WO2023190751A1 - Feuille thermoconductrice, et procédé de production d'une feuille thermoconductrice - Google Patents

Feuille thermoconductrice, et procédé de production d'une feuille thermoconductrice Download PDF

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Publication number
WO2023190751A1
WO2023190751A1 PCT/JP2023/012964 JP2023012964W WO2023190751A1 WO 2023190751 A1 WO2023190751 A1 WO 2023190751A1 JP 2023012964 W JP2023012964 W JP 2023012964W WO 2023190751 A1 WO2023190751 A1 WO 2023190751A1
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Prior art keywords
thermally conductive
conductive sheet
sheet
less
molded body
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PCT/JP2023/012964
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English (en)
Japanese (ja)
Inventor
栄治 太田
圭佑 武笠
佑介 久保
育巳 佐藤
雅彦 伊東
セルゲイ ボロトフ
直哉 大野
大地 森
真理奈 戸端
義知 宮崎
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デクセリアルズ株式会社
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Priority claimed from JP2023053547A external-priority patent/JP2023152951A/ja
Publication of WO2023190751A1 publication Critical patent/WO2023190751A1/fr

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    • 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
    • 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
    • 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

Definitions

  • the present technology relates to a thermally conductive sheet and a method for manufacturing a thermally conductive sheet.
  • This application is based on Japanese Patent Application No. 2022-058407 filed in Japan on March 31, 2022 and Japanese Patent Application No. 2023-053547 filed in Japan on March 29, 2023. These applications are incorporated by reference into this application.
  • thermally conductive sheets that meet such requirements include thermally conductive sheets using anisotropic thermally conductive materials (see, for example, Patent Documents 1 to 6).
  • Carbon fiber which is an example of an anisotropic thermally conductive material, is an anisotropic filler having a thermal conductivity of about 600 to 1200 W/(m ⁇ K) in the fiber direction. It is known that thermal conductivity can be dramatically improved by orienting the fiber direction of carbon fibers in the thickness direction of a thermally conductive sheet, which is the direction of heat transfer.
  • thermally conductive sheet with oriented carbon fibers In order to achieve low thermal resistance using a thermally conductive sheet with oriented carbon fibers, it is also important to consider the contact thermal resistance of the thermally conductive sheet. However, even if carbon fibers have high thermal conductivity, when viewed from the entire thermally conductive sheet, the contact between the adherend and the carbon fibers is point contact, and even if the carbon fibers sink into the binder resin due to pressure, There is a problem that air gets mixed in between the thermally conductive sheet and the adherend.
  • thermal resistance is thermal resistance that occurs between a thermally conductive sheet and an adherend.
  • the contact thermal resistance tends to increase as the thickness decreases, and as a result, the total thermal resistance value (thermal conduction The thermal resistance value (the sum of the thermal resistance value of the sheet itself plus the contact thermal resistance value) also tends to increase.
  • the present technology has been proposed in view of such conventional circumstances, and provides a thermally conductive sheet with a reduced total thermal resistance value.
  • the inventors of the present application have determined whether or not to suppress the average height Spk of the protruding peaks in a thermally conductive sheet containing an anisotropic thermally conductive material, an inorganic filler, and a binder resin. , or suppress the value of the average height Spk of the protruding peaks relative to the sum (Spk+Svk) of the average height Spk of the protruding peaks and the average depth Svk of the protruding valleys, and also suppress the root mean square gradient of the protruding peaks. It has been found that the above-mentioned problems can be solved by suppressing Sdq.
  • This technology is a thermally conductive sheet made of a cured product of a thermally conductive composition containing an anisotropic thermally conductive material, an inorganic filler, and a binder resin.
  • the average height Spk of the protruding peaks of the thermally conductive sheet is less than 3.5 ⁇ m, as measured using a microscope according to ISO 25178.
  • This technology is a thermally conductive sheet made of a cured product of a thermally conductive composition containing an anisotropic thermally conductive material, an inorganic filler, and a binder resin.
  • the volume Vmp of the protruding peaks of the thermally conductive sheet is 0.16 ml/m 2 or less, as measured using a microscope according to ISO 25178.
  • This technology is a thermally conductive sheet made of a cured product of a thermally conductive composition containing an anisotropic thermally conductive material, an inorganic filler, and a binder resin.
  • the value of the average height Spk of the protruding peaks (Spk/( Spk+Svk)) is 40% or less, and the root mean square gradient Sdq of the thermally conductive sheet is 1.1 or less.
  • the method for manufacturing a thermally conductive sheet involves molding a thermally conductive composition containing an anisotropic thermally conductive material, an inorganic filler, and a binder resin into a predetermined shape and curing it to form a thermally conductive sheet. a step of slicing the thermally conductive molded object into sheet shapes to obtain a sheet-like molded object; and a step of polishing the surface of the sheet-like molded object to obtain a thermally conductive sheet.
  • the step of obtaining a thermally conductive sheet the surface of the sheet-like molded body is polished so that the surface of the thermally conductive sheet satisfies Condition 1 below.
  • Condition 1 The average height Spk of the protruding peaks is less than 3.5 ⁇ m, as measured in accordance with ISO 25178 using a scanning white interference microscope with a 20x objective lens.
  • the method for manufacturing a thermally conductive sheet involves molding a thermally conductive composition containing an anisotropic thermally conductive material, an inorganic filler, and a binder resin into a predetermined shape and curing it to form a thermally conductive sheet. a step of slicing the thermally conductive molded object into sheet shapes to obtain a sheet-like molded object; and a step of polishing the surface of the sheet-like molded object to obtain a thermally conductive sheet.
  • the step of obtaining a thermally conductive sheet the surface of the sheet-like molded body is polished so that the surface of the thermally conductive sheet satisfies Condition 2 below.
  • the volume Vmp of the protruding peak is 0.16 ml/m 2 or less, as measured in accordance with ISO 25178 using a scanning white interference microscope with a 20x objective lens.
  • the method for manufacturing a thermally conductive sheet involves molding a thermally conductive composition containing an anisotropic thermally conductive material, an inorganic filler, and a binder resin into a predetermined shape and curing it to form a thermally conductive sheet. a step of slicing the thermally conductive molded object into sheet shapes to obtain a sheet-like molded object; and a step of polishing the surface of the sheet-like molded object to obtain a thermally conductive sheet. In the step of obtaining a thermally conductive sheet, the surface of the sheet-like molded body is polished so that the surface of the thermally conductive sheet satisfies Condition 3 below.
  • the present technology can provide a thermally conductive sheet with a reduced total thermal resistance value.
  • FIG. 1 is a sectional view showing an example of a thermally conductive sheet.
  • FIG. 2 is a cross-sectional view showing an example of the surface of a thermally conductive sheet.
  • FIG. 3 is a perspective view of a brush that is an example of a polishing member.
  • FIG. 4 is a perspective view for explaining an example of a method of polishing the surface of a sheet-like molded body with a brush.
  • FIG. 5 is a perspective view for explaining an example of a method of continuously polishing the surfaces of a plurality of sheet-like molded bodies with a brush.
  • FIG. 6 is a cross-sectional view showing an example of a semiconductor device to which a thermally conductive sheet is applied.
  • FIG. 1 is a sectional view showing an example of a thermally conductive sheet.
  • FIG. 2 is a cross-sectional view showing an example of the surface of a thermally conductive sheet.
  • FIG. 3 is a perspective view of a brush that is an example
  • the average particle diameter (D50) refers to the cumulative value when a cumulative curve of particle diameter values is calculated from the small particle diameter side of the particle diameter distribution, assuming that the entire particle diameter distribution is 100%. This refers to the particle diameter when 50%.
  • the particle size distribution (particle size distribution) in this specification is determined on a volume basis. Examples of methods for measuring particle size distribution include a method using a laser diffraction type particle size distribution analyzer.
  • FIG. 1 is a sectional view showing an example of a thermally conductive sheet 1 according to the present technology.
  • the thermally conductive sheet 1 is made of a cured product of a thermally conductive composition containing a binder resin 2, an anisotropic thermally conductive material 3, and an inorganic filler 4 other than the anisotropic thermally conductive material 3.
  • the thermally conductive sheet 1 has an anisotropic thermally conductive material 3 and an inorganic filler 4 dispersed in a binder resin 2, and the anisotropic thermally conductive material 3 is oriented in the thickness direction B of the thermally conductive sheet 1. There is.
  • the fact that the anisotropic thermally conductive material 3 is oriented in the thickness direction B of the thermally conductive sheet 1 means that, for example, out of all the anisotropic thermally conductive materials 3 in the thermally conductive sheet 1, the The proportion of the anisotropic thermally conductive material 3 whose long axis is oriented in the thickness direction B of the conductive sheet 1 is 50% or more, may be 55% or more, or may be 60% or more, It may be 65% or more, 70% or more, 80% or more, 90% or more, 95% or more, 99% or more. It's okay.
  • the long axis of the anisotropic thermally conductive material 3 is oriented in the thickness direction B of the thermally conductive sheet 1. It may be in the range of 60 to 120 degrees with respect to A, it may be in the range of 70 to 100 degrees, or it may be 90 degrees (substantially perpendicular).
  • a thermally conductive sheet 1 which is a first embodiment of the present technology, is made of a cured product of a thermally conductive composition containing an anisotropic thermally conductive material 3, an inorganic filler 4, and a binder resin 2.
