WO2011158942A1 - 熱伝導性シート及びその製造方法 - Google Patents
熱伝導性シート及びその製造方法 Download PDFInfo
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- WO2011158942A1 WO2011158942A1 PCT/JP2011/063955 JP2011063955W WO2011158942A1 WO 2011158942 A1 WO2011158942 A1 WO 2011158942A1 JP 2011063955 W JP2011063955 W JP 2011063955W WO 2011158942 A1 WO2011158942 A1 WO 2011158942A1
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- conductive sheet
- heat conductive
- filler
- thermally conductive
- anisotropic
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- B26D1/04—Cutting through work characterised by the nature or movement of the cutting member or particular materials not otherwise provided for; Apparatus or machines therefor; Cutting members therefor involving a cutting member which does not travel with the work having a linearly-movable cutting member
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y10T428/24479—Structurally defined web or sheet [e.g., overall dimension, etc.] including variation in thickness
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
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- Y10T428/268—Monolayer with structurally defined element
Definitions
- the present invention relates to a heat conductive sheet and a method for producing the heat conductive sheet.
- This application includes Japanese Patent Application Nos. 2010-138334 and 2010-138417 filed on June 17, 2010 in Japan, and Japanese Patent Application No. filed on March 31, 2011 in Japan. The priority is claimed on the basis of Japanese Patent Application No. 2011-79976, and these applications are incorporated herein by reference.
- the semiconductor is attached to a heat sink such as a heat radiating fin or a heat radiating plate via a heat conductive sheet.
- a thermally conductive sheet a material in which a filler (thermally conductive filler) such as an inorganic filler is dispersed in silicone is widely used.
- the inorganic filler examples include alumina, aluminum nitride, and aluminum hydroxide.
- boron nitride (BN), scaly particles such as graphite, carbon fibers, and the like may be filled in the matrix. This is due to the anisotropy of the thermal conductivity of the scaly particles.
- carbon fiber has a thermal conductivity of about 600 W / m ⁇ K to 1,200 W / m ⁇ K in the fiber direction.
- Boron nitride is known to have anisotropy in the plane direction of about 110 W / m ⁇ K and in the direction perpendicular to the plane direction of about 2 W / m ⁇ K.
- the surface direction of the carbon fibers and the scaly particles is made the same as the thickness direction of the sheet, which is the heat transfer direction. That is, by orienting carbon fibers and scaly particles in the thickness direction of the sheet, the thermal conductivity can be dramatically improved.
- the concavo-convex portion of the sheet surface becomes large and air is entrained in the concavo-convex portion because the flexible cured product is sliced while being deformed. Therefore, there is a problem that excellent thermal conductivity is not utilized.
- Patent Document 1 proposes a thermally conductive rubber sheet that is punched and sliced by blades arranged at equal intervals in a direction perpendicular to the longitudinal direction of the sheet.
- Patent Document 2 proposes that a heat conductive sheet having a predetermined thickness can be obtained by slicing a laminate formed by repeatedly applying and curing by a cutting device having a circular rotary blade. Has been.
- Patent Document 3 a laminate in which two or more graphite layers containing anisotropic graphite particles are laminated is oriented at 0 ° with respect to the thickness direction of the sheet from which an expanded graphite sheet is obtained using a metal saw. It has been proposed to cut in such a way (at an angle of 90 ° to the laminated surface).
- the thermal conductivity in the thickness direction is high, and between various heat sources (for example, various devices such as CPU, transistor, LED, etc.) and the heat radiating member.
- various heat sources for example, various devices such as CPU, transistor, LED, etc.
- the present invention makes it a subject to solve the said various problems in the past and to achieve the following objectives. That is, since the surface roughness of the cut surface is small, the present invention has low thermal resistance at the interface, and high thermal conductivity in the thickness direction. Therefore, the present invention is preferably used by being sandwiched between various heat sources and heat radiating members. It aims at providing the manufacturing method of a heat conductive sheet and a heat conductive sheet.
- an anisotropic heat conductive filler blended in a heat conductive composition by passing a plurality of slits through a heat conductive composition containing an anisotropic heat conductive filler and a filler. After being oriented in the thickness direction of the heat conductive sheet and forming without disturbing the orientation state of the anisotropic heat conductive filler, it is extruded as a block body from the die outlet.
- the cured product is cut to a predetermined thickness with an ultrasonic cutter in a direction perpendicular to the extrusion direction, so that the surface roughness of the cut surface is small, so the thermal resistance at the interface
- the thermal conductivity in the thickness direction is increased, and a thermal conductive sheet that is suitably used by being sandwiched between various heat sources (for example, various devices such as a CPU, a transistor, and an LED) and a heat radiating member can be obtained. I found out.
- the cured product of the thermally conductive composition is cut to a predetermined thickness with an ultrasonic cutter, the difference from the thickness direction of the cured product (thermal conductive sheet) cut with the ultrasonic cutter.
- the isotropic thermally conductive filler is oriented at an angle of 5 ° to 45 °, an angle is applied when a load is applied between the semiconductor element and the heat sink. This makes it easier for the anisotropic heat conductive filler to collapse (the anisotropic heat conductive filler can easily slide in the heat conductive sheet), and it is possible to improve the compressibility while suppressing an increase in thermal resistance. I found out.
- This invention is based on the said knowledge by this inventor, and as a means for solving the said subject, it is as follows. That is, ⁇ 1> Extruded product in which a thermally conductive composition containing a polymer, an anisotropic thermally conductive filler, and a filler is extruded with an extruder, and the anisotropic thermally conductive filler is oriented along the extrusion direction.
- An extrusion process for forming A curing step of curing the extruded product to obtain a cured product;
- Extruded product in which a thermally conductive composition containing a polymer, an anisotropic thermally conductive filler, and a filler is extruded with an extruder, and the anisotropic thermally conductive filler is oriented along the extrusion direction.
- An extrusion process for forming A curing step of curing the extruded product to obtain a cured product; When the cured product is cut into a predetermined thickness with an ultrasonic cutter, the anisotropic thermally conductive filler is at an angle of 5 ° to 45 ° with respect to the thickness direction of the cured product cut with the ultrasonic cutter.
- a cutting step of arranging and cutting the cured product so as to be oriented to It is a manufacturing method of the heat conductive sheet characterized by including at least.
- ⁇ 3> The method for producing a heat conductive sheet according to any one of ⁇ 1> to ⁇ 2>, wherein the average fiber length of the anisotropic heat conductive filler is 100 ⁇ m or more.
- ⁇ 4> The method for producing a thermally conductive sheet according to any one of ⁇ 1> to ⁇ 3>, wherein the anisotropic thermally conductive filler is carbon fiber.
- ⁇ 6> The method for producing a thermally conductive sheet according to any one of ⁇ 1> to ⁇ 5>, wherein the filler has an average particle diameter of 1 ⁇ m to 40 ⁇ m.
- ⁇ 7> The method for producing a thermally conductive sheet according to any one of ⁇ 1> to ⁇ 6>, wherein the filler is spherical alumina particles.
- ⁇ 8> The method for producing a thermally conductive sheet according to any one of ⁇ 1> to ⁇ 7>, wherein the polymer is a silicone resin.
- thermoconductive sheet according to any one of ⁇ 9> to ⁇ 10>, wherein the surface roughness Ra of the cut surface of the thermal conductive sheet is 9.9 ⁇ m or less.
- the conventional problems can be solved and the object can be achieved, and since the surface roughness of the cut surface is small, the thermal resistance at the interface is low and the thermal conductivity in the thickness direction is high. Further, it is possible to provide a thermal conductive sheet that is suitably used by being sandwiched between various heat sources and a heat radiating member, and a method for manufacturing the thermal conductive sheet.
- FIG. 1 is a schematic diagram showing a flow of a method for producing a thermally conductive sheet of the present invention.
- FIG. 2 is an explanatory diagram for explaining the orientation state of the anisotropic thermally conductive filler in the extrusion molding step.
- FIG. 3 is a photograph showing a state where the cured silicone product of Example 1 was cut with an ultrasonic cutter.
- 4A is an electron micrograph of the surface of the cut surface obtained by cutting the thermally conductive sheet of Example 1 with an ultrasonic cutter
- FIG. 4B is a cut obtained by cutting the thermally conductive sheet of Example 1 with an ultrasonic cutter.
- FIG. 4C is a three-dimensional graphic diagram of a cut surface obtained by cutting the heat conductive sheet of Example 1 with an ultrasonic cutter.
- FIG. 5A is an electron micrograph of the surface of the cut surface obtained by cutting the heat conductive sheet of Comparative Example 1 with a commercially available cutter knife
- FIG. 5B is a cut of the heat conductive sheet of Comparative Example 1 with a commercially available cutter knife.
- FIG. 5C is a three-dimensional graphic diagram of a cut surface obtained by cutting the heat conductive sheet of Comparative Example 1 with a commercially available cutter knife.
- FIG. 6 is a graph showing the relationship between the thermal resistance when cutting with a commercially available cutter knife and an ultrasonic cutter while changing the thickness.
- 7 is a cross-sectional photograph in the thickness direction of the thermally conductive sheet of Example 1.
- FIG. 8 is a cross-sectional photograph in the thickness direction of the heat conductive sheet according to Example 1 described in Japanese Patent Laid-Open No. 2003-200347.
- FIG. 9 is a view for explaining an angle formed by the direction of extrusion (length direction) of the cured product and the blade of the ultrasonic cutter.
- FIG. 10 is a graph showing the relationship between the angle of the carbon fiber with respect to the thickness direction of the thermally conductive sheet at a load of 1 kgf / cm 2 in Example 16, the thermal resistance, and the compressibility.
- FIG. 11 is a graph showing the relationship between the angle of the carbon fiber with respect to the thickness direction of the thermally conductive sheet at a load of 2 kgf / cm 2 in Example 16, the thermal resistance, and the compressibility.
- FIG. 12 is a graph showing the relationship between the angle of the carbon fiber with respect to the thickness direction of the thermally conductive sheet at a load of 3 kgf / cm 2 in Example 16, the thermal resistance, and the compressibility.
- FIG. 13 is a table showing the compression ratio according to the blending ratio of the first silicone resin and the second silicone resin.
- FIG. 14 is a table showing the evaluation of the combustion test and the ease of extruding the sheet base material.
