WO2016092952A1 - Poudre de nitrure de bore hexagonal, procédé de production de cette dernière, composition à base de résine, et feuillet de résine - Google Patents

Poudre de nitrure de bore hexagonal, procédé de production de cette dernière, composition à base de résine, et feuillet de résine Download PDF

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WO2016092952A1
WO2016092952A1 PCT/JP2015/079109 JP2015079109W WO2016092952A1 WO 2016092952 A1 WO2016092952 A1 WO 2016092952A1 JP 2015079109 W JP2015079109 W JP 2015079109W WO 2016092952 A1 WO2016092952 A1 WO 2016092952A1
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mass
hbn
boron nitride
powder
hexagonal boron
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PCT/JP2015/079109
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English (en)
Japanese (ja)
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雄樹 大塚
賢 深澤
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昭和電工株式会社
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B21/00—Nitrogen; Compounds thereof
    • C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
    • C01B21/064—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron with boron
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • 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
    • C08K3/38—Boron-containing compounds
    • 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 hexagonal boron nitride (hereinafter also referred to as “hBN”) powder and a resin sheet using the hBN powder, and particularly includes an aggregate composed of dense primary particles of hBN.
  • the present invention relates to a high-purity and fine hBN powder, a method for producing the hBN powder, a resin composition and a resin sheet using the hBN powder.
  • hBN particles have a layered structure similar to graphite, and hBN powder has excellent properties such as thermal conductivity, electrical insulation, chemical stability, solid lubricity, and thermal shock resistance. It is used as a heat dissipation material, solid lubricant / release agent, raw material for producing hBN sintered bodies, and the like.
  • hBN powder has a low crystallinity by mixing a boron compound such as boric acid or borax and a nitrogen compound such as melamine or urea and firing at a relatively low temperature in an ammonia atmosphere or a non-oxidizing gas atmosphere.
  • a crude hBN powder is produced, and then the obtained crude hBN is baked at a high temperature in a non-oxidizing gas atmosphere to grow crystals (Patent Documents 1 to 3).
  • a heat conductive member such as a conductive sheet and heat conductive grease.
  • hBN generally has a scaly particle shape and a high aspect ratio, if the filling rate is increased, the particles are likely to be aligned in a certain direction, and anisotropy tends to occur in the properties of the obtained resin and rubber molded product. . Thus, when anisotropy arises, characteristics, such as thermal conductivity of a heat conductive member, such as a heat conductive sheet, electrical insulation, a thermal shock resistance, will fall.
  • this additive is also not preferable because it can cause deterioration in thermal conductivity and electrical insulation.
  • the thermal conductive sheet is becoming thinner, so the presence of an additive that deteriorates electrical insulation is not preferable.
  • hBN powder having a small particle size is required in order to cope with the thinning of the heat conductive sheet.
  • Patent Document 6 describes an hBN powder having a specific crystallite size and an oxygen content within a specific range, having an average particle size of 10 ⁇ m or less, and having high fluidity and thermal conductivity.
  • both a low viscosity and a high thermal conductivity are imparted to a heat conductive resin composition.
  • the hBN powder described in Patent Document 6 has a small average particle size of 10 ⁇ m or less, its thermal conductivity is insufficient.
  • JP-A-61-286207 Japanese Patent No. 3461651 Japanese Patent Publication No. 5-85482 JP 2011-98882 A JP 2005-343728 A JP 2013-40062 JP
  • the present invention contains aggregates composed of dense primary particles of hBN (hereinafter also referred to as “aggregates”), the aggregates having high strength, high purity, and fine hBN powder, the hBN powders It is an object of the present invention to provide a resin composition and a resin sheet that can exhibit higher thermal conductivity than conventional methods using the hBN powder.
  • hBN powder containing aggregates of primary particles of hBN the powder content under a sieve having an opening of 45 ⁇ m is 80% by mass or more, the primary particle diameter is 5 ⁇ m or less, and the BET specific surface area is 15 to 25 m 2.
  • the present inventors have found that the above-mentioned problem can be solved by obtaining hBN having a 50% volume cumulative particle diameter D 50 of 10 to 15 ⁇ m / g.
  • the hBN powder contains high-strength agglomerates composed of dense primary particles of hBN, so that the agglomerates maintain their granular shape without breaking even if they are fine powders. It is thought that Moreover, since the strength of the aggregate is high and the aggregate does not break, it is considered that anisotropy does not occur in the thermal conductive sheet and high thermal conductivity can be expressed.
  • the strength of the aggregate is evaluated by the strength test described in the Examples, and is expressed by the strength when the aggregate is broken by compression (hereinafter, also referred to as “compression fracture strength”). The present invention is based on the above findings.
  • a hexagonal boron nitride powder containing an aggregate of primary particles of hexagonal boron nitride The powder content under a sieve having a mesh opening of 45 ⁇ m is 80% by mass or more, the primary particle diameter is 5 ⁇ m or less, the BET specific surface area is 15 to 25 m 2 / g, and the 50% volume cumulative particle diameter D 50 is 10 to 15 ⁇ m.
  • Hexagonal boron nitride powder [2] The hexagonal boron nitride powder according to the above [1], wherein the powder content under a sieve having an opening of 45 ⁇ m is 85% by mass or more.
  • a resin composition comprising 10 to 90% by volume of the hexagonal boron nitride powder according to any one of [1] to [6] above.
  • a resin sheet comprising the resin composition according to [7] or a cured product thereof.
  • an agglomerate composed of dense primary particles of hBN is contained, and the agglomerate is high in strength, high purity and fineness, a method for producing the hBN powder, and the hBN powder.
  • the resin composition and the resin sheet which can express higher heat conductivity than before can be provided.
  • FIG. 2 is a SEM image of an aggregate of primary particles of hBN obtained in Example 1.
  • FIG. 2 is a SEM image of an aggregate of primary particles of hBN obtained in Example 1.
  • FIG. 2 is an SEM image of an aggregate of primary particles of hBN obtained in Comparative Example 1.
  • It is a schematic diagram of the resin sheet containing the hexagonal boron nitride powder which concerns on this invention.
  • the hexagonal boron nitride powder (hBN powder) of the present invention is an hBN powder containing agglomerates of primary particles of hBN, the powder content under a sieve having a mesh size of 45 ⁇ m is 80% by mass or more, and the primary particle size is 5 ⁇ m or less, a BET specific surface area of 15 to 25 m 2 / g, and a 50% volume cumulative particle diameter D 50 of 10 to 15 ⁇ m.
  • the primary particle size of the hBN powder of the present invention is an average of 5 ⁇ m or less, preferably 0.5 to 5 ⁇ m, more preferably 1 to 4.5 ⁇ m, from the viewpoint of improving the compression fracture strength of the aggregate of primary particles. More preferably, it is 1.4 to 4 ⁇ m, still more preferably 1.8 to 3.5 ⁇ m, and still more preferably 2 to 3 ⁇ m.
