Thermally conductive sheet product and its manufacturing method

Abstract

The present invention provides: a thermally conductive sheet product wherein both surfaces of a fluorine rubber-based thermally conductive sheet are protected from foreign substances and the like, and excellent setting workability is achieved between a heat generation member and a heat dissipation member; and a method for producing this thermally conductive sheet product.　A thermally conductive sheet product which is obtained by bonding electrically insulating films to both surfaces of a thermally conductive sheet that is formed of a cured product of a thermally conductive fluorine-containing curable composition containing (A) a linear polyfluoro compound which comprises two or more alkenyl groups in each molecule, while having a perfluoro polyether structure in the main chain, (B) a fluorine-containing organohydrogen siloxane which comprises a perfluoroalkyl group or a perfluorooxyalkyl group in each molecule, or alternatively comprises a perfluoroalkylene group or a perfluorooxyalkylene group, while additionally containing two or more groups (SiH groups), wherein a hydrogen atom is directly bonded to a silicon atom, in each molecule, and which does not comprise an alkoxy group that is directly bonded to a silicon atom in the molecule, (C) a platinum group metal-based catalyst and (D) a specific amount of a thermally conductive filler.

Description

[Technical field]

[0001] The present invention relates to a thermally conductive sheet product in which electrically insulating films are attached to both sides of a thermally conductive sheet made of a cured product obtained by curing a fluorine-containing curable composition, and to a method for producing the same. [Background technology]

[0002] Thermally conductive sheets are placed between heat-generating components that generate unnecessary heat during operation, such as semiconductors such as CPUs, LSIs, and IGBTs, and heat-dissipating components such as heat spreaders and heat sinks, and serve to efficiently dissipate heat from the heat-generating components to the heat-dissipating components. In particular, the amount of heat generated by semiconductors has been increasing in recent years due to their high performance, high functionality, and miniaturization, and a rise in temperature can cause malfunctions or destruction, so various thermally conductive sheets have been proposed.

[0003] The thermally conductive sheet is obtained by heat-curing a thermally conductive composition into a sheet shape. An example of the thermally conductive composition is an addition reaction curing type thermally conductive silicone composition (Patent Document 1: JP-A-09-207275). However, the thermally conductive sheet made of the cured product of the silicone composition is prone to swelling and deterioration due to solvents such as toluene, alcohol, and gasoline, and therefore has a problem in that it is difficult to maintain its performance when used in an environment exposed to automotive oils such as ATF and CVTF.

[0004] In response to this, fluororubber-based thermally conductive sheets have been proposed in recent years. Examples include a thermally conductive fluorine-containing curable composition that gives a cured product with excellent oil resistance and thermal conductivity, and a thermally conductive fluorine-containing cured product obtained by curing the composition (Patent Document 2: JP 2017-082090 A).

[0005] Incidentally, a film may be attached to the surface of the thermally conductive sheet that comes into contact with the heat-generating or heat-dissipating member from the time of manufacture until the sheet is interposed between the heat-generating and heat-dissipating members, for the purpose of preventing adhesion of foreign matter, scratches, dirt, etc. When the sheet is interposed, the film is usually peeled off, and therefore the film needs to be easily peelable from the thermally conductive sheet (Patent Document 3: JP 2001-284504 A).

[0006] However, when the adhesiveness of the sheet surface impairs the workability of interposing the thermally conductive sheet between the heat generating member and the heat dissipating member, the film may be left as is without peeling it off. For example, when the space between the heat generating member and the heat dissipating member is narrow and the thermally conductive sheet is inserted from the side, peeling the film off and inserting it may cause the sheet to stick to the member and get caught on it, making insertion difficult. In such a case, the sheet can be inserted smoothly by inserting it without peeling the film off. In this case, the film is interposed between the heat generating member and the heat dissipating member while still attached to the sheet, so the film does not need to be peelable from the sheet.

[0007] As an example of a fluororubber-based thermally conductive sheet with a film attached, a heat transfer sheet has been disclosed in which a thermally conductive filler is provided within a matrix binder composed of a cured product of a fluorine-based compound (Patent Document 4: JP 2019-011423 A).

[0008] The heat transfer sheet disclosed in Patent Document 4 has a release sheet attached only to one side of the heat transfer sheet. Therefore, there are often problems such as foreign matter adhering to the side not covered with the release sheet or scratches. In addition, when inserting this heat transfer sheet into the narrow space between a heat generating component and a heat dissipating component, the side not covered with the release sheet may adhere to the component, making the insertion difficult. [Prior art documents] [Patent documents]

[0009] [Patent Document 1] Japanese Patent Application Publication No. 09-207275 [Patent Document 2] JP 2017-082090 A [Patent Document 3] JP 2001-284504 A [Patent Document 4] JP 2019-011423 A Summary of the Invention [Problem to be solved by the invention]

[0010] The present invention has been made in consideration of the above circumstances, and aims to provide a thermally conductive sheet product and a manufacturing method thereof, in which both sides of a fluororubber-based thermally conductive sheet are protected from foreign matter and the like, can be processed by a press molding method or the like, and has excellent interposition workability between a heat-generating component and a heat-dissipating component. [Means for solving the problem]

[0011] Means for Solving the Problems The present inventors have conducted intensive research in order to achieve the above-mentioned object, and as a result have found that a thermally conductive sheet product having electrically insulating films affixed to both sides of a thermally conductive sheet made of a cured product obtained by curing a thermally conductive fluorine-containing curable composition of a specific composition having excellent oil resistance and thermal conductivity can protect the sheet from foreign matter and the like, and also improve the ease of installation between a heat-generating component and a heat-dissipating component, thereby completing the present invention.

[0012] Therefore, the present invention provides the following thermally conductive sheet and method for producing the same. [1] (A) a linear polyfluoro compound having two or more alkenyl groups in one molecule and having a perfluoropolyether structure in the main chain: 100 parts by mass, (B) a fluorine-containing organohydrogensiloxane having in one molecule one or more groups selected from a perfluoroalkyl group, a perfluorooxyalkyl group, a perfluoroalkylene group, and a perfluorooxyalkylene group, and further having two or more hydrogen atoms (SiH groups) directly bonded to silicon atoms, and having no alkoxy groups directly bonded to silicon atoms in the molecule: an amount such that the number of hydrogen atoms directly bonded to silicon atoms in component (B) is 0.50 to 3.0 moles per mole of alkenyl groups contained in the entire composition, (C) a platinum group metal catalyst: 0.1 to 2,000 ppm by mass of platinum group metal atoms relative to the component (A), and (D) Thermally conductive filler: 100 to 4,000 parts by mass On both sides of a thermally conductive sheet comprising a cured product of a thermally conductive fluorine-containing curable composition containing At least one material selected from the group consisting of polyolefin, polyimide, polyamide, polyester, aromatic polyether ketone, polyvinyl chloride, and paper. A thermally conductive sheet product with an electrically insulating film attached. [2] The thermally conductive sheet product according to [1], wherein the thickness of the electrically insulating film is 1 to 200 μm. [ 3 ] The electrically insulating film is a polyethylene terephthalate (PET) film. ] The thermally conductive sheet product described above. [ 4 ] At least one of the electrically insulating films has a surface that contacts the thermally conductive sheet and is treated with a fluorine-containing silicone release agent. 3 ] Crab The thermally conductive sheet product described above. [ 5 ] The fluorine-containing silicone release agent is an organopolysiloxane having one or more perfluoroalkyl groups or perfluorooxyalkyl groups. 4

[0023] A thermally conductive sheet product according to the present invention. [ 6 ] The perfluoroalkyl group or the perfluorooxyalkyl group is represented by the following general formula (1) or (2): 5

[0023] A thermally conductive sheet product according to the present invention. C f'' F 2f''+1 - (1) (In the formula, f″ is an integer of 1 to 10.) [ka] (In the formula, g″ is an integer of 1 to 30.) [ 7 ] The thermally conductive fluorine-containing curable composition further contains, as component (E), 0.01 to 300 parts by mass of a fluorine-containing organosilicon compound having in one molecule one or more perfluoroalkyl groups or perfluorooxyalkyl groups and further having one or more alkoxy groups directly bonded to a silicon atom, and having no hydrogen atoms (SiH groups) directly bonded to silicon atoms in the molecule, relative to 100 parts by mass of component (A)[1] to [ 3 ] A thermally conductive sheet product according to any one of the preceding claims. [ 8 ] In the thermally conductive fluorine-containing curable composition, the component (F) may further comprise a compound represented by the following general formula (3) and the following general formula (4): F-(CF 2 CF 2 CF 2 O) a -A (3) (Wherein, A is -C b F 2b+1 (b is an integer of 1 to 3), and a is an integer of 1 to 500.) A-{(OCF(CF 3 )CF 2 ) c -(OCF 2 CF 2 ) d -(OCF 2 ) u’}-OA (4) (In the formula, A is the same as above, c and d each are an integer of 0 to 300, and u' is an integer of 1 to 300, except for the case where both c and d are 0. The repeating units may be bonded to each other randomly.) The composition contains 0.1 to 300 parts by mass of at least one nonfunctional polyfluoro compound selected from the group consisting of compounds represented by the following formula (1) to (100 parts by mass): 3 ] A thermally conductive sheet product according to any one of the preceding claims. [ 9 ] The thermally conductive fluorine-containing curable composition further contains, as component (G), 0.1 to 100 parts by mass of a polyfluoromonoalkenyl compound having one alkenyl group in one molecule and having a perfluoropolyether structure in the main chain, relative to 100 parts by mass of component (A) [1] to [ 3 ] A thermally conductive sheet product according to any one of the preceding claims. [ 10 ] The alkenyl group content of the component (A) is 0.0050 to 0.300 mol / 100 g [1] to [ 3 ] A thermally conductive sheet product according to any one of the preceding claims. [ 11 ] The perfluoropolyether structure of the component (A) is represented by the following general formula (5): -(C m F 2m O) n - (5) (In the formula, m is an integer of 1 to 6, and n is an integer of 1 to 300.) [1]~[ 3 ] A thermally conductive sheet product according to any one of the preceding claims. [ 12 ] The component (A) is represented by the following general formula (6) and the following general formula (7): [ka] (In the formula, R 1 and R 2 are each independently an alkenyl group or an unsubstituted or substituted monovalent hydrocarbon group having no aliphatic unsaturated bonds, R 1 and R 2 Of the total, at least two are alkenyl groups. 3are each independently a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group, e and f are each an integer of 1 to 150, the average value of e+f is 2 to 300, and g is an integer of 1 to 6. [ka] (In the formula, R 4 are each independently an alkylene group having 1 to 6 carbon atoms; R 5 are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms which may be substituted with fluorine. 1 , R 2 , e, f and g are the same as above.) [1] to [ 3 ] A thermally conductive sheet product according to any one of the preceding claims. [ 13 ] The component (D) is at least one selected from the group consisting of metals, metal oxides, metal nitrides, metal hydroxides, metal carbides, soft magnetic alloys, and ferrites. 3 ] A thermally conductive sheet product according to any one of the preceding claims. [ 14 ] The component (D) is alumina. 13

[0023] A thermally conductive sheet product according to the present invention. [ 15 ] The component (D) is amorphous alumina and / or spherical alumina. 14

[0023] A thermally conductive sheet product according to the present invention. [ 16 ] The average particle size of the amorphous alumina of the component (D) is 0.2 to 5 μm. 15

