WO2021251494A1 - 熱伝導性樹脂組成物及び放熱シート - Google Patents

熱伝導性樹脂組成物及び放熱シート Download PDF

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Publication number
WO2021251494A1
WO2021251494A1 PCT/JP2021/022360 JP2021022360W WO2021251494A1 WO 2021251494 A1 WO2021251494 A1 WO 2021251494A1 JP 2021022360 W JP2021022360 W JP 2021022360W WO 2021251494 A1 WO2021251494 A1 WO 2021251494A1
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Prior art keywords
inorganic filler
particle size
resin composition
heat
boron nitride
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English (en)
French (fr)
Japanese (ja)
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光祐 和田
清隆 藤
佳孝 谷口
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Denka Co Ltd
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Denka Co Ltd
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Priority to EP21821028.4A priority Critical patent/EP4148091B1/en
Priority to JP2022530640A priority patent/JP7541090B2/ja
Priority to CN202180041089.4A priority patent/CN115698187A/zh
Priority to US18/008,631 priority patent/US12305113B2/en
Publication of WO2021251494A1 publication Critical patent/WO2021251494A1/ja
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
    • C09K5/08—Materials not undergoing a change of physical state when used
    • C09K5/14—Solid materials, e.g. powdery or granular
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/38—Boron-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • 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
    • H05K7/00—Constructional details common to different types of electric apparatus
    • H05K7/20—Modifications to facilitate cooling, ventilating, or heating
    • H05K7/2039—Modifications to facilitate cooling, ventilating, or heating characterised by the heat transfer by conduction from the heat generating element to a dissipating body
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2383/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
    • C08J2383/04—Polysiloxanes
    • C08J2383/07—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
    • 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
    • C08K2003/382—Boron-containing compounds and nitrogen
    • C08K2003/385—Binary compounds of nitrogen with boron
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/001—Conductive additives
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/005—Additives being defined by their particle size in general

Definitions

  • the present invention relates to a heat conductive resin composition containing boron nitride particles and a heat radiating sheet obtained by molding the heat conductive resin composition.
  • heat-generating electronic components such as power devices, transistors, thyristors, and CPUs
  • heat-generating electronic components such as power devices, transistors, thyristors, and CPUs
  • (1) the insulating layer of the printed wiring board on which the heat-generating electronic component is mounted is made highly thermally conductive
  • the heat-generating electronic component or the printed wiring on which the heat-generating electronic component is mounted is mounted.
  • a silicone resin or an epoxy resin filled with ceramic powder is used as the insulating layer and thermal interface material of the printed wiring board.
  • hexagonal boron nitride powder which has excellent properties as an electrical insulating material such as high thermal conductivity, high insulation, and low relative permittivity, has attracted attention. There is.
  • the hexagonal boron nitride particles have a thermal conductivity of 400 W / (m ⁇ K) in the in-plane direction (a-axis direction), whereas the thermal conductivity in the thickness direction (c-axis direction) is 2 W / (m ⁇ K). It is (m ⁇ K), and the anisotropy of the thermal conductivity derived from the crystal structure and the scaly shape is large.
  • the hexagonal boron nitride powder is filled in the resin, the particles are aligned and oriented in the same direction. Then, the thickness direction (c-axis direction) of the hexagonal boron nitride particles in the resin will be aligned.
  • the in-plane direction (a-axis direction) of the hexagonal boron nitride particles and the thickness direction of the thermal interface material become perpendicular to each other, and the in-plane direction (a-axis direction) of the hexagonal boron nitride particles. )
  • the in-plane direction (a-axis direction) of the hexagonal boron nitride particles could not fully utilize the high thermal conductivity.
  • Patent Document 1 proposes the use of boron nitride powder in which hexagonal boron nitride particles as primary particles are aggregated without being oriented in the same direction.
  • the hexagonal boron nitride particles of the primary particles do not orient in the same direction, and the anisotropy of thermal conductivity can be suppressed.
  • a boron nitride powder in which hexagonal boron nitride particles of primary particles are aggregated without being oriented in the same direction in addition to those described in Patent Document 1, spherical boron nitride produced by a spray-drying method (Patent Document 2) and carbide are carbonized.
  • Boron nitride which is an aggregate produced from boron as a raw material (Patent Document 3), and aggregated boron nitride produced by repeatedly pressing and crushing (Patent Document 4) are known.
  • the doctor blade method is known as a method for continuously obtaining a thin molded body composed of a ceramic raw material powder and an organic component.
  • the doctor blade method is a method in which a uniform slurry is thinly spread on a carrier film to obtain a molded product.
  • the doctor blade method is widely used for ceramic substrates for electronic devices, ceramic packages for ICs, multilayer ceramic packages, multilayer ceramic circuit boards, ceramic capacitors and the like. From the viewpoint of mass production of thin heat dissipation sheets, it is desirable to manufacture thin heat dissipation sheets by the doctor blade method. However, it is difficult to produce a thin heat dissipation sheet while maintaining a high level of thermal conductivity.
  • an object of the present invention is to provide a heat conductive resin composition having excellent heat conductivity suitable for producing a thin molded body and a heat dissipation sheet obtained by molding the heat conductive resin composition. And.
  • the present inventors have conducted diligent research to achieve the above object, and found that when a slurry was prepared using conventional aggregated boron nitride, the boron nitride particles were peeled off from the aggregated boron nitride during the slurry preparation. It has been found that the boron nitride particles increase the viscosity of the slurry and adhere to the carrier film.
  • the present invention is based on the above findings, and the gist thereof is as follows.
