JP5418620B2 - Thermal conduction member - Google Patents

Description

  The present invention relates to a heat conducting member that can be interposed between a heat boundary surface of a heat generating element and a heat radiating member such as a heat sink or a circuit board, in particular, for cooling the heat generating element.

  CPUs used in electronic devices such as personal computers, digital video disks, and cellular phones, LSI chips such as driver ICs and memories, and light emitting elements such as LEDs are associated with higher performance, higher speed, smaller size, and higher integration. The device itself generates a large amount of heat, and the temperature rise of the device due to the heat causes malfunction and destruction of the device itself. Therefore, many heat dissipating methods for suppressing the temperature rise of the element during operation and heat dissipating members used therefor have been proposed.

  2. Description of the Related Art Conventionally, in an electronic device or the like, a heat radiating member such as a heat sink using a metal plate having high thermal conductivity such as aluminum or copper is used in order to suppress a temperature rise of an element during operation. The heat radiating member conducts heat generated by the element and releases the heat from the surface due to a temperature difference from the outside air.

  In order to efficiently transmit the heat generated from the element to the heat radiating member, it is effective to fill a slight gap generated between the element and the heat radiating member with a heat conductive material. As the heat conductive material, a heat conductive sheet or heat conductive grease containing a heat conductive filler is used, and these heat conductive materials are interposed between the element and the heat radiating member, and these heat conductive materials are used. The heat conduction from the element to the heat dissipation member is realized through the conductive material.

Sheets are easier to handle than grease, and heat conductive sheets formed of heat conductive silicone rubber or the like are used in various fields.
Thermally conductive sheets can be broadly classified into general products that emphasize handling and low hardness products that emphasize adhesion.

  Of these, general products are most often sheet A made of hard rubber of type A durometer hardness of 60 or more, and can be handled as a single product even in a thin film state of about 0.1 mm. Therefore, it is difficult to temporarily fix the element and the heat dissipating member. In order to solve this problem, a tackiness imparting type has been proposed in which a pressure-sensitive adhesive is applied to one or both sides of a thin-film heat-dissipating sheet so that it can be easily temporarily fixed. However, since the applied adhesive component does not have sufficient thermal conductivity, there is a problem that the thermal resistance of the adhesive-coated product is greatly increased as compared with the non-coated one. Moreover, since the application of the adhesive increases the thickness of the sheet itself, this also works against the heat resistance.

On the other hand, a low-hardness product is a sheet of a low-hardness heat conductive material having an Asker C hardness of 60 or less, and maintains an adhesive force that can be temporarily fixed without applying an adhesive or the like. Yes. However, in order to realize its low hardness, a large amount of plasticizer is blended in the sheet or the crosslinking is very loose, so there are difficulties in strength and handleability when thinned, and good handling In order to obtain the properties, a certain thickness or more is required. Therefore, it has been difficult to reduce the thermal resistance of the low hardness product. Further, such a low hardness product has a drawback that oil bleed is generated and neighboring elements are easily contaminated.
In addition, the following are mentioned as prior literature relevant to the present invention.

JP 2005-035264 A JP 2005-206733 A JP 2006-182888 A JP 2006-188610 A

  An object of the present invention is to provide a heat conductive member having adhesiveness that can be handled by a single layer or a thin film and can be easily fixed to an element or a heat radiating member.

  As a result of intensive studies to achieve the above object, the present inventors have formulated a heat conductive filler into an addition reaction curable silicone rubber composition and a silicone resin. The thermally conductive cured product applied and cured in a thin film on a substrate that has been subjected to surface release treatment in (1) has good surface adhesion as shown in the examples described later, Excellent peelability from the material and easy handling after peeling. It is very effective as a heat conduction member that is interposed between the exothermic element and the heat dissipating member to transmit the heat generated from the exothermic element to the heat dissipating member. It has been found that the present invention has been made.

