WO2021200966A1 - 窒化ホウ素焼結体及び複合体、並びに放熱部材 - Google Patents

窒化ホウ素焼結体及び複合体、並びに放熱部材 Download PDF

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WO2021200966A1
WO2021200966A1 PCT/JP2021/013571 JP2021013571W WO2021200966A1 WO 2021200966 A1 WO2021200966 A1 WO 2021200966A1 JP 2021013571 W JP2021013571 W JP 2021013571W WO 2021200966 A1 WO2021200966 A1 WO 2021200966A1
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Prior art keywords
boron nitride
sintered body
nitride sintered
resin
complex
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English (en)
French (fr)
Japanese (ja)
Inventor
紗緒梨 井之上
翔二 岩切
仁孝 南方
亮 吉松
竜士 古賀
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Denka Co Ltd
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Denka Co Ltd
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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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/38—Boron-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
    • H10W40/00—Arrangements for thermal protection or thermal control
    • H10W40/10—Arrangements for heating
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
    • H10W40/00—Arrangements for thermal protection or thermal control
    • H10W40/20—Arrangements for cooling
    • H10W40/25—Arrangements for cooling characterised by their materials

Definitions

  • the present disclosure relates to a boron nitride sintered body and a composite, and a heat radiating member.
  • 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 dissipation member composed of a resin and ceramics such as boron 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 and the graphitization index within a predetermined range.
  • the present disclosure provides a boron nitride sintered body having excellent adhesion to other members.
  • the present disclosure also provides a complex having excellent adhesiveness to other members. Further, in the present disclosure, by providing the above-mentioned composite, a heat radiating member having sufficiently high reliability is provided.
  • the present disclosure provides a boron nitride sintered body containing boron nitride particles and pores, which has a compressive elastic modulus of 0.8 GPa or less, in one aspect.
  • a boron nitride sintered body When such a boron nitride sintered body is sandwiched between a pair of facing members and pressed, the boron nitride sintered body is appropriately deformed, and therefore has excellent adhesion to the pair of members. Further, since the boron nitride sintered body contains pores, it is easy to impregnate the resin.
  • the boron nitride sintered body When a composite is formed by impregnating with a resin, and the composite is sandwiched between a pair of opposing members and pressed to be joined, the boron nitride sintered body has a low compressive elastic modulus and is easily compression-deformed. When deformed, the resin impregnated in the complex exudes. By the action of the exuded resin, the complex can be firmly adhered to other members. As described above, the boron nitride sintered body can easily produce a composite having excellent adhesiveness.
  • the compressive strength of the sintered body may be 1.5 MPa or more. By having such a compressive strength, it is possible to suppress breakage when used as a member.
  • the porosity of the boron nitride sintered body may be 40 to 75% by volume. As a result, the amount of resin impregnated can be sufficiently increased while maintaining the strength and thermal conductivity of the boron nitride sintered body. Such a boron nitride sintered body can form a complex that can achieve both excellent insulation and adhesiveness at a high level.
  • the bulk density of the boron nitride sintered body may be 600 to 1400 kg / m 3.
  • the amount of resin impregnated can be sufficiently increased while maintaining the strength and thermal conductivity of the boron nitride sintered body.
  • Such a boron nitride sintered body can form a complex that can achieve both excellent insulation and adhesiveness at a high level.
  • the orientation index of the boron nitride sintered body may be 20 or less. Thereby, the anisotropy of thermal conductivity can be sufficiently reduced.
  • the present disclosure provides, in one aspect, a complex comprising any of the above-mentioned boron nitride sintered bodies and a resin filled in at least a part of the pores of the boron nitride sintered body.
  • This complex contains the above-mentioned boron nitride sintered body and a resin.
  • the boron nitride sintered body has a low compressive elastic modulus, so that the composite is easily compressed and deformed.
  • the resin impregnated in the complex exudes. By the action of the exuded resin, the complex can be firmly adhered to other members. Therefore, this complex has excellent adhesiveness to other members.
