WO2023063413A1 - 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 - Google Patents

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 Download PDF

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WO2023063413A1
WO2023063413A1 PCT/JP2022/038352 JP2022038352W WO2023063413A1 WO 2023063413 A1 WO2023063413 A1 WO 2023063413A1 JP 2022038352 W JP2022038352 W JP 2022038352W WO 2023063413 A1 WO2023063413 A1 WO 2023063413A1
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spherical magnesium
magnesium oxide
spherical
ppm
elements belonging
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French (fr)
Japanese (ja)
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彰範 齋藤
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Tateho Chemical Industries Co Ltd
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Priority to JP2023554645A priority Critical patent/JPWO2023063413A1/ja
Priority to US18/701,555 priority patent/US20250026658A1/en
Priority to CN202280069132.2A priority patent/CN118103330A/zh
Priority to KR1020247011253A priority patent/KR20240087797A/ko
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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
    • 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
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/16—Solid spheres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/02—Compounds of alkaline earth metals or magnesium
    • C09C1/028—Compounds containing only magnesium as metal
    • 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
    • C01P2004/30—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
    • C01P2004/51—Particles with a specific particle size distribution
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2217—Oxides; Hydroxides of metals of magnesium
    • C08K2003/222—Magnesia, i.e. magnesium oxide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/003—Additives being defined by their diameter
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/005—Additives being defined by their particle size in general
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/006—Additives being defined by their surface area

Definitions

  • the present invention relates to spherical magnesium oxide having high sphericity and excellent moisture resistance, a method for producing the same, a resin filler containing the spherical magnesium oxide, and a resin composition containing the same.
  • Magnesium oxide has excellent electrical insulation, thermal conductivity, heat resistance, etc., and is used as a raw material for refractories, insulation for heaters, abrasives, vulcanization accelerators for rubber, pigments for paints and inks, and other industrial materials. Used for various purposes. It is also used as a resin filler for the purpose of imparting properties such as heat resistance to resins.
  • magnesium oxide is used for the purpose of imparting gas barrier properties to resin films used for packaging of foods and the like.
  • magnesium oxide is used as a white pigment added to resin.
  • Patent Document 3 magnesium oxide is used for the purpose of improving the light resistance of resin.
  • magnesium oxide is used for the purpose of improving the thermal conductivity of epoxy resin.
  • magnesium oxide when compounded in resin, magnesium oxide is highly hygroscopic, and when hydrated with moisture in the atmosphere, problems such as cracks due to volume expansion of the filler occur. However, there is a demand for magnesium oxide that does not cause the above problems and has excellent moisture resistance. In addition, when magnesium oxide is used as a resin filler, it is required to have high fillability in resin compositions in order to obtain excellent performance.
  • Patent Document 5 proposes spherical magnesium oxide having a smooth surface and being dense, which is obtained by adding a lithium compound.
  • Patent Literature 6 proposes spherical magnesium oxide having a smooth surface and excellent moisture resistance and filling properties, which is obtained by adjusting the contents of boron and iron within a certain range.
  • Patent Document 7 proposes spherical magnesium oxide obtained by adjusting the content of boron and lithium within a certain range and having excellent moisture resistance and fluidity of the resin composition when filled in a resin.
  • JP 2015-131494 A JP 2015-101614 A JP 2009-227725 A JP 2017-186578 A JP 2016-088838 A JP 2018-131378 A WO2020/203710
  • the spherical magnesium oxide obtained by the above-described method has improved moisture resistance and resin filling properties, it is necessary to control the boron content and lithium content.
  • the properties of magnesium oxide (insulation, heat resistance, thermal conductivity) are reduced, and these elements are easily eluted into the resin. There was a problem that the performance was adversely affected.
  • lithium when lithium is contained in magnesium oxide, it adversely affects the fluidity of the resin composition when it is filled in a resin, so it is desirable that the content of lithium is small.
