JP2015078296A - Curable heat conductive resin composition, manufacturing method of the composition, cured product of the composition, use method of the cured product, semiconductor device having the cured product of the composition and manufacturing method of the semiconductor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curable heat conductive resin composition capable of exhibiting heat release performance continuously even exposed under high temperature and high humidity for long time.SOLUTION: There is provided a curable heat conductive resin composition containing (A) an addition reaction product from a silphenylene compound and a polycyclic hydrocarbon, and having 2 addition reactive carbon-carbon double bonds in a molecule, (B) gallium having the melting point of 0 to 70°C or alloy thereof or both, (C) organohydrogenpolysiloxane having 2 or more hydrogen atoms bond to a silicon atom in a molecule and (D) a catalyst selected from a group of platinum and platinum compounds.

Description

  The present invention relates to a curable thermally conductive resin composition, a method for producing the composition, a cured product of the composition, a method for using the cured product, a semiconductor device having a thermally conductive layer made of the cured product, and the The present invention relates to a method for manufacturing a semiconductor device.

  An exothermic electronic component mounted on a printed wiring board, for example, an IC package such as a CPU, may be degraded or damaged due to a temperature rise due to heat generation during use. For this reason, conventionally, a heat conductive sheet having good heat conductivity is disposed between the IC package and the heat radiating member having the heat radiating fins, or heat conductive grease is applied to efficiently generate heat generated from the IC package or the like. It is well practiced to conduct heat to a heat radiating member. However, as the performance of electronic parts and the like increases, the amount of generated heat tends to increase more and more, and development of materials and members that are more excellent in thermal conductivity than conventional ones is required.

  The conventional heat conductive sheet has an advantage in work and process that it can be easily mounted and mounted. In addition, in the case of thermally conductive grease, without being affected by the unevenness of the surface of the CPU, heat radiating member, etc., following the unevenness, it is possible to adhere both without causing a gap between them, There is an advantage that the interfacial thermal resistance is small. However, both the heat conductive sheet and the heat conductive grease are obtained by blending a heat conductive filler in order to impart heat conductivity. In the case of a heat conductive sheet, workability and processing in the manufacturing process are obtained. In the case of thermally conductive grease, the appearance of the heat-sensitive electronic parts should not be affected by the use of a syringe. Since it is necessary to suppress the upper limit of the viscosity to a certain limit, in any case, the upper limit of the blending amount of the heat conductive filler is limited, and there is a drawback that a sufficient heat conductive effect cannot be obtained.

  Therefore, a method of blending a low-melting-point metal in the heat conductive paste (Patent Document 1, Patent Document 2), a granular material that functions to fix and stabilize a liquid metal in a three-phase composite (Patent Document 3). Etc. have been proposed. However, these thermally conductive materials using low-melting point metals have problems such as contamination of parts other than the coated part and leakage of oil when used for a long time. In order to solve these problems, methods for dispersing gallium or a gallium alloy in curable silicone have been proposed (Patent Documents 4 and 5). Although these compositions have solved the above-mentioned problems, when these compositions are left for a long time under high temperature and high humidity, the dispersed gallium is gradually oxidized, and the heat dissipation performance deteriorates over time. there were.

JP-A-7-207160 JP-A-8-53664 JP 2002-121292 A Japanese Patent No. 4551074 JP2013-082816

  The present invention has been made in view of the above problems, and is a curable thermally conductive resin composition having excellent thermal conductivity and capable of continuously exhibiting heat dissipation performance even when exposed to a high temperature and high humidity environment for a long time. It aims at providing the manufacturing method of this composition. Moreover, it aims at providing the usage method of this hardened | cured material as a hardened | cured material of this composition and a heat conductive layer. Furthermore, it aims at providing the semiconductor device excellent in the thermal radiation performance which has the hardened | cured material of this composition, and the manufacturing method of this semiconductor device.

（式中、Ｒはそれぞれ独立に非置換又はハロゲン原子、シアノ基もしくはグリシドキシ基で置換された炭素数１〜１２の１価炭化水素基又は炭素数１〜６のアルコキシ基である。）
で表されるケイ素原子に結合した水素原子を１分子中に２個有する化合物であり、
（ａ−２）は付加反応性炭素−炭素二重結合を１分子中に２個有する多環式炭化水素であり、前記（ａ−１）成分１モルに対して過剰モル量含有する。］
（Ｂ）融点が０〜７０℃のガリウムもしくはその合金、又はその両方： ２００〜２０，０００質量部、
（Ｃ）１分子中に２個以上のケイ素原子に結合した水素原子を有するオルガノハイドロジェンポリシロキサン：（（Ｃ）成分中のケイ素原子に結合した水素原子の個数の合計）／（前記（Ａ）成分中の付加反応性炭素−炭素二重結合の個数の合計）が０．１〜５．０となる量、
（Ｄ）白金及び白金化合物からなる群より選択される触媒：前記（Ａ）成分１００質量部に対して白金原子として０．１〜５００ｐｐｍとなる量
を含有するものであることを特徴とする硬化性熱伝導性樹脂組成物を提供する。 In order to solve the above problems, in the present invention, (A) an addition reaction product of the following (a-1) and (a-2), wherein an addition-reactive carbon-carbon double bond is contained in one molecule Two addition reaction products: 100 parts by weight,
[(A-1) is the following general formula (1)

(In the formula, each R is independently a unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms or an alkoxy group having 1 to 6 carbon atoms substituted with a halogen atom, a cyano group or a glycidoxy group.)
A compound having two hydrogen atoms bonded to a silicon atom represented by
(A-2) is a polycyclic hydrocarbon having two addition-reactive carbon-carbon double bonds in one molecule, and is contained in an excess molar amount relative to 1 mol of the component (a-1). ]
(B) Gallium having a melting point of 0 to 70 ° C. or an alloy thereof, or both: 200 to 20,000 parts by mass,
(C) Organohydrogenpolysiloxane having hydrogen atoms bonded to two or more silicon atoms in one molecule: (total number of hydrogen atoms bonded to silicon atoms in component (C)) / ((A ) The amount that the sum of the number of addition-reactive carbon-carbon double bonds in the component) is 0.1 to 5.0,
(D) Catalyst selected from the group consisting of platinum and platinum compounds: Curing characterized in that it contains an amount of 0.1 to 500 ppm as platinum atoms with respect to 100 parts by mass of component (A). An electrically conductive resin composition is provided.

  Such a curable thermally conductive resin composition has excellent thermal conductivity and can continuously exhibit heat dissipation performance even when exposed to a high temperature and high humidity environment for a long time.

Furthermore, (E) Thermally conductive filler having an average particle diameter of 0.1 to 100 μm: It is preferable to contain 0 to 1,000 parts by mass with respect to 100 parts by mass of the component (A).

  If such (E) component is contained, it can be set as the curable thermal conductive resin composition which was more excellent in thermal conductivity.

（式中、Ｒ^１は同一もしくは異種の一価の炭化水素基であり、Ｒ^２はアルキル基、アルコキシル基、アルケニル基又はアシル基であり、ａは５〜１００の整数であり、ｂは１〜３の整数である。）
で表されるポリシロキサン： 前記（Ａ）成分１００質量部に対して１０〜５００質量部
を含有することが好ましい。 Furthermore, (F) the following general formula (2)

Wherein R ¹ is the same or different monovalent hydrocarbon group, R ² is an alkyl group, an alkoxyl group, an alkenyl group or an acyl group, a is an integer of 5 to 100, and b is 1 It is an integer of ~ 3.)
It is preferable to contain 10-500 mass parts with respect to 100 mass parts of said (A) component.

