / mg, and the mode diameter is preferably 0.4 to 3.0 ⁇ m, more preferably 0.5. ⁇ 2.0 ⁇ m.
  • the mode volume and mode diameter of the present invention are measured by mercury porosimetry, where the mode volume is the maximum value of the log differential pore volume distribution curve and the mode diameter is the maximum value of the log differential pore volume distribution curve.
  • the pore diameter corresponding to the value.
  • the mode diameter is between magnesium hydroxide particles or magnesium oxide particles constituting spherical particles. Corresponds to the gap between.
  • the magnesium hydroxide particles of the present invention have a volume-based cumulative 50% particle diameter (D 50 ) of 0.5 to 20 ⁇ m by laser diffraction scattering type particle size distribution measurement. Within such a range, the viscosity does not become too high when blended with a resin or the like, and the agglomeration of particles is suppressed, so that the dispersibility is good. In addition, when magnesium hydroxide particles having such a particle size are used as a paper coating agent, the particles do not protrude from the ink receiving layer, and the particle size is not too large. Useful.
  • the D 50 of the magnesium hydroxide particles of the present invention is preferably 1.0 to 20 ⁇ m.
  • the oil absorption of the magnesium hydroxide particles of the present invention is 30 ml / 100 g or more.
  • the oil absorption amount in the present invention is the dioctyl phthalate oil absorption amount.
  • the oil absorption is an index for evaluating the filling property of the powder into the resin, and this method can be used for evaluating the filling property (magazine "Industrial Materials" vol. 39, No. 1, p. 116-117 (1991)).
  • the amount of oil absorption is determined by measuring the amount of DOP necessary to form a hard lump as a whole, by kneading while adding dropwise dioctyl phthalate (DOP) to the sample powder. Of DOP (ml / 100 g).
  • the oil absorption is 30 ml / 100 g or more, the dispersibility in resin or the like is good, and when used as a paper coating agent, the ink fixability and absorbability are good.
  • the oil absorption of the magnesium hydroxide particles of the present invention is preferably 50 to 300 ml / 100 g.
  • the magnesium hydroxide particles of the present invention may further contain a metal element of a compound used in the production process.
  • the magnesium hydroxide particles of the present invention contain 0.01 to 4.0% by mass of one or more metal elements selected from the group consisting of Zn, Zr, Hf and Ti in terms of oxides,
  • One or more additional metal elements selected from the group consisting of trivalent metal elements (excluding Zn, Zr, Hf, and Ti) are contained in an amount of 0.01 to 5.0% by mass in terms of metal elements. With these metal element contents, whiteness, ultraviolet absorption, refractive index, and the like are sufficient when magnesium hydroxide particles are used as the coating agent.
  • the content of one or more metal elements selected from the group consisting of Zn, Zr, Hf, and Ti, that is, Zn, Zr, Hf, Ti, or a mixture thereof is preferably 0.05 to
  • the content is 4.0% by mass, more preferably 0.2 to 4.0% by mass, and still more preferably 0.4 to 4.0% by mass.
  • one or more additional metal elements selected from the group consisting of divalent and trivalent metal elements are not particularly limited, and Ag, Examples include Al, B, Ba, Bi, Cd, Co, Cr, Cu, Fe, Ga, In, Mn, Mo, Ni, Pb, Sr, Tl, and V, and Al and Fe are preferable.
  • the content of one or more additional metal elements selected from the group consisting of divalent and trivalent metal elements (excluding Zn, Zr, Hf, and Ti) is preferably 0.00 in terms of metal elements.
  • the content is from 05 to 5.0% by mass, more preferably from 0.1 to 5.0% by mass, and still more preferably from 0.3 to 4.0% by mass.
  • the magnesium oxide particles of the present invention have a spherical shape in which flaky primary particles are aggregated, the mode volume of the pore distribution is 1.4 ml / mg or more, and the mode diameter is 0.4 ⁇ m or more.