  • a heat conductive resin composition obtained by blending an inorganic filler component and a resin component, wherein the inorganic filler component contains a first inorganic filler and a second inorganic filler, and the particle size distribution of the inorganic filler component is It has a first maximum point due to the first inorganic filler and a second maximum point due to the second inorganic filler, and the particle size of the first maximum point is 15 ⁇ m or more and the second maximum point.
  • the particle size of the points is two-thirds or less of the particle size of the first maximum point, and the integrated amount of the frequency from the peak start to the peak end at the peak having the first maximum point is 50% or more.
  • the first inorganic filler is a thermally conductive resin composition in which hexagonal boron nitride primary particles are aggregated and the crushing strength is 6 MPa or more.
  • the second inorganic filler is massive boron nitride particles in which hexagonal boron nitride primary particles are aggregated and the crushing strength is 6 MPa or more.
  • thermoforming a heat conductive resin composition having excellent heat conductivity suitable for producing a thin molded body and a heat dissipation sheet obtained by molding the heat conductive resin composition. ..
  • FIG. 1 is a diagram showing an example of the particle size distribution of the inorganic filler component.
  • the thermally conductive resin composition of the present invention is formed by blending an inorganic filler component and a resin component.
  • the inorganic filler component includes a first inorganic filler and a second inorganic filler.
  • the particle size distribution of the inorganic filler component has a first maximum point due to the first inorganic filler and a second maximum point due to the second inorganic filler, and the particle size of the first maximum point is Frequency between peak start and peak end at peaks of 15 ⁇ m or greater, the particle size of the second local maximum is less than two-thirds of the particle size of the first local maximum, and the peak has the first local maximum.
  • the accumulated amount of is 50% or more.
  • the particle size distribution of the inorganic filler component in the heat conductive resin composition can be measured, for example, as follows.
  • Components other than the inorganic filler component of the heat conductive resin composition are dissolved by using a solvent such as toluene, xylene, and a chlorine-based hydrocarbon, and the components other than the inorganic filler component are removed from the heat conductive composition. Then, the particle size distribution of the remaining inorganic filler component is measured using a laser diffraction / scattering method particle size distribution measuring device (LS-13 320) manufactured by Beckman Coulter Co., Ltd. When there are three or more peaks, the peak with the highest frequency of maxima is the peak having the maxima caused by the first inorganic filler, and the peak with the next highest frequency is the second. The peak has a maximum point due to the inorganic filler of. The unit of frequency in the particle size distribution is volume%.
  • the first inorganic filler is massive boron nitride particles in which hexagonal boron nitride primary particles are aggregated and have a crushing strength of 6 MPa or more.
  • the crushing strength of the lumpy boron nitride particles is less than 6 MPa, when the heat conductive resin composition is made into a slurry, a part of the lumpy boron nitride particles is peeled off from the lumpy boron nitride particles, and the viscosity of the heat conductive resin composition is high.
  • the crushing strength of the massive boron nitride particles is preferably 7 MPa or more, more preferably 8 MPa or more, still more preferably 9 MPa or more, still more preferably 10 MPa or more, and particularly preferably. It is 11 MPa or more.
  • the upper limit of the crushing strength of the massive boron nitride particles is not particularly limited, but is, for example, 30 MPa or less.
  • the crushing strength of the first inorganic filler can be measured according to JIS R1639-5. Specifically, the crushing strength of the first inorganic filler can be measured as follows. Components other than the inorganic filler component of the heat conductive resin composition are dissolved by using a solvent such as toluene, xylene, and a chlorine-based hydrocarbon, and the components other than the inorganic filler component are removed from the heat conductive resin composition. Then, the particle size distribution of the remaining inorganic filler component is measured using a laser diffraction / scattering method particle size distribution measuring device (LS-13 320) manufactured by Beckman Coulter Co., Ltd.
  • LS-13 320 laser diffraction / scattering method particle size distribution measuring device manufactured by Beckman Coulter Co., Ltd.
  • the particle size is. Five inorganic filler components having a particle size within the range of ⁇ 5 ⁇ m of the first maximum point are selected, and a compression test is performed one by one.
  • the crushing strengths of the five inorganic filler components are weibull plotted according to JIS R1625, and the crushing strength at which the cumulative fracture rate is 63.2% is defined as the crushing strength of the first inorganic filler.
  • the particle size of the first maximum point due to the first inorganic filler is 15 ⁇ m or more. If the particle size of the first maximum point due to the first inorganic filler is less than 15 ⁇ m, the thermally conductive resin composition cannot contain the first inorganic filler with a high filling, and the thermally conductive resin composition.
  • the thermal conductivity of a heat-dissipating sheet made from an object may be low. From such a viewpoint, the particle size of the first maximum point is preferably 20 ⁇ m or more, more preferably 30 ⁇ m or more, still more preferably 40 ⁇ m or more, and particularly preferably 50 ⁇ m or more.
  • the particle size of the first maximum point is preferably 100 ⁇ m or less.
  • the particle size of the first maximum point is 100 ⁇ m or less, a thin heat radiating sheet can be produced by using the heat conductive resin composition. From such a viewpoint, the particle size of the first maximum point is more preferably 90 ⁇ m or less, still more preferably 80 ⁇ m or less.
  • the particle size of the first local maximum point for example, can be adjusted by adjusting the average particle size of the first inorganic filler with a grain size of B 4 C as a raw material of the bulk boron nitride particles.
  • the particle size of B 4 C which is the raw material of the massive boron nitride particles
  • the particle size of B 4 C is decreased
  • the particle size of the first maximum point is increased.
  • the particle size becomes smaller.
  • the fact that the particle size of the first maximum point is caused by the first inorganic filler means that the maximum point of the particle size distribution of the first inorganic filler appears as the first maximum point in the particle size distribution of the inorganic filler component. .. Due to the influence of the particle size distribution of the inorganic filler components other than the first inorganic filler, the particle size of the first maximum point may be slightly different from the particle size of the maximum point of the particle size distribution of the first inorganic filler.
