WO2018139240A1 - 熱伝導性シート - Google Patents
熱伝導性シート Download PDFInfo
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- WO2018139240A1 WO2018139240A1 PCT/JP2018/000891 JP2018000891W WO2018139240A1 WO 2018139240 A1 WO2018139240 A1 WO 2018139240A1 JP 2018000891 W JP2018000891 W JP 2018000891W WO 2018139240 A1 WO2018139240 A1 WO 2018139240A1
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- Prior art keywords
- thermally conductive
- group
- silicone composition
- conductive sheet
- heat conductive
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- 0 CN(*1)C#[Mn]1=C Chemical compound CN(*1)C#[Mn]1=C 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/0427—Coating with only one layer of a composition containing a polymer binder
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
- B29C35/02—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
- B32B27/283—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polysiloxanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/12—Polysiloxanes containing silicon bound to hydrogen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/042—Coating with two or more layers, where at least one layer of a composition contains a polymer binder
-
- 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
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/044—Forming conductive coatings; Forming coatings having anti-static properties
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/541—Silicon-containing compounds containing oxygen
- C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
- C08K5/5419—Silicon-containing compounds containing oxygen containing at least one Si—O bond containing at least one Si—C bond
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/544—Silicon-containing compounds containing nitrogen
- C08K5/5477—Silicon-containing compounds containing nitrogen containing nitrogen in a heterocyclic ring
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/34—Arrangements for cooling, heating, ventilating or temperature compensation ; Temperature sensing arrangements
- H01L23/36—Selection of materials, or shaping, to facilitate cooling or heating, e.g. heatsinks
- H01L23/373—Cooling facilitated by selection of materials for the device or materials for thermal expansion adaptation, e.g. carbon
- H01L23/3737—Organic materials with or without a thermoconductive filler
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2083/00—Use of polymers having silicon, with or without sulfur, nitrogen, oxygen, or carbon only, in the main chain, as moulding material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
- B29K2995/0012—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds having particular thermal properties
- B29K2995/0013—Conductive
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2333/24—Homopolymers or copolymers of amides or imides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2383/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
- C08J2383/04—Polysiloxanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
- C08J2483/04—Polysiloxanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/001—Conductive additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/005—Additives being defined by their particle size in general
Definitions
- the present invention relates to a heat conductive sheet.
- the present invention relates to a heat conductive sheet used as a heat transfer material that can be interposed between a heat generating electronic component and a heat dissipating member such as a heat sink.
- a heat sink using a metal plate having a high thermal conductivity such as aluminum or copper is used to suppress a temperature rise of a semiconductor in operation in an electronic device or the like.
- the heat sink conducts heat generated by the semiconductor and releases the heat from the surface due to a temperature difference from the outside air.
- the semiconductor and the heat sink must be electrically insulated.
- a plastic film or the like is interposed between the heat-generating electronic component and the heat sink.
- plastic films have a very low thermal conductivity, which significantly impedes heat transfer to the heat sink.
- a semiconductor such as a transistor is fixed to a heat sink with a screw, the screw needs to penetrate the plastic film. At that time, a hole is formed in the film, and the film is broken and the insulation cannot be maintained. This problem occurs. The inability to maintain insulation is fatal for transistors and diodes.
- a heat conductive sheet in which a heat conductive resin is laminated on a glass cloth has been developed in order to impart heat conductivity that is not easily torn.
- a thermally conductive sheet in which a silicone rubber containing boron nitride powder and spherical silica powder as a thermally conductive filler is laminated on a glass cloth Patent Document 1: Japanese Patent Laid-Open No. 9-199880.
- Patent Document 2 Japanese Patent Publication No. 2 discloses a multilayer structure in which a silicone rubber layer having excellent thermal conductivity and electrical characteristics is blended with beryllium oxide, aluminum oxide, aluminum hydroxide, and the like. No. 24383) has at least a polyimide (amide) film blended with a predetermined amount of aluminum oxide or the like as an intermediate layer and a pair of outer layers on both sides of the intermediate layer and a silicone rubber layer blended with aluminum oxide or the like disposed at least.
- a thermally conductive electrical insulating member having a three-layer laminate is described.
- heat conductive electrical insulating members having a multilayer structure are unstable in adhesion between the outer layer silicone rubber layer and the intermediate layer of an aromatic polyimide film, etc. There is a problem that it is inferior.
- a silicon compound-based adhesive having at least one functional group selected from the group consisting of an epoxy group, an alkoxy group, a vinyl group, and a group represented by the formula: Si—H
- Patent Document 3 Japanese Patent Application Laid-Open No. 2004-122664
- a continuous molding method includes coating molding.
- the glass cloth is sealed with a thermally conductive silicone resin, and a thermally conductive silicone rubber layer is formed on the sealed glass cloth with a coating to continuously form the thermally conductive sheet.
- a thermally conductive sheet can be continuously produced by forming a thermally conductive silicone rubber layer on one side or both sides of the synthetic resin film by coating.
- the coating molding is very efficient because the finished sheet can be wound up continuously.
- the length in the width direction of the sheet is limited by the size of the coating apparatus, the length in the length direction is not limited, so that the degree of freedom in size during mounting is markedly increased compared to press molding.
- spherical heat conductive filler As a means for improving the surface accuracy even in coating molding, there is a method of using a spherical heat conductive filler to improve the fluidity of the heat conductive silicone resin.
- the types of spherical heat conductive fillers are limited, and each type has various problems.
- spherical alumina is relatively inexpensive, but because of its high hardness, there is a problem that the compounding kettle is scraped during compounding, and the safety of equipment and the insulation of products are lowered.
- aggregated spherical powders such as aluminum nitride and boron nitride, but they are very expensive, and there is a problem that the manufacturing cost of the heat conductive sheet becomes high.
- a non-spherical heat conductive filler having a relatively low material cost which is typified by aluminum hydroxide, and having an insulating property has a large specific surface area, and the amount that can be filled in the silicone resin is limited. Therefore, there has been a problem that the thermal conductivity is lowered. Moreover, since it is inferior in fluidity
- JP-A-9-199880 Japanese Patent Publication No. 2-24383 JP 2004-122664 A
- the present invention has been made in view of the above circumstances, and can be manufactured continuously by coating molding using an inexpensive non-spherical heat conductive filler, and can be wound into a roll, heat resistance, electrical insulation
- It is a heat conductive sheet using a synthetic resin film such as aromatic polyimide that is rich in properties and mechanical strength, and has high thermal conductivity, low contact thermal resistance, high insulation, strong interlayer adhesion, It aims at providing the heat conductive sheet which does not generate
- the present inventors have found that a thermally conductive silicone composition is formed on both sides or one side of a synthetic resin film layer such as an aromatic polyimide having excellent heat resistance, electrical insulation and mechanical strength.
- the thermally conductive silicone composition comprises an organosilicon compound component containing an adhesion-imparting agent and a non-spherical thermally conductive filler having a specific DOP oil absorption.
- the present inventors have found that a heat conductive sheet having high thermal conductivity, high insulation, strong interlayer adhesion, and not causing embrittlement during use can be produced by continuous molding. Invented the invention.
- the present invention provides the following heat conductive sheet.
- a thermally conductive sheet having a cured layer of a thermally conductive silicone composition on both or one side of an electrically insulating synthetic resin film layer, wherein the thermally conductive silicone composition contains an adhesion-imparting agent And a non-spherical heat conductive filler, the amount of the heat conductive filler is 250 to 600 parts by weight with respect to 100 parts by weight of the organosilicon compound component, and the heat conductive filler
- the thermally conductive sheet having a DOP oil absorption of 80 ml / 100 g or less.
- the heat conductive sheet according to [1] wherein the synthetic resin used for the synthetic resin film layer has a melting point of 100 ° C or higher.
- the synthetic resin used for the synthetic resin film layer is aromatic polyimide, polyamide, polyamideimide, polyester, polyolefin, aromatic polyether, fluoropolymer, or a combination of two or more thereof [1] or [2 ]
- the heat conductive sheet of description [4]
- the adhesion-imparting agent in the thermally conductive silicone composition has at least one selected from the group consisting of an epoxy group and / or an alkoxy group, and a vinyl group and a group represented by the formula: Si—H.
