JP2017190389A - Thermal conductive fluorine adhesive composition and electric and electronic component - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermal conductive fluorine-containing adhesive composition capable of highly filling a thermal conductive filler, excellent in oil resistance and thermal conductivity, further providing a cured article which rigidly adheres to various substrates such as metal and plastic, and an electric and electronic component using the same.SOLUTION: There is provided a thermal conductive fluorine-containing adhesive composition which uses a fluorine-containing organic silicon compound having one or more monovalent perfluoroalkyl group or monovalent perfluorooxyalkyl group in a molecule, further one or more alkoxy group directly bound to a silicon atom and having no epoxy group and no SiH group in the molecule, and organo polysiloxane having a SiH group, the monovalent perfluoroalkyl group or the monovalent perfluorooxyalkyl group, an epoxy group and/or a trialkoxysilyl group bound to the silicon atom via a bivalent hydrocarbon group which may contain an oxygen atom as surface treatment agents of a thermal conductive filler.SELECTED DRAWING: None

Description

  The present invention relates to a thermally conductive fluorine-containing adhesive composition and an electric / electronic component using the same.

  Conventionally, as a fluorine-containing curable composition, a linear fluoropolyether compound having at least two alkenyl groups in one molecule and a perfluoropolyether structure in the main chain, silicon atoms in one molecule From a composition comprising a fluorine-containing organohydrogensiloxane having two or more hydrogen atoms directly connected to a platinum group metal compound and heat resistance, chemical resistance, solvent resistance, mold release, water repellency, oil repellency, low temperature characteristics, etc. It has been proposed to obtain a cured product having excellent balance of properties (Patent Document 1: Japanese Patent No. 2990646).

  In addition, as a composition that gives a cured product having improved acid resistance over the cured product obtained from the above composition, a composition in which the linear fluoropolyether compound is changed has been proposed (Patent Document 2: Patent No. 2). No. 5246190).

  Furthermore, a composition in which self-adhesiveness is imparted to a metal or plastic substrate by adding an organopolysiloxane having a hydrosilyl group and an epoxy group and / or trialkoxysilyl group to these compositions has been proposed. (Patent Documents 3 and 4: Japanese Patent No. 3329717, Japanese Patent No. 5459033).

  By the way, it is known that the performance of many electric / electronic components such as CPU, power transistor, LSI and the like is deteriorated by heat generated during use. Therefore, various heat dissipation techniques are used as means for removing heat from the component. Typical examples thereof include heat-dissipating grease and heat-dissipating sheet obtained by adding a heat conductive filler to a thermosetting silicone rubber composition (Patent Documents 5 to 7: Patent No. 2938428, Patent No. 5553006, Japanese Patent No. 3952184). Furthermore, in recent years, a thermally conductive silicone adhesive composition imparted with self-adhesive properties has also been proposed (Patent Document 8: Japanese Patent No. 5445415). Thermally conductive materials made of these silicone rubbers (cured products of thermosetting silicone rubber compositions) are excellent in heat resistance, weather resistance, electrical insulation, etc., and have recently been used in the automotive field. For example, it is employed in an LED headlamp, an ECU mounted on an actuator such as a motor and a solenoid, and a battery, a motor, a converter, and the like mounted on a next-generation vehicle such as a hybrid car and an electric vehicle.

  However, since silicone rubber is easily swelled and deteriorated by solvents such as toluene, alcohol, gasoline, etc., the heat conductive material made of silicone rubber is exposed to an automotive oil such as ATF and CVTF. When used, there was a problem that it was difficult to maintain the performance. Therefore, in recent years, fluororubber-based heat conductive materials have been proposed.

For example, a composition comprising a perfluoropolyether and a thermally conductive filler has been disclosed as a fluorine-containing heat-dissipating grease having thermal conductivity (Patent Document 9: Japanese Patent Publication No. 8-22944).
In addition, a heat-resistant heat-dissipating sheet obtained by mixing a liquid fluorinated polyether and a heat conductive filler and then curing the reaction has been proposed (Patent Document 10: Japanese Patent Application Laid-Open No. 2010-232535).

  In addition, a compound having a perfluoroalkyl ether structure in the main chain and a hydrosilyl group at the molecular end, a compound having a perfluoroalkyl ether structure in the main chain and an alkenyl group at the molecular end, A heat conductive rubber sheet obtained by heating a composition containing a conductive filler has been disclosed (Patent Document 11: JP-A-2015-67736). Furthermore, a composition obtained by adding a conductive filler to the composition and a thermally conductive sheet composed of a cured product thereof have been proposed (Patent Document 12: JP-A-2015-67737).

  However, these thermally conductive materials described in Patent Documents 9 to 12 are not greased uniformly when the amount of thermally conductive filler added is increased in order to increase thermal conductivity. There was a problem that it did not become a shape, the viscosity of the composition was remarkably increased, and workability and moldability became very poor.

  Furthermore, recently, a fluororubber-based heat conductive material having self-adhesiveness has been demanded, and its appearance has been desired.

Japanese Patent No. 2990646 Japanese Patent No. 5246190 Japanese Patent No. 3329717 Japanese Patent No. 5459033 Japanese Patent No. 2938428 Japanese Patent No. 5553006 Japanese Patent No. 3952184 Japanese Patent No. 5445415 Japanese Patent Publication No. 8-22944 JP 2010-232535 A Japanese Patent Laying-Open No. 2015-67736 Japanese Patent Laying-Open No. 2015-67737

  The present invention has been made in view of the above circumstances, can be highly filled with a heat conductive filler, has excellent oil resistance and heat conductivity, and is firmly bonded to various substrates such as metals and plastics. It aims at providing the heat conductive fluorine-containing adhesive composition which gives the hardened | cured material to perform, and an electrical / electronic component using the same.

  As a result of intensive studies to solve the above problems, the present inventors have found that as a surface treatment agent for a thermally conductive filler, a monovalent perfluoroalkyl group or a monovalent perfluorooxy group in one molecule. Fluorine-containing organosilicon having at least one alkyl group, at least one alkoxy group directly bonded to a silicon atom, and having no hydrogen atom (SiH group) directly bonded to an epoxy group or silicon atom in the molecule By using the compound, it becomes possible to highly fill the thermally conductive filler, and as an adhesion imparting agent, in one molecule, a hydrogen atom (SiH group) directly bonded to a silicon atom and a monovalent perfluoro An epoxy group or trialkoxysilyl group bonded to a silicon atom via an alkyl group or a monovalent perfluorooxyalkyl group and a divalent hydrocarbon group which may contain an oxygen atom Adds organopolysiloxane that has both of them to provide a hardened product that has excellent oil resistance and thermal conductivity, and gives a cured product that adheres strongly to various substrates such as metals and plastics. The present inventors have found that an agent composition can be obtained, and have made the present invention.

（式中、Ｒ¹及びＲ²は互いに独立して、アルケニル基、又は非置換若しくは置換の脂肪族不飽和結合を有さない１価の炭化水素基であり、Ｒ¹及びＲ²の合計のうち二つ以上はアルケニル基である。Ｒ³は互いに独立して、水素原子、又は非置換若しくは置換の１価の炭化水素基であり、ｃ及びｄはそれぞれ１〜１５０の整数であって、かつｃ＋ｄの平均値は２〜３００であり、ｅは１〜６の整数である。）

（式中、Ｒ⁴は互いに独立して、炭素数１〜６のアルキレン基であり、Ｒ⁵は互いに独立して、水素原子又はフッ素置換されていてもよい炭素数１〜４のアルキル基である。また、Ｒ¹、Ｒ²、ｃ、ｄ及びｅは上記と同じである。）
からなる群より選択される１種以上の直鎖状ポリフルオロ化合物であることを特徴とする［１］〜［３］のいずれかに記載の熱伝導性含フッ素接着剤組成物。
［５］
前記（Ｄ）成分が、金属、金属酸化物、金属窒化物、金属水酸化物、金属炭化物、軟磁性合金、フェライト及びカーボンブラックから選ばれる少なくとも１種であることを特徴とする［１］〜［４］のいずれかに記載の熱伝導性含フッ素接着剤組成物。
［６］
前記（Ｄ）成分が、金、銀、銅、鉄、ニッケル、アルミニウム、金属ケイ素、ステンレススチール、アルミナ、酸化マグネシウム、酸化ベリリウム、酸化クロム、酸化チタン、酸化亜鉛、酸化ケイ素、窒化ホウ素、窒化ケイ素、窒化アルミニウム、水酸化アルミニウム、水酸化マグネシウム、炭化ホウ素、炭化チタン、炭化ケイ素及びカーボンブラックの群から選ばれる少なくとも１種であることを特徴とする［５］に記載の熱伝導性含フッ素接着剤組成物。
［７］
前記（Ｄ）成分が、アルミナであることを特徴とする［６］に記載の熱伝導性含フッ素接着剤組成物。
［８］
前記（Ｄ）成分が、不定形アルミナ及び／又は球状アルミナであることを特徴とする［７］に記載の熱伝導性含フッ素接着剤組成物。
［９］
前記（Ｄ）成分の不定形アルミナの平均粒径が、０．２〜５．０μｍであることを特徴とする［８］に記載の熱伝導性含フッ素接着剤組成物。
［１０］
前記（Ｄ）成分の球状アルミナの平均粒径が、５．０〜１００μｍであることを特徴とする［８］に記載の熱伝導性含フッ素接着剤組成物。
［１１］
前記（Ｅ）成分が、１分子中に、ケイ素原子、酸素原子及び窒素原子を含んでもよい２価の炭化水素基を介してアルコキシ基が直結したケイ素原子に結合した１価のパーフルオロアルキル基又は１価のパーフルオロオキシアルキル基を１個以上有する含フッ素有機ケイ素化合物であることを特徴とする［１］〜［１０］のいずれかに記載の熱伝導性含フッ素接着剤組成物。
［１２］
前記（Ｅ）成分が、下記一般式（４）
Ａ_fＲ⁷ _gＳｉ（ＯＲ⁶）_4-f-g （４）
（式中、Ａは互いに独立して、ケイ素原子、酸素原子及び窒素原子を含んでもよい２価の炭化水素基を介してアルコキシ基が直結したケイ素原子に結合した１価のパーフルオロアルキル基又は１価のパーフルオロオキシアルキル基であり、Ｒ⁶は互いに独立して、炭素数１〜６のアルキル基であり、Ｒ⁷は互いに独立して、非置換若しくは置換の１価の炭化水素基である。また、ｆは１〜３の整数であり、ｇは０、１又は２であって、かつｆ＋ｇは１〜３の整数である。）
で表される含フッ素有機ケイ素化合物であることを特徴とする［１１］に記載の熱伝導性含フッ素接着剤組成物。
［１３］
前記（Ｅ）成分を１０５℃で３時間加熱した時の質量減少率が５０．０質量％以下であることを特徴とする［１］〜［１２］のいずれかに記載の熱伝導性含フッ素接着剤組成物。
［１４］
前記（Ｆ）成分が、１分子中に、ケイ素原子、酸素原子及び窒素原子を含んでもよい２価の炭化水素基を介してケイ素原子に結合した１価のパーフルオロアルキル基又は１価のパーフルオロオキシアルキル基を１個以上有するオルガノポリシロキサンであることを特徴とする［１］〜［１３］のいずれかに記載の熱伝導性含フッ素接着剤組成物。
［１５］
前記（Ｆ）成分が、下記一般式（１７）で表される環状オルガノポリシロキサンである［１４］に記載の熱伝導性含フッ素接着剤組成物。

