WO2014126075A1 - 高い比表面積を有する棒状の水酸化マグネシウム粒子、及び棒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

高い比表面積を有する棒状の水酸化マグネシウム粒子、及び棒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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WO2014126075A1
WO2014126075A1 PCT/JP2014/053108 JP2014053108W WO2014126075A1 WO 2014126075 A1 WO2014126075 A1 WO 2014126075A1 JP 2014053108 W JP2014053108 W JP 2014053108W WO 2014126075 A1 WO2014126075 A1 WO 2014126075A1
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magnesium oxide
particles
magnesium hydroxide
metal elements
surface area
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PCT/JP2014/053108
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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 CN201480008719.8A priority Critical patent/CN105008281B/zh
Priority to KR1020157022195A priority patent/KR102156105B1/ko
Publication of WO2014126075A1 publication Critical patent/WO2014126075A1/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
    • C01F5/02—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
    • 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
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/10—Particle morphology extending in one dimension, e.g. needle-like
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/50—Agglomerated particles
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • 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
    • C01P2006/12—Surface area

Definitions

  • the present invention relates to rod-shaped magnesium hydroxide particles having a high specific surface area, rod-shaped 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 inkjet paper coating agents, flame retardants, heat storage materials, catalysts, and electronic materials, the following are 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.
  • the specific surface area is low and the reactivity is low.
  • An object of the present invention is to provide magnesium hydroxide particles and magnesium oxide particles having a high specific surface area, and methods for producing them.
  • the inventor has added divalent and trivalent metal element chlorides, divalent and trivalent to a dispersion containing one or more compounds selected from the group consisting of Zn, Zr, Hf, and Ti.
  • a reaction solution obtained by adding one or more compounds selected from the group consisting of nitrates of metal elements (excluding Zn, Zr, Hf, and Ti compounds) and further adding an organic acid; and a constant temperature Mixing with acicular magnesium oxide particles partially hydrated the surface of acicular magnesium oxide particles with a humidity controller etc., and by hydration reaction under high shear, excellent dispersibility, It has been found that highly reactive magnesium hydroxide particles having a high specific surface area can be obtained. Further, the present inventors have found that magnesium oxide particles having a high specific surface area 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 is a rod-like aggregate of scaly primary particles, the volume cumulative 50% particle diameter (D 50 ) measured by laser diffraction / scattering particle size distribution measurement is 1.0 to 10.0 ⁇ m, and the specific surface area Relates to magnesium hydroxide particles having a particle size of 10 m 2 / 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 0.1 to 5.0% by mass in terms of metal elements, and bivalent and trivalent metal elements
  • the hydroxide according to the above, containing 0.1 to 5.0% by mass of one or more additional metal elements selected from the group consisting of Zn (excluding Zn, Zr, Hf, and Ti) in terms of metal elements It relates to magnesium particles.
  • the present invention is a rod shape in which scaly primary particles are aggregated, the volume cumulative 50% particle diameter (D 50 ) measured by laser diffraction scattering type particle size distribution is 1.0 to 10.0 ⁇ m, and the specific surface area is 10 m.
  • 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 0.1 to 5.0% by mass in terms of metal elements, and bivalent and trivalent metal elements
  • metal elements selected from the group consisting of Zn, Zr, Hf, and Ti in an amount of 0.1 to 5.0% by mass in terms of metal elements, and bivalent and trivalent metal elements
  • 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) The reaction liquid in step (a) and the volume cumulative 50% particle diameter (D 50 ) measured by laser diffraction / scattering particle size distribution measurement are 0.1 to 10 ⁇ m, and the specific surface area is 1.0 to 20.0 m.
  • a partially hydrated acicular magnesium oxide is mixed to obtain a mixture (where, 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 metal elements with respect to partially hydrated acicular magnesium oxide. , One or more compounds selected from the group consisting of divalent and trivalent metal element chlorides, and divalent and trivalent metal element nitrates are partially hydrated with acicular magnesium oxide.
  • the organic acid is 0.01 to 3.0 mol with respect to 100 g of partially hydrated acicular magnesium oxide)
  • C mixing the liquid mixture 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 obtaining a magnesium hydroxide slurry by stirring at a temperature of 30 to 100 ° C., and
  • e filtering, washing with water and drying the magnesium hydroxide slurry of step (d) to obtain magnesium hydroxide particles.