  • an object of the present invention is to provide a spherical magnesium oxide that has high sphericity, excellent moisture resistance, and excellent fillability in a resin, even if it does not contain a certain amount of boron or lithium, and a method for producing the same.
  • the present inventors have made various studies and found that elements belonging to the third to fourth periods of the periodic table (excluding elements belonging to groups 2 and 18) By adjusting the content of, it was found that spherical magnesium oxide having high sphericity, excellent moisture resistance and excellent fillability in resin can be obtained without containing a certain amount of boron or lithium.
  • adjusting the content of yttrium also increases the sphericity, They have found that it is effective in obtaining spherical magnesium oxide that is excellent in moisture resistance and resin filling.
  • the total content of elements belonging to periods 3 to 4 of the periodic table (excluding elements belonging to groups 2 and 18) and yttrium is 500 to 12,000 ppm, Spherical magnesium oxide having a volume-based cumulative 50% particle diameter (D 50 ) in the range of 1 to 200 ⁇ m as determined by laser diffraction scattering particle size distribution measurement and a sphericity of 1.00 to 1.20 read from the SEM photograph. be.
  • the total content of elements belonging to periods 3 to 4 of the periodic table (excluding elements belonging to groups 2 and 18) is 500 to 12,000 ppm, and laser diffraction It is a spherical magnesium oxide having a volume-based cumulative 50% particle diameter (D 50 ) in the range of 1 to 200 ⁇ m by scattering particle size distribution measurement and a sphericity of 1.00 to 1.20 read from a SEM photograph.
  • D 50 volume-based cumulative 50% particle diameter
  • the present invention also resides in a resin filler containing the spherical magnesium oxide.
  • the present invention also resides in a resin composition containing the above resin filler.
  • the present invention 1) A step of reacting an aqueous magnesium salt solution and an aqueous carbonate solution, and then aggregating the produced magnesium carbonate to obtain a spherical magnesium carbonate slurry; 2) filtering, washing and drying the spherical magnesium carbonate slurry to obtain spherical magnesium carbonate particles; 3) calcining the spherical magnesium carbonate particles to obtain spherical magnesium oxide; and in at least one or more steps of 1) to 3) above, an element belonging to the 3rd to 4th periods of the periodic table in the spherical magnesium oxide after sintering (however, elements belonging to groups 2 and 18 ) and elements belonging to Periods 3 to 4 of the periodic table (excluding elements belonging to Groups 2 and 18) and yttrium so that the total content of yttrium is 500 to 12,000 ppm
  • a method for producing spherical magnesium oxide characterized by adjusting the amount of
  • the present invention 1) A step of reacting an aqueous magnesium salt solution and an aqueous carbonate solution, and then aggregating the produced magnesium carbonate to obtain a spherical magnesium carbonate slurry; 2) filtering, washing and drying the spherical magnesium carbonate slurry to obtain spherical magnesium carbonate particles; 3) calcining the spherical magnesium carbonate particles to obtain spherical magnesium oxide; and in at least one or more steps of 1) to 3) above, an element belonging to the 3rd to 4th periods of the periodic table in the spherical magnesium oxide after sintering (however, elements belonging to groups 2 and 18 The amount of elements belonging to the 3rd to 4th periods of the periodic table (excluding elements belonging to groups 2 and 18) is adjusted so that the total content of 500 to 12,000 ppm
  • a method for producing spherical magnesium oxide characterized by:
  • the present invention it is possible to provide spherical magnesium oxide with high sphericity, excellent moisture resistance, and excellent fillability in resin, and a method for producing the same.
  • FIG. 1 shows an SEM photograph of spherical magnesium oxide of Example 1.
  • the spherical magnesium oxide of the present invention has a total content of elements belonging to Periods 3 to 4 of the periodic table (excluding elements belonging to Groups 2 and 18) and yttrium of 500 to 12,000 ppm.