Therefore, the present invention is a heat conductive member having a base film on one surface of the thin film of the heat conductive cured product and a separator film on the other surface in a detachable manner,
(A) Organopolysiloxane having an alkenyl group: 100 parts by mass,
(B) Thermally conductive filler: 200 to 2,000 parts by mass,
(C) Organohydrogenpolysiloxane: an amount of 0.5 to 5.0 in terms of a molar ratio of hydrogen atoms directly bonded to silicon atoms in component (c) and alkenyl groups in component (a),
(D) Platinum-based compound: 0.1 to 1,000 ppm of component (a) in the amount of platinum-based element,
(E) Reaction control agent: required amount,
(F) R ₃ SiO _1/2 units (R represents an unsubstituted or substituted monovalent hydrocarbon group not containing an aliphatic unsaturated bond) and SiO _4/2 units, and R ₃ SiO _1/2 Silicone resin having a molar ratio of units to SiO _4/2 units of 0.5 to 1.5: a cured product of a composition having 50 to 300 parts by mass as an essential component, and the base film is represented by the following formula (7 The heat conducting member is characterized by being subjected to a release treatment with a modified silicone having a fluorine substituent selected from perfluoropolyether groups represented by (9) to (9) as a main chain.

で示されるものであることが好ましい。 In this case, it is preferable that the separator film has been subjected to a release treatment with a modified silicone having a fluorine substituent selected from a perfluoroalkyl group and a perfluoropolyether group in the main chain, and a perfluoropolyether group Are the following formulas (7) to (9)

It is preferable that it is shown by these.

  Furthermore, it is preferable that the compounding quantity of a silicone resin (f) is 99.6-300 mass parts, and the thing in which a heat conductive filler (b) is chosen from a metal, an oxide, and nitride is preferable.

  The heat conductive member of the present invention has good handleability even when the heat conductive cured product is a single layer or a thin film, and can be easily fixed by adhering to a heat generating element or a heat radiating member, and peelable from the substrate. Is also good.

The silicone rubber composition for obtaining the thermally conductive cured product of the present invention,
(A) an organopolysiloxane having an alkenyl group,
(B) a thermally conductive filler,
(C) organohydrogenpolysiloxane,
(D) a platinum compound,
(E) a reaction control agent,
(F) A silicone resin is an essential component.

  The organopolysiloxane having an alkenyl group as the component (a) used in the present invention contains at least two alkenyl groups in the molecular chain, and usually the main chain portion is basically composed of repeating diorganosiloxane units. Those consisting of are preferred.

  Specific examples of the component (a) include those represented by the following average structural formulas (1) to (3).

（式中、Ｒ¹は相互に独立した脂肪族不飽和結合を含有しない非置換又は置換の１価炭化水素基、Ｘはアルケニル基である。ａ及びｂはそれぞれ０又は１以上の正数、ｃは１以上の正数、ｄは２以上の正数である。）

(Wherein R ¹ is an unsubstituted or substituted monovalent hydrocarbon group that does not contain an independent aliphatic unsaturated bond, X is an alkenyl group, a and b are each 0 or a positive number of 1 or more, c is a positive number of 1 or more, and d is a positive number of 2 or more.)

In the above formula, examples of the unsubstituted or substituted monovalent hydrocarbon group containing no aliphatic unsaturated bond represented by R ¹ include, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert- Butyl group, pentyl group, neopentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group and other alkyl groups, cyclopentyl group, cyclohexyl group, cycloheptyl group and other cycloalkyl groups, phenyl group, tolyl Groups, xylyl groups, naphthyl groups, aryl groups such as biphenylyl groups, aralkyl groups such as benzyl groups, phenylethyl groups, phenylpropyl groups, methylbenzyl groups, and hydrogen atoms bonded to carbon atoms of these groups Groups in which part or all are substituted with halogen atoms such as fluorine, chlorine, bromine, cyano groups, etc., for example Chloromethyl group, 2-bromoethyl group, 3-chloropropyl group, 3,3,3-trifluoropropyl group, chlorophenyl group, fluorophenyl group, cyanoethyl group, 3,3,4,4,5,5,6, Examples thereof include those having 1 to 10 carbon atoms, particularly 1 to 6 carbon atoms, such as 6,6-nonafluorohexyl group, and among these, methyl group, ethyl group, propyl group, chloromethyl group are preferable. , Unsubstituted or substituted alkyl groups having 1 to 3 carbon atoms such as bromoethyl group, 3,3,3-trifluoropropyl group, and cyanoethyl group, and unsubstituted or substituted phenyl group, chlorophenyl group, fluorophenyl group, etc. Of the phenyl group. R ¹ may all be the same or different. As long as R ¹ does not require special properties such as solvent resistance, a methyl group is often selected for reasons such as cost, availability, chemical stability, and environmental burden.