  • the present disclosure provides a heat radiating member having the above-mentioned complex in one aspect. Since this heat radiating member has the above-mentioned composite, it has excellent adhesiveness.
  • the present disclosure it is possible to provide a boron nitride sintered body having excellent adhesion to other members. Further, the present disclosure can provide a complex having excellent adhesiveness to other members. Further, in the present disclosure, by providing the above-mentioned composite, it is possible to provide a heat radiating member having sufficiently high reliability.
  • FIG. 1 is a perspective view showing an example of a boron nitride sintered body (heat dissipation member).
  • the boron nitride sintered body according to the first embodiment contains boron nitride particles and pores formed by sintering primary boron nitride particles.
  • the boron nitride sintered body may be composed of boron nitride particles.
  • the compressive elastic modulus of the boron nitride sintered body may be 0.8 GPa or less, 0.7 GPa or less, or 0.6 GPa or less.
  • a boron nitride sintered body having a small compressive elastic modulus is easily compressively deformed when pressed. Therefore, the adhesion with other members is excellent.
  • the boron nitride sintered body contains pores, it is easily impregnated with the resin. Therefore, a complex impregnated with a large amount of resin can be easily produced.
  • the compressive elastic modulus of the boron nitride sintered body may be 0.02 GPa or more, or 0.2 GPa or more, from the viewpoint of maintaining its shape.
  • the compressive elastic modulus can be measured in accordance with JIS K7181 using a precision universal testing machine (trade name: Autograph AG-X) manufactured by Shimadzu Corporation.
  • An example of the compressive elastic modulus of the boron nitride sintered body is 0.02 to 0.8 GPa.
  • the compressive strength of the boron nitride sintered body may be, for example, 1.5 MPa or more, 3.0 MPa or more, or 5.0 MPa or more. By having such a compressive strength, it is possible to suppress breakage when used as a member. Compressive strength can be measured by a compression tester. The compressive strength of the boron nitride sintered body may be 20 MPa or less, 15 MPa or less, 12 MPa or less, and 10 MPa or less. The compressive strength can also be measured using a precision universal testing machine (trade name: Autograph AG-X) manufactured by Shimadzu Corporation. An example of the compressive strength of the boron nitride sintered body is 1.5 to 20 MPa.
  • the average pore diameter of the pores contained in the boron nitride sintered body may be less than 10 ⁇ m.
  • the average pore size of the pores is determined based on the pore size distribution when pressure is applied while increasing the pressure from 0.5 psia to 60,000 psia using a mercury porosimeter.
  • the horizontal axis is the pore diameter and the vertical axis is the cumulative pore volume
  • 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 that is, the volume ratio of the pores in the boron nitride sintered body may be 40 to 75% by volume or 45 to 70% by volume. If the porosity becomes too large, the strength and thermal conductivity of the boron nitride sintered body tend to decrease. On the other hand, if the porosity becomes too small, the resin content when the composite is produced tends to decrease.
  • the bulk density [B (kg / m 3 )] is calculated from the volume and mass of the boron nitride sintered body, and from this bulk density and the theoretical density of boron nitride [2280 (kg / m 3 )].
  • B (kg / m 3 ) the bulk density of the boron nitride sintered body, and from this bulk density and the theoretical density of boron nitride [2280 (kg / m 3 )].
  • Porosity (% by volume) [1- (B / 2280)] x 100 (1)
  • the bulk density B may be 600 to 1400 kg / m 3 or 800 to 1200 kg / m 3 . If the bulk density B becomes too small, the strength of the boron nitride sintered body tends to decrease. On the other hand, if the bulk density B becomes too large, the impregnation amount of the resin tends to decrease and the insulating property of the complex tends to decrease.
  • the thermal conductivity of the boron nitride sintered body may be 10 W / (m ⁇ K) or more, 15 W / (m ⁇ K) or more, and 20 W / (m ⁇ K) or more. It may be 25 W / (m ⁇ K) or more.