- FIG. 15 is a graph showing the relationship between the amount of carbon fiber blended in the thermally conductive sheet and thermal resistance.
- FIG. 16 is a table showing the blending amounts of materials constituting the heat conductive sheet.
- FIG. 17 is a perspective view showing a process of manufacturing a heat conductive sheet by slicing a sheet base material.
- FIG. 18 is an external view showing a slicing apparatus.
- FIG. 19 is a graph showing the relationship between the slicing method according to the presence or absence of ultrasonic vibration and the thermal resistance value of the thermal conductive sheet.
- FIG. 20 is a diagram illustrating a shape corresponding to the slice speed of the ultrasonic cutter and the thickness of the heat conductive sheet.
- FIG. 21 is a table showing the characteristics of the thermally conductive sheet according to the difference between the sheet base material slicing speed and the thickness of the thermally conductive sheet.
- FIG. 22 is a table showing each characteristic of the thermally conductive sheet sliced by changing the amplitude of the ultrasonic vibration applied to the cutter.
- the manufacturing method of the heat conductive sheet of this invention includes an extrusion process, a hardening process, and a cutting process at least, and also includes another process as needed.
- the heat conductive sheet of the present invention is manufactured by the method for manufacturing the heat conductive sheet of the present invention.
- the manufacturing method of the heat conductive sheet of the present invention is manufactured through a series of steps such as extrusion, molding, curing, and cutting (slicing).
- a heat conductive composition containing a polymer, an anisotropic heat conductive filler and a filler is prepared.
- the anisotropic heat conductive filler blended in the heat conductive composition by passing a plurality of slits is used in the thickness direction of the heat conductive sheet.
- the cured product 11 is cut to a predetermined thickness with an ultrasonic cutter in a direction perpendicular to the extrusion direction, so that the surface roughness of the cut surface is small, so that Thus, a heat conductive sheet having a high thermal conductivity in the thickness direction of the sheet can be produced.
- the cured product 11 obtained by curing the obtained molded body is arranged so that the extrusion direction D of the cured product 11 is at a predetermined angle with respect to the blade of the ultrasonic cutter 14 ( 9A is arranged at 45 °, FIG. 9B is arranged at 0 °, and FIG. 9C is arranged at 90 °).
- 9A is arranged at 45 °
- FIG. 9B is arranged at 0 °
- FIG. 9C is arranged at 90 °.
- the angle formed between the extrusion direction D (length direction) of the cured product 11 and the blade of the ultrasonic cutter 14 is the same as the orientation angle of the anisotropic thermally conductive filler 1 with respect to the thickness direction of the thermally conductive sheet. .
- a thermally conductive composition containing a polymer, an anisotropic thermally conductive filler, and a filler is extruded with an extruder, and the anisotropic thermally conductive filler is oriented along the extrusion direction. It is a step of forming an extruded product.
- thermoplastic polymer or a thermosetting polymer is mentioned.
- thermoplastic polymer examples include thermoplastic resins, thermoplastic elastomers, and polymer alloys thereof.
- thermoplastic resin is not particularly limited and may be appropriately selected depending on the intended purpose.
- examples thereof include ethylene- ⁇ -olefin copolymers such as polyethylene, polypropylene and ethylene-propylene copolymers; polymethylpentene, poly Fluorine resins such as vinyl chloride, polyvinylidene chloride, polyvinyl acetate, ethylene-vinyl acetate copolymer, polyvinyl alcohol, polyacetal, polyvinylidene fluoride, polytetrafluoroethylene; polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polystyrene , Polyacrylonitrile, styrene-acrylonitrile copolymer, acrylonitrile-butadiene-styrene copolymer (ABS) resin, polyphenylene ether, modified polyphenylene ether, aliphatic poly Amides, aromatic polyamides, polyamideimide, polymethacryl
- thermoplastic elastomer examples include a styrene-based thermoplastic elastomer such as a styrene-butadiene copolymer or a hydrogenated polymer thereof, a styrene-isoprene block copolymer or a hydrogenated polymer thereof, an olefin-based thermoplastic elastomer, and a vinyl chloride-based heat.
- a thermoplastic elastomer such as a styrene-butadiene copolymer or a hydrogenated polymer thereof, a styrene-isoprene block copolymer or a hydrogenated polymer thereof, an olefin-based thermoplastic elastomer, and a vinyl chloride-based heat.
- thermoplastic elastomer examples include a thermoplastic elastomer, a polyester-based thermoplastic elastomer, a polyurethane-based thermoplastic elastomer, and a
- thermosetting polymer examples include crosslinked rubber, epoxy resin, polyimide resin, bismaleimide resin, benzocyclobutene resin, phenol resin, unsaturated polyester, diallyl phthalate resin, silicone resin, polyurethane, polyimide silicone, thermosetting polyphenylene.
- examples include ether and thermosetting modified polyphenylene ether. These may be used individually by 1 type and may use 2 or more types together.
- crosslinked rubber examples include natural rubber, butadiene rubber, isoprene rubber, nitrile rubber, hydrogenated nitrile rubber, chloroprene rubber, ethylene propylene rubber, chlorinated polyethylene, chlorosulfonated polyethylene, butyl rubber, halogenated butyl rubber, fluorine rubber, urethane.
- examples thereof include rubber, acrylic rubber, polyisobutylene rubber, and silicone rubber. These may be used individually by 1 type and may use 2 or more types together.
- a silicone resin is particularly preferable from the viewpoints of excellent molding processability and weather resistance, and adhesion and followability to electronic components.
- the silicone resin is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include addition reaction type liquid silicone rubber and heat vulcanizable millable type silicone rubber using peroxide for vulcanization. It is done. Among these, an addition reaction type liquid silicone rubber is particularly preferable as a heat radiating member of an electronic device because adhesion between a heat generating surface of an electronic component and a heat sink surface is required.
- the shape of the anisotropic heat conductive filler is not particularly limited and may be appropriately selected depending on the purpose. Examples thereof include a scale shape, a plate shape, a cylindrical shape, a prismatic shape, an elliptical shape, and a flat shape. It is done. Among these, a flat shape is particularly preferable in terms of anisotropic thermal conductivity.
- anisotropic filler examples include boron nitride (BN) powder, graphite, and carbon fiber.
- BN boron nitride
- carbon fiber is particularly preferable from the viewpoint of anisotropic thermal conductivity.
- the carbon fiber for example, a fiber synthesized by pitch system, PAN system, arc discharge method, laser evaporation method, CVD method (chemical vapor deposition method), CCVD method (catalytic chemical vapor deposition method) or the like is used. Can do. Among these, pitch-based carbon fibers are particularly preferable from the viewpoint of thermal conductivity.
- the carbon fiber can be used after partially or entirely surface-treating as necessary.
- the surface treatment include oxidation treatment, nitriding treatment, nitration, sulfonation, or attaching a metal, a metal compound, an organic compound, or the like to the surface of a functional group or carbon fiber introduced to the surface by these treatments.
- the process etc. which are combined are mentioned.
- the functional group include a hydroxyl group, a carboxyl group, a carbonyl group, a nitro group, and an amino group.
- the average long axis length (average fiber length) of the carbon fibers is preferably 100 ⁇ m or more, and more preferably 120 ⁇ m to 6 mm. If the average major axis length is less than 100 ⁇ m, anisotropic thermal conductivity may not be sufficiently obtained, and thermal resistance may be increased.
- the average minor axis length of the carbon fiber is preferably 6 ⁇ m to 15 ⁇ m, more preferably 8 ⁇ m to 13 ⁇ m.
- the carbon fiber preferably has an aspect ratio (average major axis length / average minor axis length) of 8 or more, more preferably 12-30.
- aspect ratio average major axis length / average minor axis length
- the aspect ratio is less than 8, since the fiber length (major axis length) of the carbon fiber is short, the thermal conductivity may be lowered.
- the average major axis length and the average minor axis length of the carbon fiber can be measured, for example, with a microscope, a scanning electron microscope (SEM), or the like.
- the content of the anisotropic heat conductive filler in the heat conductive composition is preferably 15% by volume to 26% by volume. When the content is less than 15% by volume, sufficient heat conductivity may not be imparted to the molded body. When the content exceeds 26% by volume, the moldability and orientation may be affected. There is.
- Examples of the material of the filler include aluminum nitride, silica, alumina, boron nitride, titania, glass, zinc oxide, silicon carbide, silicon (silicon), silicon oxide, aluminum oxide, and metal particles. These may be used individually by 1 type and may use 2 or more types together. Among these, alumina, boron nitride, aluminum nitride, zinc oxide, and silica are preferable, and alumina and aluminum nitride are particularly preferable from the viewpoint of thermal conductivity.
- the filler may be subjected to a surface treatment.
- the surface treatment is performed with a coupling agent, the dispersibility is improved and the flexibility of the heat conductive sheet is improved. Moreover, the surface roughness obtained by slicing can be further reduced.
- the average particle size of the filler is preferably 1 ⁇ m to 40 ⁇ m, more preferably 1 ⁇ m to 20 ⁇ m. If the average particle size is less than 1 ⁇ m, it may cause curing failure, and if it exceeds 40 ⁇ m, the orientation of carbon fibers may be hindered and the thermal conductivity of the cured product may be lowered.
- the average particle diameter of the filler can be measured by, for example, a particle size distribution meter or a scanning electron microscope (SEM).
- the content of the filler in the thermally conductive composition is preferably 40% by volume to 60% by volume.
- the thermal conductive composition may further include, for example, a solvent, a thixotropic agent, a dispersant, a curing agent, a curing accelerator, a retarder, a slightly tackifier, a plasticizer, a flame retardant, and an antioxidant.
- a solvent for example, a solvent, a thixotropic agent, a dispersant, a curing agent, a curing accelerator, a retarder, a slightly tackifier, a plasticizer, a flame retardant, and an antioxidant.
- a stabilizer and a colorant can be blended.
- the thermally conductive composition can be prepared by mixing the polymer, the anisotropic thermally conductive filler, the filler, and, if necessary, the other components using a mixer or the like. .
- the thermally conductive composition is extruded into a mold 3 using a pump, an extruder, or the like (see FIG. 1).
- the extrusion port of the extruder is provided with a plurality of slits, whereby the anisotropic thermally conductive filler is oriented in the extrusion direction.