  • a primary particle diameter is the number average value of the long diameter of a primary particle measured by the method as described in an Example.
  • the primary particles contained in the hBN powder of the present invention may be scaly.
  • scale-like means a shape in which the ratio of the major axis of the primary particle to the thickness of the primary particle (major axis / thickness) is 5 to 20.
  • the compressive fracture strength of the aggregate formed by aggregation of the primary particles is preferably 3 MPa or more. Thereby, it is possible to prevent or suppress the breakage of the aggregates when the resin composition and the resin sheet are produced by filling the organic matrix with hBN powder or when the resin sheet is used. From this viewpoint, the compressive fracture strength of the aggregate is more preferably 4 MPa or more, further preferably 5 MPa or more, still more preferably 6 MPa or more, and still more preferably 7 MPa or more. The compressive fracture strength of the aggregate of primary particles was measured by the method described in the examples.
  • the hBN powder of the present invention has a powder content under a sieve having a mesh size of 45 ⁇ m determined using a vacuum suction type sieving machine (air jet sieve) from the viewpoint of thermal conductivity and thinning of the thermal conductive sheet. It is 80 mass% or more, preferably 85 mass% or more, more preferably 88 mass% or more. Further, the hBN powder of the present invention contains a powder on a sieve having a mesh size of 45 ⁇ m obtained using a vacuum suction type sieving machine (air jet sieve) from the viewpoint of thermal conductivity and thinning of the thermal conductive sheet.
  • the rate is preferably 20% by mass or less, more preferably 15% by mass or less, and still more preferably 12% by mass or less.
  • the powder content rate under a sieve with a mesh opening of 45 ⁇ m and on a sieve is measured by the method described in Examples.
  • the BET specific surface area of the hBN powder of the present invention is from 15 to 25 m 2 / g, preferably from 15.5 to 23 m 2 / g, more preferably from 15.5 to 1.5 from the viewpoint of improving the compressive fracture strength of the aggregate. 22.5 m 2 / g, more preferably from 16 ⁇ 22m 2 / g, even more preferably from 16 ⁇ 20m 2 / g, even more preferably 16 ⁇ 19m 2 / g.
  • this BET specific surface area is measured by the method as described in an Example.
  • the 50% volume cumulative particle diameter (hereinafter also referred to as “D 50 ”) of the hBN powder of the present invention is from the viewpoint of improving the compressive fracture strength of the agglomerates and improving the filling properties in the resin composition and the resin sheet.
  • the thickness is 10 to 15 ⁇ m, preferably 10.5 to 14.8 ⁇ m, more preferably 11 to 14.6 ⁇ m, and still more preferably 11.5 to 14.4 ⁇ m.
  • the 90% volume cumulative particle size (hereinafter also referred to as “D 90 ”) of the hBN powder of the present invention is a viewpoint of improving the compressive fracture strength of the aggregate and improving the filling property in the resin composition and the resin sheet. Therefore, the thickness is preferably 40 to 50 ⁇ m, more preferably 40.5 to 48 ⁇ m, and still more preferably 41 to 46 ⁇ m.
  • D 50 and D 90 of the hBN powder is measured by the method described in Examples.
  • the bulk density of the hBN powder of the present invention is preferably 0.3 g / cm 3 or more, more preferably 0.35 g / cm 3 or more, further preferably 0.4 g / cm, from the viewpoint of improving the compressive fracture strength of the aggregate. cm 3 or more.
  • the bulk density of hBN powder is measured by the method as described in an Example.
  • the crystallite size of the hBN powder of the present invention is preferably 200 to 500 mm.
  • the porosity of the hBN powder of the present invention is preferably 10 to 40%, more preferably 15 to 35%, still more preferably 20 to 30%, and still more preferably 25 from the viewpoint of improving the compressive fracture strength of the aggregate. ⁇ 30%.
  • the porosity is the ratio of the total pore volume expressed as the sum of the volumes of all the pores in the sample with respect to the sample volume excluding voids other than the pores of the sample.
  • the porosity of hBN powder can be measured by the method as described in an Example.
  • the average pore diameter of the hBN powder of the present invention is preferably from 80 to 400 nm, more preferably from 90 to 300 nm, still more preferably from 100 to 200 nm, and even more preferably from 110 to 400 nm, from the viewpoint of improving the compressive fracture strength of the aggregate. 150 nm.
  • the average pore diameter is the diameter (D) of the cylindrical pore when all the pores are assumed to be one cylindrical pore, and the volume of the cylindrical pore (V ) And the side area (A).
  • V ⁇ D 2 H / 4 [1]
  • A ⁇ DH [2] (In the above formulas [1] and [2], D represents the average pore diameter, and H represents the height of the cylindrical pore.)
  • the average pore diameter is an index indicating the difference in the internal structure of the hBN aggregate. When the average pore diameter is small, a large number of small voids are scattered in the hBN aggregate, and the micro hBN primary particles interfere with each other to form a structure that does not easily collapse. When the average pore diameter is large Is believed to have a structure that tends to collapse because of a small number of large voids interspersed and insufficient interference between hBN primary particles.
  • the hBN powder of the present invention contains the above-mentioned aggregate, the aggregate can maintain a granular shape, and the primary particles are in a certain direction even if the filling rate of the hBN powder in the resin composition and the resin sheet is increased.
  • the resin composition and the resin sheet obtained by using the hBN powder are excellent in thermal conductivity.
  • the purity of the hBN powder that is, the purity of hBN in the hBN powder is preferably 96% by mass or more, more preferably 98% by mass or more, and still more preferably 99% from the viewpoint of improving thermal conductivity and electrical insulation. It is 9 mass% or more, More preferably, it is 99.5 mass% or more, More preferably, it is 99.8 mass% or more.
  • the purity of this hBN powder can be measured by the method described in the examples.
  • the amount of boron oxide in the hBN powder of the present invention (hereinafter also referred to as “B 2 O 3 amount”) is preferably 0.01 to 0 from the viewpoint of improving thermal conductivity, electrical insulation and production superiority. .12% by mass, more preferably 0.02 to 0.11% by mass, and still more preferably 0.03 to 0.10% by mass.
  • the amount of B 2 O 3 can be measured by the method described in the examples.
  • the content of calcium oxide (CaO) in the hBN powder of the present invention is preferably 0.5% by mass or less, more preferably 0.2% by mass or less, from the viewpoint of improving thermal conductivity and electrical insulation.
  • content of CaO in this hBN powder can be measured by the method as described in an Example.