  Examples of the alkenyl group of X include usually those having about 2 to 8 carbon atoms such as vinyl group, allyl group, propenyl group, isopropenyl group, butenyl group, hexenyl group, cyclohexenyl group, etc. Of these, lower alkenyl groups such as vinyl group and allyl group are preferable, and vinyl group is particularly preferable.

In the formula, a is a positive number of 0 or 1 or more, preferably a positive number satisfying 10 ≦ a ≦ 10,000, more preferably a positive number satisfying 50 ≦ a ≦ 2,000. More preferably, it is a positive number satisfying 100 ≦ a ≦ 1,000. “b” is 0 or a positive number of 1 or more, preferably 0 ≦ b / (a + b) ≦ 0.5, and more preferably 0 ≦ b / (a + b) ≦ 0.1. c is a positive number of 1 or more, preferably 0 <c / (a + c) ≦ 0.5, and more preferably 0 <c / (a + c) ≦ 0.1. d is a positive number of 2 or more, preferably 0 <d / (a + d) ≦ 0.5, and more preferably 0 <d / (a + d) ≦ 0.1.
This organopolysiloxane may be used alone or in combination with a plurality of different viscosities.

  The heat conductive filler of the component (b) used in the present invention includes non-magnetic metals such as copper and aluminum, metal oxides such as alumina, silica, magnesia, bengara, beryllia, titania and zirconia, aluminum nitride, and nitride. A material generally used as a thermally conductive filler, such as metal nitrides such as silicon and boron nitride, artificial diamond or silicon carbide, can be used.

  As these heat conductive fillers, those having an average particle diameter of 0.1 to 100 μm, preferably 0.5 to 50 μm, more preferably 0.5 to 30 μm can be used. These fillers may be used individually by 1 type, and may mix and use multiple types. Two or more kinds of particles having different average particle diameters can be used. In addition, in this invention, an average particle diameter is a volume average particle diameter, and is a measured value by the micro track particle size distribution measuring apparatus MT3300EX (Nikkiso Co., Ltd.).

  The compounding quantity of a heat conductive filler is 200-2,000 mass parts with respect to 100 mass parts of (a) component, Preferably it is 300-1,500 mass parts. If the blending amount of the heat conductive filler is too large, the fluidity is lost and molding is difficult, and if it is too small, the desired heat conductivity cannot be obtained.

The organohydrogenpolysiloxane of component (c) used in the present invention has at least 2, preferably 3 or more hydrogen atoms (that is, Si-H groups) directly bonded to silicon atoms in the molecular chain. .
Specific examples of such organohydrogenpolysiloxanes include those represented by the following average structural formulas (4) to (6).

（式中、Ｒ²は相互に独立した脂肪族不飽和結合を含有しない非置換又は置換の１価炭化水素基であり、ｅ、ｈは０又は１以上の正数、ｇは１以上の正数、ｆは２以上の正数である。）

(In the formula, R ² is an unsubstituted or substituted monovalent hydrocarbon group that does not contain an independent aliphatic unsaturated bond, e and h are 0 or a positive number of 1 or more, and g is a positive number of 1 or more. The number f is a positive number of 2 or more.)

