WO2020145341A1 - Composition de résine, article moulé, composition, feuille crue, article cuit, et substrat en vitrocéramique - Google Patents

Composition de résine, article moulé, composition, feuille crue, article cuit, et substrat en vitrocéramique Download PDF

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Publication number
WO2020145341A1
WO2020145341A1 PCT/JP2020/000434 JP2020000434W WO2020145341A1 WO 2020145341 A1 WO2020145341 A1 WO 2020145341A1 JP 2020000434 W JP2020000434 W JP 2020000434W WO 2020145341 A1 WO2020145341 A1 WO 2020145341A1
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Prior art keywords
mass
less
molybdenum
plate
spinel particles
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PCT/JP2020/000434
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English (en)
Japanese (ja)
Inventor
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 JP2020565198A priority Critical patent/JP7435473B2/ja
Publication of WO2020145341A1 publication Critical patent/WO2020145341A1/fr

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    • 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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • 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 a resin composition, a molded product, a composition, a green sheet, a fired product, and a glass ceramic substrate.
  • a method of improving the heat dissipation function of the device for example, a method of imparting thermal conductivity to the insulating member, more specifically, a method of adding an inorganic filler having high thermal conductivity to the resin to be the insulating member is known.
  • the inorganic filler used include alumina (aluminum oxide), boron nitride, aluminum nitride, magnesium oxide, magnesium carbonate and the like.
  • low temperature co-fired ceramics are generally glass powder (for example, CaO-Al 2 O 3 -SiO 2 -B 2 O 3 ) with Al 2 O 3 filler of several 10% ( It is a ceramic that is made of Ag or Cu with 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 with excellent physical properties.
  • a material having a low dielectric loss tangent is required in order to process and transmit a large amount of data quickly and efficiently.
  • the filler mainly used for LTCC substrates there are crushed alumina and plate-like alumina.
  • the dielectric loss tangent peculiar to alumina is as high as 10 ⁇ 3 , a glass ceramic substrate having a low dielectric loss tangent in addition to thermal conductivity and mechanical strength cannot be formed.
  • 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.
  • spinel has been applied to applications such as jewelry, fluorescent luminescent materials, catalyst carriers, adsorbents, photocatalysts, and heat-resistant insulating materials as described above, but applications as inorganic fillers having thermal conductivity are assumed. Not not. The reason for this is that, from the viewpoint of cost, conventionally, alumina is often used, and spinel, which was known to have lower thermal conductivity than the alumina, was not expected to be used as a thermally conductive inorganic filler. is there. In addition, spinel particles have high crystallite size, excellent thermal conductivity of the particles themselves, low dielectric loss tangent, and excellent chemical resistance. However, a glass ceramic substrate having excellent mechanical strength has not yet been found.
  • the present invention has been made in view of the above circumstances, and provides a resin composition having both high thermal conductivity and low dielectric loss tangent and excellent 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 having both high thermal conductivity and low dielectric loss tangent and excellent 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 inventors of the present invention have conducted extensive studies to achieve the above object, and as a result, by using plate-like spinel particles obtained by firing plate-like ⁇ -spinel particles containing molybdenum and a magnesium compound, high thermal conductivity was obtained. It has been found that an LTCC substrate having both high refractive index and low dielectric loss tangent and also excellent mechanical strength can be obtained, and has completed the present invention.
  • the present invention includes the following aspects.
  • Composition (3) The resin composition according to (1) or (2), wherein the content of molybdenum is 0.01% by mass or more and 1% by mass or less in terms of molybdenum trioxide with respect to 100% by mass of the plate-shaped spinel particles. Stuff.
  • the composition according to. (12) In any one of (8) to (11), the content of the plate-shaped spinel particles is 10 vol% or more and 50 vol% or less with respect to 100 vol% of the total volume of the plate-shaped spinel particles and the glass component.
  • the composition as described. (13) A green sheet formed by molding the composition according to any one of (8) to (12).
  • the resin composition of the above aspect it is possible to provide a resin composition having both high thermal conductivity and low dielectric loss tangent and excellent mechanical strength.
  • a molded product obtained by molding the resin composition can be provided.
  • the composition of the above aspect it is possible to provide a composition that has both high thermal conductivity and low dielectric loss tangent and is used for producing a glass ceramic substrate having excellent mechanical strength.
