WO2020145342A1 - Particules de spinelle, leur procédé de production, composition de résine, article moulé, composition, feuille crue, article cuit et substrat vitrocéramique - Google Patents

Particules de spinelle, leur procédé de production, composition de résine, article moulé, composition, feuille crue, article cuit et substrat vitrocéramique Download PDF

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WO2020145342A1
WO2020145342A1 PCT/JP2020/000438 JP2020000438W WO2020145342A1 WO 2020145342 A1 WO2020145342 A1 WO 2020145342A1 JP 2020000438 W JP2020000438 W JP 2020000438W WO 2020145342 A1 WO2020145342 A1 WO 2020145342A1
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particles
less
mass
spinel particles
spinel
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PCT/JP2020/000438
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Japanese (ja)
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新吾 高田
建軍 袁
一男 糸谷
義之 佐野
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Dic株式会社
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Priority to JP2020565199A priority Critical patent/JPWO2020145342A1/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
    • C01F7/00—Compounds of aluminium
    • C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
    • C01F7/16—Preparation of alkaline-earth metal aluminates or magnesium aluminates; Aluminium oxide or hydroxide therefrom
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G39/00—Compounds of molybdenum
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/44—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on aluminates
    • C04B35/443—Magnesium aluminate spinel
    • 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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds

Definitions

  • the present invention relates to spinel particles, a method for producing the same, a resin composition, a molded product, a composition, a green sheet, a fired product, and a glass ceramic substrate.
  • Low temperature co-fired ceramics are generally glass powders (eg CaO-Al 2 O 3 -SiO 2 -B 2 O 3 ) with several 10% (30%) of Al 2 O 3 filler. It is a ceramic that is made of Ag or Cu having a low conductor resistance as the inner layer conductor, and can be fired at a temperature lower than the melting point of these conductor metals (1000°C or less).
  • the permittivity relative permittivity
  • Q value or dielectric loss tangent bending strength
  • thermal conductivity thermal expansion coefficient of mobile phones and in-vehicle millimeter-wave radar, WiGig, VR/head mount displays, etc.
  • LTCC substrates There is a demand for LTCC substrates with excellent physical properties.
  • crushed alumina is mentioned as a filler mainly used for LTCC substrates.
  • examples of the inorganic particles having a low dielectric loss tangent include a mixed oxide spinel of a metal element represented by MgAl 2 O 4 and having a general formula AB 2 X 4 .
  • spinel particles have been applied to applications such as fluorescent luminescent materials, catalyst carriers, adsorbents, photocatalysts, and heat-resistant insulating materials in view of their porous structure and easiness of modification.
  • Patent Document 1 discloses an insulating ceramic composition containing spinel particles.
  • the dielectric loss tangent peculiar to alumina is as high as 10 -3, and since it is made by crushing the filler, it has a wide particle size distribution and is an amorphous particle, so that a green sheet is produced. It is difficult to obtain an LTCC substrate that has both high thermal conductivity and low dielectric loss tangent, as well as impairing processability at the time.
  • spinel particles have a good dielectric loss tangent of 10 ⁇ 4 , and like alumina, those with a smaller particle size by pulverization are used, but there is a limit to the particle size adjustment, and since it is an irregular shape, Exist as agglomerated particles and may impair mechanical strength and thermal conductivity.
  • the present invention has been made in view of the above circumstances, is excellent in filler filling property and appearance during sheet preparation, has both high thermal conductivity and low dielectric loss tangent, and has excellent mechanical strength.
  • Resin composition and glass ceramic substrate And a method for producing the same.
  • the present invention provides a resin composition which is excellent in the filling property of the filler and the appearance at the time of producing the sheet, has both high thermal conductivity and low dielectric loss tangent, and is also excellent in mechanical strength.
  • the present invention also provides a molded product obtained by molding the resin composition.
  • the present invention also provides a composition used for producing a glass-ceramic substrate, which is excellent in filler filling property and appearance when producing a green sheet, has both high thermal conductivity and low dielectric loss tangent, and is also excellent in mechanical strength.
  • the present invention also provides a green sheet manufactured using the composition.
  • the present invention also provides a fired product obtained by firing the composition.
  • the present invention also provides a glass ceramic substrate including the fired product.
  • the dielectric loss tangent is low, the particle size is smaller, and by using spinel particles having a narrow particle size distribution, the filler filling property and sheet preparation It was found that a resin composition and a glass-ceramic substrate having excellent appearance, high thermal conductivity and low dielectric loss tangent, and excellent mechanical strength can be obtained, and the present invention has been completed.
  • the present invention includes the following aspects.
  • (1) The volume-based average particle diameter d50 in laser diffraction particle size distribution measurement is 0.01 ⁇ m or more and 5 ⁇ m or less, d90/d10 is 5 or less, and the content of particles of 15 ⁇ m or more is the total of all particles.
  • a composition containing the spinel particles according to any one of (1) to (4) and a glass component (15) The composition according to (14), wherein the content of the spinel particles is 10 vol% or more and 50 vol% or less with respect to a total volume of 100 vol% of the spinel particles and the glass component. (16) A green sheet formed by molding the composition according to (14) or (15). (17) A fired product obtained by firing the composition according to (14) or (15). (18) A glass ceramic substrate provided with the fired product according to (17).
  • the spinel particles and the method for producing the same in the above aspect it is possible to obtain a resin composition and a glass ceramics substrate which are excellent in the filling property of the filler and the appearance at the time of sheet preparation, have both high thermal conductivity and low dielectric loss tangent, and are also excellent in mechanical strength.
  • Spinel particles can be provided.
  • the resin composition of the above aspect it is possible to provide a resin composition which is excellent in the filling property of the filler and the appearance at the time of producing the sheet, has both high thermal conductivity and low dielectric loss tangent, and is also excellent in mechanical strength.
  • a molded product obtained by molding the resin composition can be provided.
  • composition of the above aspect there is provided a composition which is excellent in the filling property of the filler and the appearance at the time of producing the green sheet, has a high thermal conductivity and a low dielectric loss tangent, and is used in the production of a glass ceramic substrate having excellent mechanical strength. be able to.
  • the green sheet of the above aspect it is possible to provide a green sheet manufactured using the composition.
  • a baked product obtained by baking the composition can be provided.
  • glass ceramic substrate of the above aspect it is possible to provide a glass ceramic substrate including the fired product.
  • the scale bar on the left side of (A) is 20.0 ⁇ m.
  • the scale bar in the enlarged view on the upper right of (A) is 2.0 ⁇ m.
  • the scale bar on the left side of (B) to (C) is 10.0 ⁇ m.
  • the scale bar in the enlarged view on the upper right of (B) to (C) is 1.0 ⁇ m.
  • the spinel particles according to the embodiment have a volume-based average particle diameter d50 in laser diffraction particle size distribution measurement of 0.01 ⁇ m or more and 5 ⁇ m or less, d90/d10 of 5 or less, and a content of particles of 15 ⁇ m or more. Is 0.1% by volume or less based on the total volume of all particles.
  • the spinel particles according to the embodiment are excellent in the filling property of the filler and the appearance at the time of sheet production, have both high thermal conductivity and low dielectric loss tangent, and have excellent mechanical strength. can get.
  • the conventional spinel particles do not satisfy at least one of the requirements for the average particle size d50, d90/d10, and the content of particles of 15 ⁇ m or more in the above particle size distribution measurement, as shown in Examples described later. there were.
  • the conventional spinel particles because the particle size is non-uniform or indefinite, in the resulting resin composition or glass ceramics substrate, the dielectric loss tangent is low, the filling properties of the filler and the appearance during sheet preparation, It was poor in thermal conductivity and mechanical strength.
  • the spinel particles according to the embodiment have a small particle size and a narrow particle size distribution, that is, since the particle size is uniform, the filling properties of the filler and the appearance at the time of sheet production are excellent, and it is possible to exhibit excellent mechanical strength. Conceivable.
  • spinel particles contain a magnesium atom, an aluminum atom, and an oxygen atom, and thus are usually represented by a chemical composition of MgAl 2 O 4 .
  • the spinel particles according to the embodiment preferably contain molybdenum in the particles.
  • the contained form of molybdenum in the spinel particles is not particularly limited, but examples thereof include a form in which molybdenum is attached to the surface of the spinel particles, coated, bonded, or arranged in a similar form, a form in which molybdenum is incorporated into the spinel, or a combination thereof.
  • the "form in which molybdenum is incorporated into the spinel" a form in which at least a part of atoms constituting the spinel particle is replaced with molybdenum, a space that may exist inside the crystal of the spinel particle (a space generated by a defect in the crystal structure And the like), and the like in which molybdenum is arranged.
  • the atom constituting the spinel particle to be substituted is not particularly limited and may be a magnesium atom, an aluminum atom, an oxygen atom, or any other atom.
  • molybdenum is preferably contained at least in a form incorporated in spinel. When molybdenum is incorporated in the spinel, it tends to be difficult to be removed by cleaning, for example.
  • the spinel particles according to the embodiment have a volume-based average particle diameter d50 in laser diffraction type particle size distribution measurement of 0.01 ⁇ m or more and 5 ⁇ m or less, preferably 0.05 ⁇ m or more and 5 ⁇ m or less, and 0.1 ⁇ m or more and 4.8 ⁇ m or less. It is more preferably 0.5 ⁇ m or more and 4.5 ⁇ m or less, particularly preferably 1 ⁇ m or more and 4.3 ⁇ m or less, and most preferably 3.4 ⁇ m or more and 4.1 ⁇ m or less.
  • the volume-based average particle diameter d50 in the laser diffraction particle size distribution measurement is within the above range, so that when the spinel particles according to the embodiment are used in the production of a resin composition or a glass ceramic substrate, the filling property of the filler and the sheet The appearance at the time of production can be made more excellent, and the thermal conductivity and mechanical strength can be made more excellent.
  • a value measured by the method described in Examples described later can be used as the volume-based average particle diameter d50 in the laser diffraction particle size distribution measurement.
  • the spinel particles according to the embodiment have a volume-based d90/d10 in the laser diffraction type particle size distribution measurement of 5 or less, preferably 4.9 or less, more preferably 4.8 or less, still more preferably 4.7 or less, A value of 4.6 or less is particularly preferable.
  • the volume-based d90/d10 in the laser diffraction particle size distribution measurement is equal to or less than the above upper limit, the particle size distribution becomes narrower, that is, the particle size becomes more uniform, and the spinel particles according to the embodiment are used as resin compositions or When it is used for manufacturing a glass ceramic substrate, it can be made more excellent in the filling property of the filler and the appearance at the time of making the sheet, and can be made more excellent in thermal conductivity and mechanical strength.
  • the lower limit of d90/d10 is not particularly limited, and can be, for example, 1 or more, 2 or more, 3 or more, and 3.5 or more. It can be 3.7 or more.
  • the volume-based d90/d10 in the laser diffraction type particle size distribution measurement a value measured using the method described in Examples described later can be adopted.
  • the content of particles of 15 ⁇ m or more is 0.1 vol% or less with respect to the total volume of all particles, 0.05 vol% or less is preferable, and 0.01 vol% or less is more preferable. Preferably, 0% by volume is more preferable.
  • the spinel particles according to the embodiment do not substantially contain particles having a large particle size, and are used in the production of a resin composition or a glass ceramic substrate.
  • the filling property of the filler and the appearance at the time of producing the sheet can be made excellent, and the thermal conductivity and the mechanical strength can be made excellent.
  • the content of the particles having a particle size of 15 ⁇ m or more the value measured by the method described in Examples described later can be adopted.
  • the conditions of the volume-based average particle diameter d50, d90/d10, and the content of particles of 15 ⁇ m or more in laser diffraction particle size distribution measurement can be combined in any way.
  • the ratio L/S of the major axis L to the minor axis S of the spinel particles according to the embodiment is preferably 2 or less, more preferably 1.8 or less, and further preferably 1.5 or less. It is preferably 1.4 or less, and particularly preferably 1.4 or less.
  • L/S is less than or equal to the above upper limit value, the shape of the spinel particles becomes closer to a regular polygon, and when the spinel particles according to the embodiment are used for manufacturing a resin composition or a glass ceramic substrate, the filling property of the filler In addition, the appearance of the sheet can be improved, and the thermal conductivity and mechanical strength can be improved.
  • the lower limit of L/S is not particularly limited and can be, for example, 1 or more, 1.1 or more, 1.2 or more, and 1.3 or more. can do.
  • major axis L is the maximum length of the distance between two points on the contour line of the spinel particle
  • minor axis S is the distance between two points on the contour line of the spinel particle. The minimum length. L/S is an arithmetic mean value calculated using the major axis L and the minor axis S measured for at least 50 randomly selected spinel particles from an image obtained by a scanning electron microscope (SEM).
  • SEM scanning electron microscope
  • Examples of the shape of the spinel particles according to the embodiment include polyhedral shape, spherical shape, elliptical shape, columnar shape, polygonal columnar shape, needle shape, rod shape, plate shape, disk shape, flaky shape, and scale shape.
  • polyhedral, spherical, elliptical or plate-like are preferable because they are easily dispersed in the resin, and polyhedral or spherical are more preferable.