  If such (F) component is contained, the wettability of the surface of (B) component and (E) component can be improved. Therefore, the component (B) and the component (E) can be uniformly dispersed in the composition.

Furthermore, (G) the following general formula (3)
R ³ _c Si (OR ⁴ ) _4-C (3)
Wherein R ³ is each independently an unsubstituted or halogen-substituted monovalent hydrocarbon group having 1 to 20 carbon atoms, R ⁴ is each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, c Is an integer from 1 to 3.)
Or an organosilane-containing compound obtained by hydrolytic condensation or partial hydrolysis-condensation of the organosilane, or both: 1 to 100 parts by mass per 100 parts by mass of the component (A) It is preferable to do.

  If such (G) component is contained, the surface of (B) component and (E) component can be processed, and the high filling of (B) component and (E) component can be assisted. it can. Furthermore, covering the filler surface makes it difficult for the fillers to agglomerate with each other and the effect persists even at high temperatures, so that the heat resistance of the composition can be improved.

Further, (H) a control agent selected from the group consisting of an acetylene compound, a nitrogen compound, an organic phosphorus compound, an oxime compound and an organic chloro compound: 0.05 to 0.5 mass with respect to 100 parts by mass of the component (A) It is preferable to contain a part.

  If such (H) component is contained, it will act as a control agent, the progress of the hydrosilylation reaction at room temperature can be suppressed, and shelf life and pot life can be extended.

Furthermore, in this invention, it is a manufacturing method of the said curable heat conductive resin composition of this invention, Comprising:
(I) a step of obtaining a uniform mixture by kneading the components (A) and (B) at a temperature within the range of 40 to 120 ° C. and a temperature equal to or higher than the melting point of the component (B);
(Ii) stopping the kneading and cooling the temperature to below the melting point of the component (B); and (iii) the component (C) with respect to the mixture obtained in the step (ii). And a method for producing a curable thermally conductive resin composition comprising the step of adding the component (D) and kneading at a temperature lower than the melting point of the component (B) to obtain a uniform mixture. provide.

  Moreover, as a component kneaded at the said process (i), any one or more of the said (E), the said (F), and the said (G) component can be included further.

  Moreover, the component (H) can be further included as a component to be kneaded in the step (iii).

  If it is a manufacturing method of such a curable heat conductive resin composition, it is excellent in heat conductivity, and even if it is exposed to a high-temperature, high-humidity environment for a long time, curable heat conductivity that can continuously exhibit heat dissipation performance A resin composition can be obtained stably.

  Furthermore, the present invention provides a thermally conductive cured product obtained by curing the curable thermally conductive resin composition of the present invention at 80 to 180 ° C.

  If it is such a heat conductive hardened | cured material, it can be used as a heat conductive layer excellent in the heat dissipation performance.

  Further, the present invention provides a method for using a thermally conductive cured product characterized in that the thermally conductive cured product of the present invention is disposed and used as a thermally conductive layer sandwiched between a heat generating electronic component and a heat radiating member. To do.

  As described above, by using the thermally conductive cured product, the heat-generating electronic component can be efficiently radiated.

  Furthermore, the present invention is a semiconductor device comprising a heat-generating electronic component, a heat radiating member, and a heat conductive layer made of a cured product of the curable heat conductive resin composition of the present invention, There is provided a semiconductor device characterized in that a heat-generating electronic component and the heat radiating member are joined via the heat conductive layer.

  Such a semiconductor device can stably conduct and dissipate heat over a long period of time. Therefore, a highly reliable semiconductor device can be obtained.

Furthermore, in the present invention, there is provided a method for manufacturing a semiconductor device according to the present invention,
(A) applying the curable thermally conductive resin composition of the present invention to the surface of the exothermic electronic component to form a coating layer made of the composition on the surface of the exothermic electronic component;
(B) a step of pressing and fixing the heat dissipating member to the covering layer to obtain a structure comprising the exothermic electronic component, the covering layer and the heat dissipating member; and (c) 80 to 180 ° C. of the structure. And a step of curing the covering layer to form the thermally conductive layer.

  With such a method for manufacturing a semiconductor device, a highly reliable semiconductor device can be stably obtained.

  Since the curable thermally conductive resin composition of the present invention is in the form of a grease or paste before curing, it has good workability when applied onto a heat-generating electronic component such as an IC package. When the members are brought into pressure contact with each other, they can follow the irregularities on both surfaces and can be brought into close contact with each other without creating a gap therebetween, so that no interfacial thermal resistance is generated.

  Further, in the heat treatment step for curing the resin component by the addition reaction, the liquid fine particles of gallium and / or an alloy thereof contained in the composition of the present invention aggregate to form liquid particles having a large particle size. At the same time, when the liquid particles are connected to each other and a thermally conductive filler is further blended with them, they form a kind of route in the three-dimensional crosslinked network formed by curing the resin component. In addition, the path-like structure is fixed and held. As a result, heat generated from the heat-generating electronic component can be quickly conducted to the heat radiating member. Therefore, a higher heat dissipation effect can be surely exhibited than the conventional heat conductive sheet or heat conductive grease.

  Furthermore, since the gallium and / or its alloy forming the above-mentioned path is fixed and held in the three-dimensional crosslinked network of cured resin, the composition of the present invention incorporated in a semiconductor device The thermally conductive layer made of a cured product does not contaminate other parts that have been problematic in the case of the conventional thermally conductive grease, and oil does not leak out over time. Furthermore, since the particles of gallium and / or its alloy are not oxidized even under high temperature and high humidity, the reliability of the semiconductor device can be further improved.

It is a longitudinal cross-sectional schematic diagram which shows an example of the semiconductor device to which the composition of this invention is applied, and shows the state before hardening a composition. It is a longitudinal cross-sectional schematic diagram which shows an example of the semiconductor device to which the composition of this invention is applied, and shows the state after hardening a composition.

The present invention will be described in detail below.
As described above, there is a need for a curable thermally conductive resin composition that has excellent thermal conductivity and can continuously exhibit heat dissipation performance even when exposed to a high temperature and high humidity environment for a long time.

  As a result of intensive studies to achieve the above-mentioned object, the present inventors have found that a material having excellent heat conduction characteristics is a low melting point gallium or its alloy, or both, and in some cases, a heat conductive filler. It was found that by selecting and blending this with a specific resin of addition reaction curable type, a composition in which the heat dissipation performance does not deteriorate even under high temperature and high humidity can be obtained.

  Further, in the step of heat-treating the composition to obtain a cured product, liquid gallium or an alloy thereof, or both aggregate to form liquid particles having a large particle size, and at the same time, the liquid particles are further heated. When a conductive filler is blended, the route structure is fixed in the cross-linked network formed by curing the resin component to form a kind of route connected and connected to them. The knowledge that it is retained was obtained.

  The cured product obtained in this manner can be used as a heat conductive layer having a low thermal resistance by being arranged in layers so as to be sandwiched between the heat-generating electronic component and the heat-dissipating member. Heat generated during the operation of electronic components is quickly conducted to the heat dissipation member via the thermally conductive layer containing gallium, its alloy, or both fixed and held in the above structure, and has excellent heat dissipation characteristics Based on these findings, the present inventors have completed the present invention.

  Hereinafter, the present invention will be described in detail, but the present invention is not limited thereto.

