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WO2021200973A1 - Procédé servant à produire un corps composite - Google Patents

Procédé servant à produire un corps composite Download PDF

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Publication number
WO2021200973A1
WO2021200973A1 PCT/JP2021/013578 JP2021013578W WO2021200973A1 WO 2021200973 A1 WO2021200973 A1 WO 2021200973A1 JP 2021013578 W JP2021013578 W JP 2021013578W WO 2021200973 A1 WO2021200973 A1 WO 2021200973A1
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Prior art keywords
sintered body
nitride sintered
boron nitride
resin
complex
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
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PCT/JP2021/013578
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English (en)
Japanese (ja)
Inventor
仁孝 南方
裕介 和久田
真也 坂口
智也 山口
西村　浩二
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Denka Co Ltd
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Denka Co Ltd
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Priority to JP2022512554A priority Critical patent/JPWO2021200973A1/ja
Publication of WO2021200973A1 publication Critical patent/WO2021200973A1/fr
Anticipated expiration legal-status Critical
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    • 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
    • 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
    • C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
    • 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
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
    • C04B41/81—Coating or impregnation
    • C04B41/82—Coating or impregnation with organic materials
    • C04B41/83—Macromolecular compounds
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate

Definitions

  • This disclosure relates to a method for producing a complex.
  • thermal interface materials that have electrical insulation properties for electronic components or printed wiring boards. It has been used to attach it to a heat sink.
  • a composite heat radiating member composed of a resin and ceramics such as nitride is used.
  • Patent Document 1 proposes a technique for reducing the anisotropy of thermal conductivity while having excellent thermal conductivity by setting the degree of orientation of boron nitride and the graphitization index within a predetermined range.
  • the present disclosure provides a method for producing a complex which is thin and suitable as a member such as an electronic component.
  • the present disclosure is a method for producing a composite having a porous nitride sintered body and a resin filled in at least a part of the pores of the nitride sintered body in one aspect.
  • a method for producing a composite which comprises an impregnation step of impregnating a sintered body with a resin composition, and the thickness of the nitride sintered body is less than 2 mm.
  • a nitride sintered body having a thickness of less than 2 mm is impregnated with a resin porous composition. Since the nitride sintered body having such a thin thickness is used, the resin composition is impregnated into the inside of the nitride sintered body due to the capillary phenomenon. This makes it possible to produce a composite that is thin and the resin is sufficiently filled inside the nitride sintered body. Since this complex is thin and has excellent electrical insulation and thermal conductivity, it can be suitably used as a member (for example, a heat radiating member) of an electronic component or the like. However, its use is not limited to the members of electronic parts.
  • the porosity of the nitride sintered body may be 30 to 65% by volume. Thereby, the balance between the mass and the strength of the complex can be preferably maintained.
  • the average pore diameter of the pores of the nitride sintered body may be 30 ⁇ m or less.
  • the nitride sintered body does not have to have a cut surface. This makes it possible to produce a complex having sufficiently high strength and further excellent electrical insulation and thermal conductivity. In addition, a nitride sintered body and a composite can be produced with a high yield.
  • the nitride sintered body may contain boron nitride particles. As a result, both electrical insulation and thermal conductivity can be achieved at a higher level.
  • the present disclosure can provide a method for producing a complex which is thin and suitable as a member such as an electronic component.
  • FIG. 1 is a perspective view showing an example of a composite and a nitride sintered body.
  • the method for producing the composite of the present embodiment includes a sintering step of molding a raw material powder containing a nitride and firing it to obtain a nitride sintered body containing nitride particles and pores, and a nitride sintered body. It has an impregnation step of impregnating the resin composition.
  • the nitride contained in the raw material powder may contain, for example, at least one nitride selected from the group consisting of boron nitride, aluminum nitride, and silicon nitride, and preferably contains boron nitride.
  • boron nitride either amorphous boron nitride or hexagonal boron nitride can be used.
  • the raw material powder is, for example, an amorphous boron nitride powder having an average particle size of 0.5 to 10 ⁇ m and an average particle size of 3.0 to 40 ⁇ m. Hexagonal boron nitride powder can be obtained.
  • a compound containing a nitride powder may be molded and sintered to obtain a nitride sintered body.
  • a mold may be used for molding, or a cold isotropic pressing (CIP) method may be used.
  • CIP cold isotropic pressing
  • a sintering aid may be added to obtain a formulation.
  • the sintering aid may be, for example, an oxide of a rare earth element such as itria oxide, alumina oxide and magnesium oxide, a carbonate of an alkali metal such as lithium carbonate and sodium carbonate, and boric acid.
  • the blending amount of the sintering aid is, for example, 0.01 part by mass or more or 0.1 mass by mass with respect to a total of 100 parts by mass of the nitride and the sintering aid. It may be more than one part.