  • the average height Spk of the protruding peaks is less than 3.5 ⁇ m, as measured in accordance with ISO 25178 using a scanning white interference microscope with a 20x lens (hereinafter also referred to as satisfying Condition 1).
  • the thermally conductive sheet 1 increases the contact area between the thermally conductive sheet 1 and the adherend, and prevents air from entering between the thermally conductive sheet 1 and the adherend. Therefore, the contact thermal resistance can be reduced, and as a result, the total thermal resistance value can be reduced.
  • a thermally conductive sheet 1 according to a second embodiment of the present technology is made of a cured product of a thermally conductive composition containing an anisotropic thermally conductive material 3, an inorganic filler 4, and a binder resin 2.
  • the volume Vmp of the protruding peak measured according to ISO 25178 using a scanning white interference microscope with a 20x lens is 0.16 ml/m 2 or less (hereinafter also referred to as satisfying condition 2).
  • satisfying condition 2 the thermally conductive sheet 1 increases the contact area between the thermally conductive sheet 1 and the adherend, and prevents air from entering between the thermally conductive sheet 1 and the adherend. Therefore, the contact thermal resistance can be reduced, and as a result, the total thermal resistance value can be reduced.
  • a thermally conductive sheet 1 according to a third embodiment of the present technology is made of a cured product of a thermally conductive composition containing an anisotropic thermally conductive material 3, an inorganic filler 4, and a binder resin 2.
  • the ratio of the protruding peaks to the sum of the average height Spk of the protruding peaks and the average depth Svk of the protruding valleys (Spk+Svk), which is measured according to ISO 25178 using a scanning white interference microscope with a 20x lens.
  • the value of the average height Spk (Spk/(Spk+Svk)) is 40% or less, and the root mean square gradient Sdq is 1.1 or less (hereinafter also referred to as satisfying condition 3).
  • the thermally conductive sheet 1 increases the contact area between the thermally conductive sheet 1 and the adherend, and prevents air from entering between the thermally conductive sheet 1 and the adherend. Therefore, the contact thermal resistance can be reduced, and as a result, the total thermal resistance value can be reduced.
  • the thermally conductive sheet 1 satisfies at least one of Conditions 1 to 3, may satisfy two of Conditions 1 to 3, and may satisfy all of Conditions 1 to 3. It's okay. Further, it is preferable that the thermally conductive sheet 1 further satisfies the conditions described below in addition to conditions 1 to 3.
  • the thermally conductive sheet 1 may have an average height Spk of the protruding peaks of 3.0 ⁇ m or less as measured in accordance with ISO 25178 using a scanning white interference microscope with a 20x objective lens; 2. It may be 6 ⁇ m or less, 2.2 ⁇ m or less, 1.5 ⁇ m or less, 1.0 ⁇ m or less, 0.9 ⁇ m or less, 0. It may be 8 ⁇ m or less, 0.7 ⁇ m or less, 0.6 ⁇ m or less, or 0.5 ⁇ m or less.
  • the lower limit of the average height Spk of the protruding peaks of the thermally conductive sheet 1 is not particularly limited, but may be, for example, 0.4 ⁇ m or more.
  • the average height Spk of the protruding peaks of the thermally conductive sheet 1 may be in the range of 0.494 to 2.967 ⁇ m, may be in the range of 0.494 to 2.642 ⁇ m, and may be in the range of 0.494 to 2.642 ⁇ m. ⁇ 2.342 ⁇ m, 0.494 ⁇ 2.189 ⁇ m, 0.494 ⁇ 2.153 ⁇ m, 0.494 ⁇ 0.562 ⁇ m It may be a range. It is preferable that the average height Spk of the protruding peaks on at least one surface of the thermally conductive sheet 1 satisfies the above-mentioned range, and the average height Spk of the protruding peaks on both surfaces may satisfy the above-mentioned range.
  • the average height Spk of the protruding peaks of the thermally conductive sheet 1 can be measured by the method described in Examples described below. Note that the average height Spk of the protruding peaks and each value measured according to ISO 25178, which will be described later, is affected by the magnification of the objective lens of the scanning white interference microscope.
  • the thermally conductive sheet 1 may have a volume Vmp of the protruding peaks of 0.15 ml/m 2 or less as measured in accordance with ISO 25178 using a scanning white interference microscope with an objective lens set at a magnification of 20 times. .14ml/ m2 or less, 0.11ml/ m2 or less, 0.08ml/ m2 or less, 0.06ml/ m2 or less , 0.04 ml/m 2 or less, or 0.02 ml/m 2 or less.
  • the lower limit of the volume Vmp of the protruding peaks of the thermally conductive sheet 1 is not particularly limited, and may be, for example, 0.01 ml/m 2 or more, or 0.02 ml/m 2 or more.
  • the volume Vmp of the protruding peak portion may be in the range of 0.027 to 0.137 ml/ m2 , or may be in the range of 0.027 to 0.134 ml/ m2 . It may be in the range of 0.027 to 0.114 ml/ m2 , it may be in the range of 0.027 to 0.106 ml/ m2 , or it may be in the range of 0.027 to 0.102 ml/m2. It may be in the range of 2 .
  • the volume Vmp of the protruding peaks on at least one surface of the thermally conductive sheet 1 satisfies the above-mentioned range, and the volume Vmp of the protruding peaks on both surfaces may satisfy the above-mentioned range.
  • the thermally conductive sheet 1 may have (Spk/(Spk+Svk)) of 36% or less, 30% or less, or 29% or less.
  • the lower limit of (Spk/(Spk+Svk)) of the thermally conductive sheet 1 is not particularly limited, and may be, for example, 10% or more, 15% or more, or 20% or more. It may be 25% or more.
  • (Spk/(Spk+Svk)) of the thermally conductive sheet 1 may be in the range of 28.22 to 45.29%, or may be in the range of 28.22 to 39.78%, for example.
  • the thermally conductive sheet 1 may be in the range of 28.22 to 39.69%, may be in the range of 28.22 to 35.27%, or may be in the range of 28.22 to 34.90%. .
  • Spk/(Spk+Svk) on at least one surface satisfies the above-mentioned range, and Spk/(Spk+Svk) on one surface and the other surface may satisfy the above-mentioned range.
  • the average depth Svk of the protruding valleys may be 5.5 ⁇ m or less, or 4.5 ⁇ m or less. It may be 4.0 ⁇ m or less, 3.5 ⁇ m or less, 3.0 ⁇ m or less, 2.5 ⁇ m or less, 2.0 ⁇ m or less, The thickness may be 1.5 ⁇ m or less, or 1.1 ⁇ m or less.
  • the lower limit of the average depth Svk of the protruding valleys of the thermally conductive sheet 1 is not particularly limited, and may be, for example, 1.0 ⁇ m or more.
  • the average depth Svk of the protruding valleys of the thermally conductive sheet 1 may be in the range of 1.165 to 5.156 ⁇ m, may be in the range of 1.165 to 4.490 ⁇ m, and may be in the range of 1.165 to 4.490 ⁇ m. 4.291 ⁇ m, 1.165 to 3.711 ⁇ m, and 1.165 to 3.559 ⁇ m. It is preferable that the average depth Svk of the protruding troughs on at least one surface of the thermally conductive sheet 1 satisfies the above-mentioned range, and the average depth Svk of the protruding troughs on both surfaces may satisfy the above-mentioned range.
  • the average depth Svk of the protruding valleys of the thermally conductive sheet 1 can be measured by the method described in Examples described below.
  • the root mean square gradient Sdq of the thermally conductive sheet 1 is the local unevenness of the surface of the thermally conductive sheet 1 measured in accordance with ISO 25178 using a scanning white interference microscope with a 20x objective lens. Represents the average size of the slope (differential of shape). For example, when the surface of the thermally conductive sheet 1 is completely flat, the root mean square gradient Sdq is zero. Moreover, the steeper the surface of the thermally conductive sheet 1 is, the larger the root mean square gradient Sdq becomes.
  • the thermally conductive sheet 1 may have a root mean square gradient Sdq of 1.0 or less, 0.9 or less, 0.8 or less, or 0.7 or less. It may be 0.6 or less, 0.5 or less, or 0.4 or less.
  • the lower limit of the root mean square gradient Sdq of the thermally conductive sheet 1 is not particularly limited, and may be, for example, 0.1 or more, or 0.2 or more.
  • the root mean square gradient Sdq of the thermally conductive sheet 1 may be in the range of 0.278 to 1.074, may be in the range of 0.278 to 0.733, or may be 0.278. 0.730, 0.278 to 0.578, or 0.278 to 0.565. It is preferable that the root mean square gradient Sdq of at least one surface of the thermally conductive sheet 1 satisfies the above range, and the root mean square gradient Sdq of both surfaces may satisfy the above range.
  • the thermally conductive sheet 1 has an arithmetic mean curvature Spc (1/mm) of the mountain peak and a developed area ratio Sdr ( %), and when a graph is created in which the values are plotted with Spc on the horizontal axis and Sdr on the vertical axis, it is preferable that Spc and Sdr satisfy the following formula 1. In this manner, the thermally conductive sheet 1 satisfies Expression 1 in addition to Conditions 1 to 3, thereby making it possible to more effectively reduce the total thermal resistance value.
