WO2020195298A1 - Procédé de production de nitrure de bore granuleux et nitrure de bore granuleux - Google Patents

Procédé de production de nitrure de bore granuleux et nitrure de bore granuleux Download PDF

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WO2020195298A1
WO2020195298A1 PCT/JP2020/005627 JP2020005627W WO2020195298A1 WO 2020195298 A1 WO2020195298 A1 WO 2020195298A1 JP 2020005627 W JP2020005627 W JP 2020005627W WO 2020195298 A1 WO2020195298 A1 WO 2020195298A1
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boron nitride
granular
rare earth
oxide
granular boron
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PCT/JP2020/005627
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English (en)
Japanese (ja)
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尚史 楠瀬
佳範 卯野
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国立大学法人 香川大学
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Priority to JP2020549724A priority Critical patent/JP7554473B2/ja
Publication of WO2020195298A1 publication Critical patent/WO2020195298A1/fr

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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
    • 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
    • C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
    • C04B35/58—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides
    • C04B35/583—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides based on boron nitride
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins

Definitions

  • the present invention relates to a method for producing a granular boron nitride composition and a granular boron nitride composition obtained by the method. Further, the present invention relates to a resin composition containing a granular boron nitride composition and a resin, a molded product containing granular boron nitride and a resin obtained by molding such a resin composition, and a method for producing the same. Regarding.
  • Boron nitride (hereinafter, also referred to as “BN”) is an insulating ceramic and has various crystal types such as c-BN having a diamond structure, h-BN having a graphite structure, and t-BN having a multi-layer structure. It has been known.
  • h-BN has remarkably low thermal conductivity because it is relatively easy to synthesize and has excellent thermal conductivity, solid lubricity, chemical stability, and heat resistance. Attempts have been made to improve thermal conductivity by mixing a resin material with a filler. Such resin materials are used in the electric and electronic fields for heat dissipation members of integrated circuits.
  • h-BN has a laminated structure similar to graphite and has a large crystal anisotropy.
  • h-BN is macroscopically granular, it is microscopically a laminate of plate-like crystals.
  • the plate-like crystal plane corresponding to the a-axis direction of the crystal it is connected by a strong covalent bond, so that it exhibits a large thermal conductivity of nearly 400 W / mK.
  • the plate thickness direction corresponding to the c-axis direction since they are laminated by a weak Van der Waals force bond, they show only a small thermal conductivity of about 1 to 2 W / mK.
  • the plate-shaped boron nitride is oriented in the plate surface direction of the molded product, which is the flow direction of the resin composition at the time of molding.
  • the obtained molded product has a problem that it exhibits excellent thermal conductivity in the plate surface direction but low thermal conductivity in the thickness direction. Therefore, it is desired to improve the anisotropy of such granular BN.
  • Japanese Patent Application Laid-Open No. 2013-147363 describes a step of mixing boron nitride with an oxide of at least one rare earth metal selected from yttrium, cerium, and ytterbium and carbon, and heat-treating the mixture in a non-oxidizing gas atmosphere.
  • a method for producing a metal oxide-containing boron nitride containing the above is disclosed.
  • the boron nitride produced by this method has a resin composition even when a large amount of the resin composition is blended in the resin material for the purpose of improving thermal conductivity, solid lubricity, chemical stability, heat resistance, etc. It is possible to improve the thermal conductivity in the thickness direction of the molded product to be molded while maintaining good molding processability as a product.
  • thermal conductivity can be improved by producing boron nitride by the above-mentioned method, but the improved thermal conductivity is further improved as compared with the above-mentioned original thermal conductivity of boron nitride. There is room for. Another problem is that rare earth metal components such as yttrium are relatively expensive.
  • boron nitride when boron nitride is mixed with a resin material and a molded product is manufactured using the boron nitride, it is desired to further increase the thermal conductivity.
  • a rare earth metal component such as yttrium is used, it is desirable to reduce the amount used.
  • the present invention is described in the first gist.
  • Boron nitride component containing boron nitride (2) Rare earth components containing oxides of at least one rare earth element selected from yttrium, cerium and itterbium and / or precursor compounds thereof, and (3) calcium containing calcium oxide and / or calcium carbonate.
  • a method for producing a granular boron nitride composition which comprises a step of heat-treating a mixture containing components in a non-oxidizing gas atmosphere.
  • the present invention provides, in the second gist, a granular boron nitride composition obtained by the above-mentioned production method.
  • This includes, in addition to the granular boron nitride obtained by the heat treatment, other compounds derived from the components (1) to (3) contained in the mixture.
  • Such other compounds are mainly rare earth element oxides and calcium oxide, but also contain a small amount of, for example, complex oxides derived from elements present in the system (for example, Y—Ca—BO complex oxides). It can be.
  • the present invention provides the granular boron nitride contained in the above-mentioned granular boron nitride composition in the third gist.
  • This granular boron nitride is obtained by subjecting the above composition to a cleaning process using an acid to remove at least a portion of calcium oxide and a rare earth element oxide, most of the calcium oxide, preferably substantially the entire amount. be able to. Therefore, the present invention provides a method for producing granular boron nitride in the fourth gist, which method is characterized by acid cleaning of the granular boron nitride composition in the second gist.
  • the present invention provides, in the fifth gist, a granular boron nitride composition of the second gist or a resin composition comprising the granular boron nitride of the third gist and a resin material. Further, the present invention is obtained in the sixth gist by a molding method characterized by molding using such a resin material, and the present invention is obtained by such a molding method in the seventh gist. To provide a molded product to be manufactured.
  • the thermal conductivity of the obtained molded product is improved. Further, in a preferred embodiment, anisotropy regarding heat conduction of the molded product is suppressed. Even when a large amount is mixed, the thermal conductivity of the obtained molded product can be improved while maintaining good molding processability.
  • a heat radiating sheet that requires insulation, thermal conductivity, and moldability can be exemplified.
  • it is suitable for use in the fields of electricity and electronics.
  • the granular boron nitride composition or granular boron nitride of the present invention can be used as a filler that can be blended in a heat conductive paste, a heat conductive adhesive, a composition for a heat conductive molded product, or the like.
  • FIG. 1 shows the ratio (mass basis) of the average particle size of the granular boron nitride of the present invention and the sum of the rare earth component (2) and the calcium component (3) in the mixture to be heat-treated (that is, (2) + (3)).
  • FIG. 2 shows the ratio (mass reference percent) of the specific surface area of the granular boron nitride of the present invention and the sum of the rare earth component (2) and the calcium component (3) in the heat-treated mixture (that is, (2) + (3)).
  • FIG. 1 shows the ratio (mass basis) of the average particle size of the granular boron nitride of the present invention and the sum of the rare earth component (2) and the calcium component (3) in the mixture to be heat-treated (that is, (2) + (3)).
  • FIG. 3 shows the total of the thermal conductivity in the thickness direction of the molded product obtained by using the resin composition containing the granular boron nitride of the present invention and the rare earth component (2) and the calcium component (3) in the heat-treated mixture.
  • a table and graph of experimental results showing the relationship with the ratio (that is, (2) + (3)) (mass reference percentage) are shown.
  • FIG. 4 shows the thermal conductivity in the plane direction (direction perpendicular to the thickness direction) of the molded product obtained by using the resin composition containing the granular boron nitride of the present invention, and the rare earth component (2) in the mixture to be heat-treated.
  • FIG. 5 shows the degree of orientation of granular boron nitride in a molded product molded using the resin composition containing granular boron nitride of the present invention and the rare earth component in a mixture to be heat-treated when producing granular boron nitride (2).
  • a table and a graph of experimental results showing the relationship between the sum of the calcium component (3) and the sum (that is, (2) + (3)) are shown.
  • FIG. 6 is a typical SEM photograph of the granular boron nitride (but after washing) of the present invention obtained in Example 6.
  • FIG. 7 is a typical SEM photograph of the granular boron nitride composition of the present invention (however, before washing) obtained in Example 6.
  • FIG. 8 is an SEM photograph and an EDS photograph (for elements N and Y) of the granular boron nitride (but after washing) of the present invention containing yttrium oxide obtained in Example 36.
  • FIG. 9 is an SEM photograph and an EDS photograph (for N element, Ca element and Y element) of the granular boron nitride composition of the present invention (however, before washing) obtained in Example 11.
  • FIG. 10 is an SEM photograph and an EDS photograph (for element N) of the granular boron nitride (but after washing) of the present invention obtained in Example 12.
  • the boron nitride contained in the boron nitride component (1) is hexagonal boron nitride (h-BN) having a graphite structure, and in one embodiment.
  • Boron nitride is preferably powdery (or finely granular) boron nitride, preferably h-BN.
  • a commercially available hexagonal boron nitride component can be used.
  • the oxide of the rare earth element contained in the rare earth component (2) is, for example, yttrium oxide, cerium oxide or itterbium oxide, and the precursor of the oxide of the rare earth element is a preheat treatment and / or heating carried out prior to the heat treatment. Means a compound that results in such an oxide in the process.
  • a rare earth component (2) commercially available ones such as yttrium oxide and cerium oxide can be used.
  • the calcium component (3) contains calcium oxide and / or calcium carbonate, and as such a calcium component (3), generally commercially available calcium oxide, calcium carbonate or the like can be used.
  • boron nitride in boron nitride component contained in the mixture to heat treatment (1) BN
  • oxides of rare earth elements in the rare earth component (2) e.g., Y 2 O 3
  • the ratio of the total mass of calcium oxide and calcium hydroxide (if present) in the calcium component (3) (if present) is general.
  • boron nitride is 95 to 40%
  • boron nitride is 94 to 50%
  • more preferably 7 to 42% is 14 to 42%, for example 14 to 35%.
