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WO2024204441A1 - Composition thermoconductrice - Google Patents

Composition thermoconductrice Download PDF

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Publication number
WO2024204441A1
WO2024204441A1 PCT/JP2024/012455 JP2024012455W WO2024204441A1 WO 2024204441 A1 WO2024204441 A1 WO 2024204441A1 JP 2024012455 W JP2024012455 W JP 2024012455W WO 2024204441 A1 WO2024204441 A1 WO 2024204441A1
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WIPO (PCT)
Prior art keywords
thermally conductive
volume
sheet
filler
silicone
Prior art date
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PCT/JP2024/012455
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English (en)
Japanese (ja)
Inventor
祐希 細川
史博 向
憲太郎 荒
琢哉 北爪
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Bando Chemical Industries Ltd
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Bando Chemical Industries Ltd
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Application filed by Bando Chemical Industries Ltd filed Critical Bando Chemical Industries Ltd
Priority to JP2024520808A priority Critical patent/JP7606050B1/ja
Publication of WO2024204441A1 publication Critical patent/WO2024204441A1/fr
Priority to JP2024216506A priority patent/JP2025038048A/ja
Anticipated expiration legal-status Critical
Pending legal-status Critical Current

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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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/34—Arrangements for cooling, heating, ventilating or temperature compensation ; Temperature sensing arrangements
    • H01L23/36—Selection of materials, or shaping, to facilitate cooling or heating, e.g. heatsinks
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/34—Arrangements for cooling, heating, ventilating or temperature compensation ; Temperature sensing arrangements
    • H01L23/36—Selection of materials, or shaping, to facilitate cooling or heating, e.g. heatsinks
    • H01L23/373—Cooling facilitated by selection of materials for the device or materials for thermal expansion adaptation, e.g. carbon

Definitions

  • the present invention relates to a thermally conductive composition.
  • This application claims priority based on Japanese Application No. 2023-053524 filed on March 29, 2023, and incorporates by reference all of the contents of the above-mentioned Japanese application.
  • a heat-generating component such as an IC chip is usually attached to a heat-dissipating component such as a heat sink via a thermal interface material (TIM).
  • TIM thermal interface material
  • the heat generated by the heat-generating component is conducted to the heat-dissipating component via the thermal conductive material.
  • thermally conductive material for example, a thermally conductive sheet has been proposed in which spherical alumina and carbon fibers are mixed as thermally conductive fillers in a resin matrix (see Patent Documents 1 and 2).
  • a thermally conductive sheet is a component that is required to have excellent thermal conductivity, and the thermal conductivity can be increased by increasing the amount of thermally conductive filler blended in. On the other hand, if the thermally conductive sheet contains an increased amount of thermally conductive filler, the sheet becomes hard.
  • the thermally conductive sheet used for the IC chip is attached to the IC chip while applying a predetermined compressive load. The harder the thermally conductive sheet is, the greater the compressive load that needs to be applied when attaching the thermally conductive sheet to the IC chip.
  • Thermal conductive sheets may also be attached so as to simultaneously cover multiple heat generating components such as IC chips.
  • the shapes of the heat generating components are usually not the same, so the thermal conductive sheet is required to be able to deform in accordance with the different shapes of each of the heat generating components.
  • the inventors of the present invention conducted extensive research under these circumstances and have completed a thermally conductive composition that has excellent thermal conductivity, easily conforms to the shape of heat-generating components such as IC chips, and reduces the load on the heat-generating components.
  • a thermally conductive composition according to one embodiment of the present invention is a sheet-shaped thermally conductive composition comprising a resin composition containing silicone and a thermally conductive filler, When compressed and deformed by 50%, the initial compressive load value is 1.0 N/mm2 or less, and the ratio of the compressive load value after 1 minute to the initial compressive load value is 0.5 or less; The apparent thermal conductivity when compressed and deformed by 20% is 22.8 W/mK or more.
  • the thermally conductive composition according to one embodiment of the present invention has high thermal conductivity.
  • the thermally conductive composition is easily deformed so as to conform to the shape of a heat generating component such as an IC chip.
  • a heat generating component such as an IC chip.
  • FIG. 1 is a cross-sectional view showing a schematic diagram of an IC chip to which a heat sink is attached via a sheet-shaped thermally conductive composition according to an embodiment of the present invention.
  • Fig. 2A is a perspective view showing an example of a sheet-shaped thermally conductive composition according to an embodiment of the present invention
  • Fig. 2B is a partially enlarged view of the cross section taken along line AA in Fig. 2A.
  • FIG. 3 is a schematic cross-sectional view of the tip portion of an extruder and a T-die used in the production of a sheet-shaped thermally conductive composition according to this embodiment.
  • 4A to 4D are diagrams illustrating another example of the method for producing a sheet-shaped thermally conductive composition according to an embodiment of the present invention.
  • 5A to 5C are diagrams for explaining the evaluation method of the tracking ability in the examples and comparative examples.
  • a sheet-shaped thermally conductive composition comprising a resin composition containing silicone and a thermally conductive filler, When compressed and deformed by 50%, the initial compressive load value is 1.0 N/mm2 or less, and the ratio of the compressive load value after 1 minute to the initial compressive load value is 0.5 or less;
  • a thermally conductive composition having an apparent thermal conductivity of 22.8 W/mK or more when compressed and deformed by 20%.
  • This sheet-shaped thermally conductive composition has high thermal conductivity and can reduce the load on the heat-generating component after installation. It also easily conforms to the shape of the heat-generating component when installed. Furthermore, even if the heat-generating component deforms due to heat after installation, it can follow the deformation.
  • the compressive load value after 1 minute is preferably 0.4 N/ mm2 or less. In this case, it is possible to prevent a high load from being continuously applied to the IC chip after attachment.
  • the resin composition preferably contains polydimethylsiloxane as the silicone.
  • the resin composition contains, as the thermally conductive filler, an anisotropic thermally conductive filler and a non-anisotropic thermally conductive filler.
  • the resin composition preferably contains, as the thermally conductive filler, a fibrous filler, a scaly filler, and a spherical filler.
  • resin compositions are suitable as resin compositions for forming thermally conductive sheets that have high thermal conductivity and can reduce the load on IC chips.
  • the resin composition preferably contains carbon fibers, flake graphite powder, and spherical zinc oxide particles as a thermally conductive filler.