  • the present invention relates to a method for producing magnesium hydroxide particles, including a step.
  • the partially hydrated acicular magnesium oxide in the step (b) has a volume cumulative 50% particle diameter (D 50 ) of 0.1 to 10 ⁇ m by laser diffraction scattering type particle size distribution measurement, and has a specific surface area of Obtained by placing acicular magnesium oxide particles of 1.0 to 15.0 m 2 / g in a thermo-hygrostat at a temperature of 40 to 95 ° C. and a humidity of 60 to 95% for 0.5 to 24 hours, Relates to the method described in.
  • the present invention relates to the method as described above, wherein the concentration of the partially hydrated acicular magnesium oxide in the mixed solution of step (b) is 20 to 200 g / L.
  • the present invention is a method for producing magnesium oxide particles, the step of firing the magnesium hydroxide particles described above or the magnesium hydroxide particles obtained by the method described above at 500 to 1400 ° C. in an air atmosphere.
  • the present invention provides rod-shaped magnesium hydroxide particles and magnesium oxide particles in which scaly primary particles having a high specific surface area are aggregated, and methods for producing them.
  • the magnesium hydroxide particles and magnesium oxide particles of the present invention have a high specific surface area and dispersibility, and are useful in various fields.
  • the magnesium hydroxide particle and magnesium oxide particle which have a high specific surface area and a dispersibility can be manufactured easily.
  • the magnesium hydroxide particles of the present invention are rod-like aggregates of scaly primary particles, and the volume cumulative 50% particle diameter (D 50 ) measured by laser diffraction scattering type particle size distribution is 1.0 to 10.0 ⁇ m.
  • the specific surface area is 10 m 2 / g or more.
  • the shape of the primary particles of the present invention is scaly.
  • An example of a scale-like shape is shown in FIG.
  • the scaly primary particles of the present invention have a thickness in the range of 0.01 to 0.1 ⁇ m, preferably 0.01 to 0.05 ⁇ m, and the diameter of the circumscribed circle of the surface is 0.2 to 5 ⁇ m, preferably 0. The range is from 5 to 2.5 ⁇ m.
  • a rod-like particle is a particle in which scaly primary particles are aggregated and has an aspect ratio (particle length L / particle cross-sectional diameter D) of 1.5 to 20, preferably 2 to 10.
  • the needle shape refers to particles having an aspect ratio (particle length L / particle cross-sectional diameter D) of 21 to 1000, preferably 50 to 500.
  • L is in the range of 0.1 to 10 ⁇ m
  • D is specifically in the range of 0.001 to 0.5 ⁇ m.
  • the spherical shape refers to particles having a spherical shape in which the primary particles of the scales are aggregated and having an aspect ratio (particle length L / particle cross-sectional diameter D) in the range of 1.0 to 1.2. .
  • L is specifically in the range of 1 to 20 ⁇ m
  • D is specifically in the range of 1 to 20 ⁇ m.
  • Such rod-like particles in which primary particles are aggregated have uniform pores on the particle surface, and hexagonal plate-like magnesium hydroxide particles obtained by a conventional production method (see JP 2006-306658 A). Compared with the high specific surface area, the adsorptivity of liquid and gas molecules is high. In addition, when such rod-shaped particles in which primary particles are aggregated are used as a coating agent for paper, the scale-like magnesium hydroxide constituting the rod-shaped particles is not too dense, and thus the ink adsorption is good. It is.
  • the magnesium hydroxide particles of the present invention are rod-like aggregates of scaly primary particles, and the volume cumulative 50% particle diameter (D 50 ) measured by laser diffraction scattering type particle size distribution is 1.0 to 10.0 ⁇ m.
  • the specific surface area is 10 m 2 / g or more. 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.
  • the magnesium hydroxide particles having such a particle size are used as a paper coating agent, the ink fixing and absorbing properties are good. Furthermore, since the particle diameter is not too large, it is useful for optical materials and electronic materials.
  • the volume cumulative 50% particle diameter (D 50 ) of the magnesium hydroxide particles of the present invention as measured by laser diffraction scattering type particle size distribution is preferably 2.0 to 9.0 ⁇ m, more preferably 3.0 to 8.