  • Such magnesium oxide particles have excellent dispersibility in a resin or the like. Specifically, when the magnesium oxide particles having such a mode diameter are used as a paper coating agent, the fixability and absorbability of the ink are good, and the magnesium oxide particles having such a mode volume are In addition, the scale-like magnesium oxide constituting the sphere is not too dense, and the ink adsorbability is good.
  • the mode volume of the pore distribution is preferably 1.4 to 10 ml / mg, and the mode diameter is preferably 0.4 to 3.0 ⁇ m, more preferably 0.5 to 2.0 ⁇ m.
  • the magnesium oxide particles of the present invention have a volume-based cumulative 50% particle size (D 50 ) of 0.5 to 20 ⁇ m by laser diffraction scattering type particle size distribution measurement. Within such a range, the viscosity does not become too high when blended with a resin or the like, and the agglomeration of particles is suppressed, so that the dispersibility is good. Further, when used as a paper coating agent, the particles do not protrude from the ink receiving layer, and the particle diameter is not too large, which is useful for optical materials and electronic materials.
  • the volume-based cumulative 50% particle diameter (D 50 ) of the magnesium oxide particles of the present invention is preferably 1 to 20 ⁇ m.
  • the oil absorption of the magnesium oxide particles of the present invention is 30 ml / 100 g or more. If it is such a range, the dispersibility to resin etc. will be favorable, and when it is used as a paper coating agent, the fixability and absorbability of ink will be favorable.
  • the oil absorption of the magnesium oxide particles of the present invention is preferably 50 to 300 ml / 100 g.
  • the magnesium oxide particles of the present invention may further contain a metal element of a compound used in the production process.
  • the magnesium oxide particles of the present invention contain 0.01 to 4.0% by mass of one or more metal elements selected from the group consisting of Zn, Zr, Hf, and Ti in terms of oxides, and are further divalent and 3
  • One or more additional metal elements selected from the group consisting of valent metal elements are contained in an amount of 0.01 to 5.0% by mass in terms of metal elements. With these metal element contents, whiteness, ultraviolet absorptivity, refractive index, etc. are sufficient when magnesium oxide particles are used as a coating agent.
  • the content of one or more metal elements selected from the group consisting of Zn, Zr, Hf, and Ti, that is, Zn, Zr, Hf, Ti, or a mixture thereof is preferably 0.05 to
  • the content is 4.0% by mass, more preferably 0.2 to 4.0% by mass, and still more preferably 0.4 to 4.0% by mass.
  • One or more additional metal elements selected from the group consisting of divalent and trivalent metal elements are not particularly limited, and Ag, Al, B, Examples include Ba, Bi, Cd, Co, Cr, Cu, Fe, Ga, In, Mn, Mo, Ni, Pb, Sr, Tl, and V, and Al and Fe are preferable.
  • the content of one or more additional metal elements selected from the group consisting of divalent and trivalent metal elements (excluding Zn, Zr, Hf, and Ti) is preferably 0.00 in terms of metal elements. It is 1 to 5.0% by mass, more preferably 0.3 to 4.0% by mass, and still more preferably 0.4 to 4.0% by mass.
  • the method for producing magnesium hydroxide particles of the present invention comprises: (A) In a dispersion containing one or more compounds selected from the group consisting of Zn, Zr, Hf, and Ti, divalent and trivalent metal element chlorides, and divalent and trivalent metals Adding one or more compounds selected from the group consisting of elemental nitrates (excluding Zn, Zr, Hf, and Ti compounds), and further adding an organic acid to obtain a reaction solution; (B) mixing the reaction liquid in step (a) and magnesium oxide particles having an average particle size of 0.1 to 30 ⁇ m to obtain a mixed liquid; (here, One or more compounds selected from the group consisting of Zn, Zr, Hf, and Ti are 0.1 to 5.0% by mass in terms of oxides with respect to magnesium oxide, One or more compounds selected from the group consisting of divalent and trivalent metal element chlorides and nitrates of divalent and trivalent metal elements are 0.1 to 5.0% by weight, The organic acid is 0.01 to 3.0 mol with respect to 100
  • Step (a) is a step of obtaining a reaction solution for hydrating magnesium oxide.