In the above formulas (4) to (6), examples of the unsubstituted or substituted monovalent hydrocarbon group not containing an aliphatic unsaturated bond of R ² include a methyl group, an ethyl group, a propyl group, an isopropyl group, and butyl. Group, isobutyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, cyclodecyl group such as cyclopentyl group, cyclohexyl group, cycloheptyl group, etc. Bonded to aryl groups such as alkyl group, phenyl group, tolyl group, xylyl group, naphthyl group and biphenylyl group, aralkyl groups such as benzyl group, phenylethyl group, phenylpropyl group and methylbenzyl group, and carbon atoms of these groups Some or all of the hydrogen atoms are substituted with halogen atoms such as fluorine, chlorine and bromine, cyano groups, etc. Groups such as chloromethyl, 2-bromoethyl, 3-chloropropyl, 3,3,3-trifluoropropyl, chlorophenyl, fluorophenyl, cyanoethyl, 3,3,4,4,5 Examples include 5,6,6,6-nonafluorohexyl group and the like having 1 to 10 carbon atoms, particularly 1 to 6 carbon atoms. Among these, methyl group, ethyl group, propyl group are preferable. An unsubstituted or substituted alkyl group having 1 to 3 carbon atoms such as a chloromethyl group, a bromoethyl group, a 3,3,3-trifluoropropyl group, a cyanoethyl group, and a non-substituted group such as a phenyl group, a chlorophenyl group, and a fluorophenyl group. A substituted or substituted phenyl group. R ² may be the same or different from each other, but is preferably the same substituent as R ¹ .

For R ² , as in R ¹ , all methyl groups are selected for reasons such as cost, availability, chemical stability, and environmental burden unless special properties such as solvent resistance are required. There are many cases.

  Further, e in the formula is 0 or a positive number of 1 or more, preferably 0 to 500, more preferably 5 to 100. f is a positive number of 2 or more, preferably 2 to 100, more preferably 2 to 50. g is a positive number of 1 or more, preferably 1 to 100, and more preferably 1 to 50. h is a positive number of 0 or 1 or more, preferably 0 to 100, more preferably a positive number of 0 to 50.

  The amount of component (c) added is such that the Si—H group of component (c) is 0.5 to 5.0 moles per mole of alkenyl group in component (a), preferably 0.8. It is an amount to be ˜4.0 mol, and more preferably 1.0 to 3.0 mol. If the amount of Si-H group of component (c) is less than 0.5 mol with respect to 1 mol of alkenyl group in component (a), the molded sheet will not be cured, or the strength of the molded sheet will be insufficient, The problem that it becomes impossible to handle as a molded object generate | occur | produces. If the amount exceeds 5.0 mol, the sheet after molding will not have sufficient tackiness, and it will not be possible to fix itself with its own adhesion.

The component (d) platinum compound (platinum group curing catalyst) used in the present invention promotes the addition reaction between the alkenyl group in component (a) and the Si—H group in component (c). As the catalyst used in the hydrosilylation reaction, a well-known catalyst can be used. Specific examples thereof include platinum group metals such as platinum (including platinum black), rhodium and palladium, H ₂ PtCl ₄ · nH ₂ O, H ₂ PtCl ₆ · nH ₂ O, NaHPtCl ₆ · nH ₂ O. , KHPtCl ₆ · nH ₂ O, Na ₂ PtCl ₆ · nH ₂ O, K ₂ PtCl ₄ · nH ₂ O, PtCl ₄ · nH ₂ O, PtCl ₂ , Na ₂ HPtCl ₄ · nH ₂ O (where, n is an integer of 0 to 6, preferably 0 or 6.), etc.), such as platinum chloride, chloroplatinic acid and chloroplatinate, alcohol-modified chloroplatinic acid, chloroplatinic acid and olefin complex, platinum black , Platinum group metals such as palladium supported on a carrier such as alumina, silica, carbon, rhodium-olefin complex, chlorotris (triphenylphosphine) rhodium (Wilkinso Catalyst), platinum chloride, chloroplatinic acid or chloroplatinate and a vinyl group-containing siloxane.

  The amount of the component (d) used may be a so-called catalytic amount, and is usually 0.1 to 1,000 ppm in terms of mass of the platinum group metal element with respect to the component (a), preferably 0.5 to 200 ppm, More desirably, it is 1.0 to 100 ppm.

  The (e) component reaction control agent used in the present invention is for adjusting the reaction rate of the (a) component and the (c) component that proceed in the presence of the (d) component.

  Examples of the component (e) include acetylene alcohol compounds, amine compounds, phosphorus compounds, and sulfur compounds, among which acetylene alcohol compounds are desirable. Although the addition amount is arbitrary as long as it can be adjusted to a desired reaction rate, it is preferably 0.01 to 2.0 parts by mass with respect to 100 parts by mass of component (a).