  • the specific surface area is preferably 10 to 200 m 2 / g, more preferably 20 to 150 m 2 / g. In the present invention, the specific surface area is determined by the BET method.
  • the magnesium hydroxide particles of the present invention preferably have a ratio D 90 / D 10 of the volume-based cumulative 10% particle diameter (D 10 ) and cumulative 90% particle diameter (D 90 ) by laser diffraction scattering particle size distribution measurement. Is 10 or less, more preferably in the range of 1-8. With such a ratio D 90 / D 10, narrow particle size distribution of the magnesium hydroxide particles, since aggregation of particles is small, it can be obtained more excellent dispersibility.
  • 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 one or more metal elements selected from the group consisting of Zn, Zr, Hf, and Ti in an amount of 0.1 to 5.0% by mass in terms of metal elements, and are divalent and Containing 0.1 to 5.0% by mass of one or more additional metal elements selected from the group consisting of trivalent metal elements (excluding Zn, Zr, Hf, and Ti) in terms of metal elements Can do.
  • 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 0.2 to It is 4.0% by mass, and more preferably 0.3 to 3.0% 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, Ca, 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 0.1 to The amount is 5.0% by mass, preferably 0.2 to 4.0% by mass, and more preferably 0.3 to 3.0% by mass.
  • the magnesium oxide particles of the present invention are rod-like aggregates of scaly primary particles, and the 50% particle diameter (D 50 ) of volume accumulation by laser diffraction scattering type particle size distribution measurement is 1.0 to 10.0 ⁇ m, The specific surface area is 10 m 2 / g or more.
  • the shape of the primary particles of the present invention is scaly and is similar to the scaly example of FIG.
  • the scaly primary particles of the present invention have a thickness in the range of 0.01 to 0.1 ⁇ m, preferably 0.01 to 0.05 ⁇ m, and the diameter of the circumscribed circle of the surface is 0.2 to 5 ⁇ m, preferably 0. The range is from 5 to 2.5 ⁇ m.
  • Such magnesium oxide particles have excellent dispersibility in a resin or the like.
  • magnesium oxide particles having such a particle size and specific surface area have good ink fixability and absorbability when used as a paper coating agent.
  • 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.
  • the particle diameter is not too large, it is useful for optical materials and electronic materials.
  • the volume cumulative 50% particle diameter (D 50 ) of the magnesium oxide particles of the present invention as measured by laser diffraction scattering type particle size distribution is preferably 2.0 to 9.0 ⁇ m, more preferably 3.0 to 8.0 ⁇ m.
  • the specific surface area is preferably 10 to 200 m 2 / g, more preferably 20 to 150 m 2 / g.
  • the magnesium oxide particles of the present invention preferably have a ratio D 90 / D 10 of a volume-based cumulative 10% particle diameter (D 10 ) and cumulative 90% particle diameter (D 90 ) by laser diffraction scattering particle size distribution measurement. It is 10 or less, and more preferably in the range of 1-8. With such a ratio D 90 / D 10 , the particle size distribution of the magnesium oxide particles is narrow and the particles are less aggregated, so that further excellent dispersibility can be obtained.
  • 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 one or more metal elements selected from the group consisting of Zn, Zr, Hf, and Ti in an amount of 0.1 to 5.0% by mass in terms of metal elements, and are further divalent and 3
  • One or more additional metal elements selected from the group consisting of valent metal elements may be contained in an amount of 0.1 to 5.0% by mass in terms of metal elements it can. 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 0.2 to It is 4.0% by mass, and more preferably 0.3 to 3.0% 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 2 to 4.0% by mass, and more preferably 0.3 to 3.0% 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) The reaction liquid in step (a) and the volume cumulative 50% particle diameter (D 50 ) measured by laser diffraction / scattering particle size distribution measurement are 0.1 to 10 ⁇ m, and the specific surface area is 1.0 to 20.0 m.
  • Ig-loss is 2.0 to 25.0%, mixing partially hydrated acicular magnesium oxide to obtain a mixture, (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 metal elements with respect to partially hydrated acicular magnesium oxide. , One or more compounds selected from the group consisting of divalent and trivalent metal element chlorides and divalent and trivalent metal element nitrates are partially hydrated with acicular magnesium oxide.
