WO2023038151A1 - 窒化ホウ素焼結体の製造方法及び窒化ホウ素焼結体 - Google Patents

窒化ホウ素焼結体の製造方法及び窒化ホウ素焼結体 Download PDF

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WO2023038151A1
WO2023038151A1 PCT/JP2022/034234 JP2022034234W WO2023038151A1 WO 2023038151 A1 WO2023038151 A1 WO 2023038151A1 JP 2022034234 W JP2022034234 W JP 2022034234W WO 2023038151 A1 WO2023038151 A1 WO 2023038151A1
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Prior art keywords
boron nitride
sheet
sintered body
nitride sintered
mesh
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English (en)
French (fr)
Japanese (ja)
Inventor
亮 出川
敦也 鈴木
竜士 古賀
真寿美 四方堂
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Denka Co Ltd
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Denka Co Ltd
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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

Definitions

  • the present invention relates to a method for producing a boron nitride sintered body and a boron nitride sintered body.
  • thermosetting resin in an uncured state (A stage).
  • a thermosetting resin composition has been used in which the thermosetting resin is formed into a sheet shape by coating with various coaters or the like after being cured, and the thermosetting resin is made into a semi-cured state (B stage) by heating.
  • thermosetting resin in a semi-cured state (B stage), thereby reducing the unevenness of the surface of the electronic member.
  • B stage a semi-cured state
  • the thermosetting resin is completely cured by heating (C stage), and the adhesion between the electronic member making it strong.
  • the above-mentioned thermally conductive insulating adhesive sheet has an adhesive layer (an uncured state (A stage) thermosetting resin or an uncured state (A stage) thermal Since there is no need to form a ceramic powder dispersed in a curable resin, there is no need for coating work or the introduction of precision coating equipment. It's being used.
  • Patent Document 1 in a metal-based circuit board, a thermally conductive sheet is placed on a thermally conductive insulating adhesive sheet in which ceramic powder is dispersed in a thermosetting resin in a semi-cured state (B stage).
  • B stage thermosetting resin in a semi-cured state
  • Patent Document 1 there is a thermosetting resin layer with low thermal conductivity between each particle of the ceramic powder, so there is a limit to obtaining high thermal conductivity in the circuit board. rice field. As a result, there has been a problem in terms of heat dissipation in terms of thermal design requirements for electronic devices, which have become more and more difficult in recent years.
  • thermosetting resin composition As a method for improving the thermal conductivity of the metal base substrate described in Patent Document 1, for example, a sintered body having an integral structure in which non-oxide ceramic primary particles are three-dimensionally continuous is added with a thermosetting resin composition It is conceivable to use a thermally conductive insulating adhesive sheet (see, for example, Patent Document 2) using a ceramics resin composite impregnated with a material to bond a metal foil to one side of a metal base plate. This thermally conductive insulating adhesive sheet forms a continuous network of non-oxide ceramics, so that the thermal conductivity can be further increased.
  • the sintered body used for the ceramic resin composite described in Patent Document 2 is obtained by pressing a mixed powder obtained by mixing a non-oxide ceramic powder and a sintering aid into a block shape using a mold.
  • a block molded body is produced by using a CIP (cold isostatic pressing method) apparatus, and then sintered. Therefore, in order to obtain a sheet-like ceramics-resin composite, it was necessary to impregnate the sintered body with a resin and then process the sintered body into a sheet using a wire saw or the like. As a result, the manufacturing cost of the sheet-like ceramics-resin composite has been high.
  • a method of obtaining a sheet-like sintered body without processing the sintered body into a sheet for example, a method of forming a raw material of a ceramic sintered body into a sheet and firing a sheet-like molded body obtained.
  • the sheet-like sintered body obtained by this method has a low thermal conductivity, and the sheet-like sintered body is greatly warped.
  • the present invention is a boron nitride sintered body that can produce a sheet-shaped boron nitride sintered body with high thermal conductivity and small warp by using a sheet-shaped molded body that is a raw material of a boron nitride sintered body. and a boron nitride sintered body obtained by the manufacturing method.
  • the gist of the present invention is as follows. [1] A step of producing a sheet-shaped molded body of a raw material of a boron nitride sintered body and a step of firing the sheet-shaped molded body placed on a setter, wherein the step of firing the sheet-shaped molded body includes the above-described A method for producing a boron nitride sintered body, wherein a first mesh-shaped boron nitride sheet is arranged between the sheet-shaped molded body and the setter.