  • the rare earth element in the rare earth component (2): the calcium element in the calcium component (3) is preferably 1: based on the number of elements in the heat-treated mixture. It is 0.25 to 1: 4, more preferably 1: 0.5 to 1: 3, particularly preferably 1: 0.7 to 1: 2.5, for example 1: 1 to 1: 2.
  • the heat treatment is carried out in a non-oxidizing gas atmosphere.
  • the non-oxidizing gas atmosphere means an atmosphere containing no oxygen, for example, one or two kinds such as nitrogen gas, helium gas, argon gas, ammonia gas, hydrogen gas, methane gas, propane gas, and carbon monoxide gas. It is an atmosphere that includes the above.
  • the crystallization rate after dissolution of boron nitride differs depending on the type of gas used in this atmosphere. For example, in the case of argon gas, the crystallization rate becomes slow and the heat treatment time may take a long time. In order to carry out crystallization in a short time, it is particularly preferable to use nitrogen gas or a mixed gas in which nitrogen gas and another gas are used in combination.
  • the heat treatment is carried out in a nitrogen gas atmosphere.
  • the mixture to be heat-treated is preferably kept in a non-oxidizing atmosphere until it reaches a predetermined heat treatment temperature described later.
  • the non-oxidizing gas atmosphere may be in a so-called vacuum state or a reduced pressure state in which the gas is substantially contained or hardly contained.
  • the boron nitride component (1) may contain oxygen, and in that case (for example, when it is contained in the form of boron oxide), if necessary (for example, at least a part of boron oxide is converted to boron nitride).
  • the mixture may use carbon in an amount of 1% to 5% relative to the mass of boron nitride in the boron nitride component (1).
  • the mixture is carbon free, unless there is a substantial adverse effect.
  • the amount of oxygen contained is not so large (for example, it is generally based on the mass of the boron nitride component (1)). Generally, it is not necessary to use carbon because it is 5% or less, for example, 4% by mass, but the mixture may contain carbon if necessary (for example, when the amount of oxygen is large).
  • the granular boron nitride contained in the granular boron nitride composition of the present invention has an average particle diameter of preferably 9 to 25 ⁇ m, more preferably 10 to 20 ⁇ m, for example, 12 to 15 ⁇ m, and the specific surface area of the granular material. Is preferably 2 to 10 m 2 / g, more preferably 4 to 8 m 2 / g, for example 5 to 6 m 2 / g.
  • the above-mentioned average particle size and specific surface area mean values measured by the following methods, respectively:
  • the average particle size referred to in the present specification is a numerical value obtained by this measurement method regardless of the state of aggregation of the particles, and may be the average particle size of the primary particles depending on the properties of the particles. It may also be the average particle size of the secondary particles. In some cases, it is the average particle size measured in a state where both primary particles and secondary particles are mixed.
  • the granular boron nitride of the present invention produced by heat treatment is produced by dissolving boron nitride in the liquid phase formed by melting calcium oxide in addition to the rare earth element oxide in advance during the heat treatment, and then precipitating from the liquid phase. It is conceivable that. This is not bound by any theory, but the inventors have knowledge and experience regarding the formation of boron nitride and new findings regarding the above-mentioned production methods, especially SEM photographs of the resulting granules. Based on the results of the above, the formation of granules can be considered as follows. This idea is just one of the possible ideas. The present invention that boron nitride granules can be obtained by heat treatment under specific conditions is not limited by the suitability of this idea.
  • the rare earth element oxide and calcium oxide are preferentially melted to form a liquid phase, in which the granular boron nitride is dissolved.
  • the concentration of boron nitride in the liquid phase rises to a supersaturated state, and as a result, boron nitride precipitates (recrystallizes). While boron nitride is precipitated in this way, another boron nitride particle is newly dissolved in the liquid phase to become a supersaturated state, and as a result, boron nitride is further precipitated.
  • the precipitated boron nitride is bonded to form a bent form. Since there is a liquid phase in which boron nitride is dissolved exists inside and outside the bent form of boron nitride, supersaturation ⁇ precipitation occurs repeatedly there, and boron nitride crystals grow further to thicken the bent form. It becomes longer and boron nitride crystals grow gradually.
  • the bent boron nitride thus grown is bonded to another similarly grown bent boron nitride crystal, further grown inside and outside the crystal, and finally surrounded by a wall having a certain thickness.
  • boron nitride obtained by heat treatment is referred to as "granular boron nitride" in the present specification.
  • the granular boron nitride of the present invention has a strong shell structure formed by boron nitride in the form of a relatively thick wall.
  • This shell structure has a macroscopically rounded shape as a whole particle, that is, a grain (crushed) shape. In a strict sense, it is a so-called spherical, spheroidal, or polyhedral shape, and generally has a complex combination of these shapes.
  • this granular material has a relatively small aspect ratio, preferably 1 to 3, more preferably 1 to 2, and is clearly different from a granular material having a large aspect ratio such as boron nitride having a graphite structure.
  • FIG. 6 shows an example of a typical SEM photograph of the granular boron nitride of the present invention. These photographs are of granular boron nitride obtained in Example 6 described later. When this is observed in detail, it can be seen that the granular boron nitride is a so-called grain (crushed) shape having an apparent polyhedral (or spherical) shape as a whole, which is composed of bent walls.
  • An SEM photograph was also taken of the granular boron nitride composition of the present invention in a state before the oxide was removed. The photograph is shown in FIG. As can be seen by comparing the two, there was substantially no difference from the one after removing the oxide. It is possible that this can be explained by the fact that the liquid phase component composed of the added oxide remains mainly in the granular boron nitride of the shell structure.
  • the above-mentioned shell structure may include other granular boron nitride or a part thereof inside the shell structure.
  • FIG. 10 shows an SEM photograph of two different visual field parts of a cross section of a mixture of granular boron nitride obtained in Example 12 described later mixed with an epoxy resin and cured, and an EDS photograph of the nitrogen element in the photograph. Is.
  • the upper photograph is an SEM photograph.
  • the lower photograph showing the result of mapping analysis of granular boron nitride in this state for N elements using EDS (Energy Dispersive X-ray Analysis) is an EDS photograph.
  • the EDS photo corresponding to the upper left photo is the lower left photo
  • the EDS photo corresponding to the upper right photo is the lower right photo. It can be seen that the nitrogen element (white part) is present inside the shell structure of boron nitride, which appears to shine white in the SEM photograph, as can be confirmed in the EDS photograph, and therefore boron nitride is present.
  • granular boron nitride also exists inside the shell structure of granular boron nitride.
  • the internal granular boron nitride is columnar (thus three-dimensionally planar), and the inside of the outer granular boron nitride shell structure is divided, for example, bisected. ing.
  • the internal granular boron nitride fills a part of the inside of the shell structure of the granular boron nitride located on the outside.
  • the granular boron nitride thus encapsulated is a smaller shell structure, even if it is a part of the shell structure that has not yet formed the shell structure (eg, at least one or a part of the shell constituent surfaces). You may.
  • the surface constituting the shell structure may be a substantially flat surface or a bent surface forming the shell structure.
  • granular boron nitride is considered to be generated inside the shell structure in one embodiment by newly precipitating and growing boron nitride inside the already formed shell structure or a part thereof.
  • the grown granular boron nitride or a part thereof is bonded to another granular boron nitride or a part thereof, so that a part of the granular boron nitride is included.
  • the granular boron nitride containing other granular boron nitride is considered to contribute to higher the heat conduction of the granular boron nitride because it increases the heat conduction path.
  • the presence of other granular boron nitride inside also has an effect of suppressing or preventing deformation of the granular boron nitride when an external pressure is applied to the boron nitride.
  • one of the main features is that when boron nitride is precipitated from the liquid phase to form a shell as described above, a rare earth element oxide and calcium oxide are present as the liquid phase, and as a result, the result is obtained.
  • Granular boron nitride to be obtained has a thicker shell and a smaller aspect ratio. Thereby, it is possible to produce granular boron nitride having a crushing strength superior to that of various known boron nitride aggregates.
  • the degree of orientation of granular boron nitride in the molded product is about 85% or less, preferably 70% or less. It can be preferably 20 to 65%, for example 25 to 60%.
  • the particle size of the granular boron nitride particles is small, the resistance to hot press pressure is strong, so that the granular particles do not collapse and show a low (00L) plane orientation, but the resin material has high thermal conductivity.
  • granular boron nitride having a large particle size is desirable so that a high thermal conduction path can be taken for a long time.
  • the particle size of the granular boron nitride is increased, the granularity is likely to be disintegrated by hot pressing, so that the degree of orientation of the (00L) plane may be increased.
  • the granular boron nitride composition of the present invention contains a component that is finally solidified inside the shell by cooling after heating.
  • This component is mainly composed of rare earth element oxides and calcium oxide, but may contain various compounds, particularly composite oxides, as described above.
  • a portion of boron nitride that constitutes the shell structure of granular boron nitride or a part thereof may also be included.
  • the proportions of boron, rare earth elements and calcium elements contained in the granular boron nitride composition obtained by heat treatment are the proportions of these elements contained in the mixture. It is virtually the same. Therefore, the amount of rare earth element oxides and calcium oxide contained in the granular boron nitride composition is equal to the amount of rare earth element and calcium-derived oxides contained in the mixture.
  • the granular boron nitride composition usually contains 3-40%, preferably 5-37%, more preferably 8-35% of rare earth element oxides on a mass basis, in addition to boron nitride.
  • it contains 12 to 32% and contains 1 to 30%, preferably 2 to 26%, more preferably 5 to 22%, for example 8 to 15% of calcium oxide.