  • the term “polyhedron” generally means a hexahedron or more, preferably an octahedron or more, more preferably a 10-hedron or more and a 30-hedron or less.
  • the crystallite diameter of the (311) plane of the spinel particles according to the embodiment is preferably 120 nm or more, more preferably 140 nm or more, still more preferably 144 nm, even more preferably 150 nm or more, and particularly preferably 160 nm or more.
  • the upper limit of the crystallite diameter of the (311) plane is not particularly limited and can be, for example, 300 nm or less, 250 nm or less, 200 nm or less, and 190 nm or less. And can be 181 nm or less.
  • the (311) plane is one of the main crystal domains of the spinel particle, and the size of the crystal domain of the (311) plane corresponds to the crystallite diameter of the (311) plane.
  • the crystallite size of the (311) plane of the spinel particles can be controlled by appropriately setting the conditions of the manufacturing method described later.
  • XRD X-ray diffraction
  • the spinel particles contain magnesium atoms, aluminum atoms, and oxygen atoms, and are generally represented by the composition of MgAl 2 O 4 .
  • the spinel particles according to the embodiment include molybdenum.
  • the spinel particles according to the embodiment may contain unavoidable impurities, other atoms, etc., as long as the effects of the present invention are not impaired.
  • the content of magnesium atoms in the spinel particles is not particularly limited, but for example, when the molar amount of aluminum atoms is 2 mol, it is preferably 0.8 mol or more and 1.2 mol or less, and 0.9 mol or less. More preferably, it is 1.1 mol or less.
  • the content of aluminum atoms in the spinel particles is not particularly limited, but for example, when the molar amount of magnesium atoms is 1 mol, it is preferably 1.8 mol or more and 2.2 mol or less, and 1.9 mol. More preferably, it is 2.1 mol or less.
  • the content of magnesium atoms and aluminum atoms in the spinel particles can be measured by inductively coupled plasma optical emission spectroscopy (ICP-AES).
  • the content of oxygen atoms in the spinel particles is not particularly limited, but depends on the molar amount of magnesium atoms and aluminum atoms.
  • the content of oxygen atoms in the spinel particles is preferably 3.8 mol or more and 4.2 mol or less, and preferably 3.9 mol or more. It is more preferably 4.1 mol or less.
  • Molybdenum may be contained due to the manufacturing method described below.
  • the molybdenum is not particularly limited, but includes molybdenum metal, molybdenum oxide, a partially reduced molybdenum compound, and the like. Molybdenum is considered to be included in the spinel grains as MoO 3, it may be included in the spinel particles as MoO 2 and MoO like in addition to MoO 3.
  • the contained form of molybdenum is not particularly limited, and may be contained in the form of being adhered, coated, bonded, or the like on the surface of the spinel particles, or in a form in which molybdenum is incorporated into the spinel. Or a combination thereof.
  • the content of molybdenum is not particularly limited, but from the viewpoint of high thermal conductivity of the spinel particles according to the embodiment, it is preferably 1% by mass or less in terms of molybdenum trioxide with respect to 100% by mass of the spinel particles, 0 It is more preferably 0.8% by mass or less, further preferably 0.5% by mass or less, particularly preferably 0.4% by mass or less, from the viewpoint that the spinel particles exhibit higher denseness. Most preferably, it is 0.35 mass% or less.
  • the lower limit of the content of molybdenum is not particularly limited, but may be 0.01% by mass or more, may be 0.05% by mass or more, and may be 0.1% by mass or more. , 0.12 mass% or more.
  • the content of molybdenum in the spinel particles can be determined by XRF analysis. The XRF analysis is performed under the same measurement conditions as those described in Examples described later or under compatible conditions that the same measurement results are obtained.
  • the unavoidable impurities are those that are present in the raw materials or are inevitably mixed in the spinel particles in the manufacturing process, and are essentially unnecessary, but are trace amounts, and impurities that do not affect the properties of the spinel particles are included. means.
  • the unavoidable impurities include, but are not limited to, silicon, iron, potassium, sodium, calcium and the like. These unavoidable impurities may be contained alone or in combination of two or more.
  • the content of unavoidable impurities in the spinel particles is preferably 10000 ppm or less, more preferably 1000 ppm or less, and further preferably 10 ppm or more and 500 ppm or less, based on the mass of the spinel particles.
  • the other atom means one that is intentionally added to the spinel particles for the purpose of coloring, emitting light, controlling the formation of spinel particles, etc. within a range that does not impair the effects of the present invention.
  • atoms include, but are not limited to, zinc, cobalt, nickel, iron, manganese, titanium, zirconium, calcium, strontium, yttrium, and the like. These other atoms may be used alone or in combination of two or more.
  • the content of other atoms in the spinel particles is preferably 10% by mass or less, more preferably 5% by mass or less, and more preferably 2% by mass or less, relative to 100% by mass of the spinel particles. More preferable.
  • the method for producing the spinel particles according to the embodiment is not particularly limited, and known techniques may be appropriately applied. However, a production method including a step of firing a magnesium compound and an aluminum compound in the presence of molybdenum (firing step) is preferable.
  • the firing step may be a step of firing the mixture obtained in the step of obtaining the mixture to be fired (mixing step).
  • the mixing step is a step of mixing raw materials such as a magnesium compound, an aluminum compound and molybdenum to obtain a mixture.
  • the mixed state of the magnesium compound and the aluminum compound is not particularly limited. When both are mixed, simple mixing for mixing powders, mechanical mixing using a crusher or mixer, mixing using a mortar or the like is performed. At this time, the obtained mixture may be in a dry state or a wet state, but is preferably in a dry state from the viewpoint of cost.
  • the mixing ratio of the magnesium compound and the aluminum compound is not particularly limited, but the molar ratio of the aluminum element of the aluminum compound to the magnesium element of the magnesium compound (aluminum element/magnesium element) is 1.8 or more.2. It is preferable to mix so as to be 2 or less, and it is more preferable to mix so as to be 1.9 or more and 2.1 or less. The contents of the mixture will be described below.
  • the magnesium compound is not particularly limited, but examples thereof include metallic magnesium, magnesium derivatives, magnesium oxo acid salts, magnesium organic salts, and hydrates thereof.
  • the magnesium derivative include magnesium oxide, magnesium hydroxide, magnesium peroxide, magnesium fluoride, magnesium chloride, magnesium bromide, magnesium iodide, magnesium hydride, magnesium diboride, magnesium nitride and magnesium sulfide.
  • the magnesium oxo acid salt include magnesium carbonate, calcium magnesium carbonate, magnesium nitrate, magnesium sulfate, magnesium sulfite, magnesium perchlorate, trimagnesium phosphate, magnesium permanganate, magnesium phosphate and the like.
  • magnesium organic salt for example, magnesium acetate, magnesium citrate, magnesium malate, magnesium glutamate, magnesium benzoate, magnesium stearate, magnesium acrylate, magnesium methacrylate, magnesium gluconate, magnesium naphthenate, magnesium salicylate, lactic acid.
  • magnesium and magnesium monoperoxyphthalate examples thereof include magnesium and magnesium monoperoxyphthalate.
  • These magnesium compounds may be used alone or in combination of two or more. Among them, magnesium oxide, magnesium hydroxide, magnesium carbonate, magnesium acetate, magnesium nitrate or magnesium sulfate is preferable, and magnesium oxide, magnesium hydroxide, magnesium nitrate or magnesium acetate is more preferable.
  • the volume-based average particle diameter d50 in the laser diffraction particle size distribution measurement of the magnesium compound is not particularly limited, but by using one having a smaller particle diameter within the range where aggregation does not occur, homogenization during firing can be achieved, More uniform spinel particles can be obtained. It is 0.01 ⁇ m or more and 5 ⁇ m or less, preferably 0.05 ⁇ m or more and 5 ⁇ m or less, more preferably 0.1 ⁇ m or more and 4.8 ⁇ m or less, still more preferably 0.5 ⁇ m or more and 4.5 ⁇ m or less, and 0.5 ⁇ m or more and 4.3 ⁇ m or less.
  • the volume-based average particle diameter d50 in the laser diffraction particle size distribution measurement of the magnesium compound is not less than the above lower limit, particle aggregation can be more effectively prevented in spinel crystallization.
  • the average particle diameter of the magnesium compound is not more than the above upper limit value, spinel crystallization can proceed to the central portion of the particles more efficiently.
  • the magnesium compound may be a commercially available product or may be prepared by itself.
  • the reactivity can be adjusted.
  • magnesium hydroxide having a small particle size can be obtained by neutralizing an acidic aqueous solution of magnesium ions with a base. Since the obtained magnesium hydroxide having a small particle size has high reactivity, the crystallite size of the spinel obtained using this tends to be large.
  • the aluminum compound is not particularly limited, but examples thereof include aluminum metal, aluminum chloride, aluminum sulfate, basic aluminum acetate, aluminum hydroxide, boehmite, pseudoboehmite, and aluminum oxide.
  • aluminum oxide include hydrated aluminum oxide, ⁇ -aluminum oxide, ⁇ -aluminum oxide, ⁇ -aluminum oxide, ⁇ -aluminum oxide, ⁇ -aluminum oxide, and mixed aluminum oxide having two or more crystal phases. Are listed.
  • the above-mentioned aluminum compound is preferably aluminum oxide, preferably aluminum oxide having at least one crystal form selected from the group consisting of ⁇ crystal, ⁇ crystal, ⁇ crystal, ⁇ crystal and ⁇ crystal, Aluminum oxide having ⁇ crystals is more preferable.
  • the above-mentioned aluminum compound preferably contains molybdenum.
  • the molybdenum-containing form of the aluminum compound containing molybdenum is not particularly limited, but like the spinel particles, molybdenum is attached to the surface of the aluminum compound, coated, bonded, or arranged in a form similar thereto, molybdenum. And a combination thereof.
  • the “form in which molybdenum is incorporated into the aluminum compound” a form in which at least a part of atoms constituting the aluminum compound is substituted with molybdenum, a space that may exist inside the crystal of the aluminum compound (occurs due to a defect in the crystal structure)
  • a form in which molybdenum is arranged in (including a space) is included.
  • the atoms constituting the aluminum compound to be substituted are not particularly limited and may be any of aluminum atoms, oxygen atoms and other atoms.
  • aluminum compounds it is preferable to use an aluminum compound containing molybdenum, and it is more preferable to use an aluminum compound containing molybdenum.
  • an aluminum compound containing molybdenum is preferable because it is due to the following mechanism. That is, molybdenum contained in the aluminum compound plays a role of promoting nucleation at the solid phase interface, promoting solid phase diffusion of aluminum atoms and magnesium atoms, etc., so that the solid phase reaction between the aluminum compound and magnesium compound proceeds more favorably. It is supposed to do. That is, as described later, the aluminum compound containing molybdenum can have a function as an aluminum compound and molybdenum. In particular, in an aluminum compound incorporating molybdenum, molybdenum is arranged directly or in the vicinity of the reaction point, and the effect of molybdenum can be more effectively exhibited. It should be noted that the above mechanism is only an estimation, and even if a desired effect can be obtained by a mechanism different from the above mechanism, it is included in the technical scope.
  • the shape of the aluminum compound is not particularly limited, and examples thereof include polyhedron, sphere, ellipse, column, polygonal column, needle, rod, plate, disc, flakes, and scales. Among them, as described below, in the manufacturing method according to the embodiment, there is a tendency to obtain spinel particles reflecting the shape of the aluminum compound, and the resulting spinel particles are easily dispersed in the resin, polyhedral, It is preferably spherical, elliptical or plate-shaped, and more preferably polyhedral or spherical. Further, when the aluminum compound is plate-shaped, spinel particles having a large crystallite size on the (311) plane are obtained, and the thermal conductivity and mechanical strength tend to be excellent.
  • the average particle size of the aluminum compound is not particularly limited, but it is appropriately adjusted according to the particle size of the spinel particles to be obtained. Similar to the magnesium compound, by using a particle having a smaller particle size within the range where aggregation does not occur, homogenization during firing can be achieved and spinel particles having a more uniform particle size can be obtained.
  • the volume-based average particle diameter d50 in the laser diffraction particle size distribution measurement of the aluminum compound is 0.01 ⁇ m or more and 5 ⁇ m or less, preferably 0.05 ⁇ m or more and 5 ⁇ m or less, more preferably 0.1 ⁇ m or more and 4.8 ⁇ m or less, and 0
  • the thickness is more preferably 0.5 ⁇ m or more and 4.5 ⁇ m or less, still more preferably 1 ⁇ m or more and 4.3 ⁇ m or less, particularly preferably 3 ⁇ m or more and 4.3 ⁇ m or less, and most preferably 3.8 ⁇ m or more and 4.3 ⁇ m or less.
  • volume-based average particle diameter in the laser diffraction particle size distribution measurement of the aluminum compound is not less than the above lower limit, particle aggregation can be more effectively prevented in spinel crystallization.
  • the volume-based average particle diameter in the laser diffraction particle size distribution measurement of the aluminum compound is not more than the above upper limit, spinel crystallization can proceed more efficiently to the central portion of the particle.