（式中、Ｒ¹⁵は互いに独立して、非置換又は置換の１価の炭化水素基であり、Ｘは互いに独立して、ケイ素原子、酸素原子及び窒素原子を含んでもよい２価の炭化水素基を介してケイ素原子に結合した１価のパーフルオロアルキル基又は１価のパーフルオロオキシアルキル基であり、Ｙは互いに独立して、酸素原子を含んでもよい２価の炭化水素基を介してケイ素原子に結合したエポキシ基若しくはトリアルコキシシリル基である。ｋ’は１〜６の整数であり、ｌ’は１〜４の整数であり、ｍ’は１〜４の整数であり、ｋ’＋ｌ’＋ｍ’は４〜１０の整数である。但し、−（ＳｉＯ）（Ｈ）Ｒ¹⁵−、−（ＳｉＯ）（Ｘ）Ｒ¹⁵−、及び−（ＳｉＯ）（Ｙ）Ｒ¹⁵−の結合の順番は限定されない。）
［１６］
前記熱伝導性含フッ素接着剤組成物の２３℃における粘度が、１，０００Ｐａ・ｓ以下であることを特徴とする［１］〜［１５］のいずれかに記載の熱伝導性含フッ素接着剤組成物。
［１７］
［１］〜［１６］のいずれか１項に記載の熱伝導性含フッ素接着剤組成物の硬化物が、少なくともその構成の一部であることを特徴とする電気・電子部品。
［１８］
車載用である［１７］に記載の電気・電子部品。 Accordingly, the present invention provides the following thermally conductive fluorine-containing adhesive composition and electrical / electronic parts using the same.
[1]
(A) a linear polyfluoro compound having two or more alkenyl groups in one molecule and a perfluoropolyether structure in the main chain: 100 parts by mass;
(B) 1 molecule has a monovalent perfluoroalkyl group or a monovalent perfluorooxyalkyl group, or a divalent perfluoroalkylene group or a divalent perfluorooxyalkylene group, and A fluorine-containing organohydrogensiloxane having two or more hydrogen atoms (SiH groups) directly bonded to silicon atoms and having no epoxy groups and alkoxy groups directly bonded to silicon atoms in the molecule;
(C) platinum group metal catalyst: 0.1 to 2,000 ppm in terms of mass of platinum group metal atom with respect to component (A),
(D) Thermally conductive filler: 100 to 4,000 parts by mass,
(E) One molecule has at least one monovalent perfluoroalkyl group or monovalent perfluorooxyalkyl group, and at least one alkoxy group directly connected to a silicon atom, and in the molecule Fluorine-containing organosilicon compound not having a hydrogen atom (SiH group) directly bonded to an epoxy group and a silicon atom: 0.01 to 300 parts by mass,
(F) A divalent hydrocarbon which may contain a hydrogen atom (SiH group) directly bonded to a silicon atom, a monovalent perfluoroalkyl group or a monovalent perfluorooxyalkyl group, and an oxygen atom in one molecule. An organopolysiloxane having an epoxy group or trialkoxysilyl group bonded to a silicon atom via a group, or both: a thermally conductive fluorine-containing adhesive composition containing 0.1 to 20 parts by mass, The blending amount of the component (B) is an amount such that the hydrogen atom directly bonded to the silicon atom in the component (B) is 0.5 to 3 moles with respect to 1 mole of the alkenyl group contained in the composition. A thermally conductive fluorine-containing adhesive, characterized in that a cured product obtained by curing the composition gives a fluorine-containing cured product having a thermal conductivity at 25 ° C. of 1.0 W / m · K or more. Agent composition.
[2]
The thermally conductive fluorine-containing adhesive composition according to [1], wherein the linear polyfluoro compound (A) has an alkenyl group content of 0.005 to 0.3 mol / 100 g. .
[3]
The perfluoropolyether structure of the component (A) has the following general formula (1)
− (C _a F _2a O) _b − (1)
(In the formula, a is an integer of 1 to 6, and b is an integer of 1 to 300.)
The heat conductive fluorine-containing adhesive composition according to [1] or [2], wherein the composition contains a structure represented by the formula:
[4]
The component (A) is represented by the following general formula (2) and the following general formula (3).

(In the formula, R ¹ and R ² are each independently an alkenyl group or a monovalent hydrocarbon group having no unsubstituted or substituted aliphatic unsaturated bond, and the total of R ¹ and R ² is Two or more of them are alkenyl groups, R ³ is independently a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group, and c and d are each an integer of 1 to 150, And the average value of c + d is 2 to 300, and e is an integer of 1 to 6.)

(In the formula, R ⁴ is independently an alkylene group having 1 to 6 carbon atoms, and R ⁵ is independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms optionally substituted with fluorine. And R ¹ , R ² , c, d and e are the same as above.)
The thermally conductive fluorine-containing adhesive composition according to any one of [1] to [3], which is one or more linear polyfluoro compounds selected from the group consisting of:
[5]
The component (D) is at least one selected from metal, metal oxide, metal nitride, metal hydroxide, metal carbide, soft magnetic alloy, ferrite and carbon black [1] to [4] The thermally conductive fluorine-containing adhesive composition according to any one of [4].
[6]
The component (D) is gold, silver, copper, iron, nickel, aluminum, silicon metal, stainless steel, alumina, magnesium oxide, beryllium oxide, chromium oxide, titanium oxide, zinc oxide, silicon oxide, boron nitride, silicon nitride. The thermally conductive fluorine-containing adhesive according to [5], which is at least one selected from the group consisting of aluminum nitride, aluminum hydroxide, magnesium hydroxide, boron carbide, titanium carbide, silicon carbide, and carbon black Agent composition.
[7]
The heat conductive fluorine-containing adhesive composition according to [6], wherein the component (D) is alumina.
[8]
The heat conductive fluorine-containing adhesive composition according to [7], wherein the component (D) is amorphous alumina and / or spherical alumina.
[9]
The heat conductive fluorine-containing adhesive composition according to [8], wherein the amorphous particle size of the component (D) is 0.2 to 5.0 μm.
[10]
The heat conductive fluorine-containing adhesive composition according to [8], wherein the spherical particle size of the component (D) is 5.0 to 100 μm.
[11]
The monovalent perfluoroalkyl group in which the component (E) is bonded to a silicon atom in which an alkoxy group is directly connected via a divalent hydrocarbon group which may contain a silicon atom, an oxygen atom and a nitrogen atom in one molecule Alternatively, the thermally conductive fluorine-containing adhesive composition according to any one of [1] to [10], which is a fluorine-containing organosilicon compound having one or more monovalent perfluorooxyalkyl groups.
[12]
The component (E) is represented by the following general formula (4)
A _f R ⁷ _g Si (OR ⁶ ) _4-fg (4)
(In the formula, A is independently a monovalent perfluoroalkyl group bonded to a silicon atom to which an alkoxy group is directly bonded via a divalent hydrocarbon group which may contain a silicon atom, an oxygen atom and a nitrogen atom, or A monovalent perfluorooxyalkyl group, R ⁶ is independently of each other an alkyl group having 1 to 6 carbon atoms, and R ⁷ is independently of each other an unsubstituted or substituted monovalent hydrocarbon group. F is an integer of 1 to 3, g is 0, 1 or 2, and f + g is an integer of 1 to 3.)
The heat conductive fluorine-containing adhesive composition according to [11], which is a fluorine-containing organosilicon compound represented by the formula:
[13]
The heat-conducting fluorine-containing material according to any one of [1] to [12], wherein a mass reduction rate when the component (E) is heated at 105 ° C. for 3 hours is 50.0% by mass or less Adhesive composition.
[14]
The component (F) is a monovalent perfluoroalkyl group bonded to a silicon atom via a divalent hydrocarbon group which may contain a silicon atom, an oxygen atom and a nitrogen atom in one molecule, or a monovalent perfluoroalkyl group. The heat conductive fluorine-containing adhesive composition according to any one of [1] to [13], which is an organopolysiloxane having one or more fluorooxyalkyl groups.
[15]
The heat conductive fluorine-containing adhesive composition according to [14], wherein the component (F) is a cyclic organopolysiloxane represented by the following general formula (17).

(In the formula, R ¹⁵ independently represents an unsubstituted or substituted monovalent hydrocarbon group, and X independently represents a divalent hydrocarbon which may contain a silicon atom, an oxygen atom and a nitrogen atom. A monovalent perfluoroalkyl group or a monovalent perfluorooxyalkyl group bonded to a silicon atom via a group, and Y is independently of each other via a divalent hydrocarbon group which may contain an oxygen atom. An epoxy group or trialkoxysilyl group bonded to a silicon atom, k ′ is an integer of 1-6, l ′ is an integer of 1-4, m ′ is an integer of 1-4, k ′ + L ′ + m ′ is an integer of 4 to 10, provided that — (SiO) (H) R ¹⁵ —, — (SiO) (X) R ¹⁵ —, and — (SiO) (Y) R ¹⁵ — are bonded. The order of is not limited.)
[16]
The heat-conductive fluorine-containing adhesive composition according to any one of [1] to [15], wherein the heat-conductive fluorine-containing adhesive composition has a viscosity at 23 ° C of 1,000 Pa · s or less. Composition.
[17]
An electrical / electronic component, wherein the cured product of the thermally conductive fluorine-containing adhesive composition according to any one of [1] to [16] is at least a part of its configuration.
[18]
The electric / electronic component according to [17], which is for vehicle use.

  The heat conductive fluorine-containing adhesive composition of the present invention has good fluidity and excellent oil resistance and heat conductivity by combining the above components (A) to (F), and further, metal and plastic. The hardened | cured material which adhere | attaches firmly with respect to various base materials, such as can be formed.

The thermally conductive fluorine-containing adhesive composition of the present invention is
(A) an alkenyl group-containing linear polyfluoro compound,
(B) a fluorine-containing organohydrogensiloxane having a fluorine-containing organic group and a SiH group, and having no epoxy group and trialkoxysilyl group,
(C) platinum group metal catalyst,
(D) a thermally conductive filler,
(E) a fluorine-containing organic silicon compound having a fluorine-containing organic group and an alkoxy group, and having no epoxy group and SiH group,
(F) An organopolysiloxane having a SiH group, a fluorine-containing organic group, and an epoxy group and / or trialkoxysilyl group is contained as an essential component. Hereinafter, the present invention will be described in detail.

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

The alkenyl group contained in the component (A) is preferably an alkenyl group having 2 to 8 carbon atoms, particularly 2 to 6 carbon atoms, and preferably having a CH ₂ ═CH— structure at the terminal. Group, propenyl group, isopropenyl group, butenyl group, hexenyl group and the like, among which vinyl group and allyl group are particularly preferable.