  The curable thermally conductive resin composition of the present invention contains the following components (A), (B), (C), and (D) as essential components, and further (E), (F), (G), (H) component is contained.

（式中、Ｒはそれぞれ独立に非置換又はハロゲン原子、シアノ基もしくはグリシドキシ基で置換された炭素数１〜１２の１価炭化水素基又は炭素数１〜６のアルコキシ基である。）
で表されるケイ素原子に結合した水素原子を１分子中に２個有する化合物と、
（ａ−２）付加反応性炭素−炭素二重結合を１分子中に２個有する多環式炭化水素（（ａ−１）成分１モルに対して過剰モル量含有する。）と
の付加反応生成物であって、付加反応性炭素−炭素二重結合を１分子中に２個有する付加反応生成物である。 [(A) component]
The component (A) of the present invention is
(A-1) The following general formula (1)

(In the formula, each R is independently a unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms or an alkoxy group having 1 to 6 carbon atoms substituted with a halogen atom, a cyano group or a glycidoxy group.)
A compound having two hydrogen atoms bonded to a silicon atom represented by
(A-2) addition reaction with polycyclic hydrocarbon having two addition-reactive carbon-carbon double bonds in one molecule (containing excess molar amount relative to 1 mole of component (a-1)) The product is an addition reaction product having two addition-reactive carbon-carbon double bonds in one molecule.

式中のＲはそれぞれ独立に非置換又はハロゲン原子、シアノ基もしくはグリシドキシ基で置換された炭素数１〜１２の１価炭化水素基又は炭素数１〜６のアルコキシ基である。上記一般式（１）中のＲとしては、アルケニル基及びアルケニルアリール基等の脂肪族不飽和結合を有さないものであるものが好ましく、特に、その全てがメチル基であるものが好ましい。 Component (a-1) The component (a-1) is a reaction raw material of the component (A), and is represented by the following general formula (1) having two hydrogen atoms bonded to a silicon atom in one molecule. A compound.

In the formula, each R is independently a monovalent hydrocarbon group having 1 to 12 carbon atoms or an alkoxy group having 1 to 6 carbon atoms which is unsubstituted or substituted with a halogen atom, a cyano group or a glycidoxy group. As R in the general formula (1), those having no aliphatic unsaturated bond such as alkenyl group and alkenylaryl group are preferable, and those in which all of them are methyl groups are particularly preferable.

  Examples of the compound represented by the general formula (1) include silphenylene compounds such as 1,4-bis (dimethylsilyl) benzene and 1,3-bis (dimethylsilyl) benzene. In addition, the compound represented by the said General formula (1) can be used even if single 1 type also combines 2 or more types.

(A-2) Component The (a-2) component is a reaction raw material of the (A) component, and is a polycyclic hydrocarbon having two addition-reactive carbon-carbon double bonds in one molecule.

  In the component (a-2), “addition reactivity” means a property capable of undergoing an addition reaction with a hydrogen atom bonded to a silicon atom by a known hydrosilylation reaction. In addition, the component (a-2) includes (i) an addition-reactive carbon-carbon double bond formed between two adjacent carbon atoms among the carbon atoms forming the polycyclic hydrocarbon skeleton. (Ii) a hydrogen atom bonded to a carbon atom forming the skeleton of a polycyclic hydrocarbon is replaced by an addition-reactive carbon-carbon double bond-containing group, or (iii) ) Of the carbon atoms forming the polycyclic hydrocarbon skeleton, an addition-reactive carbon-carbon double bond is formed between two adjacent carbon atoms, and the polycyclic hydrocarbon skeleton is Any of the hydrogen atoms bonded to the carbon atoms being formed may be substituted with an addition-reactive carbon-carbon double bond-containing group.

で表される５−ビニルビシクロ［２．２．１］ヘプト−２−エン、下記構造式（ｙ）

で表される６−ビニルビシクロ［２．２．１］ヘプト−２−エン、上記両者の組み合わせ（以下、これら３者を区別する必要がない場合は、「ビニルノルボルネン」と総称することがある）が挙げられる。なお、このビニルノルボルネンのビニル基の置換位置は、シス配置（エキソ形）又はトランス配置（エンド形）のいずれであってもよく、また、配置の相違によって、該成分の反応性等に特段の差異がないことから、両配置の異性体の組み合わせであっても差し支えない。 As the component (a-2), for example, the following structural formula (x)

5-vinylbicyclo [2.2.1] hept-2-ene represented by the following structural formula (y)

6-vinylbicyclo [2.2.1] hept-2-ene, a combination of the two (hereinafter, when there is no need to distinguish these three, they may be collectively referred to as “vinyl norbornene”) ). In addition, the substitution position of the vinyl group of this vinyl norbornene may be either a cis configuration (exo type) or a trans configuration (end type). Since there is no difference, a combination of both isomers can be used.

[Preparation of component (A)]
The component (A) of the composition of the present invention is an addition-reactive carbon-carbon double bond with respect to 1 mole of the component (a-1) having two hydrogen atoms bonded to a silicon atom in one molecule. An excess of more than 1 mol and not more than 10 mol, preferably more than 1 mol and not more than 5 mol of the component (a-2) having 2 per molecule in the presence of a hydrosilylation reaction catalyst. Thus, an addition reaction product having no hydrogen atom bonded to a silicon atom can be obtained.

  Any conventionally known hydrosilylation reaction catalyst can be used. For example, carbon powder carrying platinum metal, platinum black, secondary platinum chloride, chloroplatinic acid, reaction product of chloroplatinic acid and monohydric alcohol, complex of chloroplatinic acid and olefins, platinum bisacetoacetate, etc. And platinum group metal catalysts such as palladium catalysts and rhodium catalysts. Moreover, about addition reaction conditions, use of a solvent, etc., it may just be as usual without being specifically limited.

  Thus, in preparing the component (A), since the component (a-2) in an excess molar amount relative to the component (a-1) is used, the component (A) is the component (a-2). ) It has two addition-reactive carbon-carbon double bonds derived from the structure of the component in one molecule. Furthermore, the residue derived from the component (a-1) is a divalent residue of a polycyclic hydrocarbon having no addition-reactive carbon-carbon double bond derived from the structure of the component (a-2). It may contain a structure bonded by a group.

That is, as the component (A), for example, the following general formula (4)
Y-X- (Y'-X) _p- Y (4)
Wherein X is a divalent residue of the compound of the component (a-1), Y is a monovalent residue of the polycyclic hydrocarbon of the component (a-2), and Y ′ Is a divalent residue of the component (a-2), and p is an integer of 0 to 10, preferably 0 to 5.)
The compound represented by these is mentioned.
In addition, about the value of p which is the number of the repeating units represented by said (Y'-X), the excess molar amount of said (a-2) component made to react with respect to 1 mol of said (a-1) component. It is possible to set by adjusting.

で表される１価の残基（以下、６者を区別する必要がない場合は、これらを「ＮＢ基」と総称し、また、６者の構造を区別せずに「ＮＢ」と略記することがある）が挙げられる。なお、上記式において、破線は結合手を示す。 As Y in the general formula (4), specifically, for example, the following structural formula

(Hereinafter, when it is not necessary to distinguish the six members, these are collectively referred to as “NB group”, and are also abbreviated as “NB” without distinguishing the structure of the six members.) May be included). In the above formula, the broken line indicates a bond.