  • the thermal conductivity (H) can be calculated by the following formula (2).
  • the thermal conductivity (H) may be 70 W / (m ⁇ K) or less, 60 W / (m ⁇ K) or less, and 50 W / (m ⁇ K) or less.
  • An example of thermal conductivity (H) is 10 to 70 W / (m ⁇ K).
  • H A ⁇ B ⁇ C (2)
  • 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 boron nitride sintered body.
  • the specific heat capacity C can be measured using a differential scanning calorimeter.
  • the boron nitride sintered body may contain components other than boron nitride.
  • the content of boron nitride in the boron nitride sintered body may be 90% by mass or more, 95% by mass or more, and 98% by mass or more.
  • the boron nitride sintered body may be in the form of a sheet (thin plate shape) as shown in FIG. Since the sheet-shaped boron nitride sintered body 10 has a small thickness t 0 , the resin composition can be smoothly impregnated. As a result, the pores of the boron nitride sintered body are sufficiently filled with the resin, and a composite having excellent insulating properties can be obtained.
  • the thickness t 0 of the boron nitride sintered body 10 may be less than 2 mm, less than 1 mm, or less than 0.5 mm.
  • the thickness t 0 of the boron nitride sintered body 10 may be 0.1 mm or more, or 0.2 mm or more.
  • the area of the main surface 10a of the boron nitride sintered body 10 may be 25 mm 2 or more, 100 mm 2 or more, 500 mm 2 or more, 800 mm 2 or more, 1000 mm 2 or more. There may be.
  • the shape of the boron nitride sintered body is not limited to the shape shown in FIG. 1, and may be, for example, a disk-shaped sheet or a C-shaped sheet having a curved main surface 10a. Further, the block-shaped boron nitride sintered body may be cut and / or polished to be processed into a sheet shape as shown in FIG. However, if processing such as cutting is performed, material loss will occur. Therefore, if a sheet-shaped boron nitride sintered body is produced using the sheet-shaped molded body, material loss can be reduced. Thereby, the yield of the boron nitride sintered body and the composite can be improved.
  • the block-shaped boron nitride sintered body is a polyhedron, for example, all sides have an appropriate length, and the block-shaped boron nitride sintered body has a larger thickness than the sheet-shaped boron 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.
  • the orientation index of the boron nitride crystal in the boron nitride sintered body may be 20 or less, 18 or less, and 15 or less. Thereby, the anisotropy of thermal conductivity can be sufficiently reduced. Therefore, in the case of a sheet like the boron nitride sintered body 10, the thermal conductivity along the thickness direction can be sufficiently increased. It is preferable that the thermal conductivity along the thickness direction of the boron nitride sintered body 10 is the above-mentioned value.
  • the orientation index of the boron nitride sintered body may be 0.5 or more, 3 or more, or 5 or more.
  • the orientation index in the present disclosure is an index for quantifying the degree of orientation of boron nitride crystals.
  • 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 composite according to one embodiment is a composite of a silicon nitride sintered body and a resin, and has the above-mentioned boron nitride sintered body and a resin filled in at least a part of the pores of the boron nitride sintered body.
  • the resin include epoxy resin, silicone resin, cyanate resin, silicone rubber, acrylonitrile resin, phenol resin, melamine resin, urea resin, unsaturated polyester, fluororesin, polyimide, polyamideimide, polyetherimide, and polybutylene terephthalate.
  • 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 boron nitride particles in the complex may be 25 to 65% by volume or 39 to 48% by volume based on the total volume of the complex.
  • the content of the fat group (total of the semi-cured product and the cured product) in the complex may be 35 to 75% by volume or 52 to 61% by volume based on the total volume of the complex.
  • a complex containing boron nitride particles and a resin in such a proportion can achieve both high adhesiveness and thermal conductivity at a high level.