  (A) As for alkenyl group content contained in the linear polyfluoro compound of a component, 0.005-0.3 mol / 100g is preferable, More preferably, it is 0.007-0.2 mol / 100g. When the alkenyl group content is 0.005 mol / 100 g or more, the degree of crosslinking is sufficient, and there is no possibility of causing a curing failure. On the other hand, if the alkenyl group content is 0.3 mol / 100 g or less, there is no possibility that the mechanical properties of the cured product obtained by curing the composition of the present invention are impaired.

The perfluoropolyether structure of component (A) is
-C _a F _2a O-
(In the formula, a is an integer of 1 to 6.)
And a large number of repeating units such as those represented by the following general formula (1).
− (C _a F _2a O) _b − (1)
(In the formula, a is an integer of 1 to 6, and b is an integer of 1 to 300, preferably an integer of 1 to 200.)

Examples of the repeating unit represented by -C _a F _2a 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-

Among these, a repeating unit represented by the following formula is particularly preferable.
-CF ₂ O-
-CF ₂ CF ₂ O-
-CF ₂ CF ₂ CF ₂ O-
-CF ₂ (CF ₃ ) CF ₂ O-

  In addition, the perfluoropolyether structure of the component (A) may be composed of one of the above repeating units, or may be composed of a combination of two or more.

（式中、Ｒ¹及びＲ²は互いに独立して、アルケニル基、又は非置換若しくは置換の脂肪族不飽和結合を有さない１価の炭化水素基であり、Ｒ¹及びＲ²の合計のうち二つ以上はアルケニル基である。Ｒ³は互いに独立して、水素原子、又は非置換若しくは置換の１価の炭化水素基であり、ｃ及びｄはそれぞれ１〜１５０の整数であって、かつｃ＋ｄの平均値は２〜３００であり、ｅは１〜６の整数である。）

（式中、Ｒ⁴は互いに独立して、炭素数１〜６のアルキレン基であり、Ｒ⁵は互いに独立して、水素原子又はフッ素置換されていてもよい炭素数１〜４のアルキル基である。また、Ｒ¹、Ｒ²、ｃ、ｄ及びｅは上記と同じである。） Preferable examples of the component (A) include linear polyfluoro compounds represented by the following general formula (2) and the following general formula (3).

(In the formula, R ¹ and R ² are each independently an alkenyl group or a monovalent hydrocarbon group having no unsubstituted or substituted aliphatic unsaturated bond, and the total of R ¹ and R ² is Two or more of them are alkenyl groups, R ³ is independently a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group, and c and d are each an integer of 1 to 150, And the average value of c + d is 2 to 300, and e is an integer of 1 to 6.)

(In the formula, R ⁴ is independently an alkylene group having 1 to 6 carbon atoms, and R ⁵ is independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms optionally substituted with fluorine. And R ¹ , R ² , c, d and e are the same as above.)

Here, examples of the alkenyl group contained in R ¹ and R ² include the same alkenyl groups as described above, and other monovalent hydrocarbon groups having no unsubstituted or substituted aliphatic unsaturated bond include: Those having 1 to 12 carbon atoms are preferable, and those having 1 to 10 carbon atoms are particularly preferable. Specifically, alkyl groups such as a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, a cyclohexyl group, and an octyl group. An aryl group such as a phenyl group or a tolyl group; an aralkyl group such as a benzyl group or a phenylethyl group; or a monovalent hydrocarbon group in which part or all of the hydrogen atoms of these groups are substituted with a halogen atom such as fluorine; Etc. R ¹ and R ² are particularly preferably a vinyl group, an allyl group, a methyl group and an ethyl group.

Examples of the unsubstituted or substituted monovalent hydrocarbon group contained in R ³ include the examples of the monovalent hydrocarbon group having no unsubstituted or substituted aliphatic unsaturated bond of R ¹ and R ² described above. Similar groups are mentioned. R ³ is preferably a hydrogen atom, a methyl group, or an ethyl group.

R ⁴ is an alkylene group having 1 to 6 carbon atoms, preferably 2 to 6 carbon atoms, and specifically includes a methylene group, ethylene group, propylene group (trimethylene group, methylethylene group), butylene group (tetramethylene group). , Methylpropylene group), hexamethylene group and the like, and ethylene group and propylene group are particularly preferable.

R ⁵ is independently a hydrogen atom or a fluorine-substituted alkyl group having 1 to 4 carbon atoms, and as a fluorine-substituted alkyl group having 1 to 4 carbon atoms, specifically, Examples thereof include alkyl groups such as a methyl group, an ethyl group, a propyl group, and a butyl group, 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. Among these, a hydrogen atom is preferable.

  Further, each of c and d is preferably an integer of 1 to 150, more preferably an integer of 1 to 100, and the average value of c + d is preferably 2 to 300, more preferably 2 to 200. Further, e is preferably an integer of 1 to 6, more preferably an integer of 1 to 4.

（式中、ｃ及びｄはそれぞれ１〜１５０の整数である。） Specific examples of the linear polyfluoro compound represented by the general formula (2) include those represented by the following formula. Me represents a methyl group, and Et represents an ethyl group.

(In the formula, c and d are each an integer of 1 to 150.)

（式中、ｃ及びｄはそれぞれ１〜１５０の整数である。）

(In the formula, c and d are each an integer of 1 to 150.)

（式中、ｃ及びｄはそれぞれ１〜１５０の整数である。）

(In the formula, c and d are each an integer of 1 to 150.)

（式中、ｃ及びｄはそれぞれ１〜１００の整数である。） Specific examples of the linear polyfluoro compound represented by the general formula (3) include those represented by the following formula.

(In the formula, c and d are each an integer of 1 to 100.)

（式中、ｃ及びｄはそれぞれ１〜１００の整数である。）

(In the formula, c and d are each an integer of 1 to 100.)

  In the present invention, the viscosity can be measured by a rotational viscometer (for example, BL type, BH type, BS type, cone plate type, rheometer, etc.). In particular, the above general formula (2) or (3) The viscosity (23 ° C.) of the linear polyfluoro compound represented by the formula is 500 to 100,000 mPa · s, more preferably 1,000 to 50,000 mPa · s, as measured by the viscosity specified in JIS K7117-1. It is preferable to be within the range. If the viscosity is 500 mPa · s or more, the storage stability of the composition of the present invention is not likely to deteriorate, and if it is 100,000 mPa · s or less, the extensibility of the resulting composition does not deteriorate. .

  Further, the degree of polymerization (or molecular weight) of the linear polyfluoro compound reflected by the number of repeating perfluorooxyalkylene units constituting the perfluoropolyether structure of the main chain is, for example, using a fluorine-based solvent as a developing solvent. It can be determined as the number average degree of polymerization (or number average molecular weight) in terms of polystyrene in gel permeation chromatography (GPC) analysis.

  These linear polyfluoro compounds can be used singly or in combination of two or more. That is, in the linear polyfluoro compound represented by the general formula (2) or (3), one kind can be used alone or two or more kinds can be used in combination. The linear polyfluoro compounds represented by (2) and (3) can also be used in combination.

[Component (B)]
The component (B) has a monovalent perfluoroalkyl group or a monovalent perfluorooxyalkyl group in one molecule, or has a divalent perfluoroalkylene group or a divalent perfluorooxyalkylene group. Furthermore, it is a fluorine-containing organohydrogensiloxane having two or more hydrogen atoms (SiH group or hydrosilyl group) directly bonded to a silicon atom and having no epoxy group and alkoxy group directly bonded to a silicon atom in the molecule, Preferably, one molecule has at least one monovalent or divalent fluorine-containing organic group and two or more hydrogen atoms directly bonded to a silicon atom, and an epoxy group, an alkoxy group directly bonded to a silicon atom, or cyclic It is a fluorine-containing organohydrogensiloxane having no other functional group other than SiH groups such as carboxylic anhydride residue, and is a cross-linking of the component (A) It is intended to function as.
However, the “other functional group” herein refers to a divalent linking group that connects a perfluoroalkyl group, a perfluorooxyalkyl group, a perfluoroalkylene group, or a perfluorooxyalkylene group and a silicon atom constituting the polysiloxane. The divalent polar group (polar structure) such as ether bond oxygen atom, amide bond, carbonyl bond, ester bond and the like which may be contained in the linking group is excluded.

  The monovalent perfluoroalkyl group, monovalent perfluorooxyalkyl group, divalent perfluoroalkylene group and divalent perfluorooxyalkylene group are compatible with the component (A), dispersibility and curing. This is a group introduced from the viewpoint of uniformity later.

（式中、ｉは１〜５０の整数、好ましくは２〜３０の整数である。） Examples of the monovalent perfluoroalkyl group or monovalent perfluorooxyalkyl group include groups represented by the following general formula (5) or (6).
C _h F _{2h + 1} − (5)
(In the formula, h is an integer of 1 to 10, preferably an integer of 3 to 7.)

(In the formula, i is an integer of 1 to 50, preferably an integer of 2 to 30.)

（式中、ｋ及びｌはそれぞれ１以上の整数、好ましくは１〜１００の整数であり、ｋ＋ｌの平均値は２〜２００、好ましくは２〜１００である。）
−ＣＦ₂Ｏ−（ＣＦ₂ＣＦ₂Ｏ）_m（ＣＦ₂Ｏ）_n−ＣＦ₂− （９）
（式中、ｍ及びｎはそれぞれ１〜５０の整数、好ましくは１〜３０の整数であり、ｍ＋ｎの平均値は２〜１００、好ましくは２〜８０である。各繰り返し単位同士はランダムに結合されていてよい。） Examples of the divalent perfluoroalkylene group or the divalent perfluorooxyalkylene group include groups represented by the following general formulas (7) to (9).
−C _j F _2j − (7)
(In the formula, j is an integer of 1 to 20, preferably an integer of 2 to 10.)

(In the formula, k and l are each an integer of 1 or more, preferably an integer of 1 to 100, and the average value of k + 1 is 2 to 200, preferably 2 to 100.)
—CF ₂ O— (CF ₂ CF ₂ O) _m (CF ₂ O) _n —CF ₂ — (9)
(In the formula, m and n are each an integer of 1 to 50, preferably an integer of 1 to 30, and an average value of m + n is 2 to 100, preferably 2 to 80. Each repeating unit is bonded at random. May be.)

The perfluoroalkyl group, perfluorooxyalkyl group, perfluoroalkylene group or perfluorooxyalkylene group and the silicon atom constituting the polysiloxane are preferably connected by a divalent linking group. The valent linking group is 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. Specifically, a group consisting of an alkylene group, an arylene group and a combination thereof, or a diorganosilylene group such as an ether bond oxygen atom, an amide bond, a carbonyl bond, an ester bond, and a dimethylsilylene group. One or more structures selected from more than one type can be exemplified, 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-
(However, Ph is a phenyl group, and Ph ′ is a phenylene group.)
And those having 2 to 12 carbon atoms.