  • the green sheet of the above aspect it is possible to provide a green sheet manufactured using the composition.
  • a baked product of the above aspect a baked product obtained by baking the composition can be provided.
  • the glass ceramic substrate of the above aspect it is possible to provide a glass ceramic substrate including the fired product.
  • the resin composition according to the embodiment contains plate-like spinel particles and a resin.
  • the plate-like spinel particles contain molybdenum in the particles.
  • the resin composition according to the embodiment may further contain a curing agent, a curing catalyst, a viscosity modifier, a plasticizer, etc., if necessary.
  • 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 plate-like spinel particles contained in the resin composition according to the embodiment include molybdenum in the particles, and the contained form of molybdenum is not particularly limited, but molybdenum adheres to the surface of the spinel particles, coating, bonding, and other forms similar thereto. And a combination of molybdenum and spinel incorporated into the spinel.
  • 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 “aspect ratio” is the ratio of the average particle diameter of spinel particles divided by the thickness.
  • plate-like as used herein means that the aspect ratio is 2 or more.
  • the “thickness of spinel particles” is the arithmetic mean value of the thickness measured for at least 50 spinel particles randomly selected from an image obtained by a scanning electron microscope (SEM).
  • the “particle diameter” is the maximum length of the distance between two points on the contour line of the spinel particle.
  • the “average particle size of spinel particles” is the arithmetic mean value of the particle sizes measured for at least 50 plate-like spinel particles randomly selected from the images obtained by a scanning electron microscope (SEM).
  • the plate-like spinel particles have a thickness of preferably 0.01 ⁇ m or more and 5 ⁇ m or less, more preferably 0.05 ⁇ m or more and 3 ⁇ m or less, still more preferably 0.1 ⁇ m or more and 1 ⁇ m or less, still more preferably 0.15 ⁇ m or more and 0.75 ⁇ m or less, It is particularly preferably 0.2 ⁇ m or more and 0.5 ⁇ m or less, and most preferably 0.2 ⁇ m or more and 0.47 ⁇ m or less.
  • the thickness of the plate-like spinel particles is within the above range, the mechanical strength can be made more excellent.
  • the plate-like spinel particles have an average particle diameter of preferably 0.1 ⁇ m or more and 500 ⁇ m or less, more preferably 0.3 ⁇ m or more and 100 ⁇ m or less, further preferably 0.5 ⁇ m or more and 50 ⁇ m or less, further preferably 1 ⁇ m or more and 30 ⁇ m or less, and 3 ⁇ m or more It is particularly preferably 20 ⁇ m or less, and most preferably 4 ⁇ m or more and 9 ⁇ m or less.
  • the surface of the molded product containing the plate-like spinel particles can be made smoother.
  • the plate-like spinel particles have an aspect ratio of 3 or more and 500 or less, preferably 5 or more and 100 or less, more preferably 7 or more and 50 or less, still more preferably 9 or more and 30 or less, particularly preferably 10 or more and 25 or less, and 14 Most preferably, it is 0.5 or more and 20 or less.
  • the aspect ratio is equal to or more than the above lower limit, the mechanical strength tends to be more excellent, while when the aspect ratio is less than or equal to the above upper limit, the surface of the molded article containing the plate-like spinel particles becomes smoother. It can be anything.
  • the conditions of thickness, average particle diameter, and aspect ratio can be combined in any manner as long as it is in a plate shape.
  • the plate-shaped spinel particles may have a circular plate shape or an elliptical plate shape, but the particle shape is, for example, a polygonal plate shape such as a hexagonal to octagonal shape that facilitates heat transfer characteristics, handleability, and manufacturing. It is preferable in terms of easiness and the like.
  • the crystallite diameter of the (311) plane of the plate-like spinel particles is preferably 60 nm or more, more preferably 65 nm or more, even more preferably 66 nm or more, even more preferably 70 nm or more.
  • the upper limit of the crystallite diameter of the (311) plane is not particularly limited and can be, for example, 200 nm or less, 150 nm or less, 100 nm or less, and 90 nm or less. And can be 82 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 plate-like spinel particles contain molybdenum.