- the shape and size of the slit are not particularly limited and may be appropriately selected depending on the intended purpose.
- Examples of the shape of the slit include a flat plate shape, a lattice shape, and a honeycomb shape.
- the size (width) of the slit is preferably 0.5 mm to 10 mm.
- the extrusion rate of the heat conductive composition is preferably 0.001 L / min or more.
- the shape, size, material and the like of the mold 3 are not particularly limited and can be appropriately selected according to the purpose.
- Examples of the shape include a hollow columnar shape and a hollow prismatic shape.
- size it can select suitably according to the magnitude
- Examples of the material include stainless steel.
- anisotropic heat conductive fillers and fillers are collected in the center direction of the heat conductive composition, and anisotropic heat conduction is performed between the surface and the center.
- the density of the filler and filler is different. That is, since the heat conductive filler and the anisotropic heat conductive filler do not protrude on the surface of the heat conductive composition (molded product) that has passed through the extruder, the heat conductive composition (molded product).
- the surface portion (the outer peripheral portion of the heat conductive sheet) of the cured product 11 obtained by curing is provided with a fine adhesiveness, and the adhesion to an adherend (semiconductor device or the like) is good.
- the anisotropic heat conductive filler protrudes from the surface in contact with the heat source or the heat radiating side, the slight adhesiveness decreases.
- the fibrous anisotropic heat conductive filler 1 is formed by extruding the heat conductive composition containing the anisotropic heat conductive filler 1 and the spherical filler 2. It can be oriented in the extrusion direction.
- the above-mentioned slight tackiness means that the film has removability with little increase in adhesive strength due to aging and wet heat, and has such tackiness that the position does not easily shift when affixed to an adherend.
- the curing step is a step of curing the extrusion-molded product to obtain a cured product.
- the molded body molded in the extrusion process can obtain a cured product completed by an appropriate curing reaction depending on the resin used.
- the method for curing the extruded product is not particularly limited and may be appropriately selected according to the purpose. However, when a thermosetting resin such as a silicone resin is used as the polymer, it can be cured by heating. preferable.
- Examples of the apparatus used for the heating include a far infrared furnace and a hot air furnace.
- the heating temperature is not particularly limited and may be appropriately selected depending on the intended purpose.
- the heating temperature is preferably 40 ° C. to 150 ° C.
- the flexibility of the cured silicone product obtained by curing the silicone resin is not particularly limited. However, it can be appropriately selected depending on the purpose, and can be adjusted by, for example, the crosslinking density of silicone, the filling amount of the thermally conductive filler, and the like.
- the cutting step is a step of cutting the cured product into a predetermined thickness in a direction perpendicular to the extrusion direction using an ultrasonic cutter.
- the cutting step is performed in the anisotropic heat with respect to the thickness direction of the cured product cut by the ultrasonic cutter when the cured product is cut to a predetermined thickness by an ultrasonic cutter.
- This is a step of arranging and cutting the cured product so that the conductive filler is oriented at an angle of 5 ° to 45 °.
- the angle between the thickness direction of the cured product (thermally conductive sheet) cut to a predetermined thickness by the ultrasonic cutter and the anisotropic thermally conductive filler is 5 ° to 45 °, and 5 ° to 30 °. Is preferred. If the angle formed is less than 5 °, the compression ratio is 0 °, and if it exceeds 45 °, the thermal resistance value may increase.
- the angle formed can be measured by, for example, an electron microscope.
- the cutting is performed using an ultrasonic cutter.
- the transmission frequency and amplitude can be adjusted, and it is preferable to adjust the transmission frequency in the range of 10 kHz to 100 kHz and the amplitude in the range of 10 ⁇ m to 100 ⁇ m. If the cutting is performed with a cutter knife or meat slicer (rotating blade) instead of an ultrasonic cutter, the surface roughness Ra of the cut surface increases and the thermal resistance increases.
- the anisotropic heat conductive filler is obtained by cutting the cured product having undergone the curing reaction into a predetermined thickness in a direction perpendicular to the extrusion direction using an ultrasonic cutter.
- a thermally conductive sheet in which (for example, carbon fibers and scale-like particles) are oriented (vertically oriented) in the thickness direction of the thermally conductive sheet can be obtained.
- the thickness direction of the cured product (thermally conductive sheet) cut with the ultrasonic cutter.
- the thickness of the heat conductive sheet is preferably 0.1 mm or more. If the thickness is less than 0.1 mm, the shape may not be maintained during slicing depending on the hardness of the cured product. Although there is a limit to orienting the anisotropic thermally conductive filler by applying a magnetic field to a thick sheet, the method for producing a thermally conductive sheet of the present invention has an advantage that the sheet thickness is not limited.
- the orientation angle of the anisotropic heat conductive filler (for example, carbon fiber, scale-like particles) with respect to the thickness direction of the heat conductive sheet is preferably 0 ° to 45 °, preferably 0 °. More preferably, it is ⁇ 30 degrees.
- the orientation angle of the carbon fiber can be measured, for example, by observing a cross section of the heat conductive sheet with a microscope.
- the surface roughness Ra of the cut surface after cutting is preferably 9.9 ⁇ m or less, and more preferably 9.5 ⁇ m or less. If the surface roughness Ra exceeds 9.9 ⁇ m, the surface roughness may increase and the thermal resistance may increase.
- the surface roughness Ra can be measured by, for example, a laser microscope.
- the heat conductive sheet of the present invention is used by being sandwiched between various heat sources (for example, various devices such as a CPU, a transistor, and an LED) and a heat radiating member, it preferably has flame retardancy for safety.
- the flame retardancy is preferably “V-0” or higher in the UL-94 standard.
- the heat conductive sheet of the present invention has a small surface roughness of the cut surface, a low thermal resistance at the interface, and a high thermal conductivity in the thickness direction, various heat sources (for example, various devices such as CPU, transistor, LED, etc.) ) And a heat radiating member.
- various heat sources for example, various devices such as CPU, transistor, LED, etc.
- a heat radiating member for example, CPU, MPU, power transistor, LED, laser diode, various batteries (lithium ion batteries, etc.) that have an adverse effect on element operation efficiency, life, etc. depending on temperature.
- various electrical devices such as various secondary batteries, various fuel cells, capacitors, amorphous silicon, crystalline silicon, compound semiconductors, wet solar cells, etc., and around the heat source of heating equipment that requires effective use of heat It is preferably used around heat pipes of heat exchangers and floor heating devices.
- the average particle diameters of alumina particles and aluminum nitride are values measured by a particle size distribution meter.
- the average major axis length and the average minor axis length of the pitch-based carbon fibers are values measured with a microscope (manufactured by HiROX Co Ltd, KH7700).
- Example 1 Provide of thermal conductive sheet- Two-component addition reaction type liquid in which 18.8 vol% of silicone A liquid (organopolysiloxane having vinyl group) and 18.8 vol% of silicone B liquid (organopolysiloxane having H-Si group) are mixed.
- a silicone resin composition was prepared by dispersing 20.1% by volume of Lahima R-A301 (manufactured by Teijin Ltd.).
- the obtained silicone resin composition was extruded into a mold 3 (hollow cylindrical shape) with an extruder to produce a silicone molded body.
- a slit discharge port shape: flat plate is formed in the extrusion port of the extruder.
- the obtained silicone molded body was heated in an oven at 100 ° C. for 1 hour to obtain a cured silicone product.
- the obtained cured silicone was sliced and cut with an ultrasonic cutter so that the thickness was 0.5 mm (see FIG. 3, transmission frequency 20.5 kHz, amplitude 50 to 70 ⁇ m).
- a square-shaped thermally conductive sheet of Example 1 having a thickness of 0.5 mm, a length of 15 mm, and a width of 15 mm was produced.
- Example 2 Provide of thermal conductive sheet-
- alumina particles (average particle size 3 ⁇ m, alumina DAW03, spherical, manufactured by Denki Kagaku Kogyo Co., Ltd.) were replaced with alumina particles (average particle size 5 ⁇ m, alumina DAW05, spherical, manufactured by Denki Kagaku Kogyo Co., Ltd.).
- a heat conductive sheet of Example 2 having a thickness of 0.5 mm, a length of 15 mm, and a width of 15 mm was prepared in the same manner as Example 1.
- Example 3 Provide of thermal conductive sheet-
- alumina particles (average particle size 3 ⁇ m, alumina DAW03, spherical, manufactured by Denki Kagaku Kogyo Co., Ltd.) were replaced with alumina particles (average particle size 10 ⁇ m, alumina DAW10, spherical, manufactured by Denki Kagaku Kogyo Co., Ltd.).
- a heat conductive sheet of Example 3 having a thickness of 0.5 mm, a length of 15 mm, and a width of 15 mm was prepared in the same manner as Example 1.
- Example 4 Provide of thermal conductive sheet- In Example 1, 1 part by volume of silicone A liquid (organopolysiloxane having vinyl group) and 17.8 volume% of silicone B liquid (organopolysiloxane having H-Si group) were mixed.
- alumina particles average particle diameter 3 ⁇ m, alumina DAW03, spherical, manufactured by Denki Kagaku Kogyo Co., Ltd.
- pitch-based carbon fibers average major axis length 150 ⁇ m, average short
- a silicone resin composition was prepared by dispersing a shaft length of 8 ⁇ m, Lahima R-A301, manufactured by Teijin Ltd., 23.4% by volume, a thickness of 0.5 mm, a length of A heat conductive sheet of Example 4 having a square shape of 15 mm and a width of 15 mm was produced.
- Example 5 Provide of thermal conductive sheet- In Example 1, 17.6 vol% of silicone A liquid (organopolysiloxane having vinyl group) and 17.6 vol% of silicone B liquid (organopolysiloxane having H—Si group) were mixed.
- Example 1 And 40.5% by volume of alumina particles (average particle diameter 3 ⁇ m, alumina DAW03, manufactured by Denki Kagaku Kogyo Co., Ltd.) and pitch-based carbon fiber (average major axis length 150 ⁇ m, average minor axis length) 8 ⁇ m, Lahima R-A301, manufactured by Teijin Ltd.) 24.3% by volume, and a silicone resin composition was prepared in the same manner as in Example 1 except that the thickness was 0.5 mm, the length was 15 mm, A heat conductive sheet of Example 5 having a square shape of 15 mm in width was produced.