  • the step of sintering the sheet-shaped molded body includes placing a ceramic plate covering the upper surface of the sheet-shaped molded body on the sheet-shaped molded body placed on the setter, and firing the sheet-shaped molded body. and the method for producing a boron nitride sintered body according to the above [1], further disposing a second mesh-like boron nitride sheet between the ceramic plates. [3] The method for producing a boron nitride sintered body according to [1] or [2] above, wherein the first mesh-like boron nitride sheet has a lattice shape.
  • the first mesh-like boron nitride sheet is a mesh-like boron nitride sheet formed into a rectangular shape by notching four corners of a rectangular mesh-like boron nitride sheet [1] to [5] above.
  • the present invention it is possible to produce a sheet-like boron nitride sintered body having a high thermal conductivity and a small warp by using a sheet-like molded body as a raw material of the boron nitride sintered body. and the boron nitride sintered body obtained by the manufacturing method can be provided.
  • FIG. 1 is a diagram for explaining the step of firing a sheet-shaped compact placed on a setter in the method for producing a boron nitride sintered body of the present invention.
  • 2(a) and 2(b) are diagrams showing an example of a mesh-like boron nitride sheet used in the method for producing a boron nitride sintered body of the present invention.
  • FIGS. 3(a) to 3(c) are diagrams for explaining a method for manufacturing an example of a mesh-like boron nitride sheet used in the method for manufacturing a boron nitride sintered body of the present invention.
  • FIG. 4 is a diagram for explaining another embodiment of the step of firing a sheet-like compact placed on a setter in the method for producing a boron nitride sintered body of the present invention;
  • the method for producing a boron nitride sintered body of the present invention includes a step (A) of producing a sheet-shaped molded body of the raw material of the boron nitride sintered body and a step (B) of firing the sheet-shaped molded body placed on the setter. including.
  • a sheet-shaped molded body is produced as a raw material for the boron nitride sintered body.
  • the raw material for the boron nitride sintered body is not particularly limited as long as it can be fired to produce the boron nitride sintered body.
  • Materials for the boron nitride sintered body include, for example, boron carbonitride (B 4 CN 4 ).
  • Boron carbide powder can be prepared, for example, by the following procedure.
  • a commercially available boron carbonitride powder may be used instead of the boron carbonitride prepared by the following procedure.
  • the mixture After mixing boric acid and acetylene black, the mixture is heated in an inert gas atmosphere at 1800 to 2400° C. for 1 to 10 hours to obtain a boron carbide lump.
  • the boron carbide mass is pulverized, washed, impurities are removed, and dried to prepare boron carbide powder.
  • Boron carbide powder is heated in a nitrogen atmosphere to obtain boron carbonitride (B 4 CN 4 ) powder.
  • the heating temperature in this nitriding treatment may be 1800° C. or higher, or may be 1900° C. or higher.
  • the heating temperature in this nitriding treatment may be 2400° C. or lower, or may be 2200° C. or lower.
  • the heating temperature in this nitriding treatment may be, for example, 1800 to 2400.degree.
  • the pressure in the nitriding treatment may be 0.6 MPa or higher, or 0.7 MPa or higher. Moreover, the pressure in this nitriding treatment may be 1.0 MPa or less, or may be 0.9 MPa or less. The pressure in this nitriding treatment may be, for example, 0.6-1.0 MPa. If the pressure in this nitriding treatment is too low, the nitriding of boron carbide tends to be difficult to proceed. On the other hand, if the pressure in this nitriding treatment is too high, the manufacturing cost tends to increase. In addition, the pressure in this disclosure is an absolute pressure.
  • the nitrogen gas concentration of the nitrogen atmosphere in the nitriding treatment may be 95% by volume or more, or may be 99.9% by volume or more.
  • the partial pressure of nitrogen may be in the pressure ranges described above.
  • the heating time in the nitriding treatment 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 sintering aid may be added to the boron carbonitride powder obtained by the nitriding treatment.
  • Sintering aids may include boron compounds and calcium compounds.
  • the total amount of the boron compound and the calcium compound may be 1 to 30 parts by mass per 100 parts by mass of the boron carbonitride powder.
  • the sintering aid contains a boron compound and a calcium compound
  • the content of the boron compound and calcium compound in the sintering aid in the fired product is 100% of the fired product.