  • the content of the resin (total of semi-cured product and cured product) in the composite may be 10 to 70% by mass, 10 to 60% by mass, and 20 to 20 to 70% by mass based on the total mass of the composite. It may be 60% by mass, 20 to 55% by mass, and 25 to 55% by mass.
  • a complex containing a resin in such a ratio can achieve both high adhesiveness and thermal conductivity at a high level.
  • the content of the resin in the complex can be determined by heating the complex to decompose and remove the resin, and calculating the mass of the resin from the mass difference before and after heating.
  • the filling rate of the resin in the complex may be 80% by volume or more, 90% by volume or more, or 92% by volume or more.
  • the resin filling rate indicates the volume ratio of the pores filled with the resin (semi-cured product + cured product) among all the pores in the boron nitride sintered body.
  • the porosity in the complex may be 20% by volume or less, 10% by volume or less, 8% by volume or less, 6% by volume or less, and 5% by volume or less. It may be 4% by volume or less. As a result, both high adhesiveness and high insulation can be achieved at a sufficiently high level.
  • the complex may further contain other components in addition to the boron nitride sintered body 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 and the heat radiating sheet may be in the form of a sheet (thin plate shape) as shown in FIG. 1, similarly to the boron nitride sintered body. Since the sheet-shaped composite 20 (heat radiating member 20) has a small thickness, it can be suitably used as a heat radiating member for electronic devices and the like. Moreover, the resin composition is sufficiently impregnated.
  • the thickness t of the complex 20 (heat radiating member 20) may be less than 2 mm, less than 1 mm, or less than 0.5 mm. From the viewpoint of maintaining a certain level of strength, the thickness t of the complex 20 (heat dissipation member 20) may be 0.1 mm or more, or 0.2 mm or more.
  • the areas of the main surfaces 20a and 20b of the complex 20 may be 25 mm 2 or more, 100 mm 2 or more, 500 mm 2 or more, and 800 mm 2 or more, respectively. It may be 1000 mm 2 or more.
  • the composite of this embodiment contains the above-mentioned boron nitride sintered body and resin.
  • the boron nitride sintered body has a low compressive elastic modulus, so that the composite is easily compressed and deformed.
  • the resin impregnated in the complex exudes.
  • the complex can be firmly adhered to other members. Therefore, this complex has excellent adhesiveness to other members. Therefore, the complex is sufficiently reliable.
  • the production method of this example includes a sintering step of sintering boron nitride powder to obtain a block-shaped boron nitride sintered body.
  • the raw material powder include amorphous boron nitride powder having an average particle size of 0.5 to 10 ⁇ m and hexagonal boron nitride powder having an average particle size of 3.0 to 40 ⁇ m. These powders may be mixed using a Henschel mixer or the like, or may be mixed in a slurry form in water or an ethanol solution using a disparizer.
  • a slurry containing such boron nitride powder may be spheroidized by a spray dryer or the like, molded, and then sintered to obtain a boron nitride sintered body.
  • a mold may be used for molding, or a cold isotropic pressing (CIP) method may be used.
  • the average particle size of each of the above-mentioned boron nitride powders is a particle size of 50% of the cumulative value of the cumulative particle size distribution in the particle size distribution measurement by the laser diffraction light scattering method.
  • the particle size distribution measuring machine include "MT3300EX" (manufactured by Nikkiso Co., Ltd.).
  • water is used as a solvent
  • hexametaphosphate is used as a dispersant
  • a homogenizer is used for 30 seconds to carry out a dispersion treatment with an output of 20 W.
  • 1.33 is used for the refractive index of water
  • 1.80 is used for the refractive index of the boron nitride powder.
  • the measurement time per measurement is 30 seconds.