  The (f) component silicone resin used in the present invention is added in order to impart tackiness to the cured product of the present invention.

The component (f) is a copolymer of R ₃ SiO _1/2 units (M units) and SiO _4/2 units (Q units), and the ratio (molar ratio) of M units to Q units is M / Q = It is 0.5 to 1.5, preferably 0.6 to 1.4, and more preferably 0.7 to 1.3.
When M / Q is less than 0.5 or when M / Q exceeds 1.5, a desired adhesive force cannot be obtained.

R is an unsubstituted or substituted monovalent hydrocarbon group containing no aliphatic unsaturated bond, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group , Neopentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, alkyl group such as dodecyl group, cycloalkyl group such as cyclopentyl group, cyclohexyl group, cycloheptyl group, phenyl group, tolyl group, xylyl group, Aryl group such as naphthyl group, biphenylyl group, benzyl group, phenylethyl group, phenylpropyl group, aralkyl group such as methylbenzyl group, and a part or all of hydrogen atoms bonded to carbon atoms of these groups, A group substituted with a halogen atom such as fluorine, chlorine or bromine, a cyano group, such as a chloromethyl group 2-bromoethyl group, 3-chloropropyl group, 3,3,3-trifluoropropyl group, chlorophenyl group, fluorophenyl group, cyanoethyl group, 3,3,4,4,5,5,6,6,6- Examples thereof include those having 1 to 10 carbon atoms, particularly 1 to 6 carbon atoms, such as a nonafluorohexyl group, and among these, a methyl group, an ethyl group, a propyl group, a chloromethyl group, a bromoethyl group, An unsubstituted or substituted alkyl group having 1 to 3 carbon atoms such as 3,3,3-trifluoropropyl group and cyanoethyl group, and an unsubstituted or substituted phenyl group such as phenyl group, chlorophenyl group and fluorophenyl group; . R may be the same as or different from each other, but is preferably the same substituent as R ¹ .

For R, as with R ¹ , all methyl groups are selected for reasons such as cost, availability, chemical stability, and environmental impact, unless special properties such as solvent resistance are required. There are many.

  (F) The addition amount of a component is 50-300 mass parts with respect to 100 mass parts of (a) component, Preferably it is 60-200 mass parts, More preferably, it is 70-150 mass parts. When the amount of component (f) added is less than 50 parts by mass or more than 300 parts by mass, the desired tackiness cannot be obtained.

  The component (f) itself is a solid or viscous liquid at room temperature, but can also be used in a state dissolved in a solvent. In that case, the amount added to the composition is determined by the amount excluding the solvent.

  In addition to this, the surface treatment agent for heat conductive fillers, pigments / dyes for coloring, flame retardant imparting agents, and various other additives for improving the functions of the composition It is possible to add in the range which does not impair.

  It is possible to obtain the thermally conductive cured product of the present invention by uniformly mixing the above components, forming the mixture into a thin film on a substrate, and curing by heating.

  The molding thickness is preferably 20 to 1,000 μm, and more preferably 30 to 500 μm. When the molding thickness is less than 20 μm, the handling is bad and the sticky feeling is lowered. On the other hand, when the molding thickness exceeds 1,000 μm, desired thermal conductivity cannot be obtained.

  Moreover, when coating and forming, it is also possible to add a solvent such as toluene to adjust the viscosity.

As the substrate on which the silicone rubber composition used in the present invention is applied, a paper or PET film subjected to a release treatment with a non-dimethyl silicone polymer is suitable.
Examples of non-dimethyl silicone polymers include modified silicones having a fluorine substituent such as a perfluoroalkyl group or a perfluoropolyether group in the main chain.
The perfluoropolyether group can be represented by the following formulas (7) to (9).

  Specific examples of the modified silicone having such a fluorine substituent include X-70-201 and X-70-258 manufactured by Shin-Etsu Chemical Co., Ltd.

  Examples of the molding method on the substrate include applying a liquid material on the substrate using a bar coater, knife coater, comma coater, spin coater, etc., but are not limited to the above-described method. Absent.