  • a total of the boron compound and the calcium compound may be included, for example, 1 to 30 parts by mass, 5 to 25 parts by mass, or 8 to 20 parts by mass.
  • the compound obtained by blending the boron carbonitride powder with the sintering aid may contain 0.5 to 40 atomic % of calcium constituting the calcium compound with respect to 100 atomic % of boron constituting the boron compound. , 0.7 to 30 atomic %.
  • Boron compounds include boric acid, boron oxide, and borax.
  • Calcium compounds include calcium carbonate, calcium oxide, and the like.
  • the sintering aid may contain components other than boric acid and calcium carbonate. Examples of such components include alkali metal carbonates such as lithium carbonate and sodium carbonate.
  • a binder may be blended in the formulation to improve moldability. An acrylic compound etc. are mentioned as a binder.
  • pulverization may be performed using a general pulverizer or pulverizer.
  • a ball mill, Henschel mixer, vibration mill, jet mill, etc. can be used.
  • "pulverization” also includes "crushing".
  • the sintering aid may be blended after the boron carbonitride powder is pulverized, or the sintering aid may be blended simultaneously with the pulverization and mixing after blending the boron carbonitride powder and the sintering aid. .
  • the compound may be powder-pressed or molded into a sheet-shaped compact, or may be made into a sheet-shaped compact by a doctor blade method or an extrusion method.
  • the molding pressure may be, for example, 5-350 MPa.
  • the sheet-shaped molding may be, for example, a sheet having a thickness of less than 2 mm. If a boron nitride sintered body is produced using a sheet-shaped compact, a boron nitride sintered body without cut surfaces can be produced.
  • the material loss due to processing can be reduced by forming the sheet form from the compact stage. Therefore, a sheet-like boron nitride sintered body and a composite of a boron nitride sintered body and a resin can be produced with a high yield.
  • Step (B) In the step (B), the sheet-like compact placed on the setter is fired.
  • the sheet-like formed body is heated and baked in an electric furnace.
  • a setter is a tool material having a container-like function on which the object to be fired is placed.
  • Materials for the setter include, for example, alumina, cordierite, silicon carbide, silicon nitride, and boron nitride. Among these materials, boron nitride is preferable from the viewpoint of suppressing contamination of the sheet molded body with impurities.
  • the shape of the setter is usually a thin rectangular shape. However, depending on the shape of the object to be fired, the shape of the setter can be appropriately changed from the thin rectangular shape.
  • the firing temperature may be, for example, 1800°C or higher, or 1900°C or higher.
  • the firing temperature may be, for example, 2200° C. or lower, or may be 2100° C. or lower. If the firing temperature is too low, grain growth tends not to proceed sufficiently.
  • the firing time may be 0.5 hours or longer, 1 hour or longer, 3 hours or longer, 5 hours or longer, or 10 hours or longer.
  • the firing time may be 40 hours or less, 30 hours or less, or 20 hours or less.
  • the firing time may be, for example, 0.5 to 40 hours, or 1 to 30 hours. If the firing time is too short, there is a tendency that grain growth does not proceed sufficiently. On the other hand, if the firing time is too long, it tends to be industrially disadvantageous.
  • the firing atmosphere may be, for example, an inert gas atmosphere such as nitrogen, helium or argon.
  • a binder When a binder is added to the composition, it may be calcined at a temperature and atmosphere at which the binder decomposes to degrease before the above-described heating.
  • a first mesh-like boron nitride sheet 1 is placed between the sheet-like compact 2 and the setter 3.
  • the gas generated from the sheet-like molded body 2 can be efficiently dispersed during baking of the sheet-shaped molded body 2, and the generation of uneven baking of the sheet-shaped molded body can be suppressed.
  • the mesh-like boron nitride sheet is not particularly limited as long as it is made of boron nitride and has a mesh-like shape (mesh shape).
  • the mesh boron nitride sheet 1 shown in FIG. 2 can be used as the first mesh boron nitride sheet.
  • FIG. 2(a) is a front view showing an example of a mesh-like boron nitride sheet
  • FIG. 2(b) is an AA sectional view of the mesh-like boron nitride sheet 1 shown in FIG. 1(a).
  • the mesh-like boron nitride sheet 1 includes first filamentary portions 1a extending in the X direction and second filamentary portions 1b extending in the Y direction perpendicular to the X direction. That is, the mesh-like boron nitride sheet 1 has a lattice shape.