  • the content of carbon in the hBN powder of the present invention is preferably 0.5% by mass or less, more preferably 0.2% by mass or less, and still more preferably 0.2% by mass, from the viewpoint of improving thermal conductivity and electrical insulation. It is 1 mass% or less, More preferably, it is 0.05 mass% or less, More preferably, it is 0.04 mass% or less.
  • the carbon content in the hBN powder can be measured by the method described in the examples.
  • Examples of the coupling agent include silane-based, titanate-based, and aluminum-based, among which silane-based coupling agents are preferable from the viewpoint of effects.
  • Examples of silane coupling agents include ⁇ -aminopropyltrimethoxysilane, ⁇ -aminopropyltriethoxysilane, ⁇ - (2-aminoethyl) aminopropyltrimethoxysilane, and ⁇ - (2-aminoethyl) aminopropyltri Ethoxysilane, ⁇ -anilinopropyltrimethoxysilane, ⁇ -anilinopropyltriethoxysilane, N- ⁇ - (N-vinylbenzylaminoethyl) - ⁇ -aminopropyltrimethoxysilane and N- ⁇ - (N-vinyl Aminosilane compounds such as (benzylaminoethyl) - ⁇ -aminopropyltrieth
  • the hexagonal boron nitride powder (hBN powder) of the present invention comprises 100 parts by mass of crude hexagonal boron nitride powder containing 20 to 90% by mass of boron nitride and 10 to 80% by mass of boron oxide, and 9 to 15 parts by mass in terms of carbon. It is preferable to obtain the carbon source by mixing and shaping the carbon source, followed by firing in an atmosphere containing nitrogen gas.
  • the hBN powder of the present invention is preferably subjected to at least one of pulverization and classification after firing to obtain an hBN powder, and more preferably, both pulverization and classification are performed to obtain an hBN powder.
  • raw hexagonal boron nitride powder and a carbon source which are raw materials used in the production method, will be described, and then each step of mixing, molding, firing, pulverization, and classification will be described.
  • the crude hexagonal boron nitride powder (crude hBN powder) used in the above production method contains 20 to 90% by mass of boron nitride and 10 to 80% by mass of boron oxide.
  • the crude hBN powder having a high boron oxide content can be easily produced as will be described later.
  • production efficiency is high.
  • the content of boron oxide in the crude hBN powder can be measured by the method described in the examples.
  • the boron nitride content in the crude hBN powder can be measured by subtracting the boron oxide content from the total mass. The method for calculating the content of boron oxide is described in the examples.
  • the hBN powder When the content of boron nitride is 20% by mass or more, the hBN powder can be produced with high efficiency using the crude hBN powder as a raw material. When the content of boron nitride is 90% by mass or less, the raw hBN powder as a raw material can be produced with high efficiency. From this viewpoint, the content of boron nitride in the crude hBN powder is preferably 45% by mass or more, more preferably 50% by mass or more, still more preferably 55% by mass or more, and still more preferably 60% by mass or more.
  • it is preferably 85% by mass or less, more preferably 80% by mass or less, further preferably 75% by mass or less, still more preferably 70% by mass or less, and preferably 45 to 85% by mass, more preferably 50% by mass. It is ⁇ 80 mass%, more preferably 55 to 75 mass%, still more preferably 60 to 70 mass%.
  • the content of boron oxide in the crude hBN powder is preferably 15% by mass or more, more preferably 20% by mass or more, still more preferably 25% by mass or more, and still more preferably 30% by mass or more. Further, it is preferably 55% by mass or less, more preferably 50% by mass or less, further preferably 45% by mass or less, still more preferably 40% by mass or less, and preferably 15 to 55% by mass, more preferably 20% by mass. -50% by mass, more preferably 25-45% by mass, and still more preferably 30-40% by mass.
  • the total content of boron nitride and boron oxide in the crude hBN powder is preferably 90% by mass or more, more preferably 95% by mass or more, still more preferably 99% by mass or more, and still more preferably 100% by mass. is there.
  • the crude hBN powder may contain other components as long as the effects of the present invention are not impaired.
  • the content of the other components in the crude hBN powder is preferably 10% by mass or less. Preferably it is 5 mass% or less, More preferably, it is 1 mass% or less, and it is still more preferable that other components are not contained.
  • the crude hBN powder can be suitably obtained by mixing a compound containing oxygen and boron and a compound having an amino group, molding, heating, and pulverizing. First, a compound containing oxygen and boron and a compound having an amino group, which are raw materials used in the production method, will be described, and then each step of mixing, molding, heating and grinding will be described.
  • the compound containing oxygen and boron may be a compound further containing hydrogen.
  • the compound containing oxygen and boron include orthoboric acid (H 3 BO 3 ), metaboric acid (HBO 2 ), tetraboric acid (H 2 B 4 O 7 ), and boric anhydride (B 2 O 3 ).
  • orthoboric acid is preferred because it is readily available and has good mixing properties with compounds having an amino group such as melamine.
  • the purity of the compound containing oxygen and boron is preferably 90% by mass or more, more preferably 95% by mass or more, still more preferably 99% by mass or more, and still more preferably 100% by mass.
  • Examples of the compound having an amino group include aminotriazine compounds, guanidine compounds, urea and the like.
  • aminotriazine compounds include melamine, guanamine, benzoguanamine, and condensates thereof such as melam, melem, and melon.
  • compounds having a nitrogen atom at each of the amino group and a site other than the amino group, such as melamine and guanidine, are preferable.
  • the purity of the compound having an amino group is preferably 90% by mass or more, more preferably 95% by mass or more, still more preferably 99% by mass or more, and still more preferably 100% by mass.
  • the compound containing oxygen and boron and the compound having an amino group are mixed.
  • wet mixing there is no restriction
  • a precursor is first formed. For example, when water is added to a mixture of boric acid or boric anhydride and melamine, a precursor represented by the molecular formula of C 3 N 3 (NH 2 ⁇ H 3 BO 3 ) 3 is obtained.
  • the wet mixing can be performed using a general mixer such as a Henschel mixer, a ball mill, or a ribbon blender.
  • the compounding ratio of the compound containing oxygen and boron to the compound having an amino group is the atomic ratio of the boron atom (B) in the compound containing oxygen and boron to the nitrogen atom (N) in the compound having an amino group (B / N) is preferably a ratio of 1/3 to 2/1.
  • B / N atomic ratio is 1/3 or more, it is prevented or suppressed that a compound having an amino group that does not become a precursor in the presence of water remains. Browning is prevented or suppressed.
  • hBN with higher crystallinity can be obtained as the number of boron atoms increases.
  • the blending amount of melamine with respect to 100 parts by mass of the compound containing oxygen and boron is preferably 30 to 65 parts by mass, more preferably 35 to 60 parts by mass, and still more preferably from the above viewpoint. Is 40 to 55 parts by mass, and more preferably 45 to 50 parts by mass.