  • a sintering aid When sintering the boron nitride powder, a sintering aid may be used. Sintering aids include, for example, oxides of rare earth elements such as ittoria oxide, alumina oxide and magnesium oxide, carbonates of alkali metals such as lithium carbonate and sodium carbonate, carbonates of alkaline earth metals such as calcium carbonate, and It may be boric acid or the like. When the sintering aid is blended, the amount of the sintering aid added may be, for example, 1.5 to 25 parts by mass and 3.0 to 22 parts by mass with respect to 100 parts by mass of the boron nitride powder. It may be a department. By setting the amount of the sintering aid added within the above range, a boron nitride sintered body having a certain degree of strength and a high porosity can be smoothly obtained.
  • 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, 2100 ° 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 koto-shaped continuous furnace, and the like. In this way, a block-shaped boron nitride sintered body can be obtained.
  • the method for producing the complex of this example includes an impregnation step and a cutting step of impregnating a block-shaped (for example, a bulk body having a thickness of more than 2 mm) boron nitride sintered body with a resin composition.
  • the resin composition may contain a main agent, a curing agent and a solvent from the viewpoint of improving fluidity and handleability.
  • an inorganic filler, a silane coupling agent, a defoaming agent, a surface conditioner, a wet dispersant and the like may be contained.
  • the resin component for example, one that becomes the resin mentioned in the above description of the complex by curing or semi-curing reaction can be used.
  • the solvent 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.
  • Impregnation is performed by adhering the resin composition to the boron nitride sintered body.
  • the boron nitride sintered body may be immersed in the resin composition. It may be carried out under pressurization or depressurization conditions in the immersed state.
  • the resin composition can be applied to the boron nitride sintered body to impregnate it. In this way, the pores of the boron nitride sintered body can be filled with the resin.
  • the impregnation step may be performed in an impregnation device provided with a closed container.
  • the pressure in the impregnating device may be increased to be higher than the atmospheric pressure and impregnated under pressurized conditions.
  • the depressurization condition and the pressurization condition may be repeated a plurality of times.
  • the impregnation step may be performed while heating.
  • the resin composition impregnated in the pores of the boron nitride sintered body becomes a resin (cured product or semi-cured product) after curing or semi-curing proceeds or the solvent volatilizes.
  • a composite having a boron nitride sintered body and a resin filled in its pores is obtained. Not all of the pores need to be filled with resin, and some of the pores may not be filled with resin.
  • Boron 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 resin-filled composite is taken out from the impregnation device, and the resin is cured by heating and / or light irradiation depending on the type of resin (or a curing agent added as needed). Or semi-cured.
  • the impregnation step may be performed under atmospheric pressure or reduced pressure conditions, impregnation under pressurized conditions, or a combination thereof.
  • the pressure in the impregnation device when the impregnation step is carried out under reduced pressure conditions may be, for example, 1000 Pa or less, 500 Pa or less, 100 Pa or less, 50 Pa or less, or 30 Pa or less.
  • the pressure in the impregnation device may be, for example, 1 MPa or more, 3 MPa or more, 10 MPa or more, or 30 MPa or more.
  • the solution containing the resin composition may be heated.
  • the viscosity of the solution can be adjusted and the impregnation of the resin can be promoted.
  • the viscosity of the solution containing the resin composition at the time of impregnation may be, for example, 500 mPa ⁇ s or less.
  • the nitride sintered body is kept immersed in a solution containing the resin composition for a predetermined time.
  • the predetermined time may be, for example, 5 hours or more, or 10 hours or more.
  • the impregnation step there may be a curing step of curing the resin filled in the pores.
  • the resin-filled composite is taken out from the impregnation device, and the resin is cured by heating and / or light irradiation depending on the type of resin (or a curing agent added as needed). Or semi-cured.
  • "Semi-hardening" also referred to as B stage
  • 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. Whether or not the resin is in a semi-cured state can be confirmed by, for example, a differential scanning calorimeter.
  • the obtained resin impregnated body is cut using, for example, a wire saw.
  • the wire saw may be, for example, a multi-cut wire saw or the like. ) Can be cut and prepared. In this way, a sheet-like complex can be obtained.