[0023] A thermally conductive sheet product according to the present invention. [ 17 ] The average particle size of the spherical alumina of the component (D) is 5 to 100 μm. 15] The thermally conductive sheet product described above. [ 18 ] The component (E) is a fluorine-containing organosilicon compound having, in one molecule, one or more perfluoroalkyl or perfluorooxyalkyl groups bonded to a silicon atom directly bonded to an alkoxy group via a divalent hydrocarbon group which may contain a carbon atom, a silicon atom, an oxygen atom, and a nitrogen atom. 7] The thermally conductive sheet product described above. [ 19 ] The component (E) is represented by the following general formula (8): D g’ R 14 h’ Si(OR 6 ) 4-g’-h’ (8) (In the formula, each D is independently a perfluoroalkyl group or a perfluorooxyalkyl group bonded to a silicon atom to which an alkoxy group is directly bonded via a divalent hydrocarbon group which may contain a carbon atom, a silicon atom, an oxygen atom, and a nitrogen atom; R 6 are each independently an alkyl group having 1 to 6 carbon atoms; R 14 are each independently an unsubstituted or substituted monovalent hydrocarbon group. Additionally, g' is an integer of 1 to 3, h' is an integer of 0 to 2, and g'+h' is an integer of 1 to 3. It is a fluorine-containing organosilicon compound represented by the formula: 7] The thermally conductive sheet product described above. [ 20 ] The component (G) is represented by the following general formula (9): Rf-(Y) h -CH=CH 2 (9) [In the formula, Rf is a group represented by the following general formula (10), F-[CF(CF 3 )CF 2 O] i -C j F 2j - (10) (In the formula, i is an integer of 1 to 200, and j is an integer of 1 to 3.) Y is -CH 2 -, -OCH 2 -, -CH 2 OCH 2 -or-CO-NR15 -Z- (Note that the left end of each of these groups is bonded to Rf and the right end is bonded to a carbon atom. 15 is a hydrogen atom, a methyl group, a phenyl group, or an allyl group, and Z is -CH 2 -, a group represented by the following structural formula (Z) or a group represented by the following structural formula (Z'). [ka] (A dimethylphenylsilylene group represented by the o-position, m-position, or p-position, the left end of which is bonded to a nitrogen atom and the right end of which is bonded to a carbon atom.) [ka] (the left end is bonded to a nitrogen atom and the right end is bonded to a carbon atom) and h is 0 or 1. It is a polyfluoromonoalkenyl compound represented by the formula: 9] The thermally conductive sheet product described above. [ 21 ] The thermal conductivity of a cured product obtained by curing the thermally conductive fluorine-containing curable composition at 25°C is 1.0 W / m K or more [1] to [ 3 ] A thermally conductive sheet product according to any one of the preceding claims. [ 22 ] The hardness of a cured product obtained by curing the thermally conductive fluorine-containing curable composition is 60 or less in type E durometer as defined in JIS K6253-3 [1] to [ 3 ] A thermally conductive sheet product according to any one of the preceding claims. [twenty three] (A) a linear polyfluoro compound having two or more alkenyl groups in one molecule and having a perfluoropolyether structure in the main chain: 100 parts by mass, (B) a fluorine-containing organohydrogensiloxane having in one molecule one or more groups selected from a perfluoroalkyl group, a perfluorooxyalkyl group, a perfluoroalkylene group, and a perfluorooxyalkylene group, and further having two or more hydrogen atoms (SiH groups) directly bonded to silicon atoms, and having no alkoxy groups directly bonded to silicon atoms in the molecule: an amount such that the number of hydrogen atoms directly bonded to silicon atoms in component (B) is 0.50 to 3.0 moles per mole of alkenyl groups contained in the entire composition, (C) a platinum group metal catalyst: 0.1 to 2,000 ppm by mass of platinum group metal atoms relative to the component (A), and (D) Thermally conductive filler: 100 to 4,000 parts by mass and an electrically insulating film is attached to both sides of a thermally conductive sheet made of a cured product of a thermally conductive fluorine-containing curable composition containing the compound, and at least one surface of the electrically insulating film that comes into contact with the thermally conductive sheet is treated with a fluorine-containing silicone-based release agent. [twenty four] (A) The following general formula (6) and the following general formula (7) [ka] (In the formula, R1 and R 2 are each independently an alkenyl group or an unsubstituted or substituted monovalent hydrocarbon group having no aliphatic unsaturated bonds, R 1 and R 2 Of the total, at least two are alkenyl groups. 3 are each independently a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group, e and f are each an integer of 1 to 150, the average value of e+f is 2 to 300, and g is an integer of 1 to 6. [ka] (In the formula, R 4 are each independently an alkylene group having 1 to 6 carbon atoms; R 5 are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms which may be substituted with fluorine. 1 、R 2 , e, f and g are the same as above.) One or more linear polyfluoro compounds selected from the group consisting of: 100 parts by mass, (B) a fluorine-containing organohydrogensiloxane having in one molecule one or more groups selected from a perfluoroalkyl group, a perfluorooxyalkyl group, a perfluoroalkylene group, and a perfluorooxyalkylene group, and further having two or more hydrogen atoms (SiH groups) directly bonded to silicon atoms, and having no alkoxy groups directly bonded to silicon atoms in the molecule: an amount such that the number of hydrogen atoms directly bonded to silicon atoms in component (B) is 0.50 to 3.0 moles per mole of alkenyl groups contained in the entire composition, (C) a platinum group metal catalyst: 0.1 to 2,000 ppm by mass of platinum group metal atoms relative to the component (A), and (D) Thermally conductive filler: 100 to 4,000 parts by mass A thermally conductive sheet product comprising a thermally conductive sheet made of a cured product of a thermally conductive fluorine-containing curable composition containing the above-mentioned compound and an electrically insulating film attached to both sides of the thermally conductive sheet. [ 25 ] (A) a linear polyfluoro compound having two or more alkenyl groups in one molecule and having a perfluoropolyether structure in the main chain: 100 parts by mass, (B) a fluorine-containing organohydrogensiloxane having in one molecule one or more groups selected from a perfluoroalkyl group, a perfluorooxyalkyl group, a perfluoroalkylene group, and a perfluorooxyalkylene group, and further having two or more hydrogen atoms (SiH groups) directly bonded to silicon atoms, and having no alkoxy groups directly bonded to silicon atoms in the molecule: an amount such that the number of hydrogen atoms directly bonded to silicon atoms in component (B) is 0.50 to 3.0 moles per mole of alkenyl groups contained in the entire composition, (C) a platinum group metal catalyst: 0.1 to 2,000 ppm by mass of platinum group metal atoms relative to the component (A), and (D) Thermally conductive filler: 100 to 4,000 parts by mass and sandwiching the thermally conductive fluorine-containing curable composition between electrically insulating films and hot pressing the composition to cure the composition into a sheet. A thermally conductive sheet comprising a cured product of the thermally conductive fluorine-containing curable composition containing the above components (A) to (D), and an electrically insulating film attached to both sides of the thermally conductive sheet. A manufacturing method for a thermally conductive sheet product. [26 ] (A) a linear polyfluoro compound having two or more alkenyl groups in one molecule and having a perfluoropolyether structure in the main chain: 100 parts by mass, (B) a fluorine-containing organohydrogensiloxane having in one molecule one or more groups selected from a perfluoroalkyl group, a perfluorooxyalkyl group, a perfluoroalkylene group, and a perfluorooxyalkylene group, and further having two or more hydrogen atoms (SiH groups) directly bonded to silicon atoms, and having no alkoxy groups directly bonded to silicon atoms in the molecule: an amount such that the number of hydrogen atoms directly bonded to silicon atoms in component (B) is 0.50 to 3.0 moles per mole of alkenyl groups contained in the entire composition, (C) a platinum group metal catalyst: 0.1 to 2,000 ppm by mass of platinum group metal atoms relative to the component (A), and (D) Thermally conductive filler: 100 to 4,000 parts by mass a step of coating a thermally conductive fluorine-containing curable composition containing the compound on a long electrically insulating film, curing the composition by heating, and then attaching the electrically insulating film onto the cured product. A thermally conductive sheet comprising a cured product of the thermally conductive fluorine-containing curable composition containing the above components (A) to (D), and an electrically insulating film attached to both sides of the thermally conductive sheet. A manufacturing method for a thermally conductive sheet product. Effect of the Invention

[0013] The thermally conductive sheet product of the present invention is a thermally conductive sheet made of a cured product obtained by curing a thermally conductive fluorine-containing curable composition having excellent oil resistance and thermal conductivity. Both sides of the thermally conductive sheet are protected from foreign matter, and the sheet can be processed as is by press molding or the like, and the sheet has excellent interposition workability between a heat-generating component and a heat-dissipating component. [Brief description of the drawings]

[0014] [Figure 1] 1 is a cross-sectional view of a thermally conductive sheet product in which an electrically insulating film is attached to both sides of a thermally conductive sheet according to an embodiment of the present invention. [Diagram 2]FIG. 1 is a cross-sectional view of a thermally conductive sheet product in accordance with another embodiment of the present invention, in which an electrically insulating film is attached to one side of the thermally conductive sheet and an electrically insulating film treated with a fluorine-containing silicone-based release agent is attached to the other side of the thermally conductive sheet. [Diagram 3] FIG. 11 is a cross-sectional view of a thermally conductive sheet product in accordance with yet another embodiment of the present invention, in which electrically insulating films treated with a fluorine-containing silicone release agent are attached to both sides of the thermally conductive sheet. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0015] As shown in Figs. 1 to 3, the thermally conductive sheet product of the present invention has a configuration in which electrically insulating films are attached to both sides of a thermally conductive sheet made of a cured product obtained by curing a thermally conductive fluorine-containing curable composition having excellent oil resistance and thermal conductivity.

[0016] The present invention will be described in detail below.

[0017] [Thermal conductive sheet products] The thermally conductive sheet product of the present invention comprises a thermally conductive sheet made of a cured product obtained by curing a thermally conductive fluorine-containing curable composition containing components (A) to (D) described below, and electrically insulating films attached to both sides of the sheet.

[0018] [Electrical insulating film] The thickness of the electrical insulating film can be changed in a wide range depending on the hardness of the thermal conductive sheet and the adhesiveness of the surface, but is usually preferably 1 to 200 μm. If the thickness of the electrical insulating film is 1 μm or more, the handling workability is not deteriorated due to the softness of the electrical insulating film, and there is no risk of the thermal conductive sheet being torn or leaving a peeling residue when peeled off from the thermal conductive sheet. On the other hand, if the thickness of the electrical insulating film is 200 μm or less, there is no risk of the handling workability being deteriorated due to the lack of flexibility of the film, and there is no risk of the adhesion to the surface of the thermal conductive sheet being deteriorated.

[0019] In addition, the substrate of the electrically insulating film is not particularly limited as long as it has electrical insulation, and known ones can be used. For example, plastic films include polyolefins such as polyethylene (PE) and polypropylene (PP), polyimide (PI), polyamide (PA), polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), aromatic polyether ketones such as polyether ether ketone, fluorine-containing polymers such as polytetrafluoroethylene and copolymers of tetrafluoroethylene and perfluoroalkyl vinyl ether, and polyvinyl chloride, and naturally occurring substrates include paper. Among these, polyethylene terephthalate (PET) is particularly preferred from the viewpoint of flexibility and mechanical strength. The film used in the present invention may be laminated with two or more of the above substrates as necessary.

[0020] In the electrically insulating film, at least one of the electrically insulating films has a surface that contacts the thermally conductive sheet treated with a fluorine-containing silicone release agent, which allows the film to be easily peeled off from the thermally conductive sheet.

[0021] From the viewpoint of releasability from the thermally conductive sheet, the fluorine-containing silicone release agent is preferably one that contains an organopolysiloxane having one or more perfluoroalkyl groups or perfluorooxyalkyl groups (for example, an organopolysiloxane having one or more perfluoroalkyl groups or perfluorooxyalkyl groups, or a solution in which the organopolysiloxane having one or more perfluoroalkyl groups or perfluorooxyalkyl groups is dissolved in a solvent).

[0022] The perfluoroalkyl group or perfluorooxyalkyl group includes groups represented by the following general formula (1) or (2). C f” F 2f”+1 - (1) (In the formula, f″ is an integer of 1 to 10.) [ka] (In the formula, g″ is an integer of 1 to 30.)

[0023] Furthermore, the perfluoroalkyl group or perfluorooxyalkyl group and the silicon atom constituting the organopolysiloxane are preferably linked by a divalent linking group, and the divalent linking group is preferably an unsubstituted or substituted divalent hydrocarbon group having 2 to 12 carbon atoms, particularly 2 to 8 carbon atoms, which may have an oxygen atom, a nitrogen atom, or a silicon atom. Specific examples include alkylene groups, arylene groups, and combinations thereof, as well as these groups interposed with one or more structures selected from the group consisting of an ether-bonded oxygen atom, an amide bond, a carbonyl bond, an ester bond, and a diorganosilylene group such as a dimethylsilylene group, and for example, -CH 2 CH 2 -, -CH 2 CH 2 CH 2 -, -CH 2 CH 2 CH 2 OCH 2 -, -CH 2 CH 2 CH 2 -NH-CO-, -CH 2 CH 2 CH 2 -N(Ph)-CO-, -CH 2 CH 2 CH 2 -N(CH 3 )-CO-, -CH 2 CH 2 CH 2 -N(CH 2 CH 3 )-CO-, -CH 2 CH 2 CH 2 -N(CH(CH 3 ) 2)-CO-, -CH 2 CH 2 CH 2 -O-CO-, -CH 2 CH 2 -Si(CH 3 ) 2 -Ph'-N(CH 3 )-CO-, -CH 2 CH 2 CH 2 -Si(CH 3 ) 2 -Ph'-N(CH 3 )-CO- (where Ph is a phenyl group and Ph' is a phenylene group.) and the like, each having a carbon number of 2 to 13. In the above structure, it is preferable that the left end is bonded to a silicon atom and the right end is bonded to a perfluoroalkyl group or a perfluorooxyalkyl group.

[0024] Furthermore, the monovalent substituent bonded to the silicon atom in this organopolysiloxane other than the perfluoroalkyl group or perfluorooxyalkyl group is an unsubstituted or substituted alkyl group or aryl group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms, such as alkyl groups such as methyl group, ethyl group, propyl group, butyl group, hexyl group, cyclohexyl group, octyl group, and decyl group; aryl groups such as phenyl group, tolyl group, and naphthyl group; and groups in which some or all of the hydrogen atoms of these groups have been substituted with halogen atoms such as chlorine atoms, cyano groups, etc., such as chloromethyl group, chloropropyl group, and cyanoethyl group. Among these, the methyl group is preferred.

[0025] The polysiloxane structure constituting this organopolysiloxane may be any of cyclic, linear, three-dimensional network, and combinations thereof. The number of silicon atoms in this organopolysiloxane is not particularly limited, but is usually 9 to 800, preferably 20 to 600, and more preferably 50 to 400.

[0026] Examples of organopolysiloxanes having one or more perfluoroalkyl groups or perfluorooxyalkyl groups include organopolysiloxanes (addition reaction products) obtained by addition and crosslinking, via a hydrosilylation addition reaction, a fluorine-containing organopolysiloxane having an alkenyl group in the molecule, represented by the following general formula (I), and a fluorine-containing organohydrogenpolysiloxane having a hydrogen atom bonded to a silicon atom (SiH group) in the molecule, represented by the following general formula (II): [ka] (In the formula, D' is independently a perfluoroalkyl group or a perfluorooxyalkyl group bonded to a silicon atom constituting the organopolysiloxane via a divalent hydrocarbon group which may contain an oxygen atom, a nitrogen atom, and a silicon atom, as described above; R 16 R is independently an alkenyl group having 2 to 20 carbon atoms, preferably 2 to 10 carbon atoms, and specific examples thereof include a vinyl group, an allyl group, and a hexenyl group. 17 are independently a monovalent hydrocarbon group having 1 to 10 carbon atoms excluding unsubstituted or substituted aliphatic unsaturated bonds, and specific examples thereof include alkyl groups such as methyl, ethyl, and propyl groups, cycloalkyl groups such as cyclohexyl groups, aryl groups such as phenyl and tolyl groups, and hydroxypropyl and cyanoethyl groups in which some or all of the hydrogen atoms of these groups have been substituted with hydroxy groups, cyano groups, etc. In addition, h'' is 1, 2, or 3, i'' is an integer of 0 or more, j'' is an integer of 1 or more, k'' is an integer of 0 or more, and i''+j''+k'' is an integer of 1 to 700. The respective repeating units may be bonded to each other randomly.) [ka] (In the formula, E' is independently the same as D' above, and R 18 is independently 17 In addition, l''' is an integer of 0 or more, m''' is an integer of 1 or more, n''' is an integer of 3 or more, and l'''+m'''+n''' is an integer of 4 to 400. The repeating units may be bonded randomly to each other.