  • the integrated amount of frequency between the peak start and the peak end at the peak having the first maximum point is 50% or more. If the integrated amount is less than 50%, the viscosity of the thermally conductive resin composition increases due to the inorganic filler other than the first inorganic filler, and a thin molded product cannot be produced by the doctor blade method. Inorganic fillers other than the first inorganic filler may adhere to the carrier film. From such a viewpoint, the integrated amount is preferably 60% or more, more preferably 70% or more. Further, the integrated amount is preferably 90% or less, more preferably 80% or less, so that the effect of containing the second inorganic filler described later can be exhibited by the inorganic filler component.
  • the integrated amount of the frequency between the peak start and the peak end at the peak having the first maximum point is generally the content (volume%) of the first inorganic filler in the inorganic filler component. Therefore, by analyzing the composition of the inorganic filler component, the inorganic filler corresponding to the first maximum point can be determined.
  • FIG. 1 is a diagram showing an example of the particle size distribution of the inorganic filler component.
  • the horizontal axis is logarithmic.
  • Reference numeral M1 indicates a first maximum point
  • reference numeral M2 indicates a second maximum point.
  • PS indicates a peak start
  • PE indicates a peak end.
  • the integrated amount of the shaded portion of the peak having the first maximum point (M1) is the frequency between the peak start (PS) and the peak end (PE) in the peak having the first maximum point (M1). It is an integrated amount.
  • the peak valley is the peak end.
  • Hexagonal boron nitride primary particles are aggregated, and the massive boron nitride particles having a crushing strength of 6 MPa or more are obtained by synthesizing boron carbide using, for example, boron and acetylene black as raw materials, with respect to the obtained boron carbide ( Bulk boron nitride particles can be produced by carrying out 1) a pressure nitride firing step and (2) a decarburization crystallization step. Hereinafter, each step will be described in detail.
  • (1) Pressurized nitriding firing step In the pressure nitriding firing step, boron carbide having an average particle size of 6 to 55 ⁇ m and a carbon content of 18 to 21% is pressure nitriding and firing. This makes it possible to obtain boron nitride suitable as a raw material for the massive boron nitride particles of the present invention.
  • the average particle size of the raw material boron carbide is preferably 6 ⁇ m or more, more preferably 7 ⁇ m or more, further preferably 10 ⁇ m or more, and preferably 55 ⁇ m or less, more preferably 50 ⁇ m or less. More preferably, it is 45 or less ⁇ m.
  • the average particle size of the raw material boron carbide is preferably 7 to 50 ⁇ m, more preferably 10 to 45 ⁇ m.
  • the average particle size of boron carbide can be measured using a laser diffraction / scattering method particle size distribution measuring device (LS-13 320) manufactured by Beckman Coulter Co., Ltd.
  • Pressurizing the carbon content of the raw material of boron carbide for use in-pressure step is desirably less than B 4 C on the composition (21.7%), it is preferable to use a boron carbide having a carbon content of 18-21% ..
  • the carbon content of boron carbide is preferably 18% or more, more preferably 19% or more, and preferably 21% or less, more preferably 20.5% or less.
  • the carbon content of boron carbide is preferably 18 to 20.5%, more preferably 19 to 20.5%.
  • the reason why the carbon content of boron carbide is set in such a range is that the smaller the carbon content generated during the decarburization crystallization step described later, the more dense agglomerated boron nitride particles are produced, and finally. This is also to reduce the carbon content of the formed massive boron nitride particles. Further, it is difficult to produce stable boron carbide having a carbon content of less than 18% because the deviation from the theoretical composition becomes too large.
  • the method for producing boron carbide as a raw material is that boric acid and acetylene black are mixed and then heated in an atmosphere at 1800 to 2400 ° C. for 1 to 10 hours to obtain a boron carbide mass.
  • Boron carbide powder can be prepared by pulverizing this raw mass, sieving it, washing it, removing impurities, drying it, and the like as appropriate.
  • the mixing of boric acid, which is a raw material for boron carbide, and acetylene black is preferably 25 to 40 parts by mass with respect to 100 parts by mass of boric acid.
  • the atmosphere for producing the boron carbide is preferably an inert gas, and examples of the inert gas include argon gas and nitrogen gas, which can be used alone or in combination as appropriate. Of these, argon gas is preferable.
  • a general crusher or crusher can be used, for example, crushing is performed for about 0.5 to 3 hours. It is preferable that the pulverized boron carbide is sieved to a particle size of 75 ⁇ m or less using a sieve net. By adjusting the average particle size of the pulverized boron carbide, the average particle size of the massive boron nitride particles can be adjusted.
  • Pressurized nitriding firing is performed in an atmosphere of a specific firing temperature and pressurizing conditions.
  • the firing temperature in the pressure nitriding firing is preferably 1700 ° C. or higher, more preferably 1800 ° C. or higher, and preferably 2400 ° C. or lower, more preferably 2200 ° C. or lower.
  • the firing temperature in the pressure nitriding firing is more preferably 1800 to 2200 ° C.
  • the pressure in the pressure nitriding firing is preferably 0.6 MPa or more, more preferably 0.7 MPa or more, and preferably 1.0 MPa or less, more preferably 0.9 MPa or less.
  • the pressure in the pressure nitriding firing is preferably 0.6 to 1.0 MPa, more preferably 0.7 to 0.9 MPa.
  • the firing temperature is preferably 1800 ° C. or higher and the pressure is 0.7 to 1.0 MPa.
  • the firing temperature is 1800 ° C. and the pressure is 0.7 MPa or more, the nitriding of boron carbide can be sufficiently promoted.