  • the blending amount of the sintering aid may be, for example, 20 parts by mass or less, 15 parts by mass or less, or 10 parts by mass or less with respect to 100 parts by mass of the total of the nitride and the sintering aid.
  • the compound may be a molded product by powder pressing or mold molding, or may be a sheet-shaped molded product by the doctor blade method.
  • the molding pressure may be, for example, 5 to 350 MPa.
  • the shape of the molded product is preferably, for example, a sheet having a thickness of less than 2 mm. If a nitride sintered body is manufactured using such a sheet-shaped molded product, a sheet-shaped composite having a thickness of less than 2 mm can be manufactured without cutting the nitride sintered body. Further, as compared with the case where the block-shaped nitride sintered body is cut into a sheet shape, the material loss due to processing can be reduced by forming the sheet shape from the stage of the molded body. Therefore, a sheet-like complex can be produced with a high yield.
  • the thickness of the sheet-like complex may be 0.1 mm or more, or 0.2 mm or more, from the viewpoint of strength.
  • the sintering temperature in the sintering step may be, for example, 1600 ° C. or higher, or 1700 ° C. or higher.
  • the sintering temperature may be, for example, 2200 ° C. or lower, or 2000 ° C. or lower.
  • the sintering time may be, for example, 1 hour or more, or 30 hours or less.
  • the atmosphere at the time of sintering may be, for example, an atmosphere of an inert gas such as nitrogen, helium, and argon.
  • a batch type furnace, a continuous type furnace, or the like can be used.
  • the batch type furnace include a high frequency furnace, a muffle furnace, a tube furnace, an atmosphere furnace, and the like.
  • the continuous furnace include a rotary kiln, a screw conveyor furnace, a tunnel furnace, a belt furnace, a pusher furnace, a large continuous furnace, and the like. In this way, a nitride sintered body can be obtained.
  • the nitride sintered body may be in the form of blocks.
  • the block-shaped nitride sintered body is a polyhedron, for example, all sides have a suitable length, and the block-shaped nitride sintered body has a larger thickness than the sheet-shaped nitride sintered body. That is, the block shape means a shape that can be divided into a plurality of sheet shapes (thin plate shapes) by cutting.
  • a cutting step is performed to process it so that it has a thickness of less than 2 mm.
  • the nitride sintered body is cut using, for example, a wire saw.
  • the wire saw may be, for example, a multi-cut wire saw or the like.
  • the composite obtained without going through the cutting step of the nitride sintered body does not have a cut surface, so that fine cracks can be sufficiently reduced. Therefore, the composite obtained without going through the cutting step of the nitride sintered body can sufficiently improve the electrical insulation property and the thermal conductivity while maintaining a sufficiently high strength. That is, it is excellent in reliability as a member such as an electronic component. Further, when processing such as cutting is performed, material loss occurs. Therefore, the composite having no cut surface of the nitride sintered body can reduce the material loss. Thereby, the yield of the nitride sintered body and the composite can be improved.
  • the sheet-like nitride sintered body having a thickness of less than 2 mm can be sufficiently impregnated with the resin composition even inside. Further, by adjusting the pore diameter of the pores in the nitride sintered body, impregnation of the resin composition due to the capillary phenomenon can be promoted.
  • the thickness of the nitride sintered body may be 0.1 mm or more, or 0.2 mm or more, from the viewpoint of strength.
  • the average pore diameter of the pores in the nitride sintered body may be, for example, 30 ⁇ m or less, 20 ⁇ m or less, 10 ⁇ m or less, 3 ⁇ m or less, 2 ⁇ m or less, or 1 ⁇ m or less.
  • the average pore diameter of the pores may be, for example, 0.1 ⁇ m or more, 0.2 ⁇ m or more, or 0.3 ⁇ m or more.
  • the average pore diameter is within the above upper and lower limit ranges, the pores are easily impregnated with the thermosetting composition.
  • the "average pore size" means a value measured by the mercury intrusion method.
  • An example of the average pore diameter of the nitride sintered body is 0.1 to 30 ⁇ m.
  • the average pore diameter of the pores is determined based on the pore diameter distribution when the pressure is increased from 0.0042 MPa to 206.8 MPa using a mercury porosimeter.
  • the pore diameter when the cumulative pore volume reaches 50% of the total pore volume is the average pore diameter.
  • the mercury porosimeter one manufactured by Shimadzu Corporation can be used.
  • the pore ratio of the nitride sintered body that is, the volume ratio of the pores in the nitride sintered body is 20% by volume or more, 25% by volume or more, 30% by volume or more, 40% by volume or more, or 45% by volume or more. good.
  • the porosity of the nitride sintered body may be 70% by volume or less, 65% by volume or less, or 60% by volume or less. If the porosity becomes too large, the strength of the obtained complex tends to decrease. On the other hand, if the porosity becomes too small, the mass tends to be heavy.