  • boric anhydride remains at a high temperature for a long time, so that the crystal growth of hBN is promoted.
  • This molding is preferably performed so that the density of the obtained molded body is about 0.6 to 0.8 g / cm 3 .
  • the atmosphere during heating is an ammonia atmosphere or a non-oxidizing gas atmosphere.
  • the non-oxidizing gas atmosphere is preferably a nitrogen gas atmosphere or an inert gas atmosphere such as argon gas. Of these, an ammonia atmosphere is more preferable.
  • the heating temperature is preferably from 800 to 1400 ° C., more preferably from 900 to 1350 ° C., still more preferably from 1000 to 1300 ° C., and even more preferably from 1050 to 1200 ° C., from the viewpoint of improving reactivity and ease of grinding. .
  • the product obtained by heating is then pulverized to obtain a crude hBN powder.
  • the pulverization method There is no particular limitation on the pulverization method, and jaw pulverization, coarse roll pulverization and the like can be employed.
  • Examples of the carbon source used in the method for producing the hexagonal boron nitride powder (hBN powder) of the present invention include graphite, carbon black, boron carbide, saccharides, melamine, phenol resin, etc., preferably graphite. .
  • the carbon content in the carbon source is preferably 90% by mass or more, more preferably 95% by mass or more, still more preferably 99% by mass or more, and still more preferably 100% by mass.
  • hBN powder hexagonal boron nitride powder
  • 9 to 15 parts by mass of the above-described carbon source in terms of carbon is mixed with 100 parts by mass of the above-described crude hBN powder.
  • the carbon source is 9 parts by mass or more in terms of carbon, grain growth of primary particles is suppressed, and nitridation of boron oxide proceeds to improve the compactness of the aggregate. Will improve.
  • the carbon source is 15 parts by mass or less in terms of carbon, the unreacted carbon component is prevented from remaining as a foreign substance, that is, a black matter, and whiteness and electrical insulation are improved.
  • the mixing amount of the carbon source with respect to 100 parts by mass of the crude hBN powder is 9 to 15 parts by mass in terms of carbon, preferably 9.5 to 14 parts by mass, more preferably 10 to 13 parts by mass, More preferably, it is 10 to 12 parts by mass.
  • wet mixing is preferable.
  • the wet mixing can be performed using a general mixer such as a Henschel mixer, a ball mill, or a ribbon blender.
  • Resin such as polyvinyl alcohol (PVA), a cellulose, a polyvinylidene fluoride (PVDF), is mentioned, Preferably polyvinyl alcohol is used.
  • the binder is preferably used as a binder aqueous solution in which these resins are dissolved in water.
  • the resin content in the aqueous binder solution is preferably 1 to 10% by mass, more preferably 1 to 5% by mass, and still more preferably 1 to 4% by mass.
  • the mixing amount of the aqueous binder solution with respect to 100 parts by mass of the crude hBN powder is preferably 1 to 20 parts by mass, more preferably 5 to 15 parts by mass, and still more preferably 8 to 12 parts by mass.
  • a binder is also converted as said carbon source.
  • the density after molding is preferably 0.5 g / cm 3 or more, more preferably from the viewpoint of improvement in strength of the aggregate formed by agglomeration of hBN primary particles, productivity, good handling, and reactivity.
  • 0.8 g / cm 3 or more more preferably 1 g / cm 3 or more, preferably 2 g / cm 3 or less, more preferably 1.8 g / cm 3 or less, still more preferably 1.5 g / cm 3 or less. Do so.
  • the molded body obtained by the above molding is fired.
  • the crude hBN powder is pressure-molded to form a compact and then fired, the boron oxide contained in the crude hBN powder in the compact reacts with the carbon contained in the carbon source, resulting in a hexagonal crystal with high compressive fracture strength. Aggregates of boron nitride (hBN) are formed, and the hBN powder of the present invention is obtained.
  • the atmosphere during firing is an atmosphere containing nitrogen gas.
  • the nitrogen gas concentration in the atmosphere containing nitrogen gas is preferably 60% by volume or more, more preferably 80% by volume or more, still more preferably 90% by volume or more, and still more preferably 99% by volume or more. Less oxygen gas is better.
  • the firing temperature is preferably 1000 to 2200 ° C. When the firing temperature is 1000 ° C. or higher, a sufficient reduction nitriding reaction proceeds. Moreover, decomposition
  • the firing time is preferably 1 to 20 hours.
  • the firing time is 1 hour or longer, the reductive nitriding reaction proceeds sufficiently, and the unreacted carbon component is prevented from remaining as a black product.
  • a calcination cost is reduced. From this viewpoint, it is more preferably 1 to 15 hours, further preferably 5 to 10 hours, and still more preferably 6 to 9 hours.
  • the drying temperature is preferably 150 to 400 ° C., more preferably 200 to 400 ° C., and the drying time is preferably 6 to 8 hours.
  • a dry vibrating sieve device [manufactured by Koei Sangyo Co., Ltd., trade name “Sato Vibrating Sieve”]
  • a sieve with an opening of 45 ⁇ m a sieving time of 60 minutes It is preferable to classify on condition.
  • the resin composition of the present invention contains 10 to 90% by volume of the aforementioned hexagonal boron nitride powder (hBN powder).
  • the content of hBN powder in the resin composition of the present invention is 10 to 90% by volume from the viewpoint of the thermal conductivity of the resin composition and the resin sheet formed by molding the resin composition and the moldability of the resin sheet. It is preferably 20 to 80% by volume, more preferably 30 to 70% by volume, still more preferably 40 to 65% by volume.
  • the resin composition of this invention uses together hBN powder which has a particle size of 45 micrometers or more in addition to the hBN powder of this invention from a heat conductive viewpoint.
  • the content of hBN powder having a particle size of 45 ⁇ m or more in the resin composition is preferably 5% by volume or more, more preferably 10% by volume or more, and further preferably 15% by volume from the viewpoint of thermal conductivity. % Or more. From the same viewpoint, it is preferably 40% by volume or less, more preferably 30% by volume or less, and still more preferably 20% by volume or less.
  • the volume-based content (volume%) of the hBN powder can be determined from the specific gravity of the hBN powder and the specific gravity of various resins used as the organic matrix.
  • the resin composition of the present invention contains a resin as an organic matrix.
  • the resin used in the present invention preferably contains one or more resins selected from thermosetting resins, thermoplastic resins, various rubbers, thermoplastic elastomers, oils and the like.
  • the thermosetting resin include epoxy resins, silicone resins, phenol resins, urea resins, unsaturated polyester resins, melamine resins, polyimide resins, polybenzoxazole resins, and urethane resins.