  • the organic acid is 0.01 to 3.0 mol with respect to 100 g of partially hydrated acicular magnesium oxide
  • C a step of mixing the mixed liquid of step (b) using a stirrer having a peripheral speed of 7 to 20 m / s at a temperature of 50 to 100 ° C .
  • D a step of obtaining a magnesium hydroxide slurry by stirring at a temperature of 30 to 100 ° C., and (e) filtering, washing with water and drying the magnesium hydroxide slurry of step (d) to obtain magnesium hydroxide particles.
  • Step (a) is a step of obtaining a reaction solution for partially hydrating magnesium hydroxide.
  • One or more compounds selected from the group consisting of Zn, Zr, Hf, and Ti are added to produce the magnesium hydroxide particles and magnesium oxide particles of the present invention. 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, Ca, Cd, Cl, Co, Cr, Cu, Fe, Ga, Hf, Zn, Zr, and Ti).
  • K, Li, Mg, Mn, Mo, Na, Ni, P, Pb, S, Si, Sr, Ti, Tl, V, Zn, and Zr) are measured, and the total content thereof is set to 100. The value is subtracted from the mass%.
  • the element constituting the target Zn, Zr, Hf, and Ti compound itself corresponds to the impurity element in the Zn, Zr, Hf, and Ti compound, the element is included in the impurity element. I can't.
  • Zn constituting ZnO is an impurity element in the compound of Zn, Zr, Hf, and Ti described above. Not included.
  • 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 a D 50 of 0.1 to 100 ⁇ m, and more preferably 0.5 to 50 ⁇ m.
  • Examples of the solvent in the dispersion liquid containing one or more compounds selected from the group consisting of Zn, Zr, Hf, and Ti include ion-exchanged water.
  • the dispersion used in the step (a) can be obtained, for example, by adding one or more compounds selected from the group consisting of compounds of Zn, Zr, Hf, and Ti to ion exchange water.
  • the divalent and trivalent metal element chlorides and divalent and trivalent metal element nitrates used in step (a) are used to control the solubility and precipitation rate of the magnesium hydroxide particles of the present invention.
  • 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 divalent and trivalent metal element chlorides and the divalent and trivalent metal element nitrates preferably have a D 50 of 0.1 to 100 ⁇ m, preferably 0.5 to 50 ⁇ m. More preferred.
  • the organic acid is added to suppress the solubility of the partially hydrated acicular magnesium oxide 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.
  • Step (b) is a step of mixing the reaction solution for hydration obtained in step (a) and partially hydrated acicular magnesium oxide particles.
  • the partially hydrated acicular magnesium oxide particles used in the step (b) have a volume cumulative 50% particle diameter (D 50 ) of 0.1 to 10 ⁇ m by laser diffraction scattering type particle size distribution measurement, and a specific surface area. 1.0 to 20.0 m 2 / g, Ig-loss is 2.0 to 25.0%, part of the surface is acicular magnesium oxide hydrated, ie partially hydrated It is acicular magnesium oxide.
  • the hydration rate is fast. Becomes too coarse and becomes agglomerated particles. Further, a D 50 of greater than 10 [mu] m, fully hydrated reaction particles containing magnesium oxide is left not proceed. D 50 is preferably 0.1 to 5.0 ⁇ m.
  • the specific surface area of the partially hydrated acicular magnesium oxide particles used in the step (b) exceeds 20.0 m 2 / g, the hydration rate becomes too fast, resulting in coarse aggregated particles.
  • the specific surface area is less than 1.0 m 2 / g, the hydration reaction does not proceed sufficiently and particles containing magnesium oxide remain.
  • the specific surface area is preferably 2.0 to 18.0 m 2 / g, and more preferably 3.0 to 15.0 m 2 / g.
  • Ig-loss (loss on ignition) showing the total of the moisture content of the partially hydrated acicular magnesium oxide particles used in the step (b) and the moisture content in the hydrate structure is 2.0-25.0% (Mass conversion). That is, Ig-loss indicates the degree of hydration in the partially hydrated acicular magnesium oxide particles in the present invention.
  • the Ig-loss is preferably 2.0 to 20.0%, and preferably 3.0 to 18. More preferably, it is 0%. In the present invention, Ig-loss is determined by measuring partially hydrated acicular magnesium oxide particles after firing at 1000 ° C. for 3600 seconds.