  • the plate-like spinel particles 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 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 plate-shaped spinel particles as MoO 3, it may be included in the plate-shaped 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 plate-like spinel particles, or in a form in which molybdenum is incorporated into the spinel. It may be contained or a combination thereof.
  • the content of molybdenum is not particularly limited, but from the viewpoint of high thermal conductivity of the plate-shaped spinel particles, it is preferably 1% by mass or less in terms of molybdenum trioxide with respect to 100% by mass of the plate-shaped spinel particles, and 0 0.8 mass% or less is more preferable, and from the viewpoint that the plate-like spinel particles exhibit higher density, 0.7 mass% or less is more preferable, and 0.65 mass% or less is further preferable, It is particularly preferably 0.61% by mass or less.
  • the lower limit of the content of molybdenum is not particularly limited, it can be 0.01 mass% or more, 0.05 mass% or more, 0.1 mass% or more, It can be 0.15 mass% or more, can be 0.2 mass% or more, can be 0.25 mass% or more, and can be 0.31 mass% or more.
  • the content of molybdenum in the plate-like spinel particles can be obtained 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 present in the raw materials or are inevitably mixed in the plate-shaped spinel particles in the manufacturing process, and are essentially unnecessary, but they are in small amounts and affect the properties of the plate-shaped spinel particles. Means impurities that do not extend.
  • 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 plate-like 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 plate-like 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 plate-shaped spinel particles is preferably 10% by mass or less, more preferably 5% by mass or less, and 2% by mass or less, relative to 100% by mass of the plate-shaped spinel particles. Is more preferable.
  • the plate-like spinel particles may be surface-treated.
  • the plate-like spinel particles may be used alone or in combination of two or more. Further, plate-like spinel particles and other fillers may be used in combination. Examples of other fillers include aluminum oxide, boron nitride, aluminum nitride, magnesium oxide, magnesium carbonate and the like.
  • the content of the plate-like spinel particles is preferably 10% by mass or more and 95% by mass or less, and more preferably 30% by mass or more and 90% by mass or less, based on the mass of the resin composition.
  • the content of the plate-shaped spinel particles is at least the above lower limit value, the high thermal conductivity of the plate-shaped spinel particles can be more efficiently exhibited.
  • the content of the plate-like spinel particles is equal to or less than the above upper limit value, a resin composition having more excellent moldability can be obtained.
  • the method for producing the plate-like spinel particles is not particularly limited, and known techniques can be applied as appropriate, but 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.
  • simple mixing for mixing powders, mechanical mixing using a crusher or mixer, mixing using a mortar or the like is performed.
  • 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 in the aluminum compound to the magnesium element in the magnesium compound (aluminum element/magnesium element) is 1.8 or more. It is preferable to mix so as to be 2.2 or less, and 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 average particle diameter of the magnesium compound is not particularly limited, but is preferably 1 ⁇ m or more and 10 ⁇ m or less, more preferably 1.5 ⁇ m or more and 5 ⁇ m or less, further preferably 2 ⁇ m or more and 4 ⁇ m or less, and particularly preferably 2.5 ⁇ m or more and 3.5 ⁇ m or more.
  • the average particle diameter 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, the manufacturing method according to the embodiment tends to obtain spinel particles that reflect the shape of the aluminum compound, and thus the plate shape is preferable.
  • the average particle size of the aluminum compound is not particularly limited, but it is appropriately adjusted according to the particle size of the plate-like spinel to be obtained.
  • the average particle size of the aluminum compound is 0.1 ⁇ m or more and 500 ⁇ m or less, preferably 0.3 ⁇ m or more and 100 ⁇ m or less, more preferably 0.5 ⁇ m or more and 50 ⁇ m or less, further preferably 1 ⁇ m or more and 30 ⁇ m or less, and more preferably 1 ⁇ m or more and 20 ⁇ m or less. More preferably, it is particularly preferably 1 ⁇ m or more and 10 ⁇ m or less, most preferably 3.8 ⁇ m or more and 7.0 ⁇ m or less.
  • the average particle diameter of the aluminum compound is at least the above lower limit value, particle aggregation can be more effectively prevented in spinel crystallization.
  • the average particle diameter of the aluminum compound is not more than the above upper limit value, spinel crystallization can proceed more efficiently to the central portion of the particles.
