WO2022181171A1 - 熱伝導シート及び熱伝導シートの製造方法 - Google Patents
熱伝導シート及び熱伝導シートの製造方法 Download PDFInfo
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- WO2022181171A1 WO2022181171A1 PCT/JP2022/003008 JP2022003008W WO2022181171A1 WO 2022181171 A1 WO2022181171 A1 WO 2022181171A1 JP 2022003008 W JP2022003008 W JP 2022003008W WO 2022181171 A1 WO2022181171 A1 WO 2022181171A1
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- conductive sheet
- thermally conductive
- heat
- fibrous filler
- heat conductive
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
- B29K2995/0037—Other properties
- B29K2995/0094—Geometrical properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
- B29K2995/0037—Other properties
- B29K2995/0094—Geometrical properties
- B29K2995/0097—Thickness
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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
- C08J2383/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
- C08J2383/04—Polysiloxanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/001—Conductive additives
Definitions
- This technology relates to a thermally conductive sheet and a method for manufacturing the thermally conductive sheet.
- This application is Japanese Patent Application No. 2021-027117 filed on February 24, 2021 in Japan and Japanese Patent Application No. 2021-055268 filed on March 29, 2021 in Japan. Priority is claimed as a basis, and these applications are incorporated into this application by reference.
- Cooling methods for devices with semiconductor elements include attaching a fan to the device to cool the air inside the device housing, attaching heat sinks such as heat sinks and heat sinks to the semiconductor device, and immersing the device in a fluorine-based inert liquid.
- heat sinks such as heat sinks and heat sinks
- immersing the device in a fluorine-based inert liquid There are known methods for When a heatsink is attached to a semiconductor element for cooling, a heat-conducting sheet is provided between the semiconductor element and the heatsink in order to efficiently dissipate the heat of the semiconductor element.
- a binder resin in which a filler for example, a thermally conductive filler such as carbon fiber
- a filler for example, a thermally conductive filler such as carbon fiber
- thermally conductive sheet In order to improve the heat dissipation properties of the thermally conductive sheet, it is required, for example, to lower the thermal resistance, which is an indicator of how difficult it is to conduct heat. In order to reduce the thermal resistance of the thermally conductive sheet, it is effective, for example, to improve the adhesion of the thermally conductive sheet to a heating element (eg, electronic component) or radiator (eg, heat sink).
- a heating element eg, electronic component
- radiator eg, heat sink
- the surface of the thermally conductive sheet obtained by slicing the thermally conductive molded body for forming the thermally conductive sheet usually has unevenness, and therefore tends to have poor adhesion. If the adhesion of the surface of the thermally conductive sheet is poor, the adhesiveness of the thermally conductive sheet to the heating element and the heat dissipating body becomes poor in the mounting process, and it tends to be difficult to sufficiently lower the thermal resistance of the thermally conductive sheet. In particular, when the compressive stress of the thermal conductive sheet is low, once the thermal conductive sheet is compressed (crushed), the repulsive force is small. It tends to be difficult for the heat-conducting sheet placed between the heating element and the radiator to follow.
- a method of pressing the surface of a thermally conductive sheet prepared by slicing a thermally conductive molded article, or a method of allowing a thermally conductive sheet prepared by slicing a thermally conductive molded article to stand still for a long period of time allows the binder component to be removed from the thermally conductive sheet.
- a method of improving the adhesion between a thermally conductive sheet and an adherend by exuding it to the surface see Patent Documents 2 and 3, for example).
- the binder component may not ooze out uniformly on the surface of the thermally conductive sheet, and there is a risk that the adhesion may vary depending on the location of the surface of the thermally conductive sheet. Also, when the thermally conductive sheet is left standing for a long time, there is a tendency similar to when the surface of the thermally conductive sheet is pressed. Further, in the prior art, no study has been made as to whether or not the restoring force of the thermally conductive sheet, particularly the restoring force of the fibrous filler, is improved when the thermally conductive sheet is compressed and released.
- This technology has been proposed in view of such conventional circumstances, and provides a thermally conductive sheet with good restoring force when compressed and released.
- the fibrous filler is dispersed in the binder resin, and the fibrous filler is arranged at an angle of 70 to 90 degrees in the thickness direction in a cross-sectional view. In this case, it was found that deterioration of thermal resistance can be suppressed by the good restoring force of the fibrous filler after compression release.
- the present technology is a heat conductive sheet in which fibrous fillers are dispersed in a binder resin, and the fibrous fillers are arranged at an angle of 70 to 90 degrees in the thickness direction in a cross-sectional view.
- the arrangement angle of the fibrous filler after release is within 10 degrees of the angle before compression in a cross-sectional view.
- Condition 1 The thickness of the heat conductive sheet is compressed to 40% of the initial thickness at room temperature for 24 hours, and then released.
- a method for producing a thermally conductive sheet according to the present technology includes steps of preparing a thermally conductive composition containing a binder resin and a fibrous filler, forming a molded block from the thermally conductive composition, and forming a molded block into a sheet. and obtaining a heat conductive sheet by slicing into a shape, and the heat conductive sheet is the heat conductive sheet described above.
- FIG. 1 is a cross-sectional view showing an example of a heat conductive sheet.
- FIG. 2 is a perspective view for explaining an example of a method for measuring the placement angle of fibrous fillers in a heat conductive sheet.
- FIG. 3 is a perspective view for explaining an example of a method for measuring the placement angle of fibrous fillers in a heat conductive sheet.
- FIG. 4 is a cross-sectional view showing an example of a heat conductive sheet before and after compression.
- FIG. 5 is a cross-sectional view showing an example of a semiconductor device to which a heat conductive sheet is applied.
- FIG. 6 is a digital microscope photograph of a cross section of the thermally conductive sheet before compression.
- FIG. 7 is a digital microscope photograph of a cross section of the thermally conductive sheet after compression release.
- the fibrous filler is dispersed in the binder resin, and the fibrous filler is arranged at an angle of 70 to 90 degrees in the thickness direction in a cross-sectional view. Further, in the heat conductive sheet according to the present technology, when compression and release are performed under condition 1 below, the arrangement angle of the fibrous filler after compression and release is within the range of 10 degrees from the angle before compression in a cross-sectional view. .
- Condition 1 The thickness of the heat conductive sheet is compressed to 40% of the initial thickness at room temperature for 24 hours, and then released.
- the heat conductive sheet according to the present technology has good restoring force when compression and release are performed as in condition 1, especially the restoring force of the fibrous filler.
- the restoring force of the fibrous filler is the degree of displacement of the arrangement angle of the fibrous filler in the cross-sectional view of the thermally conductive sheet before and after compression and release when the thermally conductive sheet is compressed and released under the condition 1 described above.
- Good restoring force of the fibrous filler means that when the heat conductive sheet is compressed and released under condition 1, the arrangement angle of the fibrous filler after compression release is the same as before compression in the cross-sectional view of the heat conductive sheet.