- the thermal conductive sheet according to any one of [1] to [3], which is a silicon compound-based adhesion imparting agent having a group.
- Aluminum hydroxide powder (1) 100 to 500 parts by mass of aluminum hydroxide powder having an average particle size of 5 to 14 ⁇ m and a DOP oil absorption of 50 ml / 100 g or less, and (2) an average particle size of 0.5 to 3 ⁇ m, It is composed of 50 to 400 parts by mass of aluminum hydroxide powder having an oil absorption of 80 ml / 100 g or less, and the ratio of the above (1) in the total amount of non-spherical heat conductive filler is 40% by mass or more.
- the non-spherical thermally conductive filler in the thermally conductive silicone composition has an amount of particles having a particle size of 45 ⁇ m or more of 0 to 0.5 mass% and an amount of particles of particle size of 75 ⁇ m or more of 0 to
- the heat conductive sheet according to any one of [1] to [7], which is 0.01% by mass.
- the organosilicon compound component in the thermally conductive silicone composition is (A) The following average composition formula (1): R 1 a SiO (4-a) / 2 (1) (In the formula, R 1 is independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and a is 1.90 to 2.05.)
- the thermal conductive sheet according to any one of [1] to [8], which contains an organopolysiloxane having an alkenyl group bonded to at least two silicon atoms in one molecule.
- (E) (E1) The following general formula (2): R 2 b R 3 c Si (OR 4 ) 4-bc (2) Wherein R 2 is independently an alkyl group having 6 to 15 carbon atoms, R 3 is independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms, R 4 Is independently an alkyl group having 1 to 6 carbon atoms, b is an integer of 1 to 3, c is 0, 1 or 2, provided that b + c is 1 to 3.
- (C) as a curing agent, (C-1a) Organohydrogenpolysiloxane: The total number of silicon-bonded hydrogen atoms in the thermally conductive silicone composition is 0.8 to 10 moles relative to the total of 1 mole of alkenyl groups in the thermally conductive silicone composition. And (C-1b) platinum-based catalyst: The amount of platinum metal in the platinum-based catalyst is 0.1 to 2,000 ppm by mass with respect to component (A). The heat conductive sheet as described in [9] or [10].
- thermoly conductive silicone composition (C) as a curing agent, (C-2) Organic peroxide: containing 0.5 to 30 parts by mass with respect to a total of 100 parts by mass of the vinyl group-containing compound in the thermally conductive silicone composition [9] or [10 ]
- the heat conductive sheet of description [13]
- the thickness of the electrically insulating synthetic resin film layer is 5 to 90 ⁇ m
- the thickness of the cured layer of the thermally conductive silicone composition is 40 to 400 ⁇ m
- the total thickness of the thermally conductive sheet is 55 to 500 ⁇ m.
- the heat conductive sheet according to any one of [1] to [12].
- thermally conductive sheet according to any one of [1] to [13], wherein the cured product of the thermally conductive silicone composition has a thermal conductivity of 1.2 W / m ⁇ K or more.
- the heat conductive sheet of the present invention can be continuously produced by coating and wound into a roll.
- a heat conductive filler is blended, not only has a cured layer of a heat conductive silicone composition having good heat conductivity, but also an aromatic polyimide having excellent electrical insulation and mechanical strength, etc. Therefore, it has sufficient strength and flexibility due to its reinforcing effect. From these points, the heat conductive sheet of the present invention is suitable as an electrically insulating heat dissipating member interposed between the heat generating electronic / electrical component and the heat dissipating component.
- cured material layer of a heat conductive silicone composition contains adhesiveness imparting agent, the hardened
- a thermally conductive filler with a small amount of DOP oil absorption is used, the sheet is not embrittled with time due to the adhesion-imparting agent. Therefore, the heat conductive sheet of the present invention has a remarkable action and effect that it is excellent in durability.
- the thermally conductive sheet of the present invention has a cured layer of a thermally conductive silicone composition on both sides or one side of an electrically insulating synthetic resin film layer.
- this synthetic resin film layer is called an intermediate
- the electrically insulating synthetic resin film layer used in the present invention is not particularly limited as long as it is a flexible and high mechanical strength synthetic resin film layer excellent in electrical insulation, and all known materials can be used. it can.
- Synthetic resins include, for example, aromatic polyimides; polyamides; polyamideimides; polyesters such as polyethylene terephthalate and polyethylene naphthalate; polyolefins; aromatic polyethers; polytetrafluoroethylene (PTFE) and tetrafluoroethylene / perfluoroalkyl vinyl ethers. Fluorine polymers such as copolymers can be mentioned.
- the synthetic resin used for the synthetic resin film layer has excellent heat resistance and mechanical strength as long as it has a melting point of 100 ° C or higher, preferably 150 ° C or higher, more preferably 200 ° C or higher, and even more preferably 250 ° C or higher. It is preferable because neither a decrease nor thermal deformation is likely to occur.
- Suitable examples of the synthetic resin film layer include, for example, Kapton (registered trademark) (trade name, manufactured by Toray DuPont Co., Ltd.), which is an aromatic polyimide film, as a heat-resistant film having a melting point of 250 ° C. or higher. Is mentioned.
- the fluoropolymer is used as the synthetic resin, it is preferable from the viewpoint of improving adhesiveness that the surface of the resulting synthetic resin film is subjected to a chemical etching treatment using a metal Na / naphthalene-based treatment liquid.
- the thickness of the synthetic resin film layer can be set according to the application form and application target of the heat conductive sheet of the present invention, and is not particularly limited, but is preferably 5 to 90 ⁇ m, more preferably 10 to 75 ⁇ m, and still more preferably The range is preferably about 10 to 40 ⁇ m. If the thickness is too thick, the thermal conductivity of the heat conductive sheet of the present invention will be hindered. Conversely, if it is too thin, the strength to be exhibited may be insufficient, and the electrical insulation performance may be insufficient. is there. In addition, it is preferable that the synthetic resin film layer used for this invention is a synthetic resin film layer which does not have a hole which reduces an electrical insulation characteristic.
- the thermally conductive silicone composition used in the present invention contains an organosilicon compound component containing an adhesion-imparting agent and a non-spherical thermally conductive filler, and the amount of the thermally conductive filler is the organosilicon compound component.
- the amount of DOP oil absorption of the heat conductive filler is 80 ml / 100 g or less with respect to 100 parts by weight.
- the thermally conductive silicone composition is not particularly limited as long as it contains a specific amount of an organosilicon compound component containing an adhesion-imparting agent and a non-spherical thermally conductive filler having a specific DOP oil absorption amount,
- the following (A) to (D) components, more preferably (E) and (F) components are preferred.
- R 1 a SiO (4-a) / 2 (1)
- R 1 is independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and a is 1.90 to 2.05.
- the component (A) used in the thermally conductive silicone composition according to the present invention is represented by the following average composition formula (1), and an organopolysiloxane having an alkenyl group bonded to at least two silicon atoms in one molecule And the main component (base polymer) of the thermally conductive silicone composition.
- R 1 a SiO (4-a) / 2 (1) (Wherein R 1 is independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10, preferably 1 to 8, carbon atoms, and a is 1.90 to 2.05.)
- R 1 is, for example, an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group; a cyclopentyl group Cycloalkyl group such as cyclohexyl group; aryl group such as phenyl group, tolyl group, xylyl group and naphthyl group; aralkyl group such as benzyl group, phenethyl group and 3-phenylpropyl group; 3,3,3-trifluoropropyl Groups, halogen-substituted alkyl groups such as 3-chloropropyl group; alkenyl groups such as vinyl group, allyl group, butenyl group, pentenyl group, hexen
- the component (A) may be in the form of oil or gum.
- the average degree of polymerization of the component (A) is preferably 20 to 12,000, more preferably 50 to 10,000.
- the average degree of polymerization can be determined, for example, as a polystyrene conversion value in gel permeation chromatography (GPC) analysis using toluene, tetrahydrofuran (THF) or the like as a developing solvent. It is preferable to obtain the average degree of polymerization (hereinafter the same).