  • Formula 1: Y 0.0143X-(12.329 ⁇ 10)
  • the developed area ratio Sdr of the interface of the thermally conductive sheet 1 is measured according to ISO 25178, and represents how much the developed area (surface area) of the defined region increases relative to the area of the defined region. . For example, when the surface of the thermally conductive sheet 1 is completely flat, the developed area ratio Sdr of the interface is 0%.
  • the thermally conductive sheet 1 preferably has an interface developed area ratio Sdr of 40% or less, may be 35% or less, may be 30% or less, may be 25% or less, It may be 20% or less, 19% or less, or 18% or less.
  • the lower limit of the developed area ratio Sdr of the interface of the thermally conductive sheet 1 is not particularly limited, and may be, for example, 0% or more, 2% or more, or 10% or more. Good too.
  • the developed area ratio Sdr of the interface of the thermally conductive sheet 1 may be in the range of 0 to 45.00%, 0 to 40.00%, or 3.45 to 45.00%, for example.
  • the developed area ratio Sdr of the interface on at least one surface of the thermally conductive sheet 1 satisfies the above range, and the developed area ratio Sdr of the interfaces on both surfaces may satisfy the above range.
  • the arithmetic mean curvature Spc of the peak of the thermally conductive sheet 1 is measured according to ISO 25178 using a scanning white interference microscope with a 20x objective lens. Represents the average of the principal curvatures of points.
  • the larger the arithmetic mean curvature Spc of the peak of the thermally conductive sheet 1 the sharper the point of contact with another object on the thermally conductive sheet.
  • the arithmetic mean curvature Spc of the peak of the thermally conductive sheet 1 is preferably 3500 (1/mm) or less, may be 3200 (1/mm) or less, and may be 2800 (1/mm) or less. 2500 (1/mm) or less, 2100 (1/mm) or less, 1700 (1/mm) or less, 1500 (1/mm) or less It may be 1200 (1/mm) or less, or 1000 (1/mm) or less.
  • the lower limit of the arithmetic mean curvature Spc of the peak of the thermally conductive sheet 1 is not particularly limited, and may be, for example, 0 (1/mm) or more, or 500 (1/mm) or more. However, it may be 900 (1/mm) or more.
  • the arithmetic mean curvature Spc of the peak of the thermally conductive sheet 1 may be, for example, in the range of 0 to 3500 (1/mm), or may be in the range of 927 to 3136 (1/mm), It may be in the range of 927 to 2475 (1/mm), it may be in the range of 927 to 2290 (1/mm), it may be in the range of 927 to 2066 (1/mm), or it may be in the range of 927 to 2066 (1/mm). , 927 to 1937 (1/mm).
  • the arithmetic mean curvature Spc of the peaks on at least one surface of the thermally conductive sheet 1 satisfies the above-mentioned range, and the arithmetic mean curvature Spc of the peaks on both surfaces may satisfy the above-mentioned range.
  • the thermally conductive sheet 1 preferably has a lower total thermal resistance value when pressurized with 0.70 kgf/cm 2 measured according to ASTM-D5470.
  • the thermally conductive sheet 1 may have a total thermal resistance value of less than 0.230°C ⁇ cm 2 /W when pressurized with 0.70 kgf/cm 2 , and not more than 0.220°C ⁇ cm 2 / W. It may be 0.200°C ⁇ cm 2 /W or less, it may be 0.190°C ⁇ cm 2 /W or less, or it may be 0.160°C ⁇ cm 2 /W or less. It's okay.
  • the thermally conductive sheet 1 may have a total thermal resistance value of 0.312° C.cm 2 /W or less when a pressure of 0.7 kgf/cm 2 is applied when the thickness is 1.0 mm. Further, the thermally conductive sheet 1 may have a total thermal resistance value of 0.525° C.cm 2 /W or less when 0.7 kgf/cm 2 is applied when the thickness is 2.0 mm.
  • the lower limit of the total thermal resistance value of the thermally conductive sheet 1 when pressurized with 0.70 kgf/cm 2 is not particularly limited, and is preferably a lower value, exceeding 0° C.cm 2 /W, such as It can be 0.05° C.cm 2 /W or more.
  • the thermally conductive sheet 1 has a total thermal resistance value of 0.143 to 0.212° C.cm 2 /W when a pressure of 0.70 kgf/cm 2 is applied when the thickness is 0.3 mm. It may be in the range of 0.143 to 0.200°C ⁇ cm 2 /W, or may be in the range of 0.143 to 0.185°C ⁇ cm 2 /W.
  • the thermally conductive sheet 1 preferably has a lower total thermal resistance value when pressurized with 1.4 kgf/cm 2 measured according to ASTM-D5470.
  • the thermally conductive sheet 1 may have a total thermal resistance value of less than 0.208°C ⁇ cm 2 /W when pressurized with 1.4 kgf/cm 2 , and not more than 0.200°C ⁇ cm 2 /W. It may be 0.190°C ⁇ cm 2 /W or less, it may be 0.180°C ⁇ cm 2 /W or less, or it may be 0.170°C ⁇ cm 2 /W or less.
  • the temperature may be 0.160° C.cm 2 /W or less.
  • the thermally conductive sheet 1 may have a total thermal resistance value of 0.289° C.cm 2 /W or less when a pressure of 1.4 kgf/cm 2 is applied when the thickness is 1.0 mm. Further, the thermally conductive sheet 1 may have a total thermal resistance value of 0.601° C.cm 2 /W or less when a pressure of 1.4 kgf/cm 2 is applied when the thickness is 2.0 mm.
  • the lower limit of the total thermal resistance value of the thermally conductive sheet 1 when pressurized with 1.4 kgf/cm 2 is not particularly limited, and is preferably a lower value, exceeding 0° C.cm 2 /W, such as It can be 0.05° C.cm 2 /W or more.
  • the thermally conductive sheet 1 has a total thermal resistance value of 0.128 to 0.179° C.cm 2 /W when a pressure of 1.4 kgf/cm 2 is applied when the thickness is 0.3 mm. It may be in the range of 0.128 to 0.166°C ⁇ cm 2 /W, or may be in the range of 0.128 to 0.165°C ⁇ cm 2 /W.
  • the thermally conductive sheet 1 preferably has a lower total thermal resistance value when pressurized with 2.1 kgf/cm 2 measured according to ASTM-D5470.
  • the thermally conductive sheet 1 may have a total thermal resistance value of 0.200°C ⁇ cm 2 /W or less when 2.1 kgf/cm 2 is applied, or 0.190°C ⁇ cm 2 / W or less. It may be 0.180°C ⁇ cm 2 /W or less, it may be 0.170°C ⁇ cm 2 /W or less, or it may be 0.160°C ⁇ cm 2 /W or less.
  • the thermally conductive sheet 1 may have a total thermal resistance value of 0.303° C.cm 2 /W or less when pressurized with 2.1 kgf/cm 2 when the thickness is 1.0 mm. Further, the thermally conductive sheet 1 may have a total thermal resistance value of 0.682° C.cm 2 /W or less when a pressure of 2.1 kgf/cm 2 is applied when the thickness is 2.0 mm.
  • the lower limit of the total thermal resistance value of the thermally conductive sheet 1 when pressurized with 2.1 kgf/cm 2 is preferably a lower value, exceeding 0°C.cm 2 /W, for example, 0.05°C. cm 2 /W or more.
  • the thermally conductive sheet 1 has a total thermal resistance value of 0.126 to 0.161° C.cm 2 /W when a pressure of 2.1 kgf/cm 2 is applied when the thickness is 0.3 mm. It may be in the range of 0.126 to 0.155°C ⁇ cm 2 /W.
  • the thermally conductive sheet 1 preferably has a lower total thermal resistance value when pressurized with 2.8 kgf/cm 2 measured according to ASTM-D5470.
  • the thermally conductive sheet 1 may have a total thermal resistance value of less than 0.190°C ⁇ cm 2 /W when pressurized with 2.8 kgf/cm 2 , and not more than 0.180°C ⁇ cm 2 /W. It may be 0.170°C ⁇ cm 2 /W or less, it may be 0.160°C ⁇ cm 2 /W or less, or it may be 0.150°C ⁇ cm 2 /W or less. It may be 0.140°C ⁇ cm 2 /W or less, or it may be 0.130°C ⁇ cm 2 /W or less.
  • the thermally conductive sheet 1 may have a total thermal resistance value of 0.327° C.cm 2 /W or less when a pressure of 2.8 kgf/cm 2 is applied when the thickness is 1.0 mm. Further, the thermally conductive sheet 1 may have a total thermal resistance value of 0.732° C.cm 2 /W or less when a pressure of 2.8 kgf/cm 2 is applied when the thickness is 2.0 mm.
  • the lower limit of the total thermal resistance value of the thermally conductive sheet 1 when pressurized with 2.8 kgf/cm 2 is not particularly limited, and is preferably a lower value, exceeding 0° C.cm 2 /W, for example It can be 0.05° C.cm 2 /W or more.
  • the thermally conductive sheet 1 has a total thermal resistance value of 0.122 to 0.157° C.cm 2 /W when a pressure of 2.8 kgf/cm 2 is applied when the thickness is 0.3 mm. It may be in the range of 0.122 to 0.153°C ⁇ cm 2 /W, or may be in the range of 0.122 to 0.150°C ⁇ cm 2 /W.
  • the thermally conductive sheet 1 preferably has a lower total thermal resistance value when pressurized with 3.5 kgf/cm 2 measured according to ASTM-D5470.