  • the gas generated from the sheet-like molded body 2 during baking of the sheet-shaped molded body 2 can be dispersed more efficiently, and the occurrence of uneven baking of the sheet-shaped molded body 2 can be further suppressed.
  • the thermal conductivity of the sintered body obtained by firing the sheet-like compact 2 can be further increased, and the warpage of the sintered body can be further reduced.
  • the opening of the first mesh-like boron nitride sheet 1 is preferably 200 to 3000 ⁇ m.
  • the mesh opening of the first mesh-like boron nitride sheet 1 is 200 ⁇ m or more, the gas generated from the sheet-like molded body 2 during baking of the sheet-shaped molded body 2 can be more efficiently dispersed.
  • the mesh opening of the first mesh-like boron nitride sheet 1 is 3000 ⁇ m or less, the strength of the first mesh-like boron nitride sheet 1 can be increased, and uneven baking of the sheet-like compact 2 can be further prevented. can be suppressed.
  • the mesh size of the first mesh-like boron nitride sheet 1 is more preferably 220 to 800 ⁇ m, still more preferably 250 to 500 ⁇ m.
  • the opening is the average value of the distance between the adjacent first filament portions 1a and the distance between the adjacent second filament portions 1b.
  • the wire diameter of the first mesh-like boron nitride sheet 1 (the width of the first wire portion 1a and the second wire portion 1b in plan view of the first mesh-like boron nitride sheet 1) is preferably 500 to 1600 ⁇ m.
  • the wire diameter of the first mesh-like boron nitride sheet 1 is 500 ⁇ m or more, the strength of the first mesh-like boron nitride sheet 1 can be increased, and at the time of firing the sheet-like formed body 2, the sheet-like formed body The gas generated from 2 can be scattered more efficiently.
  • the wire diameter of the first mesh-like boron nitride sheet 1 is 1600 ⁇ m or less, it is possible to further suppress the occurrence of uneven baking of the sheet-like compact.
  • the wire diameter of the first mesh-like boron nitride sheet 1 is more preferably 550 to 1400 ⁇ m, still more preferably 600 to 1200 ⁇ m.
  • the wire diameter is the average value of the wire diameter of the first filament portion 1a and the wire diameter of the second filament portion 1b.
  • the cross-sectional shape of the first filamentary portions 1a and the second filamentary portions 1b of the first mesh-like boron nitride sheet 1 is not particularly limited.
  • the cross-sectional shape of the first filament portion 1a and the second filament portion 1b may be, for example, circular, elliptical, triangular, quadrangular, or polygonal with pentagons or more. It may be in the shape of a star or in the shape of a star.
  • the cross-sectional shapes of the first filamentary portion 1a and the second filamentary portion 1b are preferably circular and elliptical, and more preferably circular. be.
  • the first mesh-like boron nitride sheet 1 can be produced, for example, as follows.
  • a raw material powder of boron nitride is prepared, and the raw material powder is mixed with a medium such as water and a binder to prepare a paste for manufacturing the linear portion.
  • Boron nitride raw material powders include, for example, mixtures of boron-containing compounds such as boric acid, boron oxide and borax, and nitrogen-containing compounds such as urea and melamine, and hexagonal boron carbonitride (h-B 4 CN 4 ) powder. is mentioned.
  • a sintering aid may also be added to the raw material powder.
  • the sintering aid may be, for example, yttria oxide, oxides of rare earth elements such as alumina oxide and magnesium oxide, alkali metal carbonates such as lithium carbonate and sodium carbonate, and boric acid.
  • the amount of the sintering aid to be added is, for example, 0.01 part by mass or more, or 0.01 part by mass or more with respect to a total of 100 parts by mass of the raw material powder of boron nitride and the sintering aid. It may be 1 part by mass or more.
  • the amount of the sintering aid added may be 20 parts by mass or less, 15 parts by mass or less, or 10 parts by mass or less with respect to a total of 100 parts by mass of the raw material powder of boron nitride and the sintering aid.
  • binder the same one as that conventionally used for this type of paste can be used.
  • examples include polyvinyl alcohol, polyethylene glycol, polyethylene oxide, dextrin, sodium and ammonium lignosulfonates, carboxymethylcellulose, ethylcellulose, hydroxypropylmethylcellulose, carboxymethylcellulose, hydroxyethylcellulose, hydroxyethylmethylcellulose, sodium and ammonium alginate, epoxy resins, phenols.