  • zinc oxide particles are contained as a thermally conductive filler, the thermal conductivity of the sheet-shaped thermally conductive composition is easier to increase than when alumina particles are contained.
  • carbon fiber and flake graphite powder are used in combination as a thermally conductive filler, it is easier to increase the thermal conductivity while reducing the initial load of the sheet-like thermally conductive composition compared to when only one of carbon fiber and flake graphite powder is contained.
  • the total content of the carbon fibers, the scaly graphite powder, and the spherical zinc oxide particles is preferably 50 volume % or more and 70 volume % or less.
  • the content of the carbon fibers is preferably 30 volume % or more and 45 volume % or less.
  • the "sheet-shaped thermally conductive composition” includes both a block-shaped product obtained after molding by extrusion molding or the like, and cut products (including sliced sheet-shaped products) obtained by appropriately cutting the block-shaped product.
  • cut products including sliced sheet-shaped products
  • an embodiment of the sheet-shaped thermally conductive composition will be described using a sliced sheet as an example.
  • the sheet-shaped thermally conductive composition according to the present embodiment is a member provided between an IC chip and a heat sink.
  • the thermally conductive composition is made of a resin composition containing silicone and a thermally conductive filler.
  • silicone is a polymer compound having a main skeleton formed by siloxane bonds.
  • Fig. 1 is a cross-sectional view showing an IC chip to which a heat sink is attached via a sheet-shaped thermally conductive composition according to an embodiment of the present invention.
  • Fig. 2A is a perspective view showing an example of a sheet-shaped thermally conductive composition according to an embodiment of the present invention.
  • Fig. 2B is a partially enlarged view of the cross section taken along line A-A in Fig. 2A. It should be noted that all of the drawings in this application are schematic diagrams and do not accurately reflect the actual dimensions of each component.
  • thermally conductive sheet 1 a sheet-like thermally conductive composition 1 (hereinafter also referred to as thermally conductive sheet 1) is placed between an IC chip 11 and a heat sink 12.
  • the thermally conductive sheet 1 is used with one side in contact with the IC chip 11 and the other side in contact with the heat sink 12.
  • the heat sink 12 is attached to the IC chip 11 via the thermally conductive sheet 1. Therefore, the heat generated by the IC chip 11 is dissipated by the heat sink 12 to the outside of the housing (not shown).
  • FIG. 1 shows a usage example of a thermally conductive sheet 1 attached to the upper surface of a single IC chip 11.
  • the sheet-shaped thermally conductive composition may be a thermally conductive sheet that is attached so as to simultaneously cover heat-generating components such as multiple IC chips.
  • the initial compressive load value is 1.0 N/mm2 or less.
  • a predetermined load is applied to press the thermally conductive sheet 1 onto the IC chip 11. If the flexibility of the thermally conductive sheet 1 is insufficient, the thermally conductive sheet 1 and the IC chip 11 may not adhere to each other, and gaps may occur at the interface between them. Furthermore, when a single thermally conductive sheet 1 is attached to cover multiple heat-generating components at the same time, it may not be possible to follow the shapes of all the heat-generating components, and gaps may occur between any of the heat-generating components.
  • the thermally conductive sheet 1 has an initial compressive load value of 1.0 N/mm2 or less , it can often be appropriately attached to an IC chip or the like within the range of the allowable compressive load value set for each IC chip. Furthermore, when the thermally conductive sheet 1 has an initial compressive load value of 1.0 N/mm2 or less and is attached to cover multiple heat-generating components simultaneously, it is easy for the sheet to conform to the shape of each heat-generating component.
  • the initial compressive load value is preferably 0.7 N/ mm2 or less, which is more suitable for closely adhering the thermally conductive sheet to the IC chip without applying a load to the IC chip.
  • the initial compressive load value is usually 0.1 N/mm 2 or more, but may be less than 0.1 N/mm 2 .
  • the thermally conductive sheet 1 has a ratio of a compressive load value after 1 minute has elapsed since it was compressed by 50% in the thickness direction (hereinafter referred to as a compressive load value after 1 minute) to the initial compressive load value of 0.5 or less.
  • the thermally conductive sheet 1 is easily deformed according to the shape of the IC chip 11. Therefore, when attached to the IC chip 11, it can follow the shape of the IC chip 11. It is particularly suitable for attachment so as to simultaneously cover multiple heat generating components. Furthermore, when the IC chip 11 is deformed by heat, the thermally conductive sheet 1 is easily deformed to follow the deformation. Furthermore, it is possible to prevent the IC chip from being subjected to a continuous high load.
  • the compressive load value after 1 minute of the thermal conductive sheet 1 is preferably 0.4 N/mm 2 or less.
  • the thermally conductive sheet 1 is attached to the IC chip 11 with a predetermined load applied thereto, and then the load is sufficiently released, thereby making it possible to prevent the IC chip 11 from being subjected to a large load for a long period of time.
  • the compressive load value after the lapse of one minute is more preferably 0.2 N/mm2 or less , and particularly preferably 0.15 N/mm2 or less .
  • the compressive load value after one minute has elapsed may be any value that allows the thermally conductive composition to maintain its sheet-like shape.
  • the initial compressive load value when the thermally conductive sheet 1 is compressed and deformed by 50% in the thickness direction is measured using a universal testing machine (e.g., Instron 5969 (manufactured by Instron)) as a measuring device, compressing the thermally conductive sheet 1 in the thickness direction to a thickness of "thickness before measurement x 0.5" at a compression speed of 5 mm/min, and measuring the load value at that time. Furthermore, the compressive load value per unit area ( mm2 ) is calculated based on the obtained measured value. The compressive load value after one minute is measured by measuring the load value after leaving the specimen for one minute in the state where the initial compressive load value was measured (a state where the specimen is compressed and deformed by 50% in the thickness direction). Based on the measured values, the compressive load value per unit area ( mm2 ) is calculated.
  • a universal testing machine e.g., Instron 5969 (manufactured by Instron)
  • the thermally conductive sheet 1 has an apparent thermal conductivity of 22.8 W/mK or more when compressed and deformed by 20% in the thickness direction. If the apparent thermal conductivity is less than 22.8 W/mK, the thermal conductivity is insufficient.
  • the above-mentioned apparent thermal conductivity of the thermally conductive sheet 1 is preferably 26.6 W/mK or more.