- the component (A) is a component that is cured by addition reaction or peroxide, and has 2 or more, preferably 3 or more alkenyl groups bonded to a silicon atom in one molecule.
- the amount of alkenyl group is preferably 0.0002 to 0.5 mol / 100 g. When the content of the alkenyl group bonded to the silicon atom is less than the above range, the resulting composition is not sufficiently cured when curing is performed by an addition reaction.
- the alkenyl group is preferably a vinyl group.
- the alkenyl group may be bonded to either the silicon atom at the molecular chain terminal or a silicon atom other than the molecular chain terminal, and preferably at least one alkenyl group is bonded to the silicon atom at the molecular chain terminal.
- component (A) in the case where the curing is carried out by addition reaction include, for example, a trimethylsiloxy group-capped dimethylsiloxane / methylvinylsiloxane copolymer with both ends of a molecular chain, a trimethylsiloxy group-capped methylvinylpolyethylene with a molecular chain at both ends Siloxane, trimethylsiloxy group-capped dimethylsiloxane / methylvinylsiloxane / methylphenylsiloxane copolymer, molecular chain both-end dimethylvinylsiloxy group-capped dimethylpolysiloxane, molecular chain both-end dimethylvinylsiloxy group-capped methylvinylpolysiloxane Dimethyl siloxane / methyl vinyl siloxane copolymer with dimethylvinylsiloxy group blocked at both ends of molecular chain, dimethyl siloxane / methyl vinyl siloxan
- component (A) when curing is performed using a peroxide include, for example, molecular chain both ends dimethylvinylsiloxy group-capped dimethylpolysiloxane, molecular chain both ends methylphenylvinylsiloxy group-capped dimethylpolysiloxane , Dimethylvinylsiloxy group-capped dimethylsiloxane / methylphenylsiloxane copolymer, molecular chain both ends dimethylvinylsiloxy group-capped dimethylsiloxane / methylvinylsiloxane copolymer, molecular chain both ends trimethylsiloxy group-capped dimethylsiloxane, Methyl vinyl siloxane copolymer, molecular chain both ends dimethyl vinyl siloxy group-blocked methyl (3,3,3-trifluoropropyl) polysiloxane, molecular chain both ends silanol group blocked dimethyl siloxane / methyl vinyl
- the component (A) is preferably blended in the range of 50 to 95% by mass, particularly 60 to 90% by mass, in the total amount of the organosilicon compound component contained in the thermally conductive silicone composition.
- An adhesiveness-imparting agent (B) is blended in the thermally conductive silicone composition according to the present invention.
- the synthetic resin film layer and the cured layer of the thermally conductive silicone composition exhibit strong adhesiveness to each other without causing delamination. It can be made excellent in durability over time.
- the step of applying a primer treatment for the purpose of improving the adhesiveness to the synthetic resin film layer can be omitted, the manufacturing process of the heat conductive sheet can be simplified, and the primer layer is not provided. Therefore, a thermally conductive sheet whose thermal conductivity is not reduced can be obtained.
- This adhesion-imparting agent is a silicon compound having an epoxy group and / or an alkoxy group, and further having at least one group selected from the group consisting of a vinyl group and a group represented by the formula: Si—H. Is preferred.
- the silicon compound as the adhesion imparting agent is an epoxy group, an alkoxy group, or both of them, a vinyl group, a formula : It is more preferable to have a group represented by Si—H or both, and it is more preferable to have an epoxy group, an alkoxy group or both of them, and a group represented by the formula: Si—H.
- Si—H a group represented by the formula: Si—H
- a silicon compound having a group represented by the formula: Si—H is used as an adhesiveness imparting agent, it also acts as an organohydrogenpolysiloxane as a curing agent (C) described later.
- the silicon compound as the adhesion imparting agent is an epoxy group, an alkoxy group, or It is more preferable to have both of these and a vinyl group, a group represented by the formula: Si—H, or both.
- silicon compound having such a group examples include the following. However, it is not limited to the following.
- the adhesiveness imparting agent can be used alone or in combination of two or more.
- the compounding amount of this adhesion-imparting agent (B) is usually 0.1 to 20% by mass, preferably 0.5 to 15% by mass, based on the total amount of the organosilicon compound component contained in the thermally conductive silicone composition. It is better to be in the range. If the amount is too small, the effect of imparting adhesiveness may not be exhibited. If the amount is too large, mechanical properties may be impaired, or embrittlement due to aging may occur.
- Component (C) is a curing agent.
- organohydrogenpolysiloxane is used as the curing agent (C)
- the reaction is performed in the presence of a platinum-based catalyst. Done.
- an organic peroxide is used as the curing agent (C).
- this curing agent when the thermally conductive silicone composition is cured by an addition reaction (hydrosilylation reaction), this curing agent has an average of 2 or more, particularly 2 to 30 silicon-bonded hydrogen atoms in one molecule. What consists of the organohydrogenpolysiloxane which has and a platinum-type catalyst is mix
- the group bonded to the silicon atom in addition to the hydrogen atom in the organohydrogenpolysiloxane is a monovalent hydrocarbon group having 1 to 10, preferably 1 to 8, carbon atoms not containing an aliphatic unsaturated bond.
- Straight chain alkyl groups such as methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, etc.
- Branched chain alkyl groups branched chain alkyl groups, cyclic alkyl groups such as cyclopentyl and cyclohexyl groups, aryl groups such as phenyl groups, aralkyl groups such as benzyl groups and phenethyl groups, 3,3,3-trifluoropropyl groups, 3-chloropropyl And a halogen-substituted alkyl group such as a group, preferably an alkyl group or an aryl group, particularly preferably a methyl group, Is a Eniru group.
- the viscosity of the organohydrogenpolysiloxane at 25 ° C. is not limited, but is preferably in the range of 5 to 300 mm 2 / s, particularly preferably in the range of 10 to 200 mm 2 / s.
- the molecular structure of the organohydrogenpolysiloxane is not limited, and examples thereof include linear, branched, partially branched linear, cyclic, and dendritic (dendrimer).
- the organohydrogenpolysiloxane may be, for example, a single polymer having these molecular structures, a copolymer having these molecular structures, or a mixture thereof.
- organohydrogenpolysiloxanes examples include dimethylpolysiloxane blocked with dimethylhydrogensiloxy group at both ends of the molecular chain, dimethylsiloxane / methylhydrogensiloxane copolymer blocked with trimethylsiloxy group at both ends of the molecular chain, and dimethylhydrogen at both ends of the molecular chain.
- the content of the organohydrogenpolysiloxane is an amount necessary for curing the present composition.
- the silicon atom-bonded alkenyl group in the component (A) or the above (B) When the adhesion-imparting agent contains a vinyl group, the silicon atom-bonded hydrogen atom in this component or the above-mentioned (B) adhesion-imparting with respect to 1 mol in total of the alkenyl groups in component (A) and component (B)
- the agent contains Si—H groups
- the total amount of Si—H groups in this component and component (B) is preferably in the range of 0.8 to 10 moles, and more preferably 1 to 8 moles.
- the amount is preferably within the range, and particularly preferably within the range of 1.2 to 5 mol. If the content of this component is less than the lower limit of the above range, curing will be insufficient, so that sufficient sheet strength may not be obtained, and oil bleeding may be promoted. If it exceeds 1, the sheet may become brittle or foam.
- the platinum-based catalyst is a catalyst for accelerating the curing of the composition.
- chloroplatinic acid chloroplatinic acid alcohol solution, platinum olefin complex, platinum alkenylsiloxane complex, platinum carbonyl complex, etc. Is mentioned.
- the content of the platinum-based catalyst is an amount necessary for curing the present composition.
- the platinum metal in this component is 0.1 mass unit relative to the component (A).
- the amount is preferably ⁇ 2,000 ppm, particularly preferably 10 to 1,000 ppm.
- the curing agent is an organic peroxide.
- the organic peroxide include benzoyl peroxide, di (p-methylbenzoyl) peroxide, di (o-methylbenzoyl) peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-bis ( tert-butylperoxy) hexane, di-tert-butyl peroxide, tert-butylperoxybenzoate and the like.
- the content of the organic peroxide is an amount necessary for curing the present composition.