  • the partially hydrated acicular magnesium oxide used in such a step (b) has a volume cumulative 50% particle diameter (D 50 ) of 0.1 to 10 ⁇ m by laser diffraction scattering type particle size distribution measurement, Acicular magnesium oxide particles having a surface area of 1.0-15.0 m 2 / g are obtained by placing them in a thermo-hygrostat at a temperature of 40-95 ° C. and a humidity of 60-95% for 0.5-24 hours. be able to.
  • the Ig-loss of acicular magnesium oxide as a raw material is 0.1 to 1.0%, and the Ig-loss can be increased by increasing the temperature and time placed in the thermo-hygrostat.
  • the D 50 of acicular magnesium oxide used as a raw material for the partially hydrated acicular magnesium oxide used in step (b) is preferably 0.1 to 5.0 ⁇ m.
  • the specific surface area of acicular magnesium oxide, which is a raw material for partially hydrated acicular magnesium oxide prepared in step (b), is preferably 2.0 to 15.0 m 2 / g, 3.0 More preferably, it is ⁇ 15.0 m 2 / g.
  • acicular carbonate prepared by reacting magnesium sulfate and sodium carbonate. Magnesium can be purified and calcined at 1200 ° C.
  • the amount of each component contained in the partially hydrated acicular magnesium oxide used in the step (b) and the dispersion is as follows.
  • the amount of one or more compounds selected from the group consisting of compounds of Zn, Zr, Hf, and Ti is 0.1 to 5.0 mass in terms of metal element with respect to partially hydrated acicular magnesium oxide particles. %.
  • 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 rod-like particle in which the scaly primary particles are aggregated but a hexagonal plate-like particle.
  • the scaly primary particles as in the present invention are not aggregated rod-like particles. Hexagonal columnar particles.
  • the amount of one or more compounds selected from the group consisting of compounds of Zn, Zr, Hf, and Ti is preferably 0.2 to 4.0% by mass with respect to the partially hydrated acicular magnesium oxide particles. More preferably, it is 0.3 to 3.0% by mass.
  • 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 based on partially hydrated acicular magnesium oxide particles. And 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 based on partially hydrated acicular magnesium oxide particles. In terms of metal element, it is preferably 0.2 to 4.0% by mass, and more preferably 0.3 to 3.0% by mass.
  • the amount of organic acid added is 0.01 to 3.0 mol with respect to 100 g of partially hydrated acicular magnesium oxide particles. 2. When the amount of organic acid added is less than 0.01 mol with respect to 100 g of partially hydrated acicular magnesium oxide particles, the rate of crystal precipitation becomes slow, resulting in monodispersed hexagonal plate or hexagonal columnar particles. If it is larger than 0 mol, the precipitation rate of crystals becomes too fast, resulting in coarse aggregated particles.
  • the amount of the organic acid added is preferably 0.01 to 2.0 mol with respect to 100 g of partially hydrated acicular magnesium oxide.
  • the concentration of the partially hydrated acicular magnesium oxide in the mixed solution is preferably 20 to 200 g / L, more preferably 50 to 180 g / L, and still more preferably 50 to 150 g / L. L. That is, the amount of partially hydrated acicular magnesium oxide in the reaction solution obtained in step (a) is preferably 20 to 200 g / L, more preferably 50 to 180 g / L, and still more preferably 50 to 150 g / L. adjust. If the concentration of partially hydrated acicular magnesium oxide in such a reaction solution is sufficient, 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, rod-shaped 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 excessively dispersed at the time of nucleation to form mono-dispersed hexagonal plate or hexagonal columnar magnesium hydroxide particles, and the magnesium hydroxide as in the present invention. Particles cannot be obtained.
  • the apparatus for stirring is not particularly limited as long as the above peripheral speed is satisfied, and examples thereof 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 to 360 minutes, preferably 20 to 200 minutes.
  • Step (d) is a step of stirring to obtain a magnesium hydroxide slurry at a temperature of 30 to 100 ° C.
  • the hydration reaction of the unreacted partially hydrated acicular magnesium oxide can be promoted to obtain magnesium hydroxide.