  • a gas in which the nitriding reaction proceeds is required, and examples thereof include nitrogen gas and ammonia gas, which can be used alone or in combination of two or more. Of these, nitrogen gas is suitable for nitriding and in terms of cost.
  • the concentration of nitrogen gas in the atmosphere is preferably 95% (V / V) or more, more preferably 99.9% (V / V) or more.
  • the firing time in the pressure nitriding firing is preferably 6 to 30 hours, more preferably 8 to 20 hours.
  • the boron carbide obtained in the pressure sintering step is (a) in an atmosphere above normal pressure and (b) at a specific temperature rise temperature (b). c) The temperature is raised until the firing temperature reaches a specific temperature range, and (d) the heat treatment is performed to keep the firing temperature at the firing temperature for a certain period of time.
  • agglomerated boron nitride particles in which primary particles (hexagonal boron nitride in which the primary particles are scaly) are aggregated into agglomerates.
  • the crushing strength can be 6 MPa or more.
  • the boron nitride obtained from the prepared boron carbide as described above is decarbonized and aggregated into lumpy boron nitride particles while forming scales of a predetermined size. do.
  • boron nitride obtained in the pressure sintering and calcination step is mixed with 65 to 130 parts by mass of at least one compound of boron oxide and boric acid.
  • a mixture is prepared, the obtained mixture is raised to a temperature at which decarburization can be started, and then the temperature is raised to a firing temperature of 1950 to 2100 ° C. at a heating temperature of 5 ° C./min or less until the firing temperature is 1950 to 2100 ° C.
  • Perform a heat treatment that holds for more than 0.5 hours and less than 20 hours. By performing such a heat treatment, the crushing strength can be increased to 6 MPa or more.
  • a decarburization crystallization step preferably, after raising the temperature to a temperature at which decarburization can be started in an atmosphere of normal pressure or higher, until the calcination temperature reaches 1950 to 2100 ° C. at a temperature rise temperature of 5 ° C./min or less. It is a heat treatment that raises the temperature and keeps it at this firing temperature for more than 0.5 hours and less than 20 hours.
  • the calcination temperature is 2000 to 2080 ° C. at a temperature rise temperature of 5 ° C./min or less after raising the temperature to a temperature at which decarburization can be started in an atmosphere of normal pressure or higher. The temperature is raised until the temperature reaches the maximum, and the heat treatment is performed so that the temperature is maintained at this firing temperature for 2 to 8 hours.
  • the boron nitride obtained in the pressure nitride firing step is mixed with at least one compound of boron oxide and boric acid (and, if necessary, another raw material) to prepare a mixture. After that, it is desirable to decarburize and crystallize the obtained mixture.
  • the mixing ratio of boron nitride with at least one compound of boron oxide and boric acid is preferably boron oxide and 100 parts by mass of boron nitride. 65 to 130 parts by mass of at least one compound of boric acid, more preferably 70 to 120 parts by mass of at least one compound of boron oxide and boric acid. In the case of boron oxide, it is a mixing ratio converted to boric acid.
  • the pressure condition of "(a) atmosphere above normal pressure” in the decarburization and crystallization step is preferably normal pressure or higher, more preferably 0.1 MPa or higher.
  • the upper limit of the pressure condition of the atmosphere is not particularly limited, but is preferably 1 MPa or less, more preferably 0.5 MPa or less, and further preferably 0.3 MPa or less.
  • the pressure condition of the atmosphere is preferably 0.1 to 1 MPa, more preferably 0.1 to 0.5 MPa, and further preferably 0.1 to 0.3 MPa.
  • Nitrogen gas is suitable for the above-mentioned "atmosphere" in the decarburization and crystallization step, and the concentration of nitrogen gas in the atmosphere is preferably 90% (V / V) or more, and more preferably, the nitrogen gas is a high-purity nitrogen gas. (Nitrogen concentration 99.9% (V / V) or more).
  • the temperature rise of "(b) specific temperature rise temperature” in the decarburization crystallization step may be one-step or multi-step. It is desirable to select multiple stages in order to shorten the time required to raise the temperature to the temperature at which decarburization can be started.
  • As the "first stage temperature rise” in multiple stages it is preferable to raise the temperature to a "temperature at which decarburization can be started”.
  • the “temperature at which decarburization can be started” is not particularly limited, and may be any temperature that is normally used, for example, about 800 to 1200 ° C. (preferably about 1000 ° C.).
  • the “first stage temperature rise” can be performed, for example, in the range of 5 to 20 ° C./min, preferably 8 to 12 ° C./min.
  • the "second stage temperature rise” is "(c) temperature rise to a firing temperature in a specific temperature range” in the decarburization crystallization step.
  • the "second stage temperature rise” is preferably 5 ° C./min or less, more preferably 4 ° C./min or less, still more preferably 3 ° C./min or less, still more preferably 2 ° C./min or less.
  • the "second stage temperature rise” is preferably 0.1 ° C./min or higher, more preferably 0.5 ° C./min or higher, and even more preferably 1 ° C./min or higher.
  • the “second stage temperature rise” is preferably 0.1 to 5 ° C./min.
  • the specific temperature range (firing temperature after temperature rise) in the above "(c) temperature rise to a firing temperature in a specific temperature range” is preferably 1950 ° C. or higher, more preferably 1960 ° C. or higher, still more preferably 2000. ° C. or higher, preferably 2100 ° C. or lower, more preferably 2080 ° C. or lower.
  • the fixed time holding (baking time after raising the temperature) of the above “(d) holding at the firing temperature for a certain time” is preferably more than 0.5 hours and less than 20 hours.