  • Such oxides can be reduced by acid cleaning as described above, for example, by reacting an oxide with an acid using an aqueous acid solution to convert it into a water-soluble salt, dissolving it in water, and removing it. ..
  • the thermal conductivity of the oxide is usually small, so that the oxide contained in the granular boron nitride composition does not substantially adversely affect the thermal conductivity.
  • calcium oxide can be preferentially removed by acid cleaning, so that substantially all of the calcium oxide is removed and the rare earth element oxide is partially removed.
  • the amount of rare earth element oxide contained in the granular boron nitride composition is, for example, 0.1 to 30%, preferably 1 to 15%, more preferably 2 to 12%, for example, 3 to 10% based on the mass thereof. So acid wash.
  • the present invention provides granular boron nitride with a shell structure, from at least rare earth element oxides and / or calcium oxide from the above-mentioned granules, preferably most, more preferably substantially all of the calcium oxide. It also provides another granular boron nitride obtained by removing calcium oxide. That is, the more preferred granules consist of boron, nitrogen, oxygen and rare earth elements and are substantially free of calcium.
  • the granules have a strong shell structure formed by boron nitride and contain a small amount of rare earth element oxides in addition to boron nitride.
  • the removal of the oxide may be carried out by any other suitable method other than cleaning with an acid, as long as the properties of the granular boron nitride as a filler are not excessively affected. Cleaning with an acid is advantageous in that oxides can be substantially removed without adversely affecting granular boron nitride.
  • the present invention provides a resin composition
  • a resin composition comprising granular boron nitride whose amount of oxide is preferably reduced by washing, particularly granular boron nitride which is substantially free of calcium oxide and a resin material.
  • the resin composition comprises preferably 10 to 90%, more preferably 15 to 88%, for example 30 to 85%, particularly 50 to 82% of granular boron nitride based on the total mass thereof.
  • these ranges are shown in terms of volume ratio, they correspond to about 5 to 80% by volume, about 10 to 70% by volume, and about 15 to 50% by volume, respectively, although they differ slightly depending on the apparent density of the granules.
  • the resin composition may contain the granular boron nitride composition of the present invention in the same proportion as the above-mentioned granular boron nitride.
  • the method for producing a granular boron nitride composition of the present invention is selected from a boron nitride component (1) containing boron nitride (BN, preferably hexagonal boron nitride (h-BN)), and ittrium, cerium, and itterbium.
  • BN boron nitride
  • h-BN hexagonal boron nitride
  • a mixture containing a rare earth component (2) containing an oxide and / or a precursor thereof of at least one rare earth element and a calcium component (3) is heat-treated in a non-oxidizing gas atmosphere. It is characterized by including a process.
  • the rare earth component (2) contains a precursor of an oxide of at least one rare earth element selected from yttrium, cerium and ytterbium
  • the heat treatment step or before the step is converted to the corresponding rare earth element oxide in a preheating or calcining step that may be carried out as needed.
  • the calcium component (3) contains calcium carbonate, it is similarly converted to calcium oxide. The converted material contributes to the precipitation and growth of granular boron nitride crystals as a rare earth element oxide or calcium oxide.
  • the components (1), (2) and (3) as raw materials are mixed to obtain a mixture, which is heated in a non-oxidizing gas atmosphere, for example. It is carried out by heating at 1800 to 2100 ° C.
  • the mixture may contain other components, for example, components that are inevitably contained in the production of components as raw materials.
  • the boron nitride component (1) contains excessive oxygen (for example, when it contains 5% by mass or more of oxygen because it contains boron oxide)
  • the mixture may contain carbon, and oxygen is generated by reducing with carbon. (As a result, boron nitride can be produced).
  • an appropriate dispersion medium eg ethanol, acetone, etc.
  • the slurry is uniformly mixed with a homogenizer together with a dispersion medium 5 to 20 times as much as the mixture on a mass basis. Or paste. After this is dried, it is calcined in the air (calcination, calcination or calcining) as necessary to obtain a powder in which the components constituting the mixture are uniformly mixed, and then in a non-oxidizing gas atmosphere, Heat treatment is performed at 1800 to 2100 ° C.
  • the boron nitride component (1) used in the present invention is synthesized from commercially available h-BN, commercially available t-BN, BN produced by a reduction nitride method of a boron compound and ammonia, and a nitrogen-containing compound such as a boron compound and melamine.
  • the above-mentioned BN and the like can be exemplified, and can be used without particular limitation.
  • Such a boron nitride component (1) preferably contains at least 90%, preferably at least 95%, and more preferably at least 96% of boron nitride on a mass basis.
  • the boron nitride constituting the boron nitride component (1) is preferably h-BN, but may contain other boron nitride.
  • the proportion of h-BN in boron nitride may be preferably at least 90%, more preferably at least 95%, for example at least 96%, especially at least 98%, with the rest being other boron nitride.
  • Boron nitride may be commercially available in the form of fine particles or powders.
  • boron nitride powder having a primary particle diameter of 50 nm, an agglomerated particle diameter of 3 ⁇ m, and a specific surface area of 160 m 2 / g is commercially available from Nissin Refratec Co., Ltd. as “ABN”.
  • h-BN in powder form is commercially available as "AP170S” from MARUKA Co., Ltd.
  • the boron nitride component (1) may have a total oxygen concentration of 1% by mass to 10% by mass, preferably a total oxygen concentration of 5% by mass or less. Is preferable.
  • the primary particle diameter of the boron nitride particles is generally small and the crystals are often underdeveloped, and it is easy when the boron nitride particles are mixed with other components used in the present invention and heat-treated. It is preferable because it dissolves in. If the total oxygen concentration is excessively high, when the granular boron nitride composition obtained after the heat treatment is used as a heat conductive filler, it is preferable because it contains an oxide and may not be able to achieve high heat conductivity. Absent. In that case, carbon can be added to the mixture as described above to reduce the amount of oxygen. Alternatively, the granular boron nitride composition may be washed to reduce oxides.
  • the total oxygen concentration of the boron nitride component (1) when the total oxygen concentration of the boron nitride component (1) is excessively low, it may be difficult to dissolve in the liquid phase because the purity and crystallinity of boron nitride are already good, and as a result, the crystal growth of boron nitride and the like may occur. The change is small, and it may be difficult to form an aggregated structure.
  • the total oxygen concentration in the boron nitride component (1) as a raw material can be measured by an inert gas melting-infrared absorption method using an oxygen / nitrogen analyzer manufactured by Horiba Seisakusho Co., Ltd.
  • the average particle size of boron nitride contained in the boron nitride component (1) should be 5 ⁇ m or less. Is preferable.
  • the lower limit of the average particle size is not particularly limited, but is usually 0.1 ⁇ m or more. As described above, the average particle size can be measured by a laser diffraction / scattering type particle size distribution measuring device in which granular boron nitride as a raw material is dispersed in an appropriate solvent.
  • the rare earth component (2) used in the production method of the present invention contains a precursor of an oxide of a rare earth element, this may be carried out as necessary in the heat treatment step or before the rare earth element in the baking step. It is converted into an oxide, and this oxide acts to stably precipitate and grow granular boron nitride.
  • the component that is originally an oxide contained in the rare earth component (2) also acts in the same manner.
  • the rare earth component (2) used in the production method of the present invention is heat-treated together with the boron nitride component (1), it is preferable that the rare earth component (2) has heat resistance to the heat treatment conditions.
  • rare earth element oxides such as yttrium oxide, cerium oxide, and ytterbium oxide and / or precursors thereof are used as those contained in such a rare earth component (2).
  • yttrium oxide is particularly preferable from the viewpoint of thermal conductivity and heat resistance as an oxide, and from the viewpoint of stably precipitating granular boron nitride and growing it so as to have strength.
  • the rare earth component (2) containing such an oxide a commercially available one as such an oxide can be used.
  • At least one rare earth element compound selected from yttrium, cerium and ytterbium used as a precursor for producing such an oxide may be in any suitable form, for example, liquid sol or nitrate. In the form of a water-soluble salt such as, etc., it may be carried out in the heat treatment step or before the heat treatment step as necessary, or is converted into a rare earth element oxide in the baking step.
  • the oxide is at least one selected from yttrium oxide, cerium oxide, and ytterbium oxide, and the precursor thereof brings an oxide of such a rare earth element. It is a thing.
  • at least one selected from salts of inorganic acids such as acetates, nitrates, carbonates, citrates, oxalates and sulfates of rare earth elements, salts of organic acids, chlorides and the like can be exemplified.
  • yttrium oxide, acetate of yttrium, nitrate, carbonate, citrate, oxalate, sulfate and the like are preferably used from the viewpoint of easy availability.
  • yttrium oxide, yttrium nitrate, yttrium carbonate, yttrium citrate, yttrium oxalate, yttrium sulfate and the like are used.
  • the rare earth component (2) one selected from the above-mentioned rare earth element oxide and a metal compound which is a precursor thereof may be used alone, or in another embodiment, two or more thereof may be used in combination. ..
  • the rare earth component (2) is added to the oxide of the rare earth element and / or its precursor as described above, as long as the granular boron nitride produced in the present invention is not substantially adversely affected, for example, in the production thereof. It may contain other components that are unavoidably included.
  • the calcium component (3) used in the production method of the present invention contains at least one selected from calcium oxide and calcium carbonate. Calcium carbonate is converted to calcium oxide in the heat treatment step of the present invention or prior to it, if necessary, or in a baking step.
  • the calcium component (3) may be in any suitable form, and may be, for example, a solid (for example, powder), a dispersion, or the like. Although not bound by any theory and not limiting the present invention, in consideration of the results of Examples and Comparative Examples described later, such a calcium component (3) is the above-mentioned rare earth element oxide.