- the component (A) or the (B) adhesion-imparting agent contains a vinyl group (A )
- Component and (B) component are preferably used in an amount of 0.5 to 30 parts by mass, particularly preferably 1 to 20 parts by mass with respect to 100 parts by mass in total.
- the content of this component is less than the lower limit of the above range, curing becomes insufficient, so that sufficient sheet strength cannot be obtained, and oil bleeding may be promoted, and when the upper limit of the above range is exceeded.
- the sheet may become brittle or foam.
- the non-spherical thermally conductive filler (D) blended in the thermally conductive silicone composition according to the present invention may be generally used.
- nonmagnetic metals such as copper and aluminum, alumina Metal oxides such as silica, magnesia, bengara, beryllia, titania and zirconia, metal nitrides such as aluminum nitride, silicon nitride and boron nitride, metal hydroxides such as aluminum hydroxide and magnesium hydroxide, artificial diamond, and Examples thereof include silicon carbide. These can be used alone or in combination of two or more.
- the DOP oil absorption of the non-spherical heat conductive filler is 80 ml / 100 g or less, more preferably 60 ml / 100 g or less. If the DOP oil absorption exceeds the above upper limit, the filling property of the thermally conductive filler with respect to the organosilicon compound component is lowered, the fluidity during coating is lost, the smoothness of the sheet surface is impaired, and the thermal resistance is reduced. Invite rise. In addition, it is difficult to fill the heat conductive filler in a high amount, which is disadvantageous in terms of heat conductivity.
- the DOP oil absorption is preferably 10 ml / 100 g or more. The DOP oil absorption is the amount of oil required to knead the thermally conductive filler with oil (di-2-ethylhexyl phthalate) to form a tight draw.
- the non-spherical heat conductive filler has an amount of particles having a particle size of 45 ⁇ m or more of 0 to 0.5% by mass, preferably 0 to 0.2% by mass, and an amount of particles having a particle size of 75 ⁇ m or more of 0 to 0.01% by mass, preferably 0% by mass.
- the thermal conductivity is obtained when the thermally conductive silicone composition is coated to obtain a thermally conductive sheet.
- the filler may protrude from the surface of the coating film and the smoothness of the sheet surface may be impaired.
- the amount of particles having a particle size of 45 ⁇ m or more and the amount of particles having a particle size of 75 ⁇ m or more in the non-spherical heat conductive filler are determined as follows. 10 g of thermally conductive filler is sampled and placed in an arbitrary amount of water and ultrasonically dispersed. The sieves with openings of 45 ⁇ m and 75 ⁇ m are stacked and set on a sieve shaker, and the thermally conductive filler dispersed in water is put into the shaker. The thermally conductive filler remaining on each sieve is dried and weighed.
- the non-spherical heat conductive filler is preferably aluminum hydroxide in view of heat conductivity, electrical insulation, specific gravity, flame retardancy, price, and the like.
- the average particle size is 5 to 14 ⁇ m, preferably 5 ⁇ m or more and less than 12 ⁇ m, and the amount of particles having a particle size of 45 ⁇ m or more is 0 to 0.5% by mass, preferably 0 to 0.2% by mass.
- An aluminum hydroxide powder having an amount of particles having a diameter of 75 ⁇ m or more of 0 to 0.01% by mass, preferably 0% by mass, and a DOP oil absorption of 50 ml / 100 g or less, preferably 40 ml / 100 g or less, and (2)
- the average particle size is 0.5 to 3 ⁇ m, preferably 0.5 ⁇ m or more and less than 2 ⁇ m, and the amount of particles having a particle size of 45 ⁇ m or more is 0 to 0.5 mass%, preferably 0 to 0.2 mass%, more preferably Is 0 to 0.1% by mass, the amount of particles having a particle size of 75 ⁇ m or more is 0 to 0.01% by mass, preferably 0% by mass, and the DOP oil absorption is 80 ml / 100 g or less, preferably 60 ml / 100 g.
- the amount of the component is 100 to 500 parts by mass, preferably 150 to 400 parts by mass with respect to 100 parts by mass of the organosilicon compound component, and (2) the amount of the component is the organosilicon compound component 50 to 400 parts by weight, preferably 80 to 300 parts by weight with respect to 100 parts by weight (provided that the total amount of non-spherical thermally conductive fillers is as described above).
- the ratio of the above (1) in the total amount of the non-spherical thermally conductive filler is 40% by mass or more, more preferably 50% by mass or more, the fluidity at the time of coating molding is not impaired, and the silicone resin
- the heat conductive filler can be highly filled, and the surface of the heat conductive sheet to be molded can be made smoother while achieving high heat conductivity.
- the average particle size is a value (volume basis) determined using a Microtrac MT3300EX (Nikkiso), which is a laser diffraction / scattering particle size distribution measuring device.
- the filling amount of the non-spherical thermally conductive filler (D) is 250 to 600 parts by weight, preferably 300 to 570 parts by weight with respect to 100 parts by weight of the organosilicon compound component. More preferably, it is 350 to 550 parts by mass.
- the filling amount of the non-spherical heat conductive filler is less than the above lower limit, sufficient heat conductivity cannot be obtained.
- the thermally conductive filler becomes too dense, and the composition is coated to obtain a thermally conductive sheet. In addition, the smoothness of the sheet surface is impaired, leading to an increase in thermal resistance.
- the organosilicon compound component is the component (A) described above, the component (B) in the case of a silicon compound, and the component (E) described later, the component (F) described later, and the component described above if present. It means organohydrogenpolysiloxane as the curing agent (C), and the total amount of the organosilicon compound component is the component (A) described above, the component (B) when it is a silicon compound, and if present, It means the total amount of the organohydrogenpolysiloxane as the later-described (E) component, the later-described (F) component and the above-described curing agent (C).
- the thermally conductive silicone composition according to the present invention can further contain a component (E).
- the component (E) is one or more selected from the following components (E1) and (E2).
- the component (E) improves the wettability of the non-spherical thermally conductive filler (D) and facilitates the filling of the organosilicon compound component with the thermally conductive filler, and thus the thermally conductive filler.
- the amount of filling can be increased.
- the component (E1) is an alkoxysilane represented by the following general formula (2).
- R 2 is independently an alkyl group having 6 to 15 carbon atoms
- R 3 is independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms
- R 4 Is independently an alkyl group having 1 to 6 carbon atoms
- b is an integer of 1 to 3
- c is 0, 1 or 2, provided that b + c is 1 to 3.
- examples of the alkyl group represented by R 2 include hexyl group, octyl group, nonyl group, decyl group, dodecyl group, and tetradecyl group.
- the alkyl group represented by R 2 has 6 to 15 carbon atoms, the wettability of the non-spherical heat conductive filler (D) is sufficiently improved and the heat conductive silicone composition can be obtained. Filling with the heat conductive filler is facilitated, and the low-temperature characteristics of the composition are good.
- Examples of the unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms represented by R 3 include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, and a tert-butyl group.
- R 3 is preferably a monovalent hydrocarbon group containing 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms and not containing an aliphatic unsaturated bond, and in particular, a methyl group, an ethyl group, a propyl group, Non-substituted or substituted alkyl groups having 1 to 3 carbon atoms such as chloromethyl group, bromoethyl group, 3,3,3-trifluoropropyl group and cyanoethyl group, and non-substituted groups such as phenyl group, chlorophenyl group and fluorophenyl group A substituted or substituted phenyl group is preferred.
- R 3 does not include an epoxy substituent or an alkoxy substituent.
- alkyl group represented by R 4 examples include alkyl groups having 1 to 6 carbon atoms such as methyl group, ethyl group, propyl group, butyl group, pentyl group and hexyl group.
- the component (E2) is dimethylpolysiloxane represented by the following general formula (3), in which a molecular chain fragment end is blocked with a trialkoxysilyl group.
- R 5 is independently an alkyl group having 1 to 6 carbon atoms, and d is an integer of 5 to 100, preferably an integer of 10 to 50.
- Examples of the alkyl group represented by R 5 include the same alkyl groups represented by R 4 in the above formula (2).
- the blending amount is preferably 0.01 to 30% by mass, more preferably 5 to 20% by mass, based on the total amount of the organosilicon compound component.