  • the "baking time” is more preferably 1 hour or longer, still more preferably 3 hours or longer, still more preferably 5 hours or longer, particularly preferably 10 hours or longer, and even more preferably 18 hours or shorter, still more preferably. 16 hours or less. If the firing time after the temperature rise is more than 0.5 hours, the grain growth occurs well, and if it is less than 20 hours, it is possible to reduce the grain growth from progressing too much and the particle strength to decrease, and the firing time. It is possible to reduce industrial disadvantages due to the long time.
  • the massive boron nitride particles of the present invention can be obtained through the pressure nitriding firing step and the decarburization crystallization step. Further, in the case of loosening the weak aggregation between the massive boron nitride particles, it is desirable to pulverize or crush the massive boron nitride particles obtained in the decarburization crystallization step and further classify them.
  • the crushing and crushing are not particularly limited, and a commonly used crusher and crusher may be used, and the classification is performed by a general sieving method having an average particle size of 20 ⁇ m or more. It may be used. For example, a method of crushing with a Henschel mixer or a mortar and then classifying with a vibrating sieve can be mentioned.
  • the particle size of the second maximum point due to the second inorganic filler is two-thirds or less of the particle size of the first maximum point.
  • the thermally conductive resin composition cannot contain the inorganic filler component with high filling, and the inorganic filler component cannot be contained.
  • a part of the heat-dissipating sheet may adhere to the carrier film, or the heat-dissipating sheet produced by using the heat-conducting resin composition may have a low thermal conductivity.
  • the particle size of the second maximum point is preferably 60% or less of the particle size of the first maximum point, and more preferably 55% of the particle size of the first maximum point. It is not more than the particle size of, and more preferably 52% or less of the particle size of the first maximum point.
  • the lower limit of the particle size of the second maximum point is, for example, 20% or more, preferably 30% or more or 40% or more of the particle size of the first maximum point.
  • the second maximum point can be measured in the same manner as the first maximum point. There may be a plurality of second maximum points.
  • the integrated amount of the frequency between the peak start and the peak end at the peak having the second maximum point is generally the content (% by volume) in the inorganic component of the second inorganic filler. Therefore, by analyzing the composition of the inorganic filler component, the inorganic filler corresponding to the second maximum point can be determined.
  • the cumulative amount of frequency between the peak start and the peak end at the peak having the second maximum point is 50% or less, may be 45% or less, may be 40% or less, and may be 35% or less. good.
  • the lower limit may be 10% or more, 15% or more, 20% or more, and 25% or more.
  • the second inorganic filler examples include alumina particles, aluminum nitride particles, and boron nitride particles. These second inorganic fillers can be used alone or in combination of two or more. Of these, the second inorganic filler is preferably boron nitride particles. When the second inorganic filler is boron nitride particles, the thermal conductivity of the heat radiating sheet produced by using the thermally conductive resin composition can be further increased.
  • the second inorganic filler is more preferably massive boron nitride particles in which hexagonal boron nitride primary particles are aggregated and the crushing strength is 6 MPa or more.
  • the slurry of the heat conductive resin composition when the slurry of the heat conductive resin composition is produced, a part of the second inorganic filler is peeled off from the second inorganic filler, and the viscosity of the slurry of the heat conductive resin composition increases. Can be further suppressed, and the adhesion of a part of the second inorganic filler to the carrier film can be further suppressed.
  • the lumpy boron nitride particles of the second inorganic filler can be produced by the same method as the lumpy boron nitride particles of the first inorganic filler.
  • the particle size of the second maximum point due to the second inorganic filler can be divided into three minutes of the particle size of the first maximum point. It can be 2 or less.
  • the crushing strength of the second inorganic filler can be measured according to JIS R1639-5. Specifically, the crushing strength of the second inorganic filler can be measured as follows. Components other than the inorganic filler component of the heat conductive resin composition are dissolved by using a solvent such as toluene, xylene, and a chlorine-based hydrocarbon, and the components other than the inorganic filler component are removed from the heat conductive resin composition. Then, the particle size distribution of the remaining inorganic filler component is measured using a laser diffraction / scattering method particle size distribution measuring device (LS-13 320) manufactured by Beckman Coulter Co., Ltd.
  • LS-13 320 laser diffraction / scattering method particle size distribution measuring device manufactured by Beckman Coulter Co., Ltd.
  • the particle size is.
  • Five inorganic filler components having a particle size within the range of ⁇ 5 ⁇ m of the second maximum point are selected, and a compression test is performed one by one.
  • the crushing strengths of the five inorganic filler components are weibull plotted according to JIS R1625, and the crushing strength at which the cumulative fracture rate is 63.2% is defined as the crushing strength of the second inorganic filler.
  • the integrated amount of the frequency of the particle size of 0 to 15 ⁇ m is preferably less than 60%. Then, the content of the inorganic filler having a particle size of 15 ⁇ m or more in the inorganic filler component becomes approximately 40% by volume or more, and the heat conductive resin composition can contain the inorganic filler component with a high filling, so that the heat conductive resin can be contained. The thermal conductivity of the heat dissipation sheet produced by using the composition can be further increased.
  • the integrated amount of the frequency of the particle size of 0 to 15 ⁇ m is more preferably less than 50%, further preferably less than 40%, still more preferably 30. Less than%.
  • resin component examples include epoxy resin, silicone resin (including silicone rubber), acrylic resin, phenol resin, melamine resin, urea resin, unsaturated polyester, fluororesin, and polyamide (for example, polyimide, polyamideimide, and polyether).
  • polyester eg, polybutylene terephthalate, polyethylene terephthalate, etc.
  • polyphenylene ether polyphenylene sulfide, total aromatic polyester, polysulfone, liquid crystal polymer, polyether sulfone, polycarbonate, maleimide-modified resin, ABS resin, AAS (acrylonitrile- Acrylic rubber / styrene) resin, AES (acrylonitrile / ethylene / propylene / diene rubber-styrene) resin and the like
  • silicone resin is preferable from the viewpoint of heat resistance, flexibility, and adhesion to a heat sink or the like.