- alumina particles average particle diameter 3 ⁇ m, alumina DAW03, manufactured by Denki Kagaku Kogyo Co., Ltd.
- pitch-based carbon fiber average major axis length 150 ⁇ m, average minor axis length 8 ⁇ m, Lahima R-A301, manufactured by Teijin Ltd.
- Example 6 Provide of thermal conductive sheet-
- Example 2 And 45.0% by volume of alumina particles (average particle diameter 3 ⁇ m, alumina DAW03, spherical, manufactured by Denki Kagaku Kogyo Co., Ltd.) and pitch-based carbon fibers (average major axis length 150 ⁇ m, average short) Except that a silicone resin composition was prepared by dispersing 16.0 vol% of an axial length of 8 ⁇ m, Lahima R-A301, manufactured by Teijin Ltd.), a thickness of 0.5 mm, vertical length was the same as in Example 1. A heat conductive sheet of Example 6 having a square shape of 15 mm and a width of 15 mm was produced.
- Example 7 Provide of thermal conductive sheet-
- a two-part liquid obtained by mixing 18.9% by volume of a silicone A liquid (organopolysiloxane having a vinyl group) and 18.9% by volume of a silicone B liquid (organopolysiloxane having an H—Si group).
- reaction type liquid silicone resin alumina particles (average particle diameter 3 ⁇ m, alumina DAW03, spherical, manufactured by Denki Kagaku Kogyo Co., Ltd.) 43.6% by volume, pitch-based carbon fiber (average long axis length 150 ⁇ m, average short) Except that a silicone resin composition was prepared by dispersing 18.6% by volume of an axial length of 8 ⁇ m, Lahima R-A301, manufactured by Teijin Ltd.), a thickness of 0.5 mm, vertical length was the same as in Example 1. A heat conductive sheet of Example 7 having a square shape of 15 mm and a width of 15 mm was produced.
- Example 8 Provides thermal conductive sheet-
- a square example 8 having a thickness of 0.5 mm, a length of 14 mm, and a width of 14 mm was obtained in the same manner as in Example 1 except that the outer peripheral portion of the produced heat conductive sheet was cut with a commercially available cutter knife. A heat conductive sheet was prepared.
- Example 9 Provide of thermal conductive sheet-
- pitch-based carbon fibers (average major axis length 150 ⁇ m, average minor axis length 8 ⁇ m, Lahima R-A301, manufactured by Teijin Ltd.) were used as pitch-based carbon fibers (average major axis length 100 ⁇ m, average minor axis length).
- Example 10 (Example 10) -Production of thermal conductive sheet-
- pitch-based carbon fibers (average major axis length 150 ⁇ m, average minor axis length 8 ⁇ m, Lahema R-A301, manufactured by Teijin Ltd.) were used as pitch-based carbon fibers (average major axis length 50 ⁇ m, average minor axis length).
- Example 11 Provide of thermal conductive sheet-
- a two-part liquid in which 17.3% by volume of silicone A liquid (organopolysiloxane having a vinyl group) and 17.3% by volume of silicone B liquid (organopolysiloxane having an H—Si group) were mixed.
- Example 11 A heat conductive sheet of Example 11 having a square shape of 15 mm and a width of 15 mm was produced.
- Example 12 Provide of thermal conductive sheet-
- alumina particles (average particle size 3 ⁇ m, alumina DAW03, spherical, manufactured by Denki Kagaku Kogyo Co., Ltd.) were replaced with alumina particles (average particle size 45 ⁇ m, alumina DAW45, spherical, manufactured by Denki Kagaku Kogyo Co., Ltd.).
- a heat conductive sheet of Example 12 having a thickness of 0.5 mm, a length of 15 mm, and a width of 15 mm was produced in the same manner as in Example 1.
- Example 13 Provide of thermal conductive sheet-
- 42.3 parts by mass of alumina particles (average particle size 3 ⁇ m, alumina DAW03, spherical, manufactured by Denki Kagaku Kogyo Co., Ltd.) were used as alumina particles (average particle size 3 ⁇ m, alumina DAW03, spherical, Electrochemical Kogyo Co., Ltd.).
- a heat conductive sheet of Example 13 was produced.
- Example 1 Provides thermal conductive sheet-
- the thickness of 0.5 mm, 15 mm in length, and 15 mm in width was the same as in Example 1 except that the produced silicone cured product was sliced and cut with a commercially available cutter knife so that the thickness was 0.5 mm.
- a square-shaped heat conductive sheet of Comparative Example 1 was prepared.
- FIG. 4A an electron micrograph of the surface of the cut surface of the thermal conductive sheet of Example 1 is shown in FIG. 4A
- FIG. 4B an electron micrograph of a cross section is shown in FIG. 4B
- FIG. 4C a three-dimensional graphic diagram is shown in FIG. 4C.
- FIG. 5A shows an electron micrograph of the cut surface of the heat conductive sheet of Comparative Example 1
- FIG. 5B shows an electron micrograph of a cross section
- FIG. 5C shows a three-dimensional graphic diagram.
- Example 2 (Comparative Example 2) -Production of thermal conductive sheet-
- the produced cured silicone was sliced and cut with a meat slicer (rotary blade) (Remacom Electric Slicer RSL-A19) so that the thickness was 0.5 mm.
- a heat conductive sheet of Comparative Example 2 having a thickness of 0.5 mm, a length of 15 mm, and a width of 15 mm was prepared.
- Example 3 (Comparative Example 3) -Production of thermal conductive sheet-
- the obtained silicone resin composition was laminated and applied to produce a silicone laminate, and this silicone laminate was heated in an oven at 100 ° C. for 1 hour to produce a cured silicone product. Except that the cured silicone product was sliced and cut with an ultrasonic cutter so that the thickness was 0.5 mm, a comparative example having a square shape with a thickness of 0.5 mm, a length of 15 mm, and a width of 15 mm was the same as in Example 1. No. 3 thermal conductive sheet was produced.
- Comparative Example 4 (Comparative Example 4) -Production of thermal conductive sheet-
- the obtained silicone laminate was sliced and cut using a commercially available cutter knife instead of an ultrasonic cutter, in the same manner as in Comparative Example 3, with a thickness of 0.5 mm, a length of 15 mm, and a width of 15 mm.
- a square-shaped thermally conductive sheet of Comparative Example 4 was prepared.
- Comparative Example 5 (Comparative Example 5) -Production of thermal conductive sheet-
- the obtained silicone laminate was sliced using a meat slicer (rotary blade) (Remacom Electric Slicer RSL-A19) instead of an ultrasonic cutter in the same manner as in Comparative Example 3.
- a heat conductive sheet of Comparative Example 5 having a square shape with a thickness of 0.5 mm, a length of 15 mm, and a width of 15 mm was produced.
- a test piece indicated by UL94 was produced, and the obtained test piece was subjected to a combustion test based on the UL94V vertical combustion test method.
- the burning time is the sum of two ignitions and is the average of five test pieces.
- the obtained results were evaluated according to the following criteria to any grade of UL94 “V-0”, “V-1”, and “V-2”. In addition, the thing which does not satisfy any of these was set as "fail".
- the obtained test piece was subjected to a combustion test based on the UL94V vertical combustion test method.
- the burning time is the sum of two ignitions and is the average of five test pieces.
- the obtained results were evaluated according to the following criteria to any grade of UL94 “V-0”, “V-1”, and “V-2”. In addition, the thing which does not satisfy any of these was set as "fail”.
- V-0 The average burning time after removing the ignition flame is 10 seconds or less, and all the samples do not drop the fine flame that ignites the absorbent cotton.
- V-1 The average burning time after removing the ignition flame is 30 seconds or less, and all samples do not drop the fine flame that ignites the absorbent cotton.
- V-2 The average burning time after removing the ignition flame is 30 seconds or less, and the particulate flame igniting the absorbent cotton is dropped.
- the thermal resistance of each thermal conductive sheet was measured using a thermal conductivity measuring device based on ASTM D 5470 and applying a load of 1 kgf / cm 2 .
- Example 9 had a slightly higher thermal resistance than that of Example 1 because the fiber length of the pitch-based carbon fiber was shorter.
- Example 10 had a slightly larger thermal resistance than that of Example 1 due to the short fiber length of the pitch-based carbon fiber.
- Example 11 had a larger filling amount of pitch-based carbon fibers than Example 1, and the dispersion of pitch-based carbon fibers was somewhat poor, so that the interface remained slightly peeled even after passing through the slit.
- Example 12 the average particle diameter of alumina was larger than in Example 1, and the orientation of the pitch-based carbon fibers was disturbed, so the thermal resistance was slightly increased.
- Comparative Example 1 was sliced and cut with a commercially available cutter knife as compared with Example 1, the surface unevenness was increased and the thermal resistance was increased.
- Comparative Example 2 was sliced and cut with a meat slicer (rotating blade) as compared with Example 1, the surface unevenness was increased and the thermal resistance was increased.
- Comparative Example 3 was a laminated coating compared to Example 1, peeling occurred at the interface when a load was applied. Further, since the laminated coated product was not extruded into a mold, the outer periphery did not have slight adhesiveness.
- Comparative Example 4 was a laminate coating as compared to Example 1, so that peeling at the interface occurred when a load was applied. Further, since the laminated coated product was not extruded into a mold, the outer periphery did not have slight adhesiveness. Furthermore, since the slice was cut with a commercially available cutter knife, the surface unevenness was increased and the thermal resistance was increased.
- Comparative Example 5 was a laminated coating compared to Example 1, peeling occurred at the interface when a load was applied. Further, since the laminated coated product was not extruded into a mold, the outer periphery did not have slight adhesiveness. Furthermore, since the slice was cut with a meat slicer (rotary blade), the surface irregularities were increased and the thermal resistance was increased.
- Example 14 In Example 1, the thermally conductive sheet of Example 14 was produced in the same manner as in Example 1 except that the cured silicone was sliced and cut with an ultrasonic cutter so that the thickness was 1.0 mm.
- the thickness when measured by applying a load of 1 kgf / cm 2 to the obtained heat conductive sheet was 0.9 mm.
- Example 15 In Example 1, the thermally conductive sheet of Example 15 was produced in the same manner as in Example 1 except that the cured silicone was sliced and cut with an ultrasonic cutter so that the thickness was 1.5 mm.