[0027] The organopolysiloxane may be diluted with an appropriate solvent, for the purposes of adjusting the coating amount as well as improving the ease of coating onto a film, for example, with a hydrocarbon organic solvent such as toluene, acetone, or methyl ethyl ketone, or a fluorine-based solvent such as hydrofluoroether, chlorofluorocarbon, xylene hexafluoride, perfluoroalkane, benzotrifluoride, 1,3-bis(trifluoromethyl)benzene, Fluorinert (manufactured by 3M), perfluorobutyl methyl ether, or perfluorobutyl ethyl ether.

[0028] As such a fluorine-containing silicone-based release agent, a commercially available product can be used, and specific examples of commercially available products include X-70-201S, X-70-220S, X-70-258, and X-70-411 (all manufactured by Shin-Etsu Chemical Co., Ltd.).

[0029] A preferred method for treating the surface of the electrical insulating film that comes into contact with the thermally conductive sheet with a fluorinated silicone release agent is to coat the surface of the electrical insulating film that comes into contact with the thermally conductive sheet in a thin film by a method such as gravure coating or reverse gravure coating, and then harden and fix the coating.

[0030] [Thermal conductive sheet] The thermally conductive sheet used in the present invention comprises a cured product of a thermally conductive fluorine-containing curable composition containing the below-described components (A) to (D) and, if necessary, the below-described components (E) to (G) and the like.

[0031] [Component (A)] The component (A) is a linear polyfluoro compound having two or more alkenyl groups in one molecule and having a perfluoropolyether structure in the main chain.

[0032] The alkenyl group contained in the component (A) preferably has 2 to 8 carbon atoms, particularly 2 to 6 carbon atoms, and has a terminal CH 2Those having a =CH- structure are preferred, and examples thereof include a vinyl group, an allyl group, a propenyl group, an isopropenyl group, a butenyl group, and a hexenyl group, with the vinyl group and the allyl group being particularly preferred.

[0033] The alkenyl group content in the linear polyfluoro compound of component (A) is preferably 0.0050 to 0.300 mol / 100 g, more preferably 0.0070 to 0.200 mol / 100 g. When the alkenyl group content is 0.0050 mol / 100 g or more, the degree of crosslinking is sufficient and there is no risk of curing defects. On the other hand, when the alkenyl group content is 0.300 mol / 100 g or less, there is no risk of the mechanical properties of the cured product obtained by curing the thermally conductive fluorine-containing curable composition being impaired. The alkenyl group content can be measured by proton nuclear magnetic resonance spectroscopy ( 1 It can be measured by 1 H-NMR or infrared spectroscopy (IR) using a calibration curve.

[0034] The perfluoropolyether structure of component (A) is -C m F 2m O- (In the formula, m is an integer of 1 to 6.) Examples of the repeating units include those represented by the following general formula (5). -(C m F 2m O) n - (5) (In the formula, m is an integer of 1 to 6, and n is an integer of 1 to 300, preferably an integer of 1 to 200.)

[0035] Above-C m F 2m Examples of the repeating unit represented by O- include units represented by the following formulas. -CF 2 O-, -CF 2 CF 2 O-, -CF 2 CF 2 CF 2 O-, -CF 2 (CF 3 )CF 2 O-, -CF 2 CF 2 CF 2 CF 2 O-, -CF 2 CF 2 CF 2 CF 2 CF 2 CF 2 O-, -C(CF 3 ) 2 O-

[0036] Among these, the repeating units represented by the following formula are particularly preferred. -CF 2 O-, -CF 2 CF 2 O-, -CF 2 CF 2 CF 2 O-, -CF 2 (CF 3 )CF 2 O-

[0037] The perfluoropolyether structure of the component (A) may be composed of one type of the above repeating units, or may be composed of a combination of two or more types.

[0038] Preferred examples of the component (A) include linear polyfluoro compounds represented by the following general formula (6) and the following general formula (7). [ka] (In the formula, R 1 and R 2 are each independently an alkenyl group or an unsubstituted or substituted monovalent hydrocarbon group having no aliphatic unsaturated bonds, R 1 and R 2 Of the total, at least two are alkenyl groups. 3are each independently a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group, e and f are each an integer of 1 to 150, the average value of e+f is 2 to 300, and g is an integer of 1 to 6. [ka] (In the formula, R 4 are each independently an alkylene group having 1 to 6 carbon atoms; R 5 are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms which may be substituted with fluorine. 1 , R 2 , e, f and g are the same as above.)

[0039] Here, R 1 and R 2 Examples of the alkenyl group contained in R include the same as those mentioned above, and other monovalent hydrocarbon groups that do not have unsubstituted or substituted aliphatic unsaturated bonds are preferably those having 1 to 12 carbon atoms, and particularly preferably those having 1 to 10 carbon atoms, and specific examples thereof include alkyl groups such as methyl, ethyl, propyl, butyl, hexyl, cyclohexyl, and octyl groups; aryl groups such as phenyl and tolyl groups; aralkyl groups such as benzyl and phenylethyl groups, and monovalent hydrocarbon groups in which some or all of the hydrogen atoms of these groups have been substituted with halogen atoms such as fluorine atoms. 1 and R 2 Among these, a vinyl group, an allyl group, a methyl group and an ethyl group are particularly preferred.

[0040] R 3 The unsubstituted or substituted monovalent hydrocarbon group contained in R 1 and R 2 Examples of the unsubstituted or substituted monovalent hydrocarbon group having no aliphatic unsaturated bond are the same as those of R. 3 is preferably a hydrogen atom, a methyl group, or an ethyl group.

[0041] R 4are each independently an alkylene group having 1 to 6 carbon atoms, preferably 2 to 6 carbon atoms. Specific examples include a methylene group, an ethylene group, a propylene group (a trimethylene group, a methylethylene group), a butylene group (a tetramethylene group, a methylpropylene group), a hexamethylene group, and the like. An ethylene group and a propylene group are particularly preferred.

[0042] R 5 are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms which may be substituted with fluorine, and specific examples of the alkyl group having 1 to 4 carbon atoms which may be substituted with fluorine include alkyl groups such as methyl, ethyl, propyl and butyl groups, and groups in which some or all of the hydrogen atoms of these groups have been substituted with fluorine atoms, such as a trifluoromethyl group. 5 is preferably a hydrogen atom.

[0043] Furthermore, e and f are each preferably an integer of 1 to 150, more preferably an integer of 1 to 100, and the average value of e+f is preferably 2 to 300, more preferably 2 to 200. Furthermore, g is preferably an integer of 1 to 6, more preferably an integer of 1 to 4.

[0044] Specific examples of the linear polyfluoro compound represented by the above general formula (6) include those represented by the following formulas. [ka] (In the formula, e and f are each an integer of 1 to 150.)

[0045] [ka] (In the formula, e and f are each an integer of 1 to 150.)

[0046] [ka] (In the formula, e and f are each an integer of 1 to 150.)

[0047] Specific examples of the linear polyfluoro compound represented by the above general formula (7) include those represented by the following formula: [ka] (In the formula, e and f are each an integer of 1 to 100.)

[0048] [ka] (In the formula, e and f are each an integer of 1 to 100.)

[0049] In the present invention, the viscosity can be measured by a rotational viscometer (e.g., BL type, BH type, BS type, cone plate type, rheometer, etc.), and the viscosity (23°C) of the linear polyfluoro compound represented by the above general formula (6) or (7) is preferably in the range of 500 to 100,000 mPa·s, more preferably 1,000 to 50,000 mPa·s, as determined by the viscosity measurement method specified in JIS K7117-1. If the viscosity is 500 mPa·s or more, there is no risk of the storage stability of the obtained composition being deteriorated, and if it is 100,000 mPa·s or less, there is no risk of the extensibility of the obtained composition being deteriorated. In addition, the degree of polymerization (or molecular weight) of a linear polyfluoro compound, which is reflected by the number of repetitions of perfluorooxyalkylene units constituting the perfluoropolyether structure of the main chain, can be determined, for example, as the polystyrene-equivalent number average degree of polymerization (or number average molecular weight) in gel permeation chromatography (GPC) analysis using a fluorine-based solvent as a developing solvent.

[0050] These linear polyfluoro compounds can be used alone or in combination of two or more. That is, among the linear polyfluoro compounds represented by the above general formula (6) or (7), one can be used alone or two or more can be used in combination, and the linear polyfluoro compounds represented by the above general formulas (6) and (7) can also be used in combination.

[0051] [(B) Component] Component (B) is a fluorine-containing organohydrogensiloxane having in one molecule one or more groups selected from perfluoroalkyl groups, perfluorooxyalkyl groups, perfluoroalkylene groups, and perfluorooxyalkylene groups, further having two or more hydrogen atoms directly bonded to silicon atoms (SiH groups or hydrosilyl groups), and having no alkoxy groups directly bonded to silicon atoms in the molecule, and is preferably a fluorine-containing organohydrogensiloxane having in one molecule one or more of the above-mentioned monovalent or divalent fluorine-containing organic groups and two or more hydrogen atoms directly bonded to silicon atoms, and having no other functional groups other than SiH groups, such as epoxy groups, alkoxy groups, or cyclic carboxylic anhydride residues, and functions as a crosslinking agent for component (A). However, the term "other functional groups" as used herein excludes divalent polar groups (polar structures) such as ether-bonded oxygen atoms, amide bonds, carbonyl bonds, and ester bonds that may be contained in the divalent linking group that links a perfluoroalkyl group, a perfluorooxyalkyl group, a perfluoroalkylene group, or a perfluorooxyalkylene group to a silicon atom that constitutes the polysiloxane.

[0052] The perfluoroalkyl group, perfluorooxyalkyl group, perfluoroalkylene group and perfluorooxyalkylene group are groups which are introduced from the viewpoints of compatibility with the component (A), dispersibility, uniformity after curing, and the like.

[0053] The perfluoroalkyl group or perfluorooxyalkyl group includes groups represented by the following general formula (11) or (12). C k F 2k+1 - (11) (In the formula, k is an integer of 1 to 10, preferably an integer of 3 to 7.) [ka] (In the formula, l is an integer of 1 to 50, preferably an integer of 2 to 30.)

[0054] Moreover, the above perfluoroalkylene group or perfluorooxyalkylene group includes groups represented by the following general formulas (13) to (15). -C p F 2p - (13) (In the formula, p is an integer of 1 to 20, preferably an integer of 2 to 10.) [ka] (In the formula, q and r are each an integer of 1 or more, preferably an integer of 1 to 100, and the average of the sum of q and r is 2 to 200, preferably 2 to 100.) -CF 2 O-(CF 2 CF 2 O) s (CF 2 O) t -CF 2 - (15) (In the formula, s and t each represent an integer of 1 to 50, preferably an integer of 1 to 30. The repeating units may be bonded randomly to each other.)

[0055] Furthermore, these perfluoroalkyl groups, perfluorooxyalkyl groups, perfluoroalkylene groups or perfluorooxyalkylene groups are preferably linked to silicon atoms constituting the polysiloxane by a divalent linking group, and the divalent linking group is preferably an unsubstituted or substituted divalent hydrocarbon group having 2 to 12 carbon atoms, particularly 2 to 8 carbon atoms, which may have an oxygen atom, a nitrogen atom or a silicon atom. Specific examples of the divalent linking group include alkylene groups, arylene groups and combinations thereof, as well as those in which one or more structures selected from the group consisting of an ether-bonded oxygen atom, an amide bond, a carbonyl bond, an ester bond, and a diorganosilylene group such as a dimethylsilylene group are interposed between these groups, and examples thereof include -CH 2 CH 2 -, -CH 2 CH 2 CH 2 -, -CH 2 CH2 CH 2 OCH 2 -, -CH 2 CH 2 CH 2 -NH-CO-, -CH 2 CH 2 CH 2 -N(Ph)-CO-, -CH 2 CH 2 CH 2 -N(CH 3 )-CO-, -CH 2 CH 2 CH 2 -N(CH 2 CH 3 )-CO-, -CH 2 CH 2 CH 2 -N(CH(CH 3 ) 2 )-CO-, -CH 2 CH 2 CH 2 -O-CO-, -CH 2 CH 2 -Si(CH 3 ) 2 -Ph'-N(CH 3 )-CO-, -CH 2 CH 2 CH 2 -Si(CH 3 ) 2 -Ph'-N(CH 3 )-CO- (where Ph is a phenyl group and Ph' is a phenylene group.) and the like, each having a carbon number of 2 to 13. In the above structure, it is preferable that the left end is bonded to a silicon atom and the right end is bonded to a perfluoroalkyl group, a perfluorooxyalkyl group, a perfluoroalkylene group, or a perfluorooxyalkylene group. These linking groups may be used alone or in combination of two or more in one molecule.

[0056] The monovalent or divalent fluorine-containing organic group and the monovalent substituent bonded to the silicon atom other than the hydrogen atom directly bonded to the silicon atom in the fluorine-containing organohydrogensiloxane of component (B) are unsubstituted or substituted alkyl or aryl groups having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms, such as alkyl groups such as methyl, ethyl, propyl, butyl, hexyl, cyclohexyl, octyl, and decyl groups; aryl groups such as phenyl, tolyl, and naphthyl groups; and groups in which some or all of the hydrogen atoms of these groups have been substituted with halogen atoms such as chlorine atoms, cyano groups, etc., such as chloromethyl, chloropropyl, and cyanoethyl groups. Among these, methyl groups are preferred.