  • the thermally conductive sheet 1 may have a total thermal resistance value of 0.180°C ⁇ cm 2 /W or less when pressurized with 3.5 kgf/cm 2 , or 0.170°C ⁇ cm 2 / W or less. It may be 0.160°C ⁇ cm 2 /W or less, it may be 0.150°C ⁇ cm 2 /W or less, or it may be 0.140°C ⁇ cm 2 /W or less. It may be 0.130°C ⁇ cm 2 /W or less, or it may be 0.120°C ⁇ cm 2 /W or less.
  • the thermally conductive sheet 1 may have a total thermal resistance value of 0.350° C.cm 2 /W or less when pressurized with 3.5 kgf/cm 2 when the thickness is 1.0 mm. Further, the thermally conductive sheet 1 may have a total thermal resistance value of 0.765° C.cm 2 /W or less when a pressure of 3.5 kgf/cm 2 is applied when the thickness is 2.0 mm.
  • the lower limit of the total thermal resistance value of the thermally conductive sheet 1 when pressurized with 3.5 kgf/cm 2 is not particularly limited, and is preferably a lower value, exceeding 0° C.cm 2 /W, for example It can be 0.05° C.cm 2 /W or more.
  • the thermally conductive sheet 1 has a total thermal resistance value of 0.119 to 0.156° C.cm 2 /W when pressurized with 3.5 kgf/cm 2 when the thickness is 0.3 mm. It may be in the range of 0.119 to 0.151°C ⁇ cm 2 /W, or may be in the range of 0.119 to 0.148°C ⁇ cm 2 /W.
  • FIG. 2 is a cross-sectional view showing an example of the surface of the thermally conductive sheet 1.
  • at least one surface of the thermally conductive sheet 1 is a polished surface, and it is preferable that this polished surface has polishing residue 5.
  • at least one surface of the thermally conductive sheet 1 is a polished surface, and it is preferable that the polished surface has a polishing residue 5 made of a constituent material of the thermally conductive composition detached by polishing.
  • the polishing residue 5 is, for example, a lump made of a thermally conductive composition containing a binder resin 2, an anisotropic thermally conductive material 3, and an inorganic filler 4.
  • the polishing residue 5 is present on the surface of the thermally conductive sheet 1 to such an extent that the thermally conductive sheet 1 satisfies conditions 1 to 3, for example, the polishing residue 5 is present on the entire surface.
  • the polishing residue 5 may be present almost uniformly over the entire surface, or the polishing residue 5 may be present partially (in the form of islands) on the surface, for example, as shown in FIG.
  • Whether or not the thermally conductive sheet 1 has polishing residues 5 on the surface can be determined, for example, by pasting an adhesive tape on the surface of the thermally conductive sheet 1 and then peeling off the adhesive tape. You can check whether it is transferred or not.
  • the average particle diameter and maximum particle diameter of the polishing residue 5 are not too large.
  • the average particle diameter of the polishing residue 5 may be 50 ⁇ m or less, 40 ⁇ m or less, 35 ⁇ m or less, 30 ⁇ m or less, or 20 ⁇ m or less.
  • the thickness may be 15 ⁇ m or less, 10 ⁇ m or less, or in the range of 0.5 to 40 ⁇ m.
  • the average particle diameter of the polishing residue 5 in the case of the irregularly shaped polishing residue 5, the length (diameter) of the longest part of the particle is taken into consideration.
  • the maximum particle diameter of the polishing residue 5 may be, for example, 100 ⁇ m or less, 90 ⁇ m or less, 80 ⁇ m or less, 70 ⁇ m or less, or 50 ⁇ m or less. It may be in the range of ⁇ 100 ⁇ m.
  • the thickness of the thermally conductive sheet 1 can be appropriately selected depending on the purpose, and may be, for example, 0.05 mm or more, 0.1 mm or more, or 0.2 mm or more. It may be 0.3 mm or more. Further, the upper limit of the thickness of the thermally conductive sheet 1 can be, for example, 5 mm or less, may be 4 mm or less, may be 3 mm or less, may be 2 mm or less, and may be 1 mm or less. It may be 0.5 mm or less.
  • the thickness of the thermally conductive sheet 1 can be determined by measuring the thickness B of the thermally conductive sheet 1 at five arbitrary locations and calculating the arithmetic mean value thereof.
  • the thermally conductive sheet 1 As the thermal resistance of the sheet itself becomes lower, the contribution of the contact thermal resistance to the total thermal resistance generated between the sheet and the adherend tends to increase. As mentioned above, this tendency becomes more pronounced as the sheet becomes thinner. In other words, in the thermally conductive sheet 1, as the thermal conductivity of the sheet itself increases, the proportion of the contact thermal resistance in the total thermal resistance value increases. In this technology, the contact thermal resistance is reduced by the thermally conductive sheet 1 in which the anisotropic thermally conductive material 3 is oriented in the thickness direction, by satisfying at least one of the conditions 1 to 3 described above. As a result, the total thermal resistance value can be reduced.
  • the binder resin 2, the anisotropic thermally conductive material 3, and the inorganic filler 4, which are examples of the structure of the thermally conductive sheet 1, will be explained.
  • Binder resin 2 is for holding anisotropic thermally conductive material 3 and inorganic filler 4 within thermally conductive sheet 1 .
  • the binder resin 2 is selected depending on the properties required of the thermally conductive sheet 1, such as mechanical strength, heat resistance, and electrical properties.
  • the binder resin 2 can be selected from thermoplastic resins, thermoplastic elastomers, and thermosetting resins.
  • thermoplastic resins include polyethylene, polypropylene, ethylene- ⁇ olefin copolymers such as ethylene-propylene copolymers, polymethylpentene, polyvinyl chloride, polyvinylidene chloride, polyvinyl acetate, ethylene-vinyl acetate copolymers, Fluoropolymers such as polyvinyl alcohol, polyvinyl acetal, polyvinylidene fluoride and polytetrafluoroethylene, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polystyrene, polyacrylonitrile, styrene-acrylonitrile copolymer, acrylonitrile-butadiene-styrene copolymer Polymer (ABS) resin, polyphenylene-ether copolymer (PPE) resin, modified PPE resin, aliphatic polyamide, aromatic polyamide, polyimide, polyamideimide, polymethacrylic
  • Examples include acid esters, polyacrylic acids, polycarbonates, polyphenylene sulfides, polysulfones, polyethersulfones, polyethernitrile, polyetherketones, polyketones, liquid crystal polymers, and ionomers.
  • thermoplastic elastomers examples include styrene-butadiene block copolymers or hydrogenated products thereof, styrene-isoprene block copolymers or hydrogenated products thereof, styrene-based thermoplastic elastomers, olefin-based thermoplastic elastomers, and vinyl chloride-based thermoplastic elastomers. , polyester thermoplastic elastomer, polyurethane thermoplastic elastomer, polyamide thermoplastic elastomer, and the like.
  • thermosetting resin examples include crosslinked rubber, epoxy resin, phenol resin, polyimide resin, unsaturated polyester resin, diallyl phthalate resin, addition reaction type silicone resin, condensation reaction type silicone resin, and the like.
  • crosslinked rubber examples include natural rubber, acrylic rubber, butadiene rubber, isoprene rubber, styrene-butadiene copolymer rubber, nitrile rubber, hydrogenated nitrile rubber, chloroprene rubber, ethylene-propylene copolymer rubber, chlorinated polyethylene rubber, Examples include chlorosulfonated polyethylene rubber, butyl rubber, halogenated butyl rubber, fluororubber, urethane rubber, and silicone rubber.
  • silicone resin is preferable, for example, from the viewpoint of adhesion between the heat generating surface of the heat generating element (for example, an electronic component) and the heat sink surface.
  • silicone resin for example, a two-component type silicone resin containing silicone (polyorganosiloxane) having an alkenyl group as the main component, a main resin containing a curing catalyst, and a curing agent having a hydrosilyl group (Si-H group) is used.
  • Addition reaction type silicone resins can be used.
  • silicone having an alkenyl group a polyorganosiloxane having at least two alkenyl groups in one molecule can be used.
  • the curing catalyst is a catalyst for promoting an addition reaction between an alkenyl group in the silicone having an alkenyl group and a hydrosilyl group in the curing agent having a hydrosilyl group.
  • the curing catalyst include catalysts well known as catalysts used in hydrosilylation reactions, such as platinum group curing catalysts, such as simple platinum group metals such as platinum, rhodium, and palladium, platinum chloride, and complexes of platinum and organic compounds. etc. can be used.
  • a polyorganosiloxane having a hydrosilyl group for example, a polyorganosiloxane having a hydrosilyl group (organohydrogenpolysiloxane having at least two hydrogen atoms in one molecule directly bonded to a silicon atom) can be used.
  • the ratio of the main component (silicone main component) to the curing agent component that is, the polyorganosiloxane having a vinyl group and
  • the mixing ratio of the polyorganosiloxane having a hydrosilyl group is not particularly limited, and may be such that the hydrosilyl group is in the range of 0.3 to 0.9 mol per mol of the vinyl group.
  • the mixing ratio may be in the range of 4 to 0.7 mol.
  • the content of the binder resin 2 in the thermally conductive sheet 1 is not particularly limited, and can be appropriately selected depending on the purpose.