- the amount is less than the lower limit, it may be difficult to fill the organosilicon compound component with the non-spherical thermally conductive filler (D).
- cured material obtained may become inadequate.
- the thermally conductive silicone composition according to the present invention may further contain the following (F) plasticizer.
- component (F) dimethylsiloxane represented by the following formula (4) is preferable.
- e is an integer of 5 to 500, preferably an integer of 50 to 400.
- the blending amount is preferably 0.5 to 20% by weight, more preferably 1 to 15% by weight, based on the total amount of the organosilicon compound component. If the amount is less than the lower limit, the hardness of the sheet may increase and the sheet may become brittle. If the amount exceeds the upper limit, sufficient sheet strength cannot be obtained, and oil bleeding may be promoted.
- the heat conductive silicone composition can be prepared as follows. When blending the components (A) and (D), together with the components (E) and (F), using a mixer such as a kneader, Banbury mixer, planetary mixer, Shinagawa mixer, etc. Kneading while heating to temperature. In this kneading step, if desired, reinforcing silica such as fumed silica and precipitated silica; silicone oil, silicone wetter, etc .; difficulty such as platinum, titanium oxide and benzotriazole A flame retardant or the like may be added.
- a mixer such as a kneader, Banbury mixer, planetary mixer, Shinagawa mixer, etc. Kneading while heating to temperature.
- reinforcing silica such as fumed silica and precipitated silica
- silicone oil silicone wetter, etc .
- difficulty such as platinum, titanium oxide and benzotriazole A flame retardant or the like may be added.
- the uniform mixture obtained in the kneading step is cooled to room temperature, filtered through a strainer and the like, and then, using a two-roll, Shinagawa mixer and the like, the required amount of the adhesion-imparting agent (B) and Add the curing agent (C) and knead again.
- an acetylene compound-based addition reaction control agent such as 1-ethynyl-1-cyclohexanol, a colorant such as an organic pigment or an inorganic pigment, and a heat resistance improver such as iron oxide or cerium oxide , And an internal release agent or the like may be added.
- the heat conductive silicone composition thus obtained may be directly used for the next step as a coating material, but if necessary, a solvent such as toluene may be further added.
- the curing conditions for the heat conductive silicone composition are, for example, 80 to 180 ° C., particularly 100 to 160 ° C. for 30 seconds to 20 minutes, particularly 1 minute to 10 minutes in the case of curing by addition reaction.
- it is preferably 100 to 180 ° C., particularly 110 to 170 ° C., for 30 seconds to 20 minutes, particularly preferably for 1 minute to 10 minutes.
- the thermally conductive silicone composition preferably has a cured product having a thermal conductivity of 1.2 W / m ⁇ K or more, more preferably 1.5 W / m ⁇ K or more, and even more preferably 1.7 W / m. m ⁇ K or more.
- the thermal conductivity can be measured using TPS-2500S manufactured by Kyoto Electronics Industry Co., Ltd.
- the heat conductive sheet of this invention has the hardened
- the thermally conductive sheet is obtained by applying and curing the thermally conductive silicone composition on both surfaces or one surface of the synthetic resin film layer to form a cured product layer.
- the application is preferably performed so that the thickness of the cured product layer after curing is preferably 40 ⁇ m or more and 400 ⁇ m or less, more preferably 50 ⁇ m or more and 300 ⁇ m or less.
- the thermally conductive filler contained therein may protrude and the smoothness of the surface of the thermally conductive cured layer may be impaired. If the thickness is too thick, the heat of the thermally conductive sheet may be lost. Resistance may increase.
- cured material layer of a heat conductive silicone composition on both surfaces of a synthetic resin film layer even if the hardened
- the heat conductive sheet of the present invention is continuously produced by coating the heat conductive silicone composition on both surfaces or one surface of the synthetic resin film layer to form a heat conductive cured layer.
- a conventional coating apparatus such as a comma coater, knife coater, kiss coater, etc. equipped with a drying furnace, a heating furnace and a winding device, the thermally conductive silicone composition obtained above is applied to one of the synthetic resin films.
- the solvent or the like is dried and evaporated, and in the case of curing by addition reaction, 80 to 180 ° C., preferably about 100 to 160 ° C., for 30 seconds to 20 minutes, especially In the case of curing with peroxide for 1 minute to 10 minutes, heating at 100 to 180 ° C., preferably about 110 to 170 ° C. for 30 seconds to 20 minutes, particularly 1 minute to 10 minutes to form a thermally conductive cured layer To do.
- a heat conductive sheet is obtained by forming a heat conductive hardened layer on the other side (the back side) of the synthetic resin film layer in the same manner as the surface. Coating on the front side and coating on the back side may be performed at once. The completed heat conductive sheet is continuously wound into a roll.
- the heat conductive silicone compositions on the front and back surfaces may be the same or different from each other.
- the thickness of the heat conductive sheet can be set according to the application form and application target, and is not particularly limited, but is preferably in the range of about 55 to 500 ⁇ m, more preferably about 100 to 300 ⁇ m. Generally, if the thickness is too thin, shape followability to the electronic component is deteriorated, so that there is a tendency that heat conductivity is deteriorated, and if it is too thick, there is a tendency that heat transfer characteristics are impaired. Even so, it is not preferable.
- the thus obtained heat conductive sheet preferably has an air breakdown voltage of 2 kV or more, particularly 4 kV or more when measured in accordance with JIS K6249.
- the air breakdown voltage is substantially proportional to the thickness of the heat conductive sheet.
- Component (C) 2-methylbenzoyl peroxide
- (D) component (D1)
- the average particle size is 9.3 ⁇ m
- the amount of particles having a particle size of 45 ⁇ m or more is 0.04% by mass
- the amount of particles having a particle size of 75 ⁇ m or more is 0% by mass
- the DOP oil absorption is 30 ml.
- amorphous (non-spherical) aluminum hydroxide powder (D2) having an average particle size of 1.3 ⁇ m, the amount of particles having a particle size of 45 ⁇ m or more being 0.06% by mass, and particles having a particle size of 75 ⁇ m or more Is 0% by mass, DOP oil absorption is 50 ml / 100 g, and amorphous (non-spherical) aluminum hydroxide powder (D3) (for comparison) has an average particle size of 8.2 ⁇ m and a particle size of 45 ⁇ m or more.
- Average particle size is 1.2 ⁇
- the amount of particles having a particle size of 45 ⁇ m or more is 0.06% by mass, the amount of particles having a particle size of 75 ⁇ m or more is 0% by mass, and the DOP oil absorption is 130 ml / 100 g.
- Component (E) dimethylpolysiloxane represented by the following formula (7), having an average degree of polymerization of 30, and having one end blocked with a trimethoxysilyl group
- G Synthetic resin film
- Aromatic polyimide film Product name: Kapton 50EN (manufactured by Toray DuPont Co., Ltd., 12.5 ⁇ m)
- Thermally conductive aromatic polyimide film Trade name: Kapton 150MT (manufactured by Toray DuPont Co., Ltd., 37.5 ⁇ m)
- Examples 1 to 4 and Comparative Examples 1 to 3 [Preparation of thermally conductive silicone composition] The components (parts by mass) shown in Table 1 were charged into a Banbury mixer and kneaded for 20 minutes to prepare thermally conductive silicone compositions (a) to (e).
- the heat conductivity of the cured product of the obtained heat conductive silicone composition was measured by the following method. The results are shown in Table 1.
- the obtained silicone composition was subjected to press molding at 160 ° C. for 10 minutes using a 60 mm ⁇ 60 mm ⁇ 6 mm mold and the pressure adjusted so that the thickness after curing was 6 mm. Cured into a sheet.
- a thermal conductivity meter (TPS-2500S, trade name, manufactured by Kyoto Electronics Industry Co., Ltd.) was used to measure the thermal conductivity of the sheet with a probe sandwiched between the two sheets.
- Comparative Example 3 coating on the synthetic resin film was performed as follows.
- the oven temperature was 60 ° C., 80 ° C. and 80 ° C. from the side close to the comma portion, and the coating speed was 2 m / min.
- the product in an unvulcanized state was obtained by lowering the temperature of the oven to a temperature at which toluene was volatilized and (C) the peroxide did not decompose.