  • the thickness of the aluminum compound is 0.01 ⁇ m or more and 5 ⁇ m or less, preferably 0.05 ⁇ m or more and 3 ⁇ m or less, more preferably 0.1 ⁇ m or more and 1 ⁇ m or less, still more preferably 0.15 ⁇ m or more and 0.75 ⁇ m or less, and 0.2 ⁇ m. Above 0.5 ⁇ m is particularly preferable. When the thickness of the aluminum compound is within the above range, plate-like spinel particles having a larger aspect ratio can be obtained.
  • the aspect ratio of the aluminum compound is 3 or more and 500 or less, preferably 5 or more and 100 or less, more preferably 7 or more and 50 or less, further preferably 9 or more and 30 or less, and particularly preferably 10 or more and 25 or less.
  • the aspect ratio is the above lower limit or more, plate-like spinel particles having more excellent mechanical strength can be obtained, while when the aspect ratio is not more than the above upper limit, a molded article or coating film having a smoother surface can be obtained. It becomes plate-like spinel particles that can be used.
  • 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 compound When a molybdenum compound is used as the fluxing agent when preparing an aluminum compound by the flux method, an aluminum compound containing molybdenum can be obtained via the intermediate compound aluminum molybdate. At this time, molybdenum contained in the aluminum compound may correspond to a flux impurity which is said to be a disadvantage of the flux method. However, as described above, in one embodiment of the present invention, the molybdenum contained in the aluminum compound is plate-shaped. A suitable effect can be exhibited when producing spinel particles.
  • 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 less likely 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 based on a hexagonal bipyramid 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.
  • 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.
  • the cooling method is not particularly limited, and natural cooling may be used, 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 0.86 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 plate-like 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.
  • 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.
  • the plate-shaped spinel particles can be manufactured more easily by using the plate-shaped alumina particles 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.
  • 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 lower than 1300°C, more preferably 800°C or higher and lower than 1300°C, and further preferably 900°C or higher and 1200°C or lower.
  • the firing temperature is at most the above upper limit, the plate-like spinel particles can be produced more efficiently in a shorter time.
  • the firing temperature is not more than the above upper limit, 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, plate-like 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 addition amount of the shape control agent is preferably 0.01% by mass or more and 20% by mass or less, and more preferably 0.1% by mass or more and 10% by mass or less with respect to 100% by mass of the raw material.
  • 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 amount of the shape control agent added is within the above range, it is possible to obtain plate-like spinel particles having more excellent surface smoothness. Further, the aspect ratio can be increased, and the mechanical strength tends to be superior.
  • 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 method for producing plate-like spinel particles 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.
  • plate-like spinel particles may aggregate and may not satisfy the particle size range suitable for the present invention. Therefore, the plate-like spinel particles may be pulverized, if necessary, so as to satisfy the particle size range 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 plate-like spinel particles are preferably classified in order to adjust the average particle size and improve the fluidity of the powder, or to suppress an increase in viscosity when blended in a binder for forming a 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 plate-like spinel particles can be adjusted by the presence or absence of the pulverization or classification and the selection of the conditions.
  • the plate-like spinel particles, or the plate-like spinel particles obtained by the above-mentioned production method are those with little aggregation or non-aggregation, which are likely to exhibit their original properties and are excellent in their handleability themselves, and to be dispersed. When dispersed in a medium to be used, it is preferable from the viewpoint of more excellent dispersibility.
  • the method for producing plate-like spinel particles without the above-mentioned pulverization step or classification step, if one with less aggregation or one without aggregation is obtained, it is not necessary to perform the above-mentioned step, and the purpose is excellent. Plate-like spinel particles having properties can be produced with high productivity, which is preferable.
  • 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 20% by mass or more and 65% by mass or less with respect to the mass of the resin composition. % Or less, more preferably 30% by mass or more and 63% by mass or less, still more preferably 30% by mass or more and 61% by mass or less.
  • 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 plate-like spinel particles have excellent heat conduction performance because the crystallite size of the (311) plane is larger than that of spinel particles obtained by the conventional manufacturing method.
  • the plate-like spinel particles have a high aspect ratio and have a shape having excellent heat transfer characteristics, when compounded in a resin, the plate-like spinel particles exhibit higher thermal conductivity than conventional spinel particles and alumina particles. Therefore, the resin composition according to the embodiment is preferably used as a heat conductive material.