  • the content of the binder resin 2 in the thermally conductive sheet 1 may be 20 volume% or more, may be 24 volume% or more, may be 28 volume% or more, or may be 30 volume%.
  • the content may be more than 32% by volume.
  • the upper limit of the content of the binder resin 2 in the thermally conductive sheet 1 can be 60 volume% or less, may be 50 volume% or less, or may be 40 volume% or less, It may be 38 volume% or less, 35 volume% or less, 32 volume% or less, or 30 volume% or less.
  • the content of the binder resin 2 in the thermally conductive sheet 1 can be, for example, in the range of 24 to 32% by volume, and can also be in the range of 24 to 28% by volume.
  • the binder resin 2 may be used alone or in combination of two or more. When using two or more types of binder resins 2, it is preferable that the total amount thereof satisfies the above-mentioned content.
  • the anisotropic thermally conductive material 3 is a thermally conductive material that has anisotropy in shape.
  • an example of the anisotropic thermally conductive material 3 is a thermally conductive filler having a long axis and a short axis, and a specific example is a fibrous filler.
  • the fibrous filler which is an example of the anisotropic thermally conductive material 3, is not particularly limited as long as it is fibrous and has the necessary thermal conductivity, and examples thereof include carbon fibers, aluminum nitride whiskers, and the like. In the following, a case where carbon fiber is used as the anisotropic thermally conductive material 3 will be described in detail as an example.
  • Anisotropic thermally conductive material 3 is a shape that has a long axis and a short axis, the lengths of the long axis and the short axis are different, and the aspect ratio (average major axis length/average short axis length) exceeds 1. including those that are.
  • the anisotropic thermally conductive material 3 may be used alone or in combination of two or more.
  • carbon fiber examples include pitch-based carbon fiber, PAN-based carbon fiber, carbon fiber obtained by graphitizing PBO fiber, arc discharge method, laser evaporation method, CVD method (chemical vapor deposition method), CCVD method (catalytic chemical vapor deposition method) Carbon fibers synthesized by a method such as a carbon fiber growth method) can be used. Among these, pitch-based carbon fibers are preferred from the viewpoint of thermal conductivity.
  • the average fiber length (average major axis length) of the anisotropic thermally conductive material 3 can be, for example, 50 to 250 ⁇ m, and may be 75 to 220 ⁇ m. Further, the average fiber diameter (average minor axis length) of the anisotropic thermally conductive material 3 can be appropriately selected depending on the purpose, and can be, for example, 4 to 20 ⁇ m, or 5 to 14 ⁇ m. Good too.
  • the aspect ratio of the anisotropic thermally conductive material 3 can be appropriately selected depending on the purpose. For example, from the viewpoint of thermal conductivity, it can be set to 8 or more, and may be in the range of 9 to 30. .
  • the average major axis length and average minor axis length of the anisotropic thermally conductive material 3 can be measured using, for example, a microscope or a scanning electron microscope (SEM).
  • the content of the anisotropic thermally conductive material 3 in the thermally conductive sheet 1 can be, for example, 5% by volume or more, and can be 10% by volume or more. It may be 14 volume% or more, 20 volume% or more, 22 volume% or more, 24 volume% or more, 26 volume% or more. It's okay. Further, from the viewpoint of formability of the thermally conductive sheet 1, the content of the anisotropic thermally conductive material 3 in the thermally conductive sheet 1 can be, for example, 30% by volume or less, and 28% by volume or less. There may be.
  • the content of the anisotropic thermally conductive material 3 in the thermally conductive sheet 1 can be, for example, in the range of 26 to 29% by volume, and can also be in the range of 26 to 28% by volume.
  • the inorganic filler 4 is a thermally conductive filler other than the anisotropic thermally conductive material 3.
  • the inorganic filler 4 includes, for example, spherical, powdery, granular, and other thermally conductive fillers.
  • the material of the inorganic filler 4 is preferably a ceramic filler, for example, and specific examples include aluminum oxide (alumina, sapphire), aluminum nitride, aluminum, aluminum hydroxide, and nitride. Examples include boron.
  • the inorganic filler 4 may be used alone or in combination of two or more. For example, as the inorganic filler 4, two or more types of thermally conductive fillers having different average particle diameters may be used in combination.
  • the inorganic filler 4 is at least one selected from aluminum oxide, aluminum nitride, and aluminum, taking into consideration the thermal conductivity of the thermally conductive sheet 1 and the specific gravity of the thermally conductive sheet 1. It is preferable that there be.
  • aluminum oxide and aluminum nitride may be used together, or aluminum oxide, aluminum nitride, and aluminum may be used together.
  • the average particle diameter of aluminum nitride may be in the range of 0.1 to 10 ⁇ m, for example from the viewpoint of the specific gravity of the thermally conductive sheet 1, may be in the range of 0.5 to 5 ⁇ m, and may be in the range of 0.5 to 5 ⁇ m. The range may be 3 ⁇ m or 0.5 to 2 ⁇ m.
  • the average particle diameter of aluminum oxide can be in the range of 0.1 to 10 ⁇ m, for example from the viewpoint of the specific gravity of the thermally conductive sheet 1, and may be in the range of 0.1 to 8 ⁇ m, and may be in the range of 0.1 to 8 ⁇ m. It may be in the range of 7 ⁇ m or may be in the range of 0.1 to 3 ⁇ m.
  • the average particle diameter of aluminum can be less than 15 ⁇ m, for example from the viewpoint of the specific gravity of the thermally conductive sheet 1, and may be in the range of 1 to 14 ⁇ m.
  • the content of the inorganic filler 4 in the thermally conductive sheet 1 can be appropriately selected depending on the purpose.
  • the content of the inorganic filler 4 in the thermally conductive sheet 1 can be, for example, 10 volume% or more, may be 15 volume% or more, may be 20 volume% or more, and may be 25 volume%. It may be 30 volume% or more, 35 volume% or more, 39 volume% or more, or 45 volume% or more.
  • the upper limit of the content of the inorganic filler 4 in the thermally conductive sheet 1 may be, for example, 55 volume% or less, may be 50 volume% or less, or may be 49 volume% or less. It may be 45% by volume or less, or 40% by volume or less.
  • the content of the inorganic filler 4 in the thermally conductive sheet 1 can be, for example, in the range of 39 to 49% by volume. When two or more types of inorganic fillers 4 are used together, it is preferable that the total amount thereof satisfies the above-mentioned content.
  • the content of aluminum nitride in the thermally conductive sheet 1 is in the range of 10 to 35% by volume, and the content of aluminum oxide is in the range of 5 to 25% by volume. %, the content of aluminum nitride can be in the range of 20-30% by volume, and the content of aluminum oxide can be in the range of 10-25% by volume.
  • the content of aluminum nitride in the thermally conductive sheet 1 is set in the range of 10 to 30% by volume, and the content of aluminum oxide is set in the range of 10 to 30% by volume.
  • the aluminum content can be in the range of 1 to 20% by volume, and the aluminum content can be in the range of 10 to 30% by volume.
  • the thermally conductive sheet 1 may further contain other components other than those described above, as long as the effects of the present technology are not impaired.
  • other components include coupling agents, dispersants, curing accelerators, retarders, tackifiers, plasticizers, flame retardants, antioxidants, stabilizers, colorants, and solvents.
  • the thermally conductive sheet 1 is made of anisotropic thermally conductive material 3 treated with a coupling agent and/or a coupling agent. A treated inorganic filler 4 may also be used.
  • thermally conductive sheet 1 is preferably, for example, 40 to 95 in terms of Shore OO hardness, from the viewpoint of ease of polishing and conformability to an adherend due to the flexibility of the sheet.
  • the thermally conductive sheet 1 is made of a cured product of a thermally conductive composition containing an anisotropic thermally conductive material 3, an inorganic filler 4, and a binder resin 2, and satisfies the conditions 1 to 3 described above. Since at least one condition is satisfied, the contact area between the thermally conductive sheet 1 and the adherend increases, and air is prevented from entering between the thermally conductive sheet 1 and the adherend, so the contact heat The resistance can be reduced, and as a result, the total thermal resistance value can be reduced.
  • the method for manufacturing the thermally conductive sheet 1 includes the following steps A, B, and C.
  • step A a thermally conductive composition containing a binder resin 2, an anisotropic thermally conductive material 3, and an inorganic filler 4 is molded into a predetermined shape and cured to form a molded body of the thermally conductive composition (thermal A conductive molded body) is obtained.
  • the anisotropic thermally conductive material 3 and the inorganic filler 4 are dispersed in the binder resin 2, thereby containing the binder resin 2, the anisotropic thermally conductive material 3, and the inorganic filler 4.
  • a thermally conductive composition is produced.
  • the thermally conductive composition is prepared by uniformly mixing the binder resin 2, the anisotropic thermally conductive material 3, the inorganic filler 4, and other components mentioned above as necessary using a known method. can.
  • the thermally conductive composition is extruded and then cured to obtain a columnar cured product (thermally conductive molded body).
  • the extrusion molding method is not particularly limited, and can be appropriately adopted from various known extrusion molding methods depending on the viscosity of the thermally conductive composition, the characteristics required of the thermally conductive sheet 1, and the like.
  • the extrusion molding method when extruding a thermally conductive composition from a die, the binder resin 2 in the thermally conductive composition flows, and the anisotropic thermally conductive material 3 is oriented along the flow direction.
