Classifications

• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
  • H10W40/00—Arrangements for thermal protection or thermal control
  • H10W40/20—Arrangements for cooling
  • H10W40/25—Arrangements for cooling characterised by their materials
  • H10W40/251—Organics
• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
  • H05K7/00—Constructional details common to different types of electric apparatus
  • H05K7/20—Modifications to facilitate cooling, ventilating, or heating
  • H05K7/2039—Modifications to facilitate cooling, ventilating, or heating characterised by the heat transfer by conduction from the heat generating element to a dissipating body
  • H05K7/20436—Inner thermal coupling elements in heat dissipating housings, e.g. protrusions or depressions integrally formed in the housing
  • H05K7/20445—Inner thermal coupling elements in heat dissipating housings, e.g. protrusions or depressions integrally formed in the housing the coupling element being an additional piece, e.g. thermal standoff
  • H05K7/20454—Inner thermal coupling elements in heat dissipating housings, e.g. protrusions or depressions integrally formed in the housing the coupling element being an additional piece, e.g. thermal standoff with a conformable or flexible structure compensating for irregularities, e.g. cushion bags, thermal paste
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/18—Manufacture of films or sheets
• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
  • H05K7/00—Constructional details common to different types of electric apparatus
  • H05K7/20—Modifications to facilitate cooling, ventilating, or heating
  • H05K7/2039—Modifications to facilitate cooling, ventilating, or heating characterised by the heat transfer by conduction from the heat generating element to a dissipating body
  • H05K7/20436—Inner thermal coupling elements in heat dissipating housings, e.g. protrusions or depressions integrally formed in the housing
  • H05K7/20445—Inner thermal coupling elements in heat dissipating housings, e.g. protrusions or depressions integrally formed in the housing the coupling element being an additional piece, e.g. thermal standoff
  • H05K7/20463—Filling compound, e.g. potted resin
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
  • H10W40/00—Arrangements for thermal protection or thermal control
  • H10W40/20—Arrangements for cooling
  • H10W40/25—Arrangements for cooling characterised by their materials
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
  • H10W40/00—Arrangements for thermal protection or thermal control
  • H10W40/20—Arrangements for cooling
  • H10W40/25—Arrangements for cooling characterised by their materials
  • H10W40/255—Arrangements for cooling characterised by their materials having a laminate or multilayered structure, e.g. direct bond copper [DBC] ceramic substrates
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
  • H10W40/00—Arrangements for thermal protection or thermal control
  • H10W40/20—Arrangements for cooling
  • H10W40/25—Arrangements for cooling characterised by their materials
  • H10W40/259—Ceramics or glasses
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
  • H10W40/00—Arrangements for thermal protection or thermal control
  • H10W40/70—Fillings or auxiliary members in containers or in encapsulations for thermal protection or control
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
  • H10W74/00—Encapsulations, e.g. protective coatings
  • H10W74/10—Encapsulations, e.g. protective coatings characterised by their shape or disposition
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
  • H10W74/00—Encapsulations, e.g. protective coatings
  • H10W74/40—Encapsulations, e.g. protective coatings characterised by their materials

Definitions

• the present disclosure relates to a liquid thermally conductive material, a combination of members for producing a thermally conductive sheet, a thermally conductive sheet, a heat dissipation device, and a method for manufacturing a thermally conductive sheet.
• a heat dissipation device is generally conveniently used, which dissipates heat by sandwiching thermal conductive grease or a heat conductive sheet between a heat generating body such as a semiconductor package and a heat dissipating body such as aluminum or copper.
• thermally conductive sheets are superior to thermally conductive grease in terms of workability when assembling a heat dissipation device.
• Resin sheets filled with thermally conductive fillers are also known as thermally conductive sheets.
• Various resin sheets have been proposed that are filled with thermally conductive fillers and have excellent thermal conductivity, in which highly thermally conductive inorganic particles are selected as the thermally conductive fillers, and the inorganic particles are oriented perpendicular to the sheet surface.
• thermally conductive sheets in which thermally conductive fillers (boron nitride) are oriented in a direction substantially perpendicular to the sheet surface (for example, see Patent Document 1), and carbon fibers dispersed in a gel-like substance are oriented in a direction perpendicular to the sheet surface.
• a thermally conductive sheet having an oriented structure has been proposed.
• Patent Documents 1 and 2 consider a method of suppressing thermal resistance by orienting thermally conductive fillers, carbon fibers, etc. in a direction perpendicular to the sheet surface. In order to cope with the increase in heat generation due to the higher performance and larger size of semiconductors, it is desired to further reduce the thermal resistance of thermally conductive sheets. Therefore, it is preferable to aim at lowering the thermal resistance by considering methods other than the orientation of the thermally conductive filler, carbon fiber, etc. contained in the thermally conductive sheet.
• An object of the present disclosure is to provide a liquid thermally conductive material that can reduce thermal resistance by applying it to a thermally conductive layer such as a thermally conductive sheet, the aforementioned liquid thermally conductive material or a liquid thermally conductive material containing a metal component, and to provide a liquid thermally conductive material that can reduce thermal resistance.
• a liquid thermally conductive material that has a thermal conductivity of 5 W/(m ⁇ K) or more and is used to form a liquid layer by coating at least a portion of a thermally conductive layer containing thermally conductive particles.
• the liquid thermally conductive material according to ⁇ 1> including a thermally conductive filler and a resin component.
• the resin component includes a thermosetting resin component.
• ⁇ 5> The liquid thermally conductive material according to any one of ⁇ 1> to ⁇ 4>, which has a viscosity at 25° C. of 4000 Pa ⁇ s or less.
• ⁇ 6> A combination of a member for producing a thermally conductive sheet comprising the liquid thermally conductive material according to any one of ⁇ 1> to ⁇ 5> and a thermally conductive material containing thermally conductive particles.
• ⁇ 7> A combination of a member for producing a thermally conductive sheet comprising a liquid thermally conductive material containing a metal component and a thermally conductive material containing thermally conductive particles.
• thermoly conductive sheet according to ⁇ 7>, wherein the metal component has a melting point of 50° C. or lower.
• the first liquid heat conductive material which is the liquid heat conductive material according to any one of ⁇ 1> to ⁇ 5>, located on at least a part of the main surface of the heat conductive layer, or the liquid heat containing a metal component.
• the thermally conductive particles include at least one type of graphite particle (A) selected from the group consisting of scaly particles, ellipsoidal particles, and rod-shaped particles, In the thermally conductive layer, the planar direction in the case of the scale-like particles, the long axis direction in the case of the ellipsoidal particles, and the long axis direction in the case of the rod-like particles are oriented in the thickness direction.
• the heat conductive sheet according to ⁇ 12> which is disposed between a heat generating element, a heat dissipating body, and the heat dissipating body and the heat dissipating body, and includes an adhesive layer formed by hardening the liquid layer.
• the adhesive layer is located on at least a portion of at least one of the main surface located on the heat generating body side and the main surface located on the heat radiating body side.