  In addition, 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 the component (B) have 1 carbon atom. -20, preferably 1-12 unsubstituted or substituted alkyl groups or aryl groups, for example, alkyl groups such as methyl, ethyl, propyl, butyl, hexyl, cyclohexyl, octyl, decyl, etc. A group; an aryl group such as a phenyl group, a tolyl group, or a naphthyl group, and a part or all of the hydrogen atoms of these groups are substituted with a halogen atom such as a chlorine atom or a cyano group, such as a chloromethyl group, chloro A propyl group, a cyanoethyl group, etc. are mentioned. Among these, a methyl group is preferable.

The polysiloxane structure constituting the fluorine-containing organohydrogensiloxane of component (B) may be any of cyclic, chain, three-dimensional network, and combinations thereof. The number of silicon atoms in the fluorine-containing organohydrogensiloxane is not particularly limited, but is usually 2 to 60, preferably 3 to 30, and more preferably about 4 to 30.
The component (B) has two or more SiH groups in one molecule, and the SiH group content is preferably 0.01-1 mol / 100 g, more preferably 0.02-0.9 mol / 100 g.

（式中、Ｄは独立して、上記の、酸素原子、窒素原子及びケイ素原子を含んでもよい２価の炭化水素基を介してポリシロキサンを構成するケイ素原子に結合した１価のパーフルオロアルキル基又は１価のパーフルオロオキシアルキル基であり、１価のパーフルオロアルキル基又は１価のパーフルオロオキシアルキル基としては、上記一般式（５）又は（６）で表される基が挙げられる。Ｒ⁸は独立して、上記の、炭素数１〜２０、好ましくは１〜１２の非置換若しくは置換のアルキル基又はアリール基である。また、ｐは２〜６の整数、好ましくは３〜６の整数であり、ｑは１〜４の整数、好ましくは１〜３の整数であり、ｐ＋ｑは４〜１０の整数、好ましくは４〜９の整数である。） Examples of the component (B) include those represented by the following general formulas (10) to (16).

(In the formula, D is independently a monovalent perfluoroalkyl bonded to the silicon atom constituting the polysiloxane via the above-described divalent hydrocarbon group which may contain an oxygen atom, a nitrogen atom and a silicon atom. Group or monovalent perfluorooxyalkyl group, and examples of the monovalent perfluoroalkyl group or monovalent perfluorooxyalkyl group include groups represented by the general formula (5) or (6). R ⁸ is independently an unsubstituted or substituted alkyl group or aryl group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms, and p is an integer of 2 to 6, preferably 3 to 6 is an integer, q is an integer of 1 to 4, preferably an integer of 1 to 3, and p + q is an integer of 4 to 10, preferably an integer of 4 to 9.)

（式中、Ｅは独立して、上記Ｄと同じであり、Ｒ⁹は独立して、上記Ｒ⁸と同じである。またｒは２〜５０の整数、好ましくは３〜３０の整数である。）

(In the formula, E is independently the same as D above, R ⁹ is independently the same as R ⁸ above, and r is an integer of 2 to 50, preferably an integer of 3 to 30. .)

（式中、Ｇは独立して、上記Ｄと同じであり、Ｒ¹⁰は独立して、上記Ｒ⁸と同じである。ｓは２〜５０の整数、好ましくは３〜３０の整数であり、ｔは１〜４０の整数、好ましくは１〜２０の整数であり、ｓ＋ｔは４〜６０の整数、好ましくは４〜５０の整数である。）

(In the formula, G is independently the same as D, R ¹⁰ is independently the same as R ^{8. S} is an integer of 2 to 50, preferably an integer of 3 to 30; t is an integer of 1 to 40, preferably an integer of 1 to 20, and s + t is an integer of 4 to 60, preferably an integer of 4 to 50.)

（式中、Ｊは独立して、上記Ｄと同じであり、Ｒ¹¹は独立して、上記Ｒ⁸と同じである。ｕは２〜５０の整数、好ましくは３〜３０の整数であり、ｖは１〜４０の整数、好ましくは１〜２０の整数であり、ｕ＋ｖは４〜６０の整数、好ましくは４〜５０の整数である。）

(Wherein, J is independently the same as D above, R ¹¹ is independently the same as R ⁸ above, u is an integer of 2-50, preferably an integer of 3-30, v is an integer of 1 to 40, preferably an integer of 1 to 20, and u + v is an integer of 4 to 60, preferably an integer of 4 to 50.)

（式中、Ｌは独立して、上記Ｄと同じであり、Ｒ¹²は独立して、上記Ｒ⁸と同じである。ｗは２〜５０の整数、好ましくは３〜３０の整数であり、ｘは１〜４０の整数、好ましくは１〜２０の整数であり、ｙは１〜４０の整数、好ましくは１〜２０の整数であり、ｗ＋ｘ＋ｙは５〜６０の整数、好ましくは５〜５０の整数である。）

(Wherein L is independently the same as D above, R ¹² is independently the same as R ⁸ above, w is an integer of 2 to 50, preferably an integer of 3 to 30; x is an integer of 1 to 40, preferably an integer of 1 to 20, y is an integer of 1 to 40, preferably an integer of 1 to 20, and w + x + y is an integer of 5 to 60, preferably 5 to 50. (It is an integer.)

（式中、Ｍは、酸素原子、アルキレン基、又は酸素原子若しくは窒素原子を含んでもよい２価の炭化水素基を介してケイ素原子に結合した２価のパーフルオロアルキレン基又は２価のパーフルオロオキシアルキレン基であり、２価のパーフルオロアルキレン基又は２価のパーフルオロオキシアルキレン基としては、上記一般式（７）〜（９）で表されるいずれかの基が挙げられる。また、Ｑは独立して、上記Ｄと同じであり、Ｒ¹³は独立して、上記Ｒ⁸と同じである。また、ｚは０又は１〜３の整数であり、ａ’は０又は１〜３の整数であり、ｚ＋ａ’は２〜６の整数、好ましくは３〜５の整数である。）

(In the formula, M represents an oxygen atom, an alkylene group, or a divalent perfluoroalkylene group or a divalent perfluoro group bonded to a silicon atom via a divalent hydrocarbon group that may contain an oxygen atom or a nitrogen atom. Examples of the divalent perfluoroalkylene group or the divalent perfluorooxyalkylene group that are oxyalkylene groups include any of the groups represented by the general formulas (7) to (9). Is independently the same as D above, R ¹³ is independently the same as R ⁸ above, z is an integer of 0 or 1-3, and a ′ is an integer of 0 or 1-3. (It is an integer, and z + a ′ is an integer of 2 to 6, preferably an integer of 3 to 5.)

（式中、Ｔは上記Ｄと同じであり、Ｒ¹⁴は独立して、上記Ｒ⁸と同じである。）

(In the formula, T is the same as D above, and R ¹⁴ is independently the same as R ⁸ above.)

  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.

（式中、ｂ’は１〜１０の整数である。）

(In the formula, b ′ is an integer of 1 to 10.)

（式中、ｃ’は１〜５０の整数である。）

(In the formula, c ′ is an integer of 1 to 50.)

（式中、ｃ’は１〜５０の整数である。）

(In the formula, c ′ is an integer of 1 to 50.)

（式中、ｂ’は１〜１０の整数である。）

(In the formula, b ′ is an integer of 1 to 10.)

（式中、ｂ’は１〜１０の整数であり、ｃ’は１〜５０の整数である。）

(In the formula, b ′ is an integer of 1 to 10, and c ′ is an integer of 1 to 50.)

（式中、ｂ’は１〜１０の整数であり、ｃ’は１〜５０の整数である。）

(In the formula, b ′ is an integer of 1 to 10, and c ′ is an integer of 1 to 50.)

（式中、ｂ’は１〜１０の整数であり、ｃ’は１〜５０の整数である。）

(In the formula, b ′ is an integer of 1 to 10, and c ′ is an integer of 1 to 50.)

（式中、ｂ’は１〜１０の整数であり、ｃ’は１〜５０の整数である。）

(In the formula, b ′ is an integer of 1 to 10, and c ′ is an integer of 1 to 50.)

（式中、ｂ’は１〜１０の整数であり、ｄ’は１〜２０の整数である。）

(In the formula, b ′ is an integer of 1 to 10, and d ′ is an integer of 1 to 20.)

（式中、ｃ’は１〜５０の整数であり、ｄ’は１〜２０の整数である。）

(In the formula, c ′ is an integer of 1 to 50, and d ′ is an integer of 1 to 20.)

（式中、ｂ’は１〜１０の整数であり、ｃ’は１〜５０の整数である。）

(In the formula, b ′ is an integer of 1 to 10, and c ′ is an integer of 1 to 50.)

（式中、ｂ’は１〜１０の整数であり、ｃ’は１〜５０の整数であり、ｅ’及びｆ’はそれぞれ１〜１００の整数であり、ｅ’＋ｆ’は２〜２００の整数である。）

(Wherein b ′ is an integer of 1 to 10, c ′ is an integer of 1 to 50, e ′ and f ′ are each an integer of 1 to 100, and e ′ + f ′ is an integer of 2 to 200. (It is an integer.)

（式中、ｂ’は１〜１０の整数であり、ｃ’は１〜５０の整数であり、ｇ’及びｈ’はそれぞれ１〜５０の整数であり、ｇ’＋ｈ’は２〜１００の整数である。）

(In the formula, b ′ is an integer of 1 to 10, c ′ is an integer of 1 to 50, g ′ and h ′ are each an integer of 1 to 50, and g ′ + h ′ is 2 to 100. (It is an integer.)

This (B) component may be used individually by 1 type, and may use 2 or more types together.
The blending amount of the component (B) is 0.5 to 3 hydrogen atoms (SiH groups) directly connected to silicon atoms in the component (B) with respect to 1 mol of alkenyl groups contained in the composition of the present invention. It is the quantity which becomes mol, Preferably it is the quantity (molar ratio) which becomes 0.6-2 mol. When the SiH group is less than 0.5 mol, the degree of crosslinking becomes insufficient, while when it exceeds 3 mol, the storage stability is impaired, or the heat resistance of the cured product obtained after curing is lowered.

[Component (C)]
The platinum group metal catalyst which is the component (C) of the present invention is a hydrosilylation reaction catalyst. The hydrosilylation reaction catalyst comprises an alkenyl group contained in the composition, in particular, an alkenyl group in the component (A) and an SiH group contained in the composition, in particular, an SiH group in the component (B). It is a catalyst that promotes the addition reaction. This hydrosilylation reaction catalyst is generally a noble metal or a compound thereof and is expensive, and thus platinum or platinum compounds that are relatively easily available are often used.

Examples of the platinum compound include chloroplatinic acid or a complex of chloroplatinic acid and an olefin such as ethylene, a complex of alcohol or vinylsiloxane, metal platinum supported on silica, alumina, carbon, or the like. Rhodium, ruthenium, iridium, and palladium compounds are also known as platinum group metal catalysts other than platinum or its compounds. For example, RhCl (PPh ₃ ) ₃ , RhCl (CO) (PPh ₃ ) ₂ , Ru ₃ ( CO) ₁₂ , IrCl (CO) (PPh ₃ ) ₂ , Pd (PPh ₃ ) _{4 and the} like can be exemplified. In the above formula, Ph is a phenyl group.