  • thermoplastic resin examples include polyolefin resins such as polyethylene, polypropylene, and ethylene-vinyl acetate copolymer; polyester resins such as polyethylene terephthalate, polybutylene terephthalate, and liquid crystal polyester; polyvinyl chloride resin, acrylic resin, polyphenylene sulfide resin, Examples include polyphenylene ether resins, polyamide resins, polyamideimide resins, and polycarbonate resins.
  • polyolefin resins such as polyethylene, polypropylene, and ethylene-vinyl acetate copolymer
  • polyester resins such as polyethylene terephthalate, polybutylene terephthalate, and liquid crystal polyester
  • polyvinyl chloride resin acrylic resin
  • polyphenylene sulfide resin examples include polyphenylene ether resins, polyamide resins, polyamideimide resins, and polycarbonate resins.
  • Various rubbers include natural rubber, polyisoprene rubber, styrene-butadiene copolymer rubber, polybutadiene rubber, ethylene-propylene copolymer, ethylene-propylene-diene copolymer, butadiene-acrylonitrile copolymer, isobutylene-isoprene copolymer.
  • examples thereof include polymers, chloroprene rubber, silicone rubber, fluorine rubber, chloro-sulfonated polyethylene, polyurethane rubber and the like. These rubbers are preferably used after being crosslinked.
  • thermoplastic elastomer examples include olefin-based thermoplastic elastomers, styrene-based thermoplastic elastomers, vinyl chloride-based thermoplastic elastomers, urethane-based thermoplastic elastomers, and ester-based thermoplastic elastomers.
  • oil component examples include greases such as silicone oil.
  • One of these organic matrices may be used alone, or two or more thereof may be used in combination.
  • the resin composition of the present invention is used for a heat conductive member obtained by using the resin composition and mechanical strength, heat resistance and durability of a heat conductive member such as a resin sheet formed by molding the resin composition.
  • a heat conductive member such as a resin sheet formed by molding the resin composition.
  • curable epoxy resins and curable silicone resins are particularly preferably used.
  • the content of the organic matrix in the resin composition is preferably 10 to 90% by volume, more preferably 20 to 80% by volume, and still more preferably, from the viewpoint of moldability of a resin sheet formed by molding the resin composition. Is 30 to 70% by volume, more preferably 30 to 60% by volume.
  • the volume-based content (volume%) of the organic matrix can be determined from the specific gravity of hBN powder and the specific gravity of various resins used as the organic matrix.
  • the curable epoxy resin used as the organic matrix is an epoxy resin that is liquid at normal temperature or a low softening point epoxy resin that is solid at normal temperature from the viewpoint of dispersibility of the hBN powder in the organic matrix.
  • the curable epoxy resin may be a compound having two or more epoxy groups in one molecule, and is not particularly limited, and any one of known compounds conventionally used as epoxy resins can be appropriately selected. It can be selected and used. Examples of such epoxy resins include bisphenol A type epoxy resins, bisphenol F type epoxy resins, glycidyl ethers of polycarboxylic acids, and epoxy resins obtained by epoxidation of cyclohexane derivatives.
  • epoxy resins from the viewpoints of heat resistance and workability, bisphenol A type epoxy resins, bisphenol F type epoxy resins, and epoxy resins obtained by epoxidation of cyclohexane derivatives are suitable.
  • a curing agent for epoxy resin In order to cure the curable epoxy resin, a curing agent for epoxy resin is usually used.
  • the curing agent for epoxy resin is not particularly limited, and any one of those conventionally used as curing agents for epoxy resins can be appropriately selected and used. For example, amine-based, phenol-based, acid-based, and the like. An anhydride system etc. are mentioned.
  • Preferred examples of the amine curing agent include dicyandiamide, aromatic diamines such as m-phenylenediamine, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylsulfone, and m-xylylenediamine.
  • the system curing agent include phenol novolak resin, cresol novolak resin, bisphenol A type novolak resin, triazine-modified phenol novolak resin and the like.
  • the acid anhydride curing agent include aliphatic acids such as alicyclic acid anhydrides such as methylhexahydrophthalic anhydride, aromatic acid anhydrides such as phthalic anhydride, and aliphatic dibasic acid anhydrides. And halogen-based acid anhydrides such as anhydride and chlorendic anhydride.
  • One of these curing agents may be used alone, or two or more thereof may be used in combination.
  • the amount of the epoxy resin curing agent used is usually about 0.5 to 1.5 equivalent ratio, preferably about 0.1 equivalent ratio to the curable epoxy resin, from the viewpoint of balance between curability and cured resin physical properties. It is selected in the range of 7 to 1.3 equivalent ratio.
  • an epoxy resin curing accelerator can be used in combination with the epoxy resin curing agent as necessary.
  • this hardening accelerator for epoxy resins From the things conventionally used as a hardening accelerator of an epoxy resin, arbitrary things can be selected suitably and can be used.
  • imidazoles such as 2-ethyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 2-methylimidazole, 2-ethylimidazole, 2-isopropylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, etc.
  • hardening accelerators examples thereof include compounds, 2,4,6-tris (dimethylaminomethyl) phenol, boron trifluoride amine complex, triphenylphosphine and the like.
  • These hardening accelerators may be used individually by 1 type, and may be used in combination of 2 or more type.
  • the amount of the epoxy resin curing accelerator used is usually about 0.1 to 10 parts by mass, preferably 0, with respect to 100 parts by mass of the curable epoxy resin, from the viewpoint of balance between curing acceleration and physical properties of the cured resin. Selected in the range of 4 to 5 parts by mass.
  • the curable silicone resin As the curable silicone resin, a mixture of an addition reaction type silicone resin and a silicone-based crosslinking agent can be used.
  • the addition reaction type silicone resin include at least one selected from polyorganosiloxanes having an alkenyl group as a functional group in the molecule.
  • Preferred examples of the polyorganosiloxane having an alkenyl group as a functional group in the molecule include polydimethylsiloxane having a vinyl group as a functional group, polydimethylsiloxane having a hexenyl group as a functional group, and a mixture thereof. .
  • silicone-based crosslinking agent examples include polyorganosiloxane having at least two silicon-bonded hydrogen atoms in one molecule, specifically, a dimethylhydrogensiloxy group end-capped dimethylsiloxane-methylhydrogensiloxane copolymer, Examples thereof include trimethylsiloxy group-end-capped dimethylsiloxane-methylhydrogensiloxane copolymer, trimethylsiloxane group-end-capped poly (methylhydrogensiloxane), and poly (hydrogensilsesquioxane).
  • platinum compounds are usually used as the curing catalyst.
  • the platinum compound include fine platinum, fine platinum adsorbed on a carbon powder carrier, chloroplatinic acid, alcohol-modified chloroplatinic acid, chloroplatinic acid olefin complex, palladium, rhodium catalyst, and the like. .
  • the resin composition of the present invention may contain further components as long as the effects of the present invention are obtained.