• a method for manufacturing a thermally conductive sheet comprising: ⁇ 16> A method for manufacturing a thermally conductive sheet for manufacturing the thermally conductive sheet according to ⁇ 10>, comprising: preparing a composition containing the graphite particles (A); forming the composition into a sheet to obtain a sheet; a step of producing a laminate of the sheets; slicing a side end surface of the laminate; A method for manufacturing a thermally conductive sheet, comprising the step of forming a liquid layer on at least a portion of the main surface of a sliced sheet corresponding to a thermally conductive layer obtained by slicing.
• the present disclosure includes a liquid thermal conductive material that can reduce thermal resistance by applying it to a thermal conductive layer such as a thermal conductive sheet, the liquid thermal conductive material described above, or a liquid thermal conductive material containing a metal component, and a liquid thermal conductive material that can reduce thermal resistance.
• a thermal conductive layer such as a thermal conductive sheet, the liquid thermal conductive material described above, or a liquid thermal conductive material containing a metal component
• a liquid thermal conductive material that can reduce thermal resistance can reduce thermal resistance.
• a combination of members for producing a thermally conductive sheet that can produce a thermally conductive sheet with a small resistance, a thermally conductive sheet with a low thermal resistance, a heat dissipation device equipped with the same, and a thermally conductive sheet that can produce a thermally conductive sheet with a small thermal resistance. method can be provided.
• FIG. 1 is a schematic configuration diagram of a thermally conductive sheet, which is an embodiment of the present invention.
• FIG. 1 is a schematic cross-sectional view of a heat dissipation device according to an embodiment of the present invention, in which a heat generating body is a semiconductor chip and a heat dissipation body is a heat spreader.
• FIG. 4 is a diagram showing the state of the interface according to image analysis in Examples 1 to 4 and Comparative Examples 1 to 2.
• each component may contain multiple types of corresponding substances. If there are multiple types of substances corresponding to each component in the composition, the content rate or content of each component is the total content rate or content of the multiple types of substances present in the composition, unless otherwise specified. means quantity.
• each component may include a plurality of types of particles.
• the particle diameter of each component means a value for a mixture of the plurality of types of particles present in the composition, unless otherwise specified.
• layer or film refers to the case where the layer or film is formed only in a part of the region, in addition to the case where the layer or film is formed in the entire region when observing the region where the layer or film is present. This also includes cases where it is formed.
• laminate refers to stacking layers, and two or more layers may be bonded, or two or more layers may be removable.
• the liquid thermally conductive material of the present disclosure has a thermal conductivity of 5 W/(m ⁇ K) or more, and can be applied to at least a portion of a thermally conductive layer containing thermally conductive particles to form a liquid layer. It is the material.
• a liquid thermally conductive material refers to a thermally conductive material that becomes liquid at at least a portion of the temperature between 0° C. and 50° C.
• thermal conductivity can be measured by a xenon flash (Xe-flash) method.
• the resistance (also called “contact thermal resistance”) due to the gap caused by the contact between the thermally conductive sheet and an adherend such as a heating element or heat radiator that contacts the thermally conductive sheet is the resistance of the thermally conductive particles contained in the thermally conductive sheet. It is difficult to reduce this depending on the structure and composition of the thermally conductive sheet.
• the liquid thermally conductive material of the present disclosure is a material for forming a thermally conductive sheet or the like including a liquid layer by being coated on at least a portion of a thermally conductive layer containing thermally conductive particles.
• the thermally conductive layer on which the liquid layer is formed is heat-compressed with an adherend such as a heat generating element or a heat radiator, the liquid layer flows between the thermally conductive layer and the adherend.
• the gap between the thermally conductive sheet and the adherend (for example, the gap caused by the unevenness of the thermally conductive sheet) is filled with the flowing liquid layer, so that the thermally conductive sheet and the adherend are connected through the liquid layer. Can be brought into close contact. As a result, contact thermal resistance is significantly reduced.
• the thermal conductivity of the liquid thermally conductive material is 5W/(m ⁇ K) or more, the decrease in thermal conductivity of the thermally conductive sheet due to the arrangement of the liquid layer on the thermally conductive layer is suppressed, and the thermal conductivity of the thermally conductive sheet is suppressed. Increase in thermal resistance of the conductive sheet is suppressed.
• the liquid thermally conductive material of the present disclosure preferably includes a thermally conductive filler and a resin component.
• the resin component may include a component that is liquid at 25°C.
• thermally conductive filler examples include metal-containing particles and non-metallic particles that have excellent thermal conductivity.
• the thermally conductive filler may have a thermal conductivity of 10 W/(m ⁇ K) or more, for example.
• the thermally conductive filler may be insulating or electrically conductive.
• Thermal conductive fillers include silver, aluminum oxide, aluminum hydroxide, magnesium oxide, beryllium oxide, boron nitride, aluminum nitride, silicon nitride, silicon carbide, silicon dioxide, aluminum fluoride, calcium fluoride, zinc oxide, diamond, and gallium. , indium, and tin.
• the particle size of the thermally conductive filler may be from 0.1 ⁇ m to 50 ⁇ m, and from 0.2 ⁇ m to 50 ⁇ m, from the viewpoint of excellent thermal conductivity and from the viewpoint of further reducing the gap between the adherend and the thermally conductive sheet. It may be 20 ⁇ m or 0.5 ⁇ m to 10 ⁇ m.
• the particle diameter (D50) of the thermally conductive filler is measured using a laser diffraction type particle size distribution device adapted to the laser diffraction/scattering method (for example, "Microtrack Series MT3300" manufactured by Nikkiso Co., Ltd.), and the mass cumulative particle size distribution is When the curve is drawn from the small particle size side, it corresponds to the particle size at which the mass accumulation is 50%.
• a laser diffraction type particle size distribution device adapted to the laser diffraction/scattering method
• the resin component may be a non-curable resin component, or may be a curable resin component such as a thermosetting resin or a photocurable resin component.
• the resin component preferably includes a thermosetting resin component from the viewpoint of adhesion to the adherend, thermal conductivity, etc. during curing.
• the resin component may contain one type of resin component, or may contain two or more types of resin components.
• non-curing resin component a non-curing resin component that is liquid at 25° C. is preferable, and liquid silicone compounds, liquid (meth)acrylic compounds, liquid polyester compounds, etc. are more preferable.
• thermosetting resin component a thermosetting resin component that is liquid at 25° C. is preferable, and a liquid epoxy compound, a curable liquid silicone compound, a curable liquid (meth)acrylic compound, etc. are more preferable.
• the content of the thermally conductive filler contained in the liquid thermally conductive material is, for example, 70% by mass to 98% by mass based on the total amount of the liquid thermally conductive material from the viewpoint of the balance between thermal conductivity and adhesion. It is preferably 75% by mass to 95% by mass, and even more preferably 80% by mass to 93% by mass.
• the content of the resin component contained in the liquid thermally conductive material is preferably 2% by mass to 30% by mass based on the total amount of the liquid thermally conductive material, for example, from the viewpoint of the balance between thermal conductivity and adhesion. It is more preferably 5% by mass to 25% by mass, and even more preferably 7% by mass to 20% by mass.
• the total content of the thermally conductive filler and resin component contained in the liquid thermally conductive material may be 80% by mass to 100% by mass, or 90% by mass to 100% by mass, based on the total amount of the liquid thermally conductive material. There may be.
• the liquid thermally conductive material may or may not contain components other than the thermally conductive filler and the resin component.