  When these catalysts are used, they can be used in a solid state when they are solid catalysts, but in order to obtain a more uniform cured product, chloroplatinic acid or a complex such as toluene or ethanol is used. It is preferable to use what was melt | dissolved in the appropriate solvent of (A), making it compatible with the linear polyfluoro compound of (A) component.

  The blending amount of the component (C) is an effective amount as a hydrosilylation reaction catalyst, and is usually 0.1 to 2,000 ppm, preferably 0.1 to 500 ppm, particularly preferably 0.1 to the component (A). Although it is 5-200 ppm (in mass conversion of platinum group metal atoms), it can be appropriately increased or decreased depending on the desired curing rate.

[(D) component]
(D) component of this invention is a heat conductive filler used in order to provide thermal conductivity to the composition of this invention, for example, gold | metal | money, silver, copper, iron, nickel, aluminum, metal silicon, etc. Metals, alumina, magnesium oxide, beryllium oxide, chromium oxide, titanium oxide, zinc oxide, silicon oxide and other metal oxides, boron nitride, silicon nitride, aluminum nitride and other metal nitrides, aluminum hydroxide, magnesium hydroxide Metal hydroxides such as boron carbide, titanium carbide, silicon carbide, etc., Fe-Si alloys, Fe-Al alloys, Fe-Al-Si alloys, Fe-Si-Cr alloys, Fe-Ni alloys, Fe -Ni-Co alloy, Fe-Al-Si-Cr alloy, Fe-Si-B alloy, Fe-Si-Co-B alloy soft magnetic alloy, Mn-Zn ferrite, Mn-Mg- n ferrite, Mg-Cu-Zn ferrite, Ni-Zn ferrite, Ni-Cu-Zn ferrite, ferrite such as Cu-Zn ferrite, carbon black and mixtures of two or more of these and the like.

  In the present invention, when electrical insulation is required, the component (D) is preferably a metal oxide, metal nitride, metal hydroxide, or metal carbide, particularly preferably a metal oxide. Alumina is preferred.

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

The average particle diameter of the amorphous alumina is preferably 0.2 to 5.0 μm, and more preferably 0.4 to 4.0 μm. When the average particle size is 0.2 μm or more, the viscosity of the composition of the present invention is increased, and there is no possibility that the workability and moldability of the composition are deteriorated. On the other hand, if the average particle size is 5.0 μm or less, there is no possibility that the electrical insulation of the cured product obtained by curing the composition of the present invention is impaired. As the amorphous alumina, one kind may be used alone, or two or more kinds may be used in combination. As the amorphous alumina, an ordinary commercial product can be used. The average particle diameter is a value of a volume-based cumulative average particle diameter (median diameter) D ₅₀ measured by Microtrac MT3300EX, a particle size analyzer manufactured by Nikkiso Co., Ltd.

  The average particle diameter of the spherical alumina is preferably 5.0 to 100 μm, and more preferably 7.0 to 90 μm. If the average particle size is 5.0 μm or more, the viscosity of the composition of the present invention will be high, and there is no possibility that the workability and moldability of the composition will deteriorate. On the other hand, when the average particle size is 100 μm or less, there is no fear that the spherical alumina is not uniformly dispersed in the composition of the present invention. As the spherical alumina, one kind may be used alone, or two or more kinds may be used in combination. In addition, a normal commercial item can be used for this spherical alumina. The average particle size is a value measured in the same manner as the average particle size of amorphous alumina.

  The usage-amount of this (D) component is 100-4,000 mass parts with respect to 100 mass parts of (A) component, Preferably it is the range of 200-3,500 mass parts. When the amount is less than 100 parts by mass, the thermal conductivity of the cured product obtained by curing the composition of the present invention is not sufficient, and when it exceeds 4,000 parts by mass, the component (D) is added to the present invention. It will not disperse uniformly in the composition.

[(E) component]
The component (E) has at least one monovalent perfluoroalkyl group or monovalent perfluorooxyalkyl group in one molecule, and further has at least one alkoxy group directly connected to a silicon atom, and It is a fluorine-containing organic silicon compound that does not have an epoxy group and a hydrogen atom (SiH group) directly bonded to a silicon atom in the molecule, preferably has at least one monovalent fluorine-containing organic group in one molecule, Further, fluorine-containing organosilicon compound having at least one alkoxy group directly bonded to a silicon atom and having no other functional groups such as an epoxy group, a hydrogen atom directly bonded to a silicon atom, and a cyclic carboxylic anhydride residue And serves as a surface treatment agent and / or a dispersant (wetter) for component (D). During the preparation of the composition, the component (D) is hydrophobized by the component (E), and the wettability of the component (D) with respect to the component (A) is improved. Can be added. Moreover, the dispersibility of the component (D) in the composition can also be improved.
However, the “other functional group” herein refers to an ether-bonded oxygen atom or an amide bond that may be contained in a divalent linking group that links a perfluoroalkyl group or perfluorooxyalkyl group to a silicon atom. In addition, divalent polar groups (polar structure) such as carbonyl bond and ester bond are excluded.

The monovalent perfluoroalkyl group and monovalent perfluorooxyalkyl group are groups introduced from the viewpoints of compatibility with the component (A), dispersibility, and the like.
Examples of the monovalent perfluoroalkyl group or monovalent perfluorooxyalkyl group include the groups represented by the general formula (5) or (6) described above.

The monovalent perfluoroalkyl group or monovalent perfluorooxyalkyl group is directly linked to an alkoxy group via a divalent hydrocarbon group (linking group) which may contain a silicon atom, an oxygen atom and a nitrogen atom. The divalent hydrocarbon group is preferably an alkylene group, an arylene group, or a combination thereof, or an ether bond oxygen atom, an amide bond, a carbonyl bond, or an ester bond. And one or two or more structures selected from the group consisting of diorganosilylene groups such as dimethylsilylene groups may be interposed, 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-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 -
(However, Ph is a phenyl group, and Ph ′ is a phenylene group.)
And those having 2 to 12 carbon atoms.

As said (E) component, what is represented by following General formula (4) is preferable.
A _f R ⁷ _g Si (OR ⁶ ) _4-fg (4)
(In the formula, A is independently a monovalent perfluoroalkyl group bonded to a silicon atom to which an alkoxy group is directly bonded via a divalent hydrocarbon group which may contain a silicon atom, an oxygen atom and a nitrogen atom, or A monovalent perfluorooxyalkyl group as described above, and R ⁶ independently of one another is an alkyl group having 1 to 6 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms. In particular, a methyl group or an ethyl group is preferable, and R ^{7 s} are each independently an unsubstituted or substituted monovalent hydrocarbon group, and the above-described unsubstituted or substituted aliphatic unsaturated bond of R ¹ and R ^2. And the same groups as those exemplified for the monovalent hydrocarbon group having no benzene, f is an integer of 1 to 3, g is 0, 1 or 2, and f + g is 1 to 3. (It is an integer.)

  In the component (E), the mass reduction rate (heat loss) when heated at 105 ° C. for 3 hours is preferably 50.0% by mass or less, and more preferably 40.0% by mass or less. If this mass reduction rate is 50.0 mass% or less, there is no possibility that bubbles may be generated in a cured product obtained by curing the composition of the present invention.

  Specific examples of the component (E) include the following compounds. In the following formulae, Me represents a methyl group, and Et represents an ethyl group.

（式中、ｉ’は１〜１０の整数であり、ｊ’は１〜５０の整数である。）

(In the formula, i ′ is an integer of 1 to 10, and j ′ is an integer of 1 to 50.)

（式中、ｊ’は１〜５０の整数である。）

(Where j ′ is an integer of 1 to 50)

This (E) component may be used individually by 1 type, and may use 2 or more types together.
The compounding amount of the component (E) is 0.01 to 300 parts by mass, more preferably 0.1 to 250 parts by mass with respect to 100 parts by mass of the component (A). When the amount is less than 0.01 parts by mass, the surface treatment of the component (D) with the component (E) becomes insufficient. On the other hand, when the amount is more than 300 parts by mass, the composition of the present invention is cured. The mechanical strength of the resulting cured product is impaired.

[(F) component]
The component (F) is a divalent hydrocarbon group which may contain a hydrogen atom directly bonded to a silicon atom, a monovalent perfluoroalkyl group or a monovalent perfluorooxyalkyl group, and an oxygen atom in one molecule. An organopolysiloxane having an epoxy group or a trialkoxysilyl group bonded to a silicon atom via a hydrogen atom, or both, as an adhesion-imparting agent that gives self-adhesive properties to a cured product obtained by curing the composition of the present invention It has the function of.

The monovalent perfluoroalkyl group or monovalent perfluorooxyalkyl group is a group introduced from the viewpoints of compatibility with the component (A), dispersibility, uniformity after curing, and the like.
Examples of the monovalent perfluoroalkyl group or monovalent perfluorooxyalkyl group include the groups represented by the general formula (5) or (6) described above.

The monovalent perfluoroalkyl group or monovalent perfluorooxyalkyl group constitutes a polysiloxane via a divalent hydrocarbon group (linking group) which may contain a silicon atom, an oxygen atom and a nitrogen atom. The divalent hydrocarbon group is preferably an alkylene group, an arylene group, or a combination thereof, or an ether-bonded oxygen atom, an amide bond, a carbonyl bond, or an ester bond. And one or two or more structures selected from the group consisting of diorganosilylene groups such as dimethylsilylene groups may be interposed, 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 -,
_{-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-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 -
(However, Ph is a phenyl group, and Ph ′ is a phenylene group.)
And those having 2 to 12 carbon atoms.

（式中、ｋ’は１〜６の整数、好ましくは１〜５の整数であり、ｌ’は１〜４の整数、好ましくは１〜３の整数であり、ｍ’は１〜４の整数、好ましくは１〜３の整数であり、ｋ’＋ｌ’＋ｍ’は４〜１０の整数、好ましくは４〜８の整数である。また、Ｒ¹⁵は互いに独立して非置換又は置換の１価の炭化水素基であり、Ｘは互いに独立して、ケイ素原子、酸素原子及び窒素原子を含んでもよい２価の炭化水素基を介してケイ素原子に結合した１価のパーフルオロアルキル基又は１価のパーフルオロオキシアルキル基であり、Ｙは互いに独立して、酸素原子を含んでもよい２価の炭化水素基を介してケイ素原子に結合したエポキシ基若しくはトリアルコキシシリル基である。但し、−（ＳｉＯ）（Ｈ）Ｒ¹⁵−、−（ＳｉＯ）（Ｘ）Ｒ¹⁵−、及び−（ＳｉＯ）（Ｙ）Ｒ¹⁵−の結合の順番は限定されない。） The organopolysiloxane of the component (F) is preferably a cyclic organopolysiloxane represented by the following general formula (17).