  • the size and shape of the columnar cured product can be determined depending on the required size of the thermally conductive sheet 1. For example, a rectangular parallelepiped with a vertical cross section of 0.5 to 15 cm and a horizontal cross section of 0.5 to 15 cm may be mentioned. The length of the rectangular parallelepiped may be determined as necessary.
  • step B the thermally conductive molded product obtained in step A is cut into sheet shapes to obtain sheet-like molded products.
  • the columnar cured product obtained in step A is cut into a predetermined thickness in the length direction of the column to obtain a sheet-like molded product.
  • the anisotropic thermally conductive material 3 is exposed on the surface (cut surface) of the sheet-like molded body.
  • the method for cutting the thermally conductive molded body is not particularly limited, and can be appropriately selected from known slicing devices depending on the size and mechanical strength of the thermally conductive molded body.
  • the anisotropic thermally conductive material 3 may be oriented in the extrusion direction, so the cutting direction of the thermally conductive molded body must be in the extrusion direction.
  • the angle is preferably 60 to 120 degrees, more preferably 70 to 100 degrees, and even more preferably 90 degrees (substantially perpendicular).
  • the cutting direction of the thermally conductive molded body is not particularly limited other than the above, and can be appropriately selected depending on the intended use of the thermally conductive sheet 1 and the like.
  • the sheet-like molded product obtained in step B has irregularities on its surface.
  • the sheet-like molded product obtained in step B has a plurality of convex portions 1a on the surface and concave portions adjacent to the convex portions 1a. Therefore, the sheet-like molded product obtained in step B usually tends not to satisfy the above-mentioned conditions 1 to 3.
  • air tends to get mixed in between the sheet-like molded product and the adherend, making it difficult to reduce the contact thermal resistance of the sheet-like molded product. There is a tendency.
  • step C by polishing the surface of the sheet-like molded body obtained in step B, the binder resin 2, anisotropic thermally conductive material 3, and By covering the recesses on the surface of the sheet-like molded body with the inorganic filler 4 (in other words, the polishing residue 5 scraped from the projections 1a remains in the recesses), the surface of the thermally conductive sheet 1 meets the above-mentioned condition 1. - At least one of 3 can be satisfied, the contact area between the thermally conductive sheet 1 and the adherend is improved, and air is prevented from entering between the thermally conductive sheet 1 and the adherend. However, the contact thermal resistance of the thermally conductive sheet 1 can be reduced.
  • the contact area between the thermally conductive sheet 1 and the adherend is further improved, and the surface of the thermally conductive sheet 1 and the adherend are further improved. It is considered that the mixture of air with the adherend can be more effectively suppressed, and the contact thermal resistance of the thermally conductive sheet 1 can be further reduced.
  • the sheet-like molded body is polished with a polishing member.
  • the polishing member include those that can be brought into surface contact with the surface of the sheet-like molded body for polishing.
  • abrasive members include sandpaper, wrapping films, and brushes, which are appropriately selected depending on durability, accuracy of abrasive grain size, and throughput.
  • a lapping film is a film in which abrasive grains are fixed to a resin film as a base material using an adhesive.
  • the conductive material 3 and the inorganic filler 4 can more efficiently cover the recesses on the surface of the sheet-like molded body.
  • the wrapping film for example, one using a polyester film as the base material and aluminum oxide with an average particle size of 2 to 40 ⁇ m as the abrasive grains can be used.
  • a lapping film with a nominal value of #400 to #6000 can be used as an indicator of the particle size of the abrasive grains.
  • the size and thickness of the wrapping film can be changed as appropriate depending on the size of the sheet-like molded body to be polished. For example, the thickness of the wrapping film can be 0.01 to 0.5 mm.
  • FIG. 3 is a perspective view of a brush 6, which is an example of a polishing member.
  • the brush 6 has a shape in which bristles 8 are arranged in the length direction of a columnar base material 7, as shown in FIG. 3, for example.
  • the hair material 8 is a bundle of a plurality of hairs, and has a length B, a depth C, and a width A.
  • the material of the brush 6 is not particularly limited, and for example, from the viewpoint of versatility, abrasion resistance, flexibility, bending recovery, etc., nylon, acrylic, vinyl chloride, polypropylene, polyphenylene sulfide, copper, brass, stainless steel, Materials used for brushes include horses, pigs, sheep, etc., and materials that have been treated with abrasives to improve polishing efficiency, electrostatic treatment to prevent contamination of polishing powder brushes, conductive treatment, etc. are also used. Is possible.
  • the thickness of the hair is 0.05 mm to 2.2 mm, and the length of the hair is 1 to 100 mm.
  • processing speed, etc. can be appropriately selected and used in combination within a range that does not impair the present invention.
  • FIG. 4 is a perspective view for explaining an example of a method of polishing the surface of the molded sheet 9 with the brush 6.
  • a fixing means such as a suction pad or tape (not shown) to polish the back side of the surface of the molded sheet 9 to be polished or It is preferable to temporarily fasten the end on the side where processing is to be started.
  • temporary fixing using tape when polishing with the brush 6 in the direction of D1 in FIG. to move the brush 6.
  • the means for moving the brush 6 may be manual or automatic.
  • polishing the molded sheet 9 move the brush 6 so that the tips of the bristles 8 touch the surface of the molded sheet 9 in the entire direction A, and stroke with the tips of the bristles 8. It is preferable to let
  • the polishing method is not limited to moving the polishing member in one direction from one end side 9A to the other end side 9B of the surface of the molded sheet 9.
  • polishing the surface of the molded sheet 9 from one end 9A to the other end 9B with a polishing member and polishing the surface of the molded sheet 9 from the other end 9B to one end 9A with a polishing member.
  • the polishing member may be reciprocated to polish the surface of the molded sheet 9 from one end side 9A to the other end side 9B.
  • the brush 6 when used, it may be polished by reciprocating in the D1 direction and the D2 direction from one end side 9A to the other end side 9B of the surface of the molded sheet 9 in FIG. FIG.
  • FIG. 5 is a perspective view for explaining an example of a method of continuously polishing the surfaces of a plurality of molded body sheets with a brush.
  • the polishing member when polishing a plurality of thermally conductive sheets 1 in succession, for example, the polishing member is fixed, a plurality of formed sheets 9 are placed on a conveyor 10, and the conveyor 10 is By moving, a plurality of molded sheets 9 may be polished continuously.
  • the direction of movement of the conveyor 10 may be one direction, D3 direction or D4 direction in FIG. 5, or may be reciprocated in the D3 direction and D4 direction. It is also possible to install and use a plurality of brushes. Furthermore, a rolled brush may be rotated and used.
  • only one side of the molded sheet 9 may be polished, or after one side of the molded sheet 9 is polished, the other side may also be polished.
  • the polishing method is the same as the polishing method for the brush 6 described above, as long as the wrapping film is brought into contact with the surface of the molded sheet 9 and at least one of the molded sheet 9 and the wrapping film is moved.
  • various modifications can be made in the movement method, movement direction, arrangement, and shape.
  • the number of times of polishing can be changed as appropriate depending on the polishing method, the type of polishing member, the particle size of the polishing member, etc.
  • the greater the number of times of polishing the more easily the concave portions on the surface of the sheet-like molded body 9 are covered with the binder resin 2, anisotropic heat conductive material 3, and inorganic filler 4 carved out from the convex portions 1a on the surface of the sheet-like molded body 9. Therefore, it is preferable to set the number of times to a certain number or more.
  • the number of times of polishing can be, for example, 1 or more times, 10 times or more, 20 times or more, 30 or more times, 40 times or more, 50 times or more, It may be more than 60 times, it may be more than 70 times, it may be more than 80 times, it may be more than 90 times, it may be more than 100 times, it may be more than 200 times, it may be more than 300 times, it may be more than 400 times.
  • the number of times may be more than 1,000 times, or may be in the range of 100 to 1,000 times, or may be in the range of 100 to 400 times.
  • the number of times of polishing refers to one time of polishing in one direction from one end side 9A to the other end side 9B of the surface of the sheet-like molded body 9 in FIG. 4, for example.
  • the size of the polishing residue 5 that the thermally conductive sheet 1 has on the surface can be changed as appropriate depending on the material and particle size of the polishing member used.
  • the maximum size of the polishing residue 5 can be 100 ⁇ m or less, and can also be in the range of 0.5 to 100 ⁇ m.
  • the polishing member may have the same roughness in the polishing step (step C).
  • Polishing members having the same roughness in the polishing process mean, for example, polishing members with the same abrasive grain size in step C, rather than using two or more types of polishing members with different abrasive grain sizes together. It means to use.
  • conditions 1 to 3 described above can be satisfied, and the thermal conductivity is improved.
  • the total thermal resistance value of the adhesive sheet 1 can be reduced.
  • the thermally conductive sheet 1 in the method for manufacturing the thermally conductive sheet 1, the thermally conductive sheet 1 can be polished under the conditions 1 to 1 without using two or more types of polishing members having different abrasive grain sizes in combination in step C. 3 can be satisfied, the process can be simplified.
  • step C of the method for manufacturing the thermally conductive sheet 1 two or more types of polishing members having different abrasive grain sizes may be used together.
  • the thermally conductive sheet 1 described above can be obtained.
  • the method for manufacturing the thermally conductive sheet 1 is not limited to the above-mentioned example, and may further include a pressing step D.