- This unvulcanized product is cut into an appropriate size, and the pressure is adjusted so that the thickness after curing is 130 ⁇ m using a press molding machine, and heat molding is performed by performing press molding at 170 ° C./10 minutes. Sex sheet was obtained.
- Adhesive strength between the synthetic resin film and the cured product of the heat conductive silicone composition In accordance with JIS K6259, a 180 degree peel test was performed to measure the adhesive strength. As a test sample, a thermally conductive silicone composition is applied on the surface of one side of a synthetic resin film having a thickness of 25 ⁇ m and cured by heating at 150 ° C. for 10 minutes to obtain a thermally conductive silicone composition having a thickness of 1 mm. The thing of the 2 layer structure in which the hardened
- the heat conductive sheets of Examples 1 to 4 of the present invention were continuously produced by coating molding and wound into a roll. As is clear from Table 2, the heat resistance was low and high insulation was achieved. The adhesion between the synthetic resin film and the cured product of the heat conductive silicone composition is good. Moreover, since the embrittlement after high temperature long term aging does not derive, it has excellent long term reliability.
- the amount of the non-spherical heat conductive filler (D) was less than the range of the present invention, and as a result, the thermal resistance was large. Moreover, since the adhesiveness imparting agent (B) was not blended, the synthetic resin film and the cured product of the heat conductive silicone composition were easily peeled off. In Comparative Example 2 using D3 and D4 having a large amount of DOP oil absorption, wetting of the non-spherical heat conductive filler to silicone was insufficient, and the smoothness of the sheet surface was impaired during coating, resulting in an increase in thermal resistance. . Moreover, embrittlement after aging was observed.
- the sheet of Comparative Example 3 differs from Comparative Example 2 only in that it was press-molded instead of coating molding. By press molding, a sheet having a low thermal resistance was obtained, but in press molding, the sheet cannot be continuously produced and wound into a roll. Further, as in Comparative Example 2, embrittlement after aging is observed.
- the amount of the non-spherical heat conductive filler (D) is larger than the range of the present invention, and as a result, the smooth compound was not obtained, so the coating was not performed. It was.
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Abstract
Description
〔1〕
電気絶縁性の合成樹脂フィルム層の両面または片面に、熱伝導性シリコーン組成物の硬化物層を有する熱伝導性シートにおいて、該熱伝導性シリコーン組成物が接着性付与剤を含む有機ケイ素化合物成分および非球状の熱伝導性充填材を含有し、該熱伝導性充填材の量が該有機ケイ素化合物成分100質量部に対して250~600質量部であり、かつ、該熱伝導性充填材のDOP吸油量が80ml/100g以下である前記熱伝導性シート。
〔2〕
前記合成樹脂フィルム層に用いられる合成樹脂の融点が100℃以上である〔1〕に記載の熱伝導性シート。
〔3〕
前記合成樹脂フィルム層に用いられる合成樹脂が、芳香族ポリイミド、ポリアミド、ポリアミドイミド、ポリエステル、ポリオレフィン、芳香族ポリエーテル、フッ素系ポリマー、またはこれらの2種以上の組み合わせである〔1〕または〔2〕に記載の熱伝導性シート。
〔4〕
前記熱伝導性シリコーン組成物中の接着性付与剤が、エポキシ基および/またはアルコキシ基を有し、さらにビニル基および式:Si-Hで表される基からなる群から選ばれる少なくとも1種の基を有するケイ素化合物系接着性付与剤である〔1〕~〔3〕のいずれかに記載の熱伝導性シート。
〔5〕
接着性付与剤が、下記式で示されるケイ素化合物から選ばれるものである〔4〕に記載の熱伝導性シート。
前記熱伝導性シリコーン組成物中の非球状の熱伝導性充填材が、水酸化アルミニウム粉末である〔1〕~〔5〕のいずれかに記載の熱伝導性シート。
〔7〕
水酸化アルミニウム粉末が、
(1)平均粒子径が5~14μmであり、DOP吸油量が50ml/100g以下である水酸化アルミニウム粉末 100~500質量部、および
(2)平均粒子径が0.5~3μmであり、DOP吸油量が80ml/100g以下である水酸化アルミニウム粉末 50~400質量部
から構成されてなり、かつ、非球状の熱伝導性充填材の全量における上記(1)の比率が40質量%以上である〔6〕に記載の熱伝導性シート。
〔8〕
前記熱伝導性シリコーン組成物中の非球状の熱伝導性充填材が、粒径45μm以上の粒子の量が0~0.5質量%であり、かつ粒径75μm以上の粒子の量が0~0.01質量%である〔1〕~〔7〕のいずれかに記載の熱伝導性シート。
〔9〕
前記熱伝導性シリコーン組成物中の有機ケイ素化合物成分が、
(A)下記平均組成式(1):
R1 aSiO(4-a)/2 (1)
(式中、R1は独立して非置換または置換の炭素原子数1~10の1価炭化水素基であり、aは1.90~2.05である。)
で表され、1分子中に少なくとも2個のケイ素原子に結合したアルケニル基を有するオルガノポリシロキサンを含有するものである〔1〕~〔8〕のいずれかに記載の熱伝導性シート。
〔10〕
さらに、前記熱伝導性シリコーン組成物中の有機ケイ素化合物成分として、
(E)(E1)下記一般式(2):
R2 bR3 cSi(OR4)4-b-c (2)
(式中、R2は独立して炭素原子数6~15のアルキル基であり、R3は独立して非置換または置換の炭素原子数1~12の1価炭化水素基であり、R4は独立して炭素原子数1~6のアルキル基であり、bは1~3の整数であり、cは0、1または2であり、但しb+cは1~3である。)