  • a liquid phase capable of melting and dissolving the existing boron nitride prior to the boron nitride is provided, and then the boron nitride is crystallized (that is, recrystallized) in the liquid phase. It is considered to have a function of providing a solvent for crystallization. During such crystallization, it is considered that the boron nitride crystal grows larger and aggregates and bonds to form a shell structure having a larger particle size.
  • a calcium component (3) commercially available calcium oxide and calcium carbonate can be used.
  • the rare earth element in the rare earth component (2): the calcium element in the calcium component (3) is preferably 1: 0.25 to 1: 4 based on the number of elements in the heat-treated mixture. , More preferably 1: 0.5 to 1: 3, particularly preferably 1: 0.7 to 1: 2.5, for example 1: 1 to 1: 2. If the calcium is too low, the calcium oxide component may be inadequate to provide the large particle size of the granular boron nitride, and if the calcium is too high, the rare earth element oxides are under-presenced. In some cases, the effect, particularly the effect of firmly binding granular boron nitride, may be insufficient.
  • the amount of the rare earth element oxide contained in the rare earth component (2) in the case of a precursor, converted to the corresponding rare earth element oxide
  • the ratio of the amount of calcium oxide contained (converted to calcium oxide in the case of calcium carbonate) to the amount of boron nitride and rare earth element oxides and the amount of calcium oxide in the mixture, that is, (rare earth oxide amount +) Amount of calcium oxide) / (amount of boron nitride + amount of rare earth oxide + amount of calcium oxide) is generally 5% to 60% (hence, boron nitride is 95 to 40%), preferably 6% to 50% on a mass basis. % (Thus, boron nitride is 94-50%), more preferably 7-42%, particularly preferably 14-42%, for example 14-35%.
  • the effect of stabilizing the shell structure of granular boron nitride by the rare earth element oxide and calcium oxide during heat treatment becomes small.
  • the shell structure is likely to collapse.
  • the viscosity of the resin composition melted for molding increases. Therefore, a larger force acts on the resin composition during molding, and the effect of stabilizing the shell structure tends to decrease.
  • the amount of boron nitride contained in the obtained granular boron nitride composition becomes excessively small.
  • the effect of improving the thermal conductivity may be reduced.
  • the mixture may further contain carbon, if necessary.
  • carbon black carbon black, graphite, or a carbon precursor that can be a carbon source at high temperature can be used, but carbon black is preferable from the viewpoint of easy availability.
  • carbon black carbon black such as the furnace method and the channel method, acetylene black and the like can be used.
  • the average particle size (volume-based average particle size) of these carbon blacks is arbitrary, but is preferably 0.01 to 20 ⁇ m.
  • a carbon precursor may be used in place of or in addition to the carbon described above.
  • synthetic resin condensates such as phenol resin, melamine resin, epoxy resin and furanphenol resin, hydrocarbon compounds such as pitch and tar, and organic compounds such as cellulose, sucrose, polyvinylidene chloride and polyphenylene can be used as precursors. .. Of these, those having less metal impurities such as phenol resin, cellulose, and polyphenylene are particularly preferable. These may be used alone or in admixture of two or more.
  • the amount of carbon used (as the amount of carbon produced from the carbon precursor when a carbon precursor is used) is preferably 5% by mass or less, more preferably 3% by mass or less, based on the boron nitride component (1) on a mass basis. is there.
  • the presence of carbon during the heat treatment can prevent excessive oxygen from being present. As a result, the shell structure of the granular boron nitride obtained by the oxide during the heat treatment becomes stronger. The use of more carbon than this amount may impair the stability of the shell structure.
  • the amount of carbon used By reducing the amount of carbon used, the amount of carbon remaining after the heat treatment can be minimized, and therefore, when used as a thermally conductive filler, the effect of granular boron nitride on the insulating property can be suppressed. In this sense, it is preferable that the use of carbon can be omitted. Therefore, in the method for producing aggregates of the present invention, the mixture is carbon-free.
  • the mixture containing the components (1) to (3) may contain other components as long as the production method and the produced granular boron nitride are not adversely affected. ..
  • other components include one or more inorganic substances of aluminum compounds such as aluminum nitride, aluminum hydroxide, and aluminum oxide (alumina).
  • the amount used is generally preferably 5% or less, for example, 0.1 to 3% with respect to the boron nitride component (1) on a mass basis.
  • the boron nitride component (1), the rare earth component (2) and the calcium component (3) constituting the mixture, and the above-mentioned mixture of carbon and other components contained as necessary are mixed.
  • the method is not particularly limited, and for example, dry mixing and wet mixing can be used.
  • horizontal cylindrical mixer, V-type mixer, double cone type mixer, ribbon type mixer, single shaft rod or rotor type mixer with pin, paddle type mixer, cone type screw mixer, high speed Flow type mixers, rotary disk type mixers, maller type mixers, air flow stirring type mixers, etc. are used.
  • a general mixer such as a 3-roll mixer, a conider, a botator, a high-speed flow mixer, and an ultrasonic homogenizer can be used.
  • the solvent (dispersion medium) used for wet mixing is not limited, but from the viewpoint of ease of drying and simplification of the equipment, pure water, alcohols such as ethanol, methanol and propanol, and organic solvents such as ketones such as acetone are used.
  • a mixed solvent of water and these organic solvents is preferred.
  • the mass is 5 to 20 times, particularly 5 to 10 times.
  • the method for carrying out this drying is not particularly limited, and heat drying, heat vacuum drying, or the like may be used. Generally, it is preferable to perform heat drying. On small scales, heating vacuum drying is usually used. In the case of heat drying, it is preferable that the heating temperature is 100 to 120 ° C. and the heating time is about 12 to 48 hours. If the heating temperature is too low or the heating time is too short, sufficient drying cannot be performed, and conversely, if the heating temperature is too high or the heating time is too long, it is not preferable from the viewpoint of heating cost. In the case of vacuum drying by heating, the solvent is distilled off using an evaporator at a temperature of about 50 ° C.
  • the crushing after drying may be crushing with a mortar, or another ball mill or the like can be used.
  • a mortar or another ball mill or the like can be used.
  • This average particle size can be measured by the same method as the average particle size described above.
  • the atmosphere during drying and crushing may be an air atmosphere, but it is preferably in dry air having a humidity of 50% or less in order to avoid moisture absorption.
  • calcination or calcination, that is, heat treatment at a lower temperature, which is carried out prior to heat treatment
  • calcium carbonate is used as the calcium component (3), and it is converted to calcium oxide.
  • This calcination may be performed by heating at a temperature of 500 to 700 ° C. for about 1 to 5 hours in an oxidizing atmosphere such as air. If the heating temperature during calcination is too low or the heating time is too short, conversion will be insufficient, and acid will be generated during calcination or nitrogen oxides will be generated, which is not preferable because it will damage the equipment. .. When a heating furnace capable of exhausting decomposition gas or the like during heating is used, the step of calcination may be omitted, and calcination can be performed at the same time in the subsequent heat treatment.
  • the boron nitride contained in the boron nitride component (1) may be oxidized, which is not preferable. If the heating furnace is equipped with an exhaust facility, oxidation can be avoided by exhausting the air inside the furnace. In this case, oxidation of boron nitride due to a high heating temperature and a long heating time does not matter.
  • the temperature of the heat treatment is usually 1800 to 2100 ° C, preferably 1900 to 2100 ° C, and more preferably 2000 to 2100 ° C. If the temperature of the heat treatment is lower than this range, the crystallization of h-BN becomes insufficient, an amorphous portion with undeveloped crystallization remains, and the effect of improving the thermal conductivity when used as a heat conductive filler becomes small. .. If the temperature of the heat treatment exceeds the above upper limit, the rare earth element oxide may evaporate and decompose, the shell structure cannot be maintained, and boron nitride may be decomposed.
  • the heat treatment time is usually 5 hours to 20 hours, preferably 5 hours to 15 hours. If the heat treatment time is shorter than this range, crystal growth will be insufficient, and if it is longer than this range, h-BN may be partially decomposed.
  • the heat treatment is performed in a non-oxidizing gas atmosphere, it is preferable to heat the inside of the furnace while exhausting it with a vacuum pump, continue exhausting until the amount of decomposed gas and the like associated with the heating is reduced, and then non-oxidize. While introducing the sex gas, the temperature is continuously heated to a desired temperature.
  • the standard temperature for exhausting with a vacuum pump is 200 to 700 ° C, for example, about 600 ° C, and the temperature rise rate is about 20 ° C / min while maintaining the degree of vacuum up to that temperature at about 10 -1 Pa. May be heated.
  • the non-oxidizing gas is introduced to atmospheric pressure and continued to be introduced until the end of the heat treatment.
  • the flow rate of the non-oxidizing gas depends on the size of the furnace, but usually there is no problem if it is 1 ml / min or more.
  • the temperature is raised to about 1100 ° C. at 20 to 100 ° C./min, and then from 1100 ° C. to a predetermined heat treatment temperature at 2 to 20 ° C./min. After heating at this temperature for the above-mentioned heat treatment time, it is preferable to lower the temperature to room temperature at, for example, about 5 to 50 ° C./min.
  • the method for producing granular boron nitride of the present invention also includes a step of cooling the heat-treated mixture to room temperature.
  • the firing furnaces to be heat-treated include batch-type furnaces such as muffle furnaces, tubular furnaces, atmospheric furnaces, and multipurpose high-temperature furnaces, and continuous furnaces such as rotary kilns, screw conveyor furnaces, tunnel furnaces, belt furnaces, pusher furnaces, and vertical continuous furnaces. It can be mentioned and used properly according to the purpose.