  • 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 subjecting the magnesium hydroxide particles of the present invention or the magnesium hydroxide particles obtained by the production method including the steps (a) to (e) of the present invention to 500 to 1400 in an air atmosphere. It is obtained by a method including a step of baking at 0 ° C.
  • the firing of the magnesium hydroxide particles can be performed by firing using an electric furnace or the like.
  • the firing can be achieved by a firing method including a step of raising the temperature to a firing temperature at a predetermined rate of temperature rise and a step of holding at the firing temperature for a predetermined time.
  • the rate of temperature rise is preferably 1 to 20 ° C./min, more preferably 3 to 10 ° C./min.
  • the firing temperature is 500 to 1400 ° C., preferably 600 to 1300 ° C.
  • the firing time which is the time for holding at the firing temperature, is preferably from 0.1 to 5 hours, more preferably from 0.1 to 3 hours.
  • the firing temperature is less than 500 ° C., the amount of heat is insufficient and magnesium hydroxide remains.
  • the firing temperature exceeds 1400 ° C., magnesium oxide grows and does not become rod-shaped magnesium oxide.
  • the shape of the primary particles of magnesium hydroxide particles and magnesium oxide particles obtained by the production method of the present invention is preferably scaly and is the same as the scaly example of FIG.
  • the scaly primary particles of the present invention have a thickness in the range of 0.01 to 0.1 ⁇ m, preferably 0.01 to 0.05 ⁇ m, and the diameter of the circumscribed circle of the surface is 0.2 to 5 ⁇ m, preferably 0. The range is from 5 to 2.5 ⁇ m. More preferably, by the production method of the present invention, rod-shaped magnesium hydroxide particles and magnesium oxide particles in which the flaky primary particles of the present invention are aggregated are obtained.
  • Element mass measurement method Element to be measured in particle (Ag, Al, B, Ba, Bi, Ca, Cd, Co, Cr, Cu, Fe, Ga, Hf, In, K, Li, Mg , Mn, Mo, Na, Ni, P, Pb, Si, Sr, Ti, Tl, V, Zn, and Zr) using an ICP emission analyzer (trade name: SPS-5100, manufactured by Seiko Instruments Inc.) After dissolving the sample in acid, the mass was measured. Using a spectrophotometer (trade name: UV-2550, Shimadzu Corporation), Cl was dissolved in an acid and then mass was measured.
  • ICP emission analyzer trade name: SPS-5100, manufactured by Seiko Instruments Inc.
  • Example 1 Acicular magnesium carbonate prepared by reacting a magnesium sulfate solution and sodium carbonate was fired at a firing temperature of 1200 ° C., and the 50% particle diameter (D 50 ) was 1.12 ⁇ m and the specific surface area was 10 magnesium oxide is .64m 2 / g, the temperature 80 ° C., placed 3 hours in a constant-temperature constant-humidity cabin humidity of 90% of the surface by partially hydrated, specific surface area of 13.46m 2 / g, Ig A partially hydrated acicular magnesium oxide having a loss of 9.08% was obtained.
  • reaction solution was prepared by adding 0.02 mol of propionic acid to 100 g of 100% aluminum chloride hexahydrate and 100 g of partially hydrated acicular magnesium oxide. The temperature of the prepared reaction solution was raised to 60 ° C., and 100 g of magnesium oxide whose surface was partially hydrated was added to obtain a mixed solution.
  • the temperature of the reaction liquid was raised to 95 ° C., and the peripheral speed was adjusted to 9.1 m / s with a stirrer (TK homodisper manufactured by PRIMIX Co., Ltd.) and reacted for 1 hour. Thereafter, a 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 rod-shaped magnesium hydroxide particles of the present invention.
  • TK homodisper manufactured by PRIMIX Co., Ltd.
  • Example 2 It carried out like Example 1 except having used aluminum sulfate instead of aluminum chloride.
  • Example 3 Acicular magnesium oxide is placed in a constant temperature and humidity machine at a temperature of 60 ° C. and a humidity of 90% for 12 hours to partially hydrate the surface, the specific surface area is 10.18 m 2 / g, and the Ig-loss is 21.42%. The procedure was the same as in Example 1 except that.
  • Example 4 Magnesium hydroxide produced in Example 1 was baked in an air atmosphere at 600 ° C. for 1 hour to obtain magnesium oxide particles.