で表される２価の残基が挙げられる。式中、破線は結合手を示す。
但し、上記構造式で表される非対称な２価の残基は、その左右方向が上記記載の通りに限定されるものではなく、上記構造式は、実質上、個々の上記構造を紙面上で１８０度回転させた構造をも含めて示している。 As Y ′ in the general formula (4), specifically, for example, the following structural formula

The bivalent residue represented by these is mentioned. In the formula, a broken line indicates a bond.
However, the asymmetrical divalent residue represented by the above structural formula is not limited in the left-right direction as described above, and the above structural formula is substantially the same as that on the paper. It also includes a structure rotated 180 degrees.

（式中、ｐ’は１〜１０の整数である。）
更に、本発明の（Ａ）成分は、１種単独でも２種以上を組み合わせても使用することができる。 Preferred specific examples of the component (A) represented by the general formula (4) are shown below, but the invention is not limited thereto (Note that the meaning of “NB” is as described above. ).
_{NB-Me 2 Si-p-} C 6 H 4 -SiMe 2 -NB
_{NB-Me 2 Si-m-} C 6 H 4 -SiMe 2 -NB
(In the formula, Me represents a methyl group. -PC ₆ H ₄ -represents a para-phenylene group, and -m-C ₆ H ₄ -represents a meta-phenylene group.)

(In the formula, p ′ is an integer of 1 to 10.)
Furthermore, the component (A) of the present invention can be used singly or in combination of two or more.

[Component (B)]
The component (B) of the composition of the present invention is gallium, an alloy thereof, or both having a melting point of 0 to 70 ° C. Moreover, this (B) component is a component mix | blended in order to provide favorable thermal conductivity to the hardened | cured material obtained from the composition of this invention.

  As described above, the melting point of the component (B) needs to be in the range of 0 to 70 ° C. After preparing the composition of the present invention, a low temperature of about −30 to −10 ° C., preferably −25 to −15 ° C. is required during long-term storage and transportation in order to maintain the dispersed state of each component contained in the composition. However, when the melting point is less than 0 ° C., liquid fine particles tend to aggregate during long-term storage and transportation, and it is relatively difficult to maintain the state at the time of preparation of the composition. Become. On the other hand, if it exceeds 70 ° C., it does not melt quickly in the composition preparation step, resulting in poor workability. Therefore, the range of 0 to 70 ° C. is an appropriate range as well as a necessary condition for handling. In particular, the one in the range of 15 to 50 ° C. is more preferable because the composition of the present invention is easy to prepare and easy to handle during long-term storage and transportation.

The melting point of metallic gallium is 29.8 ° C. Moreover, as a typical gallium alloy, for example, a gallium-indium alloy; for example, Ga-In (mass ratio = 75.4: 24.6, melting point = 15.7 ° C.), gallium-tin alloy, gallium-tin -Zinc alloy; for example, Ga-Sn-Zn (mass ratio = 82: 12: 6, melting point = 17 ° C.), gallium-indium-tin alloy; for example, Ga-In-Sn (mass ratio = 21.5: 16) 0.0: 62.5, melting point = 10.7 ° C.), gallium-indium-bismuth-tin alloy; for example, Ga—In—Bi—Sn (mass ratio = 9.4: 47.3: 24.7: 18) .6, melting point = 48.0 ° C.) and the like.
This component (B) can be used alone or in combination of two or more.

  The shape of the liquid fine particles or solid fine particles of gallium and / or its alloy, or both present in the composition of the present invention in an uncured state may be substantially spherical, and may include irregular shapes. Moreover, it is preferable that the average particle diameter is 0.1-100 micrometers normally, especially 5-50 micrometers. When the average particle size is 0.1 μm or more, the viscosity of the composition does not become too high, and the extensibility is sufficient. As a result, it becomes easier to perform the coating operation. Moreover, since it becomes a uniform composition in the case of 100 micrometers or less, application | coating of the thin film form to exothermic electronic components etc. becomes easy. In addition, since the shape and average particle diameter of the particles, and the dispersion state in the composition, as described above, are stored immediately at a low temperature after the preparation of the composition, until the coating process to the exothermic electronic components, etc. Can be maintained. In addition, the average particle diameter of the particle | grains of (B) component can be measured from Microtrac MT3300EX (made by Nikkiso Co., Ltd.).

  The blending amount of the component (B) is 200 to 20,000 parts by mass, preferably 2,000 to 18,000 parts by mass, more preferably 5 to 100 parts by mass of the component (A). 1,000 to 15,000 parts by mass. When the blending amount is less than 200 parts by mass, the thermal conductivity is lowered, and when the composition is thick, sufficient heat dissipation performance cannot be obtained. When the amount is more than 20,000 parts by mass, it is difficult to obtain a uniform composition, and the viscosity of the composition becomes too high, so that the composition cannot be obtained as an extensible grease. There is.

[Component (C)]
The component (C) of the composition of the present invention is an organohydrogenpolysiloxane having hydrogen atoms bonded to two or more silicon atoms in one molecule. The component (C) is, for example, the general formula (5)
R ⁵ _d H _e SiO _{(4-de) / 2} (5)
(Wherein R ⁵ is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms, preferably 1 to 10 carbon atoms, and d is 0.7 to 2.1, preferably 0.8 to 2.05, e is 0.001 to 1.0, preferably 0.005 to 1.0, and d + e is 0.8 to 3.0, preferably 1.0 to 2.5. Number.)
What is shown by can be used.

The organohydrogenpolysiloxane having hydrogen atoms bonded to silicon atoms as component (C) must have at least two hydrogen atoms bonded to silicon atoms in one molecule in order to network the composition by crosslinking. And preferably has a hydrogen atom bonded to three or more silicon atoms. Examples of the remaining organic group R ⁵ bonded to the silicon atom include methyl groups, ethyl groups, propyl groups, butyl groups, hexyl groups, alkyl groups such as dodecyl groups, aryl groups such as phenyl groups, 2-phenylethyl groups, 2 -Aralkyl group such as phenylpropyl group, halogen-substituted substituted hydrocarbon group such as chloromethyl group, 3,3,3-trifluoropropyl group, 2-glycidoxyethyl group, 3-glycidoxypropyl An epoxy ring-containing organic group (glycidyl group or glycidyloxy group-substituted alkyl group) such as a group and 4-glycidoxybutyl group is also exemplified. In particular, those having a methyl group and a phenyl group are preferred because they are easy to produce industrially and are easily available. Further, from the viewpoint of compatibility with the component (A), at least one of R ⁵ is preferably a phenyl group. The organohydrogenpolysiloxane having a hydrogen atom bonded to a silicon atom may be linear, branched or cyclic, or a mixture thereof.

  The amount of component (C) is (total number of hydrogen atoms bonded to silicon atoms in component (C)) / (total number of addition reactive carbon-carbon double bonds in component (A)). Is in an amount of 0.1 to 5.0, preferably in the range of 0.5 to 3.0. If the blending amount is smaller than 0.1, a composition having sufficient hardness cannot be obtained. If the blending amount is larger than 5.0, hydrogen atoms bonded to unreacted silicon atoms are excessively crosslinked. There is a risk of causing a decrease in reliability by causing a reaction.

[(D) component]
The catalyst selected from the group consisting of platinum and platinum compounds as component (D) of the present invention is a hydrogen atom bonded to the addition reactive carbon-carbon double bond in component (A) and the silicon atom in component (C). It is a component that promotes the addition reaction. Examples thereof include platinum alone, chloroplatinic acid, platinum-olefin complexes, platinum-alcohol complexes, platinum coordination compounds, and the like.