  • examples of such components include nitride particles such as aluminum nitride, silicon nitride, and fibrous boron nitride, and electrically insulating metal oxides such as alumina, fibrous alumina, zinc oxide, magnesium oxide, beryllium oxide, and titanium oxide.
  • electrically insulating carbon components such as diamond and fullerene, plasticizers, pressure-sensitive adhesives, reinforcing agents, colorants, heat resistance improvers, viscosity modifiers, dispersion stabilizers, and solvents.
  • an inorganic filler such as aluminum or magnesium hydroxide, a surface treatment agent such as a silane coupling agent that improves the interfacial adhesive strength between the inorganic filler and the matrix resin, a reducing agent, and the like may be added.
  • the resin composition of the present invention can be used for a heat conductive member such as a heat conductive sheet, a heat conductive gel, a heat conductive grease, a heat conductive adhesive, and a phase change sheet.
  • a heat conductive member such as a heat conductive sheet, a heat conductive gel, a heat conductive grease, a heat conductive adhesive, and a phase change sheet.
  • heat from heat-generating electronic components such as MPUs, power transistors, and transformers can be efficiently transferred to heat-dissipating components such as heat-dissipating fins and heat-dissipating fans.
  • the resin sheet it is preferable to use the resin sheet as a heat conductive sheet.
  • the resin sheet of the present invention comprises the resin composition or a cured product thereof, and is formed by molding the resin composition into a sheet. When the resin composition is curable, it is formed into a sheet and then cured.
  • the resin sheet of the present invention can be produced using the resin composition, for example, as follows. First, a suspension of hBN powder having a concentration of about 50 to 80% by mass is prepared by dispersing the hBN powder of the present invention in a suitable solvent. Next, an organic matrix is added to the suspension so that the hBN powder is contained in a proportion of 10 to 90% by volume in the total amount of the hBN powder and the organic matrix.
  • the weights of hBN powder and resin are set so as to be a desired volume% based on the specific gravity of hBN powder and the specific gravity of the resin used as the organic matrix, and each is weighed and mixed to prepare a resin composition.
  • a preparation method of a resin composition it can also prepare as follows. First, an organic matrix is prepared by mixing a resin and, if necessary, a curing agent and a solvent. Next, the hBN powder is added to the organic matrix so that the hBN powder is contained in a ratio of 10 to 90% by volume in the total amount of the hBN powder and the organic matrix.
  • the weights of hBN powder and resin are set so as to be a desired volume% based on the specific gravity of hBN powder and the specific gravity of the resin used as the organic matrix, and each is weighed and mixed to prepare a resin composition.
  • a curable epoxy resin is used as the main component of the organic matrix
  • a mixture of the curable epoxy resin, a curing agent for the epoxy resin, and a curing accelerator for the epoxy resin that is used as required is an organic matrix.
  • a curable silicone resin is used as the main component of the organic matrix, a mixture of an addition reaction type silicone resin, a silicone-based crosslinking agent, and a curing catalyst becomes an organic matrix.
  • the resin composition is coated on a substrate such as a releasable film such as a resin film with a release layer by a normal coating machine or the like, and when the resin composition contains a solvent, a far infrared radiation heater, It is made into a sheet by drying the solvent by hot air spraying or the like.
  • a melamine resin or the like is used as the release layer.
  • the resin film a polyester resin such as polyethylene terephthalate is used.
  • the organic matrix in the resin composition is not a curable organic matrix such as a curable epoxy resin or a curable silicone resin, the above-described resin sheet is directly used as the resin sheet of the present invention.
  • the resin sheet formed on the base material obtained above is optionally applied from the surface side where the resin composition of the base material is not coated.
  • the resin sheet of the present invention is obtained by further heat-treating under pressure through the substrate and curing.
  • the pressure condition is preferably 15 to 20 MPa, more preferably 17 to 19 MPa.
  • the heating conditions are preferably 80 to 200 ° C., more preferably 100 to 150 ° C.
  • substrates such as a mold release film, are finally peeled off or removed.
  • the film thickness of the resin sheet of the present invention thus obtained is preferably in the range of 50 to 150 ⁇ m from the viewpoint of moldability and lightening and thinning of electronic parts and the like in which the resin sheet is used.
  • a range of 140 ⁇ m is more preferable, and a range of 100 to 130 ⁇ m is even more preferable.
  • the resin sheet of the present invention preferably has a thermal conductivity in the thickness direction of 3 W / m ⁇ K or more, more preferably 7 W / m ⁇ K or more, still more preferably 9 W / m ⁇ K or more, and even more preferably 10 W. / M ⁇ K or more.
  • the resin sheet of the present invention may be used by laminating or burying a sheet-like, fiber-like, or mesh-like member on one or both sides and within the sheet for the purpose of improving workability or reinforcing.
  • the resin sheet thus obtained can be peeled off from the releasable film or can be in the form of a product for use as a resin sheet in a state where the releasable film is a protective film.
  • the resin sheet of this invention is good also as a structure which further provided the adhesive layer in the upper surface or lower surface of the resin sheet, and, thereby, the convenience at the time of product use increases.
  • the resin sheet of the present invention is used to transfer heat from heat-generating electronic components such as MPUs, power transistors, and transformers to heat-radiating components such as heat-dissipating fins and heat-dissipating fans. Used in between. As a result, heat transfer between the heat-generating electronic component and the heat-dissipating component is improved, and malfunction of the heat-generating electronic component can be significantly reduced.
  • Example 1 Production of crude hBN powder A mixture of 4 g boric acid, 2 g melamine and 1 g water was stirred and mixed, placed in a mold and pressed to obtain a molded body having a density of 0.7 g / cm 3 . This molded body was dried in a dryer at 300 ° C. for 100 minutes, and calcined at 1100 ° C. for 120 minutes in an NH 3 gas atmosphere. The obtained calcined product (crude hBN) was pulverized to obtain crude hBN powder (boron oxide content of 35% by mass).
  • hBN fired product is pulverized using a jaw crusher and a pin mill, and then dried using a dry vibration sieve device [manufactured by Koei Sangyo Co., Ltd., trade name “Sato Vibrating Screener”] for 60 minutes. Classification was performed using a sieve having an opening of 45 ⁇ m under the conditions. The hBN powder under the sieve after the classification was used as the hBN powder according to Example 1.
  • the hBN powder according to Example 1 obtained by classification as described above was further used with a vacuum suction type sieving machine (air jet sieve [manufactured by Alpine, model name “A200LS”]) described later, When the sieve was classified above and below the sieve with an opening of 45 ⁇ m, the powder content of the hBN powder on the sieve with an opening of 45 ⁇ m was 11% by mass, and the powder content under the sieve of 45 ⁇ m was 89% by mass. When this hBN powder was observed by SEM, it was confirmed that the primary particles contained dense hBN aggregates oriented in random directions as shown in FIG.