  • the volume-based d90/d10 of the aluminum compound in the laser diffraction particle size distribution measurement is 5 or less, preferably 4.9 or less, more preferably 4.8 or less, still more preferably 4.7 or less.
  • the volume-based d90/d10 in the laser diffraction particle size distribution measurement is not more than the above upper limit, spinel particles having a narrower particle size distribution, that is, more uniform particle size can be obtained.
  • the lower limit of d90/d10 is not particularly limited and can be set to 1 or more, for example.
  • the volume-based d90/d10 in the laser diffraction type particle size distribution measurement can be measured by the method described in Examples below.
  • the content of particles of the aluminum compound of 15 ⁇ m or more is 0.1% by volume or less, preferably 0.05% by volume or less, more preferably 0.01% by volume or less, and 0 volume% with respect to the total volume of all particles. % Is more preferable.
  • the content of the particles having a particle size of 15 ⁇ m or more is not more than the above upper limit value, spinel particles that do not substantially contain particles having a large particle size can be obtained.
  • the content of particles of 15 ⁇ m or more can be measured by the method described in Examples below.
  • the aluminum compound a commercially available product may be used, or an aluminum compound prepared by itself may be used.
  • the aluminum compound containing molybdenum can be prepared by the flux method described in detail below. That is, in a preferred embodiment, the method for producing spinel particles further includes the step of preparing an aluminum compound by the flux method.
  • the flux method is classified into the liquid-phase method, especially the solution method. More specifically, the flux method is a crystal growth method that utilizes the fact that the crystal-flux binary system phase diagram shows a eutectic type.
  • the mechanism of the flux method is presumed to be as follows. That is, as the mixture of solute and flux is heated, the solute and flux become a liquid phase. At this time, since the flux is a flux, in other words, since the solute-flux binary system phase diagram shows a eutectic type, the solute should be melted at a temperature lower than its melting point to form a liquid phase.
  • the concentration of the flux is lowered, in other words, the melting point lowering effect of the solute by the flux is reduced, and the flux evaporation serves as a driving force to cause solute crystal growth (flux). Evaporation method).
  • the solute and the flux can also cause solute crystal growth by cooling the liquid phase (slow cooling method).
  • the flux method has the advantages that crystals can be grown at a temperature much lower than the melting point, the crystal structure can be precisely controlled, and polyhedral crystals having an automorphism can be formed.
  • molybdenum contained in the aluminum compound may correspond to a flux impurity called a disadvantage of the flux method, but as described above, in one embodiment of the present invention, molybdenum contained in the aluminum compound is spinel particles. A suitable action and effect can be exhibited at the time of manufacturing.
  • the flux method includes a flux evaporation step of firing a mixture containing an aluminum source and a molybdenum compound, and a cooling step of cooling the aluminum compound crystal-grown in the firing step.
  • the aluminum source is not particularly limited, but aluminum chloride, aluminum sulfate, basic aluminum acetate, aluminum hydroxide, boehmite, pseudoboehmite, transition alumina, alumina hydrate, ⁇ -alumina, and two or more crystals. Examples include mixed alumina having a phase. Examples of the transition alumina include ⁇ -alumina, ⁇ -alumina, ⁇ -alumina and the like.
  • the above aluminum sources may be used alone or in combination of two or more. Among them, aluminum hydroxide, transition alumina, boehmite, pseudo-boehmite or alumina hydrate is preferable, and aluminum hydroxide, transition alumina or boehmite is more preferable.
  • the aluminum source may be a commercially available product or may be prepared by itself.
  • alumina hydrate or transition alumina having high structural stability at high temperature can be prepared by neutralizing an aqueous solution of aluminum. More specifically, the alumina hydrate can be prepared by neutralizing an acidic aqueous solution of aluminum with a base, and the transition alumina is prepared by heat-treating the alumina hydrate obtained above. be able to.
  • the alumina hydrate or transition alumina thus obtained has high structural stability at high temperatures, and therefore, when calcined in the presence of molybdenum, an aluminum compound containing molybdenum having a large average particle diameter tends to be obtained.
  • the shape of the aluminum source is not particularly limited, and any shape such as spherical, amorphous, structural body with aspect, sheet, etc. can be preferably used.
  • a structure having an aspect for example, a wire, a fiber, a ribbon, a tube, or the like can be preferably used.
  • the particle size of the aluminum source is not particularly limited, and a solid aluminum compound of several nm to several hundreds of ⁇ m can be preferably used.
  • the aluminum source may form a complex with an organic compound.
  • the composite include an organic-inorganic composite obtained by modifying an aluminum compound with an organic silane, an aluminum compound composite adsorbing a polymer, a composite coated with an organic compound, and the like.
  • the content of the organic compound is not particularly limited, but is preferably 60% by mass or less, and more preferably 30% by mass or less.
  • the specific surface area of the aluminum source is also not particularly limited. Since the molybdenum compound acts effectively, it is preferable that the specific surface area is large, but by adjusting the firing conditions and the amount of the molybdenum compound used, any specific surface area can be used as a raw material.
  • a shape control agent can be used to form an aluminum compound.
  • the shape control agent plays an important role in the plate crystal growth of alumina by firing an aluminum source in the presence of a molybdenum compound.
  • the state of existence of the shape control agent is not particularly limited, and for example, a shape control agent, an aluminum compound and a physical mixture, a complex in which the shape control agent is present uniformly or locally on the surface or inside of the aluminum source, and the like are preferable. Can be used.
  • the shape control agent may be added to the aluminum compound, but may be included as an impurity in the aluminum compound.
  • Shape control agent plays an important role in plate crystal growth.
  • molybdenum oxide flux method that is generally performed, molybdenum oxide is selectively adsorbed on the (113) plane of ⁇ crystals of alumina, and the crystal component is difficult to be supplied to the (113) plane, and the (001) plane or ( Since the appearance of the (006) plane can be completely suppressed, polyhedral particles having a hexagonal bipyramidal base are formed.
  • molybdenum oxide which is a flux agent, suppresses the selective adsorption of crystalline components on the (113) plane, so that the (001) plane is thermodynamically developed.
  • silicon or a silicon compound containing a silicon element, germanium or a germanium compound containing a germanium element can be used. It is preferable to use silicon or a silicon compound containing a silicon element from the viewpoint that it is possible to produce plate-like alumina particles that are less expensive and have excellent productivity.
  • An aluminum compound having a high aspect ratio can be easily produced by the flux method using silicon or a silicon compound as the shape control agent. A higher aspect ratio means a thinner plate when compared with the same particle size.
  • the size of the spinel particles formed after firing varies depending on the thickness of the plate, and by using an aluminum compound having a smaller thickness, spinel particles having a smaller particle size can be obtained.
  • the silicon compound containing silicon or silicon element is not particularly limited, and known compounds can be used.
  • the silicon compound containing silicon or a silicon element may be an artificial synthetic silicon compound or a natural silicon compound.
  • Examples of the artificially synthesized silicon compound include metal silicon, organic silane, silicon resin, silica fine particles, silica gel, mesoporous silica, SiC, and mullite.
  • Examples of natural silicon compounds include biosilica and the like. Above all, it is preferable to use organic silane, silicon resin, or silica fine particles from the viewpoint that the compounding and mixing with the aluminum compound can be formed more uniformly.
  • the silicon compounds containing silicon or silicon element may be used alone or in combination of two or more kinds.
  • the shape of silicon or a silicon compound containing a silicon element is not particularly limited, and for example, a spherical shape, an amorphous shape, a structure having an aspect, a sheet, or the like can be preferably used.
  • a structure having an aspect for example, a wire, a fiber, a ribbon, a tube, or the like can be preferably used.
  • the content of silicon with respect to 100 mass% of the aluminum compound is preferably 10 mass% or less, more preferably 0.001 mass% or more and 5 mass% or less, further 0.01 mass% or more and 4 mass% or less in terms of silicon dioxide. It is preferably 0.6% by mass or more and 2.5% by mass or less.
  • the silicon content can be determined by XRF analysis.
  • the molybdenum compound molybdenum compound is not particularly limited, metallic molybdenum, molybdenum oxide, molybdenum sulfide, sodium molybdate, potassium molybdate, calcium molybdate, ammonium molybdate, H 3 PMo 12 O 40, H 3 SiMo 12 O 40 etc. are mentioned.
  • the molybdenum compound includes isomers.
  • molybdenum oxide may be molybdenum (IV) dioxide (MoO 2 ) or molybdenum trioxide (VI) (MoO 3 ).
  • the above molybdenum compounds may be used alone or in combination of two or more. Of these, molybdenum trioxide, molybdenum dioxide or ammonium molybdate is preferable, and molybdenum trioxide is more preferable.
  • the molar ratio of the molybdenum element of the molybdenum compound to the aluminum element of the aluminum compound is preferably 0.01 or more and 3.0 or less, and more preferably 0.03 or more and 1.0 or less. preferable.
  • the molar ratio is at least the above lower limit, crystal growth of the aluminum compound containing molybdenum can proceed more favorably.
  • the aluminum compound containing molybdenum can be prepared industrially more efficiently.
  • the firing temperature is not particularly limited, but is preferably 700° C. or higher and 2000° C. or lower, more preferably 900° C. or higher and 1600° C. or lower, further preferably 950° C. or higher and 1500° C. or lower, and 1000° C. or higher 1400 or higher. It is particularly preferable that the temperature is not higher than °C. If the firing temperature is at least the above lower limit, the flux reaction will proceed more suitably. On the other hand, when the firing temperature is at most the above upper limit, the burden on the firing furnace and the fuel cost can be further reduced.
  • the state of the aluminum source and the molybdenum compound during firing is not particularly limited as long as the molybdenum compound and the aluminum source exist in the same space.
  • the flux reaction can proceed even when the two are not mixed.
  • simple mixing of powders, mechanical mixing using a crusher, mixing using a mortar, etc. can be performed, and the resulting mixture is in a dry state. It may be in a wet state.
  • the firing time is also not particularly limited, but is preferably 5 minutes or more and 30 hours or less, and more preferably 10 minutes or more and 15 hours or less from the viewpoint of efficiently forming an aluminum compound containing molybdenum.
  • the firing atmosphere is also not particularly limited, but for example, an oxygen-containing atmosphere such as air or oxygen, or an inert atmosphere such as nitrogen or argon is preferable, and corrosion is performed from the viewpoint of the safety of the practitioner and the durability of the furnace. It is more preferable to use an oxygen-containing atmosphere having no property and a nitrogen atmosphere, and it is more preferable to use an air atmosphere from the viewpoint of cost.
  • the firing device is not particularly limited, and a so-called firing furnace is usually used.
  • the firing furnace is preferably made of a material that does not react with the sublimated molybdenum compound, and more preferably a highly tight firing furnace that can efficiently use the molybdenum compound.
  • the cooling step is a step of cooling the aluminum compound crystal-grown in the firing step.
  • the cooling rate is not particularly limited, but is preferably 1° C./hour or more and 1000° C./hour or less, more preferably 5° C./hour or more and 500° C./hour or less, and 50° C./hour or more 100° C./hour. More preferably, it is less than or equal to time. When the cooling rate is equal to or higher than the above lower limit value, the manufacturing time can be further shortened. On the other hand, when the cooling rate is less than or equal to the above upper limit, the firing container is less likely to be cracked by heat shock and can be used for a longer time, which is preferable.
  • the cooling method is not particularly limited, and natural cooling or a cooling device may be used.
  • the aluminum compound obtained by the flux method contains molybdenum, it is usually colored. Although the colored color varies depending on the amount of molybdenum contained, it is usually a light blue to a dark blue color close to black, and the color tends to become dark in proportion to the molybdenum content.
  • the aluminum compound containing molybdenum may be colored in another color. For example, the compound containing molybdenum may be red when it contains chromium, and may be yellow when it contains nickel.
  • the content of molybdenum in the aluminum compound containing molybdenum is not particularly limited, but is preferably 0.1% by mass or more and 1% by mass or less and 0.2% by mass or more and 0.9% by mass in terms of molybdenum trioxide. It is more preferably at most 0.3% by mass and at most 0.9% by mass, even more preferably at least 0.5% by mass and at most 0.88% by mass, and at least 0.7% by mass. 0.87 mass% or less is particularly preferable, and 0.83 mass% or more and 0.85 mass% or less is most preferable. When the content of molybdenum is not less than the above lower limit, spinel crystal growth can proceed more efficiently.
  • the content of molybdenum is not more than the above upper limit value, the crystal quality of the aluminum compound can be improved, which is preferable.
  • the content of molybdenum in the aluminum compound can be measured by the same method as the method described in the content of molybdenum in the spinel particles.
  • the aluminum compound containing molybdenum preferably has a high ⁇ crystallization rate with molybdenum serving as a flux agent and having a crystal plane other than the (001) plane as a main crystal plane, and the ⁇ crystallization rate is 90% or more. Is more preferable.
  • the flux method includes a step of firing a mixture containing an aluminum source and a molybdenum compound, and a slow cooling step of cooling the obtained fired material to grow crystals.