  • the silicone resin is preferably one that is vulcanized with an organic peroxide and cured.
  • the viscosity of the thermally conductive resin composition at 25 ° C. is, for example, 100,000 cp or more from the viewpoint of improving the flexibility of the sheet-shaped molded product.
  • the content of the inorganic filler component in the total 100% by volume of the inorganic filler component and the resin component is preferably 30 to 85% by volume, more preferably 40 to 80% by volume.
  • the content of the inorganic filler component is 30% by volume or more, the thermal conductivity is improved and sufficient heat dissipation performance can be easily obtained.
  • the content of the inorganic filler component is 85% by volume or less, it is possible to reduce the tendency for voids to occur during molding, and it is possible to reduce the deterioration of insulating properties and mechanical strength.
  • the content of the resin component in 100% by volume of the heat conductive resin composition is preferably 15 to 70% by volume, more preferably 20 to 60% by volume.
  • the heat conductive resin composition may further contain a solvent.
  • the solvent is not particularly limited as long as it can dissolve the resin component and is easily removed from the applied heat conductive resin composition after the heat conductive resin composition is applied.
  • examples of the solvent include toluene, xylene, chlorine-based hydrocarbons, and the like. Toluene is preferred among these solvents from the viewpoint of easy removal.
  • the content of the solvent can be appropriately selected depending on the desired viscosity of the thermally conductive resin composition.
  • the content of the solvent is, for example, 40 to 200 parts by mass with respect to 100 parts by mass of the components other than the solvent of the heat conductive resin composition.
  • the thermally conductive resin composition may contain components other than the inorganic filler component, the resin component and the solvent.
  • the other components are additives, impurities, etc., and the content of the other components is preferably 5 parts by mass or less, more preferably 3 parts by mass, based on 100 parts by mass of the total of the inorganic filler component and the resin component. It is less than or equal to, more preferably 1 part by mass or less.
  • the heat dissipation sheet of the present invention is formed by molding the heat conductive resin composition of the present invention.
  • the thickness of the heat radiating sheet of the present invention is preferably 0.35 mm or less.
  • the thickness of the heat radiating sheet is more preferably 0.30 mm or less, further preferably 0.25 ⁇ m or less, still more preferably 0.20 ⁇ m or less, still more preferably 0. It is 15 mm or less, more preferably 0.12 mm or less, and particularly preferably 0.10 mm or less.
  • the heat dissipation sheet preferably contains a base material having a thickness of 0.05 mm or less.
  • the base material is not particularly limited as long as it can hold the heat conductive resin composition layer, has appropriate strength, has a thickness of 0.05 mm or less, and has flexibility.
  • Examples of the base material include paper, cloth, film, non-woven fabric, metal foil and the like. Among these, the viewpoint that the adhesiveness with the heat conductive resin composition layer is good and that the inhibition of heat conduction of the heat conductive resin composition by the base material can be suppressed by providing the opening portion.
  • cloth is preferable, and glass cloth and polyamide-imide fiber cloth are more preferable, and glass cloth is further preferable, from the viewpoint that the strength of the base material can be maintained to some extent even if the base material is thinned and the opening is widened. ..
  • the thickness of the base material is more preferably 0.03 mm or less.
  • the thickness of the base material is preferably 0.005 mm or more.
  • the heat dissipation sheet can be manufactured by the doctor blade method.
  • the heat dissipation sheet can be manufactured as follows. Raw materials other than the solvent such as the inorganic filler component and the resin component are dispersed in the solvent to prepare a slurry-like heat conductive resin composition.
  • the slurry-like thermally conductive resin composition may be simply referred to as “slurry”. Since the massive boron nitride particles used as the first inorganic filler have a high crushing strength of 6 MPa, the hexagonal boron nitride primary particles are hardly peeled off from the massive boron nitride particles when a raw material other than the solvent is dispersed in the solvent. ..
  • the viscosity of the slurry can also be reduced by increasing the amount of solvent.
  • the heat conductive resin composition when the heat conductive resin composition is molded into a sheet shape, the heat conductive resin composition foams, or when the solvent is removed from the molded body formed into the sheet shape, the heat conductive resin composition is contained. Since additives such as the vulcanizing agent and the curing agent may expire, it is desirable to reduce the viscosity of the slurry without increasing the amount of the solvent.
  • the inorganic filler dispersed after dispersing the raw materials other than the solvent of the heat conductive resin composition in the solvent. It is possible to prevent the components from aggregating and making the slurry non-uniform. If the average particle size of the inorganic filler is very small, the dispersed inorganic filler may aggregate and the slurry may become non-uniform.
  • the prepared slurry is supplied to the doctor blade device.
  • the doctor blade device flows out the slurry from the gap between the blade and the carrier film to form the thermally conductive resin composition into a sheet.
  • the thickness of the molded product can be accurately controlled by adjusting the dimensions between the blade and the carrier film and the moving speed of the carrier film. Further, in order to control the pressure of the slurry more accurately and control the thickness of the molded product more accurately, a doctor blade device having two blades may be used.
  • the slurry flowing out from the gap between the blade and the carrier film moves in the doctor blade device together with the carrier film, and while moving, it dries and solidifies to become a sheet-shaped molded product.
  • the obtained sheet-shaped molded product is, for example, pressurized and heated to be cured to obtain a heat-dissipating sheet.
  • a release agent may be applied to the surface of the carrier film so that the heat dissipation sheet can be easily peeled off from the carrier film.
  • the release agent include a silicone-based release agent, an alkyl pendant-based release agent, and a condensed wax-based release agent.