  • One or more compounds selected from the group consisting of Zn, Zr, Hf, and Ti compounds are magnesium hydroxide particles and magnesium oxide particles of the present invention to produce composite hydroxides and composite oxides. Added. Thereby, whiteness, ultraviolet absorption, refractive index and the like are improved, and the magnesium hydroxide and magnesium oxide particles of the present invention suitable for an optical material or a coating agent for inkjet paper can be obtained.
  • the compound of Zn, Zr, Hf, and Ti is not particularly limited as long as it is a compound having these metal elements, and is an oxide, hydroxide, hydride, halide (fluoride, chloride, bromide, and iodine).
  • the compound of Zn, Zr, Hf, and Ti preferably has a purity of 99.0% or more, and more preferably 99.5% or more.
  • purity refers to impurity elements (Ag, Al, B, Ba, Bi, Cd, Cl, Co, Cr, Cu, Fe, Ga, In, K, Li, Mn, Mo, Na,
  • impurity elements Al, B, Ba, Bi, Cd, Cl, Co, Cr, Cu, Fe, Ga, In, K, Li, Mn, Mo, Na
  • the contents of Ni, P, Pb, S, Si, Sr, Tl, V, Zn, Ti, and Zr are measured, and the total content is subtracted from 100% by mass.
  • a measuring method of the content of these impurity elements a measuring method using an ICP emission analyzer can be mentioned.
  • the compound of Zn, Zr, Hf, and Ti preferably has an average particle size of 0.1 to 100 ⁇ m, more preferably 0.5 to 50 ⁇ m.
  • the amount of the one or more compounds selected from the group consisting of compounds of Zn, Zr, Hf, and Ti is from 0.1 to 0.1 with respect to the magnesium oxide particles used in the step (b). 5.0% by mass.
  • the amount of the compound selected from the group consisting of Zn, Zr, Hf, and Ti is less than 0.1% by mass, when used as a coating agent, the whiteness, ultraviolet absorptivity and refractive index are not sufficient.
  • the particle shape is not a spherical particle in which the scaly primary particles are aggregated but a hexagonal plate-like particle.
  • the flaky primary particles as in the present invention are not agglomerated spherical particles. Hexagonal columnar particles.
  • the amount of one or more compounds selected from the group consisting of Zn, Zr, Hf, and Ti is preferably 0.4 to 4.0% by mass with respect to the weight of the magnesium oxide particles.
  • the dispersion containing one or more compounds selected from the group consisting of Zn, Zr, Hf, and Ti is, for example, selected from the group consisting of Zn, Zr, Hf, and Ti in ion exchange water. It can be obtained by adding the above compounds.
  • Divalent and trivalent metal element chlorides and divalent and trivalent metal element nitrates are added to control the solubility and precipitation rate of the composite hydroxide, magnesium hydroxide particles of the present invention. Is done.
  • chlorides of divalent and trivalent metal elements and nitrates of divalent and trivalent metal elements aluminum chloride, iron chloride, aluminum nitrate, and iron nitrate are preferable.
  • the chlorides of divalent and trivalent metal elements and nitrates of divalent and trivalent metal elements preferably have a purity of 99.0% or more, and more preferably 99.5% or more.
  • the chlorides of divalent and trivalent metal elements and nitrates of divalent and trivalent metal elements preferably have an average particle size of 0.1 to 100 ⁇ m, preferably 0.5 to 50 ⁇ m. Is more preferable.
  • the amount of one or more compounds selected from the group consisting of chlorides of divalent and trivalent metal elements and nitrates of divalent and trivalent metal elements is the amount of magnesium oxide particles used in step (b). On the other hand, it is 0.1 to 5.0% by mass in terms of metal element. When the addition amount is less than 0.1% by mass, the crystal precipitation rate becomes slow, resulting in monodispersed hexagonal columnar particles, and when the addition amount is more than 5.0% by mass, the crystal precipitation rate becomes too fast and coarse. Agglomerated particles.