  • Example 5 Magnesium hydroxide produced in Example 1 was baked at 800 ° C. for 1 hour in an air atmosphere to obtain magnesium oxide particles.
  • Example 6 The magnesium hydroxide produced in Example 1 was baked at 1000 ° C. for 1 hour in an air atmosphere to obtain magnesium oxide particles.
  • Example 7 The same procedure as in Example 1 was performed except that propionic acid was changed to acetic acid.
  • Example 8 The same procedure as in Example 1 was performed except that propionic acid was changed to butyric acid.
  • Example 1 The same procedure as in Example 1 was performed except that non-acicular magnesium oxide having a 50% particle size of 1.19 ⁇ m and a specific surface area of 10.82 m 2 / g was used. The Ig-loss of the raw material magnesium oxide was 0.78%.
  • Example 2 The same operation as in Example 1 was performed except that the surface of magnesium oxide was used without being partially hydrated.
  • Example 3 Example 1 except that acicular magnesium oxide was placed in a thermo-hygrostat at a temperature of 80 ° C. and a humidity of 90% for 12 hours, the specific surface area was 8.09 m 2 / g, and the Ig-loss was 26.78%. As well as.
  • [Comparative Example 4] Acicular magnesium oxide is placed in a thermostat at a temperature of 60 ° C. and a humidity of 90% for 3 hours, the specific surface area is 12.41 m 2 / g, the Ig-loss is 11.5%, and the firing temperature is 1500 ° C. The same procedure as in Example 4 was performed except that.
  • Table 1 shows the measurement results regarding the magnesium hydroxide particles and the magnesium oxide particles obtained in the above examples and comparative examples.
  • the magnesium hydroxide particles and the magnesium oxide particles of the present invention are rod-like aggregates of scale-like primary particles, and the 50% particle diameter (D 50 ) is 1.0 to 10
  • the specific surface area was 10 m 2 / g or more.
  • D is a 90 / D 10 is 10 or less, it was confirmed that superior dispersibility.
  • the particles were spherical magnesium hydroxide particles.
  • the magnesium hydroxide particles of Comparative Example 2 had a specific surface area of 8.26 m 2 / g.
  • the magnesium hydroxide particles of Comparative Example 3 were indeterminate in which aggregates of various shapes were mixed, and the specific surface area was 7.45 m 2 / g. Further, the magnesium oxide particles of Comparative Example 4 lost their shape and became irregular when the scale-like magnesium hydroxide was converted to magnesium oxide, and the specific surface area was 6.87 m 2 / g.
  • the method for producing magnesium hydroxide and magnesium oxide of the present invention can easily control the specific surface area by simply hydrating the raw material magnesium oxide with a thermo-hygrostat, etc. Can be manufactured.
  • Magnesium hydroxide particles and magnesium oxide particles of the present invention are rod-shaped, have a small 50% particle size, are uniform, have good dispersibility, and have a high specific surface area, so they are highly useful in various fields. Moreover, since the manufacturing method of this invention can prepare the above magnesium hydroxide and magnesium oxide particle
  • Magnesium hydroxide particles of the present invention include inkjet paper coating agents, flame retardants, heat storage materials, catalysts and electronic materials, etc. Magnesium oxide particles are used as optical materials, inkjet paper coating agents, catalysts and electronic materials. It can be used for applications such as materials.

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PCT/JP2014/053108 2013-02-13 2014-02-12 高い比表面積を有する棒状の水酸化マグネシウム粒子、及び棒状の酸化マグネシウム粒子、並びにそれらの製造方法 WO2014126075A1 (ja)

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US11912847B2 (en) * 2019-03-29 2024-02-27 Tateho Chemical Industries Co., Ltd Spherical magnesium oxide, manufacturing method thereof, thermal conductive filler and resin composition
CN110498435B (zh) * 2019-09-29 2021-08-31 北京镁德百世科技有限公司 一种纯化氢氧化镁的方法和从镁空气电池中回收氢氧化镁并由此制备氧化镁的方法
CN112320825B (zh) * 2020-10-26 2023-02-03 安徽景成新材料有限公司 一种固相法制备纳米氧化镁的方法
CN113980490A (zh) * 2021-11-16 2022-01-28 江西广源化工有限责任公司 一种高比表面积氢氧化镁及其制备方法和应用
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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