  • the heat dissipation sheet contains a base material
  • the heat dissipation sheet is manufactured as follows.
  • a laminated body is obtained by sandwiching a base material with two sheet-shaped molded bodies having a carrier film obtained by the doctor blade method.
  • the layer structure of the laminated body at this time is a carrier film / a heat conductive resin composition / a base material / a heat conductive resin composition / a carrier film.
  • the laminate is pressurized and heated, and the carrier film is peeled off to form a heat dissipation sheet.
  • a release agent may be applied to the surface of the carrier film so that the heat dissipation sheet can be easily peeled off from the carrier film.
  • the heat dissipation sheet can also be made by calendar processing.
  • the sheet-shaped heat conductive resin composition passes through the calendar roll, a part of the lumpy boron nitride particles may be peeled off from the lumpy boron nitride particles in the heat conductive resin composition. Therefore, it is preferable to manufacture the heat dissipation sheet by the doctor blade method.
  • particle size distribution Toluene was used to dissolve components other than the inorganic filler component of the heat conductive resin composition, and components other than the inorganic filler component were removed from the heat conductive resin composition.
  • the particle size distribution of the remaining inorganic filler component was measured using a laser diffraction / scattering method particle size distribution measuring device (LS-13 320) manufactured by Beckman Coulter Co., Ltd. Then, from the obtained particle size distribution, the first maximum value and the second maximum value, and the integrated amount of the frequency from the peak start to the peak end at the peak having the first maximum point were obtained.
  • the crushing strengths of the five inorganic filler components were weibull plotted according to JIS R1625, and the crushing strength at which the cumulative fracture rate was 63.2% was defined as the crushing strength of the first inorganic filler.
  • the crushing strength of the second inorganic filler was also measured by the same method.
  • Integrated amount of frequency of particle size of 0 to 15 ⁇ m Toluene was used to dissolve components other than the inorganic filler component of the heat conductive resin composition, and components other than the inorganic filler component were removed from the heat dissipation sheet. Then, the cumulative particle size of the remaining inorganic filler component was measured using a laser diffraction / scattering method particle size distribution measuring device manufactured by Beckman Coulter Co., Ltd. (LS-13 320). Then, the integrated amount of the frequency of the particle size of 0 to 15 ⁇ m was calculated from the obtained particle size integration.
  • Thermal resistance of the heat dissipation sheet was measured by applying a load of 1 MPa according to ASTM D5470.
  • Example 1 massive boron nitride particles were produced by boron carbide synthesis, pressure nitriding step, and decarburization crystallization step as follows.
  • Boric acid orthoboric acid
  • HS100 acetylene black
  • the synthesized boron carbide mass is pulverized with a ball mill for 1 hour, sieved to a particle size of 75 ⁇ m or less using a sieve net, washed with an aqueous nitrate solution to remove impurities such as iron, and then filtered and dried to have an average particle size of 20 ⁇ m.
  • Boron carbide powder was prepared. The carbon content of the obtained boron carbide powder was 20.0%.
  • Boron nitride (B 4 ) is obtained by filling the synthesized boron carbide into a crucible nitride and then heating it in a nitrogen gas atmosphere at 2000 ° C. and 9 atm (0.8 MPa) for 10 hours using a resistance heating furnace. CN 4 ) was obtained.
  • the synthesized massive boron nitride particles were decomposed and crushed by 15 with a Henshell mixer, and then classified with a nylon sieve having a sieve mesh of 150 ⁇ m using a sieve net. By crushing and classifying the fired product, agglomerated boron nitride particles 1 in which the primary particles were aggregated and agglomerated were obtained.
  • the average particle diameter (D50) of the obtained massive boron nitride particles 1 measured by the laser scattering method was 40 ⁇ m.
  • the crushing strength of the massive boron nitride particles 1 was 12 MPa.
  • Hardener (2,5-dimethyl-2,5-bis (t-butylperoxy) hexane, chemical agent Nourion Co., Ltd., trade name “Trigonox 101”), massive boron nitride particles, aggregated boron nitride particles and scaly nitride 0.5% by mass of silane coupling agent with respect to 100 parts by mass of total boron particles (dimethyldimethoxysilane, manufactured by Dow Toray Co., Ltd., trade name "DOWNSIL Z-6329 Silane", viscosity at 25 ° C.: 1 cp).
  • a slurry of the heat conductive resin composition was prepared by mixing for 15 hours using a turbine type stirring blade. The viscosity of the slurry was 10000 cp. Then, by the doctor blade method, the slurry is coated on a pet film (carrier film) having a thickness of 0.05 mm to a thickness of 0.2 mm, dried at 75 ° C. for 5 minutes, and formed into a sheet with a pet film.
  • the body was made.
  • a laminated body was prepared by sandwiching the glass cloth with a sheet-shaped molded body with a pet film so that the coated surface of the heat conductive resin composition was in contact with both sides of the glass cloth (thickness: 0.025 mm).
  • the layer structure of the laminated body was a pet film / a heat conductive resin composition / a glass cloth / a heat conductive resin composition / a pet film.
  • the obtained laminate was heated and pressed for 25 minutes under the conditions of a temperature of 150 ° C. and a pressure of 160 kg / cm 2 , and the pet films on both sides were peeled off to obtain a sheet having a thickness of 0.09 mm. Then, it was subjected to secondary heating at normal pressure at 150 ° C. for 4 hours to obtain a heat dissipation sheet of Example 1.
  • Example 2 The same as in Example 1 except that the blending amount of toluene was changed from 110 parts by mass to 60 parts by mass and the coating conditions of the doctor blade method were changed to prepare a heat radiating sheet having a thickness of 0.20 mm.
  • the heat dissipation sheet of No. 2 was produced.