  • the pore ratio is calculated by calculating the bulk density [B (kg / m 3 )] from the volume and mass of the nitride sintered body, and from this bulk density and the theoretical density of the nitride [D (kg / m 3 )]. , Can be obtained by the following formula (1).
  • the bulk density B of the nitride sintered body may be 500 to 2500 kg / m 3 , 700 to 2000 kg / m 3 , or 900 to 1500 kg / m 3 . If the bulk density B becomes too large, the mass of the nitride sintered body tends to increase. In addition, the filling amount of the resin tends to decrease, and the electrical insulating property of the complex tends to decrease. On the other hand, if the bulk density B becomes too small, the strength of the nitride sintered body tends to decrease.
  • the impregnation step includes an impregnation step of impregnating a sheet-shaped nitride sintered body having a thickness of less than 2 mm with the resin composition.
  • the resin composition may be thermosetting, and may be, for example, at least one compound selected from the group consisting of a compound having a cyanate group, a compound having a bismaleimide group, and a compound having an epoxy group, and a phosphine-based curing. It may contain at least one curing agent selected from the group consisting of agents and imidazole-based curing agents, and a solvent.
  • the solvent examples include aliphatic alcohols such as ethanol and isopropanol, 2-methoxyethanol, 1-methoxyethanol, 2-ethoxyethanol, 1-ethoxy-2-propanol, 2-butoxyethanol and 2- (2-methoxyethoxy).
  • Ether alcohols such as ethanol, 2- (2-ethoxyethoxy) ethanol, 2- (2-butoxyethoxy) ethanol, glycol ethers such as ethylene glycol monomethyl ether and ethylene glycol monobutyl ether, acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl
  • ketones such as ketones and hydrocarbons such as toluene and xylene. One of these may be contained alone, or two or more thereof may be contained in combination.
  • Resins include epoxy resin, silicone resin, cyanate resin, silicone rubber, acrylic resin, phenol resin, melamine resin, urea resin, bismaleimide resin, unsaturated polyester, fluororesin, polyimide, polyamideimide, polyetherimide, and polybutylene.
  • Telephthalate polyethylene terephthalate, polyphenylene ether, polyphenylene sulfide, total aromatic polyester, polysulfone, liquid crystal polymer, polyether sulfone, polycarbonate, maleimide resin, maleimide-modified resin, ABS (acrylonitrile-butadiene-styrene) resin, AAS (acrylonitrile-acrylic rubber) -Stylus) resin, AES (acrylonitrile, ethylene, propylene, diene rubber-styrene) resin, polyglycolic acid resin, polyphthalamide, polyacetal and the like can be mentioned.
  • One of these may be contained alone, or two or more thereof may be contained in combination.
  • the resin composition may contain an inorganic filler, a silane coupling agent, a defoaming agent, a surface conditioner, a wet dispersant and the like.
  • Impregnation is performed by adhering the resin composition to the nitride sintered body.
  • the impregnation method is not particularly limited, but since the nitride sintered body used here is sufficiently thin, the resin composition is sufficiently impregnated into the inside by a capillary phenomenon. Therefore, a resin composition having a high viscosity can be used, and the resin composition can be applied to the nitride sintered body to perform the impregnation step.
  • coating for example, dip coating, screen printing, transfer printing, offset printing, bar coater, air dispenser, comma coater, gravure coater, letterpress printing, concave printing, gravure printing, stencil printing, soft lithograph, bar coat, applicator, etc.
  • a spin coater, a dip coater, a rubber spatula, a brush, or the like can be used.
  • the viscosity of the resin composition may be 5000 mPa ⁇ s or less, and may be 2000 mPa ⁇ s or less. Even if the resin composition has such a high viscosity, the nitride sintered body can be sufficiently impregnated by utilizing the capillary phenomenon if the thickness is the above. From the viewpoint of sufficiently reducing the voids of the complex, the viscosity of the resin composition may be 1 mPa ⁇ s or more, and may be 5 mPa ⁇ s or more.
  • the amount of the resin composition applied to the boron nitride sintered body may be 1 to 1.5 times based on the total pore volume of the boron nitride sintered body.
  • Nitride sintered bodies and complexes may contain both closed and open pores.
  • the impregnation step there may be a curing step of curing the resin filled in the pores.
  • the composite filled with the resin (resin composition) is taken out from the impregnation device, heated and / or irradiated with light depending on the type of the resin (or the curing agent added as needed). Allows the resin to be cured or semi-cured.
  • "Semi-hardening" (also referred to as B stage) means that it can be further hardened by a subsequent hardening treatment. Utilizing the fact that it is in a semi-cured state, it may be temporarily pressure-bonded to an adherend such as a metal substrate and then heated to adhere to the adherend.
  • the semi-cured product By further curing the semi-cured product, it can be in a "completely cured” (also referred to as C stage) state.