[0057] The polysiloxane structure constituting the fluorine-containing organohydrogensiloxane of component (B) may be cyclic, linear, three-dimensional network, or a combination thereof. The number of silicon atoms in this fluorine-containing organohydrogensiloxane is not particularly limited, but is usually about 2 to 60, preferably 3 to 30, and more preferably 4 to 30. The component (B) has two or more SiH groups in one molecule, and the SiH group content is preferably 0.0100 to 1.00 mol / 100 g, and more preferably 0.0200 to 0.900 mol / 100 g. The SiH group content is measured by proton nuclear magnetic resonance spectroscopy ( 1 It can be measured by H-NMR or by quantifying the hydrogen gas evolved by cracking with a base.

[0058] Examples of the component (B) include those represented by the following general formulas (16) to (22). [ka] (In the formula, E is independently a perfluoroalkyl group or a perfluorooxyalkyl group bonded to a silicon atom constituting the polysiloxane via a divalent hydrocarbon group which may contain an oxygen atom, a nitrogen atom, and a silicon atom, as described above; R 7are each independently the above-mentioned unsubstituted or substituted alkyl group or aryl group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms. In addition, u is an integer of 2 to 6, preferably an integer of 3 to 6, v is an integer of 1 to 4, preferably an integer of 1 to 3, and u+v is an integer of 4 to 10, preferably an integer of 4 to 9. The respective repeating units may be bonded to each other randomly.

[0059] [ka] (In the formula, G is independently the same as E above, and R 8 is independently 7 In addition, w is an integer of 2 to 50, preferably an integer of 3 to 30.

[0060] [ka] (In the formula, J is independently the same as E above, and R 9 is independently 7 x is an integer of 2 to 50, preferably an integer of 3 to 30, y is an integer of 1 to 40, preferably an integer of 1 to 20, and x+y is an integer of 4 to 60, preferably an integer of 4 to 50. The respective repeating units may be bonded randomly to each other.

[0061] [ka] (In the formula, L is independently the same as E above, and R 10 is independently 7 z is an integer of 2 to 50, preferably an integer of 3 to 30, a' is an integer of 1 to 40, preferably an integer of 1 to 20, and z+a' is an integer of 4 to 60, preferably an integer of 4 to 50. The respective repeating units may be bonded randomly to each other.

[0062] [ka] (In the formula, M is independently the same as E above, and R 11is independently 7 b' is an integer of 2 to 50, preferably an integer of 3 to 30, c' is an integer of 1 to 40, preferably an integer of 1 to 20, and d' is an integer of 1 to 40, preferably an integer of 1 to 20. b'+c'+d' is an integer of 5 to 60, preferably an integer of 5 to 50. The respective repeating units may be bonded randomly to each other.

[0063] [ka] (In the formula, Q is an oxygen atom, an alkylene group, or a perfluoroalkylene group or a perfluorooxyalkylene group bonded to a silicon atom via a divalent hydrocarbon group which may contain an oxygen atom or a nitrogen atom. Examples of the perfluoroalkylene group or the perfluorooxyalkylene group include the groups represented by the above general formulae (13) to (15). In addition, T is independently the same as E above, R 12 is independently the above R 7 In addition, e' is an integer of 0 to 3, f' is an integer of 0 to 3, and e'+f' is an integer of 2 to 6, preferably an integer of 3 to 5. However, when e'+f' is 6, Q is a perfluoroalkylene group or a perfluorooxyalkylene group bonded to a silicon atom via a divalent hydrocarbon group which may contain an oxygen atom or a nitrogen atom.

[0064] [ka] (wherein X is the same as E above, and R 13 is independently the above R 7 is the same as

[0065] Specific examples of the component (B) include the following compounds. These compounds may be used alone or in combination of two or more. In the following formulae, Me represents a methyl group and Ph represents a phenyl group.

[0066] [ka] (In the formula, s' is an integer of 1 to 10. The repeating units may be bonded randomly.)

[0067] [ka] (In the formula, t' is an integer of 1 to 50. The repeating units may be bonded randomly.)

[0068] [ka] (In the formula, t' is an integer of 1 to 50.)

[0069] [ka] (In the formula, s' is an integer of 1 to 10. The repeating units may be bonded randomly.)

[0070] [ka] (In the formula, s' is an integer of 1 to 10, and t' is an integer of 1 to 50. The repeating units may be bonded randomly to each other.)

[0071] [ka] (In the formula, s' is an integer of 1 to 10, and t' is an integer of 1 to 50. The repeating units may be bonded randomly to each other.)

[0072] [ka] (In the formula, s' is an integer of 1 to 10, and t' is an integer of 1 to 50.)

[0073] [ka] (In the formula, s' is an integer of 1 to 10, and c" is an integer of 1 to 20.)

[0074] [ka] (In the formula, t' is an integer of 1 to 50, and c" is an integer of 1 to 20.)

[0075] [ka] (In the formula, s' is an integer of 1 to 10, and t' is an integer of 1 to 50.)

[0076] [ka] (In the formula, s' is an integer of 1 to 10, t' is an integer of 1 to 50, d" and e" are each an integer of 1 to 100, and d"+e" is an integer of 2 to 200.)

[0077] [ka] (In the formula, s' is an integer of 1 to 10, t' is an integer of 1 to 50, and m'' and n'' are each an integer of 1 to 50. The repeating units may be bonded to each other randomly.)

[0078] The component (B) may be used alone or in combination of two or more kinds. The amount of the (B) component is such that the amount of hydrogen atoms directly bonded to silicon atoms (SiH groups) in the (B) component is 0.50 to 3.0 mol, more preferably 0.60 to 2.0 mol, per mol of alkenyl groups contained in the thermally conductive fluorine-containing curable composition. If the amount of SiH groups is less than 0.50 mol, the degree of crosslinking may be insufficient, whereas if it is more than 3.0 mol, the storage stability may be impaired or the heat resistance of the cured product obtained after curing may be reduced.

[0079] [(C) component] The platinum group metal catalyst, which is component (C), is a hydrosilylation catalyst. The hydrosilylation catalyst is a catalyst that promotes an addition reaction between an alkenyl group contained in the thermally conductive fluorine-containing curable composition, particularly an alkenyl group in component (A), and a SiH group contained in the composition, particularly a SiH group in component (B). The platinum group metal catalyst, which is a hydrosilylation catalyst, is generally a noble metal or a compound thereof, and is expensive, so platinum or a platinum compound, which is relatively easy to obtain, is often used.

[0080] Examples of platinum compounds include chloroplatinic acid or complexes of chloroplatinic acid with olefins such as ethylene, complexes of chloroplatinic acid with alcohols or vinylsiloxanes, and metallic platinum supported on silica, alumina, carbon, etc. As platinum group metal catalysts other than platinum or platinum compounds, rhodium, ruthenium, iridium, and palladium compounds are also known, such as RhCl(PPh 3 ) 3 , RhCl(CO)(PPh 3 ) 2 , Ru 3 (CO) 12 , IrCl(CO)(PPh 3 ) 2 , Pd(PPh 3 ) 4 In the above formula, Ph is a phenyl group.

[0081] When using these catalysts, if they are solid catalysts, they can be used in a solid state; however, in order to obtain a more uniform cured product, it is preferable to use chloroplatinic acid or a complex dissolved in a suitable solvent such as toluene or ethanol, and then dissolving it in the linear polyfluoro compound, component (A), before use.

[0082] The amount of component (C) added is an effective amount as a hydrosilylation reaction catalyst and is usually 0.1 to 2,000 ppm, preferably 0.1 to 500 ppm, and particularly preferably 0.5 to 200 ppm (calculated as the mass of platinum group metal atoms) relative to component (A); however, this amount can be increased or decreased as appropriate depending on the desired curing rate.

[0083] [(D) component] The component (D) is a thermally conductive filler used to impart thermal conductivity to the thermally conductive fluorine-containing curable composition. Examples of the filler include metals such as aluminum, nonmagnetic copper, nickel, carbon black, and metallic silicon; metal oxides such as alumina, magnesium oxide, beryllium oxide, chromium oxide, and titanium oxide; metal nitrides such as boron nitride, silicon nitride, and aluminum nitride; metal hydroxides such as aluminum hydroxide; metal carbides such as boron carbide, titanium carbide, and silicon carbide; soft magnetic alloys such as Fe-Si alloys, Fe-Al alloys, Fe-Al-Si alloys, Fe-Si-Cr alloys, Fe-Ni alloys, Fe-Ni-Co alloys, Fe-Al-Si-Cr alloys, Fe-Si-B alloys, and Fe-Si-Co-B alloys; ferrites such as Mn-Zn ferrite, Mn-Mg-Zn ferrite, Mg-Cu-Zn ferrite, Ni-Zn ferrite, Ni-Cu-Zn ferrite, and Cu-Zn ferrite; and mixtures of two or more of these.

[0084] In the present invention, when electrical insulation is required, component (D) is preferably a metal oxide, metal nitride, metal hydroxide or metal carbide, particularly preferably a metal oxide, and of these, alumina is most preferred.

[0085] As the alumina of the component (D), amorphous alumina or spherical alumina is preferred from the viewpoint of significantly improving thermal conductivity, and these two types may be used alone or in combination.

[0086] The average particle size of the amorphous alumina is preferably 0.2 to 5 μm, more preferably 0.4 to 4 μm. When the average particle size is 0.2 μm or more, the viscosity of the thermally conductive fluorine-containing curable composition increases, and there is no risk of the workability or moldability of the composition being impaired. On the other hand, when the average particle size is 5 μm or less, there is no risk of the electrical insulation of the cured product obtained by curing the thermally conductive fluorine-containing curable composition being impaired. The amorphous alumina may be used alone or in combination of two or more kinds. The amorphous alumina may be a normal commercially available product. The average particle size is usually determined by measuring the cumulative volume average diameter D 50 Specifically, it can be calculated as the cumulative 50% particle diameter (D) on a volume basis measured using a particle size distribution analyzer MT3000II manufactured by Microtrack Bell Co., Ltd. 50 ) value.

[0087] The average particle size of the spherical alumina is preferably 5 to 100 μm, more preferably 7 to 90 μm. If the average particle size is 5 μm or more, the viscosity of the thermally conductive fluorine-containing curable composition increases, and there is no risk of the workability or moldability of the composition being impaired. On the other hand, if the average particle size is 100 μm or less, there is no risk of the spherical alumina not being uniformly dispersed in the thermally conductive fluorine-containing curable composition. As the spherical alumina, one type may be used alone, or two or more types may be used in combination. The spherical alumina may be a normal commercially available product. The average particle size is a value measured in the same manner as the average particle size of the amorphous alumina.

[0088] The amount of component (D) used is in the range of 100 to 4,000 parts by mass, preferably 200 to 3,500 parts by mass, per 100 parts by mass of component (A). If the amount is less than 100 parts by mass, the thermal conductivity of the cured product obtained by curing the thermally conductive fluorine-containing curable composition may be insufficient, while if the amount exceeds 4,000 parts by mass, the component (D) may not be uniformly dispersed in the thermally conductive fluorine-containing curable composition.

[0089] [(E) component] The thermally conductive fluorine-containing curable composition may optionally contain, as component (E) (optional component), a fluorine-containing organosilicon compound having, in one molecule, one or more perfluoroalkyl or perfluorooxyalkyl groups bonded to a silicon atom directly bonded to an alkoxy group via a divalent hydrocarbon group which may contain a carbon atom, a silicon atom, an oxygen atom and a nitrogen atom. More preferred as the fluorine-containing organosilicon compound are fluorine-containing organosilicon compounds having, in one molecule, one or more of the above monovalent fluorine-containing organic groups, one or more alkoxy groups directly bonded to a silicon atom and no hydrogen atom (SiH group) directly bonded to a silicon atom.

[0090] The above-mentioned (E) component acts as a surface treatment agent and / or dispersant (wetter) for the (D) component. During preparation of the thermally conductive fluorine-containing curable composition, the (D) component is hydrophobized by the (E) component, improving the wettability of the (D) component to the (A) component, allowing the (D) component to be added in a large amount to the (A) component. The dispersibility of the (D) component in the composition can also be improved.

[0091] The perfluoroalkyl group and perfluorooxyalkyl group are groups which are introduced from the viewpoints of compatibility with the component (A), dispersibility, and the like. The perfluoroalkyl group or perfluorooxyalkyl group includes groups represented by the following general formula (11) or (12). C k F 2k+1 - (11) (In the formula, k is an integer of 1 to 10, preferably an integer of 3 to 7.) [ka] (In the formula, l is an integer of 1 to 50, preferably an integer of 2 to 30.)