  The heating temperature condition for heating after molding may be a temperature at which the solvent used is volatilized when the solvent is added and the components (a) and (c) can react with each other. 60-150 degreeC from viewpoints of property etc. is desirable, and 80-150 degreeC is still more desirable. If it is less than 60 ° C., the curing reaction is slow and the productivity is deteriorated. If it exceeds 150 ° C., the film used as the substrate may be deformed. The curing time is usually 0.5 to 30 minutes, preferably 1 to 20 minutes.

  The heat-cured cured product after curing facilitates handling such as transportation and standard cut by sticking to the opposite side of the substrate using a release film similar to the substrate film as a separator film be able to. At this time, it is also possible to apply a light weight of the peeling force between the base film and the separator film by changing the processing amount and type of the release agent and the material of the film.

  The heat conductive cured product thus obtained may be a thin film by peeling off the separator film or substrate film, and then sticking it to the heating element or heat dissipation member, and then peeling off the remaining film. It can be easily arranged and exhibits excellent heat conduction characteristics.

  EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example. In the following examples,% indicates mass%.

[Example 1]
100 g of dimethylpolysiloxane having a viscosity of 600 mm ² / s sealed with a vinyl group and 600 g of alumina having an average particle diameter of 10 μm (DAW-10, manufactured by Denki Kagaku Kogyo Co., Ltd.) were added to a Shinagawa universal agitator. Charge and mix for 60 minutes, then add 0.2 g of 2% chloroplatinic acid 2-ethylhexanol solution and mix uniformly, and then add 0.2 g of 50% ethynylcyclohexanol-toluene solution and mix uniformly. Finally, 5 g of organohydrogenpolysiloxane having the following average structural formula (10) and 166 g of silicone resin toluene solution (non-volatile content 60%, M / Q (molar ratio) = 1.15) were added, and uniform To obtain a composition a. This composition a was applied to a PET film having a thickness of 100 μm coated with 1.0-g / m ^{2 of} X-70-201 manufactured by Shin-Etsu Chemical Co., Ltd. so that the thickness after air drying was 0.1 mm, After air-drying at room temperature for 10 minutes, it was cured by exposure to 100 ° C. for 10 minutes to obtain a cured product A having a thickness of 0.1 mm.

（Ｍｅはメチル基を示す。）

(Me represents a methyl group.)

[Comparative Example 1]
100 g of dimethylpolysiloxane having a viscosity of 600 mm ² / s sealed with vinyl groups, 100 g of dimethylpolysiloxane having a viscosity of 100 mm ² / s sealed with methyl groups, and alumina having an average particle size of 10 μm 600 g (DAW-10 manufactured by Denki Kagaku Kogyo Co., Ltd.) was charged into a Shinagawa universal stirrer and mixed for 60 minutes, then 0.2 g of 2% chloroplatinic acid 2-ethylhexanol solution was added and mixed uniformly. Further, 0.2 g of a 50% ethynylcyclohexanol-toluene solution was added and mixed uniformly. Finally, 5 g of organohydrogenpolysiloxane having an average structural formula (10) and 66 g of toluene were added and uniformly added. The composition b was obtained by mixing. The composition b was applied to a PET film having a thickness of 100 μm coated with 1.0 g / m ^{2 of} X-70-201 manufactured by Shin-Etsu Chemical Co., Ltd. so that the thickness after air drying was 0.1 mm, After air-drying for 10 minutes at room temperature, it was cured by exposure to 100 ° C. for 10 minutes to obtain a cured product B having a thickness of 0.1 mm.

[Comparative Example 2]
200 g of dimethylpolysiloxane having a viscosity of 600 mm ² / s sealed with a vinyl group and 600 g of alumina having an average particle size of 10 μm (DAW-10 manufactured by Denki Kagaku Kogyo Co., Ltd.) were used in a Shinagawa universal agitator. Charge and mix for 60 minutes, then add 0.2 g of 2% chloroplatinic acid 2-ethylhexanol solution and mix uniformly, and then add 0.2 g of 50% ethynylcyclohexanol-toluene solution and mix uniformly. Finally, 5 g of organohydrogenpolysiloxane having an average structural formula (10) and 66 g of toluene were added and mixed uniformly to obtain a composition c. This composition c was applied to a PET film having a thickness of 100 μm coated with X-70-201 manufactured by Shin-Etsu Chemical Co., Ltd. at a rate of 1.0 g / m ^{2 so} that the thickness after air drying was 0.1 mm. After air-drying for 10 minutes at room temperature, it was cured by exposure to 100 ° C. for 10 minutes to obtain a cured product C having a thickness of 0.1 mm.