  • the apparent thermal conductivity of the thermal conductive sheet 1 can be calculated based on the thermal resistance value ( Kcm2 /W) measured when the sheet is compressed to a thickness of "thickness before measurement x 0.8" (20% compression) and the thickness (cm) of the thermal conductive sheet at the time of measurement, according to the following calculation formula (1).
  • the thermal resistance value when compressed and deformed by 20% is measured using a thermal conductivity measuring device (e.g., TIMtester 1400 (manufactured by AnalysisTech)) with the thermal conductive sheet 1 compressed and deformed by 20%.
  • a thermal conductivity measuring device e.g., TIMtester 1400 (manufactured by AnalysisTech)
  • the thickness of the thermally conductive sheet 1 is not particularly limited, but is, for example, 0.05 mm or more and 3.0 mm or less. In this case, the thermally conductive sheet 1 can be suitably used as a member that efficiently transfers heat between the IC chip 11 and the heat sink 12.
  • the thickness of the thermally conductive sheet 1 is preferably 0.05 mm or more and 2.5 mm or less. This allows for better heat dissipation performance while ensuring conformability to the shapes of the IC chip 11 and the heat sink 12.
  • the thickness of the thermally conductive sheet 1 is less than 0.05 mm, it may not be possible to fully conform to the shapes of the IC chip 11 and the heat sink 12. Also, if the thickness exceeds 2.5 mm, the heat dissipation performance may be poor due to the thermal resistance of the sheet itself.
  • the thermally conductive sheet 1 has a rectangular shape in a plan view, for example.
  • the vertical and horizontal dimensions of the thermally conductive sheet 1 may be determined taking into consideration the dimensions of the member to which the thermally conductive sheet 1 is attached, such as the IC chip 11, and for example, both the vertical and horizontal dimensions are independently 10 mm or more and 120 mm or less.
  • the planar shape of the thermal conductive sheet 1 is not limited to a rectangle, and may be a shape other than a rectangle, such as a circle or an ellipse. In the case of a circle, the diameter is, for example, 10 mm or more and 120 mm or less. In the case of an ellipse, the major axis or minor axis is, for example, 10 mm or more and 120 mm or less.
  • the thermally conductive sheet 1 contains a matrix component 2 and a thermally conductive filler 4.
  • the components other than the thermally conductive filler are collectively referred to as matrix components.
  • weld lines may be formed in the thickness direction.
  • the matrix component 2 contains silicone, so that the thermally conductive sheet 1 has excellent heat resistance.
  • the silicone may contain a cross-linked product of silicone (hereinafter also referred to as cross-linked silicone), but from the viewpoint of easily ensuring good flexibility, it is preferable that the main component is uncross-linked silicone.
  • containing uncrosslinked silicone as a main component means that the proportion of uncrosslinked silicone in the total silicone is 50 mass % or more.
  • the silicone may be composed solely of uncrosslinked silicone. By using uncrosslinked silicone as the main component, the load after attachment to an IC chip or the like can be easily released.
  • polydimethylsiloxane which is a silicone in which all side chains are methyl groups and which does not contain unsaturated groups
  • the silicone preferably contains 50% by mass or more of the polydimethylsiloxane, more preferably 70% by mass or more, even more preferably 80% by mass or more, and particularly preferably 90% by mass or more.
  • the polydimethylsiloxane is a polymer that is poorly reactive and has excellent stability, and therefore, by increasing the proportion of the polydimethylsiloxane in the silicone, the flexibility of the thermally conductive sheet 1 can be improved.
  • the polydimethylsiloxane may be oil or millable type, but millable type polydimethylsiloxane is preferred because it has good moldability when manufacturing the thermally conductive sheet 1 by the method described below.
  • the molecular weight of the polydimethylsiloxane is preferably 60,000 or more and 700,000 or less in terms of mass average molecular weight MW.
  • mass average molecular weight MW of the polydimethylsiloxane is less than 60,000, the polydimethylsiloxane tends to bleed out from the thermal conductive sheet 1.
  • mass average molecular weight MW of the polydimethylsiloxane exceeds 700,000, the moldability and processability during production of the thermal conductive sheet 1 tend to be poor.
  • the mass average molecular weight MW of polydimethylsiloxane is the mass average molecular weight measured using gel permeation chromatography (GPC) with polystyrene as the standard substance in accordance with JIS-K7252-1:2008 "Plastics - Determination of average molecular weight and molecular weight distribution of polymers by size exclusion chromatography - Part 1: General rules.”
  • the kinetic viscosity of the polydimethylsiloxane is preferably 10,000 cps or more and 100,000 cps or less at 25° C. as measured with an Ubbelohde viscometer. If the kinetic viscosity is less than 10,000 cps, polydimethylsiloxane will easily bleed from the thermally conductive sheet 1. On the other hand, if the kinetic viscosity is more than 100,000 cps, the hardness of the thermally conductive sheet 1 will increase, and when the thermally conductive sheet 1 is disposed between an IC chip and a heat sink, the sheet may have poor adhesion and conformability to the contact surfaces with the IC chip and the heat sink.
  • the crosslinked silicone may be one that has been crosslinked by peroxide crosslinking or one that has been crosslinked by an addition reaction type crosslinking, but one that has been crosslinked by peroxide crosslinking is preferred, because crosslinked silicone crosslinked by peroxide crosslinking has better heat resistance.
  • the crosslinked silicone may be, for example, a crosslinked silicone having a crosslinkable functional group such as a vinyl group in part of the side chain (including the terminal).
  • the silicone may contain silicone having a crosslinkable functional group such as a vinyl group in an uncrosslinked state.
  • the matrix component 2 may contain other elastomer components, etc., to the extent that the required properties of the thermally conductive sheet 1 are not impaired.
  • the matrix component 2 may contain general additives such as a flame retardant, a reinforcing agent, a filler, a softener, a plasticizer, an antioxidant, a tackifier, an antistatic agent, a kneading adhesive, and a coupling agent.
  • a flame retardant include magnesium hydroxide, aluminum hydroxide, platinum compounds, triazole compounds, iron oxides such as red iron oxide and black iron oxide, etc. These may be used alone or in combination of two or more kinds.
  • the magnesium hydroxide can also function as a thermally conductive filler.
  • the matrix component 2 preferably contains a coupling agent such as a silane coupling agent as an additive.