[0092] The perfluoroalkyl group or perfluorooxyalkyl group is preferably linked to a silicon atom to which an alkoxy group is directly bonded via a divalent hydrocarbon group (linking group) which may contain a carbon atom, a silicon atom, an oxygen atom, and a nitrogen atom. The divalent hydrocarbon group may be an alkylene group, an arylene group, or a combination thereof, or may be one in which one or more structures selected from the group consisting of an ether-bonded oxygen atom, an amide bond, a carbonyl bond, an ester bond, and a diorganosilylene group such as a dimethylsilylene group are interposed between these groups, for example: -CH 2 CH 2 -, -CH 2 CH 2 CH 2 -, -CH 2 CH 2 CH 2 OCH 2 -, -CH 2 CH 2 CH 2 -NH-CO-, -CH 2 CH 2 CH 2 -N(Ph)-CO-, -CH 2 CH 2 CH 2 -N(CH 3 )-CO-, -CH 2 CH 2 CH 2 -N(CH 2 CH 3 )-CO-, -CH 2 CH 2 CH 2 -N(CH(CH 3 ) 2 )-CO-, -CH 2 CH 2 CH 2 -O-CO-, -CH 2 CH 2 CH 2 -Si(CH 3) 2 -O-Si(CH 3 ) 2 -CH 2 CH 2 CH 2 -, -CH 2 OCH 2 CH 2 CH 2 -Si(CH 3 ) 2 -O-Si(CH 3 ) 2 -CH 2 CH 2 -, -CO-N(CH 3 )-Ph'-Si(CH 3 ) 2 -CH 2 CH 2 -Si(CH 3 ) 2 -O-Si(CH 3 ) 2 -CH 2 CH 2 -, -CO-N(CH 3 )-Ph'-Si(CH 3 ) 2 -CH 2 CH 2 -Si(CH 3 ) 2 -O-Si(CH 3 ) 2 -CH 2 CH 2 CH 2 -, -CO-NH-Ph'-[Si(CH 3 ) 2 -CH 2 CH 2 ] 3 -CH 2 -, -CO-N(CH 3 )-Ph'-[Si(CH 3 ) 2 -CH 2 CH 2 ] 3 - (where Ph is a phenyl group and Ph' is a phenylene group.) and the like having 2 to 20 carbon atoms. In the above structure, it is preferable that the left end is bonded to a silicon atom and the right end is bonded to a perfluoroalkyl group or a perfluorooxyalkyl group.

[0093] The component (E) is preferably one represented by the following general formula (8). D g’ R 14 h’ Si(OR 6 ) 4-g’-h’ (8) (In the formula, each D is independently a perfluoroalkyl group or a perfluorooxyalkyl group bonded to a silicon atom to which an alkoxy group is directly bonded via a divalent hydrocarbon group which may contain a carbon atom, a silicon atom, an oxygen atom, and a nitrogen atom, as described above. In addition, R 6 are each independently an alkyl group having 1 to 6 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms, and among these, a methyl group or an ethyl group is preferable. 14 are each independently an unsubstituted or substituted monovalent hydrocarbon group, and R 1 and R 2 Examples of the unsubstituted or substituted monovalent hydrocarbon group having no aliphatic unsaturated bond include the same groups as those exemplified above. In addition, g' is an integer of 1 to 3, h' is an integer of 0 to 2, and g'+h' is an integer of 1 to 3.)

[0094] Specific examples of the component (E) include the following compounds: In the following formula, Me represents a methyl group, and Et represents an ethyl group.

[0095] [ka] (In the formula, q' is an integer of 1 to 10, and r' is an integer of 1 to 50.)

[0096] [ka] (In the formula, r' is an integer of 1 to 50.)

[0097] The component (E) may use one type alone, or two or more types in combination. The blending amount of the above component (E) is 0.01 to 300 parts by mass, more preferably 0.10 to 250 parts by mass, per 100 parts by mass of the component (A). If the blending amount is less than 0.01 part by mass, the surface treatment of the above component (D) with the component (E) may be insufficient, whereas if the blending amount is more than 300 parts by mass, the mechanical strength of the cured product obtained by curing the thermally conductive fluorine-containing curable composition may be impaired.

[0098] [Component (F)] The thermally conductive fluorine-containing curable composition may further contain, as component (F) (optional component), a compound represented by the following general formula (3) and the following general formula (4): F-(CF 2 CF 2 CF 2 O) a -A (3) (Wherein, A is -C b F 2b+1 (b is an integer of 1 to 3), and a is an integer of 1 to 500, preferably an integer of 2 to 300.) A-{(OCF(CF 3 )CF 2 ) c -(OCF 2 CF 2 ) d -(OCF 2 ) u’}-OA (4) (In the formula, A is the same as above, c and d each represent an integer of 0 to 300, preferably an integer of 0 to 150, except for the case where both c and d are 0. In addition, u' represents an integer of 1 to 300, preferably an integer of 1 to 150. The respective repeating units may be bonded to each other randomly.) At least one non-functional polyfluoro compound (i.e., a polyfluoro compound that does not contain in the molecule any functional group that can participate in at least a hydrosilylation addition reaction, such as an alkenyl group or a SiH group) selected from the group consisting of compounds represented by the following formula (I) can be blended.

[0099] The above-mentioned component (F) imparts suitable fluidity to the thermally conductive fluorine-containing curable composition and further imparts suitable hardness to the cured product obtained by curing the composition.

[0100] Specific examples of the component (F) include the following: F-(CF 2 CF 2 CF 2 O) i’ -CF 2 CF 3 (i' is an integer from 1 to 200.) CF 3 -{(OCF(CF 3 )CF 2 ) j’ -(OCF 2 ) k’}-O-CF 3 (j' is an integer from 1 to 200, and k' is an integer from 1 to 200. The repeating units may be bonded randomly.) CF 3 -{(OCF 2 CF 2 ) v’ -(OCF 2 ) w’}-O-CF 3 (v' is an integer of 1 to 200, and w' is an integer of 1 to 200. The repeating units may be bonded randomly.)

[0101] The component (F) may use one type alone, or two or more types in combination. When the above component (F) is blended in the composition, the blending amount is 0.1 to 300 parts by mass, more preferably 0.5 to 250 parts by mass, per 100 parts by mass of the component (A). When the amount is 0.1 part by mass or more, there is no risk of insufficient contribution to the flowability of the thermally conductive fluorine-containing curable composition and the hardness of the cured product obtained by curing the composition. On the other hand, when the amount is 300 parts by mass or less, there is no risk of bleeding from the cured product obtained by curing the thermally conductive fluorine-containing curable composition.

[0102] [(G) component] The thermally conductive fluorine-containing curable composition may further contain, as component (G) (optional component), a polyfluoromonoalkenyl compound having one alkenyl group in one molecule and having a perfluoropolyether structure in the main chain, which may be added as necessary.

[0103] The above component (G) imparts suitable fluidity to the thermally conductive fluorine-containing curable composition and can also impart suitable hardness to the cured product obtained by curing the composition.

[0104] As the component (G), a polyfluoromonoalkenyl compound represented by the following general formula (9) is particularly preferred. Rf-(Y) h -CH=CH 2 (9) [In the formula, Rf is a group represented by the following general formula (10), F-[CF(CF 3 )CF 2 O] i -C j F 2j - (10) (In the formula, i is an integer of 1 to 200, and preferably an integer of 1 to 150, and j is an integer of 1 to 3.) Y is -CH 2 -, -OCH 2 -, -CH 2 OCH 2 -or-CO-NR 15 -Z- (Note that the left end of each of these groups is bonded to Rf and the right end is bonded to a carbon atom. 15 is a hydrogen atom, a methyl group, a phenyl group, or an allyl group, and Z is -CH 2 -, a group represented by the following structural formula (Z) or a group represented by the following structural formula (Z'). [ka] (A dimethylphenylsilylene group represented by the o-position, m-position, or p-position, the left end of which is bonded to a nitrogen atom and the right end of which is bonded to a carbon atom.) [ka] (the left end is bonded to a nitrogen atom and the right end is bonded to a carbon atom) and h is 0 or 1.

[0105] Specific examples of the component (G) include the following: In the following formula, Me represents a methyl group.

[0106] [ka] (wherein l' is an integer from 1 to 200.)

[0107] The component (G) may use one type alone, or two or more types in combination. When the above component (G) is blended in the composition, the blending amount is 0.1 to 100 parts by mass, preferably 0.5 to 80 parts by mass, per 100 parts by mass of component (A). When the blending amount is 0.1 part by mass or more, there is no risk of insufficient contribution to the flowability of the thermally conductive fluorine-containing curable composition and the hardness of the cured product obtained by curing the composition. On the other hand, when the blending amount is 100 parts by mass or less, there is no risk of impairing the mechanical strength of the cured product obtained by curing the thermally conductive fluorine-containing curable composition.

[0108] [Other ingredients] In order to improve the practical utility of the thermally conductive fluorine-containing curable composition, various optional ingredients such as inorganic fillers (other than the ingredient (D)) and addition reaction inhibitors can be added as necessary in addition to the above-mentioned ingredients (A) to (G). The amounts of these ingredients added are arbitrary.

[0109] Examples of inorganic fillers other than component (D) include silica powders such as fumed silica (fumed silica or dry silica), precipitated silica (wet silica), spherical silica (fused silica), sol-gel silica, and silica aerogel; silica powders obtained by treating the surface of such silica powder with various organochlorosilanes, organodisilazanes, cyclic organopolysilazanes, and the like; and silica powders obtained by further treating such surface-treated silica powders with organosilanes or organosiloxanes having a perfluoroalkyl group represented by the above general formula (11) or a perfluorooxyalkyl group represented by the above general formula (12). These include silica-based reinforcing fillers; quartz powder (crystalline silica), fused quartz powder, diatomaceous earth, calcium carbonate, and other reinforcing or semi-reinforcing fillers; and inorganic pigments such as titanium oxide, iron oxide, carbon black, and cobalt aluminate.

[0110] Examples of inhibitors for hydrosilylation addition reactions include acetylenic alcohols such as 1-ethynyl-1-hydroxycyclohexane, 3-methyl-1-butyn-3-ol, 3,5-dimethyl-1-hexyn-3-ol, 3-methyl-1-penten-3-ol, and phenylbutynol; reaction products of chlorosilanes having a perfluoroalkyl group represented by the above general formula (11) or a perfluorooxyalkyl group represented by the above general formula (12) with acetylenic alcohols; 3-methyl-3-penten-1-yne, 3,5-dimethyl-3-hexen-1-yne, triallyl isocyanurate, and the like; polyvinyl siloxane; and organic phosphorus compounds. The addition of these inhibitors makes it possible to maintain appropriate curing reactivity and storage stability.

[0111] The method for producing the thermally conductive fluorine-containing curable composition is not particularly limited, and the composition can be produced by uniformly kneading the above components (A) to (G) and other optional components. However, when the component (E) is added, it is preferable to first knead the components (A), (D) and (E), and further, if necessary, the components (F) and (G), in order to efficiently perform the surface treatment of the component (D) by the component (E), and then knead the component (C), and finally knead the component (B). The other optional components may be kneaded appropriately. The components (D) and (E) may be added all at once or in portions. As the production apparatus, a mixing apparatus such as a planetary mixer, a Ross mixer, or a Hobart mixer, and further, if necessary, a kneading apparatus such as a kneader or a three-roll mixer may be used.

[0112] The thermally conductive fluorine-containing curable composition may be configured as a so-called one-liquid type in which the above components (A) to (G) and other optional components are all handled as one composition, or may be configured as a two-liquid type in which the two are mixed at the time of use.

[0113] The thermally conductive fluorine-containing curable composition is cured by heating to give a cured product having good oil resistance and thermal conductivity. The curing temperature of the composition is not particularly limited, but is usually 20 to 200° C., preferably 40 to 180° C. The curing time in this case may be appropriately selected, but is generally preferably 30 seconds to 5 hours, more preferably 1 minute to 3 hours.

[0114] The thermal conductivity of the cured product obtained by curing the thermally conductive fluorine-containing curable composition is at least 1.0 W / m K, preferably at least 1.2 W / m K, as measured at 25°C by the hot disc method. If it is less than 1.0 W / m K, it may be difficult to apply it to a heating element that generates a large amount of heat.

[0115] The hardness of the cured product obtained by curing the thermally conductive fluorine-containing curable composition, as measured by a type E durometer specified in JIS K6253-3 (so-called Asker E type hardness for soft rubber), is preferably 60 or less, more preferably 50 or less, and more preferably 1 or more. If it is 60 or less, it can deform to fit the shape of the heat-dissipating body and exhibit good thermal conductivity without applying stress to the heat-dissipating body.

[0116] [Manufacturing method for thermally conductive sheet products] Examples of methods for producing the thermally conductive sheet product of the present invention include a press molding method in which the electrically insulating film is laid on a gold plate, a sheet mold is placed on top of it, the above-mentioned thermally conductive fluorine-containing curable composition is charged, the electrically insulating film and then the gold plate are placed on top of it, and the set is heated and pressed with a heating press to cure the composition into a sheet form, thereby obtaining the thermally conductive sheet product of the present invention; and a continuous molding method in which the thermally conductive fluorine-containing curable composition is discharged onto a long piece of the electrically insulating film, coated to a constant thickness using a knife coater or a comma coater, etc., then heat-cured, and further the electrically insulating film is attached onto the cured product using a laminating roll or the like, thereby obtaining the thermally conductive sheet product of the present invention.

[0117] The press pressure in the press molding method is not particularly limited and can be appropriately selected, but if it is too low or too high, the thermally conductive fluorine-containing curable composition may not be cured to a desired thickness, so the pressure is preferably 0.1 to 100 MPa, more preferably 1 to 50 MPa.

[0118] The heating temperature during pressing in the press molding method is the same as the curing temperature of the thermally conductive fluorine-containing curable composition described above. The pressing time is the same as the curing time of the thermally conductive fluorine-containing curable composition described above. The thermally conductive sheet product after press molding may be left in an oven at the above curing temperature for post-curing.

[0119] On the other hand, in the continuous molding method, the thermally conductive fluorine-containing curable composition is continuously applied to the electrically insulating film at a constant thickness using a conventional coating device such as a knife coater, comma coater, or kiss coater equipped with a heating furnace and a winding device, and then the composition is heated and cured through a heating furnace. The curing temperature and curing time at this time are the same as those of the thermally conductive fluorine-containing curable composition described above. Then, the electrically insulating film is attached to the thermally conductive sheet made of the cured product of the thermally conductive fluorine-containing curable composition using a laminating roll or the like. The thermally conductive sheet may be left in an oven at the above curing temperature for post-curing, and then the electrically insulating film may be attached thereon. Alternatively, the electrically insulating film may be attached to the thermally conductive sheet, and then left in an oven at the above curing temperature for post-curing.