  • 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> Hexagonal boron nitride powder (oxygen content: 0.8% by mass, boron nitride purity: 99.0% by mass) having an average particle size of 8.0 ⁇ m is 40.0% by mass, and the average particle size is 13. Hexagonal boron nitride powder (oxygen content: 0.3% by mass, boron nitride purity: 99.0% by mass), which is 0 ⁇ m, is measured so as to be 60.0% by mass, and these are mixed to form a raw material powder. Was prepared.
  • a sintering aid was prepared by blending powdered boric acid and calcium carbonate. In the preparation, 60 parts by mass of calcium carbonate was added to 100 parts by mass of boric acid. 14 parts by mass of a sintering aid and 10 parts by mass of a binder (polyvinyl alcohol (“Gosenol”, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.)) were blended with respect to 100 parts by mass of the raw material powder. The obtained compound was heated and stirred at 50 ° C. until it was dissolved, and then spheroidized at a drying temperature of 230 ° C. with a spray dryer. In this way, a spheroidized mixed powder was prepared. A rotary atomizer was used as the spheroidizing device of the spray dryer.
  • the above mixed powder was filled in a cold isotropic pressure (CIP) device (manufactured by Kobe Steel, Ltd., trade name: ADW800) and compressed at a pressure of 30 MPa to prepare a molded product.
  • CIP cold isotropic pressure
  • the produced molded product was sintered by holding it at 2000 ° C. for 10 hours using a batch type high frequency furnace (manufactured by Fuji Dempa Kogyo Co., Ltd., trade name: FTH-300-1H).
  • FTH-300-1H a batch type high frequency furnace
  • the firing was carried out by adjusting the inside of the furnace under a nitrogen atmosphere while flowing nitrogen into the furnace in a standard state so that the flow rate was 10 L / min.
  • the compressive elastic modulus at 20 ° C. was determined by the following procedure according to JIS K7181.
  • the measurement was carried out under the conditions of a compression speed of 1 mm / min, a load cell of 100 kN, and 200 ° C. using a measuring device of a compression tester (trade name: Autograph AG-X manufactured by Shimadzu Corporation). The results are as shown in Table 1.
  • the compressive strength at 200 ° 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.
  • 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 was used as the measuring device.
  • the bulk density B was calculated from the volume and mass of the boron nitride sintered body.
  • the specific heat capacity C was measured using a differential scanning calorimeter (manufactured by Rigaku Co., Ltd., device name: ThermoPlusEvo DSC8230).
  • the results of thermal conductivity H and bulk density B are 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.
  • Epoxy resin manufactured by Mitsubishi Chemical Corporation, trade name: Epicoat 807
  • curing agent manufactured by Nippon Synthetic Chemical Industry Co., Ltd., trade name: Acmex H-84B
  • the boron nitride sintered body was immersed in the resin composition containing the above, and the boron nitride sintered body was impregnated with the resin composition. After impregnation, the resin was semi-cured by heating at a temperature of 150 ° C. for 60 minutes under atmospheric pressure, and cooled to room temperature (25 ° C.) to prepare a complex (before processing).
  • the semi-cured product layer constituting the surface portion of the complex was cut and removed, and then the complex was cut with a multi-cut wire saw to obtain a complex sheet having a thickness of 0.4 mm.
  • the filling rate of the resin in the complex sheet was 94.0% by volume. This content was determined by the following procedure.
  • the filling rate of the resin in the complex was determined by the following formula (4) from the bulk density and the theoretical density before and after the complex was produced.