  • a coupling agent such as a silane coupling agent
  • zinc oxide particles when contained as the thermally conductive filler, it is preferable that the matrix component 2 contains a silane coupling agent.
  • silane coupling agent examples include methyltrimethoxysilane, ethyltrimethoxysilane, propyltrimethoxysilane, butyltrimethoxysilane, pentyltrimethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, octyltrimethoxysilane, octyltriethoxysilane, decyltrimethoxysilane, decyltriethoxysilane, dodecyltrimethoxysilane, dodecyltriethoxysilane, hexadecyltrimethoxysilane, hexadecyltriethoxysilane, octadecyltrimethoxysilane, octadecyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryl
  • the thermally conductive sheet 1 contains a thermally conductive filler 4 .
  • the thermally conductive filler 4 preferably contains an anisotropic thermally conductive filler (hereinafter also referred to as an anisotropic filler) and a non-anisotropic thermally conductive filler (hereinafter also referred to as a non-anisotropic filler).
  • anisotropic thermally conductive filler hereinafter also referred to as an anisotropic filler
  • a non-anisotropic thermally conductive filler hereinafter also referred to as a non-anisotropic filler
  • an anisotropic filler refers to a filler having an aspect ratio of 2.0 or more
  • a non-anisotropic filler refers to a filler having an aspect ratio of less than 2.0
  • the aspect ratio of the thermally conductive filler refers to the larger of the ratio of the major axis of the filler to the minor axis of the filler and the ratio of the major axis of the filler to the thickness of the filler.
  • the above-mentioned major axis, minor axis, and thickness correspond to the length, width, and height, respectively, of the circumscribed rectangular solid of the filler.
  • the anisotropic filler includes fibrous filler, scaly filler, plate-like filler, thin flake filler, and the like.
  • the aspect ratio of the anisotropic filler is preferably 5.0 or more.
  • the non-anisotropic filler includes spherical fillers, irregular fillers, and the like.
  • the thermally conductive sheet 1 preferably contains, as the thermally conductive filler, a fibrous filler, a scaly filler, and a spherical filler. In this case, the thermally conductive sheet 1 is more likely to satisfy the above-mentioned predetermined compressive load characteristics and thermal resistance value.
  • the content of the fibrous filler is preferably greater than the content of the scaly filler and the content of the spherical filler. In this case, it is also easy to reduce the compressive load value while increasing the thermal conductivity.
  • the amount of scaly filler is greater than the amount of fibrous filler, it is difficult to suppress the compressive load value, and if the amount of spherical filler is greater than the amount of fibrous filler, it is difficult to increase the thermal conductivity.
  • the thermally conductive sheet 1 preferably contains, as the thermally conductive filler, carbon fibers 4C, scaly graphite powder 4G, and spherical zinc oxide particles 4Z.
  • the thermally conductive sheet 1 has the carbon fibers 4C and the graphite powder 4G oriented substantially in the thickness direction of the thermally conductive sheet 1, and the zinc oxide particles 4Z dispersed throughout the thermally conductive sheet 1.
  • the thermally conductive sheet 1 having such a configuration is particularly suitable for increasing the thermal conductivity while suppressing the initial load of the sheet-like thermally conductive composition.
  • the fiber length of the carbon fibers 4C is preferably 20 ⁇ m or more. If the fiber length is less than 20 ⁇ m, it may be difficult to form a heat conduction path, and the heat conductivity of the heat conductive sheet 1 may be poor. On the other hand, a preferable upper limit of the fiber length of the carbon fiber 4C is 500 ⁇ m from the viewpoint of ease of filling the thermally conductive sheet with the carbon fiber. The fiber length of the carbon fiber 4C is more preferably 50 ⁇ m or more and 300 ⁇ m or less.
  • the fiber diameter of the carbon fibers 4C is preferably 5 ⁇ m or more. If the fiber diameter is less than 5 ⁇ m, a heat conduction path is difficult to form, and the heat conductivity of the heat conductive sheet 1 may be poor.
  • a preferred upper limit of the fiber diameter of the carbon fibers 4C is 20 ⁇ m from the viewpoint of processability when producing the thermal conductive sheet 1 .
  • the fiber length of a fibrous filler such as carbon fiber refers to the arithmetic mean value of the length in the fiber direction determined using a microscopic image of the fibrous filler.
  • the fiber diameter of a fibrous filler refers to the arithmetic mean value of the dimension in the radial direction determined using a microscopic image of the fibrous filler. The fiber length and fiber diameter are determined by obtaining a microscopic image of the fibrous filler, randomly selecting 20 fibrous fillers from the image, measuring the length in the fiber direction and the dimensions in the radial direction of the selected fibrous fillers, and then based on the measurement results.
  • carbon fiber 4C one type of carbon fiber may be used, or two or more types of carbon fibers may be used. Carbon fibers with different thermal conductivities may be used in combination as the carbon fibers 4C. When carbon fibers with high thermal conductivity are used, the thermal conductivity increases, but the initial compression load value required for 50% compression deformation also tends to increase. Therefore, by using carbon fibers with different thermal conductivities in combination, it becomes easier to adjust the thermal conductivity and the initial compression load value of the thermal conductive sheet 1.
  • the graphite powder 4G is preferably in the form of a flake, which is suitable for orienting the powder in the thickness direction of the thermally conductive sheet 1 to enhance the thermal conductivity in the thickness direction.
  • the graphite powder 4G may contain graphite powder other than flake-like graphite powder. A combination of a flake-like graphite powder and a non-flake-like graphite powder may be used.
  • the particle size of the flake graphite powder 4G is preferably 5 ⁇ m or more and 50 ⁇ m or less. If the particle size of the flake graphite powder 4G is less than 5 ⁇ m, it is difficult to form a heat conduction path in the thermal conductive sheet 1. On the other hand, if the particle size of the flake graphite powder 4G exceeds 50 ⁇ m, it is difficult to pack densely.
  • the particle size of the flake graphite powder 4G is preferably 10 ⁇ m or more and 30 ⁇ m or less.
  • the particle size of a scaly filler refers to the maximum length D50 (50% median diameter) in the plate surface direction determined using a microscope image for measuring the particle size of the scaly filler.
  • the above particle size is determined by obtaining a microscopic image for measuring the particle size of the scaly filler, randomly selecting 20 scaly fillers from the image, measuring the maximum length of the selected scaly fillers in the plate surface direction, and then based on the measurement results.