- the thermally conductive sheet according to the present technology is placed between a heating element (e.g., IC (Integrated Circuit)) and a radiator (e.g., heat sink), even if a gap is opened between the heating element and the radiator, , the fibrous filler in the heat conductive sheet can easily and quickly follow the gap. Thereby, deterioration of the heat resistance of the heat conductive sheet can be suppressed.
- a heating element e.g., IC (Integrated Circuit)
- a radiator e.g., heat sink
- FIG. 1 is a cross-sectional view showing an example of a heat conductive sheet.
- the heat conductive sheet 1 contains a binder resin 2 and fibrous fillers 3, and the fibrous fillers 3 are arranged at an angle of 70 to 90 degrees in the thickness direction B when viewed in cross section.
- the long axis of the fibrous filler 3 is arranged within the range of 70 to 90 degrees with respect to the surface direction A of the heat conductive sheet 1 .
- the thermally conductive sheet 1 may further contain a thermally conductive material 4 other than the fibrous filler 3 .
- the arrangement angle of the fibrous filler 3 after compression and release is within 10 degrees of the angle before compression in a cross-sectional view. That is, in the heat conductive sheet 1, the angle difference of the fibrous fillers 3 before and after compression release is within 10 degrees, and the angle of the fibrous fillers 3 after compression release tends to return to the angle (position) before compression. .
- a heat conductive sheet 1 (sample) having a thickness of 2 mm and a diameter of 29 mm is compressed by 40% from the initial thickness (relative to the initial thickness) at room temperature for 24 hours, and after releasing the compression, 3 Minutes later, the arrangement angle of the fibrous filler 3 in the heat conductive sheet 1 is measured.
- the size of the thermally conductive sheet 1 is set to 29 mm in diameter and the temperature is set to room temperature in accordance with JIS K6262.
- the time is optional, and condition 1 "24 hours" is one of the times stipulated by the standard.
- the thickness of the heat conductive sheet 1 is measured, and the heat conductive sheet 1 is processed to have a diameter of 29 mm.
- the processed thermally conductive sheet 1 (sample) is sandwiched between jigs with SUS304 as the surface, and compressed by 40% with respect to the thickness of the sample.
- a spacer having a thickness of 60% of the thickness of the sample is sandwiched between the threads and the screws are tightened. After tightening the screws, check that the spacers do not move to see if the sample has been compressed to the desired thickness.
- Normal temperature refers to the range of 15 to 25° C. specified in JIS K 0050:2019 (general rules for chemical analysis methods).
- the thermally conductive sheet if the angle difference between the fibrous fillers 3 before and after compression and release exceeds 10 degrees, when the thermally conductive sheet is placed between the heat generating body and the heat radiating body, the gap between the heat generating body and the heat radiating body becomes large. When the gap opens, it becomes difficult for the thermally conductive sheet to follow the gap, and as a result, the thermal resistance of the thermally conductive sheet tends to deteriorate.
- the smaller the angle difference of the fibrous fillers 3 before and after compression release the better. It may be within 0.6 degrees, may be within 5.2 degrees, may be within 4 degrees, may be within 3.8 degrees, and may be within 3.8 to 5.6 degrees. It can be a range.
- the fibrous filler 3 before compressing the thermally conductive sheet 1 under the condition 1 described above is arranged at an angle of 70 to 90 degrees in the thickness direction B of the thermally conductive sheet 1 in a cross-sectional view of the thermally conductive sheet 1 It may be in the range of 80 to 84 degrees, or it may be in the range of 81.9 to 83.1 degrees.
- the fibrous filler 3 after compressing and releasing the heat conductive sheet 1 under the condition 1 described above is also arranged at an angle of 70 to 90 degrees in the thickness direction B of the heat conductive sheet 1 in a cross-sectional view of the heat conductive sheet 1. For example, it may be in the range of 70 to 80 degrees, or it may be in the range of 77.0 to 77.9 degrees.
- FIG. 2 and 3 are perspective views for explaining an example of a method for measuring the arrangement angle of the fibrous filler 3 in the heat conductive sheet 1.
- FIG. 2 and 3 arrow A indicates the surface direction of the sample (thermal conductive sheet 1)
- arrow B indicates the thickness direction of the sample (thermal conductive sheet 1).
- a sample 5 having a thickness of 2 mm and a diameter of 29 mm is prepared from the heat conductive sheet 1, and the central portion of the sample 5 in plan view (upper surface) is cut into a predetermined width in the thickness direction B.
- FIG. 2 and 3 are perspective views for explaining an example of a method for measuring the arrangement angle of the fibrous filler 3 in the heat conductive sheet 1.
- FIG. 2 and 3 are perspective views for explaining an example of a method for measuring the arrangement angle of the fibrous filler 3 in the heat conductive sheet 1.
- FIG. 2 and 3 arrow A indicates the surface direction of the sample (thermal conductive sheet 1)
- arrow B indicates the thickness direction of the sample (thermal conductive
- the average value of the angles of the arbitrary fibrous filler 3 measured at 5 points in the range 6B of 5 mm inside from the outer periphery and 1/3 of the top and bottom is 70 ⁇ It may be in the range of 90 degrees.
- FIG. 4 is a cross-sectional view showing an example of a heat conductive sheet before and after compression.
- the arrow in FIG. 4 means that the heat conductive sheet 1 (cut sample 6) is compressed under condition 1. That is, the upper side of the arrow in FIG. 4 is an example of the heat conductive sheet 1 (cut sample 6) before compression under Condition 1, and the lower side of the arrow in FIG. An example of conductive sheet 1 (cut sample 6).
- the fibrous filler 3 in the heat conductive sheet 1 after compression is in the thickness direction compared to the other range (for example, the central portion 6Ac of the cut surface 6A of the cut sample 6).
- the heat conductive sheet 1 according to the present technology has good restoring force when compression and release are performed as in condition 1, and in addition to reducing the angle difference of the fibrous filler 3 before and after compression release Also, the change in the outer size of the heat conductive sheet 1 before and after the compression release can be reduced.
- the heat conductive sheet 1 with a thickness of 2 mm and a diameter of 29 mm, that is, the sample 5, is compressed by 40% at room temperature for 24 hours, and the diameter of the sample 5 after 3 minutes after release is 32.0 mm or less. 0 mm or less, 30.0 mm or less, 29.9 mm or less, 29.6 mm or less, 29.5 mm or less, 29 It can also be in the range of 0.5 to 29.9 mm.
- the thermally conductive sheet 1 when the thermally conductive sheet 1 is arranged between the heating element and the radiator, even if the gap between the heating element and the radiator is widened, the external size of the thermally conductive sheet 1 is larger than the gap. and the fibrous filler 3 in the heat conductive sheet 1 can follow. Therefore, deterioration of the thermal resistance of the heat conductive sheet 1 can be suppressed more effectively.
- the heat conductive sheet 1 can reduce the change in the outer size before and after compression release, the heat conductive sheet 1 can be processed according to the shape of the heat generating element (for example, IC) to make the entire surface of the heat generating element more efficient. can be cooled.