  • Process D may be between process B and process C, or may be after process C.
  • an example of the method for manufacturing the thermally conductive sheet 1 includes, in addition to the above-mentioned steps A to C, a step D of pressing the surface of the sheet-like molded body 9 obtained in step B;
  • the thermally conductive sheet 1 may be obtained by polishing the surface of the sheet-like molded body 9 pressed in step D.
  • a pair of press devices consisting of a flat plate and a press head with a flat surface can be used. Alternatively, it may be pressed using pinch rolls.
  • the pressure during pressing can be, for example, 0.1 to 100 MPa.
  • the pressing is preferably performed at a temperature equal to or higher than the glass transition temperature (Tg) of the binder resin 2.
  • Tg glass transition temperature
  • the pressing temperature can be from 0 to 180°C, may be within the temperature range of room temperature (eg, 25°C) to 100°C, or may be from 30 to 100°C.
  • the thermally conductive sheet 1 is, for example, placed between a heat generating element and a heat radiating element, so that the heat generated by the heating element is dissipated to the heat radiating element. ).
  • the electronic device includes at least a heating element, a heat radiating element, and a thermally conductive sheet 1, and may further include other members as necessary. In this way, electronic devices to which the thermally conductive sheet 1 is applied can achieve high thermal conductivity due to the thermally conductive sheet 1 because the thermally conductive sheet 1 is sandwiched between the heating element and the heat radiating element. , the thermally conductive sheet 1 has excellent adhesion to the heating element, and excessive bleeding of the binder resin 2 from the thermally conductive sheet 1 can be suppressed.
  • the electronic device to which the thermally conductive sheet 1 is applied is such that the thermally conductive sheet 1 and the adherend meet at least one of the conditions 1 to 3 described above.
  • the contact area with the heating element and the heat radiating element is further increased, and air is prevented from entering between the thermally conductive sheet 1 and the adherend, contributing to a reduction in the contact thermal resistance of the thermally conductive sheet 1. , As a result, the total thermal resistance value can be reduced.
  • the heating element is not particularly limited, and examples include electronic components that generate heat in electric circuits, such as CPUs, GPUs (Graphics Processing Units), DRAMs (Dynamic Random Access Memory), integrated circuit elements such as flash memories, transistors, and resistors. etc.
  • the heating element also includes components that receive optical signals, such as optical transceivers in communication equipment.
  • the heat sink is not particularly limited, and includes, for example, heat sinks, heat spreaders, and other heat sinks that are used in combination with integrated circuit elements, transistors, optical transceiver casings, and the like.
  • Examples of the material for the heat sink and heat spreader include copper and aluminum.
  • the heat dissipation body may be anything that conducts heat generated from a heat source and dissipates it to the outside, such as a heat dissipator, cooler, die pad, printed circuit board, cooling fan, Peltier element, etc.
  • Examples include heat pipes, vapor chambers, metal covers, and casings.
  • a heat pipe is, for example, a cylindrical, substantially cylindrical, or flat cylindrical hollow structure.
  • FIG. 6 is a cross-sectional view showing an example of a semiconductor device to which a thermally conductive sheet is applied.
  • the thermally conductive sheet 1 is mounted on a semiconductor device 50 built into various electronic devices, and is sandwiched between a heat generating body and a heat radiating body.
  • a semiconductor device 50 shown in FIG. 6 includes an electronic component 51, a heat spreader 52, and a thermally conductive sheet 1, and the thermally conductive sheet 1 is sandwiched between the heat spreader 52 and the electronic component 51.
  • the thermally conductive sheet 1 is sandwiched between the heat spreader 52 and the heat sink 53, thereby forming a heat radiating member that radiates heat from the electronic component 51 together with the heat spreader 52.
  • the mounting location of the thermally conductive sheet 1 is not limited to between the heat spreader 52 and the electronic component 51 or between the heat spreader 52 and the heat sink 53, and can be appropriately selected depending on the configuration of the electronic device or semiconductor device.
  • the heat spreader 52 is formed into a rectangular plate shape, for example, and has a main surface 52a facing the electronic component 51, and a side wall 52b erected along the outer periphery of the main surface 52a.
  • a thermally conductive sheet 1 is provided on a main surface 52a surrounded by side walls 52b, and a heat sink 53 is provided on the other surface 52c opposite to the main surface 52a via the thermally conductive sheet 1.
  • Example 1 32% by volume of silicone resin, 14% by volume of aluminum oxide (average particle diameter: approximately 2 ⁇ m), 25% by volume of aluminum nitride (average particle diameter: approximately 1 ⁇ m), and 28% by volume of carbon fiber (average fiber length: approximately 150 ⁇ m).
  • a thermally conductive composition was prepared by uniformly mixing the above and 1% by volume of a coupling agent. This thermally conductive composition was poured into a mold (opening: 50 mm x 50 mm) having a rectangular parallelepiped internal space by extrusion molding, and heated in an oven at 100°C for 6 hours to form a columnar cured product ( A molded body block) was formed.
  • Example 1 As shown in Fig. 3, the hair thickness is 0.2 mm, the hair length (B in Fig. 3) is 25 mm, the hair bundle (depth: C in Fig. 3) is 4 mm, and the width (B in Fig. 3) is 4 mm.
  • a 70 mm nylon brush 6 manufactured by Kakuda Brush Co., Ltd. was used. Then, as shown in FIG. 4, while bending the bristles of the brush 6 so that the bristles of the brush 6 (the tips of the bristles 8) contact the sheet-like molded body 9 in the entire direction A, The brush 6 was moved in one direction 100 times from one end to the other end of the surface of the sheet-like molded body 9 in a caressing motion.
  • thermally conductive sheet By polishing the surface of the sheet-like molded body 9 in this manner, a thermally conductive sheet was obtained. Polishing was performed on both sides of the sheet-like molded body.
  • the thermally conductive sheet obtained in Example 1 had a polished surface, and had the constituent material of the thermally conductive composition detached from the surface by polishing.
  • Example 2 a thermally conductive sheet was obtained in the same manner as in Example 1, except that the number of times of polishing was changed to 1000 times.
  • the thermally conductive sheet obtained in Example 2 had a polished surface, and contained the constituent material of the thermally conductive composition detached by polishing on the surface.
  • Example 3 In Example 3, the sheet-like molded body was sandwiched between two veneers and pressed under the conditions of 70° C., 0.5 MPa, and 30 seconds, and the sheet-like molded body 9 after pressing was polished. A thermally conductive sheet was obtained in the same manner as in Example 1. The thermally conductive sheet obtained in Example 3 had a polished surface, and had the constituent material of the thermally conductive composition removed by polishing on the surface.
  • Example 4 In Example 4, 24% by volume of silicone resin, 10% by volume of aluminum oxide (average particle size: about 2 ⁇ m), 20% by volume of aluminum nitride (average particle size: about 1 ⁇ m), and aluminum (average particle size: about 6 ⁇ m) ), 26 volume % of carbon fibers (average fiber length: approximately 150 ⁇ m), and 1 volume % of a coupling agent, and a nylon brush. Instead, using a #4000 wrapping film (manufactured by 3M) with a thickness of about 100 ⁇ m, the surface of the sheet-like molded body 9 was polished 100 times in one direction from one end to the other end ( A thermally conductive sheet was obtained in the same manner as in Example 1, except that the sheet was rubbed. The thermally conductive sheet obtained in Example 4 had a polished surface, and had the constituent material of the thermally conductive composition removed by polishing on the surface.
  • silicone resin 10% by volume of aluminum oxide (average particle size: about 2 ⁇ m), 20% by volume of aluminum nitride (average particle
  • Example 5 a #2000 wrapping film (manufactured by 3M) with a thickness of about 100 ⁇ m was used instead of the nylon brush to cover the surface of the sheet-like molded body 9 from one end to the other end.
  • a thermally conductive sheet was obtained in the same manner as in Example 1, except that it was polished 100 times in one direction over the entire area.
  • the thermally conductive sheet obtained in Example 5 had a polished surface, and had the constituent material of the thermally conductive composition removed by polishing on the surface.
  • Example 6 > 28% by volume of silicone resin, 22% by volume of aluminum oxide (average particle diameter: approximately 2 ⁇ m), 23% by volume of aluminum nitride (average particle diameter: approximately 1 ⁇ m), and 26% by volume of carbon fiber (average fiber length: approximately 150 ⁇ m).
  • a thermally conductive composition was prepared by uniformly mixing the above and 1% by volume of a coupling agent. This thermally conductive composition was poured into a mold (opening: 50 mm x 50 mm) having a rectangular parallelepiped internal space by extrusion molding, and heated in an oven at 100°C for 6 hours to form a columnar cured product ( A molded body block) was formed.
  • Example 7 a thermally conductive sheet was obtained in the same manner as in Example 6 except that the thickness of the sheet-like molded body was 2 mm. Thus, the thermally conductive sheet obtained in Example 7 had a polished surface and had polishing residue on the surface.
  • Comparative Example 1 the sheet-like molded product obtained in Example 1 was used as it was. That is, in Comparative Example 1, the same procedure as in Example 1 was carried out except that the surface of the sheet-like molded body was not polished. The sheet-like molded article obtained in Comparative Example 1 did not have a polished surface, and did not have the constituent material of the thermally conductive composition detached from the surface by polishing.