  • the residue may be removed from the granular boron nitride composition obtained by the above-mentioned method.
  • This removal can be carried out by washing the granular boron nitride composition with an aqueous acid solution.
  • an oxide is removed by dissolving the salt in existing water to obtain an aqueous salt solution and removing it using a reaction that converts the residue into a corresponding water-soluble salt.
  • the acid to be used include organic acids and inorganic acids, and for example, hydrochloric acid, nitric acid, sulfuric acid and the like may be used.
  • Cleaning with this acid aqueous solution can be carried out by dispersing the granular boron nitride composition in the acid aqueous solution with stirring. Then, the composition is filtered off, washed with water to remove the residual acid, and then dried to obtain granular boron nitride. Calcium oxide and borate compounds (if present) can be easily removed in substantially all of them by acid cleaning.
  • the total amount of rare earth element oxides contained in the obtained granular boron nitride is preferably 0.1 to 30%, preferably 1 to 15%, and more preferably 3 to 10% based on the mass of the granular boron nitride. is there.
  • the remaining rare earth element oxide can be easily adjusted by appropriately selecting cleaning conditions (for example, acid concentration, amount of aqueous solution used for cleaning and / or number of cleanings).
  • the amount of rare earth element oxide in the granular boron nitride composition can be measured as follows: 1 g of an acid-washed granular boron nitride composition was added to 60 g of a 1N hydrochloric acid aqueous solution in a Teflon-lined pressure-resistant container, and after sealing, treatment was performed at 100 ° C. for 11 hours. The obtained slurry is filtered with a membrane filter, and the solution obtained by diluting the filtrate with pure water 200 times is used as an ICP (inductively coupled plasma) luminescence analyzer (ICPS-7510, manufactured by Shimadzu Corporation) for rare earth elements.
  • ICP inductively coupled plasma luminescence analyzer
  • yttrium e.g., yttrium
  • XRD analysis of the slag is confirmed to be free of peaks of rare earth element oxides.
  • the nitrogen element is present in the circumferential (or substantially circumferential) portion (that is, the cyclic portion) of the polygonal N element, and the Y element is present inside it.
  • the N element that is, boron nitride
  • Y that is, yttrium oxide
  • the granular boron nitride of the present invention is composed of a shell portion composed of boron nitride and a rare earth element oxide remaining inside the shell portion in an amount corresponding to the degree of cleaning.
  • FIG. 9 shows the results of the same analysis of the granular boron nitride composition of the present invention obtained in Example 11 described later (thus, the one in the state before the cleaning treatment was performed).
  • the upper left of FIG. 9 shows the SEM photograph
  • the upper right shows the EDS mapping result of N element
  • the lower left shows the EDS mapping result of Ca element
  • the lower right shows the EDS mapping result of Y element.
  • the N element exists in a shell structure around the granular boron nitride crystal
  • the calcium element and the yttrium element exist inside the shell structure (thus, these oxides exist).
  • the cleaning treatment reduces the amount of oxides.
  • the granular boron nitride composition of the present invention can be preferably produced by the above-mentioned method for producing a granular boron nitride composition of the present invention, and is an oxide of at least one rare earth element selected from boron nitride and ytterbium, cerium and ytterbium. And calcium oxide are contained, and boron nitride preferably has a graphite structure. These oxides can be reduced in weight by acid cleaning as described above.
  • the shell structure is strengthened by the rare earth element oxide and calcium oxide, and as a result, the strength when pressure is applied (for example, crush strength) is improved. Therefore, it can be blended with a resin material for the purpose of improving thermal conductivity anisotropy and thermal conductivity. Further, since the solid lubricity derived from granular boron nitride is maintained, the molding processability as a resin composition can be maintained well even when it is blended with a resin material, and the molded product can be formed. When manufactured, a heat conduction path in the thickness direction is likely to be formed in the molded body due to the shell structure. As a result, the thermal conductivity in the thickness direction of the molded product can be increased. In addition, the granular boron nitride of the present invention also has chemical stability, heat resistance, etc. derived from boron nitride.
  • the oxygen is generally contained as boron oxide (B 2 O 3 ).
  • boron oxide reacts with the rare earth element oxide and calcium oxide to form an oxide (for example, a composite oxide such as CaYBO 4 ) to form a liquid phase.
  • this oxide dissolves boron nitride contained in the boron nitride component (1), similarly to the rare earth element oxide and calcium oxide.
  • the shell structure can be strengthened when granular boron nitride is produced when boron nitride is recrystallized.
  • the above-mentioned composite oxides can be reduced depending on the conditions for cleaning with an acid, and substantially the entire amount can be removed.
  • the content of the rare earth element oxide in the granular boron nitride composition of the present invention is the above-mentioned present invention when the above-mentioned washing is not carried out (that is, when only the heat treatment and the subsequent cooling are carried out). It is substantially equal to the sum of the amounts of rare earth element oxides and oxides derived from their precursors (if precursors are present) contained in the mixture heat-treated by the method for producing the granular boron nitride composition of. Similarly, the content of calcium oxide is substantially equal to the sum of the amounts of calcium oxide and oxides derived from calcium carbonate (if precursors are present) contained in the heat-treated mixture.
  • the boron nitride content of the granular boron nitride composition is preferably 40 to 95%, more preferably 50 to 90%, based on the total mass of boron nitride, rare earth element oxides and calcium oxide of the granular boron nitride composition. For example, 55-85%.
  • the resin composition of the present invention particularly a thermally conductive resin composition, comprises the above-mentioned granular boron nitride and resin material of the present invention. That is, as described above, the granular boron nitride of the present invention is suitably used as a thermally conductive filler in the resin composition. In some cases, it is also possible to use a granular boron nitride composition instead of the granular boron nitride.
  • the resin material that functions as the resin that forms the matrix in the resin composition is not particularly limited, and may be, for example, a curable resin, a thermoplastic resin, or the like.
  • the curable resin may be any crosslinkable resin such as thermosetting, photocurable, and electron beam curable, but a thermosetting resin is preferable in terms of heat resistance, water absorption, dimensional stability, and the like. Especially, epoxy resin is most suitable.
  • the epoxy resin may be only an epoxy resin having one kind of structural unit, but a plurality of epoxy resins having different structural units may be combined. Further, the epoxy resin is used together with a curing agent for epoxy resin and a curing accelerator, if necessary.
  • epoxy resin an epoxy resin (hereinafter, "epoxy resin") (A) ” is preferably contained, and in particular, the mass ratio of the epoxy resin (A) to the total amount of the epoxy resin is preferably in the range of 5 to 95% by mass, more preferably 10 to 90% by mass, still more preferably. Is preferably contained in the range of 20 to 80% by mass, but is not limited to such a substance.
  • the phenoxy resin usually refers to a resin obtained by reacting epihalohydrin with a divalent phenol compound, or a resin obtained by reacting a divalent epoxy compound with a divalent phenol compound, but in the present invention.
  • a phenoxy resin which is a high molecular weight epoxy resin having a mass average molecular weight of 10,000 or more is referred to as an epoxy resin (A).
  • the mass average molecular weight is a polystyrene-equivalent value measured by gel permeation chromatography.
  • a phenoxy resin having at least one skeleton selected from the group consisting of a naphthalene skeleton, a fluorene skeleton, a biphenyl skeleton, an anthracene skeleton, a pyrene skeleton, a xanthene skeleton, an adamantane skeleton and a dicyclopentadiene skeleton is preferable. ..
  • a phenoxy resin having a fluorene skeleton and / or a biphenyl skeleton is particularly preferable because the heat resistance is further enhanced.
  • One of these may be used alone, or two or more thereof may be mixed and used.
  • the epoxy resin other than the epoxy resin (A) is preferably an epoxy resin having two or more epoxy groups in the molecule (hereinafter, may be referred to as "epoxy resin (B)"), for example.
  • epoxy resin (B) Bisphenol A type epoxy resin, bisphenol F type epoxy resin, naphthalene type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, phenol aralkyl type epoxy resin, biphenyl type epoxy resin, triphenylmethane type epoxy resin, dicyclopentadiene
  • Examples thereof include various epoxy resins such as type epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, and polyfunctional phenol type epoxy resin. One of these may be used alone, or two or more thereof may be mixed and used.
  • the epoxy resin (B) has a mass average molecular weight of preferably 100 to 5000, more preferably 200 to 2000, from the viewpoint of controlling the melt viscosity. If the mass average molecular weight is lower than 100, the heat resistance tends to be inferior, and if it is higher than 5000, the melting point of the epoxy resin tends to be high and the workability tends to be lowered.
  • the epoxy resin according to the present invention may contain an epoxy resin (hereinafter, "other epoxy resin") other than the epoxy resin (A) and the epoxy resin (B) as long as the purpose is not impaired.
  • the content of the other epoxy resin is usually 50% by mass or less, preferably 30% by mass or less, based on the total of the epoxy resin (A) and the epoxy resin (B).
  • the ratio of the epoxy resin (A) to the total epoxy resin containing the epoxy resin (A) and the epoxy resin (B) is preferably 5 as described above, with the total being 100% by mass. It is ⁇ 95% by mass, preferably 10 to 90% by mass, and more preferably 20 to 80% by mass.
  • the "total epoxy resin containing the epoxy resin (A) and the epoxy resin (B)” means that the epoxy resin contained in the resin composition of the present invention is only the epoxy resin (A) and the epoxy resin (B). Means the total of the epoxy resin (A) and the epoxy resin (B), and when another epoxy resin is contained, the total of the epoxy resin (A), the epoxy resin (B) and the other epoxy resin is used. means.