- the heat conductive sheet 1 is preferably relatively soft, and preferably has a hardness of 25 to 40 in Shore type OO, for example.
- the hardness of the heat conductive sheet 1 is within such a range, the fibrous filler 3 in the heat conductive sheet 1 after compression release and the restoring force of the external size of the heat conductive sheet 1 are improved.
- the conformability of the heat conductive sheet 1 to the adherend is improved.
- the hardness of the heat conductive sheet 1 can be measured by the method of Examples described later.
- a rubber sheet can be mentioned as a thermally conductive sheet with resilience.
- the rubber sheet generally has a high hardness (hardness) in Shore type OO, and the load on an IC as a heating element and a heat sink as a radiator is high.
- Grease liquid
- grease has low shape-following property and restoring property to an IC as a heating element.
- even a relatively hard heat conductive sheet can be crushed, and after crushing the heat conductive sheet, the angle of the fibrous filler and the heat conduction It is possible to return the outline size of the sheet.
- the heat conductive sheet 1 can be adjusted to have a Shore type OO hardness of 25 to 40, is softer than a rubber sheet, and has better restorability and conformability to an adherend than a grease (liquid) sheet. is good. That is, the heat conductive sheet 1 is soft with a hardness of 25 to 40 in Shore type OO, but has good restorability. Easy to return to external size.
- the thickness of the heat conductive sheet 1 is not particularly limited, and can be appropriately selected according to the purpose.
- the thickness of the heat conductive sheet 1 can be 0.05 mm or more, and can also be 0.1 mm or more.
- the upper limit of the thickness of the heat conductive sheet 1 may be 5 mm or less, may be 4 mm or less, or may be 3 mm or less.
- the heat conductive sheet 1 preferably has a thickness of 0.1 to 4 mm.
- the thickness of the thermally conductive sheet 1 can be determined, for example, by measuring the thickness of the thermally conductive sheet 1 at five arbitrary points and calculating the arithmetic average value thereof.
- the thermally conductive sheet 1 contains binder resin 2, fibrous filler 3, and other thermally conductive material 4, for example.
- the binder resin 2 is for holding the fibrous filler 3 and other thermally conductive material 4 within the thermally conductive sheet 1 .
- the binder resin 2 is selected according to properties such as mechanical strength, heat resistance, and electrical properties required for the heat conductive sheet 1 .
- 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, Fluorinated polymers 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 polyamides, aromatic polyamides, polyimide, polyamideimide, polymeth
- Thermoplastic elastomers 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-based thermoplastic elastomers, polyurethane-based thermoplastic elastomers, polyamide-based thermoplastic elastomers, and the like.
- Thermosetting resins include crosslinked rubbers, epoxy resins, phenolic resins, polyimide resins, unsaturated polyester resins, diallyl phthalate resins, and the like.
- Specific examples of crosslinked rubber 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, Chlorosulfonated polyethylene rubber, butyl rubber, halogenated butyl rubber, fluororubber, urethane rubber, and silicone rubber.
- a silicone resin is preferable in consideration of the adhesion between the heat generating surface of the electronic component and the heat sink surface.
- the silicone resin for example, a two-component addition reaction type silicone resin composed of a silicone having an alkenyl group as a main component, a main agent containing a curing catalyst, and a curing agent having a hydrosilyl group (Si—H group).
- the alkenyl group-containing silicone for example, a vinyl group-containing polyorganosiloxane can be used.
- the curing catalyst is a catalyst for promoting the addition reaction between the alkenyl group in the alkenyl group-containing silicone and the hydrosilyl group in the hydrosilyl group-containing curing agent.
- the curing catalyst well-known catalysts used for hydrosilylation reaction can be used.
- platinum group curing catalysts such as platinum group metals such as platinum, rhodium and palladium, and platinum chloride can be used.
- the curing agent having hydrosilyl groups for example, polyorganosiloxane having hydrosilyl groups can be used.
- the binder resin 2 may be used individually by 1 type, and may use 2 or more types together.
- the content of the binder resin 2 in the heat conductive sheet 1 is not particularly limited, and can be appropriately selected according to the purpose.
- the content of the binder resin 2 in the thermally conductive sheet 1 can be 20% by volume or more, and may be 25% by volume or more, from the viewpoint of the flexibility and resilience of the thermally conductive sheet 1. It may be 30% by volume or more, or 33% by volume or more.
- the content of the binder resin 2 in the heat conductive sheet 1 can be 70% by volume or less, and may be 60% by volume or less, from the viewpoint of the thermal conductivity and resilience of the heat conductive sheet 1. , 50% by volume or less, 41% by volume or less, or 39% by volume or less.
- the content of the binder resin 2 in the thermally conductive sheet 1 is preferably 20 to 50% by volume, for example, from the viewpoint of the restoring property of the thermally conductive sheet 1, and more than 35% by volume and 41% by volume or less. more preferably 39 to 41% by volume.
- the heat conductive sheet 1 contains fibrous fillers 3 .
- the fibrous filler 3 has a major axis and a minor axis, and the major axis and minor axis are different in length, and the aspect ratio (average major axis length/average minor axis length) exceeds 1. including.
- the fibrous filler 3 may be used singly or in combination of two or more.
- the fibrous filler 3 can be appropriately selected depending on the intended purpose. For example, metal fiber, carbon fiber, etc. can be used, and carbon fiber is preferable.
- Carbon fibers include, for example, 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), growth method) or the like can be used.
- pitch-based carbon fibers are preferable from the viewpoint of thermal conductivity.
- the average fiber length (average long axis length) of the fibrous filler 3 can be, for example, 50 to 250 ⁇ m, and may be 75 to 220 ⁇ m.
- the average fiber diameter (average minor axis length) of the fibrous filler 3 can be appropriately selected according to the purpose, and can be, for example, 4 to 20 ⁇ m, and may be 5 to 14 ⁇ m.
- the aspect ratio of the fibrous filler 3 can be appropriately selected depending on the purpose.
- the average major axis length and average minor axis length of the fibrous filler 3 can be measured with a microscope or scanning electron microscope (SEM), for example.
- the surface of the carbon fiber may be covered with an insulating film depending on the purpose.
- insulation-coated carbon fibers can be used as the carbon fibers.
- the insulation-coated carbon fiber has a carbon fiber and an insulation coating on at least part of the surface of the carbon fiber, and may contain other components as necessary.
- the insulating film is made of an electrically insulating material, such as silicon oxide or a hardened polymer material.
- the polymerizable material is, for example, a radical polymerizable material such as a polymerizable organic compound and a polymerizable resin.
- the radically polymerizable material can be appropriately selected according to the purpose as long as it is a material that undergoes radical polymerization using energy. Examples thereof include compounds having a radically polymerizable double bond. Examples of radically polymerizable double bonds include vinyl groups, acryloyl groups, and methacryloyl groups.