  • the volume-based cumulative 50% particle diameter (D 50 ) measured by laser diffraction scattering particle size distribution measurement is in the range of 1 to 200 ⁇ m, and the sphericity read from the SEM photograph is 1.00 to 1.20.
  • the spherical magnesium oxide of the present invention has a total content of elements belonging to Periods 3 to 4 of the periodic table (excluding elements belonging to Groups 2 and 18) of 500 to 12,000 ppm.
  • the volume-based cumulative 50% particle diameter (D 50 ) measured by laser diffraction scattering particle size distribution measurement is in the range of 1 to 200 ⁇ m, and the sphericity read from the SEM photograph is 1.00 to 1.20.
  • ppm in the specification means mass ppm unless otherwise specified.
  • the volume-based cumulative 50% particle diameter (D 50 ) measured by laser diffraction scattering particle size distribution measurement is in the range of 1 to 200 ⁇ m, and the sphericity read from the SEM photograph is 1.00 to 1.20, which is high.
  • Spherical magnesium oxide having excellent moisture resistance can be obtained.
  • the spherical magnesium oxide of the present invention has such a high degree of sphericity that it is excellent in fillability into resins.
  • the total content of elements belonging to the third to fourth periods of the periodic table (excluding elements belonging to groups 2 and 18) is controlled to 500 to 12,000 ppm. Therefore, the volume-based cumulative 50% particle diameter (D 50 ) by laser diffraction scattering particle size distribution measurement is in the range of 1 to 200 ⁇ m, and the sphericity read from the SEM photograph is 1.00 to 1.20. Spherical magnesium oxide with high moisture resistance is obtained.
  • the spherical magnesium oxide of the present invention has such a high degree of sphericity that it is excellent in fillability into resins.
  • the elements belonging to Period 3 to Period 4 of the periodic table specifically include sodium, aluminum, silicon, phosphorus, sulfur, and chlorine. , potassium, scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, gallium, germanium, arsenic, selenium, bromine.
  • it is preferably at least one selected from the group consisting of sodium, aluminum, silicon, phosphorus, chlorine, potassium and titanium, and at least one selected from the group consisting of aluminum, silicon, phosphorus and titanium. is more preferable.
  • At least one selected from the group consisting of aluminum, silicon and titanium is also preferred.
  • the total content of elements belonging to periods 3 to 4 of the periodic table is 500 to 12,000 ppm, preferably 500 to 10,000 ppm, more preferably 500 to 8,000 ppm. If the total content is less than 500 ppm, spherical magnesium oxide having excellent moisture resistance, high sphericity and a smooth surface cannot be obtained. If the total content is more than 12,000 ppm, excessive growth of particles and sticking between particles tend to occur, so that spherical magnesium oxide with high sphericity cannot be obtained.
  • the spherical magnesium oxide of the present invention includes, for example, sodium, aluminum, silicon, phosphorus, sulfur, chlorine, potassium, scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, gallium, germanium, arsenic,
  • the total content of selenium, bromine, and yttrium is adjusted to a predetermined amount (eg, 500-12,000 ppm, preferably 500-10,000 ppm, more preferably 500-8,000 ppm).
  • a predetermined amount eg, 500-12,000 ppm, preferably 500-10,000 ppm, more preferably 500-8,000 ppm.
  • the spherical magnesium oxide of the present invention it is also preferable to adjust the total content of aluminum, silicon, phosphorus, manganese, titanium and yttrium to the above predetermined amount. Further, for example, in the spherical magnesium oxide of the present invention, the total content of aluminum, silicon, phosphorus, manganese, and titanium may be adjusted to the above predetermined amount, or the total content of aluminum, silicon, and titanium may be adjusted to the above-mentioned You may adjust to a predetermined amount.
  • the spherical magnesium oxide of the present invention includes, for example, sodium, aluminum, silicon, phosphorus, sulfur, chlorine, potassium, scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, gallium, germanium, arsenic, At least one selected from the group consisting of selenium, bromine, and yttrium can be contained in a predetermined amount (for example, 500 to 12,000 ppm, preferably 500 to 10,000 ppm, more preferably 500 to 8,000 ppm).