  • Resins acrylic polymers such as gum arabic, polyvinyl butyral, polyacrylic acid and polyacrylamide, thickening polysaccharides such as xanthan gum and guar gum, gelling agents such as gelatin, agar and pectin, vinyl acetate resin emulsions, wax emulsions, and inorganic binders such as alumina sol and silica sol. Two or more of these may be mixed and used.
  • the viscosity of the paste is preferably high at the temperature at which it is applied. Specifically, the viscosity of the paste is preferably 1.5 to 5.0 MPa ⁇ s, more preferably 1.7 to 3.0 MPa ⁇ s, at the temperature during application.
  • the viscosity of the paste can be measured, for example, using a cone-plate rotary viscometer or a rheometer at a rotational speed of 0.3 rpm and using the measured value at 4 minutes after the start of measurement.
  • the proportion of the raw material powder of boron nitride in the paste is preferably 20 to 85% by mass, more preferably 35 to 75% by mass.
  • the proportion of the medium in the paste is preferably 15-60 mass %, more preferably 20-55 mass %.
  • the proportion of the binder in the paste is preferably 1-40% by mass, more preferably 5-25% by mass.
  • the paste can contain thickeners, coagulants, thixotropic agents, etc. as viscosity modifiers.
  • thickening agents include polyethylene glycol fatty acid esters, alkylallylsulfonic acids, alkylammonium salts, ethyl vinyl ether/maleic anhydride copolymers, fumed silica, proteins such as albumin, and the like.
  • binders are classified as thickeners because they have a thickening effect. agent can be used.
  • flocculants include polyacrylamides, polyacrylates, aluminum sulfates, polyaluminum chlorides, and the like.
  • thixotropic agents include fatty acid amides, polyolefin oxides, polyether ester surfactants, and the like.
  • a solvent for paste preparation alcohol, acetone, ethyl acetate, etc. are used in addition to water, and two or more of these may be mixed.
  • a plasticizer, a lubricant, a dispersant, a sedimentation inhibitor, a pH adjuster, etc. may be added.
  • Plasticizers include glycols such as trimethylene glycol and tetramethylene glycol, glycerin, butanediol, phthalic acid, adipic acid, and phosphoric acid.
  • Lubricants include hydrocarbons such as liquid paraffin, microwax, synthetic paraffin, higher fatty acids, fatty acid amides, and the like.
  • Dispersants include sodium or ammonium polycarboxylates, acrylic acid-based, polyethyleneimine, phosphoric acid-based, and the like.
  • Anti-settling agents include polyamide amine salts, bentonite, aluminum stearate and the like.
  • pH adjusters include sodium hydroxide, aqueous ammonia, oxalic acid, acetic acid, and hydrochloric acid.
  • a plurality of linear first coating bodies 11a extending in the X direction are formed in parallel and linearly on a flat substrate as shown in FIG. 3(a).
  • the filamentary first coated body corresponds to the first filamentary portion 1a in the intended first mesh-like boron nitride sheet 1 .
  • Various coating devices such as a small extruder and a printing machine can be used to form the first filament coating body 11a.
  • the filamentary second coating body 11b corresponds to the second filamentary portion 1b in the intended first mesh-like boron nitride sheet 1 .
  • the same coating device as used for the first filament-coated body 11a can be used.
  • a first linear coating body extending in the X direction is formed on the second filament coating body 11b. Then, a linear second coating body extending in the Y direction is formed to fabricate a mesh-like coating body.
  • the mesh-shaped coated body thus obtained is peeled off from the substrate, placed in a firing furnace, and fired. This firing yields a raw mesh boron nitride sheet.
  • the firing temperature of the mesh-like coated body may be, for example, 1600°C or higher or 1700°C or higher.
  • the firing temperature of the mesh-like coated body may be, for example, 2200° C. or lower, or 2100° C. or lower.
  • the firing time of the mesh-like coated body may be, for example, 1 hour or longer and may be 30 hours or shorter.
  • the atmosphere during firing may be, for example, an inert gas atmosphere such as nitrogen, helium, and argon.
  • a batch type furnace or a continuous type furnace can be used.
  • Batch type furnaces include, for example, muffle furnaces, tubular furnaces, atmosphere furnaces, and the like.
  • continuous furnaces include rotary kilns, screw conveyor furnaces, tunnel furnaces, belt furnaces, pusher furnaces, and koto-shaped continuous furnaces.