  • the plate-like spinel particles obtained by the above-mentioned production method have a micron-order particle size (1000 ⁇ m or less) and a large crystallite size, they are excellent in dispersibility in a resin, and thus are more excellent as a resin composition. It can exhibit conductivity.
  • the plate-like spinel particles obtained by the above-mentioned production method are particles having a uniform plate-like shape by synthesizing by the solid phase method, and are not obtained by crushing amorphous particles. Since it is not present, it has excellent smoothness and fluidity, and also has excellent dispersibility in the 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 plate-like 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 plate-like spinel particles and a glass component.
  • the plate-like spinel particles contain molybdenum in the particles.
  • each component will be described.
  • Plate-shaped spinel particles those described in the above resin composition can be used, and therefore the description thereof is omitted here.
  • the content of the plate-shaped spinel particles is preferably 10 vol% or more and 50 vol% or less, more preferably 20 vol% or more and 40 vol% or less, with respect to the total volume of the plate-shaped spinel particles and the glass component of 100 vol%. More preferably, it is 25 vol% or more and 35 vol% or less.
  • the content of the plate-shaped spinel particles is at least the above lower limit value, the high thermal conductivity of the plate-shaped spinel particles can be more efficiently exhibited.
  • the content of the plate-like spinel particles is equal to or less 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 plate-like spinel particles and the glass component.
  • the plate-like spinel is a particle, it is preferable that the glass component mixed with it is also a particle 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 the plate-like spinel particles, the difference in the average particle size between the glass powder and the plate-like 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, etc. in addition to the plate-like 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 effect 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.
  • 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 plate-like spinel particles with a glass component.
  • the composition which concerns on embodiment can be manufactured by mixing the said plate-shaped spinel particle, a glass component, a binder component, a plasticizer, and a solvent, for example.
  • 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, 35 mass% or more and 70 mass% or less are more preferable, 40 mass% or more and 60 mass% or less Is more preferable, and 40% by mass or more and 50% by mass or less is particularly preferable.
  • the content of the plate-shaped spinel particles relative to the total mass of the plate-shaped spinel particles and the glass component of 100 mass% is, for example, preferably 5 mass% or more and 50 mass% or less, more preferably 10 mass% or more and 40 mass% or less, 20 mass% or more and 35 mass% or less are more preferable, 25 mass% or more and 33 mass% or less are still more preferable, and 30 mass% or more and 31 mass% or less are especially preferable.
  • a binder component 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 the total mass of the composition of 100% by mass is, in terms of solid content, preferably 0.5% by mass or more and 10% by mass or less, more preferably 1% by mass or more and 8% by mass or less, and 3
  • the content is more preferably 5% by mass or more and 5% by mass or less, still more preferably 3.5% by mass or more and 4.5% by mass or less, and particularly preferably 4% by mass or more and 4.3% by mass or less.
  • the content of the plasticizer with respect to 100% by mass of the total composition is preferably 0.5% by mass or more and 5% by mass or less, more preferably 1% by mass or more and 3% by mass or less, and 1.1% 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 23 mass% or more and 30 mass% or less, and particularly preferably 25 mass% or more and 27 mass% or less.
  • the amount of the plate-shaped spinel particles, the glass component, the binder component, the plasticizer, and the solvent contained in the composition according to the embodiment is within the above range, the moldability of the composition and the strength and heat after firing. The conductivity can be further improved.
  • 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 clean 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 plate-like spinel particles were dispersed in the glass continuous layer, thereby forming the plate-like spinel particles and the glass.
  • a fired product in which the components are strongly adhered 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 plate-like 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 varies depending on the density of the glass component used, the density of the plate-like spinel particles, and the mixing ratio.
  • the density of the fired product (glass ceramic substrate) according to the embodiment is the density of the glass component.
  • the density of the plate-like 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).
  • 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 plate-like spinel particles in the fired product (glass-ceramic substrate) according to the embodiment are well compatible with each other and more interfaces are brought into close contact with each other to form a dense structure, The measured density of the fired product (glass-ceramic substrate) becomes closer to the theoretical density.