  • a predetermined amount for example, 500 to 12,000 ppm, preferably 500 to 10,000 ppm, more preferably 500 to 8,000 ppm.
  • the spherical magnesium oxide of the present invention preferably contains at least one selected from the group consisting of aluminum, silicon, phosphorus, manganese, titanium, and yttrium in the predetermined amount.
  • the spherical magnesium oxide of the present invention may contain at least one selected from the group consisting of aluminum, silicon, phosphorus, manganese, and titanium in the predetermined amount, or may contain aluminum, silicon, and At least one kind selected from the group consisting of titanium may be contained in the predetermined amount.
  • the boron content can be extremely low.
  • the content of boron can be for example less than 10 ppm, preferably less than 9 ppm, more preferably less than 8 ppm.
  • the content of lithium can be for example less than 15 ppm, preferably less than 10 ppm, more preferably less than 5 ppm.
  • the calcium content is, for example, preferably less than 700 ppm, preferably less than 600 ppm, and more preferably less than 500 ppm.
  • the content of calcium is 700 ppm or more, the moisture resistance tends to decrease, and it tends to be difficult to obtain spherical magnesium oxide with a high degree of sphericity.
  • the volume-based cumulative 50% particle diameter (D 50 ) measured by laser diffraction scattering particle size distribution measurement is in the range of 1 to 200 ⁇ m, preferably 5 to 100 ⁇ m, more preferably 10 to 50 ⁇ m. can. Further, for example, 10 to 150 ⁇ m is also a preferable range.
  • the sphericity that can be read from the SEM photograph, which affects the filling property into the resin is 1.00 to 1.20, preferably 1.00 to 1.15, more preferably 1.00 to 1.00. .10.
  • SEM scanning electron microscope
  • the BET specific surface area is, for example, 0.01 to 1.00 m 2 /g, preferably 0.05 to 0.80 m 2 /g, more preferably 0.10 to 0.60 m 2 /g. be.
  • the produced magnesium carbonate is aggregated to obtain a spherical magnesium carbonate slurry, 2) filtering, washing and drying the spherical magnesium carbonate slurry to obtain spherical magnesium carbonate particles; 3) The spherical magnesium carbonate particles are calcined in air to obtain the desired spherical magnesium oxide.
  • the total content of elements belonging to Periods 3 to 4 of the periodic table (excluding elements belonging to Groups 2 and 18) and yttrium in the spherical magnesium oxide after final firing is 500 to 12,000 ppm
  • the amount of elements belonging to the 3rd to 4th periods of the periodic table (excluding elements belonging to groups 2 and 18) is adjusted by adding or mixing.
  • the total content of elements belonging to Periods 3 to 4 of the periodic table (excluding elements belonging to Groups 2 and 18) and yttrium is adjusted by: a) magnesium salt aqueous solution and b) adding the compound containing the above element to the obtained spherical magnesium carbonate slurry; c) adding the compound containing the above element to the obtained spherical magnesium carbonate particles.
  • the content in the finally obtained spherical magnesium oxide is adjusted.
  • the produced magnesium carbonate is aggregated to obtain a spherical magnesium carbonate slurry, 2) filtering, washing and drying the spherical magnesium carbonate slurry to obtain spherical magnesium carbonate particles; 3) The spherical magnesium carbonate particles are calcined in air to obtain the desired spherical magnesium oxide.
  • the total content of elements belonging to Periods 3 to 4 of the periodic table (excluding elements belonging to Groups 2 and 18) in the spherical magnesium oxide after final firing was 500 by the time of final firing.
  • the amount of elements belonging to Periods 3 to 4 of the periodic table (excluding elements belonging to Groups 2 and 18) is adjusted by addition, mixing, or the like so that the concentration is up to 12,000 ppm.