  • the viscosity of the slurry was 7000 cp.
  • Example 3 The same as in Example 1 except that the blending amount of toluene was changed from 110 parts by mass to 50 parts by mass and the coating conditions of the doctor blade method were changed to prepare a heat radiating sheet having a thickness of 0.31 mm.
  • the heat dissipation sheet of No. 3 was produced.
  • the viscosity of the slurry was 8000 cp.
  • Example 4 Instead of blending 45% by volume of the massive boron nitride particles 1 having an average particle diameter of 40 ⁇ m and a crushing strength of 12 MPa, 42% by volume of the massive boron nitride particles 2 having an average particle diameter of 75 ⁇ m and a crushing strength of 12 MPa are blended. However, instead of blending 12% by volume of aggregated boron nitride particles, 11% by volume of massive boron nitride particles 3 having an average particle diameter of 38 ⁇ m and a crushing strength of 12 MPa were blended, and no scaly boron nitride particles were blended.
  • the heat radiating sheet of Example 4 was produced in the same manner as in Example 1 except that a heat radiating sheet having a thickness of 0.10 mm was produced.
  • the average particle size of the boron carbide powder was changed by changing the pulverization time of the synthesized boron carbide mass by a ball mill. It was produced by the same method as the massive boron nitride particles 1 used for the heat dissipation sheet of 1.
  • the viscosity of the slurry was 10000 cp.
  • Example 5 The heat radiating sheet of Example 5 was produced in the same manner as in Example 4 except that the coating conditions of the doctor blade method were changed to produce a heat radiating sheet having a thickness of 0.20 mm.
  • Example 6 The heat radiating sheet of Example 6 was produced in the same manner as in Example 4 except that the coating conditions of the doctor blade method were changed to produce a heat radiating sheet having a thickness of 0.27 mm.
  • Example 7 Instead of the massive boron nitride particles 2, the massive boron nitride particles 4 having an average particle diameter of 55 ⁇ m and a crushing strength of 10 MPa were blended, and the coating conditions of the doctor blade method were changed to dissipate heat with a thickness of 0.10 mm.
  • the heat dissipation sheet of Example 7 was produced in the same manner as in Example 1 except that the sheet was produced.
  • the massive boron nitride particles 4 used for the heat dissipation sheet of Example 7 were of Example 1 except that the crushing time of the synthesized boron carbide mass by a ball mill was changed to change the average particle size of the boron carbide powder. It was produced by the same method as the massive boron nitride particles 1 used for the heat dissipation sheet.
  • the viscosity of the slurry was 9500 cp.
  • Example 8 The heat radiating sheet of Example 8 was produced in the same manner as in Example 7 except that the coating conditions of the doctor blade method were changed to produce a heat radiating sheet having a thickness of 0.20 mm.
  • Example 9 The heat radiating sheet of Example 9 was produced in the same manner as in Example 7 except that the coating conditions of the doctor blade method were changed to produce a heat radiating sheet having a thickness of 0.28 mm.
  • Comparative Example 1 The point that the lumpy boron nitride particles 1 and the scaly boron nitride particles were not blended, the point that the blending amount of the aggregated boron nitride particles was changed from 12% by volume to 60% by volume, and the blending amount of the silane coupling agent was 0.5% by mass. Comparative Example 1 in the same manner as in Example 1 except that the portion was changed to 0.2 parts by mass and the coating conditions of the doctor blade method were changed to produce a heat radiating sheet having a thickness of 0.20 mm. A heat dissipation sheet was prepared. The viscosity of the slurry was 12000 cp. Further, since the viscosity of the slurry was high, it was not possible to produce a heat radiating sheet having a thickness of 0.15 mm or less.
  • Comparative Example 2 The heat radiating sheet of Comparative Example 2 was produced in the same manner as in Comparative Example 1 except that the coating conditions of the doctor blade method were changed to produce a heat radiating sheet having a thickness of 0.30 mm.
  • Example 3 A slurry was prepared in the same manner as in Example 7 except that the massive boron nitride particles 3 were changed to the massive boron nitride particles 1. However, since the viscosity of the slurry was as high as 16000 cp, it was not possible to produce a heat radiating sheet having a thickness of 0.20 mm.
  • Example 4 Same as Example 1 except that the blending amount of the massive boron nitride particles 1 was changed from 45% by volume to 12% by volume and the blending amount of the aggregated boron nitride particles was changed from 12% by volume to 45% by volume. To prepare a slurry. However, since the viscosity of the slurry was as high as 18000 cp, it was not possible to produce a heat radiating sheet having a thickness of 0.20 mm.
  • Table 1 shows the evaluation results of the heat dissipation sheets of Examples 1 to 9 and Comparative Examples 1 to 4.
  • Example 10 The silicone resin CF3110 was changed to an epoxy resin (bisphenol type epoxy resin manufactured by Mitsubishi Chemical Co., Ltd., model number; JER-807), and the curing agent Trigonox 101 (1 part by mass) was replaced with a curing agent MEH-8005 (manufactured by Meiwa Kasei Co., Ltd., 10).
  • a 0.2 mm heat dissipation sheet was prepared in the same manner as in Example 5 except that 2PHZ-PW (manufactured by Shikoku Kasei Co., Ltd., 1 material section) was added as a curing accelerator. It was measured by the method described above.
  • Example 10 Comparing the thermal resistance of Example 10 and the thermal resistance of Comparative Example 5, the thermal resistance of Example 10 was lower, which was a good result. Therefore, the effect obtained by combining a specific inorganic filler can be obtained regardless of the type of resin.

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US20230220263A1 (en) 2023-07-13
CN115698187A (zh) 2023-02-03
JP7541090B2 (ja) 2024-08-27
US12305113B2 (en) 2025-05-20

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