- the thickness when measured by applying a load of 1 kgf / cm 2 to the obtained heat conductive sheet was 1.4 mm.
- Comparative Example 6 a thermally conductive sheet of Comparative Example 6 was produced in the same manner as Comparative Example 1 except that the cured silicone was sliced and cut with a commercially available cutter knife so that the thickness was 1.0 mm.
- the thickness when measured by applying a load of 1 kgf / cm 2 to the obtained heat conductive sheet was 0.9 mm.
- Comparative Example 7 a thermally conductive sheet of Comparative Example 7 was produced in the same manner as Comparative Example 1, except that the cured silicone was sliced and cut with a commercially available cutter knife so that the thickness was 1.5 mm.
- the thickness when measured by applying a load of 1 kgf / cm 2 to the obtained heat conductive sheet was 1.4 mm.
- Example 1 Examples 14 to 15, Comparative Example 1 and Comparative Examples 6 to 7, a load of 1 kgf / cm 2 was applied in the same manner as Example 1 and Comparative Example 1, and the heat conductive sheet. The thermal resistance of was measured. In addition, the thickness when the load was applied to the heat conductive sheets of Example 1 and Comparative Example 1 (thickness immediately after cutting: 0.5 mm) with a load of 1 kgf / cm 2 was 0.4 mm. The results are shown in FIG.
- Example 1 and Examples 14 to 15 using an ultrasonic cutter were heated regardless of the sheet thickness as compared to Comparative Example 1 and Comparative Examples 6 to 7 using a commercially available cutter knife. It turned out that resistance became low and showed favorable thermal conductivity.
- Comparative Example 8 In the same manner as in Example 1 described in Japanese Patent Application Laid-Open No. 2003-200347, after applying a magnetic field at room temperature and orienting the graphitized carbon fiber surface-treated with a silane coupling agent in a certain direction, A heat conductive sheet of Comparative Example 8 having a thickness of 2 mm was prepared by thermosetting.
- FIG. 8 shows a micrograph (200 ⁇ ) of a cross section in the thickness direction of the heat conductive sheet of Comparative Example 8 obtained. Moreover, the microscope picture (200 times) of the cross section of the thickness direction of the heat conductive sheet of Example 1 is shown in FIG.
- Example 1 when the sheet is manufactured by the extrusion method, there is a portion where the carbon fibers are not oriented in the thickness direction (vertical direction) of the sheet. It was hard to break (it was hard to break).
- Example 16 A cured silicone product made of the same silicone resin composition as in Example 1 was sliced with an ultrasonic cutter (transmitting frequency 20.5 kHz, amplitude 50 to 70 ⁇ m) so as to have a thickness of 0.8 mm, and a heat conductive sheet Was made. At this time, as shown in Table 2, the angle formed between the thickness direction of the cured silicone (thermally conductive sheet) cut by the ultrasonic cutter and the anisotropic thermally conductive filler (carbon fiber) is 0 ° to 90 °. The cured silicone was placed in stages up to 0 °, ultrasonically sliced, and sample no. 1-No. 9 thermal conductive sheets were produced.
- the thermal resistance was measured in the same manner as in the above example. Further, the compression rate was measured as follows. Other physical properties were measured in the same manner as in the above examples.
- the compression rate is a value (%) indicating how much the thickness of the heat conductive sheet when a load is applied is compressed with respect to the thickness of the heat conductive sheet before measurement.
- Such a heat conductive sheet 10 is characterized by containing 10 to 25% by volume of carbon fiber and 40 to 55% by volume of aluminum oxide (alumina) alumina.
- the heat conductive sheet 10 is a sheet-like material in which, for example, a silicone resin is used as a polymer, pitch-based carbon fibers are used as a heat conductive material, and spherical alumina is used as a filler, for example.
- the heat conductive sheet 10 passes the heat conductive composition containing the polymer, carbon fiber, and alumina through the slit so that the carbon fiber is oriented in the extrusion direction, and then the obtained molded body is cured.
- the formed sheet base material 11 is formed, and the sheet base material 11 is formed by slicing the sheet base material 11 into a sheet shape in a direction orthogonal to the extrusion direction.
- the silicone resin has physical properties excellent in flexibility, shape followability, heat resistance, and the like, and is configured by mixing a first silicone resin and a second silicone resin.
- the first silicone resin is a polyalkenylalkylsiloxane
- the second silicone resin is a polyalkylhydrogensiloxane that acts as a curing agent for the polyalkenylalkylsiloxane.
- the 1st silicone resin can be obtained in the state which mixed the platinum catalyst which acts as a catalyst of the said reaction.
- the second silicone resin can be obtained in a state where the above-mentioned polyalkenylalkylsiloxane and reaction modifier are mixed in addition to the polyalkylhydrogensiloxane.
- the blending ratio of the first silicone resin is relatively high by simply blending these two resins in equal amounts by weight ratio, The blending ratio of the second silicone resin as the curing agent can be lowered.
- the thermal conductive sheet 10 is not excessively cured, and thereby a certain compression rate can be generated. Since the heat conductive sheet 10 is interposed between the heat-generating electronic component and the heat sink, it is necessary to have a predetermined compression rate in the thickness direction in order to bring them into close contact, and at least a compression of 3% or more is required. It is preferable to provide a compression ratio of preferably 6% or more, more preferably 10% or more.
- the compounding ratio of the 1st silicone resin and the 2nd silicone resin shall be 55: 45-50: 50.
- the heat conductive sheet 10 has a compression rate of 3% or more (3.82%) even when the initial thickness is sliced as thin as 0.5 mm.
- the thermal conductive sheet 10 has a compression ratio of 10.49% at an initial thickness of 1.0 mm at 52:48, and 13.21 at an initial thickness of 1.0 mm between 55:45 and 52:48. %, Both have a compression rate of 10% or more.
- the heat conductive sheet 10 has a compressibility of 3% or more in the thickness direction despite the orientation of carbon fibers in the thickness direction, it is excellent in flexibility and shape followability, The heat-generating electronic component and the heat sink can be more closely attached to dissipate heat efficiently.
- Pitch-based carbon fibers are made from pitch as a main raw material and graphitized by heat treatment at a high temperature exceeding 2000 to 3000 ° C. or 3000 ° C. after each processing step such as melt spinning, infusibilization and carbonization.
- the raw material pitch is divided into an isotropic pitch that is optically disordered and exhibits no deflection, and an anisotropic pitch (mesophase pitch) in which the constituent molecules are arranged in a liquid crystal form and exhibits optical anisotropy.
- Carbon fiber manufactured from an isotropic pitch has better mechanical properties and higher electrical and thermal conductivity than carbon fiber manufactured from an isotropic pitch. Use this mesophase pitch graphitized carbon fiber. Is preferred.
- Alumina is smaller than carbon fiber and has a particle size that can sufficiently function as a heat conductive material, and is closely packed with carbon fiber. Thereby, the heat conductive sheet 10 can obtain a sufficient heat conduction path.
- DAW03 manufactured by Denki Kagaku Kogyo Co., Ltd.
- DAW03 can be used as the alumina.
- the thermal conductive sheet 10 is a first and second silicone resin, carbon in the evaluation in the combustion test, and in the manufacture of the sheet base material 11 from which the thermal conductive sheet 10 is cut out, according to the blending ratio of carbon fiber and alumina. Evaluation of the ease of extrusion when extruding a mixed composition in which fibers and alumina are mixed into a prismatic shape from a syringe changes.
- the sheet base material 11 is formed into a prismatic shape again after passing through the slit by passing through the slit provided in the syringe and passing through the slit.
- FIG. 14 shows the evaluation in the combustion test (UL94V) of the heat conductive sheet 10 when the blending ratio of the carbon fiber to 50 g of alumina is changed, and the evaluation of the ease of extrusion when the sheet base material 11 is extruded into a prismatic shape.
- the thermally conductive sheet 10 is composed of 5.4 g of a first silicone resin (mixture of polyalkenylalkylsiloxane and platinum catalyst) as a silicone resin, and a second silicone resin (polyalkylhydrogensiloxane, polyalkenylalkylsiloxane). And 5.4 g of a mixture of reaction modifiers).
- both the 1 mm and 2 mm thick thermal conductive sheets 10 obtained evaluation equivalent to V0 in the combustion test (UL94V). Moreover, according to the heat conductive sheet 10 having a thickness of 2 mm, an evaluation corresponding to V0 in the combustion test (UL94V) was obtained by blending 8 g or more of carbon fiber with 50 g of alumina. At this time, the volume ratio of 50 g of alumina in the thermal conductive sheet 10 is 45.8% by volume, and the volume ratio of 8 g of carbon fibers is 13.3% by volume.
- the heat conductive sheet 10 can maintain good extrudability in the manufacturing process of the sheet base material 11 by blending 8 g and 10 g of carbon fiber with 50 g of alumina. That is, the sheet
- seat base material 11 can pass smoothly the slit provided in the syringe, and can maintain prismatic shape.
- the heat conductive sheet 10 can maintain ease of extrusion in the manufacturing process of the sheet base material 11 by blending 12 g and 14 g of carbon fiber with 50 g of alumina. That is, the sheet
- the heat conductive sheet 10 was slightly impaired in extrudability in the manufacturing process of the sheet base material 11 by blending 16 g of carbon fiber with 50 g of alumina. That is, since the sheet base material 11 is hard, there is a case where a part of the base material leaks from a jig for fixing the slit provided in the syringe. However, the base material that has passed through the slit can maintain a prismatic shape. At this time, the volume ratio of 50 g of alumina in the heat conductive sheet 10 is 40.4% by volume, and the volume ratio of 16 g of carbon fibers is 23.5% by volume.
- the heat conductive sheet 10 could not be extruded in the manufacturing process of the sheet base material 11 when 17 g of carbon fiber was blended. That is, since the sheet base material 11 is hard, there is a case where a part of the base material leaks from a jig for fixing the slit provided in the syringe. And the base materials which passed the slit were not couple
- the blending amount of the carbon fiber with respect to 50 g of alumina is 14 g when the sheet thickness is 1 mm and 8 g to 16 g when the sheet thickness is 2 mm, particularly when high flame resistance equivalent to V0 is required in the combustion test UL94V. It turns out that it is preferable.
- the blending amount of the carbon fiber and the thermal resistance value have a correlation.