  • the adjustment of the total content of elements belonging to periods 3 to 4 of the periodic table is performed by: a) magnesium salt aqueous solution and/or carbonate b) adding the compound containing the above element to the obtained spherical magnesium carbonate slurry; c) mixing the compound containing the above element with the obtained spherical magnesium carbonate particles; Etc. to adjust the content in the finally obtained spherical magnesium oxide.
  • the compound used for the above addition, mixing, etc. is not particularly limited as long as it is a compound containing an element belonging to the 3rd to 4th periods of the periodic table (excluding elements belonging to Groups 2 and 18). Available.
  • Yttrium is also not particularly limited as long as it is a compound containing yttrium.
  • the aluminum source is not particularly limited as long as it is a compound containing aluminum.
  • aluminum hydroxide, aluminum oxide, aluminum carbonate, aluminum chloride, aluminum nitrate, aluminum acetate, aluminum sulfate, etc. can be used.
  • the silicon source is not particularly limited as long as it is a compound containing silicon, but for example, silicon oxide, silicate, etc. can be used.
  • silicon oxide include crystalline silica, amorphous fumed silica, colloidal silica, and the like.
  • silicates include sodium silicate, magnesium silicate, potassium silicate, calcium silicate and the like.
  • the phosphorus source is not particularly limited as long as it is a compound containing phosphorus, but phosphoric acid, phosphates, etc. can be used, for example.
  • Phosphates include, for example, magnesium phosphate, sodium phosphate, potassium phosphate, and ammonium phosphate.
  • the chlorine source is not particularly limited as long as it is a compound containing chlorine, but examples include sodium chloride, magnesium chloride, potassium chloride, and calcium chloride.
  • the bromine source is not particularly limited as long as it is a compound containing bromine, but examples include sodium bromide, magnesium bromide, potassium bromide, and calcium bromide.
  • the sodium source is not particularly limited as long as it is a compound containing sodium, but examples include sodium chloride, sodium carbonate, sodium phosphate, sodium hydroxide, sodium nitrate, and the like.
  • the potassium source is not particularly limited as long as it is a compound containing potassium, but examples include potassium chloride, potassium carbonate, potassium phosphate, potassium hydroxide, and potassium nitrate.
  • the titanium source is not particularly limited as long as it is a compound containing titanium, and examples thereof include titanium oxide (anatase type, rutile type), titanium chloride, titanium hydroxide, titanium bromide, titanium fluoride, magnesium titanate, and the like. .
  • the manganese source is not particularly limited as long as it is a compound containing manganese, but examples include manganese dioxide, manganese hydroxide, manganese carbonate, manganese chloride and manganese nitrate.
  • the yttrium source is not particularly limited as long as it is a compound containing yttrium, and examples thereof include yttrium oxide, yttrium chloride and yttrium nitrate.
  • the boron content of the spherical magnesium oxide after final firing is not particularly limited.
  • Known processes can be used, such as performing treatments, adjusting temperature ramp profiles during firing, etc., or combinations thereof.
  • the content of each of the above elements can be controlled to be low by selecting raw materials that do not contain these elements and appropriately controlling the possibility of inclusion in the manufacturing process.
  • the magnesium salt in the magnesium salt aqueous solution is not particularly limited, but can be selected from, for example, magnesium chloride, magnesium nitrate, magnesium sulfate, magnesium acetate, and combinations thereof.
  • the carbonate in the carbonate aqueous solution is not particularly limited, but can be selected from, for example, sodium carbonate, potassium carbonate, ammonium carbonate, and combinations thereof.
  • the magnesium salt concentration of the magnesium salt aqueous solution is preferably 1 to 30% by mass, and the carbonate concentration of the carbonate aqueous solution is preferably 1 to 30% by mass.