  • Comparative Example 2 the pressed sheet-shaped molded product obtained in Example 3 was used as it was. That is, in Comparative Example 2, the same procedure as in Example 3 was carried out except that the surface of the sheet-shaped molded body after pressing was not polished. The sheet-like molded article obtained in Comparative Example 2 did not have a polished surface, and did not have the constituent material of the thermally conductive composition detached from the surface by polishing.
  • Comparative Example 3 a composition in which a silicone resin, carbon fibers, and other inorganic fillers were mixed was injected into a mold, and a magnetic field was applied in the thickness direction to orient the carbon fibers in the thickness direction. After that, it was cured to form a columnar cured product. By cutting (slicing) the obtained columnar cured product into a sheet with a thickness of 0.3 mm using a slicer in a direction substantially perpendicular to the length direction of the column, the carbon fibers are cut into sheets with a thickness of 0.3 mm. A sheet-like molded body oriented in the direction was obtained.
  • Comparative Example 3 after slicing the columnar cured product into 0.3 mm thick pieces, the surface of the sheet-like molded product was not polished.
  • the sheet-like molded article obtained in Comparative Example 3 did not have a polished surface, and did not have the constituent material of the thermally conductive composition detached by polishing on the surface.
  • a thermally conductive composition was prepared by uniformly mixing the above and 1% by volume of a coupling agent. This thermally conductive composition was poured into a mold (opening: 50 mm x 50 mm) having a rectangular parallelepiped internal space by extrusion molding, and heated in an oven at 100°C for 6 hours to form a columnar cured product ( A molded body block) was formed.
  • Comparative Example 5 a sheet-like molded product was obtained in the same manner as Comparative Example 4, except that the thickness of the sheet-like molded product was 2 mm.
  • ⁇ Surface property parameters of thermally conductive sheet> The surface quality parameters of the thermally conductive sheet obtained in each Example and the sheet-like molded article obtained in each Comparative Example were measured. Specifically, the average height Spk ( ⁇ m) of the protruding peaks of the thermally conductive sheet, the average depth Svk ( ⁇ m) of the protruding valleys, the volume Vmp (ml/m 2 ) of the protruding peaks, and the root mean square of the heat conductive sheet.
  • the thermally conductive sheets obtained in Examples 1 to 7 are made of cured products of thermally conductive compositions containing an anisotropic thermally conductive material, an inorganic filler, and a binder resin, and meet the conditions 1 to 3 described above. It has been found that the total thermal resistance value can be reduced by satisfying at least one of the conditions.
  • the thermally conductive sheets obtained in Examples 1 to 5 can reduce the total thermal resistance value at low loads, and specifically, the total thermal resistance value at a load of 0.70 kgf/ cm2 is 0.230. It was found that the temperature was less than °Ccm 2 /W.
  • thermally conductive sheets obtained in Examples 1 to 5 had a total thermal resistance value of 0.179°C cm 2 /W or less at a load of 1.4 kgf/cm 2 .
  • thermally conductive sheets obtained in Examples 1 to 5 had a total thermal resistance value of 0.161°C cm 2 /W or less under a load of 2.1 kgf/cm 2 .
  • thermally conductive sheets obtained in Examples 1 to 5 had a total thermal resistance value of 0.157°C cm 2 /W or less at a load of 2.8 kgf/cm 2 .
  • thermally conductive sheets obtained in Examples 1 to 5 had a total thermal resistance value of 0.156°C cm 2 /W or less at a load of 3.5 kgf/cm 2 .
  • the thermally conductive sheets obtained in Examples 1 to 7 had a polished surface, and had constituent materials (polishing residue) of the thermally conductive composition released by polishing on the polished surface.
  • This polishing residue was confirmed to be a lump containing silicone resin, carbon fiber, and other inorganic fillers (aluminum oxide, aluminum nitride, aluminum, etc.) produced by polishing.
  • the thermally conductive sheets obtained in Examples 1 to 7 have a developed area ratio Sdr of the interface of the thermally conductive sheet, which is measured according to ISO 25178 using a scanning white interference microscope with an objective lens set at a magnification of 20. 45% or less, and the arithmetic mean curvature Spc of the peak of the thermally conductive sheet was found to be 3500 (1/mm) or less.
  • FIG. 7 shows the results of Examples and Comparative Examples with the horizontal axis representing the arithmetic mean curvature Spc (1/mm) of the peak of the thermally conductive sheet and the vertical axis representing the developed area ratio Sdr (%) of the interface of the thermally conductive sheet. This is a plotted graph.
  • the thermally conductive sheets obtained in Examples 1 to 7 have an arithmetic mean curvature of the peak Spc measured according to ISO 25178 using a scanning white interference microscope with a 20x objective lens.
  • the sheet-like molded bodies obtained in Comparative Examples 1, 3 to 5 do not satisfy the requirements that the developed area ratio Sdr of the interface is 45% or less and the arithmetic mean curvature Spc of the peak is 3500 (1/mm) or less. That's what I found out.
  • the thermally conductive sheets obtained in Examples 6 and 7 and the molded sheets obtained in Comparative Examples 4 and 5 are thicker than Examples 1 to 5 and Comparative Examples 1 to 3, respectively.
  • the arithmetic mean curvature Spc of the peak, the developed area ratio Sdr of the interface of the thermally conductive sheet, the volume Vmp of the protruding peak of the thermally conductive sheet, etc. were improved, and the total thermal resistance was reduced. It became clear.
  • thermoly conductive sheet 1 thermally conductive sheet, 1a convex portion, 2 binder resin, 3 anisotropic thermally conductive material, 4 inorganic filler, 5 polishing residue, 6 brush, 7 base material, 8 bristle material, 9 sheet-shaped molded body, 10 conveyor, 50 Semiconductor device, 51 Electronic component, 52 Heat spreader, 52a Main surface, 52b Side wall, 52c Other surface, 53 Heat sink

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Abstract

L'invention concerne une feuille thermoconductrice ayant une valeur de résistance thermique totale réduite.　Cette feuille thermoconductrice (1) est composée d'un produit durci d'une composition thermoconductrice contenant un matériau thermoconducteur anisotrope (3), une charge inorganique (4) et une résine liante (2), et a une hauteur moyenne de parties de pic saillantes inférieure à 3,5 µm, telle que mesurée selon la norme ISO 25178 à l'aide d'un microscope à interférence de lumière blanche à balayage avec une lentille d'objet de 20×. La feuille thermoconductrice (1) est composée du produit durci de la composition thermoconductrice contenant le matériau thermoconducteur anisotrope (3), la charge inorganique (4) et la résine liante (2), et a un volume VMP des parties de pic en saillie d'au plus 0,16 ml/m2, telle que mesurée selon la norme ISO 25178 à l'aide d'un microscope à interférence de lumière blanche à balayage avec une lentille d'objet 20×. La feuille thermoconductrice (1) est composée du produit durci de la composition thermoconductrice contenant le matériau thermoconducteur anisotrope (3), la charge inorganique (4) et la résine liante (2), et a une valeur (Spk/ (Spk + Svk)) de l'étendue de hauteur moyenne des parties de pic en saillie à la somme (Spk + Svk) de l'étendue de hauteur moyenne des parties de pic en saillie et une profondeur moyenne Svk de parties de vallée en saillie d'au plus 40 % et un gradient carré moyen de racine Sdq d'au plus 1,1, tel que mesuré selon la norme ISO 25178 à l'aide d'un microscope à interférence de lumière blanche à balayage avec une lentille d'objet 20×.
PCT/JP2023/012964 2022-03-31 2023-03-29 Feuille thermoconductrice, et procédé de production d'une feuille thermoconductrice WO2023190751A1 (fr)

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JP2023053547A JP2023152951A (ja) 2022-03-31 2023-03-29 熱伝導性シート及び熱伝導性シートの製造方法
JP2023-053547 2023-03-29

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2017135137A (ja) * 2016-01-25 2017-08-03 東洋紡株式会社 絶縁高熱伝導性シート、およびその製法、および積層体
JP2019186555A (ja) * 2016-04-11 2019-10-24 積水ポリマテック株式会社 熱伝導性シートおよび熱伝導性シートの製造方法
US20200308465A1 (en) * 2016-06-21 2020-10-01 Sabic Global Technologies B.V. Polymer compositions exhibiting reflectivity and thermal conductivity
WO2021025089A1 (fr) * 2019-08-08 2021-02-11 積水ポリマテック株式会社 Feuille thermoconductrice et son procédé de production
JP2021136454A (ja) * 2020-02-21 2021-09-13 積水ポリマテック株式会社 熱伝導性シート及びその製造方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2017135137A (ja) * 2016-01-25 2017-08-03 東洋紡株式会社 絶縁高熱伝導性シート、およびその製法、および積層体
JP2019186555A (ja) * 2016-04-11 2019-10-24 積水ポリマテック株式会社 熱伝導性シートおよび熱伝導性シートの製造方法
US20200308465A1 (en) * 2016-06-21 2020-10-01 Sabic Global Technologies B.V. Polymer compositions exhibiting reflectivity and thermal conductivity
WO2021025089A1 (fr) * 2019-08-08 2021-02-11 積水ポリマテック株式会社 Feuille thermoconductrice et son procédé de production
JP2021136454A (ja) * 2020-02-21 2021-09-13 積水ポリマテック株式会社 熱伝導性シート及びその製造方法

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