[0120] In the continuous molding method, the thermally conductive fluorine-containing curable composition may be diluted with an appropriate solvent, for example, an organic solvent such as toluene, acetone, or methyl ethyl ketone, or a fluorine-based solvent such as 1,3-bis(trifluoromethyl)benzene, Fluorinert (manufactured by 3M), perfluorobutyl methyl ether, or perfluorobutyl ethyl ether, for the purpose of adjusting the coating workability or coating amount on the electrical insulating film.

[0121] In the thermally conductive sheet product of the present invention thus produced, the thermally conductive sheet made of the cured product obtained by curing the above-mentioned thermally conductive fluorine-containing curable composition has a thickness of preferably 0.1 to 10 mm, more preferably 0.5 to 5 mm. Furthermore, the thermally conductive sheet product of the present invention thus produced may be cut to a desired size, if necessary.

[0122] The thermally conductive sheet product of the present invention has good thermal conductivity, and is therefore suitable as a heat transfer member for transferring heat from a heat generating component, such as a semiconductor such as a CPU, an LSI, or an IGBT, to a heat dissipation component such as a heat sink, and dissipating the heat. Furthermore, since the thermally conductive sheet product of the present invention has good oil resistance, it can be used in an environment exposed to automotive oils such as ATF and CVTF, and is therefore suitable as a heat transfer member for use in LED headlamps and ECUs, as well as in on-board electric and electronic components such as batteries, motors, and converters of next-generation automobiles such as hybrid cars and electric automobiles. In addition, the thermally conductive sheet product of the present invention has an electrically insulating film attached to both sides of the thermally conductive sheet, so that the thermally conductive sheet is protected from foreign matter, and can be processed as it is by press molding, and has excellent workability for interposing between a heat generating component and a heat dissipation component. EXAMPLES

[0123] The present invention will be specifically described below with reference to examples, comparative examples, and reference examples, but the present invention is not limited to the following examples. The viscosity of the following component (A) is the measured value at 23°C as specified in JIS K7117-1. The amount of vinyl groups in component (A) was measured by infrared spectroscopy (IR) using a calibration curve. The amount of SiH groups in component (B) was measured by proton nuclear magnetic resonance spectroscopy ( 1 The average particle size of the following component (D) was measured by a particle size distribution analyzer MT3000II manufactured by Microtrack Bell Co., Ltd., and was determined as a cumulative 50% particle size (D 50 ) value.

[0124] Components (A) to (G) and compounds serving as inhibitors for hydrosilylation addition reactions used in the following Examples, Comparative Examples, and Reference Examples are shown below, in which Me represents a methyl group. (A) Component: (A-1) A linear polyfluoro compound represented by the following formula (23) (viscosity 10,900 mPa s, vinyl group content 0.0122 mol / 100 g) [ka] (where m' and n' are integers of 1 or greater, and the average of m'+n' is 90.) (A-2) A linear polyfluoro compound represented by the following formula (24) (viscosity 11,000 mPa s, vinyl group content 0.0122 mol / 100 g) [ka] (where o' and p' are integers equal to or greater than 1, and the average of o'+p' is 90.)

[0125] (B) Ingredients: (B-1) Fluorine-containing organohydrogensiloxane represented by the following formula (25) (SiH group amount 0.394 mol / 100 g) [ka] (B-2) Fluorine-containing organohydrogensiloxane represented by the following formula (26) (SiH group amount 0.0615 mol / 100 g) [ka] (However, the average value of a” is 24.)

[0126] (C) Ingredients: (C-1) Toluene solution of platinum-divinyltetramethyldisiloxane complex (platinum concentration 0.5% by mass)

[0127] (D) Ingredients: Irregular alumina and spherical alumina having average particle sizes as follows: (D-1) Irregular alumina with an average particle size of 1 μm (D-2) Spherical alumina with an average particle size of 10 μm (D-3) Spherical alumina with an average particle size of 45 μm (D-4) Spherical alumina with an average particle size of 70 μm

[0128] (E) Ingredients: (E-1) A fluorine-containing organosilicon compound represented by the following formula (27): [ka] (However, the average value of b” is 24.) (E-2) A fluorine-containing organosilicon compound represented by the following formula (28): [ka]

[0129] (F) Ingredients: (F-1) A non-functional polyfluoro compound represented by the following formula (29): F-(CF 2 CF 2 CF 2 O) x’ -CF 2 CF 3 (29) (However, the average value of x' is 30.) (F-2) A non-functional polyfluoro compound represented by the following formula (30): CF 3 -(OCF(CF 3 )CF 2 ) y’ -OCF 2 -O-CF 3 (30) (However, the average value of y' is 17.)

[0130] (G) Ingredients: (G-1) A polyfluoromonoalkenyl compound represented by the following formula (31) (vinyl group amount: 0.0239 mol / 100 g) [ka] (However, the average value of z' is 24.)

[0131] Control agents for hydrosilylation addition reactions: A compound represented by the following formula (32): [ka]

[0132] Compositions 1 to 5 were prepared as described below using the above components (A) to (G) and the compound represented by formula (32) in the prescribed amounts shown in Tables 1 and 2 below, and were molded and cured. The thermal conductivity and hardness of the cured products were measured according to the methods described below. The results are shown in Tables 1 and 2 below. Furthermore, the ATF durability of the cured products was measured according to the method described below. The results are shown in Tables 3 and 4 below.

[0133] [Preparation of Composition] First, the components (A), (D), (E), (F) and (G) were kneaded for 1 hour using a planetary mixer in the amounts shown in Tables 1 and 2 below. Next, the component (C) and the compound represented by the above formula (32) were added in the amounts shown in Tables 1 and 2 below and kneaded for 30 minutes. Finally, the component (B) was added in the amount shown in Tables 1 and 2 below and kneaded for 30 minutes to obtain compositions 1 to 5.

[0134] [Preparation of cured product] On the gold plate, a 100 μm thick PET film that has been surface-treated with a fluorine-containing silicone release agent X-70-201S (manufactured by Shin-Etsu Chemical Co., Ltd.) is placed with the surface-treated surface facing up, then a mold made of a 60 mm × 60 mm × 6 mm frame is placed on the PET film, and each composition of compositions 1 to 5 obtained as described above is poured into the mold so as to fill the inside of the mold, and the same PET film as above is placed on top of it with the surface-treated surface facing down, then a gold plate is placed, and this laminated set is press-heated at 120 ° C. × 10 minutes at a pressure of 10 MPa in a heat press molding machine. Then, the upper and lower gold plates are removed from this set, and a single-edged blade is inserted into the mold frame to cut out a sheet-like cured product with PET film attached on both sides of 60 mm × 60 mm × 6 mm thickness, and the PET film on both sides is peeled off to obtain a sheet-like cured product with a thickness of 6 mm.

[0135] [Thermal conductivity of the cured product] Using two of the above 6 mm-thick sheet-like cured products, the thermal conductivity at 25° C. was measured by the hot disk method using a thermal property measuring device TPS2500S (manufactured by Kyoto Electronics Manufacturing Co., Ltd.).

[0136] [Hardness of cured product] Two sheets of the above 6 mm thick cured product were stacked together and measured using a type E durometer in accordance with JIS K6253-3.

[0137] [Durability of hardened ATF (automotive oil)] The above 6 mm thick sheet-like cured product was immersed in automotive oil ATF WS3324 manufactured by Toyota Motor Corporation at 150° C. for 1,000 hours, and then the thermal conductivity was measured in the same manner as above.

[0138] [Table 1]

[0139] [Table 2]

[0140] [Table 3]

[0141] [Table 4]

[0142] [Press formability of thermally conductive sheet products (1)] [Example 1] A PET film with a thickness of 100 μm was placed on the gold plate, and then a mold consisting of a 13 mm × 13 mm × 1 mm frame was placed on the PET film, and the composition 1 described in Table 1 above was poured so as to fill the inside of the frame, and the same PET film as above was placed on top of it, and then a gold plate was placed, and this laminated set was press-heated at 120 ° C × 10 minutes at a pressure of 10 MPa in a hot press molding machine. Then, the upper and lower gold plates were removed from this set, and a single-edged blade was inserted into the mold frame to cut it out, thereby obtaining a thermally conductive sheet product of 13 mm × 13 mm × 1.2 mm in which the PET film was attached to both sides of the thermally conductive sheet. The obtained thermally conductive sheet product is shown in FIG. 1.

[0143] [Example 2] In Example 1, except that composition 1 was changed to composition 2 shown in Table 1 above, press molding was performed in the same manner as in Example 1, and a thermally conductive sheet product having the PET film attached to both sides of the thermally conductive sheet was obtained.

[0144] [Example 3] In Example 1, composition 1 was changed to composition 2 shown in Table 1 above, and the 100 μm PET film placed on the composition was changed to a 100 μm PET film surface-treated with a fluorine-containing silicone release agent X-70-201S (manufactured by Shin-Etsu Chemical Co., Ltd.). Except for this, press molding was performed in the same manner as in Example 1, and a thermally conductive sheet product was obtained in which a PET film was attached to the lower surface (one side) of the thermally conductive sheet and a PET film surface-treated with a fluorine-containing silicone release agent X-70-201S was attached to the upper surface (one side). The obtained thermally conductive sheet product is shown in FIG. 2.

[0145] [Example 4] In Example 1, composition 1 was changed to composition 3 shown in Table 1 above, and the 100 μm PET films placed above and below the composition were changed to 100 μm PET films surface-treated with fluorine-containing silicone release agent X-70-201S (manufactured by Shin-Etsu Chemical Co., Ltd.). Except for this, press molding was performed in the same manner as in Example 1, and a thermally conductive sheet product was obtained in which PET films surface-treated with fluorine-containing silicone release agent X-70-201S were attached to both sides of the thermally conductive sheet. The thermally conductive sheet product obtained is shown in FIG. 3.

[0146] [Example 5] In Example 1, composition 1 was changed to composition 4 shown in Table 1 above, and the 100 μm PET film placed under the composition was changed to a 100 μm PET film that had been surface-treated with a fluorine-containing silicone release agent X-70-220S (manufactured by Shin-Etsu Chemical Co., Ltd.). Except for this, press molding was performed in the same manner as in Example 1, and a thermally conductive sheet product was obtained in which a PET film that had been surface-treated with a fluorine-containing silicone release agent X-70-220S was attached to the bottom surface (one side) of the thermally conductive sheet and a PET film was attached to the top surface (one side).

[0147] [Example 6] In Example 1, composition 1 was changed to composition 5 shown in Table 1 above, and the 100 μm PET films placed above and below the composition were changed to 100 μm PET films surface-treated with fluorine-containing silicone release agent X-70-220S (manufactured by Shin-Etsu Chemical Co., Ltd.). Except for this, press molding was performed in the same manner as in Example 1, and a thermally conductive sheet product was obtained in which PET films surface-treated with fluorine-containing silicone release agent X-70-220S were attached to both sides of the thermally conductive sheet.

[0148] [Comparative Example 1] When press molding was performed in the same manner as in Example 1, except that PET films were not placed on the top and bottom of Composition 1, the thermally conductive sheet made of the cured product of Composition 1 adhered to the top and bottom metal plates. When the thermally conductive sheet was slowly peeled off from the gold plate, it was partially deformed and the thickness was partially uneven.

[0149] [Comparative Example 2] When press molding was performed in the same manner as in Example 2, except that PET films were not placed on the top and bottom of Composition 2, the thermally conductive sheet made of the cured product of Composition 2 adhered to the top and bottom metal plates. When the thermally conductive sheet was slowly peeled off from the gold plate, it was partially deformed and the thickness was partially uneven.

[0150] [Comparative Example 3] When press molding was performed in the same manner as in Example 4, except that PET films surface-treated with the fluorine-containing silicone release agent X-70-201S were not placed on the top and bottom of Composition 3, the thermally conductive sheet made of the cured product of Composition 3 ended up adhering to the gold plate. When the thermally conductive sheet was slowly peeled off from the gold plate, it was partially deformed and the thickness was also partially uneven.

[0151] [Comparative Example 4] In Example 5, press molding was performed in the same manner as in Example 5, except that the PET film surface-treated with the fluorine-containing silicone release agent X-70-220S was not placed under Composition 4, and no PET film was placed on top of that, and the thermally conductive sheet made of Composition 4 ended up adhering to the gold plate. The thermally conductive sheet was strongly attached to the gold plate, and was partially broken when peeled off from the gold plate.

[0152] [Comparative Example 5] In Example 6, press molding was performed in the same manner as in Example 6, except that PET films surface-treated with the fluorine-containing silicone release agent X-70-220S were not placed on the top and bottom of Composition 5. As a result, the thermally conductive sheet made of Composition 5 adhered to the gold plate. The thermally conductive sheet adhered strongly to the gold plate and broke partially when peeled off from the gold plate.

[0153] [Foreign matter adhesion to thermally conductive sheet products manufactured using the continuous molding method] [Example 7] Composition 1 described in Table 1 above was continuously applied to a 100 μm thick PET film using a multi-coater to a thickness of 1 mm, and then heated in a heating furnace at 120 ° C. for 10 minutes to form a thermally conductive sheet of 1 mm thickness on the PET film. Next, a laminate roll was used to attach a PET film onto the thermally conductive sheet, thereby obtaining a thermally conductive sheet product in which a PET film was attached to both sides of the thermally conductive sheet. After sprinkling metal powder with a diameter of 0.3 mm on the PET film surface of this thermally conductive sheet product, the thermally conductive sheet product was inverted 180 ° so that the PET film surface on the side where the metal powder was sprinkled was facing downward. Thereafter, the PET film surface was visually observed, and the foreign matter adhesion of the thermally conductive sheet product was evaluated by rating those without metal powder as "○" (foreign matter does not easily adhere) and those with metal powder as "×" (foreign matter easily adheres). The evaluation results were "○" on both sides.