  • the reaction between the magnesium salt aqueous solution and the carbonate aqueous solution should be carried out under conditions such that the ion concentration ratio of [Mg 2+ ]:[CO 3 2 ⁇ ] in the solution is 1.2:1 to 1:1.5. can be done.
  • an aqueous magnesium salt solution and an aqueous carbonate solution are allowed to react, and then the produced magnesium carbonate is aggregated to obtain a spherical magnesium carbonate slurry.
  • the magnesium carbonate produced by reacting the magnesium salt aqueous solution and the carbonate aqueous solution is heated to a temperature of, for example, 60 to 100° C. and held for 0.1 to 5 hours, and is subjected to laser diffraction scattering particle size distribution measurement. It can be appropriately aggregated into spheres having a volume-based cumulative 50% particle diameter (D 50 ) of 1 to 200 ⁇ m and a sphericity of 1.00 to 1.30.
  • D 50 volume-based cumulative 50% particle diameter
  • the spherically aggregated magnesium carbonate slurry is filtered, washed with water, and dried to form spherical magnesium carbonate particles, for example, by a common method in the technical field.
  • the magnesium carbonate particles obtained in the above production method may be anhydrous magnesium carbonate, normal magnesium carbonate, or basic magnesium carbonate, but basic magnesium carbonate is preferred.
  • the firing conditions of the spherical magnesium carbonate particles are not particularly limited as long as the magnesium carbonate is thermally decomposed into magnesium oxide. More preferably, it is particularly preferably from 1200°C to 1600°C. Although the firing time depends on the firing temperature, it is preferably 0.5 to 10 hours, for example. If the firing temperature is less than 1000° C., the particles are not sufficiently sintered, and if it exceeds 1800° C., the particles are sintered to form coarse agglomerates.
  • the spherical magnesium oxide of the present invention is characterized by having sufficient moisture resistance without surface treatment, but it can also be subjected to surface treatment using a known method for the purpose of further improving moisture resistance.
  • the surface treatment agent used for the surface treatment of the spherical magnesium oxide of the present invention is not particularly limited, but examples include colloidal silica, silane coupling agents, titania sol, titanate coupling agents, phosphorus compounds, alumina sol, and aluminate. zirconium-based coupling agents, zirconium-based coupling agents, and the like can be used.
  • silane-based coupling agents examples include vinyltrichlorosilane, vinyltrialkoxysilane, glycidoxypropyltrialkoxysilane, methacryloxypropylmethyldialkoxysilane, and the like.
  • Titanate-based coupling agents include, for example, tetraisopropyl titanate, tetra-normal-butyl titanate, tetraoctyl titanate, tetrastearyl titanate, isopropyl triisostearoyl titanate, tetraoctylbis(ditridecylphosphite) titanate, and bis(dioctylpyrophosphate). oxyacetate titanate and the like.
  • the phosphorus compound is not particularly limited as long as it can react with magnesium oxide to form a magnesium phosphate-based compound, but examples include phosphoric acid, phosphates, and acid phosphate esters. These may be used alone or in combination of two or more.
  • acidic phosphates include isopropyl acid phosphate, 2-ethylhexyl acid phosphate, oleyl acid phosphate, methyl acid phosphate, ethyl acid phosphate, propyl acid phosphate, butyl acid phosphate, lauryl acid phosphate, stearyl acid phosphate, and the like. .
  • aluminate-based coupling agents include aluminum isopropylate, monosec-butoxyaluminum diisopropylate, aluminum sec-butylate, aluminum ethylacetoacetate diisopropylate, aluminum tris(ethylacetoacetate), aluminum alkylacetoacetate diisopropylate. isopropylate and the like.
  • zirconium-based coupling agents examples include normal propyl zirconate and normal butyl zirconate.
  • the spherical magnesium oxide of the present invention has a high degree of sphericity, excellent moisture resistance, and excellent filling properties in resins, so it can be suitably blended into resins as a filler and is useful as a resin filler.