  • Molybdenum has a function of promoting nucleation at the interface in the solid phase reaction, promoting solid phase diffusion of at least one atom of magnesium atom and aluminum atom, and the like.
  • molybdenum in a compound containing molybdenum metal and molybdenum may be used.
  • the compound containing molybdenum include the above-mentioned molybdenum compound and the aluminum compound containing molybdenum.
  • the aluminum compound containing molybdenum can be used as a compound containing molybdenum and an aluminum compound.
  • the above molybdenum may be used alone or in combination of two or more kinds.
  • the molar ratio of molybdenum element to aluminum element of the aluminum compound is preferably 0.00001 or more and 0.05 or less, and 0.0001 or more and 0.03 or less. Is more preferable. When the molar ratio is within the above range, solid solution of the magnesium compound and the aluminum compound and spinel crystallization can proceed more favorably.
  • a magnesium compound and an aluminum compound are added in the presence of molybdenum, This is a step of crystallizing the above spinel particles by solid solution and crystallization.
  • the solid solution and crystallization are usually carried out by the so-called solid phase method.
  • the mechanism of solid solution and crystallization in the solid phase method is presumed to be as follows. That is, when heating is performed in an environment in which the magnesium compound and the aluminum compound are in contact with each other, the magnesium compound and the aluminum compound form nuclei at the interface (solid phase interface), so that the bond between the solid phases is strengthened. Then, the solid phase reaction can proceed using the formed nucleus as a carrier. At this time, the solid phase reaction is that the binary phase diagram of the magnesium compound and the aluminum compound has a eutectic type, whereby the temperature at which the magnesium compound and the aluminum compound can react at the interface is the magnesium compound or the aluminum compound alone. Lower than melting temperature can be utilized.
  • the magnesium compound and the aluminum compound react at the interface to form a nucleus, and at least one atom of the magnesium atom and the aluminum atom is solid-phase diffused through the nucleus, and the aluminum compound and the magnesium atom. Reacts with at least one of the atoms. Thereby, a dense crystal body, that is, spinel particles can be obtained.
  • the diffusion rate of magnesium atoms into the aluminum compound is relatively higher than the diffusion rate of aluminum atoms into the magnesium compound, so that spinel particles in which the shape of the aluminum compound is reflected are obtained. Tend. Therefore, it may be possible to control the shape and the average particle diameter of the spinel particles by appropriately changing the shape and the average particle diameter of the aluminum compound.
  • spinel particles can be manufactured more easily by using alumina particles having a desired shape containing molybdenum as the aluminum compound.
  • the above solid-phase reaction is performed in the presence of molybdenum.
  • molybdenum is not always clear, for example, solid-phase reaction proceeds more favorably by promoting nucleation at the interface, promoting solid-phase diffusion of at least one of magnesium and aluminum atoms, and the like. it is conceivable that.
  • flux method as a process of the reaction, first, molybdenum and an aluminum compound are reacted to form an aluminum intermediate molybdate, and then the aluminum molybdate and the magnesium compound are reacted. It is presumed to include things that do.
  • spinel particles having a plurality of metal components it is difficult to precisely control the crystal structure because a defect structure or the like is likely to occur during the firing process.
  • molybdenum it is possible to control the crystal structure of the spinel crystal. You can Thereby, the crystallite diameter of the (311) plane becomes large, and spinel particles having excellent thermal conductivity can be obtained. Since the solid phase reaction is performed in the presence of molybdenum, the obtained spinel particles may contain molybdenum.
  • Crystal control such as the crystallite size of the (311) plane of the spinel particles is controlled by the amount of molybdenum used, the type of magnesium compound, the firing temperature, the firing time, the mixed state of the magnesium compound and the aluminum compound, the presence or absence of a shape control agent.
  • the amount of the shape control agent used, the amount of impurities, and the like can be changed. The reason is that the amount of molybdenum, the type of magnesium compound, the firing temperature, the firing time, and the mixed state of the magnesium compound and the aluminum compound depend on the rate of solid solution and crystallization in the magnesium compound and the aluminum compound in the solid phase reaction. It is considered to be related.
  • the use of a highly reactive magnesium compound increases the rate of solid solution and crystallization of the magnesium compound, and the increase in the amount of molybdenum used, high temperature calcination, and long time calcination solidify at least one of magnesium and aluminum atoms. And the rate of crystallization can be respectively increased, and for example, the crystallite diameter of the (311) plane can be increased.
  • the firing temperature is not particularly limited, but is preferably 800°C or higher and 2000°C or lower, more preferably 1000°C or higher and 1600°C or lower, and further preferably 1300°C or higher and 1500°C or lower.
  • the firing temperature is not more than the above upper limit, spinel particles can be produced more efficiently in a shorter time.
  • the shape and dispersibility of spinel particles can be controlled more easily.
  • the firing time is not particularly limited, but is preferably 0.1 hour or more and 1000 hours or less, and more preferably 3 hours or more and 100 hours or less.
  • the firing time is at least the above lower limit, spinel particles having a larger crystallite size on the (311) plane can be obtained.
  • the manufacturing cost may be lower.
  • a shape control agent in order to promote the solid solution and crystallization of the magnesium compound and the aluminum compound and to control the shape.
  • the shape control agent include sodium compounds and potassium compounds.
  • the sodium compound is not particularly limited and includes sodium, sodium chloride, sodium chlorite, sodium chlorate, sodium sulfate, sodium hydrogen sulfate, sodium sulfite, sodium hydrogen sulfite, sodium nitrate, sodium carbonate, sodium hydrogen carbonate, sodium acetate. , Sodium oxide, sodium bromide, sodium bromate, sodium hydroxide, sodium silicate, sodium phosphate, sodium hydrogen phosphate, sodium sulfide, sodium hydrogen sulfide, sodium molybdate, sodium tungstate and the like. At this time, the sodium compound includes isomers as in the case of the molybdenum compound.
  • sodium carbonate, sodium hydrogen carbonate, sodium oxide, sodium hydroxide, sodium chloride, sodium sulfate or sodium molybdate is preferably used, and sodium carbonate, sodium hydrogen carbonate, sodium chloride, sodium sulfate or sodium molybdate is used. Is more preferable.
  • the sodium compounds described above may be used alone or in combination of two or more. Further, since sodium molybdate contains molybdenum, it can also have a function as the above-mentioned molybdenum compound.
  • the potassium compound is not particularly limited, potassium, potassium chloride, potassium chlorite, potassium chlorate, potassium sulfate, potassium hydrogen sulfate, potassium sulfite, potassium hydrogen sulfite, potassium nitrate, potassium carbonate, potassium hydrogen carbonate, potassium acetate, Examples thereof include potassium oxide, potassium bromide, potassium bromate, potassium hydroxide, potassium silicate, potassium phosphate, potassium hydrogen phosphate, potassium sulfide, potassium hydrogen sulfide, potassium molybdate, potassium tungstate, and the like.
  • the potassium compound includes isomers, as in the case of the molybdenum compound.
  • potassium carbonate, potassium hydrogen carbonate, potassium oxide, potassium hydroxide, potassium chloride, potassium sulfate or potassium molybdate is preferably used, and potassium carbonate, potassium hydrogen carbonate, potassium chloride, potassium sulfate or potassium molybdate is used. Is more preferable.
  • the above potassium compounds may be used alone or in combination of two or more. Further, since potassium molybdate contains molybdenum, it can also have a function as the above-mentioned molybdenum compound.
  • the amount of the shape control agent added is preferably 20% by mass or more and 90% by mass or less, more preferably 30% by mass or more and 80% by mass or less, in terms of oxide, based on 100% by mass of the raw material. , 40% by mass or more and 70% by mass or less, more preferably 50% by mass or more and 68% by mass or less, particularly preferably 55% by mass or more and 67% by mass or less, and 61% by mass or more and 66% by mass or less. Most preferred.
  • the addition amount of the shape control agent is within the above range, it is possible to obtain spinel particles that are more excellent in surface smoothness and have a more uniform particle size, and are more dispersible when dispersed in a resin or a solvent. It is possible to produce a composition that is high and highly dense. These additives are preferably mixed in the above mixing step before firing.
  • the firing atmosphere may be an air atmosphere, an inert gas atmosphere such as nitrogen gas or argon gas, an oxygen atmosphere, an ammonia gas atmosphere, or a carbon dioxide atmosphere. It may be. At this time, an air atmosphere is preferable from the viewpoint of manufacturing cost.
  • the pressure during firing is also not particularly limited, and may be under normal pressure, may be under pressure, or may be under reduced pressure, but molybdenum oxide vapor generated during firing can be efficiently generated from the firing furnace. From the viewpoint of being able to discharge, it is preferable to carry out under reduced pressure.
  • the heating means is preferably a firing furnace, which is not particularly limited.
  • firing furnaces that can be used at this time include tunnel furnaces, roller hearth furnaces, rotary kilns, and muffle furnaces. It is preferable that the firing furnace is made of a material that does not react with molybdenum oxide vapor, and it is more preferable to use a firing furnace having high airtightness.
  • the manufacturing method of the present invention may include a cooling step.
  • the cooling step is a step of cooling the spinel particles having crystal grown in the firing step.
  • the cooling rate is not particularly limited, but is preferably 1° C./hour or more and 1000° C./hour or less, more preferably 5° C./hour or more and 500° C./hour or less, and 50° C./hour or more 100° C./hour. More preferably, it is less than or equal to time. When the cooling rate is equal to or higher than the above lower limit value, the manufacturing time can be further shortened. On the other hand, when the cooling rate is less than or equal to the above upper limit, the firing container is less likely to be cracked by heat shock and can be used for a longer time.
  • the cooling method is not particularly limited, and natural cooling may be used, or a cooling device may be used.
  • the manufacturing method of the present invention may include a post-treatment step.
  • the post-treatment step is a step of removing additives and the like.
  • the post-treatment step may be performed after the above-mentioned firing step, may be performed after the above-mentioned cooling step, or may be performed after the firing step and the cooling step. Moreover, you may repeat twice or more as needed.
  • Examples of the post-treatment method include washing and high temperature treatment. These can be performed in combination.
  • the washing method is not particularly limited, but it can be removed by washing with water, an aqueous ammonia solution, an aqueous sodium hydroxide solution, an acidic aqueous solution, or the like.
  • the molybdenum content can be controlled by appropriately changing the concentration, the amount of water used, the aqueous ammonia solution, the aqueous sodium hydroxide solution, the acidic aqueous solution, the washing site, the washing time, and the like.
  • a method of high temperature treatment a method of raising the temperature above the sublimation point or boiling point of the additive can be mentioned.
  • the spinel particles may be aggregated and may not satisfy the particle size range suitable for the present invention. Therefore, the spinel particles may be pulverized, if necessary, so as to satisfy the range of the particle diameter suitable for the present invention.
  • the method for pulverizing the fired product is not particularly limited, and conventionally known pulverizing methods such as a ball mill, a jaw crusher, a jet mill, a disc mill, a spectro mill, a grinder, and a mixer mill can be applied.
  • the spinel particles are preferably classified in order to adjust the average particle size and improve the fluidity of the powder, or to suppress the increase in viscosity when blended with the binder for forming the matrix.
  • the "classifying treatment” refers to an operation of grouping particles according to the size of the particles.
  • the classification may be either wet or dry, but from the viewpoint of productivity, dry classification is preferred.
  • Dry classification in addition to classification by a sieve, there is a wind classification that classifies by the difference in centrifugal force and fluid drag force, but from the viewpoint of classification accuracy, wind classification is preferable, and an air classifier that utilizes the Coanda effect, It can be performed using a classifier such as a swirling air flow classifier, a forced vortex centrifugal classifier, a semi-free vortex centrifugal classifier, or the like.
  • the crushing step and the classification step described above can be performed at necessary stages, including before and after the organic compound layer forming step described later.
  • the average particle size of the obtained spinel particles can be adjusted, for example, by the presence or absence of the pulverization or classification and the selection of the conditions.
  • the spinel particles according to the embodiment, or the spinel particles obtained by the manufacturing method according to the embodiment, those with less aggregation or those without aggregation are more likely to exhibit the original properties and are excellent in handleability thereof. Further, it is preferable from the viewpoint of more excellent dispersibility when used by being dispersed in a medium to be dispersed.
  • the method for producing spinel particles if the above-mentioned pulverization step and classification step are not carried out, and if there is little aggregation or no aggregation, it is not necessary to carry out the step described on the left, and it has excellent properties of interest.
  • Spinel particles are preferable because they can be produced with high productivity.
  • the resin composition according to the embodiment contains spinel particles and a resin. Further, the resin composition according to the embodiment may further contain a curing agent, a curing catalyst, a viscosity modifier, a plasticizer, etc., if necessary.
  • the resin is not particularly limited, and examples thereof include thermoplastic resins and thermosetting resins.