(In the formula, k ′ is an integer of 1 to 6, preferably 1 to 5, l ′ is an integer of 1 to 4, preferably 1 to 3, and m ′ is an integer of 1 to 4. , Preferably an integer of 1 to 3, and k ′ + l ′ + m ′ is an integer of 4 to 10, preferably an integer of 4 to 8. In addition, R ¹⁵ is independently an unsubstituted or substituted monovalent group. X is a monovalent perfluoroalkyl group bonded to a silicon atom via a divalent hydrocarbon group which may contain a silicon atom, an oxygen atom and a nitrogen atom independently of each other, or a monovalent group Y is independently an epoxy group or trialkoxysilyl group bonded to a silicon atom via a divalent hydrocarbon group which may contain an oxygen atom, independently of each other. ^{SiO) (H) R 15 -} , - (SiO) (X) R 15 -, and - ( iO) (Y) R ¹⁵ - coupling of the order of is not limited).

In the above general formula (17), R ¹⁵ are each independently an unsubstituted or substituted monovalent hydrocarbon group, and examples thereof include the same groups as R ⁸ described above, and a methyl group and an ethyl group are preferable.

  X is independently of each other a monovalent perfluoroalkyl group bonded to a silicon atom via a divalent hydrocarbon group which may contain a silicon atom, an oxygen atom and a nitrogen atom, or a monovalent perfluoro group. Examples of the monovalent perfluoroalkyl group or monovalent perfluorooxyalkyl group that are fluorooxyalkyl groups include the groups represented by the general formula (5) or (6) described above.

Y is independently an epoxy group or trialkoxysilyl group bonded to a silicon atom via a divalent hydrocarbon group which may contain an oxygen atom.
As such an epoxy group, what is represented by the following general formula (18) is mentioned, for example.

In the general formula (18), R ¹⁶ may be an oxygen atom, preferably a divalent hydrocarbon group having 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms. , Alkylene groups such as methylene group, ethylene group, propylene group, butylene group, hexylene group and octylene group, cycloalkylene groups such as cyclohexylene group, oxyalkylene groups such as oxyethylene group, oxypropylene group and oxybutylene group Can be mentioned.

Specific examples of such an epoxy group include those shown below.

On the other hand, examples of the trialkoxysilyl group include those represented by the following general formula (19).
—R ¹⁷ —Si (OR ¹⁸ ) ₃ (19)

In the above general formula (19), R ¹⁷ is preferably a divalent hydrocarbon group having 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, specifically, a methylene group, an ethylene group, or a propylene group. , Alkylene groups such as butylene group, hexylene group, cyclohexylene group and octylene group. R ¹⁸ is preferably a monovalent hydrocarbon group having 1 to 8 carbon atoms, more preferably 1 to 4 carbon atoms, and specifically, an alkyl group such as a methyl group, an ethyl group, or an n-propyl group. Etc.

Specific examples of such trialkoxysilyl groups include those shown below.
_{- (CH 2) 2 -Si (} OCH 3) 3
_{- (CH 2) 3 -Si (} OCH 3) 3
_{- (CH 2) 2 -Si (} OCH 2 CH 3) 3
_{- (CH 2) 3 -Si (} OCH 2 CH 3) 3

  Examples of such component (F) include the following compounds. Me represents a methyl group, and Et represents an ethyl group.

（式中、ｂ’は１〜１０の整数である。）

(In the formula, b ′ is an integer of 1 to 10.)

（式中、ｃ’は１〜５０の整数である。）

(In the formula, c ′ is an integer of 1 to 50.)

（式中、ｂ’は１〜１０の整数である。）

(In the formula, b ′ is an integer of 1 to 10.)

（式中、ｃ’は１〜５０の整数である。）

(In the formula, c ′ is an integer of 1 to 50.)

（式中、ｂ’は１〜１０の整数である。）

(In the formula, b ′ is an integer of 1 to 10.)

（式中、ｃ’は１〜５０の整数である。）

(In the formula, c ′ is an integer of 1 to 50.)

  This (F) component may be used individually by 1 type, and may use 2 or more types together. Moreover, the usage-amount of (F) component is the range of 0.1-20 mass parts with respect to 100 mass parts of (A) component, Preferably it is the range of 0.1-10 mass parts, More preferably It is the range of 0.5-8 mass parts. When the amount is less than 0.1 parts by mass, sufficient adhesiveness cannot be obtained. When the amount exceeds 20 parts by mass, the physical strength of a cured product obtained by curing the composition of the present invention is lowered.

  In the present invention, the total amount of alkenyl groups contained in the composition of the present invention (for example, the total of alkenyl groups contained in the component (A) and optional components described later) is 1 mol of the present invention. The total of hydrogen atoms (SiH groups) directly bonded to silicon atoms contained in the composition (for example, the sum of SiH groups contained in the components (B) and (F)) is 0.51 to 3.5 mol. In particular, the amount (molar ratio) is preferably 0.6 to 2.5 mol.

[Other ingredients]
In addition to the above components (A) to (F), the thermally conductive fluorine-containing adhesive composition of the present invention includes, as an optional component, a plasticizer, a viscosity modifier, a flexible, Various compounding agents such as a property-imparting agent, an inorganic filler (other than the component (D)), a hydrosilylation addition reaction controller, and an adhesion promoter can be added as necessary. The compounding quantity of these additives is arbitrary in the range which does not impair the objective of this invention.

As a plasticizer, a viscosity modifier, and a flexibility imparting agent, linear polyfluoro compounds represented by the following general formulas (20) and (21) and / or poly represented by the following general formula (22) Fluoromonoalkenyl compounds can be used.
_{F- (CF 2 CF 2 CF 2} O) n '-Z (20)
(Wherein, Z is _{C o 'F 2o' + 1} - ' a is represented by an integer of 1 to 3) group, n' (o is an integer from 1 to 500, preferably from 2 to 300 (It is an integer.)
A '- {(OCF (CF 3) CF 2) p' - (OCF 2 CF 2) q '- (OCF 2) r'} -O-A '
(21)
(In the formula, A ′ is the same as Z above, and p ′ and q ′ are each an integer of 0 to 300, preferably an integer of 0 to 150, provided that both p ′ and q ′ are 0. In addition, r ′ is an integer of 1 to 300, preferably an integer of 1 to 150. Each repeating unit may be bonded at random.)

（ｏ位、ｍ位又はｐ位で示されるジメチルフェニルシリレン基であり、左端が窒素原子に、右端が炭素原子に結合される。）

（左端が窒素原子に、右端が炭素原子に結合される。）〕であり、ｓ’は０又は１である。］ _{Rf- (D ') s' -CH} = CH 2 (22)
[Wherein Rf is the following general formula (23)
_{F- [CF (CF 3) CF} 2 O] t '-C u' F 2u '- (23)
(In the formula, t ′ is an integer of 1 to 200, preferably an integer of 1 to 150, and u ′ is an integer of 1 to 3.)
D ′ is —CH ₂ —, —OCH ₂ —, —CH ₂ OCH ₂ — or —CO—NR ¹⁹ —E ′ — [(In these groups, the left end is Rf, The right end is bonded to a carbon atom, R ¹⁹ is a hydrogen atom, a methyl group, a phenyl group or an allyl group, E ′ is —CH ₂ —, a group represented by the following structural formula (24), or the following structural formula It is group shown by (25).

(A dimethylphenylsilylene group shown at the o-position, m-position or p-position, with the left end bonded to a nitrogen atom and the right end bonded to a carbon atom.

(The left end is bonded to a nitrogen atom and the right end is bonded to a carbon atom.)], And s ′ is 0 or 1. ]

Specific examples of the linear polyfluoro compound represented by the general formula (20) or (21) include the following.
_{F- (CF 2 CF 2 CF 2} O) v '-CF 2 CF 3
(V ′ is an integer of 1 to 200.)
_{CF 3 - {(OCF (CF} 3) CF 2) w '- (OCF 2) x'} -O-CF 3
(W ′ is an integer of 1 to 200, and x ′ is an integer of 1 to 200. Each repeating unit may be bonded at random.)
_{CF 3 - {(OCF 2 CF} 2) y '- (OCF 2) z'} -O-CF 3
(Y ′ is an integer of 1 to 200, and z ′ is an integer of 1 to 200. Each repeating unit may be bonded at random.)

  The linear polyfluoro compound represented by the general formula (20) or (21) may be used alone or in combination of two or more.

  Specific examples of the polyfluoromonoalkenyl compound represented by the general formula (22) include the following. In the following formulae, Me represents a methyl group.

（ここで、ａ”は１〜２００の整数である。）

(Here, a ″ is an integer of 1 to 200.)

  The polyfluoromonoalkenyl compound represented by the general formula (22) may be used alone or in combination of two or more.

  Examples of inorganic fillers other than the component (D) include fumed silica (fumed silica or dry silica), precipitated silica (wet silica), spherical silica (fused silica), sol-gel silica, silica aerogel, etc. A monovalent powder represented by the above general formula (5) is obtained by treating the powder or the silica powder obtained by treating the surface of the silica powder with various organochlorosilanes, organodisilazanes, cyclic organopolysilazanes, and the like. Silica-based reinforcing filler such as silica powder obtained by reprocessing with an organosilane or organosiloxane having a perfluoroalkyl group or a monovalent perfluorooxyalkyl group represented by the general formula (6), quartz Reinforcing or semi-reinforcing fillers such as powder (crystalline silica), fused silica powder, diatomaceous earth, calcium carbonate, titanium oxide Iron oxide, carbon black, inorganic pigments such as cobalt aluminate and the like.

  Examples of hydrosilylation addition reaction control agents include 1-ethynyl-1-hydroxycyclohexane, 3-methyl-1-butyn-3-ol, 3,5-dimethyl-1-hexyn-3-ol, 3-methyl- Acetylene alcohols such as 1-penten-3-ol and phenylbutynol, monovalent perfluoroalkyl groups represented by the above general formula (5), or monovalents represented by the above general formula (6) Reaction product of chlorosilane having perfluorooxyalkyl group and acetylenic alcohol, 3-methyl-3-penten-1-in, 3,5-dimethyl-3-hexen-1-in, triallyl isocyanurate, or the like, or Examples thereof include polyvinyl siloxane and organic phosphorus compounds, and the addition thereof can keep the curing reactivity and storage stability moderately.

  Examples of the adhesion promoter include carboxylic acid anhydrides, organic zirconium compounds such as zirconium alkoxide and zirconium chelate, and organic titanium compounds such as titanium alkoxide and titanium chelate.

  The manufacturing method in particular of the heat conductive fluorine-containing adhesive composition of this invention is not restrict | limited, It can manufacture by knead | mixing the said (A)-(F) component and other arbitrary components uniformly. However, in order to efficiently perform the surface treatment of the component (D) with the component (E), the components (A), (D) and (E) are first kneaded, then the component (C) is kneaded, and finally It is preferable to knead component (B) and component (F). In addition, what is necessary is just to knead | mix suitably other arbitrary components. Moreover, (D) component and (E) component may be added all at once, and may be added separately. In addition, as a manufacturing apparatus, mixing apparatuses, such as a planetary mixer, a loss mixer, and a Hobart mixer, Furthermore, kneading apparatuses, such as a kneader and a three roll, can be used as needed.