  • “curing” includes both “semi-curing” and “completely curing”. Whether or not the resin is in a semi-cured state can be confirmed by, for example, a differential scanning calorimeter.
  • the complex thus obtained is, for example, in the form of a sheet and has a thin thickness. Therefore, it is thin and lightweight, and when it is used as a member of an electronic component or the like, it is possible to reduce the size and weight of the electronic component or the like. Further, since the pores of the nitride sintered body are sufficiently filled with the resin, it is also excellent in thermal conductivity and electrical insulation. Further, in the above-mentioned production method, the complex can be produced without having a step of cutting the complex. Therefore, a highly reliable complex can be produced with a high yield.
  • the composite may be used as it is as a heat radiating member, or may be subjected to processing such as polishing to be a heat radiating member.
  • the boron nitride sintered body may be obtained by the following manufacturing method.
  • the above-mentioned description of the nitride sintered body and the composite is applied to the following manufacturing method.
  • the production method of this example is a nitriding step of calcining boron carbide powder in a nitrogen-pressurized atmosphere to obtain a calcined product containing boron nitride, and molding and heating of a compound containing the calcined product and a sintering aid.
  • This includes a sintering step of obtaining a sheet-shaped boron nitride sintered body containing boron nitride particles and pores and having a thickness of less than 2 mm, and an impregnation step of impregnating the boron nitride sintered body with the resin composition.
  • Boron carbide powder can be prepared, for example, by the following procedure. After mixing boric acid and acetylene black, the mixture is heated at 1800 to 2400 ° C. for 1 to 10 hours in an inert gas atmosphere to obtain a boron carbide mass.
  • the boron carbide mass can be prepared by pulverizing, washing, removing impurities, and drying.
  • the boron carbide powder is calcined in a nitrogen atmosphere to obtain a calcined product containing boron nitride (B 4 CN 4).
  • the firing temperature in the nitriding step may be 1800 ° C. or higher, and may be 1900 ° C. or higher. Further, the firing temperature may be 2400 ° C. or lower, and may be 2200 ° C. or lower. The firing temperature may be, for example, 1800 to 2400 ° C.
  • the pressure in the nitriding step may be 0.6 MPa or more, and may be 0.7 MPa or more. Further, the pressure may be 1.0 MPa or less, and may be 0.9 MPa or less. The pressure may be, for example, 0.6 to 1.0 MPa. If the pressure is too low, nitriding of boron carbide tends to be difficult to proceed. On the other hand, if the pressure is too high, the manufacturing cost tends to increase.
  • the pressure in the present disclosure is an absolute pressure.
  • the nitrogen gas concentration in the nitrogen atmosphere in the nitriding step may be 95% by volume or more, and may be 99.9% by volume or more.
  • the partial pressure of nitrogen may be in the pressure range described above.
  • the firing time in the nitriding step is not particularly limited as long as the nitriding proceeds sufficiently, and may be, for example, 6 to 30 hours or 8 to 20 hours.
  • a calcined product containing boron nitride particles obtained in the nitriding step and a sintering aid may be blended to obtain a compound.
  • the sintering aid may contain a boron compound and a calcium compound.
  • the compound may contain 1 to 20 parts by mass in total of the boron compound and the calcium compound with respect to 100 parts by mass of the fired product. With such a content, while suppressing the excessive grain growth of the primary particles, the grain growth is moderately promoted to promote sintering, and the primary particles of boron nitride are firmly and closely adhered to each other over a wide area. Join.
  • the formulation may contain a total of 2 to 30 parts by mass of the boron compound and the calcium compound with respect to 100 parts by mass of the calcined product, and may contain 5 to 25 parts by mass. It may contain 8 to 20 parts by mass.
  • the formulation may contain 0.5 to 40 atomic% of calcium constituting a calcium compound, or 0.7 to 30 atomic%, based on 100 atomic% of boron constituting the boron compound.
  • Examples of the boron compound include boric acid, boron oxide, borax and the like.
  • Examples of the calcium compound include calcium carbonate and calcium oxide.
  • the sintering aid may contain components other than boric acid and calcium carbonate. Examples of such a component include carbonates of alkali metals such as lithium carbonate and sodium carbonate.
  • a binder may be added to the compound. Examples of the binder include an acrylic compound and the like.
  • the fired product may be crushed using a general crusher or crusher.
  • a ball mill, a Henschel mixer, a vibration mill, a jet mill and the like can be used.
  • "crushing” also includes “crushing”.
  • the calcined product may be crushed and then the sintering aid may be blended, or the calcined product and the sintering aid may be blended and then pulverized and mixed at the same time.
  • the compound may be a molded product by powder pressing or mold molding, or may be a sheet-shaped molded product by the doctor blade method.
  • the molding pressure may be, for example, 5 to 350 MPa.