[0154] [Example 8] In Example 7, except that composition 1 was changed to composition 2 shown in Table 1 above, continuous molding was performed in the same manner as in Example 7, and a thermally conductive sheet product having PET films attached to both sides of the thermally conductive sheet was obtained. The evaluation result of the foreign matter adhesion was "○" on both sides.

[0155] [Example 9] In Example 7, composition 1 was changed to composition 2 shown in Table 1 above, and the PET film to which composition 2 was applied was changed to a 100 μm thick PET film surface-treated with fluorine-containing silicone release agent X-70-201S. Except for this, continuous molding was performed in the same manner as in Example 7, and a thermally conductive sheet product was obtained in which a PET film surface-treated with fluorine-containing silicone release agent X-70-201S was attached to the lower surface (one side) of the thermally conductive sheet, and a PET film was attached to the upper surface (one side). The evaluation result of the foreign matter adhesion was "○" on both sides.

[0156] [Example 10] In Example 7, composition 1 was changed to composition 3 shown in Table 1 above, and the PET film to be applied to the thermally conductive sheet consisting of the PET film to which composition 3 was applied and the cured product of composition 3 was changed to a 100 μm thick PET film surface-treated with fluorine-containing silicone release agent X-70-201S. Except for this, continuous molding was performed in the same manner as in Example 7, and a thermally conductive sheet product was obtained in which the PET film surface-treated with fluorine-containing silicone release agent X-70-201S was attached to both sides of the thermally conductive sheet. The evaluation result of the foreign matter adhesion was "○" on both sides.

[0157] [Example 11] In Example 7, composition 1 was changed to composition 4 in Table 1 above, and the PET film to which composition 4 was applied was changed to a 100 μm thick PET film surface-treated with fluorine-containing silicone release agent X-70-220S. Continuous molding was performed in the same manner as in Example 7, and a thermally conductive sheet product was obtained in which a PET film surface-treated with fluorine-containing silicone release agent X-70-220S was attached to the lower surface (one side) of the thermally conductive sheet and a PET film was attached to the upper surface (one side). The evaluation result of the foreign matter adhesion was "○" on both sides.

[0158] [Example 12] In Example 7, composition 1 was changed to composition 5 shown in Table 1 above, and the PET film to be applied to the thermally conductive sheet consisting of the PET film to which composition 5 was applied and the cured product of composition 5 was changed to a 100 μm thick PET film surface-treated with fluorine-containing silicone release agent X-70-220S. Except for this, continuous molding was performed in the same manner as in Example 7, and a thermally conductive sheet product was obtained in which a PET film surface-treated with fluorine-containing silicone release agent X-70-220S was attached to both sides of the thermally conductive sheet. The evaluation result of the foreign matter adhesion was "○" on both sides.

[0159] [Comparative Example 6] In Example 7, continuous molding was performed in the same manner as in Example 7, except that the PET film was not attached to the thermally conductive sheet using a laminating roll, and a thermally conductive sheet product was obtained in which the PET film was attached only to the lower surface of the thermally conductive sheet. The evaluation result of the foreign matter adhesion was "○" for the surface to which the PET film was attached, but "×" for the surface to which the PET film was not attached (the surface of the thermally conductive sheet itself).

[0160] [Comparative Example 7] In Example 8, continuous molding was performed in the same manner as in Example 8, except that the PET film was not attached to the thermally conductive sheet using a laminating roll, and a thermally conductive sheet product was obtained in which the PET film was attached only to the lower surface of the thermally conductive sheet. The evaluation result of the foreign matter adhesion was "○" for the surface to which the PET film was attached, but "×" for the surface to which the PET film was not attached (the surface of the thermally conductive sheet itself).

[0161] [Comparative Example 8] In Example 9, continuous molding was performed in the same manner as in Example 9, except that the PET film was not attached to the thermally conductive sheet using a laminating roll, and a thermally conductive sheet product was obtained in which a PET film surface-treated with a fluorine-containing silicone release agent X-70-201S was attached only to the lower surface of the thermally conductive sheet. The evaluation result of the foreign matter adhesion was "○" for the surface to which the PET film was attached, but "×" for the surface to which the PET film was not attached (the surface of the thermally conductive sheet itself).

[0162] [Comparative Example 9] In Example 10, a continuous molding was performed in the same manner as in Example 10, except that the PET film surface-treated with the fluorine-containing silicone release agent X-70-201S was not attached to the thermally conductive sheet using a laminating roll, and a thermally conductive sheet product was obtained in which the PET film surface-treated with the fluorine-containing silicone release agent X-70-201S was attached only to the lower surface of the thermally conductive sheet. The evaluation result of the foreign matter adhesion was "○" for the surface to which the PET film was attached, but "×" for the surface to which the PET film was not attached (the surface of the thermally conductive sheet itself).

[0163] [Comparative Example 10] In Example 11, continuous molding was performed in the same manner as in Example 11, except that the PET film was not attached to the thermally conductive sheet using a laminating roll, and a thermally conductive sheet product was obtained in which a PET film surface-treated with a fluorine-containing silicone release agent X-70-220S was attached only to the lower surface of the thermally conductive sheet. The evaluation result of the foreign matter adhesion was "○" for the surface to which the PET film was attached, but "×" for the surface to which the PET film was not attached (the surface of the thermally conductive sheet itself).

[0164] [Comparative Example 11] In Example 12, continuous molding was performed in the same manner as in Example 12, except that the PET film surface-treated with the fluorine-containing silicone release agent X-70-220S was not attached to the thermally conductive sheet using a laminating roll, and a thermally conductive sheet product was obtained in which the PET film surface-treated with the fluorine-containing silicone release agent X-70-220S was attached only to the lower surface of the thermally conductive sheet. The evaluation result of the foreign matter adhesion was "○" for the surface to which the PET film was attached, but "×" for the surface to which the PET film was not attached (the surface of the thermally conductive sheet itself).

[0165] [Removability of film from thermally conductive sheet (1)] [Example 13] In Example 4, when the PET film that was surface-treated with the fluorine-containing silicone release agent X-70-201S attached to both sides of the thermal conductive sheet was peeled off by hand, if it was easy to peel off and the thermal conductive sheet did not adhere to the film, it was rated as "○", and if it was peelable but the thermal conductive sheet adhered to the film, it was rated as "×" to evaluate the peelability of the film from the thermal conductive sheet. The peelability of the PET film that was surface-treated with the fluorine-containing silicone release agent X-70-201S was "○".

[0166] [Example 14] In Example 6, the releasability of the PET films that were surface-treated with the fluorine-containing silicone release agent X-70-220S and attached to both sides of the thermally conductive sheet was rated "good."

[0167] [Reference example 1] In Example 1, the releasability of the PET films attached to both sides of the thermally conductive sheet was rated "x".

[0168] [Reference example 2] In Example 2, the releasability of the PET films attached to both sides of the thermally conductive sheet was rated "x".

[0169] [Reference example 3] In Example 3, the releasability of the PET film attached to the bottom surface (one side) of the thermal conductive sheet was rated as “x”, while the releasability of the PET film that was surface-treated with the fluorine-containing silicone release agent X-70-201S and attached to the top surface (one side) was rated as “○”.

[0170] [Reference example 4] In Example 5, the releasability of the PET film that was surface-treated with the fluorine-containing silicone release agent X-70-220S and attached to the bottom surface (one side) of the thermally conductive sheet was rated as "○", while the releasability of the PET film that was attached to the top surface (one side) was rated as "×".

[0171] [Press formability of thermally conductive sheet products (2)] [Example 15] In Example 1, except that the 100 μm thick PET film was changed to a 100 μm thick polyethylene film, press molding was performed in the same manner as in Example 1, and a thermally conductive sheet product was obtained in which the polyethylene film was attached to both sides of the thermally conductive sheet.

[0172] [Example 16] In Example 1, except that the 100 μm thick PET film was changed to a 100 μm thick poly(4-methyl-1-pentene) film, press molding was performed in the same manner as in Example 1, and a thermally conductive sheet product was obtained in which the poly(4-methyl-1-pentene) film was attached to both sides of the thermally conductive sheet.

[0173] [Example 17] In Example 1, except that the 100 μm thick PET film was changed to a 100 μm thick polytetrafluoroethylene film, press molding was performed in the same manner as in Example 1, and a thermally conductive sheet product was obtained in which the polytetrafluoroethylene film was attached to both sides of the thermally conductive sheet.

[0174] [Example 18] In Example 2, except that the 100 μm thick PET film was changed to a 100 μm thick polyethylene film, press molding was performed in the same manner as in Example 2, and a thermally conductive sheet product was obtained in which the polyethylene film was attached to both sides of the thermally conductive sheet.

[0175] [Example 19] In Example 2, except that the 100 μm thick PET film was changed to a 100 μm thick poly(4-methyl-1-pentene) film, press molding was performed in the same manner as in Example 2, and a thermally conductive sheet product was obtained in which the poly(4-methyl-1-pentene) film was attached to both sides of the thermally conductive sheet.

[0176] [Example 20] In Example 2, except that the 100 μm thick PET film was changed to a 100 μm thick polytetrafluoroethylene film, press molding was performed in the same manner as in Example 2, and a thermally conductive sheet product was obtained in which the polytetrafluoroethylene film was attached to both sides of the thermally conductive sheet.

[0177] [Removability of film from thermally conductive sheet (2)] [Reference example 5] In Example 15, the peelability of the polyethylene films attached to both sides of the thermally conductive sheet was rated "x".

[0178] [Reference example 6] In Example 16, the releasability of the poly(4-methyl-1-pentene) films attached to both sides of the thermally conductive sheet was rated "x".

[0179] [Reference example 7] In Example 17, the releasability of the polytetrafluoroethylene films attached to both sides of the thermally conductive sheet was rated "x".

[0180] [Reference example 8] In Example 18, the peelability of the polyethylene films attached to both sides of the thermally conductive sheet was rated "x".

[0181] [Reference example 9] In Example 19, the releasability of the poly(4-methyl-1-pentene) films attached to both sides of the thermally conductive sheet was rated "x".

[0182] [Reference example 10] In Example 20, the releasability of the polytetrafluoroethylene films attached to both sides of the thermally conductive sheet was rated "x".

[0183] In Tables 1 and 2, the thermal conductivity at 25°C of the cured products obtained by curing Compositions 1 to 5, which are thermally conductive fluorine-containing curable compositions, was 1.0 W / m K or more. Furthermore, the hardness of the cured products was 60 or less in type E durometer. Furthermore, in Tables 3 and 4, the thermal conductivity at 25° C. of the cured product obtained by curing the thermally conductive fluorine-containing curable composition did not change before and after immersion in ATF. From the above results, the cured product obtained by curing the thermally conductive fluorine-containing curable composition has excellent oil resistance and thermal conductivity and is suitable as a heat transfer member for electric and electronic parts, particularly for in-vehicle electric and electronic parts.

[0184] The thermally conductive sheet products of Examples 1 to 6 and Examples 15 to 20 of the present invention were produced by press molding, and had no problems with press moldability. On the other hand, in Comparative Examples 1 to 5, the thermally conductive sheet adhered to the gold plate when press-molded, and when an attempt was made to peel it off from the gold plate, the thermally conductive sheet deformed, causing uneven thickness or breaking.

[0185] The thermally conductive sheet products of Examples 7 to 12 of the present invention were produced by a continuous molding method, and no foreign matter was attached to them. On the other hand, the thermally conductive sheet products of Comparative Examples 6 to 11 were produced by a continuous molding method, but had the problem of foreign matter adhering to the surface to which no film was attached (the surface of the thermally conductive sheet itself).

[0186] Furthermore, in the thermally conductive sheet products of Examples 13 and 14 of the present invention, the PET film that had been surface-treated with the fluorine-containing silicone release agent X-70-201S or X-70-220S could be easily peeled off from the thermally conductive sheet, and the thermally conductive sheet did not adhere to the peeled film. On the other hand, in the thermally conductive sheet products of Examples 1 to 3 and 5 and Examples 15 to 20, when the films that were not surface-treated with a fluorine-containing silicone release agent such as the fluorine-containing silicone release agent X-70-201S or X-70-220S were peeled off from the thermally conductive sheet, the thermally conductive sheet adhered to the film, but these thermally conductive sheet products can be interposed between a heat-generating component and a heat-dissipating component without peeling off the film.

[0187] From the above results, the thermally conductive sheet product of the present invention has an electrically insulating film attached to both sides of a thermally conductive sheet made of a cured product having excellent oil resistance and thermal conductivity, can be manufactured by a press molding method, and does not have the problem of the thermally conductive sheet adhering to the metal plate, so that even when it is interposed between a heat-generating component and a heat-dissipating component, it does not adhere to the component and has good interposition workability. Furthermore, the thermally conductive sheet can be protected from foreign matter, etc. Therefore, the thermally conductive sheet product of the present invention is suitable as a heat transfer member for electric and electronic components, particularly for electric and electronic components for vehicles.