- the number of radically polymerizable double bonds in the compound having radically polymerizable double bonds is preferably two or more from the viewpoint of strength including heat resistance and solvent resistance.
- Examples of compounds having two or more radically polymerizable double bonds include divinylbenzene (DVB) and compounds having two or more (meth)acryloyl groups.
- the radically polymerizable material may be used singly or in combination of two or more.
- the molecular weight of the radically polymerizable material can be appropriately selected depending on the purpose, and can be in the range of 50-500, for example.
- the content of structural units derived from the polymerizable material in the insulating coating can be, for example, 50% by mass or more, and can be 90% by mass or more. can also
- the average thickness of the insulating film can be appropriately selected depending on the purpose, and from the viewpoint of realizing high insulation, it can be 50 nm or more, may be 100 nm or more, or may be 200 nm or more. .
- the upper limit of the average thickness of the insulating coating can be, for example, 1000 nm or less, and may be 500 nm or less.
- the average thickness of the insulating coating can be determined, for example, by observation with a transmission electron microscope (TEM).
- Examples of methods for coating carbon fibers with an insulating film include a sol-gel method, a liquid phase deposition method, a polysiloxane method, and a polymerizable material on at least a part of the surface of the carbon fiber described in JP-A-2018-98515. Examples include a method of forming an insulating film made of a cured product.
- the content of the fibrous filler 3 in the heat conductive sheet 1 can be, for example, 5% by volume or more, or can be 10% by volume or more, from the viewpoint of the thermal conductivity of the heat conductive sheet 1. % or more, 20 volume % or more, or 25 volume % or more.
- the content of the fibrous filler 3 in the heat conductive sheet 1 can be, for example, 30% by volume or less, 28% by volume or less, and 25% by volume from the viewpoint of the moldability of the heat conductive sheet 1. It can be vol % or less, and can also be 23 vol % or less.
- the content of the fibrous filler 3 in the heat conductive sheet 1 can be, for example, 5 to 50% by volume, preferably 14 to 25% by volume. When two or more kinds of fibrous fillers 3 are used in combination, it is preferable that the total amount thereof satisfies the content described above.
- the other thermally conductive material 4 is a thermally conductive material other than the fibrous filler 3 described above, and includes, for example, an inorganic filler.
- Other shapes of the heat-conducting material 4 include, for example, a spherical shape, a crushed shape, an ellipsoidal shape, a massive shape, a granular shape, a flat shape, and the like.
- the shape of the other heat conductive material 4 is preferably a crushed shape, a spherical shape, an ellipsoidal shape, or the like from the viewpoint of filling properties. A crushed shape is preferable from the viewpoint of improving the restoring force of the fibrous filler 3 after release.
- the term "pulverized” means, for example, one having a long axis and a short axis and a length ratio of 10 or less between the long axis direction and the short axis direction.
- Other thermally conductive materials 4 may be used singly or in combination of two or more.
- the other thermally conductive material 4 is, for example, an inorganic filler.
- aluminum oxide alumina, sapphire
- aluminum nitride aluminum hydroxide
- the average particle diameter (D50) of the alumina particles may be, for example, 0.1 to 10 ⁇ m, may be 0.1 to 8 ⁇ m, may be 0.1 to 7 ⁇ m, may be 0.1 to It may be 2 ⁇ m.
- the average particle size (D50) of the aluminum hydroxide particles may be, for example, 0.1 to 10 ⁇ m, may be 0.1 to 8 ⁇ m, may be 0.1 to 7 ⁇ m, and may be 0.1 to 8 ⁇ m. It may be 1-2 ⁇ m.
- the average particle size of the other thermally conductive material 4 is obtained by calculating the cumulative curve of the particle size value from the small particle size side of the particle size distribution when the entire particle size distribution of the other thermally conductive material 4 is taken as 100%. means the particle diameter when the cumulative value reaches 50%.
- the particle size distribution is determined by volume. Examples of the method for measuring the particle size distribution include a method using a laser diffraction particle size distribution analyzer.
- the other thermally conductive material 4 may be surface-treated.
- the surface treatment includes, for example, treating the other thermally conductive material 4 with a coupling agent such as an alkoxysilane compound.
- the processing amount of the coupling agent can be, for example, in the range of 0.1 to 1.5% by volume with respect to the total amount of the other thermally conductive material 4.
- An alkoxysilane compound is a compound having a structure in which 1 to 3 of the 4 bonds of a silicon atom (Si) are bonded to alkoxy groups, and the remaining bonds are bonded to organic substituents.
- Examples of the alkoxy group that the alkoxysilane compound has include a methoxy group, an ethoxy group, and a butoxy group.
- Specific examples of alkoxysilane compounds include trimethoxysilane compounds and triethoxysilane compounds.
- the content of the other thermally conductive material 4 in the thermally conductive sheet 1 is not particularly limited, and can be appropriately selected according to the purpose.
- the content of the thermally conductive material 4 can be more than 21% by volume from the viewpoint of the restorability and thermal conductivity of the thermally conductive sheet 1. It may be vol % or more, 40 vol % or more, or 42 vol % or more.
- the content of the other thermally conductive material 4 in the thermally conductive sheet 1 can be 50% by volume or less, and may be 45% by volume or less, from the viewpoint of the resilience of the thermally conductive sheet 1. It may be 40% by volume or less.
- the content of the other thermally conductive material 4 in the thermally conductive sheet 1 is preferably 36 to 45% by volume, for example, from the viewpoint of improving the restorability of the thermally conductive sheet 1 .
- the total content of the fibrous filler 3 and the other heat conductive material 4 in the heat conductive sheet 1 is the restoration of the heat conductive sheet 1
- the content may be 50% by volume or more, may be 55% by volume or more, may be 59% by volume or more, or may be 60% by volume or more.
- the total content of the fibrous filler 3 and the other thermally conductive material 4 in the thermally conductive sheet 1 can be less than 77% by volume, and 67% by volume from the viewpoint of the resilience of the thermally conductive sheet 1.
- the total content of the fibrous filler 3 and the other thermally conductive material 4 in the thermally conductive sheet 1 is preferably, for example, 59% by volume or more and less than 65% by volume.
- the heat conductive sheet 1 may further contain components other than the components described above within a range that does not impair the effects of the present technology.
- Other components include, for example, dispersants, curing accelerators, retarders, tackifiers, plasticizers, flame retardants, antioxidants, stabilizers, colorants, and the like.
- the method for producing a thermally conductive sheet according to the present technology includes a step of preparing a thermally conductive composition containing a binder resin 2 and a fibrous filler 3 (hereinafter also referred to as step A); and a step of slicing the molded block into sheets to obtain the heat conductive sheet 1 (hereinafter also referred to as step C).
- the fibrous filler 3 is dispersed in the binder resin 2, and the fibrous filler 3 is arranged at an angle of 70 to 90 degrees in the thickness direction B in a cross-sectional view. are placed.
- the arrangement angle of the fibrous filler 3 after compression and release is within 10 degrees of the angle before compression in a cross-sectional view.