  • the ratio of the epoxy resin (A) is at least the above lower limit, the effect of improving the thermal conductivity by blending the epoxy resin (A) can be sufficiently obtained, and the desired high thermal conductivity can be obtained. ..
  • the proportion of the epoxy resin (A) is not more than the above upper limit, and in particular, when the epoxy resin (B) is 10% by mass or more of the total epoxy resin, the compounding effect of the epoxy resin (B) is exhibited, and the curable and cured product is exhibited. The physical properties of are sufficient.
  • the curing agent for epoxy resin may be appropriately selected according to the type of resin used.
  • an acid anhydride-based curing agent and an amine-based curing agent can be mentioned.
  • the acid anhydride-based curing agent include tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, and benzophenone tetracarboxylic acid anhydride.
  • amine-based curing agent examples include aliphatic polyamines such as ethylenediamine, diethylenetriamine and triethylenetetramine, aromatic polyamines such as diaminodiphenylsulfone, diaminodiphenylmethane, diaminodiphenyl ether and m-phenylenediamine, and dicyandiamide. One of these may be used alone, or two or more thereof may be mixed and used.
  • These curing agents for epoxy resins are usually blended in the range of 0.3 to 1.5 in an equivalent ratio with respect to the epoxy resin.
  • the curing accelerator may be appropriately selected according to the type of resin and curing agent used.
  • examples of the curing accelerator for the acid anhydrous curing agent include boron trifluoride monoethylamine, 2-ethyl-4-methylimidazole, 1-isobutyl-2-methylimidazole, and 2-phenyl-4-methylimidazole. Can be mentioned. One of these may be used alone, or two or more thereof may be mixed and used.
  • These curing accelerators are usually used in the range of 0.1 to 5 parts by mass with respect to 100 parts by mass of the epoxy resin.
  • the resin material used in the resin composition of the present invention may be a thermoplastic resin.
  • the thermoplastic resin include polyolefin resins such as polyethylene resin, polypropylene resin and ethylene-vinyl acetate copolymer resin, polyethylene terephthalate resin, polybutylene terephthalate resin, polyester resin such as liquid crystal polyester resin, polyvinyl chloride resin and phenoxy.
  • examples thereof include resins, acrylic resins, polycarbonate resins, polyphenylene sulfide resins, polyphenylene ether resins, polyamide resins, polyamideimide resins, polyimide resins, polyetheramideimide resins, polyetheramide resins and polyetherimide resins.
  • copolymers such as those block copolymers and graft copolymers are also included. These may be used alone or in admixture of two or more.
  • the resin material may be a rubber component, and examples of the rubber component include natural rubber, polyisoprene rubber, styrene-butadiene copolymer rubber, polybutadiene rubber, ethylene-propylene copolymer rubber, and ethylene-propylene.
  • -Diene copolymer rubber, butadiene-acrylonitrile copolymer rubber, isobutylene-isoprene copolymer rubber, chloroprene rubber, silicone rubber, fluororubber, chloro-sulfonated polyethylene, polyurethane rubber and the like can be mentioned.
  • One of these may be used alone, or two or more thereof may be mixed and used.
  • the amount of the granular boron nitride (or the granular boron nitride composition) of the present invention contained in the resin composition of the present invention is usually preferably 10 to 90% based on the mass of the resin composition. , More preferably 15 to 88%, still more preferably 30 to 85%.
  • the amount of granular boron nitride in the resin composition is less than this range, the viscosity of the resin composition (viscosity when melted) is low, the molding processability is good, but the thermal conductivity is improved. The effect can be inadequate.
  • the amount of granular boron nitride in the resin composition is larger than such a range, the viscosity of the resin composition at the time of melting becomes high, and molding tends to be difficult.
  • the resin composition of the present invention may contain other components as long as the effects of the present invention can be obtained.
  • Such components include functional resins obtained by imparting functionality to the above-mentioned resins such as liquid crystal epoxy resins, nitride particles such as aluminum nitride, silicon nitride, and fibrous boron nitride, alumina, and fibrous alumina.
  • functional resins obtained by imparting functionality to the above-mentioned resins
  • nitride particles such as aluminum nitride, silicon nitride, and fibrous boron nitride, alumina, and fibrous alumina.
  • insulating metal oxides such as zinc oxide, magnesium oxide, berylium oxide and titanium oxide
  • insulating carbon components such as diamond and fullerene
  • resin curing agents resin curing accelerators, viscosity modifiers and dispersion stabilizers.
  • the resin composition of the present invention may contain a solvent.
  • a solvent a known solvent that dissolves the resin is used.
  • examples of such a solvent include methyl ethyl ketone, acetone, cyclohexanone, toluene, xylene, monochlorobenzene, dichlorobenzene, trichlorobenzene, phenol, and hexafluoroisopropanol. These may be used alone or in admixture of two or more.
  • the solvent is used in the range of, for example, 0 to 10,000 parts by mass with respect to 100 parts by mass of a resin such as an epoxy resin.
  • the resin composition of the present invention is subjected to surface treatment such as an inorganic filler such as aluminum hydroxide and magnesium hydroxide, and a silane coupling agent for improving the interfacial adhesive strength between the inorganic filler and the matrix resin, as long as the effect is not impaired.
  • an inorganic filler such as aluminum hydroxide and magnesium hydroxide
  • a silane coupling agent for improving the interfacial adhesive strength between the inorganic filler and the matrix resin, as long as the effect is not impaired.
  • Agents, reducing agents and the like may be added.
  • the total amount of the granular boron nitride and the inorganic filler of the present invention in the resin composition is 90% by mass or less. preferable.
  • the resin composition of the present invention can be obtained by uniformly mixing the granular boron nitride (or granular boron nitride composition) of the present invention, the resin material, and other components added as necessary by stirring or kneading. Can be done.
  • a general kneading device such as a mixer, a kneader, a single shaft or a twin shaft kneader can be used, and in the mixing, heating may be performed if necessary.
  • the molded product of the present invention is obtained by molding the resin composition of the present invention.
  • a molding method of the molded body a method generally used for molding thereof, for example, injection molding or mold molding, can be used depending on the properties of the resin composition.
  • the resin composition is heated to be fluidized or plasticized as necessary, and the resin composition is molded into a molded product using a mold or the like. Therefore, the fluidized resin Some force acts on the composition. For example, pressure acts when the resin composition is filled into a mold.
  • the resin material is a curable resin (for example, phenol resin, epoxy resin, melamine resin, urea resin, etc.), a thermoplastic resin (for example, polyethylene, polypropylene, polyvinyl chloride, polystyrene, acrylic resin, etc.) can be used. Even if there is, it is considered to be applicable.
  • a curable resin for example, phenol resin, epoxy resin, melamine resin, urea resin, etc.
  • a thermoplastic resin for example, polyethylene, polypropylene, polyvinyl chloride, polystyrene, acrylic resin, etc.
  • the resin composition of the present invention when it has plasticity and fluidity, it can be molded by curing the resin composition in a desired shape, for example, in a state of being filled in a mold.
  • a method for producing such a molded product an injection molding method, an injection compression molding method, an extrusion molding method, and a compression molding method can be used.
  • the resin composition of the present invention is a thermosetting resin composition such as an epoxy resin or a silicone resin
  • the molded product can be molded, that is, cured under curing conditions according to the respective compositions.
  • the molded product when the resin composition of the present invention is a thermoplastic resin composition, the molded product can be molded under the conditions of a temperature equal to or higher than the melting temperature of the thermoplastic resin and a predetermined molding speed and pressure.
  • the molded product of the present invention can also be obtained by cutting the resin composition of the present invention into a desired shape from a molded or cured solid bulk material.
  • the amount of the resin material is 65 to 85% on a mass basis, although it depends on the blending amount of the resin material and the granular boron nitride (or the granular boron nitride composition).
  • the thermal conductivity in the direction parallel to the direction in which the force is applied during molding is usually 10 to 25 W / (m ⁇ K), preferably 15 to 23 W / (m ⁇ K), more preferably. Is 18 to 22 W / (m ⁇ K).
  • the thermal conductivity in the direction perpendicular to the direction in which pressure is applied during molding is usually 15 to 35 W / (m ⁇ K), preferably 20 to 30 W / (m ⁇ K), and more preferably 22 to 27 W / (. m ⁇ K).
  • the thermal conductivity in the parallel direction is the thermal conductivity in the vertical direction.
  • the ratio is preferably 70 to 120%, more preferably 80 to 110%, particularly 90 to 105%, and the anisotropy of the molded product with respect to thermal conductivity can be significantly suppressed, and in some cases, the anisotropy is substantially suppressed. Can be resolved.
  • the thermal conductivity in the parallel direction is similarly the heat in the vertical direction.
  • the anisotropy can be suppressed even when the granular boron nitride contains an oxide, particularly a rare earth element oxide, a Ca-rare earth element-BO composite oxide, or the like.
  • the resin composition comprises 65-85% by weight of granular boron nitride, in which case the ratio of the parallel thermal conductivity to the vertical thermal conductivity is at least about 90-105%. Is.
  • Ethanol of the obtained slurry was removed by an evaporator, and a dried powder was obtained as a mixture.
  • This powder was placed in a boron nitride crucible and heat-treated using a multipurpose high-temperature furnace (Fuji Dempa Kogyo Co., Ltd., Hi-Multi 5000) to obtain a granular boron nitride composition.
  • the composition in addition to boron nitride, contained CaYBO 4 Ca-Y-B- O -based composite oxide such like. It is considered that BO in this composite oxide is derived from the fact that the boron nitride powder used as a raw material contains 4% by weight of oxygen.