  • Resin filling rate in the composite ((composite bulk density-boron nitride sintered bulk density) / (complex theoretical density-boron nitride sintered bulk density)) x 100. ⁇ ⁇ (4)
  • Theoretical density of composite true density of boron nitride sintered body + true density of resin x (1-bulk density of boron nitride sintered body / true density of boron nitride sintered body) ... (5)
  • the bulk density of the boron nitride sintered body conforms to the measurement method of density and specific gravity by geometric measurement of JIS Z 8807: 2012, and is a sheet-shaped (rectangular) boron nitride sintered body (composite). It was obtained from the volume calculated from the length of each side (measured by a caliper) and the mass measured by an electronic balance (see item 9 of JIS Z 8807: 2012).
  • the true density of the boron nitride sintered body and the resin conforms to the method of measuring the density and specific gravity by the gas substitution method of JIS Z 8807: 2012, and the volume of the boron nitride sintered body and the resin measured using a dry automatic densitometer. (Refer to equations (14) to (17) in paragraph 11 of JIS Z 8807: 2012).
  • the resin content in the complex sheet 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 measured by burning the resin from the complex.
  • the mass of the resin was calculated from the mass difference between the boron nitride sintered body and the composite after the resin was burnt off, and the mass of this resin was divided by the mass of the composite.
  • the cohesive fracture portion is the area of the portion of the adhesive surface of the composite that has been adhered to the copper foil and that the composite has broken.
  • Example 2 Boron nitride firing was performed in the same procedure as in Example 1 except that when the molded product was produced, the mixed powder was compressed at a pressure of 35 MPa with a cold isotropic pressure (CIP) device to obtain the molded product. Bounds and complexes were made. Each measurement of the boron nitride sintered body and the composite was carried out in the same manner as in Example 1. The results are as shown in Tables 1 and 2.
  • Example 3 Boron nitride sintering was performed in the same procedure as in Example 1 except that the mixed powder was compressed at a pressure of 90 MPa with a cold isotropic pressure (CIP) device to obtain the molded product when the molded product was produced. Body and complex were made. Each measurement of the boron nitride sintered body and the composite was carried out in the same manner as in Example 1. The results are as shown in Tables 1 and 2.
  • Example 4 Boron nitride sintering was performed in the same procedure as in Example 1 except that the mixed powder was compressed at a pressure of 10 MPa with a cold isotropic pressure (CIP) device when the molded product was produced to obtain the molded product. Body and complex were made. Each measurement of the boron nitride sintered body and the composite was carried out in the same manner as in Example 1. The results are as shown in Tables 1 and 2.
  • Example 5 Amorphous boron nitride powder (oxygen content: 1.8% by mass, boron nitride purity: 97.2% by mass) having an average particle size of 0.8 ⁇ m is 40.0% by mass, and an average particle size is 13.0 ⁇ m.
  • Hexagonal boron nitride powder (oxygen content: 0.3% by mass, boron nitride purity: 99.0% by mass) was measured so as to be 60.0% by mass, and blended to prepare a raw material powder. ..
  • a boron nitride sintered body and a complex were prepared in the same procedure as in Example 1 except that this raw material powder was used. Each measurement of the boron nitride sintered body and the composite was carried out in the same manner as in Example 1. The results are as shown in Tables 1 and 2.
  • Example 6 The boron nitride sintered body and the composite were prepared in the same procedure as in Example 1 except that the method for producing the molded product was changed from cold isotropic pressure (CIP) to mold molding (molding pressure: 50 MPa). Made. Each measurement of the boron nitride sintered body and the composite was carried out in the same manner as in Example 1. The results are as shown in Tables 1 and 2.
  • Example 7 The boron nitride sintered body and the composite were prepared in the same procedure as in Example 1 except that the method for producing the molded product was changed from cold isotropic pressure (CIP) to mold molding (molding pressure: 15 MPa). Made. Each measurement of the boron nitride sintered body and the composite was carried out in the same manner as in Example 1. The results are as shown in Tables 1 and 2.
  • Example 8 A mixed powder was prepared by stirring the raw material powder and the sintering aid using a Henschel mixer without performing the spheroidizing treatment with a spray dryer.
  • a boron nitride sintered body and a composite were prepared in the same procedure as in Example 1 except that a molded product was produced by a cold isotropic pressurizing device using this mixed powder.