  • the measured density of the ceramic substrate 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 familiarity between the glass component and the plate-like 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 binder component, the plasticizer, and the solvent contained in the composition are pyrolyzed or volatilized, while the glass component is melted to form a dispersion medium constituting the fired product. Be at least part.
  • the plate-like spinel particles are dispersed in the glass component which is solidified after melting. Note that the plate-like spinel particles do not usually melt completely if they are baked at least under the above-mentioned baking conditions. Therefore, the plate-like spinel particles contained in the fired product according to the embodiment have the various characteristics described above.
  • the fired product according to the embodiment contains the plate-like 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 amount of the plate-like spinel particles and the glass component contained in the fired product according to the embodiment is within the above range, which can be more excellent in terms of strength and thermal conductivity after firing. ..
  • the thermal conductivity of the fired product (glass ceramics substrate) is preferably 1.6 W/mk or more, more preferably 1.8 W/mk or more, and 2.0 W/mk or more. More preferably, it is more preferably 2.5 W/mk or more, still more preferably 3.0 W/mk or more, most preferably 3.2 W/mk or more.
  • the upper limit of the thermal conductivity of the fired product (glass ceramic substrate) is not particularly limited, but it can be 6.0 W/mk or less, 5.0 W/mk or less, and 4.0 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) according to the embodiment is preferably 130 Mpa or more, more preferably 140 Mpa or more, further preferably 160 Mpa or more, and more preferably 180 Mpa or more. More preferably, 200 Mpa or more is particularly preferable, and 215 Mpa or more is most preferable.
  • the bending strength of the fired product (glass-ceramic substrate) is not particularly limited, but can be 300 MPa or less, 280 MPa or less, 260 MPa or less, and 252 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 purpose of incorporating the inorganic particles has been to increase the strength of the substrate and to suppress the shrinkage of the substrate.
  • thermal characteristics such as thermal conductivity
  • spinel particles have excellent characteristics among various inorganic particles.
  • the plate-like spinel particles have high thermal conductivity and are particularly excellent.
  • the glass-ceramic substrate containing the plate-like spinel particles has higher thermal conductivity and higher bending strength than the glass-ceramic substrate containing the conventional spinel particles. The reason why such an effect is obtained will be considered below.
  • the plate-like spinel particles have high thermal conductivity because they contain molybdenum in the particles.
  • the plate-like spinel particles have the above-mentioned shape and have higher crystallinity than conventional spinel particles. Further, by using the spinel particles having a large aspect ratio, when they are mixed with a glass component or another inorganic particle material, the dispersion state is most excellent for forming a heat transfer path. In addition, the spinel particles that are oriented and dispersed in the direction perpendicular to the bending direction of the fired product exert a strong interaction with the glass component that is the matrix, and have the effect of improving bending strength and elastic modulus. As a result, the calcined product is considered to have high thermal conductivity and excellent mechanical strength.
  • the glass-ceramic substrate manufactured using the plate-like spinel particles as a raw material is expected to have a low relative permittivity as low as the relative dielectric constant value of the conventional spinel particles.
  • the evaluation of the interface between the glass component in the substrate and the plate-like spinel particles was performed by chemical mechanical polishing of the substrate cross section, followed by ion milling treatment, SEM observation of the polished surface, and backscattered electron image caused by element difference. There is a method of obtaining the contrast of.
  • the porosity% can be expressed by obtaining the area ratio of the glass component phase, the plate-like spinel component phase, and the void phase.
  • the substrate has extremely few voids and excellent compactness as compared with the case of using the conventional spinel particles.
  • the substrate cross section is observed by TEM or STEM to understand the glass component near the interface and the interface, and the crystal structure and composition of the plate-like spinel particles.
  • Molybdenum remaining on the surface of the particles was removed by washing with water and drying to obtain 96 g of white powder.
  • the obtained powder had an average particle size of 7.0 ⁇ 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.
  • 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 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 A-1 was performed except that 5 g of the product (produced by Co., Ltd.) 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 performed, sharp peak scattering derived from ⁇ -alumina appeared, no alumina crystal system peak other than ⁇ crystal structure was observed, and it was 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, and washed with water and dried to remove molybdenum remaining on the surface of the particles to obtain 24.5 g of white powder. It was confirmed by SEM observation that the obtained powder was plate-shaped, had very few aggregates, and had excellent handleability. Further, when XRD measurement was performed, sharp peak scattering derived from spinel was observed.