• the liquid thermally conductive material of the present disclosure preferably has a viscosity at 25° C. of 4000 Pa ⁇ s or less, may be 0.001 Pa ⁇ s to 3000 Pa ⁇ s, and may be 10 Pa ⁇ s to 2000 Pa ⁇ s. Good too. Since the viscosity at 25°C is 4000 Pa ⁇ s or less, the liquid layer easily flows between the heat conductive layer and the adherend, so the gap between the heat conductive sheet and the adherend is suitable for the liquid layer. It tends to be buried more easily.
• the viscosity at 25° C. is measured using a rheometer at 25° C. and a shear rate of 5.0 s ⁇ 1 . Specifically, "viscosity" is measured as shear viscosity at a temperature of 25° C. using a rotary shear viscometer equipped with a cone plate (diameter 40 mm, cone angle 0°).
• a combination 1 of members for producing a thermally conductive sheet of the present disclosure includes the liquid thermally conductive material of the present disclosure and a thermally conductive material containing thermally conductive particles.
• the thermally conductive material is a material for forming the thermally conductive layer of the thermally conductive sheet.
• a thermally conductive sheet can be obtained by applying a liquid thermally conductive material to at least a portion of a thermally conductive layer made of a thermally conductive material to form a liquid layer.
• the thermally conductive material includes thermally conductive particles and is solid at 25°C.
• the thermally conductive material includes thermally conductive particles.
• Thermal conductive particles include graphite, carbon, silver, aluminum oxide, aluminum hydroxide, magnesium oxide, beryllium oxide, boron nitride, aluminum nitride, silicon nitride, silicon carbide, silicon dioxide, aluminum fluoride, calcium fluoride and oxide.
• the particles are at least one type selected from zinc.
• the thermally conductive particles are preferably graphite particles, carbon particles, and boron nitride particles, and more preferably graphite particles.
• the thermally conductive particles are preferably at least one selected from the group consisting of scaly particles, ellipsoidal particles, and rod-shaped particles, and are preferably selected from the group consisting of scaly particles, ellipsoidal particles, and rod-shaped particles. More preferably, it is at least one type of graphite particle (hereinafter also referred to as "graphite particle (A)").
• graphite particle (A) graphite particle
• the thermally conductive particles are scale-like particles, the surface direction is preferably oriented in the thickness direction of the thermally conductive material, and when the thermally conductive particles are ellipsoidal particles, the long axis direction is preferably oriented in the thickness direction of the thermally conductive material.
• the thermally conductive particles are oriented in the thickness direction of the thermally conductive material, and when the thermally conductive particles are rod-shaped particles, it is preferable that the long axis direction is oriented in the thickness direction of the thermally conductive material.
• thermally conductive particles are graphite particles (A)
• the graphite particles (A) may be oriented in the plane direction in the case of scale-like particles, in the long axis direction in the case of ellipsoidal particles, and in the thickness direction in the case of rod-like particles. preferable.
• the graphite particles (A) have six-membered ring planes in the crystal in the planar direction in the case of scale-like particles, in the long axis direction in the case of ellipsoidal particles, and in the long axis direction in the case of rod-like particles. is more preferably oriented.
• the six-membered ring plane is a plane in which a six-membered ring is formed in a hexagonal crystal system, and means a (0001) crystal plane.
• the shape of the graphite particles (A) is more preferably scaly.
• thermal conductivity tends to be further improved. This can be considered, for example, because the scale-like graphite particles are more easily oriented in a predetermined direction in the thermally conductive material.
• the six-membered ring plane in the crystal of the graphite particle (A) is oriented in the plane direction of the scale-like particle, the long axis direction of the ellipsoidal particle, or the long axis direction of the rod-like particle can be determined by X-ray diffraction measurement. It can be confirmed. Specifically, the orientation direction of the six-membered ring plane in the crystal of the graphite particle (A) is confirmed by the following method.
• a sample sheet for measurement is prepared in which the in-plane direction of the scale-like particles, the long-axis direction of the ellipsoidal particles, or the long-axis direction of the rod-like particles of the graphite particles (A) are oriented along the in-plane direction of the sheet.
• the following method may be mentioned.
• a mixture of a resin and graphite particles (A) in an amount of 10% by volume or more based on the resin is formed into a sheet.
• the "resin” used here is not particularly limited as long as it is a material that does not exhibit peaks that interfere with X-ray diffraction and can be formed into a sheet.
• an amorphous resin having cohesive strength as a binder can be used, such as acrylic rubber, NBR (acrylonitrile butadiene rubber), and SIBS (styrene-isobutylene-styrene copolymer).
• a sheet of this mixture is pressed to a thickness of 1/10 or less of the original thickness, and a plurality of pressed sheets are laminated to form a laminate.
• the operation of crushing this laminate to 1/10 or less is repeated three or more times to obtain a sample sheet for measurement.
• the graphite particle (A) is a scale-like particle, the plane direction, if it is an ellipsoidal particle, the long axis direction, and if it is a rod-like particle, the long axis direction is , it is oriented along the surface direction of the sample sheet for measurement.
• the six-membered ring plane in the crystal of graphite particles (A) is oriented in the plane direction in the case of scale-like particles, in the major axis direction in the case of ellipsoidal particles, and in the longitudinal direction in the case of rod-shaped particles.
• X-ray diffraction measurements are performed under the following conditions.
• Device For example, Bruker AXS Co., Ltd. “D8DISCOVER” X-ray source: CuK ⁇ with a wavelength of 1.5406 nm, 40 kV, 40 mA Step (measurement step width): 0.01° Step time: 720sec
• the planar direction is oriented, in the case of ellipsoidal particles, the long axis direction is oriented, and in the case of rod-shaped particles, the long axis direction is oriented in the thickness direction of the thermally conductive material.
• “is” refers to the relationship between the plane direction in the case of scale-like particles, the long axis direction in the case of ellipsoidal particles, and the long axis direction in the case of rod-like particles and the surface (principal surface) of the thermally conductive material. It means that the angle formed (hereinafter also referred to as "orientation angle”) is 60° or more.
• the orientation angle is preferably 80° or more, more preferably 85° or more, and even more preferably 88° or more.
• the orientation angle is determined by observing the cross section of the thermally conductive material with a SEM (scanning electron microscope), and for any 50 graphite particles (A), the orientation angle is determined by the in-plane direction in the case of scaly particles and the in-plane direction in the case of ellipsoidal particles. is the average value when measuring the angle (orientation angle) between the long axis direction, and in the case of rod-shaped particles, the long axis direction and the surface (principal surface) of the thermally conductive material.
• the particle size of the graphite particles (A) is not particularly limited.
• the average particle diameter of the graphite particles (A), as a mass average particle diameter, is preferably 1/2 or more and not more than the average thickness of the thermally conductive material.
• the mass average particle diameter of the graphite particles (A) is 1/2 or more of the average thickness of the heat conductive material, an efficient heat conduction path is formed in the heat conductive material, and thermal conductivity tends to improve.
• the mass average particle diameter of the graphite particles (A) is less than or equal to the average thickness of the thermally conductive material, protrusion of the graphite particles (A) from the surface of the thermally conductive material is suppressed, resulting in excellent adhesion to the surface of the thermally conductive material. There is a tendency.