  • it can be suitably used as a thermally conductive filler, a heat resistant filler, a gas barrier filler, a light resistant filler, etc., and is particularly excellent as a thermally conductive filler.
  • thermosetting resins examples include thermosetting resins and thermoplastic resins.
  • the thermosetting resin is not particularly limited, but examples thereof include phenol resin, urea resin, melamine resin, alkyd resin, polyester resin, epoxy resin, diallyl phthalate resin, polyurethane resin, and silicone resin.
  • the thermoplastic resin is not particularly limited, for example, polyamide resin, polyacetal resin, polycarbonate resin, polybutylene terephthalate resin, polyolefin resin, polysulfone resin, polyamideimide resin, polyetherimide resin, polyarylate resin, polyphenylene sulfide resin, Polyether ether ketone resin, fluororesin, or liquid crystal polymer can be used.
  • the amount of spherical magnesium oxide compounded in the resin composition of the present invention is not particularly limited, and may be appropriately determined according to the properties required of the resin composition.
  • spherical magnesium oxide may be used in the range of 0.1 to 100 parts by mass with respect to 100 parts by mass of resin.
  • the resin composition containing spherical magnesium oxide of the present invention can be used in various fields depending on the properties of the resin.
  • ⁇ Measurement method/evaluation method> (1) Method for measuring elemental content The elemental content was measured by ICP emission spectrometry. After the measurement sample was completely dissolved in acid, the content of each element was measured using an ICP measurement device (PS3520 VDD, manufactured by Hitachi High-Tech Science Co., Ltd.). In Tables 1 and 2 below, when the content of each element is below the detection limit, it is indicated as ⁇ 1 ppm as a trace amount.
  • BET method gas adsorption method
  • Macsorb manufactured by Mounttech Co. Ltd.
  • Humidity resistance evaluation by constant temperature and humidity test The humidity resistance of spherical magnesium oxide was evaluated by the mass increase rate by a constant temperature and humidity test.
  • THN040FA manufactured by Advantech Toyo Co., Ltd. was used as a constant temperature and humidity machine. 10 g of spherical magnesium oxide was exposed to an environment of 85° C. and 85% RH for 168 hours using a constant temperature and humidity machine, and then the mass increase rate was determined.
  • Example 1 Magnesium nitrate hexahydrate (manufactured by Kanto Kagaku Co., Ltd., special grade) was dissolved in ion-exchanged water to prepare an approximately 20% by mass magnesium nitrate aqueous solution. Potassium carbonate (manufactured by Kanto Kagaku Co., Ltd., special grade) was dissolved in ion-exchanged water to prepare a potassium carbonate aqueous solution of about 15% by mass. An aqueous magnesium nitrate solution and an aqueous potassium carbonate solution were reacted to synthesize magnesium carbonate such that the ion concentration ratio of [Mg 2+ ]:[CO 3 2 ⁇ ] was 1 : 1.
  • the magnesium carbonate slurry was heated to 90° C. and held for 1 hour to prepare a slurry of spherical magnesium carbonate.
  • Silicon dioxide manufactured by Kanto Kagaku Co., Ltd., special grade
  • the obtained spherical magnesium carbonate particles were calcined at 1500° C. for 1 hour using an electric furnace to obtain spherical magnesium oxide particles.
  • the particle diameter (D 50 ) of the spherical magnesium carbonate particles before firing was 20.5 ⁇ m, and the sphericity was 1.12.
  • Example 2 Spherical magnesium oxide was obtained in the same manner as in Example 1, except that silicon dioxide (manufactured by Kanto Kagaku Co., Ltd., special grade) was added so that the silicon content in the finally obtained spherical magnesium oxide was 5,000 ppm. Obtained.
  • the particle diameter (D 50 ) of the spherical magnesium carbonate particles before firing was 20.3 ⁇ m, and the sphericity was 1.12.