  • the crystallite diameter was determined from the peak of the (311) plane observed at around 37 degrees using a CALSA detector, it was confirmed to be 82 nm. Furthermore, it was confirmed from the result of the quantitative X-ray fluorescence analysis that the obtained particles contained 0.48% by mass of molybdenum in terms of molybdenum trioxide.
  • ⁇ Synthesis Example B-2 Synthesis of spinel particles Sa2 20 g of ⁇ -alumina particles A-2 obtained in Synthesis Example A-2 and 7.86 g of magnesium oxide (Kamishima Chemical Co., Ltd. average particle diameter 3.5 ⁇ m) are prepared. The same operation as in Synthesis Example B-1 was carried out except that a mixture was obtained by mixing in a mortar to obtain 24.6 g of a white powder. The obtained powder had an average particle diameter of 4.0 ⁇ m and was obtained in Synthesis Example A-2 having an average particle diameter of 3.8 ⁇ m, which is smaller than the ⁇ -alumina particles A-1 obtained in Synthesis Example A-1.
  • the same operation as in Synthesis Example B-1 was carried out except that 1.67 g of molybdenum trioxide was mixed in a mortar to obtain a mixture, to obtain 24.6 g of a white powder. It was confirmed by SEM observation that the obtained powder was plate-shaped, had very few aggregates, and had excellent handleability. Further, when XRD measurement was performed, sharp peak scattering derived from spinel was observed.
  • the crystallite size was determined from the peak of the (311) plane observed at around 37 degrees using a CALSA detector, and was found to be 88 nm.
  • the crystallite size in Synthesis Example B-1 without addition of molybdenum trioxide was calcined. It was confirmed that molybdenum trioxide contributed to the crystal growth because the crystallite diameter was larger than that of the above. Furthermore, it was confirmed from the results of the fluorescent X-ray quantitative analysis that the obtained particles contained molybdenum in an amount of 0.61% by mass in terms of molybdenum trioxide.
  • the crystallite size was found to be 66 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 0.31 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 24.6 g of white powder. When the obtained powder was observed by SEM, it was plate-shaped, but the particle shapes and particle sizes were uneven.
  • the average thickness of the plate was 1 ⁇ m
  • the average particle size determined by a laser diffraction type particle size distribution meter was 2.9 ⁇ m
  • the aspect ratio determined by the average particle size/thickness average was 2.9. The value was extremely smaller than the aspect ratio of the plate-like spinel particles obtained in 1 to B-4.
  • the value was extremely smaller than the aspect ratio of the plate-like spinel particles obtained in B-1 to B-4. Further, when XRD measurement was performed, peak scattering derived from spinel was observed. Using a CALSA detector, the crystallite size was found to be 88 nm from the peak of the (311) plane observed at around 37 degrees.
  • the average particle diameter d50 ( ⁇ m) of the prepared sample was calculated 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 suction pressure of 90 mbar, and the average particle diameter L And
  • Aspect ratio average particle diameter L of plate-like spinel particles/thickness T of plate-like spinel particles
  • 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 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.
  • 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.
  • the dielectric loss tangent was determined under the conditions of perturbation type resonator method, frequency 1 GHz, temperature 25° C., and humidity 50%.
  • 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.
  • -154 (dicyandiamide, manufactured by Ajinomoto Fine-Techno Co., Inc.) was blended as shown in Table 4 so as to be 0.95 mass% with respect to the epoxy resin.
  • the blend was kneaded with a rotation-revolution type kneader to obtain an epoxy resin composition.
  • a resin cured product having a thickness of 0.5 mm was prepared by hot press molding (curing condition 170° C. ⁇ 20 minutes).
  • the resin cured product was further cured in a dryer at 170° C. for 2 hours and 200° C. for 2 hours to obtain a molded product.
  • 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.