  Regarding the configuration of the thermally conductive fluorine-containing adhesive composition of the present invention, the components (A) to (F) and other optional components may be handled as one composition, so-called one-component type. Alternatively, a two-component type may be used, and both may be mixed at the time of use.

  The viscosity at 23 ° C. of the thermally conductive fluorine-containing adhesive composition of the present invention is preferably 1,000 Pa · s or less, more preferably 0.500 Pa · s or more and 700 Pa · s or less. More preferably, it is 00 Pa · s or more and 500 Pa · s or less. If it is 1,000 Pa · s or less, there is no possibility that workability is impaired. The viscosity is based on measurement with a rotary rheometer HAAKE ReoStress 6000 (ThermoFisher Scientific, Inc.). In addition, in order to make such a viscosity range, the combination of the kind of said (D) component and particle size is adjusted suitably, Furthermore, the kind and compounding quantity of said (E) component are adjusted suitably depending on the case. Can be controlled.

  The curing condition of the heat conductive fluorine-containing adhesive composition of the present invention is not particularly limited as long as it is in the range of 10 ° C to 200 ° C, but is preferably 20 ° C to 180 ° C, more preferably 40 ° C to 180 ° C. preferable. In addition, the curing time in that case may be appropriately selected as long as the crosslinking reaction and the adhesion reaction with the substrate are completed, but generally 5 minutes to 10 hours are preferable, and 8 minutes to 5 hours are more preferable. .

  The thermally conductive fluorine-containing adhesive composition of the present invention is made of a metal such as aluminum, magnesium, iron, nickel, copper, an inorganic material such as alumina ceramics, epoxy glass, or polybutylene terephthalate (PBT) depending on the curing conditions. It exhibits good adhesion to plastic substrates such as resins, polyphenylene sulfide (PPS) resins, acrylic resins and the like.

  The thermal conductivity of the cured product obtained by curing the composition of the present invention is 1.0 W / m · K or more as measured at 25 ° C. measured by the hot disk method, and 1.2 W / m · K. The above is preferable. When it is less than 1.0 W / m · K, it becomes difficult to apply to a heating element having a large calorific value. In addition, in order to set it as such thermal conductivity, it can control by adjusting suitably the combination of the compounding quantity of the said (D) component, a kind, and a particle size.

  The cured product obtained by curing the composition of the present invention has good thermal conductivity and exhibits good adhesiveness to various substrates, so as a heat transfer adhesive member for electric / electronic parts. Further, since the cured product of the present invention has good oil resistance, it can be used even in an environment exposed to automobile oil such as ATF and CVTF, so that LED headlamps, motors and solenoids are used. It is suitable as a heat transfer adhesive member used for an ECU mounted on an actuator such as a battery, a battery mounted on a next-generation vehicle such as a hybrid car or an electric vehicle, and an in-vehicle electric / electronic component such as a motor and a converter.

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 addition, the viscosity of the following (A) component shows the measured value in 23 degreeC prescribed | regulated to JISK7117-1. Moreover, the average particle diameter of the following (D) component is the value of the volume-based cumulative average particle diameter (median diameter) D ₅₀ measured by Microtrac MT3300EX, which is a particle size analyzer manufactured by Nikkiso Co., Ltd.

Furthermore, with respect to the following component (E), a method for measuring a mass reduction rate when heated at 105 ° C. for 3 hours is described below.
First, a tare (W ₁ ) of a clean aluminum dish is weighed using a precision balance (reading limit: 0.1 mg). Next, a sample is taken on an aluminum pan, and the mass (W ₂ ) of the aluminum pan on which the sample is placed is weighed using a precision balance. The aluminum pan on which the sample is placed is left in a thermostat at 105 ° C. for 3 hours. After heating, this aluminum dish is taken out of the thermostat and allowed to cool in a desiccator. After standing to cool, the mass (W ₃ ) of the aluminum pan on which the sample is placed is weighed using a precision balance. The mass reduction rate of this sample is obtained from the following equation.
{(W ₃ −W ₁ ) / (W ₂ −W ₁ )} × 100 Unit: mass%
W ₁ : Aluminum dish mass (g)
W ₂ : Aluminum pan mass + Sample mass before heating (g)
W ₃ : Mass of aluminum dish + Sample weight after heating (g)

[Examples 1-6, Comparative Examples 1-3]
The compounds (A) to (F) used in the following Examples and Comparative Examples and compounds that are hydrosilylation addition reaction control agents are shown below. In the following examples, Me represents a methyl group.

（但し、ｂ”及びｃ”は１以上の整数であり、ｂ”＋ｃ”の平均値は３５である。）
（Ａ−２）下記式（２７）で示される直鎖状ポリフルオロ化合物（粘度４，０８０ｍＰａ・ｓ、ビニル基量０．０２９７モル／１００ｇ）

（但し、ｄ”及びｅ”は１以上の整数であり、ｄ”＋ｅ”の平均値は３５である。） (A) component:
(A-1) Linear polyfluoro compound represented by the following formula (26) (viscosity 4,010 mPa · s, vinyl group amount 0.0299 mol / 100 g)

(However, b ″ and c ″ are integers of 1 or more, and the average value of b ″ + c ″ is 35.)
(A-2) Linear polyfluoro compound represented by the following formula (27) (viscosity 4,080 mPa · s, vinyl group amount 0.0297 mol / 100 g)

(However, d ″ and e ″ are integers of 1 or more, and the average value of d ″ + e ″ is 35.)

（Ｂ−２）下記式（２９）で示される含フッ素オルガノ水素シロキサン（ＳｉＨ基含有量０．５９８モル／１００ｇ）

(B) component:
(B-1) Fluorine-containing organohydrogensiloxane represented by the following formula (28) (SiH group content: 0.499 mol / 100 g)

(B-2) Fluorine-containing organohydrogensiloxane represented by the following formula (29) (SiH group content: 0.598 mol / 100 g)

(C) component:
(C-1) Toluene solution of platinum-divinyltetramethyldisiloxane complex (platinum concentration 0.5 mass%)

(D) component:
Amorphous alumina and spherical alumina (D-1) whose average particle size is as follows: Amorphous alumina (D-2) whose average particle size is 1 μm Spherical alumina (D-3) whose average particle size is 10 μm Of spherical alumina (D-4) having an average particle size of 70 μm

（但し、ｆ”の平均値は２４である。）
（Ｅ−２）下記式（３１）で示される含フッ素有機ケイ素化合物（１０５℃で３時間加熱した時の質量減少率１９．１質量％）

(E) component:
(E-1) Fluorine-containing organosilicon compound represented by the following formula (30) (mass reduction rate of 0.0% by mass when heated at 105 ° C. for 3 hours)

(However, the average value of f ″ is 24.)
(E-2) Fluorine-containing organosilicon compound represented by the following formula (31) (mass reduction rate of 19.1% by mass when heated at 105 ° C. for 3 hours)

（Ｆ−２）下記式（３３）で示されるオルガノポリシロキサン（ＳｉＨ基含有量０．１０１モル／１００ｇ）

（Ｆ−３）下記式（３４）で示されるオルガノポリシロキサン（ＳｉＨ基含有量０．０９２２モル／１００ｇ）

(F) component:
(F-1) Organopolysiloxane represented by the following formula (32) (SiH group content: 0.262 mol / 100 g)

(F-2) Organopolysiloxane represented by the following formula (33) (SiH group content: 0.101 mol / 100 g)

(F-3) Organopolysiloxane represented by the following formula (34) (SiH group content 0.0922 mol / 100 g)

Control agent for hydrosilylation addition reaction:
Compound represented by the following formula (35)

  In Examples 1 to 6, Comparative Example 1 and Comparative Example 2, the compounds (A) to (F) and the compound represented by the formula (35) were used in predetermined amounts shown in Tables 1 and 2 below. The composition was prepared as described above, molded and cured, and the viscosity of the composition, the thermal conductivity of the cured product obtained by curing the composition, and the hardness were measured according to the following methods. Furthermore, with respect to Examples 1 to 6 and Comparative Example 3 in which the composition was prepared as described below, the tensile shear adhesive strength and the ATF (automobile oil) durability of the cured product were measured according to the following method. The results are shown in Tables 3-6 below.

Preparation of compositions of Examples 1-6, Comparative Example 1 and Comparative Example 2:
First, the components (A), (D) and (E) were kneaded for 30 minutes at room temperature using a planetary mixer in the predetermined amounts shown in Tables 1 and 2 below, and further under reduced pressure of -98.0 kPa. The mixture was kneaded at 150 ° C. for 1 hour. Next, after cooling to room temperature, the components (C) and the compound represented by the above formula (35) were added in predetermined amounts shown in Tables 1 and 2 below, and kneaded for 30 minutes at room temperature. Finally, components (B) and (F) were added in predetermined amounts shown in Tables 1 and 2 below, and kneaded at room temperature for 30 minutes to obtain a composition.

Preparation of the composition of Comparative Example 3:
Furthermore, as Comparative Example 3, a silicone-based thermally conductive adhesive composition was prepared as follows. First, molecular chain both ends dimethylvinylsiloxy group-capped dimethylpolysiloxane (viscosity 400 mPa · s, vinyl group content 0.185 mol / 100 g) 80.0 parts by mass, molecular chain both ends trimethoxysiloxy group-capped dimethylpolysiloxane (viscosity 900 mPas) S) 5.0 parts by mass, 600.0 parts by mass of round alumina having an average particle diameter of 11 μm, and 15.0 parts by mass of dimethylsiloxane represented by the following formula (36) at room temperature using a planetary mixer The mixture was kneaded for 15 minutes and further kneaded at 150 ° C. for 2 hours under a reduced pressure of −98.0 kPa to prepare an alumina compound base. Next, after cooling to room temperature, 0.20 part by mass of the component (C) and 0.1 part by mass of ethynylcyclohexanol as a hydrosilylation addition reaction controlling agent were added and kneaded at room temperature for 15 minutes. Finally, 2.0 parts by mass of hydrogen polysiloxane represented by the following formula (37) and 0.35 parts by mass of hydrogen polysiloxane represented by the following formula (38) (dimethylpolysiloxane in the above-mentioned alumina compound base) The total amount of hydrogen atoms directly bonded to silicon atoms contained in this component is 1.0 mol) with respect to 1.0 mol of vinyl groups contained in siloxane, and kneaded at room temperature for 15 minutes. A composition was obtained.

Production of cured product:
The composition obtained as described above is poured into a 60 mm × 60 mm × 6 mm mold, press vulcanized at 150 ° C. for 10 minutes using a press molding machine, and further in an oven at 150 ° C. for 50 minutes. The sheet-like cured product having a thickness of 6 mm was obtained.

Viscosity of the composition:
It measured at 23 degreeC using rotary rheometer HAAKE ReoStress 6000 (ThermoFisher Scientific, Inc. product).