で表されるアルコキシシラン、および(E2)下記一般式(3):
で表される片末端がトリアルコキシシリル基で封鎖されたジメチルポリシロキサン
から選択される1以上を、前記熱伝導性シリコーン組成物中の有機ケイ素化合物成分の合計量の0.01~30質量%含有するものである〔9〕に記載の熱伝導性シート。
〔11〕
さらに、前記熱伝導性シリコーン組成物中に、(C)硬化剤として、
(C-1a)オルガノハイドロジェンポリシロキサン:熱伝導性シリコーン組成物中のアルケニル基の合計1モルに対して熱伝導性シリコーン組成物中のケイ素原子結合水素原子の合計が0.8~10モルの範囲となる量、及び
(C-1b)白金系触媒:(A)成分に対して白金系触媒中の白金金属が質量単位で0.1~2,000ppmとなる量
を含有するものである〔9〕又は〔10〕に記載の熱伝導性シート。
〔12〕
さらに、前記熱伝導性シリコーン組成物中に、(C)硬化剤として、
(C-2)有機過酸化物:熱伝導性シリコーン組成物中のビニル基を含む化合物の合計100質量部に対して0.5~30質量部
を含有するものである〔9〕又は〔10〕に記載の熱伝導性シート。
〔13〕
電気絶縁性の合成樹脂フィルム層の厚さが5~90μmであり、熱伝導性シリコーン組成物の硬化物層の厚さが40~400μmであり、熱伝導性シート全体の厚さが55~500μmである〔1〕~〔12〕のいずれかに記載の熱伝導性シート。
〔14〕
前記熱伝導性シリコーン組成物の硬化物が1.2W/m・K以上の熱伝導率を有する〔1〕~〔13〕のいずれかに記載の熱伝導性シート。
〔15〕
気中絶縁破壊電圧が、JIS K6249に従って測定されるとき、2kV以上である〔1〕~〔14〕のいずれかに記載の熱伝導性シート。
本発明に用いられる電気絶縁性の合成樹脂フィルム層としては、電気絶縁性に優れた柔軟で機械的強度が高い合成樹脂フィルム層であれば、特に限定されず、公知のものを全て用いることができる。合成樹脂としては、例えば、芳香族ポリイミド;ポリアミド;ポリアミドイミド;ポリエチレンテレフタラート、ポリエチレンナフタレート等のポリエステル;ポリオレフィン;芳香族ポリエーテル;ポリテトラフルオロエチレン(PTFE)、テトラフルオロエチレン・パーフルオロアルキルビニルエーテル共重合体等のフッ素系ポリマーを挙げることができる。合成樹脂中に熱伝導性粉体が分散配合されたものや、合成樹脂の結晶性を向上させて熱伝導性を向上させた熱伝導性合成樹脂フィルムを用いてもよい。さらに、結晶度を高めた合成樹脂に上記の熱伝導性粉体を分散したものを用いてもよい。また、これらの2種以上を組み合わせて合成樹脂フィルム層としてもよい。
なお、本発明に用いる合成樹脂フィルム層は、電気絶縁特性を低下させるような孔がない合成樹脂フィルム層であることが好ましい。
本発明に用いられる熱伝導性シリコーン組成物は、接着性付与剤を含む有機ケイ素化合物成分および非球状の熱伝導性充填材を含有し、該熱伝導性充填材の量が該有機ケイ素化合物成分100質量部に対して250~600質量部であり、かつ、該熱伝導性充填材のDOP吸油量が80ml/100g以下のものである。
(A)下記平均組成式(1):
R1 aSiO(4-a)/2 (1)
(式中、R1は独立して非置換または置換の炭素原子数1~10の1価炭化水素基であり、aは1.90~2.05である。)
で表され、1分子中に少なくとも2個のケイ素原子に結合したアルケニル基を有するオルガノポリシロキサン、
(B)接着性付与剤、
(C)硬化剤、
(D)非球状の熱伝導性充填材、
さらに必要により、
(E)下記(E1)および(E2)から選択される1以上、
(E1)下記一般式(2):
R2 bR3 cSi(OR4)4-b-c (2)
(式中、R2は独立して炭素原子数6~15のアルキル基であり、R3は独立して非置換または置換の炭素原子数1~12の1価炭化水素基であり、R4は独立して炭素原子数1~6のアルキル基であり、bは1~3の整数であり、cは0、1または2であり、但しb+cは1~3である。)
で表されるアルコキシシラン、および
(E2)下記一般式(3):
で表される片末端がトリアルコキシシリル基で封鎖されたジメチルポリシロキサン、
(F)可塑剤。
R1 aSiO(4-a)/2 (1)
(式中、R1は独立して非置換または置換の炭素原子数1~10、好ましくは1~8の1価炭化水素基であり、aは1.90~2.05である。)
(A)成分の平均重合度は、好ましくは20~12,000、より好ましくは50~10,000である。なお、本発明において、平均重合度は、例えば、トルエン、テトラヒドロフラン(THF)等を展開溶媒としたゲルパーミエーションクロマトグラフィ(GPC)分析におけるポリスチレン換算値として求めることができ、通常、平均重合度は数平均重合度等として求めることが好適である(以下、同じ)。
上記アルケニル基としてはビニル基が好ましい。上記アルケニル基は、分子鎖末端のケイ素原子および分子鎖末端以外のケイ素原子のいずれに結合していてもよく、少なくとも1個のアルケニル基が分子鎖末端のケイ素原子に結合していることが好ましい。
また、別の好ましい実施形態では、前記熱伝導性シリコーン組成物に含まれる硬化剤が有機過酸化物硬化剤である場合には、接着性付与剤であるケイ素化合物は、エポキシ基、アルコキシ基またはこれらの両方と、ビニル基、式:Si-Hで表される基またはこれらの両方とを有することがより好ましい。
この接着性付与剤(B)の配合量は、熱伝導性シリコーン組成物に含まれる有機ケイ素化合物成分の合計量中、通常、0.1~20質量%、好ましくは0.5~15質量%の範囲とするのがよい。前記配合量が少なすぎると、接着性付与効果が発揮されない場合があり、また、多すぎると機械的特性が損なわれたり、経時硬化による脆化が発生したりする問題を生じる場合がある。
非球状の熱伝導性充填材中の粒径45μm以上の粒子の量および粒径75μm以上の粒子の量は、以下のようにして決定される。熱伝導性充填材10gを採取し、任意の量の水中に入れて超音波分散させる。目開きが45μmと75μmの篩を重ねて篩振とう機にセットし、上記水に分散させた熱伝導性充填材を上記振とう機に投入する。各篩上に残った熱伝導性充填材を乾燥させ、秤量する。
(1)平均粒子径が5~14μm、好ましくは5μm以上12μm未満であり、粒径45μm以上の粒子の量が0~0.5質量%、好ましくは0~0.2質量%であり、粒径75μm以上の粒子の量が0~0.01質量%、好ましくは0質量%であり、DOP吸油量が50ml/100g以下、好ましくは40ml/100g以下である水酸化アルミニウム粉末、および
(2)平均粒子径が0.5~3μm、好ましくは0.5μm以上2μm未満であり、粒径45μm以上の粒子の量が0~0.5質量%、好ましくは0~0.2質量%、より好ましくは0~0.1質量%であり、粒径75μm以上の粒子の量が0~0.01質量%、好ましくは0質量%であり、DOP吸油量が80ml/100g以下、好ましくは60ml/100g以下である水酸化アルミニウム粉末
からなり、(1)成分の量が有機ケイ素化合物成分100質量部に対して100~500質量部、好ましくは150~400質量部であり、(2)成分の量が有機ケイ素化合物成分100質量部に対して50~400質量部、好ましくは80~300質量部(但し、非球状の熱伝導性充填材の合計は、上述した通りである)である水酸化アルミニウム粉末で構成されてなり、かつ非球状の熱伝導性充填材の全量における上記(1)の比率が40質量%以上、より好ましくは50質量%以上である場合、コーティング成形時の流動性を損なわず、シリコーン樹脂に該熱伝導性充填材を高充填することが可能となり、高熱伝導率を達成しつつ、成形される熱伝導性シートの表面をより滑らかにすることができる。
R2 bR3 cSi(OR4)4-b-c (2)
(式中、R2は独立して炭素原子数6~15のアルキル基であり、R3は独立して非置換または置換の炭素原子数1~12の1価炭化水素基であり、R4は独立して炭素原子数1~6のアルキル基であり、bは1~3の整数であり、cは0、1または2であり、但しb+cは1~3である。)
熱伝導性シートは、後述するように、合成樹脂フィルム層の両面または片面に上記熱伝導性シリコーン組成物を塗布・硬化させて硬化物層を形成することにより得られる。上記塗布は、好ましくは硬化後の硬化物層の厚みが好ましくは40μm以上400μm以下、より好ましくは50μm以上300μm以下になるように行われる。上記硬化物層の厚みが薄すぎると、そこに含まれる熱伝導性充填材が突出して熱伝導性硬化層表面の滑らかさが損なわれる場合があり、厚みが厚すぎると熱伝導性シートの熱抵抗が大きくなってしまう場合がある。なお、熱伝導性シリコーン組成物の硬化物層を合成樹脂フィルム層の両面に形成する場合、これら両面の熱伝導性シリコーン組成物の硬化物層は、同じ厚さであっても異なった厚さであってもよい。
(A)成分:
(A1)平均重合度8,000の、ジメチルビニル基で両末端封止したジメチルポリシロキサン
(A2)平均重合度3,000の、ジメチルビニル基で両末端封止したジメチルポリシロキサン