• thermoly conductive material such that the planar direction in the case of scale-like particles, the long axis in the case of ellipsoidal particles, and the long axis in the case of rod-like particles are oriented in the thickness direction.
• the method described in JP-A No. 2008-280496 can be used.
• sheets are produced using the composition, the sheets are laminated to produce a laminate, and the side end surfaces of the laminate are aligned (for example, 0 with respect to the normal from the main surface of the laminate).
• a slicing method (hereinafter also referred to as "layered slicing method”) can be used.
• the particle size of the graphite particles (A) used as a raw material is preferably 1/2 or more of the average thickness of the thermally conductive material as a mass average particle size, and the average thickness is You can exceed it.
• the reason why the particle size of the graphite particles (A) used as a raw material may exceed the average thickness of the thermally conductive material is that, for example, even if the graphite particles (A) have a particle size that exceeds the average thickness of the thermally conductive material, This is because the graphite particles (A) are sliced together to form the thermally conductive material, and as a result, the graphite particles (A) do not protrude from the surface of the thermally conductive material.
• the particle diameter of the graphite particles (A) used as a raw material is preferably 1 to 5 times, and 2 to 4 times, the average thickness of the thermally conductive material as a mass average particle diameter. It is more preferable that When the mass average particle diameter of the graphite particles (A) is one or more times the average thickness of the heat conductive material, a more efficient heat conduction path is formed and the heat conductivity is further improved. When it is 5 times or less the average thickness of the thermally conductive material, the area occupied by the graphite particles (A) on the surface portion can be prevented from becoming too large, and a decrease in adhesiveness can be suppressed.
• the mass average particle diameter (D50) of the graphite particles (A) is measured using a laser diffraction particle size distribution device (for example, Nikkiso Co., Ltd. "Microtrack series MT3300") adapted to the laser diffraction/scattering method, and the mass cumulative When the particle size distribution curve is drawn from the small particle size side, it corresponds to the particle size at which the mass accumulation is 50%.
• a laser diffraction particle size distribution device for example, Nikkiso Co., Ltd. "Microtrack series MT3300
• the thermally conductive material may include graphite particles other than scale particles, ellipsoidal particles, and rod-shaped particles, such as spherical graphite particles, artificial graphite particles, exfoliated graphite particles, acid-treated graphite particles, expanded graphite particles, and carbon. It may also contain fiber flakes and the like.
• the graphite particles (A) are preferably scale-like particles, and from the viewpoint of having a high degree of crystallinity and easily obtaining scales with a large particle size, scale-like expanded graphite particles obtained by crushing expanded graphite in the form of a sheet are preferred. preferable.
• the content of graphite particles (A) in the thermally conductive material is preferably 15% to 50% by volume, for example, from the viewpoint of balance between thermal conductivity and adhesion, and preferably 20% to 45% by volume. It is more preferable that the amount is 25% to 40% by volume.
• the content of graphite particles (A) is 15% by volume or more, thermal conductivity tends to improve.
• the content of graphite particles (A) is 50% by volume or less, deterioration in tackiness and adhesiveness tends to be suppressed.
• the thermally conductive material contains graphite particles other than scale particles, ellipsoidal particles, and rod-shaped particles, it is preferable that the content of the entire graphite particles is within the above range.
• the content rate (volume %) of graphite particles (A) is a value determined by the following formula.
• Content rate (volume %) of graphite particles (A) [(Aw/Ad)/ ⁇ (Aw/Ad)+(Xw/Xd) ⁇ ] ⁇ 100
• Aw mass composition (mass%) of graphite particles (A)
• Xw mass composition of other arbitrary components (mass%)
• Ad Density of graphite particles (A) (In this disclosure, Ad is calculated as 2.1.)
• Xd Density of other arbitrary components
• the thermally conductive material may contain a component that is liquid at 25° C. (hereinafter also referred to as “liquid component (B)").
• liquid at 25°C means a substance that exhibits fluidity and viscosity at 25°C, and has a viscosity, which is a measure of viscosity, of 0.0001 Pa ⁇ s to 1000 Pa ⁇ s at 25°C. .
• the viscosity of components that are liquid at 25°C is measured using a rheometer at 25°C and a shear rate of 5.0 s -1 .
• viscosity is measured as shear viscosity at a temperature of 25° C. using a rotary shear viscometer equipped with a cone plate (diameter 40 mm, cone angle 0°).
• the viscosity of the liquid component (B) at 25° C. is preferably 0.001 Pa ⁇ s to 100 Pa ⁇ s, more preferably 0.01 Pa ⁇ s to 10 Pa ⁇ s.
• the liquid component (B) is not particularly limited as long as it is liquid at 25°C, and is preferably a high molecular compound (polymer).
• the liquid component (B) include polybutene, polyisoprene, polysulfide, acrylonitrile rubber, silicone rubber, hydrocarbon resin, terpene resin, and acrylic resin. Among these, from the viewpoint of heat resistance, it is preferable that the liquid component (B) contains polybutene.
• the liquid component (B) may be used alone or in combination of two or more.
• polybutene refers to a polymer obtained by polymerizing isobutene or normal butene. It also includes polymers obtained by copolymerizing isobutene and normal butene. As for the structure, it refers to a polymer having a structural unit represented by "-CH 2 --C(CH 3 ) 2 --" or "-CH 2 --CH(CH 2 CH 3 )-". It is also sometimes called polyisobutylene.
• the polybutene only needs to contain the above structure, and other structures are not particularly limited.
• polybutenes examples include butene homopolymers and copolymers of butene and other monomer components.
• copolymers with other monomer components examples include copolymers of isobutene and styrene or copolymers of isobutene and ethylene.
• the copolymer may be a random copolymer, a block copolymer, or a graft copolymer.
• polybutene examples include NOF Polybutene TM Emmawet (registered trademark) from NOF Corporation, Nisseki Polybutene from JXTG Energy Corporation, Tetrax from JXTG Energy Corporation, and Tetrax from JXTG Energy Corporation. Examples include “Himol” and “Polyisobutylene” manufactured by Tomoe Kogyo Co., Ltd.
• the liquid component (B) mainly functions as, for example, a stress relieving agent with excellent heat resistance and humidity resistance, and a tackifying agent. Moreover, by using it in combination with a hot melt agent (E) described later, it tends to be possible to further improve cohesive force and fluidity during heating.
• the content of the liquid component (B) in the thermally conductive material is preferably 10% by volume to 55% by volume, from the viewpoint of further increasing adhesive strength, adhesion, sheet strength, hydrolysis resistance, etc. % to 50% by volume, and even more preferably 20% to 50% by volume.
• the content of the liquid component (B) is 10% by volume or more, the tackiness and adhesiveness tend to be further improved.
• the content of the liquid component (B) is 55% by volume or less, reductions in sheet strength and thermal conductivity tend to be more effectively suppressed.
• the thermally conductive material may contain an acrylic acid ester polymer (C). It is thought that the acrylic ester polymer (C) mainly functions as, for example, a tackifier and an elasticity-imparting agent that allows the thickness to be restored in order to follow warping.