  • the zinc oxide particles 4Z are preferably spherical in shape. In this case, it is easier to fill the thermal conductive sheet 1 with zinc oxide particles 4Z compared to other shapes, and the zinc oxide particles 4Z are less likely to damage components of the manufacturing equipment.
  • the particle size of the zinc oxide particles 4Z is preferably 0.1 ⁇ m or more and 10 ⁇ m or less. If the particle size of the zinc oxide particles 4Z is less than 0.1 ⁇ m, it is difficult to form a heat conduction path. On the other hand, if the particle size of the zinc oxide particles 4Z exceeds 10 ⁇ m, the orientation of the carbon fibers 4C and the scaly graphite powder 4G is easily hindered. In addition, the zinc oxide particles 4Z are more likely to damage the steel components of the manufacturing equipment.
  • the particle size of thermally conductive fillers other than fibrous fillers and scaly fillers refers to the median diameter (d50) measured using a laser diffraction/scattering method.
  • thermally conductive filler 4 contains carbon fibers 4C, scaly graphite powder 4G, and spherical zinc oxide particles 4Z
  • a preferred content of the thermally conductive filler 4 in the thermally conductive sheet 1 is such that the total content of the carbon fibers 4C, scaly graphite powder 4G, and spherical zinc oxide particles 4Z is 50 volume % or more and 70 volume % or less. If the total content of the carbon fibers 4C, the scaly graphite powder 4G, and the spherical zinc oxide particles 4Z is less than 50% by volume, sufficient thermal conductivity may not be ensured.
  • the thermal conductive sheet 1 becomes too hard and may not be able to be properly attached to an IC chip with an allowable compression load value.
  • the thermal conductive sheet 1 becomes too hard and may not be able to be properly attached to an IC chip with an allowable compression load value.
  • the thermal conductive sheet 1 is preferably 55% by volume or more and 70% by volume or less, which is more suitable for achieving both good thermal conductivity and appropriate hardness.
  • the content of the carbon fibers 4C in the thermally conductive sheet 1 is preferably 30% by volume or more and 45% by volume or less, which is suitable for ensuring good thermal conductivity of the thermally conductive sheet 1.
  • the content of graphite powder 4G is preferably 5 volume % or more and 10 volume % or less.
  • the total content of the scaly graphite powder 4G and the spherical zinc oxide particles 4Z in the thermal conductive sheet 1 is preferably 20% by volume or more and 30% by volume or less. In this case, it is more suitable to lower the compressive load value required for 50% compressive deformation while maintaining good thermal conductivity. More preferably, it is from 25 volume % to 30 volume %.
  • an example of a particularly suitable configuration of the thermally conductive filler 4 is, for example, Contains carbon fiber 4C, flake graphite powder 4G, and spherical zinc oxide particles 4Z;
  • the total content of the carbon fibers 4C, the scaly graphite powder 4G, and the spherical zinc oxide particles 4Z is 50% by volume or more and 70% by volume or less,
  • the content of carbon fiber 4C is 30% by volume or more and 40% by volume or less,
  • the content of the scaly graphite powder 4G is 5% by volume or more and 10% by volume or less,
  • the total content of the scaly graphite powder 4G and the spherical zinc oxide particles 4Z is 25 volume % or more and 30 volume % or less.
  • the thermally conductive sheet 1 can be produced, for example, by a first production method including the following steps (a) to (c). (a) preparing a silicone-based composition containing uncrosslinked silicone, carbon fiber, graphite powder, zinc oxide particles, and optional ingredients such as a flame retardant and a coupling agent; (b) molding the prepared silicone-based composition; and (c) A step of slicing the molded silicone composition into sheets.
  • step (a) of preparing a silicone-based composition is carried out.
  • uncrosslinked silicone, thermally conductive filler (carbon fiber, graphite powder, and zinc oxide particles), and further various additives added as necessary are kneaded together using a twin roll to prepare a silicone-based composition.
  • some or all of the components may be supplied in the form of a compound.
  • FIG. 3 is a schematic cross-sectional view of the tip portion of an extruder and a T-die used in the production of a thermally conductive sheet 1 according to an embodiment of the present invention.
  • the silicone composition fed into the extruder 30 is stirred and kneaded by the screw 34 and introduced into a first gap 32 of a T-die along a flow path 31 .
  • the silicone-based composition that has been stirred and kneaded in the extruder 30 is first squeezed in the vertical direction (thickness direction) by the first gap 32 into a thin strip shape.
  • the anisotropic thermally conductive filler mixed in the silicone-based composition is oriented in the flow direction (extrusion direction) of the silicone-based composition. Therefore, in the thin resin sheet 40 molded by passing through the first gap 32, the anisotropic thermally conductive filler is oriented in the plane direction of the resin sheet 40.
  • carbon fibers or scaly graphite powder corresponds to the anisotropic thermally conductive filler.
  • the flow direction of the sheet which was limited to the extrusion direction, is released and the flow direction changes to a direction approximately perpendicular to the extrusion direction.
  • the resin sheet 40 whose flow direction has changed to a direction approximately perpendicular to the extrusion direction, passes completely through the first gap 32, and is then further extruded toward the second gap 33.
  • the resin sheet 40 now approximately perpendicular to the extrusion direction, is folded and stacked in the second gap 33.
  • anisotropic thermally conductive filler carbon fiber and flake-like graphite powder
  • the anisotropic thermally conductive filler in the resin sheet 40 stacked in the second gap 33 is oriented along the thickness direction (the vertical direction in FIG. 3).
  • step (b) the silicone composition is extruded to form a resin sheet 40 in which the anisotropic thermally conductive filler is oriented in the extrusion direction, and then the resin sheet 40 is folded and laminated to produce a block.
  • step (c) the block in which the thin resin sheets 40 are laminated is sliced in a direction perpendicular to the thickness direction, resulting in a thermally conductive sheet 1 having a predetermined thickness and in which the anisotropic thermally conductive filler is substantially oriented in the thickness direction.
  • the block of resin sheet 40 produced in step (b) itself can also be used as a sheet-like thermally conductive sheet according to an embodiment of the present invention.
  • the depth of the first gap 32 and the second gap 33 (i.e., the dimensions of the first gap 32 and the second gap 33 in the direction perpendicular to the paper surface in FIG. 3) is substantially the same throughout the entire T-die. Furthermore, the dimensions of the depth of the first gap and the second gap are not particularly limited, and various design changes are possible depending on the product width of the thermally conductive sheet 1 to be manufactured.