  (D) The compounding quantity of a component is a quantity used as 0.1-500 ppm as a platinum atom with respect to 100 mass parts of (A) component. If the amount of the catalyst is less than 0.1 ppm, the effect as a catalyst may not be obtained. Even if it exceeds 500 ppm, the effect does not increase, and it is not preferable because it is uneconomical. In addition, in order to improve the dispersibility to a composition, (D) component may be diluted and used with polysiloxane, toluene, etc.

[(E) component]
In the composition of the present invention, together with the component (B), a conventionally known heat conductive sheet or heat conductive grease (E) that is blended in the heat conductive grease may be additionally blended as necessary. I can do it.

  The component (E) is not particularly limited as long as it has good thermal conductivity, and conventionally known ones can be used. For example, aluminum powder, zinc oxide powder, alumina powder, boron nitride powder , Aluminum nitride powder, silicon nitride powder, copper powder, diamond powder, nickel powder, zinc powder, stainless steel powder, carbon powder and the like. Moreover, this (E) component can be used even if single 1 type also combines 2 or more types.

  However, when a material having high reactivity with gallium such as aluminum is used, it may aggregate during mixing and kneading when preparing the composition, and uniform mixing may be difficult. In this case, first, the uniform dispersion of the liquid fine particles of the component (B) into the liquid mixture component of the component (A) was completed, and the component (B) was covered with the liquid mixture of the component (A). After reaching the state, the component (E) may be added and blended and kneaded. By doing so, aggregation of the component (E) can be prevented.

  As an average particle diameter of (E) component, it is 0.1-100 micrometers normally, Preferably it is good to set it in the range of 1-20 micrometers. When the average particle diameter is 0.1 μm or more, the viscosity of the resulting composition does not become too high, so that the extensibility is sufficient. Moreover, when it is 100 μm or less, it becomes easy to obtain a uniform composition. The average particle diameter can be measured with Microtrac MT3300EX (manufactured by Nikkiso Co., Ltd.).

  (E) The compounding quantity of a component is 0-1,000 mass parts with respect to 100 mass parts of (A) component. When the component (E) is 1,000 parts by mass or less, the viscosity of the composition becomes sufficient, and the composition can be obtained as a grease-like one having extensibility.

[(F) component]
In the composition of the present invention, the component (B) gallium and / or its alloy is hydrophobized at the time of preparing the composition, and (B) the liquid particles of the component (A) and the organopolysiloxane The polysiloxane represented by the following general formula (2) is used as the surface treatment agent (F) for the purpose of improving the wettability and uniformly dispersing the component (B) as fine particles in the matrix comprising the component (A). Can be blended.
The component (F) also has the effect of improving the wettability of the surface of the thermally conductive filler of the component (E) and improving the uniform dispersibility.

（式中、Ｒ^１は同一もしくは異種の一価の炭化水素基であり、Ｒ^２はアルキル基、アルコキシル基、アルケニル基又はアシル基であり、ａは５〜１００の整数であり、ｂは１〜３の整数である。）
で表される、分子鎖の片末端が加水分解性基で封鎖されたポリシロキサンであり、好ましくは２５℃における動粘度が１０〜１０，０００ｍｍ^２／ｓである。なお、この動粘度はオストワルド粘度計により測定することができる。 As the component (F), the following general formula (2)

Wherein R ¹ is the same or different monovalent hydrocarbon group, R ² is an alkyl group, an alkoxyl group, an alkenyl group or an acyl group, a is an integer of 5 to 100, and b is 1 It is an integer of ~ 3.)
The polysiloxane having one end of a molecular chain blocked with a hydrolyzable group, preferably having a kinematic viscosity at 25 ° C. of 10 to 10,000 mm ² / s. This kinematic viscosity can be measured with an Ostwald viscometer.

  (F) The compounding quantity of a component is 10-500 mass parts with respect to 100 mass parts of (A) component, Preferably it is 20-200 mass parts. When the blending amount is 10 parts by mass or more, when the (B) component and the (E) component are blended, the (E) component is sufficiently dispersed and a uniform grease composition is obtained. In the case of 500 parts by mass or less, the component (A) is not relatively decreased, and the finished composition is easily cured. Therefore, after the grease comprising the composition of the present invention is applied to the IC package, there is no deviation and the performance is not significantly lowered.

[(G) component]
The composition of the present invention can contain the following component (G) as an optional component. The component (G) of the present invention is an organosilane represented by the following general formula (3), an organosilane-containing compound obtained by hydrolytic condensation or partial hydrolysis condensation of the organosilane, or both.
R ³ _c Si (OR ⁴ ) _4-c (3)
(Wherein R ³ is each independently an unsubstituted or halogen-substituted monovalent hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, and R ⁴ is independently a hydrogen atom or 1 to 6 carbon atoms, (It is preferably an alkyl group of 1 to 3, and c is an integer of 1 to 3.)

  The component (G) is used to treat the surface of the component (B) and the component (E), but not only assists in increasing the filling of the filler but also covers the filler surface to fill the filler. Since the cohesion between them hardly occurs and the effect is maintained even at a high temperature, the heat resistance of the curable thermally conductive resin composition of the present invention is improved.

In the general formula (3), examples of R ³ include an alkyl group, a cycloalkyl group, and an alkenyl group. Specific examples thereof include, for example, a methyl group, an ethyl group, a propyl group, a hexyl group, Octyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl and other alkyl groups, cyclopentyl, cyclohexyl and other cycloalkyl groups, vinyl, allyl and other alkenyl groups, phenyl and tolyl groups, etc. Aralkyl groups such as aryl group, 2-phenylethyl group, 2-methyl-2-phenylethyl group, 3,3,3-trifluoropropyl group, 2- (perfluorobutyl) ethyl group, 2- (perfluorooctyl) ) Halogenated hydrocarbon groups such as ethyl group and p-chlorophenyl group. c is 1, 2 or 3, with 1 being particularly preferred. Examples of R ⁴ include a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

  (G) The addition amount of a component is 1-100 mass parts with respect to 100 mass parts of (A) component. If the addition amount is 100 parts by mass or less, oil bleeding is difficult to occur, and generation of voids can be prevented.

[(H) component]
The composition of the present invention may further contain a component (H) that is a control agent. The control agent suppresses the progress of the hydrosilylation reaction at room temperature and prolongs shelf life and pot life. Known reaction control agents can be used, and acetylene compounds, various nitrogen compounds, organic phosphorus compounds, oxime compounds, organic chloro compounds, and the like can be used.

  The compounding quantity of (H) component is 0.05-0.5 mass part with respect to 100 mass parts of (A) component. When the blending amount is 0.05 parts by mass or more, sufficient shelf life and pot life can be obtained. If it is 0.5 mass part or less, curability will become enough. These may be used after diluted with toluene or the like in order to improve the dispersibility in the composition.

[Other ingredients]
In addition to the above components, the composition of the present invention may further contain an organopolysiloxane of the general formula (6) below.
General formula (6):
R ⁶ _f SiO _{(4-f) / 2} (6)
(In the formula, each R ⁶ independently represents an unsubstituted or substituted monovalent hydrocarbon group having 1 to 18 carbon atoms having no aliphatic unsaturated bond, and f is 1.8 to 2.2. Number.)
It is an organopolysiloxane having a kinematic viscosity at 25 ° C. represented by the formula of ¹⁰ to 100,000 mm ² / s, and may be used alone or in combination of two or more.