[Comparative Example 3]
200 g of dimethylpolysiloxane having a viscosity of 600 mm ² / s sealed with a vinyl group and 600 g of alumina having an average particle size of 10 μm (DAW-10 manufactured by Denki Kagaku Kogyo Co., Ltd.) were used in a Shinagawa universal agitator. Charge and mix for 60 minutes, then add 0.2 g of 2% chloroplatinic acid 2-ethylhexanol solution and mix uniformly, and then add 0.2 g of 50% ethynylcyclohexanol-toluene solution and mix uniformly. Finally, 3.5 g of organohydrogenpolysiloxane having an average structural formula (10) and 66 g of toluene were added and mixed uniformly to obtain a composition d. This composition d was applied to a PET film having a thickness of 100 μm coated with 1.0 g / m ^{2 of} X-70-201 manufactured by Shin-Etsu Chemical Co., Ltd. so that the thickness after air drying was 0.1 mm, After air-drying at room temperature for 10 minutes, it was cured by exposure for 10 minutes in an atmosphere of 100 ° C. to obtain a cured product D having a thickness of 0.1 mm.

[Comparative Example 4]
100 g of dimethylpolysiloxane having a viscosity of 600 mm ² / s sealed with vinyl groups, 100 g of dimethylpolysiloxane having a viscosity of 100 mm ² / s sealed with methyl groups, and alumina having an average particle size of 10 μm 600 g (DAW-10 manufactured by Denki Kagaku Kogyo Co., Ltd.) was charged into a Shinagawa universal stirrer and mixed for 60 minutes, then 0.2 g of 2% chloroplatinic acid 2-ethylhexanol solution was added and mixed uniformly. Further, 0.2 g of 50% ethynylcyclohexanol-toluene solution was added and mixed uniformly. Finally, 5 g of organohydrogenpolysiloxane having an average structural formula (10) was added and mixed uniformly. e was obtained. To the PET film having a thickness of 100 μm coated with 1.0 g / m ^{2 of} X-70-201 manufactured by Shin-Etsu Chemical Co., Ltd., the thickness of the composition e after being air-dried is 0.1 mm and 0.5 mm. And cured by exposure to 100 ° C. for 10 minutes to obtain a cured product E1 having a thickness of 0.1 mm and a cured product E2 having a thickness of 0.5 mm.

[Comparative Example 5]
200 g of dimethylpolysiloxane having a viscosity of 600 mm ² / s sealed with a vinyl group and 600 g of alumina having an average particle size of 10 μm (DAW-10 manufactured by Denki Kagaku Kogyo Co., Ltd.) were used in a Shinagawa universal agitator. Charge and mix for 60 minutes, then add 0.2 g of 2% chloroplatinic acid 2-ethylhexanol solution and mix uniformly, and then add 0.2 g of 50% ethynylcyclohexanol-toluene solution and mix uniformly. Finally, 5 g of organohydrogenpolysiloxane having an average structural formula (10) was added and mixed uniformly to obtain a composition f. To the PET film having a thickness of 100 μm coated with 1.0 g / m ^{2 of} X-70-201 manufactured by Shin-Etsu Chemical Co., Ltd., the thickness of the composition f after air drying is 0.1 mm and 0.5 mm. And cured by exposure to 100 ° C. for 10 minutes to obtain a cured product F1 having a thickness of 0.1 mm and a cured product F2 having a thickness of 0.5 mm.