(D1)平均粒子径が9.3μmであり、粒径45μm以上の粒子の量が0.04質量%であり、粒径75μm以上の粒子の量が0質量%であり、DOP吸油量が30ml/100gである不定形(非球状)水酸化アルミニウム粉末
(D2)平均粒子径が1.3μmであり、粒径45μm以上の粒子の量が0.06質量%であり、粒径75μm以上の粒子の量が0質量%であり、DOP吸油量が50ml/100gである不定形(非球状)水酸化アルミニウム粉末
(D3)(比較用)平均粒子径が8.2μmであり、粒径45μm以上の粒子の量が0.06質量%であり、粒径75μm以上の粒子の量が0質量%であり、DOP吸油量が90ml/100gである不定形(非球状)水酸化アルミニウム粉末
(D4)(比較用)平均粒子径が1.2μmであり、粒径45μm以上の粒子の量が0.06質量%であり、粒径75μm以上の粒子の量が0質量%であり、DOP吸油量が130ml/100gである不定形(非球状)水酸化アルミニウム粉末
(G1)芳香族ポリイミド系フィルム:商品名:カプトン50EN(東レデュポン(株)製、12.5μm)
(G2)熱伝導性芳香族ポリイミド系フィルム:商品名:カプトン150MT(東レデュポン(株)製、37.5μm)
[熱伝導性シリコーン組成物の調製]
表1に示す量(質量部)の成分をバンバリーミキサーに投入し、20分間混練りして、熱伝導性シリコーン組成物(ア)~(オ)を調製した。
熱伝導率
得られたシリコーン組成物を、60mm×60mm×6mmの金型を用い、硬化後の厚みが6mmになるように圧力を調整して160℃で10分間プレス成形して、6mm厚のシート状に硬化させた。熱伝導率計(TPS-2500S、京都電子工業(株)製の商品名)を用い、2枚のシートの間にプローブを挟んで該シートの熱伝導率を測定した。
合成樹脂フィルムへのコーティング
表2に示す上記で得られた熱伝導性シリコーン組成物に、その量の40質量%のトルエンを添加し、プラネタリーミキサーを用いて混練りして得たコーティング材を、合成樹脂フィルムの一方の面(表面)に、コンマコーターを用いて、合成樹脂フィルムの厚みを含めた硬化後の総厚みが90μmになるように塗工し、150℃、10分間加熱して硬化させた後に巻き取った。次いで、他方の面(裏面)も同様に、シートの硬化後の総厚みが150μmとなるように塗工し、同様に硬化させた後に巻き取ることで、総厚150μmの熱伝導性シートを得た。
得られた熱伝導性シートの熱抵抗、気中絶縁破壊電圧、合成樹脂フィルムと熱伝導性シリコーン組成物の硬化物との接着強度、高温長期保管後の脆化有無を、以下の方法で測定・評価した。結果を表2に示す。
ASTM D5470に従って、50℃/0.69MPaの条件で測定した。
JIS K6249に従って測定した。
JIS K6259に準拠して、180度剥離試験を行い、接着強度を測定した。なお、試験試料として、厚さ25μmの合成樹脂フィルムの片側の表面上に、熱伝導性シリコーン組成物を塗工し、150℃、10分間加熱硬化させて、肉厚1mmの熱伝導性シリコーン組成物の硬化物層を形成させた2層構造のものを作製した。
得られた熱伝導性シートを150℃/1,000時間保管した後、180度に折り曲げた際の割れ発生有無を確認した。
Claims (15)
- 電気絶縁性の合成樹脂フィルム層の両面または片面に、熱伝導性シリコーン組成物の硬化物層を有する熱伝導性シートにおいて、該熱伝導性シリコーン組成物が接着性付与剤を含む有機ケイ素化合物成分および非球状の熱伝導性充填材を含有し、該熱伝導性充填材の量が該有機ケイ素化合物成分100質量部に対して250~600質量部であり、かつ、該熱伝導性充填材のDOP吸油量が80ml/100g以下である前記熱伝導性シート。
- 前記合成樹脂フィルム層に用いられる合成樹脂の融点が100℃以上である請求項1に記載の熱伝導性シート。
- 前記合成樹脂フィルム層に用いられる合成樹脂が、芳香族ポリイミド、ポリアミド、ポリアミドイミド、ポリエステル、ポリオレフィン、芳香族ポリエーテル、フッ素系ポリマー、またはこれらの2種以上の組み合わせである請求項1または2に記載の熱伝導性シート。
- 前記熱伝導性シリコーン組成物中の接着性付与剤が、エポキシ基および/またはアルコキシ基を有し、さらにビニル基および式:Si-Hで表される基からなる群から選ばれる少なくとも1種の基を有するケイ素化合物系接着性付与剤である請求項1~3のいずれか1項に記載の熱伝導性シート。
- 前記熱伝導性シリコーン組成物中の非球状の熱伝導性充填材が、水酸化アルミニウム粉末である請求項1~5のいずれか1項に記載の熱伝導性シート。
- 水酸化アルミニウム粉末が、
(1)平均粒子径が5~14μmであり、DOP吸油量が50ml/100g以下である水酸化アルミニウム粉末 100~500質量部、および
(2)平均粒子径が0.5~3μmであり、DOP吸油量が80ml/100g以下である水酸化アルミニウム粉末 50~400質量部
から構成されてなり、かつ、非球状の熱伝導性充填材の全量における上記(1)の比率が40質量%以上である請求項6に記載の熱伝導性シート。 - 前記熱伝導性シリコーン組成物中の非球状の熱伝導性充填材が、粒径45μm以上の粒子の量が0~0.5質量%であり、かつ粒径75μm以上の粒子の量が0~0.01質量%である請求項1~7のいずれか1項に記載の熱伝導性シート。
- 前記熱伝導性シリコーン組成物中の有機ケイ素化合物成分が、
(A)下記平均組成式(1):
R1 aSiO(4-a)/2 (1)
(式中、R1は独立して非置換または置換の炭素原子数1~10の1価炭化水素基であり、aは1.90~2.05である。)
で表され、1分子中に少なくとも2個のケイ素原子に結合したアルケニル基を有するオルガノポリシロキサンを含有するものである請求項1~8のいずれか1項に記載の熱伝導性シート。 - さらに、前記熱伝導性シリコーン組成物中の有機ケイ素化合物成分として、
(E)(E1)下記一般式(2):
R2 bR3 cSi(OR4)4-b-c (2)
(式中、R2は独立して炭素原子数6~15のアルキル基であり、R3は独立して非置換または置換の炭素原子数1~12の1価炭化水素基であり、R4は独立して炭素原子数1~6のアルキル基であり、bは1~3の整数であり、cは0、1または2であり、但しb+cは1~3である。)
で表されるアルコキシシラン、および(E2)下記一般式(3):
で表される片末端がトリアルコキシシリル基で封鎖されたジメチルポリシロキサン
から選択される1以上を、前記熱伝導性シリコーン組成物中の有機ケイ素化合物成分の合計量の0.01~30質量%含有するものである請求項9に記載の熱伝導性シート。 - さらに、前記熱伝導性シリコーン組成物中に、(C)硬化剤として、
(C-1a)オルガノハイドロジェンポリシロキサン:熱伝導性シリコーン組成物中のアルケニル基の合計1モルに対して熱伝導性シリコーン組成物中のケイ素原子結合水素原子の合計が0.8~10モルの範囲となる量、及び
(C-1b)白金系触媒:(A)成分に対して白金系触媒中の白金金属が質量単位で0.1~2,000ppmとなる量
を含有するものである請求項9又は10に記載の熱伝導性シート。 - さらに、前記熱伝導性シリコーン組成物中に、(C)硬化剤として、
(C-2)有機過酸化物:熱伝導性シリコーン組成物中のビニル基を含む化合物の合計100質量部に対して0.5~30質量部
を含有するものである請求項9又は10に記載の熱伝導性シート。 - 電気絶縁性の合成樹脂フィルム層の厚さが5~90μmであり、熱伝導性シリコーン組成物の硬化物層の厚さが40~400μmであり、熱伝導性シート全体の厚さが55~500μmである請求項1~12のいずれか1項に記載の熱伝導性シート。
- 前記熱伝導性シリコーン組成物の硬化物が1.2W/m・K以上の熱伝導率を有する請求項1~13のいずれか1項に記載の熱伝導性シート。
- 気中絶縁破壊電圧が、JIS K6249に従って測定されるとき、2kV以上である請求項1~14のいずれか1項に記載の熱伝導性シート。
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US16/480,851 US11608419B2 (en) | 2017-01-26 | 2018-01-16 | Thermally conductive sheet |
KR1020197024498A KR102443974B1 (ko) | 2017-01-26 | 2018-01-16 | 열전도성 시트 |
EP18744161.3A EP3576141A4 (en) | 2017-01-26 | 2018-01-16 | THERMO-CONDUCTIVE SHEET |
JP2018564481A JP6791271B2 (ja) | 2017-01-26 | 2018-01-16 | 熱伝導性シート及びその製造方法 |
CN201880008474.7A CN110226225A (zh) | 2017-01-26 | 2018-01-16 | 导热性片材 |
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