- the thermally conductive sheet 1 obtained by this manufacturing method has good restoring force when compression and release are performed as in Condition 1, especially the restoring force of the fibrous filler 3 . Therefore, when the thermally conductive sheet 1 is arranged between the heat generating body and the heat radiating body, even if there is a gap between the heat generating body and the heat radiating body, the fibrous shape of the heat conductive sheet 1 will fill the gap.
- the filler 3 can be easily and quickly followed. Thereby, deterioration of the thermal resistance of the heat conductive sheet 1 can be suppressed.
- step A a thermally conductive composition containing binder resin 2 and fibrous filler 3 is prepared.
- the thermally conductive composition may contain other thermally conductive materials 4 as described above.
- the thermally conductive composition may be uniformly mixed with various additives and volatile solvents by known methods.
- a molded block is formed from the thermally conductive composition.
- methods for forming the molded block include an extrusion molding method and a mold molding method.
- the extrusion molding method and the mold molding method are not particularly limited, and various known extrusion molding methods and mold molding methods can be selected depending on the viscosity of the heat conductive composition and the properties required for the heat conductive sheet 1. can be adopted as appropriate.
- the extrusion molding method when the thermally conductive composition is extruded from a die, or in the mold molding method, when the thermally conductive composition is pressed into the mold, the binder resin 2 flows, and the fibers are formed along the flow direction.
- the long axis of the shaped filler 3 is oriented.
- the size and shape of the molded block can be determined according to the required size of the heat conductive sheet. For example, a rectangular parallelepiped having a cross-sectional length of 0.5 to 15 cm and a width of 0.5 to 15 cm can be used. The length of the rectangular parallelepiped may be determined as required.
- the obtained molded block is preferably heat-cured.
- the curing temperature in thermosetting can be appropriately selected according to the purpose, and can be in the range of 60.degree. C. to 120.degree. C. when the binder resin 2 is a silicone resin, for example.
- Curing time in thermal curing can be, for example, in the range of 30 minutes to 10 hours.
- step C the molded block is sliced into sheets to obtain a thermally conductive sheet 1 in which the long axes of fibrous fillers 3 are oriented in the thickness direction B.
- the fibrous filler 3 is exposed on the surface (sliced surface) of the sheet obtained by slicing.
- the slicing method is not particularly limited, and can be appropriately selected from among known slicing devices according to the size and mechanical strength of the compact block. Examples of the slicing device include an ultrasonic cutter and a planer.
- the molding method is extrusion molding, the slicing direction of the molded block is 60 to 120 degrees with respect to the extrusion direction because the long axis of the fibrous filler 3 is oriented in the extrusion direction in some cases. preferably 70 to 100 degrees, and even more preferably 90 degrees (perpendicular).
- the arrangement angle of the fibrous filler 3 after compression and release is within 10 degrees of the angle before compression in cross-sectional view. It is possible to obtain the heat conductive sheet 1 in the range of
- the method for manufacturing the thermally conductive sheet 1 is not limited to the example described above, and for example, after the process C, it may further include a process D for pressing the sliced surface.
- the surface of the thermally conductive sheet 1 obtained in the step C is made smoother, and the adhesion with other members can be further improved.
- a pair of pressing devices comprising a flat plate and a press head having a flat surface can be used.
- the surface of the heat conductive sheet 1 may be pressed with pinch rolls.
- the pressure during pressing may be, for example, in the range of 0.1 to 100 MPa, may be in the range of 0.1 to 1 MPa, or may be in the range of 0.1 to 0.5 MPa.
- the pressing time can be appropriately selected according to the pressure during pressing, the sheet area, etc., and can be, for example, in the range of 10 seconds to 5 minutes, and may be in the range of 30 seconds to 3 minutes. .
- pressing may be performed while heating using a press head with a built-in heater.
- the pressing temperature may range, for example, from 0 to 180°C, may range from room temperature (eg, 25°C) to 100°C, or may range from 30 to 100°C.
- pressing may be performed at a temperature equal to or higher than the glass transition temperature (Tg) of the binder resin forming the compact sheet.
- Tg glass transition temperature
- the thermally conductive sheet 1 is, for example, an electronic device (thermal device) having a structure arranged between a heat generating body and a radiator so that the heat generated by the heat generating body is released to the heat radiator.
- An electronic device has at least a heating element, a radiator, and a thermally conductive sheet 1, and may further have other members as necessary.
- the heating element is not particularly limited, for example, integrated circuit elements such as CPU, GPU (Graphics Processing Unit), DRAM (Dynamic Random Access Memory), flash memory, transistors, resistors, etc. Electronic parts that generate heat in electric circuits etc.
- the heating element also includes components for receiving optical signals, such as optical transceivers in communication equipment.
- the radiator is not particularly limited, and examples include those used in combination with integrated circuit elements, transistors, optical transceiver housings, such as heat sinks and heat spreaders.
- Materials for the heat sink and heat spreader include, for example, copper and aluminum.
- a heat pipe is, for example, a cylindrical, substantially cylindrical, or flat cylindrical hollow structure.
- FIG. 5 is a cross-sectional view showing an example of a semiconductor device to which a heat conductive sheet is applied.
- the heat conductive sheet 1 is mounted on a semiconductor device 50 built in various electronic devices and sandwiched between a heat generator and a radiator.
- a semiconductor device 50 shown in FIG. 5 includes an electronic component 51 , a heat spreader 52 , and a heat conductive sheet 1 .
- sandwiching the heat conductive sheet 1 between the heat spreader 52 and the heat sink 53 , together with the heat spreader 52 a heat dissipation member for dissipating the heat of the electronic component 51 is configured.
- the mounting location of the heat 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, but can be appropriately selected according to the configuration of the electronic device or semiconductor device.
- the heat spreader 52 is formed, for example, in the shape of a square plate, and has a main surface 52a facing the electronic component 51 and side walls 52b erected along the outer circumference of the main surface 52a.
- the heat spreader 52 is provided with the heat conductive sheet 1 on the principal surface 52a surrounded by the side walls 52b, and is provided with the heat sink 53 via the heat conductive sheet 1 on the other surface 52c opposite to the principal surface 52a.
- Example 1 In Example 1, as shown in Table 1, 45% by volume of alumina particles having an average particle diameter of 2 ⁇ m and having been subjected to coupling treatment with a silane coupling agent were added to the two-liquid addition reaction type liquid silicone resin at 45% by volume, and as a fibrous filler, 14% by volume of pitch-based carbon fibers having an average fiber length of 200 ⁇ m were mixed to prepare a silicone composition. 41% by volume of the two-liquid addition reaction type liquid silicone resin containing polyorganosiloxane as the main component was used, and the completed sheet was adjusted to have a Shore type OO hardness of 25.
- the resulting silicone composition was extruded into a hollow quadrangular prism-shaped mold (50 mm x 50 mm) to form a 50 mm square silicone molding.
- the silicone molded product was heated in an oven at 100° C. for 6 hours to obtain a cured silicone product.