  • Each measurement of the boron nitride sintered body and the composite was carried out in the same manner as in Example 1. The results are as shown in Tables 1 and 2.
  • Example 9 Same as Example 8 except that the spheroidizing treatment by the spray dryer was not performed and the molded product was produced by mold molding (molding pressure: 30 MPa) instead of the cold isotropic pressurizing device. In the procedure, a boron nitride sintered body and a composite were prepared. Each measurement of the boron nitride sintered body and the composite was carried out in the same manner as in Example 1. The results are as shown in Tables 1 and 2.
  • Hexagonal boron nitride powder (oxygen content: 0.3% by mass, boron nitride purity: 99.1% by mass) having an average particle size of 18.0 ⁇ m is 40.0% by mass, and the average particle size is 13.
  • Hexagonal boron nitride powder (oxygen content: 0.3% by mass, boron nitride purity: 99.0% by mass), which is 0 ⁇ m, is measured so as to be 60.0% by mass, and these are mixed and used as a raw material.
  • a powder was prepared.
  • a boron nitride sintered body and a complex were prepared in the same procedure as in Example 1 except that this raw material powder was used.
  • Each measurement of the boron nitride sintered body and the composite was carried out in the same manner as in Example 1. The results are as shown in Tables 1 and 2.
  • Example 2 Boron nitride sintered body and composite were obtained by the same procedure as in Example 1 except that the molded product was obtained by compressing it with a cold isotropic pressure (CIP) device at a pressure of 150 MPa when producing the molded product. The body was made. Each measurement of the boron nitride sintered body and the composite was carried out in the same manner as in Example 1. The results are as shown in Tables 1 and 2.

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WO2023162598A1 (ja) * 2022-02-22 2023-08-31 デンカ株式会社 窒化ホウ素粉末の製造方法、窒化ホウ素粉末及び樹脂封止材
KR102578083B1 (ko) * 2022-06-14 2023-09-13 윌코 주식회사 질화붕소 복합체 및 그 제조 방법
WO2023204139A1 (ja) * 2022-04-21 2023-10-26 デンカ株式会社 窒化ホウ素粉末、及び、放熱シート、並びに、窒化ホウ素粉末の製造方法

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JP2016103611A (ja) * 2014-11-28 2016-06-02 デンカ株式会社 窒化ホウ素樹脂複合体回路基板
WO2017155110A1 (ja) * 2016-03-10 2017-09-14 デンカ株式会社 セラミックス樹脂複合体

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JPH0761855A (ja) * 1993-08-26 1995-03-07 Shinagawa Refract Co Ltd 窒化硼素含有耐火物
JP2016103611A (ja) * 2014-11-28 2016-06-02 デンカ株式会社 窒化ホウ素樹脂複合体回路基板
WO2017155110A1 (ja) * 2016-03-10 2017-09-14 デンカ株式会社 セラミックス樹脂複合体

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WO2023162598A1 (ja) * 2022-02-22 2023-08-31 デンカ株式会社 窒化ホウ素粉末の製造方法、窒化ホウ素粉末及び樹脂封止材
JPWO2023162598A1 (https=) * 2022-02-22 2023-08-31
JP7733803B2 (ja) 2022-02-22 2025-09-03 デンカ株式会社 窒化ホウ素粉末の製造方法、窒化ホウ素粉末及び樹脂封止材
WO2023204139A1 (ja) * 2022-04-21 2023-10-26 デンカ株式会社 窒化ホウ素粉末、及び、放熱シート、並びに、窒化ホウ素粉末の製造方法
KR102578083B1 (ko) * 2022-06-14 2023-09-13 윌코 주식회사 질화붕소 복합체 및 그 제조 방법
WO2023242828A3 (en) * 2022-06-14 2024-06-13 Wilco Inc. Boron nitride composite and manufacturing method thereof

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