  • a thermal conductivity measuring device LFA467 HyperFlash, manufactured by NETZSCH
  • 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 molded products of the PPS resin compositions obtained in Comparative Examples 1 and 2 were more dense than the molded products of the PPS resin compositions obtained in Examples 1 to 4, the denseness, the thermal conductivity, and the mechanical properties ( The results were inferior in bending strength, flexural modulus, tensile strength and tensile modulus. Further, from Tables 3 and 4, the same tendency was observed in the molded product of the nylon resin composition and the molded product of the epoxy resin composition as in the molded product of the PPS resin composition.
  • composition according to the embodiment it is possible to obtain a molded article having high thermal conductivity and mechanical properties, which is highly dense and does not impair the inherent properties of spinel particles such as dielectric constant and dielectric loss tangent. It was shown to be obtained.
  • Binder Resin C for Glass Ceramics Composition 100 parts of xylene was kept at 80° C. in a nitrogen stream and stirred, 68 parts of ethyl methacrylate, 29 parts of 2-ethylhexyl methacrylate, thioglycolic acid. A mixture of 3 parts and 0.2 part of a polymerization initiator (“Perbutyl O” (active ingredient t-butyl peroxy-2-ethylhexanoate, manufactured by NOF CORPORATION)) was 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 30/70 by volume ratio (the content of spinel particles in the glass-ceramic substrate after firing is 30 volume% with respect to the total amount of glass components and spinel particles.
  • the total amount (Nv) including the total solid content/solvent was 70% by mass, as described in Table 5.
  • 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.
  • a plurality of green sheets for substrates are laminated so that the thickness of the fired glass-ceramic substrate is 0.2 mm, pressed at 50 MPa, and fired in the atmosphere at 900° C. for 1 hour. Then, a glass ceramic substrate was obtained.
  • the resin composition according to the embodiment it is possible to provide a resin composition having both high thermal conductivity and low dielectric loss tangent and excellent mechanical strength.
  • the molded product according to the embodiment can provide a molded product obtained by molding the resin composition.
  • the composition according to the embodiment it is possible to provide a composition that has both high thermal conductivity and low dielectric loss tangent and is used for manufacturing a glass ceramic substrate having excellent mechanical strength.
  • the green sheet according to the embodiment it is possible to provide a green sheet manufactured using the composition.
  • the fired product according to the embodiment can provide a fired product obtained by firing the composition.
  • the glass ceramic substrate according to the embodiment it is possible to provide a glass ceramic substrate including the fired product.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Ceramic Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)

Abstract

L'invention concerne une composition de résine contenant une résine et des particules de spinelle lamellaires, les particules contenant du molybdène. Un article moulé selon la présente invention est obtenu par moulage de la composition de résine. Une composition selon la présente invention contient un constituant en verre et des particules de spinelle lamellaires, les particules contenant du molybdène. Une feuille crue selon la présente invention est obtenue par moulage de la composition. Un article cuit selon la présente invention est obtenu par cuisson de la composition. Un substrat en vitrocéramique selon la présente invention comprend l'article cuit.
PCT/JP2020/000434 2019-01-11 2020-01-09 Composition de résine, article moulé, composition, feuille crue, article cuit, et substrat en vitrocéramique WO2020145341A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002079114A1 (fr) * 2001-03-28 2002-10-10 Murata Manufacturing Co.,Ltd. Composition destinee a des ceramiques d'isolation et ceramiques d'isolation contenant ces compositions
WO2015137468A1 (fr) * 2014-03-14 2015-09-17 大日精化工業株式会社 Oxyde complexe thermoconducteur, son procédé de production, composition contenant un oxyde complexe thermoconducteur et son utilisation
WO2016148236A1 (fr) * 2015-03-18 2016-09-22 Dic株式会社 Particules de spinelle, leur procédé de production, et composition et moulage comprenant les particules de spinelle
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

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002079114A1 (fr) * 2001-03-28 2002-10-10 Murata Manufacturing Co.,Ltd. Composition destinee a des ceramiques d'isolation et ceramiques d'isolation contenant ces compositions
WO2015137468A1 (fr) * 2014-03-14 2015-09-17 大日精化工業株式会社 Oxyde complexe thermoconducteur, son procédé de production, composition contenant un oxyde complexe thermoconducteur et son utilisation
WO2016148236A1 (fr) * 2015-03-18 2016-09-22 Dic株式会社 Particules de spinelle, leur procédé de production, et composition et moulage comprenant les particules de spinelle
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

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