- the cured silicone material was cut with a slicer so as to have a thickness of 2.0 mm to obtain a thermally conductive sheet.
- Example 2 In Example 2, as shown in Table 1, instead of 45% by volume of alumina particles having an average particle size of 2 ⁇ m that were coupled with a silane coupling agent, 1.2 ⁇ m average particle size that was coupled with a silane coupling agent was used. A heat conductive sheet was obtained in the same manner as in Example 1 except that 45% by volume of crushed aluminum hydroxide particles were used and the hardness of the completed sheet in Shore type OO was adjusted to 30. rice field.
- Example 3 In Example 3, as shown in Table 1, 36% by volume of alumina particles having an average particle diameter of 4 ⁇ m, which were subjected to coupling treatment with a silane coupling agent, to a two-liquid addition reaction type liquid silicone resin, and an average A silicone composition was prepared by mixing 25% by volume of pitch-based carbon fiber with a fiber length of 120 ⁇ m, and 39% by volume of a two-liquid addition reaction type liquid silicone resin containing polyorganosiloxane as a main component was used. A heat conductive sheet was obtained in the same manner as in Example 1, except that the completed sheet had a hardness of 40 in Shore type OO.
- Comparative Example 1 In Comparative Example 1, as shown in Table 1, 42% by volume of alumina particles having an average particle size of 4 ⁇ m, which were subjected to coupling treatment with a silane coupling agent, to a two-liquid addition reaction type liquid silicone resin, and an average of 4 ⁇ m as a fibrous filler.
- a silicone composition was prepared by mixing 23% by volume of pitch-based carbon fiber with a fiber length of 150 ⁇ m, and 35% by volume of a two-liquid addition reaction type liquid silicone resin containing polyorganosiloxane as a main component was used.
- a heat conductive sheet was obtained in the same manner as in Example 1, except that the completed sheet had a hardness of 40 in Shore type OO.
- Comparative Example 2 In Comparative Example 2, as shown in Table 1, 21% by volume of alumina particles having an average particle diameter of 4 ⁇ m and having an average particle diameter of 1.0 ⁇ m, which were subjected to coupling treatment with a silane coupling agent, were added to a two-liquid addition reaction type liquid silicone resin.
- a silicone composition was prepared by mixing 24% by volume of 3 ⁇ m aluminum nitride particles and 22% by volume of pitch-based carbon fiber having an average fiber length of 150 ⁇ m as a fibrous filler, and a two-liquid addition reaction type liquid silicone resin.
- Comparative Example 3 In Comparative Example 3, as shown in Table 1, 36% by volume of alumina particles having an average particle diameter of 4 ⁇ m and having an average particle diameter of 1.0 ⁇ m, which were subjected to coupling treatment with a silane coupling agent, were added to a two-liquid addition reaction type liquid silicone resin.
- a silicone composition was prepared by mixing 25% by volume of aluminum nitride particles of 3 ⁇ m and 16% by volume of aluminum powder with an average particle size of 15 ⁇ m, and polyorganosiloxane was used as a two-liquid addition reaction type liquid silicone resin.
- a heat conductive sheet was obtained in the same manner as in Example 1, except that 23% by volume of the component was used and that the completed sheet had a Shore type OO hardness of 40. Thus, in Comparative Example 3, a heat conductive sheet containing no carbon fiber was obtained.
- ⁇ Bulk thermal conductivity> For bulk thermal conductivity, the thermal resistance of each thermal conductive sheet is measured by a method in accordance with ASTM-D5470, the horizontal axis is the thickness (mm) of the thermal conductive sheet at the time of measurement, and the vertical axis is the thermal resistance of the thermal conductive sheet ( °C ⁇ cm 2 /W) was plotted, and the bulk thermal conductivity (W/m ⁇ K) of the thermal conductive sheet was calculated from the slope of the plot.
- the thermal resistance of the thermally conductive sheet was measured by preparing three types of thermally conductive sheets with different thicknesses and measuring the thermally conductive sheets with different thicknesses. Table 1 shows the results.
- Example 1 ⁇ External size of sample after compression release>
- the maximum length and the shortest length were visually measured using a vernier caliper, and the average value was taken. Specifically, a sample having a thickness of 2 mm and a diameter of 29 mm was compressed by 40% of the initial thickness at room temperature for 24 hours, and the external size of the sample was measured 3 minutes after the compression was released. Table 1 shows the results.
- Fig. 6 is a digital microscope photograph of the cross section of the heat conductive sheet before compression.
- a method of calculating the angle of the carbon fibers in Sample 6 of Example 3 will be described.
- the five-point angles of carbon fiber 3A in Sample 6 of Example 3 before compression were 87 degrees, 79 degrees, 82 degrees, 93 degrees (87 degrees), and 78 degrees, and the average was 82.6 degrees. . Table 1 shows the results.
- Fig. 7 is a digital microscope photograph of the cross section of the heat conductive sheet after compression release.
- a method of calculating the angle of the carbon fibers 3A in Sample 6 of Example 3 will be described.
- the five-point angles of carbon fiber 3A in sample 6 of example 3 after compression release are 74 degrees, 79 degrees, 70 degrees, 78 degrees, and 84 degrees, with an average of 77.0 degrees. It was degrees. Table 1 shows the results.
- the fibrous filler 3 is dispersed in the binder resin 2, and the fibrous filler 3 is arranged at an angle of 70 to 90 degrees in the thickness direction B when viewed in cross section. It was found that when compression and release were performed under condition 1 described above, the arrangement angle of the fibrous filler 3 after compression and release was within 10 degrees of the angle before compression in a cross-sectional view. That is, the heat conductive sheets obtained in Examples 1 to 3 have good restoring force when compressed and released as in Condition 1, especially the restoring force of carbon fiber 3A (fibrous filler 3). I found out.
- the thermally conductive sheets obtained in Examples 1 to 3 are arranged between the heating element and the radiator, even if the gap between the heating element and the radiator opens, the gap The fibrous filler 3 in the heat conductive sheet can be easily and quickly followed. As a result, the thermally conductive sheets obtained in Examples 1 to 3 are considered to be able to suppress the deterioration of thermal resistance.
- the heat conductive sheets obtained in Examples 1 to 3 had a thickness of 2 mm and a diameter of 29 mm, were compressed by 40% at room temperature for 24 hours, and had a diameter of 32.0 mm or less 3 minutes after release. In other words, it was also found that the thermally conductive sheets obtained in Examples 1 to 3 show little change in outer size after compression is released.
- the heat conductive sheets obtained in Comparative Examples 1 and 2 when compression and release were performed under the above-described condition 1, the arrangement angle of the fibrous filler 3 after compression and release was the same as the angle before compression in cross-sectional view. It was found that it was not within the range of 10 degrees. That is, the heat conductive sheets obtained in Comparative Examples 1 and 2 have a higher restoring force when compression and release are performed as in Condition 1, especially the carbon fiber 3A, compared to the heat conductive sheets of Examples 1 to 3. It was found that the restoring force of (fibrous filler 3) was not good. In addition, it was found that the heat conductive sheets obtained in Comparative Examples 1 to 3 showed a greater change in the outer size after the release of compression than in Examples 1 to 3.