[Comparative Example 6]
200 g of dimethylpolysiloxane having a viscosity of 600 mm ² / s sealed with a vinyl group and 600 g of alumina having an average particle size of 10 μm (DAW-10 manufactured by Denki Kagaku Kogyo Co., Ltd.) were used in a Shinagawa universal agitator. Charge and mix for 60 minutes, then add 0.2 g of 2% chloroplatinic acid 2-ethylhexanol solution and mix uniformly, and then add 0.2 g of 50% ethynylcyclohexanol-toluene solution and mix uniformly. Finally, 3.5 g of organohydrogenpolysiloxane having an average structural formula (10) was added and mixed uniformly to obtain a composition g. To a PET film having a thickness of 100 μm coated with 1.0 g / m ^{2 of} X-70-201 manufactured by Shin-Etsu Chemical Co., Ltd., the thickness after air drying of this composition g is 0.1 mm and 0.5 mm. And cured by exposing to 100 ° C. for 10 minutes to obtain a cured product G1 having a thickness of 0.1 mm and a cured product G2 having a thickness of 0.5 mm.

[Comparative Example 7]
The composition a obtained in Example 1 was applied to a 100 μm PET film so that the thickness after air drying was 0.1 mm, air-dried at room temperature for 10 minutes, and then exposed at 100 ° C. for 10 minutes. And cured to obtain a cured product H having a thickness of 0.1 mm.

[Comparative Example 8]
The composition a obtained in Example 1 was applied to PET75-V0 manufactured by Nipper Co., Ltd. so that the thickness after air drying would be 0.1 mm, air-dried at room temperature for 10 minutes, and then in an atmosphere of 100 ° C. It was cured by exposure for 10 minutes to obtain a cured product I having a thickness of 0.1 mm.

  About the obtained hardened | cured material AI, the surface adhesion, bleeding property, peelability from a base material, the handleability after peeling, and thermal resistance were compared. The results are shown in Table 1.

  The bleed property is obtained by cutting a 0.1 mm thick sample into 20 mm squares together with the base material, placing the resin layer on the fine paper, placing 100 g of weight on top of it, and bringing it into close contact with the fine paper one day later. The oil transfer condition was visually confirmed and compared.

  The peelability was evaluated based on the weight when the cured thermally conductive product was peeled from the base film by hand (evaluation by touch).

  The handleability after peeling was evaluated by paying attention to the shape of the main body for the handleability of the thermally conductive cured product after peeling.

The thermal resistance is measured by measuring the heater temperature and the heat sink temperature by applying a load of 300 gf (= 29 kPa), applying a constant power to the heater, sandwiching the cured product between the heater and heat sink of the TO-3P type transistor shape. Was determined by the following equation.
Thermal resistance = (heater temperature-heat sink temperature) / applied power

Claims (5)

A heat conductive member having a base film on one surface of a thin film of a heat conductive cured product and a separator film on the other surface in a detachable manner, wherein the heat conductive cured product is
(A) Organopolysiloxane having an alkenyl group: 100 parts by mass,
(B) Thermally conductive filler: 200 to 2,000 parts by mass,
(C) Organohydrogenpolysiloxane: an amount of 0.5 to 5.0 in terms of a molar ratio of hydrogen atoms directly bonded to silicon atoms in component (c) and alkenyl groups in component (a),
(D) Platinum-based compound: 0.1 to 1,000 ppm of component (a) in the amount of platinum-based element,
(E) Reaction control agent: required amount,
(F) R ₃ SiO _1/2 units (R represents an unsubstituted or substituted monovalent hydrocarbon group not containing an aliphatic unsaturated bond) and SiO _4/2 units, and R ₃ SiO _1/2 Silicone resin having a molar ratio of units to SiO _4/2 units of 0.5 to 1.5: a cured product of a composition having 50 to 300 parts by mass as an essential component, and the base film is represented by the following formula (7 ) To (9), a heat conducting member characterized by being subjected to release treatment with a modified silicone having a fluorine substituent selected from a perfluoropolyether group as a main chain.

  2. The heat conducting member according to claim 1, wherein the separator film is subjected to a release treatment with a modified silicone having a fluorine substituent selected from a perfluoroalkyl group and a perfluoropolyether group in the main chain. Perfluoropolyether groups are represented by the following formulas (7) to (9).

The heat-conducting member according to claim 2, wherein   The heat conductive member according to claim 1, 2 or 3, wherein the amount of the silicone resin (f) is 99.6 to 300 parts by mass.   The heat conductive member according to any one of claims 1 to 4, wherein the heat conductive filler (b) is selected from a metal, an oxide, and a nitride.