R ⁶ is independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 18 carbon atoms. R ⁶ is, for example, an alkyl group such as a methyl group, an ethyl group, a propyl group, a hexyl group, an octyl group, a decyl group, a dodecyl group, a tetradecyl group, a hexadecyl group or an octadecyl group; a cyclohexyl group such as a cyclopentyl group or a cyclohexyl group Alkenyl group such as vinyl group and allyl group; aryl group such as phenyl group and tolyl group; aralkyl group such as 2-phenylethyl group and 2-methyl-2-phenylethyl group; 3,3,3-trifluoropropyl Groups, halogenated hydrocarbon groups such as 2- (perfluorobutyl) ethyl group, 2- (perfluorooctyl) ethyl group, p-chlorophenyl group and the like.

[Viscosity of composition]
As will be described later, the composition of the present invention is applied to the surface of the heat-generating electronic component, and after heat-contacting the heat-dissipating member, the composition is cured by heat treatment to form a thermally conductive layer. At this time, in order to improve workability, the composition of the present invention needs to be in the form of grease.

  For example, the composition of the present invention is accommodated in a syringe, applied from the syringe to the surface of a heat-generating electronic component such as a CPU to form a coating layer, and a heat radiating member is press-contacted thereto. Therefore, the viscosity of the composition of the present invention is usually preferably 10 to 1,000 Pa · s, particularly preferably 50 to 400 Pa · s. When the viscosity is 10 Pa · s or more, no dripping occurs at the time of application, which is preferable in terms of work. When the pressure is 1,000 Pa · s or less, extrusion from the syringe becomes easy, and the efficiency of the application work is improved. This viscosity can be measured with a spiral viscometer PC-ITL (Malcom Co., Ltd.).

[Preparation of the composition of the present invention]
The curable thermally conductive resin composition of the present invention is
(I) a step of kneading the components (A) and (B) at a temperature in the range of 40 to 120 ° C. and at or above the melting point of the component (B) to obtain a uniform mixture;
(Ii) a step of stopping kneading and cooling the temperature to below the melting point of component (B), and (iii) component (C) and component (D) with respect to the mixture obtained in step (ii) And knead | mixing at the temperature below melting | fusing point of (B) component, and can obtain by the manufacturing method including the process of obtaining a uniform mixture.

  When adding an arbitrary component, (E), (F), and (G) component can be added further by process (i). Moreover, components other than (H) component and (A)-(H) component can further be added by process (iii).

  In the above production method, a stirring / kneading machine such as a conditioning mixer or a planetary mixer provided with a heating means and, if necessary, a cooling means is used.

  In the step (i), the gallium of the component (B) or the alloy thereof, or a liquid material thereof, and optionally the thermally conductive filler of the component (E) are optionally mixed with the component (A) and, if necessary, (F ) Component or (G) component, or a mixture of both.

  It is preferable that the temperature lowering operation or the cooling operation in the step (ii) is performed promptly. In the step (ii), (B) in a liquid fine particle state uniformly dispersed in a matrix composed of a mixture of the component (A) and optionally the component (F) or the component (G) or both. The component solidifies while maintaining its average particle size and dispersion state.

  It is preferable that step (iii) is also completed in as short a time as possible. At the end of the step (iii), there is substantially no change in the dispersion state of the solidified fine particles of the component (B). And after completion | finish of this process (iii), the produced | generated composition is accommodated in a container, and it is about -30--10 degreeC rapidly, Preferably it is -25--15 degreeC in the freezer, freezer compartment, etc. It is good to save. Further, it is preferable to use a vehicle or the like equipped with a refrigeration facility for the transportation. By storing and transporting at a low temperature as described above, the composition and dispersion state of the composition of the present invention can be stably maintained even for long-term storage, for example.

[Application to semiconductor devices]
When the composition of the present invention is cured, it can be carried out by maintaining the temperature at 80 to 180 ° C. for about 30 to 240 minutes.

  The hardened | cured material of the composition of this invention can be used as a heat conductive hardened | cured material for interposing between an exothermic electronic component and a heat radiating member, and forming a heat conductive layer.

  If it is a heat conductive hardened | cured material of this invention, when using as a heat conductive layer, in order to follow the unevenness | corrugation of the surface of a component or a member, a clearance gap does not arise.

  Furthermore, in the present invention, a semiconductor device having excellent heat dissipation characteristics using the composition of the present invention, that is, a heat generating electronic component, a heat radiating member, and a cured product of the curable thermally conductive resin composition of the present invention. A semiconductor device having a thermally conductive layer can be obtained, in which a heat-generating electronic component and a heat radiating member are joined via a thermally conductive layer.

In this semiconductor device, (a) a step of applying the curable thermally conductive resin composition of the present invention to the surface of an exothermic electronic component and forming a coating layer made of the composition on the surface of the exothermic electronic component. ,
(B) A step of pressing and fixing the heat radiating member to the coating layer to obtain a structure composed of the heat-generating electronic component, the coating layer, and the heat radiating member, and (c) processing the structure at 80 to 180 ° C. It can be obtained by a production method including a step of curing the layer to form a heat conductive layer.

  The semiconductor device and the manufacturing method thereof will be described with reference to FIGS. The devices shown in FIGS. 1 and 2 are merely examples of application of the composition of the present invention to a semiconductor device, and the semiconductor device according to the present invention is limited to that shown in FIGS. That is not the purpose.

  FIG. 1 is a schematic longitudinal sectional view showing an example of a semiconductor device to which the composition of the present invention is applied, and shows a state before the composition of the present invention is cured. FIG. 2 is a schematic longitudinal sectional view showing an example of a semiconductor device to which the composition of the present invention is applied, and shows a state after the composition of the present invention is cured.

  First, the composition of the present invention in a frozen storage state is allowed to stand at room temperature and naturally thawed to form a grease. Next, the liquid composition of the present invention is accommodated in a coating tool such as a syringe.

  1. Apply the composition of the present invention from a syringe or the like to the surface of an IC package 2 such as a CPU that is a heat-generating electronic component, for example, a heat-generating electronic component mounted on the printed wiring board 3 shown in FIG. Thus, the coating layer 1 is formed. A heat dissipating member, for example, a heat dissipating member 4 having a heat dissipating fin made of aluminum, is disposed on the heat dissipating member, and the heat dissipating member 4 is pressed and fixed to the IC package 2 through the cover layer 1 using the clamp 5. .

  At this time, the clamp 5 is adjusted or selected so that the thickness of the coating layer 1 existing between the IC package 2 and the heat radiating member 4 is usually 5 to 100 μm, particularly preferably 20 to 70 μm. It is good. When the thickness is 5 μm or more, the followability of the composition of the present invention to the IC package 2 and the heat radiating member 4 is sufficient during the pressure contact, and there is no possibility that a gap is generated between the two. In the case of 100 μm or less, the thermal resistance does not become too large, so that a sufficient heat radiation effect can be obtained.

  Next, the apparatus configured as described above is passed through a heating apparatus such as a reflow furnace, and the coating layer 1 made of the composition of the present invention is cured to obtain the heat conductive layer 11 shown in FIG. . The temperature condition required for this curing is 80 to 180 ° C, particularly preferably 100 to 150 ° C. When the temperature is 80 ° C. or higher, curing is sufficient, and when the temperature is 180 ° C. or lower, there is no fear that the electronic component or the base material is deteriorated.

  In the process of raising the temperature to the temperature condition at the time of curing, the liquid fine particles of the component (B) gallium or its alloy, or both in the composition of the present invention aggregate to form liquid particles having a large particle size. At the same time, when the above component (E) is blended, it forms a kind of connected route.