- 1 Thermally conductive sheet 2 Binder resin, 3 Fibrous filler, 3A Carbon fiber, 4 Other thermally conductive material, 5 Sample, 6 Cut sample, 6A Cut surface, 6Ac Center, 50 Semiconductor device, 51 Electronic component, 52 Heat spreader, 52a main surface, 52b side wall, 52c other surface, 53 heat sink
Abstract
Description
条件1:当該熱伝導シートの厚みを24時間常温で初期厚みから40%圧縮した後に解放する。
条件1:当該熱伝導シートの厚みを24時間常温で初期厚みから40%圧縮した後に解放する。
バインダ樹脂2は、繊維状フィラー3や他の熱伝導材料4を熱伝導シート1内に保持するためのものである。バインダ樹脂2は、熱伝導シート1に要求される機械的強度、耐熱性、電気的性質等の特性に応じて選択される。バインダ樹脂2としては、熱可塑性樹脂、熱可塑性エラストマー、熱硬化性樹脂の中から選択することができる。
熱伝導シート1は、繊維状フィラー3を含む。繊維状フィラー3とは、長軸と短軸とを有し、長軸と短軸の長さが異なりアスペクト比(平均長軸長さ/平均短軸長さ)が1を超える形状であるものを含む。繊維状フィラー3は、1種単独で用いてもよいし、2種以上を併用してもよい。繊維状フィラー3は、目的に応じて適宜選択することができ、例えば、金属繊維、炭素繊維などを用いることができ、炭素繊維が好ましい。
他の熱伝導材料4は、上述した繊維状フィラー3以外の熱伝導材料であり、例えば、無機フィラーが挙げられる。他の熱伝導材料4の形状は、例えば、球状、破砕状、楕円球状、塊状、粒状、扁平状などが挙げられる。他の熱伝導材料4の形状は、充填性の観点では、破砕状、球状、楕円球状などが好ましく、熱伝導シート1の復元性、特に、熱伝導シート1において圧縮と解放を行った場合、解放後に繊維状フィラー3の復元力をより良好とする観点では破砕状が好ましい。なお、粉砕状とは、例えば、長軸と短軸を有し、長軸方向と短軸方向の長さの比が10以下であるものをいう。他の熱伝導材料4は、1種単独で用いてもよいし、2種以上を併用してもよい。
本技術に係る熱伝導シートの製造方法は、バインダ樹脂2と繊維状フィラー3とを含む熱伝導組成物を調製する工程(以下、工程Aともいう。)と、熱伝導組成物から成形体ブロックを形成する工程(以下、工程Bともいう。)と、成形体ブロックをシート状にスライスして熱伝導シート1を得る工程(以下、工程Cともいう。)とを有する。
工程Aでは、バインダ樹脂2と繊維状フィラー3とを含む熱伝導組成物を調製する。熱伝導組成物は、上述した他の熱伝導材料4を含んでもよい。熱伝導組成物は、各種添加剤や揮発性溶剤ととともに公知の手法で均一に混合してもよい。
工程Bでは、熱伝導組成物から成形体ブロックを形成する。成形体ブロックの形成方法としては、押出成形法、金型成形法などが挙げられる。押出成形法、金型成形法としては、特に制限されず、公知の各種押出成形法、金型成形法の中から、熱伝導組成物の粘度や熱伝導シート1に要求される特性等に応じて適宜採用することができる。例えば、押出成形法において、熱伝導組成物をダイより押し出す際、あるいは金型成形法において、熱伝導組成物を金型へ圧入する際、バインダ樹脂2が流動し、その流動方向に沿って繊維状フィラー3の長軸が配向する。
工程Cでは、成形体ブロックをシート状にスライスして、厚さ方向Bに繊維状フィラー3の長軸が配向した熱伝導シート1を得る。スライスにより得られるシートの表面(スライス面)には、繊維状フィラー3が露出する。スライスする方法としては特に制限はなく、成形体ブロックの大きさや機械的強度により公知のスライス装置の中から適宜選択することができる。スライス装置としては、例えば、超音波カッタ、かんな(鉋)などが挙げられる。成形体ブロックのスライス方向としては、成形方法が押出成形法である場合、押出し方向に繊維状フィラー3の長軸が配向しているものもあるため、押出し方向に対して60~120度であることが好ましく、70~100度の方向であることがより好ましく、90度(垂直)の方向であることがさらに好ましい。
熱伝導シート1は、例えば、発熱体と放熱体との間に配置させることにより、発熱体で生じた熱を放熱体に逃がすためにそれらの間に配された構造の電子機器(サーマルデバイス)とすることができる。電子機器は、発熱体と放熱体と熱伝導シート1とを少なくとも有し、必要に応じて、その他の部材をさらに有していてもよい。
実施例1では、表1に示すように、2液性の付加反応型液状シリコーン樹脂%に、シランカップリング剤でカップリング処理した平均粒径2μmのアルミナ粒子45体積%と、繊維状フィラーとして平均繊維長200μmのピッチ系炭素繊維14体積%とを混合し、シリコーン組成物を調製した。なお、2液性の付加反応型液状シリコーン樹脂は、ポリオルガノシロキサンを主成分とするものを41体積%使用し、完成後のシートのショアタイプOOにおける硬度が25となるよう調整した。得られたシリコーン組成物を、中空四角柱状の金型(50mm×50mm)の中に押出成形し、50mm□のシリコーン成型体を成型した。シリコーン成型体をオーブンにて100℃で6時間加熱してシリコーン硬化物とした。シリコーン硬化物を、厚みが2.0mmとなるようにスライサーで切断して熱伝導シートを得た。
実施例2では、表1に示すように、シランカップリング剤でカップリング処理した平均粒径2μmのアルミナ粒子45体積%に替えて、シランカップリング剤でカップリング処理した平均粒径1.2μmの破砕状の水酸化アルミニウム粒子45体積%を用いたことと、完成後のシートのショアタイプOOにおける硬度が30となるように調整したこと以外は、実施例1と同様に熱伝導シートを得た。
実施例3では、表1に示すように、2液性の付加反応型液状シリコーン樹脂に、シランカップリング剤でカップリング処理した平均粒径4μmのアルミナ粒子36体積%と、繊維状フィラーとして平均繊維長120μmのピッチ系炭素繊維25体積%とを混合してシリコーン組成物を調製したことと、2液性の付加反応型液状シリコーン樹脂としてポリオルガノシロキサンを主成分とするものを39体積%使用したことと、完成後のシートのショアタイプOOにおける硬度が40となるように調整したこと以外は、実施例1と同様に熱伝導シートを得た。