- the thermal resistance (K / W) decreases as the blending amount of the carbon fiber increases, but it can be seen that the thermal resistance value becomes stable at about 10 g or more.
- the thermally conductive sheet 10 may have a blending amount of carbon fiber of 10 g or more and 16 g or less. preferable.
- the blending amount of the carbon fiber is set to 14 g with respect to 50 g of alumina from the viewpoint of flame retardancy of the heat conductive sheet 10 and ease of extrusion of the sheet base material 11.
- the value of thermal resistance is low and stable, as shown in FIG.
- FIG. 16 shows the blending of the thermally conductive sheet 10 having a thickness of 1 mm manufactured with the optimum blending ratio (weight ratio).
- 5.4 g (7.219 wt%) of the mixture of the reaction modifier 50 g (66.8449 wt%) of the trade name DAW03 as alumina, and the trade name R-A301 (manufactured by Teijin Ltd.) as the pitch-based carbon fiber. 14 g (18.7166% by weight) was used.
- the slicing device 12 for slicing the sheet base material 11 into individual heat conductive sheets 10 in order to obtain the heat conductive sheet 10 having the composition shown in FIG. 16 will be described.
- the slicing device 12 can form the thermally conductive sheet 10 while maintaining the orientation of the carbon fibers by slicing the sheet base material 11 with the ultrasonic cutter 14. Therefore, according to the slicing device 12, it is possible to obtain the heat conductive sheet 10 having good heat conduction characteristics in which the orientation of the carbon fibers is maintained in the thickness direction.
- the sheet base material 11 is formed by putting the first and second silicone resins, alumina, and carbon fibers into a mixer, mixing them, and then extruding them into a prismatic shape of a predetermined size from a syringe provided in the mixer. Is done. At this time, as for the sheet
- the slicing device 12 includes a work table 13 on which a prismatic sheet base material is placed, and an ultrasonic cutter 14 that slices the sheet base material 11 on the work table 13 while applying ultrasonic vibration.
- the work table 13 is provided with a silicone rubber 21 on a metal moving table 20.
- the moving table 20 can be moved in a predetermined direction by the moving mechanism 22 and sequentially feeds the sheet base material 11 to the lower part of the ultrasonic cutter 14.
- the silicone rubber 21 has a thickness sufficient to receive the cutting edge of the ultrasonic cutter 14.
- the ultrasonic cutter 14 includes a knife 30 for slicing the sheet base material 11, an ultrasonic oscillation mechanism 31 for applying ultrasonic vibration to the knife 30, and a lifting mechanism 32 for moving the knife 30 up and down.
- the knife 30 has its cutting edge directed toward the work table 13 and is moved up and down by the elevating mechanism 32 to slice the sheet base material 11 placed on the work table 13.
- the dimensions and material of the knife 30 are determined according to the size and composition of the sheet base material 11 and are made of, for example, steel having a width of 40 mm, a thickness of 1.5 mm, and a blade edge angle of 10 °.
- the ultrasonic oscillation mechanism 31 applies ultrasonic vibration to the knife 30 in the slice direction of the sheet base material 11.
- the ultrasonic oscillation mechanism 31 has a transmission frequency of 20.5 kHz and amplitudes of three stages of 50 ⁇ m, 60 ⁇ m, and 70 ⁇ m. It is possible to adjust to.
- Such a slicing device 12 can maintain the orientation of the carbon fibers of the thermally conductive sheet 10 in the thickness direction by slicing the sheet base material 11 while applying ultrasonic vibration to the ultrasonic cutter 14. it can.
- FIG. 19 shows the thermal resistance value (K / W) between the thermally conductive sheet sliced without applying ultrasonic vibration and the thermally conductive sheet 10 sliced while applying ultrasonic vibration by the slicing device 12. Show. As shown in FIG. 19, the thermal conductive sheet 10 sliced while applying ultrasonic vibration by the slicing device 12 compared with the thermal conductive sheet sliced without applying ultrasonic vibration has a thermal resistance (K / It can be seen that W) is kept low.
- the slicing device 12 imparts ultrasonic vibration in the slicing direction to the ultrasonic cutter 14, and therefore, the carbon fiber has low interface thermal resistance and is oriented in the thickness direction of the thermally conductive sheet 10. This is because it is difficult to be laid down by the knife 30.
- the thermally conductive sheet sliced without applying ultrasonic vibration the orientation of the carbon fiber as the thermally conductive material is disturbed by the frictional resistance of the knife, and the exposure to the cut surface is reduced. Resistance will rise. Therefore, according to the slicing device 12, it is possible to obtain the heat conductive sheet 10 having excellent heat conduction characteristics.
- the sheet base material 11 having the blending ratio shown in FIG. 16 can be uniformly sliced with a thickness of 0.20 mm or more.
- the thermal conductive sheet 10 excluding the sample having a sheet thickness of 0.50 mm has an ultrasonic cutter 14 speed of 5 mm, 10 mm, or 50 mm per second. Even when sliced at a speed of 1, it has good heat conduction characteristics and has a compression rate of 10% or more, and is excellent in flexibility and shape followability. Moreover, even when the speed of the ultrasonic cutter 14 is sliced at 100 mm per second, the thermally conductive sheet 10 having sheet thicknesses of 0.25 mm and 0.20 mm has good thermal conductivity characteristics and is 10% or more. It has a compression ratio and is excellent in flexibility and shape followability.
- the thermal conductive sheet 10 having a sheet thickness of 0.30 mm is excellent in thermal conductivity characteristics when the speed of the ultrasonic cutter 14 is sliced at 100 mm per second, but has a compression rate of 3.72%. fell.
- the thermally conductive sheet 10 having a sheet thickness of 0.50 mm has good thermal conductivity characteristics when the speed of the ultrasonic cutter 14 is sliced at any of 5 mm, 10 mm, and 50 mm per second. It has a compression ratio of 5% or more, and has good flexibility and shape followability.
- the thermal conductive sheet 10 having a sheet thickness of 0.50 mm has good thermal conductivity when the speed of the ultrasonic cutter 14 is sliced at 100 mm per second, but has a compression rate of 2.18%. And lower than 3%, the flexibility and shape followability are lowered.
- FIG. 22 shows the characteristics of the thermally conductive sheet 10 sliced by changing the amplitude of ultrasonic vibration applied to the ultrasonic cutter 14 in three stages of 50 ⁇ m, 60 ⁇ m, and 70 ⁇ m.
- the heat conductive sheet 10 was formed at the blending ratio shown in FIG. 16, and the measurement load was 1 kgf / cm 2 .
- the amplitude is 70 ⁇ m
- the heat conductive sheet 10 has a compression rate of 2.18%, which is lower than 3% as in the conventional case, and is inferior in flexibility and shape followability.
- the amplitude is 50 ⁇ m and 60 ⁇ m
- the heat conductive sheet 10 has a compression rate of 3% or more, and has good flexibility and shape followability.
- seat base material 11 is not limited to prismatic shape, It can form in the column shape which has various cross-sectional shapes according to the shape of the heat conductive sheet 10, such as a column shape.
- spherical alumina is used as a filler, the present invention can use spherical aluminum nitride, zinc oxide, silicon powder, metal powder, or a mixture thereof.
- the heat conductive sheet manufactured by the method for manufacturing a heat conductive sheet according to the present invention has a low surface roughness of the cut surface, so the thermal resistance is low and the heat conductivity in the thickness direction is high.