  • the shape of the molded product is preferably, for example, a sheet having a thickness of less than 2 mm. If a boron nitride sintered body is manufactured using such a sheet-shaped molded product, a sheet-shaped composite having a thickness of less than 2 mm can be manufactured without cutting the boron nitride sintered body. Further, as compared with the case where the block-shaped boron nitride sintered body is cut into a sheet shape, the material loss due to processing can be reduced by forming the sheet shape from the stage of the molded body. Therefore, a sheet-like complex can be produced with a high yield.
  • the molded product obtained as described above is heated and fired in, for example, an electric furnace.
  • the heating temperature may be, for example, 1800 ° C. or higher, and may be 1900 ° C. or higher.
  • the heating temperature may be, for example, 2200 ° C. or lower, or 2100 ° C. or lower. If the heating temperature is too low, grain growth tends not to proceed sufficiently.
  • the heating time may be 0.5 hours or more, and may be 1 hour or more, 3 hours or more, 5 hours or more, or 10 hours or more.
  • the heating time may be 40 hours or less, 30 hours or less, or 20 hours or less.
  • the heating time may be, for example, 0.5 to 40 hours, or 1 to 30 hours. If the heating time is too short, grain growth tends not to proceed sufficiently.
  • the heating atmosphere may be, for example, an atmosphere of an inert gas such as nitrogen, helium, or argon.
  • an inert gas such as nitrogen, helium, or argon.
  • a boron nitride sintered body containing boron nitride particles and pores can be obtained. If a thin sheet-shaped molded product is used, a sheet-shaped boron nitride sintered body can be obtained.
  • boron nitride since boron nitride is used, it is possible to prevent the boron nitride particles from being oriented in the direction perpendicular to the thickness direction. Therefore, it is possible to reduce the anisotropy of thermal conductivity and produce a boron nitride sintered body having excellent thermal conductivity in the thickness direction. Further, the pore diameter of the pores contained in the boron nitride sintered body can be reduced as a whole.
  • a cutting step is performed to process it so that it has a thickness of less than 2 mm.
  • the boron nitride sintered body is cut using, for example, a wire saw.
  • the wire saw may be, for example, a multi-cut wire saw or the like.
  • a sheet-shaped boron nitride sintered body having a thickness of less than 2 mm can be obtained.
  • the boron nitride sintered body thus obtained has a cut surface.
  • the thickness of the sheet-shaped boron nitride sintered body may be 0.1 mm or more, or 0.2 mm or more, from the viewpoint of strength.
  • the impregnation step can be performed in the same manner as the impregnation step of impregnating the resin composition of the nitride sintered body described above. Further, after the impregnation step, there may be a curing step of curing the resin filled in the pores. In this way, a complex having a thickness of less than 2 mm can be obtained.
  • the composite obtained by any of the above-mentioned production methods comprises a porous nitride sintered body composed of nitride particles and a resin filled in at least a part of the pores of the nitride sintered body.
  • the complex may be in the form of a sheet (thin plate shape). The thickness of the complex is less than 2 mm.
  • the nitride particles that make up the nitride sintered body are formed by sintering the primary particles of the nitride (note that when the primary particles are sintered, the primary particles in the secondary particles are sintered. Including cases.). In the complex, the gaps between the nitride particles are filled with resin. Since the complex contains a porous nitride sintered body and a resin, it is excellent in electrical insulation and thermal conductivity.
  • FIG. 1 is a perspective view showing an example of a sheet-like complex.
  • the complex 10 has a thickness t.
  • the thickness t is less than 2 mm.
  • the complex 10 may include a nitride sintered body 20 that is uniaxially pressurized and sintered along the thickness direction.
  • the area of the main surface 10a of the complex may be 25 mm 2 or more, 100 mm 2 or more, 800 mm 2 or more, or 1000 mm 2 or more.
  • the complex 10 having a thickness t of less than 2 mm is thin, it is possible to reduce the size of the electronic component or the like when it is used as a member of the electronic component or the like. Moreover, since it is thin and contains resin, it is possible to reduce the weight.
  • the thickness t of the complex 10 may be less than 1 mm and may be less than 0.5 mm. From the viewpoint of easiness in producing the molded product and the sintered body, the thickness of the composite 10 may be 0.1 mm or more, or 0.2 mm or more.
  • the composite 10 is obtained by impregnating a nitride sintered body 20 having a thickness t of 2 mm or less with a resin composition. Therefore, the resin is sufficiently filled even inside. Further, since the complex 10 is manufactured by using the nitride sintered body 20 having a sufficiently small pore diameter, the resin is sufficiently filled in the pores (pores) by the capillary phenomenon. Therefore, the voids are sufficiently reduced, and the thermal conductivity and the electrical insulation are excellent.
  • the shape of the complex 10 is not limited to the square pillar shape as shown in FIG. 1, and may be, for example, a cylindrical shape or a C-shaped shape in which the main surface 10a is curved.