  • thermoplastic resin is not particularly limited, and known and commonly used resins used for molding materials and the like can be used. Specifically, for example, polyethylene resin, polypropylene resin, polymethylmethacrylate resin, polyvinyl acetate resin, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, polyvinyl chloride resin, polystyrene resin, polyacrylonitrile resin , Polyamide resin, polycarbonate resin, polyacetal resin, polyethylene terephthalate resin, polyphenylene oxide resin, polyphenylene sulfide resin, polysulfone resin, polyethersulfone resin, polyetheretherketone resin, polyallylsulfone resin, thermoplastic polyimide resin, thermoplastic urethane resin , Polyamino bismaleimide resin, polyamide imide resin, polyether imide resin, bismaleimide triazine resin, polymethylpentene resin, fluororesin, liquid crystal polymer, olefin-vinyl
  • the thermosetting resin is a resin having the property of being substantially insoluble and infusible when cured by means such as heating or radiation or a catalyst, and is generally a molding material or the like.
  • Known and conventional resins used for can be used. Specifically, for example, phenol resin, epoxy resin, urea (urea) resin, resin having a triazine ring, (meth)acrylic resin, vinyl resin, unsaturated polyester resin, bismaleimide resin, polyurethane resin, diallyl phthalate resin, Examples thereof include silicone resins, resins having a benzoxazine ring, and cyanate ester resins.
  • the phenol resin include novolac type phenol resin and resol type phenol resin.
  • Examples of the novolac type phenolic resin include phenol novolac resin and cresol novolac resin.
  • Examples of the resol type phenol resin include unmodified resol phenol resin and oil-modified resol phenol resin.
  • Examples of the oil used for oil modification include tung oil, linseed oil, walnut oil, and the like.
  • Examples of the epoxy resin include bisphenol type epoxy resin, fatty chain modified bisphenol type epoxy resin, novolac type epoxy resin, biphenyl type epoxy resin, polyalkylene glycol type epoxy resin, and the like.
  • Examples of the bisphenol type epoxy resin include bisphenol A epoxy resin and bisphenol F epoxy resin.
  • Examples of the novolac type epoxy resin include novolac epoxy resin and cresol novolac epoxy resin.
  • Examples of the resin having a triazine ring include melamine resin and the like.
  • Examples of vinyl resins include vinyl ester resins.
  • thermoplastic resins may be used alone or in combination of two or more.
  • thermosetting resins may be used, one or more thermoplastic resins and one or more thermosetting resins may be used. Good.
  • the content of the resin is preferably 5% by mass or more and 90% by mass or less, more preferably 10% by mass or more and 70% by mass or less, and 12% by mass or more and 50% by mass with respect to the mass of the resin composition. % Or less is more preferable, 14% by mass or more and 30% by mass or less is still more preferable, and 15% by mass or more and 28% by mass or less is particularly preferable.
  • the content of the resin is at least the above lower limit value, the resin composition can be provided with excellent moldability.
  • the content of the resin is equal to or less than the above upper limit value, it is possible to mold and obtain higher thermal conductivity as a compound.
  • the curing agent is not particularly limited, and known ones can be used. Specific examples of the curing agent include amine compounds, amide compounds, acid anhydride compounds, and phenol compounds.
  • amine compound examples include diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, imidazole, BF3-amine complex, guanidine derivative and the like.
  • amide compound examples include dicyandiamide, a polyamide resin synthesized from a dimer of linolenic acid and ethylenediamine, and the like.
  • Examples of the acid anhydride-based compound include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic acid anhydride, hexahydrophthalic anhydride, Methyl hexahydrophthalic anhydride and the like can be mentioned.
  • phenolic compound examples include phenol novolac resin, cresol novolac resin, aromatic hydrocarbon formaldehyde resin-modified phenol resin, dicyclopentadiene phenol addition type resin, phenol aralkyl resin (Zyloc resin), and resorcin novolac resin.
  • a polyvalent phenol compound in which a phenol nucleus is linked with a polyphenol compound an alkoxy group-containing aromatic ring-modified novolac resin (a polyvalent phenol compound in which a phenol nucleus and
  • the above-mentioned curing agents may be used alone or in combination of two or more kinds.
  • the curing accelerator has a function of promoting curing when curing the resin composition.
  • the curing accelerator is not particularly limited, and examples thereof include phosphorus compounds, tertiary amines, imidazoles, organic acid metal salts, Lewis acids, amine complex salts and the like.
  • the above curing accelerators may be used alone or in combination of two or more.
  • the curing catalyst has a function of promoting a curing reaction of a compound having a polymerizable functional group, instead of the curing agent.
  • the curing catalyst is not particularly limited, and a known and commonly used thermal polymerization initiator or active energy ray polymerization initiator can be used.
  • the curing catalyst may be used alone or in combination of two or more kinds.
  • the viscosity modifier has a function of adjusting the viscosity of the resin composition.
  • the viscosity modifier is not particularly limited and, for example, organic polymers, polymer particles, inorganic particles and the like can be used.
  • the above viscosity modifiers may be used alone or in combination of two or more.
  • the plasticizer has a function of improving processability, flexibility and weather resistance of the thermoplastic synthetic resin.
  • the plasticizer is not particularly limited, and for example, phthalic acid ester, adipic acid ester, phosphoric acid ester, trimellitic acid ester, polyester, polyolefin, polysiloxane and the like can be used.
  • the above plasticizers may be used alone or in combination of two or more.
  • the resin composition according to the embodiment is obtained by mixing the plate-like spinel particles and the resin, and if necessary, other compounds.
  • the mixing method is not particularly limited, and the mixing is performed by a known and commonly used method.
  • the resin is a thermosetting resin
  • the thermosetting resin of a predetermined blending amount, the plate-like spinel particles examples include a method in which other components are sufficiently mixed with a mixer or the like and then kneaded with a triple roll or the like to obtain a fluid liquid composition.
  • a predetermined amount of the thermosetting resin and the plate-like spinel particles, if necessary other components by a mixer or the like as a method of mixing the thermosetting resin and the plate-like spinel particles and the like in another embodiment, a predetermined amount of the thermosetting resin and the plate-like spinel particles, if necessary other components by a mixer or the like.
  • Examples include a method in which a solid composition is obtained by sufficiently mixing, then melt-kneading with a mixing roll, an extruder, or the like, and then cooling.
  • a method in which a solid composition is obtained by sufficiently mixing, then melt-kneading with a mixing roll, an extruder, or the like, and then cooling Regarding the mixed state, when a curing agent, a catalyst and the like are mixed, it is sufficient that the curable resin and the mixture thereof are sufficiently uniformly mixed, but it is more preferable that the plate-like spinel particles are also uniformly dispersed and mixed. preferable.
  • the resin is a thermoplastic resin
  • a thermoplastic resin as a mixing method of a general thermoplastic resin and plate-like spinel particles, a thermoplastic resin, plate-like spinel particles, and other components as necessary, for example, a tumbler or After premixing using various mixers such as a Henschel mixer, a method of melt-kneading with a mixer such as Banbury mixer, roll, Brabender, single-screw kneading extruder, twin-screw kneading extruder, kneader, and mixing roll can be mentioned. ..
  • the temperature of melt-kneading is not particularly limited, but is usually in the range of 100°C or higher and 320°C or lower.
  • a coupling agent may be externally added to the resin composition because the fluidity of the resin composition and the filling ability of fillers such as plate-like spinel particles can be further enhanced.
  • the adhesion between the resin and the plate-like spinel particles is further enhanced, the interfacial thermal resistance between the resin and the plate-like spinel particles is reduced, and the thermal conductivity of the resin composition is reduced. Can be improved.
  • organic silane compound examples include methyltrimethoxysilane, dimethyldimethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, iso-propyltrimethoxysilane, and iso.
  • -Propyltriethoxysilane pentyltrimethoxysilane, hexyltrimethoxysilane, octenyltrimethoxysilane, etc.
  • the above coupling agents may be used alone or in combination of two or more.
  • the addition amount of the coupling agent is not particularly limited, but is preferably 0.01% by mass or more and 5% by mass or less, more preferably 0.1% by mass or more and 3% by mass or less, based on the mass of the resin. preferable.
  • the resin composition according to the embodiment is used as a heat conductive material.
  • alumina is often used from the viewpoint of cost, and in addition, boron nitride, aluminum nitride, magnesium oxide, magnesium carbonate, etc. have been used.
  • spinel particles have been known to be inferior in thermal conductivity to alumina, so there was no idea to use spinel particles instead of alumina.
  • the above spinel particles have a large crystallite size on the (311) plane, and therefore have excellent heat conduction performance.
  • the thermal conductivity of the spinel particles is higher than that of alumina. Therefore, the resin composition according to the embodiment is preferably used as a heat conductive material.
  • the spinel particles obtained by the above production method have a small average particle size d50 (0.01 ⁇ m or more and 5 ⁇ m or less), a narrow particle size distribution (d90/d10 is 5 or less), and a large crystallite size. Since it has excellent dispersibility in the resin composition, it can exhibit more excellent thermal conductivity as a resin composition.
  • the spinel particles obtained by the above-mentioned manufacturing method are polyhedral particles having an automorphism synthesized by the solid phase method, and since they are not obtained by crushing amorphous particles, they are excellent in smoothness, Excellent dispersibility in resin. Therefore, the resin composition according to the embodiment can have very high thermal conductivity.
  • the molded product according to the embodiment is formed by molding the above resin composition.
  • the molded product is preferably used as an insulating/radiating member. As a result, the heat dissipation function of the device can be improved, and it is possible to contribute to reduction in size and weight of the device and higher performance.
  • the molded product can be used as a low dielectric material or the like. Since the spinel particles have a low dielectric loss tangent and can impart excellent mechanical strength to the molded product, it is possible to contribute to the enhancement of the communication function in the high frequency circuit.
  • composition contains spinel particles and a glass component.
  • each component will be described.
  • the content of the spinel particles is preferably 10 vol% or more and 50 vol% or less, more preferably 15 vol% or more and 45 vol% or less, and more preferably 20 vol% or more and 45 vol% with respect to the total volume of 100 vol% of the spinel particles and the glass component. % Or less is more preferable, 30 vol% or more and 45 vol% or less is still more preferable, 35 vol% or more and 45 vol% or less is particularly preferable, and 40 vol% is the most preferable.
  • the content of the spinel particles is at least the above lower limit value, the high thermal conductivity of the spinel particles can be more efficiently exhibited.
  • the content of the spinel particles is not more than the above upper limit value, a composition excellent in moldability can be obtained.
  • the composition according to the embodiment can be easily prepared by mixing the spinel particles and the glass component.
  • the glass component mixed with the particles is also particles from the viewpoint of easy mixing and handleability.
  • Examples of the compound contained in the glass component include B 2 O 3 , SiO 2 , GeO 2 , Al 2 O 3 , P 2 O 5 , V 2 O 5 , As 2 O 5 and Sb 2 used as a network former component.
  • the glass component is preferably an oxide glass containing an oxide such as the above compound as a main component.
  • containing as a main component means containing 50% by mass or more of an oxide with respect to 100% by mass of the total amount of glass components converted into oxides.
  • the glass component is preferably silicate glass containing SiO 2 as an essential component.
  • SiO 2 has an excellent effect of suppressing crystallization of glass, improving stability, and further imparting chemical stability.
  • B 2 O 3 has an excellent effect of improving the sinterability of glass and is preferably used.
  • Al 2 O 3 contributes to the stabilization of the glass phase, has an excellent effect of improving chemical stability and durability, and is preferably used.
  • ZnO and MgO are excellent in the effect of improving the water resistance of glass and are preferably used.
  • ZrO 2 is excellent in the effect of improving chemical stability and is preferably used.
  • oxides of alkaline earth metals such as BaO and CaO are excellent in the effect of improving the sinterability due to a decrease in viscosity when glass is melted, and are preferably used.
  • Na 2 O and K 2 O are preferably used because they are excellent in the effect of lowering the glass melting temperature and the glass transition temperature (Tg) and improving the sinterability.
  • the compounds listed above may be used in combination of two or more kinds, in any combination of two or more kinds, and may be contained in any proportion. More preferable compounds contained in the glass component include BaO, SiO 2 , B 2 O 3 , Al 2 O 3 , MgO, ZnO, ZrO 2 , alkaline earth metal oxides, Na 2 O, and K 2 O. Are listed. SiO 2 which is an essential component is 10% by mass or more and 60% by mass or less, B 2 O 3 is 0% by mass or more and 60% by mass or less, and Al 2 O 3 is 100% by mass based on the total amount of glass components converted into oxides.
  • MgO is 0 mass% or more and 60 mass% or less
  • ZnO is 0 mass% or more and 40 mass% or less
  • ZrO 2 is 0 mass% or more and 40 mass% or less
  • RO R is alkaline earth
  • a metal is included in a proportion of 0 mass% or more and 30 mass% or less
  • Na 2 O or K 2 O is contained in a proportion of 0 mass% or more and 30 mass% or less, which has good sinterability and excellent appearance. This is preferable because a glass ceramics substrate having excellent smoothness can be obtained, and a glass ceramics substrate having excellent chemical stability, water resistance, and strength can be obtained.
  • the glass component is SiO 2 and the group consisting of B 2 O 3 , Al 2 O 3 , MgO, ZnO, ZrO 2 , RO (R represents an alkaline earth metal), Na 2 O, and K 2 O. It is preferable to contain at least one compound selected from the following as a main component.