[0188] The present invention is not limited to the above-described embodiment. The above-described embodiment is merely an example, and anything that has substantially the same configuration as the technical idea described in the claims of the present invention and exhibits similar effects is included in the technical scope of the present invention. [Explanation of symbols]

[0189] 1. Thermally conductive sheet products 2...Electrical insulating film 3…Thermal conductive sheet 4...Fluorine-containing silicone release agent layer 1'…Thermal conductive sheet products 1''...Thermal conductive sheet products

Claims

1. (A) a linear polyfluoro compound having two or more alkenyl groups in one molecule and having a perfluoropolyether structure in the main chain: 100 parts by mass, (B) a fluorine-containing organohydrogensiloxane having in one molecule one or more groups selected from a perfluoroalkyl group, a perfluorooxyalkyl group, a perfluoroalkylene group, and a perfluorooxyalkylene group, and further having two or more hydrogen atoms (SiH groups) directly bonded to silicon atoms, and having no alkoxy groups directly bonded to silicon atoms in the molecule: an amount such that the number of hydrogen atoms directly bonded to silicon atoms in component (B) is 0.50 to 3.0 moles per mole of alkenyl groups contained in the entire composition, (C) a platinum group metal catalyst: 0.1 to 2,000 ppm by mass of platinum group metal atoms relative to the component (A), and (D) Thermally conductive filler: 100 to 4,000 parts by mass A thermally conductive sheet product comprising a thermally conductive sheet made of a cured product of a thermally conductive fluorine-containing curable composition containing the above-mentioned formula (1), and at least one electrically insulating film selected from the group consisting of polyolefin, polyimide, polyamide, polyester, aromatic polyether ketone, polyvinyl chloride, and paper, attached to both sides of the thermally conductive sheet.

2. 2. The thermally conductive sheet product according to claim 1, wherein the electrically insulating film has a thickness of 1 to 200 μm.

3. 2. The thermally conductive sheet product according to claim 1, wherein the electrically insulating film is a polyethylene terephthalate (PET) film.

4. The thermally conductive sheet product according to any one of claims 1 to 3, wherein at least one of the electrically insulating films has a surface that contacts the thermally conductive sheet and is treated with a fluorine-containing silicone release agent.

5. 5. The thermally conductive sheet product according to claim 4, wherein the fluorine-containing silicone release agent is an organopolysiloxane having at least one perfluoroalkyl group or perfluorooxyalkyl group.

6. 6. The thermally conductive sheet product according to claim 5, wherein the perfluoroalkyl group or the perfluorooxyalkyl group is represented by the following general formula (1) or (2): C f'' F 2f''+1 - (1) (In the formula, f″ is an integer from 1 to 10.) 【Chemistry 1】 (In the formula, g″ is an integer from 1 to 30.)

7. 4. The thermally conductive fluorine-containing curable composition according to any one of claims 1 to 3, further comprising, as component (E), 0.01 to 300 parts by mass of a fluorine-containing organosilicon compound having in one molecule one or more perfluoroalkyl groups or perfluorooxyalkyl groups and further one or more alkoxy groups directly bonded to a silicon atom, and having no hydrogen atoms (SiH groups) directly bonded to silicon atoms in the molecule, per 100 parts by mass of component (A).

8. In the thermally conductive fluorine-containing curable composition, the component (F) further comprises a compound represented by the following general formula (3) and the following general formula (4): F-(CF 2 CF 2 CF 2 O) a -A (3) (Wherein, A is -C b F 2b+1 (b is an integer of 1 to 3), and a is an integer of 1 to 500.) A-{(OCF(CF 3 )CF 2 ) c -(OCF 2 CF 2 ) d -(OCF 2 ) u’ }-O-A (4) (In the formula, A is the same as above, c and d each represent an integer of 0 to 300, and u′ represents an integer of 1 to 300, except for the case where both c and d are 0.) The repeating units may be bonded randomly. The thermally conductive sheet product according to any one of claims 1 to 3, wherein the thermally conductive sheet product contains 0.1 to 300 parts by mass of at least one non-functional polyfluoro compound selected from the group consisting of compounds represented by the formula:

9. The thermally conductive sheet product according to any one of claims 1 to 3, wherein the thermally conductive fluorine-containing curable composition further contains, as component (G), 0.1 to 100 parts by mass of a polyfluoromonoalkenyl compound having one alkenyl group in one molecule and having a perfluoropolyether structure in the main chain, per 100 parts by mass of component (A).

10. The thermally conductive sheet product according to any one of claims 1 to 3, wherein the alkenyl group content of the component (A) is 0.0050 to 0.300 mol / 100 g.

11. The perfluoropolyether structure of the component (A) is represented by the following general formula (5): -(C m F 2m O) n - (5) (In the formula, m is an integer from 1 to 6, and n is an integer from 1 to 300.) The thermally conductive sheet product according to any one of claims 1 to 3, comprising a structure represented by:

12. The component (A) is represented by the following general formula (6) and the following general formula (7): 【Chemistry 2】 (In the formula, R 1 and R 2 are each independently an alkenyl group or an unsubstituted or substituted monovalent hydrocarbon group having no aliphatic unsaturated bonds, R 1 and R 2 Of the total, at least two are alkenyl groups. 3 are each independently a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group, e and f are each an integer of 1 to 150, the average value of e+f is 2 to 300, and g is an integer of 1 to 6. 【Chemistry 3】 (In the formula, R 4 are each independently an alkylene group having 1 to 6 carbon atoms; R 5 are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms which may be substituted with fluorine. 1 , R 2 , e, f and g are the same as above.) The thermally conductive sheet product according to any one of claims 1 to 3, wherein the linear polyfluoro compound is one or more kinds selected from the group consisting of:

13. The thermally conductive sheet product according to any one of claims 1 to 3, wherein the component (D) is at least one selected from the group consisting of metals, metal oxides, metal nitrides, metal hydroxides, metal carbides, soft magnetic alloys, and ferrites.

14. 14. The thermally conductive sheet product according to claim 13, wherein the component (D) is alumina.

15. 15. The thermally conductive sheet product according to claim 14, wherein the component (D) is amorphous alumina and / or spherical alumina.

16. 16. The thermally conductive sheet product according to claim 15, wherein the average particle size of the amorphous alumina of the component (D) is 0.2 to 5 μm.

17. 16. The thermally conductive sheet product according to claim 15, wherein the average particle size of the spherical alumina of component (D) is 5 to 100 μm.

18. 8. The thermally conductive sheet product according to claim 7, wherein the component (E) is a fluorine-containing organosilicon compound having, in one molecule, one or more perfluoroalkyl or perfluorooxyalkyl groups bonded to a silicon atom to which an alkoxy group is directly bonded, via a divalent hydrocarbon group which may contain a carbon atom, a silicon atom, an oxygen atom, and a nitrogen atom.

19. The component (E) is represented by the following general formula (8): D g’ R 14 h’ Si(OR 6 ) 4-g’-h’ (8) (In the formula, each D is independently a perfluoroalkyl group or a perfluorooxyalkyl group bonded to a silicon atom to which an alkoxy group is directly bonded via a divalent hydrocarbon group which may contain a carbon atom, a silicon atom, an oxygen atom, and a nitrogen atom; R 6 are each independently an alkyl group having 1 to 6 carbon atoms; R 14 are each independently an unsubstituted or substituted monovalent hydrocarbon group; g' is an integer of 1 to 3, h' is an integer of 0 to 2, and g'+h' is an integer of 1 to 3.

8. The thermally conductive sheet product according to claim 7, which is a fluorine-containing organosilicon compound represented by the formula:

20. The component (G) is represented by the following general formula (9): Rf-(Y) h -CH=CH 2 (9) [In the formula, Rf is a group represented by the following general formula (10), F-[CF(CF 3 )CF 2 O] i -C j F 2j - (10) (In the formula, i is an integer from 1 to 200, and j is an integer from 1 to 3.) Y is -CH 2 --, --OCH 2 --, --CH 2 OCH 2 -or-CO-NR 15 -Z- (Note that the left end of each of these groups is bonded to Rf and the right end is bonded to a carbon atom. 15 is a hydrogen atom, a methyl group, a phenyl group, or an allyl group, and Z is -CH 2 -, a group represented by the following structural formula (Z) or a group represented by the following structural formula (Z'). 【Chemistry 4】 (A dimethylphenylsilylene group represented by the o-position, m-position, or p-position, the left end of which is bonded to a nitrogen atom and the right end of which is bonded to a carbon atom.) 【Chemistry 5】 (the left end is bonded to a nitrogen atom, and the right end is bonded to a carbon atom.) and h is 0 or 1. The thermally conductive sheet product according to claim 9, which is a polyfluoromonoalkenyl compound represented by the formula:

21. The thermally conductive sheet product according to any one of claims 1 to 3, wherein a cured product obtained by curing the thermally conductive fluorine-containing curable composition has a thermal conductivity of 1.0 W / m K or more at 25°C.

22. The thermally conductive sheet product according to any one of claims 1 to 3, wherein the hardness of a cured product obtained by curing the thermally conductive fluorine-containing curable composition is 60 or less in Type E durometer as specified in JIS K6253-3.

23. (A) a linear polyfluoro compound having two or more alkenyl groups in one molecule and having a perfluoropolyether structure in the main chain: 100 parts by mass, (B) a fluorine-containing organohydrogensiloxane having in one molecule one or more groups selected from a perfluoroalkyl group, a perfluorooxyalkyl group, a perfluoroalkylene group, and a perfluorooxyalkylene group, and further having two or more hydrogen atoms (SiH groups) directly bonded to silicon atoms, and having no alkoxy groups directly bonded to silicon atoms in the molecule: an amount such that the number of hydrogen atoms directly bonded to silicon atoms in component (B) is 0.50 to 3.0 moles per mole of alkenyl groups contained in the entire composition, (C) a platinum group metal catalyst: 0.1 to 2,000 ppm by mass of platinum group metal atoms relative to the component (A), and (D) Thermally conductive filler: 100 to 4,000 parts by mass and an electrically insulating film is attached to both sides of a thermally conductive sheet made of a cured product of a thermally conductive fluorine-containing curable composition containing the compound, and at least one surface of the electrically insulating film that comes into contact with the thermally conductive sheet is treated with a fluorine-containing silicone-based release agent.

24. (A) A compound represented by the following general formula (6) and the following general formula (7): 【Chemistry 6】 (In the formula, R 1 and R 2 are each independently an alkenyl group, or an unsubstituted or substituted monovalent hydrocarbon group having no aliphatic unsaturated bonds, and a total of two or more of R 1 and R 2 are alkenyl groups. R 3 are each independently a hydrogen atom, or an unsubstituted or substituted monovalent hydrocarbon group, e and f are each an integer from 1 to 150, the average value of e+f is 2 to 300, and g is an integer from 1 to 6.) 【Chemistry 7】 (In the formula, R 4 s are each independently an alkylene group having 1 to 6 carbon atoms, and R 5 s are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms which may be substituted by a fluorine atom. R 1 , R 2 , e, f and g are the same as above.) One or more linear polyfluoro compounds selected from the group consisting of: 100 parts by mass, (B) a fluorine-containing organohydrogensiloxane having in one molecule one or more groups selected from a perfluoroalkyl group, a perfluorooxyalkyl group, a perfluoroalkylene group, and a perfluorooxyalkylene group, and further having two or more hydrogen atoms (SiH groups) directly bonded to silicon atoms, and having no alkoxy groups directly bonded to silicon atoms in the molecule: an amount such that the number of hydrogen atoms directly bonded to silicon atoms in component (B) is 0.50 to 3.0 moles per mole of alkenyl groups contained in the entire composition, (C) a platinum group metal catalyst: 0.1 to 2,000 ppm by mass of platinum group metal atoms relative to the component (A), and (D) Thermally conductive filler: 100 to 4,000 parts by mass A thermally conductive sheet product comprising a thermally conductive sheet made of a cured product of a thermally conductive fluorine-containing curable composition containing the above-mentioned compound and an electrically insulating film attached to both sides of the thermally conductive sheet.

25. (A) a linear polyfluoro compound having two or more alkenyl groups in one molecule and having a perfluoropolyether structure in the main chain: 100 parts by mass, (B) a fluorine-containing organohydrogensiloxane having in one molecule one or more groups selected from a perfluoroalkyl group, a perfluorooxyalkyl group, a perfluoroalkylene group, and a perfluorooxyalkylene group, and further having two or more hydrogen atoms (SiH groups) directly bonded to silicon atoms, and having no alkoxy groups directly bonded to silicon atoms in the molecule: an amount such that the number of hydrogen atoms directly bonded to silicon atoms in component (B) is 0.50 to 3.0 moles per mole of alkenyl groups contained in the entire composition, (C) a platinum group metal catalyst: 0.1 to 2,000 ppm by mass of platinum group metal atoms relative to the component (A), and (D) Thermally conductive filler: 100 to 4,000 parts by mass The present invention relates to a method for producing a thermally conductive sheet product comprising a thermally conductive sheet comprising a cured product of a thermally conductive, fluorine-containing curable composition containing the above components (A) to (D), and electrically insulating films attached to both sides of the thermally conductive sheet product, the method comprising the step of: sandwiching a thermally conductive, fluorine-containing curable composition containing the above components (A) to (D) between electrically insulating films and hot-pressing the composition to cure the composition into a sheet form.

26. (A) a linear polyfluoro compound having two or more alkenyl groups in one molecule and having a perfluoropolyether structure in the main chain: 100 parts by mass, (B) a fluorine-containing organohydrogensiloxane having in one molecule one or more groups selected from a perfluoroalkyl group, a perfluorooxyalkyl group, a perfluoroalkylene group, and a perfluorooxyalkylene group, and further having two or more hydrogen atoms (SiH groups) directly bonded to silicon atoms, and having no alkoxy groups directly bonded to silicon atoms in the molecule: an amount such that the number of hydrogen atoms directly bonded to silicon atoms in component (B) is 0.50 to 3.0 moles per mole of alkenyl groups contained in the entire composition, (C) a platinum group metal catalyst: 0.1 to 2,000 ppm by mass of platinum group metal atoms relative to the component (A), and (D) Thermally conductive filler: 100 to 4,000 parts by mass a heat conductive fluorine-containing curable composition containing the above components (A) to (D) and an electrically insulating film attached to both sides of the heat conductive sheet product, the heat conductive fluorine-containing curable composition containing the above components (A) to (D) comprising the steps of coating a long electrically insulating film with a heat conductive fluorine-containing curable composition containing the above components (A) to (D), curing the composition by heating, and then attaching the electrically insulating film to the cured product.

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