  • the composite 10 and the nitride sintered body 20 do not have to have a cut surface. For example, it may be obtained by sintering a sheet-shaped molded product as shown in FIG. 1 and then impregnating it with a resin composition.
  • neither of the pair of main surfaces 10a and 10b of the complex 10 of FIG. 1 is a cut surface. Further, it is preferable that the main surface of the nitride sintered body 20 exposed on the main surfaces 10a and 10b is not a cut surface either. Thereby, fine cracks that may occur due to cutting can be sufficiently reduced. Therefore, the thermal conductivity of the complex 10 can be sufficiently increased. In addition, material loss can be reduced as compared with the case of a cut surface.
  • the surface of the complex 10 may be shaped by polishing or the like.
  • the orientation index of the boron nitride crystal may be 40 or less, 30 or less, 15 or less, and 10 or less. You can. Thereby, the anisotropy of thermal conductivity can be sufficiently reduced. Therefore, the thermal conductivity in the thickness direction of the sheet-shaped boron nitride sintered body can be sufficiently increased.
  • the orientation index of the boron nitride crystal may be 2.0 or more, 3.0 or more, 4.0 or more, or 6.0 or more. It may be 8.0 or more, 10.0 or more, or 12.0 or more.
  • the orientation index of the boron nitride crystal in the present disclosure is an index for quantifying the degree of orientation of the boron nitride crystal.
  • the orientation index can be calculated by the peak intensity ratio [I (002) / I (100)] of the (002) plane and the (100) plane of boron nitride measured by an X-ray diffractometer.
  • the porosity of the boron nitride sintered body that is, the volume ratio of the pores in the boron nitride sintered body may be 30 to 65% by volume, 30 to 60% by volume, or 35 to 55% by volume. It's okay. If the porosity becomes too large, the strength of the boron nitride sintered body tends to decrease. On the other hand, if the porosity becomes too small, the mass tends to be heavy. In addition, the content of the resin when the composite is produced tends to decrease, and the electrical insulating property tends to decrease.
  • the bulk density B of the boron nitride sintered body may be 800 to 1500 kg / m 3 , 850 to 1400 kg / m 3 , or 900 to 1300 kg / m 3 . If the bulk density B becomes too large, the mass of the boron nitride sintered body tends to increase. In addition, the filling amount of the resin tends to decrease, and the electrical insulating property of the complex tends to decrease. On the other hand, if the bulk density B becomes too small, the strength of the boron nitride sintered body tends to decrease.
  • the thermal conductivity of the nitride sintered body 20 in the thickness direction may be 10 W / (m ⁇ K) or more, 20 W / (m ⁇ K) or more, and 30 W / (m ⁇ K) or more. There may be.
  • the thermal conductivity of the nitride sintered body 20 in the thickness direction may be 60 W / (m ⁇ K) or less.
  • H is the thermal conductivity (W / (m ⁇ K))
  • A is the thermal diffusivity (m 2 / sec)
  • B is the bulk density (kg / m 3 )
  • C is the specific heat capacity. (J / (kg ⁇ K)) is shown.
  • the thermal diffusivity A can be measured by a laser flash method.
  • the bulk density B can be obtained from the volume and mass of the nitride sintered body 20.
  • the specific heat capacity C can be measured using a differential scanning calorimeter.
  • the thermal conductivity may be 20 W / (m ⁇ K) or more, 30 W / (m ⁇ K) or more, and 35 W / (. It may be m ⁇ K) or more, and may be 40 W / (m ⁇ K) or more.
  • the boron nitride sintered body may have the above-mentioned thermal conductivity in the thickness direction.
  • the thermal conductivity of the nitride boron sintered body in the thickness direction may be 60 W / (m ⁇ K) or less.
  • the resin may contain an epoxy resin from the viewpoint of improving heat resistance and adhesive strength to the circuit.
  • the resin may contain a silicone resin from the viewpoint of improving heat resistance, flexibility, and adhesion to a heat sink or the like.
  • the resin may be a cured product (C stage state) or a semi-cured product (B stage state).
  • the content of the nitride particles in the complex 10 may be 40 to 70% by volume or 45 to 65% by volume based on the total volume of the complex 10.
  • the content of the resin in the complex may be 30 to 60% by volume or 35 to 55% by volume based on the total volume of the complex 10.
  • the content of the resin in the complex 10 may be 10 to 60% by mass, 15 to 60% by mass, or 15 to 50% by mass, based on the total mass of the complex, 20. It may be up to 50% by mass, 25 to 50% by mass, or 25 to 40% by mass.
  • a complex containing a resin in such a ratio can achieve both high electrical insulation and thermal conductivity at a high level.
  • the content of the resin in the complex 10 can be determined by heating the complex 10 to decompose and remove the resin, and calculating the mass of the resin from the mass difference before and after heating.