  • containing as a main component means that SiO 2 and the above B 2 O 3 , Al 2 O 3 , MgO, ZnO, ZrO 2 , and RO( based on 100% by mass of the total amount of glass components converted into oxides.
  • R represents an alkaline earth metal), Na 2 O
  • at least one compound selected from the group consisting of K 2 O have a total mass of 50% by mass or more.
  • the glass component preferably contains SiO 2 and at least one compound selected from the group consisting of MgO and RO (R represents an alkaline earth metal) as main components.
  • containing as a main component is selected from the group consisting of SiO 2 , MgO, and RO (R represents an alkaline earth metal) with respect to 100% by mass of the total glass components converted into oxides. It means that the sum of the mass with at least one compound is 50 mass% or more.
  • SiO 2 is preferably contained in an amount of 40% by mass or more, more preferably 50% by mass or more, and 60% by mass or more based on 100% by mass of the total amount of glass components converted into oxides. It is more preferable that the content is included.
  • Examples of preferable combinations of the compounds contained in the glass component include silicate glasses such as Li 2 O—SiO 2 , Na 2 O—MgO—SiO 2 —Na 2 O—BaO—SiO 2 , and LiO—Al 2.
  • silicate glasses such as Li 2 O—SiO 2 , Na 2 O—MgO—SiO 2 —Na 2 O—BaO—SiO 2 , and LiO—Al 2.
  • Aluminosilicate glass such as O 3 —SiO 2 , MgO—Al 2 O 3 —SiO 2 , BaO—Al 2 O 3 —CaO—MgO—Al 2 O 3 —SiO 2 , PbO—ZnO—ZnO—B 2 O 3 , borate glass such as CdO—In 2 O 3 —B 2 O 3 , borosilicate glass such as Al 2 O 3 —B 2 O 3 —SiO 2 , ZnO—B 2 O 3 —SiO 2 , MgO— Examples thereof include phosphosilicate glass such as P 2 O 5 —SiO 2 and CaO—Al 2 O 3 —P 2 O 5 —SiO 2 .
  • the glass component may be in the form of glass powder.
  • the type of glass powder is not particularly limited, and various types can be appropriately used depending on the intended use.
  • the average particle diameter of the glass powder is not particularly limited, but as an example, 0.1 ⁇ m or more and 10 ⁇ m or less is preferable. When the average particle diameter of the glass powder is within the above range, the handling property is more excellent. Further, when mixed with spinel particles, the difference in average particle size between the glass powder and the spinel particles becomes smaller, and a composition in which the particles are uniformly mixed and a green sheet are obtained. Further, it is preferable that unevenness in firing is less likely to occur due to uniform heat conductivity during firing, and a more dense glass ceramic substrate can be obtained.
  • the “average particle diameter of glass powder” is a value calculated as a volume-based median diameter d50 from the volume-based cumulative particle size distribution measured by a laser diffraction/scattering particle size distribution measuring device.
  • the composition according to the embodiment may contain a binder component, a plasticizer, a solvent and the like in addition to the spinel particles and the glass component.
  • the binder component is not particularly limited as long as it can be applied as a green sheet and does not impair the effects of the present invention, and various resins can be exemplified, for example, acrylic resin, epoxy resin, urethane resin, polyvinyl. Butyral, olefin resin, methyl cellulose, polyvinyl alcohol, polyethylene oxide and the like can be mentioned. Of these, acrylic resins or epoxy resins are preferable because they are excellent in the film thickness uniformity of the green sheet, ease of coating, and handling properties.
  • acrylic resin examples include acrylic polymers, and specific examples thereof include (meth)acrylic acid polymers, (meth)acrylic acid copolymers, (meth)acrylic acid ester polymers, (meth)acrylics. Examples thereof include acid ester copolymers. Examples of the (meth)acrylic acid ester constituting the acrylic resin include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, and (meth)acrylic acid. Hexyl, heptyl (meth)acrylate, 2-ethylhexyl (meth)acrylate and the like can be mentioned.
  • plasticizer Any plasticizer can be used without particular limitation as long as it does not impair the effects of the present invention, and examples thereof include dibutyl phthalate, dioctyl phthalate, diisononyl phthalate, di-2-ethylhexyl phthalate, adipic acid diester, and adipine. Examples thereof include acid diisononyl ester, phosphoric acid ester, sebacic acid ester, low molecular weight polyester, glycerin, polyethylene glycol, polyether polyol, epoxidized soybean oil, and epoxidized linseed oil.
  • the viscosity of the composition can be reduced, the film thickness of the coating can be made uniform, and the ease of coating can be improved.
  • the solvent is not particularly limited, and any solvent can be used as long as it does not impair the effects of the present invention.
  • examples thereof include a ketone solvent, an aromatic hydrocarbon solvent, an aliphatic hydrocarbon solvent, an ester solvent, an ether solvent, an alcohol solvent and the like.
  • the ketone solvent include acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone.
  • the aromatic hydrocarbon solvent include toluene and xylene.
  • Examples of the aliphatic hydrocarbon solvent include hexane and cyclohexane.
  • ester solvent examples include ethyl acetate, normal propyl acetate, isopropyl acetate, butyl acetate and the like.
  • ether solvent examples include diisopropyl ether, methyl cellosolve, ethyl cellosolve, 1,4-dioxane and the like.
  • alcohol solvent examples include methanol, ethanol, butanol, isopropanol and the like.
  • the composition according to the embodiment if not impairing the effects of the present invention, further enhances various physical properties such as denseness, heat resistance, water resistance, and chemical resistance while maintaining high thermal conductivity.
  • an inorganic filler such as alumina, magnesium oxide, aluminum nitride, silicon carbide, zinc oxide, boron nitride or graphite, which does not correspond to these components.
  • the shape of these fillers is not particularly limited, and any shape such as spherical shape, plate shape, flake shape, fibrous shape, and amorphous shape may be used.
  • the composition according to the embodiment can be produced, for example, by mixing the spinel particles with a glass component.
  • the composition which concerns on embodiment can be manufactured, for example by mixing the said spinel particle, a glass component, a binder component, a plasticizer, and a solvent.
  • Content of the said glass component with respect to 100 mass% of total mass of a composition is 30 mass% or more and 80 mass% or less, for example, 33 mass% or more and 70 mass% or less are more preferable, 35 mass% or more and 60 mass% or less Is more preferable, 35% by mass or more and 50% by mass or less is still more preferable, and 35% by mass or more and 40% by mass is particularly preferable.
  • the content of the spinel particles with respect to the total mass of the spinel particles and the glass component of 100 mass% is, for example, preferably 5 mass% or more and 60 mass% or less, more preferably 10 mass% or more and 50 mass% or less, and 20 mass% or more. 45 mass% or less is more preferable, 30 mass% or more and 43 mass% or less is still more preferable, 35 mass% or more and 43 mass% or less is especially preferable, and 40 mass% or more and 41 mass% or less is most preferable.
  • the composition according to the embodiment can more easily retain a desired shape after itself or after being formed into a sheet.
  • the content of the binder component with respect to 100% by mass of the total composition is, in terms of solid content, preferably 0.5% by mass or more and 20% by mass or less, more preferably 1% by mass or more and 18% by mass or less, and 3
  • the content is more preferably 15% by mass or more and 15% by mass or less, still more preferably 5% by mass or more and 10% by mass or less, particularly preferably 5.5% by mass or more and 8% by mass or less, and most preferably 6% by mass or more and 7% by mass or less.
  • the content of the plasticizer with respect to 100% by mass of the total composition is, for example, preferably 0.5% by mass or more and 5% by mass or less, more preferably 1% by mass or more and 4% by mass or less, and 1.5% by mass or more.
  • the content of the solvent with respect to 100% by mass of the total composition is, for example, preferably 10% by mass or more and 50% by mass or less, more preferably 15% by mass or more and 40% by mass or less, and 20% by mass or more and 35% by mass or less. More preferably, it is more preferably 21% by mass or more and 30% by mass or less, particularly preferably 22% by mass or more and 25% by mass or less, and most preferably 23% by mass or more and 24% by mass or less.
  • the amount of the spinel particles, the glass component, the binder component, the plasticizer, the solvent contained in the composition according to the embodiment is within the above range, the moldability of the composition and the strength and thermal conductivity after firing. In terms of, it can be more excellent.
  • the above composition is suitably used for producing a glass ceramic substrate, and a green sheet can be produced using the above composition. That is, the above composition can be used as a composition for producing a green sheet used for producing a green sheet.
  • the green sheet according to the embodiment is formed by molding the above composition. That is, the green sheet according to the embodiment can be manufactured by forming the composition into a sheet (molding step).
  • the method for forming the sheet is not particularly limited, and examples thereof include forming the slurry (composition for producing a green sheet) obtained by the above method into a sheet.
  • the forming method is not particularly limited, and can be formed by a known method such as a doctor blade method, a press forming method, a rolling method, a calender roll method, etc., but the film thickness can be easily adjusted and the film thickness can be adjusted. It is preferable to form the sheet by the doctor blade method, which is excellent in uniformity.
  • the composition according to the embodiment can be formed into a sheet on a release sheet. If necessary, a drying process may be performed during or after the sheet molding. Further, after forming the sheet, it may be processed into a desired shape by a cutter, a punching die or the like.
  • the green sheet according to the embodiment may have a conductive pattern.
  • the conductive pattern can be formed by filling a through hole such as a via hole with a conductive material containing a conductive metal, printing on a green sheet, or the like.
  • the green sheet according to the embodiment can be provided as a laminated body in which a plurality of green sheets are laminated. The laminated body may be subjected to press working, if necessary.
  • the green sheet according to the embodiment may have a release sheet on the outermost surface on one or both sides.
  • the thickness of the green sheet according to the embodiment is appropriately adjusted according to the thickness of the glass ceramic substrate described later.
  • the thickness is the total thickness of the green sheets having a plurality of layers.
  • the fired product according to the embodiment is obtained by firing the above composition.
  • the fired product the fired product of the green sheet can be exemplified.
  • a glass ceramic substrate can be manufactured by firing the green sheet. That is, the glass ceramic substrate according to the embodiment includes the fired product.
  • the above composition and the green sheet can be fired by firing.
  • the binder component contained was burned off, the contained glass component was melted to form a continuous layer, and the spinel particles were dispersed in this continuous glass layer, and the spinel particle and the glass component were strongly A tightly fired product is obtained.
  • the composition and the green sheet are not particularly limited in firing conditions, and can be fired under the same conditions. Since the plate surfaces of the spinel particles in the obtained fired product are arranged in the plane direction of the fired product, it becomes possible to remarkably increase the mechanical strength in the thickness direction.
  • This fired product can be used, for example, as a glass ceramic substrate.
  • the firing temperature and firing time for firing the above composition may be, for example, about 850° C. or more and 1000° C. or less, and about 0.5 hours or more and 3 hours or less.
  • the density of the fired product according to the embodiment is different depending on the density of the glass component used, the density of the spinel particles, and the mixing ratio, and the density of the fired product (glass ceramic substrate) according to the embodiment is the density of the glass component, and
  • the density of the spinel particles can be obtained and calculated from the blending ratio (the density of the glass ceramic substrate obtained from the blending ratio is called the theoretical density). If the glass component dispersed in the composition and in the green sheet, and the molten glass at the time of firing and the spinel particles are not well compatible with each other, voids will occur at the interface between the glass component in the fired product and the spinel particles. ..
  • a layer of low-density air (0.001293 g/cm 3 ) is included in the glass ceramics, and when the density of the fired product (glass ceramics substrate) according to the embodiment is measured, the value calculated from the blending ratio Will be smaller than. Therefore, when the glass component and the spinel particles in the fired product (glass-ceramic substrate) according to the embodiment are well compatible with each other and more interfaces are adhered to each other to form a dense structure, the firing according to the embodiment is performed. The measured density of the product (glass-ceramic substrate) becomes closer to the theoretical density.
  • the sintered product (glass-ceramic substrate) according to the embodiment will have more voids.
  • the measured density is smaller than the theoretical density.
  • the denseness (%) of the fired product (glass ceramic substrate) according to the embodiment can be obtained by the following formula. It is considered that the higher the denseness value, the better the compatibility between the glass component and the spinel particles, the higher the adhesiveness, and the higher thermal conductivity and mechanical strength.
  • the density is a value obtained by the Archimedes method.
  • Density (%) (measured density (g/cm 3 )/theoretical density (g/cm 3 )) ⁇ 100
  • the thickness of the glass ceramic substrate can be, for example, 0.05 mm or more and 5 mm or less.
  • the fired product according to the embodiment contains the spinel particles and a glass component.
  • the content of the spinel particles with respect to the total mass of 100% by mass of the fired product is, for example, preferably 10% by mass or more and 60% by mass or less, more preferably 15% by mass or more and 40% by mass or less, and 20% by mass or more and 30% by mass or less. Is more preferable.
  • the content of the glass component with respect to the total mass of 100% by mass of the fired product is, for example, preferably 50% by mass or more and 90% by mass or less, more preferably 60% by mass or more and 85% by mass or less, and 70% by mass or more and 80% by mass or less. Is more preferable.