  • the raw mesh-like boron nitride sheet may be used as it is as the first mesh-like boron nitride sheet.
  • the first mesh-like boron nitride sheet 1 having a rectangular shape may be produced by notching the four corners of the rectangular unprocessed mesh-like boron nitride sheet. . This makes it possible to remove cracks and chipped portions from the first mesh-like boron nitride sheet, which occurred when the mesh-like coated body was peeled off from the substrate and placed in the firing furnace.
  • the method for producing a boron nitride sintered body of the present invention it is possible to produce a sheet-like boron nitride sintered body with high thermal conductivity and low warpage.
  • the method for producing a boron nitride sintered body of the present invention when the size is 50.0 to 52.0 mm ⁇ 47.0 to 49.0 mm ⁇ 0.40 to 0.42 mm, the amount of warpage is 0.52 mm or less. and a sheet-like boron nitride sintered body having a thermal conductivity of 45 W/mK or more can be produced.
  • the thermal conductivity of the sintered body can be measured by the method described in Examples below.
  • step (B) As shown in FIG. 4, a ceramic plate 4 covering the upper surface of the sheet-shaped molded body 2 is placed on the sheet-shaped molded body 2 placed on the setter 3, and the sheet-shaped molded body 2 is and the ceramic plate 4, a second mesh-like boron nitride sheet 5 is preferably further arranged.
  • the occurrence of uneven baking of the sheet-like compact 2 can be further suppressed.
  • the ceramic plate 4 covering the upper surface of the sheet-like molded body 2 prevents the scattering of gas generated from the sheet-shaped molded body 2 during firing of the sheet-shaped molded body 2 .
  • the second mesh-shaped boron nitride sheet 5 efficiently scatters the gas generated from the sheet-shaped molded body 2 when the sheet-shaped molded body 2 is fired.
  • a material that can be used as the setter 3 can be used for the ceramic plate 4 .
  • a mesh-like boron nitride sheet that can be used as the first mesh-like boron nitride sheet 1 can be used.
  • the ceramic plate 4 may be the same as or different from the setter 3 .
  • the second mesh-like boron nitride sheet 5 may be the same as or different from the first mesh-like boron nitride sheet 1 .
  • the sheet-like sintered body obtained by firing the sheet-like molded body in step (B) may be a dense sintered body.
  • the sheet-shaped sintered body is a porous boron nitride sintered body.
  • the porous boron nitride sintered body can be impregnated with the resin composition by applying the resin composition to the porous boron nitride sintered body.
  • the boron nitride sintered body of the present invention is produced by the method for producing a boron nitride sintered body of the present invention, and has an amount of warpage of 0.60 mm or less and a thermal conductivity of 30 W/mK or more.
  • the boron nitride sintered body of the present invention is produced by the method for producing a boron nitride sintered body of the present invention, so it has a small amount of warpage and high thermal conductivity.
  • the amount of warpage of the boron nitride sintered body of the present invention is 0.60 mm or less, preferably 0.56 mm or less, more preferably 0.52 mm or less, still more preferably 0.40 mm or less, and more More preferably, it is 30 mm.
  • the lower limit of the warp amount range of the boron nitride sintered body of the present invention is not particularly limited, but is preferably 0.06 mm, more preferably 0.07 mm, and still more preferably 0.08 mm.
  • the boron nitride sintered body of the present invention has a thermal conductivity of 30 W/mK or higher, preferably 45 W/mK or higher, more preferably 60 W/mK or higher, and even more preferably 65 W/mK or higher. is.
  • the upper limit of the thermal conductivity range of the boron nitride sintered body of the present invention is not particularly limited, it is usually 76 W/mK.
  • the amount of warpage and thermal conductivity of the boron nitride sintered body of the present invention can be measured by the methods described in Examples below.
  • the boron nitride sintered body of the present invention is preferably sheet-like (thin plate-like).
  • the thickness of the boron nitride sintered body is preferably less than 2 mm.
  • the thickness of the boron nitride sintered body may be less than 1 mm or less than 0.5 mm.
  • the thickness of the boron nitride sintered body may be 0.1 mm or more, or may be 0.2 mm or more, from the viewpoint of ease of forming the compact.
  • the boron nitride sintered body of the present invention may be a dense sintered body.
  • the boron nitride sintered bodies can be directly bonded together, or the boron nitride sintered body and the metal foil can be directly bonded together. Therefore, the boron nitride sintered body of the present invention is preferably a porous boron nitride sintered body.