  • the method for producing the thermally conductive sheet 1 is not limited to the first production method described above, and may be, for example, a second production method in which the following steps (d) to (f) are carried out.
  • 4A to 4D are diagrams illustrating the second manufacturing method.
  • step (d) of preparing a silicone-based composition is carried out.
  • uncrosslinked silicone, thermally conductive filler (carbon fiber, graphite powder, and zinc oxide particles), and various additives added as necessary are kneaded with two rolls 51.
  • a sheet is formed to prepare a resin sheet 50 (see FIG. 4A).
  • some or all of the components may be supplied in the form of a compound.
  • step (e) is carried out to mold the silicone composition.
  • the resin sheets 50 made of the silicone-based composition are folded and laminated so that the resin sheets 50 are in close contact with each other (see FIG. 4A ).
  • a laminate in which the resin sheets 50 are laminated while being folded can be obtained.
  • the anisotropic thermally conductive filler is oriented in the plane direction of the resin sheet 50 .
  • the folded-back portion of the resin sheet 50 is cut and removed using a cutter 54 (see FIG. 4B). As a result, a laminate 55 of a plurality of resin sheets 50 that are not connected to one another is obtained.
  • a step (f) is performed in which the obtained laminate 55 is sliced in a direction perpendicular to the surface direction of the resin sheet 50 using a cutter 57 (see FIG. 4C ). This allows the thermally conductive sheet 1 to be obtained (see FIG. 4D ). The thermally conductive sheet 1 can also be manufactured through such steps.
  • Silicone A polydimethylsiloxane with a mass average molecular weight of 140,000
  • Silicone B vinyl group-containing compound (MR-53, manufactured by Dow Toray Industries, Inc.) Peroxide: (Dow Toray Co., Ltd., RC-4 50P FD) mixture Silane coupling agent: octyltrimethoxysilane
  • Carbon fiber A Mitsubishi Chemical Corporation, K223HM (fibrous, fiber length: 200 ⁇ m / fiber diameter: 11 ⁇ m) Carbon fiber B: Mitsubishi Chemical Corporation, K23EHM (fibrous, fiber length: 200 ⁇ m / fiber diameter: 11 ⁇ m) Carbon fiber C: Mitsubishi Chemical Corporation, K223HM (fibrous, fiber length: 50 ⁇ m / fiber diameter: 11 ⁇ m)
  • Graphite powder Nippon Graphite Industries Co., Ltd., CPB (flake-like, particle size: 22 ⁇ m)
  • Zinc oxide particles Zinc oxide type 1 (spherical, particle size: 0.8 ⁇ m), manufactured by Sakai Chemical Industry Co., Ltd.
  • Alumina particles A DAW-03 (spherical, particle size: 5 ⁇ m), manufactured by Denka Co., Ltd.
  • Alumina particles B ASFP-09S (spherical, particle size: 1 ⁇ m), manufactured by Denka Co., Ltd.
  • Alumina particles C AP10 (scale-shaped, particle size: 10 ⁇ m), manufactured by DIC Corporation
  • Example 1 the thermally conductive sheet 1 was manufactured by the second manufacturing method. 100 parts by mass of silicone A (polydimethylsiloxane having a mass average molecular weight of 140,000), 117 parts by mass of carbon fiber A, 60 parts by mass of carbon fiber B, 60 parts by mass of graphite powder, 304 parts by mass of zinc oxide particles, and 3.8 parts by mass of a silane coupling agent were kneaded with two rolls 51 and then sheeted out to produce a resin sheet 50 made of a silicone-based composition having a thickness of approximately 1.0 to 1.2 mm.
  • silicone A polydimethylsiloxane having a mass average molecular weight of 140,000
  • 117 parts by mass of carbon fiber A 60 parts by mass of carbon fiber B
  • 60 parts by mass of graphite powder 60 parts by mass of graphite powder
  • 304 parts by mass of zinc oxide particles 304 parts by mass of zinc oxide particles
  • 3.8 parts by mass of a silane coupling agent were kneaded with two rolls
  • the volume fraction of carbon fiber A relative to the entire resin sheet 50 is 20 volume %
  • the volume fraction of carbon fiber B is 10 volume %
  • the volume fraction of graphite powder is 10 volume %
  • the volume fraction of zinc oxide particles is 20 volume %
  • the total volume fraction of the thermally conductive filler is 60 volume %.
  • the prepared resin sheet 50 is folded and laminated so that the sheets are in close contact with each other (see FIG. 4A). At this time, the carbon fibers A and B and the graphite powder are oriented in the plane direction of the laminated resin sheet 50.
  • the folded-back portion of the resin sheet 50 is cut and removed with a cutter 54.
  • the laminate 55 was sliced in a direction perpendicular to the surface direction of the resin sheet 50 (see FIG. 4C) to obtain a thermally conductive sheet 1 having a thickness of 2 mm and in which the carbon fibers and graphite powder are oriented in the thickness direction (see FIG. 4D).
  • Example 2 A thermally conductive sheet was completed in the same manner as in Example 1, except that a resin sheet 50 made of a silicone-based composition having a thickness of about 1.0 to 1.2 mm was prepared by the following method. 100 parts by mass of silicone A, 118 parts by mass of carbon fiber A, 60 parts by mass of carbon fiber B, 60 parts by mass of graphite powder, 305 parts by mass of zinc oxide particles, 4.0 parts by mass of silane coupling agent, and 16 parts by mass of magnesium hydroxide were kneaded with two rolls 51 and then sheeted out to produce a resin sheet 50 made of a silicone-based composition having a thickness of approximately 1.0 to 1.2 mm.
  • the volume fraction of carbon fiber A relative to the entire resin sheet 50 is 20 volume %
  • the volume fraction of carbon fiber B is 10 volume %
  • the volume fraction of graphite powder is 10 volume %
  • the volume fraction of zinc oxide particles is 20 volume %
  • the volume fraction of magnesium hydroxide is 2.5 volume %
  • the total volume fraction of the thermally conductive fillers is 62.5 volume %.