• the acrylic ester polymer (C) has, for example, butyl acrylate, ethyl acrylate, acrylonitrile, acrylic acid, glycidyl methacrylate, 2-ethylhexyl acrylate, etc. as main raw material components, and if necessary, methyl acrylate, etc.
• An acrylic acid ester polymer (so-called acrylic rubber) copolymerized with is preferably used.
• the acrylic ester polymer (C) may be used alone or in combination of two or more.
• the weight average molecular weight of the acrylic ester polymer (C) is preferably 100,000 to 1,000,000, more preferably 250,000 to 700,000, and even more preferably 400,000 to 600. ,000. When the weight average molecular weight is 100,000 or more, the film tends to have excellent strength, and when it is 1,000,000 or less, it tends to have excellent flexibility.
• the weight average molecular weight can be measured by gel permeation chromatography using a standard polystyrene calibration curve.
• the glass transition temperature (Tg) of the acrylic ester polymer (C) is preferably 20°C or lower, more preferably -70°C to 0°C, even more preferably -50°C to -20°C. be. When the glass transition temperature is 20° C. or lower, flexibility and adhesiveness tend to be excellent.
• the glass transition temperature (Tg) can be calculated from tan ⁇ derived from dynamic viscoelasticity measurement by tension.
• the acrylic ester polymer (C) may be present throughout the thermally conductive material by internal addition, or may be localized on the surface by coating or impregnating the surface. In particular, coating on one side or impregnating one side is preferable because strong tackiness can be imparted to only one side, resulting in a sheet with good handling properties.
• the content of the acrylic ester polymer (C) in the thermally conductive layer is preferably from 3% by volume to 25% by volume, more preferably from 5% to 20% by volume, and from 7% by volume. More preferably, it is 15% by volume.
• the thermally conductive material may contain a hot melt agent (D).
• the hot melt agent (D) has the effect of improving the strength of the thermally conductive material and improving the fluidity during heating.
• hot melt agent (D) examples include aromatic petroleum resins, terpene phenol resins, and cyclopentadiene petroleum resins. Further, the hot melt agent (D) may be a hydrogenated aromatic petroleum resin or a hydrogenated terpene phenol resin. The hot melt agent (D) may be used alone or in combination of two or more.
• the hot melt agent (D) when polybutene is used as the liquid component (B), the hot melt agent (D) should contain at least one selected from the group consisting of hydrogenated aromatic petroleum resins and hydrogenated terpene phenol resins. is preferred. These hot melt agents (D) have high stability and excellent compatibility with polybutene, so when they are used as a thermally conductive material, they can achieve better thermal conductivity, flexibility, and handleability. There is a tendency.
• hydrogenated aromatic petroleum resins include, for example, “Alcon” manufactured by Arakawa Chemical Co., Ltd. and “Imarv” manufactured by Idemitsu Kosan Co., Ltd.
• examples of commercially available hydrogenated terpene phenol resins include “Clearon” manufactured by Yasuhara Chemical Co., Ltd.
• commercially available cyclopentadiene petroleum resins include, for example, "Quinton” manufactured by Nippon Zeon Co., Ltd. and “Marcarez” manufactured by Maruzen Petrochemical Co., Ltd.
• the hot melt agent (D) is solid at 25°C and has a softening temperature of 40°C to 150°C.
• a thermoplastic resin is used as the hot melt agent (D)
• the softening fluidity during thermocompression bonding is improved, and as a result, the adhesion tends to be improved.
• the softening temperature is 40° C. or higher, cohesive force can be maintained near room temperature, and as a result, it becomes easier to obtain the necessary sheet strength and tends to be excellent in handleability.
• the softening temperature is 150° C. or less, the softening fluidity during thermocompression bonding increases, and as a result, the adhesion tends to improve.
• the softening temperature is more preferably 60°C to 120°C. Note that the softening temperature is measured by the ring and ball method (JIS K 2207:1996).
• the content of the hot melt agent (D) in the thermally conductive material is preferably 3% to 25% by volume, and 5% to 20% by volume from the viewpoint of increasing adhesive strength, adhesion, sheet strength, etc. It is more preferable that the amount is 5% by volume to 15% by volume.
• adhesive strength, heat fluidity, sheet strength, etc. tend to be sufficient, and when the content is 25% by volume or less, flexibility is insufficient. They tend to have excellent handling properties and thermal cycle resistance.
• the thermally conductive material may contain an antioxidant (F), for example, for the purpose of imparting thermal stability at high temperatures.
• an antioxidant (E) include phenolic antioxidants, phosphorus antioxidants, amine antioxidants, sulfur antioxidants, hydrazine antioxidants, and amide antioxidants.
• the antioxidant (E) may be appropriately selected depending on the temperature conditions used, etc., and phenolic antioxidants are more preferred.
• the antioxidant (E) may be used alone or in combination of two or more.
• phenolic antioxidants include, for example, ADEKA STAB AO-50, ADEKA STAB AO-60, and ADEKA STAB AO-80 manufactured by ADEKA Corporation.
• the content of the antioxidant (E) in the thermally conductive material is not particularly limited, and is preferably 0.1% to 5% by volume, more preferably 0.2% to 3% by volume. It is preferably 0.3% by volume to 1% by volume or less. When the content of the antioxidant (E) is 0.1% by volume or more, a sufficient antioxidant effect tends to be obtained. When the content of the antioxidant (E) is 5% by volume or less, it tends to be possible to suppress a decrease in the strength of the thermally conductive material.
• the thermally conductive material contains graphite particles (A), liquid component (B), acrylic acid ester polymer (C), hot melt agent (D), and other components other than antioxidant (E). It may be included depending on the situation.
• the thermally conductive material may contain a flame retardant from the viewpoint of flame retardancy.
• the flame retardant is not particularly limited and can be appropriately selected from commonly used flame retardants. Examples include red phosphorus flame retardants and phosphate ester flame retardants. Among these, phosphoric acid ester flame retardants are preferred from the viewpoint of excellent safety and improved adhesion due to the plasticizing effect.
• red phosphorus flame retardant in addition to pure red phosphorus particles, those coated with various coatings for the purpose of increasing safety or stability, those made into masterbatches, etc. may be used. Specific examples include Nobared, Nova Excel, Novaquel, and Nova Pellet (all trade names) manufactured by Rin Kagaku Kogyo Co., Ltd.
• Phosphate ester flame retardants include aliphatic phosphate esters such as trimethyl phosphate, triethyl phosphate, and tributyl phosphate; triphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, tricylenyl phosphate, and cresyl di-2,6-oxy Aromatic phosphate esters such as renyl phosphate, tris (t-butylated phenyl) phosphate, tris (isopropylated phenyl) phosphate, triaryl isopropylated phosphate; resorcinol bisdiphenyl phosphate, bisphenol A bis (diphenyl phosphate), resorcinol Examples include aromatic condensed phosphoric acid esters such as bisdixylenyl phosphate. Among these, bisphenol A bis(diphenyl phosphate) is preferable from the viewpoints of excellent hydrolysis resistance
• the content of the flame retardant in the thermally conductive material is not limited and can be used in an amount that exhibits flame retardancy, and is preferably about 30% by volume or less. From the viewpoint of suppressing deterioration of thermal resistance due to seepage, the content is preferably 20% by volume or less.