  • the boron nitride sintered body of the present invention is a porous boron nitride sintered body, for example, by applying a resin composition to the boron nitride sintered body of the present invention, the boron nitride sintered body of the present invention is coated with a resin.
  • the composition can be impregnated.
  • the average pore size of the pores contained in the boron nitride sintered body of the present invention may be less than 4.0 ⁇ m.
  • the contact area between the primary particles of the boron nitride particles can be sufficiently increased. Therefore, thermal conductivity can be further increased.
  • the average pore size of the pores may be less than 3.8 ⁇ m, and may be less than 3 ⁇ m.
  • the average pore diameter of the pores may be 0.1 ⁇ m or more, or 0.2 ⁇ m or more. It may be 75 ⁇ m or more.
  • 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 porosity of the boron nitride sintered body of the present invention that is, the volume ratio of pores in the boron nitride sintered body of the present invention may be 30 to 65% by volume, or 30 to 60% by volume. may be ⁇ 55% by volume. If the porosity is too large, the strength of the boron nitride sintered body tends to decrease. On the other hand, when the porosity is too small, the mass tends to be heavy.
  • the porosity is obtained by calculating the bulk density [B (kg/m 3 )] from the volume and mass of the boron nitride sintered body of the present invention, and combining this bulk density with the theoretical density of boron nitride [2280 (kg/m 3 ) ], it can be obtained by the following formula.
  • Porosity (volume%) [1-(B/2280)] x 100
  • the bulk density B may be 800-1500 kg/m 3 , 850-1400 kg/m 3 or 900-1300 kg/m 3 . If the bulk density B becomes too large, the mass of the boron nitride sintered body of the present invention tends to increase. On the other hand, if the bulk density B is too small, the strength of the boron nitride sintered body of the present invention tends to decrease.
  • the mesh size was adjusted to 0.5 mm and the wire diameter to 0.6 mm after firing. As described above, a mesh-like boron nitride sheet A having a size of 50 mm ⁇ 50 mm, an opening of 0.5 mm and a wire diameter of 0.6 mm was produced.
  • a crucible made of boron nitride was filled with the prepared boron carbide powder. After that, using a resistance heating furnace, heating was performed for 10 hours under conditions of 2000° C. and 0.85 MPa in a nitrogen gas atmosphere. Thus, a fired product containing boron carbonitride (B 4 CN 4 ) was obtained.
  • a sintering aid was prepared by blending powdered boric acid and calcium carbonate. In preparation, 1.9 parts by mass of calcium carbonate was blended with 100 parts by mass of boric acid. At this time, the atomic ratio of boron to calcium was 1.2 atomic % of calcium to 100 atomic % of boron. 16 parts by mass of a sintering aid was blended with 100 parts by mass of the fired product, and mixed using a Henschel mixer to obtain a powdery compound.
  • the boron nitride sintered body was taken out.
  • sheet-like (plate-like) boron nitride sintered bodies 1 to 5 were obtained.
  • the mesh-like boron nitride sheets shown in Table 1 were used.
  • no mesh-like boron nitride sheet was used.
  • the produced boron nitride sintered bodies 1 to 5 were evaluated as follows. ⁇ Amount of warpage> The surface profile of the boron nitride sintered body was measured using a 3D surface profile measuring machine (trade name “VR-3000”, manufactured by KEYENCE). Then, the height coordinates were measured along a straight line passing through the end point A and the center B of the boron nitride sintered body, and the value obtained by subtracting the lowest coordinate from the highest coordinate was taken as the amount of warpage. This measurement was performed at four end points of the boron nitride sintered body, and the maximum value was taken as the amount of warpage of the boron nitride sintered body.
  • H thermal conductivity (W/(mK))
  • A thermal diffusivity (m 2 /sec)
  • B bulk density (kg/m 3 )
  • C specific heat capacity (J/ (kg K)).
  • 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.
  • Table 1 shows the evaluation results.
  • first mesh-like boron nitride sheet 1a first filament part 1b second filament part 2 sheet-like formed body 3 setter 4 ceramic plate 5 second mesh-like boron nitride sheet 11a filament first coated body 11b filament second coated body

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JP2011178598A (ja) * 2010-03-01 2011-09-15 Hitachi Metals Ltd 窒化珪素基板の製造方法および窒化珪素基板
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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