  • Example 3 A thermally conductive sheet was completed in the same manner as in Example 1, except that a resin sheet 50 made of a silicone-based composition having a thickness of about 1.0 to 1.2 mm was prepared by the following method. 100 parts by weight of silicone A, 202 parts by weight of carbon fiber A, 67 parts by weight of carbon fiber B, 34 parts by weight of graphite powder, 348 parts by weight of zinc oxide particles, and 4.5 parts by weight of silane coupling agent were kneaded using two rolls to produce a resin sheet 50 having a thickness of approximately 1.0 to 1.2 mm.
  • the volume fraction of carbon fiber A relative to the entire resin sheet 50 is 30 volume %
  • the volume fraction of carbon fiber B is 10 volume %
  • the volume fraction of graphite powder is 5 volume %
  • the volume fraction of zinc oxide particles is 20 volume %
  • the total volume fraction of the thermally conductive filler is 65 volume %.
  • Example 4 A thermally conductive sheet was completed in the same manner as in Example 1, except that a resin sheet 50 made of a silicone-based composition having a thickness of about 1.0 to 1.2 mm was prepared by the following method. 100 parts by weight of silicone A, 232 parts by weight of carbon fiber A, 34 parts by weight of carbon fiber B, 66 parts by weight of graphite powder, 257 parts by weight of zinc oxide particles, and 3.5 parts by weight of silane coupling agent were kneaded using two rolls to produce a resin sheet 50 having a thickness of approximately 1.0 to 1.2 mm.
  • the volume fraction of carbon fiber A relative to the entire resin sheet 50 is 35 volume %
  • the volume fraction of carbon fiber B is 5 volume %
  • the volume fraction of graphite powder is 10 volume %
  • the volume fraction of zinc oxide particles is 15 volume %
  • the total volume fraction of the thermally conductive filler is 65 volume %.
  • Example 5 A thermally conductive sheet was completed in the same manner as in Example 1, except that a resin sheet 50 made of a silicone-based composition having a thickness of about 1.0 to 1.2 mm was prepared by the following method. 100 parts by mass of silicone A, 90 parts by mass of carbon fiber A, 60 parts by mass of carbon fiber B, 60 parts by mass of graphite powder, 380 parts by mass of zinc oxide particles, and 4.5 parts by mass of a silane coupling agent were kneaded using two rolls to produce a resin sheet 50 having a thickness of approximately 1.0 to 1.2 mm.
  • the volume fraction of carbon fiber A relative to the entire resin sheet 50 is 15 volume %
  • the volume fraction of carbon fiber B is 10 volume %
  • the volume fraction of graphite powder is 10 volume %
  • the volume fraction of zinc oxide particles is 25 volume %
  • the total volume fraction of the thermally conductive filler is 60 volume %.
  • Example 6 A thermally conductive sheet was completed in the same manner as in Example 1, except that a resin sheet 50 made of a silicone-based composition having a thickness of about 1.0 to 1.2 mm was prepared by the following method. 100 parts by weight of silicone A, 137 parts by weight of carbon fiber A, 45 parts by weight of carbon fiber B, 142 parts by weight of zinc oxide particles, and 2.0 parts by weight of silane coupling agent were kneaded using two rolls to produce a resin sheet 50 having a thickness of approximately 1.0 to 1.2 mm.
  • the volume fraction of carbon fiber A relative to the entire resin sheet 50 is 37.5 volume %
  • the volume fraction of carbon fiber B is 12.5 volume %
  • the volume fraction of zinc oxide particles is 15 volume %
  • the total volume fraction of the thermally conductive filler is 65 volume %.
  • Example 7 A thermally conductive sheet was completed in the same manner as in Example 1, except that a resin sheet 50 made of a silicone-based composition having a thickness of about 1.0 to 1.2 mm was prepared by the following method. 100 parts by mass of silicone A, 355 parts by mass of carbon fiber A, 40 parts by mass of graphite powder, 410 parts by mass of zinc oxide particles, and 5.0 parts by mass of a silane coupling agent were kneaded with two rolls 51 and then sheeted out to produce a resin sheet 50 made of a silicone-based composition having a thickness of approximately 1.0 to 1.2 mm.
  • the volume fraction of carbon fiber A relative to the entire resin sheet 50 is 45 volume %
  • the volume fraction of graphite powder is 5 volume %
  • the volume fraction of zinc oxide particles is 20 volume %
  • the total volume fraction of the thermally conductive filler is 70 volume %.
  • Example 1 A thermally conductive sheet was completed in the same manner as in Example 1, except that a resin sheet 50 made of a silicone-based composition having a thickness of about 1.0 to 1.2 mm was prepared by the following method. 100 parts by weight of silicone A, 135 parts by weight of carbon fiber A, 45 parts by weight of carbon fiber B, 185 parts by weight of zinc oxide particles, and 2.0 parts by weight of silane coupling agent were kneaded using two rolls to produce a resin sheet 50 having a thickness of approximately 1.0 to 1.2 mm.
  • the volume fraction of carbon fiber A relative to the entire resin sheet 50 is 37.5 volume %
  • the volume fraction of carbon fiber B is 12.5 volume %
  • the volume fraction of zinc oxide particles is 20 volume %
  • the total volume fraction of the thermally conductive filler is 70 volume %.
  • Example 2 A thermally conductive sheet was completed in the same manner as in Example 1, except that a resin sheet 50 made of a silicone-based composition having a thickness of about 1.0 to 1.2 mm was prepared by the following method. 100 parts by weight of silicone A, 335 parts by weight of carbon fiber A, 25 parts by weight of graphite powder, 320 parts by weight of alumina particles A, 105 parts by weight of alumina particles B, and 2.5 parts by weight of silane coupling agent were kneaded using two rolls to produce a resin sheet 50 having a thickness of approximately 1.0 to 1.2 mm.
  • the volume fraction of carbon fiber A relative to the entire resin sheet 50 is 40 volume %
  • the volume fraction of graphite powder is 3 volume %
  • the volume fraction of alumina particles A is 22.5 volume %
  • the volume fraction of alumina particles B is 7.5 volume %
  • the total volume fraction of the thermally conductive filler is 73 volume %.
  • Example 3 A thermally conductive sheet was completed in the same manner as in Example 1, except that a resin sheet 50 made of a silicone-based composition having a thickness of about 1.0 to 1.2 mm was prepared by the following method. 110 parts by weight of silicone A, 87 parts by weight of graphite powder, 190 parts by weight of alumina particles B, and 2.0 parts by weight of a silane coupling agent were kneaded with two rolls to prepare a resin sheet 50 having a thickness of about 1.0 to 1.2 mm.