  • the heat treatment process involves raising the temperature from room temperature to 1100 ° C. at 20 ° C./min, then raising the temperature from 1100 to 1900 ° C. at 10 ° C./min, holding at 1900 ° C. for 10 hours, and then at 20 ° C./min. It was carried out by lowering the temperature to room temperature.
  • the atmosphere of the heat treatment is maintained in a vacuum of less than 1 ⁇ 10 -1 Pa up to 400 ° C., and then nitrogen gas is introduced into the furnace to atmospheric pressure, and the state of nitrogen gas flow of 1 ml / min is maintained until the end of the heat treatment. Retained.
  • the mixture was heat-treated as described above to obtain the granular boron nitride composition of the present invention. Then, the obtained composition was washed to remove the oxides (yttrium oxide, calcium oxide) contained therein. Specifically, 2.5 g of the composition was added to 20 ml of a 3N hydrochloric acid aqueous solution in a Teflon-lined closed pressure vessel, and the mixture was reacted at 100 ° C. for 11 hours to convert the contained oxide into a water-soluble salt. Then, it was washed with pure water and filtered to remove salt, and the granular boron nitride of this invention was obtained. When the obtained granular boron nitride was subjected to XRD analysis, yttrium oxide and calcium oxide that could remain in it could not be detected.
  • Example 2 The amount of Y 2 O 3 added in Example 1 was 3.59 g (Example 2: 7.3% by volume in the total amount of the mixed powder before heat treatment), 5.70 g (Example 3: 10 in the total amount of the mixed powder before heat treatment). .9% by volume), 8.07g (Example 4: 14.6% by volume in the total amount of mixed powder before heat treatment), 10.76g (Example 5: 18.2% by volume in the total amount of mixed powder before heat treatment), 13.84 g (Example 6: 21.9% by volume in the total amount of the mixed powder before heat treatment), and the amount of CaO added in Example 1 was 0.89 g (Example 2: 2. in the total amount of the mixed powder before heat treatment).
  • Example 1 7% by volume
  • Example 3 4.1% by volume in the total amount of mixed powder before heat treatment
  • 2.00 g Example 4: 5.4% by volume in the total amount of mixed powder before heat treatment
  • Example 1 was used except for .67 g (Example 5: 6.8% by volume in the total amount of mixed powder before heat treatment) and 3.44 g (Example 6: 8.1% by volume in the total amount of mixed powder before heat treatment).
  • the granular boron nitride of the present invention was repeatedly obtained. When the obtained granular boron nitride was subjected to XRD analysis, yttrium oxide and calcium oxide that could remain in it could not be detected.
  • Example 1 the ratio of the total volume of oxides of Y 2 O 3 and Ca O contained in the mixture powder before heat treatment to the volume of the mixture was 5% by volume in Example 1 and Example 2.
  • Example 3 was 15% by volume
  • Example 4 was 20% by volume
  • Example 5 was 25% by volume
  • Example 6 was 30% by volume.
  • Example 1 was repeated except for the conditions shown in Table 1 below to obtain the granular boron nitride of the present invention.
  • the molar ratio of yttrium oxide to calcium oxide constituting the mixture is 1: 2
  • the molar ratio of yttrium oxide to calcium oxide constituting the mixture of Examples 13 to 18 is 1: 4.
  • the molar ratio of yttrium oxide to calcium oxide constituting the mixture of Examples 19 to 24 was 1: 6.
  • Example 1 was repeatedly heat-treated to obtain the granular boron nitride composition of the present invention, except that 1.97 g of CeO 2 powder was added in place of yttrium oxide to obtain 0.64 g of CaO powder, which was further washed and oxidized.
  • the granular boron nitride of the present invention from which the substance was removed was obtained.
  • cerium oxide and calcium oxide that could remain in it could not be detected.
  • Example 25 the amount of CeO 2 added was 4.15 g (Example 26: 5.9% by volume in the total amount of the mixed powder before heat treatment) and 6.59 g (Example 27: 8. in the total amount of the mixed powder before heat treatment). 8% by volume), 9.34 g (Example 28: 11.8% by volume in the total amount of mixed powder before heat treatment), 12.45 g (Example 29: 14.7% by volume in the total amount of mixed powder before heat treatment), 16.
  • Example 30 17.6% by volume in the total amount of the mixed powder before heat treatment
  • the amount of CaO added in Example 25 was 1.35 g (Example 26: 4.1 volume in the total amount of the mixed powder before heat treatment). %), 2.15 g (Example 27: 6.2% by volume in the total amount of the mixed powder before heat treatment) 3.04 g (Example 28: 8.2% by volume in the total amount of the mixed powder before heat treatment) 4.06 g
  • Example 25 was repeated except that (Example 29: 10.3% by volume in the total amount of the mixed powder before heat treatment) and 5.22 g (Example 30: 12.4% by volume in the total amount of the mixed powder before heat treatment).
  • the granular boron nitride of the present invention was obtained.
  • Example 25 the ratio of the total volume of oxides of CeO 2 and CaO contained in the mixed powder before heat treatment to the volume of the mixture was 5% by volume in Example 25 and 10 in Example 26.
  • the volume was 15% by volume in Example 27, 20% by volume in Example 28, 25% by volume in Example 29, and 30% by volume in Example 30.
  • the mixture was washed with pure water and filtered to remove salts to obtain the granular boron nitride of the present invention.
  • Treatment with the acid as compared with Example 3, because of the small concentration of hydrochloric acid used in the 100 ° C., Y 2 O 3 is partially left, other components could substantially removed.
  • 1 g of granular boron nitride obtained after filtration was added to 20 ml of a 1N hydrochloric acid aqueous solution and reacted at 100 ° C. for 11 hours in a Teflon-lined closed container, the filtrate portion was quantitatively analyzed by ICP to obtain yttrium oxide.
  • Example 4 Although it contained 1.01% by mass, the amount of calcium oxide was below the detection limit.
  • the granular boron nitride composition containing the heat-treated oxides obtained in Example 4, Example 6, Example 9, Example 11, Example 12, Example 18 and Example 24 was similarly prepared. The treatment gave the granular boron nitride of the present invention of Examples 32 to 38, respectively.
  • Comparative Example 1 was repeated by changing the amount of Y 2 O 3 powder to be added.
  • acetone was removed using an evaporator.
  • 0.8 g of a mixture as a resin composition containing granular boron nitride and an epoxy resin material remaining in a eggplant-shaped flask after removal was placed in a mold having a diameter of 15 mm, and the resin composition was thermoset by hot pressing to form a molded product.
  • the conditions for hot pressing are as follows: -Born nitrides of Comparative Examples 1 to 6, Examples 1 to 4, 7 to 10, 13 to 16, 19 to 22, 25 to 28 are hot-pressed for 120 minutes under uniaxial pressure at 125 ° C. and 70 MPa. 7. For boron nitrides of Examples 5, 6, 11, 12, 17, 18, 23, 24, 29, 30 under uniaxial pressure of 125 ° C. and 5 MPa or less, hot press for 60 minutes, followed by pressure up to 70 MPa. Hot press for 60 minutes by raising
  • ⁇ is the density of the molded body (g / cm 3 )
  • ⁇ a is the density of water at the measurement temperature (g / cm 3 )
  • m 1 is the mass of the molded body in air (g)
  • m 2 Is the mass of the molded product in water.
  • Cp is the specific heat of the molded body sample (J / g / K)
  • Cp standard is the specific heat of the reference material (J / g / K)
  • m is the weight of the molded body sample (g)
  • M is the weight of the reference material.
  • G h is the difference between the DSC curves of the empty container and the molded body sample
  • H is the difference between the DSC curves of the empty container and the reference material.
  • the thermal conductivity ( ⁇ ) is the time t 1/2 of irradiating the front surface of the molded product sample with a heat source, measuring the temperature of the back surface, and reaching 1/2 of the time ( ⁇ Tm) until the maximum temperature of the back surface is reached. Obtained from (s) and sample thickness L (m) by the following formula (3):
  • the thermal conductivity of the molded product was measured in the pressurizing direction (pressing direction) of the pressure applied during hot pressing and in the direction perpendicular to it.
  • the strength of the shell structure constituting the granular boron nitride contained in the molded body is insufficient, a part of the shell structure collapses due to hot pressing, the properties of the shell structure of the granular boron nitride are weakened, and the properties of the laminated structure are deteriorated. Become stronger. As a result, the a-axis of the broken boron nitride plate-like crystal becomes more likely to be oriented along the direction perpendicular to the hot press direction, and the (00L) plane of the boron nitride crystal (002), (004), etc. The diffraction peak becomes high.
  • the XRD diffraction pattern is measured with respect to the surface perpendicular to the pressing direction (that is, the hot pressing surface or the pressed surface) using the Lot Göring method. , Obtained by the following formula (4):
  • the lot-gering method is a method of evaluating the degree of orientation of crystals or the like using the degree of orientation calculated by the formula (4) (also referred to as a lot-gering factor).
  • the lotgering factor is 100% in the case of perfect orientation.
  • ⁇ I (hkl) is the sum of the X-ray diffraction intensities of all crystal planes (hkl) measured on the plane perpendicular to the press direction with respect to the sample of the molded product containing the aggregate.
  • ⁇ I 0 (hkl) is the sum of the X-ray diffraction intensities of all crystal planes (hkl) measured for the sample of the molded product obtained when non-oriented boron nitride is used instead of granular boron nitride.
  • ⁇ I (00L) is the X-ray diffraction intensity of a specific crystal plane (for example, a (00L) plane including (002) or (004) plane) measured for a molded product containing an aggregate.
  • ⁇ I 0 (00L) is the crystal plane of the (00L) plane measured for the non-oriented material having the same composition as the hybrid material of the specific plane when the above-mentioned non-oriented boron nitride is used. It is the sum of the X-ray diffraction intensities.