比較例1では、表1に示すように、2液性の付加反応型液状シリコーン樹脂に、シランカップリング剤でカップリング処理した平均粒径4μmのアルミナ粒子42体積%と、繊維状フィラーとして平均繊維長150μmのピッチ系炭素繊維23体積%とを混合してシリコーン組成物を調製したことと、2液性の付加反応型液状シリコーン樹脂としてポリオルガノシロキサンを主成分とするものを35体積%使用したことと、完成後のシートのショアタイプOOにおける硬度が40となるように調整したこと以外は、実施例1と同様に熱伝導シートを得た。
比較例2では、表1に示すように、2液性の付加反応型液状シリコーン樹脂に、シランカップリング剤でカップリング処理した平均粒径4μmのアルミナ粒子21体積%と、平均粒径1.3μmの窒化アルミニウム粒子24体積%と、繊維状フィラーとして平均繊維長150μmのピッチ系炭素繊維22体積%とを混合してシリコーン組成物を調製したことと、2液性の付加反応型液状シリコーン樹脂としてポリオルガノシロキサンを主成分とするものを33体積%使用したことと、完成後のシートのショアタイプOOにおける硬度が50となるように調整したこと以外は、実施例1と同様に熱伝導シートを得た。
比較例3では、表1に示すように、2液性の付加反応型液状シリコーン樹脂に、シランカップリング剤でカップリング処理した平均粒径4μmのアルミナ粒子36体積%と、平均粒径1.3μmの窒化アルミニウム粒子25体積%と、平均粒径15μmのアルミニウム粉末16体積%とを混合してシリコーン組成物を調製したことと、2液性の付加反応型液状シリコーン樹脂としてポリオルガノシロキサンを主成分とするものを23体積%使用したことと、完成後のシートのショアタイプOOにおける硬度が40となるよう調整したこと以外は、実施例1と同様に熱伝導シートを得た。このように、比較例3では、炭素繊維を含まない熱伝導シートを得た。
バルク熱伝導率は、ASTM-D5470に準拠した方法で各熱伝導シートの熱抵抗を測定し、横軸に測定時の熱伝導シートの厚み(mm)、縦軸に熱伝導シートの熱抵抗(℃・cm2/W)をプロットし、そのプロットの傾きから熱伝導シートのバルク熱伝導率(W/m・K)を算出した。熱伝導シートの熱抵抗は、厚みの異なる熱伝導シートを3種類用意して、それぞれの厚みの熱伝導シートについて測定した。結果を表1に示す。
実施例及び比較例で得られた熱伝導シートを直径29mmに加工して、評価用のサンプルを準備した。サンプルは3枚以上用意し、(1)外形サイズ確認用、(2)圧縮前の断面観察用、(3)圧縮解放後の断面観察用に用いた。
圧縮解放後のサンプルの外形サイズは、ノギスを用いて最大長と最短長を目視で測定し平均値とした。具体的には、厚み2mm、直径29mmのサンプルを24時間常温で初期厚みに対して40%圧縮し、圧縮解放してから3分後にサンプルの外形サイズを測定した。結果を表1に示す。
圧縮前のサンプル5(熱伝導シート1)の断面観察は、図2に示すように、サンプル5の中央部を厚さ方向Bに5mm幅にカミソリ刃で切断してサンプル6を得た。そして、図3に示すように、サンプル6において、外周から5mm内側かつ、断面の上下1/3の範囲6Bで、任意の炭素繊維3Aの角度を5点測定して平均値を求めた。炭素繊維3Aの角度の測定は、マイクロスコープVHX-5000(キーエンス社製)を用いて、倍率100倍で行った。炭素繊維3Aの5点の角度の測定は、サンプル6の平行を出したのち、炭素繊維3Aの角度が0度から90度になるように計測した。
圧縮解放後のサンプル6の断面観察は、圧縮前のサンプル6の断面観察と同時に行った。図2に示すサンプル5を24時間常温で初期厚みに対して40%圧縮し、圧縮解放してから3分後に、図2,3に示すように、圧縮解放後のサンプル5の中央部を厚さ方向Bに5mm幅にカミソリ刃で切断してサンプル6を得た。このサンプル6の切断面(表面)において、外周から5mm内側かつ、断面の上下1/3の範囲6Bで、任意の炭素繊維3Aの角度を5点測定して平均値を求めた。
圧縮解放前後のサンプル6における炭素繊維3Aの5点の角度の平均の差(度)を求めた。結果を表1に示す。
熱伝導シートのショアタイプOOにおける硬度は、ASTM-D2240に準拠した測定方法で、2mm厚の熱伝導シートを5枚重ねて10mm厚とし、片面5点、両面で合計10点測定した測定結果の平均値とした。結果を表1に示す。
Claims (11)
- 繊維状フィラーがバインダ樹脂に分散しており、上記繊維状フィラーが断面視で厚さ方向に70~90度の角度で配置された熱伝導シートであって、
当該熱伝導シートを下記条件1で圧縮と解放を行った場合、解放後の上記繊維状フィラーの配置角度が、断面視で圧縮前の角度の10度以内の範囲にある、熱伝導シート。
条件1:当該熱伝導シートの厚みを24時間常温で初期厚みから40%圧縮した後に解放する。 - 厚み2mm、直径29mmの当該熱伝導シートは、24時間常温で40%圧縮し、解放後3分後の直径が32.0mm以下である、請求項1に記載の熱伝導シート。
- 上記繊維状フィラーの含有量が5~50体積%である、請求項1又は2に記載の熱伝導シート。
- 上記バインダ樹脂の含有量が20~50体積%である、請求項1~3のいずれか1項に記載の熱伝導シート。
- ショアタイプOOにおける硬度が25~40である、請求項1~4のいずれか1項に記載の熱伝導シート。
- 上記バインダ樹脂がシリコーン樹脂である、請求項1~5のいずれか1項に記載の熱伝導シート。
- 上記繊維状フィラーがピッチ系炭素繊維である、請求項1~6のいずれか1項に記載の熱伝導シート。
- 上記繊維状フィラー以外の他の熱伝導材料をさらに含み、
上記繊維状フィラーと上記他の熱伝導材料の含有量の合計が65体積%未満である、請求項1~7のいずれか1項に記載の熱伝導シート。 - 上記繊維状フィラー以外の他の熱伝導材料をさらに含み、
上記他の熱伝導材料が、水酸化アルミニウム及びアルミナの少なくとも1種である、請求項1~8のいずれか1項に記載の熱伝導シート。 - バインダ樹脂と繊維状フィラーとを含む熱伝導組成物を調製する工程と、
上記熱伝導組成物から成形体ブロックを形成する工程と、
上記成形体ブロックをシート状にスライスして熱伝導シートを得る工程とを有し、
上記熱伝導シートが、請求項1~9のいずれか1項に記載の熱伝導シートである、熱伝導シートの製造方法。 - 発熱体と、
放熱体と、
上記発熱体と上記放熱体との間に配置された請求項1~9のいずれか1項に記載の熱伝導シートとを備える、電子機器。
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