  • the amounts of the spinel particles and the glass component contained in the fired product according to the embodiment are within the above ranges, the strength and thermal conductivity after firing can be further improved.
  • the thermal conductivity of the fired product (glass-ceramic substrate) according to the embodiment is preferably 1.6 W/mk or more, more preferably 1.8 W/mk or more, and 2.0 W/mk or more. Is more preferable.
  • the upper limit of the thermal conductivity of the fired product (glass ceramic substrate) is not particularly limited, it can be 4.0 W/mk or less, 3.0 W/mk or less, and 2.5 W/mk. It can be set to mk or less.
  • the thermal conductivity is assumed to be the same as the measurement conditions described in the examples described later, or under the compatible condition that the same measurement result is obtained.
  • the bending strength of the fired product (glass ceramic substrate) is preferably 130 Mpa or more, more preferably 140 Mpa or more, further preferably 142 MPa or more, and more preferably 145 Mpa or more. More preferably, it is particularly preferably 148 MPa or more, and most preferably 150 Mpa or more.
  • the bending strength of the fired product (glass-ceramic substrate) is not particularly limited, but can be 200 MPa or less, 180 MPa or less, 160 MPa or less, and 156 MPa or less. it can.
  • the bending strength shall be performed under the same conditions as the measurement conditions described in the examples described later, or under compatible conditions with which the same measurement results are obtained.
  • the above spinel particles have a more uniform particle size, and when mixed with a glass component or other inorganic particle material, the mixed state with a plurality of particles can be made uniform, and the composition can be homogenized. It is considered that this is because densification can be achieved and the adhesion with the glass component can be improved. Therefore, when it is made into a fired product with a glass component, the adhesion between the glass component and spinel particles is further enhanced, and as a result, the denseness (density) of the fired product is improved, and the thermal conductivity is high and the mechanical strength is high. It is considered to be excellent.
  • the glass-ceramic substrate manufactured by using the above spinel particles as raw material has a low relative permittivity and dielectric loss tangent to the same extent as conventional spinel particles, and is expected to have a low dielectric constant and a low dielectric loss tangent.
  • the evaluation of the interface between the glass component in the substrate and the spinel particles was performed by chemical mechanical polishing of the substrate cross section, then ion milling treatment, SEM observation of the polished surface, and contrast of backscattered electron images caused by element differences. There is a method for obtaining.
  • the porosity% can be expressed by obtaining the area ratio of the glass component phase, the spinel component phase, and the void phase.
  • the substrate has extremely few voids and excellent compactness as compared with the case of using conventional spinel particles.
  • TEM or STEM observation of the cross section of the substrate makes it possible to understand the glass component near the interface and the crystal structure and composition of the spinel particles.
  • the temperature was lowered to room temperature under the condition of 5° C./min, and the crucible was taken out to obtain 98 g of a light blue powder.
  • the obtained powder was crushed in a mortar until it passed through a 106 ⁇ m sieve.
  • 98 g of the obtained light blue powder was dispersed in 150 mL of 0.5% aqueous ammonia, the dispersion solution was stirred at room temperature (25 to 30° C.) for 0.5 hours, and the aqueous ammonia was removed by filtration. Molybdenum remaining on the surface of the particles was removed by washing with water and drying to obtain 97 g of white powder.
  • the obtained powder had an average particle size of 4.3 ⁇ m as determined by a laser diffraction type particle size distribution analyzer, and had a polygonal plate shape by SEM observation, which had very few aggregates and had excellent handleability. It was confirmed that the particles were shaped like particles. Further, when XRD measurement was carried out, sharp peak scattering derived from ⁇ -alumina appeared, and no alumina crystal system peak other than ⁇ crystal structure was observed, which confirmed that the plate-like alumina had a dense crystal structure. .. Moreover, the alpha conversion rate was 90% or more. Furthermore, it was confirmed from the results of the quantitative X-ray fluorescence analysis that the obtained particles contained 0.83 mass% of molybdenum in terms of molybdenum trioxide. Furthermore, the result of measuring the density was 3.95 g/cm 3 .
  • ⁇ Synthesis Example 2 Synthesis of ⁇ -alumina particles A-2 145.3 g of aluminum hydroxide (manufactured by Nippon Light Metal Co., Ltd., average particle diameter 2 ⁇ m), 2.85 g of silicon dioxide, and molybdenum trioxide (Taiyo Mining Co., Ltd.) The same operation as in Synthesis Example 1 was carried out except that 5 g of the product) was mixed in a mortar to obtain 98 g of a pale blue powder. The obtained powder had an average particle diameter of 3.8 ⁇ m as determined by a laser diffraction type particle size distribution analyzer, and had a polygonal plate shape by SEM observation, which had very few aggregates and had excellent handleability.
  • the particles were shaped like particles. Further, when XRD measurement was carried out, sharp peak scattering derived from ⁇ -alumina appeared, and no alumina crystal system peak other than ⁇ crystal structure was observed, which confirmed that the plate-like alumina had a dense crystal structure. .. Moreover, the alpha conversion rate was 90% or more. Furthermore, it was confirmed from the result of the quantitative X-ray fluorescence analysis that the obtained particles contained molybdenum in an amount of 0.86% by mass in terms of molybdenum trioxide. Furthermore, the result of measuring the density was 3.94 g/cm 3 .
  • the prepared sample is placed on a holder for a measurement sample having a depth of 0.5 mm and filled so as to be flat with a constant load, and the sample is set in a wide-angle X-ray diffractometer (Rint-Ultma manufactured by Rigaku Corporation), and Cu/ The measurement was performed under the conditions of K ⁇ ray, 40 kV/30 mA, scan speed 2°/min, and scanning range 10° or more and 70° or less. The ⁇ conversion rate was calculated from the ratio of the strongest peak heights of ⁇ -alumina and transition alumina.
  • the prepared sample is pretreated under the condition of 300° C. for 3 hours, and then measured using a dry automatic densimeter Acupic II 1330 manufactured by Micromeritics under the conditions of measuring temperature of 25° C. and using helium as a carrier gas. did.
  • the obtained powder was crushed in a mortar until it passed through a 150 ⁇ m sieve. Subsequently, 25 g of the obtained white powder and 100 mL of 2% by mass nitric acid were blended, alumina beads having a diameter of 5 mm were added, and 20 pieces were crushed and pulverized with a paint conditioner. Then, the dispersion solution was filtered to remove 2% by mass of nitric acid, washed with water and dried to remove molybdenum remaining on the surface of the particles, thereby obtaining 24.7 g of white powder.
  • the obtained powder had an average particle diameter of 4.1 ⁇ m and a narrow particle size distribution of d90/d10 of 4.2.
  • Example 2 Synthesis of spinel particles S-a2 20 g of ⁇ -alumina particles A-2 obtained in Synthesis Example 2 and 7.86 g of magnesium oxide (average particle size 0.6 ⁇ m manufactured by Kamijima Chemical Co., Ltd.) were mixed in a mortar. The same operation as in Example 1 was carried out except that a mixture was obtained to obtain 24.8 g of white powder. The average particle diameter of the obtained powder was 3.4 ⁇ m, and the d90/d10 was 4.1, and particles having an average particle diameter smaller than that of the spinel particles obtained in Example 1 were obtained. In addition, it was confirmed by SEM observation that the particles were polygonal and had very few aggregates, and had excellent handleability.
  • the major axis L ( ⁇ m)/minor axis S ( ⁇ m) was 1.4. Further, when XRD measurement was performed, sharp peak scattering derived from spinel was observed. Moreover, when the crystallite diameter was determined from the peak of the (311) plane observed near 37 degrees using a CALSA detector, it was confirmed to be 165 nm. Furthermore, it was confirmed from the results of the fluorescent X-ray quantitative analysis that the obtained particles contained 0.20% by mass of molybdenum in terms of molybdenum trioxide.
  • Example 3 Synthesis of spinel particles S-a3 20 g of ⁇ -alumina particles A-2 obtained in Synthesis Example 2, 7.86 g of magnesium oxide (manufactured by Kamijima Chemical Co., Ltd., average particle size 0.6 ⁇ m), and molybdenum trioxide 1 The same operation as in Example 1 was performed except that 0.67 g was mixed in a mortar to obtain a mixture, to obtain 24.7 g of a white powder. The obtained powder had an average particle diameter of 3.8 ⁇ m, and had a d90/d10 of 3.9, and particles having a narrower particle size distribution than the spinel particles obtained in Example 1 were obtained.
  • Example 4 Synthesis of Spinel Particles S-a4 20 g of ⁇ -alumina particles A-2 obtained in Synthesis Example 2, 7.86 g of magnesium oxide (manufactured by Kamijima Chemical Co., Ltd., average particle size 0.6 ⁇ m), and sodium chloride 83. The same operation as in Example 1 was carried out except that 57 g was mixed in a mortar to obtain a mixture, and 24.7 g of white powder was obtained. The obtained powder had an average particle diameter of 3.6 ⁇ m and had a d90/d10 of 3.7, and particles having a narrower particle size distribution than the spinel particles obtained in Example 3 were obtained.
  • Example 5 Synthesis of spinel particles S-a5 20 g of ⁇ -alumina particles A-2 obtained in Synthesis Example 2, 7.86 g of magnesium oxide (manufactured by Kamijima Chemical Co., Ltd., average particle size 0.6 ⁇ m), and potassium chloride 83. The same operation as in Example 1 was carried out except that 57 g was mixed in a mortar to obtain a mixture, and 24.7 g of white powder was obtained. The obtained powder had an average particle size of 3.6 ⁇ m and had a d90/d10 of 3.8, and thus the particle size distribution was narrower than that of the spinel particles obtained in Example 3, like the spinel particles obtained in Example 4. Particles were obtained.
  • Example 6 Synthesis of spinel particles S-a6 20 g of commercially available ⁇ -alumina particles (particle diameter 3 ⁇ m), 7.86 g of magnesium oxide (Kamijima Chemical Co., Ltd. average particle diameter 3.5 ⁇ m), and 1.67 g of molybdenum trioxide.
  • ⁇ -alumina particles particle diameter 3 ⁇ m
  • magnesium oxide Kamijima Chemical Co., Ltd. average particle diameter 3.5 ⁇ m
  • molybdenum trioxide was obtained in a mortar and the same operation as in Example 1 was carried out except that a mixture was obtained to obtain 24.8 g of white powder.
  • the average particle diameter of the obtained powder was 3.8 ⁇ m, and d90/d10 was 4.6.
  • the major axis L ( ⁇ m)/minor axis S ( ⁇ m) was 1.3. Further, when XRD measurement was performed, sharp peak scattering derived from spinel was observed. Further, the crystallite size was found to be 144 nm by using a CALSA detector and determining the crystallite size from the peak of the (311) plane observed near 37 degrees. Furthermore, it was confirmed from the result of the quantitative X-ray fluorescence analysis that the obtained particles contained 0.12 mass% of molybdenum in terms of molybdenum trioxide.
  • the obtained powder was crushed in a mortar until it passed through a 150 ⁇ m sieve. Subsequently, 25 g of the obtained white powder and 100 mL of 2% by mass nitric acid were blended, alumina beads having a diameter of 5 mm were added, and 20 pieces were crushed and pulverized with a paint conditioner. Then, the dispersion solution was filtered to remove 2% by mass of nitric acid, washed with water and dried to obtain 24.7 g of white powder. Although the obtained powder had an average particle size of 3.9 ⁇ m, the value of d90/d10 was 8 and the particles had a wide particle size distribution. As a result of SEM observation (see FIG.
  • the particles had polygonal shapes, but the particle shapes and particle sizes were not uniform.
  • the major axis L ( ⁇ m)/minor axis S ( ⁇ m) was also 2.3, which was an extremely large value as compared with the spinel particles obtained in Examples 1 to 6.
  • XRD measurement was performed, peak scattering derived from spinel was observed, but the peak was broader than the measurement results of the spinel particles obtained in Examples 1 to 6, and a CALSA detector was used.
  • the crystallite size was determined from the peak of the (311) plane observed near 37 degrees, it was 113 nm, which was a smaller value than the measurement results of the spinel particles obtained in Examples 1 to 6.
  • ⁇ Comparative Example 2 Synthesis of spinel particles S-b2 To 25 g of commercially available spinel particles (adjusted by sieving to an average particle diameter of 20 ⁇ m), 25 g of alumina beads having a diameter of 5 mm was added, and the mixture was pulverized using a paint conditioner. 24.7 g of spinel particle powder having a particle size adjusted to 5.0 ⁇ m was obtained. The obtained powder had an extremely wide particle size distribution with d90/d10 of 15.1. Moreover, when the obtained powder was observed by SEM (see FIG. 1(C)), it was found that the particles had irregular particle shapes and particle diameters.
  • the major axis L ( ⁇ m)/minor axis S ( ⁇ m) was also 2.5, which was an extremely large value as compared with the spinel particles obtained in Examples 1 to 6. Further, when XRD measurement was performed, peak scattering derived from spinel was observed. The crystallite size was found to be 78 nm from the peak of the (311) plane observed at around 37 degrees using a CALSA detector, and it was 78 nm, which is extremely superior to the measurement results of the spinel particles obtained in Examples 1 to 6. It became a small value.