  • the volume fraction of the graphite powder relative to the entire resin sheet 50 is 27 volume %
  • the volume fraction of the alumina particles B is 36 volume %
  • the total volume fraction of the thermally conductive filler is 63 volume %.
  • Example 4 A thermally conductive sheet was completed in the same manner as in Example 1, except that a resin sheet 50 made of a silicone-based composition having a thickness of about 1.0 to 1.2 mm was prepared by the following method. 100 parts by weight of silicone A, 1.6 parts by weight of silicone B, 0.7 parts by weight of peroxide, 180 parts by weight of carbon fiber C, and 80 parts by weight of alumina particles C were kneaded using two rolls to produce a resin sheet 50 having a thickness of approximately 1.0 to 1.2 mm.
  • the volume fraction of the carbon fibers C relative to the entire resin sheet 50 is 40 volume %
  • the volume fraction of the alumina particles C is 10 volume %
  • the total volume fraction of the thermally conductive filler is 50 volume %.
  • FIGS. 5A to 5C are diagrams for explaining a method for evaluating tracking ability.
  • the thermally conductive sheets produced in the examples and comparative examples were further cut into evaluation samples 71 each having a length of 40 mm, a width of 40 mm and a thickness of 2 mm.
  • the conformability of the evaluation sample 71 was evaluated by the following method. The results are shown in Table 1.
  • the evaluation sample 71 is placed on the lower glass plate 72.
  • An aluminum plate 75 having a length of 10 mm, a width of 10 mm, and a thickness of 1 mm is placed on the center of the upper surface of the evaluation sample 71.
  • the upper glass plate 73 is placed on the aluminum plate 75 (see FIG. 5A).
  • FIG. 5C is an enlarged view of the vicinity of region A in FIG. 5B.
  • A The maximum width of the opening was less than 1000 ⁇ m.
  • ⁇ The maximum width of the opening was 1000 ⁇ m or more.
  • Thermally conductive sheet sheet-shaped thermally conductive composition
  • matrix component thermally conductive filler
  • thermally conductive filler 4C carbon fiber
  • graphite powder 4Z zinc oxide powder
  • IC chip 12 heat sink 30 extruder 31 flow path 32 first gap 33 second gap 34 screw 40, 50 resin sheet 51, 52 53 Table 54, 57 Cutter 55 Laminate 71 Evaluation sample 72 Lower glass plate 73 Upper glass plate 75 Aluminum plate 77 Indentation

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Abstract

L'invention concerne une composition thermoconductrice stratiforme comprenant une composition de résine contenant une silicone et une charge thermoconductrice. Lorsqu'elle est soumise à une déformation par compression de 50 %, la valeur de charge de compression initiale est égale ou inférieure à 1,0 N/mm2 et le rapport de la valeur de charge de compression au bout d'une minute à la valeur de charge de compression initiale est égale ou inférieure à 0,5. La thermoconductivité apparente lorsqu'elle est soumise à une déformation par compression de 20 % est égale ou supérieure à 22,8 W/mK.
PCT/JP2024/012455 2023-03-29 2024-03-27 Composition thermoconductrice Pending WO2024204441A1 (fr)

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Citations (10)

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Publication number Priority date Publication date Assignee Title
JP2005072220A (ja) * 2003-08-25 2005-03-17 Shin Etsu Chem Co Ltd 放熱部材
JP2009197052A (ja) * 2008-02-19 2009-09-03 Asahi Kasei E-Materials Corp 樹脂組成物
JP2010007039A (ja) * 2008-05-26 2010-01-14 Sekisui Chem Co Ltd 熱伝導シート
WO2017179318A1 (fr) * 2016-04-11 2017-10-19 ポリマテック・ジャパン株式会社 Feuille conductrice de la chaleur
WO2020149335A1 (fr) * 2019-01-17 2020-07-23 バンドー化学株式会社 Feuille thermoconductrice
WO2020179115A1 (fr) * 2019-03-07 2020-09-10 富士高分子工業株式会社 Feuille thermoconductrice et son procédé de production
WO2020196477A1 (fr) * 2019-03-26 2020-10-01 三菱ケミカル株式会社 Feuille de résine thermoconductrice, feuille de dissipation de chaleur stratifiée, carte de circuit imprimé à dissipation de chaleur, et dispositif à semi-conducteurs de puissance
JP2020176182A (ja) * 2019-04-16 2020-10-29 信越化学工業株式会社 自己粘着性を有する異方性熱伝導性シート
JP2022037609A (ja) * 2020-08-25 2022-03-09 デクセリアルズ株式会社 熱伝導性シート及び熱伝導性シートの製造方法
WO2023182268A1 (fr) * 2022-03-25 2023-09-28 バンドー化学株式会社 Feuille thermoconductrice

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005072220A (ja) * 2003-08-25 2005-03-17 Shin Etsu Chem Co Ltd 放熱部材
JP2009197052A (ja) * 2008-02-19 2009-09-03 Asahi Kasei E-Materials Corp 樹脂組成物
JP2010007039A (ja) * 2008-05-26 2010-01-14 Sekisui Chem Co Ltd 熱伝導シート
WO2017179318A1 (fr) * 2016-04-11 2017-10-19 ポリマテック・ジャパン株式会社 Feuille conductrice de la chaleur
WO2020149335A1 (fr) * 2019-01-17 2020-07-23 バンドー化学株式会社 Feuille thermoconductrice
WO2020179115A1 (fr) * 2019-03-07 2020-09-10 富士高分子工業株式会社 Feuille thermoconductrice et son procédé de production
WO2020196477A1 (fr) * 2019-03-26 2020-10-01 三菱ケミカル株式会社 Feuille de résine thermoconductrice, feuille de dissipation de chaleur stratifiée, carte de circuit imprimé à dissipation de chaleur, et dispositif à semi-conducteurs de puissance
JP2020176182A (ja) * 2019-04-16 2020-10-29 信越化学工業株式会社 自己粘着性を有する異方性熱伝導性シート
JP2022037609A (ja) * 2020-08-25 2022-03-09 デクセリアルズ株式会社 熱伝導性シート及び熱伝導性シートの製造方法
WO2023182268A1 (fr) * 2022-03-25 2023-09-28 バンドー化学株式会社 Feuille thermoconductrice

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