  • the lot-gering method for evaluating the degree of orientation as described above is well known as a method for evaluating the degree of orientation of crystals, and for example, Japanese Patent Application Laid-Open No. 2011-37695 can be referred to.
  • the granular boron nitride obtained from each of the examples has a considerably larger average particle size than the boron nitrides of Comparative Examples 1 to 6 that do not use the calcium component, but the specific surface area is slightly smaller.
  • the thermal conductivity of the molded product of the present invention obtained by molding the resin composition of the present invention using such granular boron nitride as a heat conductive filler about 10 to 25 W / (m. K), and 15 to 35 W / (m ⁇ K) can be achieved in the direction perpendicular to it.
  • Such thermal conductivity is higher than that of a molded product obtained by using a known granular boron nitride as a filler as a comparative example.
  • Such a large thermal conductivity means that granular boron nitride can form an effective thermal conduction path due to the large particle size.
  • the thermal conductivity in the parallel direction is at least about 60% of the thermal conductivity in the vertical direction, and the anisotropy regarding the heat conduction of the molded body containing the granular boron nitride is suppressed. Has been done. In some cases, the particle size and consequently may exceed 100%, and anisotropy with respect to heat conduction may not be substantially observed.
  • the degree of orientation of granular boron nitride in the molded product affects the thermal conductivity of the molded product.
  • Boron nitride or plate-shaped boron nitride
  • the thermal conductivity in the direction parallel to the pressing direction at the time of molding becomes remarkably low, and as a result, the thermal conductivity anisotropy becomes large.
  • Comparative Example 8 since commercially available plate-shaped particles are added, the degree of orientation is high and the thermal conductivity in the direction parallel to the pressing direction is low.
  • the boron nitride particles are not plate-shaped, but synthetic boron nitride particles having a multifaceted structure are added.
  • the cohesive force of the boron nitride crystal is weak, it is considered that the polyhedral structure collapses into a plate-shaped boron nitride due to the force applied by press forming and is oriented. Therefore, as in Comparative Example 8, it is considered that the heat conduction along the direction parallel to the pressing direction is low by press forming.
  • the granular boron nitride produced in this example uses a rare earth element oxide in the production method. Since the rare earth element oxide promotes the assumption of dissolution and reprecipitation of boron nitride, it is said that it brings a stronger cohesive force than boron nitride having a multifaceted structure in Comparative Example 7 produced by adding only the conventional alkaline earth oxide. Conceivable. In particular, in the shell portion of the granular boron nitride produced in this example, it is considered that the integrated plate-shaped boron nitride tends to form a polyhedron or a sphere, which is considered to be a factor for increasing the strength of the granular boron nitride.
  • the granular boron nitride contained in the granular boron nitride particle composition contains an oxide inside before acid cleaning.
  • the degree of acid cleaning for example, by lowering the acid concentration used for cleaning, the amount of rare earth element oxide remaining inside can be changed. If the oxide remains in the granular boron nitride, it is expected that the strength of the shell structure of the formed boron nitride, particularly the compressive strength, can be improved. That is, when a resin composition is obtained using such granular boron nitride and molded by hot pressing, it is considered that the granular boron nitride is less likely to collapse and the degree of orientation of the (00L) plane of the molded product is lowered.
  • the granular boron nitride of the present invention is preferably 0.5 to 15% by mass, more preferably 3 to 10% by mass, and particularly 4 to 8%. Contains% by mass of rare earth element oxides.
  • the resin composition of the present invention and the molded product produced by molding the composition are, for example, a heat-dissipating sheet, a heat conductive paste, and a heat conductive material that require heat conductivity in the fields of electricity and electronics. It can be suitably used as a heat conductive filler in a sex adhesive or the like.

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Abstract

Selon la présente invention, lorsque du nitrure de bore est mélangé avec un matériau de résine et qu'un corps moulé est produit en utilisant le mélange résultant, la conductivité thermique est augmentée encore plus. De plus, lors de l'utilisation d'un constituant de terres rares, sa quantité d'utilisation est réduite.　Le nitrure de bore granuleux peut être produit à l'aide d'un procédé qui sert à produire une composition de nitrure de bore granuleux et comprend une étape de traitement thermique, dans une atmosphère de gaz non oxydant, d'un mélange composé de : (1) un constituant de nitrure de bore contenant du nitrure de bore; (2) un constituant de terres rares contenant un oxyde d'au moins un élément de terres rares sélectionné parmi l'yttrium, le cérium, et l'ytterbium, et/ou son composé précurseur; et (3) un constituant calcium contenant de l'oxyde de calcium et/ou du carbonate de calcium.
PCT/JP2020/005627 2019-03-28 2020-02-13 Procédé de production de nitrure de bore granuleux et nitrure de bore granuleux WO2020195298A1 (fr)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112919517A (zh) * 2021-03-04 2021-06-08 中国科学院苏州纳米技术与纳米仿生研究所 氧化钙掺杂的氮化硼气凝胶及其制备方法与应用
WO2023157784A1 (fr) * 2022-02-16 2023-08-24 株式会社Maruwa Corps fritté de nitrure de silicium et procédé de fabrication de corps fritté de nitrure de silicium
WO2024034604A1 (fr) * 2022-08-10 2024-02-15 国立大学法人 香川大学 Procédé de production de nitrure de bore granulaire et nitrure de bore granulaire

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013056789A (ja) * 2011-09-07 2013-03-28 Mitsubishi Chemicals Corp 粉末状窒化ホウ素組成物、およびそれを含有する複合材組成物
JP2016060661A (ja) * 2014-09-17 2016-04-25 株式会社トクヤマ 窒化硼素粉末及びその製造方法
WO2016092951A1 (fr) * 2014-12-08 2016-06-16 昭和電工株式会社 Poudre de nitrure de bore hexagonal, son procédé de production, composition de résine, et feuille de résine
JP2018165241A (ja) * 2017-03-28 2018-10-25 デンカ株式会社 六方晶窒化ホウ素粉末、その製造方法、及び化粧料
JP2019043804A (ja) * 2017-08-31 2019-03-22 株式会社豊田中央研究所 熱伝導性フィラー、熱伝導性複合材料、及び熱伝導性フィラーの製造方法

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5588722B2 (ja) 2010-04-21 2014-09-10 旭化成イーマテリアルズ株式会社 ポリオレフィン微多孔膜、及びリチウムイオン二次電池
EP3269682B1 (fr) 2011-11-29 2020-01-01 Mitsubishi Chemical Corporation Particules de nitrure de bore agglomérées, composition contenant lesdites particules, et circuit intégré tridimensionnel doté d'une couche comprenant ladite composition
DE102012104049A1 (de) 2012-05-09 2013-11-28 Esk Ceramics Gmbh & Co. Kg Bornitrid-Agglomerate, Verfahren zu deren Herstellung und deren Verwendung

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013056789A (ja) * 2011-09-07 2013-03-28 Mitsubishi Chemicals Corp 粉末状窒化ホウ素組成物、およびそれを含有する複合材組成物
JP2016060661A (ja) * 2014-09-17 2016-04-25 株式会社トクヤマ 窒化硼素粉末及びその製造方法
WO2016092951A1 (fr) * 2014-12-08 2016-06-16 昭和電工株式会社 Poudre de nitrure de bore hexagonal, son procédé de production, composition de résine, et feuille de résine
JP2018165241A (ja) * 2017-03-28 2018-10-25 デンカ株式会社 六方晶窒化ホウ素粉末、その製造方法、及び化粧料
JP2019043804A (ja) * 2017-08-31 2019-03-22 株式会社豊田中央研究所 熱伝導性フィラー、熱伝導性複合材料、及び熱伝導性フィラーの製造方法

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
KUSUNOSE TAKAFUMI; SEKINO TOHRU: "Thermal conductivity of hot-pressed hexagonal boron nitride", SCRIPTA MATERIALIA, vol. 124, 2016, pages 138 - 141, XP029698312, ISSN: 1359-6462, DOI: 10.1016/j.scriptamat.2016.07.011 *
T KUSUNOSE , Y UNO , T SEKINO: "Improvement of thermal conduction anisotropy of epoxy hybrid material by addition of aggregated boron nitride filler", LECTURE PREPRINTS OF THE CERAMIC SOCIETY OF JAPAN ANNUAL MEETING, 15 March 2018 (2018-03-15), XP009523844, ISBN: 978-4-931298 *
YOSHINORI UNO, NAOFUMI KUSUNOSE, TORU SEKINO: "1PC02: Fabrication of agglomerated boron nitride fillers from fine boron nitride particles part 2", LECTURE PREPRINTS OF THE 31ST FALL MEETING OF THE CERAMIC SOCIETY OF JAPAN; SEPTEMBER 5-7, 2018; NAGOYA INSTITUTE OF TECHNOLOGY, CERAMIC SOCIETY OF JAPAN, JP, vol. 31, 30 November 2017 (2017-11-30), JP, pages 1PC02, XP009523845, ISBN: 978-4-931298-76-7 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112919517A (zh) * 2021-03-04 2021-06-08 中国科学院苏州纳米技术与纳米仿生研究所 氧化钙掺杂的氮化硼气凝胶及其制备方法与应用
WO2023157784A1 (fr) * 2022-02-16 2023-08-24 株式会社Maruwa Corps fritté de nitrure de silicium et procédé de fabrication de corps fritté de nitrure de silicium
WO2024034604A1 (fr) * 2022-08-10 2024-02-15 国立大学法人 香川大学 Procédé de production de nitrure de bore granulaire et nitrure de bore granulaire

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