• Combination 2 of members for producing thermally conductive sheets includes a liquid thermally conductive material containing a metal component and a thermally conductive material containing thermally conductive particles.
• a thermally conductive sheet can be obtained by applying a liquid thermally conductive material containing a metal component to at least a portion of a thermally conductive layer made of a thermally conductive material to form a liquid layer.
• a preferred form of the heat conductive material in the combination 2 of members for producing a heat conductive sheet of the present disclosure is the same as the preferred form of the heat conductive material in the combination 1 of members for producing a heat conductive sheet of the present disclosure described above.
• Combination 2 of members for producing a thermally conductive sheet of the present disclosure is a thermally conductive sheet provided with a liquid layer by applying a liquid thermally conductive material containing a metal component to at least a portion of the thermally conductive layer made of a thermally conductive material. It is a material for forming sheets.
• the thermally conductive layer on which the liquid layer is formed is heat-compressed with an adherend such as a heat generating element or a heat radiator, the liquid layer flows between the thermally conductive layer and the adherend.
• the gap between the thermally conductive sheet and the adherend is filled with the fluid layer, so that the thermally conductive sheet and the adherend can be brought into close contact with each other via the liquid layer.
• contact thermal resistance is significantly reduced.
• the liquid layer contains a metal component, the liquid layer has excellent thermal conductivity, and therefore an increase in thermal resistance of the heat conductive sheet is suppressed.
• the liquid thermally conductive material containing a metal component means a thermally conductive material containing a metal component that becomes liquid at at least a portion of the temperature of 0° C. to 50° C.
• the thermal conductivity of the liquid thermally conductive material containing a metal component is preferably 5 W/(m ⁇ K) or more, and more preferably 10 W/(m ⁇ K) or more.
• the melting point of the aforementioned metal component is preferably 50°C or lower, more preferably 45°C or lower, and even more preferably 0°C to 40°C.
• the aforementioned metal components include gallium, indium, tin, and the like. Among these, metal components containing gallium are preferred.
• the thermally conductive sheet of the present disclosure includes a thermally conductive layer containing a thermally conductive material containing thermally conductive particles, and a first layer that is a liquid thermally conductive material of the present disclosure located on at least a part of the main surface of the thermally conductive layer. and a liquid layer containing a second liquid heat conductive material which is a liquid heat conductive material or a liquid heat conductive material containing a metal component.
• a preferred form of the first liquid thermally conductive material is the same as the preferred form of the liquid thermally conductive material described above.
• a preferred form of the second liquid thermally conductive material is the same as the liquid thermally conductive material containing a metal component in the aforementioned combination 2 of members for producing a thermally conductive sheet.
• the thermally conductive sheet of the present disclosure irregularities may exist on the surface that comes into contact with the adherend. At this time, most of the thermal resistance originates from the resistance (contact thermal resistance) caused by a gap caused by contact between the thermally conductive sheet and an adherend such as a heating element or a heat radiator that contacts the thermally conductive sheet.
• the liquid layer containing the first liquid thermally conductive material or the second liquid thermally conductive material is disposed on at least a part of the main surface of the thermally conductive layer, so that the thermally conductive sheet and the heating element The liquid layer flows due to heat, pressure, etc. when bonding with an adherend such as a heat radiator under heat and pressure.
• the thermally conductive sheet and the adherend are bonded under heat and pressure (for example, gaps resulting from unevenness of the thermally conductive sheet) are filled with the liquid layer.
• the thermally conductive sheet and the adherend can be brought into close contact with each other while reducing the gap between the thermally conductive sheet and the adherend, so that the contact thermal resistance is significantly reduced.
• the average thickness of the thermally conductive layer is not particularly limited and can be appropriately selected depending on the purpose.
• the thickness of the thermally conductive layer can be appropriately selected depending on the specifications of the semiconductor package used. As the thickness decreases, the thermal resistance tends to decrease, and as the thickness increases, the warp followability tends to improve.
• the average thickness of the thermally conductive layer may be 20 ⁇ m to 3000 ⁇ m, preferably 30 ⁇ m to 500 ⁇ m, more preferably 50 to 400 ⁇ m from the viewpoint of thermal conductivity and adhesion.
• the average thickness of the thermally conductive layer is given as the arithmetic mean value of three thicknesses measured at random by observing the cross section of the measurement target using an electron microscope.
• the liquid layer may be located on at least a part of the main surface of the thermally conductive layer, and the liquid layer may be located on the entire main surface, or may be located on a part of the main surface.
• a liquid layer may be located at a portion (for example, a portion that comes into contact with an adherend such as a heating element or a heat radiating element).
• the liquid layer may be located on one main surface, or the liquid layer may be located on two main surfaces.
• the maximum thickness of the liquid layer is preferably 0.5 ⁇ m to 50 ⁇ m, more preferably 0.5 ⁇ m to 30 ⁇ m, even more preferably 0.5 ⁇ m to 20 ⁇ m.
• the maximum thickness of the liquid layer is 0.5 ⁇ m or more, the gap between the adherend and the thermally conductive sheet tends to be further reduced and the contact thermal resistance can be further reduced.
• the thermal conductivity of the thermally conductive sheet is excellent, and leakage of the liquid layer to the outside when the adherend and the thermally conductive sheet are brought into contact can be suppressed. There is a tendency.
• the maximum thickness of the thermally conductive layer and the maximum thickness of the liquid layer may be measured by observing the cross section of the measurement target using an electron microscope. Alternatively, the maximum thickness of the thermally conductive layer may be measured using a micrometer, and the maximum thickness of the thermally conductive layer and the maximum thickness of the thermally conductive sheet including the liquid layer are measured. The maximum thickness of the liquid layer may be determined by subtracting the maximum thickness of the conductive layer. When liquid layers are formed on the two main surfaces of the heat conductive layer, the maximum thickness of the liquid layer means the maximum value of the total thickness of the liquid layers formed on the two main surfaces.
• the liquid layer may be curable or may be curable by heating. If it can be cured by heating, for example, the first liquid thermally conductive material preferably contains the above-mentioned thermosetting resin component that is liquid at 25°C.
• the thermally conductive sheet may have a protective film on at least one side, and preferably has a protective film on both sides. Thereby, the adhesive surface of the heat conductive sheet can be protected.
• the protective film for example, resin films such as polyethylene, polyester, polypropylene, polyethylene terephthalate, polyimide, polyetherimide, polyether naphthalate, and methylpentene, coated paper, coated cloth, and metal foils such as aluminum can be used. These protective films may be used alone or in combination of two or more to form a multilayer film.
• the protective film is preferably surface-treated with a silicone-based, silica-based, or the like release agent.
• thermally conductive sheet is not particularly limited.
• the thermally conductive sheet of the present disclosure is particularly suitable as a thermally conductive sheet (TIM1; Thermal Interface Material 1) interposed between the semiconductor chip and the heat spreader when the semiconductor chip is used as the heat generating body and the heat spreader is used as the heat radiating body.
• TIM1 Thermal Interface Material 1
• the thermally conductive sheet of the present disclosure is not limited to the following embodiments.
• the thermally conductive sheet 1 shown in FIG. A liquid layer 13 is located on the surface.