  Furthermore, the liquid particles of the component (B) are also fused to the surfaces of the IC package 2 and the heat radiating member 4 that are in contact therewith. Therefore, when the IC package 2 and the heat radiating member 4 are blended with the liquid particles of the component (B) and the component (E), the heat conductive filler is connected and connected through a kind of route. Thus, it is substantially continuous and has a high thermal conductivity. The path-like structure is fixed and held in the three-dimensional crosslinked network of the cured product formed by the addition reaction of the component (A) and the component (C).

  Further, when the semiconductor device obtained as described above is operated and used, the surface temperature of the heat-generating electronic component such as an IC package is usually about 60 to 120 ° C. With respect to this heat generation, the heat conductive layer made of the cured product of the composition of the present invention exhibits high heat conductivity as described above, and has more heat dissipation characteristics than conventional heat conductive sheets and heat conductive grease. It has a remarkably excellent action and effect of being excellent. Even when the semiconductor device is continuously operated and used for a long time, the component (B) gallium or its alloy, or both, which is included in the heat conductive layer and forms a path, is contained in the cured three-dimensional crosslinked network. Since it is fixed and held on the surface, it does not leak from the heat conductive layer.

  Furthermore, this heat conductive layer has tackiness, and has a stable flexibility even when the heat dissipation member is displaced or when used for a long period of time. It will not peel off.

  In addition, by preparing a sheet-like cured product having a desired thickness from the composition of the present invention in advance, and interposing it between a heat-generating electronic component and a heat-dissipating member in the same manner as a conventional heat-conductive sheet, Similar effects can be obtained. In addition, a sheet of a cured product of the composition of the present invention can be appropriately used as a part of another device or the like that requires heat conductivity and heat resistance.

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

  First, the following components constituting the composition of the present invention were prepared.

[(A) component]
[Synthesis Example 1] Preparation of Component (A) Into a 5 L four-necked flask equipped with a stirrer, a condenser, a dropping funnel and a thermometer, vinyl norbornene (trade name: V0062, manufactured by Tokyo Chemical Industry Co., Ltd .; 5 -Isomer mixture of approximately equimolar amounts of vinylbicyclo [2.2.1] hept-2-ene and 6-vinylbicyclo [2.2.1] hept-2-ene) 1,785 g (14.88) Mol) and 455 g of toluene were added and heated to 85 ° C. using an oil bath. To this was added 3.6 g of carbon powder supporting 5% by mass of platinum metal, and 1,698 g (8.75 mol) of 1,4-bis (dimethylsilyl) benzene was added dropwise over 180 minutes while stirring. . After completion of the dropwise addition, the mixture was further heated and stirred at 110 ° C. for 24 hours, and then cooled to room temperature. Thereafter, the platinum metal-supporting carbon is removed by filtration, and toluene and excess vinylnorbornene are distilled off under reduced pressure to obtain a colorless and transparent oily reaction product (viscosity at 25 ° C .: 12,820 mPa · s) 3,362 g. Got.

（２）ｐ−フェニレン基を３個有する化合物：約３２モル％、及び

（３）ｐ−フェニレン基を４個以上有する化合物：約２７モル％
の混合物であることが判明した。また、混合物全体としての付加反応性炭素−炭素二重結合の含有割合は、０．３６モル／１００ｇであった。 As a result of analyzing the reaction product by FT-IR, NMR, GPC and the like,
A-1:
(1) Compound having two p-phenylene groups: about 41 mol% (an example of a typical structural formula is shown below),

(2) Compound having 3 p-phenylene groups: about 32 mol%, and

(3) Compound having 4 or more p-phenylene groups: about 27 mol%
It was found to be a mixture of Moreover, the content rate of the addition reactive carbon-carbon double bond as the whole mixture was 0.36 mol / 100g.

[For comparison]
A-2: Dimethylpolysiloxane having both ends blocked with dimethylvinylsilyl groups and a kinematic viscosity at 25 ° C. of 600 mm ² / s A-3: Both ends blocked with dimethylvinylsilyl groups and having a kinematic viscosity at 25 ° C. 30,000 mm ² / s dimethylpolysiloxane

[Component (B)]
(B-1) Metallic gallium [melting point = 29.8 ° C.]
(B-2) Ga-In alloy
[Mass ratio = 75.4: 24.6, melting point = 15.7 ° C.]
(B-3) Ga-In-Bi-Sn alloy
[Mass ratio = 9.4: 47.3: 24.7: 18.6, melting point = 48.0 ° C.]
(B-4) Indium metal [melting point = 156.2 ° C.] <For comparison>

[Component (C)]

[(D) component]
D-1: A-2 solution of platinum-divinyltetramethyldisiloxane complex (100 ppm by mass as platinum atom)

[(E) component]
(E-1): Alumina powder [Average particle diameter: 7.2 μm]
(E-2): Zinc oxide powder [Average particle size: 1.0 μm]

で表される粘度３２ｍｍ^２／ｓの片末端トリメトキシシリル基封鎖ジメチルポリシロキサン [(F) component]
F-1: Structural formula below

A dimethylpolysiloxane having a one-terminal trimethoxysilyl group-blocked dimethylpolysiloxane having a viscosity of 32 mm ² / s

[(G) component]
G-1: Organosilane represented by C ₁₂ H ₂₅ Si (OC ₂ H ₅ ) ₃

[(H) component]
H-1: 1-ethynyl-1-cyclohexanol

[Examples 1-6, Comparative Examples 1-5]
[Preparation of composition]
Using the components having the compositions and amounts described in Tables 1 and 2, compositions were prepared as follows.
(A) component, (B) component, (E) component, (F) component, and (G) component are added to a conditioning mixer (made by Shinky Co., Ltd., trade name: Awatori Netaro) with an internal volume of 250 ml, The temperature was raised to 70 ° C. and the temperature was maintained, and kneading was performed for 5 minutes. The kneading was then stopped and cooled to 15 ° C.
Next, the (C) component, the (D) component, and the (H) component were added, each temperature was maintained, and each composition was prepared by kneading so as to be uniform.

  The test relating to the effect of the present invention was performed as follows.

<Preparation of cured product>
Each composition obtained in Examples 1 to 6 and Comparative Examples 1 to 5 was applied to the entire surface of a standard aluminum plate, and another standard aluminum plate was stacked on top of each other to obtain a micrometer (Mitutoyo Corporation, model: M820-25VA). ) Was adjusted to a range of 30 to 50 μm. Next, the temperature was raised to 125 ° C. in an electric furnace, and the composition was cured by maintaining the temperature for 1 hour, and then allowed to cool to room temperature to prepare a sample for measuring thermal resistance.
The thickness of each sample obtained was measured again (using the aforementioned micrometer) and the thickness of each cured composition was calculated by subtracting the known thickness of the standard aluminum plate.

<Measurement of thermal resistance>
Using each of the above samples, the thermal resistance (mm ² · K / W) of each cured composition was measured using a thermal resistance measuring instrument (Holometrics Microflash). This measurement is called “initial measurement”. Next, the above-described sample was left in a constant temperature and humidity chamber at a temperature of 85 ° C./85% relative humidity for 1000 hours, and then the thermal resistance was measured again. This measurement is “85 ° C./85% measurement after 1000 hours”.

<Measurement of viscosity>
The absolute viscosity of the composition was measured with model number PC-1TL (10 rpm) manufactured by Malcolm Corporation.