  • FIG. 1 is a schematic diagram of hBN aggregates present in FIG.
  • resin composition As organic matrix, liquid curable epoxy resin [manufactured by Japan Epoxy Resin Co., Ltd., trade name “jER828”, bisphenol A type, epoxy equivalent 184-194 g / eq] 100 parts by mass, cured A combination product with 5 parts by mass of imidazole [manufactured by Shikoku Kasei Kogyo Co., Ltd., trade name “2E4MZ-CN”] as an agent was used.
  • liquid curable epoxy resin manufactured by Japan Epoxy Resin Co., Ltd., trade name “jER828”, bisphenol A type, epoxy equivalent 184-194 g / eq
  • imidazole manufactured by Shikoku Kasei Kogyo Co., Ltd., trade name “2E4MZ-CN”
  • the hBN powder is added so that the content in the total amount of the hBN powder and the organic matrix is 60% by volume, Kurashiki Spinning Co., Ltd., Mazerustar The mixture was stirred and mixed to prepare a resin composition.
  • the volume-based content (volume%) of the hBN powder was determined from the specific gravity (2.27) of the hBN powder and the specific gravity (1.17) of the liquid curable epoxy resin used as the organic matrix.
  • Example 2 In Example 1 (2), hBN powder, resin composition and resin were the same as Example 1 except that the amount of carbon source added to 100 parts by mass of the crude hBN powder was 11 parts by mass. A sheet was produced.
  • Example 3 In Example 1 (2), hBN powder, resin composition and resin were the same as Example 1 except that the amount of carbon source added to 100 parts by mass of the crude hBN powder was 10 parts by mass. A sheet was produced.
  • Example 1 (2) the amount of the carbon source added to 100 parts by mass of the crude hBN powder was changed to 5 parts by mass, and 0.4 parts by mass of a Ca compound (calcium carbonate) was further added. Were the same as in Example 1 to prepare hBN powder, a resin composition, and a resin sheet.
  • a Ca compound calcium carbonate
  • Example 2 It is widely known as a method for producing spherical granules in place of (1) and (2) in Example 1 and in place of the hBN powder obtained in (2) in Example 1 (3). The same procedure as in Example 1 except that spherical hBN powders having the hBN powder characteristics shown in Table 2 were produced by aggregating scaly hBN by the spray drying method and sintering at 2000 ° C. Thus, a resin composition and a resin sheet were produced.
  • Example 3 In Example 1 (2), the carbon source added to 100 parts by mass of the crude hBN powder was changed to 20 parts by mass, and 0.4 parts by mass of Ca compound (calcium carbonate) was further added. Were the same as in Example 1 to prepare hBN powder, a resin composition, and a resin sheet.
  • the crude hBN powder is considered to be composed of boron oxide (hereinafter also referred to as “B 2 O 3 ”) on the surface of the powder and an internal B—O—N bond structure.
  • B 2 O 3 boron oxide
  • the internal oxygen constituting the BOH bond structure of the crude hBN is reacted by a high-temperature heat treatment in the firing step when producing hBN powder from the crude hBN powder, and gradually leaches out as B 2 O 3 on the surface.
  • Amount of B 2 O 3 surfaces, the B 2 O 3 of crude hBN powder surface was eluted by acid treatment, by measuring the amount of B 2 O 3 dissolved in the acid treatment, B 2 O 3 in terms of the amount of endogenous oxygen, The oxygen analysis of the residue after acid treatment was performed, the amount of oxygen in the residue was measured, and obtained as a B 2 O 3 equivalent amount. Specifically, it is as follows.
  • Crude hBN powder was acid treated with 0.1N dilute sulfuric acid solution.
  • the amount of ammonia generated by hydrolysis of BN in the crude hBN powder by this acid treatment was measured using a spectrophotometer [manufactured by Hitachi, Ltd., model name “U-1100”].
  • the amount of B element produced by hydrolysis of was calculated.
  • the total amount of B element present in the acid solution after the acid treatment is calculated using an ICP analyzer [SII Nano Technology Inc., model name “SPS3500”].
  • the amount of B 2 O 3 dissolved by the acid treatment was calculated from the total amount of the B element present in the acid solution after the acid treatment and the amount of the B element resulting from the hydrolysis of BN converted from the above ammonia amount. . Further, the amount of oxygen in the residue was measured using an oxygen measuring device [manufactured by LECO Japan GK, model name “TC-600”], and an amount equivalent to B 2 O 3 was calculated from the measured value. There was thus obtained, from the total amount B 2 O 3 were dissolved by acid treatment and B 2 O 3 equivalent amount, the total amount of crude hBN powder subjected to the acid treatment, the boron oxide in the crude hBN powder The content (B 2 O 3 content) was calculated.
  • BET specific surface area About the hBN powder obtained by the Example and the comparative example, the specific surface area was measured using the fully automatic BET specific surface area measuring apparatus [The Yuasa Ionics Co., Ltd. make, model name "Multisorb 16"].
  • the ultrasonic treatment was performed using an ultrasonic treatment apparatus [manufactured by Nippon Seiki Seisakusho, model name “ultrasonic homogenizer US-150V”] under the conditions of an output of 150 W and an oscillation frequency of 19.5 kHz.
  • the weight of hBN powder remaining under and on the sieve was measured, and the hBN powder content (under sieve powder content) under a sieve having a sieve opening of 45 ⁇ m and the hBN powder content (with powder through sieve) on a sieve having a sieve opening of 45 ⁇ m Content).
  • the hBN fired products obtained in Examples 1 to 3 and Comparative Examples 1 to 3 were pulverized and then classified using the dry vibration sieve device having a sieve opening of 45 ⁇ m and a sieving time of 60 minutes.
  • the hBN powder passed through a sieve having an opening of 45 ⁇ m.
  • test load was set to 10 to 1000 mN
  • load speed was set to 0.446 mN / sec
  • the hBN aggregate was compressed using a flat indenter, and the strength when the hBN aggregate was broken by the compression was determined. It was measured. The average value of these measured values was taken as the compression fracture strength.
  • the porosity and average pore diameter do not change with respect to the particle size of the hBN aggregate, and the measured values of the hBN aggregate having a particle size of 45 to 106 ⁇ m are related to the examples and comparative examples.
  • the porosity and average pore diameter of hBN powder were used. Further, the calculation was performed with the range limited to a pore diameter of 0.5 to 4000 nm.
  • hBN powders obtained in the examples and comparative examples were acid-treated with a 0.1N dilute sulfuric acid solution.
  • a 0.1N dilute sulfuric acid solution By this acid treatment, at least a part of BN in the hBN powder is hydrolyzed to generate ammonia, and the B element of BN is dissolved in the acid solution.