• the two main surfaces of the thermally conductive sheet 1 may be provided with liquid layers 12 and 13 to reduce unevenness.
• the unevenness of the heat conductive layer 11 can be filled with the liquid layers 12 and 13, and the heat conductive sheet 1 can be brought into contact with the adherend. At this time, unevenness on the surface of the adherend can also be filled with the liquid layers 12 and 13.
• the method for manufacturing the thermally conductive sheet is not particularly limited as long as it can produce a thermally conductive sheet having the above configuration.
• the method for manufacturing a thermally conductive sheet includes a step of preparing a composition containing the thermally conductive particles (also referred to as a "preparation step"), and a step of forming the thermally conductive layer using the composition (a "forming step”). ), and a step of forming a liquid layer on at least a portion of the main surface of the thermally conductive layer (also referred to as a "liquid layer forming step").
• a composition containing thermally conductive particles and optional other ingredients is prepared.
• the method for blending each component is not particularly limited, and any method may be used as long as each component can be mixed uniformly.
• the thermally conductive layer is formed using a composition containing thermally conductive particles and optional other components.
• the thermally conductive layer may be formed by forming the above-mentioned composition into a sheet shape.
• the liquid layer forming step is not particularly limited and may be any method as long as it can form a liquid layer on at least a portion of the main surface of the heat conductive layer.
• the first liquid thermally conductive material or the second liquid thermally conductive material may be applied to at least a portion of the main surface of the thermally conductive layer.
• thermally conductive sheet in which the thermally conductive particles are the above-mentioned graphite particles (A).
• the method for producing a thermally conductive sheet containing graphite particles (A) include the following method.
• the method for producing a thermally conductive sheet includes the steps of preparing a composition containing graphite particles (A) and any other components (the above-mentioned preparation step), and forming the composition into a sheet. (part of the above-mentioned formation process, also referred to as the "sheet production process”); and a process of producing a laminate of the sheets (part of the above-mentioned formation process, also referred to as the "laminate production process”).
• a step of slicing the side end surface of the laminate (part of the above-mentioned formation step, also referred to as the "slicing step"), and a step of slicing the sliced sheet (corresponding to a thermally conductive layer) obtained by slicing.
• a step of forming a liquid layer on at least a portion of the main surface (the above-mentioned liquid layer forming step).
• the method for manufacturing a thermally conductive sheet may further include a step of laminating a protective film on the thermally conductive sheet after the liquid layer forming step (also referred to as a "laminate step").
• thermally conductive sheet By manufacturing a thermally conductive sheet using such a method, an efficient thermally conductive path is likely to be formed, and therefore a thermally conductive sheet with high thermal conductivity and excellent adhesion tends to be obtained.
• ⁇ Preparation process> In the preparation step, graphite particles (A) and any other components (for example, component (B) that is liquid at 25°C, acrylic acid ester polymer (C), hot melt agent (D), antioxidant (E ), other ingredients) is prepared.
• the method for blending each component is not particularly limited, and any method may be used as long as each component can be mixed uniformly.
• the composition may be prepared by obtaining a commercially available composition. For details on the preparation of the composition, reference can be made to paragraph [0033] of JP-A-2008-280496.
• the sheet production step is not particularly limited and may be performed by any method as long as the composition obtained in the previous step can be formed into a sheet.
• at least one molding method selected from the group consisting of rolling, pressing, extrusion, and coating.
• a laminate of sheets obtained in the previous step is formed.
• the laminate may be produced by sequentially stacking a plurality of independent sheets, by folding a single sheet, or by winding one of the sheets. .
• the laminate manufacturing process reference can be made to paragraphs [0035] to [0037] of JP-A No. 2008-280496.
• the slicing step is not particularly limited and may be any method as long as it can slice the side end surface of the laminate obtained in the previous step.
• the graphite particles (A) that penetrate in the thickness direction of the heat conductive layer form an extremely efficient heat conduction path, and from the viewpoint of further improving thermal conductivity, the mass average particle diameter of the graphite particles (A) is twice or less. It is preferable to slice with a thickness of .
• JP-A-2008-280496 for details of the slicing process, reference can be made to paragraph [0038] of JP-A-2008-280496.
• the liquid layer forming step is not particularly limited and may be any method as long as it can form a liquid layer on at least a portion of the main surface of the sliced sheet (corresponding to the heat conductive layer) obtained by slicing.
• the first liquid thermally conductive material or the second liquid thermally conductive material may be applied to at least a portion of the main surface of the thermally conductive layer.
• the lamination step is not particularly limited and may be any method as long as the thermally conductive sheet obtained in the liquid layer forming step can be attached to the protective film.
• the heat dissipation device of the present disclosure includes a heat generating body, a heat dissipating body, and a heat conductive sheet of the present disclosure disposed between the heat generating body and the heat dissipating body, and a main surface of the heat conductive layer located on the side of the heat generating body. and a device in which the liquid layer is located on at least a portion of at least one of the main surfaces located on the side of the heat radiator.
• a liquid layer is located on at least a part of the main surface located on the heating element side and at least a part of the main surface located on the heat radiating element side, and the liquid layer is located on at least a part of the main surface located on the heating element side. It is more preferable that the liquid layer is located in the facing region and in the region facing the heat radiator of the main surface located on the heat radiator side.
• heating elements include semiconductor chips, semiconductor packages, power modules, etc.
• heat radiator examples include a heat spreader, a heat sink, a water cooling pipe, and the like.
• a heat radiating device using a semiconductor chip as a heat generating body and a heat spreader as a heat radiating body will be described.
• a semiconductor chip and a heat spreader are examples of a heat generating body and a heat radiating body, respectively, and the present disclosure is not limited thereto.
• a thermally conductive sheet 1 is used with one surface in close contact with a semiconductor chip 2 and the other surface in close contact with a heat spreader 3.
• the semiconductor chip 2 is fixed to the substrate 4 using an underfill material 5, and the heat spreader 3 is fixed to the substrate 4 by a sealing material 6, which presses the adhesion between the thermally conductive sheet 1, the semiconductor chip 2, and the heat spreader 3.
• one heating element and one heat radiating element are provided for one heat conductive sheet 1.
• a plurality of semiconductor chips 2 may be provided for one heat conductive sheet 1
• one semiconductor chip 2 may be provided for a plurality of heat conductive sheets 1
• a plurality of semiconductor chips 2 may be provided for a plurality of heat conductive sheets 1.
• a plurality of semiconductor chips 2 may be provided on the heat conductive sheet 1.
• a liquid layer is located on the main surface of the thermally conductive sheet 1 on the semiconductor chip 2 side and on the main surface of the thermally conductive sheet 1 on the heat spreader 3 side. For example, in the thermal conductive sheet 1 shown in FIG.
• the liquid layer 13 is located on the main surface of the thermal conductive sheet 1 on the semiconductor chip 2 side, and the liquid layer 12 is located on the main surface of the thermal conductive sheet 1 on the heat spreader 3 side. are doing. Further, the liquid layer 13 may be in contact with the semiconductor chip 2, and the liquid layer 12 may be in contact with the heat spreader 3.