  • the complex 10 may further contain other components in addition to the nitride sintered body 20 and the resin filled in the pores thereof.
  • other components include a curing agent, an inorganic filler, a silane coupling agent, a defoaming agent, a surface conditioner, a wet dispersant and the like.
  • the inorganic filler may contain one or more selected from the group consisting of aluminum oxide, silicon oxide, zinc oxide, silicon nitride, aluminum nitride and aluminum hydroxide. Thereby, the thermal conductivity of the complex can be further improved.
  • the composite 10 of the present embodiment contains the above-mentioned nitride sintered body and the resin filled in the pores thereof, it has both excellent thermal conductivity and excellent electrical insulation. Further, since it is thin and lightweight, it is possible to reduce the size and weight of the electronic component when it is used as a member of the electronic component or the like. Since the complex has such characteristics, it can be suitably used as a heat radiating member.
  • the heat radiating member may be composed of the above-mentioned composite, or may be composed of a composite with another member (for example, a metal plate such as aluminum).
  • a boron nitride sintered body may be obtained by hot pressing in which molding and sintering are performed at the same time.
  • Example 1 ⁇ Preparation of Boron Nitride Sintered Body> 100 parts by mass of orthoboric acid manufactured by Nippon Denko Co., Ltd. and 35 parts by mass of acetylene black (trade name: HS100) manufactured by Denka Co., Ltd. were mixed using a Henschel mixer. The resulting mixture was filled into a graphite crucible, in an arc furnace in an argon atmosphere, the crucible was heated for 5 hours at 2200 ° C., to give massive boron carbide (B 4 C). The obtained mass was coarsely pulverized with a jaw crusher to obtain a coarse powder.
  • This coarse powder was further pulverized by a ball mill having a silicon carbide ball ( ⁇ 10 mm) to obtain pulverized powder.
  • the carbon content of the obtained boron carbide powder was 19.9% by mass.
  • the amount of carbon was measured with a carbon / sulfur simultaneous analyzer.
  • the prepared boron carbide powder was filled in a crucible made of boron nitride. Then, using a resistance heating furnace, the mixture was heated in a nitrogen gas atmosphere at 2000 ° C. and 0.85 MPa for 10 hours. In this way, a fired product containing boron nitride (B 4 CN 4) was obtained.
  • a sintering aid was prepared by blending powdered boric acid and calcium carbonate. In the preparation, 1.9 parts by mass of calcium carbonate was added to 100 parts by mass of boric acid. At this time, the atomic ratio of boron to calcium was 1.2 atomic% of calcium with respect to 100 atomic% of boron. 16 parts by mass of the sintering aid was added to 100 parts by mass of the calcined product and mixed using a Henschel mixer to obtain a powdery compound.
  • the compressive strength at 200 ° C. and room temperature (20 ° C.) was determined by the following procedure.
  • the compressive strength was measured under the condition of a compression speed of 1 mm / min using a compression tester (trade name: Autograph AG-X manufactured by Shimadzu Corporation). The results are as shown in Table 1.
  • the orientation index [I (002) / I (100)] of the boron nitride sintered body was determined using an X-ray diffractometer (manufactured by Rigaku Co., Ltd., trade name: ULTIMA-IV).
  • the measurement sample (boron nitride sintered body) set in the sample holder of the X-ray diffractometer was irradiated with X-rays to perform baseline correction. Then, the peak intensity ratio of the (002) plane and the (100) plane of boron nitride was calculated. This was defined as the orientation index [I (002) / I (100)].
  • the results are as shown in Table 1.
  • H is the thermal conductivity (W / (m ⁇ K))
  • A is the thermal diffusivity (m 2 / sec)
  • B is the bulk density (kg / m 3 )
  • C is the specific heat capacity. (J / (kg ⁇ K)) is shown.
  • a xenon flash analyzer manufactured by NETZSCH, trade name: LFA447NanoFlash
  • the bulk density B was calculated from the volume and mass of the boron nitride sintered body.
  • the results of thermal conductivity H and bulk density B are shown in Table 1.
  • a resin composition containing an epoxy resin (manufactured by Mitsubishi Chemical Corporation, trade name: Epicoat 807) and a curing agent (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., trade name: Acmex H-84B) is applied to a dip under atmospheric pressure.
  • the mixture was applied to each of the boron nitride sintered bodies, and the boron nitride sintered body was impregnated with the resin composition. After impregnation, the resin was cured by heating at a temperature of 160 ° C. for 30 minutes under atmospheric pressure to obtain a complex.
  • This complex had a thickness (2.0 mm) equivalent to that of the boron nitride sintered body.
  • the resin content in the complex is as shown in Table 2.
  • the content (mass%) of this resin is the mass ratio of the resin to the entire complex.