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Abstract
Description
<1> ポリマー、異方性熱伝導性フィラー、及び充填剤を含有する熱伝導性組成物を押出機で押出して、前記異方性熱伝導性フィラーが押出し方向に沿って配向した押出成形物を成形する押出成形工程と、
前記押出成形物を硬化させて硬化物とする硬化工程と、
前記硬化物を、超音波カッターを用いて前記押出し方向に対し垂直方向に所定の厚みに切断する切断工程と、を少なくとも含むことを特徴とする熱伝導性シートの製造方法である。
前記押出成形物を硬化させて硬化物とする硬化工程と、
前記硬化物を超音波カッターで所定の厚みに切断する際に、前記超音波カッターで切断される前記硬化物の厚み方向に対して前記異方性熱伝導性フィラーが5°~45°の角度に配向するように前記硬化物を配置して切断する切断工程と、
を少なくとも含むことを特徴とする熱伝導性シートの製造方法である。
本発明の熱伝導性シートの製造方法は、押出成形工程と、硬化工程と、切断工程とを少なくとも含み、更に必要に応じてその他の工程を含んでなる。
前記押出成形工程は、ポリマー、異方性熱伝導性フィラー、及び充填剤を含有する熱伝導性組成物を押出機で押出して、前記異方性熱伝導性フィラーが押出し方向に沿って配向した押出成形物を成形する工程である。
前記ポリマーとしては、特に制限はなく、熱伝導性シートに要求される性能に応じて適宜選択することができ、例えば熱可塑性ポリマー又は熱硬化性ポリマーが挙げられる。
前記異方性熱伝導性フィラーの形状としては、特に制限はなく、目的に応じて適宜選択することができ、例えば鱗片状、板状、円柱状、角柱状、楕円状、扁平形状などが挙げられる。これらの中でも、異方性熱伝導性の点で扁平形状が特に好ましい。
前記充填剤としては、その形状、材質、平均粒径などについては特に制限はなく、目的に応じて適宜選択することができる。前記形状としては、特に制限はなく、目的に応じて適宜選択することができ、例えば球状、楕円球状、塊状、粒状、扁平状、針状などが挙げられる。これらの中でも、球状、楕円形状が充填性の点から好ましく、球状が特に好ましい。
前記硬化工程は、前記押出成形物を硬化させて硬化物とする工程である。
前記シリコーン樹脂が硬化したシリコーン硬化物の柔軟性は、特に制限はなく、目的に応じて適宜選択することができ、例えばシリコーンの架橋密度、熱伝導性フィラーの充填量などによって調整することができる。
前記切断工程は、第1の形態では、前記硬化物を、超音波カッターを用いて前記押出し方向に対し垂直方向に所定の厚みに切断する工程である。
本発明の熱伝導性シートは、切断面の表面粗さが小さく、界面での熱抵抗が低くなり、厚み方向の熱伝導性が高いので、各種熱源(例えばCPU、トランジスタ、LED等の各種デバイス)と放熱部材との間に挟持させて好適に用いられ、例えば温度によって素子動作の効率、寿命等に悪影響が出るCPU、MPU、パワートランジスタ、LED、レーザーダイオード、各種電池(リチウムイオン電池等の各種二次電池、各種燃料電池、キャパシタ、アモルファスシリコン、結晶シリコン、化合物半導体、湿式太陽電池等の各種太陽電池など)等の各種の電気デバイス周り、熱の有効利用が求められる暖房機器の熱源周り、熱交換器、床暖房装置の熱配管周りなどに好適に用いられる。
-熱伝導性シートの作製-
シリコーンA液(ビニル基を有するオルガノポリシロキサン)18.8体積%と、シリコーンB液(H-Si基を有するオルガノポリシロキサン)18.8体積%とを混合した二液性の付加反応型液状シリコーン樹脂に、アルミナ粒子(平均粒子径3μm、アルミナDAW03、球状、電気化学工業株式会社製)42.3体積%と、ピッチ系炭素繊維(平均長軸長さ150μm、平均短軸長さ8μm、ラヒーマR-A301、帝人株式会社製)20.1体積%とを分散させて、シリコーン樹脂組成物を調製した。
-熱伝導性シートの作製-
実施例1において、アルミナ粒子(平均粒子径3μm、アルミナDAW03、球状、電気化学工業株式会社製)を、アルミナ粒子(平均粒子径5μm、アルミナDAW05、球状、電気化学工業株式会社製)に代えた以外は、実施例1と同様にして、厚み0.5mm、縦15mm、横15mmの正方形状の実施例2の熱伝導性シートを作製した。
-熱伝導性シートの作製-
実施例1において、アルミナ粒子(平均粒子径3μm、アルミナDAW03、球状、電気化学工業株式会社製)を、アルミナ粒子(平均粒子径10μm、アルミナDAW10、球状、電気化学工業株式会社製)に代えた以外は、実施例1と同様にして、厚み0.5mm、縦15mm、横15mmの正方形状の実施例3の熱伝導性シートを作製した。
-熱伝導性シートの作製-
実施例1において、シリコーンA液(ビニル基を有するオルガノポリシロキサン)17.8体積%と、シリコーンB液(H-Si基を有するオルガノポリシロキサン)17.8体積%とを混合した二液性の付加反応型液状シリコーン樹脂に、アルミナ粒子(平均粒子径3μm、アルミナDAW03、球状、電気化学工業株式会社製)41.0体積%と、ピッチ系炭素繊維(平均長軸長さ150μm、平均短軸長さ8μm、ラヒーマR-A301、帝人株式会社製)23.4体積%とを分散して、シリコーン樹脂組成物を調製した以外は、実施例1と同様にして、厚み0.5mm、縦15mm、横15mmの正方形状の実施例4の熱伝導性シートを作製した。
-熱伝導性シートの作製-
実施例1において、シリコーンA液(ビニル基を有するオルガノポリシロキサン)17.6体積%と、シリコーンB液(H-Si基を有するオルガノポリシロキサン)17.6体積%とを混合した二液性の付加反応型液状シリコーン樹脂に、アルミナ粒子(平均粒子径3μm、アルミナDAW03、電気化学工業株式会社製)40.5体積%と、ピッチ系炭素繊維(平均長軸長さ150μm、平均短軸長さ8μm、ラヒーマR-A301、帝人株式会社製)24.3体積%とを分散して、シリコーン樹脂組成物を調製した以外は、実施例1と同様にして、厚み0.5mm、縦15mm、横15mmの正方形状の実施例5の熱伝導性シートを作製した。
-熱伝導性シートの作製-
実施例1において、シリコーンA液(ビニル基を有するオルガノポリシロキサン)19.5体積%と、シリコーンB液(H-Si基を有するオルガノポリシロキサン)19.5体積%とを混合した二液性の付加反応型液状シリコーン樹脂に、アルミナ粒子(平均粒子径3μm、アルミナDAW03、球状、電気化学工業株式会社製)45.0体積%と、ピッチ系炭素繊維(平均長軸長さ150μm、平均短軸長さ8μm、ラヒーマR-A301、帝人株式会社製)16.0体積%とを分散して、シリコーン樹脂組成物を調製した以外は、実施例1と同様にして、厚み0.5mm、縦15mm、横15mmの正方形状の実施例6の熱伝導性シートを作製した。
-熱伝導性シートの作製-
実施例1において、シリコーンA液(ビニル基を有するオルガノポリシロキサン)18.9体積%と、シリコーンB液(H-Si基を有するオルガノポリシロキサン)18.9体積%とを混合した二液性の付加反応型液状シリコーン樹脂に、アルミナ粒子(平均粒子径3μm、アルミナDAW03、球状、電気化学工業株式会社製)43.6体積%と、ピッチ系炭素繊維(平均長軸長さ150μm、平均短軸長さ8μm、ラヒーマR-A301、帝人株式会社製)18.6体積%とを分散して、シリコーン樹脂組成物を調製した以外は、実施例1と同様にして、厚み0.5mm、縦15mm、横15mmの正方形状の実施例7の熱伝導性シートを作製した。
-熱伝導性シートの作製-
実施例1において、作製した熱伝導性シートの外周部を市販のカッターナイフによりカットした以外は、実施例1と同様にして、厚み0.5mm、縦14mm、横14mmの正方形状の実施例8の熱伝導性シートを作製した。
-熱伝導性シートの作製-
実施例1において、ピッチ系炭素繊維(平均長軸長さ150μm、平均短軸長さ8μm、ラヒーマR-A301、帝人株式会社製)を、ピッチ系炭素繊維(平均長軸長さ100μm、平均短軸長さ8μm、ラヒーマR-A401、帝人株式会社製)に代えた以外は、実施例1と同様にして、厚み0.5mm、縦15mm、横15mmの正方形状の実施例9の熱伝導性シートを作製した。
-熱伝導性シートの作製-
実施例1において、ピッチ系炭素繊維(平均長軸長さ150μm、平均短軸長さ8μm、ラヒーマR-A301、帝人株式会社製)を、ピッチ系炭素繊維(平均長軸長さ50μm、平均短軸長さ8μm、ラヒーマR-A201、帝人株式会社製)に代えた以外は、実施例1と同様にして、厚み0.5mm、縦15mm、横15mmの正方形状の実施例10の熱伝導性シートを作製した。
-熱伝導性シートの作製-
実施例1において、シリコーンA液(ビニル基を有するオルガノポリシロキサン)17.3体積%と、シリコーンB液(H-Si基を有するオルガノポリシロキサン)17.3体積%とを混合した二液性の付加反応型液状シリコーン樹脂に、アルミナ粒子(平均粒子径3μm、アルミナDAW03、球状、電気化学工業株式会社製)39.9体積%と、ピッチ系炭素繊維(平均長軸長さ150μm、平均短軸長さ8μm、ラヒーマR-A301、帝人株式会社製)25.5体積%とを分散して、シリコーン樹脂組成物を調製した以外は、実施例1と同様にして、厚み0.5mm、縦15mm、横15mmの正方形状の実施例11の熱伝導性シートを作製した。
-熱伝導性シートの作製-
実施例1において、アルミナ粒子(平均粒子径3μm、アルミナDAW03、球状、電気化学工業株式会社製)を、アルミナ粒子(平均粒子径45μm、アルミナDAW45、球状、電気化学工業株式会社製)に代えた以外は、実施例1と同様にして、厚み0.5mm、縦15mm、横15mmの正方形状の実施例12の熱伝導性シートを作製した。
-熱伝導性シートの作製-
実施例1において、アルミナ粒子(平均粒子径3μm、アルミナDAW03、球状、電気化学工業株式会社製)42.3質量部を、アルミナ粒子(平均粒子径3μm、アルミナDAW03、球状、電気化学工業株式会社製)25質量部と、窒化アルミニウム(トクヤマ社製、平均粒子径1μm)17.3質量部に変えた以外は、実施例1と同様にして、厚み0.5mm、縦15mm、横15mmの正方形状の実施例13の熱伝導性シートを作製した。
-熱伝導性シートの作製-
実施例1において、作製したシリコーン硬化物を、厚みが0.5mmとなるように市販のカッターナイフでスライス切断した以外は、実施例1と同様にして、厚み0.5mm、縦15mm、横15mmの正方形状の比較例1の熱伝導性シートを作製した。
-熱伝導性シートの作製-
実施例1において、作製したシリコーン硬化物を、厚みが0.5mmとなるようにミートスライサー(回転刃)(レマコム電動式スライサーRSL-A19)でスライス切断した以外は、実施例1と同様にして、厚み0.5mm、縦15mm、横15mmの正方形状の比較例2の熱伝導性シートを作製した。
-熱伝導性シートの作製-
実施例1において、得られたシリコーン樹脂組成物を積層塗布して、シリコーン積層物を作製し、このシリコーン積層物をオーブンにて100℃で1時間加熱して、シリコーン硬化物を作製し、得られたシリコーン硬化物を、厚みが0.5mmとなるように超音波カッターでスライス切断した以外は、実施例1と同様にして、厚み0.5mm、縦15mm、横15mmの正方形状の比較例3の熱伝導性シートを作製した。
-熱伝導性シートの作製-