Thermal conductivity of cured product:
Using the two sheet-like cured products having a thickness of 6 mm, measurement was performed at 25 ° C. using a thermophysical property measuring device TPS2500S (manufactured by Kyoto Electronics Industry Co., Ltd.).

Hardness of cured product:
It measured using the type A durometer prescribed | regulated to JISK6253-3 using the said sheet-like hardened | cured material of 6 mm thickness.

Tensile shear bond strength:
Two test panels of 100 mm × 25 mm of various adherends (aluminum and epoxy glass) are sandwiched between the composition layers of the examples and comparative examples having a thickness of 1 mm so that each end overlaps by 10 mm. The composition was cured by superimposing and heating at 150 ° C. for 1 hour to prepare an adhesion test piece. Subsequently, the test piece was subjected to a tensile shear adhesion test (tensile speed: 50 mm / min) to evaluate the adhesive strength (shear adhesive force) and the cohesive failure rate.

Hardened product ATF (automotive oil) durability:
The 6 mm thick sheet-like cured product was immersed in an automobile oil ATF WS3324 manufactured by Toyota Motor Corporation at 150 ° C. for 1,000 hours, and the thermal conductivity was measured in the same manner as described above.

せん断接着力の（ ）内は凝集破壊率（面積％）を示す。

The values in parentheses for the shear adhesive strength indicate the cohesive failure rate (area%).

せん断接着力の（ ）内は凝集破壊率（面積％）を示す。

The values in parentheses for the shear adhesive strength indicate the cohesive failure rate (area%).

  In Tables 1 and 2, in Examples 1 to 6, which are the thermally conductive fluorine-containing adhesive compositions of the present invention, a grease-like uniform composition was obtained. On the other hand, in Comparative Example 1, since the component (E) was not blended, the wettability of the component (D) with respect to the component (A) was not sufficient, and a grease-like uniform composition could not be obtained. Further, as in Comparative Example 2, when the component (D) exceeds 4,000 parts by mass, the wettability of the component (D) with respect to the component (A) becomes insufficient, and a grease-like uniform composition is obtained. There wasn't.

  In Tables 3 and 4, Examples 1 to 6 which are the heat conductive fluorine-containing adhesive composition of the present invention, and Comparative Example 3 which is a silicone-based heat conductive adhesive composition used as a comparative control. Showed good adhesion to various adherends.

  However, in Tables 5 and 6, in Examples 1 to 6, which are cured products obtained by curing the thermally conductive fluorine-containing adhesive composition of the present invention, the thermal conductivity does not change before and after the ATF immersion. In contrast, Comparative Example 3, which is a cured product obtained by curing the silicone-based thermally conductive adhesive composition used as a comparative control, had a significant decrease in thermal conductivity after ATF immersion.

  From the above results, the thermally conductive fluorine-containing adhesive composition of the present invention is 100 to 4,000 parts by mass of (D) component which is a thermally conductive filler with respect to 100 parts by mass of (A) component. The cured product obtained by curing the composition is excellent in oil resistance and thermal conductivity, and further firmly adheres to various substrates such as metals and plastics. As a heat transfer adhesive member, it is suitable for electric / electronic parts, particularly for vehicle-mounted electric / electronic parts.

  The present invention is not limited to the above embodiment. The above-described embodiment is an exemplification, and the present invention has any configuration that has substantially the same configuration as the technical idea described in the claims of the present invention and that exhibits the same effects. Are included in the technical scope.

Claims (18)

(A) a linear polyfluoro compound having two or more alkenyl groups in one molecule and a perfluoropolyether structure in the main chain: 100 parts by mass;
(B) 1 molecule has a monovalent perfluoroalkyl group or a monovalent perfluorooxyalkyl group, or a divalent perfluoroalkylene group or a divalent perfluorooxyalkylene group, and A fluorine-containing organohydrogensiloxane having two or more hydrogen atoms (SiH groups) directly bonded to silicon atoms and having no epoxy groups and alkoxy groups directly bonded to silicon atoms in the molecule;
(C) platinum group metal catalyst: 0.1 to 2,000 ppm in terms of mass of platinum group metal atom with respect to component (A),
(D) Thermally conductive filler: 100 to 4,000 parts by mass,
(E) One molecule has at least one monovalent perfluoroalkyl group or monovalent perfluorooxyalkyl group, and at least one alkoxy group directly connected to a silicon atom, and in the molecule Fluorine-containing organosilicon compound not having a hydrogen atom (SiH group) directly bonded to an epoxy group and a silicon atom: 0.01 to 300 parts by mass,
(F) A divalent hydrocarbon which may contain a hydrogen atom (SiH group) directly bonded to a silicon atom, a monovalent perfluoroalkyl group or a monovalent perfluorooxyalkyl group, and an oxygen atom in one molecule. An organopolysiloxane having an epoxy group or trialkoxysilyl group bonded to a silicon atom via a group, or both: a thermally conductive fluorine-containing adhesive composition containing 0.1 to 20 parts by mass, The blending amount of the component (B) is an amount such that the hydrogen atom directly bonded to the silicon atom in the component (B) is 0.5 to 3 moles with respect to 1 mole of the alkenyl group contained in the composition. A thermally conductive fluorine-containing adhesive, characterized in that a cured product obtained by curing the composition gives a fluorine-containing cured product having a thermal conductivity at 25 ° C. of 1.0 W / m · K or more. Agent composition.   2. The thermally conductive fluorine-containing adhesive composition according to claim 1, wherein the linear polyfluoro compound (A) has an alkenyl group content of 0.005 to 0.3 mol / 100 g. . The perfluoropolyether structure of the component (A) has the following general formula (1)
− (C _a F _2a O) _b − (1)
(In the formula, a is an integer of 1 to 6, and b is an integer of 1 to 300.)
The heat conductive fluorine-containing adhesive composition according to claim 1, wherein the composition contains a structure represented by: The component (A) is represented by the following general formula (2) and the following general formula (3).

(In the formula, R ¹ and R ² are each independently an alkenyl group or a monovalent hydrocarbon group having no unsubstituted or substituted aliphatic unsaturated bond, and the total of R ¹ and R ² is Two or more of them are alkenyl groups, R ³ is independently a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group, and c and d are each an integer of 1 to 150, And the average value of c + d is 2 to 300, and e is an integer of 1 to 6.)

(In the formula, R ⁴ is independently an alkylene group having 1 to 6 carbon atoms, and R ⁵ is independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms optionally substituted with fluorine. And R ¹ , R ² , c, d and e are the same as above.)
The thermally conductive fluorine-containing adhesive composition according to any one of claims 1 to 3, which is one or more linear polyfluoro compounds selected from the group consisting of:   The component (D) is at least one selected from metal, metal oxide, metal nitride, metal hydroxide, metal carbide, soft magnetic alloy, ferrite and carbon black. 5. The heat conductive fluorine-containing adhesive composition according to any one of 4 above.   The component (D) is gold, silver, copper, iron, nickel, aluminum, silicon metal, stainless steel, alumina, magnesium oxide, beryllium oxide, chromium oxide, titanium oxide, zinc oxide, silicon oxide, boron nitride, silicon nitride. The thermally conductive fluorine-containing adhesive according to claim 5, which is at least one selected from the group consisting of aluminum nitride, aluminum hydroxide, magnesium hydroxide, boron carbide, titanium carbide, silicon carbide, and carbon black. Agent composition.   The thermally conductive fluorine-containing adhesive composition according to claim 6, wherein the component (D) is alumina.   The thermally conductive fluorine-containing adhesive composition according to claim 7, wherein the component (D) is amorphous alumina and / or spherical alumina.   The heat conductive fluorine-containing adhesive composition according to claim 8, wherein the average particle diameter of the amorphous alumina as the component (D) is 0.2 to 5.0 μm.   The heat conductive fluorine-containing adhesive composition according to claim 8, wherein the spherical particle size of the component (D) is 5.0 to 100 μm.   The monovalent perfluoroalkyl group in which the component (E) is bonded to a silicon atom in which an alkoxy group is directly connected via a divalent hydrocarbon group which may contain a silicon atom, an oxygen atom and a nitrogen atom in one molecule Or it is a fluorine-containing organosilicon compound which has one or more monovalent perfluorooxyalkyl groups, The heat conductive fluorine-containing adhesive composition of any one of Claims 1-10 characterized by the above-mentioned. The component (E) is represented by the following general formula (4)
A _f R ⁷ _g Si (OR ⁶ ) _4-fg (4)
(In the formula, A is independently a monovalent perfluoroalkyl group bonded to a silicon atom to which an alkoxy group is directly bonded via a divalent hydrocarbon group which may contain a silicon atom, an oxygen atom and a nitrogen atom, or A monovalent perfluorooxyalkyl group, R ⁶ is independently of each other an alkyl group having 1 to 6 carbon atoms, and R ⁷ is independently of each other an unsubstituted or substituted monovalent hydrocarbon group. F is an integer of 1 to 3, g is 0, 1 or 2, and f + g is an integer of 1 to 3.)
The thermally conductive fluorine-containing adhesive composition according to claim 11, which is a fluorine-containing organosilicon compound represented by the formula:   The heat-conducting fluorine-containing composition according to any one of claims 1 to 12, wherein the component (E) has a mass reduction rate of 50.0 mass% or less when heated at 105 ° C for 3 hours. Adhesive composition.   The component (F) is a monovalent perfluoroalkyl group bonded to a silicon atom via a divalent hydrocarbon group which may contain a silicon atom, an oxygen atom and a nitrogen atom in one molecule, or a monovalent perfluoroalkyl group. The thermally conductive fluorine-containing adhesive composition according to any one of claims 1 to 13, which is an organopolysiloxane having one or more fluorooxyalkyl groups. The thermally conductive fluorine-containing adhesive composition according to claim 14, wherein the component (F) is a cyclic organopolysiloxane represented by the following general formula (17).

(In the formula, R ¹⁵ independently represents an unsubstituted or substituted monovalent hydrocarbon group, and X independently represents a divalent hydrocarbon which may contain a silicon atom, an oxygen atom and a nitrogen atom. A monovalent perfluoroalkyl group or a monovalent perfluorooxyalkyl group bonded to a silicon atom via a group, and Y is independently of each other via a divalent hydrocarbon group which may contain an oxygen atom. An epoxy group or trialkoxysilyl group bonded to a silicon atom, k ′ is an integer of 1-6, l ′ is an integer of 1-4, m ′ is an integer of 1-4, k ′ + L ′ + m ′ is an integer of 4 to 10, provided that — (SiO) (H) R ¹⁵ —, — (SiO) (X) R ¹⁵ —, and — (SiO) (Y) R ¹⁵ — are bonded. The order of is not limited.)   The heat conductive fluorine-containing adhesive according to any one of claims 1 to 15, wherein the heat conductive fluorine-containing adhesive composition has a viscosity at 23 ° C of 1,000 Pa · s or less. Composition.   An electrical / electronic component, wherein the cured product of the thermally conductive fluorine-containing adhesive composition according to any one of claims 1 to 16 is at least a part of its configuration.   The electric / electronic component according to claim 17, which is for vehicle use.