  • the resin content was calculated by calculating the mass of the resin from the mass difference between the boron nitride sintered body and the composite, and dividing the mass of this resin by the mass of the composite.
  • the dielectric breakdown voltage was measured using this measurement sample.
  • the "dielectric breakdown voltage” in the present specification means a value measured by a withstand voltage tester (manufactured by Kikusui Electronics Co., Ltd., device name: TOS-8700) in accordance with JIS C2110-1: 2016. The case where the measured value was 20 kV / mm or more was evaluated as "A”, and the case where the measured value was 10 to 20 kV / mm or more was evaluated as "B". The results are shown in Table 2.
  • Example 2 10.7 parts by mass of amorphous boron nitride powder having an oxygen content of 1.7% by mass and an average particle size of 3.4 ⁇ m, and an oxygen content of 0.1% by mass and an average particle size of 16. 7.1 parts by mass of hexagonal boron nitride powder of 0 ⁇ m, 0.9 parts by mass of calcium carbonate (manufactured by Shiraishi Kogyo Co., Ltd., trade name: PC-700), and 1.6 parts by mass of boric acid are mixed with a Henschel mixer. Was mixed to obtain a mixture. Then, 380 parts by mass of water was added to 100 parts by mass of the mixture and pulverized with a ball mill for 5 hours to obtain a water slurry.
  • amorphous boron nitride powder having an oxygen content of 1.7% by mass and an average particle size of 3.4 ⁇ m, and an oxygen content of 0.1% by mass and an average particle size of 16. 7.1 parts by mass of hexagonal boron n
  • Polyvinyl alcohol (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., trade name: Gosenol) was added to this water slurry so that its concentration was 3.0% by mass, and the mixture was heated and stirred at 50 ° C. until it was dissolved. Then, a spheroidizing treatment was performed at a drying temperature of 200 ° C. with a spray dryer to obtain granulated products. A rotary atomizer was used as the spheroidizing device of the spray dryer.
  • Example 1 Each evaluation of the boron nitride sintered body thus obtained was carried out in the same manner as in Example 1. Further, using this boron nitride sintered body, a complex (thickness: 1.9 mm) was prepared in the same manner as in Example 1. Then, the dielectric breakdown voltage of the complex was measured in the same manner as in Example 1. The measurement results are as shown in Table 1.
  • Example 3 Boron nitride sintered body (thickness: 0.3 mm) in the same manner as in Example 1 except that the amount of the compound used when producing the molded product was 0.49 g and the thickness of the molded product was 0.29 mm. And a composite (thickness: 0.3 mm) was prepared.
  • Example 4 Boron nitride sintered body (thickness: 0.8 mm) in the same manner as in Example 2 except that the amount of granulated product used when producing the molded product was 1.16 g and the thickness of the molded product was 0.76 mm. ) And a composite (thickness: 0.8 mm) were prepared.
  • Example 5 Boron nitride sintered body (thickness: 1.3 mm) in the same manner as in Example 1 except that the amount of the compound used when producing the molded product was 2.11 g and the thickness of the molded product was 1.23 mm. And a complex (thickness: 1.3 mm) was prepared.

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Abstract

L'invention concerne un procédé de production d'un corps composite ayant un corps fritté de nitrure poreux et une résine chargée dans au moins certains des pores du corps fritté de nitrure, le procédé comprenant une étape d'imprégnation pour imprégner le corps fritté de nitrure avec une composition de résine, le corps fritté de nitrure ayant une épaisseur inférieure à 2 mm
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Publication number Priority date Publication date Assignee Title
WO2023190236A1 (fr) * 2022-03-31 2023-10-05 デンカ株式会社 Composite et son procédé de production, et ensemble, substrat de circuit et module d'alimentation

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05159624A (ja) * 1991-12-04 1993-06-25 Denki Kagaku Kogyo Kk 絶縁放熱板
JPH10251069A (ja) * 1997-03-14 1998-09-22 Toshiba Corp 窒化珪素回路基板及び半導体装置
WO2017155110A1 (fr) * 2016-03-10 2017-09-14 デンカ株式会社 Corps composite de résine céramique

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Publication number Priority date Publication date Assignee Title
WO2018025933A1 (fr) * 2016-08-02 2018-02-08 デンカ株式会社 Structure de dissipation de chaleur pour dispositif de circuit électrique

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05159624A (ja) * 1991-12-04 1993-06-25 Denki Kagaku Kogyo Kk 絶縁放熱板
JPH10251069A (ja) * 1997-03-14 1998-09-22 Toshiba Corp 窒化珪素回路基板及び半導体装置
WO2017155110A1 (fr) * 2016-03-10 2017-09-14 デンカ株式会社 Corps composite de résine céramique

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023190236A1 (fr) * 2022-03-31 2023-10-05 デンカ株式会社 Composite et son procédé de production, et ensemble, substrat de circuit et module d'alimentation

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