<Measurement of thermal conductivity>
The thermal conductivity was measured at 25 ° C. using TPA-501 manufactured by Kyoto Electronics Industry Co., Ltd.

<Particle size measurement>
The particle size measurement of the thermally conductive filler is a volume-based cumulative average diameter measured by Microtrac MT3300EX, a particle size analyzer manufactured by Nikkiso Co., Ltd.

  The results of each measurement of the obtained composition are also shown in Tables 1 and 2. H / Vi represents (total number of hydrogen atoms bonded to silicon atoms in component (C)) / (total number of addition reactive carbon-carbon double bonds in component (A)).

  As shown in Table 1, in Examples 1 to 6 that satisfy the requirements of the present invention, the results of the thermal resistance test after “85 ° C./85% after 1000 hours” as compared with Comparative Examples 1 to 5 Was good. On the other hand, as shown in Table 2, from Comparative Examples 1 and 2, when the component (A) does not contain the component (a-1) or component (a-2), When exposed, the heat dissipation performance deteriorates. From Comparative Example 3, when the amount of the component (B) is less than the range of the composition of the present invention, the thermal resistance increases and the thermal conductivity decreases. From Comparative Example 4, when the amount of the component (B) is larger than the range of the composition of the present invention, a non-uniform composition is obtained. From Comparative Example 5, when gallium is not included in the component (B), a non-uniform composition is obtained. From this, it was confirmed that the curable thermally conductive resin composition of the present invention is a composition that can continuously exhibit heat dissipation performance even when exposed to a high temperature and high humidity environment for a long time.

<Application to semiconductor devices>
0.2 g of the composition obtained in each of the above Examples 1 to 6 was applied to the surface of a 2 cm × 2 cm CPU to form a coating layer. A heat radiating member was laminated and cured on the coating layer to obtain a semiconductor device in which the CPU and the heat radiating member were joined via a heat conductive layer having a thickness of 20 to 70 μm. When these devices were installed and operated in a host computer, personal computer, etc., the heat generation temperature of the CPU was about 100 ° C. In any case, stable heat conduction and heat dissipation are possible for a long time. Yes, it was possible to prevent CPU performance degradation and damage due to overheat accumulation. Therefore, it was confirmed that the reliability of the semiconductor device was improved by employing the cured product of the composition of the present invention.

  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.

DESCRIPTION OF SYMBOLS 1 ... Covering layer, 2 ... IC package, 3 ... Printed wiring board, 4 ... Heat radiation member, 5 ... Clamp, 11 ... Thermally conductive layer

Claims (12)

(A) Addition reaction product of the following (a-1) and (a-2) having 2 addition-reactive carbon-carbon double bonds in one molecule: 100 parts by mass ,
[(A-1) is the following general formula (1)

(In the formula, each R is independently a unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms or an alkoxy group having 1 to 6 carbon atoms substituted with a halogen atom, a cyano group or a glycidoxy group.)
A compound having two hydrogen atoms bonded to a silicon atom represented by
(A-2) is a polycyclic hydrocarbon having two addition-reactive carbon-carbon double bonds in one molecule, and is contained in an excess molar amount relative to 1 mol of the component (a-1). ]
(B) Gallium having a melting point of 0 to 70 ° C. or an alloy thereof, or both: 200 to 20,000 parts by mass,
(C) Organohydrogenpolysiloxane having hydrogen atoms bonded to two or more silicon atoms in one molecule: (total number of hydrogen atoms bonded to silicon atoms in component (C)) / ((A ) The amount that the sum of the number of addition-reactive carbon-carbon double bonds in the component) is 0.1 to 5.0,
(D) Catalyst selected from the group consisting of platinum and platinum compounds: Curing characterized in that it contains an amount of 0.1 to 500 ppm as platinum atoms with respect to 100 parts by mass of component (A). Heat conductive resin composition. Furthermore, (E) Thermally conductive filler having an average particle diameter of 0.1 to 100 μm: It contains 0 to 1,000 parts by mass with respect to 100 parts by mass of the component (A). The curable thermally conductive resin composition according to claim 1. Furthermore, (F) the following general formula (2)

Wherein R ¹ is the same or different monovalent hydrocarbon group, R ² is an alkyl group, an alkoxyl group, an alkenyl group or an acyl group, a is an integer of 5 to 100, and b is 1 It is an integer of ~ 3.)
The polysiloxane represented by the formula: The curable thermally conductive resin according to claim 1, which contains 10 to 500 parts by mass with respect to 100 parts by mass of the component (A). Composition. Furthermore, (G) the following general formula (3)
R ³ _c Si (OR ⁴ ) _4-C (3)
Wherein R ³ is each independently an unsubstituted or halogen-substituted monovalent hydrocarbon group having 1 to 20 carbon atoms, R ⁴ is each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, c Is an integer from 1 to 3.)
Or an organosilane-containing compound obtained by hydrolytic condensation or partial hydrolysis-condensation of the organosilane, or both: 1 to 100 parts by mass per 100 parts by mass of the component (A) The curable thermally conductive resin composition according to any one of claims 1 to 3, wherein the curable thermally conductive resin composition is provided. Further, (H) a control agent selected from the group consisting of an acetylene compound, a nitrogen compound, an organic phosphorus compound, an oxime compound and an organic chloro compound: 0.05 to 0.5 mass with respect to 100 parts by mass of the component (A) The curable thermally conductive resin composition according to any one of claims 1 to 4, wherein the curable thermally conductive resin composition comprises a part. A method for producing a curable thermally conductive resin composition according to any one of claims 1 to 5,
(I) a step of obtaining a uniform mixture by kneading the components (A) and (B) at a temperature within the range of 40 to 120 ° C. and a temperature equal to or higher than the melting point of the component (B);
(Ii) stopping the kneading and cooling the temperature to below the melting point of the component (B); and (iii) the component (C) with respect to the mixture obtained in the step (ii). And a step of adding the component (D) and kneading at a temperature lower than the melting point of the component (B) to obtain a uniform mixture.   The curable heat according to claim 6, further comprising any one or more of the components (E), (F) and (G) as a component to be kneaded in the step (i). A method for producing a conductive resin composition.   The method for producing a curable thermally conductive resin composition according to claim 6 or 7, further comprising the component (H) as a component to be kneaded in the step (iii).   A thermally conductive cured product obtained by curing the curable thermally conductive resin composition according to any one of claims 1 to 5 at 80 to 180 ° C.   A method for using a thermally conductive cured product, comprising using the thermally conductive cured product according to claim 9 as a thermally conductive layer sandwiched between a heat generating electronic component and a heat radiating member.   A semiconductor device comprising: an exothermic electronic component; a heat dissipation member; and a heat conductive layer made of a cured product of the curable heat conductive resin composition according to any one of claims 1 to 5. The semiconductor device is characterized in that the heat generating electronic component and the heat radiating member are joined via the heat conductive layer. A method for manufacturing a semiconductor device according to claim 11, comprising:
(A) The curable thermally conductive resin composition according to any one of claims 1 to 5 is applied to a surface of the heat-generating electronic component, and the coating layer made of the composition is formed into the heat-generating element. Forming on the surface of the electronic component,
(B) a step of pressing and fixing the heat dissipating member to the covering layer to obtain a structure comprising the exothermic electronic component, the covering layer and the heat dissipating member; and (c) 80 to 180 ° C. of the structure. And a step of curing the coating layer to form the thermally conductive layer.

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