  • the amount of one or more compounds selected from the group consisting of chlorides of divalent and trivalent metal elements and nitrates of divalent and trivalent metal elements is 0 in terms of metal elements relative to the magnesium oxide particles. More preferably, the content is in the range of 0.4 to 4.0% by mass.
  • the organic acid is added to suppress the solubility of the magnesium oxide particles as a raw material.
  • the organic acid include aliphatic or aromatic organic acids having a carboxyl group, and formic acid, acetic acid, propionic acid, butyric acid, and benzoic acid are preferable.
  • the addition amount of the organic acid is 0.01 to 3.0 mol with respect to 100 g of the magnesium oxide particles used in the step (b).
  • the amount of organic acid added is less than 0.01 mol with respect to 100 g of magnesium oxide particles, the rate of crystal precipitation is slow, resulting in monodispersed hexagonal columnar particles, and when it is greater than 3.0 mol, the rate of crystal precipitation is high. Becomes too coarse and becomes agglomerated particles.
  • the amount of the organic acid added is preferably 0.01 to 2.0 mol with respect to 100 g of magnesium oxide used in step (b).
  • Step (b) is a step of mixing the reaction liquid for the hydration reaction obtained in step (a) and the magnesium oxide particles as the raw material.
  • Magnesium oxide particles used as a raw material have an average particle size of 0.1 to 30 ⁇ m. If the average particle size is smaller than 0.1 ⁇ m, the hydration rate becomes too fast, resulting in coarse aggregated particles. On the other hand, if the average particle diameter is larger than 30 ⁇ m, the hydration reaction does not proceed sufficiently and particles containing particulate magnesium oxide remain.
  • the average particle diameter of the magnesium oxide particles is more preferably 0.5 to 15 ⁇ m.
  • the concentration of magnesium oxide in the mixed solution is preferably 20 to 200 g / L, more preferably 50 to 180 g / L.
  • the amount of magnesium oxide in the reaction solution obtained in step (a) is preferably adjusted to 20 to 200 g / L, and more preferably 50 to 150 g / L. With such a magnesium oxide concentration in the reaction solution, the hydration reaction proceeds sufficiently.
  • the temperature of the reaction solution is preferably 50 to 100 ° C., more preferably 50 to 95 ° C., and further preferably 70 ° C. to 90 ° C. At such a temperature, the hydration reaction proceeds sufficiently.
  • Step (c) is a step of mixing using a stirrer having a peripheral speed of 7 to 20 m / s at a temperature of 50 to 100 ° C.
  • the number of rotations of stirring is adjusted to control the dispersion state during the reaction.
  • the peripheral speed is less than 7 m / s
  • spherical magnesium hydroxide in which scaly primary particles are aggregated cannot be obtained.
  • the peripheral speed is higher than 20 m / s, the magnesium hydroxide particles are sufficiently dispersed at the time of nucleation to form monodispersed hexagonal columnar magnesium hydroxide particles, and the spherical magnesium hydroxide particles as in the present invention are formed. I can't get it.
  • Examples of such an apparatus for stirring include homodispers (Primics Co., Ltd., TK homodispers).
  • the peripheral speed is preferably 8 to 18 m / s, more preferably 9 to 15 m / s.
  • the reaction temperature in the step (c) is preferably 55 to 95 ° C, more preferably 60 to 95 ° C.
  • the mixing time can be changed according to the degree of the hydration reaction, and can be, for example, 10 minutes to 360 minutes, preferably 20 minutes to 200 minutes.
  • Step (d) is a step of obtaining a magnesium hydroxide slurry by stirring for a long time at a temperature of 30 to 100 ° C.
  • the temperature is preferably 50 to 95 ° C, more preferably 70 to 90 ° C.
  • the stirring speed is not particularly limited as long as the magnesium hydroxide slurry can be sufficiently stirred.