比較例3において、得られたシリコーン積層物を、超音波カッターの代わりに市販のカッターナイフを用いてスライス切断した以外は、比較例3と同様にして、厚み0.5mm、縦15mm、横15mmの正方形状の比較例4の熱伝導性シートを作製した。
-熱伝導性シートの作製-
比較例3において、得られたシリコーン積層物を、超音波カッターの代わりにミートスライサー(回転刃)(レマコム電動式スライサーRSL-A19)を用いてスライス切断した以外は、比較例3と同様にして、厚み0.5mm、縦15mm、横15mmの正方形状の比較例5の熱伝導性シートを作製した。
各熱伝導性シートについて、UL-94規格に準拠した難燃試験を行い、難燃性を評価した。
「V-0」:点火炎を取り除いた後の平均燃焼時間が10秒間以下、かつ全試料とも脱脂綿に着火する微粒炎を落下しない。
各熱伝導性シートの表面粗さRaをレーザー顕微鏡にて測定した。
プラスチック板上に炭素繊維の配向方向と垂直に各熱伝導性シートを置き、外周部の微粘着性を確認した。
各熱伝導性シートの初期の厚みは、熱伝導測定装置を用いて測定した。
各熱伝導性シートの熱抵抗は、ASTM D 5470に準拠した熱伝導率測定装置を用い、荷重1kgf/cm2をかけて測定した。
各熱伝導性シートについて、スリット間又は積層面での剥離の有無を目視により確認した。
実施例1において、シリコーン硬化物を、厚みが1.0mmとなるように超音波カッターでスライス切断した以外は、実施例1と同様にして、実施例14の熱伝導性シートを作製した。
実施例1において、シリコーン硬化物を、厚みが1.5mmとなるように超音波カッターでスライス切断した以外は、実施例1と同様にして、実施例15の熱伝導性シートを作製した。
比較例1において、シリコーン硬化物を、厚みが1.0mmとなるように市販のカッターナイフでスライス切断した以外は、比較例1と同様にして、比較例6の熱伝導性シートを作製した。
比較例1において、シリコーン硬化物を、厚みが1.5mmとなるように市販のカッターナイフでスライス切断した以外は、比較例1と同様にして、比較例7の熱伝導性シートを作製した。
特開2003-200437号公報に記載の実施例1と同様にして、常温で磁場を印加して、シランカップリング剤で表面処理を施した黒鉛化炭素繊維を一定方向に磁場配向させた後、熱硬化して厚み2mmの比較例8の熱伝導性シートを作製した。
実施例1と同じシリコーン樹脂組成物で作製したシリコーン硬化物を、厚みが0.8mmとなるように超音波カッターでスライス(発信周波数20.5kHz、振幅50~70μm)して、熱伝導性シートを作製した。このとき、表2に示すように、超音波カッターによって切断されたシリコーン硬化物(熱伝導性シート)の厚み方向と異方性熱伝導性フィラー(炭素繊維)とのなす角度を0°~90°まで段階的に変えてシリコーン硬化物を配置して、超音波スライスし、試料No.1~No.9の熱伝導性シートを作製した。
圧縮率とは、荷重をかけた時の熱伝導性シートの厚みが、測定前の熱伝導性シートの厚みに対してどれだけ圧縮されたのかを示す値(%)である。
ところで、熱伝導性シートは、高い柔軟性、形状追従性が求められることから、シート母材である硬化物の変形を防止して、薄く均一な厚さにスライスすることが必要とされる。また、熱伝導性シートは、スライスされた表面が切断刃との摩擦抵抗によって擦られることにより炭素繊維の配向が乱れると、熱伝導特性の低下を招くことから、熱伝導性シートは、熱伝導特性、厚さの均一性、柔軟性及び形状追従性に優れることが望まれる。
熱伝導性シート10は、炭素繊維及びアルミナの配合割合に応じて、燃焼試験における評価、及び熱伝導性シート10が切り出されるシート母材11の製造時において第1、第2のシリコーン樹脂、炭素繊維、アルミナを混合した混合組成物をシリンジより角柱状に押し出す際の押出しやすさの評価が変化する。なお、シート母材11は、シリンジ内部に設けられたスリットを通過することにより炭素繊維が長手方向に配向され、スリットを通過した後、再度角柱状に成形される。
次いで、図16に示す配合からなる熱伝導性シート10を得るためにシート母材11を個々の熱伝導性シート10にスライスするスライス装置12の構成について説明する。図17に示すように、スライス装置12は、シート母材11を超音波カッター14によってスライスすることにより、炭素繊維の配向を保った状態で熱伝導性シート10を形成することができる。したがって、スライス装置12によれば、炭素繊維の配向が厚さ方向に維持された熱伝導特性が良好な熱伝導性シート10を得ることができる。
次いで、スライス装置12によるシート母材11のスライス速度とスライスされる熱伝導性シート10の厚さとの関係について検討した。上述した実施例(図16)に示す配合割合で、一辺が20mmの角柱状のシート母材11を形成し、このシート母材11を0.05mm~0.50mmまで0.05mm毎に厚さの異なる熱伝導性シート10を、超音波カッター14のスライス速度を毎秒5mm、10mm、50mm、100mmに変更してスライスすることにより形成し、各熱伝導性シート10の外観を観察した。なお、超音波カッター14に付与する超音波振動は、発信周波数を20.5kHzとし、振幅を60μmとした。
次いで、スライス装置12によるシート母材11のスライス速度と熱伝導率及び厚さ方向への圧縮率との関係について検討した。上記スライス速度及びシート厚さの検討において変形が見られなかった厚さ0.20mm、0.25mm、0.30mm、0.50mmでスライス速度が毎秒5mm、10mm、50mm、100mmの各熱伝導性シート10につき、それぞれ熱伝導率及び圧縮率を測定した。測定結果を図21に示す。
なお、図22に超音波カッター14に付与する超音波振動の振幅を50μm、60μm、70μmの3段階に変えてスライスした熱伝導性シート10の各特性を示す。熱伝導性シート10は、図16に示す配合割合で形成し、測定荷重を1kgf/cm2とした。図22に示すように、振幅を70μmとした場合には、熱伝導性シート10は、圧縮率が2.18%と、従来と同様3%より低く、柔軟性、形状追従性に劣る。一方、振幅を50μm、60μmとした場合には、熱伝導性シート10は、3%以上の圧縮率を有し、良好な柔軟性、形状追従性を備える。
なお、シート母材11は、角柱状に限定されず、円柱状など、熱伝導性シート10の形状に応じた各種断面形状を有する柱状に形成することができる。また、充填剤として球状アルミナを用いたが、本発明はこれ以外にも球状の窒化アルミニウム、酸化亜鉛、シリコン粉、金属粉末のいずれか、あるいはこれらの混合物を用いることができる。
Claims (17)
- ポリマー、異方性熱伝導性フィラー、及び充填剤を含有する熱伝導性組成物を押出機で押出して、前記異方性熱伝導性フィラーが押出し方向に沿って配向した押出成形物を成形する押出成形工程と、
前記押出成形物を硬化させて硬化物とする硬化工程と、
前記硬化物を、超音波カッターを用いて前記押出し方向に対し垂直方向に所定の厚みに切断する切断工程と、を少なくとも含むことを特徴とする熱伝導性シートの製造方法。 - ポリマー、異方性熱伝導性フィラー、及び充填剤を含有する熱伝導性組成物を押出機で押出して、前記異方性熱伝導性フィラーが押出し方向に沿って配向した押出成形物を成形する押出成形工程と、
前記押出成形物を硬化させて硬化物とする硬化工程と、
前記硬化物を超音波カッターで所定の厚みに切断する際に、前記超音波カッターで切断される前記硬化物の厚み方向に対して前記異方性熱伝導性フィラーが5°~45°の角度に配向するように前記硬化物を配置して切断する切断工程と、
を少なくとも含むことを特徴とする熱伝導性シートの製造方法。 - 上記異方性熱伝導性フィラーの平均繊維長が100μm以上である請求項1又は請求項2に記載の熱伝導性シートの製造方法。
- 上記異方性熱伝導性フィラーが、炭素繊維である請求項1~請求項3のいずれか1項に記載の熱伝導性シートの製造方法。
- 上記異方性熱伝導性フィラーの熱伝導性組成物中の含有量が、16体積%~25体積%である請求項1~請求項4のいずれか1項に記載の熱伝導性シートの製造方法。
- 上記充填剤の平均粒子径が1μm~40μmである請求項1~請求項5のいずれか1項に記載の熱伝導性シートの製造方法。
- 上記充填剤が、球形状のアルミナ粒子である請求項1~請求項6のいずれか1項に記載の熱伝導性シートの製造方法。
- 上記ポリマーがシリコーン樹脂である請求項1~請求項7のいずれか1項に記載の熱伝導性シートの製造方法。
- 請求項1から8のいずれかに記載の熱伝導性シートの製造方法により製造されたことを特徴とする熱伝導性シート。
- 熱伝導性シートにおける外周部の微粘着性が、熱伝導性シートにおける内部の微粘着性よりも高い請求項9に記載の熱伝導性シート。
- 熱伝導性シートの切断面の表面粗さRaが9.9μm以下である請求項9又は請求項10に記載の熱伝導性シート。
- シリコーン樹脂と、充填剤と、炭素繊維とを含有し、上記炭素繊維が厚み方向に配向されている熱伝導性シートにおいて、
上記充填剤が、40~55体積%の範囲で含有され、
上記炭素繊維が、10~25体積%の範囲で含有されてなる請求項9記載の熱伝導性シート。 - 上記充填剤は、40.4~45.8体積%含有され、
上記炭素繊維は、13.3~23.5体積%含有されている請求項12記載の熱伝導性シート。 - 上記炭素繊維は、上記充填剤50gに対して10g以上配合されている請求項13記載の熱伝導性シート。
- 上記炭素繊維は、上記充填剤50gに対して16g以下配合されている請求項14記載の熱伝導性シート。
- 上記シリコーン樹脂は、第1のシリコーン樹脂であるポリアルケニルアルキルシロキサンと、第2のシリコーン樹脂であるポリアルキル水素シロキサンとを白金触媒により硬反応させて、圧縮率3%となるように上記第1のシリコーン樹脂を上記第2のシリコーン樹脂よりも多く配合してなる請求項12~請求項15の何れか1項に記載の熱伝導性シート。
- 上記充填剤は、酸化アルミニウム、窒化アルミニウム、酸化亜鉛、シリコン粉、金属粉のいずれか、又はこれらの2以上の混合物である請求項16記載の熱伝導性シート。
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US9308695B2 (en) | 2016-04-12 |
US20140346710A1 (en) | 2014-11-27 |
KR20130117752A (ko) | 2013-10-28 |
EP2583993A1 (en) | 2013-04-24 |
EP2583993A4 (en) | 2014-12-24 |
TW201209972A (en) | 2012-03-01 |
TWI610407B (zh) | 2018-01-01 |
US8808607B2 (en) | 2014-08-19 |
KR101715988B1 (ko) | 2017-03-13 |
US9365001B2 (en) | 2016-06-14 |
CN102971365B (zh) | 2015-07-01 |
EP2583993B1 (en) | 2017-05-17 |
HK1179999A1 (en) | 2013-10-11 |
US20130136895A1 (en) | 2013-05-30 |
US20140349067A1 (en) | 2014-11-27 |
CN102971365A (zh) | 2013-03-13 |
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