  • the average particle diameter d50 ( ⁇ m) of the prepared sample was obtained using a laser diffraction particle size distribution analyzer HELOS (H3355) & RODOS (manufactured by Nippon Laser Co., Ltd.) under the conditions of a dispersion pressure of 3 bar and a pulling pressure of 90 mbar.
  • volume% of particles of 15 ⁇ m or more The prepared sample was measured with a laser diffraction type particle size distribution analyzer HELOS (H3355) & RODOS (manufactured by Nippon Laser Co., Ltd.) under the conditions of a dispersion pressure of 3 bar and a pulling pressure of 90 mbar, and the cumulative distribution value to the total volume of all particles was measured.
  • the volume ratio (volume%) of particles having a particle diameter of 15 ⁇ m or more (hereinafter, may be referred to as “volume% of particles having a particle diameter of 15 ⁇ m or more”) was determined.
  • Alumina beads having a diameter of 5 mm were added to 25 g of the prepared sample and treated with a paint conditioner for 4 hours to pulverize the spinel particles.
  • Pre-treatment was performed using pulverized spinel particles under the conditions of 300° C. for 3 hours, and then using a dry automatic densimeter Acupic II1330 manufactured by Micromeritics Co., Ltd., a measurement temperature of 25° C., and helium as a carrier gas. It was measured at.
  • the prepared sample is placed on a holder for a measurement sample having a depth of 0.5 mm and filled so as to be flat with a constant load, and the sample is set in a wide-angle X-ray diffraction (XRD) device (Rint-Ultma manufactured by Rigaku Corporation). , Cu/K ⁇ ray, 40 kV/30 mA, scan speed of 2°/min, and scanning range of 10° to 70°.
  • XRD wide-angle X-ray diffraction
  • the crystallite diameter (nm) of the (311) plane was obtained from the peak observed at around 37 degrees under the following conditions using an X-ray diffractometer, SmartLab, manufactured by Rigaku Corporation, and a detector CALSA.
  • the dielectric loss tangent of the produced sample was obtained by using a vector network analyzer E8361A under the conditions of perturbation type resonator method, frequency 1 GHz, temperature 25° C. and humidity 50%.
  • the spinel particles S-a1 to S-a6 obtained in Examples 1 to 6 had d90/d10 of 5 or less, a narrow particle size distribution and uniform particle size. Further, the volume% of particles of 15 ⁇ m or more was 0% by volume, and particles having a large particle diameter of 15 ⁇ m or more were not contained. Furthermore, the major axis L/S was 2 or less, and the shape was close to a regular polygon. Further, the crystallite diameter of the (311) plane was as large as 120 nm or more, and it was presumed that the thermal conductivity was high.
  • the spinel particles S-b1 and S-b2 obtained in Comparative Examples 1 and 2 were more than 5, the particle size distribution was wide, and the particle sizes were uneven. Further, the volume% of particles of 15 ⁇ m or more was 3.0% by volume and 24.6% by volume, respectively, and there were particles having a large particle diameter of 15 ⁇ m or more. Further, the major axis L/S was more than 2, which was extremely larger than the spinel particles S-a1 to S-a6 obtained in Examples 1 to 6. In addition, the crystallite diameter of the (311) plane was as small as less than 120 nm, and it was estimated that the thermal conductivity was lower than that of the spinel particles S-a1 to S-a6 obtained in Examples 1 to 6. ..
  • the obtained kneaded product was taken out from the die in a strand form to obtain a PPS resin composition.
  • This is pelletized, weighed 9 cc, injection-molded using a small injection molding machine at an injection temperature of 320° C. and a mold temperature of 140° C., and a dumbbell test piece (width 5 mm, total length 75 mm, thickness equivalent to JIS K7161-2 1BA). 2 mm) was obtained.
  • the molded products of the PPS resin compositions (Examples 7 to 12) using the spinel particles S-a1 to S-a6 obtained in Examples 1 to 6 had a high density of 95% or more. Further, since these spinel particles have a large crystallite size, even when the spinel particles are highly filled so that the ratio of the volume of the spinel particles to the total volume of the PPS resin composition is 50 vol %, the dielectric constant and dielectric loss tangent, etc. A molded product of the PPS resin composition excellent in thermal conductivity and mechanical properties (bending strength, bending elastic modulus, tensile strength and tensile elastic modulus) was obtained without impairing the original performance of the spinel particles.
  • the spinel particles S-b1 and S-b2 obtained in Comparative Examples 1 and 2 have d90/d10 higher than those of the spinel particles S-a1 and S-a6 obtained in Examples 1 to 6.
  • a large volume of particles having a size of 15 ⁇ m or more is more than 0% by volume, a major axis L/a minor axis S is more than 2, and a molded product of a PPS resin composition using these spinel particles S-b1 to S-b2 ( In Comparative Examples 3 to 4), the compactness was low. It was speculated that this was due to the non-uniformity of the particles, which promoted the local agglomeration and the influence of the meshing of the coarse particles.
  • the molded products of the PPS resin compositions obtained in Comparative Examples 3 to 4 also had thermal conductivity and mechanical properties (bending strength, bending elastic modulus, tensile strength and tensile elastic modulus) of Examples 7 to 12. It was inferior to the molded product of the PPS resin composition obtained in.
  • the agent AH-154 (dicyandiamide, manufactured by Ajinomoto Fine-Techno Co., Inc.) is described in Table 3 such that the mass ratio of the total solid content to the solvent (cyclohexanone) is 20/10 with respect to the epoxy resin.
  • the obtained molded product was cut out so as to have a size of 10 mm ⁇ 10 mm ⁇ 0.5 mm, and transferred in a direction perpendicular to a surface at 25° C. by using a thermal conductivity measuring device (LFA467 HyperFlash, manufactured by NETZSCH) by a xenon flash method.
  • the thermal diffusivity of heating and the specific heat were measured. Five samples were measured and the average value was calculated. As the specific heat, the theoretical specific heat was used rather than the composition.
  • the thermal conductivity of the epoxy resin composition was estimated from the product of the obtained thermal diffusivity, specific heat and density.
  • the obtained molded product was cut out into a size of 80 mm ⁇ 10 mm ⁇ 0.5 mm, and a three-point bending strength test was performed.
  • One side of the obtained dumbbell test piece was supported at two points so that the distance between fulcrums was 40 mm, and the crosshead was moved at a speed of 1 mm/min at an intermediate position between the two points on the side opposite to this.
  • the maximum load when the test piece was broken was measured by applying a load, and the three-point bending strength (MPa) was calculated. Five samples of the bending strength were measured and an average value was obtained.
  • the spinel particles S-b1 and S-b2 obtained in Comparative Examples 1 and 2 have d90/d10 higher than those of the spinel particles S-a1 and S-a6 obtained in Examples 1 to 6.
  • Epoxy resin composition containing spinel particles S-b1 and S-b2, which are large and have a volume% of particles of 15 ⁇ m or more of more than 0 volume% and a major axis L/minor axis S of more than 2 (Comparative Example 5 In the cases of 6), due to the non-uniformity of the particles, local aggregation is promoted and the influence of the meshing of coarse particles causes the formation of agglomerates in the coated sheet, and the appearance of the sheet is significantly deteriorated, such as streaks and foaming.
  • Binder Resin C for Glass Ceramics Composition 100 parts of xylene is kept at 80° C. in a nitrogen stream and stirred, 68 parts of ethyl methacrylate, 29 parts of 2-ethylhexyl methacrylate, 3 parts of thioglycolic acid. And 0.2 part of a polymerization initiator (“Perbutyl O” (active ingredient t-butyl peroxy-2-ethylhexanoate, manufactured by NOF CORPORATION)) were added dropwise over 4 hours.
  • Perbutyl O active ingredient t-butyl peroxy-2-ethylhexanoate, manufactured by NOF CORPORATION
  • the ratio of spinel particles to glass powder is 40/60 by volume ratio (the content of spinel particles in the glass-ceramic substrate after firing is 40 volume% with respect to the total amount of the glass component and spinel particles.
  • the total amount (Nv) including the total solid content/solvent was 70% by mass, as described in Table 4.
  • the formulation was mixed using an orbital mixer to obtain a paste.
  • the prepared paste was formed into a film on a polyethylene terephthalate film by a doctor blade method and dried with a drier to form a plurality of green sheets for substrates.
  • the glass ceramic substrates (Examples 19 to 24) using the spinel particles S-a1 to S-a6 obtained in Examples 1 to 6 have a high density. It was as high as 95% or more.
  • the content of spinel particles in the glass ceramic substrate after firing is 40 vol% with respect to the total amount of the glass component and the spinel particles, so that the content of the spinel particles is high.
  • the glass-ceramic substrate is excellent in thermal conductivity and mechanical properties (bending strength) while maintaining the good appearance of the green sheet without impairing the original performance of spinel particles such as dielectric constant and dielectric loss tangent. was gotten.
  • the spinel particles S-b1 and S-b2 obtained in Comparative Examples 1 and 2 have d90/d10 higher than those of the spinel particles S-a1 and S-a6 obtained in Examples 1 to 6.
  • the volume ratio of particles having a size of 15 ⁇ m or more is more than 0% by volume, the major axis L/the minor axis S is more than 2, and a glass ceramic substrate using these spinel particles S-b1 to Sb2 (Comparative Example 7 to In 8), streaks were observed on the green sheet due to the effect of local agglomeration due to the non-uniformity of the particles and the meshing of coarse particles, resulting in a marked deterioration of the sheet appearance.
  • the glass ceramic substrates obtained in Comparative Examples 7 to 8 have low denseness and are inferior in thermal conductivity and mechanical characteristics (bending strength) to the glass ceramic substrates obtained in Examples 19 to 24. there were.
  • the spinel particles and the method for producing the same according to the embodiment it is possible to obtain a resin composition and a glass ceramics substrate that are more excellent in the filling property of the filler and the appearance at the time of making a sheet, have both high thermal conductivity and low dielectric loss tangent, and have excellent mechanical strength.
  • Spinel particles can be provided.

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Abstract

L'invention concerne des particules de spinelle dans lesquelles la taille moyenne de particule d50 sur la base du volume telle que déterminé dans la mesure de distribution de taille des particules par diffraction laser est de 0,01 µm à 5 µm, d90/d10 est de 5 ou moins, et la quantité de particules de 15 µm ou plus est de 0,1 % en volume ou moins par rapport au volume total de toutes les particules. L'invention concerne également un procédé de production des particules de spinelle dans lequel un composé de magnésium et un composé d'aluminium sont cuits en présence de molybdène.
PCT/JP2020/000438 2019-01-11 2020-01-09 Particules de spinelle, leur procédé de production, composition de résine, article moulé, composition, feuille crue, article cuit et substrat vitrocéramique WO2020145342A1 (fr)

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CN103265278A (zh) * 2013-06-20 2013-08-28 商丘师范学院 一种无团聚MgAl2O4纳米颗粒粉体的制备方法
CN104710169A (zh) * 2015-03-17 2015-06-17 武汉科技大学 一种镁铝尖晶石超细粉体及其制备方法
JP2016222501A (ja) * 2015-06-01 2016-12-28 Dic株式会社 板状アルミナ粒子およびその製造方法
WO2017221372A1 (fr) * 2016-06-23 2017-12-28 Dic株式会社 Particules de spinelle, leur procédé de production, et composition et article moule comprenant les particules de spinelle
JP2018052747A (ja) * 2016-09-26 2018-04-05 タテホ化学工業株式会社 酸化マグネシウム含有スピネル粉末及びその製造方法

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JPS6360106A (ja) * 1986-08-28 1988-03-16 Asahi Chem Ind Co Ltd スピネル粉体およびその製造方法
JP2001002413A (ja) * 1999-06-18 2001-01-09 Sumitomo Chem Co Ltd マグネシアスピネル粉末の製造方法
JP2008273817A (ja) * 2001-03-28 2008-11-13 Murata Mfg Co Ltd 絶縁体セラミック組成物およびそれを用いた絶縁体セラミック
CN1634802A (zh) * 2003-12-30 2005-07-06 中国科学院福建物质结构研究所 用共沉淀法制备镁铝尖晶石纳米粉体
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JP2008244136A (ja) * 2007-03-27 2008-10-09 Kyocera Corp ガラスセラミック多層基板の製造方法
CN103265278A (zh) * 2013-06-20 2013-08-28 商丘师范学院 一种无团聚MgAl2O4纳米颗粒粉体的制备方法
CN104710169A (zh) * 2015-03-17 2015-06-17 武汉科技大学 一种镁铝尖晶石超细粉体及其制备方法
JP2016222501A (ja) * 2015-06-01 2016-12-28 Dic株式会社 板状アルミナ粒子およびその製造方法
WO2017221372A1 (fr) * 2016-06-23 2017-12-28 Dic株式会社 Particules de spinelle, leur procédé de production, et composition et article moule comprenant les particules de spinelle
JP2018052747A (ja) * 2016-09-26 2018-04-05 タテホ化学工業株式会社 酸化マグネシウム含有スピネル粉末及びその製造方法

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