  • the stirring speed can be set to 100 to 500 rpm with a three-spring stirrer.
  • the stirring time is not particularly limited as long as the hydration reaction proceeds sufficiently and a desired magnesium hydroxide slurry can be obtained.
  • the stirring time can be 0.5 to 6 hours.
  • Step (e) is a step of obtaining magnesium hydroxide particles by filtering, washing and drying the magnesium hydroxide slurry of step (d). Thereby, the magnesium hydroxide particle of this invention is obtained.
  • the magnesium oxide particles of the present invention are obtained by a method including a step of firing magnesium hydroxide particles obtained by the production method including the steps (a) to (e) of the present invention at 500 to 1400 ° C. in an air atmosphere. can get.
  • it is obtained by a method including a step of baking at 600 to 1300 ° C.
  • magnesium hydroxide particles are heated to 500 ° C. to 1400 ° C., preferably 600 to 1300 ° C. at a temperature rising rate of 1 to 20 ° C./min (preferably 3 to 10 ° C./min) in an air atmosphere.
  • the magnesium oxide particles of the present invention can be obtained by firing at 500 to 1400 ° C., preferably 600 to 1300 ° C. for 0.1 to 5 hours. If the firing temperature is less than 500 ° C., the amount of heat is insufficient and magnesium hydroxide remains. On the other hand, when the firing temperature exceeds 1400 ° C., magnesium oxide grows and does not become spherical magnesium oxide in which scaly primary particles are aggregated.
  • the mercury intrusion pore distribution measuring apparatus was measured using an auto pore 9410 manufactured by Micrometrics. As the mercury, a special grade mercury reagent having a purity of 99.5 mass% or more and a density of 13.5335 ⁇ 10 3 kg / m 3 was used. The maximum value (mode volume) of the log differential pore volume distribution curve obtained by mercury intrusion pore distribution measurement and the pore diameter (mode diameter) corresponding to the mode volume were determined.
  • DOP Dioctyl phthalate
  • Example 1 In a solution of ion exchange water containing 0.4% by mass of zinc oxide and 1 liter of ion exchange water with respect to magnesium oxide used in the reaction, 0.5% by mass of aluminum chloride hexahydrate in terms of metal element, The reaction solution was prepared by adding 0.03 mol of propionic acid to 100 g of magnesium oxide. The temperature of the prepared reaction solution was raised to 60 ° C., and 100 g of magnesium oxide having an average particle size of 8.8 ⁇ m was added to obtain a mixed solution. After adding magnesium oxide, the temperature of the reaction liquid was raised to 95 ° C., and the peripheral speed was adjusted to 9 m / s with a stirrer (TK homodisper manufactured by Primics) and reacted for 1 hour.
  • TK homodisper manufactured by Primics TK homodisper manufactured by Primics
  • magnesium hydroxide slurry was prepared by stirring at 90 ° C. for 4 hours at a rotation speed at which the slurry could be sufficiently stirred.
  • the produced magnesium hydroxide slurry was filtered, washed with water, and dried to obtain magnesium hydroxide particles of the present invention.
  • Example 2 The same operation as in Example 1 was performed except that the amount of zinc oxide added was changed to 3.0% by mass.
  • Example 3 The same operation as in Example 1 was performed except that the amount of zinc oxide added was 0.1% by mass.
  • Example 4 The same operation as in Example 1 was carried out except that the zinc oxide was changed to 0.5% by mass of titanium oxide.
  • Example 5 The same procedure as in Example 1 was carried out except that the amount of aluminum chloride hexahydrate added was 3.0% by mass in terms of metal element.
  • Example 6 The same procedure as in Example 1 was carried out except that the amount of aluminum chloride hexahydrate added was 0.1% by mass in terms of metal element.
  • Example 7 The same procedure as in Example 1 was conducted except that the aluminum chloride hexahydrate was changed to 0.5% by mass of iron chloride.