• the heat radiating device includes the heat conductive sheet of the present disclosure disposed between a heat generating element and a heat radiating element. Since the heating element and the heat radiating element are laminated via the heat conductive sheet, heat from the heating element can be efficiently conducted to the heat radiating element. By being able to conduct heat efficiently, the lifespan of the heat dissipation device is improved, and a heat dissipation device that functions stably even during long-term use can be provided.
• the temperature range in which the thermally conductive sheet can be particularly suitably used may be, for example, -10°C to 150°C, -10°C to 100°C, or -10°C to 80°C. .
• suitable examples of the heating element include semiconductor packages, displays, LEDs, electric lights, automotive power modules, and industrial power modules.
• the heat sink examples include a heat sink using aluminum or copper fins or plates, an aluminum or copper block connected to a heat pipe, an aluminum or copper block in which a cooling liquid is circulated by a pump, and a Peltier element and an aluminum or copper block equipped with the same.
• the heat radiating device is constructed by bringing each surface of a heat conductive sheet into contact with a heat generating element and a heat radiating element.
• the method of bringing the heating element into contact with one side of the heat conductive sheet and the method of bringing the heat radiating element into contact with the other side of the heat conductive sheet are especially suitable as long as they can be fixed in a sufficiently close state. Not restricted.
• a heat conductive sheet may be placed between the heating element and the heat radiating element, fixed with a jig that can be pressurized to approximately 0.05 MPa to 1 MPa, and the heating element may be heated in this state, or the A method of heating to about .degree. C. to 200.degree. C. can be mentioned.
• Another method is to use a press machine capable of heating and pressing at 80° C. to 200° C. and 0.05 MPa to 1 MPa.
• the preferred pressure range for this method is 0.10 MPa to 1 MPa, and the preferred temperature range is 100°C to 180°C. Excellent adhesion tends to be obtained by setting the pressure to 0.10 MPa or higher or the heating temperature to 100° C. or higher.
• the pressure is 1 MPa or less or the heating temperature is 180° C. or less, the reliability of adhesion tends to be further improved. This is thought to be because it is possible to prevent the thermally conductive sheet from being excessively compressed and becoming thinner, or from becoming too large in distortion or residual stress in peripheral members.
• the heat conductive sheet disposed between the heating element and the heat radiating element is not particularly limited as long as it is the above-mentioned heat conductive sheet.
• the thermally conductive sheet shown in FIG. 1 may be placed between a heat generating element and a heat radiating element.
• the liquid layer can be cured by heating by using a first liquid thermally conductive material containing a thermosetting resin component
• the liquid layer flows by thermocompression bonding, and the thermally conductive sheet and the adherend are bonded together.
• the thermosetting resin component is cured by heating.
• the thermally conductive sheet and the adherend can be brought into close contact with each other via the adhesive layer formed by hardening the liquid layer.
• the thermally conductive sheet may have a reduced thickness (compression rate) of 1% to 35% after the heat-conducting sheet is placed between the heat-generating element and the heat-dissipating body relative to its initial thickness before being press-bonded.
• jigs such as screws and springs may be used for fixing, and it is preferable to further fix with commonly used means such as adhesives in order to maintain close contact.
• the porosity calculated by the ratio of the area of the gas region to the area of the measurement region is 0% to 20.0%. It is preferably from 0% to 15.0%. This reduces gaps that occur when heat-compression bonding the thermal conductive sheet and the heat generating element or the heat dissipating body (for example, gaps resulting from unevenness of the heat conductive sheet and gaps resulting from unevenness of the heat generating element or heat dissipating body). . As a result, it is estimated that the contact thermal resistance is significantly reduced.
• the porosity satisfies the above numerical range in both cases of the main surface side of the thermally conductive layer where the liquid thermally conductive material is located and the main surface side of the thermally conductive layer where the liquid thermally conductive material is not located. It is preferable.
• the numerical range of the porosity of the interface can be adjusted by adjusting, for example, the viscosity of the liquid thermally conductive material at 25°C, the amount of the liquid thermally conductive material applied to the thermally conductive layer, the compressibility of the thermally conductive sheet, etc. It becomes possible.
• Example 1 to Example 4 The following materials were put into a kneader (Moriyama Co., Ltd., DS3-SGHM-E type pressurized double-arm kneader) so that the mixing ratio (volume %) was as shown in Table 1, and kneaded at a temperature of 150°C. , a composition was obtained.
• a kneader Moka Co., Ltd., DS3-SGHM-E type pressurized double-arm kneader
• the composition obtained by kneading was put into an extrusion molding machine (Parker Co., Ltd., product name: HKS40-15 type extruder) and extruded into a flat plate shape with a width of 20 cm and a thickness of 1.5 mm to 1.6 mm to obtain a primary sheet.
• the obtained primary sheet was press punched using a 40 mm x 150 mm die blade, and 61 of the punched sheets were stacked and heated at 90°C in the stacking direction with a spacer 80 mm in height in between so that the height was 80 mm. Pressure was applied for 30 minutes to obtain a 40 mm x 150 mm x 80 mm laminate.
• thermally conductive layer with a thickness of 0.11 mm. Note that the thicknesses of the thermally conductive layers used in each Example and each Comparative Example were approximately the same.
• thermoly conductive sheet A liquid thermally conductive material having the composition shown below was prepared.
• the prepared liquid thermally conductive material is applied to one or two main surfaces of the thermally conductive layer obtained as described above, and the liquid component is uniformly spread using a special spatula.
• a thermally conductive sheet was obtained in which a liquid layer was formed on two main surfaces.
• First liquid thermally conductive material (liquid material 1 in the table): Artic Silver, Inc.
• AS-05A (contains liquid ester compound and silver particles, filler content 86% by mass, viscosity at 25°C 145 Pa ⁇ s, thermal conductivity 9W/(m ⁇ K))
• Second liquid thermally conductive material (liquid material 2 in the table): JunPus International Co. , Ltd.
• JP-DX1 (contains liquid silicone compound and nanodiamond, filler content 92% by mass, viscosity at 25°C 3000 Pa ⁇ s, thermal conductivity 16W/(m ⁇ K))
• Third liquid thermally conductive material (liquid material 3 in the table): Thermal Grizzly's Conductnaut (metal containing tin, gallium, and indium, viscosity at 25°C 0.0021 Pa ⁇ s, thermal conductivity 73 W/(m ⁇ K ))
• Thermal resistance was measured using a tabletop xenon flash analyzer (LFA 467 Hyper Flash).
• LFA 467 Hyper Flash A sample with a three-layer structure was prepared by sandwiching a thermally conductive sheet with a diameter of 14 mm between 1 mm copper plates.
• the sample preparation conditions were as follows: The sample was pressurized at a temperature of 150° C. and a pressure of 0.14 MPa for 3 minutes, and then sufficiently cooled to room temperature.
• the copper surface was blackened using carbon spray, and then measured.
• the thermally conductive sheets of Examples 1 to 4 and Comparative Example 1 were compressed under the same conditions. Next, the maximum thickness of the thermally conductive sheet after compression ("thickness after compression" in Table 2) was measured using a micrometer. Regarding the maximum thickness of the liquid layer, the maximum thickness of the liquid layer was determined by subtracting the maximum thickness of the thermally conductive sheet including the liquid layer from the maximum thickness of the thermally conductive sheet not including the liquid layer.

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