  • boron oxide (B 2 O 3 ) in the hBN powder At least a part of it dissolves in the acid solution.
  • the amount of ammonia generated by hydrolysis of BN by this acid treatment was measured using a spectrophotometer [manufactured by Hitachi, Ltd., model name “U-1100”].
  • Carbon content in hBN powder The carbon content (carbon content) in the hBN powders obtained in Examples and Comparative Examples was measured using a carbon analyzer [manufactured by LECO Japan LLC, model name “CS230”].
  • the purity of the hBN powder was determined using the total amount of B 2 O 3 , CaO content and carbon content in the hBN powder measured as described above as the amount of impurities.
  • Thermal conductivity of resin sheet About the resin sheet obtained by the Example and the comparative example, the value calculated by measuring a thermal diffusivity by the model name "LFA447 NanoFlash” made from NETZSCH, and multiplying it by the theoretical value of the specific heat and density of each resin sheet. was defined as the thermal conductivity in the thickness direction of the resin sheet.
  • the theoretical value of the density of the resin sheet of each Example or Comparative Example was calculated on the assumption that the theoretical density of boron nitride was 2.27 g / cm 3 and the theoretical density of the resin component was 1.17 g / cm 3 .
  • the production conditions of the hBN powders of the above examples and comparative examples are shown in Table 1, and the evaluation results are shown in Table 2.
  • the carbon source and Ca compound in Table 1 are the crude hBN in the mixture obtained by mixing the crude hBN powder and the carbon source (in addition to the Ca compound in Comparative Examples 1 and 3) when preparing the hBN powder. Content with respect to 100 mass parts of powder is shown.
  • the hBN powders of Examples 1 to 3 contain 88 to 89% by mass of powder under a sieve having an opening of 45 ⁇ m, compared to the hBN powder obtained in the comparative example, and consist of dense primary particles. It can be seen that the compression fracture strength is high. In addition, the porosity of Examples 1 to 3 and Comparative Examples 1 to 3 showed almost constant values irrespective of other characteristics. On the other hand, as the average pore diameter becomes smaller, the BET specific surface area and the compression fracture strength become higher values, and it can be seen that the average pore diameter correlates with the BET specific surface area and the compression fracture strength. This is thought to be due to the difference in the internal structure of the hBN aggregate.
  • the particles of Comparative Example 1 having a large average pore diameter have a large pore diameter between the particles, and the hBN primary particles constitute hBN aggregates.
  • the resin sheets of Examples 1 to 3 all have a thermal conductivity of 10 W / m ⁇ K or more, indicating that the thermal conductivity is superior to the resin sheets of Comparative Examples 1 to 3. This is presumably because the agglomerates did not break during stirring and mixing, and the granule shape could be maintained as shown in the schematic diagram of FIG.
  • the hBN powder obtained in this way is used to obtain a resin sheet having a film thickness of 100 ⁇ m that is excellent in thermal conductivity and moldability.

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Abstract

L'invention concerne une poudre de nitrure de bore hexagonal contenant un agrégat de particules primaires de nitrure de bore hexagonal, où la proportion de poudre passant à travers un tamis de pores de 45 μm est de 80 % en masse ou plus, le diamètre des particules primaires est de 5 µm ou moins, la surface spécifique BET est comprise entre 15 et 25 m2/g, et le diamètre cumulé en volume à 50 %, D50, est compris entre 10 et 15 μm. L'invention concerne également un procédé de production de la poudre de nitrure de bore hexagonal, ainsi qu'une composition à base de résine et des feuillets de résine utilisant la poudre de nitrure de bore hexagonal.
PCT/JP2015/079109 2014-12-08 2015-10-15 Poudre de nitrure de bore hexagonal, procédé de production de cette dernière, composition à base de résine, et feuillet de résine WO2016092952A1 (fr)

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JP2018020932A (ja) * 2016-08-03 2018-02-08 デンカ株式会社 六方晶窒化ホウ素一次粒子凝集体及び樹脂組成物とその用途
KR20180019554A (ko) * 2015-06-17 2018-02-26 생-고뱅 생트레 드 레체르체 에 데투드 유로삐엔 질화붕소 응집체 분말
WO2018066277A1 (fr) * 2016-10-07 2018-04-12 デンカ株式会社 Grain agrégé de nitrure de bore, son procédé de production, et composition de résine thermoconductrice l'utilisant
WO2018074077A1 (fr) * 2016-10-21 2018-04-26 デンカ株式会社 Poudre fine de nitrure de bore sphérique, son procédé de production et composition de résine thermoconductrice l'utilisant
JP2018104260A (ja) * 2016-12-28 2018-07-05 昭和電工株式会社 六方晶窒化ホウ素粉末、その製造方法、樹脂組成物及び樹脂シート
WO2018139644A1 (fr) * 2017-01-30 2018-08-02 積水化学工業株式会社 Matériau de résine et stratifié
WO2019073690A1 (fr) * 2017-10-13 2019-04-18 デンカ株式会社 Poudre de nitrure de bore, sa méthode de production et élément de dissipation thermique produit à l'aide de celle-ci
WO2019130869A1 (fr) * 2017-12-27 2019-07-04 Showa Denko K.K. Poudre de nitrure de bore hexagonal et son procédé de production, et composition et matériau de dissipation de chaleur l'utilisant
JP2020100145A (ja) * 2018-12-21 2020-07-02 積水化学工業株式会社 積層体
EP3549910A4 (fr) * 2016-12-01 2020-07-29 Tokuyama Corporation Poudre de nitrure de bore hexagonal et son procédé de production
WO2020175377A1 (fr) * 2019-02-27 2020-09-03 三菱ケミカル株式会社 Poudre d'agrégat de nitrure de bore, feuille de dissipation de chaleur et dispositif à semi-conducteur
JP2021102539A (ja) * 2019-12-25 2021-07-15 デンカ株式会社 六方晶窒化ホウ素粉末及びその製造方法、並びに化粧料及びその製造方法
CN113614909A (zh) * 2019-03-29 2021-11-05 电化株式会社 复合体
JPWO2022202827A1 (fr) * 2021-03-25 2022-09-29
WO2022202824A1 (fr) * 2021-03-25 2022-09-29 デンカ株式会社 Poudre de nitrure de bore et composition de résine
WO2022202825A1 (fr) * 2021-03-25 2022-09-29 デンカ株式会社 Poudre de nitrure de bore et composition de résine
WO2022264327A1 (fr) * 2021-06-16 2022-12-22 デンカ株式会社 Poudre de nitrure de bore hexagonal et son procédé de production, et produits cosmétiques et leur procédé de fabrication
WO2023048149A1 (fr) * 2021-09-27 2023-03-30 Ｊｆｅミネラル株式会社 Poudre de charge de nitrure de bore hexagonal

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