  • Example 3> Instead of adding silicon dioxide, aluminum oxide (Kanto Kagaku Co., Ltd. special grade) was added so that the aluminum content in the finally obtained spherical magnesium oxide was 2,500 ppm. Spherical magnesium oxide was obtained by a similar method.
  • the particle diameter (D 50 ) of the spherical magnesium carbonate particles before firing was 20.2 ⁇ m, and the sphericity was 1.13.
  • Example 4 Instead of adding silicon dioxide, titanium oxide (manufactured by Kanto Chemical Co., Ltd., anatase type deer 1st grade) was added so that the titanium content in the finally obtained spherical magnesium oxide was 7,500 ppm. Spherical magnesium oxide was obtained in the same manner as in Example 1. The particle diameter (D 50 ) of the spherical magnesium carbonate particles before firing was 20.5 ⁇ m, and the sphericity was 1.13.
  • the spherical magnesium oxide of Examples 1 to 4 had high sphericity and excellent moisture resistance.
  • the spherical magnesium oxide of the comparative example was inferior in both sphericity and humidity resistance.
  • spherical magnesium oxide of Examples 5-9 was obtained as follows, and measurements and evaluations were carried out in the same manner as in Examples 1-4 and Comparative Example 1.
  • Example 5 Silicon dioxide (manufactured by Kanto Kagaku Co., Ltd., special grade) was added so that the silicon content in the finally obtained spherical magnesium oxide was 700 ppm, and the firing temperature was set to 1600 ° C. The same procedure as in Example 1 was performed. A spherical magnesium oxide was obtained by the method.
  • Example 6 Silicon dioxide (manufactured by Kanto Kagaku Co., Ltd., special grade) was added so that the silicon content in the finally obtained spherical magnesium oxide was 11,500 ppm, and the firing temperature was 1600 ° C., except that Example 1 was used. Spherical magnesium oxide was obtained by a similar method.
  • Example 7 Instead of adding silicon dioxide, sodium tripolyphosphate (Deka 1st grade manufactured by Kanto Chemical Co., Ltd.) was added so that the phosphorus content in the finally obtained spherical magnesium oxide was 1,200 ppm, and the firing temperature was adjusted. Spherical magnesium oxide was obtained in the same manner as in Example 1, except that the temperature was set at 1600°C.
  • sodium tripolyphosphate (Deka 1st grade manufactured by Kanto Chemical Co., Ltd.) was added so that the phosphorus content in the finally obtained spherical magnesium oxide was 1,200 ppm, and the firing temperature was adjusted.
  • Spherical magnesium oxide was obtained in the same manner as in Example 1, except that the temperature was set at 1600°C.
  • Example 8> Instead of adding silicon dioxide, manganese chloride tetrahydrate (manufactured by Kanto Chemical Co., Ltd., special grade) is added so that the manganese content in the finally obtained spherical magnesium oxide is 9,000 ppm, and the firing temperature is Spherical magnesium oxide was obtained in the same manner as in Example 1, except that the temperature was changed to 1600°C.
  • manganese chloride tetrahydrate manufactured by Kanto Chemical Co., Ltd., special grade
  • Example 9> Instead of adding silicon dioxide, yttrium nitrate hexahydrate (high-purity reagent manufactured by Kanto Chemical Co., Ltd.) is added so that the yttrium content in the finally obtained spherical magnesium oxide is 4,500 ppm, and Spherical magnesium oxide was obtained in the same manner as in Example 1, except that the firing temperature was 1600°C.
  • yttrium nitrate hexahydrate high-purity reagent manufactured by Kanto Chemical Co., Ltd.
  • the spherical magnesium oxide of Examples 5 to 9 had high sphericity and excellent moisture resistance.
  • the spherical magnesium oxide of the present invention has high sphericity and excellent moisture resistance. Therefore, it was found that the spherical magnesium oxide of the present invention is useful as an excellent resin filler.
  • the spherical magnesium oxide of the present invention has high sphericity and excellent moisture resistance, and is therefore useful as an excellent resin filler.

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