  • Example 8 The same procedure as in Example 1 was conducted except that aluminum chloride hexahydrate was changed to 0.5 mass% aluminum nitrate.
  • Example 9 The same procedure as in Example 1 was conducted except that the addition amount of propionic acid was changed to 0.5 mol.
  • Example 10 The same procedure as in Example 1 was performed except that propionic acid was changed to 0.02 mol of acetic acid.
  • Example 11 The same procedure as in Example 1 was performed except that propionic acid was changed to 0.02 mol of butyric acid.
  • Example 12 The same procedure as in Example 1 was performed except that the peripheral speed of the stirrer during the hydration reaction was 14 m / s.
  • Example 13 The same procedure as in Example 1 was performed except that the peripheral speed of the stirrer during the hydration reaction was changed to 7 m / s.
  • Example 14 Magnesium hydroxide produced in Example 7 was baked at 800 ° C. for 1 hour in an air atmosphere to obtain magnesium oxide particles.
  • Example 15 It carried out like Example 14 except having made calcination temperature into 1000 ° C.
  • Example 16 It carried out like Example 14 except having made calcination temperature into 1200 ° C.
  • Example 1 The same operation as in Example 1 was performed except that the amount of zinc oxide added was 6.0% by mass.
  • Example 3 The same procedure as in Example 1 was conducted except that aluminum chloride hexahydrate was changed to 0.5 mass% aluminum sulfate.
  • Example 5 The same procedure as in Example 1 was carried out except that aluminum chloride hexahydrate was not added.
  • Example 6 The same procedure as in Example 1 was conducted except that aluminum acetate hexahydrate was changed to aluminum acetate.
  • Example 8 The same operation as in Example 14 was performed except that the firing temperature was 1500 ° C.
  • the magnesium hydroxide particles and magnesium oxide particles of the present invention are spherical, have a small particle size, are uniform, and have good dispersibility, so they are highly useful in various fields. Moreover, according to the production method of the present invention, the particles as described above can be easily prepared, which is highly convenient. Examples of the use of the magnesium hydroxide particles of the present invention include inkjet paper coating agents, flame retardants, heat storage materials, catalysts, and electronic materials. Magnesium oxide particles are used as optical materials, ink jet paper coating agents, Examples include catalysts and electronic materials.

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CN105008281A (zh) * 2013-02-13 2015-10-28 达泰豪化学工业株式会社 具有高比表面积的棒状的氢氧化镁颗粒和棒状的氧化镁颗粒、以及它们的制造方法
US20210309833A1 (en) * 2019-03-29 2021-10-07 Tateho Chemical Industries Co., Ltd. Spherical magnesium oxide, manufacturing method thereof, thermal conductive filler and resin composition
EP4215486A4 (en) * 2020-09-15 2024-03-20 Denka Company Limited MAGNESIUM OXIDE POWDER, FILLER COMPOSITION, RESIN COMPOSITION AND HEAT DISSIPATION COMPONENT

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JP6817235B2 (ja) * 2017-02-17 2021-01-20 タテホ化学工業株式会社 球状酸化マグネシウム及びその製造方法
JP6901726B2 (ja) * 2017-08-31 2021-07-14 タテホ化学工業株式会社 化学蓄熱材及びその製造方法
CN113874323A (zh) * 2019-03-29 2021-12-31 达泰豪化学工业株式会社 球状氧化镁、其制造方法、导热性填料和树脂组合物
WO2023063413A1 (ja) * 2021-10-15 2023-04-20 タテホ化学工業株式会社 球状酸化マグネシウム、その製造方法、樹脂フィラー及び樹脂組成物
CN115926492B (zh) * 2022-11-07 2024-05-28 广东金戈新材料股份有限公司 一种可降低氧化镁吸油值的矿化剂制备方法及其用法

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EP4215486A4 (en) * 2020-09-15 2024-03-20 Denka Company Limited MAGNESIUM OXIDE POWDER, FILLER COMPOSITION, RESIN COMPOSITION AND HEAT DISSIPATION COMPONENT

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